You are on page 1of 1087

Fuels and

Lubricants
Handbook:
Technology,
Properties,
Performance,
and Testing
George E. Totten, Editor
Section Editors
Steven R. Westbrook
Rajesh J. Shah

ASTM Manual Series: MNL37WCD

ASTM International
100 Barr Harbor Drive
PO
Box C700
#
iMTBttmrmtM. West Conshohocken, PA 19428-2959
Printed in the U. S. A.

Library of Congress Cataloging-in-Publication Data

Fuels and lubricants handbook: technology, properties,


performance, and testing/George E. Totten, editor;
section editors, Steven R. Westbrook, Rajesh J. Shah,
p. cm.(ASTM manual series; MNL 37)
Includes bibliographical references and index.
ISBN 0-8031-2096-6
1. FuelTestingMethodology. 2. FuelAnalysis.
3. Lubrication and lubricantsAnalysis. I. Totten,
George E. II. Westbrook, Steven R., 1956-III. Shah,
Rajesh J., 1969-IV. Series.
TP321.F84 2003
662',6dc21

2003049604

Copyright 2003 ASTM International, West Conshohocken,


PA. All rights reserved. This material may not be reproduced or
copied, in whole or in part, in any printed, mechanical, electronic,
film, or other distribution and storage media, without the written
consent of the publisher.

Photocopy Rights
Authorization to photocopy items for internal, personal, or
educational classroom use, or the internal, personal, or educational classroom use of specific clients, is granted by ASTM
International (ASTM) provided that the appropriate fee is
paid to the Copyright Clearance Center, 222 Rosewood Drive,
Danvers, MA 01923; Tel: 978-750-8400; online: http://www.
copyright.com/.

Printed in Glen Bumie, MD


June 2003

Foreword
This publication, Fuels and Lubricants Handbook: Technology, Properties, Performance,
and Testing, was sponsored by ASTM Committee D02 on Petroleum Fuels and Lubricants and edited by George E. Totten, G. E. Totten & Associates, LLC, Seattle, Washington. The section editors were Steven R. Westbrook, Southwest Research Institute,
San Antonio, Texas; and Rajesh J. Shah, Koehler Instrument Company, Bohemia, New
York. This publication is Manual 37 of ASTM's manual series.

Contents
PrefaceGeorge E. Totten, Steven R. Westbropk, and Rajesh J. Shah

ix

I. PETROLEUM REFINING PROCESSES FOR FUELS


AND LUBRICANT BASESTOCKS^o/esfe / . Shah, Section Editor
Chapter 1Petroleum Oil Refining
Marvin S. Rakow

II. FUELS: PROPERTIES AND PERFORMANCE


Steven R. Westbrook, Section Editor
Chapter 2Liquefied Petroleiun Gas
Roberts. Falkiner

31

Chapter 3Motor Gasoline


B. Hamilton and Robert J. Falkiner

61

Chapter 4Aviation Fuels


Kurt H. Strauss

89

Chapter 5^Automotive Diesel and Non-Aviation Gas Turbine Fuels


Steven R. Westbrook and Richard he Cren

115

Chapter 6Introduction to Marine Petroleum Fuels


Matthew F. Winkler

145

III. HYDROCARBONS AND SYNTHETIC LUBRICANTS:


PROPERTIES AND PERFORMANCE/?a;es/i/. Shah, Section Editor
Chapter 7Hydrocarbon Base Oil Chemistry
Arthur J. Stipanovic

169

Chapter 8Hydrocarbons for Chemical and Specialty Uses


Dennis W. Brunett, George E. Totten, and Paul M. Matlock

185

Chapter 9Additives and Additive Chemistry


Syed Q. A. Rizvi

199

Chapter 10Synthetic Lubricants: Nonaqueous


Thomas F. Buenemann, Steve Boyde, Steve Randies,
and Ian Thompson

249

Chapter 11Environmentally Friendly Oils


Hubertus Murrenhoff and Andreas

267
Remmelmann

Chapter 12Turbine Lubricating Oils and Hydraulic Fluids


W. David Phillips

297

vi

CONTENTS
Chapter 13Hydraulic Fliiids
Willie A. Givens and Paul W. Michael

353

Chapter 14Compressor Lubricants


Desh Garg, George E. Totten, and Glenn M. Webster

383

Chapter 15Refrigeration LubricantsProperties and Applications


H. Harvey Michels and Tobias H. Sienel

413

Chapter 16Gear Lubricants


Vasudevan Bala

431

Chapter 17Automotive Lubricants


Shirley E. Schwartz, Simon C. Tung, and Michael L. McMillan

465

Chapter 18Metalworking and Machining Fluids


Syed Q. A. Rizvi

497

Chapter 19Petroleum Waxes


G. Ali Mansoori, H. Lindsey Barnes, and Glenn M. Webster

525

Chapter 20Lubricating Greases


Thomas M. Verdura, Glen Brunette, and Rajesh Shah

557

Chapter 21Mineral Oil Heat Transfer Fluids


John Fuhr, Jim Oetinger, George E. Totten, and Glenn M. Webster

573

Chapter 22Non-Lubricating Process Fluids: Steel


Quenching Technology
Bozidar Liscic, Hans M. Tensi, George E. Totten,
and Glenn M. Webster

587

rv. PERFORMANCE/PROPERTY TESTING PROCEDURES


Steven R. Westbrook and Rajesh J. Shah, Section Editors
Chapter 23Static Petroleum Measurement
Lee Oppenheim

635

Chapter 24Hydrocarbon Analysis


James C. Fitch and Mark Barnes

649

Chapter 25Volatility
Rey G. Montemayor

675

Chapter 26Elemental Analysis


R. Kishore Nadkami

707

Chapter 27Diesel Fuel Combustion Characteristics


Thomas W. Ryan HI

717

Chapter 28Engineering Sciences of Aerospace Fuels


Eric M. Goodger

729

Chapter 29Properties of Fuels, Petroleum Pitch, Petroleum Coke,


and Carbon Materials
Semih Eser and John M. Andresen

757

CONTENTS
Chapter 30Oxidation of Lubricants and Fuels
Gerald J. Cochrac and Syed Q. A. Rizvi

787

Chapter 31Corrosion
Maureen E. Hunter and Robert F. Baker

825

Chapter 32Flow Properties and Shear StabiUty


Robert E. Manning and M. Richard Hoover

833

Chapter 33Cold Flow Properties


Robert E. Manning and M. Richard

879
Hoover

Chapter 34Environmental Characteristics of Fuels


and Lubricants
Mark L. Hinman

885

Chapter 35Lubrication and Tribology Fundamentals


Hong Liang, George E. Totten, and Glenn M. Webster

909

Chapter 36Bench Test Modeling


Lavem D. Wedeven

963

Chapter 37Lubricant Friction and Wear Testing


Michael Anderson and Frederick E. Schmidt

1017

Chapter 38Statistical Quality Assurance of Measurement Processes


for Petroleiun and Petroleum Products
Alex T. C. Lau

1043

Index

1061

vii

Preface
There are many books on various aspects of fuels and lubricant chemistry, applications,
and testing. However, few focus on testing and none provide extensive, in-depth coverage on fluid properties and testing methodologies together. And while there are numerous national and international standards that deal with specific testing procedures
appropriate for fuels and lubricants, it is generally beyond the scope of these procedures to provide an extensive discussion of the principles behind the tests and their relationship to the properties themselves. Therefore, there is a strong need to address
these informational shortcomings in the Fuels and Lubricants industry, which is one of
the most significant tasks undertaken in this work.
The ASTM Fuels and Lubricants Handbook: Technology, Properties, Performance, and Testing is an extensive, in-depth, well-referenced handbook that provides
a detailed overview of various testing methodologies and also provides a thorough
overview of the applications-related properties being tested. Since this manual provides
an overview of all of the ASTM and important non-ASTM test procedures relating to the
application areas addressed, it is an excellent companion text to the Annual Book of
ASTM Book of Standards, or it is an invaluable reference manual on its own.
The organization of the ASTM Fuels and Lubricants Handbook: Technology, Properties, Performance, and Testing is based approximately on the committee structure
of the ASTM D.02 Petroleum Fuels and Lubricants Committee and the standards for
which each committee is responsible. The information in this text is subdivided into
four sections: I-Petroleum Refining Processes for Fuels and Lubricant Basestocks;
II-Fuels; Ill-Hydrocarbons and Synthetic Lubricants; and IV-Performance/Property
Testing Procedures.
This manual contains thirty-eight chapters covering the following topics:
An overview of petroleum oil refining processes
Liquified petroleum gas (LPG)
Aviation, automotive diesel, non-aviation gas turbine, and marine fuels
Gasoline and oxygenated fuel blends
Petroleum hydrocarbon base oil chemistry
Synthetic hydrocarbons
Environmentally friendly fluids including those formulated from vegetable oil and
synthetic ester basestocks
Lubricating oils for turbines, compressors (industrial and refrigeration), gears, and
automotive applications
Metalworking fluids
Petroleum waxes
Lubricating greases
Oils used in non-lubricating applications: heat transfer fluids and metal quenchants
Detailed discussion on: static petroleum measurement, volatility, elemental analysis,
fuel combustion characteristics, oxidation, corrosion and viscosity
Properties of coke, petroleum pitch, and carbon materials
Hydrocarbon structural analysis procedures
An extensive discussion of lubrication and wear
Environmental and toxicity testing
Statistical quality assurance testing procedures
Essentially, all of the numerous important applications and test methods involved
in the Fuels and Lubricants industry are discussed and referenced here. We strongly
believe that this book will be an invaluable resource for anyone working in this
industry, especially since this information is not available in any other single source.
ix

PREFACE
The preparation of a text of this scope was an enormous task involving many people.
The editors are deeply indebted to the authors for their h a r d work and incredible patience. Specicd thanks go to Monica Siperko and Kathy Demoga at ASTM for their continued support and encouragement throughout the development of this text. The editors are especially indebted to their families for many evenings and weekends lost to
this project. We Eilso acknowledge the vital support of Southwest Research Institute and
the Koehler Instrument Corporation.
George E. Totten
General Editor
G.E. Totten & Associates, LLC.
Seattle, WA, USA
Steven R. Westbrook
Section Editor-Fuels
Southwest Research Institute
San Antonio, TX, USA
Rajesh J. Shah
Section Editor-Lubricants
Koehler Instrument Company
Bohemia, NY, USA

Section I: Petroleum Refining Processes for Fuels and


Lubricant Basestocks
Rajesh J. Shah, Section Editor

MNL37-EB/Jun. 2003

Petroleum Oil Refining


Marvin S. Rakow^

THIS CHAPTER PRESENTS AN OVERVIEW of t h e m o d e m , integrated

oil refinery, a n d how it separates a n d processes crude oil and


other hydrocarbon feedstocks into the required array of liquid fuels a n d other products. A description of an overall, simplified refinery flow plan serves to introduce the subject and
terminology unique to the industry.
I m p o r t a n t crude oil properties a n d test methods, along
with a perspective on past, current, a n d likely future fuel
product quality and demand, is presented. Each important
refinery process is described in sufficient detail to appreciate
its purpose, operating characteristics, yield a n d quality parameters, a n d current and future utilization in light of anticipated fuels product trends.

GENERIC REFINERY FLOW PLAN


Figure 1 is a simplified block flow diagram of a fully integrated refinery utilizing the major process options in genereJ
use. Each actual plant will incorporate those options that
meet crude throughput and quality, as well as product dem a n d and quality, while striving for m i n i m u m capital and
operating cost. Since most refineries reach their current configuration by periodic revamp and expansion, it is both likely
and economically feasible for two refineries with similar feed
and product slates to have a different mix of processes to satisfy all technical a n d economic parameters.
Crude oil first undergoes physical separation by distillation
(ASTM Test Method for Distillation of Petroleum Products,
D 86-99a) to yield various boiling range streams as dictated by
the chemical processing to follow (Table 1). The atmospheric
distillation unit usually separates about one-half of the crude
oil into the indicated cuts ranging from the low boiling gases
through a gas oil. The final boiling point of the atmospheric
gas oil can range from as low as 340C t o as high as 410C.
Vacuum distillation of the atmospheric distillation unit bottoms (ASTM Test Method for Distillation of Petroleum Products at Reduced Pressure, D 1160-95) usually separates another 30% of the crude oil as vacuum gas oils having a fined
boiling point ranging from 500-575C.
Selection of downstream processing units is greatly dictated by demand and specifications of the different products,
and, particularly, increasing sulfur removal requirements.
One of the key considerations is gasoline demand. For exam-

' President, Edu-Tech Management Resources, 73 Yorktown Road,


East Brunswick, NJ 08816-3329.

Copyright'

2003 by A S I M International

pie, in the United States, one hundred volumes of crude oil


are converted into about fifty volumes of gasoline (the ratio
is about 42% o n a weight basis). Yet, crude oil typically has
only 15 to 20% of its hydrocarbons in the gasoline boiling
ramge. The fluid cataljrtic cracking unit (FCCU) is the main
process that provides the additional "gasoline" and is thus a
key process unit in the U.S. refinery flowsheet. The gasoline
to crude oil ratio is substantially lower in all other parts of the
world; thus FCCU, while in place worldwide, plays a significantly lesser role in non-U.S. refineries. Similar comparisons
are summarized for other refinery processes in Table 2.
In order of increasing boiling range, description and utilization of the distillation fractions are as follows:
CI to C4 gasesThe crude oil gases, along with gases created by the downstream process chemistry, cu^e separated
by carbon n u m b e r and hydrocarbon type in one o r more
light ends plants (also called vapor recovery units, o r "sats"
and "unsats" gas plants). Impurities, the main one being
H2S, a r e removed, with final separation providing t h e
product disposition shown in Table 3.
LSRThe light (straight run) gasolines, in most refineries,
are blended directly t o t h e gasoline pool. If a refiner is
squeezed for octane number, o r if LSR octane quality diminishes d u e t o refiner response to changing gasoline
specifications, the octane n u m b e r of this stream cem be increased by the isomerization process.
HSRThe heavy (straight r u n ) naphtha, whether from
crude oil or other process units, is too low in octane number to be economically blended in gasoline. Thus, all HSR
is processed through the catalytic reforming unit (CRU)
wherein the hydrocarbon composition is changed or "reformed" to a higher octane n u m b e r stream.
KerosineThis fraction, after appropriate cleanup (treating), is directly sold to the kerosine and jet fuel markets
and is also used as a blending component for the lighter
fuel oils and diesel fuels. Since the jet fuel market now exceeds the kerosine market in parts of the world, many refiners now label this stream the "jet" cut.
Atmospheric Gas Oil (AGO)The gas oils are generally
those distillable streams heavier than kerosine. The name
was derived in the early industry days when these oils were
thermcJly cracked to produce olefin-containing "illuminating" gases for street lighting, for example. Depending on
the final boiling point of the AGO a n d the downstream process options, t h e atmospheric distillation unit m a y jdeld
one AGO c u t o r two. The lighter portion m a y b e hydrotreated to produce low sulfur diesel, while the heavier
cut, hytrotreated or not, is typically processed in the FCCU.

www.astm.org

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

C, + C,
GASES

REF. FUEL

PROPANE

LPG
ALKYLATE
-MTBE
GASOLINE

LPG

BUTANES

CRUDE

LSR

A
T
M
D
I

S
T

ATM V

ISOMERIZATION

-GASOLINE

NAPH

HYDROTREATING

KERO

HYDROTREATING

GAS OIL

CAT
REFORMING

JET FUEL

HYDROTREATING

GASES

RESID

No. 2 FO/DIESEL

MTBE
ALKYLATION

L
V
A
C
D
I

GASOLINE

GASOLINE

GASOLINE
FLUID

LVGO

LCO

No. 2 FO

CATALYTIC
HCO
CRACKING

HVGO

DO

No. 6 FO
CARBON BLACK
H, PLANT

HYDROCRACKING

No. 6 FO
ASPHALT
VAC RESID

REFORMER FEED
JET FUEL

VISBREAKING
DEASPHALTING
COKING
HYDROCRACKING

FIG. 1Refinery block flow diagram.

Vacuum Gas Oils (LVGO and HVGO)i:\iese cuts are usually processed in the FCCU. They can be processed in a hydrocracking unit (HCU) wherein they can be converted
into catalytic reformer feed, jet and diesel fuel, and for production of lubricating oil base stocks.
Vacuum ResidThe residuum portion of crude oil is the
non-distillable cut, boiling above, say, 575C. It cannot be
distilled without causing substantial thermEd destruction
of its hydrocarbons. This cut is sold to the asphalt and
heavy fuel oil markets, or processed by the options shown
in Fig. 1.

The need for sulfur removal is on an ever-increasing path


as average crude oil sulfur content continues to increase and
product sulfur is forced to lower levels by environmental legislation. Sulfur removal, today, is accomplished in "hydroprocessing" units. Hydrotreating, wherein the goal is to
remove sulfur (and other heteroatoms) with minimum conversion of the hydrocarbon feed stream to lower boiling
molecules, is the most widely utilized. Alternatively, hydrocracking is utilized to remove heteroatoms and concurrently
convert varying amounts of "high boilers" to lower boiling
streams.

CHAPTER 1: PETROLEUM
TABLE 1Crude section cuts.
Carbon
Number
Name/Other Names
Gases
Light straight run gasohne
light n a p h t h a
LSR
gas condensate
Heavy straight run naphtha
Heavy naphtha
Naphtha
Reformer feed
Kerosine or kerosine
jet
Light atmospheric gas oil
furnace oil
diesel
Heavy atmospheric gas oil
AGO
gas oil
Light and heavy vacuum gas oils
LVGO and HVGO
Vacuum resid"
vacuum bottoms
short resid
vacuum reduced crude
asphalt

C1-C4
C5-C6

Approximate
Boiling Range, "C
-160-0
25-90

C6-C10

85-190

C9-C15

160-275

C13-C18

250-340

C16-C25

315^10

C22-C45

370-575

C40+

500+-565 +

"The corresponding bottoms from the Atmospheric Crude Tower is called:


Atmospheric Resid
Reduced Crude
Atmospheric Bottoms
Topped Crude
Long Resid

OIL REFINING

the maximum possible hydrogen. To compUcate matters, in


crude oil some carbon atoms are also bonded to sulfur, nitrogen, oxygen and metals, as well as trace amounts of other
elements.
The four hydrocarbon types, based on the above characteristics, are:
Name
Paraffin
Olefin
Naphthene
Aromatic

Chain/Ring

Saturated/Unsaturated

Example

Chain
Chain
Ring
Ring

Saturated
Unsaturated
Saturated
Unsaturated

Hexane
Hexene
Cyclohexane
Benzene

The four types are listed in the order shown after chemical analysis, and are usually referred to by the term PONA
analysis (ASTM Test Method for Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption, D 1319-98). In chain hydrocarbons, all carbon atoms
can be linked in a straight row; these are the "normal" versions, such as the example of a six-carbon hydrocarbon,
normal hexane (n-hexane). "Isomers" of n-hexane exist as
branched-chain versions; as a group, these are labeled
isoparaffins, for example i-hexanes. They are commonly
connotated as nC6 and iC6s. When a hydrocarbon type
analysis is made that includes a normal/isoparaffin split, the
normals keep the letter P, the isos take the letter I, and the
olefin/aromatic order is reversed, resulting in the acronym
PIANO. This same split is not attempted for the normal and
branched-chain olefins because of the greater number of
potential olefin structures and the lesser impact on refinery
process options.

HYDROCARBON TERMINOLOGY
There cire four basic tjrpes of hydrocarbon chemical structures. Their differences relate to the bonding between carbon
atoms and whether the carbon bonds create a chain- or ringshaped molecule. The number of electrons in the outer shell
of a carbon atom requires each atom to have four bonds to be
stable. This four-bond requirement can be peirtially met by a
carbon atom forming single or multiple bonds with adjacent
carbon atoms. Nearly all hydrocarbon molecules encountered in refining chemistry consist of all singly bonded carbons, or contain pairs of doubly bonded adjacent carbons;
the remaining bonds cu-e satisfied with hydrogen. When eill
carbon-carbon bonds in a molecule are single, it is called saturated, because it contains the maximum possible amount of
bonded hydrogen. When there cire double bonds present, the
hydrocarbon is labeled unsaturated, since it holds less than

Region
Asia/Pacific
Western Europe
Eastern Europe/FSU
Middle East
Africa
North America
So. America/Caribbean

TABLE 3Disposition of refinery C1-C4 gases.


Carbon
Number

Chemical
Name

CI
C2

Methane
Ethane
Ethylene
Propane
Propylene

C3
C4

End Uses

n-Butane
i-Butane
Butylenes

Refinery Fuel Gas (RFG)


RFG
RFG, PetrochemicEils
Liquefied Petroleum Gas (LPG)
Petrochemicals, Alkylation Unit,
Polygas or Dimerization Unit
LPG, Isomerization Unit, Gasoline
Blending
Alkylation Unit
Alkylation Unit, MTBE, Polygas or
Dimerization Unit, Petrochemicals,
Isooctane Unit

TABLE 2^Worldwide refining capacity as percent of crude.


Weight Percent on Crude Capacity
Crude Oil
Distillation,
Vacuum
Hyd retreating
Million mt/year
Distillation
FCCU
CRU
+ Hydrocracking

1020
740
540
300
160
1010
340

23
36
35
34
15
46
43

4110
Source: Oil & Gas Journal Worldwide Refining Report for January, 2001.

13
15
8
5
6
33
19

9
13
12
9
11
19
5

41
58
38
37
25
68
29

Coke

0.4
0.5
0.8
0.3
0.2
4.5
1.8

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

By chemical naming convention, all saturated hydrocarbons, the paraffins and naphthenes, end in the letters "ane,"
while all unsaturated hydrocEirbons, the olefins and aromatics, end in the letters "ene." Each of the four species has different properties and reactivity, and this plays a major role in
refinery unit selection and operation. The amount of the various heteroatoms and the m a n n e r in which they are bound to
carbon also is critical to refinery operation. These factors will
be apparent throughout the remainder of this chapter as well
as in other parts of this manual.

C R U D E OIL

almost always less dense than water, which has a specific


gravity of 1.0. Worldwide, average API Gravity is about 31
(sp. gr. = 0.87) and ranges from a high of about 45 for "light"
crudes to a low of 8-15 for the "heavy" crudes, tar sand oils,
and the like. Aromatics are the densest of the hydrocarbon
types and are therefore lowest in API, while peiraffins Eire generally highest in API gravity. As boiling point of the crude oil
increases, a r o m a t i c s content increases. Thus, high API
crudes likely have lower concentrations of high boilers and
most likely less aromatics, while low API crudes are generally
higher in aromatics and in high boilers.
Sulfur

Hydrocarbon Composition
Crude oil is composed of aromatic, paraffin and naphthene
hydrocarbons. Minor amounts of olefins may be present. Average aromatics content is about 50%; however, it can range
from as low as 2 5 % in light paraffinic crudes to as m u c h as
75% in heavy oils, such as those recovered from Canadian tar
sands. The paraffin/naphthene ratio is widely ranging and is
qualitatively identified via the labeling of many crudes as
"paraffinic" or "naphthenic." Hydrocarbon composition affects many considerations in selecting processing options, or
meeting product specifications, as shown by the following examples:

Worldwide, weight average crude oil sulfur content is about


1.25% with commercial production ranging from 0.1-6%.
Crudes low in sulfur are labeled "sweet" while those higher in
sulfur ure designated "sour." The terms derive mainly from
the foul, or sour, odor of one of the sulfur species, the mercaptans, as well as the corrosiveness of hydrogen sulfide and
the mercaptans. The split between sweet and sour was at
0.5% when average sulfur was m u c h lower than today; now,
the crossover is more likely in the 0.5-1.5% range and is usually designated by each refinery depending on its history and
capability to process higher sulfur crudes. Barring the discovery of major low sulfur crude oil pools, it is expected that
average sulfur will continue to modestly increase.

Aromatics
Because of their inherent molecular stability, they are the
bane of refining. Aromatics are the most difficult compounds
to thermally crack, hydrogenate, and desulfurize. They are
increasingly "unwanted" species in fuel products because
they are the hardest to completely combust, thus contributing more to pollution and equipment maintenance. As product aromatics content is regulated to lower levels, refinery
process severity and costs will increase. Aromatics do have
value in the refinery flow plan as a high-octane gasoline
blending component from the catalytic reforming unit and in
the recovery of chemical grade aromatic feedstocks for the
petrochemical industry.
Paraffins

and

Naphthenes

These constituents are more readily processed in the refinery.


Each offers "positive" and "negative" features, but the effects
of these species are not as severe as for the aromatics. As an
example, paraffins crack cleanly and thus yield m i n i m u m
coke, but, in fuel blends, they raise pour point and are more
difficult to octane-upgrade in the CRU.
Density
The density of chemiceJ compounds is expressed as specific
gravity (sp. gr.). In the petroleum industry, this weight/volu m e relation is expressed worldwide as "API (American
Petroleum Institute), or commonly as "API Gravity", per the
formula "API = (141.5/sp.gr.) - 131.5 (ASTM Test Method
for API Gravity of Crude Petroleum and Petroleum Products,
D287-92). The formula was adapted from the Baume density
equation used for sulfuric acid. Its value is the creation of a
whole n u m b e r scale to more readily discern one crude oil
from another, rather than using decimals, since crude oils are

Nitrogen
Generally, nitrogen content is about 5-20% of sulfur content
in most crudes. This is a helpful circumstance because nitrogen removal requires greater process severity than sulfur removal since nitrogen is mostly bound in ring form while a
greater percent of sulfur is bound in chain form. Heteroatom
removal from rings is more difficult than from chains. Many
California crude oils are high in nitrogen content, often
equaling sulfur content, and thus require greater process
severity than other crudes of equal sulfur content.
Metals
Organometallic compounds are predomineintly found in the
vacuum resid. Important metals are nickel, vanadium, copper and iron, with nickel (Ni) and vanadium (V) usually in
highest concentration. Ni + V levels in resid range from a few
p p m to as m u c h as 1000 ppm. The metals, particularly Ni,
have an adverse effect on catalyst performance and have
specified maximum limits in products such as heavy fuel oil
and petroleum coke. This can affect crude selection options
for many refinery process configurations and product slates,
as well as in process selection for future refinery revamp/expansion projects.
Oxygen
Acids, particularly naphthenic acids, and phenols constitute
the main organic oxygen compounds in crude oil. A substantial portion are in the naphtha, kerosine, and gas oil boiling
ranges. These compounds are readily eliminated via hydrogenation, and will pose less concern as more hydrotreating is

CHAPTER
added to the flow plan to achieve greater sulfur removal. If
these streams are not hydrotreated, the acids are usucJly removed by many variations of caustic treating.

PRODUCTS
The main refinery products, except for the gas streams shown
in Table 3, are automotive gasoline, kerosine/jet fuel. No. 2
and No. 6 fuel oils, and No. 2 diesel fuel. Changes to the refinery flow plan have mainly been driven by changes in crude
oil quality, and in specifications and demand for these products. It should be noted that all industry fuels and lubricants
are presented in this manual including a complete presentation and discussion of test methodology and properties.
Gasoline
The first meaningful specifications evolved in the 1920s.
From this beginning until 1990, the two key control properties have been "octane number" and "volatility." Octcine number, the measure of the engine to resist the rapid "pinging"
noise, called "knock," due to improper combustion, steadily
increased as engines became larger and more powerful, peaking in the eeirly 1970s. The refinery met the required octane
appetite of the car population by instcJling processes that
produce high octane streams, such as the FCCU, CRU, and
alkylation and isomerization. In addition, organolead compounds, mainly tetraethyllead (TEL), were used to add about
eight octane numbers to the gasoline pool.
Two laboratory octane n u m b e r test methods are used to
measure and control this gasoline quality parameter, the Research Octane N u m b e r (RON) and Motor Octane N u m b e r
(MON), per ASTM Test Methods for Research Octane Numb e r a n d Motor Octane N u m b e r of Spark-Ignition Engine
Fuel, D 2699-97a and 2700-97, respectively. Their different
operating conditions, detailed in this manual, act to delineate
and bracket the potential for knock in the automobile population. In most of the world, RON is the value the consumer
sees at the "pump," while in the United States and Canada,
the average of both the RON and MON is the guiding specification.
The first significant response to pollution from vehicular
emissions came with the passage of the U.S. Clean Air Act in
1973. This legislation stipulated that the m a i n pollutants
emitted from the automobile tailpipe; namely, u n b u m e d hydrocarbons, carbon monoxide and nitrogen oxides, had to be
reduced by 90%. The automotive industry chose to use a catalyst to comply with this regulation. This "catalytic converter" requires platinum, or other noble metal such as palladium, to effect the desired emissions reduction chemistry.
Platinum's activity, however, is adversely affected by lead. As
a result the oil industry had to remove lead from gasoline and
would have lost the eight octane numbers from the addition
of TEL. The Act also required an increase in fuel economy
from 12.5 mpg (5.35km/l) to 27.5 mpg (11.77km/l). This led
to a reduction in vehicle weight and power, which in turn reduced octane appetite by about four numbers. Thus, the net
effect on the U.S. oil industry from 1974 through the mideighties was to add about four octane numbers to the base
gasoline pool. This was achieved mainly by the addition of

1: PETROLEUM

OIL REFINING

process technology such as catalytic reforming and alkylation. However, the industry also introduced organic oxygenates to gasoline blends, initially alcohols and then ethers,
since such compounds have high octane quality (Table 4).
Of the three utilized alcohols, the only surviving member is
ethanol, which is used in the U.S. through the help of government price subsidy. Concern for water solubility, corrosion, and emissions problems from the alcohols, verified or
not, drove the U.S. refining industry to the ethers. The first,
a n d still dominant, ether was methyl tertiarybutyl ether
(MTBE), which was initially provided by ARCO Chemical
converting tertiarybutyl alcohol, a by-product from their
propylene oxide process, to the isobutylene feed needed to
make the ether.
Volatility requirements can be described as the control of
the boiling range of the gasoline to assure that the automobile operates properly during startup, warm-up, and hot operation. Gasoline specifications assure that there is a proper
balance among the C5 through C l l hydrocarbons that constitute the gasoline boiling reuige, and that the final boiling
point is limited. Volatility control also includes the need to
add liquefied n-butane to provide sufficient vapor pressure
(ASTM Test Method for Vapor Pressure of Petroleum Products (Reid Method), D 323-99a) to ensure cold engine startup.
This results in "seasonal" volatility grades wherein butane
content and boiling range Eire varied to match expected ambient temperature.
As industry used the oxygenates to meet octane number requirements, data showed oxygenates can reduce pollutants
such as carbon monoxide (CO) and nitrogen oxides (NO^).
And, as analysis of the effect of various gasoline constituents
on tailpipe emissions became better defined, it became apparent that other compositional changes would be beneficial.
This was addressed by passage of the U.S. Clean Air Act
Amendments in 1990. This legislation, and subsequent regulations such as those enacted in Ccdifomia, has substantively
changed the entire composition of gasoline (Table 5), per
ASTM Specification for Automotive Spark-Ignition Engine
Fuel, D 4814-99. As a result, the refinery has undergone continuous change to meet the cleaner fuel product requirements. These changes, initiated in the U.S., are being adopted
throughout most of the world; in some instances, legislation
in other locales is resulting in even more severe specifications
(Table 6).

TABLE 4The oxygenates.


Blending
Actual
RVP, kPa RON MON

Source

Name

Alcohols
Methanol
Natural Gas
Ethanol
Crops
t-butyl alcohol Propylene Oxide By-Product
Alcohol
Ethers
MTBE
TAME
ETBE
TAEE
DIPE

133
130
109

99
96
93

54
27
17
6

118
111
118

100
98
102

Olefin

Methanol
Isobutylene
Methanol
Isoamylene
Ethanol
Isobutylene
Ethanol
Isoamylene
(Propylene + Water)

"Average of RON and MON.

32
16
12

104"

8 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


Jet Fuel

TABLE 5History of U.S. gasoline specifications.


Pre-1974
Regular Grade
RON
MON
Pb, g/1
Premium Grade
RON
MON
PB, g/1
RVP, kPa
Oxygen, %w
Benzene, %w, max
90% Dist., C, max
Aromatics, %w
Olefins, %w
Sulfur, p p m w

94
86
0.8
100
90
0.9
62-103
0

1992-1994

1974-1991
Remove Pb,
Increase Fuel
Economy

91
83
0.1

"

98
88
0.1

1995+
91
83
0
98
88
0
50-90
2.0-2.7*
0.8-1.0
165-180
20-35
4-10
30-150

2.7*

0.3-1.0"

185-190
30-45
8-15
300-500

'^Optional use for octane number improvement.


'Mandatory in locales requiring "oxy fuel" or reformulated gasoline.

TABLE 6Gasoline specifications in U.S. and Europe.


California

United States
1998-2000
2004

Locale Year
Oxygen, %w
MTBE, %w
Benzene, %w
Sulfur, p p m w
Aromatics, %v
Olefins, %v

2.0-2.7
11.0-14.8
0.95-1.0
150-350
25-32
6-12

0.0-2.7
Unknown
0.8-1.0
30-150
20-30
4-9

Europe

1996

2000

2005

2.0
11.0"
0.8-1.0
30
25
4-6

2.7
14.8
1.0
150
35
14

2.7
14.8
1.0
10-30
30-35
12-14

''MTBE banned by 2003, but enforcement is currently on hold.

Today's military and commercial aircraft use jet fuels that are
produced almost exclusively from the kerosine fraction of
crude oil or similar boiling range cuts from certain refineiy
processes (Table 7). Key requirements focus on sulfur and
aromatics contents, clean burning characteristics, and storage stability (ASTM Specification for Aviation Turbine Fuels,
D 1655-99). Increasingly, refineries use hydrotreating technology, as well as crude slate selection, to meet specifications
and aircraft power demand. Legislative reduction in sulfur
and aromatics is not currently anticipated.
F u e l Oil
The various fuel oil grades are shown in Table 8 (ASTM
Specification for Fuel Oils, D 396-98). The major products
are No. 2 and No. 6 fuel oils. No. 2 fuel oil, commonly called
furnace oil or home heating oil, is the fuel used for residential and small commercial oil heating systems. No. 6 fuel oil
is commonly called industrial or heavy industrial fuel oil
when used by utilities for electricity and steam generation.
It is called Bunker, or Bunker C, fuel when used by the marine industry for those ships powered by "furnaces." Nos. 1,
4, and 5 are specialty products. For example, No. 1, also
known as stove oil, is a kerosine-type blend for small stovelike non-atomizing b u r n e r s a n d some farm equipment,
while Nos. 4 and 5 are lower viscosity industrial fuel oils for
smaller commercial furnaces such as those used by schools
and hospitcds.
Sulfur content is an important quality parameter. While
most No. 2 fuel oil is specified at 0.5%, maximum, (ASTM
Test Methods for Sulfur in Petroleum Products, D 129-95,
D 1266-98, and D 2622-98, for example) m u c h product has
considerably lower sulfur because of the n e w low sulfur
diesel requirement. Many refiners have found that the added
cost to desulfurize No. 2 fuel oil to match diesel specifications may be offset by reducing the n u m b e r of separate products, providing increased product blending options and reducing storage and distribution costs. No. 6 fuel oil sulfur
ranges from 0.25-3.5% depending on end use and locale. It is
anticipated that average "six-oil" sulfur content will decrease
over time.

TABLE 7Jet fuel specifications.


775-840
Density, kg/m^
204
10% Dist, C, max
Final Boiling Point, C, max
288-300
Flash Point, C, min
38-60
Aromatics, %v, max
20-25
Sulfur, %w, max
0.3-0.4
MercaptEin Sulfur, %w, max
0.002
Freeze Point C, max
- 4 0 to -47

TABLE 8Fuel oil specifications.


Grade
Uses
Density, kg/m^, max
90% Dist, C, max
Flash Point, C, min
Pour Point, C, max
Sulfur, %w, max
Viscosity
mm^/s @ 40C
min
max
mm^/s @ 100C
min
max

No. 1
Stove
and Farm

No. 2
Home
Heating

850
288
38
-18
0.3-0.5

876
338
38-55
-6
0.3-0.5

1.3
2.1

1.9
3.4

No. 4

No. 5

No. 6

Light
Industrial

Medium
Industrial

Heavy Ind'l
& Marine

55
-6

55

60
0.25-3.5

5.5
24.0
5-9
9-15

15
50

CHAPTER
TABLE 9Diesel fuel specifications.
No. 1

No. 2

No. 4

Uses

Farm,
City Bus

Automobile
Truck,
Railroad

Railroad,
Marine,
Stationary Engine

90% Dist, C, max


Sulfur, ppmw, max
Cetane No., m i n
Flash Point, C, min
Aromatics, %w, max

288
10-5000
40-55
38-55
10-35

338
10-5000
40-55
52-55
10-35

20 000
30
55

Grades

Diesel Fuel
Key diesel fuel specifications and major uses eire shown in
Table 9 (ASTM Specification for Diesel Fuel Oils, D975-98b).
The U.S. Clean Air Act Amendments also required the reduction of sulfur to 0.05% (500 ppmw), maximum, for over-theroad usage; namely, buses, trucks, and automobiles. The legislation did not require lower sulfur for other use such as the
railroad and marine industry. Again, as with the fuel oils,
m u c h No. 1 and 2 diesel is made "low sulfur" for all markets
to minimize product distribution costs. Driven initially by
European and California legislation, diesel fuel sulfur is being further reduced toward 10-50 ppmw, requiring more severe hydrotreating.
While the U.S. law did not substantially constrain aromatics content, California law did, requiring reduction of aromatics to as low as 10%. Worldwide adoption of this level of
dearomatization will be difficult to achieve near-term, but a
trend toward lower aromatic content diesel is occurring. This
is being affected in part by requiring higher Cetane N u m b e r
diesel fuel (ASTM Test Method for Cetzuie Number of Diesel
Fuel Oils, D613-95). Aromatics decrease "cetane rating."
P o u r point (ASTM Test Method for Pour Point of
Petroleum Products, D97-96a) and cloud point (ASTM Test
Method for Cloud Point of Petroleum Products, D5771-95)
are importctnt parameters to assure proper flow of fuel oils
and diesel fuels under all anticipated ambient temperatures.
Pour point must be low enough to prevent solidification of
the entire fuel while cloud point must be low enough to assure that normal paraffins will not solidify and block fuel
flow in piping or through nozzles.

CRUDE OIL PREPARATION


AND SEPARATION
A refinery may process just one crude oil or u p to as many as
a few dozen, depending on factors such as captive crude supply, access to ocean and river delivery, and pipeline supply logistics. At a refinery handling multiple crudes, individucil
crude oils are usually fed sequentially over variable lengths of
time. Some of the crude oils may first be blended in intermediate crude storage tanks to reduce the effects of substcintial
changes in crude oil quality on the process units.
In almost all refineries, the crude oil slate is processed as in
Fig. 2. Crude oil is first "descJted" to reduce entrained and
dissolved salts, mainly sodium, m a g n e s i u m and calcium
chlorides, to a n acceptable level a n d to remove "debris" such
as mineral matter resulting from transportation. The crude
oil is then physiccJly separated by distillation in atmospheric

1: PETROLEUM

OIL REFINING

a n d v a c u u m towers/columns/crude u n i t s to provide the


streams in Table 1. Many refineries incorporate a preflash
column before the atmospheric tower to remove a portion of
the lower boiling components. This improves subsequent cut
point control and flexibility in the atmospheric tower, and
can increase m a i n c o l u m n capacity. A complex heat exchange network is used to warm the crude to desalter temperature and then to furnace inlet temperature.
Desalting is accomplished by mixing 100 parts of crude oil
with about 3-10 parts of water at about 120-140C. Emulsifier or demulsifier additives may be used to aid either the
mixing of crude and water or separation of the two after mixing. Electrically charged plates may also be used to coalesce
water to aid in separation. The desalted water is then sent to
wastewater treatment and, if necessary, for stripping of undesired contaminants such as benzene.
After further heat exchange, usually to 210-240C, the
crude is sent through multi-pass furnaces to attain atmospheric column inlet temperature in the range of 340-410C.
Then, by control of top column reflux a m o u n t and temperature, reboil, and p u m p a r o u n d / p u m p d o w n parameters, the
desired cuts are obtained.
Atmospheric column bottoms are usually sent to the vacu u m tower to recover the vacuum gas oils to a final boiling
point (FBP) as high as 575C, although 540-565C may be
more common. The ability to reach desired FBP depends on
m a x i m u m furnace outlet temperature a n d its concomitant
coke laydown on the furnace coils vs. economic run length,
and attainable vacuum. Vacuums in the range of 7-25mm Hg
absolute are usually achieved using steam ejector systems or
vacuum p u m p s .

PROCESSES FOR GASOLINE AND


DISTILLATE YIELD A N D QUALITY
Fluid Catalytic Cracking
This is the predominant process for converting high boiling
gas oils a n d resid into lower boiling streams, mostly gases, a
gasoline blending component and a light gas oil for No. 2 fuel
oil blending, fts place in the refinery is mainly driven by the
yields and compositions of the product components, the ability of the process to vary product yield/composition, a n d
lower capital investment cind operating costs compared to alternative process options.
Figure 3 depicts the process operating principles. Many
equipment configurations and catalysts are employed, but
the essence of the process is reactor and regenerator "vessels," vapor phase fluidization of the catalyst in each vessel,
flow of catalyst between the two vessels, thermal cracking of
the feed in the reactor and removal of coke from the catalyst
in the regenerator. Much of the design variations cire related
to engineering improvements and the increased processing
of poorer quality feed, which in t u r n has been enabled by
greatly increased activity of today's catalysts.
Fresh feed and, if desired, heavy product recycle, are introduced into the reactor. The feed vaporizes and thermally
cracks in about 1-3 s at about 525-550C, to yield a potential
variety of product s t r e a m s exemplified in Table 10. Coke
forms in the reactor section due to rapid polymerization of
olefins a n d aromatics as cracking chemistry occurs. This

10 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK
Condenser

0iS^SI I

Atmospheric
Distillation

*'Wet Gas
*LPG

Reflux

Light
"B-' Water
r'stabifeation'l Straight Run
-*
and.
^
L.SpJtttinjtJ_*

xr

~ ) P Stripper

Naphth:
Kerosene

Crude

Stripper
Steam

-Water

* Diesel

Preheat
Desaiteri
"Gas Oil

Steam

Brim
Preheat L f i j J
Preflash
Drum

Vacuum
Distillation

Furnace^i=J
-Topped Crude

Steam

Non-condensat)les
and steam

PreCondenser
High Pressure
Steam
NonC.W. condensables
O

QHot Wbll Accumulator [)


^ Heavy
Gas Oil

Naphtha

Sour Water

Topped
Crude
Q Ejectors

Coil
Steam

Stripping
> Vacuum Resid
Steam
FIG. 2Atmospheric and vacuum distillation units.

coke "lays down on" the fluidized catcJyst particles, diminishing their activity. The "coked-up" catalyst is continuously
removed from the reactor section and transported with air to
the regenerator wherein controlled combustion converts the
coke into a "flue gas" consisting mainly of carbon monoxide
(CO), carbon dioxide (CO2), water (H2O), and sulfur and nitrogen oxides (SOx and NOx) resulting from the presence of
sulfur and nitrogen in the feed. This combustion raises the
catalyst temperature to 680-760C which, in turn, supplies
most or all of the heat to raise fresh feed to its reactor temperature as the "hot" regenerated catalyst is continuously removed from the regenerator and re-mixed with fresh feed. In
fact, many FCC units operate in heat balance, meaning that
all heat to raise the feed to reactor temperature is supplied by
the regenerated catalyst.

CO, a pollutant, must be removed from the regenerator flue


gas. Even if CO emissions were not an issue, economics of
maximizing heat recovery would dictate oxidation of CO to
CO2. This is accomplished by the use of combustion additives
in the regenerator, improved regenerator design and operation, and external secondary combustion in a CO or waste
heat boiler. SOx and NOx pollutants face refinery emission
limits. Acceptable levels in the flue gas can be achieved with
regenerator additives, various flue gas scrubbing processes,
or by installing "cat feed hydrotreaters" to reduce the sulfur
and nitrogen content in the FCCU feed.
Run length between scheduled turnarounds for inspection
and maintenance is 3-5 years. Longer runs have resulted
from ongoing improvements to the overall design that include multistage regeneration, improved cyclones and feed

CHAPTER
nozzles, and taking advantage of favorable FCCU process
economics. Factors favoring economics include the ability to
produce high yields of high-value gas and gasoline from low
value feed, substantial yield flexibility resulting from catalyst
selection and variable operating parameters, operation at essentially atmospheric pressure, and no addition of hydrogen
as is required in the hydrcracking process.
The cyclone systems in both the reactor and regenerator are
mechanical devices to collect the catalyst carried out of the
dense phase fluidized beds by the respective cracked product
and flue gas vapors. Although thousands of tons of catalyst
circulate each day, cyclone efficiency is so close to 100% that
losses are kept in the 1-10 ton-per-day range. The losses from
the reactor are returned via the downstream product recovery
train. Losses from the regenerator are collected and then disposed, thus creating the need for daily catalyst replacement.
Early catalysts were silica-alumina "clays" incapable of
processing resid and limited in activity. Today's catalysts
contain various highly active zeolites, combined with appropriate silica-alumina bases, which permit the processing of
heavier, dirtier feed, as well as provide increased yields of

Reactor Vapor

Reactor

Reactor Riso'

Regenerator
/

Spent-Catalyst
Stripper

Combustor
Riser
Catalyst
Cooler
(Future)
Combustor

Spent-Catalyst
Standpipe

RecirculatedCatalyst
Standpipe

RegeneratedCatalyst
Standpipe

CooledCataiyst
Standpipe
(Future)

Chargestock

t
Combustion Air
UitGas
FIG. 3Fluid catalytic cracking unit.

1: PETROLEUM

OIL REFINING

11

TABLE 10FCCU yields.


Operating Mode

Gasoline

Gas

Distillate

Reactor Products, %w
C1-C2
C3s
C4s
Gasoline
Light Cycle Oil
Heavy Cycle Oil
Coke on Catalyst

3
6
11-12
46-52
15-19
7-8
6

6
22
20
27
12
5
8

2
4
8
38
35
9
4

light products without the overproduction of coke. Catalyst


formulations can be chosen to maximize gasoline yield and
octane number, gas yield and olefin content; tolerate resid
metals; and resist higher regenerator temperature resulting
from additional coke p r o d u c t i o n from the higher carbon
residue level in the resid portion of the feed.
Reactor effluent is taken to the "cat main fractionator"
wherein the main separation occurs to yield the olefin containing gases, gasoline blending streams, a light gas (cycle) oil,
and a heavy gas (cycle) oil. If the heavy gas oil has the right
properties, it, or a heavier portion of it, may be sold as feed to
produce carbon black for the manufacture of tires and printing inks. If so, it will be labeled carbon black oil, decant oil,
slurry oil, or clarified oil. It is the heavy gas oil that is used as
the "washing" stream at the b o t t o m of the fractionator to remove the catalyst to the settler and then back to the reactor.
The gases undergo further absorption and distillation to
achieve the desired separation for various end uses. Some refiners select feed, catalyst and operating conditions to maximize olefin gas yield at the expense of gasoline and/or light
cycle oil yield. This has been done to meet growing demand
for propylene as a petrochemical feedstock and to provide
butylenes for MTBE and alkylation feed.
The "cat" gasoline, a major gasoline blending component
used throughout the world, is treated for mercaptan sulfer removal prior to product blending for odor and corrosion control. Removal of other sulfer compounds, or just the sulfur
atoms themselves, will be required to meet future demand for
low sulfer gasoline. While desulfurization via hydrotreating
will r e m a i n a d o m i n a n t technology for some time, other
sulfer removal technologies, for example utilizing extraction
or oxidation, are in various stages of commercicdization.
The light cycle oil is mainly blended to No. 2 fuel oil. As
feeds to the "cat" unit get dirtier, and as demand for cleaner
fuels grows, the refiner will be faced with an increasing need
to reduce the sulfur, nitrogen, and aromatics content of this
stream, if for n o other reason than to provide blending flexibility into the diesel fuel markets. Heavy cycle oil yield is very
low in today's operation; most refiners blend this cut to No. 6
fuel oil, while some recycle it to extinction in the reactor. It
was this recycle of the FCCU gas oil in the early days of this
process that gave rise to labeling them light and heavy cycle
oil in addition to light and heavy gas oil.
Key fluid catalytic cracking process variables include:
Catalyst circulation rate, commonly called the "cat-to-oil
ratio"
Reactor temperature
Catalyst activity
Feed residence time

12

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

The cat to oil ratio, in the weight range of 4 to 15, can be


varied within the Umits of maintaining the necessary pressure balances and vessel vapor velocities so that catalyst flow
and bed fluidization are properly maintained. Reactor temperature will vary with cat-to-oil ratio, regenerator temperature and catcdyst cooling, and from feed preheat for those
units having feed furnaces. Process severity is mainly defined
in terms of conversion of the heavy feed into gas and gasoline, and is expressed as 100 minus the product streams boiling above gasoline. Conversion typically ranges from
50-85%. Lower conversion is desired to meiximize light cycle
oil yield for blending No. 2 fuel oil during the oil heating season, while higher conversion is set to meet gasoline a n d
olefin gas deniEmd.
Catalytic R e f o r m i n g
This process is an essential part of every refinery that desires
to use the heavy straight run naphtha fraction from crude, or
similar boiling range material from a n o t h e r process unit
such as the hydrocracker, as a gasoline component. The feed,
usually a C6-C10 cut, is too low in octane n u m b e r to be economiccdly blended to the gasoline pool. The "cat reformer"
converts low octane n u m b e r peiraffins and naphthenes in the
feed into "high octane" aromatics in the product. Typical feed
unleaded RON is 40-65 while product is 94-103.
There Eire three main reactor configurations, two of which
are shown in Fig. 4; all accomplish essentially the same
chemistry.
SemiregenerativeFixed bed reactors, all operating in series.
CyclicFixed bed reactors in series; one out of service on
rotating basis for catalyst regeneration.
ContinuousMoving bed reactors in series with "continuous" catalyst regeneration.
The evolution from the original semiregenerative reformer
to today's continuous unit was driven by "competing chemistry" within the process and by the need for higher octane
n u m b e r product to help replace the lost octanes from lead.
Hydrogen must be added with the naphtha feed to minimize
coke formation and laydown on the catcdyst and achieve economic run length, since catalyst performance is readily diminished by coke. Higher operating pressure aids in reducing coke formation chemistry. However, the goal is to
maximize the conversion of naphthenes to aromatics since
higher eiromatics content translates into higher octane number reformate. Lower operating pressure increases aromatics
yield since it makes it easier for hydrogen to "escape" from
the naphthene. The continuous process is thus able to operate at lower pressure because the resulting higher coke make
can be removed "continuously." In actuality, a catalyst particle tcikes about five days to migrate from the top of the first
reactor to the bottom of the last; such r u n length in the fixed
bed "semi-regen" reformer would be unacceptable.
The original catalyst that enabled this chemistry consisted
of an alumina base promoted with 0.25-0.75% platinum. Today's catalysts may contain just the platinum promoter; may
be bi- or tri-metallic using additional metals such as rhenium
and tin; may have the alumina base converted to the more
acidic chloride form by treatment with chlorine or chloroform, for example; or may utilize appropriate zeolites. In any

case, the sensitivity of the catalysts to coke, and to deactivation from heteroatoms such as sulfur and nitrogen, requires
that the naphthas first be hydrotreated.
Fresh hydrotreated naphtha feed plus recycle hydrogen is
heated to reactor temperature of about 500-530C in a furnace and fed to the first reactor. The over-riding chemistry is
endothermic dehydrogenation of naphthenes to aromatics.
Thus, as the feed progresses down through the catalyst, as
m u c h as 60C cooling occurs from top to bottom in the first
reactor, reducing activity and hence aromatics yield. The net
effect is that octane n u m b e r gcdn in one reactor is not enough
to make the process attractive. Therefore, the reactor effluent
is reheated in a second furnace, or in a second coil within the
same furnace, back to 500-530C and fed to a second reactor,
and so on, until desired octane product is attained. Cat reformers usually consist of three reactors although as many as
five are utilized.
Typical yields at two product RON levels are shown in
Table 11. The net hydrogen produced from aromatics formation is the m a i n source of hydrogen in the refinery for its
desulfurization and related needs. Refineries are in "hydrogen balance" if all such hydrogen can be provided by the reformers. If not, refiners purchase hydrogen or build their
own hydrogen plants.
Figure 5 depicts the main process parameters of catalytic
reforming; namely, the "yield-octane" relationship. Higher
octane n u m b e r d e m a n d requires higher reactor temperature
and/or longer residence time. Both will cause more of the
naphtha feed to crack into gas and thus reduce gasoline 3rield.
"Reformer severity" is uniquely defined as the unleaded RON
of the C5 + liquid product, the second major gasoline blending component. In fact, the gasoline streams from the fluid
cat cracker emd cat reformer make u p about two-thirds of the
world's gasoline.
Significant changes in feed composition to the reformer
a n d in downstream utilization of the reformate are occurring, related to the move toward cleEmer fuels. The major
source of benzene in gasoline is catal3^ic reformate. The
trend is to reduce benzene to a m a x i m u m of 1%, with the potential for even lower limits being legislated in parts of the
world. When the p u s h for lower benzene content began,
worldwide benzene levels ranged from as low as 1.6% in the
U.S. to as high as 5% in pEirts of Europe and Asia. Refiners
can reduce benzene concentration as follows:
1. Remove benzene precursors from the feed. This is accomplished by increasing the initial boiling point of the heavy
naphtha feed, or, in essence, raising the cut point between
light and heavy straight run naphtha. This results in less
feed available to the reformer and lower octane quality in
the resultant higher boiling range light straight r u n
stream.
2. Leave the benzene precursors in the feed. In this case, refiners can then distill the C6 cut from the reformate. Benzene can be extracted from this cut for chemical sale, or the
benzene can be reacted with olefins to produce alkylbenzenes. The C6 cut can also be hydrotreated to convert benzene to cyclohexEine with a resultant loss in octane number.
Clcciner gasoline also mcindates lower final boiling point
and lower total aromatics. This requires the refiner to eliminate a substantial portion of high boiling fraction from the
naphtha feed and, in some cases, to r u n the reformer at lower

CHAPTER 1: PETROLEUM OIL REFINING


Semiregenerative Catalytic
Reforming Unit
Net hydrogen
Compressor

Recycle hydrogen

Off Gas

^^-^c^O

Heavy
Naphtha

C3s&C4s

Separator

Reformate

Continuous Catalytic
Reforming Unit

Spent Catalysi
Product
'Separatiofi
Naphtha &
Recycle Gas

FIG. ASemiregenerative and continuous catalytic reforming units.

13

14 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

severity to yield less total aromatics. Beside the loss of octane


number and yield, these changes likely yield less by-product
hydrogen, a costly ingredient needed for desulfurization
chemistry.
Catalytic reformate also plays an important role in the
petrochemical industry by being a major source of benzene,
para-xylene, ortho-xylene, and toluene primary feedstocks.
The recovery of these aromatics is illustrated in Fig. 6. Total
reformate, or a narrower C6-C8 cut, is fed to a liquid-liquid
extraction column where it is contacted countercurrently
with a solvent with known selective solubility for aromatics.
The main solvents are sulfolane or di- to tetra-ethylene glycols. The aromatics, called the extract, are then distilled from
the reusable solvent. The rejected paraffins and naphthenes,
called raffinate, must find a new home which can include the
solvent/spirits market or as feed to ethylene plants running
on naphtha; recycling the raffinate to a high severity catalytic
reformer is usually not economically attractive. The "pure"
aromatics in the extract are then separated in a series of distillation columns, except for meta- and para-xylene, which
have virtually identical boiling points. Their separation is accomplished either by crystallization, which takes advantage
TABLE 11Catalytic reforming unit yields.
Reformer Severity

102

94

Yield, %w
Hydrogen
CI + C2
C3
iC4
nC4
C5+ Reformate

3.0
3.7
3.5
1.8
2.5
85.5

1.7
1.0
1.8
1.4
2.1
92.0

of their widely different freeze points, or by adsorption with


molecular sieves, which takes advantage of their different
molecular diameters.
Isomerization
This process mainly converts normal paraffins into isoparaffins. The technology is employed to increase the octane quality of light straight run gasoline/naphtha by converting npentane and n-hexane into mixed C5-C6 isoparaffins. The
process is also used to convert n-butane into isobutane to either provide feed to the alkylation process or as a step in the
process to make MTBE when isobutylene is not available.
A simplified process flow diagram is shown in Fig. 7. Fresh
feed, along with recycle hydrogen, is heated to reactor temperature of 180-260C by heat exchange or a furnace. The
feed then flows down through a fixed bed of catalyst that is
similar to reforming catalyst. Operation may be oncethrough, or with peirtial or total recycle of unconverted nparaffin. The recycle can be recovered using distillation to
separate lower boiling isoparaffin product from the normals,
or adsorption with molecular sieves to separate smaller diameter n-paraffins from isoparaffins. Recycle yields a greater
octane number increase at the expense of higher capital investment and operating cost. Octane improvement generally
ranges from 5-25 numbers depending on feed composition
and process configuration.
Because of the low reactor temperature, thermal cracking
of the feed is very low, in the order of 1-2% compared to
12-20% in the CRU. However, the sensitivity of the catalyst to
coke laydown still requires the presence of hydrogen to minimize coke formation and hence provide satisfactory activity
and run length.

96

High Aromatics Feed

2
g>

Low Aromatics Feed

76
94

96

98

100

RON without Pb
FIG. 5CRU yield/octane relationship.

102

104

CHAPTER

1: PETROLEUM

OIL REFINING

15

'^Raffinue

Bxtfictio
^Tnadngind
Fnctiamtioii
Feed

LSGBflD
EEXTRACTOR
S'STRlPfCR
RC - RECOVERY COLUMN
SR - SOLVB^TREOENERATOR
FIG. 6Solvent extraction unit for btx recovery.

Alkylation
The reaction of an olefin with an aromatic or isoparaffin is labeled alkylation. Benzene is alkylated with ethylene to eventually produce styrene, and with propylene to eventually produce phenol. These "petrochemical" technologies are found
in some refineries. But the "alky" process that is part of the
typical refinery flow plan (Fig. 1) is the reaction of C3-C5
olefins with the paraffin isobutane.
The process requires that the paraffin be branched to provide a reactive tertiary carbon atom, bonded to only one hydrogen. Normal paraffins, having only primary or secondary
carbon atoms, are not sufficiently reactive. Isopentane could
be used, but it is already a clean, high-octane liquid contained in the C5 part of the gasoline pool. Thus, the gas isobutane becomes the obvious choice since it is reactive, not part
of the gasoline pool, and reasonably available in the refinery
as a crude oil component, as well as in the C4 product from
processes s u c h as the FCCU, CRU, a n d hydroprocessing
units.
The chemistry can be accomplished with any olefin. Ethylene is not used because it is expensive to recover, operating
pressure would have to be considerable since the process is
carried out in the liquid phase, and the resulting alkylate octane quality is poor compared to processing higher molecular weight olefins. Propylene is a n "alky" feed in many units,
but its use competes against its value as a petrochemical feed
for polypropylene, propylene oxide, and linear alpha olefins.
The butylenes are the predominant alky feed because of their

availability, cost t o separate into chemical grade components, and high octane quality of the alkylate. However, as
the light olefin content of gasoline diminishes due to evolving
legislation, refiners may also find it economically attractive
to use amylenes as alky feed, instead of converting them to
lower octane pentanes in a hydrotreater.
In many refineries, there is insufficient isobutane to match
the availability of olefins from the FCCU and cokers. The
missing iC4 can be produced by isomerizing available nC4,
by purchase from the natural gas condensate pool, or from
nearby refineries lacking an alky plant.
The catalysts that are commercially employed are 98-99%
sulfuric acid (H2SO4), or concentrated hydrofluoric acid
(HF) because the chemistry requires a very strong acid. Commercialization of solid-type catalyst is in progress. The process in concept is simple: pressurize the system to liquefy the
hydrocarbon feeds, mix them with the strong liquid acid, and
separate the alkylate from the catalyst. The process in reality
is complex because of acid carryover into the alkylate; formation of acid-hydrocarbon molecules; significant exothermic heat of reaction; the need for substantial excess isobutane to suppress olefin polymerization; high catalyst
consumption and utility cost in the case of H2SO4; and safety
considerations, especially with hydrofluoric acid.
Sulfuric acid alkylation m u s t r u n at low temperature,
namely, about 5-10C, in order to minimize olefin polymerization, acid consumption, and by-product yield. This requires refrigeration of the catalyst and feed, and substantial

16 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK

4Mafenp
Hydiogra

[ ^

ri
c:^

X
.J^

iall:^^

OM

sr

LEGEMD
D-DRYER
R-REACrOR
ST STABILIZER

C5-C

booMnli
FIG. 7Isomerization unit.

mixing energy because of the acid's high viscosity. Most alky


units used sulfuric acid from the commercialization of the
process in the 1940s until the 1970s, the period when energy
cost was low. In addition, H2SO4 consumption is substantial
at about 0.1 kg per kg alkylate. Since the early 1970s, most
new units have been H F alky plants to counteract higher energy cost. H F alkylation operates at about 25-50C negating
refrigeration, acid viscosity is so much closer to that of the
hydrocarbons that designs can accomplish the chemistry in
piping or in simpler mixing vessels, and acid consumption is
only about 0.001 kg per kg alkylate. However, the use of H F
poses a more serious safety concern than H2SO4 in the event
of a n acid release. A sulfuric acid spill will cause soil and
g r o u n d w a t e r contamination; however, hydrofluoric acid,
which boils at 20C, will release a vapor cloud of H F as it escapes emd depressurizes. Releases of H F at a n u m b e r of U.S.
refineries in the 1980s led to significant re-engineering to assure process safety and "save" the process from legislative extinction.
A simplified flow diagram is shown in Fig. 8 for an H F alkylation unit. Key highlights include separation of the acid from

alkylate, cooling of recycle acid, recovery and recycle of isobutane, cleanup of alkylate, and separation of products. Typical
product yields, quality, and disposition are shown in Table 12.
MTBE
Oxygenates were introduced into the gasoline pool in the
1970s to help replace the lost octanes from lead additives.
Their use has now been mandated in many parts of the world
based on data showing their ability to reduce harmful vehicle
emissions. The majority of worldwide use of MTBE is by
commodity chemical p u r c h a s e . However, a substantial
a m o u n t is made within the refinery gate, in particular in the
United States. Typically, the MTBE unit is installed in front
of a n alkylation unit. The C4 cut from the FCCU is first fed to
the MTBE unit where the isobutylene is reacted with purchased methanol. The effluent C4 paraffin and olefin stream,
minus isobutylene, is then sent to the alky plant.
MTBE has helped the refiner meet gasoline d e m a n d and
octane, and is being adapted for blending worldwide. In fact,
during the 1980s and much of the 1990s, it was the fastest

CHAPTER 1: PETROLEUM OIL REFINING


FEED
PRElKEATMEm-

REACTION
SECTION

BOSIRIFFER

DEFKOPANIZER

17

HFSnUFPER

Mixed
Batane*

OUfin
Feed
"j

DiyingAnd
Diokfin
Saianlioa

FIG. 8HP alkylation unit.


TABLE 12HF alkylation unit yield and quality.
Olefin Feed

C3 + C4

C4

Yields, %w
4-10
Propane
n-Butane
2-5
3-6
80-93
Alkylate
76-90
Alky Bottoms"
3-8
3-8
1
Alky Tar*
1
Alkylate Dist, C
Initial BP
40
40
75
10%
70
100
30%
90
105
100
50%
110
70%
105
125
90%
120
195
Final BP
190
96
RON, without Lead
93
MON, without Lead
92
94
^Too high boiling for gasoline. Usually blended to diesel and fuel
oil.
' A "waste" stream of high molecular weight. May be processed in
cracking units, burned as fuel, or disposed.

growing "chemical," with usage now surpassing 20 million


mt per year. However, the use of this ether and perhaps other
ethers could be reduced or banned because of concern for
contamination of drinking water from gasoline storage tank
leakage, as detected in parts of the U.S. Should this happen,
refiners will again have to find substitute streams to replace
lost octane and "barrels." This issue could become economically critical to the refiner and consumer as the industry simultaneously reduces gasoline and diesel fuel sulfur, as well
as gasoline aromatics and olefins.
TAME, the ether produced by reacting isoamylene with
methanol, has entered the refinery picture because it can provide an opportunity to reduce the C5 olefin content of gasoline. A number of MTBE plants have been revamped to handle the higher boiling olefins. However, if MTBE use is

banned, it is likely that TAME will suffer the same fate.


Ethanol continues to be used, particularly in the United
States and Canada, and some refiners are substituting
ethanol for the ethers.
Other technologies utilizing isobutylene, beside alkylation,
are being added to the refinery flowsheet. One example is the
dimerization of isobutylene to isooctene, followed by its conversion to isooctane via hydrogenation.

PROCESSES FOR HETEROATOM REMOVAL


AND AROMATIC/OLEFIN SATURATION
The main technology for removing unwanted heteroatoms
such as sulfur and nitrogen, and for reducing aromatics euid
olefin concentration in refinery liquid streams, is by contacting the stream with hydrogen in the presence of a catalyst,
and at appropriate temperature and pressure. The vocabuIciry to identify the numerous applications is extensive and
not universally consistent. The most common generic name
is hydroprocessing. This has been further divided into three
categories; hydrotreating, hydrorefining, and hydrocracking,
to delineate process severity for desired product cleanliness,
as well as feed and product boiling range. Currently, hydrotreating and hydrocracking are the two most widely used
names for this technology, with the trend to place hydrorefining within the hydrotreating category.
Process severity, with respect to the above vocabulary, is defined by percent conversion (Table 13), or how much of the
feed is thermcdly cracked into lower molecular weight, lower
boiling product. Conversion is usually defined as 100 minus
the amount of product in the same boiling range as the feed.
The vocabulary also expands to include the word desulfurization, since sulfur reduction has been and remains the key need
for hydroprocessing, in addition to denitrogenation and
dearomatization. Some of the myriad names and abbrevia-

18

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

TABLE 13Hydroprocessing terminology.


Conversion, %w
Hydrotreating (HT)
Hydrorefining (HR)

"0"
As little as possible

Hydrocracking (HC)
Additional Terminology
HDS
HDT
HDN
HDA

25 +

NHT
DDS
MHC
ARDS
VRDS

Objectives
Cleanup without conversion
Cleanup of higher boiling streams
with minimum conversion
Cleanup + Conversion

Hydrodesulfurization
Hydrotreating
Hydrodenitrogenation
Hydrodearomatization

(HDA is also used for Hydrodealkylation


of Toluene to Benzene)

Naphtha Hydrotreater
Distillate Desulfurizer
Mild Hydrocracking
Atmospheric Resid Desulfurization
Vacuum Resid Desulfurization

tions for this technology are also listed in Table 13. The refinery streams that can/must undergo hydroprocessing, and the
reasons for the process selection are summarized in Table 14.
An example of a simplified process flow diagram is shown
in Fig. 9. Fresh feed, with hydrogen recycle and make-up hydrogen for the a m o u n t c o n s u m e d by the hydrogenation
chemistry, are heated to reaction temperature in a furnace
and then fed downflow through one or more fixed catalyst
bed reactors in series. After the desired reactions have occurred, the remainder of the process involves the recovery of
a high purity hydrogen recycle stream, separation of any
cracked hydrocarbon gases from the desulfurized liquid
product, as well as distillation of the liquid into appropriate
cuts. Start-of-run r e a c t o r t e m p e r a t u r e ranges from 2 8 5 400C a n d pressure from 900-20 000 kPa; generally, the
higher the boiling range axid "dirtiness" of the feed and the
greater the desired cracking severity and dearomatization,
the greater is the required temperature, pressure and n u m b e r
of reactors, as well as chemical hydrogen consumption. Excess hydrogen via the recycle is needed to minimize coke formation and laydown on the catalyst; this recycle is about 3-5
times the expected hydrogen consumption.

cess of hydrogen to minimize coke production, this runaway


can increase reactor temperature by u p to 60C per minute,
creating an unsafe operating condition. Refineries therefore
usually cap furnace outlet temperature at about 435-440C.
Thus, processing heavier, dirtier feed at higher severity,
which requires higher start-of-run temperature, results in
shorter r u n length and/or multiple reactors.
The metal promoters on the alumina base end up in their
oxide form from the drying of the finished catalyst. After being in the reactor for a short time the metal oxides will convert to sulfides from the hydrogen reducing atmosphere,
combined with the production of hydrogen sulfide. The oxide
form is overactive and can cause temperature excursion, increased coking, and partial catalyst deactivation from
changes in the alumina and metal promoter structure. Thus,
cobalt-moly and nickel-moly catalysts must be "presulfided"
or "presulfurized" prior to the start-of-run. This can be done
in-situ by adding compounds such as dimethyldisulfide to a
feed to condition the catalyst, for about one to two days, or it
can be done ex-situ wherein the catalyst is pretreated by the
manufacturer, and then shipped and loaded to assure that
the metals remain in the sulfide form.

The catalysts comprise the widest selection among all the refinery processes because this technology is used to "clean" all
refinery streams from light straight r u n gasoline through vacu u m resid. The two most common formulations consist of
combinations of cobalt and molybdenum or nickel and molybd e n u m promoters on an alumina base. The "cobalt-moly" catalyst, as it is typically called, is preferred for sulfur removal
while the "nickel-moly" combination is active for nitrogen removal and some aromatics saturation. Some catalysts also utilize nickel-tungsten. Noble metal catalysts such as platinum as
well as zeolites are now employed, in particular for deep
deciromatization. Cobalt-moly and nickel-moly catalysts contain in the range of 3-25% promoter metals depending on feed
properties and planned hydroprocessing severity.
Hydroprocessing is exothermic and increases with hydrogenation severity. Reactor outlet temperature in a fixed bed
reactor can be as m u c h as 35C greater than inlet temperature when processing vacuum gas oils and resid. Further, as
the run proceeds, slow b u t inevitable loss of catalyst activity
due to coke and metals laydown occurs and is compensated
by raising furnace outlet temperature. Hydrogenation reaction rate increases with temperature and at about 470C, can
result in a "runaway" reaction. Since there is always an ex-

At the end of a run, burning the coke off can regenerate the
"coked up" catalyst. This also is accomplished in-situ or exsitu. Ex-situ removal more efficiently removes the coke, but
at increased cost. If performed in-situ, the catalyst will usually remain in the reactor for 2-4 runs, after which refiners
will d u m p the spent catalyst and replace it with fresh material. Spent catalyst is usually then taken to hazardous waste
disposal. If the catalyst has been used to process resid, it may
be sent for nickel and vanadium recovery or to a process that
can remove enough of the feed metals to reactivate the catalyst and allow its reuse.
Hydrogen consumption and throughput rate, often called
"space velocity," are two of the key process and economic
variables. As the boiling range of the feed, and thus its heteroatom and aromatics content, increases, it can be expected
that hydrogen consumption will increase a n d throughput
will need to decrease to increase residence time. A similar response occurs for a given feed as conversion increases. Examples of yield, hydrogen consumption and residence time
for different feeds are shown in Table 15.
Hydroprocessing will continue to play a n ever-increasing
role in worldwide refining. The factors driving this conclusion are:

CHAPTER 1: PETROLEUM OIL REFINING

19

TABLE 14Hydroprocessing options.


Stream
Lt Str Run Gasoline
Hvy Str Run Naphtha
Coker Naphtha

B.P.

Sulfur

For the Reduction of


Nitrog.
Arom.

Diolef.

Acids
X
X

FCCU GasoHne
Catalytic Reformate
Kerosine/Jet
Lt Attn Gas Oil
Atm Gas Oil
Coker Gas Oil

Vac Gas Oil


Vac Gas Oil

Resid

End Use
Isomerization Unit Feed
Cat Reformer Feed
Gasoline Blending, Cat
Reformer Feed
Low Sulfur Gasoline
Low Benzene Gasoline
Jet Fuel, Low Sulfur Diesel
Low Sulfur Diesel
Gasoline Blending, Cat
Reformer Feed, Jet Fuel,
Diesel Fuel
FCCU Feed
Gasoline Blending, Cat
Reformer Feed, Jet Fuel,
Diesel Fuel, Lube Oil
Base Stocks
Cat Reformer Feed,
Jet Fuel, Diesel Fuel,
FCCU Feed, Coker Feed,
No. 6 Fuel Oil

"Boiling Point Range


HEATER IffTSTQ. REACTOR

lEAlER 9 0 STTO. REACTOR

STABIUZER HlACnONATOR
LightEmli

FIG. 9Fixed bed hydroprocessing unit.


The sulfur content of crude oil has been increasing over
the years and is expected to continue that trend, barring
major discoveries of low sulfur crudes.
The sulfur content of fuel products, as we know them today, has been decreasing and this trend is expected to accelerate as the world seeks cleaner fuels.

3. The aromatics content of fuel products has been decreasing and this trend should continue and expand worldwide.
The technology and catalysts to achieve these results are
available; the only missing ingredient is money. If gasoline,
jet fuel, and diesel fuel continue as the major sources of
transportation fuels, then the industry will be forced to uti-

20 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


TABLE 15Hydroprocessing unit yields.
Feed
Density, kg/m^
Sulfur, p p m w
Nitrogen, p p m w
Initial Boiling Ft., C
50% Distilled
Final Boiling Ft.
Products
Naphtha
Yield, %w
Density
Sulfur
Nitrogen
Jet/Diesel
Yield
Density
Sulfur
Nitrogen
Atm Gas Oil
Yield
Density
Sulfur
Nitrogen
Hydrogen Consumption,
%w of Feed

FCCU LCO +
Coker Gas Oil

FCCU
LCO

Crude
VGO

940
22 400
940
220
275
375

935
28 000
1 000
365
470
575

980
8600

24
730
<1
<1

27
770
<1

35
810
<20
1

68
865
<20

94"
900
500
120

215
280
385

38
825
<20
<2
1.4

2.8

3.1

"Includes AGO

lize hydroprocessing for virtually every such product, worldwide.

PROCESSES FOR RESID CONVERSION AND


UPGRADING
Processing of resid has its unique pEirameters and constraints
because of its composition. It, among the crude oil cuts, is:
the highest in carbon residue resulting in high rates of coke
production or laydown on catalyst.
the highest in sulfur, contaminEtnt metals, aromatics and
usually nitrogen, resulting in high operating severity
and/or hydrogen consumption.
The easiest way for the refiner to handle resid is to sell it.
Its two m a i n markets Eire asphalt for road paving, roofing,
and the like, and No. 6 fuel oil for utility and marine energy.
To a lesser extent, resid is used by some refiners as a feed for
the production of hydrogen. The asphalt market is finite, and
the "six oil" market is limited to the a m o u n t that can be sold
economically to compete with other fuels such as cocJ and
gas. The net result is that the average refiner cannot dispose
of Eill of its resid via the above scenarios. In addition, the concern for air pollution is driving the world toward the use of
lighter, cleaner fuels. In response, a group of technologies
have established their place in the refineiy flowsheet to clean
resid and convert it into lower boiling streams. These processes yield products of a higher hydrogen to carbon ratio
than that of the resid feed, essentially the result of the cracking and/or saturation of its aromatics, which have the lowest
hydrogen to carbon ratio among the hydrocairbon types cind
crude oil fractions. The industry has categorized these technologies as accomplishing this desired chemistry by carbon
rejection or by hydrogen addition. There Eire dozens of resid

upgrading processes in commercicd operation; however, six


have established a prominent position, as follows:
Carbon Rejection
Hydrogen Addition
Visbreaking
Fixed Bed Hydrocracking
Solvent Deasphalting
Fluidized Bed Hydrocracking
Delayed Coking
Fluid Coking/Flexicoking
Table 16 shows a regional s u m m a r y of the worldwide installations for these technologies.
Visbreaking
This is a thermEtl cracking process using heat alone to partially crack the resid feed to lower boiling products. Most
commercial units operate in the 20-30% conversion range,
thus, 70-80% of the product r e m a i n s in the resid boiling
range. The attractiveness of the process is alluded to in its
name; although most of the product is in the same boiling
reinge as the feed, this material is significantly lower in viscosity than the feed. Hence, the heat treatment reduces or
"breciks" the viscosity of the remaining resid, leading to the
process name. The value of visbreciking is in utilizing the unconverted resid to blend No. 6 fuel oil. This product is made
by blending lower boiling, higher VEJUC streams, commonly
named cutter stocks, to reduce or cut the high viscosity of the
resid in order to meet product specifications. By lowering
resid viscosity, less cutter stock is required.
There are very few visbreakers in North America since this
area has substantial gas production and is oriented toward
lighter fuels. The opposite pattern exists in Europe, for example, where there are over 60 million metric tons of visbreaking capacity to meet that region's greater utilization of
heavier fuels, in general. Furthermore, until recently, Europe
has been a gas-poor region.
There are two m a i n vEtriations t o the visbreaking flowsheet:
one is the soEiker coil visbreaker, the other the soaker drum
visbreaker, as in Fig. 10. Both subject the resid feed to heating in a furnace; in the soaker coil unit, all thermal cracking
tcikes place in the furnace coil, while in the soaker d r u m unit,
the feed is partially cracked in the furnace at about 30C
lower temperature and the cracking is completed by providing increased residence time in the drum, as follows:
Residence Time, min.
Soaker Coil
Soaker Drum

Temperature, "C
465^85
435^55

1-2
4-8

The original driving force for the sociker drum process was
to minimize coking in the furnace coil and thus increase run
length. However, improvements in furnace design have narrowed the differences in process severity so that either process may be selected.
TABLE 16Resid process capacity.
Capacity, Million mt/year
Process

Worldwide

North
America

Western
Europe

AsiaPacific

Visbreaking
Delayed Coking
Fluid Coking
Fixed and Fluid Bed
Hydrocracking

159
155
24

11
96
8

62
13
1

21
16
3

110

35

10

48

CHAPTER 1: PETROLEUM
FRACTIONATION
TOWER
HEATER

START

^>-4vvv1-

ftd

I i

QUENCH

f
RESID

FRACTIONATION
TOWER

X-

SOAKER

HEATER

START

TT

()--^^-^

QUENCH

RESID

FIG. 10Visbreaking unit.

TABLE 17Visbreaking unit yields.


Feed
Initial Boiling Pt., C
Yield, %w
Density, kg/m^
Sulfur, %w
Viscosity, m^/s @ SOX

345
970
4.1
720

Resid
Product
345
78
990
4.3
250

Feed
540

Resid
Product

1015

540
72
1035

100 000

45 000

Typical product yields are shown in Table 17. The thermally cracked gases contain olefins, but less than FCCU
gases, and provide an added source of petrochemiccd and
alkylation unit feeds. Visbroken light naphtha can be blended
into gasoline after removal of diolefins and mercaptan sulfur,
and the heavy naphtha can be sent to the cat reformer hydrotreater (often called the naphtha hydrotreater) for olefin
saturation and sulfur/nitrogen removal, followed by octane
number upgrading in the reformer. The visbroken gas oils
will usually be blended to the fuel oil pool, but can be hydrocracked for diesel and jet fuel blending, or hydrotreated to
yield additional FCCU feed.
Solvent Deasphalting
This is the only process of the six in which no chemical
changes to the molecules occur. The process is based on the
low solubility of asphaltene-type residuum oil molecules in
low molecular weight paraffins. Asphaltenes are highly aromatic, difficult to crack, and contain the majority of the sulfur, nitrogen, and metals heteroatoms that are found in resid.
In the deasphalting process, feedstock, usually vacuum resid,
is mixed with a paraffin solvent, either propane, butane or

OIL REFINING

21

pentane. The "cleaner" resid components dissolve in the


paraffin while the dirtier asphaltenic ones do not. Thus the
process yields "clean resid feed" that can be economically
processed in another unit, typically the FCCU. In fact, the
process is oft-times defined as being used to provide incrementally clean "cat feed."
As the molecular weight of the paraffin increases, more of
the resid dissolves in the solvent. The part that dissolves in
the solvent is most commonly labeled deasphalted oil (DAO)
since the solvent has rejected the asphaltenes. The reject raffinate, mostly asphaltenic, is labeled pitch, tar, or simply asphaltenes. Figure 11 depicts the typical separation of heteroatoms between the DAO and pitch. The effect is usually
most pronounced for the metals, with lesser benefit for nitrogen and less yet for sulfur. Percentages of recovered DAO
for the chosen paraffin solvents are:
Solvent

Percent DAO

C3
C4
C5

25-40
50-65
80-95

The process consists of a mixing vessel or column running


at sufficient pressure to liquefy the solvent and dissolve the
DAO, separation of the DAO/solvent from the pitch, and recovery of the recyclable solvent from the DAO by distillation
and stripping. The process can also be designed with two
contact vessels operating at different temperatures to yield a
third, intermediate-cleanliness cut, usually labeled resin.
This may be done to give the refinery a more flexible scheme
for selling and further upgrading the various resid cuts. An
engineering feature that has played a role in reducing solvent
recovery cost sets the solvent recovery at temperature and
pressure such that the solvent is at or near its critical conditions. This significantly reduces solvent heat of vaporization
as well as its solubility in the DAO.
Today's fluid cataljrtic cracking cateJysts, if chosen for high
metals tolerance, can accept cat feed with as much as 30 ppm
Ni 4- V. A resid at 300 ppm metals permits the addition of
10% resid as incremental cat fee, ignoring the effects of carbon residue, nitrogen, and sulfur. However, based on typical
data (Fig. 11), the deasphalter can yield up to 75% "cleaner"
resid feed, at least from the constraint of metals that could
poison the catalyst. It is such performance that leads to the
incorporation of the deasphalting process into the refinery
flowsheet.

Delayed Coking
This is the dominant resid upgrading process in the U.S. and
is showing growth in Europe and, in particular. South America. Like visbreaking, this is also a thermal cracking process.
Unlike visbreaking, this process runs at essentially 100% conversion; all of the resid feed is converted into other products;
namely, cracked gases, coker naphthas and gas oils, and
coke. While the cracked gases and liquids are assumed to
have higher market value than the resid feed, it is the market
utilization and pricing of some of the coke that further helps
to drive favorable economics.
A schematic of the process is shown in Fig. 12. The cracking chemistry takes place in pairs of "drums." Cracked gases
and liquids leave the top of each drum, while the product

22 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

100

80

o
<

60

40

/y

o
20

^C

f. I

i^^^A

C^C^^ ,

^'^^""
40

20

60

80

100

DEASPHALTED-OIL YIELD, WT. %


FIG. 11Resid solvent deasphalting unit: DAO quality.

Quench

XZ

^r^^ (nh
L5^

I
Coke Drums

Fumace Steam

'Gasoline

Stripper
Steam
* Light Gas Oil
Heavy Gas Oil

Rc
\

'Gas

Fresh Feed

Main
Column
^^ ~ ^''^^'^ recycle

FIG. 12Delayed coking unit.

CHAPTER
coke r e m a i n s in the d r u m s . At start-up, both d r u m s are
empty. The resid is fed to one d r u m for u p to a day while the
other drum remains idle. On the second day, feed is cracked
in the other d r u m while the coke that has filled the first d r u m
is removed (decoked). This back and forth coke removal creates the continuous process. Drums have t3rpically been sized
to hold 24 h of coke make, since it required that amount of
time to decoke early units. Improvements to the decoking operation have enabled many units to r u n in 12-18 h cycles.
This has led to increased capacity revamps in existing units
or the opportunity to build smaller drums in new plants.
In a typical design, the resid fresh feed enters the bottom
section of the coker product m a i n fractionator. This provides
for heat balance in the distillation column bottom, the picku p of coke fines carried from the drums with the cracked
products, and the removal of a heavy coker gas oil product
for recycle to improve lighter product yield. Some fractionator designs also recover a lower boiling gas oil recycle. The
feed/recycle is then heated to cracking temperature, about
490-510C, in the coker furnace. Steam is usually added to
the feed to increase furnace coil velocity and thus minimize
coke laydown on the furnace tubes as the feed reaches cracking conditions. The purpose is to delay coking as much as
possible until the feed enters the bottom of the drum, hence
the process name.
The time-temperature parameters in the drum cause complete conversion of the resid. As coke is produced, steirting at
the bottom, the feed, which is part vapor-part liquid, continues to crack. As coke forms, it provides surface-induced
cracking as the feed passes through it. This operation succeeds because most of the coke that is produced is amorphous and spongy and is actually named sponge coke; thus,
the fresh feed is able to pass through.
The cracked p r o d u c t s are recovered and separated in
equipment similar to other processes. An example of 5rields
and quality is shown in Table 18. Unlike the FCCU, changes
in operating parameters, in this case temperature, pressure
and recycle ratio, have only a minor effect on product yields,
to the point that yields can be approximated based solely on
resid feed properties, in particular aromatics content, by using either carbon residue (ASTM Test Method for Conradson
Carbon Residue of Petroleum Products, D189-97) or API
gravity as the predictor. Coker n a p h t h a has lower octane
quality compared to cat gasoline. In addition, it must be selectively hydrogenated because non-catalytic cracked naphtha has a m u c h higher diolefin content, making it thermally

TABLE 18Delayed coking unit yields.


Density,
kg/m'

Resid Feed
Products
H2S

C1-C4
Naphtha
Atm Gas Oil
Vac Gas Oil
Coke

1025

Sulfur,
%w

Nitrogen,
ppmw

2.9

3000

0.5
0.95
1.9
3.7

70
600
2200

Carbon
Residue,
%w

22

Ni + V ,
ppmw

250

Yield,
%w

1.1
11.1
10.4
32.4
12.0
33.0

740
850
960

2.5

2
750

1: PETROLEUM

OIL REFINING

23

unstable and subject to polymerization and gum formation


even during storage at ambient conditions. Because of its inherent instability, it is often call wild naphtha. The coker gas
oils may be blended to fuel oil or hydrotreated for unsaturates and sulfur reduction.
Removal of the sponge coke from a full drum involves the
following steps:
Switch and Steam-outFeed
flow is switched from one
d r u m to the other. The coke is then stripped with steam to
remove entrained vapor and liquid product. The stripping
steam-hydrocarbon mix is also fed to the main fractionator. The coke typically contains 4-10% liquids after stripping. This "green" or raw coke may require further "drying" to below 0.5% liquids, via calcining, to meet market
needs.
CoolingThe d r u m is next filled with water to cool the
coke to about 90-95C. This is required to prevent spontaneous combustion of hot coke and allow for safe handling
when the drum is opened. The resultant steam production
is recovered either in the main fractionator when hot, or in
a unit called a blowdown system when it is at lower temperature.
Coke RemovalIn most designs, the d r u m heads are removed, a hole is drilled through the center of the coke, and
then high pressure water jets are used to break up the coke.
The drilling/jet equipment in most existing units operates
from drilling rigs placed on top of the drums. Large capacity coker drums can be as much as 8 m in diameter and
30-38 m in height. The drilling equipment would add Einother 38 m to the elevation, making this unit easily recognized. In early units, the coke was dumped into railroad
hopper cars directly below the elevated drums. In today's
units, coke is dumped into pits and the coke is then moved
by front-end loader or conveyor system to the transport
cars. Most of the engineering improvements in today's designs focus on reducing the time and complexity in this
step of the process.
ReheadThe heads are rebolted to the drum, the system is
pressure tested, and then hot gas such as cracked product
vapors from the operating drum, or flue gas from the coker
furnace, is passed through the empty d r u m to warm the
steel shell sufficiently to avoid thermal shock when fresh
hot feed is reintroduced.
Three types of coke can be m a d e . In usual operation,
80-98% of the coke will be sponge coke. The others are shot
coke and needle coke. Shot coke, which is hard and pelletlike, has no value other than as fuel and its yield must be minimized. Needle coke, which consists mainly of crystalline
elongated "needles," is highly valued and some cokers can be
run, if given the proper resid feed properties and unit operating parameters, to produce mostly needle coke.
About one-third of delayed coker sponge coke, after calcining, is sold to the aluminum industry to form the "carbon"
anode to produce the pure metal from aluminum oxide by
electrolysis. Depending on its electrical conductivity,
strength, and contaminant levels of sulfur and resid metals
(Ni + V), calcined sponge coke c o m m a n d s a selling price
about 2-5 times its fuel value. Needle coke may be sold to the
steel industry for operation in arc furnaces to yield high quality metallurgical steels. This coke may sell for as m u c h as
5-12 times its fuel value.

24

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Fluid Coking/Flexicoking
These technologies also convert all of the resid feed into
cracked products and coke. The chemistry takes place, however, in a reactor containing vapor phase fluidized coke particles. The heated feed is sprayed onto the coke through feed
nozzles around the reactor circumference. The product coke
deposits on the fluidized coke, which is continuously removed from the reactor. In the fluid coking process, sufficient coke is burned in a separate "burner" vessel to raise its
temperature so that this hot coke will maintain heat balance
upon its recirculation to the reactor. In the Flexicoking process, essentially all of the coke is converted to a low heat content gas in a third "gasifier" vessel, the hot gas then reheats
the circulating coke via heat transfer in what was the fluid
coker burner vessel. As an example, if the chemistry yields
30% coke in the reactor, net coke from the fluid coker will be
a b o u t 20-24%, b u t will only be a b o u t 0.5%, as a p u r g e
stream, from the Flexicoker.
The net coke from the fluid coker is in the form of shot coke
and can only be used as fuel. Because the delayed coking process yields a higher average value of coke, it accounts for
about 85% of worldwide coking capacity. The Flexicoking
process provides the refiner the option of generating a fuel
gas that can be scrubbed of H2S, instead of coke laden with
sulfur, nitrogen and metals. Because the gasifier operates on
steam and air, rather than steam and oxygen, the resulting
gas heat content is in the range of 3000 to 4500 kJ/m^.
Cracked gas and liquids yields from the fluid coking process are similar to yields from the delayed coking process. A
washing section is installed above the reactor to prevent carryover of coke fines to the coker main fractionator, produce
a coker gas oil recycle and, as a result, control coker gas oil
final boiling point.

an equilibrium catalyst activity can be maintained. This eliminates the need to raise feed inlet temperature as run length
progresses, as required in fixed bed units. In addition, the
a m o u n t of recirculating liquid product required for proper
catalyst bed operation is usually sufficient to provide a complete heat sink for the exothermic heat of reaction; thus, the
reactor essentially operates isothermally. This permits startof-run temperature as high as 435C, which is not technically
or economically feasible in fixed bed reactors. This temperature, in turn, provides enough thermal energy to substantially
crack vacuum resid, and, from the presence of hydrogen at
high pressure, typically 15000-18000 kPa, enough hydrogenation reactivity to yield substantially desulfurized lower
boiling products.

TABLE 19ARDS unit yields.


Products
Feed Naphtha
Boiling Range, C 405 + 30-175
Yield, %w
1.1
Density, kg/m^
990
740
Sulfur, ppmw
44 000
200
Nitrogen, ppmw
2800
20
Viscosity,
105
m2/s @ 100C

LGO
175-345
8.8
865
300
200

HGO
345-550
52.7
910
1300
400
10

Vac
Resid
550-134.i
980
11000
2800
2700

Fixed Bed Hydrocracking


Any boiling range material from crude oil can be hydrogenated. As the boiling range increases, required operating
severity increases. In order to desulfurize, dearomatize, and
crack resid-containing feed, multiple fixed bed reactors in series are required. Commercial installations have utilized
from 2-6 reactors to attain desired process severity. However, most commercial units are usually designed to operate
on feeds no dirtier than atmospheric resid, based on capital
investment and operating cost, since running on v a c u u m
resid substantially increases severity. Existing atmospheric
resid hydrocrackers, oft times labeled ARDS units (Table 13),
produce clean products as exemplified in Table 19.
Fluidized B e d Hydrocracking
This is a liquid phase, fluidized catalyst bed process and is
more commonly called expanded or ebullated bed hydrocracking. In this process, depicted in Fig. 13, fresh resid feed,
along with hydrogen, is introduced into the bottom of the reactor. Liquid product is also recycled to the reactor bottom to
provide needed hydraulic lift to expand the catalyst bed by
about one-third. When this occurs, the catalyst goes into random motion to create fluid bed behavior. This allows "spent"
catalyst to be withdrawn from the reactor each day and replaced with fresh material. Therefore, unlike fixed bed units.

Recycle Oil

FIG. 13Fluidized bed resid hydrocracking reactor.

CHAPTER 1: PETROLEUM OIL REFINING

25

TABLE 20Fluidized bed resid hydrocracking unit yields.


Products @ 66% Conversion
Boiling Range, C
Yield, %w
Density, kg/m'
Sulfur, p p m w
Nitrogen, p p m w

Products @ 80% Conversion

Feed

Naph

LGO

HGO

Vac Res

Naph

LGO

HGO

Vac Res

565 +

C5-175
9
710
300
85

175-345
18
860
800
480

345-565
32
920
2500
1900

565 +
34
1010
12 400
5200

C5-175
12
710
900

175-345
23
860
2700
630

345-565
38
930
11800
2500

565 +
20
1060
27 800
7000

1037
54 000
4000

Conversion levels of 50-90% have been commercially attained. And, the unit can process any quality feed, recognizing that heavier, dirtier feeds will require lower throughput
rate (space velocity), and increased hydrogen consumption
and catalyst replacement rate. Examples of yields and quality
for a representative resid feed are shown in Table 20.

PROCESSES FOR LUBE OIL BASE


STOCK PRODUCTION
Lubricating oil base stocks are produced from the vacuum
gas oils. While lube oil quality requirements are extensive,
process requirements are mainly driven by base oil viscosity
index, "cleanliness," and pour point. With respect to hydrocarbon composition, the overall requirements are that finished base stocks cannot contain aromatics, and are limited
in normal paraffin content. Aromatics must be removed or
converted to naphthenes because of their adverse effect on
oxidation stability and hot lube performance. Viscosity index
(VI) is the measure of the change in viscosity with temperature. High VI, which equates to the least change of viscosity,
is most desired. Normal paraffins provide the highest VI
among the hydrocarbon types. However, n-paraffins are also
highest in pour point; hence, their concentration in finished
lubes must be limited to avoid solidification.
There are two main process routes to produce the base oils.
The original, and still predominant, scheme incorporates
three process steps: first, aromatics are removed by solvent
extraction; secondly, normeJ paraffin content is reduced via
crystallization (dewaxing), and, thirdly, the remaining isoparaffins and naphthenes are hydrotreated to remove other
components such as organic acids, sulfur compounds and
the like that would adversely affect long term "cleanliness."
A newer process utilizes one-step high severity hydrocracking at about 18000 kPa. Under such high pressure, and with
the proper catalyst, the aromatics are completely saturated to
naphthenes, the other heteroatom-containing components
are hydrotreated as above, and a reasonable amount of the
normal paraffins are isomerized to isoparaffins, via the ability of the catalyst to effect isomerization activity as well as hydrogenation chemistry, to meet pour point requirements. If
the refiner is running a highly paraffinic crude slate, it may
still be necessary to dewax the hydrocracked product.
Aromatic extraction of vacuum gas oil is similar in concept
to extraction of catcJytic reformate, except the solvents are
different. The most widely used solvent had been phenol, but
it has been banned because of its carcinogenicity. Solvents
used today include furfural and n-methylpjrrolidone.
Dewaxing is accomplished by chilling the gas oil until the
n-paraffins solidify. The process name derives from the end

use of the n-paraffins as wax product. The two largest markets for this wax are the maJcing of candles and the coating of
cardboard cartons for the preservation of fruits and vegetables from farm to table. Separation of the solid paraffin crystals from the mother liquor is aided by solvents such as
methyl ethyl ketone and urea.
The refiner usually supplies some 4 to 9 lube base oils, that
vary mainly in viscosity, to lube plants that blend, package,
and ship finished product. The largest single market for lube
oil base stocks is for the production of motor oils. Hundreds
of other products, including greases, are also prepared for a
myriad of industrial needs. Overall, this is still a specialty
area of refining, accounting for only 1% of crude oil capacity.

OTHER REFINERY PROCESSES


while the refinery cannot run without the processes included
in this section, they are usually placed in the "other" category
since they do not contribute directly to the production of hydrocarbon streams for fuel product blending.
Hydrogen Production
Petroleum refineries, industry wide, long ago lost their ability to satisfy the need for hydrogen via recovery from the catalytic reforming process. The hydrogen shortfall can be satisfied either by buying hydrogen "across the fence," or by
building a refiner-owned plant inside the gate. Worldwide,
refinery hydrogen plant capacity has surpassed 300 million
m^/day.
There are two process routes to hydrogen: the catalytic reaction of low molecular weight hydrocarbons with steam,
and the non-catalytic gasification of heavier hydrocarbons
with oxygen. The former is known as steam reforming or
steam-methane reforming, while the latter is oft-times called
partial oxidation.
Steam Reforming
This process basically utilizes two-step or three-step chemistry, depending on when the plant was built. Older units typically involve three separate catalytic reactions, while process
innovation has reduced many of today's flowsheets to two
catalytic steps, followed by physical separation of product
components.
The first reaction, which gives rise to the process name,
"reforms" the hydrocarbon feed into a hydrogen-rich synthesis gas, per the following theoreticeJ equation:
CH4 + H2O = 3H2 + CO
The reforming takes place at about 800C over a nickel catalyst placed inside tubes within a furnace. This design is re-

26 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


quired due to the high endothermicity of the reaction. The
high temperature also results in coke formation, but the coke
reacts with excess steam to yield additional synthesis gas.
With methane as the feed, the coke usucJly reacts as fast as it
forms to keep the catalyst and tubes clean. Heavier feedstocks such as LPG, refinery fuel gas particularly containing
C3 +, or light naphtha, can cause coke buildup and limit r u n
length. A n a p h t h a hydrocarbon feed may also require hydro treating to remove heteroatoms, such as sulfur and chlorine, to protect the reforming catalyst.
The second reaction, called "water gas shift," catalytically
converts or shifts the CO to CO2, per the following equation:

Partial Oxidation

CO + H2O = CO2 + H2
This exothermic reaction takes place at about 350C over a
fixed bed of iron oxide catalyst. Some plants employ a lower
temperature second catalytic shift using a copper-zinc catalyst to convert any remaining CO. The product gas is then
treated for CO2 removed; the carbon dioxide is then vented or
recovered.
Unfortunately, the hydrogen product gas may still contain
u p to 1-3% CO/CO2 which will adversely affect catalyst in a
hydrotreater. Thus, a third reaction, called methanation, may
be employed to reduce impurities to acceptable levels. This
step is carried out in a fixed bed using a nickel catalyst and
uses a small amount of the product hydrogen, per the following chemistry:

Sulfur Recovery
Hydrogen sulfide is removed from refinery gas and liquid
streams via contact with liquid or solid absorbents and adsorbents. Among the dozen or so choices, the ones most
widely used in refineries are the ethanolamine liquid absorbents. As a result, this step on the sulfur recovery flowsheet is commonly ccilled "amine treating." After the H2S has
been separated from the hydrocarbons, it is converted into elemental sulfur in the sulfur recovery unit (SRU) by the Claus
process and its m3rriad variations. Recovery of sulfur from refineries and from natural gas production now accounts for
the majority of sulfur supply to its end users.
The most commonly used amine treating absorbents, or
solvents as they are normally called, are the primary amine,
monoethanolamine (MEA); the secondary amine, diethanolamine (DEA), and the tertiary amine, methyldiethanolamine
(MDEA). Selection is based on concentration of H2S in the
hydrocarbon gas stream, a m o u n t of other acid gas components such as carbonyl sulfide and carbon dioxide, and the
relative solvent activity compared with useable concentration of amine in water.
The hydrocarbon feed stream is contacted countercurrent
to a "lean" solvent, free of H2S, in absorbers (Fig 14). The sol-

CO/CO2 + H2 = CH4 + H2O


Most of the newer steam reformers substitute adsorption
for third-step chemistry to remove impurities from the hydrogen. The gases from the shift reactor pass through beds of
molecular sieve that alternately adsorb and desorb unconverted CO and the CO2, as well as other impurities such as nitrogen and methEine, but not the hydrogen. The product hydrogen gas usually exits the beds at 99.9% purity. The beds
are most commonly desorbed by reducing pressure; hence,
the process name pressure swing adsorption. The desorbed
material is usueilly then blended as part of the fuel required
for the reformer furnace. Other sieve beds can be used to separate CO2 for product sale.

Sweet Gas
Lean
Amine

-^MQ-J'

(POX)

The advantage of this process is that the chemistry requires no


catalyst, and zmy hydrocarbon can be used as feed including
heavy gas oils, resid, coke and coal. Its disadvantages are the
need for oxygen, high reactor temperature, and more complex
gas cleaning. On balance, most hydrogen plants are steam reformers; partial oxidation will be chosen when there is no access to natural gas or other low moleculeir weight feeds, or
when sale or utilization of high molecular weight refinery
streams Eind coke is not feasible or economically attractive.
The POX process reacts hydrocarbon and oxygen at about
1300-1550C to yield a H2/CO synthesis gas. The oxygen is
usually p u r c h a s e d over-the-fence. The "syngas" is next
treated for removal of sulfur compounds, which will include
carbonyl sulfide in addition to H2S. The scrubbed syngas is
then sent to catalytic shift conversion and hydrogen purification in similar manner to steam reforming.

^Ll

Mal<eup
-Water

Amine
Stripper
Sour Gas

Amine
Contactor

Flash
tank

Rich Amine

CKl

Lean Amine
FIG. 14^Amine treating unit.

Acid
'Gas

CHAPTER 1: PETROLEUM OIL REFINING


vent picks u p the acid gases and exits the absorber as a "rich"
solvent. This stream is then sent to a regenerator where solvent reboil provides the heat to strip the H2S from the solvent. The solvent is t h e n cleaned a n d recycled to the absorber. The solvent may be filtered at one or more places in
the flowsheet to remove impurities, such as iron sulfides, that
can cause equipment fouling and loss of solvent efficiency in
the absorber.
The conversion of H2S to sulfur involves two chemical reactions; namely:

27

chemical. Other outlets include its use as a cross linking


agent for the manufacture of tires via the vulcanization process for synthetic rubber, and as a blending component in the
manufacture of road asphalt. However, the increasing production of sulfur from refinery hydrotreating and from the
cleanup of natural gas has helped depress sulfur prices and
not every refinery is able to sell all of its production.

REFINERY POLLUTION CONTROL

H2S + 3/2O2 = SO2 + H2O


2H2S + SO2 = 3S + 2H2O
Thus, Claus plants consist of a b u r n e r to convert about
one-third of the H2S to SO2, followed by multiple fixed bed
catalytic reactors to react the SO2 with the remaining hydrogen sulfide to produce elemental sulfur, as in Fig. 15. Older
Claus plants leave enough H2S in the vent gas that a second
catalytic process is needed to convert this dilute H2S stream.
This added step is commonly labeled "tail gas cleanup."
Some of the newer Claus plant catalysts and designs claim no
need for this last cleanup step.
The Claus plant sulfur is a vapor as it leaves the reactors. It
is cooled to produce liquid or molten sulfur and can be taken
to market in that form via tank trucks or railroad cars, or it is
further cooled to yield a solid yellow powder. This powder
can be sold or stored in this form, or converted to prills or
into blocks, depending on end use.
Sulfur has many markets; the largest is for the production
of sulfuric acid, which in turn is the world's largest selling

AIR
COMPRESSOR

THERMAL
REACTOR

Many parts of the world have imposed very strict control on


refinery pollutants. The three categories are air, wastewater,
and particulates. Air pollution has mainly concentrated on
sulfur oxides and nitrogen oxides and refineries will have a
limit on allowable emission levels, established over some time
frame, with higher levels cJlowed for short periods due to unit
upsets. Three of the key emissions "points" during normal operations are furnaces, boilers, and the FCCU; flare systems become part of the formula when unit upsets take process gases
and liquids to flare from the opening of relief valves.
Wastewater treatment involves many process steps and
parts of its complexity are related to refinery unit selection
and operations. Many waste streams will first be sent to settling ponds and API separators to allow solids and various hydrocarbon liquids to be separated from the water. The water
will then undergo some n u m b e r of biological treatment steps
until "clean" water is produced. Some of the wastewaters are
recycled back to parts of the refinery while the rest is sent to
disposal via deep wells, for example.

SULFUR
SULFUR
CONVERTER CONDENSER REHEATERS

Rcycle HydfOKWi SIMMB CM

AeUQu
Fran Ajidiit
RMNnnlioQ

AddOM
From Sour Water Stripper

Com.
FIG. 15Claus unit.

28

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

Particulate emissions can result from improper operation


of the catalyst recovery section on the cat cracker regenerator. This Ccin occur from loss of cyclone efficiency that in turn
will overload the flue gas solids removal system, or from malfunction in the solids removal system itself. Obviously, any
furnaces and boilers running on coke or coal require control
of particulate emissions.

COGENERATION
Refineries continue to add "cogen" plants to the flow sheet.
They offer the opportunity to convert various low value fuels
or blend components into electricity. The electricity, in turn,
can be used to supply part or all of the refinery's needs, or the
plant can be large enough to permit the refiner to sell electricity to nearby utilities. With the advent of utility supply
and price deregulation, this option can take on added attractiveness. Cogen feeds range from gases to heavy fuel oils to
delayed and Quid coke.

PRODUCT BLENDING
Blending equations have been developed over the decades to
allow the refiner to optimally blend the fuel products with a
high degree of accuracy. The equations may be relatively simple for properties such as viscosity, or relatively complex for
predicting blended gasoline octane number. These equations
have been built into the refinery computer models with the
goal that each batch of product will be blended correctly and
will meet specifications at m i n i m u m cost. While the computer models and test methods continue to improve, most
product is still blended by mixing the computer-indicated
components in a product storage tank, sampling the tank,
and then waiting for appropriate laboratory data to certify
that the blend meets specifications. Some refineries do online product blending, meaning that components are mixed
directly into a product pipeline, for example, with key tests
being performed using on-line instrumental analysis. On-line
octane analyzers are being used for gasoline blending, and
newer test methods such as near and mid-infrared are beginning to replace m o r e complex or time-consuming older
methods.

REFINING OPTIONS FOR THE FUTURE


The key issues facing the refiner will be mainly driven by:
Crude oil quality
Clean fuels legislation
Product demand and mix
Alternative transportation options
Crude oil and product pricing
Crude oil quality is expected to slowly worsen. The most
critical parameter continues to be sulfur, but any increase in
the percentage of resid from increased use of heavier crude
oils will also play an important role as the world moves towEird a lighter fuel product mix. The rate of change is obviously related to the crude oil assay quality of new discoveries.

Based on historic data and recent findings, it is not likely that


enough sweet, light crudes can be b r o u g h t to market to
counter the expected declining trend. Another factor is crude
pricing. When higher prices, say, $145/metric ton ($20/barrel) and above, prevail, the economics of producing heavier,
higher sulfur crude obviously improves and, if sufficient
price spread between heavy and light crude results, then the
refiner has a greater economic incentive to process poorer
qucJity crude. In addition, as the industry adds desulfurization capacity to meet future low sulfur fuels demand, some of
this process capacity can be designed or revamped to handle
dirtier crude. If the demand for today's fuel products continues to increase, then more and more refiners will have no
choice but to process poorer quality crude oils.
Gasoline and No. 2 diesel will be the products that face the
near term drive to cleaner fuels. The key changes to gasoline
specifications, and their impact on refining, are:
Boiling PointContinuing reduction to the E50, E70, E80
and E90, (the maximum temperature when 50, 70, 80, or
90% of the gasoline has evaporated by distillation), for example, will diminish product supply at existing refinery
crude capacity and flow sheet configuration. To meet gasoline demand, refining capacity and/or cracking units will
have to be expanded just to replace the higher boiling cuts
being removed from the blending pool.
AromaticsReduction
in total aromatics and, in particular, the higher boiling aromatics, can only effectively come
from removal of the heavy portion of straight r u n naphtha
feed to catalytic reformers, and from lower severity reformer operation. Incorporation of b o t h options m a y
maintain gasoline yield, but will result in less hydrogen byproduct. Dearomatization of heavy reformate is not expected to be economically attractive.
Benzene^Among the benzene reduction options presented
earlier, it is expected that extraction for petrochemical Scile
or removal of the C6 cut from reformer feed will prevail.
The latter will increasingly require isomerization of the
deeper-cut, lower octane number, light straight run gasoline.
OlefinsThe olefins in the C5-C6 fraction of cat gasoline
will be reduced. Likely process options are to install "light
cat gasoline" hydrotreaters, which will reduce octane number followed by isom units to octane-upgrade, to take at
least the C5 cut to alkylation units, or to convert the
isoamylenes to TAME, provided ethers are not banned.
SulfurCat gasoline provides 85-100% of gasoline sulfur
and most of this sulfur is concentrated in the higher boiling fraction. Refiners will have the choice of hydrotreating
some portion or all of the cat gasoline, or deeply desulfurizing cat feed. Process selection will eJso depend on final
realized gasoline sulfur specifications. Capitcd and operating costs to remove sulfur from "cat feed" are so m u c h
higher that, on the surface, the only apparent choice is to
treat the cat gasoline. However, cat gasoline hydrotreating
reduces octane while cat feed h5ftrotreating can improve
FCCU conversion without increasing coke on catalyst. Catalyst manufacturers and petroleum refiners continue to develop improved catalysts that will desulfurize cat gasoline
with m i n i m u m octane loss. The overall effect is that either
process option, or both, may be selected, based in part on

CHAPTER
the refinery's crude slate and overall fuel product demand
balance. It is also euiticipated that some of the new sulfur
removal processes will gain substantial commercial acceptance, offering a n opportunity to meet future gasoline sulfur specifications with p e r h a p s less octane n u m b e r loss
and less hydrogen consumption.
OxygenatesAs worldwide legislation for cleaner fuels
spreads, every region or country appears to be requiring
the use of oxygenates for pollution abatement, with the
concomitant octane benefit. It is not possible to know if the
expected b a n on MTBE in California and the consideration
of a countrywide ban by the U.S. Congress will cause a similar worldwide response. Removal of MTBE will likely
place a b a n on TAME, increase interest in ethanol, require
an increase in cat reforming, cat cracking and edkylation
capacity, increase the need for isomerization of light
straight r u n gasoline and introduce the chemical conversion of isobutylene to isooctane.
The quality of No. 2 diesel fuel will mainly focus on sulfur
and aromatics. As the world likely adopts a m a x i m u m sulfur
specification in the 10-50 p p m w range and some reduction
in aromatics concentration, refiners will in turn install or revamp middle distillate hydrotreaters that have the flexibility
to achieve deeper aromatics saturation with perhaps only the
need for a catalyst changeout.
Future product demand may be virtually impossible to predict. For example, in the U.S., the rapid acceptance of the van
and sport utility vehicle in place of the standard car led to a
decrease in overEiU vehicle fuel economy because of lack of
regulation for such vehicle tjrpes. This is in the process of being corrected but, meanwhile, gasoline demand in the U.S. is
increasing at rates exceeding earlier estimates.
Alternative sources of vehicle power create a long-term
uncertainty for the refiner. Natural gas and LPG are available in varying degree in m a n y parts of the world; LPG is a
readily available automotive fuel in European countries, for
example. Ignoring availability, the main detriment to rapid
expansion of these fuels is the needed supply and distribution infrastructure. Electricity-driven vehicles, via the battery, are not likely to play any substantive role unless a major b r e a k t h r o u g h in energy efficiency is found. Vehicles
powered o n externally-supplied hydrogen have little hope of
p e n e t r a t i n g the marketplace because of high p r o d u c t i o n
cost, delivery infrastructure, and safety. However, hybrid
battery/gasoline powered vehicles will be available shortly.
The fuel cell may have an impact on future refineries. This
would be intriguing if it becomes technically and economically feasible t o produce a hydrogen/CO synthesis gas by
steam reforming of naphtha "under the hood," since this liquid can take the place of gasoline or diesel fuel without any
changes at the "pump." Should this occur, octane n u m b e r
becomes a non-issue, the value of catalj^ic reforming, fluid
catalytic cracking and, hence, alkylation would diminish,
and hydrotreating and hydrocracking to supply additional
"clean" n a p h t h a would increase, also requiring a major increase in refinery hydrogen.
Crude a n d product pricing has become a substantive unknown for the refiner. On the crude oil side, the difficulty
has been unexpected changes in price, as well as the inability to predict future prices or the price spread between

1: PETROLEUM

OIL REFINING

29

sweet/light crudes and sour/heavy crudes. On the product


side, refiners have not always been able to obtain a reasonable return on investment for the legislated changes in fuels
specifications. The net effect in the late 1990s resulted in low
refining margins. This, in turn, has led to a sustained period
of unusually high refinery utilization rates^where 80-90%
had been considered the norm, rates have recently ranged
between 93-98%. Thus, refineries have opted for longer r u n
length, which, in turn, has pushed many of the process units
to their limit. It is expected that this mode of operation will
continue until the cleaner fuels program is in place, refinery
capacity is in better balance with demand, and crude prices
stabilize.

ASTM STANDARDS
Number

Title

D 86-99a
D 1160-95

Method for Distillation, of Petroleum Products


Method for Distillation of Petroleum Products
at Reduced Pressure
D 1319-98
Method for H y d r o c a r b o n Types in liquid
Petroleum Products by FIA
D 287-92
Method for API Gravity of Crude Petroleum
and Petroleum Products
D 2699-97a Method for Research Octane Number
D 2700-97
Method for Motor Octane Number
D 323-99a
Method for Vapor Pressure of Petroleum Products (Reid Method)
D 4814-99
Specification for Automotive Spark-Ignition
Engine Fuel
D1655-99
Specification for Aviation Turbine Fuels
D 396-98
Specification for Fuel Oils
D 975-98b
Specification for Diesel Fuel Oils
D 129-95
1
D 1266-98
f Methods for Sulfur in Petroleum Products
D 2622-98
J
D 613-95
Method for Cetane Number of Diesel Fuel Oils
D 97-96a
Method for Pour Point of Petroleum Products
D 5771-95
Method for Cloud Point of Petroleum Products
D 189-97
Method for Conradson Carbon Residue of
Petroleum Products
NOTE: The above are listed in order of appearance in text.

BIBLIOGRAPHY
[1] Wauquier, J.-P., Crude Oil. Petroleum Products. Process Flowsheets, 1st edition. Editions Technip, Paris, 1995.
[2] Wauquier, J.-P., Separation Processes, 1st edition, Editions Technip, Paris, 2000.
[3] Leprince, P., Conversion Processes, 1st edition. Editions Technip, Paris, 2000.
[4] Gary, J. H. and Handwerk, G. E., Petroleum Refining Technology
and Economics, 4th Edition, Marcel Dekker, Inc., NY, 2001.
[5] Kaes, G. L., Refinery Process Modeling, 1st edition, The Athens
Printing Co., Athens, GA, 2000.
[6] Meyers, R. A., Ed., Handbook of Petroleum Refining Processes,
1st and 2nd editions, McGraw-Hill Book Co., NY, 1986 and 1997,
respectively.

30 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


[7] Maples, R. E., Petroleum Refinery Process Economics, 2nd edition, PennWell Books, Tulsa, OK, 2000.
[8] Chang, T., "Worldwide Refining Report," Oil & Gas Journal, Vol.
98.51, December 2000, pp. 56-120.
[9] "Refining Processes 2000," Hydrocarbon Processing, Vol. 79, No.
11, November 2000, pp. 85-142.
[10] Tromeur, P., Guibard, I., Harle, V., and Pike, M., "Hydroprocessing Atmospheric and Vacuum Residues," Petroleum Technology Quarterly, Vol. 5, No. 1, Spring 2000, pp. 21-27.
[11] Shorey, S. W., Lomas, D. A., and Keesom, W. H., "Use FCC Feed

Pretreating Methods to Remove Sulfur," Hydrocarbon Processing, Vol. 78, No. 11, November 1999, pp. 43-51.
[12] Swaty, T. E., Nocca, J. L., and Ross, J., "What are the Options to
Meet Tier 11 Sulfur Requirements?," Hydrocarbon
Processing,
Vol. 80, No. 2, February 2001, pp. 62-70.
[13] Law, D. v . , "Hydrocracking: Past, Present and Future,"
Petroleum Technology Quarterly, Vol. 5, No. 4, Winter 2000/2001,
pp. 55-63.
[14] Chang, T., "Worldwide Catalyst Report," Oil & Gas Journal, Vol.
97, No. 39, September 1999, pp. 45-68.

Section II: Fuels: Properties and Performance


Steven R. Westbrook, Section Editor

MNL37-EB/Jun. 2003

Liquefied Petroleum Gas


Robert J. Falkiner^

utilize the butane. Temperate climates with large seasonal


temperature changes could use propane in the winter and BP mixtures in the summer. However, the logistics of seasonal
distribution and air/fuel calibration changes, coupled with a
more than adequate propane supply, generally favors the use
of propane throughout the year.
The same properties that make LPG so useful contribute to
some of the unique challenges in using it safely. Water/ice/hydrate properties are unique. Pressurized systems are more
prone to leaks, even when the equipment is idle. The heavier
than air vapor density allows accumulation in low points and
cavities in the absence of ventilating air flow. When mixed
with air in the right ratio in the narrow range, it has the
potential for high destructive power in the event of a n
ignition source that results in an explosion or fire. Consequently, persons handling LPG and installing equipment are
tjrpically required to be trained and licensed. A variety of
safety devices and procedures are used, and LPG is odorized
to help detect potentially dangerous leaks.

LIQUEFIED PETROLEUM GAS ( L P G ) IS A GENERIC TERM FOR

ETHANE (C2) TO BUTANE (C4) h y d r o c a r b o n mixtures t h a t


can exist as liquids u n d e r modest pressures at a m b i e n t
temperatures.
Methane (CI, natural gas) must be refrigerated to less
than 259F to be condensed by compression to Liquefied
N a t u r a l Gas (LNG). Pentane a n d heavier hydrocarbons
(C5 + , condensate) are liquids at ambient temperature and
pressure, and are used in the manufacture of gasoline,
n a p h t h a fuels, and solvents. Ethame, propane, and butane
are gases at standard temperature and pressure, but can be
liquefied by compression and condensation of the vapor at
ambient temperature. Propane (C3), Butane (C4), and butane/propane mixtures (C3/C4 or B-P mix) have ideal properties for a fuel, widely used throughout the world in an
amazing variety of applications. They are stable, high-energy content, relatively low sulfur, clean burning fuels that
can be transported economically as a liquid, and be used either as a liquid or a gas. Pure component properties are
given in Figs. 1-4. Propane can be used from about -40C
to 45C, and butane from 0C to about l l O X (about 0-250
psig vapor pressure) or higher depending upon equipment
pressure ratings. The LPG tank is always under pressure at
normal operating temperatures above the normal boiling
point of about 42C, so there is no need for a fuel p u m p
or electrical components for most applications. This maJses
LPG ideally suited to a wide variety of portable, mobile or
remote applications, using mechanically reliable and simple
equipment. Propane applications tend to be robust and reliable as a result.

HISTORY
The LPG industry did not start until about 1904, more than
40 years after the start of North American crude oil and natural gas production a r o u n d 1860. Natural gas (methane)
cooking and lighting appliances were commonplace by 1900,
but it was difficult to make the gaseous fuel portable. It was
not feasible to transport and store compressed natural gas
(CNG) in the bulky pressure vessels of the day.
LPG is the ideal fuel for mobile and remote gas applications. It is a high BTU content liquid at typical ambient temperatures and modest (<250 psig) pressures, that is practical
for storage and transportation. It can be used like natural gas
once vaporized, in natural gas appliances adapted to gaseous
LPG mixtures with small adjustment for air/fuel ratio.
The early years of the industry were cheiracterized by the
need to solve the immediate problems of the day, without any
standardization or regulatory controls. LPG was one of the
first c o n s u m e r goods transported and sold in pressure
vessels. There were many economic and technical challenges
to produce, transport, and t h e n sell it to the public. The
industry was at the forefront of many areas of research and
development, ranging from processes, equipment and
appliances for m a n u f a c t u r e and use, to analytical test
methods for composition a n d properties. The results (in
retrospect) were predicable, a n d excesses abounded. However, in a short n u m b e r of years, the emerging industry was
compelled by marketing a n d regulatory forces to develop

This chapter deals mostly with ASTM D1835 "Commercial


Propane" and "Special Duty Propane" grades. The same distribution equipment, rail/truck tanks and storage vessels can
be used for propane or B-P mixtures so it is not outwardly
apparent what grade of LPG is being used in any region or
application. The t e r m s "propane," "LPG," and "HD5" are
c o m m o n l y used interchangeably (although this is not
technically correct). ASTM D 1835 and GPA 2140 specifications exist for "Commercial B-P Mixtures," but this is rarely
used for consumer applications in North America. There is
n o current Canadian (CGSB) specification for B-P Mixtures,
as the winter temperatures are too cold, and winter butane
d e m a n d is high for winter gasoline production. Polar
climates must use propane year round for low temperature
operability. Tropical climates (no winter temperatures, no
w i n t e r gasoline) tend to use B-P mixtures year r o u n d to
' Imperial Oil Ltd., Quality Assurance Operations and Development,
Toronto, Ontario M5W 1K3, Canada.

31
Copyright'

2003 by A S I M International

www.astm.org

32

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

10.000.0
1

1000.0

'

-=>3
s:*>?''P-

n<L,

-4

100.0

j ^ s^
xoH

9>

_,-:^2

'(.^

i^
'^ ^
^

y y y
/

_,*
' ^

t f

; ^

r^

_,-

^ ^

=^

x'

-^ Z
/'
/
/

y y

^^-^

^
^ ot^

^
i.o_

,-'

HI"
^ So*"?

^^'

r^

^
^

ip

.^

uft<;

'S5^

PX

/^

''

40

60

80

^!i /

4P5/

5^

20

.^

M , .

^^

y\

'>'
?

v^

y-

- z ^ : - _1^^;z: ^r^ ::z 7 * _ > *-7"


z
:c^ _^
^'^
/
^

M^.'^1

< \^
o.t_

prf

77^
-'

\4

^^ ^

~"
s^

<'

' " . v e ^ S5^


.-

-'^

f\

<-^
^^

"^

10.0

3-

c<

<n^

. . /

'^ y -<i^ P ^
r

s^ ;- - , < i :

5^^
/*

_^

.^'

100

200

300

400

SOO

600

Temperature, F
FIG. 1High temperature vapor pressures for light hydrocarbons. Reprinted with permission from the Gas Processors
Association.

products and practices that were acceptable to the pubhc.


Most of the standards and regulations that were developed in
the early years endure today.
History of t h e LPG Industry
LPG was originally derived from both natural gas or crude oil
production, so the industry has two related historical roots.
Refining a n d various petroleum conversion processes
became additional sources later.
The Chinese first transported natural gas, as well as brine
and oil, during the Shu Han dynasty (AD 221) from shallow
wells and seepages, through simple pipelines made of hollowed b a m b o o logs [1]. The m a i n sources of early North
American gas were from numerous surface "seeps" and "gas
springs" in Ontario, Pennsylvania and Southern California.
The "burning spring" at Niagara Falls, below the cataract,
was described early in the 1800s, and was due to a flow of gas
from the Niagara shales, which underlie the limestone of the
Falls [2]. The first small scale commercial distribution in
North America was probably in Fredonia, New York in 1820
using small bore lead pipe distributing gas from a purposebuilt shallow well. There are records of oilfield gas being
supplied to several Pennsylvania towns by 1872. The first

large scale commercial application was the piping of gas to


Pittsburgh in 1883, about 20 yeEirs after the discovery of oil in
Pennsylvania. By the early 1900s, a 20 in. pipeline 165 miles
long, was being used for natural gas production [3], and
longer pipelines soon followed.
The use of petroleum pitch from surface "seeps" date back
to recorded time [4], and these were the first source of North
American crude production around the Lake Erie basin, at
Enniskillen township in Southern Ontario a n d Titusville,
Pennsylvania in 1859/60. Early cable "drilling" consisted of
"punching a hole in the earth by repeatedly lifting and dropping a heavy cutting tool hung from the end of a cable," and
collecting the crude in a wooden crib [5]. It produced virtually no associated gas or LPG, these having weathered off
from the shallow formation. Advances in drilling technology
quickly allowed deeper wells that hit shallow high-pressure
oil and gas bearing formations, at first with near disastrous
consequences. The first "gusher," in the spring 1862, "spewed
oil above the treetops and covered 50 acres with oil 1-3 feet
deep, and p o u r e d enough oil into Black Creek to blacken
Lake St. Clair"[6]. The flow disappeared after several months
as suddenly as it began, after m o r e t h a n a n estimated 5
million barrels "floated off the waters of Black Creek"[7].
Additional discoveries were made in rapid succession all over

CHAPTER 2: LIQUEFIED PETROLEUM

N^''^55^
il'
S^ s\

\ ? %*Ji-

s
=

rj^

sS ^-^

Sh, ' t

-*-(i

';'""< ' ^

**>>1 ^

^ ? ^ i r
^ \ ^

^ >

y*'.

fel';!

I- 8t

*^s

1 "{'"T' *

""
o.

- _ - j ^

!"iu

'x

-s":

^>,

"<

^ .

o
o

w
Q.
(0

m
O

(>
1

b
o

"* ^
-

(0
(0

Oo

*">

^
4

"S"""

"

.> V1

<u
a
5
o
0)

. s.

0)

<(0
o

'< ^ ^

o
w

(0
(0
V

>. * ^^

'N:

>

(B

s
o

^%
!>* X

c
o

Hi

"1

GAS

Q.
V

oc

0)

c
o
a

\
k

CD
U
O

TJ

O)

'

(0
(0
(0

-i -
a- 0 _

" 1

Q.
(S

>

r 8

a>
a

E
(U

8S S

o "O
Olid 'aimtajil iodoA

2oS 3

o
ot

a.

33

10000

100

300

200

400

500

600

n-Butane
Rsfsrenes Stales:

T / G

H(sat liqO'100 Btu/lb # T(trp)


S<aat. Iq.) c0Btu/lb'F@T(lrp)

700
10000

7'o^

:41000

1000

(0

100

(0

CD

10

Enthalpy, Btu/lb
FIG. 3n-Butane P-H diagram. Reprinted with permission from the Gas Processors Association.
100

10000

200

300

400

m/

Propane
Rstorence Slates:
H(sat. llq.HOO Btu/lb T(trp)
S(sat. l i q . ) ' 0 Btu/lb'T O T(trp)

^1

500

600

700
10000

-^*- -

1000

1000

<0

'co

a..
100

100

3
CO
CO

10

Enthalpy, Btu/lb
FIG. 4Propan P-H diagram. Reprinted with permission from the Gas Processors Association.

34

CHAPTER 2: LIQUEFIED PETROLEUM


the United States, in virtually every state from the Appalacha
to the Pacific. The industry remained regionalized around
these local sources, until the legendary Spindletop East
Texas, Panhandle and Oklahoma discoveries, and the post1900 development of crude oil and gas pipelines.
The discovery of large oil and gas fields in the early 1900s
resulted in an immediate excess production of LPG and light
naphtha hydrocarbons, far beyond the capability of developing markets to consume them. The ratio of gas to liquid
and the quality of production varied widely between different
production formations. At one extreme was low sulfur
content "dry" or "non-associated" gas, essentially pure
methane with little or no condensable liquid in the underground formation. This was ideal for distribution by gas
pipeline, especially in areas such as southern California and
the central United States where the gas wells were close to
cities, and the terrain allowed easy pipeline excavation. At the
other extreme was "sour" and "wet" gas that contained both
high sulfur and high propane and heavier content that condensed to a hydrocarbon liquid with even modest compression. "Wet" gas was generally "associated" with an underlying
crude reservoir, either as a gas cap or dissolved in the crude
at high underground temperature and pressure. Wet gas
from either crude or gas wells produced a liquid condensate
(NGL, natural gas liquid) when the gas was compressed for
distribution. Condensate had few uses, and for more than
50 years was burned or vented as a byproduct of crude and
natural gas production.
The wasteful practice of flaring enormous quantities of gas
from oil wells was eventually realized to be extremely detrimental to the amount of oil that could be recovered (see retrograde condensation). The gas pressure in a formation
helped force the oil to the surface. Excessive venting and depressurization left large portions of the crude unrecovered.
Moreover, the practices of one gas or crude producer affected
the yield of others in the same formation, since the crude and
gas could flow underground between producers whose
ownership rights were determined by surface surveys. This
resulted in several decades of litigation and regulatory development to establish fair and equitable means to balance the
often-conflicting social and economic goals [8].
The regulated recovery of liquids from ever increasing gas
and crude production resulted in a steadily increasing NGL
and LPG production, without adequate markets to consume
them. This was aggravated by increasing production of
deeper and higher pressure crude and gas reservoirs with
higher liquid condensable content. Whole industries appeared (and disappeared) based on the chronically depressed
price of LPGs and NGLs, and seasonal demand of natural
gasoline. Gas liquids were transported long distances to
find new outlets, with even some marine exports in large
drums from California. In the 1930s almost all of the world's
carbon black was manufactured from cheap Texas panhandle gas and gas liquids (eventually replaced by various
"coking" processes).
Hundreds of butane/air, propane/air, and LP-gas distribution plants were built to distribute gas to smaller towns and
cities. Most were gradually replaced by expansion of natural
gas pipeline distribution system, but a few remain in isolated
or remote areas of North America. This is commonplace in
some areas of the world with low domestic natural gas pro-

GAS

35

duction, where imported LPG is vaporized centrally, and


distributed locally in gas pipelines.
A balanced North American C3/C4 supply and demand was
achieved about 1950. This was mostly due to increased industrial or "chemicals" demand rather than the more modest
growth of consumer fuels markets. The alkylation process
converted C3/C4 into gasoline, and large-scale seasonal storage in underground salt caverns, natural formations and
large storage spheres balanced out the seasonal swings in
heating demand. Later, LPG became a preferred feedstock
for gas cracking and plastics manufacturing.
The LPG fuels industry has always been in excess supply.
The "chemicals" market is now more than twice the size of the
LPG fuels market. This tends to make LPG fuels economically
attractive in a wide variety of niche markets, wherever the
properties of LPG offer an advantage, and/or the economic return is higher than alternate BTU or chemicals value.
History of LPG
The first uses of LPG mixtures were for heating, cooking, and
lighting in remote or mobile applications that could not be
serviced by natural gas or manufactured gases (town gas,
coal gas, water gas, etc.). Natural gas distribution was limited
to mainly urban markets, that were supplied by relatively
short low pressure pipelines from regional gas wells or "town
gas" plants. Mobile applications included railway coach
lighting and heating, where high BTU liquid storage was a
great advantage over compressed gas (Pinsch gas) or carbide
gas (acetylene). Remote applications included smaller cities
and suburban areas, where underground pipelines were not
economically or technically feasible. In fact, "Rockgas" was
an early reference to the alternative to pipeline gas in areas
where buried pipelines were not feasible due to bedrock or
rocky terrain [9].
The earliest consumer use of LPG was "Blaugas" in Germany about 1904. Several plants were established in the
United States afterward [10]. This was a foul mixture obtained
by thermal cracking of hydrocarbon fuel oils, similar to town
gas production, but at lower temperatures that favored
greater condensable liquid yield. Composition was essentially
uncontrolled, and the mixture contained a large amount of
dissolved hydrogen, methane, LPG, gasoline range hydrocarbons and heavy ends, with a vapor pressure of up to 750-1800
psi at ambient temperature [11]. The first steel tanks imported
from Germany were called "bottles," a term still used today in
the "bottle gas" market. The early high-pressure cylinders
were bulky and extremely heavy. Up to 7 lbs. of steel was
transported for every pound of relatively low BTU fuel.
The earliest "Blaugas" sets used in United States had two
replaceable liquid cylinders and a third permanent gas cylinder that fed the appliance through a low-pressure gas regulator. The sets were expensive, since three "bottles," valves and
regulators were required instead of one. Liquid flowed via a
dip tube in the liquid cylinders through a valve or a "wet"
pressure regulator, where it vaporized into the third cylinder.
This maintained a relatively constant composition of gas and
avoided the problems associated with "weathering" or multicomponent distillation with the broad cut liquid being used
(although this process was not well understood at the time).
It was common in 1912 for such sets to lose many pounds of

36

MANUAL

3 7: FUELS

AND LUBRICANTS

HANDBOOK

gas daily. Stoves leaked too [12]. Even so, the industry was
modestly successful. Some "Blaugas" plants remained in operation into the 1920s b u t were all gradually displaced by
LPG recovered from crude/natural gas production a n d
refining. Small regional businesses were built up around individual supply sources and different gas mixtures and gas
sets. While the sets were relatively successful, they did experience problems from residues and ice causing regulators to
malfunction. Gasoline and heavier hydrocarbons collected in
the gas bottle, and had to be periodically drained out. Success
depended more on the ability of the equipment to tolerate the
mixture than anything else. There were no specifications to
control dryness, icing, residues, or composition.
The first commercial use of LPG produced from crude oil
or natural gas was in 1912, indirectly as result of a burgeoning demand for gasoline due to mass production of automobiles after 1908. Condensable liquids were reported as early
as 1893 in natural gas (methane) cryogenic drying processes
for natural gas distribution. There are indications of a lowpressure condensate from crude oil p r o d u c t i o n being
distributed in wooden barrels in the 1900-04 era, but it was
the automobile that changed everything. Automotive gasoline had to be liquid in atmospherically vented tanks, but
volatile enough to evaporate when mixed with air in a carburetor. The automobile created an i m m e d i a t e d e m a n d for
naphtha from crude oil as well as condensate from natural
gas or crude p r o d u c t i o n . Customers w h o b o u g h t a quart
of l a m p oil now w a n t e d gallons of gasoline. The liquid
condensate from gas production, called "casinghead gasoline," became a preferred product for sale to early refiners for
blending into gasoline, and a new industry was b o m . LPG
was displaced in importance by the frantic scramble to produce casinghead gasoline, which was m o r e profitable, at
least in the wintertime, when there was a strong demand. Initicdly, a high-pressure condensate was allowed to "weather"
in standing tanks, until enough boiled off that it was "acceptable" for use in gasoline. The limits of acceptability were only
loosely defined at the time, but these fundamental requirements eventually led to the "weathering test" and "vapor
tension" specification requirements many years later.
Propane a n d b u t a n e continued to be problematic byproducts from both crude and gas production. Propane was
too volatile to be a significant portion of gasoline, and not
volatile enough for even moderately pressurized natural gas
distribution networks pipelines. It was essentially worthless,
so there was a large economic incentive for producers to include as m u c h of the volatile propane/butane as possible into
casinghead gasoline. While m a n y of the blends provided
good fuels for the engines of the day, "a frantic scramble to
meet demands, coupled with not a little ignorance, began to
create significant problems" [13]. Many serious incidents occurred due to excessive volatility and evaporative losses that
sometimes exceeded 40%, and from boiling and over pressuring rail cEirs. In 1915, a rail car explosion killed 47 persons, injured more than 500, and virtually destroyed the town
of Ardmore, Oklahoma. Casinghead gasoline was almost universally condemned, and developed such a poor reputation
that one major refiner stopped using it in gasoline a n d
advertised it as a consumer benefit. By 1919, the last major
refiner announced that it was n o longer in the market for casinghead gasoline, and declared, "specifications were urgently

needed" [14]. As late as 1921, there were more than 100 different specifications for casinghead gasoline, most of them
meaningless and many based on what a producer may have
been producing on a particular day [15].
In April 1921, representatives from 31 companies formed
the Association of Natural Gasoline Manufacturers (ANGM),
following upon two previous efforts to organize gas processors. This Association later became the Natural Gasoline Association of America (NGAA), and now the Gas Processors
Association (GPA). Its purpose was to impose both business
a n d technical controls on the unruly new industry. They
created a new, m o r e acceptable product, called "natural
gasoline" to replace "casinghead gasoline." The ANGM
moved quickly to develop technical standards and related tariff agreements, a n d to improve operations. Within three
months, the first specifications were written for seven grades
of natural gasoline A-G, and four grades of blended natural
gasoline m o t o r fuel. The Natural Gasoline specifications
were based on density (API gravity) and percent recovered
(by evaporation). The lower gravity grades were preferred for
gasoline blending a n d c o m m a n d e d a higher price. The
blended gasoline grades were defined by a wider set of specifications, including gravity, end point, initial boiling point,
vapor tension, color, and an important new concept, percent
recovery in a standard distillation test. Boiling point criteria
and the distillation test marked significant advances in the
development of m o d e r n specifications [16]. The blended
gasoline specifications were intended to eliminate practices
such as "dumbbell" blending of kerosene with "wild" casinghead gas to give a blend with a naphtha range gravity that did
not work well in automobiles. The blended gasoline specifications were eliminated two years later, deferring to specifications developed elsewhere by the refining industry. The
natural gasoline specifications were modified several times
both for definition for the grades and for test methods as they
were developed, and are still published today by the GPA.
In 1910, a Pittsburgh motorcar owner walked into U.S. Bureau of Mines chemist Dr. Walter Snelling's office, complaining that the gallon of gasoline he had purchased was only half
a gallon by the time he got home. He thought the government
should look into why consumers were being cheated because
the gasoline was evaporating at a rapid and costly rate. Dr.
Snelling took u p the challenge and discovered that the evaporating gases were propane, butane, and other hydrocarbons.
Using coils from an old hot water heater and other miscellaneous pieces of laboratory equipment. Dr. Snelling built a
still that could separate natural gasoline into its liquid and
gaseous components [17]. This resulted in a 1913 patent for
a continuous process "to obtain the most volatile ingredient
or mixture in the form of a liquid gas under pressure" by fractional condensation of compressed heated vapors of natural
gasoline [18,19]. This virtually eliminated b o t h excessive
pressure and residue problems, and became the keystone of
the m o d e m LPG industry. The first m o d e m LP business venture, American Gasol Co., was founded by Snelling, and three
prominant "gas men" of the time, Frank Peterson and two
cousins, C. L. a n d A. N. Kerr. The products were called
"Gasol" (propane) a n d "Gasolite" (butane). The company
failed for lack of markets and the burden of cylinder and distribution costs, and was sold two years later. Snelling went
back to the U.S. Bureau of Mines explosives research, and the

CHAPTER
three "gas men" went into the casinghead gasohne business,
which was more profitable at the time.
The three "gas men" returned to the LPG business after
WWI. A. N. Kerr became president of the Casinghead Gasohne Association about 1915, one of the failed predecessors of
the ANGM (GPA). The Kerrs founded the Rockgas Products
Co. in Pittsburgh, and in 1925 the Imperial Gas Company in
Los Angeles. They tried to develop other markets for the light
ends, such as LP-gas/air town gas distribution plants and for
cutting steel. In 1932, the Kerrs authored the first chapter of
the Handbook of Butane Propane Gases on "A Chronology of
Liquid Gas Development"[20].
In 1912, F r a n k Peterson of the Bessemer Gas Engine
Company p u r c h a s e d rights to a 1909 patent to inject
naphtha gasoline into hot compressed natural gas to absorb
casinghead gasoline. He later patented a multistage compression/liquefaction process in 1912 [21]. These "hot blending" and "compression" processes were licensed to customers
using Bessemer compressors and gas engines. In 1914 he
patented "a liquefied fraction of n a t u r a l gas containing
ethane, propane and butane, substantially free of heavier hydrocarbons and from methane"[22]. He also developed one of
the first tests to estimate the "wetness" of a gas sample based
on absorbing/desorbing the sample in a mineral seal oil. Details of the test were held closely by the Bessemer Company,
which ran the test for $5 per sample. The fee was returned to
any prospective producer who purchased Bessemer equipment [23]. The close association of the liquids producers and
equipment suppliers has endured and evolved into today's
GPA and GPSA (Gas Processor Suppliers Association).
The LPG industry grew very slowly prior to 1932. In the
early years, it was inhibited by a shortage of tanks and materials due to WWI, by the wide variety of LPG mixtures and
equipment, and by competition from the casinghead and natural gasoline business. The entire infrastructure for LPG was
new, and there were many technical problems (and costs) associated with production, transportation, equipment, and
appliances. E q u i p m e n t a n d transportation costs were of
p a r a m o u n t importance, since the cost of the fuel itself was so
low. During this period there was litigation on several patents
associated with the production (and therefore the use) of
LPGs of various compositions. Most notable were the Saybolt
patent for absorbtion, held by Standard Oil, and the "stabilization" patent, held by the Carbon and Carbide Company
(now Union Carbide). Both patents were eventually held to be
invalid. In addition, the first significant regulations on tanks,
rail cars, equipment, tariffs, production limits, etc., were
p u t in place, t h r o u g h Government agencies such as the
B u r e a u of Explosives, Interstate Transport Commission,
Texas Railroad Commission, National Fire Protection
Association, and others.
Many now-familiar company and brand names appeared,
including Blaugas, Phillips (Philgas), Rockgas, Carbide (Pyrofax), Skelly (Skelgas), Shell (Shellane), and S t a n d a r d
(Flamo). Phillips and Carbide were two of the founding members of the ANGM (NGAA, GPA), and are generally credited
with developing the m o d e m LPG business. Frank Phillips,
founder of Phillips Petroleum, purchased the Snelling patent
rights, and marketed "Philgas" in the mid 1920s. Phillips
established an active research department, and did much of
the early laboratory research on liquefied gas. George G.

2: LIQUEFIED

PETROLEUM

GAS

37

Oberfell and Richard C. Alden, co-authors of the then classic


reference book "Natural Gasoline," were recruited by Phillips
to defend against the Carbide patent infringement litigation
on the pipestill "stabilization" process. The company also
benefited from the close proximity and association with the
USBM research station in Bartlesville, OK. Prior to 1920,
Oberfell had studied hydrocarbon behavior at the USBM in
Pittsburgh, and after early association with Frank Petersen,
spent five years pioneering development of low pressure absorber systems for a leading producer of natural gasoline
[24]. The Phillips research group grew to include K. H.
Hachmuth, (dryness, CoBr test), T. W. Legatski (author of the
original GPA LPG specification) and D. L. Katz (hydrocarbon
phase behavior, hydrates). The company was instrumental
in developing acceptable rail cars, freight rates equivalent
to gasoline, a n d large consolidated facilities that made
production more cost efficient.
The NGAA (GPA) developed additional specifications for
commercial propane and butane after the expiration and/or
settlement of the composition and processing patents. These
were first reported in the Proceedings of the 11th annual
Convention 1932 [25], and later published as the forerunner
of GPA 2140-Liquefied Petroleum Gas Specifications. However, there were no test methods attached to the first specifications. These were added over the years as the technology
was developed.
At the same time, the California producers and marketers
were active in related technical Eireas. The California Natural
Gasoline Association formed in 1925 as a technical society of
individuals, rather than a trade association of corporate members [26], and provided high caliber technical leadership to
the emerging industry. Western Gas published many technical articles in Butane-Propane News [27], Eind the first edition
of the "Handbook Butane-Propane Gases" in 1932. While not
a standard or specification, the handbook contained a large
amount of technical information on LPG production, distribution and use. It was an important reference book for the entire industry, including the "downstream" distribution and
marketing segments not covered by the GPA. These handbooks were maintained into the 1980s. They are no longer in
print, but are still widely available in technical libraries. Additioneil information may be available from other gas industry associations that have been active over the years, such as
the National Bottled Gas Association (now NPGA [28]), Compressed Gas Association (CGA [29]), or other regional gas
marketing associations such as the Pacific Gas Marketers Associations, Pacific Gas Association, and others. These were involved in development of related areas, such as equipment,
pressure vessel, appliance, installation and transportation
codes, standards and regulations. However, they do not appear to have been active in development of either product
standards or test methods for consumer LPG products that today is under the jurisdiction of ASTM.

HistoryLPG Properties a n d Thermodynamics


Many people consider the work conducted in this area during
the 1920s and 30s to be synonymous with the development of
Chemical Engineering as a separate discipline.
High pressure crude, condensates, and LP gases have physical properties and a commercial importance that made them

38 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

the principle target of early research in thermodynamics and


chemical processing. LPG and NGL were probably the first
commercially important, large volume materials that were
handled and processed near or above the critical temperature
of components or mixtures.
Critical phenomena had been observed in single components as early as 1823. In 1861, Thomas Andrews observed
the similar phenomena when he found that carbon dioxide
could not be liquefied at any pressure at temperatures higher
than 31C. He hypothesized that such a state existed for all
fluids and called it the "critical point" [30]. Andrews's
experiments were first made public in the 1863 edition of W.
A. Miller's textbook entitled "Elements of Chemistry" [31].
The phenomena of isothermally condensing a gas mixture to
form liquid by reducing pressure and isobarically heating a
gas-liquid mixture to form a single-phase liquid were first observed by J. D. Kuenen in 1892 when he was studying the
phase behavior of the binary system (carbon dioxide +
chloromethane). He called these phenomena "retrograde
condensation" of the first kind and the second kind,
respectively [32].
In the mid 1920s Dr. Walter Podbielniak developed the
first practical low temperature fractional distillation test
that allowed the composition of NGL mixtures to be accurately determined [33]. The "Pod" column was quickly
adopted by the industry and improved over the years both
in accuracy and automated operation. It was the industry
standard until it was eventually replaced by gas chromatographic analysis in the mid 1950s. "Downhole" samples
from high pressure formations taken at underground temperature and pressure were found to contain substantial
amounts of dissolved "liquid" methane. This violated the
then accepted principle within the industry that no material
could be a liquid above its critical temperature. The theories
on retrograde condensation in gas processing by Dr. Lacy
in a 1932 API paper were greeted with a great deal of
skepticism by the gas processing industry [34], but it certainly put technology development into high gear. This
caused quite a stir at the time, as retrograde condensation
was, as the name implies, the exact opposite of what was expected. This created a great need to understand the phase
behavior of high-pressure and supercritical mixtures, both
for crude oil reservoir pressure management and for production of high-pressure condensate. Within a decade of intensive research and development, cycling plants for
methane re-injection, liquefaction (refrigerated liquid natural gas), LPG dehydration, and sweetening processes were
all commercialized.
A large amount of technical data generated in this era is
still used today. For example, the tables and graphs in the last
published edition of the "Handbook Butane-Propane Gases"
were essentially unchanged from the first edition, published
in 1932. Similarly, the GPSA Engineering Data Book has
been in continuous publication, and the 11th edition is now
available in U.S. engineering or metric versions, and on CDROM. Tables of information for installers that are derived
from this data is still in use today in publications such as
NFPA 58 and CAN/CSA-B 149.2 (the respective United States
and CDN "propane installation codes"). There is a large
amount of related work on other vapor-liquid equilibria for
the LPG gases, their mixtures, and other materials that are

commercially important for manufacture and use of LPG.


This includes water [35], H2S, C02, COS, N2, mercaptan,
and others [36].
Development of Thermodynamic Equation of State (EOS)
methods now allows calculation of most properties of even
complex mixtures directly from composition [37]. In most
cases, properties such as vapor pressures, enthalpies, bubble
points, dew points, adiabatic flash compositions and the like,
can be calculated about as accurately as they can be measured
directly. This includes LPG mixtures around their critical
points, and "retrograde" condensation, and more recently
temiaiy solid/liquid/vapor and hydrate systems [38].

LPG S P E C I F I C A T I O N S
History of ASTM LPG Standards
Virtually all of the technical developments relating to ASTM
standards were done through GPA/GPSA member companies, and Government/Industry sponsored Research at organizations such as the USBM, Institute of Gas Technology
(IGT) and Gas Research Institute (GRI). The GPA research
reports and standards and the GPSA Engineering Data Book
have been a primeiry source of technical information for the
industry. These are available on a commercial basis, both to
GPA members and non-members [39].
The GPA maintained the LPG and NGL standards from
first publications in 1921-32 until 1960. By this time, LPG
had become an important consumer fuel, widely available
and with an ever increasing diversity of applications. National Standards were needed to ensure universal acceptance
throughout the downstream industry, and to address
potential regulatory and liability issues inherent to producer
only-specifications. In 1961, ASTM published D1835 specifications for commercial propane and butane that were technically identical to the GPA specifications, including GPA test
methods. In 1964, ASTM published D2154 Special Duty
Propane, which was similar to GPA HD-5, but later incorporated this grade into D1835 in 1975, adding butane-propane
mixtures. The GPA 2140 specifications are still maintained
by the GPA, and remain technically equivalent to ASTM
D1835. ASTM test methods adapted from the original GPA
methods are now used in both standards.
Specifications and many test methods for LPG/NGL products not covered in D1835 are still maintained by the GPA.
This includes GPA 3132, which is the current version of the
original 1932 Natural Gasoline specification, and a variety of
other NGL products, chemical feedstocks, sampling methods, and test methods. The GPA 2140 LPG specification is
widely used for contractual purposes within the upstream
gas and fractionation segments of the industry. The products
covered under ASTM D1835 and GPA 2140 specifications are
often referred to as "spec" products. All of the others tend to
be called NGL's, such as C2+ ("see-two plus," meaning
ethane and heavier), fC4 (field butane), etc. For example,
"spec butane" means that it conforms to one of the consumer
products in D1835 or GPA 2140, or another industry specification or purchase/sale contract. The composition of "NGL
Mix," or "C2-I-" or "condensate "can vary over wide ranges,
and are not manufactured to strict composition limits.

CHAPTER 2: LIQUEFIED PETROLEUM GAS


NGL mixes and other "non-spec" products are not sold to
the pubUc. They are intermediate products, suitable for
transport and storage, but intended for further processing.
They are manufactured and sold between companies with the
technical resources to define and control the quality within
the available processing capabilities at the time. They usually
have additional test methods and limits for both purity and
trace components that may be deleterious in downstream
processing [40]. This can vary over wide limits under
contract terms.
The sampling and test methods are still important for
"non-spec" products, but not for the same reasons as for the
"spec" products in D1835. For example, the market value of
an NGL mixture is determined by the composition, since
once fractionated, the ethane, propane, iso-butane, butane
and C5-I- condensate fractions each have their own market
value. The market value of an NGL mix is therefore dependent on the accuracy of the analysis, but the composition
may vary over wide limits as agreed to by the purchaser and
seller. As a result, no ASTM product specifications are necessary for these materials, but many ASTM/GPA sampling and
test methods are used. The accuracy and precision of these
methods are still very important to the industry.
ASTM D1835 specifications for "commercial propane" and
"butane-propane mix" do allow the purchaser and seller to
agree on composition limits for propane/propylene and
butane/propane. These grades could be used as specialty consumer fuels, such as brazing gas (or higher BTU heating fuels, or aerosol propellants), and are therefore included in the
ASTM standard. The ASTM standards are rarely used for
commercial contracts such petrochemical feedstocks and the
like, as even nominally similar processing units can have
different feedstock requirements. Processing contractual
agreements tend to be less restrictive on composition, and
more restrictive on trace contaminants, depending upon the
capability and tolerance of the intended processing unit.
In North America, propane is the only widely available LPG
fuel for consumer use. Ethane and butane are used in other
fuels and chemicals applications. Ethane is converted to ethylene and used predominately in the manufacture of plastics
and chemicals. Butane is used predominately as a blending
component in winter gasoline, an alkylation feedstock to
make high octane unleaded gasoline, gas cracker feedstock
for chemicals production, or as a refinery fuel gas when the
price for butane drops below the industrial price of natural
gas. Propane is sometimes referred to as "butane" in the North
American retail market, and several companies still use "butane" in their corporate name. The reason has its roots in history [41 ], as butane was more prevalent in the early years, but
has since been replaced by propane. Similarly, "HD5"
propane is inherently a reference to GPA 2140 grade HD5
(Heavy Duty, 5% max propylene). HD5 grade was developed
to limit minimum octane number for engine applications, and
similar grades are found in all international specifications
(See AutoPropane). The ASTM D 1835 "special duty" propane,
and CGSB 3.14 "Type 1" propane are generally taken to be
functionally equivalent to GPA 2140 "HD5" propane, differing
only in some sampling and test method options. Even when
contracts are written around specifications that make no reference to "HD5," the designation "HD5" tends to be used in
conversation, because it is more recognized.

39

The ASTM and GPA LPG specifications have withstood the


test of time remarkably well. They have undergone numerous
revisions in response to improved technology and/or industry
needs [42]. The vast majority of these have been associated
with sampling procedures and test methods, and only occasionally with minor changes to the limiting values [43]. The
actual composition and properties of LPG produced in 1932
is essentially unchanged from LPG produced today.
The ASTM D 1835 standard has formed the basis for many
international standards, including ISO 9162, and at this time
is the framework for virtually all the world-wide commerce in
LPG [44].
Sampling
There are three sampling methods commonly referenced in
North America: ASTM D 3700 (floating piston cyhnder), D
1265 (80% fill "open" cyhnder), and GPA 2174 (floating
piston cylinder and on-line composite sampler).
None of the sampling procedures are guaranteed to obtain a representative sample for all specifications or test
methods, under all conditions. For example, a floating piston cylinder is capable of taking a liquid sample with no
vapor generation that can deplete light ends and dissolved
gases. However, machined interior metal surfaces can make
this unreliable for trace levels of corrosive materials that
can react with the interior surfaces, especially for longer
term storage or transport. An 80% fill cylinder can have an
interior coating to make it less prone to loss of trace corrosive molecules. However, the composition is slightly
changed by venting liquid to establish the 20% vapor space
that is necessary to protect against over pressure from thermal expansion of the liquid.
ASTM and CGSB are addressing this by allowing the use of
coated D 1265 cylinders for routine use for "specification"
products, where the small but predictable loss of light ends is
not significant. Laboratory measurements and Equation of
State calculations confirm that the vapor pressure reduction
between using D 3700 and D 1265 is less than 1.6 psi at the
208 psig specification limit. This is not significant with respect to the reproducibility of the vapor pressure test
method, and would only be of concern at or near the
specification limit, at high (7-8%) ethane contents [45,46].
The D 2163 hydrocarbon composition by gas chromatograph (GC) method is being revised to allow D 1265 "for composition," with a recommendation that D 3700 floating piston
cylinder method be used for highly accurate results or when
trace gas analysis is required. ASTM D 3700 is currently
being revised to limit the scope to ASTM D 1835 "spec" products. This avoids the complications from sampling high pressure NGL's that may contain separated phases, inert gases,
and corrosive materials (for example, from production prior
to processing). A new appendix documents the various problems that must be addressed for sampling "non-spec" products. GPA 2174 (Obtaining liquid hydrocarbon samples for
GC) will be recommended for sampling "non-spec" NGLs and
related materials. This also facilitates revision of D 2163
(composition by GC) to include options for using Flame Ionization Detectors (FID) for specification products. FIDs are
very linear detectors for hydrocarbons, but do not detect "inerts" (N2, Ar, CO2, etc.) that do not combust in a hydrogen

40

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

flame. These are not normally present in "spec" products, except at very low p p m levels t h a t are not significant for
intended use (see Composition below).

Composition and Calculated Properties (Octane,


Density, Vapor Pressure)
D 1835 products composition limits are set at levels that are
stringent enough to satisfy the vapor pressure, octane
(olefin), a n d volatility/residue r e q u i r e m e n t s of the vast
majority of existing applications and equipment. Small composition differences within the bounds of the specification
are generally not significant, a n d do not affect either the
value or the end use. For example, propane containing 1-2
ethane has the same value and uses as propane with 5-6%
ethane. Similarly, propane containing 1% propylene has the
same commercial value a n d uses as 5% propylene. As a
result, "Specification" products in D 1835 are relatively noncritical for hydrocarbon composition.
The D 1835 products are relatively simple mixtures of a
small n u m b e r of components. This makes it feasible to estimate several properties that tend to blend linearly by simple
linear sum calculations. Calculation based on weighted linear s u m of component values per D 2598 can be used as an
alternate to D 1267 Reid vapor pressure, density and octane.
Similarly linear sum of C4+ (butane and heavier) can be used
as an alternate to D 1837 volatile residue.
C o m p o s i t i o n b y GC
Very little history was found on ASTM D 2163, Method for
Analysis of Liquefied Petroleum (LP) Gases a n d Propane
Concentrates by Gas Chromatography
The D 2163 GC method was originally based on u p to four
different packed columns and thermal conductivity detectors
using calibrant gas calibration procedures. Two of the colu m n packings were discontinued due to toxicity. The method
was expanded to allow other capilliary/PLOT^ columns and
alternate detectors, but retained the original calibration
procedures and precision statement. The method is currently
being u p d a t e d to allow columns based on resolution
performance, as well as FID detectors using response factors
referenced to methane, or other detectors of equivalent performance using calibrant gas procedures. D 3700 will be the
recommended sampling procedure, but D 1265 will be allowed for routine use, except where highly accurate results
are required for trace gases (see sampling above).
Octane

Propylene has a low pure component octane value, and requires individual control (5% max) because it can be varied
widely in commercial grade. Traces of the other olefins are
effectively controlled by the m a x i m u m vapor pressure
(ethylene) a n d m a x i m u m C4-t- content (butanes, butylenes
and heavier).
The defining specification for ASTM D1835 "Special Duty"
propane (GPA 2140 HD5) is the m a x i m u m 5 vol% propylene
content, intended to control the m i n i m u m octane n u m b e r for
severe service engine applications (HD5 is "Heavy Duty, 5%
maximum propylene"). Propane meeting the special grade
(HD5) specification would have a n octane rating of 95 or
greater by the D 2623 LP-method (if it were run). Commercial
grade with higher propylene content can still be used for
lower severity engine applications. The true HD5 (propane
optimized engines) market has yet to materialize.
This has resulted in decades of debate for the need for actual octane n u m b e r determination versus a linear sum calculation. Gasoline and LPG blending is known to be non-linear,
but the LPG calculation method has prevailed This is probably more because the composition limits of "HD5" propane
are restrictive enough that non-linear blending effects are too
small to be significant. The same cannot be expected for
blends of significantly broader composition [47], or for optimized engine applications that are more optimized for the
fuel. In addition, there are some discrepancies in the pure
component octane values used in ASTM D 2598, EN 589 and
the original ASTM Motor LP Knock Test Method Development as documented in SAE 670055. These differences are
relatively small, generally within 1 octane number. However,
it may be necessary in the future to optimize either the calculation or the engine determined octane number, or as more
recently suggested, by methane number.
The methane n u m b e r of a gaseous fuel is a knock engine test
using conditions similar to D2699 MON, but using methane
and hydrogen as the primary reference fuels. The method has
not been standardized to date. The advantage of the methane
n u m b e r is that the test can be extended to include all gaseous
fuels, including hydrogen, natural gas, LPGs cuid their mixtures, inert diluent gases such as N2 and CO2, and potentially
other combustible gases such as CO and HH3. In principle, it
is possible to relate methane n u m b e r to octane number, but
there are several difficulties in practice. The octane scale, with
iso-octane having a value of 100, is extended to 120 with the
addition of about 6 mL/usg tetraethyl lead. This tends to make
the test increasingly insensitive to non-linear fuel effects in
the high range, and the use of TEL even in the lab is problematic. Similarly, the methane n u m b e r does not respond well to
fuel effects at the low end of its range. Even so, a reasonably
good correlation has been found to exist [48,49].

ASTM D 2623, Test Method for Knock Characteristics of Liquefied Petroleum (LP) Gases by the Motor (LP) Method was
originally used to rate octane n u m b e r of LPG mixtures. This
used a standard CRC knock engine fitted with an LP-gas carburetor. It was withdrawn because the octane n u m b e r of
these simple mixtures could be accurately estimated by linear
blending of component octanes based o n GC analysis per D
2598.

Methane n u m b e r also appears to lend itself reasonably well


to calculation based on composition. If so, then the calculation method would be preferred for routine operations,
similar to D 2598 for LPG today.
This is a potential area of future research and standardization.

^ PLOT: Porous Layer Open Tubular (usually KCl deactivated


alumina for LPG analysis).

Some recent publications indicate that the olefin content of


propane relate to cleanliness, stability or tailpipe emissions

Olefins

CHAPTER
in a similzir m a n n e r to gasoline [50,51]. However, there are
some significant differences, and there is no consensus at this
time. Propane tanks are not atmospherically vented, so there
is no oxidative stability concerns for propane, as there is for
gasoline and other fuels. LPG carburetor vaporizer deposits
are associated with non-volatile residues, and not oxidative
gums from fuel olefins, thiophenes and other trace reactive
c o m p o n e n t s of gasoline. However, developers of m o d e r n
LPG electronic fuel injection (EFI) systems have experienced
significant difficulties with both inorganic and organic deposits that interfere with the proper operation of injectors.
Propane derived from crude oil and natural gas contains essentially n o olefins. Propane from refinery cracking processes
contain olefins, which may can either processed further (alkylation, polygas), separated for propylene sales, or blended into
propane u p to specification or contractual limits. Refinery
propane usucJly requires removal of propylene to meet the
ASTM "Special Duty" or GPA HD5 specification.
A recent study and review sponsored by the California Air
Resources Board (CARB) r e c o m m e n d e d relaxation of the
propylene a n d volatile residue specifications for a u t o
propane, citing that a 10% propylene/5% butane fuel gave the
best equivalent emissions performance [52]. The Board also
recommended a new limit of 0.5% m a x i m u m butenes, pentanes, and heavier. These changes were proposed to preserve
and enhance the current supply of auto propane fuel in California, while maintaining adequate emissions performance.
About half the propane produced in California is a byproduct
of refining processes [53].
This is a possible area of future research and standardization
Vapor Pressure
Historically, vapor pressure was the most critical LPG specification, being responsible for most of the serious problems
in the early days of the industry (see History of LPG). Vapor
pressure is invEiriably tied to pressure vessel and safety valve
certification and transportation regulations, so it is generally
viewed to be critical for regulatory compliance. However,
m o d e m pressure vessel standards as well as LPG production
e q u i p m e n t a n d analyzers have all b u t eliminated vapor
pressure as a significant operational problem.
Certification standards vary by jurisdiction, but typically, a
large safety margin is built into the system. For example, a
typical consumer cylinder pressure rated for 250 psig "working pressure" would be pressure tested after manufacture to
twice this (500 psig) and equipped with a "pressure relief
valve" (pressure safety valve or vent) 250-500 psig, 50-100%
of the test pressure. Propane, at the maximum specification
pressure, would have to be heated to over 140F to even reach
the opening ("cracking") pressure of the safety relief valve. In
addition, the actual burst pressure is controlled to typically at
least three times the working pressure (manufacturers are required to pressure test 1 cylinder out of each lot to destruction as a quality control procedure for the quality of steel and
welds). It is common practice for the manufacturer to "overbuild" cylinders to eliminate any uncertainty in the costly
certification process. For example, sample cylinders rated for
1800 psig working pressure are often tested at about 5000
psig, a n d have burst pressures far in excess of m i n i m u m

2: LIQUEFIED

PETROLEUM

GAS

41

three times the working pressure, often in the 12-15 000 psig
range. Finally, all consumer cylinders, storage vessels, trucks,
and rail cars require periodic inspection and recertification.
These considerations have essentially eliminated LPG vapor
pressure (VP), per se, as a significant problem.
The LPG VP specifications indirectly control the maximum
concentration of light ends, principally ethane in propane
and propane in butane. The manual "Reid" VP test method
was developed in a competition in the 1920s to improve upon
the original U.S. Bureau of Mines "vapor tension" method
(essentially a pressure gage on a length of 2 in. pipe). The
competition was won by Dr. Reid (D323 Reid method), and
an adaptation of this is used in D 1267 for higher VP (>26
psi) LPGs. The test has changed little over the years. Many
laboratories are no longer equipped to r u n the LPG Reid
Method. It is now much more common to calculate VP from
composition by D 2163 using calculations in D 2598 than it is
to run a manned D 1267 Reid VP. However, D 2598 method
has no component VP data for m e t h a n e (if it is present),
which may force the use of the manual method in some circumstances. In addition, D 2598 VP calculation is known to
be biased high (e.g., conservative) at high ethane contents,
due to use of a component VP extrapolated from above the
critical point of ethane.
By historical convention, the VP of LPG is reported in
"gage" or "gauge" pressure in pounds per square inch relative
to atmospheric pressure (psig). The pressure gauge used in
the D 1267 LPG Reid method reads zero at the start of the
test, but unlike D 323 or D 4953 the apparatus starts out liquid filled, and no air is introduced into the test apparatus
during the test. The test result is essentially the partial pressure of the LPG relative to atmosphere, a n d the absolute
pressure is higher by the barometric pressure at the time of
the test. This has caused significant confusion over the years
when using pressure transducers calibrated in psia units, or
when reporting in metric units (kPa), which by definition
would be interpreted as being an absolute pressure. As a result, the specifications require reporting in kPa (gage), which
is not a true SI unit. Also, this difference is sometimes confused with the high bias at high ethane contents when using
D 2598 calculation.
ASTM is currently developing a s t a n d a r d test m e t h o d
based on newer instrumentation similar to D 5191 and D
6378 for gasoline. This method uses an absolute pressure
transducer, so this requires that atmospheric pressure be
subtracted from the result to report a VP (gage) final result.
There is no universally accepted criteria for setting the maximum VP specification for propane, and this is an area for future research and international standardization. The first
GPA VP specification was 225 psig at 105F set to meet the insulated rail tank car requirements of Interstate Commerce
Commission (ICC). In 1955, the specification was revised to
215 psig at 100F, mainly to use a single water bath for both
natural gasoline and propane. Still later in 1955, the VP was
lowered to 210 psig at 100F to meet United States DOT safety
standards for rail tank cars [54]. A variety of other regulatory
limits also exist. This includes DOT 173.301 (f) (2), which limits VP in cyhnders to 300 psig at 1 SOT, Section 170.314 (c) 225
psig at 105F, and Section 173.315 (c) (1) cargo and portable
tanks at 250 psig at 115F [55]. Other regulatory requirements
would be expected in different jurisdictions. The origined HD5

42

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

VP specification was 200 psig to promote heavy-duty engine


applications, but was reset to the current 208 psig limit when
this market failed to develop as expected.
Higher vapor pressure specifications allow slightly more
ethane to be included in the blend, which increases supply
slightly, and is potentially beneficial for very low (<-35C)
temperature operations. However, higher ethane content in
the gas phase can cause overly lean air/mixtures for some appliance applications with first vapor withdrawal from a full
tank, and rich operation from essentially pure propane when
the tank is near empty. This wide swing in air/fuel ratio and
the attendant problems of calibrating the air/fuel ratio in
vapor withdrawal service also prompted the industry to
reduce the VP from 215 to 210 psig in 1955.
Current ISO 9162 specifications have a maximum VP of
1550 kPa at 40C, compared to 208 psig (1435 kPa) at 100F
for ASTM, GPA, and CGSB. This difference is larger than the
difference in VP due to the small difference in test temperature. Equation of state calculations indicate that the ISO
standard would correspond to about 213 psig at 100F, making the ASTM standard more conservative by about 5 psig.
This difference is generally not significant in day-to-day
operations
The practical maximum for a universal multi-use fuel
probably lies somewhere between the current ASTM limits of
208 and the estimated ISO hmit of 213 psig at 100F.
This is a possible area of future research and standardization
Volatility Residue ("Weathering")
Most consumer propane applications withdraw vapor from
the storage tank (vapor withdrawal) utilizing ambient air
temperature to provide the latent heat of vaporization. This
works well down to about 35C or lower, until the VP with
auto-refrigeration of propane is not sufficient to satisfy appliance demand. Even thermal radiation to a black night sky
can take away several degrees of operating temperature,
which can be important when arctic nights can be up to six
months long.
The Volatility of Liquefied Petroleum (LP) Gas test (ASTM
D 1837) is an indicator of the nonvolatile materials present in
LP gas [56], and is intended to ensure that most of the LPG is
available for use, and that low volatility components do not
accumulate with repetitive tank fills. The tank will lose all
pressure and "suck a vacuum" below the normal boiling
point of the remaining components, requiring supplemental
heating, pumps and/or external vaporizers. If, for example,
excessive butane were collected in a tank after repetitive fills,
the user could experience low pressure when the level indicator showed plenty of "propane" (actually butane) still left in
the tank. This is aggravated by the strong temperature dependence of the "k" factor, or enrichment of the propane in
the vapor relative to butane. The selective vaporization of the
lighter components and retention of heavier components becomes more efficient as the temperature decreases, making
this an increasing concern in colder climates.
The original weathering test was called the Mercury Freeze
Test, but was commonly called the weathering test, or the
"tinkle and thud" test. The mercury was used as a temperature indicator, since no thermometers were then available for

-40C. One hundred milliliters of pre-cooled liquid propane


was allowed to boil off ("weather") in a glass tube with a large
drop of liquid mercury. Initially, the liquid propane temperature would be at or below the normal boiling point of
propane (42C), and the mercury would be a solid (melting
point = 39C), and then maJce a "tinkle" sound in the glass
when shaken. The temperature of the remaining liquid would
increase as the lighter components boiled off. If a sufficient
quantity of butane or heavier components were present, the
mercury would melt as the temperature of the remaining liquid rose above -39C, and "go thud" (a colloquialism for
"failure" in some circles). The pass/fail criterion was that no
more than 2 ml of liquid (mainly butane and heavier)
remained when the mercury melted.
One artifact of the test was that propane near the specification limit could pass at high altitude (low barometric
pressure), but could fail at low altitude (higher barometric
pressure). The boiling point of the mixture changed with
pressure, but the melting point of mercury did not. The test
was modified when suitable low temperature alcohol thermometers became available. The 1960 version of the method
reported the temperature when 5 ml of liquid remained, corrected for barometric pressure. The original pass/fail limit of
+ 36F was retained for butane and b-p mixtures, and a new
limit of -37F (-38.3C) was set for propane. The advent and
wide use of the chromatograph permitted addition of a quantitative limit of 2.5 vol% C4+ in propane and 2.0 vol% C5-Ifor butanes, based on GPA tests showing equivalence with
the weathering test. The weathering test was at one time going to be withdrawn, but it is still widely used as a field check,
and it was retained.
These limits are known to be conservative, even for cold
weather operations, confirmed by GPA tests at the University
of North Dakota in the winter of 1977-78 using 5-15 vol% butane. However, there has never been any compelling technical or economic justification to change this specification
[57], and the current limits are essentially unchanged from
the original intent in 1932.
Dryness of Propane
Consumers need reliable operations when it is cold, but this
is when icing is most prone to occur. As a result, "dryness" of
propane is probably the most critical of all specification for
downstream marketers and users. However, "dryness" is a
difficult property to quantify in the LPG world.
The "dryness" of propane is determined by specification
performance tests that indicate the suitability of use of the
LPG, but do not quantitatively measure water content. The
dryness criteria are so stringent that "on-spec" propane generally avoids the free water, ice, and hydrate formation regions under the conditions of most end use applications.
However, some applications, such as an inadequately heated
liquid vaporizer, may require even lower water contents,
and/or use of cryostatic de-icers such as methanol to avoid icing with propane that meets the specification "dryness"
criteria.
Propane and propane-butane mixtures are the only consumer fuels with a "dryness" specification that requires the
water content to be well below the equilibrium saturation
level. It is not adequate to use visual rating criteria, such as D

CHAPTER

2: LIQUEFIED

PETROLEUM

GAS

43

4176 "Clear and Bright," or "visually free of undissolved water" that is used for butane (and other fuels). It takes about
20-40 p p m of free water in a fuel to visually detect a haze
with the unaided eye. In essence, visual ratings only require
t h a t the fuel does not contain a n excessive a m o u n t of
undissolved ("free") water.
The butane test relies on visual detection of water collected
in the bottom of the sample cylinder, and not a haze rating.
The less stringent criteria is because auto-refrigeration of butane does not cause temperatures low enough to cause ice/hyd r a t e formation. As a result the same criteria applies to
b u t a n e as for other fuels.
Simple tank draining, which leaves the remaining propane
saturated with water, is not nearly enough to meet the LPG
"dryness" criteria. The presence of free water at any time in a
propane system is sufficient to put the product severely off
spec and unusable without dehydration or the addition of
methanol (see cautions below). This is critical for proper operation of LPG handling equipment and appliances. Ice accumulation can block vapor or liquid fuel lines, Eind disrupt
proper operation of mechanical equipment, such as pumps,
meters, filters, VEJVCS (fuel lock-offs), and especially regulators (vaporizor/regulators). Icing can occur very quickly, and
can be difficult to diagnose.
"Wet" propane is anything that does not pass the "dryness"
criteria, including the approximately 30-100% saturation
range, even when there is no free water. For example, a storage tank of LPG that is deemed to be "wet" may or may not
have any free water at the bottom of the tank. Water saturated LPG (but n o free water) fails all of the dryness criteria
by a wide margin. The presence of any free water amounts to
"gross" contamination.
"Wet" propane that does not contain free water responds
extremely well to low levels of methanol. Unlike ethanol, IPA,
and higher moleculetr weight alcohols, methanol does not increase the solubility of water in propane (or any other fuel).
It is a popular misconception that methanol is an effective
de-icer because it increases the solubility of water in the fuel.
Methanol decreases the solubility of water in fuels, and causes
phase separation when it is injected into water-saturated fuel.
The phase-separated liquid is non-freezing, so it will not cause
ice/hydrate blockage. When the LPG is sub-saturated with
water, the methanol remains dissolved in the propane along
with the soluble water. It phase separates along with the water whenever the temperature gets cold enough, and prevents
the separated water/methanol mixture from freezing. If the
m e t h a n o l concentration is high enough in the separated
phase, it wiU not freeze at temperatures down to the normal
boiling point of propane of 43C (i.e., nominal 50/50 vol%
methanol/water mixtures Eire commonly used as windshield
de-icing fluid good down to 40C).

in LPG service, mostly because they lack the volatility to


provide icing protection in the vapor space.
The meaningfulness of the valve freeze test becomes questionable when the LPG contains anti-icing agents. The ASTM
D 2713 method is stated to be "non-applicable" when antiicing agents are present. The current ISO and ASTM wording
of the "not applicable" footnotes are currently different, and
subject to interpretation. This is Ein area of never ending controversy, a n d is probably the highest priority area for
research and standardization.
None of the current LPG dryness methods (valve freeze,
CoBr, Dew Point) have valid precision statements. The
pass/fail criteria Eire set at levels that historically have been
shown and are known to be suitable for most end uses. The
most c o m m o n test for LPG dryness (D2713) is based on a
"valve freeze" criteria, where flow is restricted by ice/hydrate
formation in a restrictive orifice in a standard valve. The
pass/fail criterion is intended as an indicator, to prevent a
broader range of problems, and not just freezing of a small
orifice valve flashing liquid p r o p a n e at 42C. The other
common test methods are based on the color of the hydrate
of Cobalt Bromide exposed to equilibrium vapor, and the water dew p o i n t of the equilibrium vapor. Similarly, the
pass/fail criteria are set at a stringent enough level to avoid a
broad range of problems based on field experience.

Methanol is very effective in LPG systems at preventing


freezing of separated phases, but if mis-handled can aggravate the a m o u n t of separated phase that can accumulate at
tank b o t t o m s , and can propagate phase separated phases
through the distribution system.
Other alcohols or glycols form "glass" phases with water,
becoming increasingly viscous on t e m p e r a t u r e drop, b u t
without freezing in the traditional sense. They are often described as forming "slushy ice" that is very resistant to accumulation or blockage. However, these are reirely if ever used

It is initially counter-intuitive that the concentration of water


in equilibrium propane vapor, withdrawn from the vapor
space of a storage tank, increases as the t e m p e r a t u r e decreases. This is the key point of understanding water phase
behavior in propane, and the related problems of dryness of
propane.
Water has a low solubility in LPG, similar to other "pure"
parafins such as pentane, isomerate or alkylate. Since so little water is present, it is often confusing why dr3rness is so important for propane, much more so than for other fuels that

It is relatively easy to meet the dryness criteria for propane


with m o d e m production processes. However, the occasional
process failure of individual producers can affect m a n y
others in pipeline gathering systems. Seasonal brine cavern
storage, field dehydration facilities, steam/air cleaning of
storage tanks, hydrostatic testing, a n d use of c o m m o n
marine, pipeline, rail and truck facilities at EJI stages of distribution provide many opportunities for sporadic water contamination.
In the occurrence of an off-spec dryness event, the technical difficulties of sampling and analysis can be enormous, and
never certain. It is easy to show that propane is "on-spec," because the requirement is so stringent. However, when you are
trying to figure out why the fuel is "off-spec," the "dryness" of
propane quickly becomes the most exasperating specification, even if it is not the most critical [58].
There is a general correlation between water content and
the "drjmess" criteria, but even this is not certain due to nonlinearity of water solubility in propane with temperature,
relative linearity of the K ratio with temperature, and the possible presence of alcohol (especiEilly methanol), ice, and hydrates. There are additional factors that mEike the dryness of
LPG nvuch m o r e complicated t h a n simple solubility and
freezing for the other fuels. These are discussed below.
Phase Behavior

of Dissolved

Water in

Propane

44

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

contain more water. This section assumes no hydrate formation, similar to other fuels. Hydrates will be considered
immediately following.
The formation of "free" or undissolved water from a drop
in temperature is similar to other fuels, except that it occurs
at a lower concentration level due to lower solubility. The solubility of water in fuels increases with the temperature and
aromatics content of the fuel, ranging from about 100 p p m w
in low aromatics parafinic fuels to over 500 weight p p m in
high aromatics content gasoline or diesel fuels at 70F [59], A
drop in temperature of water-saturated fuel causes the phase
separation of a bulk (undissolved or "free") water phase to
form as a "haze" of small water droplets. These tend to coalesce into larger droplets and gravity settles them to the bottom of the storage tank. Pure water ice (not hydrate) will only
freeze if the temperature is below freezing. Since the solubility of water in propane is already low, there is m u c h less
water available to phase separate with a drop in temperature.
As a result, classical "fuel line freezing" is not very prevalent
in liquid propane systems, and most problems are associated
with smaller, m o r e easily plugged orifices in valves a n d
regulators than in m u c h larger diameter fuel lines.
If free w a t e r is present (e.g., grossly c o n t a m i n a t e d
propane), dispersed droplets can "super-cool" below freezing
in cold gases or liquids, including propane. This can result in
rapid ice accumulation that tends to be most severe in the - 4
to 10C range, very similar to automotive carburetor icing
and aircraft wing or propeller icing ("rime" icing). As each super-cooled droplet impinges on a surface, a portion of the water spontaneously freezes, adding to the surface ice deposit at
the impingement point. The remaining liquid water droplet is
heated to 0C by the heat of fusion, but is rapidly cooled again
by the surrounding cold fuel. This causes the remaining water to either freeze, or to form another smaller super-cooled
liquid droplet, which can repeat the process to extinction.
Flow patterns can create a small impingement point, and filter/screen surface area that is already plugged diverts flow to
unobstructed areas. This can result in a very fast and efficient
plugging mechanism. Ice accumulation in pipe elbows, meters, filters and screens is often associated with "snap" cooling to just below freezing, a condition that favors formation
of super-cooled water hazes and "rime icing." Ice accumulated under these conditions often looks like a translucent
"milky white" thick coating t h a t appears to have been
"painted" on. These conditions are more commonly found in
production facilities, prior to final drying, but can occur during downstream distribution if water has gotten into the system. Methanol is very effective at eliminating rime icing,
since only a very small concentration of methanol in the separated phase is required to reduce the freezing point to less
than about -10C.
Propane fuel systems are sealed under pressure, and not
vented to the atmosphere. Tanks in the distribution system
are never allowed to be totally liquid filled for safety reasons.
An equilibrium vapor phase is therefore always present in
downstream distribution (but not necessarily in production
facilities). Most end use applications draw equilibrium vapor
from the top of the tank, and large tanks always have a Pressure Relief Valve (Pressure Safety Valve or vent in other jurisdictions). These are safety devices that vent vapor in the
event of an overpressure situation. As a result, the water con-

tent a n d freezing behavior of the vapor phase is just as


important as the liquid phase.
A c o m m o n phrase in the literature is that propane vapor
has a much higher capacity for water than propane liquid.
This is true, but doesn't provide much clarity. Water, with a
molecular weight of 18, would have physical properties
closer to niethane (mw 16) and Neon (mw 20) if it were not
for hydrogen bonding. Hydrogen bonding results in a very
dense, high boiling liquid water phase instead of a light low
molecular weight gas. However, when water is dissolved in
propane at low p p m levels, there is little hydrogen bonding
between the water molecules, a n d it behaves like a low
molecular weight dissolved gas. Dissolved water in propane
is much more volatile t h a n propane, and becomes enriched in
the vapor phase.
The "K" ratio, or ratio of water concentration in the equilibrium propane vapor vs. the water concentration in the
liquid propane decreases with increase in temperature, ranging from over 20 (mole/mole) at low temperatures down to
about 5 at high ambient temperatures. Essentially the VP of
propane increases faster with increasing temperature than
water, in essence "diluting" the water vapor at higher temperatures. Unfortunately, this makes the propane vapor in
the tank more h u m i d when it is cold t h a n when it is hot,
making propane vapor more prone to icing.
Several operational artifacts come as result of this phase
behavior that are not intuitively obvious. For example, this
also tends to moderate the absolute a m o u n t of water per unit
volume in the vapor phase over a wide temperature range.
Propane vapor tends to be more prone to water condensation/freezing than p r o p a n e liquid. "Wet" off-spec propane
can be brought on-spec by venting equilibrium vapor, essentially distilling the water out [60], and this process will be
more efficient at cool or cold temperatures. Large sample
sizes are needed to do a valve freeze or CoBr test, because the
sample changes water content as you withdraw equilibrium
vapor during the test. The CoBr and Dew Point tests are more
stringent at cold storage tank temperatures than hot. The
valve freeze test (on the liquid) is not affected when the tank
is full, but could be affected when the tank is nearly empty
(large vapor space = large volume to enrich water in vapor,
depleting or drying out the remaining small volume of liquid). Under some circumstances, it is very difficult to obtain
a representative sample. Simply exasperating!
LPG Gas

Hydrates

It is not widely appreciated how prevalent hydrates can be in


LPG systems. Few people outside of research laboratories
have ever seen a gas hydrate, even though thermodynamically they are the most stable form of solid ("ice") in propane
systems. In fact, pure water ice is unlikely to form in liquid
propane systems at all, unless the water content is very high,
and free water is present in the propane liquid, either on the
tank bottom or as a dispersed haze in the liquid.
Gas hydrates are a class of ice-like clathrate solids formed
from water and low molecular weight C1-C5 hydrocarbons,
including propane [61]. They consist of water "cages" that surround or "enclathrate" the hydrocarbon molecules. Hydrate
formation can be a significant problem for cold weather operations for gas and gas liquids production and processing, especially prior to dehydration. They can form in LPG process-

CHAPTER
ing equipment, pipelines, and even under deep-sea conditions
due to gas seepage into cold ocean water (with the potential of
becoming a significant "new" energy resource) [62,63]. Hydrate blockages in pipes can be very hazardous. Depressurizing one side of the line can result in the hydrate blockage becoming a ballistic projectile, with the capability of causing
considerable damage. The propane-water and methane-water
systems have been studied in great detail due to their commercial importance. Several GPA and other research reports
are available detailing the phase behavior of hydrates [64].
The c o m m o n industry "rule of t h u m b " is that hydrate formation requires free water to be present, and that it cannot
occur with sub-saturated, on-spec propane. Technically, this
is not true, but it is good enough for most applications, with
some caveats to cover high dissolved water contents and high
pressures. Technically, free water does not have to be present
for propane hydrate to form, but in such cases, there is so little soluble water available for hydrate formation that it is
rarely a problem, or at least is not a more severe problem
t h a n if only water ice were formed. The presence of free
w a t e r in the hydrate formation t e m p e r a t u r e range can
cause severe problems because m u c h larger quantities of
hydrate can form. Below freezing, there is no practical reason
to differentiate between hydrates and water ice in most
applications.
Propane hydrates are stable above the freezing point of
water. The higher the pressure, the higher the temperatures
at which they are stable. They can form at any temperature
below about 5.5C (42F) in propane at its saturated VP. No
externally applied pressure (for example, a pump) is required
for propane hydrates to form. Externally, the symptoms of
having ice or hydrates in LPG systems are virtually identical.
They both form only when it's cold, they both accumulate
and plug lines and orifices, and they both are "melted" by
methanol, leaving the same a m o u n t of liquid methanol/water
mixture at the bottom of the tank. The problems are the
same, the fix is the same, and the result is the same. Most of
t h e time, it doesn't matter, a n d there is n o need to
differentiate between water ice and propane hydrate.
Gas hydrates are the "phantoms" of the LPG world, and are
notoriously difficult to "diagnose" when they do occur. They
decompose (sublime) to water and hydrocarbon gas at ambient pressures very quickly, since they are essentially solids
with a VP of about 80 psi. The sublimation rate can be high
enough to support a burning flame [65]. Often they are gone
by the time the e q u i p m e n t is depressurized and opened
for inspection.
It is always uncertain whether hydrate, pure water ice, or
both are involved when icing occurs in LPG systems. The
biggest difference is that "icing" can occur between 0 and
about 4.5C in LPG systems, due to hydrate formation. It is
r a r e for the t e m p e r a t u r e to be stable in this range long
enough during a n icing episode to make it obvious that hydrate and not water ice is the cause. The day/night temperature difference is generally m u c h larger than this. However,
even w h e n this occurs, people will generally first tend to
think that the thermometer is off by a couple of degrees, or
that there is some auto-refrigeration somewhere, rather than
a hydrate event occurring above 0C.
Hydrates can form both in the liquid and vapor phases, but
there are some differences in behaviors that can be important

2: LIQUEFIED

PETROLEUM

GAS

45

in some situations. Firstly, hydrates tend to form at free-water surfaces. This is because propane type II hydrate has a
composition of a b o u t 17.1:1 mole ratio of waterrpropane,
which greatly exceeds the propane solubility in water. As a result, when a tank containing free water is cooled towards
zero, it will tend to form a thin layer of hydrate on the water
surface, like the first thin skin of ice on a pond, puddle, or ice
cube tray. The hydrate layer becomes a barrier for propane
diffusion, effectively limiting the rate of further hydrate formation. As the t e m p e r a t u r e drops further below 0C, the
underlying "metastable" water can freeze to water ice.
Thermodynamically, the hydrate and water ice should not
exist together; they are only there due to a kinetic rate limitation. Under thermodynamic equilibrium conditions, water
ice would not form until all of the propane is consumed first
forming hydrate, leaving water or water ice in equilibrium
with hydrate, and no propane liquid. As a result, mixing and
turbulence are invariably factors in hydrate formation from
propane liquid.
Secondly, hydrates can form very quickly on tank surfaces
exposed to the vapor space by deposition from the vapor (i.e.,
the opposite of sublimation). The equilibrium concentration
of water is always higher in the vapor phase, which favors hydrate formation from the vapor. This can be a very fast and
"efficient" process, as there is no kinetic barrier, and the water
vapor and propane are already mixed. Only the rate of diffusion and convection of the water vapor limit the rate of hydrate formation. Hydrate formation from saturated equilibrium vapor depletes water from the vapor phase, essentially
dehydrating it. Additional water will vaporize from the liquid,
and contribute to additional hydrate formation. If liquid water were in the tank bottom, and one waited long enough, all
of the water would eventually form hydrate at the tank bottom, or dissolve into the liquid propane, vaporize, and form
hydrate on the vessel walls that are exposed to the vapor. This
process would continue until all the free water was consumed,
leaving only hydrate on the tank bottom and vapor walls. The
liquid propane in equilibrium with the hydrate can still be "off
spec" near the high end of the hydrate formation range. The
real fun begins when the tank gets emptied out and re-filled
with dry or warmer propane, which immediately goes "offspec" for no apparent reason, or the temperature changes
rapidly, and slugs of water or chunks of "ice" show up.
This can result in some truly exasperating situations when
investigating water related problems in cold LPG systems.
You are never sure if free water is present, or if the liquid or
vapor is in equilibrium, or if any sample is representative.
The basic concept of obtaining representative samples is
s o m e w h a t uncertain. You generally don't have a b o t t o m
drain, and you can't see inside of the tank liquid or vapor
space. When you open it up, it's all gone. This, plus the inherent difficulties of sampling/measuring low p p m levels of
water and methanol in LPG makes reliable quantitative measurement of water virtually impossible in cool/cold weather,
without extraordinary attention to sampling and analytical
detail. Throw in a couple of different test methods with no
precision statements, no calibrants, no reference standards,
no QCs and uncertain correlation, and "exasperating" is an
understatement.
It is left to the reader's imagination the many hours of stimulating conversation possible between the lab, the process

46

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

engineer, the plant manager, and the receipt terminal. This is


a potential area of future reseetrch and standcirdization.
Fortunately, the high VP of methanol makes it a very effective means to eliminate ice or hydrate formation in both the
liquid a n d vapor phase. Methanol, the lowest molecular
weight alcohol, partitions between liquid and vapor phases
closest to water, a n d tends to protect b o t h phases from
freezing.
Unfortunately, the specifications are silent on the use of
methanol, the test methods are inconsistent in response to
methanol, and there is no consensus between the upstream
and downstream industries on the intent and extent of use of
methanol in LPG. This is a potential Eirea of future research
and standardization.
Recently, some non-cryoscopic kinetic "hydrate inhibitor"
additives have been commercialized for processing/pipelining applications, but these are not applicable to specification
products [66].
Auto-refrigeration
Like any gas (except hydrogen) near ambient temperature,
p r o p a n e vapor will undergo Joule-Thomson (JT) cooling
when depressurized (flashed) across a veJve, orifice, pressure
regulator, or other device. The cooling effect is dependent on
the process, whether it is adiabatic (a valve) or isentropic
(turbo-expander) or polytropic (something in between). The
JT cooling effect is not very large, about 0.25F per psi drop in
the 30--40F range for propane, but this can be significant under certain conditions. In small regulators, the JT cooling is
offset by heat gained from the environment, tending to be
isothermcd at low flow rates (high heating from ambient air,
low JT cooling from low flow). However, as the appliance dem a n d and gas flow increases, there may not be enough convective heating to overcome the JT cooling, and the system
tends toweird adiabatic conditions. If the inlet propane vapor
is near water saturation (off-spec) and only slightly above the
freezing point, the cooling effect can be sufficient to cause
phase separation and ice formation at the expansion point.
Similarly, if the valve or regulator body is cooled below freezing, then the high-pressure propane vapor at the regulator
inlet could be cooled below freezing by the cold valve body.
This results in inlet freezing, upstream of the point of
vaporization, where the actual cooling occurs. A commercial
technical bulletin (LP-24) is available from a regulator manufacturer dealing with vapor regulator inlet line freezing from
these effects [67]. Ice will tend to accumulate over time in a
flowing system, until a blockage is eventually formed. If the
propane liquid is substantially sub-saturated (i.e., on-spec),
the cooling from expansion of equilibrium vapor is generally
not enough to cool the vapor to the water saturation temperature (dew point), and no ice/water is formed (one reason why
HD5 and functionally equivalent specs are where they are).
When liquid propane is depressurized or "flashed," a fraction of the liquid will vaporize, cooling the entire mixture
down to the boiling point and dew point of the liquid/vapor
mixture (they are the same if the mixture is in equilibrium).
This cooling effect is large, for example resulting in liquid
and gaseous propane at about 42C at atmospheric pressure. MoUier diagrams (pressure-entropy), pressure enthalpy
diagrams, or tables of thermodynamic properties can be used
to quantify temperatures, pressures, enthalpies and entropies

for a variety of conditions. Flashing liquid propane into even


moderate vacuums can attain temperatures below 80C.
The vapor pressure and solubility of water in propane below
42C is extremely low, so essentially all the dissolved water
that was present is converted to hydrate/ice. Liquid propane
vaporization systems almost always require external heating,
b o t h to convert all of the liquid to vapor, and to prevent
eventual freeze u p from ice. Transient conditions, for
example startup of automobile vaporizer/regulators in very
cold weather, t e n d to be p r o n e to icing, until the engine
coolant gets w a r m enough to keep the vaporizer above
hydrate/freezing temperatures.
The methanol addition rates t h a t are r e c o m m e n d e d in
various codes and standcirds for new tanks or for when moisture is present) are intended to remove the free water in the
tank, and leave only a small a m o u n t of methanol/water mixture prior to putting into service. They are not intended to
provide protection where gross water contamination has occurred or to allow weak water/methanol mixtures with high
freezing points to remain in the tank. For this reason, the
standards generally require inspection and removal of free
methanol/water prior to putting the tank into service.
Methanol is effective at preventing freeze-ups to very low
temperatures, but there is no universally accepted criteria for
how much methanol to add to propane during downstream
distribution as a preventative m e a s u r e . Many companies
have optimized methanol addition rates based on actual temp e r a t u r e s and/or dryness test results. These are effective
strategies with a relatively sound technical basis (see phase
behavior of m e t h a n o l ) . This is a potential area of future
research and standardization.
Butane, with a normal boiling point of neetr 0C is not capable of creating ice freezing conditions by auto-refrigeration
u n d e r normeJ conditions of use, and is treated as in other fuels with only a "visually cleeir" requirement. However, if butane is used below ambient pressure, the same precautions
may have to be used, as the boiling point at reduced pressure
is below the freezing point of water, a n d ice/hydrate cam form.
Butane, propane and their mixtures are widely used as the
working fluid in large industrial and chemical process refrigeration applications, such as industrial chillers, gas processing, refinery gas processing, or reactor cooling in alkylation
processes. These are usucJly integrated into the production
processes themselves, so they are n o t very "visible," even
though they are very large and very commonplace. All generally require some provision for w a t e r removal and icing
protection.
Phase Behavior

of Methanol

in

Propane

Methanol is a unique material in the LPG world. It is the only


alcohol with a lower molecular weight (31) than propane, and
the only one to be concentrated into the vapor (like water). As
a result, it tends to partition and "travel" with the water, making it very effective in preventing freeze-up in both the liquid,
vapor, and condensed vapor phases. The freezing point depression properties of methanol in water are very good, providing protection down to -40C [68] and below. Methanol,
being a small molecule, has a high diffusion coefficient and is
very effective at dissolving water and hydrates. No other alcohol has this broad range of beneficial properties, so methanol
is the only alcohol that is commonly used in LPG systems.

CHAPTER
The use of methanol is mandated under certain codes and
standards to minimize free water from tanks prior to putting
t h e m into service or if water is reasonably expected to be
present [69].
Methanol works by creating either a second non-freezing
separated phase in the liquid, in the vapor (hydrate), or the vapor if re-condensed. Methanol/water mixtures will not freeze,
but will gravity settle, and tend to collect at tank bottoms,
where it can be difficult to remove. This can promote other
problems such as corrosion and resulting sediment and filter
plugging, which is undesirable in the downstream applications. As a result, there is a general consensus that propane
should be manufactured as dry as necessary for "normal" operations, and that methanol should be used as needed for new
tank commissioning, and cold weather operations in downstream (post refining) distribution and use.
Methanol is equally difficult to detect as water at low p p m
levels, especially in the field. As a result, the actual amounts
of water or methanol present are rarely measured directly. It
is also recognized that methanol interferes with some of the
c o m m o n "dryness" test methods once it has been added to
propeme. D2713 "valve freeze" test is quite explicit in stating
that the test does not apply to LPG containing antifreezing
agents (although it is commonly used for this purpose in
spite of this caveat). The CoBr test is believed to be relatively
i m m u n e to methanol, but this test is not widely used. The
chilled mirror dew point test is affected by methanol, since it
phase separates with water. Electronic hygrometers (dew
point meters) m a y or may not be affected by m e t h a n o l
depending upon the principle of operation.
In colder climates, it is common for methanol to be added
to bulk storage during distribution as a preventative measure. Long-term field experience indicates that this is a n effective strategy to minimize regulator freeze-up problems, so
long as addition is controlled to the m i n i m u m required. Different companies have applied mzmy different criteria, in the
absence of reliable field tests that can be used to monitor and
control water/methanol. This is an area of r e c o m m e n d e d
focus for future research and standcirdization
A 50 wt% methzmol/water mixture (common windshield
wiper Emti-freeze in cold climates) will not freeze down to
below 40C. Therefore, as long as any separated
methanol/water phase is at least this concentrated, no freezeu p is possible under typical conditions of LPG use. Methanol
is more soluble in propane than water, so more remains in
the propane phase in equilibrium with the methanol/water
separated phase. Limited low temperature solubility data indicates that the methanol solubility in propane in contact
with a 50 wt% methanol/water solution at -40C is about
400-800 p p m w [70]. This indicates that it would take about
400-800 p p m w methanol to prevent freezing down to about
40C at ambient pressures for w a t e r saturated p r o p a n e
(about 100 p p m w at 70F). This is smaller than the solubility
of methanol in propane at ambient temperature, so methanol
use tends to be "robust" so long as gross overdoses are
avoided (and a dry grade of methanol is used). Slightly lower
treat rates would be expected for lower water contents, or if
freezing protection was only required to a higher temperature. The lower limit to eliminate all solid formation at -40C
would be expected to correspond to the 400-800 p p m w solubility of methanol in propane u n d e r these conditions. The ab-

2: LIQUEFIED

PETROLEUM

GAS

47

solute values of water/methanol solubility in LPG below the


saturation levels and at varying olefin levels are not accurately known. This is a suggested area of research a n d
standardization.
Ethanol and iso-propanol have a higher solubility and lower
vapor pressure than methanol in liquid propane. They require
a significantly higher treat rate per p p m w of water present to
prevent formation of solids at 40C in both the liquid and
equilibrium vapor. To date, methanol is technically and economically the best de-icer for propane.
In general, over-addition of methanol should be avoided, as
drops in temperature or contact with water can result in most
of the methanol phase separating in distribution and storage
and causing problems. For example, if w a r m propane containing 1% methanol either cooled down to 20C or were
contacted with water, then more than half of it will phase
separate and settle to the bottom of the storage tank as a
non-freezing water/methanol mixture. This would amount to
500-1OOOL for a large rail car. This large volume of
methanol/water mixture has the potentieJ to accumulate in
downstream storage, to the point where individual small
deliveries could contain gross quantities of water/methanol.
It is generally accepted that methanol should not be used
as an alternative to proper dehydration during production,
and that periodic use should be minimized. For the producer,
the answer is to consistently make LPG very dry, and avoid
periodic "slugs" of water. For the marketer, who is subject to
the downstream sources of water, the answer is to monitor,
and only use methanol when required during cold weather.
This is also an area of r e c o m m e n d e d research a n d
standardization.
Sources

of

Water

Water can be introduced into propane distribution systems


from a vairiety of sources. Faulty production can leave excess
dissolved water or free water in the LPG due to inadequate
dehydration. Water is used for hydrostatic pressure testing of
large pressure vessels including tanks, trucks, and rail cars.
Steam is used to clean and "inert" tanks for maintenance and
change of service. Water can become trapped in tanks from
previous wet loads due to internal "dead volume" at the
bottom of tanks due to valves or piping that is recessed for
physical protection, a c o m m o n requirement of safety codes.
Exposure of tanks to the atmosphere can result in moist air
condensing water on inside surfaces, where it becomes
trapped, and accumulates with each diurnal heat/cool cycle.
Free water in trucks or rail czirs tends to be persistent because
of the low water solubility of water in p r o p a n e . A small
a m o u n t of water in a truck or rail car can render m a n y
subsequent loads "off-spec."
Recent changes to rail car pressure vessel certification requirements provide another opportunity to further reduce
the use and occurrence of steam cleeming and hydrotesting of
large pressure vessels (truck/rail). Work is ongoing in this
cirea and several programs are planned. This is a suggested
area of research and standardization.
Measurement

of Water in LPG

There has cJways been a desire in the LPG industry to have better test methods for "dryness," especially for production and
terminal bulk receipts, which are the two main control points

48

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

(See "dryness" sections above). This has been an elusive goal


for many years, due the technical difficulties involved.
The criteria for pass/fail on the CoBr test are as follows [71]:
Color

Per Cent Humidity^

Green
Blue
Lavender
Pink

Very Dry
From nearly 0% to 30%
From 30% to 52%
From 52% to 100%

Pass (rcirely seen)


Pass
Fail
Fail

It is generally accepted that a 60 s valve freeze pass is about


equivalent to a CoBr pass, or a 26C dew point and less than
about 35 p p m w water in the LPG liquid phase. However,
these are not exact relationships, and there are several complicating factors due to differences in phase behavior with
temperature and composition. Different people have made
different assumptions in estimating equivalence between water content, the liquid propane phase, and the CoBr test results. During the CoBr test, the equilibrium vapor sample is
preconditioned with an ice bath to 32F and 50 psig, slightly
below the saturation vapor pressure at 32F. Most people
assume the humidity values in the table to apply at 32F in
doing the equivalence calculations. The a u t h o r noted that
"the values in this table were determined by series of tests on
propane vapor containing various amounts of water over a
temperature range of from 35-70F. The percents at which
the changes of color take place seem to be somewhat affected
by t e m p e r a t u r e . However, the determinations were not
accurate enough to assign closer values in the table."
In the test, the actual humidity of the sample is determined
by the bulk tank or bulk sample temperature, not the 32F
test t e m p e r a t u r e . The humidity of the equilibrium vapor
varies inversely with temperature at constant liquid water
content, due to the change in the "K" ratio. Therefore, there
is no single p p m water level of water in liquid propane that
corresponds to a CoBr (or Dew Point) pass/fail level. The
equivalence level is inherently temperature dependent.
Both the CoBr and Dew Point test methods are most severe
(conservative) at the lower temperature ranges. One can estimate the amount of water in liquid propane that is required
to pass the test on the known dependence of "K" ratio and
water dew point (vapor pressure) in gases. This depends on
what assumptions are made about the humidity level for failure condition (32% or 40%) and to what temperature the humidity shown in the table applies (32F versus 60F). A
propane sample taken at 32F has variously been estimated to
require less than 10-20 p p m w water in the liquid to obtain a
passing result. A sample taken at 100F has been estimated to
require less than 20-35 p p m w in the liquid to obtain a passing result. This temperature dependence is not recognized in
the test methods. However, the pass/fail criteria are severe
enough that propane obtaining a passing result is considered
suitable for use regardless of the temperature of the sample.

^ The humidity of the equilibrium vapor is dependent on temperature, since the wt. "K ratio varies from about 10 at 60F to about 15
at 32F. As a result, both the CoBr and Dew Point test methods are
more severe (conservative) at 32F than at 60F (or higher). This temperature dependence is not considered in the test methods, and the
same pass/fail criteria is applied regardless of the temperature of the
storage tank and equilibrium vapor.

Similarly, the CoBr sind Dew Point tests would be expected


to be somewhat influenced by gas composition, and especially by olefin content. Olefins have a higher affinity for water, and a correspondingly lower "K" ratio. Directionally,
higher propylene content would make the test less severe, requiring higher liquid water contents to obtain a test failure.
This difference has not been quantified, and is generally not
considered to be significant for commercial propane.
There are a n u m b e r of other anal3^ical techniques that can
be used for the anedytical determination of water in LPG.
Some methods, such as the Karl Fisher, can be used but are
difficult to apply to LPG, because of the physical properties.
Others, such as vapor phase determinations, can be influenced by sample size due to the very high "K" ratio of dissolved
water in propane. The cobalt bromide test, for example, recommends at least 15 gallons of LPG sample if the test cannot
be done at the storage tank with the equilibrium vapor. In
other cases, such as terminals supplied from underground
cavern storage, there is n o source of equilibrium vapor available on-site, because all the vessels are liquid filled.
Electronic hygrometers and "dew point" meters [72,73]
have been successfully used, and while they have the necessary sensitivity, and are widely used in the natural gas industry [74], they are not currently recognized in the LPG
standard. Care must be taken with their use, especially for
calibration a n d QC procedures to ensure that results are
valid. Several new ASTM procedures are now available that
allow adoption of on-line analytical techniques to product
certifications, and LPG "dryness" is a prime candidate for
these new methods. Many companies have installed solid
state electrometric probes at production facilities to monitor
drying operations, and there is emerging interest in having
these included as an alternate test method in the standard.
This is a recommended area of research and standardization.
Sampling and sample introduction also needs special care
and attention. Formation of hydrates can metke the storage
time prior to analysis a factor. At high temperatures and humidity levels, the air in the lab can contain 20 000-40 000
ppmv water vapor, and there can be more water adsorbed on
sample lines a n d cylinders t h a n is in an on-spec sample.
More than one analyst has falsely reported the humidity level
of a plastic sample transfer line as an off spec LPG result.
Recently, a new stain tube was developed for use as a field
test in natural gas pipelines that has a lower sensitivity to trace
glycol used in natural gas dehydrating systems [75]. These
stain tubes still have an interference from methanol, but may
still have some application as a field test, for example on terminal receipts prior to the addition of methanol. These calibrated in the range 2-10 Ib/MMscft (traditional units for natural gas), which is equivalent to about 40-220 ppmv (multiply
by mole weight ratio 18/44 = 0.41 to convert to mass p p m assuming ideal gas at low pressure). This is in the correct range
for use on LPG equilibrium vapor, so it can likely be adapted
to use for LPG. This would be very similar to the GPA and
CGSB field methods for mercaptan odorant (see odorization),
that use similar stain tubes calibrated in traditionetl natural
gas industry units, with appropriate conversion factors.
At present there is no standard test method for the use of
stain tubes, or electronic hygrometers or dew point meters
for LPG specifications. The ASTM natural gas standards
that use these m e t h o d s currently do not include LPG in

CHAPTER
the scope. This is another area of recommended research and
stEmdardization.
R e s i d u a l Matter (Oil Stain & R e s i d u e )
Non-volatile materials that are soluble in liquid propane tend
to a c c u m u l a t e at the point of p r o p a n e vaporization as a
residue or gum that can interfer with the proper operation of
some equipment. The oil stain test attempts to concentrate
non volatile residues that can be visually detected by putting
it dropwise on a clean filter paper. This test is quite subjective a n d can be influenced by the grade of filter paper, or
color of the residue. Historically, the main purpose of the test
was to detect traces of compressor oils, a c o m m o n occurence
in the early days of the industry, but less c o m m o n today.
Other sources of heavy naaterials can be heat transfer fluids
from distillation processes, caustic, amine and glycols used
in some processes, greases and "pipe dope," sample cylinders, hose plasticizers, or cross contamination with other hydrocarbon fuels and lubricants if any c o m m o n equipment is
used in distribution.
Contaminants that form "oily residues" or "waxy solids"
with auto-refrigeration of vaporizing propane, especially in
association with fine particulates, can interfere with proper
operation of safety lock-offs, overpressure vents and regulators. Non volatile additives are generally not recommended
for use in propane intended for vaporizing service, and specific warnings are included in D130 copper corrosion test
pertaining to corrosion inhibitors ("masking agents"). Some
higher boiling or polymeric materials may interfere with catalytic heaters or automotive catalysts if present in the liquid
propane. ASTM specifications currently do not include limites for higher t e m p e r a t u r e evaporation limits. This is a
potential area of future research a n d standardization.
Propane is a very poor solvent for parafin wax (n-parafins
or near parafins) or for asphaltenes, and has been used in
commercial de-waxing and de-ashpalting processes. Contamination of LPG with "black" oils that contain asphaltenes
(IFO, HFO, Bunker, Pitch, Crude) or distillate fuels that contain wax (diesel, furnace oil, marine gas oils, kerosene, Jet)
can result in the precipitation and collection of waxy or asphaltene solids. This can cause m u c h more severe operational
problems than an oily liquid because of more severe impacts
on equipment. Care must be taken to prevent cross contamination of these materials. Sources for such contamination can
include leaking heat exchangers, pipeline "dead legs" or idle
p u m p loops, meter provers or other distribution equipment
that may be inadequately cleaned from a previous service.
Nonvolatile additives may be beneficial for certain applications, such as detergent/dispersant additives for autopropane,
similar to gasoline. However, this can introduce the need for
a segregated fuel, since they can still be detrimental to vaporizing services. Maintaining a single universal grade would
require additive injection at the point of dispensing. This is a
potential area of future research and standardization.

2: LIQUEFIED

PETROLEUM

GAS

49

door use. The original "lamp" method is still listed in most


specifications, but rarely, if ever used. A variety of newer instrument methods are in common use, and are under consideration for inclusion in LPG specifications. Recently, the
requirement was changed to include the sulfur contribution
from added mercaptan odorant, which is effectively a tightening of the standard. The California ARB "HDIO" standard
has an 80 p p m maximum sulfur limit.
All LPG specifications have some provision for the control
of corrosive sulfur compounds to protect copper and copper
based alloys commonly used in fittings and connections in
storage, transportation, a n d appliances. ASTM D1838 is essentially a modified ASTM D130 copper coupon corrosion
test using pressure rated equipment for LPG. The same grade
of copper strip and preparation procedures are used, and the
strip is suspended on a hook fixed to the outage (ullage) tube
in a purpose built stainless steel test cylinder with an O-ring
removable top closure.
Sulfur based corrosion in LPG is a surprisingly complex
subject, due to the chemistry of the reactive sulfur species that
can be present, smd the nature of the test [76]. Mixtures of certain sulfur compounds are more corrosive than each alone,
even if the individual compounds were present at higher concentrations. This can lead to occasionally bizarre situations
where two on-spec propane batches go "off-spec" upon mixing. The classic case is w h e r e one batch contains a small
amount of dissolved elemental sulfur (S8), and the other a
trace of H2S (hydrogen sulfide) or COS (carbonyl sulfide).
Each batch can be on spec by a wide margin, but the mixture
can show a persistent fail, or even worse, an occasional fail.
There is nothing like a persistent occasional fail to go into "dispute mode," with no hope of short-term technical resolution.
Many hours of stimulating conversation are made possible
between shippers on a c o m m o n pipeline system or storage facility with such events. Each may sanctimoniously claim the
others to b e at fault, presenting credible data to prove their
innocence with consistent Cu corrosion passes. Try devising
a "round robin" to resolve that dispute.
In the vast majority of cases, corrosion problems in LPG
are associated with H2S, Sg (elemental sulfur, eight member
ring), COS (carbonyl sulfide), RSSxR (alkyl polysulfides),
HSSxH (polysulfanes), H2O (water) and O2 (in air). The most
important are usually H2S (improper treating), Sg (usually
from oxidation of H2S) and COS hydrolysis (reaction with
H2O to form CO2 and H2S). Mixtures of H2S and elemental
sulfur (Sg) form very reactive polysulfur intermediates that
are very corrosive, and react very quickly with most common
metals. Trace H2S and Sg U'e legendary for their difficulty to
sample and analyze. Fortunately, lead acetate paper is very
sensitive as a field test for H2S. Sampling and analysis for
trace Sg is always problematic.
Almost all copper corrosion problems are a direct result of
inadequate treating at the time of manufacture, and/or the
highly non-linear blending characteristics of different sulfur
types in propane from different sources.

Corrosion, H2S, a n d Sulfur

Contziminants

Historically, the total sulfur content of LPG (sometimes


called the volatile sulfur content) was always much lower
than for other fuels, and this was important, especially for in-

Magnetic

Residues

("Black Deposits")

and

Particulates

The occurance of iron oxide/sulphide magnetic residues was


studied by the Propane Gas Association of Canada (PGAC

50

MANUAL

3 7: FUELS

AND LUBRICANTS

HANDBOOK

[77]) as a result of widespread problems especially in automotive LPG fuel systems [78]. Iron particulates either from
heat treating "mill scale" or corrosion processes can adversely affect the operation of components that magnetically
attract and trap these materials in the working mechanisms
(e.g., magnetically coupled level gauges and electronic
solenoid valves). Collection of gross a m o u n t s of solid
residues (magnetic or otherwise) can adversely affect operation of filters, filter lock-offs, regulators, mixers, pressure release valves, etc., by mechancial blockage. Two to ten micron
(absolute. Beta 5000) filters have been found to be effective to
remove these materials with good filter life (granular well
behaved filter calie).
Ammonia
A m m o n i a is not used in the production process, a n d is
generally removed by gas stripping and distillation if it is
present. Anhydrous a m m o n i a is widely used in agriculture as
a fertilizer, and is transported in the same pressure rated
equipment as LPG. It is c o m m o n for rail and truck cargo vessels to transport "anhydrous" during the spring and s u m m e r
growing season. The s a m e rail or truck cargo tanks are
converted to LPG service for the fall and winter heating season. This is advantageous for optimal use of transportation
equipment, but offers increased chance of cross contamination without adequate cleaning in the change of service
procedure.
Anhydrous e q u i p m e n t a n d LPG p r o d u c t i o n e q u i p m e n t
generally use only carbon or stainless steel fittings. Brass
(copper alloy) veilves and fittings are commonly used in LPG
systems, particularly those at the dealer and consumer level.
Ammonia can cause stress crack corrosion in brass and copper fittings at concentrations above about 5-10 ppmv [79].
There is no firm specification or guideline on the maximum
allowable ammonia concentration of propane for either short
or long term exposures, Eind a level of < l p p m (detection by
field litmus paper test) is usually recommended.
Field tests based on color change of wet red litmus p H
paper are adequate to detect ammonia down to about 1 ppm,
and provide an effective go/no-go test after change of service
or at any time during distribution [80].
The time required for the color change due to the field test
can also be used to judge the severity of the contamination.
Very high (>20 ppm) concentrations cause a strong color
change in only a few seconds. Moderately high (5 ppm) will
cause a medium color change in about 10 s and low ( < l p p m )
will cause slight change in about 30 s.
The litmus test is very sensitive to any material with even a
slightly higher than 7.0 pH. This includes saliva (depending
on what was last eaten), high p H potable ("tap") water in
some regions, or soaps or detergents that may have been used
to wash the hands or equipment.
Controlled tests indicated that p r o p a n e with low concentrations of a m m o n i a would have n o effect on the
concentration of ethyl mercaptan odorant [81].
Halocarbons

(Refrigerants)

There have been rare occasions of contamination of LPG


with halocarbon refrigerants or fire retardant (Freon ^M or
Halon ''*'). These materials are miscible with propane, and
will form noxious gases upon combustion.

Naturally Occurring Radioactive Materials


(NORM)
Sludges and tank scale from propane storage tanks, trucks
and rail cars, and filters/screens may contain Naturally
Occurring Radioactive Material (NORM) in the form of lead
210 (Pb'^'"). Similarly, equipment used for the transfer of
propane such as product pipelines, pumps and compressors
may have detectable levels of radioactive lead 210 on inner
surfaces. Workers involved in cleaning, repair or other
maintenance of inner surfaces of such equipment should
avoid breathing dust generated from such activities. Suitable
codes of practice should be developed for these activities detailing appropriate occupational hygiene and disposal practices [82].

VOLUME CORRECTION FACTORS (VCF)


FOR LPGS AND NGLS [83]
LPG has the lowest density, largest thermal expansion and
compressibility and highest operating pressure of the comm o n fuels. It is the only fuel where compressibility is significant e n o u g h that it can be taken into account both for
calibration of composition test methods and custody transfer
metering. The original set of Volume Correction Factors
(VCF) were developed in an NGAA (GPA) sponsored research
p r o g r a m in 1942. It was first published as GPA standard
2142. These factors were later adopted as national and
international measurement standards as ASTM/IP 1250.
The Volume Correction Factors (VCFs) are used to correct
observed volumes to the volume that would be observed at
standard conditions (60F, 14.969 psia). These standard conditions serve as a way to equitably use volumetric measures
in general commerce. They are derived from actual density
measurements on a wide range of LPG/NGLs, and are essentially the average values of the coefficients of thermal and
pressure expansion. These factors are strongly correlated to
the density of the material (e.g., the lower density the mixture, the more compressible it is). As a result, the calculations
are iterative, and separate tables are published, each covering
a narrow range of densities. The differences are small, but
they do have large economic impacts because of the large
volume of material involved.
D 1250 is the ASTM standard for calculating the VCF of a
petroleum mixture. This standard essentially directs the use
of procedures published in the American Petroleum Institute
(API) Manual of Petroleum Measurement Standards (MPMS).
As of 1999, there are several procedures that may be used to
calculate the VCFs:
Chapter 11.1, Volume Correction Factors, gives procedures
to determine the VCFs due to temperature for crude oils,
refined products, and lubricating oils. However, since the
upper limit on API gravity is 100 it applies only to the
heaviest of LPG.
Chapter 11.2.1, Compressibility Factors for Hydrocarbons:
0-90 "API Gravity Range, and 11.2. IM, Compressibility Factors for Hydrocarbons: 638-107 kg/m^ Range, give procedures to determine the VCFs due to pressure. Like Chapter
11.1, since the upper limit on API gravity is 90 it applies
only to the heaviest of LPG.

CHAPTER
Chapter W.l.l, Compressibility Factors for Hydrocarbons:
0.350-0.637 Relative Density (60F / 60"F) and -50F to
140 F Metering Temperature, and 11.2.2M, Compressibility
Factors for Hydrocarbons: 350637 kg/m^ Density
(ISV)
and 46C to 60C Metering Temperature, also give procedures to determine the VCFs due to pressure. These
procedures cover the lower densities indicative of most
LPG and NGL.
Until 1998, the VCFs due to temperature for the LPG and
NGL not covered by Chapter 11.1 were calculated from a variety of sources. The major source was a set of Petroleum
Measurement
Tables published in 1953 by ASTM International and the Institute of Petroleum (IP). New implementation procedures for liquids with relative densities (60760)
of 0.3500 to 0.6880 (272.8 to 74.2API) were p u b h s h e d
in 1998 as Technical Publication TP-25 Temperature Correction For The Volume Of Light Hydrocarbons. This is a GPA
publication, but GPA, API, and ASTM have jointly adopted it
[84]. These procedures are based on an experimental program sponsored by all three above organizations. Based on
this expanded database the TP-25 factors are different by as
much as 0.2-0.8% from the 1953 Table factors.
The underlying procedure in TP-25 is quite different from
the fairly empirical equation forms used in the other standards. The TP-25 factors are determined from the interpolation of the properties of reference fluids via a corresponding
states formulation. Corresponding states theory has a rich
history for the use of correlating various t h e r m o d y n a m i c
properties. This particular formulation is unique in that it
uses the relative density at 60F as the interpolating variable.
The calculation of the density at a temperature is based on a
comparison of the properties of the reference fluids at the
same reduced conditions. All the reference materials and critical properties required to do the calculations are available in
the standard.
The organization of the VCF standards in the API Manual
of Petroleum Measurement Standards is being changed. The
revised Chapter 11.1, Temperature and Pressure Volume Correction Factors for Generalized Crude Oils, Refined Products,
and Lubricating Oils, will combine the previous Chapter 11.1
and 11.2.1 temperature and pressure correction procedures
into a single unified procedure. The nominal API gravity
range will be 10 to 100, so it will still only cover the heaviest of LPG. Two important changes will be that the single set
of procedures will be valid for the customary and metric standard temperatures (60F, 15C, and 20C) and for measurem e n t temperatures and pressures in customary or metric
units. Chapter 11. Iwas approved for D 1250-2002 and will be
published in 2003.
The revised Chapter 11.2, Temperature and Pressure Volume Correction Factors for Light Hydrocarbons, will use the
TP-25 procedure as the basis for the temperature portion of
its VCF procedures. It will cover the range of relative densities (60/60) of 0.3500-0.6880 (272.8-74.2API), just like TP25. Like the revised Chapter 11.1, this will contain a single set
of procedures valid for the customary and metric standard
temperatures (60F, 15C, and 20C) and for measurement
temperatures and pressures in the customary or metric units.
Technical work is being done to incorporate pressure correction procedures. It is expected that this revised Chapter 11.2
will also be published in 2003.

2: LIQUEFIED

PETROLEUM

GAS

51

The VCFs are always based on averages on a range of materials, or by interpolation between reference standards. Individual mixtures that have similar density but different
composition than either the average or reference may have
significantly different expansion coefficients. Use of the
standard VCFs will give a biased result on these mixtures.
Provisions are made in the standards for contracting parties
to determine and use VCFs based on density measurements
on the individual material or mixture. Alternatively, to minimize uncertainty, contracting parties may specify that the
density determination used for custody transfer be obtained
as close to the standard conditions as possible. This is easily
done for temperature, but is more complicated for pressure.
In the past, pressure correction was often omitted or ignored,
or based on measurements done at the time and temperature
a n d pressure of custody transfer. To accommodate existing
industry practices, the new standard TP-25 contains two sets
of tables, one for temperature correction alone, and the other
for combined temperature and pressure correction.

AUTO PROPANE
LPG has been used as a spark ignition motor fuel for over 40
years, especially in fleet and workplace applications. The primary advantages over gasoline in these markets are related to
availability, cost, and tailpipe emission levels. Fleet operations can operate from centrally located refueling sites,
avoiding the need for widespread availability at retail gasoline service stations. The lower operating cost for fuel may
offset the cost of conversion, with a net benefit for high
mileage applications such as taxi or delivery fleets. The
breakeven mileage generally varies between 5000 to 25 000
km/year, depending mostly upon the presence and level of
Government incentives for conversion cost, registration and
differential fuel taxation. The tailpipe and environmental
benefits depend mostly upon the technology and calibration
of the engine using the fuel and to a lesser extent on the properties of the fuel itself. However, with equivalent levels of
technology, LPG tends to have a significant advantage with
emissions and emissions toxicity.
Historically, both gasoline and propane employed similar
carburetor and intake manifold configurations. This allowed
widespread "aftermarket" conversion of engines from gasoline to LPG, using engine coolant driven vaporizer/regulators
and various gas injector devices. These could be plates that
could be "bolted on" above or below the existing liquid gasoline carburetors for dual fuel operation, or gas carburetors
for dedicated LPG use.
LPG carburetor engines generally have lower tailpipe hydrocarbon and carbon monoxide (HC,CO) emissions than the
equivalent technology gasoline engine, when no computer
feedback engine control strategies are used. This is primarily
due to reduction/elimination of fuel enrichment for idle, throttle transient and high power engine operation. This made
propane a preferred fuel for such indoor engine applications
as forklifts, where indoor CO emissions must be minimized.
The widespread introduction of tailpipe catalysts and electronic fuel injection systems to meet increasingly more stringent emission standards has made aftermarket conversions
increasingly challenging on recent model automobiles to

52

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

LPG. Second generation conversion systems attempted to


use the onboard sensors to control a parallel LPG injection
system, often with very good results. However, the increased
cost and engineering sophistication tends to limit application
to a few high volume platforms. Each has to be re-engineered
with every change to the gasoline system, and then maintained in the field. Even so, several of these conversions have
been quite successful, but the overall rate of North American
conversions declined.
Recently, the highly integrated fuel injector/intEike manifold
designs and more complex onboard control and diagnostic
systems have become the norm [85], but these significantly increase the cost and complexity of conversion. Current Tierl,
Tier2 and more recently hybrid gasoline electric vehicles offer
exceptional emissions performance. On the horizon are mandated lower emission standards and gasoline reformulation
that will further reduce or possibly eliminate the tailpipe
emission advantage once enjoyed by LPG conversions. With
reduced environmental credits. Governments have tended to
reduce incentives for conversion, resulting in longer break
even time for operators [86]. As a result, the size of the North
American LPG conversion fleet is declining rapidly, OEM
built LPG dedicated or dual fuel vehicles is increasing. Major
North American OEMs offer current technology LPG powered
low emissions light duty cars, trucks, and vans. Recently,
there has been renewed interest in development of low emission LPG vehicles in the Pacific Rim and in Europe.
OEM vehicles are predominately factory conversions of
truck and van platforms aimed at fleet use [87,88]. The North
American carmaker's message to the p r o p a n e industry is
clear: The carmakers expect the s u p p o r t of the major
p r o p a n e industry players if they are to produce, sell and
maintain OEM vehicles [89].
This experience is different in other parts of the world, depending mostly upon fuel cost and tax structure. There is a
general agreement that the technical problems either can or
have been solved (depending upon who you tcJk to). This includes gaseous or liquid fuel injection systems that address
many of the problems of earlier systems, including tolerance
to trace contaminants, same as gasoline or diesel fuel.
Several manufacturers of advanced fuel LPG injector
systems have experienced problems with particulate/residues
in various areas of the country. Magnetic residues (predominately magnetite "mill scale" and tank cortosion products)
have been especially disruptive to some electronic solenoid/
injector designs. Widespread introduction of these systems is
likely to put additional emphasis on "cleanliness" of propane,
similar to that required for gasoline for fuel-injected cars.
Several OEMs have expressed concern for the m a x i m u m
sulfur contents of "HD5" propane, although typical sulfur
contents are significantly less than current specification levels. These are now higher than some reformulated gasoline
specifications (RFG) This is a potential area of future
research and standardization.
The use of a sulfur containing odourant (ethyl mercaptan)
adds u p to 30 p p m w sulfur to propane, which is significant
with respect to future RFG regulations. This is another area
of recommended research and standardization.
There is an opportunity for LPG fuels to compete favorably, and even preferentially in future "clean fuels" markets,
especially if factored into future engine/drivetrain design.

LPG could be an ideal fuel for emerging micro-turbine applications a n d high-temperature partial oxidation (POx) fuel
cells. LPG can be produced in high purity and low sulfur that
may be necessary for these applications.
LPGSAFETY AND HANDLING
LPG F l a m m a b i l i t y
Propane is flammable in the a t m o s p h e r e at ambient
conditions between about 2-9.5 vol%, the Lower and Upper
Explosive Limit (LEL a n d HEL), respectively. This corresponds to about 0.3 psia peirtial pressure for the LEL, and
about 1.4 psia partial pressure for the HEL. LPG is normally
handled at pressures m u c h higher than this. LPG must be refrigerated to less than 100C before the equilibrium vapor
pressure enters the explosive range. This is virtually unattainable in normal operations and would only be a concern in
some research or specialty applications. Thusly, physical
mixtures of gases, especicdly in air, is always more important
for LPG t h a n "flash point" considerations.
Flammability is not a fundamental or t h e r m o d y n a m i c
property of any material. It depends upon the circumstances
at the time, including gas mixture, temperature, pressure, ignition energy, turbulence, aerosol, catalyst and even the nature of the surface and shape of the containment vessel. The
lower explosive limit is less sensitive to these effects than the
higher explosive limits. For example, the LEL is almost totally insensitive to the a m o u n t of "diluent" gas added [90,91].
The HEL is the most impacted with dilution by inert gas, essentially decreasing almost linearly to near the LEL at about
40-50% dilution (10-13% oxygen vs. 2 1 % undiluted). The
flammable envelope terminates at the point that the HEL
meets the LEL.
The explosive envelope tends to enlarge at higher temperatures, but again more on the HEL side vs. the LEL side. The
change in LEL is in fact quite small, with only an 8% relative
change in LEL with a 100C increase in temperature from
ambient [92].
In general, it appears that any increase in temperature,
pressure, gas composition, ignition energy, or configuration
has a m u c h more profound effect on the HEL than the LEL.
Use of the LEL determined at ambient conditions can reasonably be expected to apply over a very wide range of conditions in typical LPG handling situations. This is not true for
the HEL, which varies widely with similar changes in gas
composition, temperature, and pressure.
LPG H a n d l i n g
Most jurisdictions require that persons involved with the
handling or transport of LPG or installing LPG equipment
be trained and licensed. This generally does not include final connection of portable cylinders to consumer appliances
using approved fittings, but usually does include filling
of the portable cylinders or automobiles at the point of retail sale.
LPG, like any fuel, is safe if properly handled. It has a relatively n a r t o w explosive range, so explosions are rare. However, spills and fires are similar to other volatile fuels and
solvents. Certain properties of propane should be understood

CHAPTER
to p r o m o t e safety in handling the fuel, and a p p r o p r i a t e
responses in the event of a spill or emergency response.
LPG vapor is about 50% heavier t h a n air (molecular weight
44 versus 29). Vapors will tend to settle in low points and cavities in the absence of a ventilating air flow. Propane/air mixtures have densities closer to air, and are more easily mixed
and dispersed from thermal or a m b i e n t air currents. For
example, a mixture of one volume of propane vapor (MW 44)
diluted 9:1 with air will only be 5% heavier than air (about
the same relative difference as sea water a n d fresh water). It
will still be above the explosive range, but will be prone to
dispersion from ambient air currents. The heavier than air
vapor density allows a potential and usually temporary pooling. Leaking gases tend to exit from high-pressure sources at
a sufficient velocity to stir the air mass and cause mixing.
They will only tend to accumulate in low spots only in very
quiescent conditions.
When propane or propane/air mixtures (above the HEL)
collect in low spots, there will cilways be an interface at the
top of the vapor pool that is in the flammable range. This will
b u m very similarly t o any other flammable liquid. A very
good safety demonstration is to fill a tall (high 1/d) nominal
500 m L beaker with pure LPG vapor, and leave it open in full
view for the duration of the training session. When asked after several hours, most attendees generally believe that the
"volatile gas" has escaped and is rapidly dispersing itself
through the cosmos. However, lowering a match slowly below the rim convinces everyone that not very much gas has
escaped, a n d for approximately the next 15 s, you can see the
flame level drop in the beaker, as the pool fire consumes the
propsme. This is a "worst case" demonstration, as ambient air
currents cannot penetrate and mix a tall vessel very far. However, it does serve to show that propane rich pockets of gas
can be stable for hours, days, and even weeks in the absence
of strong wind or air currents of a velocity sufficient to mix
the ambient atmosphere. It is important to vacate and properly ventilate an enclosed area that may have been subject of
a propane leak in the absence of ventilating airflow.
Small liquid leaks can turn large volumes of area into explosive mixtures under "ideal" circumstances. At room temperature, one liquid liter of propane expands to about 240
Liters of gas, which at 2% LEL is sufficient to create 12 000 L
of explosive atmosphere. It takes only a small liquid leak to
create a n explosive atmosphere in a confined area, if the
propane becomes well mixed. Since the entire system is under pressure, leaks can occur even when equipment is idle,
and collect over a long period of time.
Gas-Air mixtures may be brought below the flammable
limit by dilution with large volumes of non-flammable gasses
such as nitrogen, carbon dioxide, steam or air [93] (see
flammability above). Some precautions should be taken to
prevent ignition by static discharge with some CO2 fire extinguishers. A gas inerted area may still present an asphjrxiation
hazard. The rapid venting of gas and especially of gas/liquid
aerosols can create static chcirging situations. As a result, ignition of vented "vapors" can occur at any time, depending
u p o n circumstance.
Gas mixtures inside of the flammable region do not "bum"
like a pool fire. They forcefully explode, generating a shock
wave a n d a sharp "firecracker" type of sound. The largest energy release is when the mixture is at stoicheometric, and the

2: LIQUEFIED

PETROLEUM

GAS

53

potential of the resulting explosion is at its most powerful


point. A one foot (25 cm) diameter round balloon filled with
a stoicheometric mixture will provide a bang loud enough to
startle m o s t people in a typical small training room. The
same bcJloon filled with p u r e propane vapor (no air) will produce a fireball that will rise 6-8 feet. A larger balloon will
leave a black scorch mark from the pool fire on the ceiling
(measure carefully, do your safety checks, and have a fire
extinguisher at hand).
The flammability of n e a r explosive mixtures has not been
extensively studied in the presence of a stable combustion
source. Witness descriptions and injuries indicate that very
large h e a t energy releases are possible in n e a r explosive
atmospheres.
Very few people have ever seen liquid propane. It is a clear
colorless liquid that can easily be mistaken for water under
certain circumstances, particularly in cold weather. When
propane liquid is sprayed into a collection container, only a
portion of the liquid initially vaporizes^just enough to provide the heat of vaporization and cool the remaining liquid
down to the 42C boiling points at ambient pressure. For
example, if liquid propane at 70F is sprayed into a collection
container, only about 40 wt% of the propane will vaporize,
and the majority will be collected as a liquid in the container.
The lower the starting temperature, the higher the yield of
liquid. Propane liquid must be over 200F (near the critical
point) before all of the propane will vaporize upon flashing to
ambient pressure.
Once collected, the liquid propane in the open container
will stay at its boiling point, and boil at a rate determined
by the heat transfer into the container. If the container is
made of a material that is a good insulator, such as a plastic cup or pail, it can take several hours for the liquid
propane to evaporate even at high ambient temperatures.
Under stagnant air conditions, the heavier than air cold vapor itself provides additioned insulation as it spills over the
top of the container. If the container is metal, then the boiling rate is generally very high initially, until a layer of accumulated ice or frost provides some insulation. If a spill occurs at low temperature onto frozen ground or snow, the
resulting liquid pool can be persistent for hours. If the spill
occurs at r o o m temperature onto a concrete floor, the evaporation rate is extremely fast. Liquid propane at room temperature on a horizontal surface tends to exhibit the
"Liedenfrost effect" where the liquid behaves like water
droplets bouncing on the top of a hot stove, essentially riding on its own rapidly forming vapor. A spill under such circumstances, for example a severed hose or inadvertently
opened valve, can barely leave time for occupants to vacate
the area. Some jurisdictions require "excess flow" valves on
consumer cylinders to limit the flow rate of a free flowing
propane discharge in the absence of a backpressure.
Any propane or BP mix liquid at atmospheric pressure has
a normeJ boiling point that is far below the freezing point of
water (and flesh and skin) and can cause "frost bite" or freezing "bums." Many a finger has been superficially frozen with
LPG liquid inadvertently sprayed inside of a difficult to
remove glove.
The rapid removal of vapor from a tank will cause the
remaining liquid in the tank to sub-cool. For example, in the
"worst case," if the valve is opened wide venting to the atmo-

54

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

sphere at 70F, the hquid will cool down to the boiling point
(-42C) after about 40 wt% of the liquid has vaporized. High
appliance demand and rapid vapor withdrawal rates generally results in a large amount of condensation or frost accum u l a t i o n on the exterior of the c o n t a i n e r due to this
refrigeration effect.
LP-Gas vapor upstream of the regulator can condense to a
liquid if the lines external to the tank are at a lower temperature than the tank, and this requires special attention to detail, especially in cold climates. For example, during snap
cool situations, outside vapor lines cool down faster than the
bulk storage tank, due to the higher thermal mass of the tank.
The higher storage tank pressure causes condensation of liquid propane in the vapor lines. This can result in vapor lines
becoming filled with condensed liquid propane under snap
cool conditions.
Propane has a m u c h higher coefficient of thermal (and
pressure) expansion than other hydrocarbon fuels. Heating
an overfilled propane vessel can result in thermal expansion
of the liquid until the cylinder is fully liquid filled (the vapor condenses as the liquid expands). Very high pressures,
exceeding several thousand psi, can be generated with further heating and liquid expansion in a liquid filled ("hydraulically locked") cylinder. Pressure safety vents will generally prevent this, b u t the resulting leak of liquid can
become a fire hazard. All transportation codes require cylinders to be only partially filled for this reason, but it is not
commonly appreciated that this is relative to a reference
temperature (traditionally 80vol% fill at 60F). This protects
against hydraulic lock u p to over 140F for liquid fill at
60F. If the cylinder is filled at a temperature lower than
60F, it may be necessary to further reduce the fill density
for storage and transport. Consult the authority having jurisdiction for the applicable requirements.

LPG S a m p l e C y l i n d e r A p p r o v a l s
Consult the Authority having Jurisdiction for pressure vessel
certification r e q u i r e m e n t s for LPG sample cylinders (US
DOT in United States and Transport Canada in Canada). At
present there is no international approval process for pressure cylinders. Authorities in adjacent or other jurisdictions
m a y not approve cylinders approved in one jurisdiction.
Cylinders must be approved in all the jurisdictions in which
they are used for sample transport. Cylinders approved by the
Authority having Jurisdiction u n d e r "equivalent level of
safety" criteria are acceptable provided that they are used in
accordance with the applicable permits or exemptions. For
example, users may not subsequently alter valves or pressure
venting devices that are part of a permit or exemption. Periodic cylinder inspections may be required [94].
LPG E x p o s u r e
The health effects caused by exposure to LP Gases are much less
serious than its fire and explosion risk. LP gases at low concentrations are non-toxic, and liquids have limited ingestion routes
due to the physical properties of the materials. The Occupational Exposure Limits (GEL) are based mostly on the need to
avoid the explosive hazards by a wide margin. This is t5^ically
20% of the LEL or lower, which is a much lower level than
would be set for short or long term toxicity, or Eixphyxiants.

LP Gases at very high (explosive) concentrations are believed to be non-toxic, fast acting anaesthetic agents, as well
as being simple asphj^iants. The terminology "propane narcosis" is sometimes used, but this is not accurate. Narcotics
generally refer to drugs that act at opiate receptor sites,
which is not where general anaesthetic gases act. However,
the term "narcosis" is quite generic. The c o m m o n definition
is "to put to sleep, partially or totally" due to a general depression of the Central Nervous System (CNS), even though
sleep, anaesthesia and narcotics are distinctly different in
medical terms. There are some early references to LP gas
being tried or used as a medical anaesthetic, and one of the
LPG patent claims by F.P Peterson in 1914 was for use "in
surgery as an anesthetic" [95]. However, only cyclopropane,
nitrous oxide, ethers, and various halocarbons were used
clinically as anaesthetic gases, usually in combination with
other drugs.
Persons exposed to high levels of LPG gas and experiencing CNS depression effects are in a very dangerous
situation, since they are breathing explosive gas mixtures.
Any ignition source could produce a fire or explosion, resulting in injury or death. Individuals vary widely in their
susceptibility and tolerance to these effects. At high concentrations, the effects of narcosis and h3^oxia will be confounded, as they are outwardly similar in many respects,
and will occur simultaneously. There is a range of symptoms with increasing concentration from the onset of CNS
effects, hypoxia, and asphyxiation: disorientation, lightheadedness, dizziness, drowsiness, loss of physical coordination, impaired judgment, drunkenness, unconsciousness,
and death.
The CNS effect is believed to be dependent upon the concentration of the gas in the lipid bi-layer (cell wall m e m brane) of nerve cells. Different gases would be expected to
have a different potency, and require higher or lower exposures to obtain the same CNS effect. The relative solubility of
different gases in olive oil (surrogate for lipid), water (surrogate for blood), can be compared to a very wide range of
materials that have well known physiological responses. By
this method, the onset of einaesthetic effects is estimated to
be n e a r the lower explosive limit (2%) for butane, a n d
about twice the LEL (4%) for propane. Iso-butane causes
drowsiness in a short time in concentrations of 1%, with no
apparent injuries from i-C4 or n-C4 after 2-hour exposure at
concentrations u p to 5% [96].
The rapidity of both the onset and recovery of CNS effects
from gas exposure depends upon the speed at which the gas
is transported into and out of the body. This is dependent
upon the concentration of the gas in air, the breathing and
blood circulation rate, and the relative solubility of the material in lipid (oil) and blood (water). Gases with low water
(blood) solubility and high oil (lipid) solubility tend to be the
fastest acting. The large volume of blood/water in the body
tends to act as a "buffer" for water-soluble compounds, slowing accumulation and depletion from the nerve cells. The solubility properties of LPG lie close to cyclopropane, between
those of nitrogen and nitrous oxide/diethyl ether, where the
rates are well known. Cyclopropane anaesthetic, which is 4-5
times more soluble in water than propane, is not altered or
combined in the body; the major part is exhaled within 10
min, while full desaturation takes several hours [97]. LPG
exposure above the explosive limit would be expected to in-

CHAPTER
duce CNS effects quickly, certainly in less than 15 min, and
probably in less than 5 min.
Persons installing new equipment, flushing lines, repairing,
or re-lighting appliances, or investigating gas leaks are also
the most likely to be exposed to high LP-gas concentrations. A
Consumer Products Safety Commission (CPSC) study noted
that new LPG installations are more prone to accidents than
new natural gas installations and sponsored a n u m b e r of studies relating to LPG odorization [98]. While the lighter than air
density and higher LEL of methane are undoubtedly major
factors, the CNS effects may help explain the occasionally
bizarre circumstances of some LPG accidents.
The knowledge of possible impairment can be critical in
making decisions effective in reducing the accident rate. For
example, a person flushing a line might realize the need to
take a fresh air break instead of a "smoke" break, or ventilate
the area if it is u n d e r s t o o d t h a t the light-headed or tired
feeling may be due to explosive gas concentrations.
Anaesthetics also sensitize the myocardium to the effects
of epinephrine. Cardiac a r r h y t h m i a can occur when very
high concentrations of LP gases (above the HEL for propane)
are inhaled when the epinephrine level is elevated (e.g., anxiety, exertion) cind possibly during hypoxic conditions. Ccirdiac arrhythmia can have a sudden onset even with brief
exposures a n d may result in sudden death. This is an extreme
condition that is usually associated with substance abuse
(commonly called "huffing"). Similar problems have been reported in the nitrous oxide bottle gas industry. Additional
information is available on the web site of the Compressed
Gas Association [99].
LPG Odorization
LPG odorization requirements reside in different jurisdictions in different countries. The U.S. requirements are not in
the ASTM D1835 specifications, but in NFPA 58 and 19 CFR,
and State Regulations. Canadian requirements are in the
CGSB LPG product specifications that are referenced in various Provincial and Federal Regulations.
Historically, manufactured gas was odorized as a warning
aid due to the risk of carbon monoxide poisoning. Manufactured gas often contained high levels of CO, which was a
higher risk than flammability. Over time, a variety of matericils, including mercaptans, acetylene, and mixed refinery sulfides were used as odoureints. LPG production from sweet
natural gas wells had no olefins and a low sulfur content, so
had a n intrinsically low odor. Initially, there was no requirement to odorize gas distributed for fuel purposes, as it was
non-toxic relative to manufactured gases. However, a number of fires and explosions with non-odorized natured gas and
LPG highlighted the need to odorize as a warning aid to detect leaks. LPG odorization is now a regulated requirement in
all North American jurisdictions.
Natural Gas Euid LPG odorization has been the subject of
substantial product liability litigation, stretching over several
decades of work on the technical, political, and legcd issues
involved. These are summarized in a series of IGT sponsored
technical symposia [100], CPSC, GPA, NPGA, PGAC, and
BERC sponsored rescEirch, as well as transcripts of various
product liability cases. Current North American Odorization
practices are based on 1977 BERC smalysis [101] indicating
ethyl mercaptan (EtSH, or EM) to be a preferred odorant

2: LIQUEFIED

PETROLEUM

GAS

55

over tetrahydrothiophene (THT). N u m e r o u s other studies


continue to indicate the EtSH remains the odorant of choice,
particularly for cold climates, where the relatively high
volatility of EtSH is the closest to that of propane at low temperature [102]. The volatility of E t S H and other potential
odorants has been extensively studied and reported in IGT
and GPA research reports.
Odorants are not effective wEiming agents in all cases.
Propane vapor is heavier than air and initially tends to settle Eind accumulate in low points and cavities. Persons in
the vicinity of low points and cavities may not be exposed to
localized gas pockets, b u t m a y b e at risk from an ensuing
fire or explosion. S u b s e q u e n t diffusion or convection
can distribute LPG vapors t h r o u g h o u t a n area. Certain
odorants are polar and/or chemically reactive, and can be
depleted by reaction or adsorption. People differ in their
ability to smell, and the sensitivity to odors generally decreases with age or with impaired physical conditions such
as colds or respiratory allergies. Prolonged exposure to
odorants can cause olfactory desensitization. Other odors or
distractions can reduce the effectiveness of odorants as
warning agents [103].
Mercaptan odorants are susceptible to oxidation u n d e r
certain conditions, especially at high temperature and in the
presence of water, oxygen, or high oxidation state (red) rust
[3]. This is commonly referred to as "odorant fade"[103]. It is
now genercdly accepted that propane tanks in continuous service do not experience odorant fade since there is no source
of oxidant [104,105,106]. Much industry activity continues to
focus on identifying a n d eliminating situations that can
result in odorant fade. In general there is a m u c h higher
awareness in the industry for the detrimental effects of air,
rust, and water in pressure vessels [107-109].
Recent changes to rail car pressure vessel certification requirements provide another opportunity to further reduce
the use and occurrence of steam cleaning and hydrotesting of
large pressure vessels (truck/rail). Work is ongoing in this
area and several programs are being planned.
Odourants can be partially or fully removed by absorption,
for example in cases where the LPG has permeated through
clay-like soils that have high surface absorption capacity.
GPA, ASTM, and CGSB have developed field tests for
mercaptan odorants using stain tubes, and this allows reliable semi-quantitative monitoring of odorant levels during
distribution. ASTM D 6273-98 Standard Test Method for Natu r a l Gas Odor Intensity (odor m e t e r "sniff test") can be
applied to LPG as well natural gas. These are not necessary
for monitoring odourization equipment, as verification of
proper tj'pe and quantity of odourant can be done by a variety of means. These include measures of weight, volume,
injection pulses, on-line analysis, calibrated "day pots," etc.
and these features are generally included in commercially
available odorant injection systems. An NPGA/PGAC Joint
Task Force on LP-Gas Odorization developed a set of recommendations in 1991 to assist in their desire to improve LPG
safety. All producers and terminal operators w h o odorize LPGas should establish formal, rigid procedures and responsibilities for proper odorization [110]. These sire advisory in
n a t u r e a n d compliance is voluntary. I n d e p e n d e n t crosschecks have found to be effective to detect several "single
fault" injector system failure m o d e s that could otherwise
have gone unnoticed [111].

56

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

USES OF LPG
Industrial
fork lifts, indoor carburetor engines (floor sweepers, washers, etc.)
oxy/propane cutters, heating/annealing, high pressure
welding
"plumber" torches, portable soldering irons, small torches
hand torches (pallet shrink wrap, localized heating/burning)
worksite heating/ventilating (lineman's tents, below grade
sites)
refrigeration (compressor cycle), evaporation, or specialty
(vap pipes)
pavement heating for grinding/recycling, roofing tar
heating
ground thawing, ice/snow melting, concrete heating, etc.
propellant for aerosol sprays, cosmetics, shaving cream,
perfumes, etc.
propellant for paint sprayers, paint airbrush (including PB
mix)
solvent for cleaning, reaction, diluent/chilling, precipitation
remote "smart" gen sets with remote start/stop, telemetry
integrated standalone packages (power generation, ventillate, heat/cool)
portable soil/trash reclamation, sterilization
jackhammers (construction road work)

portable generator sets (fixed on larger RVs)


golf carts, maintenance equipment, turf and lawn mowers
pyrotechnic/flame special effects
Aviation
airport r a m p equipment (i.e., airstairs, luggage tugs, etc.)
12/24 Vdc piston engine pre-heat (indirect fire)
hot air balloon
Marine
LPG powered "jet" boats
"overslung" barbecue/cooking
Emergency
standby generators, compressors, heat/cool
stable long term emergency fuel supply
Mining
mineshaft ventilation air heating
mine site cookhouse stoves, quarters heating
water pumps to liberate coal seam methane
Medical

Power

cyclopropane anesthetic
microturbine and distributed power systems
stationary generators
standby fuel for gas interruptible supply

Transportation
autopropane (conversions) and OEM
cargo heaters, engine coolant pre-heaters, ice removal
heavy duty truck alternate fuel (fumigation and OEM)
hydrocarbon fuel for reforming fuel cell applications
retrofit of small engines to tighter emission standards
utility right of way maintenance
micro-turbine hybrid vehicles
Agriculture
grain drying, bam/brooder heaters, orchard heaters, weed
control
general shop heat/power/oxy welders, etc.
Colorado Potato Bug eradication, potato guns
farm animal m a n u r e dehydration/sterilization (esp. swine/
chicken)
weed control as alternative to herbicides to control runoff
"scare crow" devices
irrigation water pumps
Utility

Gas

bulk or refrigerated storage for peak shaving in NG systems


bulk vaporizer, distribution of LPG like NG

Acknowledgments
The author acknowledges review and significant technical input from Dr. H. ICing, ExxonMobil Research (hydrates), John
Jachura (VCF/density), Dr. D.Y. Peng (Peng-Robinson EOS),
Dr. H.J. Ng, DBRA Research Associates (Ng-Robinson EOS,
hydrates), Larry. R. Robertson, DaimlerChrysler (autopropane), Alex Spatura, Adept Group, (autopropane a n d
extensive review), Ian Drummond, lOL Industrial Hygiene
(exposure/CNS), Dr. Byrick, Uof Toronto (CNS), Dr. Roth,
University of Calgary (CNS), Nancy Bourque, lOL Research
Library (literature and patent searches), Tim Eaton, Superior
Propane Inc.(uses). Thanks to Mark Sutton and Ron Brunner
(GPA) for access to draft publication TP16 on history of LPG
specs (hopefully to continue to publication). Special thanks
to Ron Cannon (GPA, retired) for input, review, and liberal
reference to his excellent book "The Gas Processing IndustryOrigins and Evolution." This is highly recommended
reading for anyone in the industry, and a good book for both
libraries and reception areas.
The author acknowledges the support of Imperial Oil Ltd.
for the information/communications resources used in the
preparation of this chapter.

Residential
cooking, heating, clothes drying, hot water
catalytic/radiant/pipe radiant heaters, mantel lights
h o m e barbeques, refillable lighters, hair curlers, b b q
lighters
fixed installation mobile home heating/cooking
Recreation
mobile RVs/trailers cooking/heating, absorption cycle
refrigeration

REFERENCES
[1] Tiratsoo, E. N., Natural Gas, Scientific Press Ltd, London,
1967, p. 20.
[2] Redwood, B.,A Treatise on Petroleum, S'^ ed., Charles Griffon &
Company, Ltd., London, Lippincott, Philadelphia, 1926, pp. 82,
219.
[3] Tiratsoo, E. N., Natural Gas, Scientific Press Ltd, London,
1967, p. 20.

CHAPTER 2: LIQUEFIED PETROLEUM GAS 57


[4] Redwood, Sir Boverton, A Treatise on Petroleum, 5th ed.,
Charles Griffon & Company, Ltd., London, Lippincott,
Philadelphia, 1926, p. 1.
[5] Purdy, G. A., Petroleum, Prehistoric to Petrochemicals, Copp
Clark Publishing Co., Toronto, 1958, p. 96.
[6] Purdy, G. A., Petroleum, Prehistoric to Petrochemicals, Copp
Clark Publishing Co., Toronto, 1958, p. 27.
[7] Redwood, Sir Boverton, A Treatise on Petroleum, 5''' ed.,
Charles Griffon & Company, Ltd., London, Lippincott,
Philadelphia, 1926, p. 77.
[8] Railroad Commission of Texas, Austin, TX, Available:
http://www.rrc.state.tx.us/history/hist.html.
[9] Handbook Butane-Propane Gases, First ed., G. H. Finley, Ed.,
Western Gas, Los Angeles, 1932, p. 16.
[10] Handbook Butane-Propane Gases, First ed., G. H. Finley, Ed.,
Western Gas, Los Angeles, 1932, p. 11.
[11] Little, A. S., "Blaugas in the United States of America," Gas
World, Vol. 60, pp. 563-4.
[12] Handbook Butane-Propane Gases, First ed., G. H. Finley, Ed.,
Western Gas, Los Angeles, 1932, pp. 10,11,18.
[13] Cannon, R. E., "The GAS Processing IndustryOrigins and
Evolution," Gas Processors Association, Tulsa, OK, 1993, p. 61,
Available: http://www.gasprocessors.com/default.asp, March
7, 2002.
[14] Cannon, R. E., "The GAS Processing IndustryOrigins and
Evolution," Gas Processors Association, Tulsa, OK, 1993, p. 64,
Available: http://www.gasprocessors.com/default.asp, March
7, 2002.
[15] Cannon, R. E., "Liquefied Petroleum Gas Quality/Quality Control," GPA Draft Technical Publication TP23, Gas Processors
Association, Tulsa, OK, 1999, p. 8.
[16] Cannon, R. E., "The GAS Processing IndustryOrigins and
Evolution," Gas Processors Association, Tulsa, OK, 1993, p. 80,
Available: http://ww.gasprocessors.com/default.asp, March 7,
2002.
[17] "About Propane Gas," Available: http://www.propanegas.com.
Energy Source Inc., Feb. 20, 2003.
[18] Snelling, W. O., "Process of Refining Natural-Gas Gasoline,"
U.S. Patent 1,056,845, U.S. Patent and T r a d e m a r k Office,
Washington, D.C., Mar. 25, 1913.
[19] "Liquid Gas Made by M o d e m Prometheus," including reprint
from Pittsburgh Sunday Post, Sept. 8, 1912, Butane-Propane
News, June 1999, p. 22.
[20] Chapter 1, Handbook Butane-Propane Gases, First ed., G. H.
Finley, Ed., Western Gas, Los Angeles, 1932, p . 16.
[21] Peterson, F. P., "Art of Condensation of Gases and Vapors into
their Liquid Forms," U.S. Patent 1,031,664, U.S. Patent and
Trademark Office, Washington, D.C., 1912.
[22] Peterson, F. P., "Gas," U.S. Patent 1,094,864, U.S. Patent and
Trademark Office, Washington, D.C., 1914.
[23] Cannon, R. E., "The GAS Processing IndustryOrigins and
Evolution," Gas Processors Association, Tulsa, OK, 1993, p. 28,
Available: http://www.gasprocessors.com/default.asp, March
7, 2002.
[24] Cannon, R. E., "The GAS Processing IndustryOrigins and
Evolution," Gas Processors Association, Tulsa, OK, 1993, p.
113, Available: http://www.gasprocessors.com/default.asp,
March 7, 2002.
[25] Legatski, T. W., "The Properties of Liquefied Petroleum Gases
as Affecting Specifications with a Discussion of the Problem of
Odorization," Proceedings of the NGAA Convention, Tulsa, OK,
1932.
[26] Cannon, R. E., "The GAS Processing IndustryOrigins and
Evolution," Gas Processors Association, Tulsa, OK, 1993, p. 74,
Available: http://www.gasprocessors.com/default.asp, March
7, 2002.
[27] http://v\rww.bpnews.com, Feb. 18, 2003.
[28] http://www.npga.org, Feb. 18, 2003.

[29] http://www.cganet.com, Feb. 18, 2003.


[30] Peng, D. Y., Professor of Chemical Engineering, University of
Saskatchewan, co-author of the Peng-Robinson Equation of
State, personal communication.
[31] Miller, W. A., Elements of Chemistry, Theoretical and Practical,
Vol. I, 3rd ed., J. W. Parker and Son, London, 1867, p. 328.
[32] Kuenen, J. D., Theorie der Verdampfung und Verflussigung
von Gemischen, E a r t h Verlag, Leipzig, 1906.
[33] Podbielniak, Walter J., Ph.D. Thesis, Chemical Engineering
Department, University of Michigan, 1928.
[34] Cannon, R. E., "The GAS Processing IndustryOrigins and
Evolution," Gas Processors Association, Tulsa, OK, 1993, p.
167, Available: http://www.gasprocessors.com/default.asp,
March 7, 2002.
[35] Kolayashu, R. and Katz, D. L., "Vapor-Liquid Equilibria for Binary Hydrocarbon-water Systems," Industrial and Engineering
Chemistry, Feb. 1953, p. 440.
[36] Engineering Data Book, Gas Processors Supply Association
(GPSA); Technical Standards a n d Research Reports, Gas
Processors Association (GPA). Available http://www.gasprocesssors.com/default.asp, March 7, 2002.
[37] GPA research reports and c o m p u t e r programs. Available
http://www.gasprocessors.com/default.asp, March 7, 2002.
[38] Robinson, D. B., Ng, H. J., DBR Software, Available: www.
dbra.com/Engineering_Software/sm_introduction.htm,
Feb. 18,2003.
[39] Gas Processors Supply Association (GPSA), Engineering Data
Book and GPA Technical Standards and Research Reports,
http://www.gasprocessors.com/default.asp, March 7, 2002.
[40] Cannon, R. E., Liquefied Petroleum Gas Quality/Quality Control, Draft GPA Technical Publication TP-23, Gas Processors
Association, Tulsa, OK, 1996, p. 6.
[41] Handbook Butane-Propane
Gases, Vol. 1, 6th ed., ButaneP r o p a n e News, Inc., Arcadia, CA, 1983, p. 5, Available:
http://www.bpnews.com.
[42] Sutton, C , Cannon, R. E., "The Evolution of LP-Gas Specifications," Presented at a Joint Meeting of the Canadian Natural
Gas Processing Association and Propane Gas Association of
Canada, Calgary, Alberta, Sept. 9, 1977., p. 2
[43] Cannon, R. E., Liquefied Petroleum Gas Quality/Qusdity Control, Draft GPA Technical Publication TP-23, Gas Processors
Association, Tulsa, OK,
[44] Sutton, C. and Cannon, R. E., "The Evolution of LP-Gas Specifications," presented to a Joint Meeting of the Canadian Natural Gas Processing Association and Propane Gas Association of
Canada, Calgary, /Uberta, Sept. 9, 1977, p. 2.
[45] ASTM c o m m i t t e e D02-H meeting minutes, 1998, 1999,
ASTM International, West Conshohocken, PA, Available:
www.astm.org.
[46] Falkiner, R. J., Pickard, A. L., et al., "Sampling and Shipping
Liquid Propane," presented at t h e IGT Odorization
Symposium, Chicago, IL, 1998.
[47] Shanerberger, E., Ford Motor Company (ret.), ASTM
Committee D02-SCA, 2001, personal communication.
[48] Kubesh, J., King, S., and Liss, W., Effect of Gas Composition
on Octane N u m b e r of Natural Gas Fuels, SAE #922359, Society
of Automotive Engineers, Warrendale, PA, 1992.
[49] Callahan, T., Kakockzi, R, et al., "Engine Knock Rating of
Natural GasesExpanding the Methane Number Database,"
ASME Proceedings, ICE-Vol. 27-4, Book No. G l O l l D ,
American Society of Mechanical Engineers, NY, 1966.
[50] Hewitt, J., "Finding a Premium for Propane," Propane Vehicle,
Oct. 1998, p. 17.
[51] Hewitt, J., "Quality Begins with an 'H'," Propane Vehicle, June
1998, p. 17.
[52] Brasil, T, et al., "Proposed Amendments to the Specification for
LPG used in Motor Vehicles (Staff Report and Initial Statem e n t of Reasons)," California Air Resource Board (CARB) Sta-

58 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


tionary Source Division, October 1998, Available: http://
www.arb.ca.gov/regact/lpgspecs/isor.pdf.
[53] "CARB to Require HD-10 Propane Spec for Motor Fuel Use,"
Butane-Propane News, November 1998, p. 17.
[54] Sutton, C. a n d Cannon, R. E., "The Evolution of LP-Gas
Specifications," presented at a Joint Meeting of the Canadian
Natural Gas Processing Association and Propane Gas Association of Canada, Inc., Calgary Alberta, Sept. 9, 1977.
[55] Cannon, R. E., Liquefied Petroleum Gas Quality/Quality Control, Draft GPA Technical PubUcation TP-23, Gas Processors
Association, Tulsa, OK, 1999, p. 18.
[56] ASTM Manual on Significance of Tests for Petroleum Products,
MNL 1, 5 * ed., G. V. Dyroff, Ed., ASTM International, West
Conshohocken, PA, 1989.
[57] Cannon, R. E., Liquefied Petroleum Gas Quality/Quality Control, Draft GPA Technical Publication TP-23, Gas Processors
Association, Tulsa, OK, p. 23.
[58] Cannon, R. E., Liquefied Petroleum Gas Quality/Quality Control, Draft GPA Technical Publication TP-23, Gas Processors
Association, Tulsa, OK, 1999, p. 30.
[59] Aviation Fuel Properties, Coordinating Research Council Docu m e n t No. 530, 1983, Available: Society of Automotive
Engineers, www.sae.org/servlets/index, Feb. 18, 2003.
[60] H a c h m u t h , K. H., "Dehydrating Commercial Propane,"
Butane-Propane News, Jan. 1932.
[61] Davidson, D. W., Water: A Comprehensive Treatise, Vol. 2, F.
Franks, Ed., Plenum Press, NY, London, 1973, p. 115.
[62] Sloan, H. A., "The Phase Behavior of the Propane-Water System: A Review," Canadian Journal of Chemical
Engineering,
Vol. 68, Feb. 1990.
[63] Smelik, E. A. and King, H. E. Jr., "Crystal Growth Studies of
Natural Gas Clathrate Hydrates Using a Pressurized Optical
Cell," American Mineralogist, Vol. 82, 1997, p p . 88-98.
[64] Gas Processors Association, Research Reports, Available:
www.gasprocessors.com/default.asp.
[65] Suess, E., B o h r m a n n , G., et al., "Flammable Ice," Scientific
American, Vol. 281, No. 5, Nov. 1999, p. 76.
[66] "Application of Proprietary Kinetic Hydrate Inhibitors in Gas
Flow Lines," OTC 11036, Offshore Technology Conference,
Houston, May 6, 1999.
[67] "Plain Facts about Freezing Regulators," Technical Bulletin
LP-24, Fisher Controls, McKinney, TX, Available: www.fishercontrols.com, Feb. 18, 2003.
[68] "Concentration Properties of Aqueous Solutions: Methanol
Table 32," CRC Handbook of Chemistry and Physics, 75th ed.,
CRC Press, Cleveland, OH, p. D231.
[69] CAN/CSA B149.2-00: Propane Storage and Handling Code, Appendix A.4.2, "Moisture Removal," Canadian Standards Organization, CSA International, Available: csa-intemational.org.
[70] Fig. 20-52, Engineering Data Book, 11th ed.. Vol. 2, GPSA, Gas
Processors Suppliers Association, 1998, Available: http://www.
gasprocessors.com/gpsabook.html.
[71] H a c h m u t h , K. H., "Dehydrating Commercial P r o p a n e , "
Butane-Propane News, Jan. 1932.
[72] http://www.shawmeters.com, http://www.panametrics.com,
http://www/meeco.com
[73] Ardis, M., "Moisture Sensors for Process Organic Liquids, Sensors," Helmers Publishing Inc., Peterborough, NH, Nov. 1988.
[74] Mychajliw, B. J., "Determination of Water Vapor Content in
Natural Gas," IGT Symposium on Natural Gas Odorization,
Natural Gas Quality and Energy Measurement, Chicago, IL, July
26-28, 1999.
[75] Roberson, R., "New Low Range Pipeline Dew Point Detector
Tube," Acadiana Flow Measurement Society (ASMS), April
1998, Sensidyne, Inc.
[76] Pybum, C. M. and Lennox, R. K., "The Effect of Sulfur Compound Interactions on the Copper Corrosion Test in Propane,"

[77]
[78]

[79]

[80]
[81]

[82]

[83]

[84]

[85]

[86]

[87]

[88]
[89]
[90]

[91]

[92]

[93]
[94]

[95]
[96]
[97]

presented at the 57th Annual GPA Convention, Mar. 20-22,


1978.
"The Occurrence of Magnetic Residues in Vehicle Propane
Tanks," Sept. 2002, Available: http://www.propanegas.ca
Hohenberg, E. G., "The Occurrence of Magnetic Particulate
Residues in Vehicle Propane Tanks," M.Sc. Thesis and report
to the PGAC Residue and Odorant Committee, University of
Manitoba, 1992, Available: http://www.propanegas.ca.
Operational Reference Note #173 "Recommended Procedures
for Placing Interchangeable Anhydrous Ammonia," and Operational Reference Note #172 "Recommendations for Preventing A m m o n i a C o n t a m i n a t i o n of LP-Gas," NPGA Technical
Publications T122, T123, Available: www.npga.org.
"Suggested Field Tests for Contamination in Propane," NPGA
#151-99, Available: www.npga.org.
Goetzinger, J. W. and Ripley, D. L., "Final Report Effect of
Ammonia on LP-Gas Odorant," Research Report NIPER/BDM0220, prepared for the U.S. DOE Bartlesville Project Office,
Available from the Gas Processors Association, http://gasprocessors.com.
Pickard, A. L., Chairman, PGAC Residue and Odorant Committee (ret.), submitted to the Canadian General Standards
Board (CGSB) committee o n Gasoline a n d Alternate Fuel
Standards, private communication.
Juchura, J., M a r a t h o n Oil, and Kopen, E., (InterProvincial
Pipelines), ASTM SC E o n static petroleum measurement,
personal communication.
Beaty, R. E. and Brown, D. R., "Longstanding Partnership
Results in Review of Critical Petroleum Tables," ASTM
Standardization News, Dec. 1998, p. 26.
HoUemans, B., "LPG E q u i p m e n t Technology in Light Duty
Vehicles," presented at The World LPG Forum, Paris,
France, 1997, Available: http://www.planet-interkom.de/sven.
geitmann/ LPG.htm.
Annual Windsor Workshop Symposia, N a t u r a l Resources,
Canada a n d the U.S. D e p a r t m e n t of Energy, Available:
http://www.gasprocessors.com/default. Mar. 7, 2002.
Yates, S. E., "Technical Highlights of the Dodge Propane (LPG)
R a m Van/Wagon," P r o p a n e Technology Toptec, Toronto
Colony Hotel, Toronto Ontario, Canada,
fttp:\www.daimlerchrysler.com, http://www.ford.coni, search
"LPG."
P r o p a n e Vehicle Resource Guide, 2nd ed., RP Publishing,
Denver, CO, 1997.
Coward, H. F. and Jones, G. W., "Limits of Flammability of
Gases and Vapors," U.S. Bureau of Mines Bull. No. 503, U.S.
Government Printing Office, Washington, D.C., 1952.
MoUer, W. O., Molname, M., and Sturm, R., "Limiting Oxygen
Concentration: Recent Results and their Presentation in Chemsafe," presented at The 9 * International Symposium on Loss
Prevention and Safety Promotion in the Process Industries,
May 1998, Barcelona, Available: http://ptb.de/de/org/3/33/331/moeller.htm.
Affens, W. A., "Flammability Properties of Hydrocarbon
Fuels Part 1.," Report #6270, U.S. Naval Research Laboratory,
1965.
Handbook/Butane-propane
Gases, Sixth ed., Butane Propane
News Inc., Arcadia, CA, 1983, p. 8.
Falkiner, R. J. and Pickard, A. L., et eil., "Sampling and Shipping Liquid Propane," presented at the IGT
Odorization
Symposium, Chicago, IL, July 1998.
Peterson, "Gas," U.S. Patent 1,094,864, U.S. Patent a n d
Trademark Office, Washington, D.C., April 28, 1914.
Encyclopedia of Chemical Technology, 4th ed.. Vol. 13, John
Wiley and Sons, NY, 1994, p. 823.
Handbook of Compressed Gases, Second ed.. Compressed Gas
Association, Inc., NY, p. 312.

CHAPTER 2: LIQUEFIED PETROLEUM GAS 59


[98] "Nitrous Oxide Safety and Security," Consumer Product Safety
Commission (CPSC), Feb. 26, 2003, Available: http://www.cganet.com/N20/default.htm.
[99] Compressed Gas Association, Available: http://www.cganet.com, Feb. 18, 2003.
[ 100] Symposia on Natural Gas and LPG Odorization, Institute of Gas
Technology, the following years: 1980, 1987, 1990/92, 1994,
1995, 1996, 1997, 1998, 1999, Available: http://www.gasprocessors.com, search "odorization."
[101] Wiseman, M. L., et al., "A New Look at Odorization Levels
for P r o p a n e Gas," Bartlesville Energy Research Centre,
Bartlesville, OK, 1977, BERC/Rl-77/1, Available: U.S. Energy
Research and Development Administration (ERDA), Technical
Information Centre,
[102] "Humcin Response Research Evaluation of Alternate Odorants
for LP-Gas," GPA Research Report RR-129, Gas Processors
Association, Tulsa, OK, Available: www.gasprocessors.com/default.asp.
[103] CAN/CGSB 3.14 Liquefied Petroleum Gas (Propane). Sect. 7.3,
"Precautionary Notes-Odourant," 1988.
[104] Campbell, I. D.," Factors Affecting Odorant Depletion in LPG,"
presented at the First Symposium
on LP-Gas
Odorization
Technology, Dallas, TX, April, 1989.
[105] Hines, W. J. and Hefley, C. G., "Field Test Program of Measuring Odorant in Continuous Use Tank LP-Gas Tanks," Symposia

[106]

[107]

[108]

[109]

[110]
[111]

on Natural Gas and LPG Odorization, Chicago, IL, Institute of


Gas Technology/GAS Research Institute, 1990.
Faulconer, H., "Field Testing for Ethyl Mercaptan in LP-Gas
Storage Tanks in Four Marketing Areas," Symposia on Natural
Gas and LPG Odorization,
Chicago, IL, Institute of Gas
Technology/GAS Research Institute, 1990.
Marshall, M. D. jind Palladino, C. A., "Ethyl Mercaptan Stability after Refill of New and Air-Exposed used LP-Gas Storage
Tanks," Symposia on Natural Gas and LPG
Odorization,
Chicago, IL, Institute of Gas Technology/GAS Research
Institute, 1990.
Parclay, A. T., et al., "Rail Car Field Test Evaluation Ethyl Mercaptan Odorant in Propane," Symposia on Natural Gas and
LPG Odorization, Chicago, IL, Institute of Gas Technology/GAS Research Institute, 1992.
Poirer, M. A., Falkiner, R. J., and Pickard, A. L., "Odorant
Fade in Stenched Rail Car Cleaning," Symposia on Natural
Gas and LPG Odorization,
Chicago, IL, Institute of Gas
Technology/GAS Research Institute, 1998, Available:
www.npga.org.
www.adspec.net/safety/report/report.htm, April 8, 2003.
Bull, D. E. and Falkiner, R. J., "Risk Management: Verifying
LPG Odourization Rates," Symposia on Natural Gas and LPG
Odorization, Chicago, IL, Institute of Gas Technology/GAS
Research Institute, 2001.

MNL37-EB/Jun. 2003

Motor Gasoline
B. Hamilton^ and Robert J. Falkiner-^

nology levels, and have produced the "World Wide Fuel Charter" (WWFC) on this basis. The WWFC receives serious
consideration when nations and economic regions are revising fuel specifications, even though it is not an accredited
consensus standard, and is the subject of ongoing technical
debate. ASTM Standard Practices, Test Methods and Specifications continue to be key to domestic and International
Specifications and Regulations, and are used globally
through affiliated ISO Standard Writing Organizations.
Specifications for n e w generations of engines (electric/
hydraulic hybrids, gasoline direct injection, fuel cells, microturbines) and catalysts (lean b u r n , heated, selective reduction, HC absorption, particulate trap) have yet to be
developed. The trend continues to be more restrictive in composition and variation than in previous gasolines.

T H E SPARK IGNITION ENGINE HAS REMAINED THE POWER PLANT OF

CHOICE for personal transport for almost a century, and the


fuel specifically formulated for SI engines is called gasoline
(U.S.) or petrol (UK). Gasoline h a s evolved continuously
since it was first produced in quantity to meet the burgeoning demand from mass production of the automobile in the
early 1900s. It was first produced from light naphtha batch
distilled from crude oil and liquid condensate from natural
gas production, and in the early days, had no test methods or
specifications at all (see Chapter 2, Liquefied Petroleum Gas).
It became a carefully formulated mixture of hydrocarbons
and additives, seasonally blended to m a t c h local ambient
conditions, providing good performance and efficiency for
constantly changing vehicle fleet. More recently, gasoline has
been reformulated to reduce various emissions and minimize
the impact of automobiles on urban air quality.
For the first 60 years of gasoline production, formulation
and manufacture were focused on optimizing desirable performance properties, cost, and yield. Increased octane allowed increased engine power and fuel efficiency. Volatility
was controlled to minimize vapor lock, carburetor icing,
stalls, sag, hesitation, hard starting, and other measures of
"driveability" performance. Stability additives were developed to minimize auto-oxidation, and detergents to keep carb u r e t o r s clean. Increased yield from crude oil and other
sources made gasoline more available and affordable. Gasoline properties are increasingly influenced by regulatory requirements intended to reduce air and water pollution during
manufacture, distribution, and use. Gasoline is controlled at
many regulatory levels, including national, state/provincial,
and in some cases, city or municipal.

HISTORY OF GASOLINE
L e a d e d Gasoline ("Pre-control")
In the late 19th century, fuels, for the automobile were coal
tar distillates and the lighter fractions from the distillation of
crude oil. It's believed that a gasoline fraction was separated
by Joshua Merrill in Boston, and was used for lighting. It was
also used in Nicolaus Otto's first four-stroke cycle engine in
1876. By the late 1800s the early refiners were producing
volatile gasoline by batch distillation from crude oil. Natural
gas producers were making volatile naphtha from the hydrocarbon condensed from compressed natural gas (condensate,
casinghead, or "natural" gasoline). There were no standard
test methods or national specifications, or definition of quality. Some of the earliest standard test methods were not developed until the 1920s, allowing development of the first
widely accepted gasoline specifications. Some test methods
developed in the 1920s are still in use today, such as the Reid
Vapor Pressure (originally developed for casinghead gasoline) and Distillation (the oldest currently used ASTM gasoline test method, first published in 1930). The D86 was based
on tests developed for casinghead or "natural gasoline" by the
predecessor organization of the Gas Processors Association
(GPA). The data triggered a n intensive discussion of the relationship between gasoline distillation profile (volatility) and
engine performance, such as vapor lock, oil dilution, knock,
and "sooting."

The current generation of North American "Tier 0" and


"Tier 1" vehicles for current emissions standards have converged towards electronic fuel injected engines and "3-way
catalyst" emission control systems. Globally, automakers are
facing increasingly stringent "Tier 1" emissions limits for the
2004-2009 time period. While it has been recognized that
meeting the Tier 2 emission standards will be a challenge for
gasoline vehicles, the U.S. EPA does not expect t h a t any
major technological innovation will be required to achieve
compliance. However, low sulfur gasoline must be available
for these standsirds to be feasible. In turn, the automakers are
promoting global fuel specifications based on vehicle tech' Research Associate, Industrial Research Limited, P.O. Box 31310,
Lower Hutt, New Zealand.
^ Fuels Technical Associate, Quality Assurance and Development
Group, Imperial Oil Ltd., I l l St. Clair Ave. W., Toronto Ontario,
Canada.

Automotive engines were rapidly being improved and required a more consistent and suitable fuel. New test methods,
specifications, and refining processes were developed to better separate and increase the octane of components. Com61

Copyright'

2003 by A S I M International

www.astm.org

62

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

pression absorption and continuous fractional distillation in


"pipestills" replaced batch distillation with a continuous process in the 1920s. The first "sweetening" processes were
developed to remove smelly and corrosive sulfur compounds.
Thermal cracking was introduced just prior to World Weir I,
followed by steam cracking, coking, fluid catalytic cracking,
reforming, catalytic hydrogenation (hydrotreating), a n d
many others. Gasoline specifications were developed to control the composition, properties and performance of the finished gasoline, with the three m a i n areas of octane, volatility,
and cleanliness.
Fixed bed cracking/reforming was introduced in the early
1930s, which significantly increased the octane of "cat-naphtha" relative to "straight-run" or thermally cracked naphtha,
with a good alkyl lead response. Higher octane of the gasoline
components allowed production of some of the first "premium" gasoline, called "high-test" at the time, a reference to
their higher octane n u m b e r test result. During World War II,
continuous fluid cat cracking and semi-continuous reforming processes were developed, along with cateJytic desulfurization, which further increased the alkyl lead response. Processes were developed to convert C3 and C4 olefins from cat
cracking into gasoline by polymerization (polygas) and alkylation (alkylate). Highly leaded cracked naphtha, reformate,
and alkylate blends were ideal for aviation gasoline for high
compression and turbo/supercharged aviation engines developed during WWII, using "performance number" octane ratings based on the increased percent power attained above the
baseline of 100% iso-octane fuel. With rare exception, all post
WWII North American automotive gasoline contained TEL.
In the early 1950s changes in engine designs and driving
patterns required the re-introduction of the Research Octane
Rating. Automakers utilized military technology to continue
to increase the engine compression ratio, requiring higher
octane n u m b e r fuels. The octane race occurred during the
1960s, as high performance engines required fuels with increased octane. The octane increase was non-linear with
alkyl lead concentration, with diminishing returns, so there
was an economic limit to the maximum amount used. The
m a x i m u m permitted concentration in gasoline was 1.14g
Pb/1, which was well above the optimum alkyl lead response
for most refinery streams. Highly leaded premium gasoline
was produced for use in high-compression ratio big-block
"muscle cars," with RON as high as about 105. For the interested reader, a more detailed discussion of the history of
gasoline is presented elsewhere [1-3].

H i s t o r y o f Alkyl L e a d i n G a s o l i n e
During the 1910s, laws prohibited the storage of gasoline on
residential properties, so Charles F. Kettering modified a
Spark Ignition (SI) engine to r u n on kerosene. However the
kerosene-fueled engine would "knock" and crack the cylinder
head and pistons. He assigned Thomas Midgley, Jr. to confirm that the cause was the kerosene droplets vaporizing on
combustion, as he presumed. Midgley demonstrated that the
knock was caused by a rapid rise in pressure after ignition,
not during pre-ignition as believed. The combination of TML
and TEL along with alkyl bromide and chloride alkyl lead
scavengers were widely used stEirting shortly after discovery
by teams led by Thomas Midgley Jr. in 1922 [4-6]. Several

e m i n e n t public health officials campaigned against the


widespread introduction of alkyl leads [7], but after a review,
the U.S. Surgeon General decided in favor of use in 1926. The
toxicity of TEL soon became apparent, as it was originally
handled and added in concentrated form at the point of sale.
This was changed to point of production to eliminate handling of alkyl lead concentrates outside of refineries, where it
could be better controlled.
Alkyl lead is unique among organometallic additives in that
alkyl halides were effective "alkyl lead scavengers" to prevent
buildup of alkyl lead oxides and related solids in the engine
and exhaust system. This allowed lead Eilkyls to be used at
m u c h higher concentrations than any other organometallic.
The alkyl lead chloride and bromide had a lower melting
point and higher vapor pressure than the oxide, resulting in
the alkyl lead being "scavenged" and expelled with the exhaust. About 1-1.5 times the molar amount ("theories") to
make the alkyl lead tetrahalide was used to provide good
scavenging. Aviation gasoline uses only one theory of alkyl
bromide to protect against chloride induced corrosion of the
hotter exhaust valves. Tricresyl phosphate (TCP) has also
been used as a alkyl lead scavenger (mostly in avgas), to form
alkyl lead phosphate that has a lesser tendency to form glowing deposits, foul spark plugs, or accumulate deposits in aviation exhaust side turbochargers.

History of Octane Ratings


In 1921, the Co-operative Fuel Research Committee (CFRC)
was formed to research fuels and engine performance [8].
The CFR engine was developed to evaluate knock performance of fuels under controlled conditions, measuring knock
intensity with a bouncing pin knockmeter. In 1927 Graham
Edgar developed a n octane rating scale based on high and
low reference fuels, and showed that fuels had Octane Ratings between 40-60. This became the C.F.R. Research Octane
N u m b e r in 1930. The RON test method was first published in
1932, became a tentative method in 1947, and was adopted as
an ASTM standard in 1951.
Graham Edgar used two pure hydrocarbon isomers that
could be produced in sufficient purity and quantity as reference fuels for rating the anti-knock ability of fuel. These were
"normal heptane," which was commercially available in sufficient purity from the distillation of Jeffrey pine oil, and "an
octane, named 2,4,4-trimethylpentane" that he first synthesized (commonly Ccdled isooctane today, although there are
17 different isomers possible, and about five prevalent C8 isomers from C4 alkylation). The heptane and iso-octane were
given the arbitrary octane n u m b e r s of 0 and 100, respectively. These have similar volatility properties (see Table 1),
specifically boiling point, thus the varying ratios 0:100 to
100:0 would have consistent vaporization behavior. The volu m e percentage of isooctane in the binary blend that gave the
same knock intensity as the fuel being tested was assigned as
the Octane Number of the sample.
The early work quickly identified that the "highest useful
compression ratio" (efficiency, power) was related to the CFR
Research octane number. The sulfur-containing gasoline was
initially restricted because sulfur in gasoline inhibited the octane-enhancing effect of the alkyl lead. In addition, different
fuels had different "susceptibility" or octane response to the

CHAPTER

3: MOTOR

GASOLINE

63

TABLE 1Selected properties of normeil heptane and iso-octane.


Normal heptane
Iso octane

Melting Point, C
-90.7
-107.45

Boiling Point, "C


98.4
99.3

alkyl leads. Parafins have the best alkyl lead response, followed by napthenes, olefins, and aromatics, while the response of alcohols is negative. The RON of the gasoline could
be increased from 60 to 75, and the "highest useful compression ratio" increased from 5.3 to 6.8, increasing the constantspeed fuel economy by about 30%.
The Motor Octane N u m b e r (MON) was developed in 1932,
using conditions that better matched actual vehicle knock
performance climbing the long constant grade hill at Uniontown, Pennsylvania. This method is similar to the operating
conditions of the current Motor Octane procedure [9,10]. The
MON test was a tentative method from 1933 to 1939, when it
was adopted as a n ASTM standard. During the late 1940s
through the middle 1960s, the Research method became the
m o r e i m p o r t a n t rating because milder conditions m o r e
closely represented the octane requirements of the vehicle
current engines and driving conditions. Most retail fuels were
marketed according to their research octane rating.
1 9 6 3 C l e a n Air A c t , V e h i c l e E m i s s i o n S t a n d a r d s
a n d Alkyl l e a d P h a s e d o w n
During the late 1950s and 1960s, ambient air quality deteriorated, especially in densely populated urban areas. ReseEirch
quickly identified the "primary pollutants" in raw exhaust
(HC, CO, and NOx) and sunlight driven photochemical reaction to be a major source of SMOG (SMoke + fOG). Ground
level ozone and other "secondary poUutcints" are formed by
photochemical reactions driven by sunlight. The concentrations of pollutants followed a daily pattern determined by
driving cycles ("rush hours"), daytime sunlight intensity, and
local geography and wind patterns, with the most severe area
in the U.S. being southern California. The original Clean Air
Act was passed in 1963 "to protect and enhance the quality of
the Nation's air resources." The first vehicle emissions standards were imposed in California in 1966 a n d Federally in
1968. The early attempts to reduce HC and CO with carburetor calibrations and thermal reactor ("thermactor," air +
time delay) type exhaust systems were only about 60% effective for HC. However, this was still a larger drop (est. 10.6
g/mile to 4.1 g/mile HC) than all of the emission reductions
since, due to the high emission rates at the time. A n u m b e r of
attempts were made to develop "lead-tolerant catalysts" and
"alkyl lead traps" that would allow continued use of leaded
gasoline. However, several new potential problems with continued widespread use of leaded gasoline were found, and
R&D to develop viable exhaust oxidation catalysts went into
high gear.
Alkyl lead is a toxin by itself, and there was a drive to reduce exposure levels from m a n y sources, ranging from alkyl
lead solder in pipes, food cans, toothpaste tubes, alkyl lead
pigment in paints, and edkyl leads in gasoline. In addition, the
alkyl lead scavengers ethyene dibromide and ethylene dichloride could react with u n b u m e d hydrocarbons in the exhaust

Density, g/ml
0.684
0.6919

Heat of Vaporization, MJ/kg


0.365 at 25C
0.308 at 25X

to form traces of organo-halogen c o m p o u n d s , including


dioxins [11]. It is unlikely that high levels of TEL use would
have continued even if a lead-tolerant catalyst h a d been
found.
Separate regulations were put in place to minimize the
amount of alkyl lead (primeirily TEL) used in the remaining
leaded gasoline produced and sold, creating "low lead" in a
series of reductions in 1985/86. A smaller fill nozzle diameter
was adopted for nonleaded gasoline to prevent misfueling
catalyst cars with leaded gasoline. In the United States, alkyl
lead could not be knowingly added to nonleaded gasoline,
and the maximum allowable concentration of 0.05 g/usgal
(13 rng/L) was applied as a contamination limit for "incidental contact" with leaded fuels during distribution. Other jurisdictions have slightly different legal definitions and cont a m i n a t i o n limits for nonleaded gasoline, b u t the t e r m s
"nonleaded" and "unleaded" tend to be used interchangeably,
even if this is not technically or legally correct in all cases.
Octane ratings of leaded gasoline decreased from the "octane
race" levels, a b o u t 1.5-3 AKI lower for RUL a n d PUL,
respectively.
Some predominately smEJl engines were designed for 87
AKI nonleaded fuel, but were "alkyl lead tolerant," because
they could meet the emission standards of the time without a
catalytic converter, so could use either leaded or nonleaded
gasoline.
The last p r e m i u m leaded gasoline was sold in 1981, and the
last regular leaded in 1996 in the United States, and in 1990
in Canada.
Alkyl alkyl lead has been credited variously with allowing
rapid development of high power Eind efficiency SI engines,
and even being a deciding factor in aviation in World War II.
It is not widely appreciated that Thomas Midgley's other famous discovery, perfluorocarbon refrigerEint, had the same
dichotomous history [12] as alkyl lead. It provided enormous
social benefits, b u t was eventually b a n n e d d u e to stratospheric ozone depletion. It was replaced with less long-lived
halocarbons that are decomposed at lower altitudes.
Nonleaded Gasoline
Introduction of the first Conventional Oxidation Catalyst
(COC) systems required nonleaded a n d low phosphorous
gasoline to protect the exhaust catalyst over the useful lifetime of the car. Alkyl lead Euid phosphorus are potent catalyst
"poisons" that slowly decreased catalytic activity, eventually
resulting in near total deactivation of the converter. Phosphorous contents were reduced to sub-ppm levels by eliminating the use of phosphate ester based corrosion inhibitors.
Alternate corrosion inhibitor additives were readily available,
so phosphorus reduction did not pose a problem to fuel manufacturers. It did require the automzikers to significEintly reduce oil consumption, as the only remaining significant
source of phosphorous was from crankcase lubricant. Re-

64

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

placing the octane boost from alkyl lead was a big problem
for the fuel manufacturers, as there was n o readily available
replacement. This required significant changes to both fuel
and engine design.
Gasoline manufacturers found that it was possible to produce, on average, a nonleaded regular gasoline with an 87
AKI and about 91 RON in the United States, and a premium
95 RON in Europe and elsewhere. United States automakers
built engines with EGR and reduced compression ratios initially around 8:1 for use on 87 AKI non-leaded gasoline to reduce engine-out NOx to regulated levels. Air injection reduced HC and CO by oxidation over a COC. Efficiency and
fuel economy were reduced because of the compression ratio
reduction. However, this was more t h a n offset by Corporate
Average Fuel Economy (CAFE) regulations in 1975 that required average LDV fuel economy determined in standard
tests to increase over a period of years u p to 27.5 mpg. This
was accomplished with a variety of technologies. Vehicle
size, weight, and rolling/wind resistance were dramatically
reduced ("downsizing"). The majority of the fleet converted
to front wheel drive, using more efficient transverse L4 and
V6 engines and transmissions, both using lower viscosity and
friction modified lubricants.

The United States EPA may grant waivers for nonleaded


gasoline formulations that are shown by testing to not cause
or contribute to emission device failures. A waiver request is
granted if the EPA does not decline the application after 180
days. In 1978, the EPA granted the first waiver for 10% by volu m e of ethanol. The EPA subsequently issued waivers for
gasoline containing a variety of alcohols, ethers, and mixtures, of which MTBE and ethanol (gasohol) are the most
commercially important today. A complete technical assessment (including extensive references) for the application of
alcohols and ethers as fuels and fuel components is available
from API [14].
In 1981 the EPA ruled that fuels with u p to 2 wt% oxygen
from aliphatic alcohols or ethers were "substantially similar"
and thus did not need a waiver. In 1991 the maximum oxygen
content was increased to 2.7 wt% oxygen. To ensure sufficient base gasoline was available for ethanol blending, the
EPA also ruled that gasoline containing u p to 2 vol% of
MTBE could subsequently be blended with 10 vol% of
ethanol.

Premium unleaded (PUL) gasoline was introduced in the


United States later, in response to the higher Octane Requirement Increase (ORI) relative to historical experience
with leaded fuels. This allowed production of "premium preferred" or "premium required" cars, predominately turbocharged and knock sensor equipped engines that could
take advantage of the increased octane. ASTM specifications
do not m a n d a t e octane number, and historically U.S. fuel
producers set octane numbers in response to market forces.
In North America the most c o m m o n octane grades are now
RUL87, MUL89, PUL91/92, and SUL93/94.

As the tailpipe emissions were reduced by improved exhaust


emission control systems, other h y d r o c a r b o n emission
sources became more important. This includes hydrocarbons
from evaporation or fugitive emissions of gasoline during
distribution and storage, vehicle refueling, vehicle at rest, or
vehicle during use. The United States CAA required summer
reductions in VP in two phases in 1989 and 1992, to reduce a
number of fugitive emission sources (running loss, diurnal,
refueling.. .). Summer vapor pressure controls have virtually
eliminated hot driveability problems. They tend to be design
related, appearing as "select model" problems when they
occur.
Stage 1 vapor control systems reduce truck loading vapor
emissions at terminals and at service stations during loading
and unloading of trucks. At the service station, the vapor
space of the truck is connected to the vapor space of the underground tank, whose vapor is displaced ("vapor balanced")
back into the truck during fuel delivery. The truck returns to
the terminal, where the hydrocarbon saturated air delivery
truck are collected and sent to a Vapor Recovery Unit (VRU)
or to a Vapor Destruction Unit (VDU, combustor, flare) as the
truck is loaded.
Stage 2 systems reduce point of sale vehicle refueling emissions. Vapors from the vehicle tank are vapor balanced with
the underground storage tank, or sent to an absorber or combustor. Newer systems incorporate vapor p u m p s to remove
the exact amount of air from the fill pipe as volume of gasoline dispenses, and do not require the rubber nozzle "snout"
to make a vapor tight seal. These systems are recognized by
air slots near the nozzle tip to remove air from the fill spout
via an annular tube in the delivery hose. Vehicles are also
equipped with enhanced activated carbon canisters (bigger
capacity than required for diurnal control) to treat the vehicle tank vapor while refueling. These are subsequently desorbed by a small airflow and burned in the engine during
normal use, once specified vehicle speeds and coolant temperatures are reached. Some activated carbons used in older
vehicles do not function efficiently with oxygenates, but mod-

1 9 7 0 U S E P A C l e a n Air A c t a n d 1 9 7 7 A m e n d m e n t
The 1970 U.S. Clean Air Act (CAA) established the Environmental Protection Agency and required a 90% reduction in
automotive emissions by 1975 (HC/CO) and 1976 (NO^). This
resulted in the widespread introduction of conventional oxidation catcilysts and nonleaded gasoline in 1975 in response
to the HC and CO standards. These regulations were "technology forcing" especially for NO^, and the U.S. Congress put
an interim NOx standard in place until 1978. The 1977 Clean
Air Act Amendments required reduction in HC in 1980 and
CO and NOx in 1981. This resulted in the widespread introduction of sophisticated "three-way catalysts" computer controlled closed loop air-fuel ratio control with exhaust oxygen
sensors in most 1981 model year cars. The 1977 CAA amendments contained the first provisions that controlled the properties of "future" gasoline. It had a general requirement that
gasoline be "substantially similar" to fuel or fuel additives
used to certify 1975 or subsequent years vehicles [13]. The
intent was that future gasoline would not render the new catalysts or emission controls ineffective over time. The EPA
subsequently promulgated the "substantially similar" ruling,
which had a more detailed definition of the meaning. It eilso
provided that additives containing only C, H, O, N, S (which
combust to the regulated emissions) did not require a waiver
at concentrations below 0.25 vol%.

Vapor Controls

CHAPTER
ern carbon canister systems can reduce evaporative emissions by more than 95% from uncontrolled levels. On-board
canister systems tend to make Stage 2 balancing redundant
as the on-road population equipped with enhanced canister
systems increases.
1 9 9 0 CAA A m e n d m e n t s ( R e f o r m u l a t e d a n d
Conventional Gasoline)
A more complete technical discussion on Reformulated Gasoline (RFG) is contained in ASTM Research Report D02:1347
[15], and in numerous other Government and Industry Publications [16]. Officially published sources of information should
always be used for regulatory compliance purposes. A summary
of the United States EPA gasoline, additive, and related regulations is available at http://www. epa.gov/otag/gasoline.htm.
A chronology of EPA emissions control regulations is available at http://www.epa.gov/ otag/12-miles.htm.
The 1990 Clean Air Act (CAA) amendments and California
Air Resources Board (CARB) Phase 2 (1996) specifications
required further reductions in tailpipe emissions, more stringent test procedures and vehicle on-board monitoring technology, and new "clean fuels" programs. These established
emission limits for reformulated gasoline, compared with
typical 1990 "baseline" gasoline. The first stage, the "Simple
Model" was an interim stage between 1 Jan. 1995 to 31 Dec.
1997. The second stage, the "Complex Model" h a d two
phases: Phase I (1995-1998) and Phase II (2000+).
Metropolitan regions with severe ozone air quality problems were required to use reformulated gasoline containing
at least 2.0 wt% oxygen to reduce 1990 volatile organic carbon compounds by 15% (1994), and reduce specified toxic
emissions by 15% (1995) and 2 5 % (2000). Because of a lack
of data, the EPA was unable to define the required parameters for the CAA, so an advisory committee containing representatives of regulatory, petroleum industry, environmental,
and consumer interests recommended a two-stage system for
implementation ("reg-neg"). The EPA also gave the refining
industry a choice of standard, based on either "per gallon,"
(Never To Exceed, NTE, or "cap" limit), or "averaged," based
on volumetric averages over an annual or seasonal production period (Yearly Pool Average, YPA, or summer/winter). In
some jurisdictions, regulations include requirements around
sampling, test methods, and validation/demonstration of test
proficiency, as well as certified third party testing, auditing,
and field "attest" monitoring.
Areas in attainment with air quality objectives continued to
use "conventional gasoline." The "anti-dumping" provisions
of the regulation ensured that the quality of conventional
gasoline was not degraded to facilitate production of RFG.
Conventional gasoline must be blended to provide equivalent
emissions of the national baseline gasoline (default for domestic or import), or individual refiner's baseline based on
prior production. The intent of these "anti-dumping" restrictions was to ensure emission improvements and non-attainment did not result in emission increases in areas currently
in attainment with the National Ambient Air Quality Standards (NAAQS). Emission improvements had to be made by
increased refinery processing for the manufacture of RFG.
The Auto-Oil Air Quality Improvement Research Program
(AQUIRP, "Auto-Oil") provided the basis for the "simple" and

3: MOTOR

GASOLINE

65

"complex" models used in EPA and most other North American gasoline regulations. Measured emissions were correlated to gasoline properties in a wide variety of vehicle emission system types. These spreadsheet type correlation models
predict emissions from all sources associated with using
gasoline in vehicles. They tcike into account the time of year
(winter/summer), gasoline composition as measured by eight
parameters (called the model parameters), and an assumed
on-road vehicle fleet with a mixture of various generations of
emission control tjrpes. A copy of the complex model spreadsheet ("Final.exe") can be downloaded from the EPA web
site. California Phase 2 RFG allows a "Predictive Model,"
similar to the EPA complex model, as an alternative to the
original Phase 2 composition based requirements.
For Phase I, for example, the CAA specifies no increase in
NOx emissions, reductions in VOC by 15% during the ozone
season, and specified toxins by 15% all year. These criteria
indirectly established vapor pressure and composition limits
that refiners had to meet. The percent reductions are calculated with the complex model, which predicts volatile organic
compounds (VOC), specified toxic air pollutants (TOx), and
nitrogen oxides (NOx) as a function of eight composition related model inputs. Sulfur, benzene, vapor pressure, %oxygen and aromatics have the largest impact on predicted emissions. D86 evaporation volumes E200 and E300, and olefin
content have lesser, but still significant impact. Federal regulations reduced vapor pressure and benzene directly, however, aromatics or other parameters could be limited to meet
emissions criteria [17]. For example, a fuel with the maxim u m permitted 1.0% benzene requires total aromatics to be
limited to about 27% to meet the emissions reduction
requirements.
Federal (EPA) RFG and California Phase 2 RFG composition limits require the use of oxygenate. The California Phase
2 RFG requires the hydrocarbon composition of the RFG to
be significantly more modified than the existing oxygenated
gasoline to reduce unsaturated hydrocarbons, volatility, benzene, sulfur, and the reactivity of emissions. California Phase
2 does not require the use of oxygenates in the summertime
if using the "Predictive Model" except for federal ozone noncompliance areas of the state where the EPA RFG limits apply as well.
Oxygenates were first added to gasoline as a high percentage level blend component (as opposed to a p p m level deicer) to extend gasoline supply supported by some State and
Provincial Governments with a reduced gasoline tax rate. In
1992, 2 wt% oxygen gasoline was mandated in cold, high altitude areas starting in 1994, as a means to "lean" the mixture, and reduce unburned HC and CO by over 10% in carb u r e t e d vehicles. However, some oxygenates such as
methanol, ethanol, and light ethers increase the vapor pressure of the gasoline, causing increased evaporative emissions
that reduced or reversed the benefit. Newer Tier 0 and later
technology cars have very fast adaptive feedback loops to
control the oxygen content in the exhaust to near stoichiometric using the oxygen sensor [18]. These vehicles are much
less sensitive to fuel effects, so the net benefit of oxygenates
decreases with time, as the older predominately carbureted
engines are retired from service. Other researchers have observed similar reductions when oxygenates are added to reformulated gasoline on older and newer vehicles, but have

66

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

also shown that NOx levels may increase, as also may some
regulated toxics [19-21].
By 2000, MTBE was the preferred oxygenate in RFG, but
concerns about toxicity and water pollution were mounting.
MTBE has a m u c h higher (4.3 wt%) solubility in water t h a n
hydrocarbons, a relatively low bio-degradability, and very
low o d o r threshold. This makes MTBE objectionable in
potable water at trace concentrations, and a concern for water contamination from spills, leaks and marine engines using gasoline-containing MTBE. In 1999, California applied to
the Federal government for a waiver from the Federal RFG
requirement concerning oxygen content to eliminate MTBE.
However, that application was declined in J u n e 2001. In
March 2000, the EPA provided advance notice of its intent to
initiate rulemaking pursuant to section 6 of the Toxic Substances Control Act (TSCA) to eliminate or limit the use of
MTBE as a fuel blend component. Several U.S. FederEil and
individual state bills have proposed elimination of MTBE
since t h e n including two U.S. Federal Energy bills. At the
time of this writing, use of MTBE is likely to be either banned
or significantly restricted.
Canadian refiners m u s t meet either a 1.0 wt% benzene
NTE, or optionally a 0.95 wt% YPA and 1.5 wt% NTE, effective July 1, 2000. In addition, a 72/91 summer/winter Benzene Emission N u m b e r (BEN) requirement is based on the
complex model, not including olefins. The BEN is the s u m of
exhaust a n d n o n e x h a u s t benzene, excluding calculation
terms of the complex model using olefins. There eire several
measurement and reporting differences between the U.S. and
Canadian RFG regulations. One Canadian province (BC) has
VOx and NOx requirements based on the full complex model,
but using a BC baseline gasoline for the calculation. Severed
other Canadian Provinces have standalone s u m m e r Vapor
Pressure regulations. Canadian vehicle emission standards
have tended to follow closely u p o n U.S. 49 state requirements, with some differences in phase in schedules.

2 0 0 4 + Vehicle and Fuel Regulation (Future RFG)


In April 2000, new Federal Tier 2 criteria for vehicle emissions and fuels were announced phased in beginning in 2004
and extending to 2007+. OfficieJly published sources of information should always be used for regulatory compliance
purposes. Full details of the regulations cire available on the
United States EPA website at http://www.epa.gov/otaq/cert/veh-cert/bOOOOl.pdf (Document EPA420-B-00-001). Copy of
the final rulemaking is available at http://www.epa.gov/OMS/regs/ld-hwy/tier-2/frm/fr-t2pre.pdf.
These stcindards apply to both diesel and gasoline powered
light duty vehicles, and to fuels for these vehicles. The regulations allow early-adopters to obtain credits that cEin be used
later and traded, encouraging rapid introduction of low sulfur gasoline, starting in 2000, well ahead of the 2006 deadline. Temporary, less stringent standards will apply to a few
small refiners t h r o u g h 2007. I n addition, temporary, less
stringent steindards will also apply to a limited geographic
cirea in the western U.S. for the 2004-2006 period.
Most U.S. refiners and importers must meet a corporate
average gasoline sulfur standard of 120 p p m and a cap of 300
p p m beginning in 2004. In 2005 the cap remains at 300 ppm,
with the corporate average reducing to 90 p p m and refinery

average at 30 ppm. In 2006, the average will be 30 p p m and


cap 80 p p m , with some areas and refineries having until
2006-2009 to comply. The EPA also n o t e d that gasoline
should not be advertised as "low sulfur gasoline" unless it
contains 95 p p m sulfur or lower.
California has legislated faster implementation of a 30
YPA, 80 NTE sulfur standard, and others, such as North Carohna's SB 953. Part II of that law, NCOS 119-26.2, proposes
the same for after January 1, 2004.
The Tier 2 LDV stcindards are the same for cars and light
duty trucks, whether diesel or gasoline, so include both nonmethEuie organic gases (NMOG) and Particulate Matter requirements (PM essentially for diesels and NMOG essentially
for gasoline). Different phase in periods apply for different
size vehicles. Light duty car a n d truck phase-in starts in 2004
with 100% compliance by 2007. M e d i u m duty passenger
vehicles and heavy light duty trucks will be phased in beginning in 2008, with full compliance in 2009. A new class of
medium-duty passenger vehicles (MDPV), < 10,000 GVW, includes large Sport Utility Vehicles (SUV) and vans intended
to carry less thzin 12 passengers. These will be treated the
same as HLDT and have interim emission standards that expire in 2008.
The standard defines 11 "Bins" rEinging from Bin #1 "Zero
Emission" to Bin #11, which is compEirable to current LDV
standards. The average Bin #5 NOx = 0.07 g/mile which represents a reduction of about 70% from current levels. The
highest emissions Bin #9 to #11 expire after the phase in period, contributing to a lower long-term average. More stringent particulate matter emission standards are established in
2004 for most light trucks. The NMOG standards vary depending on which of various individual sets of emission standards manufacturers choose to use in complying with the average NOx standard.
The Tier 2 Vehicle emission program increases the useful
life of the vehicle to 120 000 miles and introduces new, more
severe evaporative emission test procedure. This is expected
to result in widespread adoption of "deadhead" gasoline fuel
systems, that place the fuel p u m p , filter, and pressure regulator inside of the gasoline tank, with n o liquid gasoline
return line from the engine compartment back to the teink.
This eliminates a n u m b e r of external mechanical connections that contribute to the fugitive emissions etnd life of vehicle compliance.
The Canadian Environmental Protection Act (CEPA) requires refiners and importers to meet either a 170 ppmw sulfur NTE over a 30 month interim period ending Dec 31, 2004,
or a 150 p p m average with an 300 NTE in the last half of the
interim period. Gasoline is required to be 30 p p m YPA, 80
p p m NTE starting Jan 1, 2005. One Province (Sask.) has impending oxygenate (ethanol) requirements for 2005.

GASOLINE PROPERTIES
Gasoline Composition
Hydrocarbons
Gasoline can contain over 500 different hydrocarbons with
between 4 and 14 carbon atoms per molecule. Detailed descriptions of structures can be found in any chemical or
petroleum text discussing gasoline [22]. The C3 and lighter

CHAPTER
hydrocarbons are too volatile to be used as a blending component of gasoline. Both methane and propane are widely
used as an SI engine fuel using pressurized fuel systems and
various designs of gaseous carburetors or fuel injectors. Hyd r o c a r b o n s larger t h a n about C14 are too heavy (nonvolatile), and tend to contribute inordinately to oil dilution
and incomplete combustion a n d "soot" related problems.
These functional limitations result in gasoline having a typical boiling range of about 25-225C at atmospheric pressure.
Vapor pressure, Driveability Index (DI) a n d model based
emission criteria all tend to narrow this boiling range by removing the highest and lowest volatility ranges.
The type and concentration of the various hydrocarbons in
any given gasoline blend can be determined by high resolution gas chromatography, typically using 50-100 meter capillary columns to obtain the high resolution required. The
n u m b e r of different hydrocarbons in any given blend depends upon the tj^e and severity of processing at any given
refinery. Composition surveys [23] on nonleaded gasoline
showed that gasoline blended with high percentages alkylate
or low severity reformate could contain less than 175 different hydrocarbon types. Gasoline blended with catalytically
cracked naphtha tended to contain more than 350 different
molecules.
U.S. regulations use a n ASTM external calibration GCMass Spec method for regulatory benzene and aromatic reporting. Current versions of the ASTM GC method peak
tables identify over 400 different hydrocarbons by formula,
and a n additional 50+ as "unknown." Most methods also
measure the c o m m o n oxygenates if present. Since the FID
detector is linear, the percentages of parafins, olefins,
napthenes, indanes, aromatics, and unknowns can be estimated by linear sum (commonly called a PONAU or PIANO
methods, which are acronyms of the first letter of the hydrocarbon t5rpes detected). With over 400 compounds identified,

3: MOTOR

GASOLINE

67

there is usually less than 2.5% "unknown" content in a typical RUL and less than 1% in a typical PUL. There are small
concentrations of additional isomers that are undoubtedly
present below the nominal 50 p p m w detection level of the
standard methods using Flame Ionization Detectors. These
tend to be highly branched CIO to C14 olefins, isoparafins,
and napthenes because of the large n u m b e r of isomers that
can be produced within each carbon n u m b e r in this range.
The magnitude of the "undetected" hydrocarbons can be inferred to be less than about 0.5% for a complex gasoline by
comparing results of high and low resolution methods.
The m u c h smaller number of isomers possible for aromatics makes the measurement of aromatics by FID detectors
more feasible since essentially all of the possible aromatics
up to about CI2 are identified. As a result, Canadian regulations use a Cap-GC/FID method for both benzene and total
aromatic reporting.
Saturated

Hydrocarbons

(Paraffins,

Alkanes)

Saturates are the most chemically stable species, and comprise 20-80% of gasoline, with 30-60% being typical. The octane ratings of these compounds depend on the branching
and n u m b e r of cEirbon atoms. The octane primary reference
fuels are both saturated hydrocarbons (0 = heptane, 100 =
224 trimethylpentane). Additional information is presented
in Table 1. The interested reader is directed to a standard organic chemistry text for further detail on these and the other
classes of hydrocarbons.
Unsaturated

Hydrocarbons

Unsaturated hydrocarbons are less stable as compared to


saturates. The upper limit of both olefins and aromatics can
be limited by emissions or other specifications. Table 2 contains information about the various classes of unsaturated
hydrocarbons.

TABLE 2Unsaturated hydrocarbons.


Alkenes

Dienes

Alkynes
Arenas
(Aromatics)

PNA (Polynuclear
Aromatics)
PAH (Polycyclic Aromatic
Hydrocarbon)

Olefins, contain single carbon-carbon double bonds


Usually stable, depends upon molecular type
Clean burning, reduces VOC but increases NMOG reactivity
More reactive than alkanes, higher octane ratings.
Present in gasoline 0-25% (10-15% typical)
Olefins containing more than one carbon-carbon double bond
Usually unstable especially if conjugated (n, n+2 double bonds)
More be significantly higher reactivity, toxicity and air reactivity
<<1 % generally required for stability
Acetylenes, contain carbon-carbon triple bonds
Considered very reactive, only present in trace amounts, and usually in some poorly-refined gasolines
<<0.1% generally required
Very stable, high octane. 10-50 vol% (25-35 vol% typical).
Tend to be limited by emission models
Benzene > > > toxicity than other aromatics, regulated separtately
Alkyl benzenes not considered smoke precursors, as they have vaporized and are not present at the
end of combustion, (see PNA)
Condensed ring aromatics (naphthalenes, alkyl napthalene, trace 3 ring)
Generally controlled to < < 1 vol% by boiling point or other specifications (220-225C vs. 260C
dimethyl napthalene)
Di-alkyl PNA are potent smoke precursors, and are very detrimental to spark ignition engine
operations.
Naphthalene and methylnaphthalene boil at 218C and 230C and are not considered to be potent
smoke pre-cursors. Di-methylnaphthalenes boiling above allows it to ring close on de-hydrogenation
to form a larger PNA. It turns it from a "chain ender" molecule to a "smoke precursor". The extra
methyl group on the aromatic allows this process to continue to completion of a multi-ring smoke
molecule.
Many other control measures can be used to control the same property.

68

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 3Properties of selected oxygenates.

Methanol
Ethanol
MTBE
ETBE
TAME
Gasoline

Oxygenates

Energy Content,
Net MJ/kg

Heat of Vaporization
MJ/kg

Oxygen Content
Wt%

19.95
26.68
35.18
36.29
36.28
42-44

1.154
0.913
0.322
0.310
0.323
0.297

49.9
34.7
18.2
15.7
15.7
0.0

(as Blend

Components)

See History of Gasoline (nonleaded and RFG). Table 3 provides properties of selected oygenates that are used as gasoline blend components.
Gasoline Additives
Additives are compounds added in trace a m o u n t s (<2500
p p m in the EPA "substantially similar" ruling), to enhance
some property of the fuel, or performance of the engine, vehicle, or emissions. Specifications and regulations allow for
additive use, and in some cases, require additive use, for example deposit control additives (DCA), which are beneficial
for in-use emissions.
Oxygenates

(De-icers,

Gas Line

Anti-Freeze)

Aliphatic alcohols and ethers added at 5-15 vol% are considered to be blending components and not "additives." However, at lower concentrations, low molecular weight alcohols,
especially methanol, ethanol, and iso-propanol, are effective
de-icing additives, commonly available as "gas line antifreeze." Alcohols are typically used in the 500-2500 ppmv
(0.05-0.25 vol%) range for this purpose, and function by preventing traces of water (typically from temperature drop and
condensation) from freezing in the vehicle fuel system. A
higher rate may be required for larger water contaminations,
or to prevent carburetor icing, which is accumulation of ice
in the carburetor throat and throttle plate. The cooling of
high humidity combustion air is caused by throttling (Joule
Thompson cooling) and fuel evaporation heat of vaporization
(auto-refrigeration). Gasoline with higher VP, Eind lower TIO
and T50 (high "front end" volatility) has a higher propensity
for producing carburetor icing
IPA is approved as aviation fuel system icing inhibitor
(FSII Type 2) at a treat rate of 1 vol% in aviation gasoline
(ASTM D 4171). Other alcohols and glycols have also been
used for carburetors or fuel line icing, including hexylene glycol, propylene glycol, dipropylene glycol, and various glycol
ethers. Methanol is the most commonly used for gasoline fuel
line freezing protection in fuel-injected vehicles in cold climates. De-icers are not commonly used in automotive fuels
in warm/cool climates, due to the low population of carbureted engines susceptible to carburetor icing. Some carbureted utility engines may require alcohols for operation in severe icing conditions ( > 8 5 % relative humidity, 0-10C).
Alkyl Lead

Compounds

Alkyl lead compounds are n o longer used in North American


automotive gasoline, because of the detrimental effects on
exhaust catalysts and concerns for health effects of alkyl lead

in the environment (see History of Gasoline). Nonleaded


specifications and regulations limit alkyl lead contamination
to 5 mg/L (Canada) and 0.05 g/gal (13 mg/L) (U.S.).
ASTM D 910 Aviation Gasoline lOOLL (low lead) has been
reformulated from the original 100/130 grade with the addition of aromatics (toluene) to reduce TEL to the lowest level
necessary to maintain the octane number and aircraft performance. Avgas is generally handled in segregated distribution systems, so is generally not a significant source of alkyl
lead contamination in automotive gasoline. With no other
source of alkyl lead contamination, typical trace alkyl lead
levels in North American gasoline are usually undetectable
by standard test methods.
Methylcyclopentadienyl

Manganese

Tricarbonyl

(MMT)

As the toxicity of the alkyl lead and the halogenated scavengers became of concern, alternatives were considered. The
most notable of these is methylcyclopentadienyl manganese
tricarbonyl (MMT), an organo-manganese compound with
similar antiknock properties as TEL, but at m u c h lower concentrations to obtain about 1-2 octane n u m b e r increase. It
was used in the United States in nonleaded gasoline in the
mid 1970s, b u t a n application for an EPA waiver was declined in October 1978, effectively banning it in nonleaded
gasoline in the United States. In December 1995, the EPA was
forced to grant the waiver in U.S. conventional gasoline (not
RFG), and MMT can be used in conventional gasoline up to
1/32 g Mn/usg (8.3 mg/L) in all states except California, where
it is regulated separately [24]. In a separate case, the court
held that EPA's new rules that require pre-meirket testing of
new gasoline additives did not apply to MMT. The EPA has
stated it intends to monitor MMT use, but MMT was used in
only 0.02% of gasoline in 1998.
MMT has a high toxicity in concentrated form, but the
combination of relatively low volatility and its miscibility
with aromatic hydrocarbon solvents allows it to be stored
and handled with tj^ical equipment. MMT is light unstable
with a half life of about 30 s in strong sunlight, forming a
characteristic red "rust" colored precipitate (Mn02). This oxide is softer t h a n iron oxides, and is not considered to be
abrasive even at much higher concentrations than typically
used in gasoline.
MMT has been in continuous use in Canada since the first
introduction of nonleaded gasoline in 1972 to a maximum of
18 mg/L Mn, without major incidents. Most problems attributed to MMT are associated with excessive exhaust or catalyst temperatures. These cause the manganese oxide to "ceram" and form a gas impermeable glass that can coat and
effectively deactivate the catalyst [25] This is also associated
with front face catalyst plugging, due to the "sticky" nature of
the glass. Field experience indicates that this is not a serious
problem in tj^jical driving cycles, including Tier 0 and 1 vehicles equipped with OBDII emission control monitoring systems. Two provincial inspection a n d m a i n t e n a n c e (I&M)
programs using IM240 (d3mo driving cycle) and ASM2525
(25 m p h steady state dyno) test cycles have not found or identified any emissions related problems due to MMT on model
years 1982 to present.
Proponents claim benefits in NOx reduction, protecting the
catalyst from long term deactivation by sequestering catalyst
poisons (Zn, P, Pb) or coke, fuel cost benefits, emissions re-

CHAPTER
duction from reduced refining severity, and lack of adverse
health effects. Opponents cite high exhaust temperature catalyst plugging, exhaust gas sensor "rich shift" for the NOx effect, spark plug tracking, and the potential for adverse health
effects.
Dozens of controlled and noncontrolled tests and surveys
over 35 years have failed to conclusively resolve the debate
[26,27,28], probably because the test result depends upon the
specific automobile year and model being tested and how the
test is done.
Several countries are considering MMT as an alkyl lead replacement additive to facilitate alkyl lead phasedown.
Iron based

Organo-metallics

Other compounds that enhance octane have been suggested,


b u t usually have significant problems such as toxicity, cost,
a n d increased engine wear, especially if used at high
concentrations.
Dicyclopentadienyl iron (ferrocene) a n d nickel carbonyl
have been promoted as alternatives to alkyl lead and MMT.
For example, the addition of 0.02-0.04 g/L ferrocene with
0.05-0.10 g/L tertiary butyl acetate is reported to increase the
AKI of susceptible gasoline hydrocarbon feedstocks by 4-6.
More recently, ferrocene has been promoted as an octane
enhancer at lower levels of 9 mg/L Fe to avoid any significant
deposition or wear problems. The benefit is reduced to about
1-1.5 octane n u m b e r at this level (similar to MMT). Unlike
m a n g a n e s e oxides, iron oxides do not ceram at high
temperature.
Iron pentacarbonyl (Fe(CO)5) was used in Germany at levels of 0.5% or less in gasoline during the 1930s. While the cost
was low, the carbonyl decomposed rapidly when the gasoline
was exposed to light to form iron oxides. It also has a relatively high vapor pressure, and is extremely toxic in concentrated form, so must be handled with care. Use of the additive
at high concentrations in gasoline caused excessive deposition of iron oxide (Fe304) on the spark plug insulator, causing short circuits. The precipitation of iron oxides in the lubricating oil also led to excessive wear rates [29].
Iron picrate (trinitro phenate) and related oil soluble iron
chelates are sometimes sold as aftermarket additives with
various performance claims, but are not used in commercial
production.
Performance

Additives

Most other additives are added to address specific safety or


p e r f o r m a n c e properties of gasoline. Typical examples
include:
1. Oil-soluble dye was originally added to leaded gasoline at
about 10 p p m to prevent misuse of leaded gasoline as an
industrial solvent, and is now also used to identify grades
or brand of product. Red dyes are currently used in the
U.S. and Canada to mark fuels that have different taxation
rates for different uses.
2. Antioxidants (oxidation inhibitors) typically phenylene diamines (PDA) or hindered alkyl phenols, are added to slow
down oxidation of hydrocarbons, especially unsaturated
hydrocarbons. These additives are "sacrificial," and once
consumed, the oxidation reactions rapidly become autocatalytic, increasing exponentially in rate to form soluble
and insoluble gum ("varnish").

3: MOTOR

GASOLINE

69

3. Metal Deactivators, typically about 10 p p m of chelating


agent such as N,N'-discJicylidene-l,2-propanediamine is
added to inhibit copper catalyzed air oxidation of gasoline
4. Ferrous Corrosion Inhibitors, about 5-20 p p m of oilsoluble surfactants, are added to prevent aqueous-based
corrosion caused either by water condensing from watersaturated gasoline, or from condensation from air onto the
walls of almost-empty gasoline tanks that drop below the
dew point. Many pipelines require addition of corrosion
inhibitor for protection of pipeline and storage tanks. The
NACE 0172 "rust" test is commonly used to establish
addition rate for corrosion protection. A variety of comp o u n d s are effective as corrosion inhibitors, including
dimer carboxylic acid esters, amides, alkanolamides, and
hydroxyesters. Phosphorus based corrosion inhibitors are
no longer used in nonleaded gasoline because phosphorus
is a potent catalyst poison, and is controlled by both ASTM
specification and regulation. ASTM specifications allow,
but do not require, corrosion inhibitor or corrosion
testing.
5. Lubricity additives are occasionally used in gasoline, and
are usually similar in chemistry to corrosion inhibitors,
but at higher treat rates.
6. Copper corrosion inhibitors are occasionally used to mitigate sulfur-based corrosion of copper or other easily corroded base metals if/when used in fuel systems.
7. Anti-wear additives are used to control wear in the upper
cylinder and piston ring area that the gasoline contacts,
and for valve sticking. They are usually very light hydrocarbon oils ("top" oils, "solvent" oils), although synthetics
are now preferred, due to potential problems with combustion chamber deposits. If permitted, phosphorus-based
additives can also be used in engines without exhaust catalyst systems.
8. Cleanliness or Deposit-modifying Additives are used to
mitigate (keep clean) or reduce (clean up) deposits. Some
specific types of deposits are discussed below.
Carburetor DepositsAdditives
were required w h e n
crankcase blow-by positive Crankcase Ventilation (PCV)
and exhaust gas recirculation (EGR) controls were introduced (in the 1950s on some engines). Some fuel
components reacted with these gas streams to form deposits on the throat, throttle plate and idle air bleeds of
carburetors and some throttle body injectors.
Fuel Injector DepositsDeposits can form in the annulus
or sealing surfaces in some pintle needle or poppet valve
injector designs during hot soak (>100C), suspected to
be mainly from the oxidation and polymerization of the
least volatile or unsaturated hydrocarbons. The additives that prevent and unclog these tips are usually polybutene succinimides, polyisobutylamines, or polyether
amines, and are often used in combination with "fluidizer" or "solvent" oil.
Intake Valve DepositsIVDs caused major problems in
the mid-1980s with widespread introduction of electronic fuel injectors a n d three way catalyst systems.
Some vehicles experienced severe driveability problems
even when fully warmed, even though the amount of deposit was considered acceptable by historical carbureted
engine standards. It was proposed those new fuels and
engine designs were producing a more porous deposit

70

MANUAL

3 7: FUELS

AND LUBRICANTS

HANDBOOK

on the valve tulip (fuel side) face. The close proximity of


the liquid fuel injector caused some liquid fuel to be absorbed in the deposit, causing lean/rich transients resulting in hesitation, misfire, and excess emissions. Deposit Control Additives (DCA) were mandated in 1992 in
California and Federally in 1995 and by CGSB specification in 1994 due to the emissions increase. Intake valves
operate about 300C, and if the valve is kept wet with
thermally stable oil in conjunction with a dispersant/detergent, deposits tend not to form. Solvent oil/dispersant/detergent additives that are effective with IVD also
tend to be effective for fuel injector deposits. Gasoline
factors implicated in these deposits include unsaturates
and alcohols, as well as oil leakage through the valve
guides.
Combustion Chamber DepositsCCD were targeted in
the 1990s, as they are responsible for significant increases in emissions. Severe deposit accumulation resulted in CCD interference (CCDI) where the deposit
contacted the cylinder head at TDC, resulting in noise,
and eventual engine damage. Additives have a limited
ability to remove pre-existing CCD, so DCA additives are
tested for their propensity to avoid formation of CCD relative to the base gasoline. Gasoline factors that contribute to heavier deposits are the presence of alcohols
or olefins. Gasoline manufacturers now routinely use
additives that prevent IVD and also maintain the cleanliness of injectors. These usually include surfactant and
light oil to maintain the wetting of important surfaces.
Intake valve deposits can also have significant adverse
effects on emissions, and deposit control additives are
now standard to reduce emissions and provide clean engine operation.
Trace Constituents

and

Contaminants

1. Free Water"haze" is considered to be a contaminant, associated with corrosion, filter plugging, and freezing problems. The large difference in density usually allows water
to settle out from traditional gasoline, and most additive
packages are checked for any propensity to stabilize a water haze and prevent water dropout. Gasoline components
are often dried at the refineries supplying gasoline into
very cold winter distribution systems, to prevent water to
phase separate due to condensation on cooling down.
Most specifications have a dryness, "clear and bright,"
(such as ASTM D 4176 for distillate fuels) or some similar
"suitable for use" criteria.
2. Sulfur, nitrogen, and oxygen are naturally occurring trace
constituents of crude oil, and are present in fuels at the
p p m level. These CEin be present as ashless, combustible,
additives. Nitrogen is typically not regulated in gasoline
formulation because the source of nitrogen in NOx emissions is from atmospheric N2, and not the fuel. The maxim u m sulfur specification prior to regulation was t3^ically
0.1-0.15 wt%. Current California a n d future U.S. a n d
Canadian regulations will reduce sulfur to a yearly pool average 30 p p m by 2005/6. Regulated changes to the baseline
gasoline used in any predictive model based regulation
equates to a change in the gasoline production required for
equivalence, including sulfur, which has a large impact on
the predicted emissions. This would restrict the use of any

sulfur containing additives in the future. (See Reformulated Gasoline for more detail.)
3. Gasoline may be contaminated by other partially soluble
or miscible liquids, such as kerosene, diesel, and oxygenates. Oxygenated fuel can have a higher solubility of
water-soluble contaminants, as well as allowing water-soluble c o m p o n e n t s to c o n t a m i n a t e any fresh water that
comes into contact with it.
4. "Adulterants" or "extenders" have occasionally been deliberately added to gasoline to increase the volume sold. Materials used have included new or used solvents, used lube
oil, formic/acetic acid, heJogenated solvents, refrigerants,
dry cleaning solvents, silicon oils/caulking/adhesives, and
even PCBs. Deliberate adulteration is usually involved
with a criminal activity for illegal waste disposal or fuel tax
fraud. Some jurisdictions now have "contaminated fuels
regulations" that prohibit these activities.
5. Particulate contaminants, such as dirt and corrosion products, can be readily removed by standard filtration procedures, and increasingly stringent cleanliness requirements
are resulting in a n increasing use of microfiltration at
truck loading and/or point of sale.

GASOLINE COMBUSTION
Spark Ignition

Engines

Spark ignition engines are ideally suited for light duty transportation uses. Their relatively lightweight (compared to
other internal combustion engines), wide REM range, broad
torque band, and high maximum RPM/power provide good
performance with a m i n i m u m number of transmission gears.
Vehicle spark ignition engines are air throttled to control
power, a n d have inherent limitations on peak cylinder temperatures and pressures due to engine "knock," so are thermally less efficient than compression ignition engines. As a
result, diesel engines d o m i n a t e the high torque, low r p m
heavy-duty truck, marine, locomotive, and stationary power
applications. Smaller high-speed diesel engines comprise
only a small percentage of the light duty vehicle market in
North America, but are more prevalent in Europe. This is
driven mainly by their significantly higher fuel efficiency,
which provides a significant market advantage, especially in
regions with high fuel prices.
Electronic fuel injection has replaced carburetors on essentially all Tier 0, Tier 1, and later model automobiles. This
facilitates "closed loop" computer control of air/fuel ratio, to
maintain exhaust composition within a n a r r o w range required for optimal operation of a "3-way" catalyst. The name
"3-way" is a reference to effectiveness for all three regulated
exhaust emissions: u n b u r n e d hydrocarbons (HC), carbon
monoxide (CO) by air oxidation, and oxides of nitrogen (NOx)
by chemical reduction with HC/CO. These systems require
the engine to operate in a narrow air-fuel ratio band on both
rich and lean side of stoichiometric, to maintain both the regulated emissions HC, CO, and NOx and O2 in the optimal
range where they react to extinction.
Hybrid gasoline-electric vehicles couple internal combustion engines with an electric motor for peak power and transient engine operations to obtain ultra-low "steady state"
emissions with no significant loss in performance. A smaller,

CHAPTER
generally m u c h higher voltage battery set stores enough
power for several minutes of high power electric motor operation for cold start or accelerations. This allows a n u m b e r of
very efficient and ultra low emission driving cycles, since the
majority of SI engine emissions are due to transient operations and cold start, before the catalyst heats up. The SI engine can shut down (zero emissions) during cold start or if
required for urban ZEV emissions. It can run at steady state
(for example on the highway) letting the electric motor handle variable power requirements (hills, wind load, comers,
etc.) that would otherwise cause increased emissions from
transient SI operation. It can be r u n at a higher steady state
power, using the electric motor as a generator to recharge the
batteries. Elimination of transients tends to provide highway
fuel efficiency in urban driving cycles, and ultra low emissions (lower t h a n the Super Ultra Low Emission Vehicle
(SULEV) level. The 2004 Tier 2 LDV Bin #2 NMOG standard
of 0.01 g/mile is about a 90-95% reduction from current levels (0.125-0.25 g/mile), over 99.8% reduction from the 1990
levels (4.1 g/mi), and 99.9% reduction from precontrol
(est. 10.6 g/mile).
Other hybrid vehicle types have been proposed, such as
diesel-electric or gasoline-hydraulic, or gasoline-flywheel,
but only gasoline-electric are being commercialized at this
time. It is anticipated that both current RFG and 30 p p m sulfur future RFG will be compatible with hybrids, but that the
lower sulfur will provide slightly lower in-use emissions.
Gasoline Direct Injection (GDI) engines (Spark Ignition Direct Injection, SIDI, etc.) have thermodynamic efficiencies
between SI and diesel engines, and may be commercialized
in the near future. Fuel requirements for GDI have not been
established. Exhaust particulate matter may be more critical
for GDI than for current engine/emissions systems.
Engine

Management

Systems

Engine management systems are now an important part of


the strategy to reduce automotive pollution. A typical m o d e m
engine system would monitor and control: mass airflow (or
MAP/RPM calculated air flow), exhaust oxygen sensor
(lambda sensor), knock (vibration/noise) sensor, EGR, throttle plate angle, manifold air temperature and pressure, crank
angle, and transmission gear. These systems can compensate
for altitude (MAP), ambient air temperature (MAT), fuel oct a n e (knock sensor), humidity, a n d gasoline composition
(oxygen sensor, adaptive map). The engine control module
(ECM, computer) then sets the ignition timing and fuel injector open time (fuel flow), and fuel injection timing with
crank angle that are appropriate for the current engine operating conditions.
Almost all TierO/1 engine control systems incorporate
"adaptive memory maps" or adaptive learning strategies. The
fuel m a p (or schedule) conceptually consists of three blocks
of data organized like three sheets in a spreadsheet, with the
rows and columns representing different RPM and manifold
vacuum, which together define the engine load. The three
sheets contain fuel injector open time for the factory "baseline" settings, the long-term block learn, and the short-term
block learn. Conceptually, the data is a c o m p u t e r binary
n u m b e r such as 0 to 255 for an 8-bit computer. This might
represent, for example, how many milliseconds the fuel injector should be held open, since open time is proportional to

3: MOTOR

GASOLINE

71

fuel volume delivered at constant pressure. The adaptive


maps would start out at mid-range (128), and the total number of milliseconds injector open time would be the sum of
the corresponding cells of the three tables for the engine
speed and load at that instant of time. The ECM would modify them according to the response of the oxygen sensor. If it
was consistently lean for several seconds (too much oxygen
in the exhaust) then the ECM will add one n u m b e r to the fast
learn block, making it 129, and adding one unit of time to the
injector open time, slightly enriching the mixture. This continues until the fast learn block hits its upper limit, when the
ECM t3?pically adds one to the long term block cell, and resets
the fast learn to its mid value. The long term and fast learn
blocks are similar to a "course and fine" control, where the
fast learn steps are smaller, but occur faster. The long term
map, as the n a m e implies, adjusts for long term trends, for
example a slow drop in fuel rail pressure due to a p u m p wearing out over the lifetime of the car, a partially plugged fuel filter, or slowly fouling fuel injectors. The fast learn block takes
care of smaller but faster changes, such as changing altitude,
humidity, or tank to tank gasoline composition differences,
such as switching between high and low aromatic or oxygenated gasoline. This is also the reason that composition
mandates are less effective for newer cars than older cars,
especially oxygenates for cold high altitude CO control, as the
ECM quickly adjusts the air-fuel ratio according to the oxygen sensor readings at the time.
One artifact of this system is that a dead or disconnected
battery can cause memory loss of the adaptive maps, so that
the vehicle drivability can be very poor while the ECM
reloads the m a p with data appropriate for the car, engine,
fuel, and ambient conditions at the time.
All U.S. a n d Cdn LDVs n o w have on-board diagnostics
version II (OBDII) that monitor the critical emission system
components for conditions that cause high tailpipe emissions
or are detrimental to continued operation. The ECM lights
the Malfunction Indicator Light (MIL) light on the dash,
commonly called the "check engine" light. OBDII warns of
malfunctions such as engine misfires, exhaust catalyst failure
(inferred from oxygen sensor time delays), and evaporative
emissions failure such as a leaking gas cap (fuel tank pressure). Chronic misfire, for example causes combustion of unb u m e d air/fuel on the catalyst, with the potential to generate
so much heat that the catalyst activity drops, or the catalyst
substrate melts.
The air-fuel ratio is controlled at part throttle by a closed
loop system using the oxygen sensor in the exhaust and the
knock sensor (if equipped). Typical engine calibrations
enrich the air-fuel ratio for smoother, stall free idle when in
closed loop control, and hold a faster idle after cold start
when in open loop, until the catalyst becomes heated and
"lights off." The a m o u n t of idle enrichment used is often
adjusted according to the air t e m p e r a t u r e at the time of
engine start (similar to the function of a choke on a carburetor acting against a bimetal temperature spring that held the
choke on longer when cold until the engine heated up).
Air - Fuel Ratio and

Stoichiometry

Ideally, hydrocarbons and oxygenates in gasoline combust


smoothly to form water, carbon dioxide, and heat energy,
with no other by-products. Non-ideal combustion affects

72 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


emissions, efficiency, engine durability, and vehicle operation. Severe engine knock is associated with loss of efficiency
a n d engine damage. If there is excess fuel ("rich" air/fuel
ratio), the combustion is not complete, and carbon monoxide
(CO) will be formed, Eilong with u n b u m e d or partially burned
hydrocarbons (HC). As CO can be burned to produce CO2, it
is " u n b u m e d " fuel, so t h e r e is a d r o p in efficiency a n d
increase in emissions. Nitrogen oxides are formed as a result
of conversion of nitrogen (N2) in air to various nitrogen
oxides (NOx). High peak combustion temperatures promote
NOx ("lean" air/fuel ratio, high intake air temperature, low
humidity, high barometric pressure, high load).
The required mass or volume of air to provide sufficient
oxygen to achieve this complete combustion is the "stoichiometric" mass or volume of air. Insufficient air creates "rich"
mixtures, and excess air creates "lean" mixtures. The stoichiometric mass of air for a gasoline is related to the carbon:
hydrogen ratio of the fuel. The procedures for calculating the
stoichiometric air-fuel ratios are fully documented in SAE J
1829 [30]. However, oxygen (20.9476 vol%). Nitrogen
(78.084%), and Argon (0.934%) comprise 99.966 vol% of the
atmosphere. The use of nominal masses (O2 = 16) versus natural abundance masses (O2 = 15.994) and ideal gas assumption (vol% = mole) will result in errors of less than 0.5%, because the errors tend to cancel (nominal MW of nitrogen
lower than natural abundance offset by higher MW of Argon
vs. nitrogen).
As a result, it is c o m m o n to assume that the non-oxygen
component of the air is nitrogen, which can be added to the
equations when the exhaust compositions are required. The
error is generally m u c h smaller than the analytical uncertainty of the actual carbon hydrogen ratio of a real gasoline,
by elemental analysis or cap GC. If needed, exact molecular
weights can be calculated from molecular formula and standard periodic tables weight, or from ASTM GC method peak
tables for individual hydroccirbons.
For n o r m a l h e p t a n e C7H16 with a molecular weight =
100.204:
C7H16 + 1 1 0 2 ^ 7CO2 + 8H2O
The chemical stoichiometric combustion of hydrocarbons
with oxygen can be written as:
CxHy + (x + (y/4))02 -^ XCO2 + (y/2)H20
t h u s 1.000 kg of CyHife requires (1/100.204) * 11 * 2 *
16 = 3.513 kg of O2 and using approximation,
(3.513 kg of O2 + (3.513/32)
* (28*79.0524/20.9476) = 15.113 kg of air.
(Air-fuel ratio = 15.113 vs 15.179)
Gasoline

Energy

Content

The energy content (heat of combustion) is the total amount


of energy obtained by combustion of gasoline under standard
conditions, usually at STP, as if the fuel and air started at STP,
and the combustion products are cooled down to STP. Energy
captured at other conditions will be different. For example,
emitting a hot exhaust from an engine will not capture the
heat energy from cooling the exhaust back to STP.
The heat of combustion is useful to compare fuels under
the same standard conditions. It is measured by combusting

all the fuel inside a b o m b calorimeter and measuring the heat


released as evidenced by a t e m p e r a t u r e increase u n d e r
controlled conditions. If the combustion is not complete,
carbon monoxide (CO) and/or unburned or partially combusted fuel will be formed, resulting in a lower than true
energy content. The reported heat of combustion depends on
what happens to the water produced from the combustion. If
the water remains as a gas, then it cannot release the heat of
vaporization, thus producing the net (or lower) heat of combustion. If the water were condensed back to the original fuel
temperature, then the gross (or higher) heat of combustion is
reported.
For internal combustion engines, the net heat of combustion is more appropriate, as the water is emitted as vapor.
The engine cannot utilize the additional energy available
when the steam is condensed back to water. This is sometimes confused for lower emd higher thermal efficiency of
diesel versus spark ignition engines or the lower/higher net
heating value of diesel fuel versus gasoline. However, the
net/gross or lower/higher heating value oiany fuel is simply a
reference to whether the water of combustion is condensed
and captured by the process, or exhausted as a vapor and lost
to the process.
Standard heats of combustion for hydrocarbon molecules
and for reactions involved in combustion are available from
a number of engineering and chemistry texts and references.
This includes ASTM Dataseries DS4B, Physical Constants of
Hydrocarbon and Non-Hydrocarbon Compounds, and others.
Because all the data are available, the calorific value of fuels can be estimated quite accurately from calculation detailed GC analysis or by correlation with hydrocarbon fuel
properties such as the density, sulfur content, and aniline
point (which indicates the aromatics content).
Oxygenates contain oxygen that has already reacted in the
production process, and cannot provide additional energy at
the point of use in the engine, so they have significantly lower
energy contents. For an engine that can be optimized for oxygenates, more volumetric fuel is required to obtain the same
power. However, the decrease in volumetric fuel efficiency
(mpg) tends to be less than the energy content decrease. See
Table 4 for properties of selected oxygenates.
For a water-cooled SI engine with 2 5 % useful work at the
crankshaft, the losses may consist of 35% coolant, 33% exhaust, and 12% surroundings. SI engines have inherently
lower thermal efficiencies than diesel engines, mainly due to
throttling of the engine at partial power, and higher diesel engine compression ratio. Even at wide open throttle, equivalent displacement CI engines have higher thermal efficiency
because of higher compression ratio, so this advantage extends over the entire operating range.
Octane rating is fundamentally not related to the energy
content, although the actual hydrocarbon a n d oxygenate
components used in the gasoline will determine both the energy release and the antiknock rating. However, it is possible
to make correlation between energy content and octane that
are mostly meaningless and often confusing. For example,
addition of ethanol to a blend can increase the octane, while
decreasing the energy content, while adding pure aromatic
increases both. Add to this the difference between energy per
fuel liquid volume versus energy per fuel weight, and one can
generate octane versus energy graphs that go up, down, or

CHAPTER

3: MOTOR

GASOLINE

73

TABLE 4ASTM research and motor octane number test conditions.


ASTM D 2700 MON
ASTM D 2699 RON
Cooperative Fuels Research
Cooperative Fuels Research
Engine
(CFR)
(CFR)
600 RPM
Engine Speed
900 RPM
Variable with Barometric P.
38C
Intake Air Temperature
88 kPa at 19.4X,
101.6 kPa at 52.2C (Temperature
Tuned with Toluene Standardization
Fuel 22C from lAT)
Intake Air Humidity
3.56-7.12 g HzO/kg dry air
3.56-7.12 g HaO/kg dry air
149C (Temperature Tuned with
Not Specified
Intake Mixture Temperature
Toluene Standardization Fuel
141-163''C)
lOOX
100C
Coolant Temperature
57C
Oil Temperature
57C
Ignition Advance
Variable with Comp. Ratio
13 degrees BTDC (fixed)
14-26 degrees BTDC
Carburetor Venturi
14.3 mm
Variable with Altitude
14.3 mm at 0-500 m
Test Method

sideways, dependent entirely on what materials and units are


chosen.
Gasoline Octane Performance Properties
Combustion

and Knock

in

Engines

The critical fuel property of gasoline for internal combustion


engines is resistance to engine "knock," expressed as the octane n u m b e r of the gasoline. During a normal (no knock)
combustion cycle, a flame front travels smoothly from the
point of ignition at the spark plug outweird toward the cylinder walls. While this is occurring, the "end gas," or u n b u m e d
fuel/air mixture ahead of the flame front is heated and compressed. If the end gases ignite before the flame front arrives,
the resulting sudden pressure wave reverberates across the
combustion chamber, causing an audible engine knock. This
adversely affects output power and dramatically increases
heat transfer to the piston and other combustion chamber
surfaces. While this can cause damage on its own if severe
enough, knock induced preignition can cause rapid catastrophic engine failure. This tends to be a runaway condition.
Once started, it gets progressively worse until eventual engine failure, unless the throttle/load is cut quickly, as failure
can occur in less than a few minutes. High heat transfer during heavy knock can cause deposits or sharp edges (for example combustion chamber deposit or exposed thread of a
spark plug) to overheat. This can act as a "glow plug" type ignition source, causing ignition of the charge before the spark
on the next combustion stroke "preignition." This leads to excessively high combustion chamber temperature and pressure from combustion closer to TDC, and rapidly increasing
knock intensity. Initial stages of knock damage look like pitting on the piston top, as if it had been attacked with an ice
pick or awl. The increased temperature and heat transfer to
the piston top eventually causes melting of the crown land
down to the rings. The final stage is either catastrophic engine failure from thrown connecting rods (metal softening
near the piston wrist pin, causing the piston to separate from
the connecting rod), or engine seizure (expansion of the piston, excessive friction heat, and loss of lubrication). Either

condition is sufficient to ruin one's day (in addition to the


engine).
The octane (and autoignition temperature) of various hydrocarbons is related to their ability to withstand preflame
conditions without decomposing into species t h a t could
auto-ignite before the flame-front arrives. Unburned "end
gases" ahead of the flame front encounter 700C temperatures due to compression and heat transfer, and commence a
series of complex preflame reactions. These reactions occur
at different t h e r m a l stages, with the first stage (around
400C) commencing with the addition of molecular oxygen to
alkyl radicals. The internal transfer of hydrogen atoms within
the new radical forms an unsaturated, oxygen-containing
species following this stage. These new species are susceptible to chain branching involving the HO2 radical during the
intermediate temperature stage (400-600C), mainly through
the production of OH radicals. Above 600C, the most important reaction that produces chain branching is the reaction of
one hydrogen atom radical with molecular oxygen to form O
and OH radicals.
' Common antiknock additives work by interfering at different points in the preflame reactions. The alkyl lead antiknock
compounds interfere with hydrocarbon chain branching in
the intermediate temperature range, where HO2 is the most
important radical species. Alkyl lead oxide, either as solid
particles, or in the gas phase, reacts with HO2 and removes
it from the available radical pool. This reduces the major
chain branching reaction sequence that results in undesirable, easily auto-ignitable hydrocarbons [31,32]. Oxygenates
retard the progress of the low t e m p e r a t u r e or cool-flame
reactions, consuming radical species, particularly OH radicals and producing u n s a t u r a t e d hydrocarbons like isobutene. The iso-butene would, in turn, consume additional
OH radicals and produce unreactive, resonantly-stabilized
radicals, such as allyl- and methyl allyl-, as well as stable
species such as allene, which resist further oxidation [33,34].
Anti-knock

Ratings

of Fuels

The Anti Knock Index (AKI) is the average of the Research


Octane Number (RON, D 2699) and Motor Octane Number

74

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

(MON, D 2700), sometimes expressed as (RON+MON)/2 or


(R+M)/2. The on-line Comparitor Engine method D2885 determines octane numbers that are equivalent to "lab" RON
and MON values, and can be used for blend certification and
release. The RON and MON methods use two primary reference fuels, n-heptane and 224 trimethyl pentcine, assigned octane numbers of 0 and 100, respectively. The knocking intensity of the test fuel is c o m p a r e d to that of reference fuel
blends. The volume percent of iso-octane in the blend that
gives the same knock intensity as the test fuel is taken as being the octane n u m b e r of the test fuel (See History of Octane
Rating).
The same standard engine is used for both tests, but r u n at
different test conditions. The conditions of the MON engine
tend to simulate hot, highway driving, whereas the RON test
is more like heavy acceleration from a traffic light. The difference between the RON a n d MON for a given gasoline
("sensitivity") depends upon the composition of the blend.
The RON and MON of parafins and isoparafins is almost the
same, so high isoparafins (low aromatic, low olefin) blends
tend to have low sensitivities, sometimes below four numbers. Aromatics have intermediate sensitivities and olefins
have the highest sensitivity, so gasolines that have high catalytically cracked content (high olefins) will have high sensitivity (RON-MON), as high as about 14.
ASTM D 4814 recommends a m i n i m u m MON of 82 for Regular grade gasoline heavy-duty engine applications, but uses
AKI for all other recommended uses. Two different 87 AKI
gasolines with extreme compositions could have a RON/MON
of 94/80 or 89/85. On average they would give similar perform a n c e over a range of engine operating conditions, but for
certain applications one may be preferred over the other. For
a n engine operating under more MON like conditions, the
87/85 blend will provide knock free operation at more severe
conditions than the 97/80 blend. In the late 1960s select European automakers experienced catastrophic engine failures
on high speed Autobahn runs, even though the Research Octane of the fuel was within specification. They discovered that
either the MON or the Sensitivity (the numerical difference
between the RON and MON) also had to be specified to ensure
adequate performance under severe high speed Autobahn
condition. Similarly, many marine and utility engines run at
high load and WOT, and are susceptible to knock damage
from too low a MON. In the late 1970s and early 1980s several
automotive and marine OEMs promoted development of an
even more severe octane method, due to concerns that the
high octane contribution from alcohol in the MON test did not
appear under their most severe wide open throttle engine operating conditions. However, this was not pursued, Eind some
OEMs recommended higher octane 89-91 AKI grades or no
oxygenates or methanol for severe marine, snowmobile, outboard, or utility engine applications.

and cylinder casting can be adjusted relative to the


crankshaft using a crank handle to obtain the desired compression ratio. The engines have a special four-bowl carburetor that permits individual bowl air-fuel-ratio adjustment
and provides rapid switching between reference fuels and
samples. A magnetorestrictive detonation sensor in the combustion chamber now measures the rapid changes in combustion chamber pressure caused by knock, and the amplified signal is measured on a "knockmeter" with a 0-100 scale.
Only one company currently manufactures these engines, the
Waukesha Engine Division of Dresser Industries, Waukesha,
Wisconsin, 53186.
Two related methods can be used to obtain the octane
n u m b e r of the test fuel, the bracketing procedure or the
"compression ratio" procedure. For the bracketing method,
the engine compression ratio is adjusted to produce a m i d
range knock intensity of about 50 on the knockmeter, with
the air-fuel ratio adjusted on the carburetor bowl to obtain
m a x i m u m knock. At least two blends of primary reference fuels are made, one that is one octane n u m b e r above the expected rating, and another that is one octane number below
the expected rating. The PRF blends are placed in different
bowls with their air-fuel ratios adjusted for maximum knock
during rating. The higher-octane reference fuel should produce a reading of around 30-40, and the lower reference fuel
should produce a reading of 60-70. The actual fuel rating is
interpolated from the knockmeter readings of the sample and
the two PRFs.
For the CR procedure, a calibration curve is prepared of
knock intensity versus compression ratio for a PRF blend
that has a n octane n u m b e r within prescribed limits from the
sample. The octane n u m b e r of the sample is the octane number of the single PRF used to calibrate the engine, corrected
for barometric pressure and difference in knock intensity using the calibration curve. The D2885 "comparator" method
uses the CR procedure, but using a Standard Reference Fuel
(SRF) instead of a PRF (see D 2885).
Motor Octane Rating ASTM D 2700
The conditions of the Motor method represent severe, sustained high engine speed, high load (but not wide-open throttle) driving. For most hydrocarbon-fuels, including those
with either alkyl lead or oxygenates, the Motor Octane Number (MON) will be lower than the Research Octeine Number
(RON).
Research

For Anti-Knock

Rating

Fuels

Automotive octane ratings are determined in a standardized


single-cylinder engine with a variable compression ratio (CR
4:1 to 18:1), operated under standard conditions (Table 4)
Cooperative Fuels Research (CFR) engine. The cylinder bore
is 82.5 m m ; the stroke is 114.3 m m , giving a displacement of
612 cm^. The piston has four compression rings, and one oilcontrol ring. The intake valve is shrouded. The single head

ASTM D 2699

The research m e t h o d settings represent typical high load


(throttle opening) and low to medium engine speeds resulting in low inlet mixture temperatures and moderate loads on
the engine. See Table 5 for test conditions
On-Line

Procedure

Octane Rating

Analyzer

Octane Rating ASTM

D 2885

On-line octane rating analyzers used in refineries are described in ASTM D 2885, taking a continuously flowing slip
stream of gasoline from current production, and measuring
the RON and MON continuously. The same engines and conditions are used, so consequently results Eire equivalent to the
laboratory MON or RON procedure.
Instead of "bracketing" the test fuel with primary reference
fuels, D 2885 uses "Standard Reference Fuels," commonly

CHAPTER
called "protos" or "gold protos" that are production gasoline
that have been rated by about 20 different laboratories, and
assigned the average value determined by the group. The SRF
is required to be close in octane to the test fuels, so that the
difference in octane n u m b e r can be derived from the difference in knock intensity between the SRF and the test fuel.
Standard Reference Fuels are developed through cooperative exchange programs, usuedly administered in association
with an accredited Standcirds Writing Organization. Examples in North America are National Exchange Group under
the auspices of ASTM, the Canadian Cooperative Exchange
under the auspices of the CGSB, and the Rocky Mountain Exchange, representing refiners in high altitude areas (now associated with the NEG).
Octane Distribution

Throughout

Fuel Boiling

Range

Severe knock can be experienced in some engines if octane


level is not distributed throughout the boiling range of a fuel,
for example a low octane front end with a high octEine back
end. This "octane distribution" is most critical during changes
in mixture flow in manifolds, such as sudden full throttle acceleration at low speed and high load. Under these conditions,
manifold pressure drops suddenly at low airflow. The fuel can
segregate by boiling range in the manifold, with the very
volatile fraction reaching the combustion chamber first and,
if that fraction is deficient in octane, then knock will occur until the less volatile, higher-octane liquid fractions eirrive.
Historically, small displacement engines tend to be the
most affected, as they experience the largest changes in manifold conditions during n o r m a l u r b a n driving. Large displacement engines equipped with "hot spot" manifolds, intake mEinifold runners, etc., tended to be the least affected.
Most urbcin driving was at relatively low throttle range and at
high manifold vacuum that tended to moderate these effects.
The delta RON ratings Eire not currently used in the U.S.
M o d e m engines with short inlet meinifolds and Port Fuel
Injection are usually less sensitive to fuel octane distribution.
However, the addition of nonhydrocarbon components into
reformulated gasoline of different volatility may affect sensitive engines.
Leaded fuel octane distribution was good, as the tetramethyl alkyl lead and tetraethyl alkyl lead octane volatility profiles were well characterized, and TML-TEL ratio could be
adjusted to provide distribution of octane throughout the
boiling range. Nonleaded gasoline must be properly blended
without using TML to obtain acceptable results.
The "Delta RON" test was developed to measure the difference in octane between the front ind back "half" of the gasoline. The fuel is distilled to a specified temperature, which is
usually 100C. Both the parent fuel and the distillate fraction
are t h e n rated using the Research Octane m e t h o d . The
difference between these is the delta RON (100C), usually
just called the delta RON.
During the 1990s, there have been some concerns in Europe about the high sensitivity of some commercially available nonleaded fuels.
Octane Number

Requirement

(ONR) of

Vehicles

The actual octane requirement of a vehicle is called the Octane N u m b e r Requirement (ONR). It is determined by monitoring for the onset of knock while accelerating the vehicle

3: MOTOR

GASOLINE

75

using a series of progressively lower octane fuels. Three sets


of fuels are used: the primary reference fuels (PRF), and two
full boiling range fuels with high and low sensitivity (RONMON). In Europe, delta RON (100C) fuels are also used. The
lowest octane fuel that provides knock free acceleration is the
ONR of the vehicle under the conditions of the test. Results
are then used to predict the performance of typical commercial gasolines.
The original "Uniontown" road octane rating procedure
used in development of the original MON test (see History
of Octane Ratings) has been replaced by a procedure developed by the Coordinating Research Council (CRC). In the
CRC E-15 procedure, the vehicle is tested under a proscribed
set of environmental conditions and loads. The procedure
"trained raters" to detect audible knock during a series of
part throttle accelerations using decreasing octane fuels until trace knock is detected. Three different series of gasolines
were used to establish the RON versus MON response of each
vehicle, a zero sensitivity primary reference fuel, and two full
boiling range fuels with low and high Severity (difference
between RON a n d MON). These three fuels represent the
extremes of RON and MON blending. By testing a large
n u m b e r of cars, it is possible to statistically predict what percentage of the on-road car population would be "satisfied"
(no knock) with different RON/MON fuel blends. It is comm o n to apply a correction factor or offset between technical
raters and typical drivers, who have a m u c h lower threshold
for detecting knock and perceiving it to be a problem.
Historically, operating conditions that require maximum
octcine are not consistent, but most often occur during fuUthrotde acceleration from low starting speeds using the highest gear available. These can be difficult to reproduce on a
chassis dynamometer, so a distinction was always made between an on-road and a dyno result. M o d e m dynomometers
with better simulation of inertial, road, and wind loads and
engine cooling, produce equivalent results. A benefit is that
the conditions can be more tightly controlled, so results do
not require corrections for temperature, pressure, and humidity differences from the standard conditions at the time
of the test.
Historical engine management systems used a system of
centrifugal "bob weights" in the distributor for speirk advance
and a "vacuum break" to delay spark advance/retard at low
speed, high load. With only two parameters to change in
addition to the basic spark timing of the engine, one or two
areas of high knock anywhere o n the speed/load range
resulted in conservative timing at other conditions. If the critical area was under MON like conditions, then the car would
be found to respond most to MON. M o d e m engine management systems can adjust the octane requirement by modifying engine conditions that will vary the octane n u m b e r
requirment, so adaptive learning systems are preconditioned
prior to testing.
The m a x i m u m ONR is of most interest, as that usually
defines the r e c o m m e n d e d fuel. However, it is recognized
that trained raters are more sensitive to engine knock than
typical drivers, and that the general populace will have a
higher threshold for both detecting knock and perceiving it
as being severe. As a result, it is common to apply a correction factor or offset from technical ratings to predict consumer satisfaction.

76

MANUAL

ONREngine

3 7 ; FUELS AND LUBRICANTS


Design

HANDBOOK

Parameters

The design of the engine and vehicle significantly affect the


fuel octane r e q u i r e m e n t for b o t h RON a n d MON. In the
1930s and 40s, most vehicles would have been sensitive to the
Research Octane of the fuel, almost regardless of the Motor
Octane. In North America, this tended to change after WWI
with widespread adoption of automatic transmissions, which
made engines operate under more MON like conditions more
of the time. For many years, the CRC did octane surveys of
each new model year of cars, and the results were widely used
to estimate the on-road octane requirement, and the best
RON/MON combinations to satisfy the most cars (on average) with the lowest octane blends. Different weightings were
p u t on RON a n d MON, for example (R+3M)/4 to better
match the measured octane n u m b e r to the average octane requirement of the on-road car population.
The advent of electronic adaptive engine controls and use
of knock sensors tends to have a more consistent spark and
fuel m a p over the entire engine speed and load range, including transients like transmission shift points. This tends
to m a k e adaptive feedback control cars equally likely to
knock under any condition and equally responsive to RON
and MON. This tends to make the AKI a good predictor of
field performance in recent model cars.
Retarding spark timing for the purpose of knock reduction
causes loss of power a n d efficiency that can be incorporated
into knock rating procedures, for example by measuring increase in acceleration times with progressively lower octane
rating fuels.
ONRManifold

Air Temperature

and

Pressure

Increasing the air-fuel charge temperature and pressure increases the peak cylinder temperature and pressure, and thus
the tendency to knock. M o d e m engines generally pre-heat intake air to a controlled temperature above ambient. Throttling the air to a lower manifold pressure results in a much
lower peak cylinder pressure/temperature, and a lesser tendency to knock. Fuel evaporation and PVT expansion across
the throttle plate cool the intake mixture, making it slightly
sensitive to the engine temperature, which adds heat in the
manifold and during the compression stroke. Increasing the
coolant temperature in a CFR engine by about 10C increases
the octane n u m b e r r e q u i r e m e n t by about 2 AKI, so the
coolant temperature must be tightly controlled for octane
rating. Increasing the intake air (RON) or intake mixture
(MON) temperature increases the octane requirement (increases the severity of the test). This is used to advantage in
the RON and MON tests to "temperature tune" engines in different laboratories using Toluene Standardization Fuels
(TSF). This ensures that the test severity of different engines
is a relative constant over a broad range of fuel compositions,
since PRF are low aromatic, and TSF are high aromatic.
ONRCompression

Ratio

An increase in Compression Ratio will require an increase in


fuel octane for the same engine design. Increasing compression ratio increases the theoretical thermodynamic efficiency
of an engine according to the standard equation
Efficiency = 1 ((l/compression ratio)^(gamma1)),
where G a m m a = ratio of specific heats at constant pressure

and constant volume of the working fluid (for most purposes air is the working fluid, and is treated as an ideal gas).
Thermal efficiency reaches a maximum at a compression
ratio of about 17:1 for gasoline fuels in a SI engine, and
fuel-injected engines with carefully designed mixture charge
concentrations and intake/combustion chamber design has
reached 12:1 on retail fuels with 98-100 RON. Continued
advances in engine technology have allowed gradual increase in compression ratio without increasing ONR from
87 AKI. This has been used to either increase fuel efficiency
in economy cars or to have higher power engines at the
same fuel efficiency in larger cars. These engines have substantially higher compression ratio t h a n the "historical"
curve established with the CRC engine (see History of Octane Rating].
ONRThe

Air-Fuel

Ratio

Stoichiometric combustion (air-fuel ratio = 14.7:1 for a typical non-oxygenated gasoline) is neither maximum power,
which occurs around air-fuel 12-13:1 (Rich), nor maximum
thermal efficiency, w h i c h occurs a r o u n d air-fuel 16-18:1
(Lean). Air-fuel ratio can also be used as a knock control
strategy, although at a severe emissions debit for a three-way
catalyst emission system. Enrichment is also used during full
throttle operation to reduce knocking while providing better
power and driveability. Recent changes in U.S. emissions
testing cycles will promote more control of wide-open throttle mixture settings. Enrichment has also been used as a n
"emergency" strategy in turbocharged cars, as an alternative
to suddenly dropping turbo boost (power) to prevent runaway knock during an emergency or passing maneuver. On
average, there is an increase or decrease in ONR of about 2
AKI for each unit's increase (leaning) or decrease (enriching)
of the air-fuel ratio, respectively. This response varies considerably between engines and at different RPMs. In the CFR
octane n u m b e r tests, the carburetor float bowl level is adjusted to change the air-fuel ratio. The air-fuel ratio that produces the maximum knock intensity for that fuel is then used
to determine the octane n u m b e r of that fuel.
ONREngine

Spark

Timing

Advancing the spark timing dramatically increases the


tendency to knock. The tendency to knock increases as spark
advance is increased. For an engine with recommended 6
BTDC (Before Top Dead Center) timing and 93 RON fuel,
retarding the spark 4 lowers the octane requirement to 91,
whereas advancing it 8 requires 96 octane fuel. This
response varies considerably between engines and is most
pronounced at high RPM for any given engine (mostly an
artifact of delay time being measured by crank angle rotation
rate).
In older engines, the basic timing was set by rotating the
distributor until the #1 cylinder spark was set at a prescribed
crank angle. Spark was advanced for RPM with a centrifugal
"bob weight" on the distributor shaft, and retarded for load
with a manifold vacuum diaphragm actuator acting against
the spring loaded distributor plate. The timing of the spark is
advanced sufficiently to ensure that the fuel-air mixture
b u m s in such a way that maximum pressure of the burning
charge is about 15-20 after TDC. Heavy knock will tend to
occur if peak temperature/pressure occurs earlier than this

CHAPTER 3: MOTOR GASOLINE


point early in the power stroke, involving a larger quantity of
end gases igniting at high pressures (gas densities). Light
knock usually occurs later in the power stroke, involving less
end gas and a lower cylinder temperature and pressure (gas
densities). A good analogy is that larger waves in higher density mercury inherently carry more energy and destructive
power than smaller waves in lower density water.
Knock sensors equipped engine management systems retard ignition timing if knock is detected. If very low octane fuels are used, several octane numbers below the vehicle's ONR
at the time, the ECM will have to retard spark timing so much
to eliminate the knock that both performance and fuel economy will significantly decrease. Maximum efficiency occurs
when the engine is at incipient knock for the fuel being used
at the time, so trace or incipient knock is sometimes referred
to as "the sound of economy."
Unlike fuel maps, knock sensor data is generally not used
to advance timing, only to retard it as an engine protection
strategy. The ECM will retard timing ("knock back spark")
quickly until knock sensor indicates that it has stopped. It
will then slowly advance the timing toward baseline, until
trace knock re-appears, and store that value in the memory
map. Strategies to actively advance timing are more risky,
since a failed knock sensor could cause the ECM to advance
timing into sustained heavy knock and engine damage. Some
systems are capable of "testing" the knock sensor by advancing timing on individual cylinder firings to create a single or
small number of knocking cycles, to see if the knock sensor is
still functioning. A "dead" knock sensor can be particularly
damaging on a turbocharged car, or a "premium required"
car, if run on too low an octane fuel.
ONREffect of Engine Deposits
Typical new engines using nonleaded gasoline have an ONR
of about 4-6 AKI lower than the same engine at 25 000 km,
although some may experience 6-9 ONI, and some engines
can experience ONI of over 12 octane, depending upon driving cycle, engine, and fuel/lube. This Octane Requirement Increase (ORI) is attributed to the formation of a mixture of organic and inorganic deposits resulting from both the fuel and
the lubricant. They build up and tend to reach an equilibrium
quantity in about 10-15 000 miles. However, differences in
driving cycles can result in different equilibrium levels, with
sustained hot engine operation tending toward the low end,
and cooler "stop and go" driving cycles tending toward the
high end.
Combustion chamber deposits produce the ORI by several
mechanisms:
Reducing the combustion chamber volume, effectively
increasing the compression ratio
Reducing wall thermal conductivity, increasing the
combustion chamber temperatures
Catalyzing undesirable pre-flame reactions that produce
end gases with low auto-ignition temperatures.

GASOLINE SPECIFICATIONS.
ASTM or CGSB gasoline specifications are not legal requirements unless they are required (referenced) in a regulation by
a government authority having jurisdiction.

77

In the United States and Canada, a mixture of Federal,


State, and Provincial Government legislation and attendant
regulations proscribes gasoline requirements. Some states
and associations of states may also specify regional gasoline
properties to achieve regional environmental objectives
that are within their jurisdiction. These regulations may
reference accredited ASTM consensus standards, with or
without modifications. In some cases, ASTM sampling
and test methods are reproduced in regulations. This can
cause update problems, such as use of the wrong procedures for regulatory purposes, when either party changes
procedures.
The U.S. gasoline specifications and test methods are listed
in several readily available publications, including the
Federal Register, and the current Annual Book of ASTM
Standards.
ASTM D 4814, Specification for Automotive
Spark-Ignition Engine Fuel
The scope of the standard states that "This specification
guides in establishing requirements of automotive fuels
for ground vehicles equipped with spark-ignition engines."
It was first published as ASTM D 439 in 1937, and significantly revised to include oxygenates including "gasohol"
(10% ethanol) and other alcohol blends that had EPA waivers
(see 1970 EPA Clean Air Act). Several test methods were
developed or modified for use with oxygenated fuels, such
as Dry Reid Vapor Pressure, Tv/1, and new methods added
such as water tolerance and phase separation temperature
requirements.
It is a complex specification with many details that are beyond the scope of this chapter. However, in all cases, the requirements and the test method for each requirement fall
into one of two categories, those that measure the properties
or quality at the time of sampling, and those that predict
some future condition or performance. For example, a "Clear
and Bright" procedure evaluates whether the fuel is "suitable
for use" at the time of custody transfer or sale to end consumer. An oxidation stability result, on the other hand, is a
"predictive" test, intended to predict if the fuel will be acceptable in the future, after some time in storage prior to sale
or use. Many tests are "rig" tests that rate relative performance of the gasoline to provide a reasonable estimate of
how the gasoline will perform in actual use. For example, D
130 (Test Method for Detection of Copper Corrosion from
Petroleum Products by the Copper Strip Tarnish Test) measures the relative degree of corrosivity under a proscribed set
of conditions. It uses a static coupon of a specified copper alloy, prepared in a specified way, exposed to the product for a
specified period of time at a specified temperature. In the
vast majority of cases, a "pass" on the D 130 test means that
the fuel will not cause significant corrosion to any copper
alloy parts exposed in the fuel system, and will be widely
acceptable to a broad range of vehicle fuel systems. However,
if the in-use conditions for any fuel system component
are more severe than the D 130 test conditions, then damage
could occur even with a fuel that passes D 130. This could
happen if the component is heated hotter than test conditions, or the part is in a "rubbing or rolling" tjfpe of service that continually removes the protective oxide/sulfide

78

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

layer, or the part metallurgy is more easily corroded than the


D 130 copper strip.
ASTM has two publications that are highly recommended
to those not familiar with details or intent of the test methods
or specification. ASTM Manual on Significance of Tests for
Petroleum Products [35] and Guide to ASTM Test Methods for
the Analysis of Petroleum Products and Lubricants [36] are
both instructive on reasons for the test and explanation of
what and how the test is intended to measure. IdecJly, performance or "rig" tests Eire representative of actual in-use vehicle requirements. Hopefully these two goals always coincide, but it is always possible to "pass the test and fail the
field" as any experienced fuels chemist will agree. Passing all
the tests does not guarantee that the fuel is "suitable for use"
in all cases, especially in cases such as unusual contamination, or new car technology for which the existing standard
tests don't consider, or when in-use conditions are more severe than in the standard test method. Specifications Emd test
methods are in a continual state of being updated as technology continually advances.
Some gasoline requirements pertain to all volatility classes
(see Table 5).
Anti-knock

Index

(AKI)

Anti-knock Index (AKI), also k n o w n as (RON+MON)/2,


"Pump Octane," ((R+M)/2), or "Road Octane" is the average
of the Research Octane Number and Motor Octane Number.
Dispensing p u m p "posting" requirements are based on AKI.
The only accurate m e t h o d of m e a s u r i n g knock is to use
standard knock rating engines in ASTM D 2699/D 2700 or D
2885, although several "field test m e t h o d s " are used for
screening purposes. The ASTM gasoline standard does not
mandate octane levels, but lists levels appropriate for different applications. While limits are not specified, changes in
engine requirements according to season and location are
discussed. Fuels with an AKI of 87, 89, 91 (nonleaded), and
88 (leaded) are listed as typical for the U.S. at sea level.
However, higher altitudes may specify lower octane numbers. Altitude derating of octane is m u c h less for nonleaded
versus leaded gasoline because Tier 0/1 cars use manifold
absolute pressure/temperature (MAP/MAT) sensors to calculate air density, or absolute mass air flow sensors to control
air fuel ratio.

TABLE 5Detailed requirements for all volatility classes.


Lead Content, max, g/L
(g/U.S. gal)
Non leaded
Leaded
Copper Strip Corrosion,
max
Solvent-Washed Gum
Content, mg/100 mL,
max
Sulfur, max, mass%
Non leaded
Leaded
Oxidation Stability,
minimum, minutes
Water Tolerance

0.013 (0.05)
1.1 (4.2)
No. 1

0.10
0.15
240
Water tolerance limits in terms of
maximum temperature for
phase separation are given in
Table 13 of the specification.

Volatility
Volatility is measured by the ASTM D 86 distillation, the
Vapor/Liquid ratio Temperature (Tv/1 = 20), and one of
several vapor pressure test methods, most commonly ASTM
D 5191, which is used for regulatory reporting. All of the
volatility measurements are somewhat related thermodynamically, being various combinations of vapor pressure
and cumulative boiling volumes. However the relationships
are not exact, because the standard tests are not ideal
thermodynamic processes. Some examples of various ASTM
D 86 distillation effects are given in Figs. 1-3. An illustration of approximate vapor pressure and volatility relationships is given in Fig. 4, comparing typical fuels with pure
hydrocarbons.
Distillation, Evaporation Temperatures, and Driveability IndexThe distillation volatility of a finished gasoline can be
expressed in several ways. One set uses the temperature at
fixed distillation points, such as the TIO, T50, and T90, related indices such as Volume Average Boiling Point (VABP)
or ASTM Driveability Index (DI)
Driveability Index = DI = 1.5 * TIO + 3 * T50 + 1.0 * T90
Maximum DI limits are specified in ASTM D 4814 for each
Volatility Class, ranging from 569-597C, or 1200-1250F.
Note that the conversion of DI from Centigrade to Farenheit
units is DI(F) = DI(C) * 9/5 + 176, where 176 is the sum of
the coefficients (1.5 + 3.0 -f- 1.0) * 32. Many companies use
volume percent evaporated (%Evap, or D-l-L) at fixed temperatures, which have an advantage over Txx controls, because they blend more linecirly, and are more easily adapted
to linear programming (LP) optimization controls. Both are
in c o m m o n use at the operational level, because ASTM requires Txx type controls while the complex model requires
E200 a n d E300. The complex model spreadsheet has a conversion from Txx to Exxx built into the model.
Vapor Pressure and Tvfl^ASTM vapor pressure specifications
are based on VP measured under standard conditions of 4:1
vapor liquid ratio at 100F and Tv/1 20 to control gasoline
front-end volatility. The Tv/120 is the temperature at which 20
volumes of vapor cire formed from one volume of the original
liquid, measured by ASTM D 2533 or D 5188. The intent is to
produce an isobaric flash prediction, something that is well
within the capabilities of m o d e m thermodynamic equation
of state (EOS) calculations.
A Tv/120 corresponds to about 10% of the gasoline vaporized under conditions of the test (a fully vaporized gasoline
would have a V/L of about 220-280 depending upon the
blend). As a result, there is a good correlation between measured Tv/1 and linear sums of the VP a n d TIO, T20 u p to
T50, so it is much more common to calculate Tv/1 than to
measure it. Some companies use an index based on VP emd
%Evap at lower temperatures, historically 70C (158F).
These are often called Vapor Lock Indices or "Hot Fuel
Handling," a reference to the origined purpose of these specifications. A v/1 of 20 was originally chosen because, on average, a carbureted engine diaphragm type fuel p u m p could
handle about 20 volumes of vapor along with the 0.9 volume
of the remaining liquid (Tv/1 = 20). Any higher temperature
(more vapor) would cause the p u m p to become "vaporlocked," and not be able to satisfy engine fuel dememd, cans-

CHAPTER 3: MOTOR GASOLINE


-Base

Max Summer Dl

Msx Dl High Mid-fill

79

-High Volatility

250

JMax Final Boiling Point (FBP) = 225 C

200
Max Summer T90 = 190 J

150u
p

I
100
Typical Summer RUL
Volatility Dl = 1150 .

IMin / Max Summer


T50 Range = 77-121

50

Higliest Summer
Volatility T50 = 70
Max Summer T10 = 70

10

20

30

40

li
50

60

70

80

90

100

Volume % Evaporated
FIG. 1ASTM D 86 distillation and driveability index.

ing stalls or rough engine operation. The temperature when


this occurs is called the Vapor Lock Temperature. The
ASTM specification has vapor-lock protection temperatures
based on a regional database of ambient temperature and
elevation (barometric pressure).
Fuel injected vehicles generally have submerged in-tank
fuel pumps, and operate at much higher liquid fuel line
(fuel rail) pressures, so eire much less prone to vapor lock
problems. However, certain forms of vapor lock can occur.

but are usually due to other mechanical factors and not


high ambient temperature. For example, a worn out fuel
pump may not put out enough pressure to prevent vapor
formation in the fuel rail during a hot shutdown. The vehicle could experience a hard hot starting or no-start condition, because much lower mass vapor flow through the injector would cause an over lean air-fuel ratio. Similarly, a
partially blocked primary filter ("pick-up sock") can cause
vapor lock on the suction side of the submerged pump at

80 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


-Ethanol

MTBE

Base

250

200

/
/
150

100

50
Significant decrease in T50 caused by
azeotrope effect of ethanol

10

20

30

40
50
60
Volume % Evaporated

70

80

90

100

FIG. 2ASTM D 86 distlllation-ethanol and MTBE.

high temperatures. Routing fuel lines in areas that have


high shutdown heat soak temperatures can also cause a hot
restart problem.
Gasoline and Gasohol Blending
The distillation volatility is controlled within specification
limits by varying the relative ratios of blend components to
make a finished gasoline. These range from butane (normal
boiling point 0C) to the highest boiling components with Final Boiling Points slightly higher than the 225C FBP specifi-

cation for the finished gasoline. The vapor pressure is controlled below specification maximums by limiting the
amount of butane in winter and northern summer grades,
and butane plus some pentanes in the lowest vapor pressure
summer grades (below about 8 psi VP.)
Ethanol at 10 vol% (gasohol) increases the measured VP at
100F by about 0.8 in a high aromatic gasoline to about 1.2
psi in a low aromatic gasoline. Ethanol is more soluble in
aromatics than saturates so the vapor pressure increase is
slightly influenced by aromatic content of the base fuel.

CHAPTER 3: MOTOR GASOLINE

81

- A S T M D 8 6 P R EOS
250 ^

TypiCcil inoroase in ASTM DBG final


di&hllalioM tuiiippidluic due to higher
tlian one theoretical plate and icflux
due to he.it lush at higci toinpci.ituics

JThcmiodynaniic Bubble Point


200 -

I Sciniplcs of this gasoline will not flash oi boil .it


toinpcratuicR bolow the bubble point, even if it is
at .1 tcnipciaturp iiighcr than thn ASTM D86 Initial
' Boiling Point

O 150
^ rhcoieticnl Single pl.itc distilkition cuivc

ffl 100

'Typical liiiti.il volume loss .iiid "hool" on start of ASTM D8b


distilljtiuii b.iuscd by cumbin.ition of.

50

- gipatiii than one theoictii..)! pl.itp distillation finin licitiiig of


glassw.irc .iiid reilux duiing starl of thn distilLition
- nun condensing ,iir HC v.ipor mixturi> at st.iit of test

AS1MD86lnili.ii
Boiling Point iJBP)

20

10

40

30

50

70

60

90

80

100

Volume % Evaporated

FIG. 3ASTM D 86 versus Peng-Robinson Equation of State.

100000
ASTM V.ipur Pri<s-.iiii- ri-iii^ji'i.iliiip

10000

1000

..-
Ntiiiii.il riu'lini) Piiiiil rii-.<.-iir>-

100

10

0.

CJ
A|iuiuxiiii.1li R.m.ii-! V.i|iiii l>ii-.-iiii'

'C5
CM'

il -W" i" Fl.i .'1 ''HI.; T.>ii,|.i 1...SII11

C6

Cq

CIO
- 0.1

-0.01

-100

-80

100

-50

200

Temperature ( C )
FIG. 4Vapor pressure relationships for fuels. Log P versus 1/T.

300

82

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

Several jurisdictions allow a nominal 1 psi waiver to accommodate "splash bending" of ethanol with a base gasoline.
EPA has issued a waiver that does not require conventional
gasoline with 9-10% ethanol to meet the required specifications between 1 May and 15 September (see Nonleaded
Gasoline).
ASTM

Volatility

Class

Specifications

ASTM D 4814 gasoline specification defines six volatility


classes of increasing vapor pressure, Tv/1 and Driveability
Index (DI). The TIO, T50 min/max and T90, FBP max limits
define the allowable range of individual parameters within
each volatility class. VP and DI are generally the key blending p a r a m e t e r s for b o t h regulatory and specification
compliance.
Insufficient volatility may result in difficult starting in cold
weather, poor cold start and warm-up driveability, engine
deposits and crankcase oil dilution, and increased tailpipe
emissions. Excessive front-end volatility can produce poor
fuel economy, poor hot driveability in fuel injected engines,
vapor lock a n d c a r b u r e t o r icing in older engines, and
increased r u n n i n g loss and evaporative emissions. The
higher boiling fractions of the gasoline have significant
effects on the emission levels of undesirable hydrocarbons
and aldehydes. A reduction of 40C in the final boiling point
will reduce the levels of benzene, butadiene, formaldehyde,
and acetaldehyde by 25%, and will reduce HC emissions by
20% [37]. Similar emission effects were found in the auto-oil
program, and as a result, there are three volatility model parameters in the complex model,VP, E200, E300 (Vapor pressure, percent evaporated at 200F and 300F, respectively)
that influence predicted evaporative, tailpipe, and toxics
emissions. The E200 and E300 model parameters have the
least influence of all the model inputs on the predictive model
emissions, and are often set at "worst case" values for the
purpose of blend planning (although actual values must be
used for reporting).
Maximum

Alkyl lead

Content

The alkyl lead limits remain to cover fuels for off-road vehicles. Leaded fuels can contain u p to 0.1 g Pb/usg (equivalent
0.029 g Pb/L low alkyl lead in Canada), but none are made
commercially. Nonleaded gasoline can contain u p to 0.013 g
Pb per liter in the U.S. (contamination limit with no deliberate addition) and 0.005 g Pb/L in Canada to protect catalytic
converters. (See sections on alkyl lead phasedown and nonleaded gasoline for more detail).
Copper

Corrosion

Copper, silver, brass, and other "soft metal" alloys are susceptible to corrosion from reactive sulfur molecules. The ASTM
D 130 "copper corrosion" test is intended to ensure that fuels
are not corrosive to these trace components under normal use
conditions. More severe conditions could require even lower
levels of corrosive sulfur. The total sulfur content is not correlated with D 130 test performance, and in fact, some additives that are effective at mitigating copper corrosion themselves contain sulfur (see additives). Only the most reactive
types of sulfur molecules cause or contribute to D 130 copper
corrosion. The copper strip test responds to reactive sulfur,
whereas the sulfur content reports the total sulfur content.

The D 130 test is a "static" coupon test, and may overpredict durability for more easily corroded alloys such as silver,
or for rubbing, rolling, or heated soft alloy fuel system components. Field problems have been experienced with some
copper fuel p u m p commutators, silver alloy fuel sender unit
resister arrays and silver plated crankcase bearing cages with
gasoline that passes D 130. In general, silver alloys should not
be used in gasoline fuel systems without provisions for protection from sulfiding. Copper alloy components that are exposed to heat or rolling/rubbing action that removes the protective oxide layer should be tested for long-term durability
with a gasoline containing traces of corrosive sulfur (H2S,
elemental sulfur).
Maximum

Sulfur

Content

Current ASTM and CGSB standards allow 0.10% mass maxim u m sulfur content for nonleaded gasoline, but lower levels
are required by various sulfur regulations (California or
Canadian Sulfur in Gasoline regulation). Sulfur is oxidized to
SO2 over the catalyst, so essentially competes for reactive
sites that could otherwise be effective for HC, CO or NOx conversion. This appears as a temporary decrease in catalyst activity at high fuel sulfur levels, and leads to the requirement
for ultra low sulfur fuels to attain ultra low emissions.
Sulfur can be indirectly limited by RFC composition
controls based on emission models (U.S. EPA complex
model, BC TOx/NOx a n d Canadian CEPA Benzene in
Gasoline regulation Benzene Emission N u m b e r (BEN) requirements. Both Canada and the United States have regulations in place that will reduce sulfur to 30 p p m YPA phased
in between 2002 and 2010, coincident with introduction of
low emission Tier 2 vehicles (See "Reformulated Gasoline"
for more details).
Maximum

Phosphorus

Content

The EPA limits phosphorus in all gasoline to 1.3 mg/L P, because phosphorus is a potent catalyst poison, and this limit
is reflected in the ASTM specification (see alkyl lead
phasedown section for additional details). Typical levels of
phosphorus in nonleaded gasoline are undetectable by the
standard test methods.
Oxidation

Stability

Like all organic material, hydrocarbons are susceptible to air


oxidation over long periods of time. The peroxides formed
from hydrocarbon oxidation are auto-catalytic, leading
to "runaway" reaction if not controlled. Reaction rates are
generally higher with u n s a t u r a t e d hydrocarbons, and are
catalyzed by parts per billion levels of soluble metals such as
copper. Motor gasoline may be stored up to six months, or
m o r e . They must not form soluble g u m that collects
at the point of vaporization, or precipitated insoluble g u m
("varnish"), or form soluble peroxides that will attack
rubber/elastomers in the fuel system.
Antioxidants are added to most gasolines to slow down the
rate of oxidation and prevent the oxidation from becoming
autocatalytic, by forming a stable radical oxidation product
that does not react further. The antioxidant is sacrificial, and
is gradually consumed during this process. Once depleted,
the reactions will become autocatalytic, and the gasoline will
eventually "break" and form peroxide gums as fast as oxygen

CHAPTER
can diffuse into the liquid (mass transfer controlled oxidation). Some gasolines also require metal deactivators to mitigate catalysis from 10-100 p p b traces of copper (most commonly from trace level corrosion of copper and brass alloys
in contact with the gasoline during manufacture, distribution, or use).
Oxidation stability tests generally expose a heated sample
of gasoline to oxygen for a prescribed period of time to accelerate the rate of oxidation and predict on a relative basis
how long the fuel will be stable under more tj^ical conditions. In the ASTM D 525 Oxidation Stability test, the fuel
sample is heated with oxygen inside a pressure vessel, and the
time until significant oxygen uptake (pressure drop, "break
point") occurs is a relative measure of stability. The criteria
are where the pressure drop exceeds 2 psi per 15 min. The autocatalytic reaction rate increases exponentially, becoming
mass transfer controlled, and consuming all of the remaining
oxygen in only 15-30 min. ASTM D 4814 requires a m i n i m u m
of 240 min (4 h) breakpoint, which is sufficient for most storage and distribution systems. This may require a higher level
at the point of manufacture, since the measured oxidation
stability will decrease over time as the sacrificial anti-oxidant
is consumed. Other procedures not used in D 4814 are to
weigh the oxidative g u m formed after a breakpoint test,
(commonly termed a "4 hour gum"), or longer term storage
time tests at milder conditions to better simulate field storage
conditions.
It is common practice to add sufficient antioxidant to meet
a 360-600 min oxidation stability at the point of production,
so that 240 min is obtained at the point of sale. Factory fill
gasoline generally requires a much-fortified gasoline for this
purpose, as storage times of automobiles prior to Scile can be
several months. This is especially true for some specialty fleet
applications, such as police fleets, that may be made in large
production runs, with the cars stored for six m o n t h s or
more before going into service. Hydrocarbons air oxidation
has been extensively studied, and is well documented in the
literature.
Soluble
Gum")

Gum

(Unwashed

and Solvent

Washed

"Existent

ASTM D 4814 limits unwashed gum to 5 mg/100 mL, and has


no washed (Existent Gum) requirement (used for aviation
gasoline). D 381 measures the amount of fuel soluble oxidative gums and nonvolatile additives remaining after evaporation in the air (i.e., total nonvolatile materials in solution).
Solvent washed "Existent Gum" measures the a m o u n t of
gums remaining in fuel evaporated u n d e r air and t h e n
washed with heptane to remove additives and heavier hydrocarbons. Heptane is a poor solvent for highly oxidized, high
molecular weight gums. The heptane soluble portion is relatively low molecular weight material that can accumulate at
any point of gasoline vaporization (intake system deposits)
and react further to form insoluble gums. The heptane insoluble portion is representative of the more fuel-insoluble gum
that can contribute to gum/varnish residue problems, for example filter plugging, sticking carburetor float bowl pintle
needles where there is no vaporization, as well as intake system deposits where there is vaporization.
Washed and unwashed gums measure the amount of gum
formed in the fuel u p to the time of the test, as no significant

3: MOTOR

GASOLINE

83

additional gum is formed under the relatively mild conditions of the test procedure. It is not predictive of future
quality. It can identify help identify stale "peroxidized" fuels
in the marketplace; Washed Existent gum is often reported
to verify that a high unwashed gum is due to the presence
of Deposit Control Additives that contribute to unwashed
gum. A fuel that has both high ( > 1 0 mg/lOOmls) washed
and u n w a s h e d g u m are generally considered suspect or
unacceptable.
Water

Tolerance

D 6422 Water Tolerance (phase separation) method measures the highest temperature at which phase separation of
gasoline - alcohol blends occur. It is not applicable to hydrocarbon or ether oxygenated fuels. Water tolerance is particularly critical for gasoline containing alcohol. The separated
lower phase alcohol-water-hydrocarbon phase settles to the
bottom of the tank where the p u m p suctions are, and tends
to get moved down the distribution system and into cars if
not found and removed. The remaining gasoline layer is often off-spec after phase separation due to loss of octane from
alcohol and aromatics extracted into the alcohol layer. If dispensed into a vehicle tank, it will not burn in engines, and so
it causes immediate stalls, and requires a complete fuel system draining and cleaning. Like water, aqueous alcohol separated phases contribute to corrosion and pickup of rust/dirt,
etc., and are also associated with accelerated filter plugging.
Methanol has a low solubility in gasoline and requires a
cosolvent if used in gasoline blending for that reason. Adding
methanol to an oxygenated fuel will increase the measured
separation temperature while adding ethanol, IPA, or other
low MW alcohols will decrease the measured separation temperature.
Water tolerance of gasoline with alcohols is very temperature dependent; consequently diverse limits are established
for the U.S. The limits vary according to location and month.
For Alaska, North of 62 latitude, it changes from 41C in
Dec-Jan to 9C in July, but remains 10C all year in Hawaii,
since it never gets that cold. This is the same control strategy
as for s u m m e r t i m e high temperature and Tv/1 or VP, but
using the daily low t e m p e r a t u r e s versus the daily high
temperatures.
Other Nonspecification Properties
Autoignition

Temperature

The autoignition temperature of a fuel or even a single


molecule is not a thermodynamic property. It is the temperature at which high temperature decomposition products
will spontaneously c o m b u s t without a n external ignition
source. It is heavily dependent on the conditions at the time
of the test, including such factors as what type and shape of
container is used, and how long to wait to see if autoignition
occurs. The conditions can be varied to simulate a specific
situation, and it is not intended to reflect engine conditions.
There is a general correlation between the octane n u m b e r
of a fuel and the auto ignition temperature, because both are
determined by molecular structure. Long straight chain hydrocarbons produce large amounts of easily auto-ignitable
pre-flame decomposition, and tend to have low auto ignition
temperatures and octane numbers. Branchy and aromatic

84

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

hydrocarbons are more resistant, and have higher auto ignition temperatures and octane numbers. However, correlation
is not precise enough to be useful, and several lab rig tests
based on auto ignition temperatures or related "cool flame"
or "pre-flame" properties to predict engine octane numbers
have failed to date. Autoignition temperature of gasoline and
other fuels can be measured by ASTM E 659, Standard Test
Method for Autoignition Temperature of Liquid Chemicals.
Heat of Combustion

and Adiabatic

Flame

Temperature

See section on Gasoline Energy Content for a discussion of the


gross and net heat of combustion (He). The He of gasoline
can be measured by ASTM D 4809, Heat of Combustion of
Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision
Method), or estimated by a n u m b e r of ASTM and other correlations.
The adiabetic flame temperature is the highest temperature that combustion gases can attain under standard starting conditions u n d e r adiabatic (no heat loss) conditions,
where all of the energy of combustion goes toward heating
the combustion gases. There are only slight differences in
combustion temperatures of blended gasolines, and the actual temperature in the combustion chamber is determined
by other factors, such as load, spark timing, and engine design. The exhaust gas temperature is much below the adiabatic flame temperature because m u c h of the energy combustion has been extracted as PVT work.
The adiabatic flame temperature can be measured directly
as a peak flame t e m p e r a t u r e (no applicable ASTM test
m e t h o d ) , or estimated from the carbon/hydrogen ratio,
stoichiometric formula and heat of combustion, or calculated from composition with a suitable thermodynamics calculation, or estimated from density correlations (similar to
the He).
Flammability

(LEL and

HEL)

The Lower and Higher Explosive limits (LEL, HEL) are the
m i n i m u m and maximum hydrocarbon vapor concentrations
that will support combustion. The LEL is related the flash
point of distillate fuels. Below the LEL there is too little hydrocarbon fuel to support combustion, while above the HEL
there is too little air (oxygen) to support combustion. The stoichiometric mixture lies between the LEL and HEL, and represents the mixture of complete combustion, maximum adiabatic flame temperature, and maximum energy release from
combustion of explosion. Distillate fuels are handled below
their LEL (Flash Point). Gasoline and naptha fuels are normally handled above their HEL. Mixtures of gasoline and distillate fuels, or fuels with equilibrium vapor pressures that
place the vapor space in the explosive range are extremely
dangerous. Any ignition source can cause Ein explosion in the
vapor space or in fuel lines and vents. Once ignited, a flame
can propagate down any pipe or vent that contains a combustable mixture. Fuels with vapor spaces in the explosive
range require specialized equipment and procedures for safe
handling (flame arrestors, anti-static provisions, gas inerting,
etc.).
The higher and lower explosive limits for gasoline are only
rarely a concern. The vapor pressure of gasoline keeps it well
over the HEL most of the time. It is only in extremely cold
weather that a properly formulated winter gasoline can enter

the HEL explosive range. This can be estimated from PengRobinson Equation of State calculations, since the LEL will
occur when the vapor phase concentration of butane/pentane
hydrocarbons will be in the 1.5-2 vol% range, and the HEL in
the 7-8 vol% range. At 14.7 psia barometric pressure, this
corresponds to a range of 0.1-0.2 psia and 1.0-1.2 psia hydrocarbon vapor pressure for the LEL and HEL respectively.
Using these values, a typical 14.5 VP winter gasoline would
be expected to have an LEL ranging from about 75 to - 6 0 F
and HEL from about 25 to 15F, depending upon composition. A t5^ical 7.8 VP s u m m e r gasoline would be expected
to have an LEL ranging from about 50F to 35F and an
HEL from 5-15F. Canadian CGSB gasoline standards have a
m i n i m u m VP to provide a wide margin between the HEL and
the VP at extreme cold temperatures for various times of
year.
Diluent gases are much more effective at reducing the HEL
than increasing the LEL for all flammable hydrocarbon gas
mixtures. The flammable region disappears with the addition
of about 30% CO2 or 45% N2, and almost all of this change is
due to reduction in HEL and not increase in LEL hydrocarbon concentration [38,39]. From this it can be estimated that
N2 gas containing less than about 10 vol% oxygen is nonflammable with hydrocarbon vapors, a "rule of t h u m b " that
is often useful for developing procedures for safe handling of
gasoline in nonstandard conditions.
Heat Capacity, Thermal
and Heat of
Vaporization

Conductivity,

The thermodynamic bulk properties of gasoline are rarely a


concern for automotive gasoline, but are occasionally required for the sizing of specialized handling equipment.
Gasoline has a heat capacity of about 0.5 BTU/lb.F (0.5
cal/gm.C), which is about half that of water. Hydrocarbons
would be considered to be a good insulator in the absence of
convective flow heat transfer with a thermal conductivity of
about 0.08 BTU/hr.ft.F near room temperature, about 20%
that of water (.35 BTU/hr.ft.F). Because they are essentially
nonpolar, the heat of vaporizations of gasoline hydrocarbons
are only about 10-20% that of water on an enthalpy per mass
basis. Light aliphatics, such as butane, are in the low range,
while branched isoparafins, etc. are in the high range, with
single ring aromatics in mid range. As a result, a fully blended
gasoline has a heat of vaporization near a midrange of about
15% of water, or about 140 BTU/lb (80 kcal/kg). More detailed information is available in standard chemistry and engineering handbooks and manuals. There are no standard
ASTM tests for these properties, but they are well documented in the thermodynamics literature.
Viscosity

and

Lubricity

The viscosity of gasoline is rarely a concern for automotive


gasoline. It is considered to be a very low viscosity fluid at
typical a m b i e n t t e m p e r a t u r e s with a typical viscosity of
about 0.5 cSt at room temperature, which is only slightly
lower than water (0.9 cSt) at the same temperature. Viscosity
does not change very much with temperature, similar to density, thermal conductivity, etc. Unlike more viscous lubricants and heavier fuels, inherently low viscosity liquids such
as gasoline and LPG are not very sensitive to temperature.
For example, a 0.7 cSt liquid would only be expected to de-

CHAPTER
crease viscosity to about 0.1 cSt, with an increase of 100
centigrade [40]. Lubricity is determined by trace polar
molecule content, b u t is generally very p o o r for gasoline.
Clean absorbent treated gasoline range hydrocarbons (low
polar content) are often used as the "poor" standard in lubricity test calibrations. Pumps for gasoline service must be
chosen carefully due to the low lubricity and propensity for
accelerated p u m p wear. Centrifical, gerotor, internal gear,
and other low contact p u m p designs are preferred over ordinary gear pumps, which are seldom suitable for gasoline service. Similar wear problems can occur in some positive displacement meters. The high vapor pressure of gasoline can
result in localized cavitation in some p u m p designs, with the
damage easily misdiagnosed as corrosion and/or wear. Engine mounted fuel p u m p s are usually diaphragm pumps, and
low pressure in-tank fuel p u m p s are usually turbine (centrifical) p u m p s for these reasons. High pressure automotive in
tank fuel p u m p s are usually two stage turbine/positive displacement pumps, with the second stage tjrpically usually being a roller vane or gerotor type for use in a very "dry" (low
lubricity) fuel.
There are a n u m b e r of standard ASTM viscosity test methods suitable for gasoline, such as D 445, S t a n d a r d Test
Method for Kinematic Viscosity of Transparent and Opaque
Liquids (the Calculation of Djoiamic Viscosity). Adaptations
of several lubricity test m e t h o d s originally developed for distillate fuels can be applied to lighter hydrocarbons, although
not covered with the scope (naptha range solvents are used as
calibrants). These include D 6078 and D 6079, Scuffing Load
Ball on Cylinder and High Frequency Reciprocating Rig Tests.
Conductivity

and Static

Electricity

Conductivity is rarely a concern for automotive gasoline, but


is occasionally m e a s u r e d if there is a concern for static
buildup during p u m p i n g . Retail dispensing hoses/nozzles
and vehicle fill spouts Eire internally grounded, so there is
generally enough static dissipation to avoid problems. Some
static incidents have occurred with very low conductivity
gasoline in plastic fuel lines (replaced by more conductive
plastic). Recently, ignitions have occurred during cold
weather with containers filled while sitting in plastic bed liners (insulators) of pick-up trucks. Ignitions from static discharge from gloves/clothing during refueling are believed to
be due to static accumulation on clothing, and not to charge
accumulation from gasoline.
Conductivity dissipating additives are effective in gasoline,
but do not provide protection if the charging rate is excessively high, and hardware changes are required. The same
principles of electrostatics apply to gasoline as to other hydrocarbon fuels, except that the vapor space of gasoline tanks
are normally well above the HEL at the time and temperature
of use [41]. This is rarely a factor for automotive, as there is
little opportunity for vapor accumulation a n d ignition. In
generzJ, gasoline should only be transferred under conditions
where there is free flow of air and good ventilation.
Several standard ASTM test methods are available to measure conductivity of gasoline and other fuels. Static cheirging
tendency is highly dependent upon equipment configuration.
Consult ASTM D 4865, Guide for Generation and Dissipation
of Static Electricity in Petroleum Fuel Systems for more information.

Density,

Refractive

Index,

3: MOTOR
and Dielectric

GASOLINE

85

Constant

Density, Dielectric Constant, and Refractive Index are all


"bulk properties" of hydroccirbons that depend upon the n u m ber of atoms, charges, and electrons per unit volume. When
the composition is limited to only hydrogen and carbon in hydrocarbon fuels, there are strong scientifically based relationships between these properties, and a strong correlation between them for all fuels. Dielectric constant is rarely a concern
for gasoline, but is occasionally needed for some capacitance
gauging systems. For reasons of composition, the dielectric
constant of hydrocarbon fuels (not oxygenates) can be estimated as the square of the refractive index at the required
temperature. The dielectric constant is a "bulk property" of
the fluid, similar to refractive index and density. All can be estimated with reasonable accuracy for oxygenates blends by
volumetrically averaging the oxygenate and the hydrocarbon
component dielectric constants, refractive index, or density.
Both refractive index and dielectric constant can be used to
estimate the density of a blend, which in turn is strongly correlated to Eiromatics content for typiccil blends. Both dielectric
constant and refractive index have been used as control parameters for racing fuels for these reasons. Some commercially available field instruments use these principles to estimate oxygenate contents from optical measurements.
Gasoline vapor (predominately butane/pentane) is heavier
than air and can accumulate in low spots and cavities in the
absence of a ventilating flow of air (see Chapter 2, Liquified
Petroleum Gas).
Several s t a n d a r d ASTM test m e t h o d s are applicable to
liquid a n d gas density, refractive index, a n d dielectric
constant.

ASTM/IP METHODS
ASTM No.
D 4806

IP No.

D 4814
D86

123

D 130

154

D 323
D 3 81

131

D 525

40

D665

135

D 1266

107

Title
Specification for Denatured Fuel
Ethcinol for Blending with Gasolines
for Use as Automotive Spark-Ignition
Engine Fuel
Specification for Automotive SparkIgnition Engine Fuel
Test Method for Distillation of
Petroleum Products
Test Method for Detection of Copper
Corrosion from Petroleum Products
by the Copper Strip Tarnish Test
Test Method for Vapor Pressure of
Petroleum Products (Reid Method)
Test Method for Existent Gum in Fuels by Jet Evaporation
Test Method for Oxidation Stability of Gasoline (Induction Period
Method)
Test Method for Rust-Preventing
Characteristics of Inhibited Mineral
Oil in the
Presence of Water
Test Method for Sulfur in Petroleum
Products (Lamp Method)

86 MANUAL 37: FUELS AND LUBRICANTS


D 1298

160

D 1319

156

D2276

216

D2533
D2622
D2699

237

D2700

236

D2709

D2885

D3116
D3120

D3227

342

D3231
D3237
D3341
D3348

D3606

D3710

D3831

D4052

D4045

365

HANDBOOK

Test Method for Density, Relative


Density (Specific Gravity), or API
Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method
Test Method for Hydrocarbon Types
in Liquid Petroleum Products by
Fluorescent Indicator Adsorption
Test Method for Particulate Contaminant in Aviation Fuel
Test Method for Vapor-Liquid Ratio
of Spark-Ignition Engine Fuels
Test Method for Sulfur in Petroleum
Products by X-Ray Spectrometry
Test Method for Knock Characteristics of Motor Fuels by the Research
Method
Test Method for Knock Characteristics of Motor and Aviation Fuels by
the Motor Method
Test Method for Water and Sediment in Distillate Fuels by Centrifuge
Test Method for Research and Motor
Method Octane Ratings Using OnLine Analyzers
Test Method for Trace Amounts of
Lead in Gasoline
Test Method for Trace Quantities of
sulfur in Light Liquid Petroleum
Hydrocarbons by Oxidative Microcoulometry
Test Method for Mercaptan Sulfur in
Gasoline, Kerosine, Aviation Turbine, and Distillate Fuels (Potentiometric Method)
Test Method for Phosphorus in
Gasoline
Test Method for Lead in Gasoline by
Atomic Absorption Spectroscopy
Test Method for Lead in GasolineIodine Monochloride Method
Test Method for Rapid Field Test for
Trace Lead in Unleaded Gasoline
(Colorimetric Method)
Test Method for Benzene and
Toluene in Finished Motor and
Aviation Gasoline by Gas Chromatography
Test Method for Boiling Range Distribution of Gasoline and Gasoline
Fractions by Gas Chromatography
Test Method for Manganese in Gasoline by Atomic Absorption Spectroscopy
Test Method for Density and Relative Density of Liquids by Digital
Density Meter
Test Method for Sulfur in Petroleum
Products by Hydrogenolysis and
Rateometric Colorimetry.

D 4053
D 4057
D 4294

336

D 4420
D 4815
D 4953
D 5059

228

D 5188
D 5190
D 5191
D 5453
D 5482
D 5580

D 5599

408

D5845

D 6422

Test Method for Benzene in Motor


and Aviation Gasoline by Infrared
Spectroscopy
Practice for Manual Sampling of
Petroleum and Petroleum Products
Test Method for Sulfur in Petroleum
Products by Energy Dispersive X-ray
Fluorescence Spectroscopy
Test Method for Aromatics in Finished Gasoline By Gas Chromatography
Test Method for Determination of C,
to C, Alcohols and MTBE in Gasoline
by Gas Chromatography
Test Method for Vapor Pressure of
Gasoline and Gasoline-Oxygenate
Blends (Dry Method)
Test Methods for Lead in Gasoline
by X-Ray Spectroscopy
Test Method for Vapor-Liquid Ratio
Temperature Determination of Fuels
(Evacuated Chamber Method)
Test Method for Vapor Pressure of
Petroleum Products (Automatic
Method)
Test Method for Vapor Pressure of
Petroleum Products (Mini Method)
Test Method for Total Sulfur in Light
Hydrocarbons, Motor Fuels, and
Oils by Ultraviolet Fluorescence
Test Method for Vapor Pressure of
Petroleum Products (Mini Method Atmospheric)
Test Method for Benzene, Toluene,
p,/m xylene, o-xylene, C9 and Heavier Aromatics in Finished Gasoline
by Gas Chromatography
Test Method for Oxygenates in Gasoline by Gas Chromatography and
Oxygen Selective Flame Ionization
Detection
Test Method for MTBE, ETBE,
TAME, DIPE, Methanol, Ethanol,
and tert - Butanol in Gasoline by Infrared Spectroscopy
Water Tolerance (Phase Separation)
of Gasoline - Alcohol Blends

BIBLIOGRAPHY
[1] Owen, K. and Coley, T., Automotive Fuels Reference Book, 2nd
ed.. Society of Automotive Engineers, Warrendale, PA, 1995.
[2] Gibbs, L. M., "Transportation FuelsAutomotive Gasoline,"
Encyclopedia of Energy Technology and the Environment, John
Wiley and Sons, NY, 1995, pp. 2675-2698.
[3] Poulton, M. L., Alternative Fuels for Road Vehicles, Computational Mechanics Publications, Wit Press, Southampton, UK,
1994.
[4] Goodger, E. M., Hydrocarbon Fuels, Macmillan, London, 1975.
[5] Goodger, E. M., Alternative Fuels, MacmillEin, London, 1980.
[6] "Alcohol Fuels," "Gasoline and Other Motor Fuels," "Hydrogen

CHAPTER 3: MOTOR GASOLINE


Energy," and "Fuel Cells," Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed., M. Howe-Grant, Ed., Wiley, NY, 1993.
[7] The Automotive Handbook, any edition, Bosch, Society of Automotive Engineers, Warrendale, PA.
[8] Automotive Electrical/Electronic Systems, Society of Automotive
Engineers, Warrendale, PA.
[9] Heywood, J. B., Internal Combustion Engine Fundamentals, 1st
ed., McGraw-Hill, NY, 1988.
[11] Heisler, H., Advanced Engine Technology, Edward Arnold, London, 1995.
[12] Poulton, M. L., Alternative Engines for Road Vehicles, Computational Mechanics Publications, Wit Publishers, Southampton,
UK, 1994.
[13] SAE J312 and J1297, SAE Handbook, Vol. 1, Society of Automotive Engineers, Warrendale, PA, 1994.
[14] Proceedings of the International Symposium on Alcohol Fuels, Held
every two years and most of the ten conferences have good technical information, especially the earlier ones, various publishers.
[15] Alternative Transportation Fuels: An Environmental and Energy
Solution, D. Sperling, Ed., Quorum Books, Wetport, CT, 1989.
[16] Hunt, V. D., The Gasohol Handbook, Industrial Press, NY, 1981.
[17] Part 4, "Detonation and Combustion," The Science of Petroleum,
Oxford University Press, 1938.
[18] Hobson, G. D., Modem Petroleum Technology, any edition, Wiley, NY.
[19] DS 4B, Physical Constants of Hydrocarbon and Non-Hydrocarbon Compounds, ASTM International, West Conshohocken, PA,
1991.
[20] Technical Data Book for Petroleum Refiners, American
Petroleum Institute, Washington, D.C.
[21] Engineering Data Book, Gas Processors Suppliers Association,
Tulsa, OK.
[22] Handbook of Chemistry and Physics, CRC Press, Boca Raton, FL.
[23] Chemical Engineers Handbook, McGraw Hill, NY.
[24] Chemistry Webbook, National Institute of Standards and Technology (NIST), Gaithersburg, MD, www.webbook.nist.gov.
[25] An Index of Selected Thermodynamic Data Handbooks, Thermodex, http://thermodex.lib.utexas.edu.
[26] "Chemiccd and Physical Properties," LSU Libraries, Louisiana
State University, Baton Rouge, LA, http://www.lib.lsu.edu/sci/
chem/properties .html.
[27] TRC Thermodynamic TablesHydrocarbons, Thermodynamics
Research Center, Texas A&M University, College StationTexas,
NIST, Boulder, CO.

REFERENCES
[1] Owen, K. and Coley, T., Automotive Fuels Reference Book, First
ed.. Society of Automotive Engineers, Inc., Warrendale, PA,
1990.
[2] Gibbs, L. M., "How Gasoline Has Changed," SAE Report No.
932828, Society of Automotive Engineers, Warrendale, 1993.
[3] Purdy, G. A., Petroleum, Prehistoric to Petrochemicals,Copp
Clark Publishing Co., Toronto, 1958.
[4] Kaufman, K. B., "Midgley: Saint or Serpent?," Chemtech, December 1989, pp. 717-725.
[5] Midgley, T. and Boyd, T. A., Industrial and Engineering Chemistry Research, Vol. 14, 1922, pp. 589, 849, 894.
[6] Midgley, T., "Problem + Research -I- Capital = Progress," Industrial and Engineering Chemistry Research, Vol. 31, 1939, pp.
504-506.
[7] Dying for Work: Workers' Safety and Health in 20th Century America, D. Rosner and G. Markowitz, Eds., Indiana University Press,
Bloomington, IN, 1987.
[8] Goodger, E. M., Petroleum and Performance, Butterworths Scientific Publications, London, 1953, p. 166

87

[9] Campbell, J. M. and Boyd, T. A., "Methods of Knock Rating. 15.


Measurement of the Knocking Characteristics of Automotive
Fuels," The Science of Petroleum. Oxford University Press, Oxford, Vol. 4, 1938, pp. 3057-3065.
[10] Gibbs, L. M., "How Gasoline Has Changed," SAE Report
#932828, Society of Automotive Engineers, Warrendale, PA,
1993.
[11] Kaiser, E. W., Siegl, W. O., Cotton, D. F., and Anderson, R. W.,
"Effect of Fuel Structure on Emissions from a Spark-Ignited Engine. 2. Naphthene and Aromatic Fuels," Environmental Science
and Technology., Vol. 26, 1992, pp.1581-1586.
[12] Berstein, M., "Thomas Midgley and the Law of Unintended Consequence," Invention and Technology, Vol. 17, No. 4, Spring
2002.
[13] Gibbs, L. M, "Transportation FuelsAutomotive Gasoline," Encyclopedia of Energy Technology and the Environment, John Wiley and Sons, NY, 1995, pp. 2675-2698.
[14] Gibbs, L. M., et al, Alcohols and Ethers A Technical Assessment
of Their Application as Fuels and Fuel Components, API Publication #4261, American Petroleum Institute, Washington D.C.
[15] "Research Report on Reformulated Spark-Ignition Engine
Fuel," ASTM RR: D02-1347, ASTM International, West Conshohocken, PA (updated regularly).
[16] "Federal Reformulated Gasoline," Chevron Technical Bulletin
FTB 4, Chevron, San Ramon, CA, 1994.
[17] Gibbs, L. M, "Transportation Fuels^Automotive Gasoline," Encyclopedia of Energy Technology and the Environment, John Wiley and Sons, NY, 1995, pp. 2675-2698.
[18] "Motor Gasolines Technical Review (FTR-1)," Chevron Products Company, San Ramon, CA, 1996.
[19] "Initial Mass Exhaust Emissions from Reformulated Gasolines," Technical Bulletin No. 1, Auto/Oil Air Quality Improvement Research Program, Coordinating Research Council, Inc.,
Atlanta, GA, December 1990, pp. 5-7.
[20] "Mass Exhaust Emissions Results from Reformulated Gasolines," Technical Bulletin No. 4, Auto/Oil Air Quality Improvement Research Program, Coordinating Research Council, Atlanta, GA, May 1991
[21] "Exhaust Emissions of Toxic Air Pollutants Using RFGs," Technical Bulletin No. 5, Auto/Oil Air Quality Improvement Research Program, Coordinating Research Council, June 1991.
[22] Kettering, C. F., "The Effect of the Molecular Structure of Fuels
on the Power and Efficiency of Internal Combustion Engines,"
Industrial Engineering and Chemistry Research, Vol. 36, 1944,
pp. 1079-1085.
[23] Composition of Canadian Unleaded Gasoline, available from
Canadian Petroleum Products Institute, Ottawa Ontario,
Canada, 1994.
[24] Reisch, M., "EPA Told Not To Ban Ethyl's Fuel Additive," Chemical & Engineering NewsM, 24 April 1995, p. 8.
[25] "Gasoline and Other Motor Fuels," Kirk-Othmer Encyclopedia of
Chemical Technology, 4th ed.. Vol. 12, M. Howe-Grant, Ed., Wiley, NY, 1993.
[26] Kozole, K. H., "1996 In-Use Vehicle Emission Survey Program,"
CPPI Report No. E12-B005248-Final, Canadian Petroleum
Products Institute, Ottawa, 1996, Available: http://www.cppi.ca.
[27] "Response to the Sasol report of 23 May 01 and the Ethyl report
of July 2001," presented at the IPIECA, September 2001, Delta
Motor Corporation, Shannon, Ireland, Aug. 24, 2001.
[28] "MMT Global Update to IPIECA," presented at the IPIECA,
Shannon, Ireland, September 2001.
[29] Calingaert, G., "Section 11, Anti-knock Compounds," The Science of Petroleum, Vol. 4, Oxford University Press, Oxford, 1938,
pp. 3024-3029.
[30] SAE J 1829: Stoichiometric Air-Fuel Ratios o f Automotive FuelsRecommended Practice, SAE Handbook, Vol. 1, Society of
Automotive Engineers, 1994.

88 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


[31] Westbrook, C. K. a n d Pitz, W. J., "The Chemical BUnetics of Engine Knock," Energy and Technology Review, Feb/Mar 1991,
pp. 1-13.
[32] Westbrook, C. K. and Pitz, W. J., "The Chemical Kinetics of Engine Knock," Energy and Technology Review, Feb/Mar 1991,
pp. 562-566.
[33] Westbrook, C. K. and Pitz, W, J., "The Chemical Kinetics of Engine
Knock," Energy and Technology Review, Feb/Mar 1991, pp. 1-13.
[34] Westbrook, C. K., "The Chemistry Behind Engine Knock,"
Chemistry & Industry (UK), 3 Aug 1992, pp. 562-566.
[35] Dyroff, G., Manual on Significance of Tests for Petroleum Products, 5th ed., MNL-1, ASTM International, West Conshohocken,
PA, 1993.
[36] Nadkami, K., Guide to ASTM Test Methods for the Analysis of
Petroleum Products and Lubricants, MNL-44, ASTM International, West Conshohocken, PA, 2000.
[37] Schuetzle, D., Siegl, W. O., Jensen, T. E., Dearth, M. A., Kaiser,
E. W., Gorse, R., et al., "The Relationship between Gasoline

[38]

[39]

[40]
[41]

Composition a n d Vehicle Hydrocarbon Emissions: A Review of


Current Studies and Future Research Needs," Environmental
Health Perspectives Supplements, Vol. 102, No. 4, 1994, pp. 3-12.
Coward, H. F. and Jones, G. W., "Limits of FlammabiHty of
Gases and Vapors," U.S. Bureau of Mines Bulletin 503, U.S.
Government Printing Office, Washington, D.C., 1952.
MoUer, W. O., Molname, M., and Sturm, R., "Limiting Oxygen
Concentration: Recent Results and their Presentation in Chemsafe," Presented at the 9th International Symposium on Loss Prevention and Safety Promotion in the Process Industries, May
1998, Barcelona, Available: http://www.ptb.de/de/org/3/33/331/
moeIler.htm.
Perry, R. H. and Chilton, C. H., Chemical Engineer's Handbook,
Fifth ed., pp. 3-346.
Bustin, W. M. and Dukek, W. G., "Electrostatic Hazards in the
Petroleum Industry," Electronic and Electrical Engineering Research Studies, Research Studies Press Ltd., UK, John Wiley and
Sons, NA, 1983.

MNL37-EB/Jun. 2003

Aviation Fuels
Kurt H. Strauss^

publication of a specification for a n 82 octane unleaded


grade, intended for the certification of new engines having
low octane requirements. Table 1 lists the pertinent aviation
gasoline properties in D 910, while Table 2 contains the requirements for D 6227, Grade 82 UL.

HISTORY
Aviation Gasoline
EARLY AIRCRAFT ENGINES WERE OPERATED o n ordinary straight-

r u n motor gasoline well into the 1920s [ 1 ]. Research then isolated uncontrolled combustion as a major source of engine
overheating and failures, prompting a search for ways to cure
the problem. The big step came in 1921 with the invention of
tetraethyl lead (TEL), a n unequaled knock resistance enhancer. The same period saw the development of the heptane-isooctane scale still in use today for rating antiknock
properties in terms of octane numbers. For aviation gasoline,
the concept of rating knock resistance in special single cylinder engines resulted in the Aviation Octane Test Method (D
614), which tested fuels under lean fuel mixture conditions
simulating cruise operation. (In 1970 this method was replaced in the specification by the Motor Octane Method, D
2700.) An aviation gasoline specification, issued by the U.S.
Air Corps in 1938, listed a 68 octane grade containing n o lead
and a 92 octane grade with a m a x i m u m of 6 mL TEL/gallon.
As engine power output was increased by supercharging the
fuel/air mixture, a second rating method, D 909, came into
use to evaluate performance u n d e r rich take-off conditions,
so that by World War II both rating methods were required.
Engine designers soon discovered the performance benefits
of high octane, which permitted a higher octane fuel t o develop more power in a given engine or allowed a reduction in
engine size with the same power output. Research on high
octane fuel thus received a high priority and resulted in a 100
octane fuel by the beginning of World War II. While t h e
heroic performance of the RAF is widely recognized, it would
have been impossible without the 100 octane fuel.

Jet Fuel
Because of different combustion requirements, jet fuel
started as a completely different portion of the petroleum
barrel [2]. Early British engines used domestic kerosine, a
fuel that has not changed drastically over the years. German
engines, also military, were operated on a mixture of kerosine and naphtha, probably to extend fuel availability. The
progression of U.S. military fuels is illustrated in Table 3.
Both JP-3 and JP-4, which are blends of kerosine and naphtha, reflected Air Force concern over fuel availability, while
JP-5 is tailored t o Navy r e q u i r e m e n t s for carrier combat
safety. JP-7 is a supersonic fuel in very limited use. Today, the
Air Force operates almost entirely on JP-8; in fact, this grade
has become the primary battlefield fuel to be used in gas turbine and diesel powered ground vehicles as well as combat
aircraft.
For civil use, ASTM issued specification D 1655 in 1959,
containing three grades. Jet A and A-1 were kerosine-type fuels differing only in freezing point, while Jet B was the civil
version of JP-4. Currently consideration is being given to removing Jet B from D 1655 and placing it into a separate specification. The key properties of Jet A and A-1 are illustrated in
Table 4. Corresponding specifications are issued by the UK
Ministry of Defence as defence standards (Def Stans), with
Def Stan 91 -91 [3] being the technical equivalent of ASTM Jet
A-1. Jet A meeting D 1655 is the civil aviation fuel in the U.S.;
Jet A-1 meeting the combined requirements of D 1655 and
Def StcUi 91-91 is the civil fuel elsewhere. There is no British
grade corresponding to Jet A. The latest effort at a true international jet fuel standard is a series of guidelines [4] issued in
1999 by the IntemationEd Air Transport Association (lATA),
which includes Jet, A, Jet A-1, the Russian TS-1, and a Jet B
grade.

The dramatic j u m p in aviation activity in the late '30s and


'40s witnessed a n increasing n u m b e r of aviation gasoline
grades, ultimately standardizing on five grades ranging from
80/87 to 115/145. ASTM recognized this situation by issuing
D 618 as a civil aviation gasoline specification in 1944 to be
replaced in 1947 by D 910. However, jet engine introduction
forced a steady decrease in gasoline volume and reduced the
n u m b e r of grades over time so that by the '70s only two
grades, a low lead content 80 and a high lead 100 grade, remained in commercial production. The 100 Low Lead grade
(lOOLL) was introduced late in that period, permitting a single fuel t o satisfy the requirements of both low and high octane engines. The latest change in this picture was the 1997

AIRCRAFT A N D ENGINE DESCRIPTIONS


Aviation Gasoline
Although a n u m b e r of military and some commercial aircraft
engines were liquid cooled, all engines produced after World
War II have been air cooled. These engines are generally of

' 69 Brookside Rd., Portland, ME 04103.


89
Copyright'

2003 by A S I M International

www.astm.org

90 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 1Key specification requirements for aviation gasoline."
Knock Value, lean mixture
Motor method
Octane number, min
tCnock value, rich mixture
Superchange rating
Octane number, m i n
Performance number, min
Tetraethyl lead, mL TEL/L max
gPb/L max
Dye content
Blue dye, mg/L max
Yellow dye, mg/L max
Red dye, mg/L max

Grade 80

Grade lOOLL

Grade 100

80.0

99.5

99.5

ASTM Test MeAod


D2700
D909

87.0
0.13
0.14
0.2
none
2.3

130.0
0.53
0.56

130.0
1.06
1,12

2.7
none
none

2.7
2.8
none

D 3341 or D 5159

Requirements for All Grades


Density at 15C, kg/m^
Distillation
Initial boiling point, '
Fuel evaporated
10%vatC
40%v at C
50%v at C
90%v at C
Final boiling point, C
Sum of 10% + 50% evap. temperatures. "C
Recovery volume, %
Residue volume, %
Loss volume, %
Vapor pressure, 38C, kPa
Freezing point, C
Sulfur, %m
Net specific energy, MJ/kg
Corrosion, copper strip, 2 h @ 100C
Oxidation stability (5 h aging)
Potential gum, mg/100 mL
Lead precipitate, mg/lOOmL
Water reaction, vol change, mL
Electrical conductivity, pS/m

Report

D 1298 or D 4052
D86

Report
max
min
max
max
max
min
min
max
max
min
max
max
max
min
max

75
75
105
135
170
135
97
1.5
1.5
38.0
49.0
-58
0.05
43.5
No. 1

max
max
max
max

6
3

D 323 or D 5190
or D5191
D2396
D 1266 or D 2622
D 4529 or D 3338
D323
D873

D 1094
D2624

2
450

''For complete specification requirements, refer to D 910.

TABLE 2 --Key requirements for grade 82 UL aviation gasoline."


Property

Knock value, lean mixture


Motor method octane number
Color
Dye content
Blue dye, mg/L
Red dye, mg/L
Distillation temperature, C at % (svaporated
10%v
50%v
90%v
End point
Residue, %v
Recovery, %v
Loss, %v
Net speciflc energy, MJ/kg
Freezing point, C
Vapor pressure, kPa
Lead content, g/L
Cu strip corrosion, 3 h @ 50C
Sulfur, %m
Potential gum (5 h aging)
mg/L
Alcohols and ether content
Combined methanol and etheinol, %ni
Combined aliphatic ethers, methanol and
ethanol as %m oxygen
"Refer to D 6227 for complete specification requirements.

Requirement

ASTM Test Method

D2700
min

82.0
purple

max
max

7.5
1.9

max

70
66-121
190
225
2
95
3.0
40.8
-58
62
38
0.013
No. 1
0.07

D2392
D86
max
max
max
min
max
min
max
max
min
max
max
max

D 3338, D4529 or D 4809


D2386
D 4953, D 5190, D 5191,
or D 5482
D 3237 or D 5059
D130
D 1266, D 2622, D 3120
D 4294 or D 5453
D873
D4815, D 5999, or D 5845

0.3
2.7

CHAPTER 4: AVIATION FUELS 91


TABLE 3U.S. military jet fuel chronology.
Date of
Issue

Grade

Specification

1944

JP-1

1946
1947

JP-l"
JP-S"

1951

JP-4

1952

JP-5

1956

JP-6''

AN-F-32, changed
to MIL-F-5616
not issued
AN-F-58, changed
to MIL-F-5624
MIL-F-5624, now
MIL-PRF-5624
MIL-F-5624, now
MIL-PRF-5624
MIL-F-25656

1980

JP-7

1979

JP-8

MIL-T-38219, now
MIL-PRF-38219
MIL-T-83133, now
MIL-DTL-83133

NATO
Symbol

the intermittent combustion, four cycle variety with a wet


crankcase oil system. In radial engines the cylinders are arranged in a circle with 7 o r 9 cylinders in a row and a n engine
having one or m o r e rows. Alternately, in flat engines the
cylinders lie horizontally and oppose each other. Most of today's production engines are the flat or pancake type with 4
to 8 cylinders. Some engines contain a supercharger to compress the air and thereby increase the mass flow through the
engine. The engine drives a propeller directly from the
crankshaft or through a set of speed reduction gears. Fuel is
carried either in rubber bladders or removable metal tanks,
often in the wings, and flows to cEirbureted engines by gravity or is pumped to a fuel-injected engine by a tank-mounted
submerged boost p u m p . A low pressure engine p u m p then
supplies the fuel into the carburetor to be mixed with air or
injects it into the intake manifold under low pressure. In either case the fuel has to be evaporated by the time it reaches
the cylinder because only vapors will b u m . Each cylinder
contains two spark plugs for safe operation. Water or a water-alcohol mixture may be injected both to help cool the en-

Volatility
and Freeze Point

l l O ^ F m i n flash
60C max freeze
2 psi max RVP
5-7 psi RVP
F-40

2-3 psi RVP

F-44

140F min flash


- 4 6 C max freeze
High thermal stab.
- 5 4 C max freeze
140F min flash
- 4 3 C max freeze
100F min flash
- 4 7 C max freeze

F-34

"Canceled.

TABLE 4Key specification requirements for jet fuel grades Jet A, A-1, and B.'
Property

Composition
Acidity, total, mg KOH/g
Aromatics, %v
Sulfur, mercaptan, %m
Sulfur, total, %m
Volatilitv
Distillation temp., C
10% recovered, temp.
20% recovered, temp.
50% recovered, temp.
90% recovered, temp
Final boil, point, temp
Distill, residue, %v
Distill, loss, %v
Flash point, "C
Density at 15C, k g W
Vapor pressure, 38C, kPa
Fluiditv
Freezing point, C
Viscosity, -20C, mm^/s
Combustion
Net specific energy, MJ/kg
One of following shall be met:
(1) Smoke point, m m
(2) Smoke point, m m and
Naphthalenes, %v
Corrosion
Copper strip, 2 h @ 100C
Stability
Thermal, 2.5 h at 260C
Filter press, drop, m m Hg
Tube deposit less thsm
Contaminants
Existent gum, mg/100 mL
Water reaction
Interface rating
Additives
Electrical conductivity, pS/m
If Additive is used
If required by purchaser

max
max
max
max

Jet A or Jet A-1

JetB

0.1
25
0.003
0.3

25
0.003
0.3

ASTM Test Method

D3242
D1319
D3227
D 1266, D 1552, D 2622
D 4294 or D 5453
D86

max
max
max
max
max
max
max
min

205
report
report
300
1.5
1.5
38
775-840

meix
max
max

- 4 0 Jet A
- 4 7 Jet A-1
8.0

145
190
245
1.5
1.5
751-802
21
-50

D 56 or D 3828
D 1298 or D 4052
D 323 or D 5191
D 2386, D 4305,
D 5901 or D 5972
D445

min

42.8

42.8

D 4529, D 3338 or D 4809

min
min
max

25
18
3.0

25
18
3.0

D1322
D1322
D 1840

max

No. 1

No. 1

D 130

max

25
Code 3

25
Code 3

D3241

max
max

7
lb

D381
D 1094

lb
D2624

max
min

"For complete specification requirements refer to D 1655.

450
50

450
50

92 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

gine and to increase power output. In addition to these traditional engines, other designs, particularly for ultralight aircraft, are being introduced but are not described in detail in
this chapter. Exhaust gases are discharged through mufflers,
turbochargers or directly into the atmosphere. Compared to
today's automobile engines, all these aircraft engines are relatively simple and unsophisticated.
With rare exceptions, aircraft piston engines are operated
with separate throttle and manual fuel/air mixture controls,
whether carbureted or fuel injected. On high performance
aircraft the pilot also controls the engine speed by means of
separate manual propeller controls. During takeoff and climb
the fuel/air mixture is maintained "rich;" the purpose of the
excess fuel is to help cool the engine at high power conditions. The fuel/air mixture is "leaned out" during cruise for
optimum fuel consumption. "Rich" in this context refers to a
mixture in which the fuel/air ratio is well above the stoichimetric ratio, while lean operation is run as close as possible
to stoichimetric without overheating the cylinders.
Jet Fuel
Jet engines operate on a completely different principle. Air
flows through a compressor, is guided into a combustion section where fuel is injected and burned and the resulting exhaust gases are expanded in the turbine section, and then expelled into the atmosphere. The turbine section drives the
compressor, while the remaining energy in the exhaust
stream either reacts on the engine parts to push the engine by
"jet propulsion" or is used to drive a propeller in "turboprop"
fashion. For more efficient operation, a large single stage

compressor or "turbofan" may be mounted in front of the engine. This fan is driven by its own turbine section by a shaft
running through the core engine. Military engines may add
extra thrust by injecting fuel into the exhaust stream and
burning it in an afterburner at the expense of greatly increased fuel consumption. Unlike reciprocating internal
combustion engines, these engines operate with continuous
combustion where an igniter serves only to start combustion
and is then turned off. Gas turbine engines operate with lean
fuel/air ratios well below stoichimetric (with considerable excess air) to provide turbine inlet gas temperatures below the
normal combustion temperatures.
The fuel system of a modem transport aircraft is illustrated
in Fig. 1. The fuel is carried mostly in the wing structure
where metal junctions are sealed with an elastomer and the
entire inside surface is coated with epoxy paint to prevent
corrosion. Elastomeric bags are generally not used for fuel
storage, mostly to save weight. From the tankage, fuel is
pumped by boost pumps to the engine high pressure pump.
The engine pump normally builds fuel pressure in two stages
with the first stage a centrifugal pump and the second stage
a gear pump capable of delivering fuel at pressures as high as
10 MBCa (1400 psi.). The fuel control, the heart and brains of
the fuel system, then meters the proper amount of fuel to the
combustion system with the excess fuel being bypassed back
to the second stage pump inlet. Fuel enters the combustion
system through a fuel manifold, which distributes fuel
around the engine and into fuel nozzles in the combustion
chamber. Note that the fuel passes through a series of heat
exchangers, which reject heat from the hydraulic system,
from the engine oil system, and from the auxiliary power sys-

Fueltank
Fuel quantity
gage

Nozzles

uiuaiiuu
umiij
lanifold /
ssembly /

A/Cheat
exchanger
Fuel bypass

iLPress Stage\HPress Stage|

Engine oil heat


exchanger
tkiti

Fuel
Control

FilterX
Engine Pump
Assembly
FIG. 1Turbofan fuel system.

Integrated
gen. drive
oil heat exch.

CHAPTER 4: AVIATION FUELS

93

Horizontal
Stabilizer
I Tank (optional)
Surge Tank

Reserve Tank No. 3


Main Tank No. 3

Main Tank No. 4

Reserve Tank No.2

\y<

>y

DryBay

Center Wing Tank


Surge Tank\
Main Tank N o . 2 /

/
MainTankNo.l f

Tank

Fuel Tank Volumes


Liters

Main Tanks No. 2 and 3


Main Tanks No. 1 and 4
Center Wing Tank
Reserve Tanks No. 2 and 3
Horizontal Stabilizer Tank
Total Usable Volume

Gallons

47 675
17 030
65 220
5020
12 540

12 594
4499
17 229
1326
3313

217 211

57 381

FIG. 2Boeing 747-400 fuel tankage.

tern. (In some systems the heat from the hydraulic system is
rejected in the fuel tanks.) Additional heat is added to the fuel
by energy losses in the pump and by fuel recirculation
through the pump. More heat goes into the fuel from the
compressor discharge air, which the fuel passes through to
get into the combustion system. This heat path highlights another important function of the fuel, to serve as the heat sink
that carries away excess heat from other systems and allows
other systems to operate.
Figure 2 illustrates the tankage arrangement of a Boeing
747-400 aircraft. At takeoff, each engine is supplied fuel from
its own tank. After takeoff, fuel is taken selectively from the
center wing tank first to control wing stresses. For a typical
flight each engine is started by rotating the compressor spool
to start air flowing. When airflow is sufficient to start combustion, fuel is injected and the fuel/air mixture is ignited.
The engine then accelerates under its own power to idle operating speed and above. Maximum power at take-off is limited by either throttle demand or turbine inlet temperature
limits. Take-off power is reduced as the aircraft climbs and is
further reduced at cruise altitude to minimize fuel consumption. At the end of cruise, power is further decreased to near
idle for descent. Because heat rejection is almost constant
but fuel flow is near minimum, the descent portion of the

flight creates the highest fuel temperatures. In this entire


flight the pilot controls all engine power settings with a single throttle lever, while the engine fuel control adjusts, for all
the variables.

PERFORMANCE REQUIREMENTS AND


THEIR IMPLEMENTATION
A review of aviation gasoline and jet fuel specifications will
show that all are based on Vcirious performance tests rather
than closely defined product compositions. In turn, most of
the performance tests are empirical and do not define a property on an absolute basis; indeed many were developed to
solve specific operating problems. The following sections
outline vetrious challenges faced by aviation fuels and their
solutions.
Low TemperatureFuel Related
Jet Fuel
Aviation fuels have to operate in an extremely wide temperature environment. In particular, jet fuel is exposed to very low
temperatures due to operating conditions and fuel system de-

94

MANUAL

3 7: FUELS

AND LUBRICANTS

HANDBOOK

sign. This leads to two differing problems, one being normal


operation at cJtitude, the other involving steirting at very low
temperatures. In the wing tanks the fuel is in direct contact
with the lower wing skin which in turn is exposed to ambient
t e m p e r a t u r e s as extreme as 100C (148F). Although
aerodynamic heating at cnaise will wEirm the bottom wing
surface some 20-25C or 36-45F, the resultant fuel temperatures at the wing skin Ccin still be very low. At these low temperatures certain types of hydrocarbons in jet fuel come out
of solution. The most critical molecules are straight chain
paraffins [5] because they have the highest crystallization
temperatures of the hydrocarbons normally in jet fuel. When
these compounds come out of solution, they form a wax crystal matrix that can prevent the liquid fuel within the matrix
from flowing into a boost p u m p inlet [6]. Only 8-10% of normal paraffins in the fuel are required to form such a matrix.
For safe operation the fuel freezing point is defined as the
temperature at which the fuel is 100% liquid. This temperature is determined by D 2386 in which a sample is cooled in
an isopropyl-dry ice bath until a crystal haze appears. The
sample is then weirmed until the last crystal disappears. That
melting temperature is reported as the "freezing point". Using the melting point avoids possible super cooling of the
sample during the cooling cycle. At this writing, three other
tests are permitted as alternates. They include D 5901 (Freezing Point of Aviation Fuels^Automated Optical Method), D
5972 (Freezing Point of Aviation FuelsAutomatic Phase
Transition Method) and D 4305 (Filter Flow of Aviation Fuels at Low Temperatures). However the last method cannot
be used when fuel viscosity exceeds 5.5 cs at 20C (4F).
In case of dispute, D 2386 is the referee method.

-50

-30

-10

10

In-flight aircraft operation is not permitted below a fixed


fuel temperature differential above the specification maxim u m freezing point. This limit is called out in the flight manual of each aircraft. For Boeing aircraft the differential is 3C
or 5F, and for Airbus aircraft it is 4C or 7F. Operation at
lower fuel t e m p e r a t u r e s is avoided by aircraft routing
through w a r m e r air, by using a fuel of lower freezing point,
or in flight by increasing aircraft speed or decreasing altitude
when this condition appears imminent [7]. Limited U.S. Air
Force research also shows possible promise for additives that
lower fuel freezing points [8]. However, the practicality of
such additives in unproven.
Viscosity is the limiting property for jet engine starting because of its influence on fuel droplet size during atomization.
Viscosity is measured by D 445 and typical fuel viscosities are
plotted against temperature in Fig. 3 [9]. Engines are designed to start with fuel viscosities u p to a m a x i m u m of 12 cs
[10], a viscosity reached around - 4 0 C ( - 4 0 F ) for either Jet
A or A-1. However, specifications allow a m a x i m u m viscosity
of 8 cs at 20C (4F), which is taken as equivalent to 15 cs
at 40C. Starting problems are therefore occurring at far
N o r t h e r n latitudes, particularly in helicopters, and are
avoided by the use of Jet B or JP-4 fuel, which has lower viscosity and increased volatility.
Aviation

Gasoline

Aviation gasoline low temperature performance tends to center on engine starting. While fuel volatility is the key to fuel
evaporation a n d engine starting, the tight volatility limits
allow little flexibility and force solutions other than fuel selection. Starting difficulties at low temperatures are com-

30

50

70

Ten^rature, C
FIG. 3Typical viscosities vs. temperature.

90

110

CHAPTER 4: AVIATION FUELS


0.10

0.06

95

0.04

0.02

Jet A, Jet A-1. JP-8


Aviation Gasoline

:
o
"2

II

0.007
0.006

20

40

60

80

100

Ten^rature, C
FIG. 4Water solubility vs. temperature.

pounded by increased lubricating oil viscosities and decreased battery performance. High altitude operation does
not normally present a low temperature problem because
gasoline has a very low freezing point and most piston engine
aircraft do not fly at extremely high eJtitudes.
Low TemperatureWater Related
All hydrocarbons can dissolve a very limited amount of water. Saturation limits for jet fuel and for aviation gasoline are
shown in Fig. 4 [9]. When water-saturated fuel is cooled, water comes out of solution as free water. These low levels of
free water do not present cin operating problem. However, as
the fuel temperature goes below 0C or 32F, this free water
freezes into ice crystals that can plug filters and other fine
passages. The problem is avoided by placing filters into a
warmer part of the fuel system, by applying heat to critical filters when water freezing temperatures are noted, or by including an anti-icing additive in the fuel. Diethylene glycol
monomethyl ether (diEGME), as described by specification
D 4171, Type III, can be added to jet fuel or aviation gasoline
as an anti-icer in concentrations of 0.10-0.15% by volume.
Ethylene glycol monomethyl ether (EGME) is no longer
listed in D 4171, but is still in limited use. Isopropyl alcohol,
per D 4171 Type II, may only be added to aviation gasoline.
Here specification D 910 warns that the addition of isopropyl
alcohol to the 100 grade may lower its knock ratings. Both
additives only keep limited amounts of free water from freez-

ing and neither affects wax precipitation. Water concentrations significantly exceeding saturation levels Ccin overwhelm
these additives. Techniques for monitoring free water levels
etnd keeping excess water out of aircraft are discussed later
under Quality Control. The freezing of atmospheric moisture
on the throttle plate causes carburetor icing in piston engines; it is due to evaporative cooling by gasoline and trace
levels of water in fuel play no part.
High Temperature
Exposure to high temperatures represents one major difference between aviation gasoline and jet aircraft fuel systems,
in fact, high temperature exposure has not occurred in aviation gasoline-powered aircraft. Jet fuel presents a completely
different picture. The first incidents, in the early 1950s, took
place in military J57 engines that suffered plugging of nozzle
filter screens by fuel-caused carbon deposits [11]. Such plugging radically altered the exhaust gas temperature pattern at
the turbine inlet and resulted in turbine blade failures. In this
engine the fuel manifold that distributed fuel to the individual nozzles was located in the hot compressor discharge air
and some fuels formed carbon deposits in the manifold under reduced fuel flow conditions. These deposits broke off
and plugged fuel nozzles. The particulsir problem was solved
by manifold redesign, but it also alerted the industry to the
need for tailoring high temperature performance into the
fuel.

96 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

FIG. 5Jet Fuel Thermal Oxidation Tester (JFTOT).

Extensive research has pinpointed trace levels of certain


molecules and metals to be the criticeJ peirticipants in high
temperature oxidation reactions. Heteroatoms containing
sulfur and/or nitrogen have been investigated in a number of
model studies [12], which have found them to be as much as
20 times more reactive than the base fuel. Oxidation transforms these molecules into higher moleculctr weight materials, which become insoluble and can plug filters or screens or
deposit on hot surfaces. In turn, such deposits have broken
loose or have caused sliding parts to stick. Thus, these reactions involve only a tiny fraction of the total fuel going
through the engine, but their effect becomes significant because of the very large fuel volumes handled over a long period of time. Ultimately, the basic reason for fuel degradation
is the fuel's use as a heat sink as pointed out under Engine Descriptions. To curb the problem, the engine design approach
has been to limit liquid fuel temperature to a maximum of
190C (325F) [13]. However, fuel oxidation is a function of
both temperature and exposure time so that lengthy residence
times at temperatures below this maximum have resulted in
operating difficulties. Paradoxically, improving engine design
over the years has increased the severity of fuel exposure be-

cause more efficient engines have reduced fuel flows and


therefore cause higher heat inputs into the fuel [14].
Fuel constraints have also been instituted. Although specific heteroatoms have been found to oxidize rapidly in
model studies, the large variety of materials involved in high
temperature oxidation as well as their low concentration precludes their analytical identification on a routine basis.
Therefore, the jet fuel specification requires a performance
test, the Jet Fuel Thermal Oxidation Tester (JFTOT) by D
3241, to screen out product with unsatisfactory characteristics. The unit is illustrated in Fig. 5. In the apparatus, fuel is
pumped over a heated tube under pressure and then through
a metal screen with 17 micron openings, with both tube and
filter being maintained at a temperature of 260C (500F).
Filter pressure drop is monitored during the test, and at the
end of the test, tube deposit color is competred to a color
standard. Normally the test is run only at the specification
minimum requirement conditions and the quality margin
available above this limit is unknown. Like many other timedependent tests the thermal stability test has poor precision,
but the visual rating of deposit color plays a major part in the
poor precision [15]. Over the years, differing methods for rat-

CHAPTER 4: AVIATION FUELS


ing of tube deposits have been proposed and rejected. Most
recently, a method of measuring deposit volumes by an ellipsometric technique [16] has been developed as an alternate to
the visual rating but has not been adopted.
An interesting side issue has been the catalytic effect of certain metals on these high temperature reactions. This topic is
further discussed in the section on Corrosivity.
Combustion
More than any other performztnce requirement, combustion
requirements influence the differences between aviation
gasoline and jet fuel.
Aviation Gasoline
The requirements of spark-ignited reciprocating engines
have shaped aviation gasoline since its earliest uses. As the
mixture of air and fuel vapor enters the cylinder and is compressed, the mixture must be ignited at a critical time in the
engine cycle to provide maximum power through the expansion of exhaust gases. Mixture autoignition, either through
compression ("dieseling") or by glowing deposits, will cause
a loss of power and can result in detonation with severe mechaniccd damage. Aircraft engines Eire particularly vulnerable
because of the extensive use of aluminum alloys and other
low melting point meteJs. Compression ignition cjin be alleviated by spark timing retardation as well as maximum
power reduction. However, either approach causes a performance loss. Thus the importance of fuel knock resistance
through adequate octanes cannot be overemphasized.
Gasoline knock resistance is measured by the lean and rich
engine tests mentioned earlier. In the lean mixture method,
D 2700, the test variable is compression ratio, which is the ratio of the total volume displaced by the piston to the volume
above the piston at the top of the compression stroke. When
testing Ein unknown fuel in the single cylinder D 2700 engine,
this ratio is increased until knock is detected. The condition
is then rated by making blends of n-heptane and isooctane
and adjusting the ratio of the components until a match is
noted with the test fuel. The percent isooctane in the matching blend is the test fiiel's octane number. If fuel octane exceeds 100, the match is made with pure isooctane containing
differing levels of TEL. Because the specification requires

ratings by the old Aviation method, D 2700 contains conversion tables from the Motor method to the Aviation method. It
is noted in passing that the Motor Method is the only rating
method used for both aviation and motor gasolines.
The rich rating method, D 909, is more complex. Engine
output is measured and controlled by a dynamometer. Air
into the engine is compressed Eind cooled. Both fuel and air
flow to the engine are metered. Engine loading by the dynamometer is increased at constant fuel/air ratio until knock
occurs. The same process is repeated at increasing fuel/siir ratios to develop a curve of knock-limited engine output against
fuel/cdr ratio. This curve is bracketed by similar curves using
isooctane with varying concentrations of TEL as reference
fuels. The test fuel rating is established by interpolation between reference fuel curves cind is usually expressed in terms
of performzince numbers, which are directly proportional to
the engine power output. Thus, with a fuel having a performance number of 130 the engine developed 30% more power
than on straight isooctane.
There are currently several research programs [17] related
to knock testing and combustion requirements of aviation
piston engines. The first program is establishing the octane
requirements of a great variety of current production engines
to get an up-to-date definition of the relationship of the single cylinder laboratory engines to fl5'ing hardware. As part of
this effort, an Engine Octane Rating method has been issued
as D 6424. Preliminary results indicate that, while the old,
large radicd engines are sensitive to both lean and rich knock
characteristics, the flat or pancake engines seem to be critiCcJ in the cruise or lean operating mode only. The second program is pointed toward the development of a high octane, unleaded aviation gasoline. That search is driven by the fact that
100 octane aviation gasoline is the only lead-containing fuel
left in the U.S. petroleum inventory and there is environmental pressure to eliminate lead wherever it exists. Ultimately,
the two programs should indicate the practicality of developing an unleaded gasoline, which will satisfy the current inventory of engines requiring high octane fuel.
Jet Fuel
A typical jet fuel combustion system is illustrated in Fig. 6.
Air is discharged from the compressor at pressures up to 20

Outer combustor casing


Fuel nozzle

Inner liner

Turbine
inlet

Jet igniter

Primary comlnistion
zone

97

Secondary
zone

FIG. 6^Turbofan combustion system.

9 8 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

atmospheres (300 pounds per square inch) and temperatures


as high as 450C (840F) into the combustion system between
the outer and inner liners. The air then enters the inner Hner
through holes and slots carefully placed and sized to control
the air and gas flow patterns. Fuel is injected and atomized
through one or more nozzles into the primary combustion
zone, where, after ignition, it will bum at temperatures approaching 2000C (3500F). Such gas temperatures exceed
the operating limit of the turbine section and therefore more
air is added in the secondary zone to reduce exhaust gas temperatures to maximum levels of 800-1200C or 1500-2200F.
Thus, air provides oxygen for combustion, creates local turbulence to stabilize flame location, cools the inner liner surface, and finsJly reduces exhaust gas temperatures. Note that
the fuel line to the nozzle must go through the hot compressor dischcirge air and the engine designer must guctrd against
excess heat flow into this line.
In the early days much effort was spent to discover a jet
fuel property that would improve engine efficiency the way
that octane improves piston engine performance [18]. No
such performance parameter has been found for jet engines.
Fuel specification tests therefore serve primarily to limit undesirable components that could shorten engine life. In general, paraffinic molecules provide the cleanest combustion
while aromatics tend to create the opposite conditions.
Several tests are used to measure fuel combustion quality.
The simplest test is the Smoke Point, D 1322. A lamp with a
fuel reservoir contains a wick that can be lowered and raised
and furnishes fuel to a flame. When the wick is raised, the
flame increases in height, but at some height the flame begins
to smoke. This height varies with fuel composition. The maximum flame height at which no smoke occurs is defined as
the fuel smoke point. Although the smoke lamp represents a
very simple combustion process, a large amount of research
has validated the good relationship between this test and engine combustion, with fuels having higher smoke points
showing cleaner combustion with reduced engine smoke or
soot as well as decreased flame radiation in older engines.
Engine studies have highlighted the poor combustion quality
of double ring aromatics or naphthalenes and these are therefore measured by ultraviolet absorption at 245 nanometers
with a spectrophotometer (D 1840). Another much more
complex test, the Luminometer (D 1740), was designed to
rate fuels by measuring the radiation from a smoke lamp
flame, but the close correlation between this test and the
smoke lamp has caused the test to fall into disuse. Lastly, the
measurement of total aromatics by fluorescent indicator absorption (D1319) or by high performance liquid chromatography (D 6379) is also listed as a combustion test. However,
this measurement does not correlate as closely with engine
performance as does the Smoke Point and its prime significance is as an indication of elastomer compatibility. Hydrogen content by D 3701 has been proposed as a combustion
quality indicator and a substitute for aromatic content but
has not been accepted in civil specifications because its relationship to elastomer compatibility is not established. Specification combustion requirements are listed in Table 3.
Minor fuel composition changes have little or no effect on
combustion quality [19]. Therefore, low concentrations of organic materials as additives have little, if any, effect on combustion. Additives containing heavy metals have reduced en-

gine smoke or soot but are not permitted because of ash formation. [20].
The level of sulfur oxides in the exhaust is directly related
to the total sulfur content of the fuel and any required reduction of these oxides has to be achieved by reducing total sulfur content below currently allowed levels. Nitrogen oxides,
on the other hand, are purely an engine design function depending primarily on the maximum combustion temperatures, the amount of mixing in the primary combustion zone,
and the time at maximum temperature. Fuel characteristics
play no part [19]. The same can be said for carbon monoxide
emissions in which fuel does not play a significant role [19].
Because the ultimate purpose of fuel is to furnish heat energy, the minimum heat content or specific energy is controlled. Water vapor formed during combustion is not condensed in any aviation engine, therefore the net specific
energy is specified. As mentioned in D 910, the minimum
specification level for aviation gasoline is high enough to effectively limit the total amount of aromatics to about 25%.
Specific energy (formerly called heat content) can be measured in a calorimeter per D 4809, where a small amount of
fuel is burned in a pressure vessel, which in turn is immersed
in a water bath. The released energy is calculated from the
temperature increase of the water bath. Extremely precise
thermometry is required for the desired accuracy of the results. Specific energy can also be estimated by equations
based on pertinent fuel characteristics. One estimation
method, D 4809, uses fuel density and aniline point; another,
D 3338, includes density, boiling point and aromatic content
as variables. D 3338 is gaining in popularity because of aniline toxicity and because the required variables are already
being determined to assure overall specification compliance.
Volatility and Flammability
Volatility, a fuel's tendency to evaporate, plays a significant
part on the ground and in the air. Some performance requirements overlap between the two fuel t5rpes, others do not.
Aviation Gasoline
Aviation gasoline volatility is a major factor in engine operation because proper ignition requires fuel in vapor form. The
fuel, therefore, has to evaporate in the intake manifold before
reaching each cylinder. This is particuleirly important during
starting. Volatility also affects vapor formation in fuel lines,
which occurs when line pressure drops below the vapor pressure of the fuel, usually due to local overheating at low line
pressures. Vapor lock takes place when the combined volumes of vapor and liquid in the line exceed the volumetric capacity of the engine pump so that the engine no longer gets
the required amount of fuel. As a result, the engine will not
run until liquid fuel flow is restored. Lastly, volatility determines the flammability of the vapor space (ullage space)
above the fuel. This property is discussed later in this section.
Jet Fuel
Fuel volatility tends to have different effects on jet fuel operation. Too high a volatility CcUi cause excessive evaporation or
even boiling in aircraft tankage during rapid climb when fuel
vapor pressures equal the rapidly decreasing atmospheric
pressures at altitude. That problem caused the 1950s shift

CHAPTER 4: AVIATION FUELS


280

260
240
220
200
180
160

140
120
100
80
60
40
20
0

99

Jet A

JetA-l,JP-8

JetB,JP-4

\
\

'

1
20

1_
40

Avgas

60

80

100

Percent Evaporated

FIG. 7Fuel boiling ranges.

from JP-3 to JP-4 fuel by the U.S. Air Force [2]. Ullage
flammability in aircraft tankage is of concern and depends on
fuel type as well as in-tcink temperatures and pressures. Aside
from some effect on engine stcirting at very low temperatures,
fuel volatility is not a major factor in jet engine operation.
Fuel volatility is normally defined by the product's boiling
range and its vapor pressure. The boiling range is measured
in a simple distillation apparatus, D 86, in which fuel is
boiled off and then condensed at atmospheric pressure under
closely controlled conditions. The test result is a relationship
of boiling temperatures to fuel percent evaporated. Typical
results for Jet A [21 ], Jet A-l/JP-8 [23], Jet B/JP-4 [21 ] and aviation gasoline [22] are plotted in Fig. 7. The boiling range distribution can also be measured by gas chromatography, D
2887, where the molecular distribution of a sample is compared to a standard mixture of known boiling points.
Fuel vapor pressure is routinely measured at 38C (100F)
by D 323 or D 5191. The resuh of the test, called the Reid vapor pressure (RVP), is the sum of the partial pressures of the
fuel constituents plus the partial pressures of dissolved air
and water measured at a vapor to liquid ratio of 4:1. A true,
absolute vapor pressure where the vapor space approaches 0
can be obtained at any temperature with D 6378. A summary
of typical absolute vapor pressures against temperature is
shown in Fig. 8 [9], but absolute vapor pressure is not determined on a routine basis.
Reid vapor pressure is specified for aviation gasoline and
Jet B but not for Jet A or A-1 because for these fuels the RVP
results are too low to be reliable. Instead, volatility for the
kerosine-type fuels is measured by the flash point test. Fuel
in a closed cup is immersed in a water bath, which is warmed
at a specified rate. Starting 10C (18F) below the expected
flash point temperature, a small flame is repeatedly inserted
into the cup, which is closed between flame immersions. The
fuel temperature at which a flash of flame appears and disappears is reported as the flash point. The standard test in D
1655 is the Tag Closed Cup method, D 56, but other flash
point tests are also in use. Because of differing surface to volume ratios and different heating rates these tests often give
consistently different results and these differences have to be
considered when comparing test results [24].

Vapor pressure and flash point, while related, do not measure the same property. The former measures the pressure
exerted by a fuel at a specific temperature, while the latter indicates the lowest temperature at which a flammable fuel/air
mixture is created. Typical fuel flammability ranges at sea
level are summarized in Table 5 [9]. Below the lean limit
there is not enough fuel vapor in the air for combustion,
while above the rich limit there is not enough air. Only within
the flammability limits is the mixture ignitable with an energy source like a spark or flame. The drastic differences between aviation fuels are apparent. These flammability limits
are not absolute but are influenced by the test equipment and
test conditions and serve only as general guides with regard
to vapor space flammability. For example, the fuel/air ratio in
a large storage tank is maximum at the fuel surface and decreases with increasing distance above the fuel. Tank vapor
space or ullage flammability therefore can vary in a tank, particularly because temperature is also not usually uniform.
Flammability limits are also strongly influenced by the effect
of ambient pressure on evaporation rate. Thus the change in
flammability limits with increasing altitude (decreasing pressure) is shown in Fig. 9. The subject of aircraft tank flammability is being revisited as the result of the 1997 crash of TWA
Flight 800, which is attributed to the explosion of the "empty"
center tank in the fuselage [25].
Fuel Metering
The measurement of fuel quantity and fuel flow is important
both for ground and for flight operations. On the ground

TABLE 5TyplcEil fuelflammabilitylimits at sea level.


Flammability Concentration Limits, %v
Lower (lean) limit
Upper (rich) limit

Avgas

JetB

Jet A

JP-5

1.2
7.0

1.3
8.0

0.6
4.7

0.6
4.6

Flammability Temperature Limits, C


Lower (lean) limit
Upper (rich) limit

-44
-12

-23
18

53
77

64
102

100 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

>

20

40

60

80

100

120

HO

Temperature, "C
FIG. 8Typical vapor pressures vs. temperature.

product is bought, sold, or transferred on a volume basis.


Fuel volume changes with temperature, so the volume is usually corrected to a standcird temperature using the equations
or tables in D 1250. Use of the corrections results in consistent inventories and product transfers. In the U.S. the standard temperature is 60F, outside the U.S. it is 15 or 20C. Although different only in the fourth significant place, the
volume difference between 60F and 15C becomes significant for leirge fuel volumes. All aircraft fuel measurement is
on a mass basis: whether desiling with total aircraft take-off
and landing weight, maintaining mass balances and trim in
flight or when metering fuel flow into the engine and its combustion system.
Volume is measured in U.S. gallons or in liters. Mass units
include density in kg/m^ at 15C, relative density - the ratio of
fuel density to water density, usually at 15C, and API Gravity,

an arbitreiry scale, at 60F. All are measured by hydrometer, D


1298, or by digital density meter, D 4052. Fuel height in most
jet aircraft tcuiks is measured by gages based on fuel dielectric
constant. These fuel heights are converted into tank volumes
eind transformed electronically into mass units during aircraft
loading. Other aircraft gaging system use ultrasonic signals to
measure tank fuel height. To deliver the proper fuel flow to
the combustion system the engine fuel control is programmed
to meter volume and to correct for fuel density and fuel temperature as well as other parameters.
Aircraft Range
Aircraft range is controlled by the total heat content of the
fuel in the aircraft. Maximum range is limited either by the
maximum allowable aircreift take-off weight (weight-limited)

CHAPTER 4: AVIATION FUELS


or by the total volume of tankage on the aircraft (volume limited). Either one is determined by fuel density and, in special
cases, an optimum fuel density has been selected for a particular long distance flight. In normal operations such an approach is not feasible. Aircraft operations have to EJIOW for
the density range permitted by specifications and routes,
which require maximum range, are usually avoided, particularly because atmospheric conditions such as winds Eind payload variability play a major part in determining fuel quantity
requirements.
CoiTOsivity

Copper
One of the early compatibility problems has been fuel attack
of system metals, particulcirly copper or copper-containing
materials. In aircraft fuel systems this frequently involved
fuel attack on bronze pump bearings. The primary fuel constituents involved in copper corrosion are elemental sulfur
and hydrogen sulfide, although acidic components may also
play a part. The most common source of hydrogen sulfide has
been incomplete stripping of the gas after refinery hydrotreating. Elemental sulfur (S), which is sulfur uncombined with other elements, has tended to result from the
chemicEd reduction of water-soluble sulfates in tank bottoms
by sulfate reducing bacteria or by the oxidation of hydrogen
sulfide. Elementcil sulfur has also been a byproduct of older

101

mercaptan conversion processes such as Bender or Doctor


treating. Both elemental sulfur and hydrogen sulfide are corrosive to copper at levels of around 1 ppm [26], but exact levels at which unacceptable corrosion occurs seem to depend
on the presence of other trace materials such as mercaptans.
Rather them limit either elemental sulfur or hydrogen sulfide, copper corrosion is therefore minimized by the copper
corrosion test, D 130, where pure copper is exposed to fuel at
100C (212F) for 2 h. Copper appearance is compared to a
standard color chart and only minimal discoloration is permitted. In addition, contact with copper or copper-containing eilloys is avoided as much as possible in aviation fuel systems and good housekeeping will prevent the proliferation of
sulfate reducing bacteria.
For jet fuel systems there is zdso great concern over copper
content in the fuel as the result of copper corrosion. Copper
concentrations as low as 15-20 ppb have adversely affected
thermal stability and copper levels above 30-50 ppb have decreased this property below the specification minimum [27].
Copper sources have included refinery heat exchangers,
bronze heating coils in marine tankers as well as bronze fuel
systems in Navy aircraft carriers. The reactant in an old mercaptan conversion process, Linde sweetening, can also be a
copper source.
Unfortunately, the relationship between the corrosion of
copper or bronze parts and the pickup of copper in jet fuel is
not clesu-ly established. Compatibility with copper-containing parts in the fuel system is controlled by the copper corro-

80
Temperature, C
FIG. 9Flammability limits vs. altitude.

100

102 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

sion requirement in the specification, but fuel passing tfiis requirement can dissolve the very low levels of copper, which
in turn can wreck thermal stability. At present the most reliable way to avoid pickup is to avoid contact with the metal or
to add an approved metal deactivator to chelate and deactivate the trace levels of copper in fuel.
Cadmium
The corrosion of cadmium-plated parts has been attributed
to mercaptan sulfur compounds, particularly in the presence
of water [28]. Mercaptan sulfurs are measured by D 3227 or
are limited qualitatively by the Doctor test, D 4952.
Steel
A form of corrosion in which the fuel plays an indirect role is
the rusting of mild steel by free water in fuel. Such corrosion
shortens the life of steel components but also is the source of
solid contamination, which ultimately has to be removed
from aviation fuels. U.S. military jet fuels require the presence of fuel-soluble corrosion inhibitors, generally dibasic
acids, which form a protective molecular layer on the steel
surface. MIL-PRF-25017 defines the requirements for this
t3^e of additive and approved additives are listed in the Qualified Products List for the specification. The dual function of
these additives as lubricity agents as well as corrosion inhibitors is discussed later in this chapter. Because these materials are surface-active and can interfere with water removal in the filter-coalescing process, their use in civil fuels
is very limited. Multi-product pipelines are protected by placing the additive into the non-aviation products. Fuel systems
at airports are usually internally coated to prevent rusting.
Galvanizing or zinc coating is not an acceptable method for
rust prevention in aviation systems because of the sacrificial
nature of zinc, which can react with the TEL in aviation gasoline or dissolve into jet fuel to form an ash during combustion.
Storage Stability
Petroleum products in long term storage are subject to low
temperature oxidation, which may cause the formation of
high molecular weight products that become insoluble and
precipitate out. Olefins formed during cracking are particularly prone to such degradation and are avoided in aviation
fuels. Straight-run jet fuels have excellent storage stability
due to the presence of natural oxidation inhibitors. However,
processes such as hydrocracking or high pressure hydrotreating destroy these inhibitors, leaving the product vulnerable to oxygen attack. In jet fuels such peroxide formation
[29] has led to repeated localized incidents of nitrile rubber
deterioration in military service [28]. Such elastomer attack
has not been reported with civil fuel in the U.S., probably due
to the greater amount of fuel commingling. Similar degradation tends to occur in aviation gasoline, which contains no
natural oxidation inhibitors and is therefore routinely inhibited with oxidation inhibitor additives.
Peroxide formation is prevented by oxidation inhibitors,
normally hindered phenols, which scavenge free radicals that
are the first step in the complex oxidation process [12]. Acceptable inhibitors are listed by composition in the jet fuel
and aviation gasoline specifications. To be effective, these in-

hibitors must be injected into the fuel as early as possible,


preferably into the run-down line from the processing unit.
Aviation gasoline susceptibility to oxygen attack is evaluated
in the Oxidation Stability test, D 873, in which fuel is exposed
to pure oxygen under pressure at 100C (212F) for 5 or 16 h.
The fuel is then evaporated and the residue ("gum"), together
with any lead precipitate, is weighed. Based on storage tests
conducted during World War II, passing test results are considered equivalent to one year of desert storage.
Tests on straight-run jet fuels in the 1960s showed oxidation at high temperatures to occur before oxidation at storage
temperatures. In fact, storage stability has not been a problem for such fuels. The D 873 requirement was therefore removed from D 1655. However, heavily hydrotreated or hydrocracked jet fuels should contain oxidation inhibitor to
assure the absence of peroxide formation. A test to establish
peroxide-forming tendencies has been published by CRC
[30], but is not yet approved by ASTM and has not been included in specifications.
Lubricity
In jet engine fuel systems a number of sliding metal surfaces
are lubricated by fuel. Under low contact pressures (hydrodynamic lubrication conditions) fuel viscosity assures separation of these parts. Under increased contact pressures or
higher sliding velocities (boundary lubrication) fuel viscosity
alone will not prevent metal to metal contact and a thin layer
of adsorbed polar material is also required to prevent surface
damage. Such material is present in straight-run fuels in very
low but adequate concentrations, but it is destroyed by high
pressure hydrotreating or hydrocracking. Such fuels have
therefore allowed metal to metal contact resulting in destructive wear of gears in high pressure pumps and sticking
of close-fitting servo valves in flow controls [31].
"Harsh" or "hard" fuels can be identified in the Ball on
Cylinder Lubrication Evaluator (BOCLE test), D 5001. Under a specified load, a stationary steel ball rubs against a rotating cylinder for 30 min. The contact area is submerged in
the test fuel and the entire test atmosphere is maintained at
a temperature of 25C (77F) and a relative humidity of 10%.
Afterward the ball wear scar is measured under a microscope. There are currently no specification limits for this
test, but a wear scar above 0.85 mm represents a very "hard"
fuel. Today the test is used primarily by engine accessory
manufacturers who have to qualify their components on
very hard fuels to assure satisfactory field performance.
However, under pressure from the New Zealand airworthiness authorities, the latest issue of DefStan 91-91 is the first
international specification to include a lubricity requirement for certain fuels.
In service, very hard fuels can be rendered acceptable by
the addition of as little as 10% straight-run product [32]. This
effect illustrates why lubricity problems have not been more
wide spread, having generally been averted by the extensive
commingling in most jet fuel systems. Problems have occurred in locations where hard fuels from a single supply
point were not mixed with other fuels and were supplied directly to aircraft. Even then different components responded
differently and failures occurred only on certain parts, mostly
on older units not qualified on hard fuel.

CHAPTER 4: AVIATION FUELS


Aside from hardwEire improvements, problem solutions include blending of hcird fuels with strciight-run product or the
addition of lubricity agents. Experience has shown fuel soluble
corrosion inhibitors to perform as lubricity agents, although
minimum dosages may differ for each use. Acceptable additives are covered by two military specifications and their qualified products lists. U.S. specification, MIL-PRF-25017, and
British Standard Def Stan 68-251 define additives suitable as
both corrosion inhibitors and lubricity agents. Neither of these
additive types are currently listed in civil specifications.
Static Electricity
Hydrocarbons are extremely poor electriccJ conductors but
usually contain trace levels of ionizable materials, which
carry charges of static electricity. With the fuel at rest the
charges neutralize each other. When fuel is moved, ions of
opposite charge are separated and an electrical charge is generated [33]. Local turbulence generated by pumps or filters
increases the charge, which is carried along unless the flow
velocity is reduced sufficiently for the charges to recombine.
When the fuel comes to rest, the charge leaks to ground. The
time required for the charge to bleed off depends upon the
fuel's conductivity. If conductivity is low, the charge may not
leak off gradually but be dissipated instead in the form of a
spark, which can become an ignition source. This process
takes place independent of system bonding or grounding.
However, all components of the fuel system, including the
aircraft, are electrically interconnected or "bonded" to eliminate the possibility of spEirks due to stray currents or lightning.
Static electricity problems can be minimized by slowing
the flow in lines, particularly after a filter, by providing an inert atmosphere over the fuel or by adding a conductivity improver additive to the fuel. Stadis 450 is the only conductivity improver approved for jet fuel and for aviation gasoline.
Outside the U.S. the additive is required in all jet fuel. In the
U.S., conductivity improver use in jet fuel is limited because
commonly used clay treaters in terminals remove the additive so that the fuel would require additive reinhibition. Instead, the emphasis is on providing charge relaxation by system design and operation. Guide D 4865 provides an
excellent review of the subject.
Other Properties
Data on other jet fuel properties not covered by specifications
such as thermal conductivity, specific heat, enthalpy, heat of
vaporization, thermal expansion, dielectric properties, and
bulk modulus will be found in the CRC Handbook on Aviation Fuel Properties [9]. This handbook includes data on both
commercial and military fuels.
FUEL MANUFACTURING
Aviation Gasoline
Low octane aviation gasoline can be straight-run gasoline
(grade 80) or based on premium grade motor gasoline (grade
82UL). The high octane grades (100 LL or 100) are based on
alkylate made by the process described in the following equa-

103

tion:
Catalyst

C4 olefins + isobutcuie

Alkylate

The olefins are separated from catalytic cracker products


while the catalyst is hydrofluoric or sulfuric acid. Alkylate
consists of branched chain paraffins, mostly iso-octctne. This
composition makes it a very high octane material of high
veilue to the refinery which can use the material to increase
the octane of either aviation or motor gasoline. In view of this
competition, as well as the low demeind for high octane aviation gasoline compared to motor gasoline, there is concern in
the aviation community regarding the long term availability
of the high octane aviation gasoline. This concern is sharpened by the uncertain future of tetraethyl lead. Like other
petroleum products, the ultimate availability of this fuel is expected to be determined by market forces.
Some blending is usually cEirried out for the high octane
gasoline. Isopentane increases vapor pressure, while toluene
increases the "rich" rating. Tetraethyl lead, along with the required scavenger and dye, is normally needed to reach the
necessary minimum octane levels. Oxidation inhibitor is always added to obtain storage life. Overall, aviation gasoline
has become a specialty product and, in the U.S., it is the only
remaining fuel containing lead.
Jet Fuel
Jet fuel processing starts with its separation from crude oil by
distillation, with the jet fuel fraction in the 150-290C
(300-550F) boiling range. Depending on the crude, a few
such streams are directly suitable as jet fuel, but most require
further treating. Mercaptan sulfurs are converted to disulfides primarily by Merox treating; alternatively, they Eire converted by hydrotreating to hydrogen sulfide which is stripped
from the product. Other sulfur compounds may be removed
by more severe hydrotreating. An increasing number of refineries are hydrocracking heavier streams to make high
qucdity jet fuel with good low temperature characteristics. To
control thermal stability, streams from catalytic or thermal
cracking Eire excluded or are saturated by severe hydrotreating. Contacting by activated clay removes polar materials
that deteriorate fuel-water separation and which may also
adversely affect thermal stability. Salt driers may be used to
remove free water.
Unless a refinery makes jet fuel by hydrocracking, jet fuel
yield and quality are dependent on product boiling range and
on the crude slate. Table 6 shows the general effect of changing boiling range on jet fuel properties when the product is
made by distillation, followed by mercaptan treating [34].
Availability is maximized by making product with the widest
possible boiling range. In turn, the boiling range tends to be
limited on the low distillation end by flash point, while the
maximum distillation end point is controlled by the specification freezing point. The wide rEinge of yield and resultant
qucdity for some typical crudes are illustrated in Table 7 [35].
The table also reflects the difficulty of simultaneously improving critical properties when using a single crude oil.
As pointed out in the section on History, commercial kerosine was the original jet fuel. Today, mEiny refineries make a
single product saleable as either jet fuel, commerciEil kero-

104

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 6Effect of boiling range changes on product quality.


Lowering Initial Boiling Point
Increases
Decreases
Smoke point
Density
Hydrogen content
Flash point
MJ per kg
Aromatic content
Vapor pressure
Naphthalenes
Freezing point
Viscosity
MJ per m^

Increasing Final Boiling Point


Increases
Decreases
Density
Smoke point
Hydrogen content
Aromatic content
MJ per kg
Naphthalenes
Freezing point
Viscosity
MJ per m^

Leading to
Better combustion quality
Better low temperature properties
Higher gravimetric heat content
Poorer handling safety
Lower volumetric heat content

Leading to
Lower combustion quality
Poorer low temperature properties
Lower gravimetric heat content
Higher volumetric heat content
Unchanged handling safety

sine, or diesel blending stock by having this product meet the


specifications for the other products. Such a product is referred to as dual branded kerosine and is divided and suppHed to the differing uses at the distribution terminal. However, this approach has become more complex by differing
maximum sulfur limits for the two products in many parts of
the world. An additional complication in the U.S. is an EPA
requirement for red dye in high sulfur diesel fuel.
A current source of controversy and ongoing discussion is
the effect of non-petroleum crude starting materials and new
processing on jet fuel quality. Jet fuel specifications are performance based and reflect past experience. Therefore, they
cannot guarantee satisfactory performance when a major
change from past practice occurs. For example, using coal or
biomateriaJs as starting materials raises questions that can
only be answered by additional testing beyond current specifications.

compatibility with system materials. However, the procedures do not disclose whether an additive will affect performance that has to be evaluated by other testing. A similar
protocol does not exist for aviation gasoline, which has seen
very few additive changes over the years.
It should be noted that ASTM does not confer additive approval. Such approval must be initiated by the airframe and
engine manufacturers and approved by the airworthiness
agencies. Additive listing in ASTM aviation fuel specifications simply recognizes such approvals.
Specific Additives
Most additives are described in earlier sections of this chapter under specific properties, but Table 8 lists all jet fuel additives contained in D 1655 together with their permitted
dosages. Oxidation inhibitors, metal deactivator, and conductivity improver may be added at the discretion of the refiner. Other additives, such as fuel system icing inhibitors,
can only be added with the agreement of the purchaser. The
fuel manufacturer or fuel handler must declcire all additives
and their concentration. Several military specifications make
mandatory the addition of oxidation inhibitor, conductivity
improver, icing inhibitor, and corrosion inhibitors. Two new
additive categories are u n d e r active consideration by the
ASTM committee and could be in the specification by the
time this article is printed. These additives are leak detection
materials smd biocides.

ADDITIVES
General
Allowable additives in aviation fuels are tightly controlled for
safety and operational reasons. The procedures for evaluating the compatibility of additives with aviation turbine fuels
a n d with aircraft fuel system materials are spelled out in
ASTM Practice D 4054. The primary purpose of this practice
is to standardize additive testing requirements so that an additive manufacturer does not have to repeat the process for
each engine or airframe manufacturer. The testing procedures are very detailed and lengthy to assure satisfactory

A new jet fuel additive category in military use are thermal


stability improvers, termed JP-8 -1-100 because they are intended to add 100F (55C) to the u p p e r thermal stability
limit of the fuel [13]. The additive combination consists of ox-

TABLE 7Effect of crude oils on straight-run product quality.


Crude Oil Source
Property

Alaska

California

Boiling Range, C
Yield, %v
Density, kg/m^
Sulfur, %m
Smoke point, m m
Freezing point, C

Indonesia

Arabia

Libya

8.7
801
0.009
28
-32

12.3
817
0.214
24
-40

13.5

200-260
10.3
828
0.093
20
-44

5.7
0.43
17
-70

0.04
23
-40

CHAPTER
TABLE 8Jet fuel additives listed in D 1655-98b.
Antioxidants, 24 mg/L maximum
2,6-ditertiary-butyI phenol
2,6-ditertiary-butyl-4-methyl phenol
2,4-dimethyl-6-tertiary-butyl phenol
75% min. 2,6-ditertiary-butyl phenol, plus 25% max. mixed tertiary
and tritertiary-butyl phenols
55% min. 2,4-dimethyl-6-tertiary-butyl phenol, plus 15% min, 2,6ditertiary-butyl-4-methyl phenol, remainder as monomethyl and
dimethyl tertiary-butyl phenols
72% min. 2,4-dimethyl-6-tertiary-butyl phenol, 28% max. monomethyl and dimethyl tertisiry-butyl phenols
Metal deactivator, 2mg/L max at mainufacture of fuel, for retreatment
to total of 5.7 mg/L max N,N-disalicylidene-] ,2-propane diamine
Electrical conductivity additive, 3 mg/L max at manufacture of fuel,
for retreatment to total of 5 mg/L max
Stadis 450
Fuel system icing inhibitor, 0.10-0.15%v
Diethylene glycol monomethyl ether (diEGME)
Leak detection additive, 1 ppm max
Tracer A

idation inhibitor, metal deactivator and proprietary detergents and dispersants. Because the combination contains
powerful surfactants, currently only water-absorbing type filter media (commonly called filter-monitors) will operate in
the presence of water and the additive. However, a major effort to develop filter-separators capable of handling the additive holds considerable promise.
Table 9 shows the aviation gasoline additives and their permitted dosages as listed in D 910. They include tetraethyl lead
fluid, which must contain two atoms of ethylene dibromide
per atom of lead as well as one or more of three different
color dyes. Blending two or more of the approved dyes makes
additional colors. While dyes were originally required to
identify any fuel containing lead, today they serve both to
identify lead-containing fuel and to distinguish between the
several grades of aviation gasoline. Oxidation inhibitors, conductivity improver and fuel system icing inhibitors are also
permitted. Note that aviation gasoline can include isopropyl
alcohol as an icing inhibitor, but jet fuel Cctnnot.

TRANSPORTATION
Pipelines
In the U.S. most jet fuel is moved from the refinery by large
multi-product pipelines handling all fuels from gasoline to
diesel fuel. Lines with diameters as large as 40 in (100 cm) are
employed. These lines are normally operated on a fungible
basis where each product meets a single specification. All
suppliers meet that specification, the products then commingled and supplier identity is lost. Differing products are not
physically separated from each other, but operating the line
under turbulent flow conditions minimizes product mixing
at the interface between products. Each pipeline product cycle has its own product sequence to minimize interface material, which is an off-specification mixture of at least two
dissimilar fuels. Pipeline flow is maintained by controlling
pressure a n d flow volume while p r o d u c t s are constantly
added and removed. Products move at a speed of approximately 5 m p h (8 km/h) and, in one pipeline, take about two

4: AVIATION

FUELS

105

weeks to get from Texas to New Jersey, a distance of about


1500 miles (2500 km). Along each pipeline there are breakout
terminals, which are collections of tanks serving as distribution centers. Such tanks are also used to temporarily hold
product where pipeline diameters change. In a number of instances jet fuel is moved from a terminal to an airport by
pipeline as well. In most instances such pipelines are smaller
and are usually restricted to jet fuel.
Marine Transport
Outside the U.S., jet fuel tends to move from the refinery in
so-called "clean" tankersas distinguished from black oil
ships, which carry crude oil or residual fuel oil. Tankers vary
tremendously in size, although the largest ones carry only
crude oils. As in pipelines, product sequencing is carefully
controlled to minimize mixing. To reduce contamination by
other products, shippers try to maintain certain compartments or the entire vessel in jet fuel. Tanker compartments
today are usually epoxy coated to extend their life and also to
make t h e m easier to clean. E a c h c o m p a r t m e n t contains
cleaning equipment, which directs a high pressure spray of
hot or cold sea water against the inside of the compartment.
However, cleaning procedures must be CEirefuUy controlled
to avoid contaminating jet fuel with cleaning compounds. A
complicating factor in the handling of jet fuel is the inerting
of compartment ullage space with engine flue gases. Such
compartments are kept seeded under slight overpressure and
are normally not open for inspection or thorough cleaning.
Marine transport on inland waterways is usually by barges,
which may carry their own propulsion equipment or may be
moved by tugs. Their construction tends to be more basic
than that of tankers and usually does not include internal
cleaning equipment. As a result operators tiy to keep barges
in the same fuel grade as m u c h as possible.

TABLE 9Aviation gasoline additives listed in D 910-98.


Anti-knock agent, maximum dosage depends on grade
Tetraethyl lead plus sufficient ethylene dibromide to provide two
atoms of bromine per atom of lead
Dyes, maximum dosage depends on grade
Blue:
1,4-dialkylamino-anthraquinone
Yellow: p-diethylamino-azobenzene or 1,3-benzenediol 2,4bis[(alkylphenyl)azo-]
Red:
alkyl derivatives of azobenzene-4-azo-naphthol
Antioxidants, 12 mg/L max
2,6-ditertiary-butyl phenol
2,6-ditertiary-butyl-4-methyl phenol
2,4-dimethyl-6-tertiary-butyl phenol
75% min. 2,6-ditertiary-butyl phenol, plus 25% max. mixed tertiary
and tritertiary-butyl phenols
75% min. di- and tri-isopropyl phenyls plus 25% mstx. di- and tritertiary butyl phenols
72% min. 2,4-dimethyl-6-tertiary-butyl phenol, 28% max. monomethyl and dimethyl tertiary-butyl phenols
N,N'-di-isopropyl-para-phenylenediamine
N,N'-di-secondary-butyl-para-phenylenediamine
Fuel system icing inhibitors
Isopropyl alcohol (IPA, propein-2-ol), max dosage recommended
by aircraft manufacturer
Diethylene glycol monomethyl ether (diEGME), 0.10-0.15%v
ElectricjJ conductivity additive, 3 mg/L max, for retreatment 5 mg/L
max total dosage
Stadis 450

106 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Product is loaded into tankers by shore-based pumps or by


gravity if shore tanks have sufficient elevation above the
tanker. Off-loading, on the other hand, is by pumps located
in the lowest part of the tanker or barge. This mode of operation tends to leave a small amount of product at the bottom
of a compartment when the pump loses suction. The effect of
mixing this residue with the next product is covered in more
detail in the section on quality control.
Road Transport
Smaller volumes of product, particularly when moved relatively short distances, are handled by road transport. Such
tanker trucks have several compartments and do not have
pumps aboard. Product is unloaded by gravity into underground tanks or into a pump that lifts the product into aboveground tanks. Truck size and weight is limited by road restrictions. When possible aviation products are isolated to
specific trucks to minimize contamination. Most aviation
gasoline is moved by truck because the volumes are too small
for pipeline movements. Compared to large pipelines or water transport, truck transport is the most expensive mode of
product transportation.
Rail Transport
In some areas of the world aviation fuel is moved in rail Ccirs.
Rail transport does not have the flexibility of road transport;
in the U.S. it is limited to Alaska.
Airports
Airport fuel systems vary widely depending on the type of
product and the volumes handled by the airport. Low octane
aviation gasoline at small airports is handled through cabinet
dispensers similar to those in service stations. These units
contain a meter, a hose, and a simple filter. The aircraft is
parked at the dispenser and fuel is placed into the aircraft
"over wing" through the hose and a hand-held nozzle. At
larger airports, high octane gasoline or jet fuel is loaded into
tank trucks called fuellers, which drive to the aircraft. These
fuellers incorporate a fuel tank divided into several compartments, two or more hoses, a filter, a meter, a pump, and other
ancillary equipment. The hose may make a solid connection
with the aircraft through a pressure coupling or the fuel may
be placed into smaller aircraft over wing with a hand-held
nozzle. To avoid misfuelling, gasoline and jet fuel should not
be carried on the same vehicle. Also, where possible, different nozzle sizes with matching filler restrictors are used for
aviation gasoline and jet fuel. The advantage of fueller vehicles is their flexibility of positioning; the disadvantage is
ramp congestion, particularly when as many as four or five
truckloads are required for a jumbo jet. Airport congestion is
minimized by the use of hydrant systems. Two or more storage tanks are linked to the passenger terminal by a large diameter pipeline, which runs underground alongside the aircraft loading gates. Each gate has at least one hydrant pit
containing an underground pressure connection. Trucks,
termed hydrant vehicles, have one large hose, which is coupled to the underground connection. Fuel moves through
that hose, a meter, a filter and other plumbing and ultimately

gets into the aircraft through one or more hoses coupled directly to the aircraft fuel system. The entire hydrant system,
from the storage onward, is pressurized by a series of pumps
that maintain operating pressure right up to the aircraft. Underground pressures of 700-1000 kPa (100-150 psi) are common but must be reduced to 315 kPa (45 psi) maximum at the
aircraft inlet [36]. Unlike a fueller there is no pump abocird
the hydrant vehicle. A hydrant system avoids ramp congestion but permzinently fixes the location of fueling stations. All
major airports and many smaller ones incorporate hydrant
systems. VirtUcdly all airport fuel systems are commingled
systems where each fuel grade meets the same specification
and there is no segregation by individual suppliers.
B o n d e d Fuel
A separate fuel designation, applicable only to international
transportation, is "bonded fuel." Legally such fuel enters a
country under bond and must leave the country in international transportation use. Bonded fuel is not subject to domestic taxes such as excise or sales taxes. Depending on customs regulations, bonded fuel must be handled as a
completely segregated product in its own handling systems
while the fuel is in the country or it can be handled in regular distribution systems as long as its entire volume is accounted for. While originally developed for marine transport,
the concept is equcdly applicable to aviation and is used in
some airports for intemationsJ flights. Its use is limited by
economics as well as local customs regulations.

QUALITY C O N T R O L
General Philosophy
Quality control is intended to protect the fuel properties
needed for safe aircraft operation. Toweurd that purpose aircraft certification requires the fuel to fully meet the specification to which the aircraft was certified. This process starts
at the refinery where aviation fuel must fully meet the pertinent specification. In addition, fuel quality also has to meet
other requirements not in the specification. In their simplest
form those requirements are expressed as "clean and dry."
However, on its way from the refinery to the airport fuel is exposed repeatedly to water, solid contaminants and to other
fuels in multiproduct systems. Quality control therefore becomes an exercise in avoiding that type of contamination,
which cannot be corrected in the field, and removing other
contaminants at reasonable expense by placing appropriate
removal equipment at critical points in the system.
Contaminants
Any material not originally part of the fuel is considered a
contaminant. That definition includes free water, solids such
as rust or sand, microbial material, other fuels, unapproved
additives as well as more unusual materials such as solvents,
fertilizers, plastics, or paints soluble in aviation fuels.
Because aviation gasoline and jet fuel have different critical properties, quality control procedures as well as contamination removal equipment differ for each fuel type and are
described separately in the following sections.

CHAPTER 4: AVIATION FUELS


Aviation Gasoline
While all properties must meet pertinent specifications at the
aircraft, the most sensitive properties of high octane aviation
gasoline are the octane ratings and the volatility. Octane ratings are readily degraded by contamination with other distillate products. The lower the octane of the distillate, the
greater the adverse effect. Experience has shown the "rich"
rating to be the more sensitive, particularly because the
"rich" rating of most aviation gasolines tends to have less
margin above the specification minimum. This problem can
only be avoided by eliminating possible contact with other
fuels such as might occur in switching between different
products in transports. Volatility degradation occurs through
evaporation in storage and results in vapor pressure decreases and changes in distillation cheiracteristics. Depending on which component is lost through evaporation, there
may also be a decrease in octane rating. Unfortunately, none
of these effects are readily predictable. Instead it is necessary
to reestablish the specification compliance status at specified
locations or time intervals.
Solids and free water removal is carried out primarily by
settling in tankage at a rate of 15 min per ft (45 min per m) of
depth [37] and by further removal of solids with micronic filters. Because of the lower density and viscosity of gasoline
compcired to jet fuel, contaminant removed from aviation
gasoline is simpler and less complex as will be seen in the jet
fuel section.
There are no industry-wide quality control procedures for
aviation gasoline. Instead, each company foUows its own procedures, which tend to be similar throughout the industry.
Gasoline is fully tested against specification requirements at
the refinery and is then subjected to limited retesting upon
arrival at the distribution terminal. The tests normally run at
that location are listed in Table 10, but they can differ between suppliers. Sample handling must be done in accordance with D 5842 to avoid the loss of volatile components,
which can result in a low vapor pressure. Gasoline is again inspected on airport arrival for appeeirance, color, and density.
Only a single product grade should be carried in the transport
to the airport and in the fueling vehicle on the airport. In addition, product that has been in storage with no product
movement in or out should be checked for specification complicince at six-month intervals.
Jet Fuel
Jet fuel contamination can be divided into two broad categories: that which can be removed in the field and that which
cannot. The first category includes various solid contaminants and water, while the second category includes other fu-

TABLE 10Terminal receipt tests for aviation gasoline.


Knock rating by ASTM D 909 (If not available, knock rating by ASTM
D 2700)
Distillation by ASTM D 86
Reid vapor pressure by ASTM D 323, D 5191, or D 5190
Tetraethyl lead content by ASTM D 3341 or D 5059
Color by ASTM D 2392
Existent gum by ASTM D 381
Electrical conductivity (if required) by ASTM D 2624

107

els or other materials soluble in jet fuel. Unlike aviation gasoline, a major concern is over contamination with more
volatile materials that will lower the flash point. Solid and
water removal are more difficult with jet fuel because both
the density and viscosity of jet fuel are higher than those of
aviation gasoline. The equipment to remove contaminants as
well the quality control procedures are therefore more elaborate. In addition, a number of specialized field contamination detection procedures are in use.
Contamination Removal Equipment
Filter-Separators
The heart of contamination removal equipment is the filtersepcirator, shown diagrammatically in Fig. 10. Two sets of
cylindrical filter elements are mounted on a deck plate or a
meinifold in the case. First stage elements are termed coalescers, the second stage are separators. Both types usually
have a 6 in (15 cm) diameter; the total element length is proportioned to the maximum rated flow. Fuel flow in the first
stage elements is from inside to outside and outside to inside
in the second stage. In the first stage, at least one filtration
layer consists of tightly packed, hydrophobic glass fibers,
which force smeJl free water droplets to coalesce into leirger
droplets as fuel pushes the water droplets through the layer
[38]. Other layers remove and hold solid particulates. Most of
the coeJesced droplets slide down the outside of the first stage
elements. Those water droplets too small to settle between
stages Eire prevented from exiting with the fuel by the second
stage, which is also hydrophobic. This second stage is made
of Teflon-coated wire mesh or a special synthetic fabric supported by a perforated meted cylinder. The coalesced free water collects in a sump at the bottom of the case and is removed by manually opening a drain valve. A high water
indicator, usually a float or an electronic water level probe in
the sump, shuts off the entire fuel flow if the water level rises
too high and threatens to be carried out with the clean fuel.
A direct reading differential pressure gauge measures the total pressure drop across both sets of elements.
Filter-separators are designed to keep operating when subjected to contaminated fuel. Their minimum performance is
governed by an industry specification issued by the American
Petroleum Institute as API Specification 1581. This specification delineates the solid and free water concentrations
added during qualification testing and dictates the maximum
levels of both contamineint types permitted in the effluent.
The latest version of the specification, Issue 4, was published
in early 2000 and to take effect in January 2002. It contains
three test fuel types. Category C is Jet A plus a conductivity
improver, a corrosion inhibitor aind a sulfonate. Category M
is JP-8 or JP-5 containing military additives. Category MlOO
is Category M plus the JP-8 + 100 additive. Category C is intended for civil use, while the other two categories are for the
U.S. military. Two performance levels are called out. Type S
is to be used where significant solids and water are expected.
Type S-LD, with a lower dirt holding capacity, is intended
where significcint water but low solids are expected. The standard solid contaminant is 90%m A-1 ultrafine dust and 10%
m Copper as red iron oxide. These are major changes from Issue 3 which specified Fischer red iron oxide of about 0,1 micron particle size as the solid contamineint and did not in-

108 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

iST STAGE
COALSECER ELEMENTS
(INSIDE TO OUT fLOW)

2ND STAGE
SEPARATOR ELEMENTS
(OUTSIDE TO IN FLOW)

INLET MANIFOLD
UTLET MANIFOLD

INLET

OUTLET

FIG. 10Cutaway of filter-separator.

elude military fuels. Nominal coalescer pore size is expected


to be between 0.3 to 0.5 microns. Second stage pore size is
much coarser and is not designed for dirt removal. Approvals
cover only specific elements in specific housings and are not
transferable to other housings.
While the U.S. military has issued its own specifications in
the past, the current trend is toward the use of equipment
meeting the industry specification, API 1581.
Water-Absorbing Cartridges or Monitors
Sometimes called fuses, these units are designed as a last
chance safeguard, which shuts down a system in the presence
of water in the fuel. Their primary component is a cellulose
layer that normally expands when wetted. By tightly constraining this layer, it compresses when wetted and shuts off
fuel flow. Monitor elements are 2, 4, or 6 in. in diameter, depending on the application. The total length of elements is directly proportional to the rated flow of the filter. Because of
their operating mode, monitors are located only at the last filtration point just ahead of the aircraft, where they may be the
only final filter or be placed after a filter-separator. Alternatively, some operators use them as a second stage in place of
the separator elements. Monitors can also be the final filters
in aviation gasoline system. They are not normally placed

further upstream because the elements have to be replaced in


case of a shutdown by free water.
Two specifications govern monitor performance. MIL-M81380 is issued by the U.S. Navy. A specification issued by the
Institute of Petroleum (IP) is similar but requires a higher
solids holding capacity. This specification is being replaced
by a joint API/IP specification, API 1583. Both specifications
severely limit the amount of free water that Ccin pass through
the monitor before it closes off. These units generally have a
nominal 1 micron pore size rating. Latest specification revisions eJso guard against media migration under greatly reduced flow rates.
Clay Treatment Vessels
While similar in external appearance to filter-separators, the
elements in clay treatment vessels are filled with activated
clay to adsorb polar materials such as surfactants. This clay
is the same as mentioned earlier in the Manufacturing section, the big difference being in the depth of clay as well as
the rate at which fuel passes through the clay. This difference
results in a 50 times reduction in contact time and a similar
reduction in the vessel's capacity to remove surfactants. Field
clay treatment vessels are therefore considered "polishing"
units with rather limited adsorption capacity. They are nor-

CHAPTER 4: AVIATION FUELS


mally intended to remove traces of polar additives picked up
by jet fuel in multiproduct transportation systems. However,
this adsorptive capacity has mitigated against the general use
of conductivity additive because the wide presence of clay
field units in the U.S. would remove the additive and require
constant additive reinhibition. Conversely, outside the U.S.
the additive is in general use and clay treaters are not. There
are no government or industry performance specifications
covering clay treatment vessels.
Micronic Filters (also Microfilters or Prefilters)
Another weapon in the cleanup arsenal consists of filter elements, usually made of pleated paper and mounted in a pressure vessel. These units remove only solid particles, but they
do so at a much lower cost than filter-coalescers and are
therefore placed ahead of filter-separators when significcmt
solid contamination occurs. Nominal pore sizes rajiging generally from 0.3-2 microns are in widest use in jet fuel and
from 0.5-5 microns for aviation gasoline, with the optimum
pore size selected on the basis of operating experience. Here
again, there are no government specifications for these units.
A specification for microfilters dated April 2002 has been issued as API/IP 1590.

109

fuel usually being a water white color. Color rating methods


include Saybolt color by D 156, or the more recent tri-stimulus method, D 6045. Either method is seriously handicapped
by the fact that on-specification jet fuel can have a range of
colors and color, as such, is not a jet fuel performance parameter. Only a change from the original fuel color is therefore useful as a possible indicator of contamination, which
has to be ruled out by specification tests.
A requirement peculiar to the U.S. involves the use of red
dye to identify high sulfur diesel fuels and heating oils as well
as untaxed diesel fuel and heating oil. While the dye is not required in jet fuel, a number of cases of jet fuel contaminated
with red dye have occurred by the mixing of jet fuel with dyed
product. Because of possible adverse effects on thermal stability, the use of dye-contaminated fuel in aircraft is not permitted. A Boeing service letter [40] specifies the use of white
bucket appearance as the measure of fuel acceptability. A
portable spectrometer capable of measuring dye levels quantitatively is under development in ASTM but is not currently
approved. An extensive program is also underway at the
Southwest Research Institute to establish acceptable dye
concentrations in high temperature engine components [41].
Solid Particles

Filter Locations
Although there are no industry standards for terminal installations, fuel receipts tend to go through a micronic filter into
tankage. When going out of terminaJ tankage to an airport
the fuel passes through em optional micronic filter, followed
by a clay treatment vessel and last through a filter-separator.
At the airport the minimum filtration is through a filter-separator into storage, a filter-separator out of storage into fueling trucks, or into a hydrant system and through a final filterseparator on the fueling vehicle into the aircraft. Filtration
into storage may be supplemented by a micronic or a clay
unit, while the final filtration unit may be a monitor in place
of or in addition to the final filter-separator.
Contamination Detection Equipment
Much of the following equipment, while in extensive worldwide use, has not been standardized by ASTM, but is described in detail in ASTM Manual 5 [39].
Visual Appearance
The appearance of jet fuel is routinely checked in either a
one-liter jar made of clear glass or a white porcelain or stainless steel bucket. The glass is more likely to disclose the presence of fine, suspended material, while the bucket allows the
examination of a larger sample easily taken from a large
drain line. In addition, the white bucket has proven most sensitive to product color, which can indicate contamination
with other darker or dyed fuels. However, such appearance
checks are only a gross measure of possible contamination
and do not disclose levels of solids or free water that are not
visible to the neiked eye. More sensitive tests for contamination are described in the following sections.
Product Color
Quantitative color measurement can be used for the detection of other petroleum products having darker colors, jet

Solid particles are collected on special membrane filters


made of mixed cellulose acetate esters with an absolute pore
size of 0.8 microns. Filter membrane requirements are detailed in ASTM Research Report RR-D02-1012. For particle
collection the membranes are mounted in plastic monitors
that are encased in a brass housing. A fixed volume of fuel is
bled through the membrane off a flowing line under pressure. The solids content of the sample can be established
quantitatively by weighing the dried membrane or the dirt
level can be described by comparing the membrane color to
a standard chart. Both approaches are described in D 2276.
Because of the normal variability in particle size, color, and
density, there is no direct relationship between the two types
of assessments. The mass measurement must be done under
laboratory conditions, while the color rating is carried out in
the field.
Free Water
A number of water detection methods, ranging from coarse
to precise, are in general use. Water finding paste, which
changes color on contact with a water layer, is smeared on
gaging sticks or tapes to disclose the depth of the water layer
in a storage tank or ship's compartment. This process is often
called a "water cut." Suspended, free water is detected by several methods. Three methods used at plane-side include the
Shell Detector, the Velcon Hydrokit, and the Metrocator test
[39]. Each test is calibrated to show a visible color change at
the presence of either 15 or 30 ppm of free water, these levels
being called out in quality control procedures. These tests not
only eliminate the operator judgement involved in visual examinations, but are also more sensitive than the eye of a
trained operator who normally can detect a water haze down
to the 50 ppm level. The most sensitive test for undissolved
water is the Aqua-Glo test, D 3240, which can detect undissolved water down to 2-3 ppm. This test is based on the reaction of free water with a fluoresceine dye, which impregnates a fiberglass disk. After passing 500 mL of fuel through

110 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

the disk, einy increased level of fluorescence due to water is


measured under ultraviolet light and is translated into ppm
of free water.
Water content can also be established in the laboratory by
the Karl Fischer titration procedure, D 6304. However, this
procedure measures total water content or the sum of dissolved and free water. Because aviation fuel filters do not remove dissolved water, measuring only free water by the preceding tests is a more effective way of checking the operation
of filter-separators or monitors.
Surfactants
Surfactants, or more properly surface active agents, are
molecules in which one portion is polar and is water soluble
(hydrophilic). The other portion is non-polar and is oil soluble (hydrophobic). As a result surfactants affect the surface
characteristics of fuel-water systems. Their concentration is
highest at the interface between water and hydrocarbon and
results in a decrease of the interfacial tension. Mixing the
fuel-water-surfactant system will form emulsions, which can
prevent small water droplets from settling out. In addition,
surfactants can affect the surfaces of fibers in filter-coalescers and prevent them from coalescing small water
droplets. Such cocdescers Eire considered disarmed. On the
other hand, surfactants do not appear to affect monitor performance.
Surfactants are widely used in the petroleum industry as
corrosion inhibitors, lubricity agents, conductivity improvers, gasoline detergents, and cutting oil emulsifiers.
While coalescers are designed to operate with certain specific
jet fuel additives, which are surfactants, other surfactants
will disarm the elements and have to be detected and removed. Of two available tests the less sensitive test, D 1094,
measures the ability of water and fuel to separate cleanly after mild shaking. Because of its dependence on ultra-clean
glassware this test should be performed in the laboratory. A
much more sensitive test, D 3948, evaluates the ability of a
miniature coalescer to remove very fine fuel droplets from a
fuel-water emulsion. By being self-contained and utilizing
disposable components this procedure can be conducted in
the field and avoids possible contamination by sample containers. As already mentioned, surfactants are removed from
jet fuel by clay treaters, which adsorb polcir materials.
Microorganisms
Many microorgstnisms can metabolize hydrocarbons, others
can utilize sulfur. Some require oxygen, others need its absence. Mciny exist naturally in soil or ground water. All have
one common characteristicthey must have undissolved,
free water to grow and reproduce. As a result, most microbial
growth is at the fuel-water interface. Metabolic products,
usually acidic, tend to be corrosive to metals, particularly aluminum. These products may also act as surfactants. Microorganisms commonly form slimes or mats that can plug
screens or filters. Unfortunately for jet fuel, the problem microbes prefer to metabolize normEil paraffins in the C12 and
higher range [42], molecules that are a common constituent
in jet fuels.
The most reliable defense against microbicil growth is the
elimination of free water in jet fuel systems. Frequent draining of all sumps and system low spots is sai important part of

such precautions. An alternative is the use of approved biocides mentioned earlier, but the possible adaptation of specific microbes to a biocide has to be kept in mind. The simplest form of detection is a visual and olfactory examination
of water samples from jet fuel systems. Dark or black water,
together with a foul or rotten odor, are usually indicative of
microbial activity. Laboratory testing can indicate the viability and type of microorganisms, but system inspection is usually the best indicator of whether cleaning is required. Much
more detailed information on the subject of microorganisms
in hydrocarbon systems will be found in a new standard
guide, D6469.
Quality Control Procedures
U.S. Procedures
Similcir to aviation gasoline, jet fuel is fully certified against
pertinent specifications at the time of manufacture. In the
U.S. this is normally D 1655, Grade Jet A. Quality is often
rechecked after arrivEil in the terminal with the tests listed in
Table 11. However, this test lineup is experience-based and
Ccin differ significantly from one company to einother; thus,
some shippers require complete specification recertification
of product introduced into their system. Product is settled in
storage for one hour per foot of fuel depth [37]. The pressure
drop across each filter is checked daily. Sumps are drained at
least weekly and after receipt of product. Periodically, usually
once a month, the proper operation of the filter-separator is
checked by rurming a membrane test emd a free water check.
Once approved and settled, the product is shipped to the
airport by transport or pipeline. However, none of these operations are governed by industry standcirds and it is the responsibility of the operating company to furnish on-specification, "clear and bright" fuel to the airport.
Airport quality control is more systematic. The Air Transport Association of America (ATA) has issued a specification,
ATA 103, which is recommended for its member airlines or
virtually EJI U.S. eind Canadian airlines. Additionally, member airlines can require the specification to be followed by independent airport biel dealers who supply these airlines. All
jet fuel delivered to U.S. airports must meet ASTM D 1655 in
order to meet the certification requirements of the various
aircraft. As indicated in Table 12, when ATA 103 is to be followed, certain tests must be furnished by the shipper on the
specific shipment. Other tests are conducted at the airport
during and after product receipt. Additional periodic testing
to be carried out at the airport is listed in Table 13. Failure to
meet any of these requirements is cause for immediate investigation.

TABLE 11Terminal receipt tests for jet fuel.


Density by ASTM D 1298 or D 4052
Distillation by ASTM D 86
Flash point by ASTM D 56 or D 3828
Freezing point by ASTM D 2386, D 4305," D 5901, or D 5972
Existent gum by ASTM D 381
Water reaction by ASTM D 1094
Electrical conductivity (if required) by ASTM D 2426
"If D 4305 is used it must be accompanied by measuring viscosity
at -20"'C by ASTM D 445.

CHAPTER
It should be noted that ATA 103 includes other aspects of
airport quality control as well, but these do not directly involve fuel quality.
International

Procedures

Somewhat similar procedures are followed outside the U.S,


the primary difference being the issuing authority. Here the
procedures are being issued as guidelines by the Interna-

TABLE 12Airport quality control per ATA 103.


Airport Receipt Requirements
Specification: ASTM D 1655, Jet A or A-1
Pipeline or Marine Delivery
Truck or Rail Delivery
Tests from Shipper

Visual-white bucket
API Gravity @ 60F (15C)
Distillation
Flash point
Freeze point
Water reaction
Copper corrosion
Existent gum

Visual-white bucket
API gravity eO^FClS^C)

FUELS

111

tional Air Transport Association (lATA) to be used by individual airline members as part of contractual requirements
with suppliers. Ultimately, it is hoped to merge ATA 103 with
the LATA Guidelines to create a single set of worldwide airport quality control procedures, but the success of this endeavor cannot be predicted at this time.
Aircraft

Procedures

Small amounts of water can become a problem if the water is


not removed from tank sumps. Older aircraft require a routine sumping procedure to remove the settled free water
while newer aircraft have a water scavenging system that performs this function automatically. If small quantities of water are allowed to accumulate, boost p u m p inlet screens can
ice over, biological growths can develop and, if large quantities are allowed to accumulate, exposure to engine flame-out
is possible.

OVERVIEW AND CONCLUSIONS

Testing During Receipt at Airport

When: Beginning (after line


displacement)
Every 2 h
Near end
What: Visual-white bucket
API gravity (within 1)
Membrane color
2 dry max/1 gsillon
3 wet max/1 gallon
A msix particles
Free water 15 ppm msix
Flash point (multiproduct
line only)

4: AVIATION

From compartment
before unloading
Visual-white bucket
API gravity (within 1)

After Receipt on Tank Contents

Visual-white bucket
API Gravity @ eCF (15C), within 1
Distillation, within 8C
Flash point, within SX"
Freezing point, within 3C
''Variability allowed from supplier's certificate.

For safety reasons, specifications and handling procedures


for aviation fuels are more tightly controlled than for other
products. Minor changes in fuel properties, cleanliness, or
contamination levels can have unanticipated effects on jet
engine performance because of the complexity of m o d e m jet
engines and the massive amounts of fuels that flow through
the engines. The current aviation fuel supply and delivery system is based on accumulated experience, which has evolved
over a long period of time. There is a reluctance to make
changes because the impact of such changes cannot always
be predicted without a thorough investigation. The challenge
for the future will be for the aviation technical community to
anticipate, identify, and eliminate possible fuel-related problems. These problems could arise from the incorporation of
new non-traditional supplies, changes in refinery processing,
the reformulation of transportation fuels resulting from
tough, new environmental regulations, changes in the transportation of fuel to the aircraft, and new engine emd aircraft
requirements. An additional challenge could come from measures required to improve aircraft safety. Resolution of prob-

TABLE 13Airport fuel quality requirements per ATA 103, other required checks.
Daily Required Checks
Filter pressure drop
Change elements at 15 psi
Monitor pressure drop
Change elements at 25 psi
Drain filter sumps
Inspect with white bucketone gallon sEimple minimum
Drain storage tank sumps
Inspect with white bucketone gallon sample minimum
Drain fueling truck
Inspect with white bucketone gallon sample minimum
Monthly Required Checks

Downstream each airport filter

Free water
Membrane color
Particulate assessment

15 ppm max
2 dry/gal or 3 wet/gal
A max

Drain hydrant system low points


Other Requirements

Filter element specification


Monitor element specification
Replace coalescer elements
Replace monitor elements
Inspect storage tanks
Suggested settling time

API 1581, Group B (Group C for final vehicle)


IP specification for monitors
Yearly, with one year extension
Every two years
Yearly
1 h per ft (3 h per m) of vertical depth

112 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

lems can have an impact on legal issues such as the assignment of liability and can have large financial consequences.
The complexities of the interactions between the technical,
legal, and financial aspects associated with aviation fuels can
therefore make it difficult at times to resolve problems, but
such problems must be addressed to maintain and, if possible, improve the reliability of the entire system.

ASTM STANDARDS
Unless otherwise indicated all of the following standards are
current.
No.

Title

D 56
D 86
D 130

Test Method for Flash Point by TAG Closed Tester


Test Method for Distillation of Petroleum Products
Test Method for Detection of Copper Corrosion
From Petroleum Products by Cu Strip Tarnish Test
Test Method for Saybolt Color of Petroleum Products
Test Method for Vapor Pressure of Petroleum Products (Reid Method)
Test Method for Kinematic Viscosity of Transparent cind Opaque Liquids
Test Method for Knock Characteristics of Aviation
fuels by the Aviation Method (discontinued 1970)
Specification for Aviation gasoline (discontinued
1946)
Test Method for Oxidation Stability of Aviation Fuels (Potential Residue Method)
Test Method for Knock Characteristics of Aviation
gasoline by the Supercharge Method
Specification for Aviation Gasoline
Guide for Petroleum Measurement Tables
Practice for Density, Relative density (Specific
Gravity) or API Gravity of Crude and Liquid
Petroleum Products by Hydrometer Method
Test Method for Hydrocarbon Types in Liquid
Petroleum Products by Fluorescent Indicator Adsorption
Test Method for Smoke point of Aviation Turbine
Fuels
Specification for Aviation Turbine Fuels
Test Method for Luminometer Numbers of Aviation
Turbine Fuels
Test Method for Naphthalene Hydrocarbons in Aviation Turbine Fuels by Ultraviolet- Spectrophotometry
Test Method for Freezing Point of Aviation Fuels
Test Method for Color of Dyed Aviation Gasolines
Test Method for Knock Characteristics of Motor
and Aviation Fuels by the Motor Method
Test Method for Mercaptan Sulfur in Gasoline,
Kerosine, Aviation Turbine and Distillate Fuels (Potentiometric Method)
Test Method for Undissolved Water in Aviation Turbine Fuels
Test Method for Thermal Oxidation Stability of Aviation Turbine Fuels (JFTOT Method)
Test Method for Estimation of Net Heat of Combustion of Aviation Fuels

D 156
D 323
D 445
D 614
D 618
D 873
D 909
D 910
D 1250
D 1298
D 1319
D 1322
D 1655
D 1740
D 1840
D 2386
D 2392
D 2700
D 3227
D 3240
D 3241
D 3338

D 3701 Test Method for Hydrogen Content of Aviation Turbine Fuels by Low Resolution Nuclear Magnetic
Resonance
D 3948 Test Method for Determining Water Separation
Characteristics of Aviation Turbine Fuels by
Portable Separometer
D 4052 Test Method for Density and Relative Density of
Liquids by Digital Density Meter
D 4171 Specification for Fuel System Icing Inhibitor
D 4305 Test Method for Filter Flow of Aviation Fuels at
Low Temperatures
D 4809 Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision
Method)
D 4865 Guide for Generation and Dissipation of Static
Electricity in Petroleum Fuel Systems
D 4952 Test Method for Qualitative Analysis of Active Sulfur Species in Fuels and Solvents (Doctor Test)
D 5001 Test Method for Measurement of Lubricity of Aviation Turbine Fuels by the Ball-On-Cylinder Lubricity Evaluator (BOCLE Test)
D 5191 Test Method for Vapor Pressure of Petroleum Products (Mini Method)
D 5842 Practice for Sampling and Handling of Fuels for
Volatility Measurement
D 5901 Test Method for Freezing of Aviation Fuels (Automatic Optical Method)
D 5972 Test Method for Freezing of Aviation Fuels (Automatic Phase Transition Method)
D 6045 Test Method for Color of Petroleum Products by the
Automatic Tristimulus Method
D 6227 Specification for Grade 82 Unleaded Aviation Gasoline
D 6304 Test Method for Determination of Water in
Petroleum Products, Lubricating Oils, and Additives by Coulometric Karl Fisher Method
D 6378 Test Method for Determination of Vapor Pressure
(VPx) of Petroleum Products, Hydrocarbons and
Hydrocarbon-Oxygenate Mixtures (Triple Expansion Method)
D 6424 Test Method for Octane Rating Naturally Aspirated
Spark Ignition Aircraft Engines
D 6469 Standard Guide for Microbial Contamination of Fuels and Fuel Systems
OTHER STANDARDS
U.S. Military Aviation Turbine Fuel and Additive
Specifications^
No.

Title

MIL-PRF-5624

Turbine Fuel, Aviation Grades JP-4, JP-5,


and JP-5/JP-8 DT
MIL-PRF-25017 Inhibitor, Corrosion/Lubricity Improver,
Fuel Soluble
MIL-DTL-27686 Inhibitor, Icing, Fuel System
MIL-PRF-38219 Turbine Fuel, Low Volatility (Grade JP-7)
^ These standards are available from Defense Printing Service Detachment Office, 700 Robbins Ave., Piiiladelphia, PA 19111-5094.

CHAPTER 4: AVIATION FUELS 113


MIL-M-81380
MIL-DTL-83133

Monitor, Contamination, Aviation Fuel


Dispensing System
Turbine Fuel, Aviation, Kerosine Type
(Grade JP-8)

U. K. M i l i t a r y A v i a t i o n T u r b i n e F u e l a n d A d d i t i v e
Specifications
These standards are available from Ministry of Defence, Directorate of Standardization, 65 Brown Street, Glasgow G2
SEX.
No.
Title
ATF High Flash AVCAT/FSII
ATF Wide Cut AVTAG/FSII
AVGAS Gasoline Aviation 80 and
lOOLL (low lead)
Turbine Fuel, Aviation Kerosine
Defence Standard 91-91
Type, Jet A-1
Defence Standard 91-251 Fuel System Icing Inhibitor
(FSII)
Defence Standsird 68-251 Fuel Soluble Pipeline Corrosion
Lubricity Improving Additive
Defence Standard 91-86
Defence Standard 91-87
Defence Standard 91-90

Industry Specifications
API/IP 1581 Specifications and Qualification Procedures for
Aviation Jet Fuel Filter/Separators
API/IP Specification for Similarity for API/IP 1581 Aviation
Jet Fuel Filter/Separators
API/IP 1583 Specifications and Qualification Procedures for
Aviation Fuel Filter Monitors with Absorbent T5rpe Elements
API/IP Specifications and Qualification Procedures for Aviation Fuel Microfilters
ATA 103, Standards for Jet Fuel Quality Control at Airports
LATA Guidance Material for Aviation Turbine Fuels Quality
Control and Operating Procedures, Incorporating Joint Inspection Group Guidelines for Joint Airport Depots and
Joint into Plane
lATA Guidance Material for Aviation Turbine Fuels

REFERENCES
[1] Ogsten, A. R, "A Short History of Aviation Gasoline Development, 1903-1980," Preprint No. 810848, SAE, West Coast International Meeting, Seattle, WA, 3-6 August 1981, Society of Automotive Engineers, Warrendale, PA.
[2] Dukek, W. G., "Aviation Fuel: Its Energy has Knit the World,"
Standardization News, ASTM International, West Conshohocken, PA, April 1998.
[3] Defence Standard 91-91: Turbine Fuel, Aviation Kerosine, Type
Jet A-1, Issue 3, Ministry of Defence, Directory of Standardization, Glasgow, FG2 SEX, United Kingdom, November 1999.
[4] Guidance Material for Aviation Turbine Fuel, fourth edition. International Air Transport Association, Montreal, Canada, March
1999.
[5] Winkle, T. L., Affens, W. A., Beal, E. A., Hazlett, R. N., and
DeGuizeman, R., "The Distribution of Higher n-Alkanes in Partially Frozen Middle Distillate Fuels," NRL Report 8869, Naval
Research Laboratory, Washington, DC, 10 April 1985.
[6] Smith, M., Aviation Fuels, G. T. Foulis & Co Ltd, Henley-onThames, Oxfordshire, United Kingdom, 1970, pp. 272-278.

[7] Honsberger, B. A., "Jet A Exposure to Freezing on Very Cold


Temperatures," Boeing Company CommercicJ Airplane Group,
presented to CRC Group on Low Temperature Performance of
Aviation Turbine Fuel, June 1991.
[8] Unpublished minutes of the CRC Low Temperature Performance of Aviation Turbine Fuels, Coordinating Research Council, Atlanta, GA, May 1999.
[9] Aviation Fuel Properties, CRC Report No. 530, Coordinating Research Council, Atlanta, GA, 1983.
[10] Final Report, Fuel Tank Harmonization Working Group of Aviation Rulemaking Advisory Committee, Federal Aviation Administration, Washington, DC, July 1998.
[11] Rogers, J. D., "Turbine Fuel Thermal Stability," SAE Preprint
103T, Society of Automotive Engineers, National Aeronautic
Meeting, Los Angeles, CA, 5-9 Oct. 1959.
[12] Thermal Oxidation Stability of Aviation Turbine Fuels, Monograph /, R. N. Hazlett, Ed., ASTM International, West Conshohocken, PA, 1991, pp. 72-91.
[13] Heneghan, S. P., Zabamik, S., Ballal, D. R., and Harrison, W. E.,
Ill, "JP-8 + 100: TheDevelopmentof High-Thermal-Stability Jet
Fuel," Transactions oftheASME, Vol. 118, September 1996.
[14] Strauss, K. H., "Survey of Current Engine Conditions," CRC Report 573, Coordinating Research Council, Atlanta, GA, 1983.
[15] Strauss, K. H., "Thermal Stability Testing of Jet Fuel - A Critical
Review," Technical Paper 881532, Society of Automotive Engineers, Aerospace Technology Conference, Anaheim, CA, 3-6
Oct. 1988.
[16] Baker, C, David, P., Taylor, S. E., and Woodward, A. J., "Thickness Measurement of JFTOT Tube Deposits by EUipsometry,"
Proceedings of 5th International Conference on the Stability and
Handling of Liquid Fuels, Rotterdam, 1994, pp. 433^47.
[17] Unpublished minutes of the Groups on Aviation Engine Octane
Rating and Unleaded Avgas Development, Coordinating Research Council, Atlanta, GA, 1995.
[18] Sherwood, W. D., "SST FuelsA Major Airline Concern,"
Preprint 911C, Society of Automotive Engineers, National Aeronautic and Space Meeting, Los Angeles, CA, 5-9 Oct. 1964.
[19] Gleason, C. C, Oiler, T. L., Shayeson, M. W., and Bahr, D. W.,
"Evaluation of Fuel Character Effects on FlOl Combustion System," AFAPL-TR-79-2018, General Electric Company, Cincinnati, OH, June 1979.
[20] Lefebre, A. H., "Influence of Fuel Properties on Gas Turbine
Combustion Performance," AFWAL-TR-84-2104, Purdue University, Lafayette, IN, January 1985.
[21] Dickson, C. L., "Aviation Turbine Fuels, 1998," National Institute for Petroleum and Energy Research, NIPER-175 PPS,
March 1998.
[22] Blade, O. C, "Aviation Fuels, 1964," U.S. Dept. of Interior, Bureau of Mines, Petroleum Products Survey No. 39, 1964.
[23] Rickard, G. K. and Fulker, R., "The Quality of Aviation Fuel
Available in the United Kingdom Annual Survey 1997," Technical Report DERA/MSS1/TR980069/1.0, Version 1.0, Department
of Defence, United Kingdom, May 1998.
[24] Gibbons, T. R., "Flash Point Methods Applicable to Jet Fuel,"
Factors in Using Kerosine Jet Fuel of Reduced Flash Point, STP
688, ASTM International, West Conshohocken, PA, 1979.
[25] Final Report, Fuel Taiik Harmonization Working Group of Aviation Rulemaking Advisory Committee, Federal Aviation Administration, Washington, DC, July 1998.
[26] Smith, M., Aviation Fuels, G. T. Foulis & Co. Ltd., Henley-onThames, Oxfordshire, United Kingdom, 1970, pp. 369-371.
[27] Hazlett, R. N., Thermal Oxidation Stability of Aviation Turbine
Fuels, Monograph 1, ASTM International, West Conshohocken,
PA, 1991, pp. 111-113.
[28] Smith, M., Aviation Fuels, G. T. Fouhs & Co. Ltd., Henley-onThames, Oxfordshire, United Kingdom, 1970, pp. 117-118.
[29] "Determination of the Hydroperoxide Potential of Jet Fuels," CRC
Report 559, Coordinating Research Council, Atlanta, GA, 1988.

114 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


[30] Pande, S. G, Black, B. H., and Hardy, D. R., "Development of a
Test Method for t h e Determination of the Hydroperoxide Potential and Antioxidant Effectiveness in Jet Fuel During Long
Term Storage," CRC Report 614, Coordinating Research Council, Atlanta, GA, 1998.
[31] "Aviation Fuel Lubricity Evaluation," CRC Report 560, Coordinating Research Council, Atlanta, GA, 1983.
[32] Defence Standard 91-91: Turbine Fuel, Aviation Kerosine, Type
Jet A-1, Annex B, Ministry of Defence, Directory of Standardization, Glasgow, FG2 8EX, United Kingdom.
[33] Bustin, W. M. and Dukek, W. G., Electrostatic Hazards in the
Petroleum Industry, Research Studies Press Ltd, Letchworth,
England, 1983.
[34] Strauss, K. H., "Future U.S. Jet FuelA Refiner's Viewpoint,"
AIAA-81-0770, AIAA/SAE ASCE 1981 International Air Transportation Conference, Atlantic City, 26-28 May 1981.
[35] "Crude Assays," Oil and Gas Journal, April through August 1983

[36] Smith, M., Aviation Fuels, G. T. Foulis & Co. Ltd., Henley-onThames, Oxfordshire, United Kingdom, 1970, pp. 192-196.
[37] Robertson, A. G., "Jet Fuel Settling," Shell Aviation News, Vol.
351, 1967, pp. 17-28.
[38] Hughes, V. B., "Aviation Fuel Handling: New Mechanistic Insight into the Effect of Surfactants on Water Coalescer Performance," Proceedings of 6th International Conference on Stability a n d Handling of Liquid Fuels, Vancouver, 12-17 Oct. 1997.
[39] Manual of Aviation Fuel Quality Control Procedures, Second
Edition, ASTM Manual 57, R. Waite, Ed., ASTM International,
West Conshohocken, PA, 1995.
[40] "Aircraft Use of Dyed Fuel," Boeing Service Letter for 707, 727,
737, 747, 757, 767, and 777 Series, 22 Nov. 1996.
[41] Unpublished minutes of the CRC Group o n Dye In Aviation Turbine Fuels, Coordinating research Council, Atlsinta, GA, 1996 to
date.
[42] Churchill, A. V., "Microbial Fuel Tank Corrosion: Mechanisms
andContributoryFactors,"MaferJaisProtecft'ora, Vol. 2,1963, p. 18.

MNL37-EB/Jun. 2003

Automotive Diesel and


Non-Aviation Gas Turbine Fuels
Steven R. Westbrook^ and Richard LeCren^

The diesel engine is now fully established in a variety of applications on land and in marine use. On land, it serves to
power trains, buses, trucks, and automobiles; to run construction, petroleum drilling, and other off-road equipment;
and to be the prime mover in a wide range of power generation and pumping applications. At sea, it serves both to provide main propulsion power and run auxiliaries.
Gas turbine engines also serve in a wide range of applications. Over half the larger industrial gas turbines are in electric-generation use. Other uses include gas pipeline transmission, co-generation systems, and transportation. In the
military, gas turbines power a number of combatant ships
both as main propulsion units and as the power source for
auxiliary uses. Gas turbines are also used to power some military ground vehicles such as main battle tanks.
The quality criteria and methods for testing fuels for land
and marine diesel engines and for non-aviation gas turbines
are sufficiently similar to address in a common chapter. Obviously, certain criteria and tests will apply to one or the
other rather than both. For example, the cetane number,
which is a critical property for diesel fuels, is of limited significance for gas turbine fuels. Conversely, sodium and vanadium content are important in assessing gas turbine fuels,
but not those used in diesel engines. This chapter presents information regarding fuels for both automotive diesel engines
and gas turbines.
The petroleum industry started in the 1850s. Two factors
were especially important as impetus. Machines were being
developed and they needed oil for lubrication. Also, oil lamps
were being used to light homes and offices and the whale oil
traditionally burned in these lamps was growing increasingly
expensive. James Young, a Scotsman, had recently patented
a process for converting coal to coal oil. Coal oil was less expensive than whale oil but smoked and produced a foul smell
when burned. Then, in 1857, lamp maker A.C. Ferris produced clean-burning kerosine that did not have a bad smell
[1]. The oil used for making the kerosine was being skimmed
from natural crude oil seeps until Colonel Edwin Drake
drilled into one of the seeps, near Titusville, Pennsylvania, using a rig of the type used for drilling brine wells. An oil boom
was bom.
During the 1860s, oil exploration and drilling expanded to
Ohio, Termessee, New York, Kentucky, Colorado, and Califor-

nia. From this time until about 1900, kerosine for oil lamps
was the most valuable fraction of the petroleum barrel. The
fraction now known as gasoline was considered surplus and
burned. The heavier residual fraction was typically dumped
into pits or other convenient dumping grounds. The middle
distillate fraction, which would eventually be used in diesel engines, was used in the town gas industry. It was used "either as
a source of domestic gas, or for enriching or carburetting water gas, or as an absorbing agent or 'wash oil' for removing condensable constituents from coal gas" [2]. This is the reason
that this fraction is still often referred to as gas oil. Throughout this time, the middle distillate fraction of the petroleum
barrel was primarily a leftover product with no leirge market.
The invention of the diesel engine changed that for the better.
Compression Ignition Engines

' Manager, Petroleum Products Technology, Southwest Research Institute, P.O. Drawer 28510, San Antonio, TX 78228.
^ Consultant Engineer, Gas Turbine Combustion & Fuels, Retired,
3760 Sioux Avenue, San Diego, CA 92117.

Since it's beginning in the 1890s, the diesel engine quickly became the engine of choice for many industrial and marine applications, applications where the larger, heavier, slower
speed engine excelled in cost and performance when compared to alternative power plants of the time. However, the
diesel engine saw only limited use in automotive and aviation
applications. After World War I, shortages of gasoline in Germany helped stimulate work on the diesel engine, especially
as an automotive engine. Diesel engines were used for
propulsion on the Hindenburg.
Suppljdng fuel to the engine was the major obstacle to a
higher-speed, lower-weight engine suitable for automotive
use. Compressed air injection was complicated and the required air pump could not be substantially reduced in either
size or weight. In 1922, Robert Bosch set out to develop a
fuel-injection system for diesel engines [3]. By early 1923,
about a dozen different designs had been developed and initial trials were underway by mid-1923. A final design was approved in 1925 and the first series production fuel-injection
pump was on the market.
The fuel-injection system opened the door for wide spread
use of the diesel engine in previously untried applications. By
the mid-1930s there were large numbers of diesel-powered
trucks and buses in service; but only small numbers of dieselpowered automobiles. By the beginning of World War II in
1939, the diesel engine was in widespread use as an automobile engine. The German military also used diesel engines for
many of their vehicles, including some aircraft [4]. Gasoline
engines, because of the logistics problems faced with a twofuel supply system, powered the Allied Forces almost exclusively. Following World War II; the greater fuel economy of

115
Copyright'

2003 by A S I M International

www.astm.org

116 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

>.
(0
Q

a.

m
CD

0 J

1950

1960

1970

1980

1990

2000

Year
Source: U.S. Energy Information Administration
FIG. 1Diesel fuel supplied to the transportation sector.

the diesel engine caused a rapid increase in the use of the engine for automotive applications throughout Europe. The
abundance of inexpensive gasoHne in the United States lowered incentives for adopting the diesel engine in trucks and
automobiles. Even still, throughout this period, the diesel engine climbed in popularity for use in railroad, marine, and
heavy-construction equipment applications. The use of the
diesel engine increased until virtually 100% of current marine, trucking, railroad, construction, and much of the stationary power generation applications operate on diesel engines. The fuels used in these engines have, over time, varied
from natural gas to crude oil but the middle distillate, number 2 grade liquid fuel, is the fuel of choice for many of these
applications. Figure 1 shows the increase in diesel fuel usage
for transportation since 1949 [5].

DIESEL FUEL SPECIFICATIONS


From the turn of the twentieth century until the mid-1930s
there existed no widely used consensus specification for fuel
for diesel engines. Those needing diesel fuel likely bought
whatever was available on the market that seemed like a usable fuel. In 1934, ASTM Committee D2 published D 396,
Standard Specification for Burner Fuels. This specification
covers fuels for fuel-oil burning equipment (such as home
heating oils). However, fuels of grades 1 and 2 in this specification would have probably been acceptable for most diesel
engines of the time. D 396 was used in many purchase contracts as the controlling specification, thereby allowing both
buyer and seller to agree on the minimum quality of the fuel.
Starting in the eeirly to mid-1930s, the demand for diesel fuel
began to rise at a steady rate in most of the industriEilized nations of the world. (During World War II, this demand slowed
some owing to the essentially 100% use of gasoline by the Allied Forces.) Diesel engines were becoming increasingly sensitive to the quality of the fuel in order to maintain optimum
engine performance.

Following World War II, it was recognized that D 396 did


not sufficiently specify the quality of the fuel needed for
newer diesel engines. D 396 contains no specification for the
ignition quality of the fuel, as an example. So, in 1948, Committee D2 published D 975-48 T, Tentative Specifications for
Diesel Fuel Oils.
Fuel Grades
When first published, D 975 contained specifications for
"three grades of Diesel fuel oils suitable for various t5rpes of
Diesel engines." The grades were No. 1-D, No. 2-D, and No. 4D. Table 1 provides a description, of each grade, from the
1948 standard and the 1996 standard. It is interesting to note
that the description of Grade 2-D in the 1948 version did not
include automotive applications, reflecting the fact that
diesel engines were for heavy-duty use and large trucks. Fuel
grades Low Sulfur No. 1-D and Low Sulfur No. 2-D were
added in 1993. These latter grades were added to comply with
40 CFR Part 80Regulation of Fuels and Fuel Additives: Fuel
Quality Regulations for Highway Diesel Fuel Sold in 1993
and Later Calendar Years.
The limiting properties included in the 1948 specification
were flash point, pour point, water and sediment, carbon
residue, ash, distillation, viscosity, sulfur, copper strip corrosion, and cetane number. Since then, pour point has been removed from the specification table. Other changes to the
specification table have also occurred over the years. Table 2
is a summary of many of the major changes.

DIESEL FUEL PROPERTIES


Table 3 contains the specific requirements for the fuels
covered by D 975. The properties listed in that table, along
with other selected properties of importance, are discussed
below.

CHAPTER 5: GAS TURBINE FUELS


TABLE 1Descriptions of the fuels covered by
Specification D 975.
Grade

D 975-48 T

D 975-98b

No. 1-D

A volatile distillate
fuel oil for engines
in service requiring
frequent speed and
load changes.

A special-purpose, light
distillate fuel for
automotive diesel engines
in applications requiring
higher volatility than that
provided by Grade No.
2-D fuels.

Low Sulfur
No. 1-D

Not Applicable

A special-purpose, light
distillate fuel for
automotive diesel engines
requiring low sulfur fuels
and requiring higher
volatility than that
provided by Grade Low
Sulfur No. 2-D.

No. 2-D

A distillate fuel oil of


low volatility for
engines in industrial
and heavy mobile

A general-purpose, middle
distillate fuel for
automotive diesel engines,
which is also suitable for
use in non-automotive
applications, especially in
conditions of frequently
varying speed and load.

Low Sulfur
No. 2-D

Not Applicable

A general-purpose, middle
distillate fuel for automotive diesel engines
requiring low sulfur fuel.
It is also suitable for use
in non-automotive
applications, especially in
conditions of varying
speed and load.

No. 4-D

A fuel oil for low and


medium speed
engines.

A heavy distillate fuel, or a


blend of distillate and
residual oil, for low- and
medium-speed diesel
engines in nonautomotive applications
involving predominantly
constant speed and load.

Density
Density is the mass per unit volume of the fuel. This property
is not specified in D 975. However density is a fundamental
physical property that can be used in conjunction with other
properties to characterize both the light and heavy fractions
of petroleum cind petroleum products. Accurate determination of the density of petroleum products is also necessary for
the conversion of measured volumes to volumes at the standard temperature of 15C (60F). While density is a factor
governing the quality of crude petroleum, it is an uncertain
indication of petroleum product quality unless correlated
with other properties.
The two methods most commonly used to measure density
are:
ASTM D 1298, Standard Test Method for Density, Relative
Density (Specific Gravity), or API Gravity of Crude
Petroleum and Liquid Petroleum Products by Hydrometer
MethodThe sample is brought to the prescribed temperature a n d transferred to a cylinder at approximately the
same temperature. The appropriate hydrometer is lowered

117

into the sample and zJlowed to settle. After temperature


equilibrium h a s been reached, the hydrometer scale is
read, and the temperature of the sample is noted. If necessary, the cylinder and its contents may be placed in a constant t e m p e r a t u r e b a t h to avoid excessive t e m p e r a t u r e
variation during the test.
ASTM D 4052, Standard Test Method for Density and Relative Density of Liquids by Digital Density Meter^A small volu m e (approximately 0.7 mL) of liquid sample is introduced
into an oscillating sample tube and the change in oscillating frequency caused by the change in the mass of the tube
is used in conjunction with calibration data to determine
the density of the sample.
API gravity (D 1298) is another measure of the density of fuel
that has been used for years. A fuel with a high API gravity is
a low-density fuel and a low API gravity fuel is a high-density
fuel. It is calculated with the following formula:
API gravity, deg = (141.5/S)-131.5
Where 5 = density, kg/nr' at 15C

TABLE 2Summary of the major changes" to Specification


D 975 since it was first published.
Year
Changes
1948
First published as a tentative standard.
1950
Changes to pour point and viscosity limits.
1953
Further clzirification of pour point and copper strip
corrosion limits.
1959
Table 1 was revised to add a 90% distilled minimum
temperature for Grade 2-D, and add a revised minimum viscosity at 100F for Grade 2-D.
1960
The nomograph for the calculated cetane index
method (then an appendix to the specification)
was revised.
1964
Section 2 was added to specify that the properties of
the fuel apply at the time and place of delivery.
Section 4 was amended to permit use of Method D
56 as Ein alternate for Method D 93 to determine
flash points of Grade 1-D fuels.
1965
The viscosity and 90% distillation requirements for
Grade 2-D were revised.
1966
The sulfur limit for Grade 2-D was lowered from 1.0
wt% to 0.7 wt%. The cetane index method was removed from the appendix and became D 976.
1967
The standard was adopted without revision and was
no longer a tentative method.
1968
The sulfur limit for Grade 2-D was lowered from 0.7
wt% to 0.5 wt%.
1973
The allowable amount of water and sediment in
Grade 1-D was raised from trace to 0.05 volume
percent.
1974
The cloud point requirement and the U.S. 10th percentile temperatures were added as an appendix.
These are used to help set cloud point limits.
1978
The viscosity limits were lowered for all grades.
1988-1990
Several changes in format. Standard D 4737 replaced D 976 for the calculation of cetane index.
1992
Grades 1-D low sulfur and 2-D low sulfur were
added to the table. A footnote on the use of blue
dye in high sulfur fuel was also added to Table 1.
1994
An appendix on the lubricity of diesel fuel was
added.
1996
The footnote regarding the use of blue dye was
changed to reflect changes in the federal regulations, which now require red dye.
"Not all changes are included. Editorial revisions and most of the changes
to appendices were left oft this list.

118 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 3Detailed requirements for diesel fuel oils."

Property
Flash Point, C, min.
Water and Sediment, % vol, max
Distillation Temperature, C 90 % % vol
Recovered
min
max
Kinematic Viscosity, mm^/S at 40C
min
max
Ash % mass, max
Sulfur, % mass, max^
Copper strip corrosion rating mjix 3 h
at SOX
Cetane number, min''
One of the following properties must
be met:
(1) Cetane index, min.
(2) Aromaticity, % vol, msix
Cloud point, C, max
Ramsbottom carbon residue on 10%
distillation residue, % mass, max

ASTM Test
Method^

Grade Low
Sulfur
No. 1-D^

Grade Low
Sulfur
No. l-D"''

Grade
No. 1-D'

Grade
No. 2-0*'

38
0.05

52
0.05

38
0.05

52
0.05

D93
D2709
D 1796
D86

Grade
No. 4-D'
55
0.50

282'^
338

288

288

282^*
338

D445
D482
D 2622
D129
D130

1.3
2.4
0.01
0.05

1.9
4.1
0.01
0.05

No. 3

D613
916f
1319'"
2500
524

1.3
2.4
0.01

1.9
4.1
0.01

5.5
24.0
0.10

0.50
No. 3

0.50
No. 3

2.00

No. 3

40"

40"

40'

40'

40
35

40
35

0.15

0.

0.15

30'

0.35

"To meet special operating conditions, modifications of individual limiting requirements may be agreed upon between purchaser, seller, and manufacturer.
''The test methods Indicated are the approved referee methods. Other acceptable methods are Indicated in 3.1.
"Under United States regulations. If Grades Low Sulfur No. 1-D or Low Sulfur No. 2-D are sold for tax exempt purposes then, at or beyond terminal storage
tanks, they are required by 26 CFR Part 48 to contain the dye Solvent Red 164 at a concentration spectrally equivalent to 3.9 lbs per thousand barrels of the solid
dye standard Solvent Red 26, or the tax must be collected.
''when a cloud point less than 12C is specified, the minimum flash point shall be 38C, the minimum viscosity at 40C shall be 1.7 mm^/s, and the minimum
90% recovered temperature shall be waived.
'Under United States regulations. Grades No. 1-D, No. 2-D, and No. 4-D are required by 40 CFR Part 80 to contain a sufficient amount of the dye Solvent Red
164 so Its presence Is visually apparent. At or beyond terminal storage tanks, they are required by 28 CFR Part 48 to contain the dye Solvent Red 164 at a concentration spectrally equivalent to 3.9 lbs per thousand barrels of the solid dye standard Solvent Red 26.
'^Other sulfur limits can apply In selected areas in the United States and In other countries.
^These test methods are specified in 40 CFR Part 80.
''Where cetane number by Test Method D 613 Is not available, Test Method D 4737 can be used as an approximation.
'Low ambient temperatures as well as engine operation at high altitudes may require the use of fuels with higher cetane ratings.
'It is unrealistic to specify low temperature properties that will ensure satisfactory operation at all ambient conditions. In general, cloud point (or wax appearance point) may be used as an estimate of operating temperature limits for Grades Low Sulfur No. 1; Low Sulfur No.2; and No.l and No. 2 diesel fuel oils.
However, satisfactory operation below the cloud point (or wax appearance point) may be achieved depending on equipment design, operating conditions, and the
use of flow-improver additives as described in X4.1.2. Tenth percentile minimum air temperatures for U.S. locations are provided in Appendix X4 as a means of
estimating expected regional temperatures. This guidance Is general. Some equipment designs or operation may allow higher or require lower cloud point fuels.
Appropriate low temperature operability properties should be agreed upon between the fuel supplier and purchaser for the Intended use and expected ambient
temperatures.

Even though, as use of the International System of Units (SI)


becomes more common, use of API gravity decreases, API
Gravity is arguably the most widely used cheiracteristic for
"mass" of petroleum.
Ignition and Combustion Characteristics
(Cetane Number)
The first diesel engines were large and slow-speed and were
not particularly sensitive to the quality of the fuel they
burned. As steady improvements were made to the engine,
there was a need to improve fuel quality as well. Gradually,
the heavier, more viscous, diesel fuels disappeared with
lighter and higher speed engines. The higher speed engines
are more sensitive to the ignition quality of the fuel; therefore, cetane numbers became the property of greatest concern to both producers and users. Diesel engine performance
is a function of compression ratio, injection timing, the manner in which fuel and air are mixed, and the resulting ignition
delay or time from the start of injection to the beginning of

combustion. The nature of the fuel is an important factor in


reducing ignition delay. Physical characteristics such as viscosity, gravity, and mid-boiling point are influential. Hydrocarbon composition is also important as it affects both the
physical and combustion characteristics of the fuel. Straightchain paraffins ignite readily under compression, but
branched-chain peiraffins and aromatics react more slowly.
The first widely used measure of ignition quality was the
diesel index, calculated as:
Diesel Index = [(API Gravity)(Aniline Point)] /100
The aniline point is the lowest temperature at which equal
amounts of fuel and aniline are completely miscible. Aromatic compounds tend to exhibit higher density than paraffinic compounds and they are better solvents. Therefore, a
fuel that is high in aromatics will generally have a lower aniline point than a fuel that is high in paraffins. So, a high
paraffin fuel will tend to have a higher API Gravity and a
higher aniline point. This combination results in a higher
diesel index, which indicates better starting characteristics.

CHAPTER 5: GAS TURBINE FUELS


The diesel index equation may be misleading, especially with
blended fuels and fuels treated with ignition-improver additives.
By the mid-1930s, it was determined that a better measurement of ignition quality was needed. The result was an
engine test:
ASTM D 613 Standard Test Method for Ignition Quality of
Diesel Fuels by the Cetane MethodThe cetane number of a
diesel fuel is determined by comparing its ignition quality
with those for blends of reference fuels of known cetane
numbers under standard operating conditions. Varying the
compression ratio for the sample and each reference fuel to
obtain a fixed "delay period," that is, the time interval between the start of injection and ignition does this. When
the compression ratio for the sample is bracketed between
those for two reference fuel blends differing by not more
than five ceteine numbers, the rating of the sample is calculated by interpolation.
This test involves operating a standard, single cylinder,
variable compression ratio engine using a specified fuel flow
rate and time of injection (injection advance) for the fuel
sample and each of two bracketing reference fuels of known
cetane number. The engine compression ratio is adjusted for
each fuel to produce a specified ignition delay, and the cetane
number is calculated to the nearest tenth by interpolation of
the compression ratio values.
The cetane number scale uses two primary reference fuels.
One, n-hexadecane (normal cetane), has excellent ignition
qualities and, consequently, a very short ignition delay. This
fuel was arbitrarily assigned a cetane number of 100. The second fuel, a-methylnaphthalene, has poor ignition qualities
and was assigned a cetane number of zero. The a-methylnaphthalene was later replaced with heptamethylnonane,
which was calibrated against the original fuels and assigned
a cetane number of 15. The cetane number scale is now defined by the following equation for volumetric blends of the
two primary reference materictls:
Cetane Number = % n-cetane
-F 0.15 (percent heptamethylnonane)
In practice, the primary reference fuels are only utilized to
calibrate two secondary reference fuels. These are selected
diesel fuels of mixed hydrocarbon composition, which are
designated as "T" and "U". "T" fuel typically has a cetane
number of approximately 75 while "U" fuel is usucilly in the
low 20 cetane number range. Each set of "T" and "U" fuels are
paired and test engine calibrations define the cetane numbers for volumetric blends of these two secondaries [6]. In
general, the contribution of various fuel components to bulk
fuel cetane number can be described as follows [7]:
Normal Paraffins > Branched Paraffins > Normal Olefins
> Branched Olefins > Naphthenes > Aromatics
=> Decreasing Cetane Number =>
Higher cetane number fuels tend to reduce combustion
noise, increase engine efficiency, increase power output,
start easier (especially at low temperatures), reduce exhaust
smoke, and reduce exhaust odor. To assure acceptable cold
weather performance, most modern diesel engines require a

119

minimum cetane number of 40 [8] and this is the requirement in D 975. Many engine manufacturers are now pushing
to raise the specification minimum limit to 50 cetane in order to meet new engine emission requirements (see the discussion of the Worldwide Fuels Charter below).
Cetane Index
Two ASTM test methods for calculating approximate cetetne
numbers were also developed for situations when performing
the engine test was not feasible. Two ASTM methods, and the
equations for each, are:
ASTM D 976, Standard Test Method for Calculated Cetane
Index of Distillate Fuels
Calculated Cetane Index = 454.74 - 1641.416 D
+ 774.74 0^-0.554 5 + 97.803 (log 5)^
Where:
D = density at 15C, g/mL, determined by Test
Method D 1298, and
B = mid-boiling temperature, C, determined by
Test Method D 86 and corrected to standard
barometric pressure.
ASTM D 4737, Standard Test Method for Calculated Cetane
Index by Four Variable Equation
CCI = 45.2 + (0.0892)(rioN) + [0.131 + (0.901)B][r50N]
+ [0.0523 - (0.420)B][r90N]
+ [0.00049][(rioN)^ - (T'OTN)^] + 1075 -H 605^
Where:
CCI - Calculated Cetane Index by Four Variable Equation,
D = Density at 15C, determined by Test Method D
1298,
DN =D- 0.85,
B

= [e(-3-5XDN)] _ 1^

Tio = 10% recovery temperature, C, determined by Test


Method D 86 and corrected to standard barometric
pressure,
TioN Tio 215,
Tso = 50% recovery temperature, C, determined by Test
Method D 86 and corrected to standard barometric
pressure,
T50N = Tso ~ 260,
Tgo = 90% recovery temperature, C, determined by Test
Method D 86 and corrected to standard barometric
pressure,
TgoN = T90 310
Both methods utilize fuel density and distillation values in
their calculations. Standard D 4737 is the more widely used
method since it is the most recent and it better represents
current diesel fuels. Some limitations of calculated cetane index include:
1. It is not applicable to fuels containing additives for raising
cetane number.
2. It is not applicable to pure hydrocarbons, synthetic fuels,
alkylates, or coal tar products.
3. Correlation is fair for a given type of fuel but breaks down
if fuels of widely different composition are compared.
4. Appreciable inaccuracy in correlation may occur when
used for crude oils, residuals (or blends containing residuals), or products having end points below 260C.

120

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Numerous other cetane index equations/models have been


developed, used, and compzired to the ASTM equations but
they have never been formaHzed as a n ASTM standard. Additional information concerning some of these non-ASTM
methods can be found elsewhere [9-11].

Volatility / Distillation
The distillation characteristics of a diesel fuel exert a great influence on performance. Two methods are commolily used to
measure distillation characteristics:
ASTM D 86, Standard Test Method for Distillation
of
Petroleum Products^A 100 mL sample is distilled u n d e r
prescribed conditions that are appropriate to its nature.
Systematic observations of thermometer readings and volumes of condensate are made, and from these data, the results of the test are calculated and reported.
ASTM D 2887, Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography
The boiling range distribution determination by distillation is simulated by the use of gas c h r o m a t o g r a p h y . A
non-polar packed or open t u b u l a r (capillary) gas chromatographic column is used to elute the hydrocarbon components of the sample in order of increasing boiling point.
The column temperature is raised at a reproducible lineeir
rate and the area u n d e r the c h r o m a t o g r a m is recorded
throughout the analysis. Boiling points are assigned to the
time axis from a calibration curve obtained under the same
chromatographic conditions by analyzing a known mixture of hydrocarbons covering the boiling range expected
in the sample. From these data, the boiling range distribution can be obtained.
Method D 86 is the specified method in D 975 for measuring distillation characteristics. Figure 2 is a plot of distillation
data for a single, typical diesel fuel using both methods. It is
obvious from this plot that the two methods can give quite
different results. For most fuels, results like these are typical;

with more deviation at the beginning and end of the distillation Eind less deviation at the center. For this reason, D 2887
is not Ein accepted eJtemative to D 86 for specification purposes. That will remain the case until a suitable correlation
(correction factor) between the two is determined.
Figure 3 is the D 2887 gas c h r o m a t o g r a m for the fuel
shown in Fig. 2. The chromatogram illustrates the usefulness
of the D 2887 method. The time axis can be correlated to carbon n u m b e r by using a known standard. Therefore, it is possible to obtain a "picture" of the carbon n u m b e r distribution
in a given fuel. This method is also useful for identifying contaminants such as gasoline a n d engine oil.
The average volatility requirements of diesel fuels vary
with engine speed, size, cind design. However, fuels having
too low volatility tend to reduce power output Eind fuel economy through poor atomization, while those having too high
volatility m a y reduce p o w e r o u t p u t a n d fuel economy
through vapor lock in the fuel system or inadequate droplet
penetration from the nozzle. I n general, the distillation range
should be as low as possible without adversely affecting the
flash point, burning quality, heat content, or viscosity of the
fuel. If the 10% point is too high, poor starting may result. An
excessive boiling range from 10-50% evaporated may increase warm-up time. A low 50% point is desirable to minimize smoke and odor. Low 90% cind end points tend to ensure low carbon residuals and minimum crankcase dilution.
The temperature for 50% evaporated, known as the midboiling point, usucdly is taken as a n overall indication of the
fuel distillation chziracteristics when a single numerical value
is used alone. For example, in high-speed engines a 50%
point above 302C might cause smoke formation, produce
objectionable odor, cause lubricating oil contamination, and
promote engine deposits. At the other extreme, a fuel with excessively low 50% point would exhibit too low a viscosity eind
heat content per unit volume. Therefore, a 50% point in the
range of 232-280C is desirable for the majority of higher
speed diesel engines. This t e m p e r a t u r e range usually is
broadened for Icirger, slower speed engines [12].

100

D86
D2887

80

I
40

on

20 -

0-"
100

150

200

250

300

350

400

450

Distillation Temperature, C
FIG. 2Distillation curves for a typical no. 2 diesel fuel (methods D 86
vs. D 2887).

CHAPTER 5: GAS TURBINE FUELS

Time
FIG. 3D 2887 gas chromatogram of a typical diesel fuel.

For the above reasons, some points on the distillation curve


are considered more important and are included in fuel specifications more often. Specification D 975 contains only a
limit on the 90% point. Other specifications include requirements for initial boiling point (more so for gasoline), 10%,
50%, and to a lesser degree, 95% and final boiling point.
Viscosity
The method for measuring viscosity of diesel fuel is:
ASTM D 445, Standard Test Method for Kinematic Viscosity
of Transparent and Opaque Liquids (and the Calculation of
Dynamic Viscosity)The time is measured for a fixed volume of liquid to flow under gravity through the capillary of
a calibrated viscometer under a reproducible driving head
and at a closely controlled and known temperature. The
kinematic viscosity is the product of the measured flow
time and the calibration constant of the viscometer.
The unit of measurement for this method is square millimeters per second (mm^/s), also known as centistokes (cSt).
This is currently the most widely used unit of fuel viscosity
measurement in the United States. Other units used in the
past, and occasionally still used in the present, include Saybolt Universal Seconds (SUS) and centipoise.
For some engines it is advantageous to specify a minimum
viscosity because of power loss due to injection pump cuid injector leakage. Maximum viscosity, on the other hand, is limited by considerations involved in engine design and size, and
the characteristics of the injection system. Fuel viscosity exerts a strong influence on the shape of fuel spray. High viscosities can cause poor atomization, large droplets, and highspray jet penetration. With high viscosities, the jet tends to be
a solid stream instead of a spray of small droplets. As a result,
the fuel is not distributed in, or mixed with, the air required
for burning. This results in poor combustion, accompanied
by loss of power and economy. In small engines, the fuel
spray may impinge upon the cylinder walls, washing away
the lubricating oil film and causing dilution of the crankcase
oil. Such a condition contributes to excessive wear [13].
Low fuel viscosity results in a spray that is too soft and does
not penetrate far enough in the combustion chamber for

121

good mixing. Combustion is impaired and power output and


economy are decreased. Low viscosity can lead to excessive
leakage past the injection pump plunger. Fuel metering becomes inaccurate and engine efficiency is reduced. Wear of
the fuel system components may increase because lubricating properties of fuels tend to decrease with viscosity.
Fuel viscosities for high-speed engines range from 1.8-5.8
centistokes (cSt) at 38C. Usually the lower viscosity limit is
established to prevent leakage in worn fuel injection equipment as well as to supply lubrication for injection system
components in certain types of engines. During operation at
low-atmospheric temperatures, the viscosity limit sometimes
is reduced to 1.4 cSt at 38C to obtain increased volatility etnd
sufficiently low pour point. Fuels having viscosities greater
than 5.8 cSt usually are limited in application to the slowerspeed engines. The very viscous fuels commonly used in large
stationary and mcirine engines normally require preheating
for proper pumping, injection, and atomization.
Cloud Point
All diesel fuels contain dissolved paraffin wax. As the temperature of the fuel decreases, so does the solubility of the
wax in the fuel. At some point wax crystals will begin to precipitate. If enough wax precipitates the crystals can block fuel
flow through screens, filters, and other restricted passages in
the fuel system. The temperature at which the wax precipitation occurs depends upon the origin, type, refining, and boiling range of the fuel. This temperature is known as the cloud
point of the fuel. As the cloud point goes up, the suitability of
the fuel for low-temperature operation decreases. The cloud
point of the fuel can be measured by the following methods:
ASTM D 2500, Standard Test Method for Cloud Point of
Petroleum ProductsThe specimen is cooled at a specified
rate and examined periodically. The temperature at which
a cloud is first observed at the bottom of the test jar is
recorded as the cloud point.
The following methods are variations of D 2500, including,
both automatic and automated methods:
ASTM D 3117, Standard Test Method for Wax Appearance
Point of Distillate Fuels
ASTM D 5771, Standard Test Method for Cloud Point of
Petroleum Products (Optical Detection Stepped Cooling
Method)
ASTM D 5772, Standard Test Method for Cloud Point of
Petroleum Products (Linear Cooling Rate Method)
ASTM D 5773, Standard Test Method for Cloud Point of
Petroleum Products (Constant Cooling Rate Method)
For all grades of fuel listed in D 975, any of these test methods may be used to measure cloud point. Method D 2500 is the
specified method and the others are considered alternates. In
case of dispute. Test Method D 2500 is the referee method.
Cloud point is the only control for low temperature operability listed in the diesel fuel specification, D 975. Footnote
J to Table 1 in D 975 reads as follows:
It is unrealistic to specify low temperature properties that
will ensure satisfactory operation at all ambient conditions. In general, cloud point (or wax appearance point)
may be used as an estimate of operating temperature limits for Grades Low Sulfur No. 1: Low Sulfur No. 2; and No.

122 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

October10th Percentile Minimum Temperatures


FIG. 4Example 10th percentile minimum ambient temperature map from D 975.

1 and No. 2 diesel fuel oils. However, satisfactory operation below the cloud point (or wax appearance point) may
be achieved depending on equipment design, operating
condition, and the use of flow-improver additives... Tenth
percentile minimum air temperatures for U.S. locations
are provided.. .as a means of estimating expected regional
temperatures. This guidance is general. Some equipment
designs or operation may allow higher or require lower
cloud point fuels. Appropriate low temperature operability
properties should be agreed upon between the fuel supplier
and purchaser for the intended use and expected ambient
temperatures.
The tenth percentile temperatures Eire presented for each
U.S. state, except Hawaii, for each month from October to
March. They are presented in both tabular format and in
maps. Figure 4 is an example of one of the maps.
Realistic options to reduce the cloud point include:
1. Dilute the fuel with a low wax fuel such as grade No. 1 or
kerosine.
2. Treat the fuel with special additives.
3. Refine the fuel from crude(s) with lower wax content or refine the fuel to a lower end point.
4. It is also possible to add insulation and heaters to the vehicle fuel system. This will not change the cloud point of
the fuel but will improve the low temperature operation.

Pour Point
Before a fuel can be burned in an engine it must first be
pumped from the fuel tank. The lowest temperature at which
a fuel can be pumped is known as the pour point of the fuel.
Test methods for measuring pour point include:
ASTM D 97, Standard Test Method for Pour Point of
Petroleum ProductsAfter preliminEiry heating, the sample
is cooled at a specified rate and examined at intervals of
3C for flow characteristics. The lowest temperature at
which movement of the specimen is observed is recorded
as the pour point.
The following methods are variations of D 97, including,
both automatic and automated methods.
ASTM D 5949, Standard Test Method for Pour Point of
Petroleum Products (Automatic Pressure Pulsing Method)
ASTM D 5950, Standard Test Method for Pour Point of
Petroleum Products (Automatic Tilt Method)
ASTM D 5985 Standard Test Method for Pour Point of
Petroleum Products (Rotational Method)
The pour point should be considered only a guide to the
lowest temperature at which a fuel can be used. In general,
pour points are from 3-6C below the cloud point for a given
fuel; however, it is not uncommon for the difference to be as
much as 11 C.

CHAPTER 5: GAS TURBINE FUELS


For any given fuel, there will be no wax precipitation problems at temperatures above the cloud point. At temperatures
below the pour point, it is highly unlikely that the fuel will
give satisfactory performance. It is not unusueJ to obtain satisfactory engine performance with a fuel at ambient temperatures between the cloud point and pour point. The degree of
performance and the temperature depend on the engine, the
vehicle design, and the fuel system configuration. Vehicles
and fuel systems with small diameter lines, constrictions,
small porosity strainers and filters, and fuel lines exposed to
ambient temperatures or wind will tend toward poorer performance. Systems with insulation, supplemental heaters, or
large sections of the fuel system in close proximity to engine
heat can probably expect better performance at lower temperatures [14].
Low-Temperature Flow Test
As discussed above, the mere presence of wax crystals in a
fuel does not guarantee the fuel will plug filters or other fuel
system components. The tendency of a fuel to plug screens
and filters at low temperatures is a dynamic property dependent on the size and shape of the wax crystals. (Vehicle fuel
system design is also a factor as discussed earlier.) For this
reason, numerous dynamic tests for low temperature operability have been developed. ASTM standardized one such
test in 1985:
ASTM D 4539, Standard Test Method for Filterability of
Diesel Fuels by Low-Temperature Flow Test (LTFT)The
temperature of a series of test specimens of fuel is lowered
at a prescribed cooling rate. Commencing at a desired test
temperature and at each 1C interval thereafter, a separate
specimen from the series is filtered through a 1 l-fjun screen
until a minimum LTFT pass temperature is obtained. The
minimum LTFT pass temperature is the lowest tempera-

ture, expressed as a multiple of 1C, at which a test specimen can be filtered in 60 s or less. Alternatively, a single
specimen may be cooled and tested at a specified temperature to determine whether it passes or fails at that temperature.
Figure 5 is a diagram of the LTFT test apparatus. The LTFT
was designed to yield results indicative of the low temperature
flow performance of the test fuel in some diesel vehicles. The
test method is especially useful for the eveiluation of fuels containing flow improver additives. Please refer to Report No.
528 from the Coordinating Research Council for a more detailed discussion [15]. The LTFT was developed in the United
States to simulate the low temperature behavior of diesel fuel
in the fuel tank of a diesel truck left overnight, in a cold environment, with its engine off. J. E. Chandler, zmd others, have
demonstrated that this test has shown excellent correlation
with field studies [16-18]. In spite of the demonstrated correlation to field performance, the LTFT is not as widely used as
some other tests. The primary reason for this is the slow cooling rate (1C per hour), which means that the time required
completing an analysis can range from 12-24 h. Such test
times are generally impractical for routine fuel testing.
Cold FUter Plugging Point
The Cold Filter Plugging Point, CFPP, was developed for use
in Europe. The Institute of Petroleum publishes the method
under the designation IP 309. It is similar to the LTFT with
the following exceptions:
The fuel is cooled by immersion in a constant temperature
bath, making the cooling rate non-linear but comparatively
much more rapid (about 40C per hour).
The CFPP is the temperature of the sample when 20 mL of
the fuel first fails to pass through a wire mesh in less than
60s.

Glass Tubing
6 10 Min Throughout
Vacuum Gage
Point A

Heavy Rulit>er Ttibing


4 10 15 OD
2 Vacuum System
Rubber Stopper

Storage Lid

200 ML Sample
Glass Stem
Quality Flex lObing

Sample Container
300 ML Tall-Form
Beaker

123

Sample Receiver
400 ML Tall-Form
Beaker

All Diminensions in Millimeters

t-TFT Sample Filtration Assembly


FIG. 5LTFT sample filtration assembly (D 4539).

124 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

While the CFPP is the preferred method in Europe and is


used in several European specifications, it appears to overestimate the benefit of using some additives, most especially for
vehicles manufactured in North America [19,20].
Cleanliness
Diesel fuel cleanliness can mean many things to many people. It is safe to say that most users would consider any fuel
that is visually free of undissolved water, sediment, and suspended matter a clean fuel. Indeed, this is the cleanliness
(workmanship) requirement stated in D 975. However, it is
known that microscopic particulates in the fuel can lead to
problems just as serious as the visible contaminants. The
three most common methods of measuring cleanliness of
diesel fuel are:
ASTM D 2709, Standard Test Method for Water and Sediment in Middle Distillate Fuels by CentrifugeA 100-mL
sample of the undiluted fuel is centrifuged at a relative centrifugal force of 800 for 10 min. at 21-32C (70-90F) in a
centrifuge tube readable to 0.005 mL and measurable to
0.01 mL. After centrifugation, the volume of water and sediment that has settled into the tip of the centrifuge tube is
read to the nearest 0.005 mL and reported as the volumetric % water and sediment by centrifuge.
D 2709 is the method currently specified in D 975. It is used
to measure the amount of visible water, sediment, and suspended matter. This method gives no effective measurement
of the presence or amount of microscopic particulates. Many
would consider the level of contamination sufficient to produce readable results in this test to be gross contamination.
However, this is an extremely sensitive test for contamination. The human eye is capable of seeing very small macroscopic particles and the presence of 1 or 2 such particles
could be considered a failure. In practice, the person conducting the test must exercise judgment based on experience
and the requirements of the end use for the fuel.
ASTM D 4860, Standard Test Method for Free Water and Particulate Contamination in Mid-Distillate Fuels (Clear and
Bright Numerical Rating)Visual inspection of the fuel
sample for free water and particulate matter is performed
immediately when the sample is taken. A glass container is
used to view for water haze, and the fuel sample is swirled
to create a vortex to detect the presence of particulate matter. A numerical rating for free water is obtained by filtering a portion of the fuel sample at a programmed rate (50
mL/45 s) through a standard fiberglass coalescer/filter. A
portion of the effluent is used to establish a reference (100)
level by a light transmittance measurement. Another portion of the unprocessed (unfiltered) fuel sample is then
compared to the 100 reference-level. The results are reported on a 50-100 scale to the nearest whole number. A
test can be performed in 5-10 min.
D 4860 was developed to give a means to quantify the level
of cleanliness of a fuel. As with D 2709, D 4860 only provides
a valid measurement of visible contamination. The benefit of
this method is that the measurement is now an objective
measure of cleanliness. While this test does provide a quantitative result, it is far less sensitive than D 2709.
Three other methods used to determine cleanliness of
diesel fuels are D 6217, D 2068, and D 6426. D 6217 could be

considered a combination of the best features of the two previous methods. It is sensitive to small amounts of particles
and is even capable of detecting microscopic particulates. It
is also a quantitative measure of the cleanliness of the fuel.
The quantitative measure is milligrams of particulate (contamination) per liter of fuel. Currently there is no consensus
standard with a specification limit for D 6217. Many user
specifications, including some federal and military diesel fuel
specifications, include a limit of 10 mg per liter for the results
of this analysis. Most users have found fuel that meets this
limit to give satisfactory performance in the vehicle.
ASTM D 6217, Standard Test Method for Particulate Contamination in Middle Distillate Fuels by Laboratory Filtration^A measured volume of about 1 L of fuel is vacuum filtered through one or more sets of 0.8 /u,m membranes.
Each membrane set consists of a tared nylon test membrane and a tared nylon control membrane. When the level
of particulate contamination is low, a single set will usually
suffice; when the contamination is high or of a nature that
induces slow filtration rates, two or more sets may be required to complete filtration in a reasonable time. After the
filtration has been completed, the membranes are washed
with solvent, dried, and weighed. The particulate contamination level is determined from the increase in the mass of
the test membranes relative to the control membranes, and
is reported in units of glw? or its equivalent mg/L.
ASTM D 2068, Standard Test Method for Filter Plugging Tendency of Distillate Fuel OilsA sample of the fuel to be
tested is passed at a constant rate of flow (20 mL/min)
through a glass fiber filter medium. The pressure drop
across the filter is monitored during the passage of a fixed
volume of test fuel. If a prescribed maximum pressure drop
is reached before the total volume of fuel is filtered, the actual volume of fuel filtered at the time of maximum pressure drop is recorded.
The primary weakness of visual and gravimetric method is
that there is no generally accepted correlation between the
results of the test and the performance of the fuel in a vehicle
fuel system. That is, how long could the vehicle operate on
that fuel before the fuel filter plugs or the water separator
fails? The British Navy first developed D 2068 as a dynamic
test of the cleanliness of fuel for shipboard gas turbine engines [21]. The test was designed around the specific requirements of gas turbine powered ships in the British Navy. The
most important requirement was that the shipboard fuel filters had a nominal porosity of 1 /am. As such, a 1 /u,m pore
size glass fiber laboratory filter is used in the test. Over the
years the test apparatus was upgraded, making it more automated.
ASTM D 6426, Standard Test Method for Determining Filterability of Distillate Fuel Oils^A sample is passed at a constant rate (20 mL/min) through a standard porosity filter
medium. The pressure drop across the filter and the volume of filtrate are monitored. The test is concluded either
when the pressure drop across the filter exceeds 170 kPa
(25 psi) or when 300 mL have passed through the filter. Results are reported as either the volume that has passed
through the filter when a pressure of 170 kPa (25 psi) has
been reached or the pressure drop when 300 mL have
passed through the filter. In the latter case, the volume, if
and when 105 kPa (15 psi) was exceeded, is also recorded.

CHAPTER 5: GAS TURBINE FUELS


D 6426 is a modification of Method D 2068. The first difference between the two methods is the pump used in each:
D 2068 uses a piston pump whereas D 6426 uses a peristaltic
pump. The second difference that D 2068 uses a 13-mm diameter, 1 fim pore size fiher and D 6426 uses a specially constructed test specimen, which is called an F-cell Filter Unit. It
is a disposable, precalibrated assembly consisting of a shell
and plug containing a 2 5-mm diameter nylon membrane filter of nominal 5.0/am pore size, nominal 60% porosity, with
a 17.7-mm^ effective filtering area. Figure 6 is a schematic diagram of the complete test apparatus.
Despite the differences in equipment, both D 2068 and D
6426 have the same pass/fail criteria. A fuel fails the test if the
pressure drop across the filter reaches 105 kPa (15 psi) before
300 mL of test fuel passes through the filter.

(D)

FLOW ADJUSTMENT KNOB

DISPLAYS
PRESSURE VOLUME VOLUME
(psi) ((Si 0-25 psi) ((a! 0-15 psi)

PRESSURE
TRANSDUCER
PERISTALTIC PUMP
\
PULSE
\
DAMPENrNG
/lECIIANISM

ay

PLA,STIC TIP
TYGON
TUBING
RUBBER STOPPER (VENTED)
FILTER CELL

METAL TUBE (STAINLESS STEEL)


TUEL RESERVOIR

"FUEL SAMPLE

FUEL FLOW
COLLECTION
CONTAINER

PROCESSED FUEL

FIG. 6Schematic diagram of filterability apparatus (D 6426).

At this writing, neither D 2068 nor D 6426 enjoys


widespread use in the U.S. However, of the two methods, D
6426 is gaining the greatest acceptance in the U.S. This is due
to two primary reasons: 1) the equipment to conduct D 6426
is more readily available than the equipment for D 2068; and,
2) the F-cell test specimen is regarded as more representative
of automotive fuel filters than is the filter in D 2068. Despite
the general recognition that the F-cell is more representative
of automotive fuel filters, numerous attempts to correlate the
results from D 6426 with fuel filter plugging/filter life have
failed [22].

Stability
For the purposes of this discussion, fuel stability is defined as
the resistance of the fuel to physical and chemical changes
brought about by the interaction of the fuel with its environment.
The chemistry of diesel fuel stability (instability) is complex. In general, it involves the chemical reaction of precursor species to form molecules of higher molecular weight.
The higher molecular weight species then become insoluble
deposits in the form of either gums or particulates. The precursor species are usually sulfur and/or nitrogen containing
compounds, olefins, and organic acids. The reactions are often initiated by the oxidation of the precursors. Some dissolved metals, especially copper but also zinc and even iron,
are known to catalyze the oxidation reactions. In the case of
copper, as little as 10-30 parts per billion of dissolved copper
is sufficient to catalyze deleterious reactions, depending on
the fuel. The mechanism proposed by Pedley [23] (shown in
Fig. 7) is perhaps the most cited example of these types of reactions. Although this mechanism explains many of the earlier findings on diesel stability, it does not account for the for-

oxldatlon

Phenalenes

125

1
Phenalenones

Indoles

Acid

Indolylphenalenes

Acid/Oxidation

Fuel Insolubles

FIG. 7Proposed mechanism of diesel fuel insolubles formation.

126

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

m a t i o n of all diesel fuel sediments. Other_useful reaction


schemes have been proposed [24-27]. The solvent strength of
the fuel is also a factor in that a high-solvency fuel can keep
some of the high molecular weight species in solution.
Because the reactions and interactions Eire so numerous
and complex, it is quite possible to blend two very stable fuels and obtain a very unstable fuel. In this case, each fuel possesses one or more of the required precursor compounds.
When the fuels are mixed, the reactions proceed, and sediment is formed. Yet, had these two fuels never been blended,
neither single fuel would have significantly degraded in storage. There are three tjrpes of stability usually of concern for
diesel fuel. They are thermal, oxidation, and storage. Each of
these will be discussed separately.

20

""" /

/ /
/ -^ '

18
16
M

tX

s,

s'

10

//

/ ""^
\

T h e r m a l stability is the resistance of the fuel to change


caused by thermal stress (elevated temperature). The recognized ASTM test method is:
D6468, Standard Test Method for High Temperature Stability of Distillate FuelsTwo 50-mL volumes of filtered middle distillate fuel are aged for 90 or 180 min at 150C in
open tubes with air exposure. After aging and cooling, the
fuel samples are filtered. The amount of filterable insolubles is estimated by measuring the light reflectance of the
filter pads. An unused filter pad and a commercial black
standard define the 100 and 0% extremes of the reflectance
rating range, respectively.
This method is based on a test that has been known by several names, such as: the Nalco 300F Test, the EMD-Diesel
Fuel Stability Test, the Union Pacific Diesel Blotter Test, the
du Pont F 21 Test, and the Octel F 21 test [28]. This test differs from most other accelerated stability tests in that the test
temperature is much higher and the amount of insolubles
formed is estimated rather than measured gravimetrically. In
the earlier versions of the test, the a m o u n t of insoluble
residue formed during aging was estimated by comparing the
test filter to a set of visual stEuidards called reference blotters.
Filter pads from the test were rated on a scale from 1 to 20
with a rating of 1 assigned to a filter pad that is essentially
free of sediment. A rating of 7 or less was typically considered
a pass. The reference pads were produced in both gray and
brown-tone prints. The reference pads were also produced to
represent samples that were filtered through a Biichner funnel or through a standard m e m b r a n e filter holder. The reference blotters were generally considered satisfactory to rate
test filters that had sediment similar in appearance (color
and shape) to that depicted on the reference blotter. However, the visual ratings were subjective and different raters
had been found to rate the same pad as everything from a 4
to an 11. Also, raters within the same laboratory tended to
train each other, thus compounding the possibility for error.
Henry [29] described a rating technique (originally proposed
by Chevron Oil Company) t h a t used a reflectance m e t e r
rather than a visual comparison. Figure 8 shows the relationship of visual and reflectance pad ratings. As expected, the reflectance meter method yielded greatly improved precision
compared to the reference blotters. The reflectance meter
was the technique selected when the method was standardized [30].

/
Thermal Stability

V^

/
//

/
^

ujl2

,y

\&

MULTILABORATORY
VISUAL RATINGS

y
/^

100

>

VISUAL RATINGS IN
ONE LABORATORY

'

80

60

"JO

20

PERCENT REFLECTION
(PHOTOVOLT MODEL 670 REFLECTION HETER WITH SEARCH UNIT W)

FIG. 8Relationship of visual and reflection pad ratings.

Arguably, this test is the most often used method to monitor/predict fuel stability. The primary reason for its popularity is the short test time and simple equipment requirements.
This has made the 150C test, in one form or another, especially popular with many pipeline companies and others with
the need to monitor the quality of fuel but do it rapidly. Stavinoha and Westbrook demonstrated that this test has poor
correlation to the generally accepted test for storage stability
of diesel fuel (see D 4625 below) [31]. Bacha [32] and Henry
[33] reported that the 150C test provides an indication of
thermal stability of distillate fuels exposed to high temperatures. The test method can be useful for investigation of operational problems related to fuel thermal stability. When D
6468 is used to m o n i t o r fuel in production or storage, a
change in filter rating can indicate a relative change in inherent stability of the fuel. No quantitative relationship exists
between pad ratings and the gravimetric mass of filterable insolubles formed during the test. Additional information on
the interpretation of results is found in Appendix XI of the
test method.

Oxidation Stability
Oxidation stability is the resistance of the fuel to change under severely oxidizing conditions. In addition to exposing the
fuel to excess amounts of oxygen, oxidation stability tests
usueJly incorporate elevated test temperatures to accelerate
reaction rates. The method commonly used to measure oxidation stability of diesel fuel is:
ASTM D 2274, Standard Test Method for Oxidation Stability
of Distillate Fuel Oil (Accelerated Method)^A 350-mL volu m e of filtered middle distillate fuels is aged at 95C
(203F) for 16 h while oxygen is bubbled through the sample at a rate of 3 L/h. After aging, the sample is cooled to ap-

CHAPTER
proximately room temperature before filtering to obtain
the filterable insolubles quantity. Adherent insolubles are
then removed from the oxidation cell and associated glassware with trisolvent. The trisolvent is evaporated to obtain
the quantity of adherent insolubles. The sum of the filterable and adherent insolubles, expressed as milligrams per
100 mL, is reported as total insolubles.
Because for m a n y years this was the only standardized
method to measure stability of middle distillate fuels, it became a part of n u m e r o u s fuel specifications (mostly government/military) and was widely used as a predictor of fuel
storage stability. Despite the wide acceptance as a storage
stability test, most researchers agreed that, in fact, the results
of D 2274 had very poor correlation to actual, ambient storage of the fuel. In addition, the precision of the test was extremely poor. Many researchers have worked to improve the
test. Chief a m o n g these is E. W. White of the U.S. Navy
[34,35]. Some of the factors he identified as having an effect
on the results of the test are: the purity of the oxygen, stray
light impinging the sample during aging (especially ultra-violet light), contact with metal surfaces (especially copper),
filter drying time, and heating bath configuration. Based on
the work of White and others, many needed improvements
were made to the method. The precision of the test is better
now than when it was first published by ASTM. However, despite the improvements, the results continue to have poor
correlation to ambient storage. Because this poor correlation
is now more widely known, the use of the method to assess
the stability of diesel fuels is very low.

5: GAS TURBINE

FUELS

127

TABLE 4Factors that influence the quality of


diesel fuel in storage.
Can lead to tank corrosion,
Presence of Water
microbiological growth, and
entrained water.
Can accelerate or slow chemical
Storage temperature
reactions in the fuel.
(ambient temperature)
Fixed roof tanks allow greater tank
Vented, fixed roof tank
vs. floating roof tank
breathing, which promotes water
condensation, oxygen replenishment
in the ullage, and increases airborne
contaminants in the fuel.
Lined vs. unlined
storage tanks

Lined tanks (those with an interior


coating) reduce or prevent exposure
of the fuel to metal surfaces. This
reduces corrosion of the tank. Metal
surfaces can also catsdyze some fuel
degradation reactions.

Microbiological
contamination

Leads to degradation of the fuel by


metabolic by-products, corrosion of
metallic storage tanks, and
emulsification of water and fuel.

Agitation of the fuel


through tank filling
and/or circulation of
the fuel
Crude oil source and
refining techniques

Promotes increased concentrations of


air/oxygen and water in the fuel.
These factors influence the chemical
composition of the fuel.

Commingling of fuels

The mixing of two stable fuels can, on


rare occasions, result in antagonistic
chemical reactions.

Storage Stability
Storage stability is generally defined as the fuel's resistance to
change during storage at ambient temperature and conditions. Ambient storage is storage of the fuel in drums, storage
tanks, vehicle fuel tanks, or similar containers in the out-ofdoors. There are many factors that can influence the storage
stability of a given fuel. The most c o m m o n factors are listed
in Table 4. The two tests for storage stability are:
ASTM D 4625, Standard Test Method for Distillate Fuel Storage Stability at 43C (nOF)Four-hundred
mL volumes
of filtered fuel are aged by storage in borosilicate glass containers at 43C (110F) for periods of 0, 4, 8, 12, 18, and 24
weeks. After aging for a selected time period, a sample is removed from storage, cooled to room temperature, and analyzed for filterable insolubles and for adherent insolubles.
ASTM D 5304, Standard Test Method for Assessing Distillate
Fuel Storage Stability by Oxygen OverpressureA 100-mL
aliquot of filtered fuel is placed in a borosilicate glass container. The container is placed in a pressure vessel that has
been preheated to 90C. The pressure vessel is pressurized
with oxygen to 800 kPa (absolute) (100 psig) for the duration of the test. The pressure vessel is placed in a forced air
oven at 90C for 16 h. After aging and cooling, the total
amount of fuel insoluble products is determined gravimetrically and corrected according to blank determinations.
All petroleum fuels u n d e r g o chemical reactions during
storage. The results of these reactions are usually g u m s ,
acids, and/or particulates. The n u m b e r and rate of these deleterious reactions depends on the concentrations of reaction
precursors, the concentration of oxygen available for oxida-

tion reactions, the presence of catalytic species such as metals, the a m o u n t of light, and the storage temperature. As
mentioned above, the resistance of the fuel to these reactions
is defined as its storage stability. Most researchers cJso go a
step further and define inherent storage stability as the resistance to change in the absence of environmental factors such
as metals and contaminants (i.e., in the absence of catalytic
effects).
The inherent stability is important because it is a measure
of the useful storage life of the fuel. For most diesel fuels under normal storage conditions,it may take several months or
even years for the deleterious reactions to generate enough
by-products to cause fuel-related p r o b l e m s . A user w h o
would like to store fuel would like to know what that length
of time is prior to putting the fuel in storage. To predict the
storage stability, therefore, we must simulate the storage and
measure the quantities of insolubles formed. To accelerate
the process, the test must be performed at an elevated temperature. The question is how high above ambient to conduct
the test so as to accelerate the reactions and still keep the results representative of storage at ambient temperature. The
Arrhenius [36] equation described in Fig. 9 can be used to estimate the reaction rates for fuels stored at ambient to
slightly above ambient temperatures. Under this relationship, the reaction rate is accelerated approximately 1.7-3
times for every 10C rise in temperature. The problem is that,
as the temperature rises, reactions that would not normeJly
occur during ambient storage (or would occur with very low
probability) now begin to occur. The high-temperature reactions result in other types of compounds, which can skew the

128

MANUAL

37: FUELS AND LUBRICANTS

k = Ae'^''

or

HANDBOOK

k=A,J^

where:
Ea = activation energy
R = gas constant
T = absolute temperature
A = frequency factor (collision frequency)
Taking the natural logarithm of both sides and rearranging gives:
lnfe=(-Ea/RXl/T) + lnA
Therefore, a plot of In A: versus 1/T gives a straight line whose slope is
equal to -Ea/R and whose intercept is In A
FIG. 9Arrhenius equation.

results of the aging test. Two early studies [37,38] demonstrated the correlation between storage at 43C and ambient
storage. They determined that 13 weeks at 43C is equivalent
to one year at ambient. Over the years, this relationship has
been redefined as 1 week at 43 C is equal to 1 month at ambient. These studies also established storage at 43C as the
standard accelerated storage test, against which all other accelerated storage stability tests are compared. This test works
so well because the test temperature is such a small increase
over ambient that the relative importance of the various reactions that create insolubles are not appreciably changed.
This makes the 43C storage test an ideal research tool for
studying storage stability of diesel fuels.
Ironically, that which makes the 43 C test such a useful research tool also makes it useless for quality assurance and
quzility control applications because of the long test times.
For this reason, m u c h effort has been expended over the past
25-30 years to develop a rapid test for fuel storage stability.
In this context, rapid is generally defined as test times of 16
hours or less. Very little success came of these efforts, with
one exception. The U.S. Navy developed a test method that
was eventucdly standardized as ASTM D 5304 \39'\. The applicability of the test method was demonstrated in a project
conducted during 1992-1993 [40].
Flash Point
Flash point is specified in D 975 primEuily for safety during
transport, storage, and handling. A low flash point fuel can be
a fire hazard, subject to flashing, with possible continued ignition and explosion. Low flash point can also indicate contamination with low-flash fuels such as gasoline. The flash
point of a fuel has no significant relation to the performance
of the fuel in the engine. Auto-ignition temperature is not influenced by variations in flash point.
There are five ASTM test m e t h o d s for measuring flash
point of diesel fuels:
ASTM D 56, Standard Test Method for Flash Point by Tag
Closed TesterThe specimen is placed in the cup of the
tester and, with the lid closed, heated at a slow constant
rate. An ignition source is directed into the cup at regular
interveJs. The flash point is taken as the lowest temperature at which application of the ignition source causes the
vapor above the specimen to ignite.

ASTM D 93, Standard Test Methods for Flash Point by Pensky-Martens Closed Cup Tester^A brass test cup of specified dimensions, filled to the inside msirk with test specimen and fitted with a cover of specified dimensions, is
heated and the specimen stirred at specified rates by either of two defined procedures (A or B). An ignition
source is directed into the test cup at regular intervals
with simultaneous interruption of the stirring until a flash
is detected.
ASrM D 3828, Standard Test Methods for Flash Point by
Small Scale Closed Tester Method AFlash/No Flash Test
A specimen of a sample is introduced by a syringe into the
cup of the selected apparatus that is set and maintained at
the specified temperature. After a specific time a test flame
is applied and an observation made as to whether or not a
flash occurred.
Method BFinite (or Actual) Flash Point^A specimen of a
sample is introduced into the cup of the selected apparatus
that is maintained at the expected flash point. After a specified time a test flame is applied and the observation made
whether or not a flash occurred. The specimen is removed
from the cup, the cup cleaned, and the cup temperature adjusted 5C (9F) lower or higher depending on whether or
not a flash occurred previously. A fresh specimen is introduced and tested. This procedure is repeated until the flash
point is established within 5C (9F). The procedure is then
repeated at 1C (2F) intervals until the flash point is determined to the nearest 1C (2F). If improved accuracy is
desired the procedure is repeated at 0.5C (1F) intervals
until the flash point is determined to the nearest 0.5C
(1F).
ASTM D 6450, Standard Test Method for Flash Point by Continuously Closed Cup (CCCFP) TesterThe lid of the test
chamber is regulated to a temperature at least 18C below
the expected flash point. A 1 mL test specimen of a sample
is introduced into the sample cup, ensuring that both specimen and cup are at a temperature at least 18C below the
expected flash point, cooling if necessary. The cup is then
raised and pressed onto the lid of specified dimensions to
form the continuously closed but unsealed test chamber
with an overall volume of 4.0 0.2 mL. After closing the
test chamber, the temperatures of the test specimen and
the regulated lid are edlowed to equilibrate to within 1C.
Then the lid is heated at a prescribed, constant rate. For the
flash tests, an arc of defined energy is discharged inside the
test chamber at regular intervals. After each ignition, 1.5
0.5 m L of air is introduced into the test chamber to provide
the necessary oxygen for the next flash test. The pressure
inside the continuously closed but unsealed test chamber
remains at ambient barometric pressure. The exceptions
are for the short time during the air introduction and at a
flash point. After each arc, the instantaneous pressure increase above the ambient barometric pressure inside the
test chamber is monitored. When the pressure increase exceeds a defined threshold, the temperature at that point is
recorded as the uncorrected flash point.
Each of these three test methods contains an introduction
that is similar to the following:
This flash point test method is a dynamic test method and
depends on definite rates of temperature increase to control
the precision of the test method. The rate of heating may

CHAPTER
not in all cases give the precision quoted in the test method
because of the low thermal conductivity of certain materials. To improve the prediction of flammability,
Test
Method D 3941, an equilibrium method was developed in
which the heating rate is slower. This allows the vapor
above the test specimen and the test specimen to be at
about the same temperature.
ASTM D 3941, Standard Test Method for Flash Point by the
Equilibrium Method with a Closed-Cup
ApparatusThis
method covers the determination of the flash point of hquids in which the specimen a n d the air/vapor mixture
above it are approximately in temperature equilibrium.
The test method is limited to a temperature range from
32-230F(0-110C).
Method D 3941 should b e used to measure Eind describe the
properties of material, products, or assemblies in response to
heat and flame u n d e r controlled laboratory conditions. It
should not be used to describe or appraise the fire hazard or
fire risk of materials, products or assemblies under actUcJ fire
conditions. However, results of this test may be used as elements of a fire risk assessment that takes into account all of
the factors that are pertinent to a n assessment of the fire hazard of a particular end use.
It is important to note that while D 3941 may be an acceptable alternative m e t h o d for some applications, the
method(s) listed in a given specification, such as D 975,
should not be replaced without prior knowledge and consent
of all interested parties. This is because the measured flash
point of a fuel is dependent not only on the composition of
the fuel but also on the apparatus used to make the measurement. ASTM Manual 9 describes many flash point test methods, both U.S. and international [41]. It also lists pertinent
specifications/standards worldwide.
Lubricity
Diesel fuel functions as a lubricant in certain items of fuel injection equipment such as rotary/distributor fuel p u m p s and
injectors. In limited cases, fuel with very specific properties
can have insufficient lubricating properties that can lead to a
reduction in the normal service life of fuel p u m p s or injectors. Two fuel chciracteristics that affect equipment wear are
low viscosity and lack of sufficient quantities of trace components, which have a n affinity for metal surfaces. If fuel viscosity meets the requirements of a particular engine, a fuel
film is maintained between the moving surfaces of the fuel
system components. This prevents excessive metal-to-metal
contact and avoids premature failure due to wear. Simileirly,
certain surface-active molecules in the fuel (such as acids and
heteroatomics) adhere to, or combine with, metallic surfaces
to produce a protective film that also can protect surfaces
against excessive wear. The concern about fuel lubricity is
limited to the use of fuels with viscosities lower than those
specified for a particulcir engine. Also of concern is the use of
fuels that have been processed in a manner that results in the
elimination of the trace levels of the surface-active species
that act as lubricating agents. Presently, the only fuels of the
latter type shown to have lubricity problems resulted from
sufficiently severe processing to reduce aromatics substantieJly below current levels. Research is in progress to identify
the chciracteristics of such fuels and where the use of a lu-

5: GAS TURBINE

FUELS

129

bricity improver additive is required, to ensure satisfactory


operation in the sensitive areas of the vehicle fuel system
[42].
Work in the area of diesel fuel lubricity is ongoing by several organizations, such as the International Organization for
Standardization (ISO) and the ASTM Diesel Fuel Lubricity
Task Force u n d e r Subcommittee E of Committee D2 [43].
These groups include representatives from the fuel injection
equipment manufacturers, fuel producers, and additive suppliers. The charge of the ASTM task force has been the recommendation of test methods and a fuel specification for
Specification D 975. At this writing, two test methods are approved:
ASTM D 6078, Standard Test Method for Evaluating Lubricity of Diesel Fuels by the Scuffing Load Ball-on-Cylinder Lubricity Evaluator (SLBOCLE)^A 50-mL test specimen of
fuel is placed in the test reservoir of an SLBOCLE and adjusted to the test temperature of 25C. When the fuel temperature has stabilized, 50% relative humidity air is used to
aerate the fuel at 0.5 L/min while 3.3 L/min flows over the
fuel for 15 min. During the remainder of the test sequence,
the 50% relative humidity air flows over the fuel at a rate of
3.8 L/min. A load a r m holding a non-rotating steel ball and
loaded with a 500 g mass is lowered until it contacts a partially fuel immersed polished steel test ring rotating at 525
rpm. The ball is caused to rub against the test ring for a 30s break in period before beginning an incremental-load or
a single-load test. Wear tests are conducted by maintaining
the beJl in contact with the particJly immersed 525- rpm
test ring for 60 s. For incremental load tests, the test ring is
moved at least 0.75 m m for each new load prior to bringing a new ball into contact with the test ring. The tangential friction force is recorded while the ball is in contact
with the test ring. The friction coefficient is calculated
from the tangential friction force. In the incremental-load
test, the m i n i m u m applied load required to produce a friction coefficient greater than 0.175 is an evaluation of the
lubricating properties of the diesel fuel. In the single-load
test, a friction coefficient less than or equal to 0.175 indicated the diesel fuel passes the lubricity evaluation, while a
friction coefficient greater than 0.175 indicated the diesel
fuel fails the lubricity evaluation.
ASTM D 6079 Standard Test Method for Evaluating Lubricity of Diesel Fuels by the High-Frequency Reciprocating Rig
(HFFR)^A 2-mL test specimen of fuel is placed in the test
reservoir of an HFRR and adjusted to either of the staxidard
temperatures (25 or 60C). The preferred test temperature
is 60C, except where there may be concerns about loss of
fuel because of its volatility or degradation of the fuel because of the temperature. When the fuel temperature has
stabilized, a vibrator arm holding a non-rotating steel ball
and loaded with a 200-g mass is lowered until it contacts a
test disk completely submerged in the fuel. The ball is
caused to r u b against the disk with a 1-mm stroke at a frequency of 50 Hz for 75 min. The ball is removed from the
vibrator a r m and cleaned. The dimensions of the major
and minor axes of the wear scar are measured under lOOX
magnification and recorded.
A diagram of the test apparatus a n d a list of the test conditions for D 6078 and D 6079 are given in Figs. 10 and 11, respectively.

130 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


OUTFUTTO
rmcTioM necxMUMNO
DEVICE

LOAD
. " ^ Q

P'O.

3 ^ ^ COtfTACT U>Ap

MEAW-OUTT
FNCUMATIC
PWTOM
S c h e m a t i c D i a g r a m of t h e Scuffing L o a d Ball-on-Cylinder
Lubricity Evaiuator (not including Instrumentation)

MANDREL ASSEMBLY

SCREWS W REQ'a
BUTTON HEAD
8-32

DRIVESHAFT ASSEMBLY

Ring and Mandrel Assembly (Cylinder)


Parameter

Test Conditions Value

Fluid volume
50 1.0 mL
Fluid temperature
25 1C
Conditioned air^
50 1 % relative tiumidity at 25 1C
Fluid pretreatment: 0.50 U min air flowing through and 3.3 L/min air flowing
over the fluid for 15 min
Fluid test conditions: 3.8 L/min air flowing over the fluid
Cylinder rotational speed
525 1 rpm
Applied Load
Break-in period
500 g
Incremental-load test
500 to 5 000 g
Single-load test
user defined'
Test Duration
Break-in period
30 s
Wear tests
60s
*Fifty percent humidity should be achieved using equal volumes of dry and
saturated air. The SLBOCLE has a water column through which air passes and it
is assumed to be saturated when it exits this column.
"The applied load for the single test Is set at the pass/fail requirement for the fuel
being evaluated.
FIG. 1 0 T e s t e q u i p m e n t a n d t e s t c o n d i t i o n s f o r s c u f f i n g l o a d b a l l - o n cylinder lubricity e v a i u a t o r ( D 6 0 7 8 ) .

CHAPTER 5: GAS TURBINE FUELS

131

Lubricity Task Force is also working on possible revisions to


the standard HFRR test to make it more sensitive to low levels of lubricity additive.

Test Plata
Loading

Aromatics

Schematic Diagram of HFRR (not including


instrumentation)
Test Conditions
Fluid volume
Stroke length
Frequency
Fluid temperature

Relative humidity
Applied load
Test duration
Bath surface area

2 0.20 mL
1 0.02 mm
50 1 Hz
25 2C
or
60 2C
>30%
200 1 g
75 0.1 min
6 1 cm^

FIG. 11Test equipment and test conditions for high frequency reciprocating rig (D 6079).

The inclusion of a single fuel specification in the main


table of specification D 975 for Grade No. 2 requires further
research because:
1. the correlation of the data among the two test methods and
the fuel injection equipment needs further clarification,
2. both methods in their current form do not apply to all fueladditive combinations,
3. the reproducibility values for both test methods are large.
In the meantime, the following information may be of use
and serve as a general guideline to fuel suppliers and users.
Westbrook and coworkers recommended that users monitor their fuel injection pumps for possible trends of abnormal
wear rates if the fuel has a scuffing load value between 2000
and 2800 g in Test Method D 6078 [44]. According to this paper, fuels with values below 2000 g will, in all probability,
cause accelerated wear in fuel lubricated rotary-t5Tpe fuel injection pumps. It should be noted that a properly-additized
fuel might provide protection for fuel-wetted components
and yet not produce significant D 6078 test results as compared to the non-additized fuel.
Work at ISO indicates that a fuel with a 450-micron wear
scar diameter or lower value at 60C in Test Method D 6079
(380 micron at 25C) should protect all fuel injection equipment [45]. Other SAE publications present data to show that
some fuels and fuel/additive combinations can have values
above this level and still provide sufficient lubricity protection to the equipment.
Pump stand testing of fuels, although more expensive and
time consuming, is a more accurate means of evaluating the
lubricity of diesel fuel. At the time of this writing, the ASTM
Diesel Fuel Lubricity Task Force is working on the development and standardization of a pump stand test method. The

Diesel fuel contains many types or classes of compounds including paraffins, naphthenes, olefins, and Eiromatics. Compounds that contain heteroatoms such as sulfur, nitrogen,
and oxygen are also present. Aromatics warrant discussion
because 1) they have an effect on the combustion quality of
the fuel, 2) typically, they are the only hydrocarbon type
listed in diesel fuel specifications (including D 975), and 3)
increased amounts of aromatics can have a negative impact
on vehicle emissions.
It is well known that an increase in the total aromatics content of a diesel fuel can (and usually does) have an adverse effect on the ignition quality, i.e., cetane number of the fuel.
Several methods are available for the measurement of aromatic content. They eire described below:
ASTM D1319, Standard Test Method for Hydrocarbon Types
in Liquid Petroleum Products by Fluorescent Indicator AdsorptionApproximately 0.75 mL of sample is introduced
into a special glass adsorption column packed with activated silica gel. A small layer of the silica gel contains a
mixture of fluorescent dyes. When the entire sample has
been adsorbed on the gel, alcohol is added to desorb the
sample down the column. The hydrocarbons are separated
in accordance with their adsorption affinities into aromatics, olefins, and saturates. The fluorescent dyes are also
separated selectively, with the hydrocarbon types, and
make the boundaries of the aromatic, olefin, and saturate
zones visible under ultraviolet light. The volume percentage of each hydrocarbon type is calculated from the length
of each zone in the column.
This test method was originally developed for the analysis
of gasoline (spark ignition engine fuel). It is for determining
hydrocarbon types over the concentration ranges from 5-99
volume % aromatics, 0.3-55 volume % olefins, and 1-95 volume % saturates in petroleum fractions that distill below
315C. The test method may apply to concentrations outside
these ranges, but the precision has not been determined.
Samples containing dark-colored components that interfere
in reading the chromatographic bands cannot be analyzed.
D 1319 was applied to and specified for diesel fuel usually
because no other suitable method was available. As suitable
methods became standardized they grew in use but have not
replaced D 1319 in D 975. This is because the requirement for
aromaticity currently included in D 975 comes from the requirement in 40 CFR Fart 80. Since federal law requires D
1319, it is the method listed in D 975. Method D 5186, described below, is more appropriate for diesel fuel and is often
used in place of D 1319. However, in case of dispute, D 1319,
by virtue of it's status as the legislated method, is considered
the referee method.
ASTM D 5186, Standard Test Method for Determination of
Aromatic Content and Polynuclear Aromatic Content of
Diesel Fuels and Aviation Turbine Fuels by Supercritical
Fluid ChromatographyA small aliquot of the fuel sample
is injected onto a packed silica adsorption column and

132

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

eluted using supercritical carbon dioxide mobile phase.


Mono-aromatics and polynucleEir aromatics in the sample
are separated from non-aromatics and detected using a
flame ionization detector. The detector response to hydrocarbons is recorded t h r o u g h o u t the analysis time. The
chromatographic areas corresponding to the mono-aromatic, polynuclear aromatic, and non-aromatic components are determined and the mass % content of each of
these groups in the fuel is calculated by area normalization.
This test method covers the determination of the total
amounts of mono-ciromatic and polynuclear aromatic hydrocarbon compounds in motor diesel fuels, aviation turbine fuels, and blend stocks by supercritical fluid chromatography (SFC). The range of aromatics concentration to
which this test method is applicable is from 1-75 mass %.
The range of polynuclear aromatic hydrocarbon concentrations to which this test method is applicable is from 0.5-50
mass %.
ASTM D 6591, Standard Test Method for Determination of
Aromatic Hydrocarbon Types in Middle Distillates, High Performance Liquid Chromatography Method with Refractive
Index DetectionA known mass of sample is diluted in the
mobile phase, a n d a fixed volume of this solution is injected into a high performance liquid chromatograph, fitted with a polar column. This column has little affinity for
the non-aromatic hydrocarbons while exhibiting a pronounced selectivity for aromatic hydroccirbons. As a result
of this selectivity, the aromatic hydrocarbons are separated
from the non-aromatic hydrocarbons into distinct bands in
accordcince with their ring structure. At a predetermined
time, after the elution of the di-aromatic hydrocarbons, the
column is back flushed to elute the polycyclic aromatic hydroccirbons as a single sharp band.
Method D 2425 offers a more detailed analysis but requires
considerable investment in i n s t r u m e n t a t i o n a n d sample
preparation time. For these reasons, it is not typically used
for routine ctnalysis of diesel fuel.
ASTM D 2425, Standard Test Method for Hydrocarbon Types
in Middle Distillates by Mass SpectrometryThis
test
method covers an analytical scheme using the mass spectrometer to determine the hydrocarbon types present in
virgin middle distillates 204-343C (400-650F) boiling
range, 5-95 volume % as determined by Method D86.
Samples with average carbon n u m b e r value of paraffins
between C 12 and C 16 and containing petraffins from C I O
and C 18 can be analyzed. Eleven hydrocarbon types are
determined. These include: paraffins, non-condensed cycloparaffins, condensed di-cycloparaffins, condensed tricycloparaffins, alkylbenzenes, indans or tetraJins, or both,
CH n.io (indenes, etc.), naphthalenes, CnH n.14 (acenaphthenes, etc.), CnH .i6 (acenaphthylenes, etc.), and tri-cyclic
aromatics.
Method D 5292 also offers more information than D 1319
or D 5186. However, the results are reported in mole% rather
than mass or volume percent, which are normally required in
specifications.
ASTM D 5292, Standard Test Method for Aromatic Carbon
Contents of Hydrocarbon Oik by High Resolution Nuclear
Magnetic Resonance SpectroscopyThis test method cov-

ers the determination of the aromatic hydrogen content


(Procedures A and B) 8ind aromatic carbon content (Procedure C) of hydrocarbon oils using high-resolution nuclear
magnetic r e s o n a n c e (NMR) spectrometers. Applicable
samples include kerosines, gas oils, mineral oils, lubricating oils, coal liquids, and other distillates that are completely soluble in chloroform and Ccirbon tetrachloride at
ambient temperature. For pulse Fourier-transform (FT)
spectrometers, the detection limit is t5^ically 0.1 mol %
aromatic hydrogen atoms a n d 0.5 mol % aromatic carbon
atoms. For continuous wave (CW) spectrometers, which
are suitable for measuring aromatic hydrogen contents
only, the detection limit is considerably higher and typically 0.5 m o l % aromatic-hydrogen atoms. The reported
units are mole percent, aromatic- hydrogen atoms and
mole% aromatic-Ccirbon atoms. This test method is not applicable to samples containing more than 1 mass % olefinic
or phenolic compounds. This test method does not cover
the determination of the percentage mass of aromatic compounds in oils since NMR signals from both saturated hydrocarbons a n d aliphatic substituents o n aromatic ring
compounds appear in the same chemical shift region. For
the determination of mass or volume% aromatics in hydrocarbon oils, chromatographic or m a s s spectrometry
methods can be used.
It should be noted that there are several standard methods
for the analysis of aromatics. Each method yields a slightly
different result and each is considered appropriate in different situations. One reason for this apparent inconsistency is
that since a single molecule can contain several chemical
moieties, it is possible to include it in several hydrocarbon
classes. For example, a molecule could contain an aromatic
ring, a pciraffinic side chain, and a naphthenic ring. How
should this molecule be classified? A hierarchy was established to address this situation. Under this hierarchy, aromatics are on top, then olefins, followed by naphthenes, and
finally paraffin. Using this hierarchy, the example compound
would be considered an aromatic compound.
The level of aromatics in the fuel is also important as it
relates to the potential for elastomer and seed swell problems. This is especially true for older vehicles/fuel systems.
Depending on the type of elastomer, prolonged exposure to
relatively high levels of aromatics, followed by a sudden decrease in the amount of aromatics, can cause elastomeric
seals to shrink and thus leak. If the elastomers are too old
and have taken a set, they Cctn also crack or break. This phenomenon was widely seen in late 1993 and early 1994 when
mcindated reductions in fuel sulfur and aromatics content
went into effect. In most instances, the problems were
solved by installing new seals made of less sensitive elastomer.
Heat Content
The heat content or heat of combustion of a fuel is the
amount of heat produced when the fuel is burned completely.
Gross and net heats of combustion are the two values measured for the heat of combustion.
The gross heat of combustion is the quantity of energy released when a unit mass of fuel is burned in a constJint volu m e enclosure, with the products being gaseous, other than

CHAPTER 5: GAS TURBINE FUELS 133


water that is condensed to the hquid state. The fuel can be either hquid or soUd, and contain only the elements carbon, hydrogen, nitrogen, and sulfur. The products of combustion, in
oxygen, are gaseous carbon dioxide, nitrogen oxides, sulfur
dioxide, and liquid water.
The net heat of combustion is the quantity of energy released when a unit mass of fuel is burned at constant pressure, with all of the products, including water, being gaseous.
The fuel can be either liquid or solid, and contain only the elements carbon, hydrogen, oxygen, nitrogen, and sulfur. The
products of combustion, in oxygen, are carbon dioxide, nitrogen oxides, sulfur dioxide, and water, all in the gaseous
state. For c o m p o u n d s with the same n u m b e r of c a r b o n
atoms, heat content increases as you go from aromatics to
naphthenes to paraffins, on a weight basis. The reverse order
is correct if you measure on a volume basis. The same is true
for fuels. Denser fuels, such as diesel, have higher heat content on a volume basis. Less dense fuels, such as gasoline,
have higher heat content on a weight basis. Chevron has reported typical heat content values that demonstrate this relationship (see Table 5).
Heat of combustion is usually reported in units of megajoules per kilogram (MJ/kg). Conversion factors to other
units are given in Table 6. Heat of combustion can be estimated by calculation from selected properties or measured
using b o m b calorimetry. The m e t h o d s typically used for
diesel fuel are discussed below.
ASTM D 4868, Standard Test Method for Estimation of Net
and Gross Heat of Combustion of Burner and Diesel Fuels
This test method covers the estimation of the gross and net
heat of combustion of petroleum fuel. The calculations use
the fuel density, sulfur, water, and ash content. The equations for estimating net a n d gross heat of combustion used
in this method were originally published in the National
Institute of Standards and Technology (NIST) Publication
No. 97. The equations are:
Calculate the gross heat of combustion of the fuel corrected
for the sulfur, water, and ash content in accordance" with the
following equation:
Q^ (gross) = (51.916

8.792^2 X 10- ')


[1 (x+y

+s)] + 9.420s

where:
Q

d
X
y
5

= gross heat of combustion at constant volume,


MJ/kg,
= density at 15C, kg/m^,
= mass fraction of water (% divided by 100),
= mass fraction of ash (% divided by 100), eind
= mass fraction of sulfur (% divided by 100).

TABLE 5Typical density and heat content value of


different fuels.
Fuel

Density,
g/cm^

Regular gasoline
Premium gasoline
Jet fuel
Diesel fuel

0.735
0.755
0.795
0.850

Net Heat of
Combustion,
Btu/lb

18
18
18
18

630
440
420
330

Net Heat of
Combustion,
Btu/gal

114
116
122
130

200
200
200
000

TABLE 6Conversion factors for heat


of combustion values.
1 cal (International Table calorie) = 4.1868 J
1 Btu (British thermal unit) = 1055.06 J
1 cal (I.T.)/g = 0.0041868 MJ/kg
1 Btu/lb = 0.002326 MJ/kg

Calculate the net heat of combustion of the fuel corrected


for the sulfur, water and ash content in accordance with the
following equation:
Qp (net) = (46.423 - 8.792^^ x 10"* + 3.70d X 10"^)
X[l

- (x+y

+ s)] + 9.4205 + 2.449;c

where:
Qp = net heat of combustion at constant pressure,
MJ/kg,
d = density at 15C, kg/m^,
X = mass fraction of water,
y = mass fraction of ash, and
s = mass fraction of sulfur.
This test method is useful for estimating, using a minimum
n u m b e r of tests, the heat of combustion of burner and diesel
fuels for which it is not usually critical to obtain very precise
heat determinations. This test method is purely empirical. It
is applicable only to liquid hydrocarbon fuels derived by normal refining processes from conventional crude oil. This test
method is valid for those fuels in the density range from 750
to 1000 kg/m^ and those that do not contain an unusually
high aromatic content. High aromatic content fuels will not
normally meet fuel specification criteria for this method.
This test method is not applicable to pure hydrocarbons. It is
not intended as a substitute for experimental measurements
of heat of combustion.
According to the m e t h o d the estimation of the heat of
combustion of a hydrocarbon fuel from its density, sulfur,
water, and ash content is justifiable only when the fuel belongs to well-defined classes for which a relationship between these quantities have been derived from accurate experimental measurements on representative samples of these
classes. Even in these classes, the possibility that the estimate
may be in error by large amounts for individual fuels should
be recognized. This test method has been tested for a limited
number of fuels from oil sand bitumen and shale oil origin
and has been found to be valid. The classes of fuels used to
establish the correlation presented in this test method are
represented by the following specifications:
1. D 396 Fuel Oils Grades 1, 2, 4 (light), 4, 5 (hght), 5 (heavy),
and 6
2. D 975 Diesel Grades 1-D, 2-D, and 4-D
3. D 1655 Aviation Turbine Jet A, Jet A-1, and Jet B
4. D 2880 Gas Turbine Grades 0-GT, 1-GT, 2-GT, 3-GT and 4GT
5. D 3699 Kerosine Grades 1-K and 2-K
ASTM D 4809, Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision Method)This test method covers the determination of the heat of combustion of hydroccirbon fuels. It was

134 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

designed specifically for use with aviation turbine fuels


when the permissible difference between duplicate determinations is of the order of 0.2%. It can be used for a wide
range of volatile and nonvolatile materials where slightly
greater differences in precision can be tolerated. Under
normal conditions, the method is directly applicable to
such fuels as gasoline, kerosine, Nos. 1 and 2 fuel oil, Nos.
1-D and 2-D diesel fuel and Nos. 0-GT, 1-GT, and 2-GT gas
turbine fuels.
The increased precision is obtained through the improvement of the CcJorimeter controls and temperature measurements.
ASTM D 240, Standard Test Method for Heat of Combustion
of Liquid Hydrocarbon Fuels by Bomb CalorimeterThis
test method covers the determination of the heat of combustion of liquid hydrocarbon fuels ranging in volatility
from that of light distillates to that of residual fuels. Under
normal conditions, this test method is directly applicable
to such fuels as gasoline, kerosine, Nos. 1 and 2 fuel oil,
Nos. 1-D and 2-D diesel fuel, and Nos. 0-GT, 1-GT, and 2GT gas turbine fuels. This test method is not as repeatable
and not as reproducible as Test Method D 4809.
In this method the net heat of combustion is represented
by the symbol Q n and is related to the gross heat of combustion by the following equation:
Q {net, 25C) = Qg {gross, 25C) - 0.2122 X H
where:
Q (net, 25C) = net heat of combustion at constant
pressure, MJ/kg
Q (gross, 25C) = gross heat of combustion at constant
volume, MJ/kg
H = mass % hydrogen in the sample

Total Sulfur
The test methods for measuring total sulfur in diesel fuel, as
prescribed in D 975 are:
ASTM D 2622, Standard Test Method for Sulfur in Petroleum
Products by Wavelength Dispersive X-ray Fluorescence SpectrometryD 2622 is prescribed for the measurement of total sulfur in Grades Low Sulfur No. 1-D and No. 2-D. This
test method covers the determination of total sulfur in liquid petroleum products and in solid petroleum products
that can be liquefied with moderate heating or dissolved in
a suitable organic solvent. The applicable concentration
range will vary to some extent with the instrumentation
used and the nature of the sample. Optimum conditions
will allow the direct determination of sulfur in essentially
paraffinic samples at concentrations exceeding 0.0010
mass%.
ASTM D 129, Standard Test Method for Sulfur in Petroleum
Products (General Bomb Method)The sample is oxidized
by combustion in a bomb containing oxygen under pressure. The sulfur, as sulfate in the bomb washings, is determined gravimetrically as barium sulfate.
D 129 is the prescribed method for the determination of total sulfur in Grades No. 1-D, No. 2-D, and No. 4-D. This test

method covers the determination of sulfur in petroleum


products, including lubricating oils containing additives, additive concentrates, and lubricating greases that cannot be
burned completely in a wick lamp. The test method is applicable to any petroleum product sufficiently low in volatility
that it can be weighed accurately in an open sample boat and
containing at least 0.1% sulfur.
ASTM D 4294, Standard Test Method for Sulfur in Petroleum
Products by Energy-Dispersive X-Ray Fluorescence SpectroscopyThis test method covers the measurement of sulfur in hydroccirbons such as naphthas, distillates, fuel oils,
residues, lubricating base oils, and nonleaded gasoline.
The concentration range is from 0.05-5mass%.
ASTM D 5453, Standard Test Method for Determination of
Total Sulfur in Light Hydrocarbons, Motor Fuels and Oils by
Ultraviolet FluorescenceThis test method covers the determination of total sulfur in liquid hydrocarbons, boiling
in the range from approximately 25400C, with viscosities
between approximately 0.2 and 10 cSt (mm/s^) at room
temperature. This test method is applicable to naphthas,
distillates, motor fuels and oils containing 1.0 to 8000
mg/kg total sulfur.
ASTM D 1266, Standard Test Method for Sulfur in Petroleum
Products (Lamp Method)This test method covers the determination of total sulfur in liquid petroleum products in
concentrations from 0.01-0.4 mass %. A special sulfate
analysis procedure is described in the method that permits
the determination of sulfur in concentrations as low as 5
mg/kg.
ASTM D1552, Standard Test Method for Sulfur in Petroleum
Products (High-Temperature Method)This test method
covers three procedures for the determination of total sulfur in petroleum products including lubricating oils containing additives, and in additive concentrates. This test
method is applicable to samples boiling above 177C
(350F) and containing not less than 0.06 mass% sulfur.
Two of the three procedures use iodate detection. One employs an induction furnace for pyrolysis, the other a resistance furnace. The third procedure uses IR detection following p5Tolysis in a resistance furnace.
The sulfur content of diesel fuel is known to affect particulate matter (PM) exhaust emissions because some of the sulfur is converted to sulfate particles in the exhaust. The
amount that is converted varies by engine; but reducing total
sulfur produces a linear decrease in PM in nearly all engines.
Fuel sulfur can also adversely affect cylinder wear (through
the formation of acids) and deposit formation (many sulfur
compounds are known deposit precursors).
Copper Strip Corrosion
The test method for copper strip corrosion is D 130.
ASTM D 130, Standard Test Method for Detection of Copper
Corrosion from Petroleum Products by the Copper Strip Tarnish Test^A polished copper strip is immersed in a given
quantity of sample and heated at a temperature and for a
time characteristic of the material being tested. At the end
of this period the copper strip is removed, washed, and
compared with the ASTM Copper Strip Corrosion Standards (this is an adjunct available from ASTM Headquarters).

CHAPTER 5: GAS TURBINE FUELS 135


The copper strip corrosion test covers the detection of the
corrosiveness to copper of aviation gasohne, aviation turbine
fuel, automotive gasohne, natural gasoline, or other hydrocarbons having a Reid vapor pressure no greater than 124
kPa(18psi).
Crude petroleum contains sulfur compounds, most of
which are removed during refining. However, of the sulfur
compounds remaining in the petroleum product, some can
have a corroding action on various metals and this corrosivity is not necessarily related directly to the total sulfur content. The effect can vary according to the chemical types of
sulfur compounds present. The copper strip corrosion test is
designed to assess the relative degree of corrosivity of a
petroleum product. It is very rare to find a commercially
available diesel fuel that fails the D 130 test.

such as amyl nitrate, hexyl nitrate, or octyl nitrate, causes a


higher carbon residue value than observed in untreated fuel,
which can lead to erroneous conclusions as to the coke-forming propensity of the fuel. Test Method D 4046 can detect the
presence of alkyl nitrate in the fuel.
The carbon residue value of burner fuel serves as a rough
approximation of the tendency of the fuel to form deposits in
vaporizing pot-type and sleeve-type burners. Similarly, provided alkyl nitrates are absent (or if present, provided the test
is performed on the base fuel without additive) the carbon
residue of diesel fuel correlates approximately with combustion chamber deposits. The carbon residue value of gas oil is
useful as a guide in the manufacture of gas from gas oil. In a
gas turbine it can be an indication of the tendency to form
carbon deposits in the combustor.

Carbon Residue

Ash

Carbon residue is the residue formed by evaporation and


thermal degradation of a carbon containing material. The
residue is not composed entirely of carbon but is a coke that
can be further changed by carbon pyrolysis. The term carbon
residue is retained in deference to its wide common
usage.The test method for carbon residue, as listed in the
diesel fuel specification is D 524.
D 524, Standard Test Method for Ramsbottom Carbon
Residue of Petroleum ProductsThe sample, after being
weighed into a special glass bulb having a capillary opening, is placed in a metal furnace maintained at approximately 550C. The sample is thus quickly heated to the
point at which all volatile matter is evaporated out of the
bulb with or without decomposition while the heavier
residue remaining in the bulb undergoes cracking and coking reactions. In the latter portion of the heating period,
the coke or carbon residue is subject to further slow decomposition or slight oxidation due to the possibility of
breathing air into the bulb. After a specified heating period, the bulb is removed from the bath, cooled in a desiccator, and again weighed. The residue remaining is calculated as a percentage of the original sample, and reported
as Ramsbottom carbon residue. Provision is made for determining the proper operating characteristics of the furnace with a control bulb containing a thermocouple, which
must give a specified time-temperature relationship.
This test method covers the determination of the amount
of carbon residue left after evaporation and pyrolysis of an
oil, and is intended to provide some indication of relative
coke-forming propensity. This test method is generally applicable to relatively nonvolatile petroleum products that partially decompose on distillation at atmospheric pressure.
Petroleum products containing ash-forming constituents as
determined by Test Method D 482 will have an erroneously
high carbon residue, depending upon the amount of ash
formed. Values obtained by this test method are not numerically the same as those obtained by Test Method D 189, or
Test Method D 4530. Approximate correlations have been derived (Fig. 12) but need not apply to all materials that can be
tested because the carbon residue test is applicable to a wide
variety of petroleum products. The Ramsbottom Carbon
Residue test method is limited to those samples that are mobile below 90C. In diesel fuel, the presence of alkyl nitrates

Ash is the non-combustible material in a fuel oil. It can be


present as either solid material or oil or water-soluble metallic compounds. These solid particles are the same as those often designated as sediments. The concern for fuel systems is
that these solid particles can result in wear and erosion ultimately resulting in substandard or failing performance. The
test method for ash is D 482.
ASTM D 482, Standard Test Method for Ash from Petroleum
ProductsThe sample, contained in a suitable vessel, is ignited and allowed to bum until only ash and carbon remain. The carbonaceous residue is reduced to an ash by
heating in a muffle furnace at 775C, cooled and weighed.
This test method covers the determination of ash in the
range 0.001-0.180 mass %, from distillate and residual fuels,
gas turbine fuels, crude oils, lubricating oils, waxes, and
other petroleum products, in which any ash-forming materials present eire normally considered to be undesirable impurities or contaminants. The test method is limited to
petroleum products that are free from added ash-forming additives.
Knowledge of the amount of ash-forming material present
in a product can provide information as to whether or not the
product is suitable for use in a given application. Ash can result from oil or water-soluble metallic compounds or from
extraneous solids such as dirt and rust.
Low-Sulfur Diesel Fuel and Dyed Diesel Fuel
The Clean Air Act Amendments of 1990 established standards
for highway diesel fuel. The standards, in part, made it illegal
as of October 1, 1993, to manufacture, sell, supply, or offer
for sale diesel fuel for highway use that has a sulfur content
greater than 0.05% by weight (this amount is also commonly
expressed as 500 ppm). Similarly, it is illegal for any person
to use fuel that has sulfur content greater than 0.05% by
weight in any highway vehicle. EPA also requires diesel fuel
not intended for use in highway vehicles be dyed in order to
segregate it from highway fuel. Internal Revenue Service
(IRS) regulations require that tax-exempt diesel fuel be dyed
regardless of the sulfur level of the fuel.
The original EPA regulation mandated the addition of a
blue dye to fuel with greater than 500-ppm total sulfur.
However, the Federal Aviation Administration soon ex-

136

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

100
80
60
40
30
20

i
s
s
t

CJ

Q_
i.r

^^.
*^

4
3
2

is
^5

li *o

eo
Q=

1.0
0.8
0.6

0.4
0.3

^
S

0.2

0.02 0.03

0.06

0.10
0.08
0.06
0.04
0.03
0.02

0.01
0.01

0.10

0.2 0.3 0.4 0.60.81.0

3 4

6 8 10

20

30 40 60 80 100

CONRAOSON CARBON RESIDUE, PER CENT BY WEIGHT


(ASTM D 189)

NOTE 1^All dimensions are in millimetres.


FIG. 12Correlation of conradson carbon residue (D 189) with ramsbottom carbon
residue (D 524).

pressed their concern that blue-dyed fuel might be confused


with the most c o m m o n grade of aviation gasoline, which is
also dyed blue. Based on this, the EPA changed the requirements to the use of red dye. The EPA now requires "visible
evidence of the presence of red dye" to identify high sulfur
fuels intended for off-road use. This typically requires that
oil companies add a level of red dye equivalent to 0.75
pounds per 1000 barrels of a solid Solvent Red 26 dye standcird. Solvent Red 26 was selected as the dye standard because it is a unique chemical and available in pure form.
Diesel fuels are actually dyed with liquid concentrates of
Solvent Red 164 because this dye is more fuel soluble and
less costly than the standard. Solvent Red 164 is a mixture
of isomers that are very similar to Solvent Red 26, except
the former incorporates alkyl chains to increase the solubility in petroleum [46].
Under the EPA regulations, any red dye seen in the fuel of
a vehicle operating on-road triggers a n analysis of the fuel's
total sulfur content. Penalties are assessed based on the measured sulfur content of the fuel, rather than the mere presence of red dye.
The IRS tcikes a slightly different path with its regulations.
They require that tax-exempt diesel fuels, both low sulfur and

high sulfur, have a m i n i m u m level of Solvent Red 164 that is


"spectrally equivalent to 3.9 pounds per 1000 barrels" of Solvent Red 26. This is over five times the a m o u n t required under the EPA regulations. The IRS holds that the excessive dye
amount is required to allow detection of attempted tax evasion even after a five-fold dilution of the dyed fuel with
undyed fuel. In practice, diesel fuel is taxed as soon as it
leaves a terminal unless it has been dyed.
The change, in 1993, to low sulfur diesel fuel for on-road
use brought numerous problems. Some of these include:
A marked increase in the number of fuel lubricity related
failures of fuel-wetted engine components. This is primarily attributed to the fact that the hydrotreating required to
remove the sulfur also removes naturally occurring fuel
components that would have improved the lubricity of the
fuel.
The requirements to dye the fuel at the early stages of the
distribution process m e a n that dyed fuel is often transported through pipelines. While not a c o m m o n occurrence,
red dyed diesel fuel has been known to contaminate other
fuels in the system. This occurs either through actual mixing of the diesel with the other product or contamination
of the other product with red dye residue on the wzJls of the

CHAPTER
pipeline following a shipnient of dyed fuel. In the cases
where the contaminated fuel has been aviation fuel, the result is usually the requirement to dispose of the contaminated fuel since most jet engines are not certified to operate on fuel with red dye.
Under the EPA regulations, kerosine used for home heating and other off-road applications must contain the red
dye. Since this fuel is not tcixed, the IRS does not require
the presence of the dye. Unfortunately, the evidence regarding the possible health effects of using red-dyed fuel in
un-vented kerosine heaters is minimal. Therefore, m a n y
users of these heaters are reluctcuit to use red-dyed kerosine. However, if the user wants un-dyed kerosine, they
must pay the tax so that it will not have to be dyed u n d e r
the IRS regulations. Understandably, m a n y kerosine
heater users are upset about having to pay the tcix. The laws
do allow a refund of the tax, however, and many users (and
in some cases, suppliers) are taking the necessary steps to
reclaim those monies. There is also work underway to develop information on the potential health effects of burning the dyed fuel in un-vented heaters. Users are encouraged to check with their fuel suppliers for additional
information.
Seal swell and elastomer compatibility problems brought
about by the reductions in ciromatic content in low sulfur
fuels. This is discussed in the section on aromatics.
It should be noted that the reductions in allowable sulfur
have also had some positive effects. Aside from the obvious
improvements in engine emissions, the hydrotreating required to remove the sulfur often means that the fuel has
significantly better stability characteristics (through the removal of precursors). The concomitant removal of aromatics can also bring some improvement to the ignition quality of the fuel.
The requirement to reduce sulfur levels in diesel fuel is now
a "fact-of-life" throughout the world. At the time of this writing, the EPA is proposing legislation to reduce the maximum
allowable sulfur level to I S p p m b y J u n e 1, 2006 [47]. The primary impetus for this continued reduction in sulfur is the
need to protect exhaust-treatment devices installed on diesel
engines, many of which are poisoned by sulfur.
World Wide Fuel Charter
The World-Wide Fuel Charter was jointly developed by the
E u r o p e a n Automobile Manufacturers Association (ACEA),
the Allieuice of Automobile Manufacturers, the Engine Mcinufacturers Association (EMA), the Japan Automobile Manufacturers Association (JAMA), and numerous associate mem-

5: GAS TURBINE

FUELS

137

bers and supporting organizations [48]. In a letter dated April


2000, the members stated that the "Charter was first established in 1998 to promote greater understanding of the fuel
quality needs of motor vehicle technologies and to harmonize
fuel quality world-wide in accordance with vehicle needs."
The Charter contains four categories of gasoline and diesel
fuel as follows (see Table 7 for a listing of selected diesel fuel
properties):
Category 1: Markets with n o or minimal requirements for
emission control, based primarily on fundamental vehicle/engine performance concerns.
Category 2: Markets with stringent requirements for emission control or other market demands. For example, meirkets requiring US Tier 0 or Tier 1, EURO 1 and 2, or equivalent emission standards.
Category 3: Markets with advanced requirements for emission control or other market demands. For example, markets requiring US California LEV, ULEV, and EURO 3 and
4, or equivalent emission standards.
Category 4: Markets with further advanced requirements
for emission control, to enable sophisticated NOx and particulate matter after-treatment technologies. For example,
markets requiring US California LEV-II, US EPA Tier 2,
and EURO 4.
Premium Diesel Fuel
As discussed above, environmental regulations promulgated
under the Clean Air Act Amendments have resulted in significant changes to the automotive diesel fuel manufactured
and sold in the United States. These changes, coupled with
rapidly changing engine technology, created the need to address several fuel properties to ensure proper performance,
while cJso minimizing engine maintenance problems. There
is also a segment of the automotive diesel fuel market that believes that they can benefit from a fuel supply with properties
different from or in addition to, the m i n i m u m ASTM D 975
specifications. Many fuel suppliers sell such fuels at a higher
price. As a marketing tool, this fuel is often called "premium
diesel fuel." Other terms or descriptions have also been used.
At the time of this writing, two major groups have proposed
definitions for premium diesel. Those two groups are the Nationeil Conference on Weights and Measures (NCWM) and
the Engine Manufacturers Association (EMA). In both cases,
the proposed premium diesel is based on varying one or more
fuel properties.
To ensure that the fuel consumer gets a "premium" product for the higher price, the National Conference on Weights
and Measures (NCWM) took steps to develop a standardized

TABLE 7Selected property specifications from world-wide fuel charter.


Property

Category 1

Category 2

Category 3

Category 4

Cetane Number, min


Cetane Index, min
Sulfur, max, mass %
Lubricity, HFRR scar dia @60C, (xm
Particulates, mg/L
Total Aromatics, mass %

48
45
0.50
400
No Requirement
No Requirement

53
50
0.030
400
24
25

55
52
0.003
400
24
15

55
52
Sulfur-free
400
24
15

138 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 8Diesel fuel properties referenced in NCWM definition


of premium diesel fuel.
Heating Value, Gross,
Btu/gallon, min

D240

Cetane number, min


Low temperature
operability

D613
D 2500 or
D4539

Thermal stability, 180 min.


150C, reflectance, min
Fuel injector cleanliness
Flow loss, % max
CRC rating, % max

D6468

138 700

47.0
2C maximum
above the D 975
tenth percentile
minimum
ambient air
temperature
80%

L-10 Injector
6.0
10.0

definition of premium diesel. An NCWM task force composed of representatives from the oil industry, additive manufacturers, independent labs, and government agencies, with
the assistance of ASTM, prepared a set of requirements to define premium diesel. In late 1997, the NCWM task force recommended that a fuel must meet any two of the five criteria
listed in Table 8 before it can be labeled "premium diesel."
The NCWM adopted the plan at its 84th conference in 1999
[49]. The definition became a model law and was automatically adopted by some states; elsewhere, it will only become
effective if a state specifically adopts it.
The EMA issued a Recommended Guideline (FQP-IA) for
a premium diesel fuel. The proposed values are listed in
Table 9. From the EMA consensus position:
This diesel fuel is considered to be "premium" insofar as it
may assist in improving the performance and durability of
engines currently in use and those to be produced prior to
2004. It is not intended to enable diesel engines to meet any
emissions standard or, in general, to improve engine exhaust emissions... It is intended as a "living document" in
that, as other needs or test procedures are identified, the
recommendation will be upgraded [50].
The most significant aspects of this Consensus Position are
its requirements for a minimum fuel lubricity, increased
cetane number, improved cold weather performance, detergency, thermal stability, minimum energy content, and specifications regarding overall fuel "cleanliness."
Alternative Fuels
As in the early 1980s, research with alternative fuels is again
on the increase. Whereas the earlier work centered on the
suitability of alternative fuels to power diesel engines; most
of the current work is evaluating the potential these fuels offer to reduce engine emissions [51]. Fischer-Tropsch Liquids
and Biodiesel are the fuels that seem to show up the most in
the current literature and reports.
Fischer-Tropsch Synthesis is the process whereby natural
gas or coal is converted into hydrocarbons. The product hydrocarbons are usually upgraded to middle distillate products such as kerosine and diesel fuel. Typically Fischer-Tropsch diesel fuels have high cetane numbers, often greater than
70 cetane, no aromatic compounds, no sulfur, and a density
of around 0.78 kg/L [52]. The Fischer-Tropsch liquids have

been evaluated as a diesel fuel and as a blend component


with conventional petroleum diesel fuel.
Schaberg, et al. [53] tested two variations of the Sasol distillate fuels, a 2-D diesel fuel, a CARB (California Air Resources Board) diesel, and three blends of the Sasol fuel with
the 2-D fuel. The Sasol fuels produced significantly lower engine emissions than the 2-D and CARB fuels. The fuel blends
reduced emissions in proportion to the amount of the Sasol
fuel in the blend. Other resesirchers have shown similar improvements in regulated emissions, with the use of FischerTropsch fuels, as well [54-56]. The most significant potential
problem associated with the use of these fuels is lubricity.
Fischer-Tropsch fuels have very poor lubricity properties.
There may also be some elastomer/seal swell problems, especially in older fuel systems, since these fuels have no aromatic compounds.
Biodiesel is also a potential alternative to conventional,
petroleum-derived diesel. Biodiesel is a renewable source of
energy. In the United States, Biodiesel is a fuel comprised of
mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats, designated BIOO. Biodiesel is registered with the U.S. EPA as a fuel and a fuel additive under
Section 211(b) of the Clean Air Act. There is, however, other
usage of the term biodiesel in the market place. Biodiesel is
typically produced by a reaction of a vegetable oil or animal
fat with an alcohol such as methanol or ethanol in the presence of a catalyst to yield mono-alkyl esters and glycerin. The
finished biodiesel derives approximately 10% of its mass
from the reacted alcohol. The alcohol used in the reaction
may or may not come from renewable resources. Biodiesel
blend is a mixture of biodiesel fuel with petroleum-based
diesel fuel designated BXX, where XX is the volume % of
biodiesel.

TABLE 9EMA recommended guideline (FQP-IA).


Property

Flash point, C, min


Water Eind sediment, % vol, meix
Water, ppm max
Sediment, ppm max
Distillation, C, % vol recovery
90% max
95% max
Viscosity, 40C, cSt
Ash, % mass, max
Sulfur, % mass, max
Copper corrosion, max
Cetane number, min
Cetane index, min
Ramsbottom carbon on
10% residue, % mass, max
API gravity, max
Lubricity, g, min
Accelerated stability, mg/L, max
Detergency
CRC rating, max
Depositing test, % flow loss, max
Low temperature flow, C

Test Method

D93
D2709
D 1744
D 2276 or
D5452
D86
D445
D482
D2622
D 130
D613
D4737
D524
D287
D 6078(1)
D2274
L-10 Injector
D 2500 or
D4539

Requirements

52
0.05
200
10
332
355
1.9^.1
0.01
0.05
3b
50
45
0.15
39
3100
15
slO.O
s6.0
(2)

NOTE: Alternatively, lubricity can be measured by D 6079 with a maximum


wear scar diameter of 0.45 Jim at 60C.
Diesel fuels must pass the Cloud Point (D 2500) or Low Temperature
Flow Test (D 4539) at the use temperature.

CHAPTER 5: GAS TURBINE FUELS 139

OH
O

JL
\ ^ ^

J.
+

"^^lalyst

HO

3(GH30H)

3(RCOOCH3) +
OH

O.^ ^ O

Triglyceride

3 iVIetlianol

"^^*^'^'

3 methyi-estiiers +

Glycerol

R is usually 1 6 - 1 8 carbons with 1 - 3 0 = 0 bonds.

FIG. 13Reactions of vegetable oil to form methyl-esthers.

TABLE 10Detailed requirements for biodiesel (BlOO)."


Property

Flash point
(closed cup)
Water and
sediment
Kinematic
viscosity, 40C
Sulfated ash
Sulfur^
Copper strip
corrosion
Cetane number
Cloud point
Carbon residue"
Acid number
Free glycerin'^
Total glycerin^

Test
Method''

Limits

Units

D93

100.0

minC

D2709

0.050

max % volume

D445

1.9-6.0"

mm 2/s

D874
D2622
D 130

0.020
0.05
No. 3

max % mass
max % mass
max

D613
D2500

40
Report to
customer
0.050
0.80
0.020
0.240

min
C

D4530
D664

max % mass
max mg KOH/g
% mass
%mass

"To meet special operating conditions, modifications of individual limiting


requirements may be agreed upon between purchaser, seller, and manufacturer.
''The test methods indicated are the approved referee methods. Other acceptable methods are indicated in 5.3.
"SeeXl.3.1.
'^Other sulfur limits can apply in selected areas in the United States and in
other countries.
"Carbon residue shall be r u n on the 100% sample (see 5.2.10).
'See Annex 1 for test method. A gas chromatographic technique is being
converted to a standard test method.
*The test m e t h o d is u n d e r ASTM consideration by Subcommittee
D02.04.OL.

Soybean oil is the largest source of biodiesel in the United


States, however, oil from other plants is sometimes used.
Biodiesel is a mixture of fatty acid methyl esters. The oils are
combined with methanol in a process known as transesterification (Fig. 13).
The resulting mixture of fatty acid methyl esters has chemical and physiccJ properties similar to those of conventional
diesel fuel. Provisional Specification 121 is the ASTM specification for Biodiesel Fuel (BlOO) Blend Stock for Distillate
Fuels. (At this writing, ASTM is working to approve PS 121 as
a standard specification.) Table 10 contains the detailed re-

quirements for BlOO as found in PS 121. Diesel engines can


run on B1 GO; however, most of the testing in this country has
been done on blends of biodiesel a n d low sulfur diesel. A
blend of 20% biodiesel with 80% low sulfur diesel (B20) has
been tested in numerous applications across the country. The
limited testing thus far completed has shown that this fuel
produces lower emissions of particulate matter, hydrocarbons, a n d carbon monoxide t h a n conventional diesel fuel.
NOx emissions can be slightly higher thcin with conventional
diesel, unless the fuel system injection timing is optimized
for B20.
BlOO has good lubricity properties and contains essentially
no sulfur or aromatics. However, it has a relatively high pour
point, which could limit its use in cold weather. Biodiesel is
biodegradable, but this property may lead to increased biological growth during storage. Biodiesel is also more susceptible to oxidative degradation than petroleum diesel.
Other eJtemative fuels that have been investigated for use
in diesel engines include ethers, alcohols, naphtha, and various gaseous fuels. Each of these has some advantage (such as
reduced engine emissions) associated with its use. However,
much work remains to be done with these fuels, including
building a distribution infrastructure, before they will be
widely used in diesel engines.

GAS TURBINE FUELS


This section discusses the fuels used in non-aviation (industrial) gas turbine applications. The specification for industrial gas turbine fuels is D 2880, Standard Specification for
Gas Turbine Fuel Oils. Table 11 contains the specific requirements for the fuels covered by D 2880. Comparison of
the specifications for diesel fuels and gas turbine fuels shows
that gas turbine fuels actually have fewer requirements.
Many of the individual property requirements of both specifications are equivalent for corresponding grades. This is
demonstrated in Tablel2. The main differences are due to
operational difference of diesel versus gas turbine. As an example, diesel fuel has a cetane number requirement whereas

140 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 11Detailed requirements for gas turbine fuel oils at time and place of custody transfer to user.'
ASTM
Test Method"

Property

Graded''
No. 0-GT
f
0.05

No. l-GT'^

No. 2-Gr

No. 3-GT

No. 4-GT

38 (100)
38 (100)
55(130)
Flash point C (F) min
D93
66 (150)
0.05
0.05
Water and sediment
D2709
1.0
% vol max
D1796
1.0
Distillation Temperature C (F)
D86
90 % volume recovered
282
min
max
288
338
Kinematic viscosity 2 mm/s^
D445
At40C(104F)
f
1.3
1.9
5.5
min
5.5
max
2.4
4.1
50.0
At 100C (212F) max
50.0
Ramsbottom
0.15
0.35
Carbon residue on 10% distillation
D524
0.15
Residue % mass, max
0.01
0.01
D482
0.01
0.03
Ash % mass, max
Density at 15C k g W
D 1298
max
850
876
-18
D97
-6
Pour pointC (F) max
"To meet special operating conditions, modifications of individual limiting requirements may be agreed upon between purchaser, seller, and manufacturer.
''Gas turbines with waste heat recovery equipment may require fuel sulfur limits to prevent cold end corrosion. Environmental limits may also apply to fuel sulfur in selected areas in the United States and in other countries.
"The test methods indicated are the approved referee methods. Other acceptable methods are indicated in 6.1.
''No. 0-GT includes naphtha, Jet B fuel and other volatile hydrocarbon liquids. No. 1-GT corresponds in general to specification D 396 Grade No. 1 fuel and D
975 Grade 1-D diesel fuel in physical properties. No. 2-GT corresponds in general to Specification D 396 No. 2 fuel and D 975 Grade 2-D diesel fuel in physical
properties. No. 3-GT and No. 4-GT viscosity range brackets specification D 396 Grades No. 4, No. 5 (light). No. 5 (heavy), and No. 6, and D 975 Grade No. 4-D diesel
fuel in physical properties.
"Under United States regulations. Grades No. 1-GT and No. 2-GT are required by 40 CFR Part 80 to contain a sufficient amount of dye Solvent Red 164 so its
presence is visually apparent. At or beyond terminal storage taniks, they are required by 26 CFR Part 48 to contain the dye Solvent Red 164 at a concentration spectrally equivalent to 3.9 lbs per thousand barrels of the solid dye standard Solvent Red 26.
'when the flash point is below 38C (100F) or when kinematic viscosity is below 1.3 mm^/s at 40''C (104F) or when both conditions exist, the turbine manufacturer should be consulted with respect to safe handling and fuel system design.
*For cold weather operation, the pour point should be specified 6C below the ambient temperature at which the turbine is to be operated except where fuel
heating facilities are provided. When a pour point less than 18C is specified for Grade No. 2-GT, the minimum viscosity shall be 1.7 mm^/s and the minimum
90% recovered temperature shall be waived.

TABLE 12Comparison of specification requirements


for selected distillate fuels.
Parameter

D396

D975

D 2069

D 2880

D 3699

Flash point
Water & sediment
Distillation
Viscosity
Carbon residue
Ash
Copper strip corrosion
Density
Pour point
Sulfur
Cetane #
Cloud pt.
Freezing point
Burning quality
Saybolt color
NOTE: An asterisk indicates the property is included in the specification.

gas turbine fuel does not. Because the specifications are so


similar, most fuels sold under one specification would also
meet the requirements of the other. For this same reason, the
properties and test methods for diesel fuel, as discussed
above, are equally applicable to gas turbine fuels.
Gas Turbine Fuel Requirements
Industrial gas turbines are basically the same as aviation gas
turbines in operation. A simple gas turbine has three major

components: compressor, combustor, and turbine. The purpose of the compressor is to raise the pressure of the operating fluid usually a ratio of 10 to 20 to 1. It is desirable to accomplish this pressure increase as efficiently as possible to
maximize the available thrust or horsepower, because the efficiency determines how much horsepower is required for
the compression. The purpose of the combustor is to raise the
temperature of the operating fluid. The combustor inlet temperature depends on the pressure ratio and efficiency of the
compressor. In more complicated cycles some of the heat in
the exhaust is recovered and used to increase the combustor
inlet temperature, which reduces the required temperature
rise across the combustor and thus the amount of fuel required. Current combustor outlet temperatures are in the
1093-1482C (2000-2700F) ranges. The combustor must accomplish this temperature rise efficiently. Current combustion efficiencies are in the 99%-f range at most operating
conditions. Additionally the outlet temperature profiles have
specific requirements.
A gas turbine combustor operates at fuel-air ratios less
than stoichiometric and below the lower flammability level.
Figure 14 is a simplified diagram of how the air is introduced
in a conventional combustor i.e., not a low emission combustor. The figure shows the distribution of air for a combustor with an overall air to fuel ratio of 70 to 1. About four
parts of air per part of fuel are introduced in the swirler to
help stabilize the flame zone. Then, in the primary zone, 12
parts of air per part of fuel are introduced to provide enough

CHAPTER 5: GAS TURBINE FUELS

141

COMBUSTOR AIR DISTRIBUTION


FULL LOAD

46

Parts
Air

OVERALL
AIR-FUEL
RATIO = 70

P = PRIMARY
S = SECONDARY
D = DILUTION OR TERTIARY
SW = SWIRLER
F = FUEL

FIG. 14Simplified diagram of gas turbine.

air to provide approximately the stoichiometric amount of


air required, making a total of 16 parts of air per part of fuel.
In the secondary zone an additional 6 parts of air per of part
of fuel are introduced making a total of 22 parts of air per
part of fuel, which completes the reaction. The rest of the air
(48 parts of air per part of fuel) is used to cool the combustor
walls and to dilute the air-stream temperature down to the
design turbine inlet temperature.
The major difference between an aviation gas turbine and
an industrial gas turbine is that the aviation generates thrust
to propel the airplane by exhausting hot gases at high temperatures and velocities. The aviation turbine section only
has to generate enough horsepower to drive the compressor.
In an industrial gas turbine the gases that would be exhausted in an aviation gas turbine are expanded across additional turbine stages to generate shaft horsepower that can be
used to drive generators, pumps, gas compressor, etc.
Many industrial gas turbines use gaseous fuels but others
use a variety of liquid fuels ranging from naphtha to residual
oils. Aviation gas turbine fuel requirements are quite narrow
because of the varying operating conditions (altitude, temperature, etc.), which impose limitations on volatility, viscosity, distillation range, etc. Industrial gas turbines are usually
stationary. This means atmospheric conditions do not
change as drastically as with aviation gas turbines.
The operating conditions for the combustors for the two
applications vary. Many industrial gas turbines operate at or
necir design point for extended periods where an aviation gas
turbine operates at take-off (full power) for a short time eind
then the power level is reduced to cruise for the duration of
the flight. In the following paragraphs, selected requirements
specific to gas turbine operation will be discussed.
The first consideration is light-off (initiating the combustion process and accelerating the engine to idle). Factors such
as the tjrpe of fuel injection system, fuel viscosity, and fuel
volatility are important. In earlier gas turbines, the fuel injectors or nozzles were of the pressure atomizing type simileir

to those used in some heaters. Lower flow nozzles of this type


are particularly sensitive to viscosity, which is why many engine company specifications have a meiximum viscosity limit
regardless of temperature. More modern fuel injection systems, which utilize air to assist the atomization of the fuel,
are less sensitive to viscosity but some limit is still required.
Another factor to be considered for light-off is the volatility
of the fuel. The initial boiling point of the fuel must be considered because, even if the fuel is well atomized, if it is too
heavy, light-off might not consistently occur.
Smaller gas turbines (<10kW) tend to use distillates, while
larger engines also use a mix of distillates and residuals or
pure residuals. Additional problems resulting from residual
fuels include carbon deposits, increased combustor skin temperatures, and exhaust smoke.
Trace Metal Limits
The effects of trace metals such as sodium, potassium, vanadium and lead on gas turbines are discussed in Appendix X2
of D2880. The sulfur content also is important because of its
interaction with sodium and potassium as well as the effects
on exhaust emissions. These trace metals rarely occur in distillate fuels at the refinery. Since they can be introduced at
some point after the refinery, D2880 specifies that the limits
apply at the entrance of the combustor.
Trace metals refer both to those metals present as metallic
compounds in solution and to metals present in particulates
like rust. They are dissolved or suspended either in the fuel
hydrocarbons or in free water present in the fuel. Although
lower levels of trace metals in a fuel will promote longer turbine service from a corrosion standpoint, the specification of
excessively low levels may limit the availability of the fuel or
materially increase its cost. Table 13 suggests levels of trace
metals that would probably yield satisfactory service.
Sodium and potassium can combine with vanadium to
form eutectics, which melt at temperatures as low as 566C

142

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 13Trace metal limits of fuel entering turbine


combustor(s).''
Trace Metal Limits, mg/kg
Designation
No. 0-GT
No. 1-GT
No. 2-GT
No. 3-GT
No. 4-GT

Vanadium
0.5
0.5
0.5
0.5

Sodium plus
Potassium

Calcium
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
(Consult turbine manufacturers)

Lead
0.5
0.5
0.5
0.5

"Test Method D 3605 may be used for determination of vanadium, sodium,


calcium, and lead.

and can combine with sulfur in the fuel to yield sulfates with
melting points in the operating range of the gas turbine.
These compounds produce severe corrosion, and for turbines
operating at gas inlet temperatures above 650C, additives
that control such corrosion are not yet in general use. Accordingly, the sodium-plus-potassium level must be limited,
but each element is measured separately. Some gas turbine
installations incorporate systems for washing oil with water
to reduce the sodium-plus-potassium level. In installations
where the fuel is moved by sea transport, the sodium-pluspotassium level should be checked prior to use to ensure that
the oil has not become contaminated with sea salt. For gas
turbines operating at turbine inlet gas temperatures below
650C (1200F), the corrosion due to sodium compounds is
of minor importance and can be further reduced by siliconbase additives. A high sodium content is even beneficial in
these turbines because it increases the water-solubility of the
deposits and thereby increases the ease with which gas turbines can be water-washed to obtain recovery of the operating performance.
Calcium is not harmful from a corrosion standpoint; in
fact, it serves to inhibit the corrosive action of vanadium.
However, calcium can lead to hard-bonded deposits that are
not self-spalling when the gas turbine is shut down, and that
are not readily removed by water washing of the turbine. The
fuel washing systems used at some gas turbine installations
to reduce the sodium and potassium level will also significantly lower the calcium content of fuel oil.
Vanadium can form low melting compounds such as veinadium pentoxide that melts at 691C, and causes severe corrosive attack on all of the high temperature alloys used for gas
turbine blades. If there is sufficient magnesium in the fuel, it
will combine with the vanadium to form compounds with
higher melting points and thus reduce the corrosion rate to
an acceptable level. The resulting ash will form deposits in
the turbine and will require appropriate cleaning procedures.
When vanadium is present in more than trace amounts either
in excess of 0.5 mg/kg or a level recommended by the turbine
manufacturer, it is necessary to maintain a weight ratio of
magnesium to vanadium in the fuel of not less than 3.0 in order to control corrosion. An upper limit of 3.5 is suggested
since larger ratios will lead to unnecessarily high rates of ash
deposition. In most cases, the required magnesium-to-vanadium ratio will be obtained by additions of magnesium-containing compounds to the fuel oil. The special requirements
covering the addition of and type of magnesium-containing
additive, or equivalent, shall be specified by mutual agreement between the various interested parties. The additive will

vary depending on the application, but it is always essential


that there is a fine and uniform dispersion of the additive in
the fuel at the point of combustion.
For gas turbines operating at turbine inlet gas temperatures below 650C, the corrosion of the high-temperature EJloys is of minor importance, and the use of a silicon-base additive will further reduce the corrosion rate by absorption
and dilution of the vEinadium compounds.
Lead Ccin cause corrosion and, in addition, it can spoil the
beneficial inhibiting effect of magnesium additives on vanadium corrosion. Since lead is only rarely found in significant
quantities in crude oils, its appearance in the fuel oil is primarily the result of c o n t a m i n a t i o n during processing or
transportation.

ASTM STANDARDS
No.
D 56
D 86
D 93
D 97
D 129
D 189
D 240
D 445

D 482
D 524
D 613
D 976
D 1266
D 1298

D 1319

D 1552
D 2068
D 2274
D 2425
D 2500
D 2622

D 2709

Title
Test Method for Flash Point by Tag Closed Tester
Test Method for Distillation of Petroleum Products
Test Methods for Flash Point by Pensky-Martens
Closed Cup Tester
Test Method for Pour Point of Petroleum Products
Test Method for Sulfur in Petroleum Products
(General Bomb Method)
Test Method for Conradson Carbon Residue of
Petroleum Products
Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by B o m b Calorimeter
Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity)
Test Method for Ash from Petroleum Products
Test Method for Ramsbottom Ceirbon Residue of
Petroleum Products
Test Method for Ignition Quality of Diesel Fuels by
the Cetane Method
Test Method for Calculated Cetane Index of Distillate Fuels
Test Method for Sulfur in Petroleum Products
(Lamp Method)
Test Method for Density, Relative Density (Specific
Gravity), or API Gravity of Crude Petroleum and
Liquid Petroleum Products by Hydrometer Method
Test Method for H y d r o c a r b o n Tjrpes in Liquid
Petroleum Products by Fluorescent Indicator Adsorption
Test Method for Sulfur in Petroleum Products
(High-Temperature Method)
Test Method for Filter Plugging Tendency of Distillate Fuel Oils
Test Method for Oxidation Stability of Distillate
Fuel Oil (Accelerated Method)
Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry
Test Method for Cloud Point of Petroleum Products
Test Method for Sulfur in Petroleum Products by
Wavelength Dispersive X-ray Fluorescence Spectrometry
Test Method for Water and Sediment in Middle Distillate Fuels by Centrifuge

CHAPTER
D2887

Test Method for Boiling Range Distribution of


Petroleum Fractions by Gas Chromatography
D 3117 Test Method for Wax Appearance Point of Distillate
Fuels
D 3828 Test Methods for Flash Point by Small Scale Closed
Tester
D 3941 Test Method for Flash Point by the Equilibrium
Method with a Closed-Cup Apparatus
D 4052 Test Method for Density a n d Relative Density of
Liquids by Digital Density Meter
D 4294 Test Method for Sulfur in Petroleum Products by
Energy-Dispersive X-Ray Fluorescence Spectroscopy
D 4530 Test Method for Determination of Ccirbon Residue
(Micro Method)
D 4539 Test Method for Filterability of Diesel Fuels by
Low-Temperature Flow Test (LTFT)
D 4625 Test Method for Distillate Fuel Storage StabiUty at
43C(110F)
D 4737 Test Method for Calculated Cetane Index by Four
Variable Equation
D 4809 Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision
Method)
D 4860 Test Method for Free Water and Particulate Cont a m i n a t i o n in Mid-Distillate Fuels (Clear a n d
Bright Numerical Rating)
D 4868 Test Method for Estimation of Net and Gross Heat
of Combustion of Burner and Diesel Fuels
D 5186 Test Method for Determination of Aromatic Content and Polynuclear Aromatic Content of Diesel
Fuels and Aviation Turbine Fuels by Supercriticcd
Fluid Chromatography
D 5292 Test Method for Aromatic Carbon Contents of Hydrocarbon Oils by High Resolution Nuclear Magnetic Resonance Spectroscopy
D 5304 Test Method for Assessing Distillate Fuel Storage
Stability by Oxygen Overpressure
D 5453 Test Method for Determination of Total Sulfur in
Light Hydrocarbons, Motor Fuels and Oils by Ultraviolet Fluorescence
D 5771 Standard Test Method for Cloud Point of Petroleum
Products (Optical Detection Stepped Cooling
Method)
D 5772 Test Method for Cloud Point of Petroleum Products
(Linear Cooling Rate Method)
D 5773 Test Method for Cloud Point of Petroleum Products
(Constant Cooling Rate Method)
D 5949 Test Method for Pour Point of Petroleum Products
(Automatic Pressure Pulsing Method)
D 5950 Test Method for Pour Point of Petroleum Products
(Automatic Tilt Method)
D 5985 Test Method for Pour Point of Petroleum Products
(Rotational Method)
D 6078 Test Method for Evaluating Lubricity of Diesel Fuels by the Scuffing Load Ball-on-Cylinder Lubricity
Evaluator (SLBOCLE)
D 6079 Test Method for Evaluating Lubricity of Diesel Fuels by the High-Frequency Reciprocating Rig
(HFFR)
D 6217 Test Method for Particulate Contamination in Middle Distillate Fuels by Laboratory Filtration

D 6426
D 6450
D 6591

5: GAS TURBINE

FUELS

143

Test Method for Determining Filterability of Distillate Fuel Oils


Test Method for Flash Point by Continuously
Closed Cup (CCCFP) Tester
Test Method for Determination of Aromatic Hydrocarbon Types in Middle DistillatesHigh Perform a n c e Liquid Chromatography Method with Refractive Index Detection

REFERENCES
[1] Hyne, N. J., "Petroleum," Comptons Encyclopedia, Vol. 18, Encyclopedia Britannica, Inc., Chicago, 1991, pp. 263-264.
[2] Hobson, G. D. and Pohl, W., Modem Petroleum Technology,
Fourth Edition, Applied Science Publishers, Ltd. on behalf of
The Institute of Petroleum, London, 1975.
[3] Diesel Fuel Injection, 1st edition, U. Adler, Ed., Robert Bosch,
GmbH, 1994.
[4] Owen, K. and Coley, T., Automotive Fuels Handbook, Society of
Automotive Engineers, Inc., Warrendale, PA, 1990.
[5] Energy Information Administration, "Annual Energy Review,"
U.S. Department of Energy, 1999.
[6] Manual on Significance of Tests for Petroleum Products, 6th ed.,
G. V. Dyroff, Ed., ASTM International, West Conshohocken, PA,
1993.
[7] Dom, P., et. al., "The Properties and Performance of Modern Automotive Fuels," SAE Report No. 861178, Society of Automotive
Engineers, Warrendale, PA, 1986.
[8] Clerc, J. C, "Cetane Number Requirements of Light Duty Diesel
Engines at Low Temperatures," Report No. 861525, Society of
Automotive Engineers, Warrendale, PA, 1986.
[9] "Diesel Fuels: Performance and Characteristics," SAE SP-675,
Society of Automotive Engineers, Warrendale, PA, 1986.
[10] Pande, S. G. and Hardy, D. R., " Ap Practical Evaluation of Published Cetane Indices," Fuel, Vol. 69, No. 4, April 1990, pp.
437-442.
[11] Gulder, O. M., et. al,, "Ignition Quality Rating Methods for
Diesel FuelsA Critical Appraisal," SAE No. 852080, Society of
Automotive Engineers, Warrendale, PA, 1985.
[12] Manual on Significance of Tests for Petroleum Products, 6th ed.,
G. V. Dyroff, Ed., ASTM International, West Conshohocken, PA,
1993.
[13] Manual on Significance of Tests for Petroleum Products, 6th ed.,
G. V. Dyroff, Ed., ASTM International, West Conshohocken, PA,
1993.
[14] Westbrook, S. R., et. al., "Fuel System Design Considerations for
Diesel and Gas Turbine Engine Powered Military Vehicles," Proceedings of the Second International Conference on Long-Term
Storage Stabilities of Liquid Fuels, Southwest Research Institute,
San Antonio, TX, 1986, pp. 416-425.
[15] "Diesel Fuel Low-Temperature Operability Field Test," Coordinating Research Council Report No. 528, Coordinating Research Council, Inc., Atlanta, GA.
[16] Chandler, J. E., "Comparison of All-Weather Chassis Dynamometer Low-Temperature Operability Limits for Heavyand Light-Duty Trucks with Standard Laboratory Methods,"
SAE Report No. 962197, Society of Automotive Engineers, Warrendale, PA, 1999.
[17] Chandler, J. E., "Evaluation of Faster LTFT and SFPP for Protection of Low Temperature Operability in North American
Heavy Duty Diesel Trucks," SAE Report No.932769, Society of
Automotive Engineers, Warrendale, PA, 1993.
[18] Chandler, J. E. and Zechman, I. A., "Low-Temperature Operability Limits of Late Model Heavy-Duty Diesel Trucks and the
Effect Operability Additives and Changes to the Fuels Delivery

144 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


System Have on Low-Temperature Performance," SAE Report
No.2000-01-2883, Society of Automotive Engineers, Warrendale, PA, 2000.
[19] "The Cold Filter Plugging Point of Distillate Fuels," A European
Test Method, CEC Report No. P-01-74, Coordinating European
Council, Leicester, UK, 1974.
[20] Coley, T., et. al., "New Laboratory Test for Predicting Low-Temperature Operability of Diesel Fuels," Journal of the Institute of
Petroleum, Vol. 52, No. 510, June 1966.
[21] Hiley, R. W., "Filterability of Degraded Fuels," Proceedings of the
2nd International Conference on Long-Term Storage Stabilities of
Liquid Fuels, San Antonio, TX, July 29-August 1, 1986.
[22] Beal, E. J., Hughes, J. M., and Hardy, D. R., "An Improved Fuel
Filterability Test," Proceedings of the Sixth International Conference on Stability and Handling of Liquid Fuels, Vancouver, B.C.,
Canada, October 1997.
[23] Pedley, J., et. al., "Storage Stability of Petroleum-Derived Diesel
Fuel," Fuel, Vol. 68, 1989, pp. 27-31.
[24] Taylor, W. F. and Frankenfeld, J. W., "Chemistry and Mechanism of Distillate Fuel Stability," Proceedings of the Second International Conference on Long Term Storage Stabilities of Liquid
Fuels, San Antonio, TX, July 1986.
[25] Beaver, B., "Long Term Storage Stability of Middle Distillate
Fuels from a Chemical Mechanistic Point of View. Part 1," Fuel
Science and Technology International, Vol. 9, No. 10, 1991, pp.
1287-1335.
[26] Beaver, B., "Long Term Storage Stability of Middle Distillate Fuels from a Chemical Mechanistic Point of View. Part 2," Fuel Science and Technology International, Vol. 10, No. 1, 1992, 1-37.
[27] Wechter, M. A. and Hardy, D. R., "The Use of Macromolecular
Oxidatively Reactive Species (SMORS) to Predict Storage Stability of Mid-Distillate Diesel Fuels," Proceedings of the 4th International Conference on Stability and Handling of Liquid Fuels,
Orlando, FL, November, 1991.
[28] Henry, C. P., "The du Pont F21 149C (300F) Accelerated StabiUty Test," Distillate Fuel Stability and Cleanliness, ASTM STP
751, L. L. Stavinoha and C. P. Henry, Eds., ASTM International,
West Conshohocken, PA, 1981, pp. 22-33.
[29] ibid.
[30] Research Report RR:D02-1463, ASTM International, West Conshohocken, PA.
[31] Stavinoha, L. L. and Westbrook, S. R., "Accelerated Stability
Test Techniques for Middle Distillate Fuels," Distillate Fuel Stability and Cleanliness, ASTM STP 751, L. L. Stavinoha and C. P.
Henry, Eds., ASTM International, West Conshohocken, PA,
1981, pp. 3-21.
[32] Bacha, J. D. and Lesnini, D. G., "Diesel Fuel Thermal Stability at
300F," Proceedings of the 6th International Conference on Stability and Handling of Liquid Fuels, Vancouver, B.C. Canada, October 13-17, 1997, pp. 671-684.
[33] Henry, C. P., "The du Pont F21 149C (300F) Accelerated StabiUty Test," Distillate Fuel Stability and Cleanliness, ASTM STP
751, L. L. Stavinoha and C. P. Henry, Eds., ASTM International,
West Conshohocken, PA, 1981, pp. 22-33.
[34] White, E. W., " A Study of Test Variables Affecting Results Obtained in the ASTM D 2274 Accelerated StabiUty Test," Proceedings of the Second International Conference on Long-Term Storage Stabilities of Liquid Fuels, San Antonio, TX, October 1986.
[35] White, E. W. and Bowen, R. J., "A Study of Variables Affecting
Resuhs Obtained in the ASTM D 2274 Accelerated Stability
Test; Parts 2 & 3-Effects of Selected Chemical and Physical Factors," Proceedings of the Third International Conference on Stability and Handling Liquid Fuels, London, U. K., September
13-16, 1988.
[36] Chang, R., Chemistry-5th ed., McGraw-Hill, New York, 1994.
[37] Anon., "Storage Stability of Distillate Fuels and Blends," Bureau
of Mines Summary Report 1, Petroleum Experiment Station,

[38]

[39]

[40]

[41]
[42]

[43]

[44]

[45]

[46]

[47]

[48]

[49]

[50]
[51]

[52]

[53]

[54]

[55]

[56]

Bartlesville, OK; WPRA-BuMines Cooperative Distillate Fuel


Storage Stability Program, published by Western Petroleum Refiners Association, Tulsa, OK, 1956.
Garner, M. Q. and White, E. W., "Correlation of Long-Term
Storage and Accelerated Stability Tests," Distillate Fuel Stability
and Cleanliness, ASTM STP 751, L. L. Stavinoha and C. P. Henry,
Eds., ASTM International, West Conshohocken, PA, 1981, pp.
34-46.
Hardy, D. R., Hazlett, R. N., Beal, E. J., and Burnett, J, C , "Assessing Distillate Fuel Storage Stability by Oxygen Overpressure," Energy and Fuels, Vol. 3, No. 1, 1989, pp. 20-23.
Turner, L. M., et. al., "Use of ASTM D 5304 in Assessing Unstable Diesel Fuel," Proceedings of the Fifth International Conference
on Stability and Handling of Liquid Fuels, Rotterdam, the
Netherlands, October 3-7, 1994.
Wray, H. A., "Memual on Flash Point Standards and Their Use,"
Manual #9, ASTM International, West Conshohocken, PA, 1992.
ASTM D 975-98b, Appendix X3, Annual Book of ASTM Standards, Vol 05.01, ASTM International, West Conshohocken, PA,
1998.
Nikanjam, M., Crosby, T., Henderson, P., Gray, C , Meyer, K.,
and Davenport, N., "ISO Diesel Fuel Lubricity Round Robin
Program," SAE Paper No. 952372, SAE Fuels and Lubricants
Meeting, October 16-19, 1995, Toronto, Canada.
Westbrook, S. R, et. al., "Survey of Low Sulfur Diesel Fuels and
Aviation Kerosines from U.S. Military Installations," SAE Technical Paper 952369, Society for Automotive Engineers, Warrendale, PA 1995.
Nikanjam, M., Crosby, T., Henderson, P., Gray, C , Meyer, K.,
and Davenport, N., "ISO Diesel Fuel Lubricity Round Robin
Program," SAE Paper No. 952372, SAE Fuels and Lubricants
Meeting, October 16-19, 1995, Toronto, Canada.
Bacha, J., Blondis, L., Freel, J., Hemighaus, G., Hoekman, K.,
Hogue, N., et al., Diesel Fuels Technical Review (FTR-2), Chevron
Products Company, Sein Francisco, CA, 1998.
"Proposed Heavy-Duty Engine and Vehicle Standards and Highway Diesel Fuel Sulfur Control Requirements," United States
Environmental Protection Agency, EPA420-F-00-022, May
2000.
The interested reader can find additional information at the following internet sites: www.acea.be; www.autoalliance.org;
www.engine-manufacturers.org.
Handbook 130, "Uniform Laws and Regulations in the Areas of
Legal Metrology and Engine Fuel Quality" (2000 Edition), as
adopted by the 84th National Conference on Weights and Measures, 1999.
EMA Consensus Position, Joint EMA/TMC P u m p Grade Specification for Premium Diesel Fuel.
Jett, B. T. and Kirkpatrick, A. T., "Alternative Fuels for DI Engines," SAE No. SP-1412, Society of Automotive Engineers,
Warrendale, PA, 1999.
Grimes, G., "Economics and Experience of Blending FischerTropsch Diesel at Paramount Petroleum," presented at Gas-toLiquids Processing 99, May 17-19, 1999, San Antonio, TX.
Schaberg, P. W., et al, "Diesel Exhaust Emissions Using Sasol
Slurry Phase Distillate Process Fuels," SAE No. 972898, Society
of Automotive Engineers, Warrendale, PA, 1997.
Clark, N. N., et. al., "Transient Emissions Comparisons of Alternative Compression-Ignition Fuels," SAE No. 1999-01-1117, Society of Automotive Engineers, Warrendale, PA, 1999.
Clark, N. N., et. al., "On-Road Use of Fischer-Tropsch Diesel Fuels," SAE No. 1999-01-2251, Society of Automotive Engineers,
Warrendale, PA, 1999.
Mintz, M. M., Wang, M. Q., and Vyas, A. D., "Fuel-Cycle Energy
and Emissions Impacts of Propulsion System/Fuel Alternatives
for Tripled Fuel-Economy Vehicle," SAE Report No. 1999-011118, Society of Automotive Engineers, Warrendale, PA, 1999.

MNL37-EB/Jun. 2003

Introduction to Marine
Petroieum Fuels
Matthew F. Winkler^

T H E MODERN PETROLEUM INDUSTRY began during the late 19th

century, although small quantities of petroleum were obtained as early as the 14th century. In Pennsylvania, Edwin
Drzike drilled the first oil well in 1859, striking oil at a depth
of 21 m. Drake's oil well was generally accepted as the start of
the petroleum industry. Kerosine or lamp oil was the object
of the early refining industry. The simple distillation process
was conducted to obtain as m u c h lamp oil as possible from
the Pennsylvania crude oil.
In 1870, the S.S. Constantine was the first of many sea vessels converted from coal to fuel oil. While trading in t h e
Caspian Sea, the vessel burned the residue from refined Russian crude oil. Early oil burners were primitive a n d ineiBcient, b u t the crude oil was plentiful a n d n o attempt was
m a d e to b u m the fuel oil economiccJly.
In the early years of oil firing, t h e marine industry a n d
Lloyd's Register considered oil-fired instcJlations as experimental, with the vast majority of vessels still powered by coal
at t h e end of the 19th century.
Early 20th century fuel oils were used to a greater extent
in steam boilers and the marine industry experimented with
oil-fired diesel engines in the M/T Vulcanus in 1910 and the
MA'^ Seletndia in 1911. Then, during the period u p to the
outbreak of the first World War, fuel oil was used increasingly in Marine Merchant vessels, predominantly in steam
boilers.
In the early 1920s, zJmost all motor ships r a n on a distillate
fuel CcJled "diesel oil" while the oil-fired steam ships burned
a residual fuel called "boiler fuel." The quality difference between the diesel oil and the boiler fuel was considerable.
In t h e mid-1920s, some m o t o r ships h a d experimented
with burning boiler fuel in the m a i n a n d auxiliary engines.
However, there was no commercial benefit in burning boiler
fuel, since the smedl price differential between diesel fuel cind
boiler fuel was offset by the increased mainteneince costs (resulting from burning boiler fuel).
By the beginning of World W a r II, about half of the world
marine fleet was oil fired. Of those ships, half were steam a n d
half were diesel powered.
As society increased the usage of distillate fuels for automotive, truck, railroad, and aircrzift, the increasing demand
for distillate fuels increased the cost differential between distillate fuels and residuals. This economic incentive prompted
the Mcirine Industry to improve t h e technical feasibility of
burning residual fuels (boiler fuels) in marine diesel engines.
' Vice President, Seaworthy Systems, Inc., P.O. Box 965, Essex, CT
06426.

In the late 1940s and throughout the 1950s, motor ship fuel
systems a n d marine diesel engines struggled to operate on
residual fuels a n d to control reliability a n d m a i n t e n a n c e
costs. The successful combination of modified diesel engines,
improved fuel handling, a n d purification systems, together
with, new, reformulated cylinder lube oils led to the economic use of residual fuels in motor ships.
By the mid-1960s, about half of the world merchant fleet
tonnage was powered by diesel engines. Then, the distillate
and residual fuel costs were jolted sharply upward in 1973
and again in 1979 by t h e Middle Eastern oil suppliers restricting oil supplies and raising crude oil prices. This caused
the metrine fuel expenditure to become a significemt factor in
the ship owner's operating costs, and caused overeJl propulsive efficiency to take on renewed significance. The result
was the rapidly declining popularity of steam-powered vessels. The m u c h m o r e thermally efficient a n d economical
diesel engine led to the dominant position in merchant vessels that it still enjoys today.
The goal of m o d e m m a r i n e diesel engines is to operate
with fuel efficiency a n d reability on cracked a n d heavier
residual fuels. Marine residual fuels provide the main source
of energy that is used to transport the world's sea trade. More
ton-miles are moved by ship than by all other transportation
means combined. Therefore, marine fuels have become even
more importcint today to world trade.

PETROLEUM CRUDE OIL REFINING


Crude oil must be carefully refined to produce the main usable products, such as gases, gasoline, kerosine, jet fuels,
diesel fuels, lubricating oil base stocks, petrochemical feed
stocks, waxes, bitumens, residucJ fuels, and even petroleum
coke. The method and degree of the refining of crude oil a n d
its inherent properties determine the quality and quantity of
any petroleum product produced.
Refining, design, a n d production of main petroleum products are dictated by the local, national, or international requirements for light and middle distillate products as well as
for petrochemiceJ feed stocks, which are the higher profit
products produced from crude oil. Recently, govemmentcJ
regulations to reduce air pollution have controlled sulfur,
carbon/aromatic a n d oxygen content, etc., of distillate and
residual fuels.
The basic refining processes are distillation, cracking,
blending, and storage.

145
Copyright'

2003 by A S I M International

www.astm.org

146 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Distillation
Fractional or atmospheric distillation is the oldest and most
basic refining process. The heated crude is charged to the
tower under pressure and a portion flashes to vapor while the
rest stays in the tower as a liquid residue. It consists of boiling
the crude oil in a pipe-still at atmospheric pressure up to
371F. Then the hydrocarbon vapors are directed to a fractionating tower, as shown in Fig. 1. As the various lighter hydrocarbons of the crude oil vaporize at different rates, the
lighter, more volatile vapors rise high in the tower before condensing and being drawn off. The heavier, less volatile vapors
condense and are collected lower in the tower. The residual
fraction is drawn off at the bottom. The fractions drawn from
the tower are called straight-run or virgin products.
In the 1950s, '60s, and early '70s, straight-run fuels produced from atmospheric distillation were the main residual
fuels used in marine diesel engines. Straight-run fuels provided good ignition quality, clean combustion, ease of fuel
handling, ease of water separation, storage stability, and
solid compatibility. Since the density was usually below 985
Kg/m^, the shipboard settling tanks and old style centrifugal
purifiers provided adequate treatment to remove water and
sediment from the fuel.
At complex refineries, the next refining process is vacuum
distillation of the heavy bottoms from the atmospheric distillation unit. This process is a modified atmospheric process
where the pressure in the fractionating tower is reduced below atmospheric to a partial vacuum, as in Fig. 2. The atmospheric tower residual is the feed stock for the vacuum distillation process to yield additional heavy distillates, and will
further concentrate the metals and carbon content into the
vacuum bottoms. The vacuum bottom residuals are generally
used as feed stocks for other refinery processes. They are generally not available as marine fuels due to the very high viscosity. The vacuum bottoms can be further refined by using

another (secondary) process called "viscosity breaking" or


"visbreaking." In this process, the vacuum bottoms are
heated to a higher temperature and higher pressure for
cracking, although not as high as in the thermal cracking process. The high viscosity feed stock is converted to a residual
fuel that is much lower in viscosity. While this visbroken fuel
could be used as marine residual fuel with little or no blending with a lower viscosity distillate, it has higher density,
higher carbon content, higher asphaltenes, and poorer ignition quality characteristics. Visbroken fuels are usually less
stable and less compatible with other residuals than the original vacuum feed stock. These characteristics can present
problems for the fuel handling, fuel purification, and diesel
combustion process, which could lead to vessel delays and increased maintenance for the diesel engine.
Cracking
When heat is applied to hydrocarbons, their molecular energy increases and these molecules move faster. Additionally,
if pressure is applied to the liquid hydrocarbon and temperatures are increased further, the energy within the molecules
can rupture the Ccirbon-carbon and carbon-hydrogen bonds,
and the molecules "crack" into more, smaller molecules that
have different chemical structures. Cracked products are hydrogen deficient compared to straight-run products of the
same boiling range and some of the new, smaller molecules
are unsaturated. Further, these unsaturated molecules tend
to be more volatile and can be more unstable.
Two basic cracking processes can be used. The older of the
two cracking processes is thermal cracking, which typically
occurs at about 13 bar and 520-560C. The long-chain residual oil molecules are cracked or broken, producing some
short chain molecules and additional long-chain molecules.
These cracked hydrocarbons are then vaporized in a flash
chamber and flow to the fractionating tower where they are

GASEOUS

FRACTIONING
TOWER

GASOLINE
NAPHTHA
KEROSENE
CRUDE
HEATER

NO. 2
DISTILLATE

REDUCED CRUDE
NO. 5 - 6 RESIDUE

FIG. 1Atmospheric distillation of crude oil.

_.CRUDE

OIL

CHAPTER 6: INTRODUCTION

TO MARINE PETROLEUM FUELS

147

VACUUM
DISTILLATION
CHARGE
HEATER

HEAVY
^
DISTILLATE

REDUCED
- CRUDE
OIL

VACUUM BOTTOMS

GASOLINE

"A,^

VISBREAKER
BLENDED WITH
CUTTING STOCKSNO. 6 EUEL OIL

DISTILLATE-

"^y"
RESIDUUM
FIG. 2Vacuum distillation.

condensed to produce additional light and heavy distillates.


Therefore, thermal cracking increases the yield of distillate
fuels from crude oil and reduces the yield of residual fuels.
Thermal cracking concentrates metallic content, carbon content, and asphaltene content into the residual fuel, which reduces combustion quality, increases carbon deposits, increases sulfur emissions, and decreases stability and
compatibility of the thermally cracked residual.
The more modem cracking process uses a catalyst to reduce the temperatures and pressures at which hydrocarbon
cracking occurs and, therefore, has been named (fluidic) catalytic cracking, or FCC, as shown in Fig. 3. Catalytic cracking
used a powdered (Quidized) catalyst, typically an alumina-silica based material, which is in direct contact with the liquid
hydrocarbon feed stock. By definition, a catalyst is a substance that aids and accelerates a chemical reaction, but
which itself undergoes no permanent compositional change.
When kept in constant agitation and circulation by air, steam
or hydrocarbon vapor, the fine powdered catalyst flows like a
fluid. In the beginning of the FCC process, hot, preheated hydrocarbon feed stock enters the reactor and is mixed with
hot, regenerated, powdered catalyst. Within the FCC reactor,
the hot feed stock vaporizes and fluidizes the catalyst at the
same time. Cracking then takes place within the reactor and
the hot, cracked hydrocarbon vapors pass into the fractionating tower. These lighter, cracked vapors are then separated
into gases, gasoline components, light gas oil, heat oil, and a
heavier product known as cycle oil.
The catalyst works in a continuous cycle. During the cracking reaction, the powdered catalyst particles become Ccirbon

coated and fall to the bottom of the reactor. The carbon coating is removed in the regenerator, since the catalyst is expensive. Once cleaned, the regenerated catalyst returns to the incoming hydrocarbon feed stock to start the cycle over.
During the FCC process, a small amount of slurry oil is produced that contains small particles of catalyst known as cat
fines. The slurry oil is normally decanted to reduce the concentration of "cat fines" and then the slurry oil is blended into
the residual fuel stream. A number of cases have been documented where catalyst fines have been delivered to ship owners in large quantities. These catalyst particles Eire very heird
and abrasive and have caused rapid and severe wear to fuel
injection pumps, fuel injectors, cylinder liners, piston rings,
piston grooves, and stuffing box seals. This is most evident
where conventional centrifugation and filtration have been
ineffective. Effective five to seven micron filtration of the
residual fuels has proven to control damages from cat fines.
Hydrocracking is a process that uses high pressures and
the addition of hydrogen to crack refinery residues and to upgrade the resulting products through the addition of hydrogen. Lighter hydrocarbon products exhibit lower viscosities
and lower sulfur levels because of hydrocracking. Since hydrogen is added during the process, this process is more expensive than thermal or catalytic cracking.
Refinery Blending and Storage
Marine fuel oils are blends of products from several different
processes. Combustion characteristics, handling properties,
stability characteristics, and storage stability are all affected

148 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

FRACTIONING
TOWER
GASOLINE
REACTOR

NO 2
DISTILLATE
- -e-ATALYST-

HEAVY
GAS OIL

FIG. 3Fluidic catalytic cracking.

by the composition of the blend. The blending processes begin at the refinery. Heavy products produced at the refinery
cire expected to be in the residual fuel blend to varying degrees. The blending process allows lower quality residuEils to
be converted into more suitable fuel oils by the addition of
small qucintities of lighter cutter stock, such as light or heavy
distillates, or by adding cycle oils. When distillate/residual
blends eire made, the solubility of the different components in
each other is important. When components Eire completely
soluble, the blend is considered compatible. Whenever a
blend is contemplated, the compatibility of the resulting
blend must be eveduated beforehand to prevent incompatibility problems that can cause excessive sludge accumulation
in storage, centrifugation, and filtration, and stratification in
the storage tanks.
As the refinery processes improve, and as crude oil distillate yields improve, a continuing decrease in the overall quality of cracked residuals used to produce blends for marine fuels can be expected.
In many refineries in the United States, all residual products are directed to the petroleum cokers, which convert the
residual products into light distillates and solid hydrocarbon
coke. At these refineries, n o residual fuels are sold or made
for the marine fuel industry. In the future, marine fuels could
compete with "cokers" for their feed stock requirements. Ano t h e r use for residual fuel for U.S. a n d E u r o p e a n power
plants is decreasing due to environmental restrictions,
thereby decreasing overall availability of residual fuel.
A large percentage of fuel contamination can be traced to
the hydrocarbon storage and transportation process. Water
and debris (solids and fibers) are frequently introduced into
the marine fuel originating from barge and tanker transport,
pipe line transport, and shore side tank storage. A more de-

tailed description of contamination can be found in the next


section.

PETROLEUM FUEL OIL CHARACTERISTICS


Fuel PropertiesPhysical
Viscosity

(D-445)

The viscosity of a fuel is a measure of the fuel's resistance to


flow. As a fuel is heated, the viscosity decreases, and as fuel
is cooled, the viscosity increases. Marine residual fuels Eire
still selected and purchased on the basis of a limiting viscosity due to restrictions on fuel storage, handling, or engine fuel
injection equipment. However, viscosity aJone is not the sole
quality indicator, despite the fact that many purchasers of
m a r i n e fuels believe this to be t r u e . When purchasing
straight-run (distilled, but not cracked) residuals, this practice of associating low viscosity with high quality became established. This false sense of quality assurance was then cEirried over into bu5ring m o d e m blended and cracked marine
residuals. As more intensive cracking and processing procedures are used to produce future marine fuels, the relationship between fuel viscosity and fuel qucJity becomes more
and more misleading. For example, some heavily cracked 180
cSt residuals have poorer overedl quality than the less-processed 380 cSt residuals.
Meirine residual fuels are preheated to lower the viscosity
for more efficient fuel bunkering, trsinsfer, settling, centrifugation, fuel injection, and atomization. With preheating, the
viscosity of residual fuels drops and it is easier to separate
solids and water from the fuel. However, a limitation of 99C
should not be exceeded because the water may flash to steeim

CHAPTER

6: INTRODUCTION

and, therefore, the centrifuge water seal would be lost. As a


general rule, after centrifugation, fuel should not be heated
above 150C, since some chemical changes may occur, gases
may be given off, or water may vaporize to form steam pockets in suction piping. An increase in primary fuel p u m p pressure could be necessary to prevent water/fuel vapor from
forming the more volatile fuel components in the fuel returns
piping from the injection pumps. Additionally, all m o d e m fuel
systems should be closed (pressurized) systems with n o access
to atmospheric pressure in mixing or vent tanks. Older ships
with open mixing tank systems should be upgraded to closed
and pressurized fuel systems at the next yard period to better
cope with m o d e m , cracked, blended residual fuels [1,2].
Another important parameter would be the viscosity index
(VT) of the fuel, which is determined according to ASTM D
2270. The viscosity index is the linear relationship between
viscosity and temperature. As a general rule, the lower the
viscosity index the higher the fuel density for a given fuel viscosity because of the higher concentration of cracked residuals present. A m o d e m cracked residual fuel could have a VI
of 10-15, whereas the older straight-run residuals can have a
VI as high as 80. Many of the published temperature viscosity/temperature curves and tables are based on residual fuels
with a VI of 65-70. Care should be exercised w h e n using
these charts and tables since cracked residual blends can deviate widely from these data, since they are more viscous at
lower temperatures. It is very important that a viscosity monitoring and control system is used and calibrated periodically. By using these viscosity controllers, variations in viscosity indices from stem to stem will be automatically
compensated [3].
Density

(D

1298)

The density of a fuel is the mass-per-unit volume and is expressed as grams-per-milliliter (g/mL) for liquid fuels. In reality, density and specific gravity have very similar values
and, for approximate purposes, could be considered the
same. Originally, specific gravity at 60F was predominantly
used but, currently, meuine fuels will specify density at 15C
superceding specific gravity as the common usage. In 1977,
the Worldwide Marine Industry officially adopted SI units,
although it has tciken many years for the Marine Bunker Industry to adjust to the SI units.
Since all liquid hydrocarbon fuels expand their volume
when heated, their weight-per-unit volume decreases. Therefore, the density (and specific gravity) must be reported at a
standard temperature even though another temperature may
have been used in the test method. ASTM D 1550 contains
volume correction tables for reference.
The significance of fuel density revolves around the waterfuel separating technology, such as centrifugal separators or
settling tanks that operate on the difference of the densities
between the water and the fuel. Older centrifugal sepeirators
(purifiers) were limited to fuels at or below 991 density at
50C to control water removal efficiencies. The removal of
free water and salt water are important to control damage,
corrosion, and deposits in fuel injection systems; turbo
chargers and boilers in diesel; and gas turbine engines. The
more m o d e m centrifugal separators can efficiently remove
water u p to a fluid density of 1.012 at 50C.

TO MARINE

PETROLEUM

FUELS

149

A marine fuel with a high density indicates that the fuel is


heavily aromatic from being heavily cracked. Higher density
fuels are likely to possess poor ignition and/or combustion
qualities and could cause increased wear to the mechanical
components of the diesel engine.
Ignition Quality (D 613 for
Distillates)
(ISO 8217, Annex B for
residuals)
The ignition quality of all marine residual and distillate fuels
is most important for diesel engines, since combustion starts
each cycle of operation. This is not critical for continuous
combustion cycles, such as those used for steam boilers and
gas turbine engines. In a diesel engine cycle there is always a
delay between the beginning of fuel injection and the start of
ignition or the initial combustion of fuel. In a distillate fuel,
the ignition queJity is indicated by the cetane number/cetane
index. The ignition quality in a residual or blended fuel oil is
indicated by the Calculated Carbon Aromaticity Index (CCAI)
number. The lower the cetane number/index of a fuel or the
higher the CCAI number, the poorer the ignition quality of
the fuel. This translates into a longer ignition delay, a lower
period of time between the start of fuel injection and the beginning of fuel ignition, and the rapid pressure rise associated with fuel ignition. The results of poorer ignition quality
can be loss of power, poorer fuel economy, higher NOx emissions, and even diesel engine damage [4,5].
The characteristics of the crude oil and the degree of refinery cracking are largely responsible for the ignition quality of
a marine fuel. The combination of highly cracked fuels with
high densities and blended or visbroken fuels with low viscosities results in the highest CCAI numbers and the poorest
ignition qualities for diesel engines. These high CCAI n u m b e r
fuels can cause serious operational limitations on medium
speed and high speed diesel engines that have the greatest
sensitivity to ignition quality. Large, medium speed diesels
and slow speed diesel engines operating at less than 400 RPM
are m u c h less sensitive to the ignition quality of the marine
fuel. Although m e a n piston speed has been considered a
more precise method to categorize diesel engine speed, the
Marine Industry generally accepts a slow speed diesel engine
to operate below 249 RPM, a medium speed diesel engine between 250 u p to 899 RPM, and a high speed diesel engine
above 900 RPM.
The ignition quality of a marine fuel can be calculated by a
CCAI nomograph or an equation. Most people use the nomograph to derive the CCAI, which is found in Fig. 4. The International Mcirine Fuel Testing Laboratories calculate and list
CCAI based on analyzed viscosity and density from the fuel
analysis reports.
Heating

Value (D

4868)

Heating value is the quantity of heat produced by the combustion of a unit of marine fuel under specified conditions.
The gross heating value is the sum of the heat produced by
the total combustion of the fuel and the heat released by the
condensation of the water and SOx gases formed during combustion. This is primjuily applicable to a steam boiler power
plant. The net heating value is the gross heating value minus
the heat released by the condensation of the water (vapor)
produced during combustion and the sulfur and metals con-

150 MANUAL 37: FUELS AND LUBRICANTS


^1

800
820

HANDBOOK
^800
810

840
-820
860
830

-3

880
-840
900
-850
920
940

860

960

870

980

880

1000

890

1020
-900
1040
910

-920
5000
930
20000
50000

(added) test flame but before it will bum continuously (fire


point). The flash point is an important indicator of the fire
and explosion hazards associated with a marine fuel. The test
equipment and test procedure are very important in obtaining accurate test results. A carefully conducted test will not
miss light fuel contamination that can depress the real flash
point. For most marine fuels that require heating, a minimum flash point of 60C is a prerequisite for storage safety.
Even though marine fuels may test above 60C for a flash
point, after fuels are heated in storage tanks, vapors can collect in the head space of the storage tanks that can flash below 60C, which can cause safety concerns. Volatile vapors
can be produced at the surface of the hot heating coils so controlling steam temperature (and pressure) of the heating coils
and maintaining flash arrester screens on aJl tank vents are
critical for shipboard safety [6].
Pour Point (D 97)
Pour point is an indicator of the ability of a marine fuel to
flow at low temperatures. It is considered the lowest temperature at which the fuel will flow when cooled under controlled conditions. Pour point is not related to fuel quality but
depends on the type of crude oil, refining process used, and
the use of fuel additives. As the fuel temperature drops, the
wax components begin to crystallize and impede the flow
characteristics of the fuel. When stored, marine fuels should
never be permitted to reach their pour points, because once
the fuel congeals, pumping may not be possible until the fuel
is heated 10C above its pour point. If a fuel has congealed,
much more time must be allowed for heating since the congealed fuel will not naturally flow to the heating coils.

-950

FIG. 4Nomograph for determining tlie CCAI. International


Organization for Standardization (ISO). This material is reproduced from ISO 8217:1996 with permission of the American National Standards Institute on behalf of ISO. No part of this material may be copied or reproduced in any form, electronic
retrieval system or otherwise or made available on the Internet,
a public network, by satellite or otherwise without the prior
written consent of the American National Standards Institute,
25 West 43rd Street, New York, NY 10036.

tent. The net heating value is apphcable to a diesel engine. To


obtain the full net heating value from a marine fuel, the diesel
engine must burn the fuel completely. As marine fuels increase in density and carbon content, it becomes increasingly
difficult to completely "bum-out" the fuel. To achieve complete combustion ("bum-out"), all carbon must bum to carbon dioxide, all hydrogen must bum to water vapor, and all
sulfur must bum to sulfur dioxide.
The net heating value will be primairily influenced by density, water content, and sulfur content. As the fuel density increases, the carbon-to-hydrogen ratio increases, causing
there to be relatively less hydrogen with its higher heating
value per unit weight. This results in a decrease in the net
heat released during combustion. Water and sulfur also
cause the net heating value to be lower.
Flash Point (D 93)
The flash point is the lowest temperature at which a marine
fuel will support instantaneous combustion (a flash) from the

Ash (D 482)
Ash from the marine fuels includes the inorganic metallic
content, other non-combustibles, and miscellaneous contamination. Metallics can contain a mixture of aluminum, calcium, potassium, iron, vanadium, nickel, silicon, and
sodium. Ash deposits can cause localized overheating and
corrosion to the metal surfaces where they adhere, especially
to the exhaust valves. Excessive ash can cause abrasive wear
of the cylinder liners, piston rings, injection pumps, fuel
valves, and injection tips. Catalyst fines can result in just such
abrasive damage.
In marine fuels, some of the dispersed and insoluble metallic compounds can be removed onboard by settling, centrifugation, and filtration. However, fuel soluble metallics cannot
be reduced by shipboard fuel handling equipment [7-9].
Cat Fines (ISO 10478)
Catalyst (CAT) fines are small particles of aluminum silicate
used as a fluidic catalyst in the catalytic cracking units at
modem refineries. Cat fines can be carried over from the catalytic cracker and can be found in marine fuels. Cat fines are
very hard and abrasive and can cause excessive wear of engine components, particularly fuel pumps, cylinder liners,
piston rings, and piston ring grooves.
To prevent severe abrasive damage, cat fines must be limited by fuel specification restrictions or by shipboard removal settlement, centrifugation, or fine filtration of five to
seven micron control. Cat fine control can be monitored by
testing the treated fuel for aluminum/silicon levels [10,11].

CHAPTER
Water (D 95) (D

6: INTRODUCTION

4176)

Water is a contaminant that enters mEuine fuels during transport, usually when taken by tanker or barge over water. Salt
water can cause greater problems in marine fuels then fresh
water. Salt water has been considered the greatest single
cause of fouling, deposits, and corrosion, especially in the
higher temperature regions of the power plant. The presence
of water can initiate microbial growth in marine fuels. These
simple organisms must live in the water at the tank bottom
and feed on the marine fuel at the water/fuel interface.
Water in the marine fuels can cause large volumes of centrifuge sludge as a result of water-sludge emulsification during centrifugal separation.
Because of upcoming IMO and EPA exhaust gas emission
regulations, diesel engines may start using water in fuel
emulsions (made with potable water) to reduce oxidizes in
nitrogen (NOx), particulates and smoke. These water-in-fuel
emulsions can consist of u p to 50% additional potable water
and must be intentionally-made emulsions with a tightly controlled water droplet size and a control on all larger size
droplets. Lastly, whenever the diesel engine is shut down, all
emulsion must be purged out of the fuel system such that the
shut down diesel fuel injection system contains no water-infuel emulsion [12].

TO MARINE

PETROLEUM

FUELS

151

360

340

320
1500 P S I ,
900 P S I x

300

I1

300 F*SI

280

260

OPSI^

Fuel PropertiesChemical
Sulfur

(D

240

4294)

Sulfur is a nonmetallic element that is chemically bound into


the marine fuel. Sulfur originates in crude oil and is concentrated into the higher density residual fractions. The mEirine
residual fuel has capped sulfur content at 4.5 weight percent
to begin to control oxides of sulfur (SOx). When sulfur is
burned in the diesel engine it causes several problems, primarily in promoting corrosive wear of the piston rings and
cylinder liners and by causing deposits in the ring zone. During the combustion process, sulfur dioxide and sulfur trioxide form in the cylinder. These sulfur compounds then combine with water vapor to form sulfurous and sulfuric acid,
which can cause aggressive corrosion.
When sulfuric acid vapor leaves the cylinder and contacts
low t e m p e r a t u r e surfaces of the heat recovery boiler, the
gaseous sulfuric acid condenses and forms highly corrosive
(liquid) sulfuric acid. So, in addition to ring and liner damage, the sulfuric acid can attack valve guides, as well as the
cooler parts of the heat recovery boiler.
Diesel engines can be designed to prevent low temperature
corrosion by maintaining surface temperatures above the
sulfuric acid condensation temperature, as shown in Fig. 5.
Sulfur in marine fuels is normally neutralized by using an alkaline (TBN) lube oil additive. The fuel sulfur level should be
balanced against the lube oil TBN additives to just neutralize
the sulfur. If too m u c h alkaline additive (TBN) is used, a
harmful (abrasive) level of alkaline material is produced that
can increase the wear of the cylinder liner and the piston
rings. The average sulfur level in marine fuels today is 2.8-3.0
weight percent.
Carbon Residue

(D 524)

Carbon residue is the coked material that remains after the


marine fuel has been exposed to high temperatures under

220
0

Sulfur [%]
FIG. 5Acid dew point for diesel engine fuels. Reprinted with
the permission of the Society of Naval Architects and Marine
Engineers (SNAME). Material originally appearing in SNAME
publications cannot be reprinted without written permission
from the Society, 601 Pavonia Ave., Jersey City, NJ 07306.

controlled conditionsthe laboratory test for Micro Carbon


Residue gives an overall guide to the carbon forming tendencies of the marine fuel. As heavier crude oils are refined with
the more intensive, secondary cracking process, the carbon
concentration in the marine fuel can approach 18-20 weight
percent. Further, as the carbon content increases, the asphaltene content typically increases as well. Asphaltenes are
high molecular weight hydrocarbons that can adversely affect combustion, residue formation, a n d the compatibility of
marine fuels. These high Ccirbon content marine fuels have
poor combustion chciracteristics; increased carbon deposit
forming tendencies on injection nozzles; pistons and ports of
two stroke engines; increased ignition delays; and slow burning constituents that can increase the thermal loading of
diesel engine components [13].
The asphaltene content in marine fuels influences the compatibility of blends of light and heavy fuels and blends of marine fuels from different liftings. An increase in purifier sludge
discharge or filter fouling is an early indication of incompatibility of fuels being mixed and/or high asphaltene levels.
Therefore, fuels taken on-board in different ports should be
segregated in separate tanks (as on-board m u c h as possible)

152 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

and mixing fuels from different tanks on a single vessel should


be avoided.
Compatibility (ISO 10307-2)
Compatibility is the ability of a fuel to form a homogeneous
mixture that is neither separated nor altered by chemical,
time, or temperature interaction. Marine residual fuel blends
can be considered a colloidal dispersion of high molecular
weight substances (asphaltenes) held in a chemical and/or
physical equilibrium in the fuel. If the equilibrium forces are
disturbed, the high molecular weight components (usually
asphaltenes) are precipitated and dropped out of solution to
form a sludge or sediment. This can result in rapid tank
sludge buildup, clogged strainers, fouled filters and purifiers,
and damaged viscometers. Once into the diesel engine, incompatibility can cause rapid fuel injection pump sticking,
fuel injector deposits, exhaust valve deposits, turbo-charger
turbine nozzle and blade deposits, and carbon fouled waste
heat boilers [14].
Vanadium and Nickel (ISO 14597)
Vanadium and nickel are metallic elements that exist as fuelsoluble organometallic compounds. Vanadium and nickel,
originate in the crude oil and are concentrated in the marine
residual fuels by the various refinery operations. Depending
on the origin of the crude oil, the vanadium and nickel levels
of the fuel can vary widely.
In the combustion process, vanadium and nickel can combine (bond) with sodium (from salt water contamination) to
produce very aggressive, low melting point compounds that
are responsible for accelerated deposit formation and high
temperature corrosion of diesel engine components such as
piston crowns, exhaust valves, and turbo charger turbine
nozzles. Figure 6 shows for the relationship between vanadium and sodium. In steam boilers, these contaminants, together with sodium, can cause accelerated fouling of the
screen tubes and the superheater tubes as well as serious
high temperature corrosion of the superheater tubes. Gas
turbine engines are the most sensitive to both contaminants
due to the very high temperatures of the turbine section.
These contaminEints are fuel soluble, therefore they cannot
be removed from the fuel on the ship. If they are troublesome
to a particular engine, they must be limited at the time of fuel
purchase. The effects of vanadium and nickel can be neutralized by using a metallic fuel additive such as magnesium or
calcium.

Fig. 7, which shows the critical ratios of metcdlic components


and the large effect upon the ash melting temperature. It is
the molten form of sodium, vanadium, and nickel that causes
the severe hot corrosion and deposits to form. No power
plant is beyond this problem since it affects steam boilers,
diesel engines, and gas turbine engines.
Oxidation (Storage) (ISO 3735)
Marine residual fuels are tjrpically stored in heated tankage
on shore and in the ship. The higher storage temperatures
and the presence of air in the head space above the fuel in the
storage tank both combine to age the fuel. As marine fuels
age, they oxidize and begin to polymerize, forming sludge,
gum, and resin that can foul heaters and filters as well as fuel
injectors, combustion chambers, and the exhaust system. Oxidation products can vary in form: some are soluble in marine fuels while others are insoluble and result in the formation of an organic sediment [11].
Sediment (ISO 3735)
The insoluble organic products that result from oxidation of
marine fuels can combine with inorganic insolubles, such as
rust, cat fines, and sand, to produce sediment. This sediment
1600

Sodium (ISO 10478)


Sodium is a metallic element that is extremely active chemically. Generally, marine fuels are essentially sodium free
when leaving the refinery. The vast bulk of the sodium in marine fuels originates through Scilt water contamination during
transport by tank ship or barge and can be removed by settling tanks or by centrifugal separator. Sodium or salt (NaCl),
if present in significant quantities, will become involved in
severe high temperature corrosion and deposit problems.
When unfavorable ratios of vanadium combine with
sodium in the fuel, they react during combustion (at high
temperatures) to produce eutectic compounds with ash melting points within the engine's operating temperatures. The
relationship between sodium and vanadium can be seen in

100

VA
ITO

55

'

B5

'

3D

~2!r

Mixture Proportion [%]

FIG. 6Bonding relationship for vanadium and sodium.


Reprinted with the permission of the Society of Naval Architects and Marine Engineers (SNAII/IE). IVIaterlal originaiiy appearing in SNAIVIE publications cannot be reprinted without
written permission from the Society, 601 Pavonia Ave., Jersey
City, NJ 07306.

CHAPTER 6: INTRODUCTION

TO MARINE PETROLEUM FUELS

153

1600

1500
/

3Na20*V205

1400
o

1300

vp^

Q.

NA20*V 2O/5V2O
O)

1200
N a j O-V^Os

w
<

2Na20*V205

1100
5Na zO-V^O/ 11V 2 0 \

1000

900
0

10

20

PRACTICAL FO ULING
ZONE

30
P

40

50

60

70

80

90

NajO, MOL Percent

INCREASED FOULING RATE


FIG. 7Phase diagram for sodium and vanadium. Reprinted with permission from ABS, Houston, TX.

can damage high-pressure fuel injection pumps and fuel injectors. Sediment can be removed by gravity settling, filtration, and by centrifugal separators.
Fuel Additives
A fuel additive can be any material that, when added to a marine fuel, changes its properties, characteristics or performance. As secondary refinery processing cracks fuels more
severely, the resultant meirine fuel quality becomes more difficult to handle, store, and combust efficiently. The increased
amounts of metallic components, ash levels, and carbon contents adversely affect the performance of the fuel treatment
system and the power plant itself. Fouling and corrosion of
engine components and increased tank, centrifuge, and filter
sludge levels can present costly challenges for the ship's engineers. As fuel cracking intensifies, the fuel density increases
and it can make the centrifugal removal of free and emulsified water more difficult.
In addition to the conventional methods of settlement, centrifugation, and filtration, a chemical (additive) approach
Cin sometimes offer a solution to a particular problem. The

chemical additives that have been the most effective are the
stabilizers and dispersants, ash modifiers, biocides, demulsifiers, and emulsifiers [14].
Stabilizers and Dispersants
Stabilizers and dispersants tend to control the formation of
new sludge and to aid in the dispersion of existing sludge. By
limiting sludge, more of the hydrocarbon content of the
sludge can be burned and there is less sludge to incinerate or
to offload in the next port. Asphaltenes can significantly contribute to sludge production. By dispersing the asphaltenes
into very small particles with dispersant additives, sludge can
be reduced. Some additives work by using surfactants to facilitate a surface film formation at the fuel/asphaltene interface to stabilize the asphaltenes. The additional surface tension reduction tends to break the asphaltenes into minute
particles and stabilizes the fuel.
Additive additions are typically known as "tank treatments." Usually, when this additive is first used, it dissolves/disperses existing sludge and organic sediment and it
places a heavy burden upon the centrifugal separators and
filters as it begins to clean up tanks, piping, etc.

154

MANUAL

Ash

Modifiers

37: FUELS AND LUBRICANTS

HANDBOOK

These ash modifying materials can react with corrosive elements of the fuel during combustion to raise the melting temperatures above the critical temperatures, thereby avoiding
high temperature corrosion. Magnesium compounds represent one of the more popular ash modifiers since they are
available in many forms and are relatively inexpensive. Prior
to combustion, these chemicals are added so that the magnesium combines with the vanadium (from the fuel) to form
harmless, high-melting compounds that no longer adhere to
and corrode the exhaust valves and seats, piston crowns and
turbo charger nozzles in diesel engines and the superheater
tubes in boilers. It is preferred to know the vanadium-plusnickel content of the fuel to determine the proper additive usage. Overdosing of ash modifiers could produce h a r d deposits within the cylinder of a diesel engine, which can lead
to abrasive wear of the piston rings and cylinder liners.
Demulsifiers
These chemical additives cause small water droplets to coalesce and separate more readily from the marine fuel. They
are typically added to the fuel storage tank before bunkering
fuel. They allow better water settling in storage, in the settling tank, and in the centrifugal purifier. These demulsifiers
are most effective when the water in the fuel exists as a fine
dispersion or as an emulsion.
Biocides
These chemicals are toxic to microbiological growth in marine fuels, tanks, and piping. This growth typically lives in the
water at the bottom of a fuel tank and feeds on the fuel at the
interface between the fuel and the water. Since this growth
must live in water, the goal of good housekeeping practices is
to keep the tank bottoms drained of water. This is a challenge
since fuel transport is usually by barge or tanker over seawater. A small quantity of biocide will keep the overall fuel system free of microbiological growth. Biocides should be selected carefully since some are fuel soluble a n d some are
water soluble.

F u e l Oil I m p a c t o n E x h a u s t E m i s s i o n s
There are several marine fuel properties that can impact exhaust gas emissions. Sulfur is the first fuel property to be regulated by international and domestic rules. The International
Maritime Organization (IMO) has limited sulfur to a maxim u m of 4.5%. Some localized regions, such as the Baltic Sea,
have imposed even lower sulfur levels.
The next emission to be regulated will be Oxides of Nitrogen (NOx). The IMO will restrict new marine diesels installed
after 2000 to NOx limits based upon the rotational speed of
the engines. Slow speed engines have the highest limits,
medium speed next, and high speeds have the lowest limits.
The nitrogen content of marine fuels does contribute to NOx
emissions, b u t to date, no organization has attempted to limit
fuel nitrogen.
Ignition quality, cetane for distillate fuels and CCAI for
residual fuels, has an impact on NOx produced in a diesel engine. Usually, the lower the ignition quality of the fuel, the
higher the NOx exhaust emissions.

Exhaust particulates and smoke b o t h relate to the ability of


the diesel engine to completely and efficiently b u m the marine fuel so little or no solid carbonaceous material remains.
Therefore, the higher the micro carbon residue and asphzJtene content, the higher the Ccirbonaceous pcuticulates and
smoke that can be expected.
Lastly, if stack opacity is regulated or if excessive smoking
is prohibited, the marine fuel should not contain used lube
oil (either supplied with the fuel at bunkering or as the result
of the disposal of used lube oil from the diesel engines on
board). Used lube oil in marine fuels results in a blue colored
haze in the exhaust gases that cannot be reduced until all of
the marine fuel with used lube oil has been burned.
P e t r o l e u m F u e l Oil T o x i c i t y
Marine fuel oils present a minimal health hazard when the
engineers practice high standards of personal and industrial
hygiene. A caution, however, is that extended exposure to
marine fuels can cause skin dermatitis and even skin cEuicer.
To minimize this possibility, these precautions should be
considered.
Minimize skin and eye contact with marine fuels by modifying work procedures, if necessary.
Always wear protective clothing, especially impermeable
gloves and eye protection.
If clothing becomes fuel soaked, remove it and thoroughly
wash the affected skin with soap and water.
Avoid carrying fuel soaked rags in pockets.
Do not use light hydrocarbon solvents for removing fuel
from the skin. Always avoid inhaling hydrocarbon solvent
vapors.
Avoid inhaling hot fuel mist or vapors since the fuel could
contain contaminants such as waste solvents, acids, and
strong base mixtures that can sometimes get dumped into
marine fuel tanks.
Avoid accidental injection of marine fuel into the skin during the testing of fuel injection equipment by following test
equipment directions and maintaining protective shields
in place.

PETROLEUM FUEL SPECIFICATIONS


When the combined requirements of the commercial and
military marine fuels are considered, marine fuels represent
a small fraction of the refinery capacity. Marine fuels and, in
particular residual fuels, are the end products of the major
shore side fuel producers' needs. Therefore, the refineries'
production is driven by shore side needs and the remainder
is delivered into the marine industry. It is little wonder that
the unique needs of the marine industry have little impact
upon the quality of marine fuels [15].
Commercial m a r i n e fuels range from gas oil to m a r i n e
diesel fuel, to blended marine diesel fuel, to blended residuals, to heavy residuals.
Gas oils are clean, high quality, 100% distillate diesel fuels
that are shipped and handled clean. If gas turbines are used
in commercial service, the specifications will likely cedl for
gas oil to maintain the very, very low trace metallic contamin a n t levels required for long life. Gas oils are typically used
for emergency and lifeboat diesels.

CHAPTER

6: INTRODUCTION

Marine diesel oils (MDO) can be two very different fuels.


MDO-light is similcir to gas oil but is handled in dirty barges
that carry residucd fuels. This produces a dark colored fuel,
which is essentially all distillate, with a little additional sedim e n t and a carbon residue below 0.2% (by mass).
MDO-heavy is roughly 85% MDO-light blended with 15%
residual fuel and handled dirty in a residual fuel barge. Since
MDO-heavy contains about 15% residual fuel content, this
should only be used in diesel engines that are designed to
have a blended residual fuel capability. The carbon residue of
MDO-heavy is typically above 1.5% (by mass).
Heavy Residual Fuels (HFO) have high viscosity and density and, in many situations, they must be blended to a lower
viscosity and a lower density to be used in marine vessels.
Most marine residual fuels are blends of different residual
fuel stocks with lighter stocks, such as MDO and cycle oil.
The blending process can r e d u c e sulfur, c a r b o n content,
vanadium and ignition quality, as well as viscosity and density. Residual fuels are still generally classed by viscosity,
however, m a n y other properties are considered before a
residual fuel selection is made.
International Specifications
The International Orgcinization for Standardization (ISO) has
written a basic International Marine Fuel Specification 8217
and revised it several times since the original document was
published in 1987. The most recent revision was published in
1996. The ISO relies on the guidance Eind advice of the International Council on Combustion Engines (CIMAC), Heavy Fuel
Committee, which consists of engine builders, major oil companies, bunker suppliers, treatment equipment builders and
consultants. CIMAC also publishes a distillate and residual fuel
specification but, since it is not voted upon by an international
membership, it truly doesn't carry an international importance.
The International Maritime Organization (IMO) has proProperty
Density at 15C, kg/m^
Kinematic viscosity at 40C, cSt *
Flash point, C
Pour point (upper), C"
Winter quality

Summer quality
Cloud point, C
Carbon residue on 10% bttns,
Ramsbottom, % mass
Carbon residue, Ramsbottom, % mass
Ash, % mass
Sediment by extraction, % mass
Water, % vol
Cetane number
Visual inspection
Sulfiir, % mass
Vanadium, mg/kg

TO MARINE

PETROLEUM

FUELS

155

duced a document called Annex VI of MARPOL 73/78, the regulations for the prevention of air pollution from ships, which
caps the sulfur level in marine fuels at 4.5 wt. percent and has
a provision that will restrict the NOx production from marine
diesel engines after Jan 1, 2000. As time moves forward, the
IMO will continue to regulate and restrict air pollution from
marine diesel engines. In some cases, as in the SOx emissions,
the air pollution control will be regulated by restricting fuel
properties. Therefore, although the IMO MARPOL regulations are not strictly fuel specifications, they will achieve
some of their regulation by restricting marine fuel properties,
as has already been done with a fuel sulfur cap.
ASTM Marine Fuel Specifications
The ASTM D 2069-98 Fuel Specifications are similar to the
ISO 8217 standard in many ways. Figure 8 shows the ASTM
detailed requirements for marine distillate fuels, and Fig. 9
shows the ASTM requirements for marine residual fuels.
Military F u e l Specifications
Military marine fuels consist of all distillate fuels that meet
an individual country's fuel specifications but most also conform to North Atlantic Treaty Organization (NATO) fuel
specifications as well. Military fuels place additional restrictions u p o n these distillate fuels to support the unique, multipurpose military requirements, as well as to provide for extended storage times. In the U.S. Mihtary, the MIL-F-16884
fuel specification requires a clean, stable distillate, somewhat
similar to marine gas oil, with additional properties and testing required before acceptance. Therefore, MIL-F-16884,
Diesel Fuel Marine (DFM), and NATO F-76 are the same fuel
that requires dedicated clean handling to prevent transport
contamination, which can cause the fuel to tail out of specification.
Limit
max.
min.
max.
min.
max.
max.
max.
max.
max.
max.
max.
max.
min.
max.
max.

DMX
a

1.40
5.50
43

DMA
890.0
1.50
6.00
60

DMB
900.0

DMC
920.0

11.0
60

14.0
60

-6
0

0
6

0
6

0.25
0.01
0.07
0.30
35

2.50
0.05

2.0

2.0
100

-16"
0.20

0.20

0.01

0.01

45

40

1.0

1.5

0.30

"There may be a maximum limit in some locations.


*lcSt=.lmm^/s
"Purchasers should ensure that this pour point is suitable for the equipment on board, especially if the vessel
operates in both the northern and southern hemispheres.
*rhis fuel is suitable for use without heating at ambient temperatures down to -15C.
TTiis fuel shall be visually clear and bright.
FIG. 8ASTM D-2069-98, Detailed Requirements for lUlarine Distillate Fuels.

156 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK
The U.S. Navy uses a ciistillate fuel, JP-5, for aircraft gas
turbine engines anci selected high speed diesel engines. This
fuel is lighter than MIL-F-16884. It differs from other aircraft
fuel primarily by its higher flash point requirements (60C vs.
38C). JP-5 fuel must be handled and stored clean.

o o

w-1

1/^

CO

(^

o o

Environmental Considerations
O

o o
r<1 f l

It is possible that localized environmental regulations could


place more stringent limitations, beyond the International
anci/or Domestic Regulations, on fuel specifications. As previously reviewed, limits on sulfur, carbon content, and ignition quality could be imposed to achieve a local regulation. If
a catalytic converter was installed, the use of a very low sulfur fuel would be prudent to preclude premature catalyst
fouling and poisoning.

fN
fN

fN
fN

FUEL TESTING

3
O

fN
fN

O
22
&
o

_:
0)
O

1/-1
ro

CO
CO

fN

rs

a
3>

o o

a>
x:
g

o
fN

u
PQ

O
O
CO m

DC

CD

.c

E
o
o

1-

fi
CD

o
o

a
o

^
ro
3
(0

o
o

o
>%
X3
fO

fS

fN

.
^_,
c
0

.0}

I ^o
3

cr
0)

nj
Q.

Q.

'3

Q.

c
o

CB

<C
O
c

E
'5
cr

0}

' l -

c
o
"c

M
IT)

^
^-^
D
CO

(U
O

>

o
^

>

HH

DC

u.

CO
CD

0)
<B

OT

-O

CD

0)

A known fuel quality has been determined to be fundamental


to reliable marine diesel engine operation. A comprehensive
fuel sampling and testing program is essential to ensure the
quality of the marine fuel lifted, and to ensure that the ship's
fuel treatment system can properly clean, heat, and pump
this fuel to the diesel engine for efficient combustion, good
fuel economy, and low exhaust stack emissions. Even if the
marine fuel is refined clean, shore side handling and storage,
as well as marine fuel movements, can and frequently do contaminate the fuel such that poor engine operation, accelerated wear, or serious exhaust gas violation can occur. It is
critical that the ship's fuel treatment system can properly
treat the bunkered marine fuel so that clean, high quality fuel
can flow to the diesel engines.

o>

CO
0
CM

cfi
S
1-

<

J>
d
iZ

Fuel Sampling
Fuel sampling is the critical first step in obtaining knowledge
about the newly bunkered marine fuel. For a fuel test and
analysis to be meaningful, it is critical that a representative
sample be taken during the delivery of the fuel. A representative sample requires continuous sampling throughout the entire bunkering operation, since marine fuels can stratify or
can vary the blending ratios during the delivery period. Most
marine fuel testing services provide detailed directions and
equipment to take a continuous, representative sample. Also,
ASTM D 4057 can provide detailed instructions on taking a
representative sample. The old practice of taking a "spot or
grab" sample is no longer acceptable.

in

O
en

_l

U
o
> o

in

-I|

t^iu o

"5

u
o

I
o
Q.

i
I

3
CO

Shore Side Analysis

Cl>

Sending the representative sample to a shore side laboratory


as soon as possible for accurate and complete analysis is
strongly recommended. In addition to a comprehensive analysis, a shore side laboratory can confirm that a fuel meets the
ISO purchase specifications and can alert the crew to contaminants, incompatibility, abrasives, excessive water content, and other damaging aspects of the bunkered fuel.
Lastly, since these independent shore side laboratories provide an unbiased analysis, they can facilitate the resolution of
disputes quickly and at low cost.

3
CO O

<= E S5
> > T - CO

O g

cd

9i^l

i.

CHAPTER 6: INTRODUCTION
On Board Testing
Since the shore side testing can take 24-72 h, some operators
prefer to supplement the shore side testing with quick, simple on board tests that are helpful in the short term. These
quick on board tests provide the immediate results often
needed to support decisions on fuel treatment system alignments, adjustments, and operations. The alignments and adjustments of the centrifugal separators can be effected by fuel
density, water content, compatibility, abrasive content, etc.
Typical on board tests include those for viscosity, density,
water, compatibility, and particle content.

FUEL STORAGE SYSTEMS


Steam, diesel, and gas turbine marine fuel storage, settling,
and transfer systems are very similar. Figure 10 illustrates a
steam propulsion plant with a 600 cSt residual fuel and diesel
oil fill, transfer, and storage system. A diesel engine propulsion plant with its fill, storage, transfer, and centrifuged purification system is illustrated in Fig. 11.
The marine fuel transfer system provides the following
functions:
To transfer marine fuel from any storage tank to any other
tank, such as to the settling tank.
To strip solids and water from the bottom of the settling
tank(s) through the stripping and drain connections.
The marine residual fuel and marine diesel fuels are
bunkered through deck fill connections that should have sampling connections installed to allow continuous, representative fuel samples to be taken as the fuel is taken aboard.
Heated tanks are used for storing marine residual fuels, and
unheated tanks for marine diesel fuels and gas oils. From the
residual fuel storage tanks, the transfer pumps forward the
fuel to the settling tank(s). The residual fuel settling tanks begin the fuel treatment process by settling gross water and
solids to the bottom. As soon as the settling tank is filled, it is
heated to 80C, but not higher than 10C below the fuel's flash
point. By heating the fuel, the viscosity is reduced, the gravity
settling process is enhanced, and the fuel deaerates as well.
Once settled, the fuel is forwarded to the boiler fire front,
after additional heating, as illustrated in Fig. 12. The settling
tank bottom drain connections permit the removal of settled
water, sludge, and solids to the sludge tank.
In the fuel transfer system, all piping should be traced,
heated, and insulated to prevent the marine residual fuel
from solidifying in the piping. The residual fuel storage tanks
all have heating coils to control tank temperature and to
maintain the fuel at 10C above the pour point until it is
transferred to a settling tank.
From the safety standpoint, experience has proven that explosive atmosphere can collect in the tank headspace even
though the fuel oil temperature is well below the flash point.
This condition exists when cracked marine fuels contact hot
heating coils that are significantly hotter than the bulk fuel
temperature. Further, if shore side petroleum waste products
have been mixed with the marine fuel, the lower flash point
of the waste products could greatly lower the flash point of
the bulk marine fuel. Even worse, this lower flash point may
not be reported if the shore side sample was taken prior to the
introduction of the waste. Therefore, the crew must fre-

TO MARINE PETROLEUM FUELS

157

quently inspect and maintain the condition of the flame arrester screens on the fuel tank vent lines, and careful and safe
use of the ullage equipment is imperative.
In a steam propulsion plant system, a duplex heater set
heats the fuel to the atomizing viscosity prior to the fuel
reaching the boiler fire front.
In a diesel engine propulsion system, the settling tank delivers heated residual fuel to the purifier heater set prior to
the centrifugal separator(s). It is important that the residual
fuel temperature to the separator stably remain at 98-99C to
maintain high separator efficiency and to prevent boiling of
the water (in the fuel) within the separator.
Service tanks or day tanks provide an additional opportunity to further settle water and solids from the heated residual fuel. The service tank can be filled by the centrifugal separators and provides additional time for deaeration.

FUEL TRANSFER SYSTEMS


The fuel transfer pump(s) is provided to move fuel from storage to settling tank(s). The positive displacement transfer
pump(s) is protected by coarse suction strainers, pressure relief valves, and pump bypass lines. The flow rate of the transfer pump is established by the engine's fuel consumption rate
and the capacity of the settling tank. The operational flexibility of the transfer system is provided by the arrangement of
the valves in the system. This valving can permit the fuel to
be pumped from any storage tank to any settling tank or to
other storage tanks.

STEAM PLANT FUEL SERVICE SYSTEM


The simplest of the service systems is that of a steam plant. It
consists of storage, settling, and service tanks; transfer and
service pumps; and heater sets (see Fig. 10). The treatment
system consists of a heated settling tank that allows solids
and gross water to fall to the bottom of the tank [4].
The service system is also very simple, consisting of a
pump, a heater, and a pressure (or flow) regulating controller. Most modern systems incorporate a quick-closing
fuel valve to shut down fuel flow if there is a flame out, loss
of combustion air, or loss of fuel pressure.
Two fuel service pumps, with one in standby, are provided
and each is capable of supplying the total fuel flow plus an
additional msirgin, with the excess flow diverted back to the
settling tank. Service pumps are typically of the positive displacement type that are fitted with a pressure relief bypass,
remote shut downs, and isolation valves (for servicing). The
pressurized fuel flows to the service heater sets where the
temperature is increased to provide for the proper fuel viscosity for atomization. The two heater sets (one in standby)
are steam heated shell and tube or plate type heat exchangers, each with the capability of increasing the fuel to 145C.
It is important to use properly sized heat exchangers and lowpressure steam supply to prevent overheating the fuel as it
passes through the heat exchanger. After the heater sets, the
fuel passes through duplex strainers, a viscometer, and a flow
meter and then to the burner management system at the
boiler Are front. All residual fuel piping must be trace heated
(usually by steam) and insulated.

158 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

5
<
>

>

^^

Q:

UJ

o
o

(/)
>

Z)
(/)

i
Q.

Q:

OD

ii

Q.

m a:
o o o <
[/)
< o
o tE u U J

<

tr

CL

<

a ^ X *zt I1 1^b ^

<

1
Q:

CL

or

<

CL

z:

en

an

>
@

(/I

Zl

<

o
o
Q
Z

X1

1
o
a
2

>

6>

i
I
0)

cCO

I
1

CHAPTER 6: INTRODUCTION TO MARINE PETROLEUM FUELS 159

I
a

I
M
C
(S

c
a>

M
tt
Q

I
u.

160 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

< o
3 LU
Q '
00 2

^ <

_i "
< Q
UJ en

on ^
Q

LiJ
a:

<

ST

UJ O

I
o

^
OWBACK-PRESSURE
CONTROL VALVE

in

C>K}C^HXH
{x^

COMBUSTION
CONTROL VALVES
{xy{>KI-H::^:H>K}-

Q 00

CHAPTER 6: INTRODUCTION
The marine diesel fuel storage (see Fig. 11) provides a separate fuel supply for cold boiler start up and for the emergency diesel generator. A small diesel fuel service tank is used
to provide clean fuel for emergency operation when neither
steam nor electricity is available. This diesel service tank is
located high in the machinery space so that gravity will supply enough fuel pressure to start the boilers and diesel generators in an emergency.

DIESEL PLANT FUEL SYSTEM


Diesel engine power plants require more intensive and complex fuel systems than those of steam plants. The contaminants, water, solids, and debris that may have been allowable
in a steam plant must be removed prior to diesel engine operation. When burning residual fuels in diesel engines, the
basic principles of settling, pumping, heating, and treating
are common to slow speed and medium speed diesels alike. A
typical residual fuel and diesel fill, transfer, storage, and
treatment system for diesel engine power plants can be seen
in Fig. 11. All residual fuel piping should be insulated and, if
the viscosity exceeds 380 cSt at 50C, trace heating should be
included under the insulation.
Whenever emergency shutdowns occur to a diesel engine
operating on residual fuel, the viscous fuel will remain in the
piping and heaters, and also in the injection pumps and high
pressure piping. If all piping and components have trace
heating and insulation, it is not a problem since the residual
fuel can be reheated and its temperature controlled by recirculation prior to restart. If the emergency will keep the engine shut down for a lengthy time, the residual fuel should be
purged from the piping with marine diesel fuel and this will
eJlow the trace heating system and the recirculating pump to
be secured. Additionally, if Einy maintenance is planned for
the fuel injection system, the work will be faster and easier
with marine diesel fuel in the piping system.
When bunkering residual fuel and marine diesel fuel, both
enter through sepjirate deck connections. Both deck connections must incorporate sampling equipment to permit continuous, representative sampling during the entire lifting.
This is considered the point of custody transfer and these
samples will be key should a quality dispute arise.
As was the procedure in steam plants, marine residual fuels for diesel plants are transferred to the settling tank(s) by
a transfer pump through a coarse strainer. The best practice
is to duplex transfer pumps to prevent pumping problems.
If a demulsifier chemical is to be used to aid in water or
particulate removal, the demulsifier should be metered into
the suction strainer ahead of the transfer pump. Demulsifier
chemicals work by facilitating the separation of water and
solids from the residual fuel, and this process begins in the
settling tank(s). After the settling tank(s), the centrifugal purifiers and clarifiers, from two to four centrifuges, are typically installed to treat the residual fuel. These units include
supply pumps, heaters, and automated controllers. Centrifugal separators, set up as purifiers and clarifiers, are widely
used. They are considered a reliable and efficient method for
treating and cleaning marine diesel fuel and marine residual
fuels if properly maintained and adjusted. Centrifugal purifiers have the clear advantage of being capable of removing
large quantities of water and particulates. The centrifuge ser-

TO MARINE PETROLEUM FUELS

161

vice pumps, fuel heaters, sludge tank, and interconnecting


piping must be designed to match and support the needs of
the centrifuge.
The piping system must be configured to allow centrifuge
operation in parallel or in series as either purifier/purifier,
clarifier/clarifier, or purifier/clarifier. The centrifugal processed residual fuel then passes through very fine duplex filtration units that remove abrasive catalytic particles (cat
fines) that pass through the centrifuges. After these fine filters, the residual fuel enters the service/day tank.
From the service tank, the residual fuel is forwarded to the
diesel engine through the residual fuel service system as seen
in Fig. 13. The service system raises the residual fuel temperature up to the fuel injection temperature as controlled by a
viscometer. An advanced service system will include a homogenizer to treat the residual fuel just prior to injection into
the diesel engine. The service system flows two or three times
the maximum fuel consumption of the diesel engine. Older
fuel service systems are atmospheric pressure mixing tanks,
while modem practice is to pressurize the entire system, remove the mixing tank, and add a mechanical deaerator to
eliminate gases and water vapor from the injection pump discharge flow.
The marine diesel fuel system moves fuel from storage to
the service tank by a transfer pump or by a centrifugal purifier. The fuel can be transferred from the service tank to the
emergency diesel generator service tank by either transfer
pump or centrifugal purifier.

DIESEL FUEL SYSTEM COMPONENTS


Centrifuges
The recommended centrifuge flow capacity is the quantity that
can be treated at the highest separating efficiency. This flow
capacity is based upon the d5Tiamic viscosity of the residual
fuel at the temperature of separation. The maximum separation temperature has an upper limit of 98C. There is a risk of
the loss of the water seal in the centrifuge due to the formation
of steam bubbles. A thorough review of each centrifuge manual will determine recommended maximum flow rates for any
given residual fuel. The rule is to reduce the fuel flow through
the centrifuge to slighfly above the fuel consumption of the
diesel engine. Avoid the temptation to rush the fuel through
the centrifuge and into the service tank so it overflows back to
the settling tank and is recentrifuged. Peak centrifuge operation efficiency occurs when the flow is reduced to increase the
residence time of the fuel within the centrifuge while maintaining a stable fuel temperature of 98C.
Two properly sized, correctly adjusted and operated, selfcleaning centrifuges are considered absolutely necessary to
provide a reliable diesel fuel treatment system. Most diesel
engine warranties become invalid if adequate centrifuges are
not used effectively. The following fundamental principles
are necessary to establish and maintain effective centrifugal
separator procedures for marine residual fuels.
The centrifugal separators are the foundation of the diesel
fuel treatment system.
To treat contaminated marine fuels, supplementary systems are required in addition to the centrifuges. These supplementary systems consist of fine filtration, demulsifier

162 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


00
LU

E
4)
(0

>.
(A
V
U

z
o
zbJ
2

<
2

>
^
^
0)
3

>
.E
O)
c

>
(0
0)

J>
1^

3 I
/5 <

/)>
j j

r -I
1 D^

Q_0

<i

CD ' - '

LJ O
5 UJ

-"HX

LJ

5
UJ

oz

d
iT

CHAPTER

6: INTROD

chemicals, combustion catalyst chemicals, and homogenizer/emulsifiers.


Each centrifuge must be supplied with a complete manual,
all necessary parts to operate as a purifier and as a clarifier,
a complete set of spare parts, seals, gaskets, etc., and a
complete set of specialized tools.
The combined centrifuge flow rate (for parallel operation)
and the single centrifuge flow rate (for series operation)
must not exceed the diesel engine demand by more than
10%.
All residual fuel centrifuges should be operated continuously, even in port. This reduces fuel contaminants and increases the effective time for fuel treatment.
To properly adjust and operate a centrifuge, these residual
fuel properties must be known:
1. viscosity
2. density
3. fuel oil compatibility
4. water content
5. ash content (or bottom sediment content)
6. catctlyst fines content (as measured by aluminum plus
silicon content)
With this residual fuel information, fuel treatment decisions can be made.
Whenever a residual fuel from a different bunkering is
transferred to the settling tank, a density check of this new
origin fuel should be made to determine if a gravity disk
change is needed in the purifier.
Since the centrifugal separator is the foundation of the
residual fuel treatment system, its reliable and efficient operation is critical to the durability and reliability of the diesel
engines. The operation of the centrifuge must be thoroughly
understood by all shipboard engineers so they cein immediately troubleshoot any problems. The following conditions
can cause mal-operation of the centrifuges.
Improper residual fuel handling such as improper or inadequate blending, incompatible residual fuels, and emulsified fuels.
Improper flow rate, such as varying flow rates, excessive
flow rates, or varying densities.
Improper temperature control, such as varying temperatures or temperatures below 98 C.
Improper water/fuel interface inhibiting a uniform flow of
fuel through all disks, usually caused by the installation of
an improper gravity disk. As the residual fuel properties
change, the gravity must be checked and changed (if necessary) to control the water/fuel separation zone for maxim u m efficiency.
Improper operation with a water-in-fuel emulsion blocking
efficient water and solids removal through the sludge zone.
Overloading the centrifuge with a n accumulation of
sludge, which is usually caused by extended desludging intervals or by incompatible residual fuels.
Another area of concern is the centrifuge valving to prevent
contamination from passing through the centrifugal separators during start up. Immediately after the separators, valving should allow the recirculating of residual fuel back to the
settling tank during the centrifuge start up process. During
start up, a considerable time must be given to allow the flow
rate and the fuel temperature to be increased and stabilized

UCTION

TO MARINE

PETROLEUM

FUELS

163

before the separator efficiency has optimized. If residual fuel


is recirculated to the settling tank during this time, no contamination will be passed on to the service tank. Once stabilized, the valving can be switched to allow properly centrifuged fuel to flow to the service tank.
Proper practice requires at least two centrifugal separators
to be properly sized, adjusted, and operated. When operating
at the recommended flow rate for m a x i m u m separating efficiency, each of the two separators must be capable of treating the maximum fuel rate of the diesel engine(s) plus approximately a 10% margin. For normal operation, the series
method of a purifier followed by a clarifier is the preferred
flow path. The first separator operates as a purifier to remove
sludge, sediment, a n d water. The second separator is arranged as a clarifier to remove any remaining sediment or
catalyst fines from the residual fuel. Additionally, the clarifier
provides a backup to the purifier should it malfunction.
Parallel centrifugal separator operation is recommended
when the residual fuel contains a high water content. The
parallel operation allows each sepsirator to operate as a purifier at one-half the normal fuel flow rate. By doubling the residence time in each purifier, the water removal efficiency of
each purifier is enhanced. In the parallel configuration, both
purifiers provide the highest cleaning efficiency and, therefore, the cleanest fuel to the diesel engine. There is just one
problem: if either purifier should malfunction, there would
be n o second stage of centrifugal separation to prevent contamination from directly entering the diesel engine.
The decision to operate in series or parallel is a judgment
that the ship's engineers must make based upon reviewing
the analysis of the representative sample taken during the entire bunkering operation. The fuel analysis must be examined
for viscosity, density, water content, sediment, ash, catalyst
fines, and compatibility in addition to the expected voyage
fuel flow rate.
Filters a n d Strainers
All marine residual fuel systems use coarse strainers to provide gross protection from very large fuel contaminants. But
in diesel power plants, fine filtration serves a major function
in controlling highly abrasive solids from reaching the engine. It is because of the high ash, sediment, and catalyst
fines content of marine residual fuels that supplemental fine
filtration is recommended. Even though the fine filtration is
considered as backup to the centrifugal separator system,
these filters are essential to ensure that the fuel delivered to
the diesel engine is free of damaging abrasive particles. All
fine filtration should be duplexed to allow cleaning and replacement of filter elements without a n interruption in fuel
flow. An effective fine filtration system can provide positive
protection from abrasive particles that would normally damage high pressure injection pumps, injection VcJves, injection
nozzles, cylinder liners, piston rings, and piston ring grooves
in the piston. Typically, these fine filters require the filter elements to be replaced at 2 0 0 0 ^ 0 0 0 h intervals under normal
operating conditions.
Additionally, fine residual fuel filters can be used with homogenizers to reduce the asphaltene and sludge removal by
filters. In fact, most of the matter collected in fine filters is
non-particulate, organic hydrocarbon material. The basic

164

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

function of a homogenizer is to disperse the sludge and asphaltenes in the residual fuel to prevent the removal of these
hydrocarbons while passing through the fine filter. Therefore, the homogenizer can greatly increase the life of the filter elements as well as reduce the total quantity of sludge removed from the residual fuel. The reduction in sludge burden
reduces the problems and expense of sludge removal and decreases the wasted heating value of the lost sludge.
Some fine filters have the ability to remove trace quantities
of free water missed by the purifiers. Even though trace water removal might seem insignificant, shipboard testing has
shown a 100% increase in injection p u m p life after the addition of fine filters to remove the trace water from the marine
residual fuel. It is critical that the water sumps in fine filters
are drained daily to prevent water from rising above the
sump level and wetting the filter elements.
Self-cleaning or auto-flushing filters contain metallic
screens that automatically or periodiccdly back flush to clean
sections of the screen to allow for continuous operation. The
sludge and debris back flushed must be treated and finally
discarded. A problem can arise when filtering even a mildly
incompatible fuel since the increased sludge volume can require the filter to back flush u p to 400 times a day. This can
cause increased wear on back flushing components and on
the screen, as well as produce a Icirge volume of sludge for
disposal.
There are two t3rpes of replaceable, cjirtridge-type fuel filters: the surface type a n d the depth type. Surface elements
are similar to metal screens that have a limited thickness.
They can be made from cellulose, fiberglass, felt, or metal.
Surface filter elements are frequently pleated to increase the
filtration surface area within a given space and to increase
the element's life. A problem with surface filters is that organic sludge and/or asphtdtenes, together with solids, cEin accumulate on the surface of the filter and seal the surface. This
results in rapidly increasing pressure across the filter, which,
in turn, limits the useful filter life.
A depth filter is designed so that the entire depth of the element works as a progressive filter. This allows the contaminants to be controlled throughout the element's depth Eind reduces the buildup of contaminants on the surface that can
reduce filter life. This feature is especially important for fuels
with residual components that can cause problems for surface filtration.

Boost Systems and Deaeration


The boost or service system consists of two p u m p s (one running, one standby) providing fuel to the boost heater sets, the
viscometer, the homogenizer, the final filter, and to the diesel
engine injection system. Duplex strainers of 20 to 40 mesh
protect the boost p u m p s from tank and piping debris.
Modern fuel systems use deaeration units t h a t remove
gaseous bubbles from the return fuel from the engine. These
systems are closed and pressurized to prevent fociming and
frothing of the hot residual fuel. Older systems were open to
the atmosphere in the mixing t a n k where the r e t u r n fuel
mixed with the incoming fuel and the gaseous bubbles were
intended to dissipate within the tank. All older/boost systems
should be upgraded to closed, pressurized systems at a convenient yard period. Closed, pressurized systems should use

deaerator units to remove any gaseous or vapor bubbles from


the r e t u r n fuel before the fuel gets back to the injection
p u m p s . Closed, pressurized boost systems stre the best to prevent operating problems when operating on high viscosity
residual fuels, b u t they do require additional circulating
p u m p s to be effective.
Fuel Service Heaters
Two fuel heaters are needed in the service or booster system,
with one clean heater on standby. Steam is the normal heating m e d i u m for the t5rpical shell a n d tube or plate style
heaters. Frequently, duplex 20 to 40 mesh strainers protect
the heater sets from piping debris. The heater sets should
have the capability of heating the fuel to 150F without thermally stressing the fuel in the heater (and coking the heaters).
Heaters made from stainless steel, titanium, and aluminum
are preferable over copper-based materiEds. The temperature
control for the heater(s) should be the automatic viscometer.
Viscosity Control
The automatic viscometer continuously samples and measures the viscosity of the fuel and controls the steam to the
heaters to maintain a preset injection viscosity to the engine's
fuel injection system. This is critical since viscosity control is
a major factor in efficient fuel injection into the diesel engine.
Real time, accurate viscosity measurement is very important
because of the low viscosity index of m o d e m , highly cracked
residual fuels. Since the viscometer is critical to correct fuel
viscosity control, the units should be checked and ccdibrated
periodically. A valved bj^Dass line, together with isolation
vEdves before and after the viscometer, can provide the means
to service the unit without a main engine shutdown.
Fuel Supply Flowmeter
To accurately measure the engine's fuel consumption, a fuel
supply flowmeter is needed. A mass flowmeter or a positive
displacement type of meter that is reliable and accurate is
recommended. A corrosion resistant material should be used
on EJI oil wetted internal surfaces. Some fuel system arrangements require the use of a second fuel flowmeter to measure
the return fuel from the engine's injection system. In these
systems, the return flow must be subtracted from the fuel
flow to determine the fuel used by the engine. The return
flowmeter should be the same type a n d model as the fuel
flowmeter.
Fuel Final Filter
Since the high pressure injection p u m p s are sensitive to any
debris, the boost system should be fitted with a final simplex
10 micron filter located just before the supply to the fuel injectors. This filter should be fitted with a differential pressure
indicator. Some operators opt to use self-cleaning final filters
to minimize manpower.
B a c k Pressure Control
To minimize foaming, cavitation, and vapor formation in the
fuel returning from the fuel injections pumps, a positive pres-

CHAPTER 6: INTRODUCTION
sure of 350 kPa will be needed for high viscosity residucil fuel
that requires a high preheat for proper injection viscosity.
Homogenizer
As residual fuels become more dense with a higher viscosity
and higher carbon and asphaltene contents, homogenizers
will become more important to aid in the preparation of the
fuel for injection, complete combustion, and the reduction of
exhaust peirticulates cmd opacity (smoke). Very simply, a homogenizer disperses insoluble hydrocarbon clusters in the
residual fuel, completely disperses all free water and cem produce a stable, water-in-fuel emulsion (when potable water is
added to the fuel prior to the homogenizer). The homogenizer breaks up the insoluble hydrocarbon materials and
sludges into very fine particles that aid ignition and burnout
of the high boiling range, high molecular weight materials.
There are several different types of homogenizers available,
but the most effective operate on cavitation and shear principles, and require significant power to operate. Other units
operate on some ultrasoniccJly. As fuels become more heavily cracked, the use of homogenizers will increase. When
used regularly, homogenizers can reduce the unbumed fuel
particles that cause waste heat boiler fires (from unbumed
fuel particles).

TO MARINE PETROLEUM FUELS

165

engines operate at sustained metcJ temperatures over twice


those found in diesel engines, the cleanliness requirements of
the fuel are much more severe than those for diesel engines.
In gas turbine engines, it is criticcJ to control metallic compounds, insoluble and soluble fuel contaminants, dissolved
water soluble metallic contaminants, fire water, solids, and
sometimes microbial contaminants [16,17].
The gas turbine fuel treatment system is similar to the
diesel engine system except for the more intensive treatment
needed to all but eliminate metallic contamination in the
fuel. Where some metallics, such as vanadium and nickel
cannot be (practically) removed by fuel treatment, they can
be neutralized using fuel additives. For example, marine
diesel engines can operate well at hundreds of parts-per-million of metallic contaminants, whereas gas turbines must
have metallic contaminants in the single digit parts-per-million range, or less. This critical requirement places great emphasis on all aspects of fuel purchase, sampling, delivery,
storage, and treatment. The fuel treatment system must consistently and reliably control fuel contaminzmts without upsets or malfunctions. Additioneilly, most gas turbine manufacturers strongly recommend that starting, warming up, and
shutting down be done with a clean, contaminant-free, light
distillate fuel. Once the engine has been warmed up and stabilized, the residual/crude oil can then be introduced into the
fuel system.

Emulsifiers
Emulsifiers are units that produce a controlled, stable, waterin-fuel emulsion of residucd fuel. Emulsifiers can be homogenizers with the addition of potable water. The IMO has considered water-in-fuel emulsions as the most cost-effective
method to reduce NOx exhaust emissions for existing marine
diesel engines. If marine diesel NOx reductions ever mandate
the control of NOx on existing ships, water emulsion retrofits
will be the primary technology utilized.
Waste Heat Economizers
As diesel engines become more efficient and slower ship
speeds result in reduced diesel engine loads, the heavily
cracked fuels are not completely burned out in the diesel engines. The residue of unbumed cylinder lube oil added to the
organic fuel residue causes the waste heat economizer to experience a greater rate of tube fouling, soot fires, and major
economizer (iron or hydrogen) fires. Since the mid 1980s, the
incidence of economizer fires has steadily increased. The homogenizer Ccm minimize the unbumed residual fuel residues
and, if potable water is added to produce water in fuel emulsions, the economizer can be maintained in a cleaner condition. Chemical additives used in the residucd fuel can also
benefit the cleanliness of the economizer.
As a minimal precaution, waste heat boilers should instcJl
cind monitor the economizer exit temperature and the pressure drop across the unit to warn the engineers about an impending fire.

GAS TURBINE FUEL SYSTEM


Gas turbine engines can operate on gaseous and liquid fuels,
including limited residual fuels and crude oils. Since these

Tankage
The fuel treatment system actually begins with the fuel tamks,
since the initial settlement for free water and solids occurs in
storage. Gas turbine fuel tanks should be fitted with floating
suctions and fill line diffusers. The floating suctions draw the
cleanest fuel from the top of the tank continuously, allowing
more time for the settlement of contaminants in the mid and
lower regions of the tanks. A fill line diffuser reduces the velocity of the fuel and redirects it during tank filling to prevent
reentrainment of tank bottom settlement. Also, it all but eliminates currents in the tank that hinder settling.
Since metallic contamincmts are to be minimized, coating
the inside tank surfaces with an inert, non-metallic coating,
such as an epoxy, is recommended. Under no circumstances
should a zinc type coating be considered.
Fuel Treatment
As with all marine fuel treatment systems, the centrifugal
separator is the foundation and keystone of the system. But,
with gas turbine systems, this separator system becomes
much more comprehensive and complicated [18]. A modem
residual fuel or crude oil burning gas turbine usually requires
two stages of water washing, centrifuging at reduced flow
rates, the use of demulsifying chemical additives, and the use
of metallic neutralizing fuel additives (see Fig. 14). Demulsifying chemicals reduce the tendency of residual fuels to readily emulsify with water. Since these emulsions are difficult to
break in the sepjirator, the use of a demulsifier is recommended to prevent a problem during water washing of the
gas turbine fuel.
Figure 14 shows a typical two-stage water washing gas turbine system using a demulsifying additive. The staged water

166 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


o
XQUJ.

cr
C)
h-

^
o

X
00

P^^

1 ^
LJ<
C/lh^

<,

LU

o
1

1 LJJ
Q: 3
LiJ _ |

Z)

tLi-

^
(/)

<L^

5Ld

washing system is used to reduce the sodium level to below


one part-per-million. The system operates by use of a metering pump that adds a demulsifying additive to the untreated
residual fuel. The in-line heater set increases the fuel temperature up to 97-99C. The demulsifier and heated residual
fuel are thoroughly mixed with 98C recycled wash water in
the first mixing tank before flowing to the first centrifugal
separator. Five to ten percent clean water wash water at 98F
is then metered into the discharge of the first centrifuge and
mixed in the second mixing tank. The residual and water
mixture then flow to the .second centrifugal separator for final water and solids removal.
To maintain an effective gas turbine treatment system, all
treated fuel must pass through a monitor that reads the water content in the residual fuel after the second separator.
The separators must also remove solid contaminants such
as catalyst particles, sand, rust, and debris from the fuel to
prevent damage and wear to the gas turbine fuel nozzles. Additionally, these aggressive solids can cause severe erosion to
the turbine blades and turbine nozzles.
The final step in the gas turbine fuel treatment process is to
inhibit/neutralize the vanadium and nickel with a chemical
additive. These additives are metered into the clean fuel
stream just prior to gas turbine usage. Oil soluble additives,
which are the easiest to use, are cost effective for vanadium
and nickel levels below 150 PPM.
Above 150 PPM, additive cost dictates more economical
water soluble or oil dispersable magnesium additives as an
alternative. These alternative additives have low operating
costs but higher capital costs.
(0
Heater sets for gas turbine residual fuels should be low
a
density designs to prevent heater deposits and to prevent
destabilizing of any additives used with these fuels.
Gas turbine treatment systems require filtration to remove
(5
all solids above five microns. This level of filtration of residual fuel requires a specialized filtration medium that is an all
organic, depth type, system. This is critical since gas turbines
have a lower tolerance than diesel systems for solid contaminants.
Lastly, a final filter, not necessarily a five micron unit,
should protect the gas turbine from any piping or system related debris.
In addition to using a clean distillate for starting and stopping the gas turbine engine, a fast acting bypass system
should be installed to allow the distillate to purge out the
residual fuel from the gas turbine's lines in case of an emergency shutdown, stall, or trip. If residual fuel solidifies in the
piping of the gas turbine, the engine will require disassembly
prior to restart.

I
I
2

CONSTRUCTION MATERIALS
In a typical gas turbine treatment system, iron-based materials, steel, and stainless steel are all valid material choices. It
is important that no copper, copper alloys, zinc or any of its
alloys (such as galvanized) be allowed to come into direct
contact with the fuel. Copper and zinc alloys or coating must
never be used in tubes or coils within heaters nor in any coating or cladding for fuel storage tanks. It is essential to avoid
the use of any galvanized piping or tank plating, as well as the

CHAPTER

6: INTRODUCTION

popular zinc-rich tank coatings. The preferred tank coating


would be an epoxy type coating.

TO MARINE

D396
D2880
(also see D 4418)

PETROLEUM

FUELS

167

Fuel Oils (Steam Plant Spec)


Gas Turbine Fuel Oils (G.T. Spec.)

Conclusions
The supply of marine residual fuels will experience pressure
from three eireas. Refineries will receive heavier crude oils,
which will result in higher density, higher carbon content
marine residual fuels. Then as refineries upgrade, there is
more pressure to increase the intensity of cracking that will
result in fuels with more ignition problems and higher carb o n contents. Lastly, the shore side (and to a lesser extent
marine) environmental regulations will require cleaner burning fuels with less sulfur and less aromatics. This will divert
more difficult, heavier fuels into the marine market. The net
result will be that more difficult fuels will increase in the marine market.
Then, from the engine manufacturers, come new diesel engines with higher Brake Mean Effective Pressure (BMEP),
higher fuel injection pressures, that are more demanding of
ignition quality and are more sensitive to fuel contaminants.
The combustion of the residual fuel supply quality and the
trend in m o d e m diesel engine design will demand larger,
more efficient fuel treatment equipment to be assembled into
more comprehensive fuel treatment systems to preclude operating problems and schedule interruptions. Older diesel
ships should upgrade fuel treatment systems to prevent problems caused when older fuel treatment equipment/systems
try to cope with m o d e m cracked fuels.
As gas turbine engines continue to grow in the military marine and in cruise ships, their fuel treatment systems must
maintain the highest fuel quality and least contamination of
any marine engine. Since gas turbine engines use only 100%
distillate fuels, the problems are initially easier, but one load
of contaminated fuel can cause severe hot corrosion damage,
so continued vigilance is needed to prevent fuel related problems.

ASTM STANDARDS
No.
D 445
D 1298
D 613 for Distillates
D 4868
D 93
D
D
D
D

97
482
95
4176

D 4294

D 524
D 2069-98

Title
Kinematic Viscosity of Transparent &
Opaque Liquids
Density by Hydrometer
Cetane N u m b e r of Diesel Fuels
Estimation of Net and Gross Heat of
Combustion of Petroleum Fuels
Flash Point by Pensky-Martens Closed
Cup
Pour Point of Petroleum Products
Ash from Petroleum Products
Water by Distillation
Free Water and Particulate Contamination in Distillate Fuels
Sulfur in Petroleum Products by Energy-Dispersive X-ray Fluorescence
Spectroscopy
Carbon Residue, Conradson,
of Petroleum Fuels
Marine Fuel Specifications

OTHER STANDARDS
ISO
ISO 8217, Annex B for Residuals: Calculated Carbon Aromaticity Index Calculation
ISO10478, Cat Fines: Digestion & Analysis of Catalyst Particles
ISO 10307-2, Compatibility: Total Sediment Potential of
Petroleum Fuels
ISO 14597,Vanadium and Nickel: Determination of Vanadium and Nickel in Liquid Fuels^Wavelength Dispersive
X-Ray Fluorescence Spectrometry
ISO 10478, Sodium: Sodium Content of Petroleum Fuels
ISO 3735, Storage Oxidation: Storage Oxidation of
Petroleum Fuels
ISO 3735/10307-1, Sediment: Total Sediment Existent of
Petroleum Fuels
ISO 8217, Petroleum ProductsFuels (Class F): Specifications of Marine Fuels
Military F u e l Specifications
MIL-F-16844: All Purpose Marine Distillate Fuel

REFERENCES
[1] Winkler, M. F., Residual Fuel Oil User's Guidebook, Volume 4,
Diesels; and Volume 3, Gas Turbines; Southwest Research Institute for Electric Power Research Institute, May 1988. EPRIAP-5826.
[2] Leigh-Jones, C, A Practical Guide to Marine Fuel Oil Handling,
The Institute of Marine Engineers, London, 1998.
[3] Winkler, M. F., The Influence of Fuel Quality on the Performance,
Operation, and Maintenance of Diesel Propulsion Engines, Maritime Administration, U.S. Dept. of Commerce, March 1979.
[4] Winkler, M. F., Relationship of Fuel Quality to Marine Boilers and
Diesel Engine Performance, The Society for Marine Port Engineers, NY, January 1978.
[5] Barnes, G. K., Liddy, J. P., and Marshall, E. G., "The Ignition
Quality of Residual Fuels," CIMAC Paper 25, International
Council of Combustion Engines, 1 Birdcage Walk, Westminster,
London SW1H911, UK, June 1987.
[6] The Flammability Hazards Associated with the Handling, Storage
and Carriage of Residual Fuel Oil, Oil Companies International
Marine Forum (OCIMF), 27 Queen Anne's Gate, London,
SWIH, 9BU, December 1989.
[7] Winkler, M. F., "Coping with Today's FuelsDistillate and
ResidualDiesel and Steam," Society of Naval Architects and
Marine Engineers, Jersey City, NJ. Presented at the SNAME
Chesapeake Marine Engineering Symposium, Washington,
D.C., January 1984; Society of Marine Port Engineers, NY,
March 1982; National Maritime Show, Baltimore, March 1982.
[8] Winkler, M. F., "Fuel Management: Coping With Future Fuels,"
Marine Engineering/Log Magazine, March 1983.
[9] Newbery, P. J., Davies, T. A. C, and Chomske, K. M., "Heavier
Residual Fuels for Marine Diesel Engines," MotorShip Magazine,
West Sussex RH16 3DH, UK. Presented at the 6th International
Motorship Conference, London, March 1984.

168 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


[10] Winkler, M. F., Systems Design for Future Fuels-Steam and
Diesel, Society of Marine Port Engineers, Avenel, NJ, 1983.
[11] Winkler, M. F., "Operational Problems and Marine Fuel Oils,"
Presented at the International Conference and Long-Term Storage Stabilities, San Antonio, TX, Jixly 1986; Society of Automotive Engineers Conference, Washington, D.C., May 1986.
[12] Winkler, M. F., "Shipboard Fuel Handling and Treatment For
Diesel Engines," presented at the ASTM International SjTnposium on Marine Fuels, Miami, FL, December, 1983; Society of
Maritime Arbitrators, NY, October 1983; Fort Schuyler Forum
sponsored by Society of Marine Port Engineers, NY, March 1981.
[13] Fisher, C. and Lux, J., BUNKERS: An Analysis of the Practical.
Technical and Legal Issues, Second Edition, 1994, Lloyd's of London Press, NY, 1994.

[14] Winkler, M. F., "Diesel Fuel Systems to Prevent Operational


Problems," presented at the S.A.E. Marine Propulsion Technology Conference, 14 May 1986, Washington, D.C.
[15] ISO 8216-0: Petroleum Products - Fuels (Class F) - Classification
- Part 0: General, International Organization for Standardization, Geneva, Switzerland, 1986.
[16] Winkler, M. F., "Management of Gas Turbine Fuel Systems,"
Gas Turbine International Magazine, March-April 1977.
[17] Winkler, M. F., "Management of Residual Fuel Systems for Gas
Turbines," Gas Turbine International Magazine, May-June 1977.
[18] Winkler, M. F., "Management of the Gas Turbine Fuel Systems,"
ASTM International, October 1973; Society of Automotive Engineers, Canada, August 1971; Society of Automotive Engineers,
Philadelphia, November 1970.

Section III: Hydrocarbons and Synthetic Lubricants:


Properties and Performance
Rajesh J. Shah, Section Editor

MNL37-EB/Jun. 2003

Hydrocarbon Base Oil


Chemistry
Arthur J. Stipanovic^

chemistry:
provide a brief overview of the base oil market and identify
emerging trends,
outline the refinery processing scenzirios typical of current
base oil production in the United States,
review the chromatographic and spectroscopic techniques
most commonly used to characterize base oil composition,
provide a comparison of hydrocarbon tjrpe distributions
for base oils obtained by several different refinery processes, including re-refined oils,
review important chemical mechanisms leading to the oxidation and degradation of base oils,
outline composition/performance relationships for base oils
in various automotive and industrial lubricant applications.

HYDROCARBON BASE FLUIDS COMMONLY USED in the formulation

of engine oils, industrial lubricants, greases, and other products, are composed of a broad spectrum of molecular species
including aromatic, paraffinic, a n d cycloparaffinic (naphthenic) molecules [1-4]. Over the past severeil decades, new
separation methods and analytical techniques have made it
possible t o accurately characterize and quantify the hydrocarbon t5^es that exist in base oil while relating these compositional pEirameters to crude oil source and refining conditions. F o r example, ASTM test m e t h o d D 2549 exploits
column chromatography to separate a base oil into saturate
and aromatic fractions while D 2786 and D 3239, mass spectrometry techniques, further sub-divide each fraction into a
group of molecular types. As a result, the physical and chemical properties of base fluids are now m u c h better understood
and, in some cases, it has become possible to predict the performance of a formulated lubricant directly from base oil
composition using statistical m e t h o d s o r neural network
modeling [3-8].

LUBRICANT B A S E OIL M A R K E T
Refining Capacity i n the United States

From the perspective of lubricant applications, among the


most important properties that depend directly on base oil
composition include viscosity index (VI), oxidative/thermaJ
stability, low temperature fluidity, a n d additive solubility.
Other significant parameters such as kinematic viscosity and
volatility are influenced primarily by molecular size although
composition may play a role as well. As will be discussed in
this chapter, each of these performance parameters is influenced differently by subtle changes in the hydrocarbon type
distribution of the base oil and, as a result, they are sensitive
to crude oil source and refinery processes. Further, since base
oil refining technology is changing at a revolutionary pace, it
is increasingly important that lubricant formulators appreciate the impact of base oil chemistry on product performance.
Although synthetic fluids such as polyalphaolefins a n d
polyesters have grown in their importance in many lubricants, this chapter will focus on mineral oil base fluids derived from crude oil via a n u m b e r of refinery processes. For
most lubricant product lines such as engine oils and industrial process oils, mineral basestocks account for greater than
90% of the commercieJ product volume, although the marketplace penetration of S5rnthetics is increasing modestly [9].
The organization of this chapter will focus on the following
issues in base oil technology a n d hydrocarbon lubricant

Since most lubricants typically contain in excess of 80% base


oil by volume, their physical and chemical properties play a
key role in defining the ultimate performance profile of a lubricant and the additive technology that must be employed in
formulation. In addition, the marketplace availability, cost,
and qucdity of base oil are critical considerations in defining
the economics and performance of a finished product. As a
result, lubricant development requires a n understanding of
both the base oil meirket and the techniccil issues surrounding specific product requirements.
On a global basis, the market for hydrocarbon-based mineral oils a n d wax exceeds 10 billion gallons per year [10]
while annual U.S. production is approximately 3.5 billion
gallons [11], of which about 20% is designated as "naphthenic" and 80% "paraffinic" (these terms will be defined below). A profile for the eleven largest base oil refiners in the
U.S. is provided in Table 1.
Petro-Canada, a major base oil producer in Canada, provides a n additional 230 MM gallons/year from its Mississauga, Ontario plant while Imperial Oil in Samia, Ontario refines a n additional 92 MM gallons/year. Annual base oil
re-refining capacity in the U.S. and Camada is estimated to be
approximately 62 MM gallons and 32 MM gallons, respectively, as outlined in Table 2 [11].
B a s e Oil M a r k e t P r i c e s

' Director, Analytical and Technical Services, Faculty of Chemistry,


State University of New York, College of Environmental Science and
Forestry, 123 Jahn Laboratory, One Forestry Drive, Syracuse, NY
13210.

Although the market price of base oil varies dynamically over


time in response to crude cost and availability as well as re169

Copyright'

2003 by A S I M International

www.astm.org

170 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

TABLE 1Production of lubricating oils and waxes1999 [11].


Refiner
Exxon
Equilon"
Sun
Motiva*
Excel Paralubes"
Chevron
Pennzoil-Quaker State
Mobil
Valero Energy Corp.'*
Cit-Con
MarathonAshland

Location
Baton Rouge, LA
and Baytown, TX
Deer Park, TX,
Martinez, CA and
Wood River, IL'
Tulsa, OK and
Yabucoa, PR
Port Arthur, TX
Westlake, LA
Richmond, CA
Rouseville, PA and
Shreveport, LA
Beaumont, TX
Paulsboro, NJ
Lake Charles, LA
Catlettsburg, KY

Capacity
(mm GallonsA'ear)
577
298
271
269
269
214
199
180
176
146
130

"Shell/Texaco joint venture. Formerly Shell base oil refineries.


^Shell/Texaco/Star Enterprise joint venture. Formerly a Star Enterprise
refinery.
"Conoco/Pennzoil joint venture.
''Formerly a Mobil refinery.
'Since the 1999 NPRA report, the Wood River facility no longer produces
lubricants.

TABLE 2Re-refined base oil production in the U.S.


and Canada [11].
Refiner
Evergreen Oil Inc.
Safety-KUeen Corp.
Hub Oil Company
Mohawk Lubricants Ltd.
Safety-Kleen Corp.

Location
Newark, CA
East Chicago, IL
Calgary, Alberta
N. Vancouver, BC
Breslau, Ontario

Total

Capacity
(mm GallonsATear)
12.3
50.6
3.1
6.1
23.0

95.0

gional refinery supply/demand issues, Table 3 provides a general reflection of base oil prices in early 1999, when crude oil
averaged less than $20/bbl compared to 2000 when crude
cost climbed above $25/bbl [12 A,B]. Table 3 also illustrates
that base oil prices generally increase with increasing viscosity grade due to several factors including: the "natural"
molecular weight range of the crude sources used for lubricant manufacture and the extra refining required for heavier
distillate streams, since they are t3rpically richer in aromatics
and sulfur-containing molecules. Based on an average price
of $1.00 per gallon, domestic base oil refiners generate revenues in excess of $3.5 billion annually.
Future Refining Trends
Although basestock demand is growing only modestly in
North America at less than 3% per year [9], other regions of
the world are expanding more quickly [10]. Specifically, certain South and Central American and Asian countries are experiencing lubricant growth demand in excess of 5% per
year. In all cases, an evolution to higher quality base stocks,
such as Group II and III oils, defined below, is evident on a
worldwide basis [13]. As a result of extreme competition to
produce and utilize Group II base stocks and an overall reduction in demand for naphthenic stocks, the base oil refin-

ing capacity in North America has decreased by approximately 8% from 1980 to 1995 [10].

BASE OIL REFINING AND PROCESSING


TECHNOLOGY
Crude oil sources from which lubricant-grade mineral oils
are refined contain thousands of molecular species differing
in chemical constitution and size [14]. Base oil manufacture
is, therefore, a very complex process that fractionates
molecules based on molecular weight (size) and composition to yield a product with appropriate viscosity and chemical stability. At least five processing stages may be employed
to produce a lubricant base oil: 1) crude distillation; 2) deasphalting to remove very heavy fractions of the crude; 3) solvent extraction or hydrogen refining to remove undesirable
aromatics and heteroaromatic species; 4) solvent or catalytic
dewaxing to remove linear paraffins (wax), which can crystallize, causing poor flow properties at low temperatures;
and 5) hydrogen finishing or clay treatment to remove trace
quantities of heteroaromatic species, olefins, or other
molecules that could cause stability problems [10]. In addition to removing undesirable molecular species, refining
generally increases the viscosity index (VI) of a distillate. VI
reflects the relationship between base oil viscosity and temperature and is calculated from kinematic viscosities
recorded at 40C and 100C (ASTM D 445) using an empirically derived procedure defined in ASTM D 2270. All hydrocarbon-based mineral oils decrease in viscosity with increasing temperature as shown in Table 4. Comparing two
oils that have an identical viscosity at 100C (4 cSt), a lower
VI oil will have a lower viscosity above 100C and a higher
viscosity below 100C than a higher VI oil. In general, higher
VI products are considered more desirable because they
maintain a greater fraction of their viscosity and lubricating
properties at high temperatures (100-150C) while exhibiting lower viscosity, better fluidity, and improved pumpability at very low temperatures (0C and lower) when treated
with pour point depressant additives. The specific molecular
components of base oil responsible for high VI will be discussed below.

TABLE 3Market prices of paraffinic base oil in the U.S. ($/gd).


Base Oil Viscosity

Average Cost
('99/'00)

Range of Prices
('99/'00)

Low (90-150iV)
Medium (200-250yV)
Heavy (500-600A^)
Bright Stock (Very Heavy)

0.85/1.17
0.86/1.18
1.00/1.27
1.19/1.52

0.79-1.04/1.07-1.23
0.80-1.04/1.07-1.27
0.94-1.17/1.20-1.37
1.16-1.31/1.41-1.53

TABLE 4VI: The effect of temperature on viscosity.


Temperature
Oil VI

CC

40C

100C

150C

75
100
125
150

192
155
117
92

21.0
19.5
17.7
16.3

4
4
4
4

1.87
1.91
1.97
2.03

CHAPTER 7: HYDROCARBON

BASE OIL CHEMISTRY

171

TABLE 6Relationship of SUS to


kinematic viscosities for a 100 VI
base oil.

Distillation
Two distillation units are typically required to effectively
fractionate crude oil for use in lubricants [10]. First, an atmospheric still is employed to selectively remove gases and
other light products such as gasoline and naphtha from the
lube distillate stream. Secondly, the remaining stock is distilled under reduced pressure in a vacuum distillation unit
yielding a number of viscosity fractions appropriate for various applications. Typical boiling points for each crude oil
fraction are shown in Table 5. The distillation cut corresponding to lubricating oils typically consists of molecules
that range in size from 20-40 carbon atoms per molecule.
Most refineries fractionate the distillate into 3-5 distinct viscosity grades, historically called "neutrals," for which 100C
kinematic viscosity values range from 3-5 cSt for so-called
"light neutral oils," 6-9 cSt for "medium neutrals" and > 10
cSt for "heavy neutrals." In commercial practice, the viscosity grade designation for base oils, such as 100 Neutral
(lOON), was based on the Saybolt Universal Second (SUS)
system of measuring viscosity that is no longer widely utilized. Table 6 illustrates the relationship between "historic"
SUS viscosity grades and kinematic viscosities obtained from
ASTM D 445.

thenic molecules are insoluble in the extraction solvent while


multi-ring aromatics (polynuclear aromatics), sulfur and nitrogen compounds, olefins, and other undesirable species are
dissolved in the polar solvent phase. After phase separation,
the non-polar phase containing the base oil is stripped of
residual polsir solvent and is usually hydrogen treated as discussed below. Furfural, phenol, and N-methyl-2-pyrolidone
(NMP) are commonly used as extraction solvents [10,11].

Propane Deasphalting

Hydrogen Refining/Hydrocracking

For certain heavy distillates and vacuum residua, base oils of


very high viscosity (Bright Stocks) can be refined through
propane deasphalting [10]. In this process, liquefied propane
under relatively high pressure is used to precipitate insoluble,
high molecular weight aromatic hydrocarbons such as asphaltenes and to extract other compounds (typically termed
"resins"), which could be deleterious to the performance of
the base oil being refined. Sulfur and nitrogen compounds as
well as certain metals can also be removed by propane deasphalting.

Although solvent refining is effective in improving the quality of distillates in the manufacture of base oils, a significant
yield loss is normally associated with the extraction process.
This loss can be economically unacceptable for distillates derived from relatively poor crude oils that contain high concentrations of heavy aromatic compounds. Fortunately, it is
also possible to improve the quality of a raffinate through
various catalytic processes in which high-pressure hydrogen
(1500 - 4000-1- psi) is employed to saturate aromatic
molecules while cracking other large molecules to smaller
compounds of molecular weight appropriate for base oils
[10]. Olefins as well as sulfur and nitrogen containing compounds are also reacted and removed by hydrogen processing. Because aromatics are converted to saturated compounds, hydrogen processing normally increases VI.

Solvent Refining
For basestocks of low to moderately high viscosity, solvent
refining has been employed extensively and on a worldwide
basis; this refining technology is probably the most popular
method. Solvent refining removes undesirable polar and
highly condensed aromatic molecules from the distillate and,
in doing so, significantly increases VI. In this process, distillate is mixed with an insoluble polar solvent that creates a
two-phase system. Ideally, desirable paraffinic and naphTABLE 5Distillation cuts of crude oil [14, 15].
Fraction

Boiling Range (C)

Ethane, butane, propane gases


Light naphtha
Heavy n a p h t h a
Gasoline
Kerosine
Stove oil
Lights gas oil
Heavy gas oil
Lubricating oils
Vacuum gas oil
Resid

<0
to 150
150-205
to 180
205-260
205-290
260-315
315-425
>400
425-600
>600

Kinematic Viscosity
at 100C (cSt)
3
4
6
8
10
12
14
16
18

SUS Viscosity
at 100F
70
100
200
310
430
560
710
870
1000

Dewaxing
Essentially, all crude oil and base oil distillates contain a
small fraction of linear paraffins (wax) [14] that can crystallize at low temperatures. For engine oils, transmission fluids,
and other lubricants that must remain liquid and pumpable
to temperatures approaching -40C, it is necessary to remove as much wax as possible from the basestock. To accomplish this task, at least two techniques are commonly
used to remove wax: solvent dewaxing (SDW) and catalytic
dewaxing (CDW). For SDW, the base oil is first diluted in a
solvent (toluene, for example) and then the mixture is added
to a wax non-solvent (typically ketones such as methyl ethyl
ketone-MEK). The mixture is then chilled to low temperatures to precipitate wax as a solid and is then collected by filtration. SDW is a batch process. In the CDW procedure, a
shape selective catalyst is exploited to "crack" the paraffins
into smaller, volatile segments that can be fractionated by
distillation. CDW is a continuous process and, as a result, en-

172

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

joys m a n y advantages over SDW. However, since CDW is


more efficient in removing wzix and other branched pEiraffins
than is SDW, the resulting base oil VI is usually reduced since
paraffins contribute to high VI. More recently, several processes have been developed that isomerize wax to brsmched
isomers that do not crystallize as readily as linear peiraffins.
As a result, VI is preserved by the hydroisomerization process
cind very high VI oils (>120 VI) can be made directly from
wax as a feedstock. Several API Group III base oils, to be defined below, are synthesized from a pEiraffin hydroisomerization procedure.
Hyfinishing (Hydrofinishing)
At the conclusion of the refining steps detailed above, base
oils still may contain small quantities of sulfur, nitrogen, organic acids, and partially hydrogenated aromatics that can
cause the base oil to exhibit poor color stability and an increased tendency to form sludge or other insolubles [10]. Historically, base oils were "finished" using either a sulfuric acid
procedure or clay contacting. Unfortunately, both of these
procedures jield potentially hazardous byproducts that require careful disposal to avoid environmental contamination.
As a result, most m o d e m refineries use a catal3^ic hydrogenation process called hyfinishing to remove trace levels of
impurities from base oil. Hydrogen pressures are typically
500-1000 psi, which are below the levels required for hydrocracking. Hyfinishing decreases the aromatic content of a
base oil slightly while significantly lowering sulfur and nitrogen levels. Byproducts of hyfinishing include H2S, NH3, and
CO2, which result from the cracking and hydrogenation of
undesirable organic molecules containing S, N, or O heteroatoms.
B a s e Oil R e - r e f l n i n g
The reclamation of base oil from used engine oils and industrial lubricants has become a n important process from both
an environmental protection and economic perspective. In
the U.S., a Presidential Executive Order spurred the development of re-processing technology in October 1993, requiring
that all federal agencies establish procedures to purchase lubricants containing at least 2 5 % re-refined base oil. Many
municipalities have adopted this requirement for contract
purchases of lubricants as well. Although a n u m b e r of processing m e t h o d s can be used to recycle spent lubricants,
most commercial re-refiners utilize at least three stages:
heating to remove water and residual low molecular weight
hydrocarbons (fuels), distillation to separate hydrocarbons
from polar oxidation products (sludge, varnish, other insolubles), residual fuel components, organometallic additives,
etc., followed by hydrotreating to reduce sulfur, nitrogen,
and polynuclear (multi-ring) aromatic levels. In at least one
commercial re-refining process, a p r o p a n e deasphalting
stage is employed to remove undesirable by-products etnd additives prior to re-distillation.
N a p h t h e n i c vs. Paraffinic B a s e Oils
The widely used term "naphthenic" base oils represents those
stocks produced from naphthenic crude as defined by the
U.S. Bureau of Mines Classification of Crude Oils [16]. In this

system, crude fractions that boil in the range typical of base


oils (250-275C and 275-300C; at 1 atm) are naphthenic if
they have a n API gravities of < 3 3 a n d < 2 0 , respectively.
Paraffinic oils for the same boiling ranges provide API gravities of > 4 0 and > 3 0 . API gravity (ASTM D 287) is sensitive to
the relative ratio of paraffins, cycloparaffins, and aromatics
in a crude or base oil. Higher paraffinic cheiracter increases
API gravity. A significant feature that distinguishes most
naphthenic crudes is a very low natural level of linear paraffins or wax, which enables the production of base oils with
very low pour points and excellent low temperature fluidity,
essential in some applications such as refrigeration oils.
Naphthenic base oils also have a relatively high aromatic
content, which has limited their use in other applications
where higher toxicity is a concern. Due to improvements in
dewaxing methodology and concern over the potenticd adverse health effects of naphthenic base oils, the market share
of these stocks has steadily decreased over the past decade
(see Ref 11 and earlier issues of the annual NPRA survey).

B A S E OIL CHARACTERIZATION
Hydrocarbon Type Analysis
The chemiCcd composition of lubricant base oil is strongly
dependent o n a n u m b e r of factors. These include crude oil
source, molecular weight range (generally higher molecular
weight crudes are richer in multi-ring aromatics), the refining process (solvent vs. hydroprocessing), the degree of refining, and the effectiveness of the finishing process.
Determining the chemical compositional profile of base
oil is usually initiated with a chromatographic separation
procedure to isolate the aromatic and saturate fractions
of the sample. ASTM method D 2549 involves an open colu m n procedure using a bauxite column packing with polar
and non-polar organic solvents to elute the aromatic and saturate fractions, respectively. In this procedure a sample of
base oil is applied to the top of the column, which is then
flushed sequentially with solvents of increasing polarity. Saturated molecules, including both paraffins and naphthenic
molecules, bind to the column less strongly than ciromatic
compounds and, as a result, they elute from the column with
n-pentane (non-polar) while the aromatics require "stronger"
polar solvents (chloroform/ethyl alcohol) to be eluted. Typical aromatic and saturate levels determined by D2549 for a
series of base oils, refined by different methods, are given in
Table 7. It may generally be concluded that base oils contain
a preponderance of saturate compounds and that the level of
aromatics for a solvent refined base oil increases with viscosity grade largely because heavier distillates contain higher

TABLE 7Composition of base oils.


Refining Process - SUS
Viscosity Grade

% Saturates

% Aromatics

Solvent Refining (SR)lOOA?


SR Medium Viscosity320N
SR High Viscosity850A^
Bright Stock
Hydrocracked 100
Hydroisomerized 100
SRNaphthenic Crude

70-90
65-75
60-70
50-60
90-100
95-100
60-70

10-30
25-35
30-40
40-50
0-10
0-5
30^0

CHAPTER 7: HYDROCARBON
levels of aromatics. Further, hydroprocessing techniques,
specifically hydrocracking and hydroisomerization, drastically reduce aromatic level. In addition, base oils processed
from naphthenic crudes typically exhibit a high aromatic
content and a very low level of paraffins (<8%).
A related column chromatography method, ASTM D 2007,
is based on a clay-silica gel adsorption procedure that resolves a base oil sample into aromatic, saturate, and polar
fractions. In this procedure, the following solvents are used
to elute the hydrocarbon fractions: n-pentane (elutes saturates), toluene (elutes aromatics), and toluene/acetone
(elutes polars). ASTM D 2007 was chosen as the preferred
method for base oil characterization in the so-called
"Base Oil Interchangeability Guidelines" established by the
American Petroleum Institute (API) in API Publication
1509 - Engine Oil Licensing and Certification System (API
Address: 1220 L Street NW, Washington, DC 20005-4070,
www.api.org). In this publication, the API concludes
that "Not all base oils have similar physical or chemical
properties or provide equivalent engine performance in engine testing
The API Base Oil Guidelines were developed
to ensure that the performance of engine oil products is not
adversely affected when different base oils are used interchangeably by engine oil blenders" (API 1509). Under these
guidelines base oils are grouped into three categories according to composition, VI, and sulfur content as shown in Table
8. Group IV is reserved for polyalphaolefins and Group V includes other basestocks not included in Groups I-IV.
API Publication 1509 also defines which engine tests are
required when interchanging a base oil in an approved gasoline or diesel engine oil formulation using the base oil definitions above. Currently in the U.S., approximately 1.76 billion
gallons of annual production of paraffinic base oil is Group I
while 870 million gallons/year is Group II [11]. The ratio of
Group II to Group I has increased significantly since the early
1990s and most new base oil plants utilize refining technology that provides Group II stocks.
In reference to the ASTM D 2007 procedure, it should be
noted that a hydrocarbon analysis technique based on ThinLayer Chromatography with Flame-Ionization Detection has
TABLE 8 --API lubricant base stock categories
API Group
I
II
III

% Saturates

% Aromatics

VI (1)

% Sulfur (2)

<90
>90
>90

>10
<10
<10

<120
>80, <120
>120

>0.03
<0.03
<0.03

"Viscosity Index by ASTM D 2270.


^Sulfur content by any of the following: ASTM D 2622, D 4294, D 4927,
D3120.

TABLE 9Typical saturates distribution of lOON (4 cSt)


base oils.
Relative Volume %
Hydrocarbon Type

Group I

Group II

Group III

Paraffins
Monocycloparafflns
DlcyloparafHns
Tricycloparafflns
TetracycloparafHns
Pentacycloparafflns
Hexacycloparaffins

23.9
14.7
11.3
8.1
9.9
6.6
4.2

22.0
23.1
19.2
11.7
9.3
7.2
5.6

70.2
11.8
5.3
1.8
1.6
0.6
2.5

Total

78.7

98.0

93.7

BASE OIL CHEMISTRY

173

TABLE 10Typical aromatic distribution of lOON (4 cSt)


base oils.
Relative Volume %
Hydrocarbon Type

Group I

Group II

Group III

Monoaromatics
Diaromatics
Triaromatics
Tetraaromatics
Pentaaromatics
Thiophenaromatics
Unidentified Aromatics
Total

11.7
3.1
1.1
0.8
0.4
1.6
2.7
21.4

0.9
0.6
0.2
0
0
0.1
0.2
2.0

4.0
0.9
0.2
0.1
0.1
0.4
0.6
6.3

TABLE 11Typical aromatic sub-categories for a 70A^


group I base oil.
Hydrocarbon Type

Volume %

Monoaromatics

Total
13.2

Alkylbenzenes
Naphthenebenzenes
Dinaphthenebenzenes
Diaromatics

6.94
3.37
2.92

Naphthalenes
Acenaphthenes, dibenzofurans
Flourenes
Triaromatics

0.91
0.89
0.77

Phenanthrenes
Napthenephenanthrenes
Tetraaromatics

0.45
0.22

Pyrenes
Chrysenes
Pentaaromatics

0.08
0.17

Perylenes
Dibenzanthracenes
Thiophenoaromatics

0.06
0.03

Benzothiophenes
Dibenzothiophenes
Naphthobenzothiophenes
Unidentified Aromatics

0.23
0.50
0.0

2.6

0.7

0.3

0.1

0.7

Total Aromatics

1.5
19.0

demonstrated that "the ASTM method does not always yield


pure fractions of each hydrocarbon type and cross contamination introduces considerable inaccuracies in the results" [17].
These deviations are attributed to column overloading, incomplete separation, and incomplete recovery of fractions
from the column for D 2007.
Spectrometric Identification of Base Oils
Components
Although Nuclear Magnetic Resonance (NMR) [18,19], Ultra
Violet (UV; ASTM D 2008), and Infrared Red (IR) spectroscopies [20], along with a number of chromatographic techniques [21] have been successfully employed to characterize
the compositional profile of lubricant base oils, several mass
spectrometry (MS) techniques have evolved into standard
ASTM methods suitable for base oil analysis. Once base oil
saturate and aromatic fractions are isolated by the column
chromatography procedures discussed above, each fraction
can be subjected to further analysis and sub-catergorization
by mass spectrometry using ASTM Methods D 2786 and D
3239. Tables 9-11 contain the major sub-categories of satu-

174 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

rated and aromatic molecular groups resulting from these


MS techniques for typical Group I, II, and III base oil types.
Representative molecular structures for the hydrocarbon
types outlined in Tables 9 and 10 eire given in Tables 12 and
13. It should be noted that actual "base oil" molecular structures would contain a greater number of carbon atoms than
shown in Tables 12 and 13. The structures shown are illustrative of the chemical functionality of base oil, however. A
more general discussion on the characterization of
petroleum fractions by MS is the subject of an excellent review article by Altgelt and Boduszynski [22].
ASTM D 3239 further subdivides the aromatic fraction detailed in Table 10 into sub-categories as illustrated in Table
11 for a Group I base oil.
NMR Spectroscopy of Base Oils
Although a detailed review of NMR spectroscopy as applied
to base oil characterization is beyond the scope of this chapter, it should be emphasized that '^C-NMR spectroscopy is an
extremely useful method to distinguish aromatic from saturated carbon atoms in base oil while quantifying the length
and degree of branching for peiraffinic components. Recent

papers by Sarpal [18,23] and Sahoo [24] demonstrate the potential of this method in characterizing base oil. Aromatic
carbon atoms exhibit resonances at chemiced shifts ranging
from 100-160 while saturated carbons (paraffins and naphthenes) provide shifts in the range of 10-60 ppm [24]. From
the information in Table 14, it is also possible to estimate the
average peiraffinic chain length of base oils by developing ratios of chain ends (-CH3 groups) to -CH2- groups well separated from chain ends.
A relatively new pulse protocol called DEPT expands the
utility of ^^C-NMR for base oils in that it provides individual
spectra for each carbon atom t3?pe CH where n = 0-3
thereby increasing resolution and the ability to quantify carbon species [23]. In using NMR to study base oils, care must
be taken, however. '^C-NMR is inherently non-quantitative
since each carbon atom relaxes at a rate depending on its surroundings and complete relaxation is required for integration data to be quantitative. Since carbon nuclei relaxation
times can be on the order of seconds, total relaxation between NMR pulses is not typically achieved. As a result, the
use of a so-called relaxation agent, such as chromium acetylacetonate, is essential with base oils to ensure complete relaxation enabling quantitative integration.

TABLE 12Molecular structure of base oil hydrocarbon types.


Hydrocarbon
Types

Paraffins (inclndes isoparaffins)

Mononaphthenes

Dinaphthenes

Trinaohthenes

Monoaromatics

Structures

\A/^/\

-0oCc;r
V^A^A^-JY^

^<y^

Indanes:
Aromatic / Naphthene "Hybrid"

Diaromatics

/lL^js*^j,,Jk^

CHAPTER 7: HYDROCARBON

BASE OIL CHEMISTRY

175

TABLE 13Molecular structure of base of hydrocarbon types (Continued).


Stmctures

Hydrocarbon
Types

Triaromatics

Tetraaromatics

Thiophene

-o^
0

Benzothiophene

CO

Dibenzothiophene

0:p

Napthobenzothiophene
s

TABLE 14Structural parameters derived from '^C-NMR.


R-Group
CHa
CH3
CH2
CH2
CH2
CH2

Description (1)
Short Branch E n d
Long Branch E n d (a)
Adjacent to Long Chain E n d (p)
Near Chain End (7)
Adjacent to Long Chain CH2 (8)
Middle of Long Chain (e)

Typical Chemical
Shift (ppm)
11.4
14.1
22.7
32.0
30.1
29.7

B A S E OIL C H E M I S T R Y
Oxidation Reactions
Hydroccirbon oxidation chemistry is of great importance in
the ukimate appHcation of base oils and lubricants, since at
the high temperatures typical of most lubricating environments, oxidation can lead to undesirable oil thickening, the
formation of insoluble sludge and varnish deposits, and the
creation of potentially corrosive organoacid compounds. Although this subject has been extensively covered in many ex-

cellent reviews and texts [2,25-31 ], it is worthwhile to discuss


several key mechanisms. As shown in Fig. 1, hydrocarbon oxidation proceeds through a number of steps involving free
radicals:
The initiation stage can be triggered by peroxide or hydroperoxide impurities in the oil [32] or by the thermal cracking of hydrocarbons on hot metal surfaces in cin engine, for
example. Once a radiceJ is formed it can readily extract a hydrogen atom from hydrocarbon molecule (R-H), which is
subsequently very reactive toward oxygen (O2) 3rielding a peroxide radical (R02). Table 15 compares the relative hydrogen atom abstraction reaction rates for primary, secondary,
and tertiary carbon atoms when attacked by a peroxy radical
(sec-alkyl- COO) and a t-butoxy radical ((CH3)3CO) [33].
These data show that hydrogen atoms cffe removed more
easily (faster reaction rate) in the order tertiary > secondary
> primEiry, which is directly related to the stability of the radical that is formed. This observation suggests that molecular
structures such as linear parafBns will have greater resistance to oxidation compared to other branched paraffins or
cycloloparafKns that contain a relatively greater proportion

176 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


Initiation:

I*

I-I
R-H + !

Propagation:

I-H + R*

->

R02*

R02 + R-H
Termination:

ROOH + R*

R + R02 "

-> ROOR

2R02

-R-O4-R

R-O4-R

-p. O2 +Non-Radical

Products
FIG. 1Hydrocarbon oxidation by free radicals.

TABLE 15-Relative hydrogen abstraction rates.


Molecule
Radical

CeHs CH3

sec-alkyl-COO

1
R-CH3
1

(CH3)3CO.

Cj6^5^'l2^H3

9
R2CH2

12

C6H5CH-(CH3)2

14
R3CH
44

TABLE 16Reactivity of substrate molecules


toward the phenyl radical.
Relative Reactivity
per a-Hydrogen
Substrate Molecule
1
Primary Aliphatic
10
Cyclopentane
9
Cyclohexane
72
Indane (See Table 12)
92
Acenapthalene

of secondary or tertiary hydrogen atoms. The rate of free radical propagation is Eilso very dependent on ring geometry and
adjacent function groups as shown in Table 16 for phenyl
radicals [33].
As oxidation proceeds, propagation reactions involving
peroxy radical addition to other hydrocarbon molecules typically result in the formation of polar compounds and higher
molecular weight species, which may ultimately increase the
viscosity of the oil. The combination of oligomeric and polymeric radicals during the termination phase of oxidation can
also cause a molecular weight increase and viscosity enhancement. Studies on the autoxidation of n- hexadecane
(linear CI8 paraffin) at temperatures of 160-180C have illustrated that Ccirboxylic acids, hydroperoxides, ketones, alcohols, and esters Eire all formed over a period of hours. It is
interesting to note, however, that this "model system" exhibited a significant increase in viscosity while only a "modest"
increase in molecular weight was observed [31].
A useful oxidation model for thin hydrocarbon films on
metal surfaces has been developed by Professor E.E. Klaus
a n d his co-workers at the Pennsylvania State University
[34-36]. They have shown that if Molecule A is oxidized it
forms Molecule B that initially has the same molecular
weight as A. At this stage, both A and B can volatilize to A'

and B', respectively, which can Hmit further reactivity by


evaporation from the hquid phase system. As oxidation continues, B undergoes condensation-type polymerization reactions to yield molecule P that has a high molecular weight but
is still soluble in the hydrocarbon liquid phase. As a result, P
is capable of significantly increasing the viscosity of the lubricant being oxidized. As a polymer, P is not volatile and remains in bulk solution and in contact with the metal surface.
Through further oxidation and thermal decomposition, P becomes an insoluble deposit of very high molecular weight on
metal surfaces. This model has been effective in predicting
deposits in both gasoline and diesel engine tests as well as
high temperature oxidative oil thickening in many applications.
Although hydrocarbon oxidation can have a profound effect on the properties of a lubricant, this process can, fortunately, be controlled by the use of antioxidant additives.
These molecules will be discussed more extensively in another chapter of this manual. Very generally, antioxidants
function either by scavenging radical species or by decomposing peroxides to unreactive products. Radical scavengers
include hindered phenols such as t-butylphenol, quinines,
and certain amines. Zinc dialkyldithiophosphate, a common
antiwear compound, also serves in a peroxide decomposing
capacity as well.

I m p a c t o f S u l f u r C o m p o u n d s o n B a s e Oil
Chemistry
Throughout the evolution of base oil refining and processing
technology, sulfur content has been employed as an indicator
of product quality and a predictor of lubricant performance.
In this context, the t e r m "sulfur" relates to soluble,
organosulfur compounds that occur naturally in crude oil in
contrast to elemental, yellow sulfur. Current domestic base
oil sulfur concentrations typically range from <0.05 wt% to
0.4% for light base stocks and u p to 0.8-1.0% for heavier viscosity grades. In other regions of the world, it is not uncomm o n to observe sulfur levels in excess of 1.5-2.0%. From the
perspective of base oil chemistry, how the organosulfur content impacts lubricant performance is very complex and depends, to a large extent, on the ultimate application and the
nature of the additives used in the formulation. Although current manufacturing trends suggest that a very low sulfur content is most desirable for base oil, it has historically been
thought that higher sulfur levels directionally improve base
oil oxidation stability as well as friction a n d wear performance.
The pioneering work of Dennison and Conduit [37] in the
1940s concluded that "the oxidation stability of refined
petroleum lubricating oils is the result of small quantities of
natural sulfur compounds and not of any inherent stability of
the hydrocarbon fraction itself. In the absence of the natural
sulfur compounds the hydrocarbon fraction oxidizes rapidly
and, in the initial stages of the reaction, autocatalytically."
This work clearly illustrated that certain sulfur containing
compounds, specifically monothioethers containing at least
one aliphatic or cycloaliphatic group attached to the sulfur
atom (sulfides), were very potent antioxidants in lubricants.
These authors were successful in selectively removing the
sulfur compounds from a mineral oil while keeping other

CHAPTER

7: HYDROCARBON

BASE

OIL CHEMISTRY

177

TABLE 17Oxygen uptake of base oilimpact of sulfur compounds.


Oxygen Uptake at 1 h, 171C
(cm^ per 100 g oil)
Sulfur Compound Added
Base Fluid
0.1% Natural Organosulfur
Base Oil E (102 VI, 0.1% S)
100
Desulfurized Base Oil E
None
>2000
Desulfurized Base Oil E
+1.4% cetyl phenyl sulfide
190
Desulfurized Base Oil E
+ 1% bis(phenylethyl) sulfide
50
0.53% Organosulfur
170
Base Oil A (8 VI, 0.53%S)
Desulfurized Base Oil A
None
>5000
Desulfurized Base Oil A
1% dicetyl sulfide
90
Desulfurized Base Oil A
2% dicetyl sulfide
<10
Desulfurized Base Oil A
3% dibenzothiophene
>5000

compositional variables constant. They observed that the


high temperature oxidation rate of the sulfur-free oil was
m u c h higher than the original sulfur-containing base fluid.
In these experiments oxygen uptake by base oil was monitored over time (hours) at 171 C under atmospheric pressure.
Typical data are provided in Table 17.
Table 17 illustrates that desulfurized base oils exhibit very
poor oxidation inhibition compared to the original base oil
and that certain sulfur compounds, specifically organosulfides, can significantly reduce the rate of oxidation at high
temperature. Sulfur-containing aromatic molecules, however, such as dibenzothiophene, did not appear to act as antioxidants and may actually increase the rate of oxidation
slightly (data not shown). Further work reviewed by Harpp
et. al. [32] revealed that sulfides in themselves are not antioxidants but rather they become active when oxidized to
SO2, SO3 and related organo-sulfonic acids. These authors also report that thiophenes (or thioaromatics) have "no
stabilizing effect on hydrocarbon oil oxidation" and they
were not able to identify a molecular mechanism through
which antioxidation could occur.
More recently, using both statistical and neured network
modeling techniques, Stipanovic, Smith, and co-workers
[3,4] have shown that base oil thioaromatic content can be
directly correlated to an increase in oxidation and deposit
formation level observed for crankcase engine oils in the
ASTM Sequence HIE and VE gasoline engine tests. These observations were attributed to an increase in the rate of free
radical propagation in the engine oil at high temperature
based on data reported by Russel [33]. As shown in Table 18,
the free radical hydrogen a t o m abstraction rate is m u c h
higher for thiophenes than other hydrocarbons for at least
two types of radicals that could occur in hydrocarbon systems. As a result, it is reasonable to conclude that propagation reactions can be accelerated by the presence of thioaromatic molecules, such as benzothiophene, although data
specific to alkylperoxy radicals, of significance in hydrocarbon oxidation, are not readily available.
The role of sulfur compounds as natureJly occurring base
oil stabilizers has some very interesting implications. It is
well known that untreated, sulfur-free synthetic base oils,
such a polyalphaolefins, oxidize more readily in tests such as
the Rotary Bomb Oxidation Test (RBOT;ASTM D 2272) than
conventional mineral oils that contain sulfur compounds.
However, if appropriate antioxidants are added to both t5^es
of base fluids, the PAOs typically respond with better longterm oxidation stability. Severely hydrocracked, low sulfur
Group II and III base oils exhibit similar behavior.

TABLE 18Relative reactivity of hydrocarbon radicals.


Substrate Species:
Radical

CH3 - X X =

Phenyl*
Phenyl*
Phenyl*
Phenyl*

Alkyl
Phenyl
Benzothiophene
2-Thiophene

RCH2*
RCH2*

Phenyl
2-Thiophene

Relative Reaction Rate


per Hydrogen Atom
1
9
14
15
65
210

TABLE 19Impact of basic nitrogen compounds on the oxidation


of hexadecane (Cu catalyst, 0.6% butylated hydroxy toluene
(BHT) added as an antioxidant).
Compound
Hexadecane (HD)
HD + 3-n-butylpyridine
HD -1- 2,4-dimethylquinoline
HD + 2-methylindole

HD + Carbazole
HD + Phenanthridine

Effective Nitrogen
Concentration (ppm)

RBOT Lifetime
(min.)

10
5
2
9
4.5
2
11
6
0.2
10
10

596
216
248
296
306
324
405
501
516
578
576
440

Nitrogen C o m p o u n d Reactivity
Nitrogen containing molecules found in base oils can also accelerate oxidation and deteriorate the useful lifetime of lubricants. More specifically, "basic nitrogen" compounds (socalled proton acceptors) such as various pyridine derivatives,
can act at very low concentrations (below 10 p p m based on
N) in deteriorating oxidative stability [6,38,39]. Oxidation
lifetime for the straight chain paraffin hexadecane, a base oil
"model compound," in the presence of small quantities of
"basic nitrogen" are shown Table 19. The data clearly illustrate that such species can promote oxidation rate in the
ASTM D 2272 RBOT procedure. These results illustrate that
the molecular structure of the "basic nitrogen" compound influences the oxidation reaction. More specifically, Yoshida
et. al [38] have found that reducing the pKb of the nitrogen
group enhances the overall rate of oxidation.
In addition to these model compound studies, statistical
and neural network modeling methods have demonstrated
that RBOT lifetimes for prototype industrial oils (hydraulic

178

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

fluids and turbine oils) also decrease with increasing base oil
basic nitrogen content. Further, thermal sludge formation
and oxidation onset determined by a high pressure differential scanning calorimetry technique indicated a deterioration
with higher levels of basic nitrogen [6].
Olefins
Although crude oils Eire generally relatively low in olefin content [10], base oil processing techniques can introduce
olefins, especially at high temperatures, due to "cracking" reactions. In the presence of heat or UV light, olefins can polymerize to form higher molecular weight products that can
color the base oil or actually cause sediment. In general,
olefins can be removed during the process of hydrofinishing
or by clay treatment discussed above [10].

CHEMICAL COMPOSITION/LUBRICANT
PERFORMANCE CORRELATIONS
As previously discussed, base oils contain a broad spectrum of
paraffinic, cycloparaffinic, and aromatic molecules, the distribution of which varies with crude source and refinery processing. More importantly to the lubricant chemist and engineer, each of these hydrocarbon types can exert a different
effect on the ultimate physical and chemical properties of the
base oil and, ultimately, the lubricant from which it is formulated. Table 20 illustrates the relationship between hydrocarbon type and performance for several important properties.
B a s e Oil R h e o l o g y a n d C o m p o s i t i o n
The flow properties, or rheology, of a lubriccint strongly reflect the composition of the base oil used in its formulation.
Comparing hydrocarbons of similar molecular weight, paraffins (especially linear paraffins) provide the highest positive
contribution to base oil VI while aromatics and naphthenes,
particulcirly multi-ring structures, strongly decrease VI. Base
oils of high VI Eire generally preferred for lubricants because
they provide higher viscosity at high temperatures and lower
viscosities at low temperatures, provided they are properly
treated to inhibit wax crystallization. In the absence of effective pour point depression, higher VI oils containing elevated
levels of wax display poor low temperature fluidity as wax
crystals form network structures that Eire resistant to flow. In
most cases, polymeric pour point depressant additives eliminate wax crystallization and, u n d e r these circumstances,
base oils rich in paraffins can exhibit excellent rheological
properties at low temperatures.

In engine oils, poor cold temperature fluidity can reduce


pumpability to the extent that oil stcirvation causes catastrophic engine failure. To protect against this occurrence, the
SAE J300 Engine Oil Viscosity Classification specifications
include two ASTM tests, D 3829 and D 5293, which measure
both the high shear viscosity and pumpability, respectively,
of engine oils to assure that a motor will start and have sufficient oil fluidity to assure good lubrication. A low temperature viscosity limit is also included in the specifications for
many geeir oils and transmission fluids. This viscosity is determined using a very low shecir Brookfield Viscometer operating at 5 to 40C, depending o n viscosity grade. The specific test method is described in ASTM D 2983.
Composition/Performance Correlations for
Engine Oils
Gasoline cind heavy duty diesel engine oils probably represent the most sophisticated lubricant formulations in terms
of physical a n d chemical requirements and, subsequently,
their additive packages are very complex. Engine oils must
provide a fluid lubricating film for sliding metal-to-metal
interfaces at high t e m p e r a t u r e s while neutralizing acidic
combustion gases; minimizing oxidation and corrosion; suspending insoluble combustion a n d lubricant oxidation byproducts; reducing wccir and the tendency to foam; etc. Since
each of these characteristics can be influenced by base oil
composition, considerable attention has been focused on relating specific molecular components to engine performance.
Murtay and co-workers [1,2] were among the first to use
base oil compositional data derived from mass spectrometry
to develop statistical correlations between oxidation in the
ASTM Sequence IIIC and HID oxidation engine tests and
base oil hydrocarbon type distribution. These authors observed that a regression function including saturate content
plus total sulfur concentration predicted viscosity increase
very well for a series of engine oils formulated to be API SE
quality. In this function, higher levels of saturates and sulfur enhance performance. Viscosity Index edone was not
found to be a good predictor of performance for oils originating from different crude, sources, but it did correlate reasonably well for samples derived from a single crude. Murray also demonstrated that during the course of oxidation
reactions, the level of both saturates and aromatics decreased while the concentration of polcir compounds increased significantly. For example, in the ASTM Sequence
IIIC engine test, a SAE lOW-30 oil that was originally 74.1%
saturates, 13.6 % aromatics, and 4.9% polars exhibited an
end-of-test composition of 46.1% saturates, 7.9% aromatics,
cind 33% polars.

TABLE 20Performance characteristics of base oil components.


Base Oil Proprety

ParaiBns

Naphthenes

Aromatics

Viscosity Index (VI)


Low Temperature Fluidity"
Low Temperature Fluidity*
Pour Point
Oxidation/Thermal Stability
Solvent for Additives

Excellent
Poor
Excellent
Poor
Excellent
Poor

Poor-Good
Good
Good
Good
Poor-Good
Good

Poor
Good
Good
Excellent
Poor
Excellent

"Unadditized.
''Treated with a pour point depressant.

CHAPTER
Roby and co-workers were also successful in developing
statistical correlations between base oil composition and performance in the ASTM Sequence HID and VD gasoline engine tests [40]. For high temperature oxidation in the HID
procedure, it was learned that no single base oil parameter
provided a good correlation to viscosity increase but a regression equation including nitrogen content (ASTM D
4629), olefin n u m b e r (ASTM D 460), sulfur content (ASTM D
1552) and saturates (column gradient elution chromatography) provided an excellent fit (R-squared = 0.97) to the observed data. For oxidation control, high levels of saturates
and sulfur compounds were beneficial while elevated olefin
and nitrogen levels contributed to poor performance. In the
Sequence VD gasoline engine test, which eveJuates deposit
formation at relatively low levels of oil oxidation, the individual variables discussed above all showed good correlations
(R-squared values > 0.79) to varnish formation with higher
nitrogen, olefin, and sulfur content being detrimental. Average engine varnish ratings in the Sequence VD improved with
increasing base oil saturates content, however.
More recently, base oil effects in the Sequence HIE and VE
engine tests have been studied [3,4] using Partial Least
Squares (PLS) and neural network modeling methods. These
authors evaluated the engine test performance of a group of
different base oils (approx. 12 oils) formulated into engine
oils using similar additive technology. For the Sequence HIE
oxidation test, viscosity increase and piston skirt varnish ratings generally improved with paraffin content while reacting
negatively to high levels of multi-ring naphthenes, multi-ring
aromatics, and thioaromatics. Total sulfur content was found
to reduce viscosity increase and piston deposits in the Sequence HIE, consistent with its antioxidant effect discussed
earlier. For the Sequence VE test, total sulfur, thioaromatics,
and multi-ring aromatics all enhanced the formation of varnish deposits.
Using the PLS modeling protocol described in Ref 3, it is
possible to predict the engine test performance of lubricants,
assuming a c o m m o n passenger car engine oil additive technology, using base oil compositional features as input. In this
fashion, the potential Sequence VE varnish ratings for engine
oils formulated from a population of base oils representing
typical U.S. production were predicted. Ratings are based on
a visual examination of a n u m b e r of engine pairts where 10.0
corresponds to a totally clean part, 5.0 is the m i n i m u m "passing" rating, and <4.0 corresponds to a very poor engine oil
formulation. API Group I oils gave varnish values of 5.0 or
less. Group II oils exhibited improved varnish ratings in the
range of 5.5-5.8, while Group III and IV oils provided ratings
of 6-6.5.
In a separate study, a group of re-refined oils (RR) were
evaluated and, on average, predictions suggested that they
would perform at levels comparable to "virgin" oils (VO) assuming normeJ test-to-test vEiriability. These results are summarized in Table 2 1 .
Several generalizations can be made about the role of base
oil composition in heavy duty diesel engine oils where oil
thickening due to the accumulation of soot cind piston ringland deposits are important considerations in several industry standard tests. Base oils of comparatively high saturates
content have been found to perform better in the Mack T-8
engine test than oils of higher aromatic content. This test

7: HYDROCARBON

BASE

OIL CHEMISTRY

179

TABLE 21Predicted engine test results for a re-refined


and virgin base oils in formulated engine oils.
Test Rating
Sequence HIE
Piston skirt varnish
(10 = "Clean";
8.9 = "Passing")
% Viscosity increase
( < 3 7 5 % = "Pass")
Sequence VE
Average engine varnish
(10 = "Clean";
5 = "Passing")

High
Result
(VO/RR)

Average
Result
(VO/RR)

Low
Result
(VO/RR)

9.21/9.34

8.92/8.95

8.63/8.7

283/219

192/163

73/65

5.45/5.51

4.93/5.08

4.32/4.8

measures engine oil viscosity increase as a function of soot


level under conditions that result in very little oil oxidation,
and it is very sensitive to the chemical nature of the dispersant used in the additive package. It has been speculated that
the strong base oil effect could be due to the impact of base
oil solvency on the dispersant and its ability to interact with
and stabilize soot particles from aggregation. Base oils with
high aromatic concentration strongly solvate the dispersant
molecule and perhaps, the solvation shell inhibits the dispersant from properly interacting with soot. For oil ringland deposits, evidence suggests that base oils high in saturates content are not effective in washing away deposit precursors in
the ring belt region of the piston and, as a result, deposits
form more readily. Since this mechanism could be very dependant on additive chemistry, its universality has not been
established. API document 1509 also details the relationship
between base oil group and the engine testing required when
base oils are interchanged in heavy duty diesel engine oil formulations. A more detailed analysis of the impact of base oil
composition on the performance of heavy duty diesel engine
oils has recently been published by Cherrillo and Huang [41].

B a s e Oil E f f e c t s i n I n d u s t r i a l L u b r i c a n t s
Although base oil composition can play an important role in
defining the performance of engine oils, additive chemistry
and concentration can largely overcome potential deficiencies of a pEirticular basestock. Typically a 10-15% treat level
of dispersant/inhibitor package is added to a motor oil to control oxidation, deposits, etc. In industrial lubricants, however, formulation economics dictate very low additive treat
levels, usually less than 2% for products such as hydraulic
fluids, turbine oils, quenching oils, and other process fluids.
As a result, product quality is linked more directly to base oil
composition.
The work of Murray cited above [1] also demonstrates that
industrial oil oxidation lifetimes in the D 943 oxidation test
a n d the D 2272 Rotary B o m b Oxidation Test (RBOT) increased with increasing saturate levels for 150 N oils containing an oxidation inhibitor. Sulfur content played a minor
role, however, presumably because the inhibitor effectively
controlled oxidation. For the D 943 test, Firmstone and coworkers [4] showed, using Partial Least Squares models, that
increases in base oil peiraffin content, sulfur concentration,
VI, and aniline point enhance oxidation lifetime, while cycloparafHns, multi-ring aromatics, and nitrogen content have

180 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

a negative impact. In a study by Mooken on the stability of


turbine oils, D 943 eind D 2272 results improved with higher
levels of saturates and sulfur while lower concentrations of
aromatics and basic nitrogen were most beneficial [39].
The impact of evolving base oil quality toward Group II
and III stocks on the performance of greases and other industrial oils has been recently reviewed [42]. For base oils
containing only negligible quantities of aromatic compounds
and essentially no heteroatomic species, oxidation stability
was found to be influenced positively by paraffin content and
negatively by polycyclic naphthenes.
Influence of Base Oil Composition o n the
Viscosity-Pressure Coefficient
Most organic fluids, including lubricant base oils, exhibit a
reversible viscosity increase with the application of high
pressure due to the molecular mobility restrictions imposed
by the forces being exerted [43]. This phenomenon is especially important for lubricants, since in most mechanical applications, films of fluid are compressed between sliding surfaces under very high loads. The degree to which a fluid
thickens under high pressure is given by the following expression [43,44]:
log Tjl 7)0 = P a where: T) = Viscosity at pressure P
Tjo = Viscosity at atmospheric
pressure
P = Pressure
a = Viscosity Pressure
Coefficient
In this expression, if pressure is given in MPa (megaPascals),
the viscosity-pressure coefficient for a base oil is t5^ically
9-15 GPa~'' The importance of a in the process of lubrication
is multifold. In the so-called hydrodynamic regime of lubrication, the film thickness of fluid that protects the mechani-

cal device from high friction and premature weeir is dependent on the high shear viscosity of the lubricant and its viscosity-pressure coefficient [45]. Thicker lubricant films are,
therefore, produced by fluids exhibiting a higher a value.
However, in the design of many fuel economy enhancing "energy conserving" lubricants, a less viscous film is desired
since mechanical energy can be wasted if the film is too robust. In these cases, lubricants of lower a are favored. In
other applications such as Continuously Variable Transmissions (CVTs), where the fluid must provide high levels of traction, a very high a is needed [46].
Based on the importance of a in the design and application
of lubricants, effort has been focused on determining the relationship between base oil structure and its response to high
pressure [44]. Figure 2 illustrates the magnitude of viscosity
increase that can be expected for typical lubricant base oils,
over pressure ranges not uncommon in certain mechanical
devices, plotted by API base oil groups. These data were
recorded using a falling body viscometer [47].
In general, Group IV (polyalphaolefin) fluids provide the
lowest increase in viscosity with increasing pressure, followed by Group III, Group I, Group II, and finally napthenic
base oils. In this specific example, a statistical analysis [48]
revealed that the Group III and IV oils provided the lowest a
values because these products were very high in paraffin content (>60%), while Group I and II products provided intermediate performance because they contained less paraffins
and higher levels of naphthenic ring compounds (>40%).
Since the cycloparaffin ring structure is sterically very bulky,
it is especially sensitive to applied forces and contributes significantly to increasing the viscosity-pressure coefficient for
base oils. Planar aromatic rings appear to pack with less difficulty. Under pressure, paraffins are easily compressed and
can actually be induced to crystallize if pressures are sufficiently high. In the design of CVT fluids, molecules are synthesized to optimize their steric bulkiness [46].
A number of other procedures are also available to calculate the viscosity-pressure coefficient for base oils from com-

Group I -*- Group 11 -A- Group III -r Group IV - Naphthene

100

200

300

400

500

600

Pressure (MPa)
FIG. 2Viscosity - pressure relationships for base oils at 100C (nominaiiy 4 est at
100C, 1 atmosphere pressure).

CHAPTER
positional data and/or other bulk fluid properties [44,49].
Roelands [44] has shown that the viscosity-pressure relationship for base oil can be predicted solely from atmospheric
viscosity (TJO) a n d a knowledge of the percentage of
carbon atoms in a aromatic ring structure (CA) and the percentage of naphthenic (cycloparaffinc) carbons (Cn). Johnston determined that the pressure-viscosity coefficient could
be calculated from ambient pressure fluid density and the
viscosity/temperature relationship (specifically viscosity at
two temperatures is needed) [49]. More recently, Spikes and
co-workers have shown that the thickness of a lubricant film
under conditions of elastohydrodynamic lubrication (EHD)
can be related to a by the following expression obtained from
a high-speed ultrathin film interferometry technique [45]:

7: HYDROCARBON

BASE

OIL CHEMISTRY

181

and solubilize this plasticizer is an important consideration.


In other cases, certain base oil molecular fractions can actually dissolve into the rubber matrix causing it to swell. Although most lubricant base oils are relatively inert in their
ability to deleteriously interact with a variety of elastomeric
materials commonly in use, high aniline point products, such
as Group IV polyalphaolefin (PAO), can cause elastomer
cracking after long periods of exposure at high temperatures
due to a loss in plasticity. In many cases, a so-called seal swell
agent can be successfully added to PAO to maintain good seal
characteristics. At the other extreme, low aniline point naphthenic base stocks can cause seals to swell excessively also
creating operational problems. As a result, for any base oil
system, rubber compatibility should be evaluated carefully in
formulating a lubricant product.

h oc U 0-*^ 7, 0*" a 0 "

where: h = film thickness measured by interferometry, U is


the mean entrainment speed, and TJ is the low pressure dynamic viscosity.
B a s e Oil S o l v e n c y E f f e c t s
In any lubricajit formulation, base oils are required to dissolve polar additive compounds and to ultimately disperse
polar oxidation products that are formed during use. For this
reason, the so-called aniline point of a base oil can be a critical parameter in defining its compatibility with additives and
the byproducts of use. Aniline point is determined by ASTM
D 611 a n d represents the t e m p e r a t u r e at which aniline,
(C6H5MNH2), a polar aromatic compound, becomes miscible
with a hydrocarbon base oil. At low temperatures, base oil
and aniline are not miscible but as temperature is raised they
become a single phase at the aniline point, commonly expressed in F. In general, base oils of low aromatic/high saturates content have high aniline points (>230F, 110C), conventional solvent refined base oils have m o d e r a t e aniline
points (200-215F, 93-102C) and naphthenic base oils have
a very low aniline point (<150F, 65C). As a result, aniline
point can be viewed as a sensitive index of the "solvent
power" of a base oil t o w a r d polymeric VI improvers,
organometallic friction modifiers and anti-wear agents, detergents, anti-oxidants, and other molecules. In severe cases,
additives soluble in low to medium aniline point base oils
might experience limited solubility in high aniline point
products. In these cases, improved solubility can be attained
by adding a small fraction of a very polar synthetic basestock
such as polyolester or an alkylbenzene to the high aniline
point base oil thereby increasing its "solvent power."
Due to concerns over the potential toxicity of aniline, some
effort has been devoted to eliminating this procedure. It has
been found using chemometric techniques that proton and
'^C-NMR spectral data can be correlated to aniline point with
a high degree of accuracy, possibly creating an opportunity
to use NMR directly as an index of base oil solvency [48].
Rubber Compatibility
In many service applications, lubricant products come in
contact with rubber (elastomer) seals, gaskets, o-rings, and
other components. Since most elastomers include a plasticizer to soften the material, the ability of a base oil to remove

Biological P r o p e r t i e s of B a s e Oils
Since lubricants can come in direct contact with humans in
some applications, the biological toxicity of base oils is a concern especially for those products containing high concentrations of polycyclic aromatic hydrocarbons (PAHs). These
compounds have been found to be mutagenec and carcinogenic axid the International Agency for Research on Cancer
has classified 18 PAHs as cancer causing [50 and references
therein]. From a molecular structure perspective, these 18
molecules each have in common a 4-6 fused aromatic ring
system and a so-called 3-sided concave "bay region" similar
in structure to the geometries shown for triaromatic and tertaaromatic molecules shown in Table 13.
Probably the most well established method to assess the
potential mutagenicity/carcinogenicity of base oils is the IP
346 Method that uses dimethylsulfoxide (DMSO) extraction
to isolate PAHs. By correlation to mouse skin painting studies, it was determined that base oils exhibiting DMSO-extractable levels exceeding 3 wt % should be considered carcinogenic [50]. F u r t h e r work by Nessel a n d co-workers
indicated that a level of 5% IP 346 extractables might be a
more appropriate target [50]. This group also developed a
NMR-based method to characterize the concentration of hydrogen atoms in the so-called "bay region" of PAHs and they
have compared these data to IP 346 results and t u m o r incidence results obtained from skin painting studies as shown in
Table 22. Based on these results, Nessel proposes that a limit
of 1500 p p m of bay region hydrogen atoms be established as
a limit of carcinogenicity [50]. NMR enjoys the advantage of
being much faster and less expensive than other methods of
assessing the toxicological effects of base oils.
Unpublished results generated by the author indicate that
the IP 346 method correlates reasonably well to the multiring aromatic content obtained from ASTM D 3239 for relatively light to m e d i u m viscosity base oils (70-150N or 3-5 cSt
at 100C). However, it underestimates the aromatic content
of m e d i u m to heavy grades (320-850N). Presumably the
DMSO extraction procedure of IP 346 is not effective in solubilizing higher molecular weight aromatics. It was not established, however, if these heavier aromatics promoted a mutagenic or carcinogenic response in animal tests. It is
possible that their relatively large size restricts their molecular mobility and ability to be adsorbed into the tissue of animals.

182

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 22Base Oil Carcinogenicity: A comparison of techniques.


Base Oil/Petroleum Stream

NMR - Bay Region


Hydrogens (ppm)

IP 346 - % DMSO
Extractables

Tumor
Incidence - %

Extracted/Hydrotreated paraiEnic oil


Extracted/Nonhydrotreated paraffinic oil
Hydrotreated naphthenic oil
Straight-run hydrotreated gas oil
Processed paraffinic blend
Unrefined vacuum distillate
Vacuum distillate aromatic extract
Catalytically cracked gas oil

Up to 39
Up to 86
100-600
100-200
1500
1500-3200
3800-9000
3800-5600

<1.0
<1.4
2.5-6
5-6
5-6
5-12
12-15
16-43

0
0
0
0
36-54
20-60
60-90
4-40+

TABLE 23Joint ASTM/IP lubricant test methods.


ASTM Test
Number

IP Test
Number

D 445-97

71

D 611-82
D 2270-93

2
226

D 4629-96

379

are: Institute of Petroleum: www.petroleum.co.uk, ASTM International: www.astm.org

Method Description

Kinematic viscosity cmd


cal'c of dynamic viscosity
Aniline point determination
Cal'c of viscosity index from
kinematic viscosity
Organically bound nitrogen

Biodegradability
The ability of a lubricant to degrade naturally in the environment is becoming an increasingly important property that is
directly related to the composition and molecular weight of
the base oil employed in its formulation [52,53]. Currently,
several standcird experimental protocols are widely utilized
to evaluate the biodegradability of a lubricant: ASTM D 5864
(fully formulated lubricants), D 6006 (hydraulic fluids), and
the European method CEC-L-33-T-82. Voltz has shown that
hydraulic fluids based on hydrocarbon mineral oils only degrade to an extent of 40% after 25 days in the CEC test while
synthetic, ester-based fluids are degraded almost entirely
(>90%) [53]. Synthetic hydrocarbons and polyethylene glycols were found to display intermediate behavior with maxim u m degradation levels of 70% and 55%, respectively.
In addition to composition, the size of a base oil molecule
can influence its biodegradability. Weller has reported using
the CEC protocol, that 2 and 4 cSt PAOs degrade at reasonably high levels, 75% and 65% respectively, while 6, 10, and
100 cSt PAO samples degraded less than 20% [54]. Similar results have been reported for other types of base oil suggesting
a limiting molecular size exists above which an organism
cannot adsorb and biodegrade hydrocarbon molecules.

INTERNATIONAL STANDARDS
As shown in Table 23, many of the ASTM experimental test
procedures outlined in this chapter have analogs in the Institute of Petroleum (IP) Standard Test Methods published in
the UK. Several examples are given below where the ASTM
and IP organizations share a single test method: in m a n y
other cases, the ASTM and IP have developed methods to determine the same lubricant property (sulfur content, low
temperature viscosity, base oil aromatics, etc) through the
application of somewhat different procedures. Each organization maintains an web site with extensive capabilities of
searching for specific methods. The addresses for each site

CONCLUDING REMARKS
It was the objective of this chapter to demonstrate that hydrocarbon base oils are a complex collection of molecules
whose diverse individual properties combine to determine
the performance characteristics of a formulated lubricant.
Examples and references have been provided that support
this objective and serve to highlight the overall importance
and complexity of base oil technology as an integral part of
the lubricant industry.
In addition, an effort was made to highlight those anal34ical techniques and predictive modeling procedures that enable the chemical composition of a base oil to be determined
and then exploited to predict how it will behave in actual
product applications. Although further research and method
development is still needed, a future can be envisioned where
actual engine tests, bench oxidation tests, or biological assays
are not needed to confirm the quality/toxicology of a base oil
relying, instead, on predictive modeling.

STANDARDS
ASTM
No.
D 92-01

IP
No.
36

D 93-00

34

D
D
D
D

97-96a
189-01
297-92
445-97

15

D
D
D
D
D
D
D
D

482-00
524-00
611-82
892-01
943-99
1492-96
1500-98
2007-01

D 2008-91

71

2
146
157

Method Description
Flash and Fire Points by Cleveland
Open Cup
Flash Point by Pensky-Martens
Closed Cup Tester
Pour Point of Petroleum Products
Conradson Carbon Residue
API Gravity
Kinematic Viscosity and Cal'c of
Dynamic Viscosity
Ash in Petroleum Products
Ramsbottom Carbon Residue
Aniline Point Determination
Lubricant Foaming
Oxidation of Inhibited Oils
Bromine Index
ASTM Color
Aromatics, Saturates, Polars in
Base Oil
UV Absorbance of Petroleum
Products

CHAPTER 7: HYDROCARBON BASE OIL CHEMISTRY


D 2270-93

226

D 2272-98
D 2500-99
D 2549-91

219

D 2622-98
D 2710-99
D 2786-91
D 2887-01
D 2983-01
D 3228-96
D 3239-91
D
D
D
D
D

3339-95
3829-93
4289-97
4530-00
4624-93

D 4629-96
D 4636-99
D 4683-96

379

D 4741-00
D 4742-96
D 4871-00
D 4927-96
D 5293-99
D 5480-95
D 5481 -96
D
D
D
D
D

5483-95
5776-99
5800-00
5864-00
5949-96

D 5950-96
D 5985-96
D 6006-97
D 6074-99
D 6082-00
D 6366-99
D 6616-01
E 1687-98

Cal'c of Viscosity Index from Kinematic Viscosity


Oxidation Stability-Rotating Vessel
Cloud Point of Petroleum Oils
Aromatic / Non-Aromatic Separation
Sulfur by X-Ray Fluorescence
Bromine Index by Electrometric
Titration
Hydrocarbon Types of Saturates
Simulated Distillation (Volatility)
Low Temperature Brookfield Viscosity
Kjeldahl Nitrogen
Aromatics Molecular Types in
Base Oil
Acid Number
Borderline Pumping Temperature
Elastomer Compatability
Carbon Residue-Micro Method
High Temp / High Shear Viscosity
by Capillary Viscometry
Organically Bound Nitrogen
Corrosiveness of Hydraulic Oils
High Temp / High Shear Viscosity
by TBS
High Temp / High Shear Viscosity
by Tapered Plug
Oxidation by Thin Film Uptake
Guide For Universal Oxidation
Test
Elemental Analysis
Cold Cranking Viscosity of Engine
Oils at - 5 t o - 3 5 C
Volatility by Gas Chromatography
High Temp / High Shear Viscosity
by Capillary Viscometry
Oxidation of Grease by DSC
Bromine Index
Noack Volatility
Aquatic Aerobic Biodegradation
Pour Point by Automatic Pressure
Pulse
Pour Point by Automatic Tilt
Pour Point by Rotation
Biodegradability of Hydraulic Fluids
Guide to Characterizing Hydrocarbon Base Oils
High Temperature Foaming
Trace Nitrogen
High Temp / High Shear Viscosity
byTBSatlOOX
Carcinogenic Potential of Metalworking Fluids

REFERENCES
[1] Murray, D. W., MacDonald, J. M., White, A. M., and Wright, P.
W., "The Effect of Basestock Composition on Lubricant Oxidation Performance," Petroleum Review, February 1982, pp. 36-40.

183

[2] "Base Oils for Automotive Lubricants," Special Publication SP526, Society of Automotive Engineers, Warrendale, PA, 1982
(and references therein).
[3] Stipanovic, A. J., Smith, M. P., Firmstone, G. P., and Patel, J. A.,
"Compositional Analysis of Re-Refined and Non-Conventional
Lubricant Base Oils: Correlations to Sequence VE and IIIE
Gasoline Engine Tests," SAE Publication 941978, Society of Automotive Engineers, Warrendale, PA, 1994.
[4] Firmstone, G. P., Smith, M. P., and Stipanovic, A. J., "A Comparison of Neural Network and Partial Least Squares Approaches in Correlating Base Oil Composition to Lubricant Performance in Gasoline and Industrial Oil Applications," SAE
Publication 952534, Society of Automotive Engineers, Warrendale, PA, 1995.
[5] Smith, M. P., Stipanovic, A. J., Firmstone, G. P., Cates, W. M.,
and Li, T. C, "Comparison of Mineral and Synthetic Base Oils
for Bench and Engine Tests," Lubrication Engineering, Vol. 52,
No. 4, 1995, pp. 309-314.
[6] Yoshida, T., Igarashi, J., Stipanovic, A. J., Thiel, C. Y., and Firmstone, G. P., "The Impact of Basic Nitrogen on the Oxidative and
Thermal Stability of Base Oils in Automotive and Industrial Applications," SAE Publication 981405, Society of Automotive Engineers, Warrendale, PA, 1998.
[7] Stipanovic, A. J., Firmstone, G. P., and Smith, M. P., "Having
Fun with Base Oils: Predicting Properties Using Neural Networks," Preprints (ACS Division of Petroleum Chemistry, Inc.),
Vol. 42, No. 1, 1997, pp. 284-286.
[8] Patel, I. A., Smith, M. P., Powers, J. R., Whiteman, J. R., and
Prescott, G. P., "Composition and Performance of a Hydroisomerized Wax Base Oil, Preprints (ACS Division of Petroleum
Chemistry, Inc.), Vol. 42, No. 1, 1997, pp. 200-203.
[9] "1997 Report on U.S. Lubricating Oil Sales," National
Petroleum and Refiners Association (NPRA), October, 1998.
[10] Sequeira, A., Jr., Lubricant Base Oil and Wax Processing, Marcel
Dekker, Inc., NY, 1994.
[11] "1999 Lubricating Oil and Wax Capacities of Refiners and ReRefiners in the Western Hemisphere," National Petroleum and
Refiners Association (NPRA), 1999.
[12] A) Lubricants World, March 1999, p. 8.; B) Lubricants World,
March 2000, p. 8.
[13] Comitius, T., "Basestock Market Outlook," Lubricants World,
November 1998, pp. 16-23.
[14] Speight, J. G., The Chemistry and Technology of Petroleum, 2"^
Edition, Marcel Dekker, Inc., NY, 1991.
[15] BP Petroleum, "Petroleum Refinery Products and Processes,"
Our Petroleum Industry, 1911, p. 230.
[16] Lane, E. C. and Garton, E. L., "Base of a Crude Oil," U.S. Bureau
of Mines-Report of Investigation 3279, Washington, DC, 1935.
[17] Barman, B. N., "Hydrocarbon-Type Analysis of Base Oils and
Other Heavy Distillates by Thin-Layer Chromatography with
Flame-Ionization Detection and by the Clay-Gel Method," Journal of Chromatography Science, Vol. 34, 1996, pp. 219-225.
[18] Sarpal, A. S., Kapur, G. S., Mukherjee, S., and Jain, S. K., "Characterization by 13C-NMR Spectroscopy of Base Oils Produced
by Different Processes," FMS/, Vol. 76, No. 10, 1997, pp. 931-937.
[19] Adhvaryu, A., Pandey, D. C, and Singh, I. D., "Effect of Composition on the Degradation Behavior of Base Oil," Preprints (ACS
Division of Petroleum Chemistry, Inc.), Vol. 42, No. 1, 1997, pp.
225-228.
[20] Coates, J. P. and Setti, L. C, "Infrared Spectroscopic Methods
for the Study of Lubricant Oxidation Products," ASLE Transactions, Vol. 29, No. 3, 1985, pp. 394-401.
[21] Altgelt, K. H. and Gouw, T. H., Chromatography in Petroleum
Analysis, Marcel Dekker, NY, 1979.
[22] Altgelt, K. H. and Boduszynski, M. M. "Composition and Analysis of Heavy Petroleum Fractions," Marcel Dekker, Inc., NY,
1994.

184 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


[23] Sarpal, S. A., Kapur, G. S., Chopra, C , Jain, S. K., Srivastava,
S. P., and Bhatnagar, A. K., Fuel, Vol. 75, No. 4, 1996, pp. 4 8 3 490.
[24] Sahoo, S. K., Sharma, B. K., and Singh, I. D., "NMR Studies of
Lube Distillates for Making Quality Base Oils," Preprints (ACS
Division of Petroleum Chemistry), Vol. 45, 1999.
[25] Igarashi, J., "Oxidative Degradation of Engine Oils," Japanese
Journal of Tribology, Vol. 35, No. 10, 1990, pp. 1095-1104.
[26] Korcek, S. and Jensen, R. K., "Relation Between Base Oil Composition and Oxidation Stability at Increased Temperatures,"
ASLE Transactions, Vol. 19, No. 2, 1975, pp. 83-94.
[27] Korcek, S., Johnson, M. D., Jensen, R. K., and Zinbo, M., "Determination of High-Temperature Antioxidant Capability of Lubricants and Lubricant Components," Industrial
Engineering
Chemistry, Prod. Res. Dev., Vol. 25, 1986, pp. 621-627.
[28] Colclough, T., "Role of Additives and Transition Metals in Lubricating Oil Oxidation," Industrial Engineering Chemistry, Vol.
26, 1987, pp. 1888-1895.
[29] Hsu, S. M., Ku, C. S. and Lin, R. S., "Relationship between Lubricating Basestock Composition and the Effects of Additives on
Oxidation Stability," SAE Publication SP-526, Society of Automotive Engineers, Warrendale, PA, 1982, pp. 29-56. (Also see
references therein, especially 1-4).
[30] Ofunne, G. C , Maduako, A. U., and Ojinnaka, C. M., "High Temperature Oxidation Stability of Automotive Crankcase Oils and
Their Base Oils," Tribology International, Vol. 23, No. 6, 1990,
pp. 407-412.
[31] Blaine, S. and Savage, P. E., "Reaction Pathways in Lubricant
Degradation.2. n-Hexadecane Autoxidation," Industrial Engineering Chemistry, Vol. 30, 1991, pp. 2185-2191.
[32] Harpp, D. N., Robertson, J., Laycock, K., and Butler, D.,
"Organosulfur Antioxidants in Hydrocarbon Oils," Sulfur Reports, Vol. 4, No. 6,1985, pp. 195-227.
[33] Russel, G. A., in Free Radicals, Vol. I, J. K. Kochi, Editor, John
Wiley and Sons, NY, 1973, pp. 275-331.
[34] Palekar, V. M., "Bench Scale Evaluation of Automotive
Crankcase Lubricants," Ph.D. Thesis, The Pennsylvania State
University, August 1996, pp. 57-61.
[35] Lee, C. J., Klaus, E. E., and Duda, J. L., "Evaluation of Deposit
Forming Tendency of Mineral and Synthetic Base Oils Using the
Penn State Micro-Oxidation Test," Lubrication Engineering, Vol.
49, No. 6, 1993, pp. 4 4 1 ^ 4 5 .
[36] Palekar, V. M., Duda, J. L., Klaus, E. E., and Wang, J., "Evaluation of High Temperature Liquid Lubricants Using the Penn
State Micro-oxidation Test," Lubrication Engineering, Vol. 52,
No. 4, 1996, pp. 327-334.
[37] Dennsion, G. H. and Conduit, P. C , "Oxidation Of Lubricating
OilsMechanism of Sulfur Inhibition," Industrial Engineering
Chemistry, Vol. 37, No. 11, 1945, pp. 1102-1108.
[38] Yoshida, T., Igarashi, J., and Watanabe, H., "Pro-Oxidant Properties of Basic Nitrogen Components in Base Oil," Proceedings of
the 11'^ International Colloquium Tribology, Esslingen, Germany, January 1998.

[39] Mooken, R. T., Saxena, D., Base, B., Satapathy, S., Srivastava, S.
P., and Bhatnagar, A. K., "Dependence of Oxidation Stability on
Base Oil Composition," Lubrication Engineering, 1997, p p .
19-24.
[40] Roby, S. H., Supp, J. A., Barrer, D. E., and Hogue, C. H., "Base
Oil Effects in t h e Sequence HID and Sequence V-D Engine
Tests, SAE Publication 892108, Society of Automotive Engineers, Warrendale, PA, 1989.
[41] Cherrillo, R. A. and Huang, A., "The Increasing Significance of
Base Oils in the Evolution of Heavy-Duty Diesel Engine Oils,"
1999 National Petroleum Refiners Association (NPRA), LW-99130, Houston, TX, 1999.
[42] Kramer, D. C , Ziemer, J. N., Cheng, M. T., Fry, C. E., Reynolds,
R. N., Lok, B. K., et al., "Influence of Group II and III Base Oil
Composition on VI and Oxidation Stability," National Lubricating Grease Institute (NLGI), Paper 9907, Tucson, AZ, 1999.
[43] Fresco, G. P., Klaus, E. E., and Tewksbury, E. J., "Measurement
and Prediction of Viscosity-Pressure Characteristics of Liquids," Journal of Lubrication Technology (ASME
Transactions),
Paper No. 68-Lub-8, 1968, pp. 1-7.
[44] Roelands, C. J. A., Vlugter, J. C , and Waterman, H. I., "The Viscosity-Temperature-Pressure Relationship of Lubricating Oils
and Its Correlation with Chemical Constitution," Journal of Basic Engineering, December 1963, pp. 601-610.
[45] Guangteng, G. and Spikes, H. A., "Boundary Film Formation by
Lubricant Base Fluids," Society of Tribologists and Lubrication
Engineers, Presentation 95-MP-7D-3, Chicago, IL, 1995.
[46] Tsubouchi, T., Abe, K., and Hata, H., "Quantitative Correlation
Between Molecular Structure of Traction Fluids and Their Traction Properties (Part 2): Precise Investigation into Molecular
Stiffness," Japanese Journal of Tribology, Vol. 39, No. 3, 1994,
pp. 373-381.
[47] Bair, S., "An Experimental Verification of the Significance of
the Reciprocal Asymptotic Isoviscous Pressure," ASLE Tribology
Transactions, April, 1993.
[48] A. J. Stipanovic, Unpublished Results.
[49] Johnston, W. G., "A Method to Cedculate the Pressure-Viscosity
Coefficient from Bulk Properties of Lubricants," ASLE Transactions, Vol. 24, No. 2, 1980, pp. 232-238.
[50] Nessel, C. S., Coker, D. T., King, A. G., and Mumford, D. L., "Carcinogenic Assessment of Lubricant Base Oils by Proton NMR,"
Preprints (ACS Division of Petroleum Chemistry), Vol. 42, No. 1,
1997, pp. 251-254.
[51] Trauth, E. J., "Future Product Development Needs-Comprehensive Life-Cycle Analyses," Lubricants World, July 1998, pp. 20-25.
[52] Tocci, L., "Clean Hydraulic Fluids," Lubes'n'Greases, November
1998, pp. 4 2 ^ 4 .
[53] Voltz, M., "Biodegradability of Lubricant Base Stocks and Fully
Formulated Products," Proceedings, ACS Petroleum Division
Symposium, San Diego, CA, 1994.
[54] Weller, D. E., Perez, J. M., and Keay, R. E., "Biodegradable Gear
Oils," Preprints (ACS Division of Petroleum Chemistry), Vol. 42,
No. 1, 1997, p p . 242-245.

MNL37-EB/Jun. 2003

Hydrocarbons for Chemical


and Specialty Uses
Dennis W. Brunett, ^ George E. Totten, ^
and Paul M. Mattlock^

ETHYLENE (C2), PROPYLENE (C3), AND THE C4 PRODUCTS (butene-

DISCUSSION

1, butene-2, isobutylene and 1,3-butadiene) are monomers of


enormous industrial importance. Among the numerous uses
of ethylene are the synthesis of ethylene glycol, which is used
for antifreeze formulation, and the production of polyethylene terephthalate. Ethylene is also used for polyethylene
manufacture and as a co-monomer in the production of various synthetic rubbers.
The primary method for the production of ethylene and
other light olefins is steam cracking. Steam cracking is performed both on liquefied petroleum gases (LPGs) and on liquid feedstocks. LPGs include ethane, propane, and/or butane.
Liquid feedstocks are generally paraffinic or naphthenic and
include n a p h t h a and petroleum condensates. When these
feedstocks are thermally "cracked," the resulting product
stream contains a complex mixture of hydrocarbon comp o u n d s . The process challenge is to separate the various
product components at the desired purity.
The purity of the individual products is set by their ultimate use. For example, some polymerization processes are
especially sensitive to particular contaminsLnts in monomer/
co-monomer feeds. Some of these impurities poison catalysts or reduce their efficiency. Others may degrade the
physical or performance properties of the polymer products. Because olefin purity is so important to downstream
processing, it is essential that producers and consumers
alike utilize a standard set of well-tested and widely accepted antdytical procedures to measure and control the
quality of these chemicals. The ASTM D.02.0D Subcommittee on Hydrocarbons for Chemical and Specialty Uses has
developed such a series of analytical standards for the
petrochemical industry.

Commercial Production of Synthetic


Hydrocarbons
Basestocks

In this chapter, a brief overview of the most common industrieJ production methods of C2, C3, and C4 synthetic hydrocarbons is provided. Typical purity standards and comm o n classes of impurities are also discussed. The chapter
also includes various types of ASTM analytical procedures
and the separation principles involved.

' The Dow Chemical Company, 2501 North Brazosport Blvd.,


Freeport.TX 77541.
^ G. E. Totten & Associates, LLC, PO Box 30108, Seattle, WA 98103.
^ The Dow Chemical Company, 771 Old Saw Mill River Road, Tarrytown, NY 10591.

2003 by A S I M International

Hydrocarbon

Production

The unsaturated synthetic hydrocarbons such as ethylene,


propylene a n d butenes m a y be produced either by steam
cracking saturated hydrocarbons (ethane, propane, Eind butane), or by steam cracking feedstocks such as virgin crude
oil fractions (naphtha, kerosine, and gas oil). In addition,
ethylene may also be produced from crude oil directly [1].
Different types of feedstocks may be used for the production of synthetic hydrocarbons. The primary feedstocks are
the "gas liquids." Gas liquids include ethane, propane, and
butane, all sepeiration products from natural gas. The second
class of feedstocks is the refinery off-gases. Refinery off-gases
are mixtures of hydrogen, m e t h a n e , ethylene, ethane,
propane, a n d others. A typical off-gas contains approximately 20 mol% ethane, 16 mol% ethylene, 3.6 mol% C3
derivatives, with the remaining components being hydrogen,
methane, and acid gases. Off-gases are obtained from refinery operations.
Liquid feedstocks include various petroleum fractions derived from crude oil processing (naphtha, kerosine, atmospheric gas oil and vacuum gas oil) as well as liquid condensates from natural gas processing (natural gasolines) and
natural gas condensates such as Algerian and Brega condensates. They are defined by their boiling points. The approximate boiling ranges of the petroleum fractions are provided
in Table 1 [2].
Raffinates are residues from extraction processes such as
for aromatics recovery. These feedstocks t3^ically possess a
broad range of compositions and boiling ranges.
The composition of the crude oil fractions varies with the
source as shown in Table 2 [1]. The type of feedstocks will
affect the composition of the product being produced. Generally, the heavier the feedstock, the greater the amount of
by-products. In addition to feedstock composition, the composition of the product stream resulting from steam cracking
is also d e p e n d e n t on t e m p e r a t u r e , residence time, and
steam/hydrocarbon ratio. The optimization of the residence
time, coil outlet temperature and coil outlet pressure (cracking severity) for a given feedstock are the most critical variables in determining the product mix.
The second most frequently used method of ethylene production is recovery from refinery gas. Alternate methods are

185
Copyright'

for Synthetic

www.astm.org

186 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 1Approximate boiling point
ranges for different liquid feedstocks.

mined based on the product mix required. Table 3 provides a


list of the different types of feedstocks typically used in steam
crackers for the production of ethylene.

Boiling Range
(F)

Liquid Feedstock

Ethylene

Naphtha
Full range
Light
Heavy
Kerosine
Atmospheric gas oil
Light
Heavy
Vacuum gas oil
Gas condensates

80-430
80-300
250-430
400-500

Dependency of Reaction Product and By-Product Complexity


on Feedstock StructureEthylene
may be produced commercially by thermal cracking of hydrocarbons, recovery from refineiy off-gas, recovery from coke-oven gas, or dehydration
of ethanol. In practice, almost all of the high purity ethylene
produced in the U.S. is the result of steam cracking. Table 4
[3] lists various ethylene manufacturing facilities a n d the
method of ethylene generation.

400-680
600-800
800-1100
80-530

TABLE 2Typical composition of feedstocks used for


synthetic hydrocEirbon production.
Component
Origin
Density (g/mL)
Sulfur content (mass %)
ASTM boiling range (F)
IBP
50%
EP
BMCI
PONA analysis (mass %)
Paraffins
Olefins
Monocyclic naphthenes
Polycyclic naphthenes
Monocyclic aromatics
Polycyclic aromatics

Naptha

Kerosine

Gas Oil

Kuwait

North Sea

Kuwait,
North Sea
0.839
0.1

0.724
0.04
28
121
175

0.801
0.03
180
206
242
29.7

220
290
380
27.7

72.3

50.9

41.8

16.7

15.8
10.5
14.9
7.9

19.2
14.1
20.9
4.0

11.0

known using feed streams from coal, ethanol, coke oven gas
and other sources, but these are rarely used. Therefore, S5T1thetic hydrocarbon p r o d u c t i o n from these alternative
sources will not be discussed in detail here.
The value of BMCI shown in Table 2 refers to the Bureau
of Mines Correlation Index. BMCI is used to estimate the
amount of ethylene in feedstocks. Higher numbers indicate
m o r e aromatic character. BMCI is calculated from the
following equation:
BMCI = VABP +

48640
473.7(^.5)

456.8

Production

[1]

Where: VABP is the volume average boiling point (K) and dis
is the density in g/mL at 15C.
The BMCI value estimates the extent of naphthenic and aromatic content of a hydrocarbon feedstock emd is calibrated for
hexane to yield 0% and pure benzene to yield 100%.
Synthetic hydrocarbon feedstocks are typically low in sulfur content. High sulfur feedstocks may be used, but these
materials produce larger quantities of acid gases, which must
be removed from the resulting products. Low chloride feedstocks should be used as chlorides may cause irreparable
damage in the furnace tubes due to chloride stress cracking
and corrosion.
It is possible to obtain any of the synthetic hydrocarbons
from any feedstock by steam cracking. Higher paraffinic content materials yield higher conversion to short-chain olefins.
The choice of feedstock for a steam cracker is typically deter-

In the steam cracking process, steam is added to the hydrocarbon feed stream to:
1. Reduce the partial pressure of the hydrocarbon
2. Reduce the high-temperature residence time
3. Reduce coke formation in the reactor. (Carbon monoxide
and hydrogen are formed by reaction of steam with carbon
at the high temperatures encountered in the reactor. This
is the famous "water-gas" reaction.)
Ethylene product yield, like that of other synthetic hydrocarbons, correlates with the carbon/hydrogen ratio of the
components in the feedstock being steam cracked. Generally,
as the feedstock becomes heavier (which is typically accompanied by increasing amounts of naphthenes and aromatics
and a corresponding lowering of the C/H ratio), the reaction
products become heavier and more aromatic, while conversion yields to lighter olefins decrease.
E t h a n e m a y be produced by Ci chemistry by thermal
cracking of methane at 1000C as shown in Scheme 1 [4].
This is not the preferred commercial route to ethane, however, because the bond dissociation energy of a CH bond of
93.3 kcal/mol is considerably higher than a CC bond-dissociation process of 71.0 kcal/mol [9], making this an energy inefficient process.
CH4 - CHs*
2CH3* -^ CH3 - CH3
S c h e m e 1Formation of ethane from methane.
Ethylene m a y be produced by the dehydrogenation of
ethane as shown in Scheme 2. This reaction process, like all
thermal cracking processes, is accompanied by side reactions, which lead to the formation of aromatic and naphthenic hydrocarbon ring structures.
CH3 - CH3 ^ CH2 = CH2 + H2
S c h e m e 2Ethylene formation by dehydrogenation of
ethane.
TABLE 3Selected feedstocks for synthetic hydrocarbon
production.
Gases or Gas Liquid Products
Ethane
Propane
Butane
Refinery off-gases

Liquid Feedstock
Naphtha
Kerosine
Raffinates from extraction processes
Atmospheric gas oil
Vacuum gas oil
Natural gasoline
Gas condensates

CHAPTER 8: HYDROCARBONS FOR CHEMICAL AND SPECIALTY USES 187


T A B L E 4 S u m m a r y o f ethylene process m e t h o d s u s e d ;in t h e U n i t e d States.
PRODUCT
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLfeNE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE
ETHYLENE

COUNTRY
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA

COMPANY
BPCHEM.
BP CHEM.
COND.VISTA
CPCHEM
CPCHEM
CPCHEM
CPCHEM
CPCHEM
CPCHEM
DOW
DOW
DOW
DOW
DOW
DOW
DOW
DOW
DUPONT
EQUISTAR
EQUISTAR
EQUISTAR
EQUISTAR
EQUISTAR
EQUISTAR
EQUISTAR
EQUISTAR
EXXONMO.CH
EXXONMO.CH
EXXONMO.CH
EXXONMO.CH
EXXONMO.CH
FORMOSA PL
FORMOSA PL
HUNTSMANC
HUNTSMANC
HUNTSMAN C
JAVELINAC
SHELL CHEM
SHELL CHEM
SHELL CHEM
SHELL CHEM
SHELL CHEM
SUNOCO CH.
SUNOCO CH.
TEXAS EAST
WESTLAKECA
WESTLAKEPC
WESTLAKEPC
WILLIAMS 0

SITE

AVJimx
ALVIN/TX
LAKECWLA
OEDAR BAYO
PORTAR/TX
SWEENY/TX
SWEENYm(
SWEENY/TX
SWEENY/TX
FREEPORT/T
FREEPORT/T
PLAQUEMINE
PUQUEMINE
SEADRIFT/TX
TAFT/U
TAFT/U
TEXAS CITY/rx
ORANGE/TX
CHANNELVIE
CHANNELVIE
CHOC.BAYOU
CLINTON/IA
CORPUS/TX
LfiPORJEfTX
LAKECH/LA
MORRIS/IL
BATON R/LA
BAYTOWN/TX
BAYTOWN/TX
BEAUMON/TX
HOUSTOWrX
POINT CX5MF/TX
POINT CMF/TX
ODESSAAJS
PORTAR/TX
PORTNECHE
CORPU^TX
DEER PA/rX
DEER PA/rX
NORCO/LA
NORCO/U
NORCO/LA
BRANDENBUR
CLAYMONT/D
LONGVIE/TX
CALVERT CI
LAKECHAA
LAKECHflJ^
GEISMAR/LA

ROUTE
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBOI
HYD-CARK)N
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARODN
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
RFRY-QAS
HYD-CARBON
RFRY-GAS
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON

TECHNOLOQY
STCRACKIN
ST CRACKIN
ST CRACKIN
STCRACKIN
ST CRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
ST CRACKIN
ST CRACKIN
ST CRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
ST CRACKIN
ST CRACKIN
ST CRACKIN
STCRACKIN
ST CRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
ST CRACKIN
ST CRACKIN
ST CRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
ETH RECOV
ST CRACKIN
N.A.
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
ST CRACKIN
STCRACKIN
STCRACKIN
ST CRACKIN
STCRACKIN
ST CRACKIN

LICENSOR START
NA.
1975
1977
BRAUN
N.A.
1^8
1977
LUMMUS
1970
LUMMUS
1957
N.A.

N.A.
1967
BRAUN
1978
BRAUN
1991
DOW
1972
1994
BRAUN
HA.
1972
DOW
1980
1957
N.A.
1967
LUMMUS
1978
LUMMUS
N.A.
1969
LUMMUS
1967
1976
UMIMUS
LUMMUS
1977
1980
N.A.
1^8
KELLOGG
S&W
1980
KELLOGG
1991
N.A.
1971
LUMMUS
1972
1972
LUMMUS
KELLOGG
1979
1997
EXXON
N.A.
1961
N.A.
1978
1994
KELLOGG
2001
KEUOGG
N.A.
1965
1979
S&W
N.A.
1978
N.A.
0
1978
KELLOGG
N.A.
0
KELLOGG
1975
1981
KELLOGG
N.A.
2000
1952
N.A.
1961
N.A.
1974
KELLOGG
BRAUN
1964
KELLOGG
1991
1997
LUMMUS
1968
LUMMUS

188 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


The structural complexity of the product stream increases
with the carbon chain length of the feedstock. This is illustrated by the thermal cracking of propane to jdeld ethylene
a n d propylene shown in Scheme 3 [15]. The first two reactions in Scheme 3 yield the primary products [5,6]. Fair proposed that butenes and methane were the most probable decomposition products [15].
C3H8 -^ C2H4 + CH4

40%

C3H8 -^ C3H6 + H2

36%

C3H8 -^ 14C4H8 + CH4

10%

C3H8 -^ VzCjUe + Yi C3H6 + ^CH4

14%

S c h e m e 3Ethylene formation from propane.


The primary thermal cracking reaction products from nbutane and i-butane are shown in Scheme 4 [8]. It was shown
by Fair that no ethylene is formed from the branched substrate, t'-butane [8].
n - C4H10 -^ CH4 + C3H6
n - C4H10 -^ C2H6 + C2H4
n C4H10 > H2 + n C4H8

Additional reaction processes shown in Scheme 6 were


proposed for temperatures greater than 800C [11].
C2H3* -> C2H2 + H
C2H4 <-> C2H2 + H2
C2H2 + C2H4 > condensation products + CH4
C2H4 -^ carbon black + H2
S c h e m e 6^Additional ethane thermal decomposition reaction processes occurring above 800C.
Laidler determined the reaction mechanism for the formation of ethane from the thermal decomposition of propane
shown in Scheme 7 [12]. Laidler proposed that only the H,
CH3 and CsH?* radicals are involved in the chain propagation
steps and that C2H5, formed by ethane decomposition, is not
regenerated. Termination occurs by methyl and propyl radical
recombination or by the recombination of two methyl radicals.
C3H8 -> CH3 + C2H5
C2H5' + CjHg ^ C2H6 + C3H7*
H + C3H8 ^ H2 + C3H7

n - C4H10 ^ H2 + 2C2H4

CH3 + CjHg ^ CH4 + C3H7*

i - C4H10 -^ CH4 + C3H6

C3H7* -^ CH3 + C2H4

/ - C4H10 -^ H2 + i - C4H8

C3H7 ^ H + C3H6

S c h e m e 4Primary reaction products formed by thermal


cracking of n-butane and i-butane.
Thermal Cracking Reaction MechanismHydrocarbon
thermal cracking reactions have been studied in detail for many
years [5,7,9-13]. The Kalinenko cmd Brodski reaction mechanism for the thermal decomposition of ethane below 800C
is provided in Scheme 5.
C2H6 ^ 2CH3
H + [C2H6, CH4, C2H4, C3H8, C4H10] -> H2
+ [C2H5, CH3, CzHj*, C3H7, C4H9*}
CH3 + [C2H6, H2, C2H4] -^ CH4 + [C2H5, H, CzHj*]
CjHs* + [H2, CH4, C2H4] ^ C2H6 + [ H, CH3, C2H3]
C2H3* + [H2, CH4, C2H6} ^ C2H4 + [ H, CH3, CzHs*]
CH3 + C2H5* <-> C3H8
2C2H5* <-> C4H10
C2H3 + [C2H5, CH3, C2H3] ^ [C4H8, C3H6, C4H6 }
C2Hs -^ C2H4 + H
C2H5* -t- C2H4 O C4H9*
C4H9 <^ C3H6 + CHj*
C2H3 + C2H4 ^ C4H7*
C4H7* -^ H + C4H6
C4H10 -> CH3 + C3H7*
S c h e m e 5-Kalinenko and Brodski ethane thermal decomposition reaction mechanism (less than 800C).

CH3* + C3H7* -^ CH4 + C3H8 or CH3 + CH3* -^ C2H6


C3H7* + C3H7* -^ C S H M or C2H6 + CjHg
S c h e m e 7Laidler mechanism of the thermal decomposition of propane.
The mechanism of formation of ethane from the thermal
decomposition of butane [13] and higher alkanes [15] have
also been studied but will not be discussed here.
There are n u m e r o u s reactions involved in hydrocarbon
thermal decomposition. In the absence of equilibrium processes, the initial chain scission reaction of the hydrocarbon
substrate is unimolecular. The primary decomposition products lead to olefins and by-products. Activation energies for
thermal decomposition of hydrocarbons vary from 70-79
cal/g-mol at 500-1000C [16].
Thermal decomposition of propylene is also unimolecular
with reported activation energies varying from approximately 59-67 cal/g-mol [5,7,17-19]. Reaction mechanisms
and kinetics have been reported for other potential ethylene
feedstocks including; propylene [17,20], n-butene [17], n-butane [8,17,20,21], j-butane [8,17,20], n-butylene [20], and ibutene [17].
Commercial Production of EthyleneSteam cracking is the
most common method used to produce ethylene. The desired
feedstock is diluted with steam and passed through a high-temperature furnace. There are numerous patented designs employing vertical or horizontal gas-fired tubes (direct heating),
fluidized bed heated tubes (indirect heating), and other heat
sources. Figure 1 provides a schematic illustration of a steam
cracking unit used to produce ethylene. The reaction products
and yields are controlled by the feedstock, cracking temperature, residence time, and other plant-specific variables.

CHAPTER 8: HYDROCARBONS FOR CHEMICAL AND SPECIALTY USES 189


Example of Front End Depropanizer/Front End Reactor Process

>

r:

Acid Gas
Removal

Compression

Quench

Fuel Oil Product

* Pyrogasoline Product

Chilling
Train

Dryers

Secondary
Dryers

Acetylene
Reactors

H2. CH4.

Compression

Depropanizer
C-4+

Ethylene
Recovery

Demethanizer

(H2, CH4)
_w Off-Gas

Deethanizer

Ethylene
Refiigeration

Ethylene
" Product

C-2 Splitter

Propylene
Product

T}

Pyrogasoline
Product

-*\ C-3 Splitter


C-2's, C-3's

prude C-4
Product

C3,C3=,MA, PD
Ethane
Recycle

Propane
Recycle

FIG. 1Schematic illustration of a steam-cracking unit used for the production


of ethylene.
The reaction is quenched (stopped) by cooling the product
stream rapidly to about 600F (315C), a temperature where
olefinic products are typically stable. The cooling process is
performed through a heat exchanger or by coinjection with
water or oil.
The by-products formed during ethylene synthesis by
steam cracking include:
1. AcetyleneThe a m o u n t of acetylene that is formed depends on the feedstock a n d cracking severity. Although
acetylene can be isolated in high purity, it is usually converted to ethylene. This is performed over a catalyst. Catalyst selectivity is very important. If the catalyst is too active
ethane will be produced not only from the hydrogenation
of the acetylene but also some of the ethylene (negative selectivity) yielding a net loss of ethylene production. Because acetylene cannot be distilled out of the ethylene, hydrogenation is the preferred technique for removal.
During the hydrogenation process, a liquid product, green
oil, is produced composed of hydrocetrbons increasing in
chain length by multiples of 2. This material must be removed because of the possibility of downstream fouling in
low temperature portions of the distillation process (demethanizer, C2 splitter, and cold train). This green oil is
typically returned to the process mixed with the fuel oil
stream also produced in the cracking process.
2. PropylenePropylene is also produced by hydrocarbon pyrolysis (steam cracking or catalytic cracking). Other methods are used reirely. Some processes upgrade refinery material to a more pure, polymer grade, but the production
process still occurs in a refinery. The third m e t h o d is
propane dehydrogenation, but this is currently not being
used to any appreciable extent in North America or South
America. Some dehydrogenation is being done in Western
Europe and Southeast Asia. There is a very small amount
of propylene being produced in South Africa from coal.
3. Methylacetylene and Propadiene^Depending on the plant,
methylacetylene and propadiene (allene) can be removed

from the propylene in the same reactor as acetylene if the


cracked gas is first "depropanized" rather than "de-ethanized." The stream containing Cj to C3 hydrocarbons is then
sent to the reactors, followed by various distillations for purification of both ethylene and propylene. The C4 and heavier material is generally not hydrogenated, but simply distilled after the C3 and lighter material is removed. There are,
however, some facilities that hydrogenate the raw gas stream
after removal of the heavier components in the quench system. Methylacetylene and propadiene are typically of very
low concentrations and are typically not isolated. However,
they can be isolated and sold as welding gases.
4. Butadiene andButenes1,3-Butadiene
is produced by distillation of the crude C4 material from the mixture followed by solvent extraction of the m o n o m e r . In North
America, butadiene is derived from the steam cracking of
LPGs or liquid feeds, followed by extractive distillation of
the crude C4 cut of the cracked gas.
5. PyrogasolineIn ethylene production, one of the by-products is called pyrogasoline, which is commonly known as
"pyrolysis gasoline" or "pygas." The lightest components in
this stream are the C5 compounds, which include isoprene
and piperylene. Cyclopentadiene is dimerized in this process and later recovered as dicyclopentadiene. Pyrolysis
gasoline is used as a feedstock in C5 S3Tithetic hydrocarbon
production. (The subject material for this chapter is limited
to C2, C3, and C4 synthetic hydrocarbons.) Pjrolysis gasoline
is also the primary feedstock for the extraction of benzene.
The total product stream from the cracking process is purified before distillation by multi-step treatments, which may
include:
Oil and/or aqueous quenching of the hot cracked gas for removal of heavier components (C5 and heavier),
Compression of the remaining cracked gas to remove the
remainder of the heavier hydrocarbons,
Conversion of residual sulfur to hydrogen sulfide Eind subsequent removal by zeolite absorption,

190 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


Acid gases removal by caustic extraction or amine absorption,
Carbon dioxide removal by absorption or extraction,
Drying to remove residual water after compression,
Acetylenic materials removal by selective hydrogenation or
extraction,
Methane removal by low temperature fractionation or selective adsorption or selective absorption.
The process challenge in the production of ethylene, like
other synthetic hydrocarbons, is obtaining pure ethylene
from the complex reaction mixture after cracking. This is accomplished primarily by distillation after the product stream
has been treated. Table 5 provides a listing of typical specifications for ethylene produced in this way. Table 6 summarizes
the typical physical properties of ethylene and other synthetic
hydrocarbons.

Propylene Production
Propylene is most often produced by either steam cracking or
cataljrtic cracking. Propylene is a major by-product from ethylene production when feedstocks heavier than ethane are
used. In steam cracking, generally, the heavier the feedstock,
the greater the a m o u n t of propylene produced relative to ethylene. It is not unusual for propylene production to amount to
40-70% of ethylene production [1]. It should be noted, however, propane and low boiling liquid feedstocks may not conform to this pattern if the cracking severity is low. This is why
such plants are more often called "olefin plants." Since ethylene and propylene are co-produced in the same units, propylene production will not be detailed separately here.
Table 7 provides a summary of typical product specifications for polymer grade propylene. The physical properties of
propylene are summarized in Table 6.
Butylene and Butadiene Production
Reaction Chemistry and MechanismButadiene
may be synthesized by dehydrogenation of n-butenes at 1100-1250F
(593-677C) over a metal catalyst as shown in Scheme 8 [21].
However, due to the relatively high temperatures required for
conversion, the reaction selectivity is often poor. Reaction

TABLE 5Typical product specification


for ethylene.
Composition
99.9 mol% min
0.1 mol%max
1 mol ppm max
1 mol ppm max
10 mol ppm max
1 mol ppm max
1 mol ppm max
1 mol ppm max
2 mol ppm max
1 mol ppm msix
1 mass ppm max

Component
Ethylene
Methane and ethane
Hydrogen
Acetylene
Propylene and propane
Oxygen
Carbon monoxide
Carbon dioxide
Water
Methanol
Total sulfur

C4H8 O C4H6 + H2
Scheme 8Butadiene synthesis by butene dehydrogenation.
temperatures may be reduced to 750-1100F (399-593C),
thus permitting improved selectivity, by introducing air
(steam + oxygen) into the reaction (oxidative dehydrogenation) as shown in Scheme 9. Catalysts that have been reported
to produce good yields include: bismuth molybdate, mixed ox-

TABLE 6Thermophysical properties of C2, C3 and C4 hydrocarbons."


Property
Molecular weight
Triple point
Temperature, C
Pressure, kPa
Latent heat of fusion, J/mol
(at melting point)
Normal boiling point
Temperature, C
Latent heat of vaporization, J/mol
Density of the liquid, mol/dm^
Specific heat of the liquid, J m o l ^ ' K " '
Viscosity of the liquid, Pas
Surface tension of the liquid, N/m
Specific heat of the ideal gas (25C),

Ethylene [1]
28.05
-169.19
0.11
3350

-103.71
13 540
20.27
67.4
1.61 X 10""
0.0164
42.84

Propylene
42.08
-185.26
9.54 X 10"^
3003

-47.6
18 420
14.47

1-Butene

Cis-2-Butene

Trans-2-Butene

1,3-Butadiene

56.11

56.11

56.11

54.09

-185.35

-138.91

-105.55

-108.92

3848

7309

9757

7980

1.92 X lO""*
.0167
62.49

-6.25
21 917
11.15
118
1.98 X lO"'*
.0160
88.49

3.72
23 349
11.43
127
1.73 X 10"''
.0156
76.89

91.8
4.62
5.52
0.2750
2.058

146.4
4.02
4.153
0.2760
2.719

0.88
22 757
11.17
1.79 X 10"^
.0160
86.00

-4.4
22 597
12.03
123.6
1.98 X 10"^
.0176
77.13

162.4
4.21
4.277
0.2720
2.712

155.5
4.10
4.207
0.2740
2.707

151.9
4.33
4.525
0.2700
2.541

1.6
10.0
385

1.6
9.7
325

1.6
9.7
324

2.0
11.5
420

297.1

213.7

234.1

281.1

Jmor^K"'
Critical point
Temperature, C
Pressure, MPa
Density, mol/dm^
Compressibility factor
Gross heat of combustion of the gas
(25X), MJ/mol
Limits of flammability of atmospheric
pressure at 25C
Lower limit in air, mol%
Upper limit in air, mol%
Autoignition temperature in air at
atmospheric pressure, "C
Vapor pressure at 25C, kPa

9.2
5.042
7.635
0.2813
1.411

2.7
36
490
7065

"Values from a variety of sources and are believed accurate.

1.9
11.1
455
1156

CHAPTER 8: HYDROCARBONS FOR CHEMICAL AND SPECIALTY USES


TABLE 7Typical product specification
for propylene.
Component
Propylene
Paraffins
Hydrogen
Ethylene
Acetylene
Methylacetylene
Propadiene
C-4 Hydrocarbons
Carbon dioxide
Carbon monoxide
Methanol
Oxygen
Water
Sulfur

Concentration
99.5 mol% min
0.4 inol% max
5 mol ppm max
100 mol ppm max
1 mol ppm max
5 mol ppm max
5 mol ppm max
5 mol ppm max
5 mol ppm max
5 mol ppm max
5 mol ppni max
2 mol ppm max
10 mass ppm max
1 mass ppm max

stream is quenched by cooling, washed in a wash tower to remove oxygenated bjrproducts, and finally scrubbed with an
oil to extract the organic products from nitrogen and carbon
dioxide. The hydrocarbons Eire removed by stripping them
from the oil a n d then using extractive distillation to recover
the butadiene.
Most of the butadiene production in the world today is obtained as a by-product of ethylene manufacture (see Table 8).
When there is excess capacity, butadiene may be selectively
hydrogenated to butenes. Alternatively, excess butadiene

POSSIBLE MODIFICATION OF EXISTING COMMERCIAL OPERATIONS


TO INCLUDE OXIDATIVE DEHYDROGENATION OF BUTENES

PHILLIPS PETROLEUM COMPANY

ides of tin and antimony, mixed oxides of molybdenum and


tellurium and nickel, calcium and chromium phosphates [27].

Shchukin studied the mechanism and reaction kinetics of


butadiene synthesis by oxidative dehydrogenation and reported the mechanism illustrated in Scheme 10 [24]. K ( 0 )
and K ( ) represent the oxidized and reduced state of the catalyst respectively. The values xj, X2, Vi, and V2 are reactant
and product coefficients. The reaction order was reported to
be approximately 0.5 with respect to 1-butene and oxygen
[25].

PETRO-TEX CHEMICAL COMPANY

n-BUTANE

C4H8 + 1^02 ^> C4H6 + H2O


S c h e m e 9Butadiene synthesis by oxidative dehydrogenation of n-butane and n-butenes.

n-BUTANE

BUTANE CATALYTIC
DEHYDROGENATION
(HOUDRY)

BUTANE CATALYTIC
DEHYDROGENATION
BUTANE

BUTANE AND BUTENES


BUTENES SEPARATION
(FURFURAL EXT. DIST.)

; BUTANE ONLY ;

'-in
BUTADIENE SEPARATION
1 BUTENES SEPARATION i
(FURFURAL EXT. DIST.)

BUTADIENE
I BUTENES i

BUTENE DEHYDROGENATION

K ( 0 ) + C4H8 -^ K(OC4H8)

CAT^kYTIC

r 'o)(YDiHYDROGENATibNi

j f STEAM

K(OC4H8) -^ K(C4H8) + H2O -^ C4H6 + K ( )

i.-i

K(OC4H8) + xiK(O) -^ V1CO2 + V1H2O + (xi + 1)K( )


K(0) -f- C4H68 <-> K(OC4H6)

191

BUTADIENE SEPARATION
(FURFURAL EXT. DIST)

K(OC4H6) + X2K(0) -^ V2CO2 + y4V2H20 + (X2 + 1)K( )

AIR

*.

BUTENE
OXYDEHYDROGENATION
CATALYTIC

4 . . I BUTADIENE SEPARATION

K ( ) + O2 ^ K ( 0 2 ) + K ( ) ^ 2 K ( 0 )
S c h e m e 10Mechanism of butylenes synthesis by oxidative dehydrogenation.
The first reaction in Scheme 10 can act to isomerize 1butene into cis- and trans-2-butene [26]. The reactivity of the
butene isomers on an aluminum oxide catalyst decreases in
the following order: 1-butene > cis-2-butene > trans-2b u t e n e [27]. Unsaturated carbonyl c o m p o u n d s can b e
formed as byproducts. Adzhamov reports that these carbonyl
compounds inhibit the oxidative dehydrogenation process
and butene isomerization [28]. Other by-products that are
possible include furan, acetaldehyde, acetone, acrolein,
formaldehyde, methyl ethyl ketone, methyl vinyl ketone, and
other carbonyl compounds and carbon dioxide [27].
Commercial Butadiene Production Processes^Two industrial
processes for butadiene production by oxidative dehydrogenation are the Phillips Petroleum Company Process [24,25]
and the Petro-Tex Chemical Company Process [22]. These
two processes are illustrated schematically in Fig. 2 [30,31].
The butene feed stream is typiccJly mixed with steam and air
and passed through a fixed-bed reactor. The reaction product

BUTADIENE
Note: BROKEN LINES INDICATE AN ENLARGEMENT OF AN EXISTING
OPERATION OR THE ADDITION OF A NEW OPERATION.

FIG. 2Comparative illustration of Butadiene production by


the Phillips and the Petro-Tex processes.

TABLE 8Typical product composition


for C4 Hydrocarbon product stream.
Component
C3 Hydrocarbons
1,3 Butadiene
Ethyl acetylene
Vinylacetylene
cis-Butene-2
fran5-Butene-2
Isobutene
1-Butene
n-Butane
Isobutane
C5 Hydrocarbons
Total Sulfur

Composition
0.1 mol% max
35-75 mol%
0.2-0.5 mol%
0.7-1.4 mol%
4-5 mol%
4.5-6.5 mol%
20-30 mol%
15-25 mol%
5-15 mol%
0.5-1 mol%
0.1 mol% max
5 mass ppm max

192 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

may be completely hydrogenated to butanes. In recent years,


many of the dedicated butadiene production units have been
shut down.
Butadiene separation from an oxidative dehydrogenation
product stream or from the product stream of an ethylene
steam cracker is typically performed by an extractive distillation. The butadiene boiling point is too close to other products to permit effective separation by fractionation in a conventional distillation process. There is no consensus on the
best solvent system but extractive distillation systems that
have been reported include N-methylpyrrolidone, dimethylformamide, furfural, acetonitrile and dimethylacetamide
[32-34].
Analytical Test Methods
The above discussion has provided a general overview of the
production of ethylene, propylene and C4 hydrocarbons including butanes and 1,3-butadiene. Included in this discussion is the generation of various by-products, many of which
exhibit deleterious effects on downstream processes. This
section provides a review of the ASTM procedures for product characterization. This will be done by dividing these
methods into those that are applicable for ethylene, propylene, C4 hydrocarbons, and other related methods.
Ethylene Characterization
Guide for Analysis of Ethylene (Guide D 5234)^When various
producers and users of ethylene deal with anal3rtical results,
inconsistency of units and test methods may cause major errors. D5234 provides an overview of the typical concentrations of possible components found in ethylene, analytical
methods, and units of measure. Although this guide cannot
be used as a specification, it can provide a starting point for
specification development. It can also be used as a starting
point for identifying suitable test methods for ethylene product characterization.
Determination of Hydrocarbon Impurities in Ethylene (Test
Method D 6159)This method determines the amounts of
certain impurities that could impair the performance of high
purity ethylene. Test Method D 6159 is used for the determination of methane, ethane, propane, propylene, acetylene,
iso-butane, propadiene, butane, trans-2-butene, 1-butene,
iso-butene, cis-2-butene, methyl acetylene and 1,3 butadiene
by a gas chromatographic procedure. This test method does
not determine all possible impurities. Carbon monoxide, carbon dioxide, water, alcohols, nitrogen oxides, carbon disulfide, and hydrocarbons higher than decane are not determined by D 6159. These products must be determined by
other procedures.
This test is conducted by injecting the as-received ethylene
sample into a capillary gas chromatograph that is equipped
with a 6-port sampling valve and two wide bore capillary
columns connected in series. The columns are a dimethyl silicone column and a porous layer open tubular (PLOT)
AI2O3/KCI column. A flame ionization detector is used. The
hydrocarbon impurities are determined and the total impurities are used to calculate the ethylene content.
Determination of Ethylene, Other Hydrocarbons and Carbon
Dioxide (Test Method D 2505)Test Method D 2505 is used to

determine carbon dioxide, methane, ethane, acetylene and


other hydrocarbons in high-purity ethylene. Hydrogen, nitrogen, oxygen, and carbon monoxide are determined in accordcince with Test Method 2504. Ethylene concentration is determined by subtracting the sum of the percentages of
hydrocarbon and non-hydrocarbon impurities from 100%.
This method is applicable over the range of impurities from
1-500 parts per million by volume.
In this method, the sample is sepetrated in a gas chromatograph utilizing four different packed columns with helium as
a carrier gas. Methane and ethane are determined using a
silica gel column. Propylene and heavier hydrocarbons are
determined using a hexamethylphosphoramide (HMPA) column. Acetylene is determined by using, in series, a hexadecane and a squalene column. Carbon dioxide is determined
using a column packed with activated charcoal impregnated
with a solution of silver nitrate in /3,/3'-oxydipropionitrile.
Calibration data are obtained using standard samples containing the impurities, carbon dioxide, methane, and ethane
in the range expected to be encountered. Calibration data for
acetylene are obtained assuming that acetylene has the same
peak area response on a weight basis as methane. Calculations for carbon dioxide, methane, and ethane are conducted
using the peak-height measurement.
Propylene Characterization
Guide for Analysis of Propylene Concentrates (Guide D 5273)
Standard Guide D 5273 lists the major grades of propylene
produced in North America. Standard Guide D 5273 is intended to provide information on the likely composition of
propylene concentrates and on probable ways to test them.
Since there are currently no ASTM test methods for determining all components of interest. Standard Guide D 5273
provides information on other potentially available test
methods. This guide is not intended to be used as a standard
for any grade of propylene concentrate.
Method for Liquefied Petroleum (LP) Gases and Propylene Concentrates (Test Method D 2163)D-2163 determines the composition of LP gases and propylene concentrates. The components measured are ethane, propane, propylene, n-butane,
isobutane, butylene, and isopentane. The components can be
measured so long as their concentration is above 0.1%. This
information is useful when the product is to be sold either as
a chemical intermediate or as a fuel. The component distribution data of LP gases and propylene concentrates can be
used to calculate physical properties such as relative density,
vapor pressure, and motor octane.
Test Method D 2163 involves the separation of the components of LP gas by gas chromatography emd comparing them
to corresponding components separated under identical operating conditions from a reference standard or from pure
hydrocarbons. The chromatogram of the sample is interpreted by comparing peak heights or areas with those obtained on a reference standard mixture or pure hydrocarbon
of interest.
Determination of Trace Hydrocarbon Impurities in Propylene
Concentrates (Test Method D 2712)Test Method D 2712 is
used to determine ethylene, total butylenes, acetylene,
methyl acetylene, propadiene, and butadiene at levels of
5-500 ppm each in propylene concentrates. Trace levels of

CHAPTER 8: HYDROCARBONS
these components may affect the commercial use of propylene concentrates.
In Test Method D 2712, a relatively large volume of sample
is charged to a gas partition chromatograph equipped with a
column that will separate trace hydrocarbon constituents
from the major components. Any column or combination of
columns may be used providing that they exhibit the necessary resolution. Various columns that have been used successfully are provided in Table 1 of Test Method 2712.
Determination of Trace Methanol in Propylene Concentrates
(Test Method D 4864)Methanol is a common impurity in
propylene. It can have a deleterious effect on various processes that use propylene as a feedstock. Test Method D 4864
determines methanol in propylene concentrates in the range
of 4 ^ 0 parts per million by weight.
For Test Method D 4864, a known weight of water is measured into a sample cylinder containing a known amount of
liquefied propylene. The contents in the cylinder are shaken
and the water/methanol phase is withdrawn. A reproducible
volume of the extract is then injected into a gas chromatograph equipped with either a thermal conductivity or a flame
ionization detector. The methanol concentration is calculated from the area of the methanol peak using calibration
and extraction factors obtained from synthetic blends of
known methanol content.
Determination of Trace Carbonyl Sulfide (COS) in Propylene
(Test Method D 5303)This test method measures traces of
COS in propylene in the range of 0.5-4.0 parts per million by
mass. In propylene producing processes, COS usually remains with the C3 and must be removed since it affects product quality. COS acts as a poison to commercial polymerization processes, resulting in deactivation and costly process
downtime. Accurate gas chromatographic determination of
trace COS in propylene involves unique analyticcJ problems
because of the nature of COS and idiosyncrasies of trace level
analyses. These problems result from the reactive and adsorptive nature of COS, the low concentrations being measured, the tj^e of detector needed, and interferences from the
propylene sample matrix. Test Method D 5303 addresses
these analytical problems and ways to properly handle them
to assure accurate and precise analysis.
Separation of the COS from propylene is accomplished by
gas chromatography. A relatively large volume of sample is
injected onto a gas chromatograph equipped with a single
packed column and flame photometric detector. The separation is achieved isothermally at 10-50C. Calibration data,
based on peaJi areas, are obtained using a known gas standard blend of COS in the range expected for the sample. The
COS peak area in the sample is measured and the concentration of COS is calculated.
C-4 Product Characterization
Guide for Analysis of 1,3-Butadiene (Standard Guide D
5274)Standard Guide D 5274 covers the analysis of I,3-butadiene products produced in North America. Standard
Guide D 5274 is intended to provide information on the likely
composition of 1,3-butadiene products and possible ways to
test them. Since there are currently no ASTM test methods
for determining all components of interest. Standard Guide
D 5274 provides information on other available test methods.

FOR CHEMICAL AND SPECIALTY USES

193

This guide is not intended to be used as a specification for butadiene products.


Butylene Analysis by Gas Chromatography (Test Method D
4424)This is a gas chromatographic analysis of commercial butylenes, butylene concentrates, and butane-butylene
mixtures. This test method is designed to determine:
propane, propylene, isobutane, n-butane, 1-butene, isobutene, trans-2-butene, cis-2-butene, 1,3-butadiene, iso-pentane and n-pentane at concentrations of about 0.05% or
greater. It does not cover high-purity 1-butene or high-purity
isobutene streams.
Test Method D 4424 involves the gas chromatographic separation of a sample on a packed column with either helium
or hydrogen carrier gas. The separated components are detected using a thermal conductivity detector or a flame ionization detector. Calibration data are obtained using either
relative response factors or by using a standard ceJibration
blend.
Determination of Butadiene Purity and Hydrocarbon Impurities (Test Method D 2593)Test Method D 2593 determines
1,3-butadiene impurities such as propane, propylene, iso-butane, n-butane, 1-butene, isobutylene, propadiene, trans-2butene, cis-2-butene, 1,2-butadiene, 1,4-pentadiene, methyl-,
dimethyl-, ethyl-, and vinyl-acetylene in polymerization
grade butadiene by gas chromatography. Impurities including butadiene dimer, carbonyls, inhibitor, and residue are
measured by other procedures, and can be used with this procedure to give a complete composition of the butadiene.
Determination of Butadiene Dimer and Styrene in Butadiene
Concentrate (Test Method D 2426)Test Method D 2426 measures butadiene dimer (4-vinylcyclohexene-l) and styrene in
"recycle" and specification grade butadiene concentrates by
gas chromatography. This is done by injecting the sample
into a gas chromatograph equipped with either a thermal
conductivity or flame ionization detector with sensitivity sufficient to detect 0.01% of butadiene dimer. Any packed column may be used that is capable of resolving the butadiene
dimer and styrene as discrete peaks. The quantity of the components of interest is determined from the chromatogram by
comparing their peak areas or heights with those of a synthetic sample.
Determination of Nonvolatile Residue in Polymerization Grade
Butadiene (Test Method D 1025)This method covers the determination of nonvolatile material in polymerization grade
butadiene. Test Method D 1025 involves taking a measured
volume of liquid butadiene and allowing it to evaporate at
room temperature from a small glass evaporating dish until
only a residue remains. Heating the dish to a constant weight
completes the evaporation. The weight gain in the evaporation dish is the nonvolatile residue.
Determination of Peroxides in Butadiene (Test Method D
5799)Butadiene polyperoxide is a very dangerous reaction
product of butadiene and oxygen. This peroxide has been reported to cause violent explosions in vessels that are used to
store butadiene. Due to the inherent dangers of peroxides in
butadiene, specification limits are usually set for their presence. Test Method D 5799 determines the peroxide content of
a sample of commercial butadiene in the concentration range
of 1-10 ppm by mass.

194

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

For this method, a known mass of butadiene sample is


placed in a flask and evaporated. The residue is then refluxed
with acetic acid and sodium iodide. The peroxides oxidize iodide to iodine, which is then titrated with standard sodium
thiosulfate solution using visual end-point detection. Interfering traces of iron are complexed with sodium fluoride.
Determination of Carbonyls in CA Hydrocarbons (Test Method
4423)Test Method D 4423 covers the determination of carbonyls (ketones and aldehydes) in butadiene. The presence of
carbonyl species can have a deleterious effect upon butadiene polymer properties or on the butadiene polymerization
reaction. Test D 4423 measures carbonyl in the range of 0-50
ppm, calculated as acetaldehyde.
A measured a m o u n t of the sample is added to an alcoholic
hydroxylamine hydrochloride solution t h a t has been adjusted to a given p H indicator coloration using either alcoholic acid or base. The carbonyls will react with the hydroxylamine hydrochloride releasing an equivalent a m o u n t of
hydrochloric acid. The solution is then titrated with standard
base to the original coloration. A blank containing only
methanol and sample is titrated and the sample's results are
calculated using the blank adjustment. Results are reported
as mg/kg carbonyls as acetaldehyde.
Determination
of Total Inhibitor Content (Test Method D
1157)Test D 1157 measures p-?ert-butylcatechol (TBC) in
pol3mierization or recycle grades of butadiene or other C4 hydrocarbon mixtures. TBC is commonly added to commercial
butadiene in amounts of 50-150 mg/kg as an oxidation inhibitor. It is important that the sample not contain other phenolic material, as they will be measured as catechol. In general, all phenols and their quinone oxidation products are
included in the calculated catechol content. Small amounts
of polymer do not interfere. This test method is applicable
over the range of TBC from 50-500 mg/kg.
The catechol is separated from butadiene in Test Method
D 1157 by evaporation. The residue is dissolved in water
and an excess of ferric chloride is added. The intensity of
the yellow-colored complex is compared in a photoelectric
colorimeter with that produced by a known concentration
of the catechol.
Determination of Trace Volatile Chlorides in Butane-Butene
Mixtures (Test Method D 2384)Test Method D 2384 is used
to determine trace amounts of volatile chlorides in butanebutene mixtures. Such information is valuable in cases where
the chloride is deleterious in the use of this product. Chloride
contributes to corrosion problems in processing units in instances where further processing of this material is involved.
The test methods included in Test Method D 2384 cover the
determination of the total volatile organic chlorides in concentrations from 10-100 p p m in buteine-butene mixtures.
The sample is first combusted in one of two ways. In lamp
combustion, the sample is burned in an atmosphere of carbon dioxide and oxygen or in purified air. The halogen-containing combustion products are absorbed in dilute sodium
carbonate solution. In oxy-hydrogen combustion, the sample
is burned in an oxy-hydrogen atomizer burner, and the combustion products are absorbed in a dilute solution of sodium
carbonate.
Chloride determination may be performed by amperometric titration or spectrophotometrically. For amperometric
titration, the chloride ion in aqueous solution is titrated am-

perometrically with standard silver nitrate solution, using a


standard saturated calomel electrode as the reference electrode. The diffusion currents are plotted against the corresponding volumes of silver nitrate solution used and the end
point is taken as the intersection of the straight-line portions
of the curve. This method is not directly applicable in the
presence of other substances that combine with silver ion or
oxidize chloride ion in dilute acid solution.
The chloride ion concentration may also be obtained spectrophotometriccilly by reaction of the chloride ion in the absorber solution with mercuric thiocyanate to release thiocyanate, which forms a reddish-orange complex with Fe^^.
The intensity of the color is measured at 460 n m with a spectrophotometer or filter photometer. Bromides, sulfides, ammonia, tobacco smoke, and more than 25 fx,goi hydrogen peroxide in the test solution interfere in the spectrophotometric
procedure.
ASTM Butadiene Measurement Tables (Standard D 1550)
ASTM D 1550 consists of a series of tables allowing the specific gravity of butadiene or concentrated butadiene (60% butadiene or greater) at 15.6/15.6C to be calculated from the
density measured at a different temperature. The density is
measured by means of a hygrometer.
General Methods
Microcoulometric Determination of Sulfur in Petroleum Gas
(Test Method D 3246)Test Method D 3246 determines sulfur in petroleum gas. Trace quantities of sulfur in hydrocarbon products can be harmful to many catalytic chemical processes. M a x i m u m permissible levels of total sulfur are
normally included in specifications for such hydrocarbons. It
is recommended that this test method be used to provide a
basis for agreement between two laboratories when the determination of sulfur in hydrocarbon gases is important. For
liquefied petroleum gas, total volatile sulfur is measured on
an injected gas sample. For such a material, a liquid sample
must be used to measure total sulfur. Test Method D 3246
covers the determination of sulfur in the range of 1.5-100
p p m by mass in hydrocarbon products that are gaseous at
normal room temperature and pressure.
The test procedure involves injecting a sample of the hydrocarbon into a c o m b u s t i o n tube m a i n t a i n e d at a b o u t
800C having a flowing stream of gas consisting of 80% oxygen and 20% inert gas. Oxidative pyrolysis converts the sulfur to sulfur dioxide which then flows into a titration cell
where it reacts with triiodide ion present in the electrolyte.
The triiodide is reduced by the sulfur dioxide, and is coulometrically replaced. The toted current required to replace the
triiodide is a measure of the sulfur present in the sample injected.
The reaction occurring in the titration cell as sulfur dioxide
enters is:
li" + SO2 + H2O -^ SO3 + 3I~ + 2H+
The triiodide consumed is generated coulometrically from:
31" ^ 1 3 + 2 e '
These microequivalents of triiodide (iodine) are equal to the
number of microequivalents of titratable sample ion entering
the titration cell. A liquid blend containing a known amount

CHAPTER

8: HYDROCARBONS

of sulfur is used for calibration. This is the same chemistry as


is used in the well-known Karl Fisher water titration.
Gas Chromatographic
Determination
of
Noncondensahle
Gases in C2 and Lighter Hydrocarbon Products (Test Method D
2504)Test Method D 2504 covers the determination of hydrogen, nitrogen, oxygen, and carbon monoxide in parts per
million by volume range in C2 and lighter hydrocarbon products. In this test, the sample is separated in a gas-solid chromatographic system using molecular sieves as the solid adsorbant. The concentration of the gases to b e analyzed is
calculated from peak heights or areas. Argon can be used as
a carrier gas for the determination of hydrogen concentrations below 100 p p m by volume. Argon, if present in the sample, interferes with oxygen determination.
Determination of Organic Hydrogen in Petroleum Fractions
(Test Methods D 1018 and D 4808)Test D 1018 determines
the percent organic hydrogen contained by a sample. Knowledge of the organic hydrogen content of petroleum products
can be helpful in assessing performance characteristics. For
Test Method D1018, the petroleum product is burned from a
cotton wick in an a t m o s p h e r e of purified air. The water
formed is collected from the combustion gases by a desiccant
(CaCli) and weighed. The a m o u n t of organic hydrogen can be
calculated based on the water formed during combustion.
Continuous wave, low-resolution nuclear magnetic resonance spectroscopy provides a simpler, more precise alternative method for determination of organic hydrogen content
of petroleum products. It is described in Test Method D4808.
The NMR spectrum of the petroleum oil to be analyzed is
compared to a reference. The spectrometer nondestructively
records the absolute concentration of hydrogen atoms in the
reference and test sample. The result is expressed as hydrogen content (on a mass basis) of the sample. Table 9 summarizes which test variants that eire typically used with different
petroleum products within D 4808.
Determination of Paraffin, Naphthene and Aromatic Hydrocarbons (Test Method D 5443)Test Method D 5443 provides for
the determination of paraffins, naphthenes, and aromatics in
low olefinic hydrocarbon streams having final boiling points
of 200C or less. The m e t h o d uses multi-dimensional gas
chromatography. Hydrocarbons with boiling points greater
t h a n 200C and less t h a n 270C are reported as a single
group. Olefins, if present, are hydrogenated and resultant saturates are included in the paraffin and naphthene distribution. Aromatics boiling at C9 and above are reported as a single a r o m a t i c group. This test m e t h o d is not intended to
determine individual components except for benzene and
toluene that Eire only Cg and C7 aromatics, respectively, and
cyclopentane, that is the only C5 naphthene. The lower limit
of detection for a single h y d r o c a r b o n c o m p o n e n t is 0.05
mass %.

AND SPECIALTY

USES

195

This is a complicated gas chromatography method. Molecular size is determined by using boiling point columns or
molecular sieve columns. Polar columns separate by polarity.
Hydrogenation is done on column using a platinum lined
column a n d hydrogen gas. In addition, t e m p e r a t u r e programming is used for separation.
Determination of Boiling Range (Test Methods D 2892 and D
2887)Test Method D 2892 details procedures for the production of a liquefied gas, distillate fractions, and residuum
of' standardized quality o n which analytical data can be obtained, and the determination of yields of the above fractions by b o t h mass and volume. From the above information, a graph of temperature versus mass-percent distilled
can be produced. This distillation curve corresponds to a
laboratory technique, which is defined at 15/5 (15 theoretical plate column, 5:1 reflux ratio) or TBP (true boiling
point). This test m e t h o d can also be applied to any
petroleum mixture except liquefied petroleum gases, very
light naphthas and fractions having initial boiling points
above 400C.
Alternatively, the boiling range distribution of petroleum
fractions may be determined by gas chromatography using
Test Method D 2887. This test m e t h o d is applicable to
petroleum products and fractions having a final boiling point
of 538C (1000F) or lower at atmospheric pressure and is
limited to samples having a boiling range greater than 55C
(100F) and having a vapor pressure sufficiently low enough
to p e r m i t sampling at a m b i e n t t e m p e r a t u r e . For m o r e
volatile p e t r o l e u m fractions, including oxygenated compounds. Test Method D 3710 should b e used.

ASTM STANDARDS
No.
D 1018
D 1025
D 1157
D 1550
D 2163

D 2384
D 2426
D 2504

D 2505
TABLE 9ASTM D 4808 test procedures available for
different petroleum products.
Approximate Boiling Range
"C (-F)
Petroleum Products
Test Method
A
Light distillates
15-260(60-500)
B
Middle distillates
200-370 (400-700)
B
Gas oil
370-510(700-950)
C
Residual
510+ (950+)

FOR CHEMICAL

D 2593
D 2712
D 2887

Title
Standard Test Method for Hydrogen in Petroleum
Fractions
Test Method for Nonvolatile Residue of Polymerization Grade Butadiene
Test Method for Total Inhibitor Content (TBC) of
Light Hydrocarbons
ASTM Butadiene Measurement Tables
Test Method for Liquefied Petroleum (LP) Gases
and Propylene Concentrates by Gas Chromatography
Test Methods for Traces of Volatile Chlorides in
Butane-Butene Mixtures
Test Method for Butadiene Dimer and Styrene in
Butadiene Concentrates by Gas Chromatography
Test Method for Noncondensahle Gases in C2 and
Lighter H y d r o c a r b o n Products by Gas Chromatography
Test Method for Ethylene, Other Hydrocarbons,
and Carbon Dioxide in High-Purity Ethylene by
Gas Chromatography
Test Method for Butadiene Purity a n d Hydrocarbon Impurities by Gas Chromatography
Test Method for Hydrocarbon Traces in Propylene Concentrates by Gas Chromatography
Test Method for Boiling Range Distribution of
Petroleum Fractions by Gas Chromatography

196

MANUAL

D 2892
D 3246
D 3710

D 4423
D 4424
D4808

D 4864

D
D
D
D

5234
5273
5274
5303

D5443

D 5799
D 6159

3 7; FUELS AND LUBRICANTS

HANDBOOK

Test Method for Distillation of Crude Petroleum


(15-Theoretical Plate Column)
Test Method for Sulfur in Petroleum Gas by Oxidative Microcoulometry
Test Method for Boiling Range Distribution of
Gasoline a n d Gasoline Fractions by Gas Chromatography
Test Method for Determination of Carbonyls in C4
Hydrocarbons
Test Method for Butylene Analysis by Gas Chromatography
Test Method for Hydrogen Content of Light Distillates, Middle Distillates. Gas Oils, and Residua
by Low-Resolution Nuclear Magnetic Resonance
Spectroscopy
Test Method for Determination of Traces of
Methanol in Propylene Concentrates by Gas Chromatography
Guide for Analysis of Ethylene Product
Guide for Analysis of Propylene Concentrates
Guide for Analysis of 1,3-Butadiene Product
Test Method for Trace Carbonyl Sulfide in Propylene by Gas Chromatography
Test Method for Paraffin, Naphthene, and Aromatic Hydrocarbon type Analysis in Petroleum
Distillates Through 200C by Multidimensional
Gas Chromatography
Test Method for Determination of Peroxides in
Butadiene
Test Method for Determination of Hydrocarbon
Impurities in Ethylene by Gas Chromatography

OTHER STANDARDS
D e u t s c h e s I n s t i t u t fur N o r m u n g ( D I N )

ISO 6684:1982

ISO 6792:1982

150 7381:1986

ISO 7382:1986

ISO 8174:1986

ISO 8175:1986

ISO 8176:1986

International Organization for Standardization


(ISO)
ISO 6377:1981

ISO 6378:1981

ISO 6379:1981

ISO 6380:1981

ISO 6381:1981

Light Olefins for Industrial UseDetermination of Impurities by Gas ChromatographyGeneral Considerations


Butadiene for Industrial UseDetermination of Hydrocarbon Impurities
Gas Chromatographic Method
Ethylene for Industrial UseDetermination of H y d r o c a r b o n Impurities
Gas Chromatographic Method
Propylene for Industrial UseDetermination of Hydrocarbon Impurities
Gas Chromatographic Method
Ethylene and Propylene for Industrial

Ethylene and Propylene for Industrial


UseDetermination of Acetone, Acetonitrile, Propan-2-ol, and Methanol
Gas Chromatographic Method
Propylene for Industrial UseDeterm i n a t i o n of OligomersGas Chromatographic Method
Butadiene for Industrial UseDetermination of Active tert-butyl-catechol
(TBC)(4-(1,1 -dimethylethyl)-! ,2-benzenediol)- High Performance Liquid
Chromatography Method

UOP
UOP 212-77

DIN 51872-4 (1990)

Testing of gaseous fuels and other


gases; determination of the components; gas Chromatographic procedure
DIN 51872-5 (1996) Testing of gaseous fuels and other
gases; determination of the components - Part 5; capillary gas chromatographic procedure

UseDetermination of Traces of Carbon Monoxide and Carbon Dioxide


Gas Chromatographic Method
Butadiene for Industrial UseDetermination of tert-butyl-catechol (TBC)
(4-( 1,1 - d i m e t h y l e t h y l ) - 1 , 2 - b e n z e n e diol)Spectrometric method
Butadiene for Industrial UseDetermination of Oxygen and Argon in the
Gaseous Phase Above Liquid ButadieneGas Chromatographic Method
Butadiene for Industrial UseDeterm i n a t i o n of OligomersGas Chromatographic Method
Ethylene for Industrial UseDetermination of Traces of Polar Comp o u n d s P r e p a r a t i o n of Condensate
Samples by Low-temperature Technique

UOP 344-87
UOP 496-63T
UOP 542-88

UOP 569-79
UOP 603-88

UOP 772-77
UOP 791-94

UOP 834-82

UOP 845-90

Hydrogen Sulfide, Mercaptan Sulfur


and Carbonyl Sulfide in Hydroccirbon
Gases by Potentiometric Titration
Moisture in Hydrocarbon Streams Using a n On-line Analyzer
Carbonyl Compounds in Light Hydrocarbon Gases
Trace Diolefins, Acetylenes, and Noncondensable Hydrocarbons in LPG by
Gas Chromatography
Methanol in Petroleum Distillates and
LPG by Gas Chromatography
Trace Carbon Monoxide and Carbon
Dioxide in Hydrogen and Light
Gaseous Hydrocarbons by Gas Chromatography
Mercaptan Sulfur in LPG by Microcoulometry
Sulfur Components in LPG or C5 Minus Hydrocarbon Fractions by GCSCD
Arsine in Ethylene by Electrothermal
Atomic Absorption Spectrophotometry
Trace Alcohols in LPG by Gas Chromatography

CHAPTER 8: HYDROCARBONS FOR CHEMICAL AND SPECIALTY USES 197


REFERENCES
[1] Kniel, L., Winter, O. and Stork, K., Ethylene: Keystone to the
Petrochemical Industry, Marcel Dekker Inc., NY, 1980.
[2] Ma, J. J. and Scheeline, H. W., "Ethylene," Process Economics
Program, Report No. 28B, Stanford Research Institute, Menlo
Park, CA, March 1978.
[3] World Light Olefins Analysis, Vol II, Chemical Market Associates, Inc., Houston, TX, December 2000, pp. 8-11.
[4] Germain, E. and Maurel, R., "Thermal Decomposition of Pure
Methane at 1000C in a Pipe Still," Genie Chimique, Vol. 88,
1962, pp. 122-127
[5] Sherwood, P. W., "Production of Ethylene from Petroleum
Sources, Part I.," Petroleum Refiner, Vol. 30, No. 9, 1951, pp.
220-225.
[6] Sherwood, P. W., "New Advances in Ethylene Production-I,"
Petroleum, Vol. 19, May, 1956, pp. 161-164.
[7] Martin, R., Dzierzynski, M., and Niclause, M., "Thermal Decomposition of Propane, 1. Introduction a n d Experimental
Study of the Pyrolysis of Pure Propane," Journal of Chemie
Physique, Vol. 61, No. 3, 1964, pp. 286-297.
[8] Fair, J. R., Perkins, T. K., and Rice, H. F., "Comparing Olefin
Unit Feedstocks," Petroleum Refiner, Vol. 34, No. 11, 1955, pp.
185-189.
[9] Rice, F. O., "The Thermal Decomposition of Organic Compounds from the Standpoint of Free Radicals. I. Saturated Hydrocarbons," Journal of the American Chemical Society, Vol. 53,
May 1931, pp. 1959-1972.
[10] Davis, H. G. and Williamson, K. D., "The Kinetics of Pyrolysis
of E t h a n e and Related Hydrocarbons," World
Petroleum
Congress Proceedings, Vth, Section 4, Paper 4, New York, 1959,
pp. 1-17.
[11] Kalinenko, R. A. and Brodskii, A. M., "A Kinetic Scheme
for E t h a n e Pyrolysis as an Aid to Optimization of Processes
Yielding Ethane," Kinetika I Kataliz, Vol. 6, No. 5, 1965, p p .
826-830.
[12] Laidler, K. J., Sagert, N. H., and Wojciechowski, B. W., "Kinetics and Mechanisms of the ThermjJ Decomposition of Propane.
1. The Uninhibited Reaction," Proceedings of the Royal Society of
London, Series A, 1962, London, Vol. 270, pp. 242-266.
[13] Pumell, J. H. and Quinn, C. P., "The Pyrolysis of n-Butane," Proceedings of the Royal Society of London, Series A, Vol. 270, London, pp. 267-284.
[14] Greensfelder, B. S., Voge, H. H., and Good, G. M., "Catalytic and
Thermal Cracking of Pure Hydrocarbons," Industrial and Engineering Chemistry, Vol. 4 1 , No. 11, 1949, pp. 2573-2584.
[15] Fair, J. R., Mayers, J. W., and Lane, W. H. "Commercial Ethylene Production by Propane Pyrolysis in a Molten Lead Bath,"
Chemical Engineering Progress, Vol. 53, No. 9, 1957, p p .
433^38.
[16] Bartlit, J. R. and Bliss, H., "ICinetics of Ethane Pyrolysis," American Institute of Chemical Engineers Journal, Vol. 11, No. 3,
1965, p p . 562-572.

[17] Fair, J. R. and Rase, H. F., "Process Design of Light Hydrocarbon Cracking Units," Chemical Engineering Progress, 1954, Vol.
50, No. 8, pp. 415-420.
[18] Schutt, H. C , "Optimum Temperature Profile for Endothermic
Conversions in Tubular Reactors," Zeitschrift fuer Elektrochemie. Vol. 65, 1961, pp. 245-255.
[19] Buell, C. K. and Weber, L. J., "Ethylene Production by Cracking
of Ethylene-Propylene Mixtures," Petroleum Processing, Vol. 5,
March 1950, pp. 266-272.
[20] Kamptner, H. K., Krause, W. R., and Shilken, H. P., "High-Temperature Cracking," Chemical Engineering, Feb. 28 1966, pp.
93-98.
[21] Schutt, H. C. and Zdonik, S. B., "Processing Scheme-Pyrolysis
Methods," Oiland Gas Journal, Vol. 54,2 April 1956, pp. 99-103.
[22] Haddeland, G. E., "Butadiene," Process Economics Program,
Report No. 35, Stanford Research Institute, Menlo Park, CA,
March 1968.
[23] Anonymous, "New Plants and Facilities, CE Construction
Alert," Chemical Engineering, April 5 1971, pp. 111-116.
[24] Nolan G. J., Hogan R. J., and Farba F., Jr., "2-Butene Dehydrogenation Catalyst," U.S. Patent 3,501,547, 17 March 1970.
[25] Friedman, L., Womeldorph, D. E., a n d Stevenson, D. H.,
"Houdry Dehydrogenation for Olefin Production," Proceedings
of the American Petroleum Institute, Sect. Ill, Vol. 38, 1958, pp.
203-212.
[26] Shchukin, V. P., Ven'yaminov, S. A., and Boreskov, G. K. "IronAntimony Oxide Catalysts of Partial Oxidation. III. Kinetics and
Mechanism of the Oxidative Dehydrogenation of Butylenes,"
Kinetika I Kataliz, Vol. 11, No. 5, 1970, p p . 1236-1242.
[27] Echigoya, E., Watanabe, T., and Sano, H., "Studies on Oxidative
Dehydrogenation of Butylenes over Bismuth Molybdate Catalyst," Journal of the Chemical Society of Japan, Industrial Chemistry Section, Vol. 73, No. 5, 1970, pp. 933-937.
[28] Skarchenko, V. K., "Oxidative Dehydrogenation of Hydrocarbons," International Chemical Engineering, Vol. 9, No.l, 1969,
pp. 1-23.
[29] Adzhamov, K. Y., Alkhazov, T. G., Belen'kii, M. S., and Lisovskii,
A. E., "Effect of Carbonyl Compounds on the Oxidative Dehydrogenation of Butenes," Kinetika i Kataliz, Vol. 9, No. 6, 1968,
pp. 1279-1284.
[30] Newman, F. C , "Process for Butadiene Manufacture by Oxydehydrogenation of Butenes," Industrial and Engineering Chemistry, Vol. 62, No. 5, 1970, p p . 42-47.
[31] Husen, P. C , Deel, K. R., and Peters, W. D., "Phillips Butadiene
Process is Success," Oil and Gas Journal, 2 Aug 1971, pp. 60-61.
[32] Reis, T., "Compare Butadiene Recovery Methods Processes, Solvents and Economics," Petro/Chem Engineer, August 1969, pp.
12-22.
[33] Reis, T., "Butadiene Extraction," Chemical and Process Engineering, March 1970, pp. 65-69, 72-76.
[34] Baron, T., "Precise Separations and Selective Extractions are
Keys to Petrochemicals," Oil and Gas Journal, 1971, July 5, Vol.
67, No. 27, p p . 100-102.

MNL37-EB/Jun. 2003

Additives and Additive


Chemistry
Syed Q. A. Rizvi^

M O S T UNTREATED OR NON-FORMULATED LUBRICANTS, i.e., mineral

base oils and synthetic basestocks, do not possess the properties necessary to perform effectively in today's demanding
lubricating environments. To function in such environments
properly, base fluids need the help of chemicals called additives. Additives improve the lubricating ability of base oils, either by enhancing the desirable properties already present or
by adding n e w properties. Such properties include suitable
viscosity, slipperiness, high film-strength, low corrosivity,
low pour point, good cleansing and dispersing ability, low
toxicity and low flammability [1]. Most of today's lubricants
are formulated lubricants, and additives are their integral
part. The 1998 world consumption of lubricant additives is
estimated at 2.588 million metric tons, of which North America a n d Western Europe consumed 67%. This estimate is
based on 1995 SRI data [2] and the estimated growth rate.

LUBRICANT COMPOSITION
A formulated lubricant comprises a base fluid and a performance package, and in the case of multigrade oils, an additional viscosity modifier. The performance package contains
a n u m b e r of additives, the quantity of which is a function of
their quality (the ability to deliver the necessary performance), the quality of the base fluid (governed by its physical
and chemical properties), and the lubricant's intended use.
The performance package can make u p to 30%, and sometimes even higher, of the total lubricant composition, depending upon the desired performance level and the severity
of the end-use requirements [3]. In general, poor-quality base
fluids need better additives a n d in larger amounts than base
fluids of good quality. Likewise, applications such as engine
oils a n d automotive gear oils, which place a higher demand
on the lubricant, require superior additives than those that
are less demanding. Engine oils account for the largest shaire
of the additive use.

LUBRICANT BASESTOCKS
Lubricants perform a variety of functions to prolong the life
of the equipment. These include lubrication (reduction of
friction and wear), dissipation of heat, corrosion control, prevention of excessive deposit formation, dispersion of use-gen' Research and Development Manager, Lubricant Additives Division, King Industries, Inc., Science Road, Norwalk, CT 06852.

erated contaminants, and water separation or demulsibility.


While some of these functions are common to all lubricants,
others are more specific to the equipment being serviced.
M o d e m lubricants are formulated from a range of base fluids and chemical additives. The primary function of the base
fluid is to facilitate lubrication; that is, to provide a fluid layer
between moving surfaces to minimize friction, hence heat
and wear. The base fluid in addition functions as a carrier of
additives; hence, it must be able to keep them in solution under normal operating conditions.
The base fluid can be of mineral origin, synthetic chemical origin, or biological origin. While mineral oil basestocks
are obtained directly from petroleum fractionation, synthetic basestocks are manufactured through transformations of petroleum-derived organic chemicals. Partly synthetic (semisynthetic) basestocks are compatible mixtures
of mineral oil and synthetic basestocks. Recently, a great
deal of interest has surfaced regarding the use of basestocks
of biological origin (vegetable a n d animal oils). Their
biodegradable nature and non-petroleum origin are two major reasons for this impetus. For some industrial applications, such as metalworking, even water is used to deliver
chemicals to parts that need protection. Section 2 of the
ASTM Manual contains discussion on basestocks.
Although many base fluid properties are modified or enhanced by the use of additives, knowledge of such properties
is critical to the formulator. These include density, viscosity
(both at low and high temperatures), foaming characteristics,
seal compatibility, oxidation resistance, corrosivity, the viscosity-temperature relationship (VI), low-temperature properties (such as cloud point and pour point), and high-temperature properties (such as volatility and flash point) [4a].
Viscosity, defined as an oil's resistance to flow, is critical to
its function as a lubricant. Inappropriate viscosity leads to ineffective lubrication and can lead to equipment damage. A
n u m b e r of parameters, such as temperature, pressure, and
shear forces, affect viscosity. Of these, temperature has the
most profound effect; therefore, knowledge of viscosity-temperature relationship or VI of an oil is important to a formulator.
The low-temperature properties of a lubricant include
cloud point and pour point. When a sample of oil is cooled,
its viscosity increases in a predictable manner until wax crystals start to form. On further cooling, the matrix of wax crystals becomes sufficiently dense to cause an apparent solidification of oil. Although this oil does not p o u r u n d e r the
influence of gravity, it can be moved if sufficient force is applied: for example, by applying torque to a rotor that is sus-

199
Copyright'

2003 by A S I M International

www.astm.org

200

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

pended in oil. Cloud point is the temperature at which the


first signs of wax formation (haziness) can be detected. Pour
point is the lowest temperature at which the sample of oil
flows by gravity alone. High viscosity oils may cease to flow
at low temperatures because of further increase in viscosity
rather than because of wax formation. Pour points may be
higher thsin cloud points.
The high-temperature properties, such as volatility and
flash point, of a base oil are governed by its distillation temperature, or the boiling range. Volatility is important because
it is a n indication of the oil's tendency to be lost during service due to vaporization, for example, in a hot engine. The
methods used to determine volatility include ASTM Distillation Curves, thermogravimetric analysis (ASTM D 6375), Eind
Noack volatility (ASTM D 5800). Flash point is the lowest
temperature at which auto-ignition of the vapor above the
heated sample occurs. Flash point of an oil is important from
a safety point of view and is used to classify flammable liquids into hazard grades.
Density is important because oils may be formulated by
weight but measured by volume. Demulsibility is the ability
of a n oil to separate water. Foaming characteristics determine the tendency of the oil to form foam and the stability of
the foam once it is formed. Seal compatibility of the oil is also
important because the oil in most applications comes in contact with elastomer seals. If seals are damaged, the lubricant
will be lost and the equipment will be left unprotected.
Oxidative resistance of the base oil depends largely upon
the structure of the hydrocarbons present. Lubricants that do
not contain aromatic structures, or structures with unsaturation, have better oxidative stability than those that do. Oxidation of the base oil results in the formation of polar compounds that are either corrosive or lead to the formation of
resin, deposits, and sludge, which can impair proper functioning of the equipment. Previously, sulfur content of base
oils was used as an indicator of their natural resistance to oxidation. This is because many naturally occurring organosulfur compounds in crude oils are moderately effective in destroying organic peroxides and breaking the oxidation chain
mechanism. However, m o d e m refining processes, used to
enhance other desirable properties of base oils, result in the
removal of these beneficial compounds.
The base oil should not contain components that promote
corrosion. Corrosion tests usually involve bringing the oil
sample in contact with a metal, such as iron, copper, or silver, u n d e r controlled conditions. Discoloration of metal,
changes in its surface condition, or weight loss reflect corrosive tendency of the oil.

PERFORMANCE PACKAGE
Lubricant additives are usually supplied as performance
packages that are blended in basestocks to yield formulated
lubricants. This is not the case in some applications, such as
metalworking fluids, where the end user may purchase the
individual additives and blend them in base oil prior to use.
In the U.S., foixaulated lubricants are expected to meet performance requirements generally established by the Society
of Automotive Engineers (SAE), American Petroleum Institute (API), U.S. Military, Original Equipment Manufacturers

(OEMs), and the end-users. In Europe, ACEA (Association


des Constructeurs Europeens de I'Automobiles), CEC (Conseil Europeens de Coordination pour les Developments des
Essais de Performance des Lubrifiants et des Combustibles
pour Moteurs), ATC (Technical Committee of Petroleum Additive Manufacturers), and ATIEL (Association Technique de
rindustries Europeenne des Lubrifiants) have collaborated
in a m a n n e r similar to their American counterparts to come
u p with their own engine oil classification system, called the
E u r o p e a n Engine Lubricant Quality Management System
(EELQMS). The system does include some individual OEM
requirements. In Japan, the Japanese Automobile Standards
Organization (JASO) and, in India, Bureau of Indicin Standards perform these functions.
The performance package contains many classes of additives [5,6]. The primary functions of each class are briefly described below.
Stabilizers/Deposit Control AgentsMinimize the amount of
deposit formation. Oxidation Inhibitors control oxidative decomposition of lubricant and additives. Dispersants keep normally insoluble c o n t a m i n a n t s dispersed in the lubricant.
Detergents prevent metal attack by acidic byproducts of combustion and oxidation and keep metal surfaces free of deposits.
Film-Forming AgentsEither increase durability of the lubricant film or form chemical films on metal surfaces. Friction
modifiers generally lower the coefficient of friction, thereby
leading to improved fuel economy and wear control. Antiwear a n d extreme pressure agents protect metal surfaces
against wear and equipment seizure. Rust and corrosion inhibitors prevent corrosion and rusting of metal parts that
come in contact with the lubricant.
Polymeric Additives^Alter physical properties, such as viscosity and pour point, of lubricants. Viscosity modifiers minimize the rate of viscosity decrease with an increase in temperature. Pour point depressants enable a lubricant to flow at
low temperatures. Emulsifiers promote mixing of water and
oil to form an emulsion. Some hydraulic and metalworking
lubricants are of emulsion type. Demulsifiers enhance water
separation from oil c o n t a m i n a t e d with water. Foam inhibitors prevent the lubricant from forming persistent foam.
Other AdditivesPerform
miscellaneous other functions.
Seal swell agents swell elastomer seals. Dyes are used to color
code lubricants and fuels. Biocides prevent degradation of
high water-based lubricants due to microbial attack. Couplers help stabilize water/organic microemulsions.
Most lubricant additives, except perhaps some viscosity
modifiers and p o u r point depressants, comprise a n
oleophilic ("hydrocarbon-loving") hydrocarbon group and a
polar functionality [7]. The polar functionality typically contains oxygen, nitrogen, sulfur, and or phosphorus. Figure 1
identifies polar and non-polar portions in the oleic acid
molecule. All additives must initially be oil soluble; hence, the
presence of a hydrocarbon group of sufficient carbon chain
length is essential.
Lubricant additives perform their function either in the
bulk lubricant or on surfaces. The former type includes oxidation inhibitors, detergents, and dispersants and the latter
type includes rust inhibitors, antiwear agents, and extreme
pressure (EP) agents. Additives may be designed either by al-

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY

POLAR MOIETY
Surface Active Group

NON-POLAR MOIETY
Oleophilic Group
Consistsof a hydrocaibon
chain

Contains oxygen, nitrogen,


sulfur, or plK^honis

POLAR GROUP
Surface-active

NONPOLAR GROUP
Oil-solubllizing
H H H H H . H H

H3C' X X X W

HH

H H

HH

H!

>^ >^ '>^ ^i ^^"

HHHHHH|!,,!,HHHHHH

;o

Oleic Acid
FIG. 1A general representation of a typical additive
molecule.

tering the strength of the polar functionahty or by changing


the size of the hydrocarbon chain. Changing the strength of
the polar functionality alone is difficult and has its limitations. Changing the size of the hydrocarbon group, on the
other hand, is much easier. In practice, both strategies are
used. Whether an additive performs its function on the surface or in the bulk lubricant depends on its polar to non-polar
ratio. With the strength of the polar moiety constant, additives with small hydrocarbon groups have higher polar to
non-polar ratio than those with large hydrocarbon groups. As
a consequence, EP agents and rust inhibitors, which require
more surface activity, have small hydrocarbon groups; and
dispersants and detergents, which require a higher solubility
in oil, contain large hydrocarbon groups. Except in very few
cases, a connecting group or a link is necessary to connect
("tie") the two functionalities together. The importance of
such a group is described in detail in the dispersants section.
StabilizersADeposit Control Agents
This class of additives controls deposit formation. These additives do so by inhibiting oxidative breakdown of the lubricant to deposit precursors and by suspending those already
formed in the bulk lubricant. Oxidation inhibitors intercept
the oxidation mechanism and dispersants and detergents do
the suspending part.
Oxidation Inhibitors
All lubricants, by virtue of being hydrocarbon based, are susceptible to oxidation [7,8]. Many lubricants contain three
major components: base oil, additives, and viscosity modifier, all of which have the susceptibility to oxidize. Each tj^e
of basestock, mineral, vegetable, or synthetic, has a stable
threshold beyond which stabilizers or oxidation inhibitors
are needed to retard oxidation. In terms of oxidative stability,
synthetic oils eire the most stable and vegetable oils are the
least stable. The oxidative stability of mineral oils is intermediate between the two.
Most lubrication applications expose lubricants to oxygen
in some manner. Oxygen reacts with hydrocarbon molecules

201

that make up the lubricant. The reaction sites, in order of decreasing ease of attack, are benzylic, allylic, tertiary alkyl, secondary alkyl, cind primary alkyl hydrogens. The result is the
formation of hydroperoxides and peroxy or other radicals.
The rate of oxidation of hydrocarbons in addition depends
upon the amount of oxygen, presence or absence of nitrogen
oxides (NOx, a general term used for NO and NO2), ambient
temperature, and the presence or absence of metal ions.
Hydrocarbon oxidation is a three-step process, and comprises initiation, propagation, emd termination (Fig. 2). Initiation involves the attack of atmospheric oxygen or of nitrogen
oxides (NOx) on hydrocarbon molecules. The result is the formation of hydroperoxides (ROOH) and alkyl (R*) and peroxy
(ROO') radicals. During the propagation stage, hydroperoxides decompose either on their own or in the presence of metal
ions to alkoxy (RO') and peroxy radicals. These react with the
lubricant hydrocarbons to form a variety of additional radicals and oxygen containing compounds, such as alcohols,
aldehydes, ketones, and carboxylic acids [see the chapter on
Oxidation]. Aldehydes and ketones are highly reactive and can
form polymers in the presence of acids, such as nitric and sulfuric acids. These acids result from the interaction of nitrogen
oxides and sulfur oxides, products of combustion, with water.
Carboxylic acids attack iron, copper, and lead, present in the
mechanical equipment, to form metal carboxylates that further increase the rate of oxidation. During the termination
stage, the radicals either self-terminate or terminate by reacting with oxidation inhibitors [8]. Oxidation inhibitors (InH)
circumvent the radical chain mechanism by promoting deRH

O2

ROOH

RH

O2

ROO-+H

RH

+-NO,

'

Initiation

R- + HNOx

ROOH

>v

RO- + OH-

ROOH + Fe+2

-*-

RO- OH' + Fe+3

ROOH + Fe*'

-*

ROO- + Fe*^ + H*

ROO - RH

-*

ROOH R-

ROO-

-*-

R- O2

RO - ! RH

-*

R O H -I- R-

OH- + RH

*-

H2O

ROO- + ROO-

*-

RR + 2O2

ROO- + InH

*-

ROOH + In-

RO- + InH

-^

ROH + In-

R- + InH

-*

R H I n -

> Propagation

R-

>-

Termination

RH = Hydrocarbon

ROOH = Hydroperoxide

RO- = Alkoxy Radical

R - = Alkyl Radical

InH = Inhibitor

In- = Inhibitor Radical


FIG. 2Oxidation mechanism.

202

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

composition of hydroperoxides and taking reactive radicals


out of the oxidation process by reacting with them. Oxidation
inhibitors can be classified as hydroperoxide decomposers,
radical scavengers, or metal deactivators, depending upon the
mode of their controlling action.
Sulfur containing compounds, such as sulfides a n d dithiocarbamates, and phosphorus containing compounds, such as
phosphites and dithiophosphates, act as hydroperoxide decomposers. Nitrogen a n d oxygen containing c o m p o u n d s ,
such as arylamines and hindered phenols, act as radical scavengers [8,9]. These chemicals convert chain-propagating
hydroperoxides and radicals to innocuous products. Some
inhibitors, such as dithiophosphoric acid derivatives and
dithiocarbamates are extremely potent oxidation control
agents. This is because they act both as hydroperoxide decomposers and as radical scavengers. They in addition possess antiwear properties.
Transition metals can act as both oxidation initiators (promoters) and oxidation inhibitors, depending upon their oxidation state [8]. They act as promoters if they facilitate the
formation of free radicals, and they act as inhibitors if they
remove free radicals from the oxidation process [10]. For example, heavy metals, such as iron and lead, and their salts are
well known as oxidation promoters [11,12]. Metal deactivators, another class of oxidation inhibitors, are used to control
oxidation under such circumstances. These inhibitors, primarily used in fuels, form complexes with metal ions via
chelation, thus taking t h e m out of the chain reaction.
Ethylenediaminetetraacetic acid derivatives and N,N-disalicylidene-l,2-propanediamine represent the m o s t p o p u l a r
members of this class. The structures of common inhibitors

are provided in Fig. 3. Synthetic methods for polysulfides,


phosphites, and dithiophosphoric acid and dithicarbamic
acid derivatives are described in the antiwear and extreme
pressure agents section. Those for synthesizing alkylphenols
are provided in the detergents section. Hindered phenols,
such as 2,6-di-?-butyl-4-methylphenol (BHT), a n d diaryla m i n e are p r e p a r e d by reacting phenol, alkylphenol, or
diphenylamine with an olefin in the presence of a Lewis acid
catalyst. The salicylidene meted deactivator is a product of
phenol, formaldehyde, and ethylenediamine.
Some oxidation inhibitor combinations are synergistic.
That is, they reflect an effect greater than the additive effect
of two or more inhibitors. Such combinations usually, but
not always, consist of compounds that intercept oxidation by
two different mechanisms. An example is the combination of
a sulfur compound with an arylamine or a hindered phenol
[13].
Oxidation inhibitors cire used in almost all lubricants, with
gasoline and diesel engine oils and automatic transmission
fluids accounting for ~ 60% of the total use. High temperature and high air exposure applications require a higher level
of oxidation protection. Zinc diaJkyl dithiophosphates are the
primary inhibitor tj^pe, followed by eiromatic amines, sulfurized olefins, and phenols.
A n u m b e r of tests are used to assess a lubricant's oxidation
stability under accelerated oxidation conditions. ASTM Sequence IIIE/IIIF (viscosity increase), ASTM Sequence VE/VG
(sludge and varnish formation), and CRC L-38 (bearing corrosion) tests are used for engine oils. The CRC L-60-1 test is
used for gear oils a n d the ASTM D 943 and ASTM D 2272
tests are commonly used for turbine oils.

1. Hydroperoxide Decomposers
R-S-(S)rS-R

X = 0 or 1; R = alkyl or functionalized alkyl

DialkyI polysulfide
RQ.,,S
(R0)2R,
H

:>-c'

Zn

RO'%

CHo

R
DialkyI hydrogen
phosphite

Alkylphenol

Zinc dialkyi
dithlophosphate

2. Radical Scavengers

Methylene coupled
dlthlocarbamate

3. lUletal Deactivators

2,6-DI-f-butyl-4-methylphenol

Alkylated diphenylamine

[BHT (Butylated hydroxytoiuene)]


N, N-Disalicylldene-1,2-propanediamine
FIG. 3Commonly used oxidation inhibitors.

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY

203

Hydroperoxide

RCH2CH(CH3)2 + O2
CH3
_,OH
R<hr^=S:,^~.

O2

'^"-X^-^*^^

Hydroperoxide

*-

RCH2CH(CH3)2 +

Alkene
RCH2CH(CH3)2 + N O ,

HNO,

o-

R ^ ^ C H 3

R^^N^CHj

. OH

CH3
CH3
Hydroperoxide
O

Alltoxy radlcai

.OH

O+ NO,

R ^ x k , ^ ^

MONO

Allyloxy radical

Hydroperoxide

o-

ONO
/

RCH2CH(CH3)2

I
RCH2CH(CH3)2

Nitrite Ester

RCH2CH(CHi)2 + NO2

RCHiCHCCHjlj-

RCH=CH(CH3)2

NO2
NItroalkane

ONO2
+ NO2 *

Aliyioxy radical

^<!x^;^^^/^
Nitrate Ester

FIG. 4Formation and decomposition of nitrite and nitrate esters.

Dispersants
Dispersants are additives that suspend oil-insoluble resinous
oxidation products and particulate contaminants in the bulk
oil. By doing so, they minimize sludge formation, particulaterelated abrasive wear, viscosity increase, and oxidationrelated deposit formation. Dispersants perform these functions by:
solubilizing polar contaminants in their micelles.
stabilizing colloidal dispersions in order to prevent aggregation of their particles and their separation out of oil.
suspending such products, if they form, in the bulk lubricant.
modifying soot to minimize its aggregation and oil thickening.
lowering surface/interfacial energy of dirt to decrease its
tendency to adhere to surfaces.
Dirt is a generic term that describes undesirable materials
that result from oxidative degradation of the lubricant, the
reaction of chemically reactive species (such as carboxylic
acids) with the metal surfaces in the engine, or the decomposition of thermally unstable lubricant additives, such as extreme pressure agents.

In gasoline-fueled engines, nitrogen and oxygen present in


the air-fuel mixture react at high temperatures to form NO
and NO2. These oxides can react with hydrocarbons of the
fuel and the lubricant to form nitroalkanes and nitrite and nitrate esters [14,15]. The mechanism of their formation is
shown in Fig. 4. These esters and the hydroperoxides generated from the direct oxidation of the lubricant either thermally or hydrolytically decompose to form highly oxygenated
monomeric species [14]. These can polymerize to a slight degree under the influence of heat to form resin, varnish, lacquer, deposits, and sludge (Figs. 5 and 6). Resin is made up
of oligomeric molecules with an approximate molecular
weight of 500-700. Varnish, lacquer, and deposits comprise
materials of much higher molecular weight. The sludge, depending upon the severity of the operation, can be watery in
consistency or thick like a semi-solid.
In diesel-fueled engines, soot from the combustion chamber is the key component of carbon and lacquer deposits that
occur on pistons, and sludge. These deposits result when soot
combines with resin. In general, lacquer is rich in resin, and
carbon is rich in soot. Sludge results when soot combines
with the oxygenated species, oil, and water [16]. Local piston
temperatures and the lubricant's ash-producing tendency

2 0 4 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

Partially Combusted Fuel

Fuel

JNOx
Liquid Nitrated and Oxygenated lUlonomers

Oil Insoluble Products (Resin)


\
\

Lubricant

Carbon
Water
\
Solids

/
Varnish

Resin

-Sludge

-" Varnish
Accumulate as
deposits in areas
of low oti velocity

Resin-coated
Soot Particles
Resin + Soot
Soot-coated
Resin Particles
Resin + Soot + Oil + Water

-*-

Lacquer

Sludge

FIG. 5Mechanism of deposit formation.

^
A

Soot

Resin

o-

Additive

FIG. 6Mechanism of soot-resin-additive interaction.

(ASTM D 482) have a profound effect on the composition of


carbon deposits. High temperatures and lubricants with high
metal content primarily produce deposits with high residue
and low organic content [17]. Metals are the main source of
ash. Basic detergents contain meted and therefore are considered to contribute towards ash. Zinc dialkyl dithiophosphates also contribute, but only slightly.

Because of low oil-solubility, resin tends to separate out as


amber lacquer on hot piston surfaces. If oil contains soot,
soot separates with resin to form "resin-coated soot particles,"
which appear as black lacquer. As the soot level increases,
more and more soot associates with resin to form "sootcoated resin particles." These events are shown in parts A and
B of Fig, 6. The size and the composition of these particles do
not allow them to adhere to metal surfaces. However, they
can collect in areas of low oil flow, such as piston grooves, as
deposits.
Dispersants suppress the interaction between resin and
soot particles, by preferentially associating with them and, at
the same time, keeping them suspended in the bulk lubricant.
Since both resin and soot particles are polar in character, either by their very nature or due to adsorbed polar impurities,
the dispersant associates with these particles via its polar
end. As mentioned earlier, all additive tj^es, except some viscosity modifiers and pour-point depressants, contain a polar
functional group and a non-polar oleophilic hydrocarbon
moiety. The polar group, which in dispersants is oxygen or
nitrogen-based, attaches itself to oxidation products, such as
resin, soot, and sludge peirticles. The oleophilic hydrocarbon
group keeps them suspended in oil [16]. These situations are
depicted in parts C and D of Fig. 6.
The performance of dispersants can be explained by considering the concepts of steric stabilization and electrostatic
stabilization. According to steric stabilization, once the dispersant molecules attach themselves to either resin or soot
particles, their long hydrocarbon chains prevent agglomeration of the particles [16]. This is depicted in Fig. 7. The electrostatic mechanism is based on repulsion between particles

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY


Hydrocarbon Chains of
Adsorbed Dispersant

Separation
Distance
FiG. 7iVIeclianism of steric stabiiization.

c : ^ ^

Particle ) ^

cAi,

c^^

FIG. 8Tlie meclianism of eiectrostatic stabiiization. (a) by


ionized dispersant. (b) by un-ionized dispersant.

205

with like charges, which minimizes agglomeration. The development of charged particles in a low-dielectric medium,
such as oil, can be explained in two ways [18]. According to
the first explanation, the dispersant is already ionized and
through adsorption imparts a chcirge to the particle (depicted
by mechanism A in Fig. 8). According to the second explanation, the non-ionized dispersant adsorbs onto the surface of
the particle, an acid-base reaction involving the transfer of a
proton or another ion occurs, and the counter-ion desorbs resulting in the formation of a charged particle. Particles with
like charges repel one another, thereby preventing agglomeration. This is shown in part B of the exhibit. Neutral and high
soap detergents, discussed in next section, are believed to
perform via this mechanism. It is important to note that for
certain classes of dispersants, both mechanisms might be operating simultaneously.
Interestingly, empirical data suggest that the ionic mechanism, although it seems unlikely due to the organic nature of
the lubricant medium, does operate [18].
The essential performance features in a dispersant are its
thermal and oxidative stability, its low-temperature properties, and above all its ability to disperse soot, deposits, and
deposit precursors. Poor thermeJ stability can impair a dispersant's ability to disperse polar oxidation and decomposition products in the bulk lubricant. Poor oxidative stability
can make a dispersant contribute towzirds deposit formation.
Low temperature properties of the modem lubricants are
gaining importance. The use of light base oils to meet low
temperature requirements in finished lubricants is no longer
possible because of the volatility specifications (ASTM D
5480 and D 5800). The use of pour point depressants for
paraffinic oils has limited utility because it only affects some
low temperature properties, such as pour point, but not others, such as cold cranking. Base oil manufacturers therefore
use a number of strategies to develop base oils with good low
temperature properties. These include isomerization via hydrocracking and use of special synthetic oils as additives. Because dispersant is a major component in engine oil formulations, its structure can antagonize low-temperature
properties of these oils. And of course soot and deposit control, or dispersancy, are the primary functions of a dispersant. If a dispersant does not possess these properties, it is
not effective as an additive.
A dispersant contains three structural features: a hydrocarbon group, a polar group, and a group that connects the two
together, the connecting group or a link. These are depicted
in Fig. 9 by a graphic representation of a disperscuit molecule.
While each structured feature affects a different property or
properties in a dispersant, all three are essential to a dispersant's oversdl performance. The nature of the hydrocarbon

Connecting Group

Nitrogen or o)^gen _
Derived Functionality

FiG. 9Graphiic representation of a dispersant molecule.

206

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

group impacts all key properties, namely, thermal and oxidative stability, low-temperature performance, and dispersancy. Its structure can influence a dispersant's thermal and
oxidative stability and low-temperature properties. Its degree
of branching can improve or hurt the low temperature properties and compatibility with the additive package. Its molecular weight can affect dispersancy. The hydrocarbon radical
in dispersants is oligomeric or polymeric and is usually
aliphatic in nature. It contains 70 to 200 or more carbon
atoms to ensure good oil solubility. A polyisobutenyl alkyl
group is the most commonly used hydrocarbon group. In
some dispersants, the hydrocarbon moiety is derived from a
high molecular weight polymer, such as olefin copolymer,
polyacrylate, polymethacrylate, or styrene-ester polymer.
Such dispersants can also function as viscosity modifiers and
are appropriately called dispersant viscosity modifiers.
The link is the weakest portion of the dispersant molecule
because of its chemical structure. It can fall apart thermally
or chemically, making a dispersant ineffective. The most
commonly used polar groups are alcohol and amine derived.
They can oxidize, hydrolyze, and or thermally degrade and
make dispersant molecule lose its structural integrity. The
size and the nature of the polar group (whether it is oxygen
or nitrogen-based) determine dispersancy.
Chemical classes suitable for use as dispersants include
cilkenylsuccinimides, alkenylsuccinate esters, high molecular
weight amines, Mannich bases, and phosphonic acid derivatives. Polyisobutenylsuccinic acid derivatives (succinimides
and succinate esters) are commercially the most commonly
used dispersant types.
Both succinimides and succinate esters are prepared from
alkenylsuccinic anhydrides. Polyisobutylene (the most com-

monly used polyalkylene) of molecular weight between 440


and 5000 is reacted with maleic anhydride, either thermally
or in the presence of chlorine, to yield a succinic anhydride.
Reaction of the succinic anhydride with amines (polyalkylene-polyamines and heterocyclic polyamines) results in the
formation of succinimide dispersants. The corresponding reaction of the succinic anhydride with alcohols, especially
polyhydric alcohols, results in the formation of succinate ester dispersants. Figure 10 summarizes the syntheses of
alkenylsuccinimides and alkenylsuccinates. Mannich dispersants are produced by the condensation of a high molecular
weight alkylphenol (polyisobutylphenol), an aldehyde, and
polyalkylene-polyamines. Phosphonic acid ester dispersants
are prepared by reacting phosphonic or thiophosphonic
acids with ethylene oxide or propylene oxide. The starting
acids are obtained from the hydrolysis of olefin-phosphorus
pentasulfide adducts. The preparation of Mannich products
and phosphonic esters is described in Fig. 11.
While in most cases starting polyalkylene has a molecular
weight of 1000 or 2000, the resulting succinimide and succinate dispersants have molecular weights that are 3-7 times
higher. This is due to the bifunctionality of the alkenylsuccinic anhydride and the polyfunctionality of the alcohols and
amines that are used to make dispersants. The result is the
formation of bridged structures that increase a dispersant's
dirt-suspending ability via more extensive interaction. The
bridged structure of a dispersant is graphically depicted in
Fig. 12.
Dispersants have major uses in gasoline engine oils, diesel
engine (heavy-duty and railroad) oils, natural gas engine
oils, and aviation piston engine oils. Dispersants are also
used in automatic transmission fluids and gear lubricants.

PIB

<"
Polyisobutylene

PIB

Polyisobutenyl
Succinic Anhydride

Maleic Anhydride

""'^ ~ |

H2NCH2CH2NHCH2CH2N

,NCH2CH2NHCH2CH2l<^

\
Alkylenepolyamlne
Polyisobutenylsucclnlmlde

Polyisobutenyl
Succinic Anhydride

H2

R'

,C

PIB

PIB

HOH2C-CCH2OH

R
Polyisobutenyl
Succinic Anhydride

Polyol

V
o

R'

/
Y~CH20
R

<j^^CH20R

Polylsobutenylsuccinate Ester
FIG. 10Synthesis of alkenylsuccinimides and alkenylsuccinates.

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY

207

MANNICH DISPERSANTS

?"

Js.,.CH2NCH2CH2NHCH2CH2Nv

CH2O + H2NCH2CH2NHCH2CH2N
R'

'^

Alkylenepolyamine

Polyaminomethylalkylphenol

Alkylphenol

R=Polyisobutyl Group
PHOSPHONIC ACID DISPERSANTS

PIB

Polylsobutylene

P2S5

Adduct

PIBP-OH

Phosphorus
Pentasulfide

or

OH

PIBP-OH
OH

Polyisobutylenethiophosphonic Acids

S
11
PIBP-OH
I
OH

Alkenylphosphonic
Acid

Pro

Propylene Oxide

S
II

CH3
I

PIBPOCH2CH O H
I
OCH2CH O H

Bis-hydroxypropyl
Alkenylthiophosphonate

I
CH,

FIG. 11Synthesis of Mannich and phosphonic acid dispersants.

Nitrogen or Oxygen Derived


Functtonallty
\

Aikenylsuccinic acid or Alkylphenol


Derived Connecting Group

Alkylene or Pdyalkyleneamine
Derived Bridging Group

Hydrocarbon
Groups

Nitrogen or Oxygen Derived


Functtonality

Altenylsuccinic acid or Alkylphenol


Derived Connecting Group

FIG. 12A representation of the bridged structure of a dispersant.

208 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


Gasoline a n d heavy-duty diesel engine oils account for
75-80% of the toted dispersant use. Succinimide and succinate ester (pentaerythritol esters of polyisobutenylsuccinic
anhydride) dispersants are used in both gasoline and diesel
engine oils. High molecular weight amines and Mannich
dispersants are used in gasoline engine oils only. Succinimide dispersants are often used in automatic transmission
fluids, power steering fluids, and, to a limited extent, in gear
oils. Both types are also used as fuel additives. The use of
phosphonate dispersants is generally restricted to non-engine lubricants. This is because engine oils have a phosphorus limit due to its adverse effect on catalj^tic converters.
The formulators prefer to use zinc dialkyl dithiophosphates
instead because they are potent oxidation inhibitors as well
as good antiwear agents.
In gasoline and diesel engine oils, the effectiveness of a dispersant is determined by its ability to suspend oil-insoluble
products of combustion, oxidation, and oil degradation. In
the laboratory screen tests, this is assessed by a dispersant's
ability to either disperse lamp black or used engine oil sludge.
However, in the laboratory engine tests, such as the ASTM
Sequence VEA'^G Test and various diesel engine tests (Caterpillar IK, IM-PC, IN, IP, and IR), a pass rating in varnish,
sludge, and deposits is required.
Detergents

low. The excess base per equivalent of acid in metal hydroxide-containing detergents is generally lower t h a n t h a t in
metal carbonate-containing detergents. Detergents are described chemically in terms of their metal ratio, soap content,
sulfated ash (ASTM D 874), degree of overbasing or conversion, and total base n u m b e r (TBN) [5].
Let us represent a detergent, for example a basic calcium
sulfonate, by the general formula (RS03)vCaw(C03)a:(OH)y ,
where v, w, x, and y denote the n u m b e r of sulfonate groups,
the n u m b e r of calcium atoms, the n u m b e r of carbonate
groups, and the n u m b e r of hydroxyl groups, respectively. The
metal ratio is defined as the total equivalents of metaJ per
equivEdent of acid. Since calcium is a divalent metal, each
atom of calcium represents two equivedents. Hence, the metal
ratio can be Ccilculated by the equation.
Metal Ratio =

The degree of overbasing describes the ratio of equivalents of


the metal base to equivalents of the acid substrate and is usually expressed as conversion. Conversion indicates the
a m o u n t of inorganic materied relative to that of the organic
material and is expressed as the n u m b e r of equivalents of
base per equivalent of acid times 100.
Conversion

Detergents perform functions similar to those of dispersants;


that is, they suspend oxidation products and sludge particles
in the lubricant. Detergents, in addition, have the ability to
neutralize acidic combustion and oxidation products; therefore they control rust, corrosion, and resinous build-up in the
engine. Detergents, like dispersants, contain a surface-active
polar functionality a n d a n oleophilic hydrocarbon group
with an appropriate n u m b e r of carbon atoms to ensure good
oil solubility. Sulfonate, phenate, carboxylate, salicylate, and
phosphonate are the common polar groups present in detergent molecules.
Detergents eire metal salts of organic acids. Common acids
that are used to sjrathesize these compounds include alkylbenzenesulfonic acids, alkylphenols, carboxylic acids, and
alkenylphosphonic and alkenylthiophosphonic acids. The
quantity of metal used may be equal to or in excess of the precise amount (stoichiometric amount) necessary to completely
neutralize the acid function. When the metal is present in the
stoichiometric amount, the detergents are called "neutral."
When it is present in excess, they are called "basic, overbased,
or superbased." The general formulas for basic metal sulfonate, metal phenate, and metal carboxylate are given below.
(RS03)a M xMfcCOs yM(OUX
Basic Sulfonate
(RPhO)aM xMfcCOa yM{OU)c
Basic Phenate
(RCOO)aM xMbCOs >'M(OH)<;
Basic Carboxylate
Where a,b, and c = 1 or 2, depending upon if the metal M is
monovalent or divalent.
Detergents may contain the excess base as metal hydroxide, metal carbonate, or both. For noncarbonate detergents,
X in the above formulas is zero. For carbonate detergents, y is

2\v

N u m b e r of equivalents of base ^ .
Number of equivalents of acid
2w

X 100

In other words, conversion is the metal ratio times 100. Neutral detergents have a conversion of 100 because the ratio of
equivalents of base to the equivalents of acid is 1. Soap content refers to the a m o u n t of neutral organic acid salt and reflects a detergent's cleansing ability, or detergency, and dirt
suspending ability. The soap content can be determined by
the use of the following formula.
Percent soap

Formula weight [(RS03)2 Ca] X 100


Effective formula weight

Effective formula weight is the combined weight of all


atoms that make u p the formula (RS03)vCaw(C03);c(OH),
plus that of the diluent. The percent sulfate ash is the ash obtained after treating the detergent with sulfuric acid and ignition. The knowledge of ash-producing tendency of a lubricant is important to the formulator (ASTM D 482). This
is because combustion of the lubricant results in ash that
can contribute to deposits in those areas of the engine that
are in close proximity to the combustion chamber, such as
the piston top land and the groove behind the top piston
ring.
The total base number, or TBN, of the detergent indicates
its acid neutralizing ability and is expressed as mg KOH/g of
additive. Both the acid n u m b e r and the base number are expressed in this fashion. The convention regarding its use and
the details on how to calculate acid and base numbers are described in the ASTM Standard D 974. TBN can be calculated
from the number of equivalents of the excess metal after salting the acid, that is (2w v), as follows.
TBN (mg KOH/gm)

(2w - v) X 56100
Effective formula weight

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY


For a monovalent metal, (w v) will be used instead. In addition to the alkylbenzenesulfonic acids, alkylphenols, carboxylic acids, and alkenylphosphonic acids that were mentioned earlier, sulfur-coupled and methylene-coupled
alkylphenols are also used as detergent substrates. The methods of synthesis of these substrates are presented in Fig. 13.
Alkylbenzenesulfonic acids are obtained by sulfonating alkylbenzenes. The products obtained by sulfonating alkylaromatics from petroleum refining are referred to as "natural"
sulfonates and those obtained by sulfonating cilkylaromatics
from the catalytic alkylation process are referred to as "3501thetic" sulfonates.
Alkylphenols eire prepared from phenol and an olefin by the
use of an acid catalyst. These alkylphenols can be further reacted with sulfur, sulfur dichloride, or formaldehyde to form
sulfur-bridged and methylene-bridged alkylphenols. Alkylsalicylic acids are prepared by the use of the Kolbe process,
which involves reacting an alkali metal phenate with carbon
dioxide. Alkenylphosphonic acids are the hydrolysis products
of polyisobutylene-phosphorus pentasulfide adducts.
Detergents are prepared by reacting an organic acid with
an appropriate metal base in the presence of a polar promoter. Overbasable metals that can be used to prepare basic
detergents are lithium, sodium, and potassium in Group I
and magnesium, calcium, strontium, and barium in Group II
of the periodic table. Aluminum is the only overbasable metal

in Group III. The ability to overbase is directly related to a


metal's base strength. For Group I metals, basicity increases
from lithium to sodium to potassium. For Group II metals, it
increases from magnesium to calcium to strontium to barium. It is, therefore, most difficult to overbase lithium in
Group I and magnesium in Group II.
Metals commonly used to make detergents are sodium,
magnesium, calcium, and barium. Of these, calcium and
magnesium are used most widely, with a clear preference for
calcium due to its lower cost. The use of barium is being limited due to both the toxicity and the economic concerns. The
bases of choice are caustic (sodium hydroxide) for sodium
detergents; lime (calcium hydroxide) for calcium detergents;
magnesium oxide for magnesium detergents; and barium hydroxide for barium detergents. For basic detergents that contain excess base, the base may be present as is or as metal carbonate. In practice, virtually all commercial detergents are
overbased to some extent. For example, commercial "neutral" sulfonates have a TBN of 30 or less. "Basic" detergents
typically have a TBN of 200 to 500.
Sulfonate, salicylate, and carboxylate detergents are commercially available as calcium and magnesium salts. Phenate
detergents are available as calcium salts and phosphonate detergents are available as barium salts only. Basic calcium sulfonates make up ~ 65% of the total detergent market, followed by phenates at ~ 31%.
SO3H

SO,
!<
R
Alkylbenzenesulfonic
Acid

Alkylbenzene

COOK
Olefin
Plienol

R=Alkyl Group

Sulfur CoupledAlkylphenol
or Phenol sulfide

PIB
Polyisobutylene

Methylene Coupled
Alkylphenol

H,0

P,S
2*5

Adduct

Phosphorus
Pentasulfide

209

RIBP-OH
I
OH

Polyisobutenylphosphonic
Acid

X = O or S
FIG. 13Detergent substrates.

210

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK
with these compounds and keep t h e m in solution. The mechanism by which detergents perform is analogous to that of
dispersants, which is shown in Figs. 7 and 8. Depending upon
the lubricant's end-use, insoluble by-products may be soot,
acidic decomposition products, or deposit-forming resinous
species [14,16]. Detergents control the buildup of these undesirable contaminants by keeping equipment surfaces clean
and neutralizing acidic products from lubricant oxidation
and decomposition. They keep surfaces clean by forming a
protective film via adsorption and by suspending depositforming species in the bulk oil through association [7].
Detergents can also act as oxidation inhibitors, depending
u p o n the n a t u r e of their functional group. For example,
phenates, sulfurized phenates, and salicylates possess oxidation-inhibiting properties, primarily due to the presence of
the phenolic functional group.

The method of preparation of neutral and basic detergents


is outhned in Fig. 14 and the general structures for neutral
detergents are shown in Fig. 15. Basic detergents can be considered neutral detergents that contain excess base in an associated form. The structure of detergents can be envisioned
as a reverse micelle, with a n a m o r p h o u s metal carbonate
molecule encapsulated by metal soap molecules with their
non-polar ends extended into the oil. This is depicted in Fig.
16.
Detergents are used in lubricants to perform functions similar to those of dispersants: that is, to keep oil-insoluble byp r o d u c t s of c o m b u s t i o n and oil oxidation in suspension.
These products, which are polar organic compounds, include
alkyl nitrites and nitrates, nitroalkanes, carbonyl compounds
(aldehydes, ketones, and carboxylic acids), and oligomers resulting from their thermal reaction. Detergents associate

Substrate + Metal Oxide or Hydroxide


M0
M{OH)

-*-

Neutral Salt

stoichiometric Amount

Substrate + IMetal Oxide or Hydroxide


M0
iW{OH)

^ ^ Basic or Overbased
Salt

No CO,

Stoicliiometnc Excess

Basic Salts = Neutral Salts M0, M(OH) or MnCOs


R/l = Na, Mg, Ca, Ba

n 1 or 2

FIG. 14Synthesis of detergents.

0)xlWI

^?\.S03)xM

0)xlWI
R

R
Metal Salicylate

Metal Sulfonate

or

Sulfur and Methylene Bridged Phenates

s
RP-O
I
I
O-IW

r. n
RP-O
'
'

Metal
Phosphonate

Metal
Thiophosphonate

0-iw

II
II
R_p_s-p-R
I I

o^ .o

X = 1 or 2
Y = S or CHa
lUI = Na, lUlg, Ca

M
Metal
Thiopyrophosphonate

FIG. 15Idealized structures for neutral detergents.

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY

211

O
II

-s-o

'6 \
II

-s-o
II

Sulfonate
Head Group

Hydrocarbon
Group

Basic Sulfonate Inverse Micelle


Structure Size: 100-150A

Neutral Calcium Sulfonate


FIG. 16Micellar structure of detergents.

Additive It/lolecule

Metal Surface

Mack T-6, T-7, T-8/E, T-9, and T-10). Detergents have additionEil use in automatic transmission fluids and tractor hydraulic fluids. However, their use in these applications is not
to control deposits but to modify the fluid's frictional properties.
Film-Forming Agents

Physisorption

Cliemisorption

o o o o o o
o o o o o o
Chemical Reaction
FIG. 17Modes of additive - surface interactions.

Detergents have major use in crankcase lubricants. Gasoline and diesel engine oils account for over 75% of the total
detergent consumption. Detergent treatment levels in engine
lubricant formulations are fairly high, with marine diesel engine lubricants containing the highest detergent concentrations. Marine engines use high-sulfur fuel, which leads to
acidic combustion products (sulfuric acid). Therefore, lubricants for these engines need the base reserve of the "basic"
detergents for neutralization.
Detergency in diesel engine oils is evaluated by using both
single cylinder engine tests (Caterpillar IK, IM, IN, IP, and
IR) and multicylinder engine tests (GM 6.2L and 6.5L; and

Lubrication is necessary to facilitate the counter-movement


of two sliding surfaces. This function, which is usually performed by the base oil, can be enhanced by using high viscosity oils [19]. However, beyond a certain threshold temperature, the lubricant fails to form an effective film, and
friction and wear can result. The lubricant's film-forming
ability under such circumstances can be made more efficient
by using film-forming agents. Such agents can interact with
metal surfaces either through adsorption or chemical reaction. PhysicaJ adsorption, or physisorption, is a weaker association of the additive with metal than chemical adsorption,
or chemisorption, which in turn is weaker than chemical reaction. During adsorption, an additive molecule generally
keeps its structural integrity. In a chemical reaction, however, it has the tendency to lose it because it gets converted
into new molecules. The modes of interaction of additive
molecules with the surface [20] are depicted in Fig. 17.
Friction Modifiers
Friction modifiers are agents that modify the frictional properties of a lubricant. These are long-chain molecules with a
polar end group and a non-polar linear hydrocarbon chain.
The polar end groups either physically adsorb onto the metal
surface or chemically react with it while the hydrocarbon
chains extend into the lubricant. These chains associate with
one another and the lubricant to form a strong lubricant film
[21]. This is shown in Fig. 18.
These additives are used to decrease or increase friction,
depending upon the application. In engine lubricants and
gear oils, their primary function is to reduce friction, minimize wear and noise, and improve fuel economy by lowering
the power loss. In transmission and hydraulic fluids, these
additives are used to facilitate timely engagement and disengagement of clutches and bands to assure smooth and noise-

212 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK
Cohesion or Association
with Lubncant

\ ^

Ifl
\!*

"

"

^ ^ ^

" X ^ ^ " A ^ ^V^


H ^

^ H

HtOT fVSft<

HHZH" H^^HH ^ ^ H ^
QH^H

H-4HQ H ^

^
Hfi^

(A) Physisorption
(B) Chemisorption
FIG. 18Adsorption of polar additives on the metal surface.

Crankcase Temperature (C)


FIG. 19The effect of friction-modified lubricant on engine
power loss.

free operation. The effect of friction modifiers on the engine


power loss [22] is depicted in Fig. 19. At low ambient temperatures, where lubricant viscosity is high enough to form
an effective lubricating film, friction modifiers have little effect in minimizing power loss due to friction. However, at
high temperatures, friction modifiers become more effective
because of the loss of lubricant viscosity, which may lead to

boundary lubrication. Figure 20 shows the friction-reducing


capability of these additives in automatic transmission fluids. At low sliding speeds, where metal to metal contact is
likely; friction modifiers interact with surfaces in the manner
discussed above and minimize such contact, and the associated rough shifting. However, at high speeds, their effect is
not as dramatic because such speeds promote hydrodynamic
lubrication. These additives minimize brake chatter in tractors in an analogous manner.
Due to government regulations, increasing fuel costs, and
efforts to conserve resources, lubricants that can provide better fuel economy are becoming more desirable. Energy Conserving engine lubricants are designated as Energy Conserving I (EC-I) or Energy Conserving 11 (EC-II), depending upon
the extent of fuel conservation [23]. While the use of friction
modifiers helps, other factors such as the lubricant viscosity
grade, the type of viscosity modifier used, and the nature of
the other additives present in the lubricant, all play an important role [24].
Frictional properties of transmission and hydraulic fluids
are extremely important. The frictional compatibility of the
fluid with the functioning parts of transmissions and wet
brakes and wet clutches in tractors assures their smooth and
noise-free (chatter-free) operation. Frictional properties play
an equally important role in gear oils. In standard applications, friction-modified gear oils not only protect gears and
axles against frictional damage but they also contribute to-

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY

213

TABLE 1The effect of friction modifiers in gear oils.

0.16

LFW-1 Machine

Coefficient of Friction

GL-5 gear oil (80W-90)


GL-5 gear oil (80W-90)
+ 1% friction modifier
GL-5 gear oil (75W)
GL-5 gear oil (75W)
+ 1% friction modifier

0.057
0.054
0.055
0.052
Coefficient of Friction

20

30

40

50

60

Sliding Speed (cm/s)


FIG. 20Friction reducing ability of an automatic transmission
fluid.

LVFA Machine

Static

Dynamic

GL-5 gear oil (75W)


GL-5 gear oil (75W)
+ 1% friction modifier
GL-5 gear oil (75W)
+ 1% oleic acid
GL-5 gear oil (75W)
+ l%ArmeenHT

0.070
0.050

0.052
0.042

0.052

0.043

0.062

0.050

O SAE 7SW Oil + Friction Modifier


SAE 75W Semi-syntlietic Oli

wards fuel economy. For limited-slip axles, which contain


friction clutches and cones, friction-modified gear lubricants
minimize noise arising from stick-slip. LFW-1 (Alfa Laval
Load, Friction, and Wear Test) and LVFA (Low-Velocity Friction Apparatus) data for gear oils showing the effect of friction modifiers on friction [25] are presented in Table 1. As
can be seen from the table, friction modifiers decrease static
and dynamic coefficient of friction in both the single grade
and the multigrade oils. In general, friction-modified gear
oils show an increase in axle-efficiency relative to normal
gear oils. This is shown in Fig. 21. Axle efficiency is better
both for urban and highway driving. Axle efficiency is believed to have a positive correlation with fuel economy.
Under heavy loads, the EP agent replaces the friction modifier and takes over the function of preventing damage. As the
load decreases, friction modifiers again come into action.
Friction modifiers have a finite life, which is related to their
oxidative and thermal stability. These additives are commonly used in gasoline engine oils, automatic transmission
fluids, tractor hydraulic fluids, power steering fluids, shock
absorber fluids, and metalworking fluids. In passenger car
applications, these additives help in meeting federal government-mandated fuel economy requirements. In ATFs and
limited slip axle lubricants, friction modifiers are used to
control clutch and band engagement. Antisquawk additives,
which are functionally similar to friction modifiers, are used
to reduce objectionable mechanical noise, such as squawk
and chatter. Antisquawks are primarily used in automatic
transmission and tractor hydraulic fluids, automotive gear
oils, and some industrial oils.
This class of additives includes fatty alcohols, fatty acids,
fatty amides, molybdenum compounds, and graphite. For the
fatty alcohol and fatty acid families, friction-modifying properties are a function of the length and the structure of the hydrocarbon chain and the nature of the functional group.
Long and linear-chain materials reduce friction more effectively than short and branched-chain materials. Also, fatty
acids are better than fatty amides, which in turn are better
than fatty alcohols. Saturated acids, containing a 13 to 18
carbon chain, are generally preferred. Lower molecular
weight fatty acids are avoided because of their corrosivity.
Fatty acid derivatives are the most commonly used friction

110

Sump Temperature (C)


FIG. 21The effect of a friction modifier on axle efficiency of
a gear oil.

modifiers. Graphite presents problems when used in conventional lubricants; hence, at present, its use is limited to
greases.
The effectiveness of friction modifiers and antisquawk
agents is judged by the lubricant's performance in LVFA and
SAE # 2 tests. Their load-carrying capacity is determined by
the film strength tests, such as the Timken test.
Antiwear and Extreme Pressure Agents
Wear occurs in all equipment that has moving parts in contact. Three conditions that can lead to wear are surface-tosurface contact, surface contact with foreign matter, and erosion due to corrosive materials. Wear resulting from
surface-to-surface contact is frictional or adhesive wear,
from contact with foreign matter is abrasive wear, and from
contact with corrosive materials is corrosive wear. Fatigue
wear is an additional tjrpe of wear that is common in equipment where surfaces are not only in contact but also experience repeated stresses for prolonged periods. Abrasive wear
can be prevented by installing an efficient filtration mechanism to remove the offending debris. Corrosive wear can be
controlled by using additives that neutralize the reactive
species that attack the metal surfaces. The control of adhesive wear requires the use of additives called antiwear and extreme pressure (EP) agents.

214

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

Under normal conditions of speed and load, two metal surfaces are effectively separated by a lubricant film; a condition
identified as hydrodynamic lubrication. An increase in load or
a decrease in speed promotes metal-to-metal contact. This
causes a temperature rise in the contact zone due to frictional
heat, which results in the loss of lubricant viscosity a n d
hence its film-forming ability. With a progressive increase in
load and/or a decrease in viscosity, the nature of lubrication
changes from hydrodynamic to mixed-film to boundary lubrication. Antiwear additives and EP agents offer protection under mixed-film andboundary lubrication conditions [26]. This
is shown in Fig. 22, Part B [27].
Antiwear and EP additives both provide protection by a
similar mechanism, except that EP additives typically require
higher activation temperatures and load than the antiwear
additives. Simply stated, antiwear additives perform under
mild conditions and EP additives perform under severe conditions. The severity of conditions is determined by the "load
factor" experienced by the additive and the temperature at
which the additive functions. Load is a function of equipment speed and service. Heavy loading requires the use of extreme pressure agents and mild loading requires the use of
antiwear agents. Thus, it is important to consider both the
load and the temperatures that the equipment is likely to experience before selecting these additives.
Antiwear agents are commonly used in engine oils, automatic
transmission fluids, power steering fluids, and tractor hydraulic
fluids. Extreme pressure agents are used in other power-transmitting fluids, gear oils, shock-absorber fluids, and metalwork-

ing fluids. For GF-2 and API SH and SJ quality engine oils, ASTM
Sequence IIIE and VE engine tests are used to determine the effectiveness of antiwear agents. However, for API SL and ILSAC
GF-3 categories (approved in 2001), ASTM Sequence IIIF, IVA,
and VG engine tests are used. To determine the performance of
EP agents in gear oils, the CRC L-37 and CRC L-42 axle tests are
used. The general effectiveness of these additives in metalworking fluids is determined by Timken, Four-Ball, and Falex tests.
Extreme pressure additives are usually supplemented with antiwear additives to make the formulations effective at lower temperatures and under milder loading conditions as well.
Most antiwear and extreme pressure agents contain sulfur,
chlorine, phosphorus, boron, or combinations thereof. The
classes of compounds that inhibit adhesive wear include alkyl
and aryl disulfides and polysulfides, dithiocarbamates, chlorinated hydrocarbons, and phosphorus compounds such as
alkyl phosphites, phosphates, dithiophosphates, and
alkenylphosphonates.
Both antiwear and extreme pressure additives function by
thermal decomposition and by forming products that react
with the metal surface to form a solid protective layer. This
solid metal film fills the surface cavities (asperities) and facilitates effective film formation, thereby reducing friction
and preventing welding and surface wear. The meted films
consist of iron halides, sulfides, or phosphates, depending
upon the antiwear and EP agents used. Friction modifiers
differ from antiwear and extreme pressure agents in that they
form the protective film via physical Eind chemical adsorption instead of chemical reaction.

LubricantFilm
FLUID-FILM LUBRICATION
Surfaces well separated by
the bulk lubricant film

.. * J
c

Lubricant
Film

1 Boundary Lubrication
MIXED-FILM LUBRICATION
Both the bulk lubricant and
the boundary film play a
role

! \ / - ^ Mixed-film Lubrication

u.

"5
c
a>

8
o

Fluid-film Lubrication

.ZN.
P
(A) RELATIONSHIP OF VISCOSITY (2),
SPEED (AO, AND LOAD (P) TO
FRICTION AND FILM THICKNESS

FIG. 22Types of lubrication.

BOUNDARY LUBRICATION
Performance essentially
depends upon the quality of
the boundary film

(B) GRAPHIC REPRESENTATION OF

LUBRICANT FILM THICKNESS IN


DIFFERENT LUBRICATION REGIMES

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY

4R0H

+ P2S5

.^'
(R0)2P,

215

+ H2S

SH
DialkyI Dtttiiophosphoric
Acid

2 (RO)2P.

.^'

(R0)2P\ .

ZnO

SH
DiaikyI Dithjophosphoric
Acid
Activated
Olefin

Zn

H2O

Zinc DialkyI
Dithioptiosphate

2 CH2=CH<
OR

i^l<

2 (ROhP,

Zn
J2

5 Cn2 CH2

Zinc Diaryl
Oithiophosptiate

C.

OR
DialkyI Ditliiophosphate
Ester
THERMAL STABILITY:

Aryl > Primary Alkyl > Secondary Alkyl


ANTIWEAR ACTION:
Secondary Alkyl > Primary Alkyl > Aryl
FIG. 23Syntiiesis of dialkyi dithiophosphoric acid derivatives.

The film-formation by these additives is a two-step process.


The adsorption of the chemical onto the metal surface occurs
first. It is followed by the formation of chemically reactive
species due to thermal decomposition or hydrolysis.
Antiwear AgentsZinc salts of dithiophosphoric acids are the
most widely used antiwear agents. These salts, in addition to
providing antiwear protection, act as oxidation and corrosion inhibitors. They find major use in gasoline and diesel engine oils and industrial lubricants.
Zinc dialkyi dithiophosphates or zinc diaryl dithiophosphates cire S3aithesized by reacting the respective dithiophosphoric acids with zinc oxide. The dithiophosphoric acid
derivatives that do not produce ash on combustion (ashless)
can be prepared by reacting the dithiophosphoric acids with
alkylene oxides, such as ethylene oxide or propylene oxide, or
with materials that contain activated double bonds, such as
cilkyl acrylates and methacrylates. The synthetic scheme to
prepare these materials is shown in Fig. 23. Dithiophosphoric acids are products of reaction of an alcohol or a phenol
with phosphorus pentasulfide.
Thermal and hydrolytic stability of these products depends
upon the nature of the organic group. Dialkyi dithiophosphates derived from primary alcohols are more thermally stable than those derived from secondary alcohols, and are used
extensively in formulating gasoline and automotive diesel engine oils. Diaryl dithiophosphates, although thermally the
most stable in this family, are hydrolytically the least stable
and, with some exceptions, are not very effective antiwear
agents. Therefore, they do not get much use.

Dithiophosphoric acid derivatives decompose, generally


below 200C, to form thiols, olefins, polymeric alkyl thiophosphates, and hydrogen sulfide [28,29]. The antiwear performance of these derivatives depends upon their thermal
stability, which in turn depends upon whether the alkyl
groups are primary or secondary. Primary dialkyi dithiophosphates decompose via an alkyl transfer mechanism to
form zinc monoalkyl dithiophosphate and an alkyl thiophosphate ester. Through a series of steps, these materials are
converted into zinc phosphate and trialkyl tetrathiophosphate, along with a variety of other products [28]. Trialkyl
tetrathiophosphate appears to be the major thermal decomposition product, as shown by ^'P nuclear magnetic resonance (NMR) spectroscopy.
Secondary alkyl zinc dithiophosphates lose an olefin via ;8elimination to form a product with free dithiophosphoric
acid functionality. This product can further decompose by
the loss of hydrogen sulfide or another olefin to form a
thioanhydride and a variety of other products. Trialkyl
tetrathiophosphate is again the major product. The aromatic
zinc dithiophosphates are believed to decompose by a free
radical mechanism to phenol and a number of phosphorus
and sulfur-containing products. Besides the thermal mechanism described above, these additives can also decompose
oxidatively to form products that are potent oxidation inhibitors. The details of their oxidation-inhibiting properties
were discussed in the oxidation inhibitors section and the oxidation chapter of this manusil. It is important to note that
the oxidation inhibiting action of these additives is indepen-

216

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

dent of the nature of the alkyl group, but their antiwear action is not. Aliphatic zinc dialkyl dithiophosphates have better antiwear performance t h a n a r o m a t i c derivatives. And
among ahphatics, the secondary alcohol derived are better
than those that are primary alcohol derived.
Extreme Pressure Agents^Alkyl and aryl disulfides and polysulfides, dithiocarbamates, chlorinated hydrocarbons, dialkyl hydrogen phosphites, a n d salts of alkyl p h o s p h o r i c
acids are the c o m m o n extreme pressure (EP) agents.
Polysulfides are synthesized from olefins either by reacting
with sulfur or sulfur halides, followed by dehydrohalogenation. Sulfurization of olefins with elemental sulfur, or sulfur
and hydrogen sulfide, yields organic sulfides and polysulfides
[28,30]. Dialkyldithiocarbamates are prepared either by neutralizing dithiocarbamic acid (resulting from the low-temperature reaction of a dialkylamine and carbon disulfide)
with bases, such as zinc oxide or antimony oxide, or by its addition to activated olefins, such as alkyl acrylates [31]. The
synthesis of these materials is described in Fig. 24 and Fig.
25, respectively.
Alkyl and aryl phosphites are obtained by reacting an alcohol or a phenol with phosphorus trichloride or by a transesterification reaction [32]. Alcohols a n d phenols react with
phosphorus pentoxide to yield a mixture of an alkyl (aryl)
phosphoric acid and a dialkyl (diaryl) phosphoric acid [33].
These acids, when treated with bases, form salts. Alkyl phosphates can also be prepared by the oxidation of phosphites.
The preparation of eJkyl phosphites is outlined in Fig. 26 a n d
of alkyl phosphates is outlined in Fig. 27.
The extent of EP protection in equipment depends upon
the conjunction temperature of the two metal surfaces in
contact [34]. Figure 28 shows a direct correlation between
the conjunction temperature and the degree of EP protection
needed. The equipment that operates at low speeds and high
loads generally requires more EP protection than equipment
that operates at high speeds and low loads. This is because

the former generates higher temperatures as a consequence


of the increased friction.
Disulfides and polysulfides decompose o n metal surfaces
at t e m p e r a t u r e s above 200C to form a protective sulfide
layer. The thickness of this layer depends on the quantity and
the lability of sulfur in the additive. Sulfurized fatty oils and
sulfurized olefins are the most commonly used products in
this class.
Chlorine-containing compounds provide protection under
boundary lubrication conditions, via the formation of a metal
chloride film. A detrimental aspect of chlorine-based E P
agents is the formation of hydrogen chloride in the presence
of moisture, which can cause severe corrosion problems.
Chlorinated paraffins with 40-70% chlorine by weight were
once popular. However, environmental concerns about the
negative effects of chlorine are limiting the use of these additives.
Phosphorus c o m p o u n d s react with the metal surface to
make a metal phosphite or a metal phosphate protective film.
Such a film forms at a m u c h higher temperature than that
formed by sulfur EP agents. Tricresyl phosphate is the bestknown phosphorus EP agent. Dialkyl hydrogen phosphites
[35] and phosphonic and phosphoric acid salts are other examples of such EP agents.
As mentioned earlier, the EP mechanism can be considered a two-step process. The first step involves adsorption of
the EP agent onto the metal surface and the second step involves its chemical reaction with metal to form the EP film.
After being adsorbed on the surface, these materials thermally decompose to reactive m e r c a p t a n s or p h o s p h o r u s
compounds that form the EP film. Probable mechanisms by
which zinc dialkyl dithiophosphates form EP films is depicted in Fig. 29. Organic halides, often not used in m o d e m
formulations because of the environmental concerns, form
an iron halide protective film, by reacting with the metal surface via a similar mechanism [36]. Organic polysulfides are

RCHaCH=CH2
Olefin

Sg

I
Heat
RCH=CHCHa

RCH=CHCHz

RCHz

Sx

I
+

Sa

I
R-CH2-CH-CH3

RCH2CHCH2

RCH
Organic Poiysutfides
+
R

Dithiolethione
FIG. 24Olefin sulfurization.

RCH2CHCH3

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY

RjNH

RzN ct

CSj

Oialkylamine

217

SH

Carbon
Disulfide

Ditliiocarbamic
Acid

lUletai Oxide
or IHydroxidey

CH2=CHCOOR

Activated
Olefin

//

M = Zn or Sb
X = 2 or 3

R2N C '

R2NC

SCH2CH5-COOR
Metal Dithiocarbamate

Dithiocarbamate Ester

FIG. 25Synthesis of dithiocarbamic acid derivatives.

PCI,

3 HCI

Triaryl Phosphite

.^
(R0)2P.

PCI3

3 ROH
Alcohol

{PhO)3P

2 H C I + RCI

DialkyI Hydrogen
Phosphite

2 ROH

H2O

^
(R0)2P.

DialkyI Hydrogen
Phosphite

Triphenyl
Phosphite

(CH30)2P^

2 ROH

H
Dimethyl Hydrogen
Phosphite

(RO)2p^

3PhOH
Phenol

2CH3OH

Diallcyl Hydrogen
Phosphite

Methanol

FIG. 26Synthesis of alkyl and aryl phosphites.

converted into dicJkyl disulfide, which reacts with the metal


to form the metcJ sulfide EP film [37,38].
These inorganic films, which are only a few molecules
thick, have low shear strength and are removed during the
movement of the surfaces in contact. This situation is represented in Fig. 30. Removal of the EP film can expose fresh
metal, and the film-forming process is repeated. Each time
the film is removed, the metal is removed with it. One way of
looking at the process of EP protection is the controlled wear
of rough surfaces, as shown in Fig. 31.
In general, formulators use different tjrpes of EP agents in
combination because of the possible synergism [36,39]. The
synergism between sulfur and chlorine-containing EP agents
is shown in Fig. 32, where average scar diameter is plotted as

a function of the applied load [36]. When only disulfide is


used, weld occurs at a load of 250 kg, and the scar diameter
is about 2.15 mm (Graph A). When a similar level of alkyl
chloride is used, the weld load stays the same but the scar diameter improves to 1.74 mm (Graph B). Combining the two
types of EP agents to deliver an amount equal to that in the
previous cases increases the weld load to 350 kg and decreases the scar diameter to 1.6 mm (Graph C), thereby indicating a synergism between the two chemistries. A further increase in the amount of disulfide and chloride shows weld
resistance beyond the load of 500 kg (Graph D). Similar sjoiergism exists between phosphorus and sulfur chemistries
[39]. The formation of active new compounds may be responsible for the synergism.

218

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

3R0H
Alcohol

P2O5

II
ROPOH +

Phosphorus
Pentoxide

OR

II
ROPOH
I
OH

DialkyI and MonoalkyI


Phosphoric Acids

R'NHa

Metai Base

/
Metal Salts

Amine Salts

P=0
Triaryl Phosphite

Triaryi Phosphate

FIG. 27Synthesis of alkyl and aryl phosphates.


40C-

Many effective extreme pressure and antiwear additives


are corrosive to metals. Therefore, lubricants using them are
typically formulated to optimize a balance between corrosivity and extreme-pressure and antiwear protection.

O
S^35fl|

52
3
(B
a> 30C
Q.

ffi
I-

I 25q

lilHPI^a

u
c
5*200

o
u

[ZESSIS
15a-

FIG. 28Extreme pressure (EP) protection requirements vs


conjunction temperature.

Some additives in a formulation can diminish the effectiveness of EP/AW agents. These include surface-active additives,
such as certain friction modifiers, oxidation inhibitors, rust
inhibitors, metal deactivators, detergents, and dispersants.
These components either irreversibly adsorb on the surface
and interfere with the EP mechanism, or they form complexes
with EP agents, thereby rendering them inactive [40,41]. The
same is true of some highly polar basestocks. This type of antagonism is quite common for some lubricants, such as gear
oils, where EP agents form the core of the formulation.
Antiseize additives are a separate class of antiwear additives, which perform independently of temperature. They improve boundary lubrication by forming the protective film
through deposition. Molybdenum disulfide and graphite,
common additives of this type, are generally used in greases,
some industrial oils, and various break-in lubricants.

Rust and Corrosion Inhibitors


Corrosion is a general term used to describe the destructive
alteration of metal by chemical or electrochemical action of
its environment. It primarily involves a heterogeneous reaction, which causes a metal to change from its nascent form
(metallic state) to an oxidized form (ionic state). All metals
except noble metals are thermodynamically unstable under
atmospheric conditions and get converted into their oxidized
form. On the other hand, noble metals, such as gold, platinum, iridium, and palladium, are resistant to attack by the
environment and are therefore found in nature in the free
form.
There are many types of corrosion, but a lubricant supplier
is primarily concerned with corrosion in the presence of electrolytes (electrochemical corrosion) and in the absence of
electrolytes (chemical corrosion). Common electrolytes that
lead to electrochemical corrosion include water, acids, alkalis, and salts. Chemical substances that cause chemical corrosion include acids, alkalis, and sulfur. In alloys, corrosion
can be selective or nonselective. It is selective if a particular
metal is corroded in preference to others. It is nonselective if
all metals in the alloy are corroded at the same rate.
Electrochemical corrosion involves the reaction of metals
in the presence of electrically conducting solutions, or electrolytes, and occurs in two stages: the anodic process and the
cathodic process. In the anodic process, metal goes into solution as ions with extra electrons left over. The process can
be considered an oxidation. The cathodic process involves
the reaction of thus generated electrons with water and oxygen to form the hydroxide ions. The process can be considered a reduction. In solution, metal ions combine with hydroxide ions to form metal hydroxides, or hydrated oxides.

RO.

RO

K
RO.

FeO Fe
OFe Fe
FeO Fe
OFe Fe
fFeO Fe
sii OFe Fe
FeO Fe
OFe Fe
FeO Fe
\^''''' OFe Fe
FeO Fe

S>>ii

RS

-Olefin

OR
I
S=PSZrw
I
O

EP Film
containing
Sulfur and
Phosphorus
Compounds

K
s=psziw-X
Fe

Fe
or
Fe203

RO

POLYMER

Adsorption

Fe

or
Fe203

Reaction

FIG. 29The mechanism of boundary film formation by zinc dialkyi dithiophosphates.

FIG. 30Protective boundary film vs shear.

Original Profile

Worn Profile
FIG. 31Controlled wear of asperities to produce submicron
debris.

200

300

Applied Load (l<g)


A 9.1% Di-t-Octyl Disulfide
B 8.52% t-Octyi Chloride
C 4.55% Di-t-Octyi Disulfide + 4.36% t-Octyi Chloride
D 9.1% Di-t-Octyl Disulfide + 8.52% t-Octyl Chloride

FIG. 32Wear - load diagram, the ASTM procedure, showing


synergism between chlorine and sulfur extreme pressure (EP)
agents.

220

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

The rate of electrochemical corrosion depends upon the nature of the metal oxide film, the presence or absence of a polar solvent such as water, the presence or absence of an electrolyte (salts, acids, or bases), and the temperature.
Chemical corrosion, on the other hand, does not need an
electrolyte and can occur both in aqueous and organic media.
It involves the attack of corrosive species, such as acids,
bases, and sulfur, on metals. The damage occurs when the resulting compounds are removed.
Factors that affect corrosion include internal factors and
external factors [42]. Internal factors are directly related to
the metal itself, and include its composition, structure, surface condition, oxidation potential, a n d the presence of
stresses. External factors pertain to the environment and include the nature of the oxide film, acidity, alkalinity, the presence of electrolytes, the presence and reactivity of the aggressive species, and the temperature. While the role of these
factors is considered elsewhere [42], we are especially interested in the oxidation potential of various metals.
Oxidation potentials of the elements that make u p the metallurgy of m o d e m mechanical equipment are provided in Fig.
33. The elements that are primarily used to fabricate metal
parts are shown by bold italic symbols. The potentials reported in the table are relative to hydrogen with a value equal
to 0. Positive values indicate ease of oxidation and negative
values indicate resistance to oxidation. Because of hydrogen
being the reference point, we can directly compare these values to assess the relative oxidative tendency of various metals. The higher the oxidation potential, the easier it is for the
metal to oxidize. Metals in the left column of the table with
smaller values are therefore less susceptible to oxidation, and
corrosion, than those in the right column. The values with
slash indicate a metal's first and second oxidation potentials.
For example, for iron, 0.44 represents the oxidation potential
of the Fe to Fe"^^ transition and 0.04 represents the oxidation
potential of the Fe to Fe^^ transition. The same is true for
copper. Of the metals of interest, aluminum is the easiest to
oxidize, followed by iron and lead. Copper with negative values is the most resistant of the metals listed in the table.
Of the external factors listed above, acidity, alkalinity, the
presence of the reactive species, and the temperature have
the largest impact. The presence of acids and bases can accelerate corrosion. In lubricant applications, acids result

from the oxidation of the fuel sulfur and the basestock. Lubricant contains additive derived bases, both organic and inorganic, which are usually weak a n d therefore pose little
problem by themselves. However, the reaction between the
acidic and the basic species results in salts, which can promote corrosion because they are electrolytes. The lubricant
also contains additives that can lead to acidic decomposition
products. Some of these additives are sulfur and phosphorus
compounds that are added to the lubricant to improve its oxidative stability and antiwear performance. These can corrode metals either directly or by forming aggressive chemical
species via decomposition. Higher temperatures, which are
typically encountered in the internal combustion engines,
can accelerate corrosion as well.
Metallurgy in automotive equipment commonly contains
iron (Fe), copper (Cu), lead (Pb), chromium (Cr), manganese
(Mn), antimony (Sb), a l u m i n u m (Al), vanadium (V), zinc
(Zn), nickel (Ni), and tin (Sn). Protecting four of these elements against corrosion is of primary interest: iron, which is
the principal metal used to forge the engine and the auxiliary
equipment; copper, which is present in bearings and seals;
lead, which is also present in bearings; and aluminum that is
used in newer cars and trucks to make them lighter for better
fuel economy.
Protection against corrosion is necessary because it can
lead to a loss of metal thereby lowering the integrity of the
equipment and resulting in its malfunction. In addition, corrosion exposes fresh metal that can wear at an accelerated
rate and result in metal ions that can act as oxidation promoters.
Corrosion of iron and its alloys, sometimes referred to as
ferrous corrosion or rust, is primarily electrochemical in nature. It can occur b o t h in liquid and vapor phase and needs
water, electrolyte, and oxygen. In an internal combustion engine, water results from fuel combustion, oxygen comes from
the air, and electrol3?tes are metal salts that form by the reaction of metals and certain additives with combustion and oxidation acids. This type of corrosion mainly occurs in engines
that are run in short cycles (stop-and-go driving). Rust initiates when water sets u p a localized electrochemical reaction
between the surface iron and the iron oxide layer. Nascent
iron acts as the anode, and the iron oxide layer acts as the cathode. Iron emits electrons and forms ferrous ions that are re-

Electrode Reaction
M

Metal

M"* +

Lithium = Eo of +3.05
Hydrogen = Eg of 0.00

nQ

Eo Volts

Metal

Eo Volts

Lead(Pb)

0.13

Zinc (Zn)

Tin (Sn)

0.14

Chromium (Cr)

0.86/0.74

0.25

Manganese (Mn)

1.18/0.283

Nickel (Ni)
Iron (Fe)
Copper (Cu)

0.76

0.44/0.04

Vanadium (V)

1.18

-0.S2l-O.34

Aluminum (Al)

1.66

FIG. 33Oxidation potentials of common metals found In steel.

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY


leased into the medium. The electrons migrate to the cathode
(oxide layer) and form hydroxide ions by reacting with oxygen
and water. Ferrous ions and hydroxide ions then combine to
form ferrous hydroxide, which is subsequently oxidized to ferric hydroxide, loses water, and becomes rust [12]. The mechanism of rust formation is depicted in Fig. 34, Part A.
Corrosion of copper and bronze, or yellow metal corrosion,
is chemical in nature and occurs due to the attack of aggressive species on metals. Such species result from the oxidation
and the combustion of hydrocarbon materials such as fuel,
base oil, and sulfur-containing additives. Yellow metal corrosion results when chemically reactive materials such as acids,
bases, or sulfur, attack copper or copper oxide. The result
is the formation of ionic copper compounds that are removed, thereby causing metal damage. This is shown in Fig.
35, Part A.
Lead corrosion involves a preferential removal of lead from
copper-lead beeirings, sometimes referred to as lead-leaching,
and primarily occurs in diesel engines. While its mechanism
is not well understood, it may partly be due to the attack of
chemically aggressive species on metal. Certain classes of additives, such as dispersants, appear to aggravate the situation. Aluminum corrosion is very slow because the aluminum
oxide film is tenacious and is not easy to remove.
For protection, corrosion-inhibiting additives are used.
These additives are of two types: acid-neutralizers and filmformers. The acid neutralizing agents are additives that neutralize aggressive acidic materieds and make them innocuous.
Film-formers attach themselves to metal surfaces to form an
impenetrable protective film [12]. Film formation can occur
via physical adsorption or chemical adsorption. In the first
case, the resulting film is of a somewhat transient nature. In
the second case, however, it is more persistent. Film formation occurs when these additives interact with the metal surface via their polsir ends and associate with the lubricant via
their non-polar ends, in a manner similar to that of the friction modifiers. Since these additives have high surface affinity, they can compete with extreme-pressure and antiwear
agents and impede their function. The rust-inhibiting mechanism and the corrosion-inhibiting mechanism via film-formation are shown in Parts B of Figs. 34 and 35, respectively.
Figure 36 depicts the probable nature of the copper corrosion-inhibiting film. Part A shows copper inhibition by a
commercially available dimercaptothiadiazole (DMTD)
derivative and part B shows inhibition by tolyltriazole, another commercial product. In the former case, it is the lubricant associated with the hydrocarbon chain that acts as a
protective film and in the latter case, it is the adsorbed additive that primarily acts as a protective film [12].
Chemical types used to inhibit corrosion of ferrous metals
include polyethoxylated alkylphenols, neutral and basic sulfonates, alkenylsuccinic acids, alkyl phosphites and phosphates, alkanolamines, and polymeric amines. Those used to
inhibit yellow metal corrosion mainly include oil-soluble heterocyclic compounds such as triazoles and dimercaptothiadiazole (DMTD) derivatives. For lead corrosion, no effective
inhibitors are known. The only way to control lead-leaching
appears to be through proper balancing of the additive package.
Structures of the common corrosion inhibitors are shown
in Fig. 37. Long chain organic molecules, such as alka-

221

PROBLEM
>- Lubricant

Part A
Rust

Cathodic Reaction (C)


O2 + 2H20 + 4e

^ 40H"

Anodic Reaction (A)


Fe

Fe^* + 2e

SOLUTION
y Lubricant

Parte
Protective
Layer

Iron
' Metal

FIG. 34The mechanism of rust Inhibition.

PROBLEM

S S S S
S S S S S

ss s s
sss s

Corrosive
Materials

>- Lubricant

Part A

mmxm

'^^^^^^'^^^^^^^^^'^i^^'^^^^^^'^^^i^ Copper Oxide

SOLUTION

s s s s
SSSSS

Corrosive
Materials

^^ s
^SSs

Parte
Deactivator
Film

s '^ss <. , s ^ \

. Copper
Metal

Ss s s
sss s

^s^

"* Lubricant

^ ^ ^ i * ^ ^ ^ ^ - ^ ^ " ^ ^ ' ^ ^ ' ^ ^ * ^ ^ ^ ^ ^ ^ ' ^ - ^ ' ^ ^ ^ ^ ^ Copper Oxide

www^

. Copper
Metal

FIG. 35The mechanism of copper deactivation.

nolamines, cire examples of physical adsorbers. Phosphoric


acid, dithiophosphoric acid, and succinic acid derivatives are
examples of chemical film-formers. Basic detergents are excellent rust and corrosion inhibitors since they provide protection both by neutralizing acids and by forming physically-

N-N
>-Lubricant

"SSR
Cu O Cu O Cu O Cu O Cu O Cu OCu O Cu O Cu O Cu O Cu O Cu
O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O
Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu
O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O

Oxide
l^yer

(a)

vProtective
'^Film
Nc. JJ-R

KyN-fl

N>yN-R

KyN-R

1
<
~Cu 0"Cu 0"Cu b'Cu <5 Cu'd Cii'dCu O'Cu'CJCu O Cu D Cii O Cu"
O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O
Oxide
Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu
L^yer
O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O

(b)
FiG. 36Copper passivators and mode of thieir action.

LCT^I

^^\.0(CH2CH20)xCH2CH20H

Ca

Polyethoxyiated Ptienol

Neutral Calcium Sulfonate

Lpr-]

II

RCH C - O H
CHCOH

Ca. xCaCOs
2

II

Basic Calcium Sulfonate

Alltenylsuccinic Acid

II

) - - P - O H . R'N

.CH2CH2OH

RN

Aiitylammonlum
Phosphates

OR
\H2CH2OH

R O P - O H . R'NHa^

Diethanolamine

OH

RSS^^^S
\\
//
N-N

SSR

RS

SH
N
N-N

Dimercaptothiadiazole Derivatives
FIG. 37Corrosion iniiibitors.

X
Alicylbenzotriazole

CHAPTER
adsorbed films. For many applications such as gear oils, rust,
and corrosion, inhibitor systems are required to provide both
vapor-phase and liquid-phase protection, i.e., for surfaces
above and below the lubricant level.
Corrosion inhibitors have major uses in engine oils, gear
oils, metalworking fluids, and greases. Thiadiazole and triazole derivatives are especially useful in protecting against
nonferrous or yellow metal corrosion.
Metal corrosion is measured by a variety of tests, depending upon the application. For GF-2 and API SH and SJ quality oils, CRC L-38 Test (copper/lead), the ASTM Sequence
IID Rust Test (ASTM D 5844), and Cummins Bench Corrosion Test (copper/lead/tin) are used. For GF-3 and API SL
quality oils, ASTM Sequence VIII (unleaded L-38 Test;
ASTM D 6709) and Ball Rust Test (ASTM D 6557) are used.
For gear oils, CRC L-13, L-21, and L-33 Tests are used for
rust and the ASTM D 130 Test is used for copper. For industrial products, the ASTM D 665 Test is used for rust and
the ASTM D 130 Test is used for copper. For hydraulic and
metalworking fluids, a n u m b e r of ASTM specified tests are
utilized [3].
Polymeric Additives
Materials with polymeric structures are the key components
in high-performance lubricants. They can be used as lubricant basestocks (see synthetic lubricants) or to enhance a lubricant's inherent properties, such as viscosity and p o u r
point. They can also be used as starting materials to prepare
certain classes of additives, such as dispersants and detergents. The materials used for this p u r p o s e are m o r e oligomeric than polymeric, i.e., their molecular weight is relatively lower. Polymeric additives used in lubricants comprise
viscosity modifiers, p o u r point depressants, emulsifiers and
demulsifiers, and foam inhibitors.
Most polymeric materials are compositions that consist of
polymer chains of varying sizes. The bulk properties of these
compositions depend upon the average molecular weight of
the polymer chains. The molecular weights of poljoneric materials are expressed as n u m b e r average, weight average,
z-average, (z-l-1) average, and viscosity average molecular
weights [43,44]. Of these, number-average (Mn), weight-average (Mw), and z-average (Mz) molecular weights are most
often used to describe polymer compositions. The numberaverage molecular weight (Mn) represents chemical stoichiometry cind is useful in carrying out chemical reactions involving polymers. The weight-average molecular weight
(Mw) cortelates with mechanical properties, such as tensile
strength and modulus in plastics, films, and fibers, and the
viscosity-improving behavior of the polymers. The z-average
molecular weight (Mz) largely influences the polymer's viscoelastic properties, such as melt elasticity. While average
molecular weight information is important, it is the molecular weight distribution that is more useful in understanding
the polymer properties. The molecular weight distribution is
m e a s u r e d by polydispersity
index or heterogeneity
index,
which is the ratio of the weight-average molecular weight to
the number-average molecular weight, or Mw/Mn. For
monodisperse polymers, which contain molecules of essentially the same chain length, the value of this index is close to
1. For polydisperse samples, it is greater than 1 because of

9: ADDITIVES

AND ADDITIVE

CHEMISTRY

223

the greater contribution of the higher molecular weight fractions in the molecular weight-determining process.
The polydispersity index is a function of the polymerization
method. It is closer to 1 for polymers derived from anionic
polymerization, 1.5-2.0 for polymers derived from step
growth polymerization, between 2 and 5 for polymers derived from radical polymerization, and above 5 for polymers
derived from polymerization using coordination catalysts.
Viscosity

Modifiers

Mineral oils, which are effective lubricants at low temperatures, become less effective at high temperatures. At these
t e m p e r a t u r e s , their film-forming ability (in the hydrodynamic lubrication regime) diminishes due to a drop in viscosity. Prior to the use of viscosity modifiers, this problem
was partly overcome through seasonal oil changes. In winter,
low-viscosity oils were used and in s u m m e r high-viscosity
oils were used. The invention of viscosity modifiers led to the
introduction of multigrade oils thereby relieving the owner
from seasonal oil changes.
The principal function of a viscosity modifier is to minimize viscosity variations with temperature. Previously, viscosity index was used as a measure of an oil's response to
temperature changes. Viscosity index (VI), which is derived
from the viscosity of the oil at 40C and 100C, is no longer
meaningful. This is because most m o d e m equipment operates at extreme temperatures ( - 4 0 to +150). At these temperatures, the viscosities do not conform to those predicted
by the viscosity index [4b,45].
Viscosity modifiers are polymers with average molecular
weights of 10000 to 150000; but those with molecular
weights between 10000 and 20000 are used most often. These
chemicals are added to low-viscosity oils to improve their
high-temperature lubricating characteristics. Viscosity modifiers minimize viscosity change with a change in temperature. This is a practical m e a n s of extending the operating
range of mineral oils to higher temperatures, without adversely affecting their low-temperature fluidity.
Viscosity modifiers cause an increase in oil's viscosity at cJl
temperatures, except that thickening at lower temperatures
is less than that at higher temperatures. At low temperatures,
the polymer molecules occupy a small volume and therefore
have a m i n i m u m association with the bulk oil, or a small hydrodynamic volume. Hydrodynamic volume is the volume of
the polymer and the associated oil. The effect is a marginal
viscosity increase. At high temperatures, however, the situation is reversed because the polymer chains extend or expand
as a consequence of the added thermal energy. This increases
polymer's association with the bulk oil due to an increase in
its surface area [7]. The result is an effective increase in viscosity. Another way to describe this phenomenon is that at
higher t e m p e r a t u r e s the polymer becomes more soluble,
thereby causing viscosity to increase. The effect of a polymer
on the viscosity-temperature (VT) properties of an oil is depicted in Fig. 38. Note that the VT line for the viscosity-modified oil has a lower (shallower) slope than that for the base
oil, thereby indicating a lower drop in viscosity with increasing temperature. Figure 39 illustrates the mechanism of oilthickening by viscosity modifiers.
Variable thickening of oil by viscosity modifiers at low and
high temperatures allows the formulation of mutigrade oils.

224 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

The multigrade oils are designed to provide adequate viscosity at high temperatures for engine protection and low viscosity at low temperatures for easy startability. Figure 40 shows
the VT characteristics of single grade and multigrade oils.
It is technically inaccurate to assess low-temperature viscosities of the Vl-improved oils by linearly extrapolating the
VI (or VT) curves based on 40 and 100C viscosities. This is
because such oils can show an inflection at low temperatures
thereby leading to erroneous viscosity estimates [4a]. The
low-temperature viscosities of the Vl-improved oils should be
determined experimentally. It is also important to note that
superior viscosity-temperature relationship of the multigrade
oils, as expressed by the viscosity index, is not solely due to a
greater preferential swelling of the polymer at higher temperatures. The use of low-viscosity oils with good viscositytemperature behavior to prepare these oils makes a substantial contribution towards the overall effect [46]. In addition
to affecting the VT relationship, viscosity modifiers affect a
lubricant's other properties. These include pour point, dis-

Viscosity-modified Oil

Base Oil

Temperature
FIG. 38The effect of viscosity modifier on VT relationship
of an oil.

persancy, fuel economy, and, indirectly, the extreme pressure


performance.
Commercially available viscosity modifiers belong to two
general classes: olefin-based polymers and ester polymers.
The olefin-based polymers include polyisobutylenes (PIBs),
olefin copolymers (OCPs), and hydrogenated styrene-diene
(STDs) polymers. OCPs from ethylene-propylene mixtures
are called EPRs and those from ethylene-propylene-diene
mixtures are called EPDMs. Ester polymers include polymethacrylates (PMAs) and styrene ester polymers (SEs).
Viscosity modifiers find major use in multigrade engine
oils and gear oils, transmission fluids, power steering fluids,
greases, and some hydraulic fluids. Olefin copolymers are of
the most popular type, followed by polymethacrylates,
styrene-diene polymers, and styrene-ester polymers. OCPs,
EPRs, and EPDMs find extensive use in engine lubricants.
Olefin-based

Polymers

These include polyisobutylenes, butyl rubbers, and olefin


copolymers. Polyisobutylenes (PIBs) and butyl rubbers are
both isobutylene-derived, except that PIBs are of somewhat
lower molecular weight than butyl rubbers. Unlike PIBs that
are derived from pure isobutylene, butyl rubbers Eire made
from isobutylene containing 3-8% diene in the monomer
mixture. Both types are manufactured by Lewis acid-catalyzed polymerization.
Olefin copolymers (OCPs) are block polymers with rubberlike properties. They are prepared from olefin mixtures by
vanadium-based Ziegler-Natta catalysis. In ethylene-propylene polymers (EPRs and EPDMs), the ethylene to propylene
ratio and their proper distribution in the backbone are critical to the polymer's low-temperature properties. OCPs are inferior to polymethacrylates in this regard and generally require pour point depressants to improve the low-temperature
performance of lubricants containing them. These polymers
find wide use in passenger Ccir motor oils and diesel engine lubricants. Alpha-olefin copolymers, the lower molecular
weight analogues of OCPs, are prepared by polymerizing aolefins in the presence of a Lewis acid. These polymers find
use in lubricants, such as power steering pump lubricants and
gear oils, which require enhanced shear stability. The PIBs of
2000 to 3000 molecular weight are used as viscosity modifiers
in gear lubricants, hydraulic fluids, and industrial oils.

Effective Volume in Oil Flow s Volume of Polymer Molecule +


(Hydrodynamic Volume)
Volume of Associated Oil
Polymer
Molecule

Oil Associated
with Polymer
Poor-4^
Low ' ^

SOLUBILITY
TEMPERATURE

Good
High

FIG. 39The mechanism of oil thickening by viscosity modifiers.

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY

SAE30

SAE 10W-30

-20
0
20
Temperature (C)-

120

FIG. 40Viscosity-temperature characteristics of single


grade and multigrade oils.

Styrene-diene polymers (STDs) can be of the diblock or random-block type and are produced by anionic polymerization
of stjrene and butadiene or isoprene. This type of poljrmerization produces polymers with a narrower molecular weight
distribution than those obtained by the use of Ziegler-Natta
and Friedel-Crafts catalysts or the free radical initiators. That
is, their Mw/Mn is closer to 1. Because of the narrow molecular weight distribution, these polymers possess the best thickening power of the types discussed so far. However, the presence of the aromatic rings and the double bonds makes these
polymers more susceptible to oxidation. This problem is
somewhat overcome by catalytically hydrogenating the double bonds. Figure 41 schematically presents the synthesis of
these types of polymers. Recently, a different type of polymer,
labeled a "star" polymer, also called radial isoprene, has become commercially available. It has thickening power similar
to that of the styrene-diene type, but has better shear stability.
A clustered polyanion prepared from divinylbenzene and
styrene forms the center of the star, and the rays are made up
of the polymerized diene monomer units. Commercial olefinbased polymers include Exxon's Paratone series, Texaco's
TLA products, and Shell's Shell Vis polymers.
Ester Polymers
These include polymethacrylates and styrene-ester polymers.
Polymethacrylates (PMAs) are produced by free radical polymerization of alkyl methacrylate. Since free radical polymerization produces polymers with relatively broad molecular
weight distribution, such polymers have low thickening efficiency. Because of this, polymethacrylates have only moderate viscosity-improving ability. However, the alkyl group in
the ester portion of the polymer can be altered to obtain products that have the best oil solubility and optimum viscosityimproving properties. In addition, these polymers have good

225

compatibility with a large number of refined and synthetic


basestocks and eire superior to olefin copolymers both in oxidative and thermal stability and in low-temperature properties. Because of these attributes, PMAs find extensive use in a
number of lubricants. Such lubricants include automotive engine oils, gear oils, automatic transmission fluids, hydraulic
fluids, industrial oils, and greases.
Styrene-ester polymers are prepared by first copolymerizing styrene and maleic anhydride and then esterifying the intermediate alternating copolymer using a mixture of alcohols. Normally, the esterification step is taken to about 90%
or more, followed by post neutralization using a bifunctional
or polyfunctional amine. Because of the presence of the basic
nitrogen, these polymers function both as a dispersant and as
a viscosity modifier.
Figure 42 summarizes the methods of synthesis for polyacrylate and styrene ester type viscosity modifiers. Commercially available ester polymers include Rohm and Haas's Acryloid series and Lubrizol's 3700 series products. Polymers
containing both OCP and ester based functionalities are also
available. These are made either via grafting of an ester on to
the OCP or by copolymeriztion of an alkyl acrylate and axi
olefin. Rohm GMBH's Viscoplex polymers belong to this class.
Thickening EfficiencyThickening efficiency and shear stability are the two most important considerations for selecting
a polymer for use as a viscosity modifier. Thickening efficiency is a direct function of a polymer's molecular weight.
More specifically, it is a function of the length of the pol5rmer
backbone. Basically, the longer the backbone, the greater the
thickening efficiency. On an equal weight basis, a high
molecular weight polymer provides higher viscosity than a
low molecular weight polymer, as long as structural features,
such as branching, are similar.
Since thickening efficiency of a polymer depends upon its
molecular weight, different polymers must therefore be compared on an equal molecular weight basis. For a given molecular weight, OCP has greater thickening power than styrenediene polymer, which in turn has greater thickening power
than polymethacrylate. The relationship between the polymer's molecular weight and the viscosity improving effect, or
thickening, is presented in Fig. 43.
Shear-Related Viscosity LossThe viscosity loss in a viscosity-modified lubricant can result from mechanical, thermal,
and oxidative degradation of the polymer. Unlike mineral
oils, which primarily exhibit Newtonian rheology, polymerthickened oils exhibit viscoelastic rheology. That is, their viscosity depends upon the degree of mechanical stress (shear).
When oils containing viscosity modifiers are subjected to
moderate shear stress, viscosity decreases until it approaches
the viscosity of the polymer-free oil. The mechanical or shear
viscosity loss is generally encountered in those equipment
parts that intermesh. Journal bearings, vane pumps, and gear
pumps are examples of such parts. The speed of the moving
surfaces also influences the shear rate and hence viscosity.
The viscosity loss of a lubricant is directly proportional to the
applied shear rate, as shown in Fig. 44. The higher the shear
rate, the greater the loss in viscosity. Piston rings experience
low shear rates; hence, the lubricant in this region experiences a low viscosity loss. Conversely, rod bearings cause
high shear; hence the lubricant in this region undergoes a
high viscosity loss. The viscosity loss in the regions of main

1. Polyolefin

'^3^N
C=CH2
H3C

CH3

Acid
-=SS.

-CH2-C
CH3 J n
Polyisobutylene

Isobutylene
2. Olefin Copolymer

CH3

Ziegler
m CH2=CH2

CH3CH=CH2

Ethylene

~f~ CH2
\


Natta cat.

Propylene

CH2'~i CHCH2'm

Ethylene Propylene Copolymer

3. Styrene-Diene Poilymers
CH3
-CHCH2-

CH=CH2

CHCH=CCH2-

CH,
+

n CH9CH

Styrene

Anionic
^1
Initiator

C-CHo

Isoprene

Styrene-dlene Polymer

FIG. 41Synthesis of olefln-based polymers.

CHa

CH3
Radical
Initiator

H2C=cCOOR
Alkyl Methacrylate

-CH,0I
COOR
Alkyl Methacrylate Polymer

He=CH2

-CH-CHjCHCHRadical
Initiator

Styrene

%
Maleic
Anhydride

'I

o^ "o" ^o

Styrene-maleic
anhydride Polymer

-CH-CH2CHCH0=C
I
NH

II

R'
1. ROH
/
2. H2NCH2(CH2)xNI

C=0
I
OR

R'

Styrene Ester Polymer


FIG. 42Synthesis of alkyl methacrylate and styrene ester polymers.

CHAPTER
bearings a n d cylinder walls that have intermediate shear
rates falls in between.
The viscosity loss can be temporary or permanent. If the
viscosity bounces back to the original viscosity when the
stress is removed, it is termed as temporary viscosity loss.
This t j ^ e of loss is due to the reversible deformation of the
polymer u n d e r the influence of shear forces, which minimizes the association between the polymer and the lubricant.
Temporary viscosity loss, shown in Fig. 45, is desired in lubricants because it decreases the viscous drag at low temperatures and therefore could contribute towards fuel economy
[47].
The viscosity loss is considered p e r m a n e n t if after the
shear forces are removed, the viscosity does not revert to its
prior value [47]. Permanent viscosity loss occurs when the
polymer in the viscosity-modified oil breaks down to the
lower molecular weight fragments u n d e r the influence of
shear [48]. This type of viscosity loss is not desired because a
formulated lubricant will not stay in its viscosity grade.
Whether temporary or p e r m a n e n t , viscosity loss depends
upon the shear stability of the polymeric viscosity modifier
used, which is a function of its molecular weight. More

9: ADDITIVES

AND ADDITIVE

nii-mf
X 100
mi-mo

m;

FIG. 43Thickening as a function


of molecular weight.

227

specifically, it is the function of the size of the polymer backbone. This relationship, which holds within a polymer type,
is shown in Fig. 46.
High molecular weight polymers generally lose viscosity at
a higher rate u n d e r shear than low molecular weight polymers. Hence, the lubricants thickened with low molecular
weight polymers are more likely to maintain their viscosity in
the desired viscosity range than the lubricants thickened with
high molecular weight polymers. Figures 47 and 48, respectively, depict the temporary and the permEinent viscosity loss
in oils containing viscosity modifiers of two different molecular weights [47]. As can be seen, in both cases the lower
molecular weight polymer experiences a lower viscosity loss.
The problem of viscosity loss due to shear can be alleviated
by pre-shearing the high molecular weight polymer prior to
blending, or by choosing a more shear-stable polymer. Shear
stability, which can be defined as the ability of a lubricant to
resist viscosity loss under the influence of shear, primarily relates to the permanent viscosity loss. Shear stability of a polym e r is inversely related to its molecular weight: the lower the
molecular weight, the higher the shear stability. The percent
loss of viscosity in polymer-thickened oils is expressed in
terms of their shear stability index, SSI, which can be represented as follows.
SSIr^

Molecular Weight -

CHEMISTRY

= Initial viscosity of lubricant with the viscosity modifier, cSt


mi = Final viscosity (viscosity after shear) of lubricant with
the viscosity modifier, cSt
rrio = Viscosity of the lubricant without the viscosity modifier, cSt
T
= Temperature in C at which the viscosities are measured
Shear stability requirements for different applications parallel the severity of the lubricating environment. Engine lubrication is mostly hydrodynamic in nature; hence, the lubri-

Shear Rate ^SZ.\


FIG. 44The effect of shear rate on viscosity in different parts of an engine.

228

MANUAL

3 7: FUELS

AND LUBRICANTS

HANDBOOK

cants of low shear stability are adequate. Gear lubrication, on


the other hand, is boundary in nature and therefore requires
lubricants of high shear stability. Transmission and hydraulic fluids fall in between the two in terms of these requirements. This is shown in Fig. 49.
The relationship between the polymer's molecular weight
and its viscosity-improving effect, and the relationship between the polymer's molecular weight and its shear stability
are presented in Fig. 50 [4]. Specific viscosity TJ^^/C can be
used as a measure of a polymer's molecular weight since the
solution viscosity of the polymer-thickened lubricant is directly related to the molecular weight of the polymer. Specific viscosity is the absolute viscosity of a liquid relative to
that of water at the same temperature. As depicted in the exhibit, both the polymer's viscosity-improving ability and the
shear sensitivity increase with an increase in its molecular
weight (an increase in the specific viscosity). Higher shear
sensitivity implies lower shear stability.

polymer molecules react with oxygen to form hydroperoxides


and peroxy radicals (see the oxidation inhibitor section).
These species can disproportionate to form a n u m b e r of lower
molecular weight oxygenated compounds. This type of degradation not only causes a loss in viscosity but the resulting polar compounds also form varnish and coke deposits, in a
manner similar to that of lubricants. The mechanism of oxidative degradation of pol5rmers is shown in Fig. 52.
If one compares various classes of polymers in terms of desirable properties, OCPs are the best with respect to treated
cost, but st5Tene-diene types (SB and SI polymers) are the
best with respect to overall performance. OCP-g-PMA is the
best choice if both the cost and the performance are considered, which is usually the case.
Dispersant

Viscosity

Modifiers

Dispersant polymers, or dispersant viscosity modifiers


(DVMs), are hydrocarbon polymers that have a dispersant
moiety attached to them. These materials are used as viscos-

A n u m b e r of tests are available to measure the viscosity improving properties and the shear stability of polymers in lubricants. The shear stability of a lubricant is measured by the
CRC L-38 Test, FZG Shear Test, Sonic Shear Test (ASTM D
2603), Orbahn Shear Test, Bosch Injector Test, and the Tapered Bearing Simulator Test (ASTM D 4683, D 4741, and D
6616). In terms of severity, the Tapered Bearing Test is the
most severe, followed by the FZG Test, Orbahn Test, and the
CRC L-38 Test.
Viscosity Loss Due to Polymer DegradationIn addition to mechanical breakdown (shear), polymers can undergo thermeJ
and oxidative degradation. Thermal degradation occurs when
the polymerization process is reversed under the influence of
heat. Polymers break down via chain scission to form lower
molecular-weight fragments. The consequence is a loss in viscosity. This type of degradation, which is more prevalent in
aromatic polymers due to their ability to form more stable allylic and benzylic radicals, is shown in Fig. 51. Oxidative
degradation occurs when weak carbon hydrogen bonds in the

Molecutar Weight

>

FIG. 46Shear stability as a function of polymer molecular weight.

Vjvelogt^
f ^ OH mm

^ ~ "

Polvmer-containina
Oil

N. [Temporary
\ w Shear Loss
^

Base
Oil

lU

102

10*

10

106
to*
Shear Rate,-=(3-1)

FIG. 45Temporary viscosity loss due to shear.

1 .

107

108

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY

'

\Mn=20,000
Mn=40,000\

2"

u
>

Base Oil
1

io3

^&^

io5
10^
Shear Rate (s-i)

io7

lo^

FIG. 47Temporary viscosity loss due to shear.

/
/

'

^=40,000

229

or 4-vinylpyridine, imparts dispersancy directly. Grafting of


maleic anhydride, on the other hand, leads to a substituted
succinic anhydride or succinic acid that must be reacted with
polyalkylene-polyamines to introduce a dispersant functionality. At present, no commercial products made in this manner appear to be on the market. Antioxidant functionality can
also be introduced in either of these two ways. Grafting is
common in the case of OCP and SD type polymers, but for
PMAs, copolymerization is more prevalent.
Commercially available DVMs have two distinct functionalities, a polymeric backbone (the VM portion) and a dispersant moiety. Thus, their physical, mechanical, and chemical
properties will depend upon both the inherent properties of
the VM portion of the molecule and the dispersant functionality. In addition, some properties will depend upon both
these functionalities, either due to synergism or antagonism.
The properties that relate to the VM portion of the molecule
are thickening efficiency, shear performance, thermal and
oxidative stability, and low temperature properties, and
those pertaining to the dispersant portion are oxidative and
chemical stability, and dispersancy. Considering the theorized mechanism of the dispersant action, it is reasonable to
assume that the dispersancy will relate to both the basicity
and the molecular weight of the DVMs. Based on thepKa values of the different functional groups, one would expect
dimethylamino group to be more basic than pyridyl group,
which in turn is expected to be more basic than 2-keto pyrrolidinyl group. Hence, one would anticipate dispersancy to follow the same order.

^
^

Mn=20,000

1
10

1
20

lOOT

30

80
Gear Oil

Shear Time (min)


FIG. 48Permanent viscosity loss due to shear.
O .
C60

ity modifiers with added dispersancy. The molecular weights


of these materials are usually much higher than those of the
polymeric dispersants and can range 25000-500000. These
additives are derived from high molecular weight olefin
copolymers (OCPs), polymethacrylates (PMAs), styrenedienes polymers (SD) of linear or star configuration, and
styrene-ester polymers (SEs).
Dispersancy in these polymers is introduced by including
basic nitrogen or surfactant type oxygen-containing
monomers during the polymerization process. The monomers that are commonly used for this purpose are shown in
Fig. 53. The dispersant functionality is introduced either by
grafting or through copolymerization. Grafting involves attaching a dispersant moiety, or its precursor, to an already
formed polymer. Copolymerization, on the other hand, involves the use of a monomer, which can provide dispersancy
during the formation of the polymer. Grafting of or copolymerization with a nitrogen-containing monomer, such as 2-

Tractor
Transmission
Fluids

|40|

to
Hydraulic
Fluids

Automatic
Trimsmissiori
Fluids

20

Engine
Oils '
0.1

04
1
3
Weight Average Molecular Weight (IMWxIO-^

FIG. 49Shear stability requirements for various lubricants.

230

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

i2or

0.01

0.05

0.10

0.15

specific Viscosity % ^ c (cm^/g)

0.20

0.25

>

FIG. 50The effect of specific viscosity on oil viscosity and shear stability.

FIG. 51Mechanism of thermal degradation of


styrene-diene polymers.

Pour Point

Depressants

The p o u r point is the lowest temperature at which a fuel or


oil will pour when cooled under defined conditions. In general, pour point is indicative of the a m o u n t of wax (straightchain paraffins) in an oil. At low temperatures, wax tends to
separate as crystals with a lattice type structure. These crystals can trap a substantial amount of oil via association, inhibit oil flow, and ultimately hinder proper lubrication of the
equipment.
Base oil suppliers remove most of the wax during
petroleum refining. However, complete dewaxing of base oils
is not practical because of process limitations, economics,
and the desirable presence of wax due to its high VI character [7]. For mineral oils to function effectively at low temperatures, the additives called pour point depressants are used.

Current practice favors mild dewaxing in combination with


the use of p o u r point depressants.
A good p o u r point depressant can lower the pour point of
a lubricant by as much as 40C. These additives are commonly used in mineral oil-based lubricants that are designed
for applications with operating temperatures usually below
0C. Pour point depressants have virtually n o effect on the
temperature where wax crystals start to precipitate (cloud
point) or the amount of wax that separates. They essentially
act as wax-crystal modifiers and function by altering crystal
shape and size. They do this either by absorption onto the
surface of the newly formed crystals or by co-crystallizing
with the precipitating wax. Both mechanisms inhibit lateral
crystal growth and keep the bulk oil fluid. Of the commercial
pour point depressants, edkylaromatics are believed to perform via the absorption mechanism and aliphatic polymers
via co-crystallization [45].
The molecular weight and the structure of the poljTneric
pour point depressants enable them to be effective over a
wider range than their low molecular weight counterparts.
The extended range of performance in the case of polymers is
believed to be due to their limited solubility in petroleum
fractions. As the temperature decreases, different polymer
segments become successively co-crystallizable.
A good p o u r point depressant must possess one or more of
the following structural features.
Polymeric structure
Waxy and nonwaxy components
Comb structurecomb structure meajis a short backbone
with long pendent groups
Broad molecular weight distribution
Most commercial pour point depressants are organic polymers, although some nonpolymeric substances have been
shown to be effective. Tetra (long-chain)alkyl silicates,
phenyltristearyloxysilane, a n d pentaerythritol tetrastearate
are examples of the nonpolymeric t3rpe. Commercial pour

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY

231

[-H-]
CH3
O2

.0-

Bond Cleavage
Other Oxidation Products
(Tliese include Carboxyiic Acids and Esters)
IHeat, Oj, and
Cataiysts

Varnish a n d C o k e Deposits
FIG. 52Mechanism of oxidative degradation of polymers.

CH3

CH,

CH2=CCOCH2CH2N ^

II

'

"

/
\

CH,
R

1-Vinyl-2-pyrrolidinone
or N-Vinylpyrrolidinone

Dimethylaminoethyl
Methacrylate

R'

Alkylnaphthalene

Alkylphenol
R, R' = Waxy Alkyl Groups

0\

CH3

A-A

CH2=CCOCH2CH2N

2- or 4-Vinylpyridlne

Morpholinoethyl
Methacrylate

CH3

CH,

CH-CH2OHOH-

i r
Styrene Ester

CH3
-OH,0
COOR
Alkyl Methacrylate
Polymer

FIG. 54Structures of c o m m o n pour point depressants.

CH2=CC0(CH2CH20|-[-CH2CHO-]R
O
Polyether Ester of
Methacryllc Acid
FIG. 53Monomers used in synthesizing dispersant viscosity modifiers.

point depressants include alkylated naphthalenes, poly(alkyl


methacrylates), poly(alkyl fumarates), styrene esters, oligomerized alkylphenols, phthalic acid esters, ethylene-vinyl acetate copolymers, and other mixed hydrocarbon polymers.
Figure 54 contains the structures of poly(alkyl methacrylates), alkylaromatics, and stjrene-ester polymers, which are
the most commonly used chemical types. High molecular
weight polymethacrylate derivatives can act both as viscosity

modifiers and pour point depressants. When this chemistry


is used for viscosity improvement, the need for a pour point
depressant is minimized.
Pour point depressants are used at treatment levels of 1%
or lower. In nearly all cases, there is an optimum concentration above and below which the pour point depressants become less effective. The key structural difference between
pour point depressants and viscosity improvers of the same
class is that viscosity improvers consist of long backbones
with short pendent groups and pour point depressants consist of short backbones with large pendent groups. This difference is depicted in Fig. 55.
Pour point depressants are used in engine oils, automatic
and power transmission fluids, automotive gear oils, tractor
and industrial hydraulic fluids, and circulating oils. The per-

232

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

VISCOSITY MODIFIER Long Backbone, Short Branches

POUR POINT DEPRESSANT Short Backbone, Long Branches

FIG. 55Viscosity modifier vs pour point depressant - structural ditlerence.

formance of a pour point depressant is determined in each


basestock by one or more of the following tests:
ASTM D 97For pour point of petroleum oil.
ASTM D 3829Borderline pumping test.
ASTM D 2602^Apparent viscosity at low temperature using cold-cranking simulation.
ASTM D 5949Automatic Pressure Pulsing Method for
pour point of petroleum products.
ASTM D 5950Automatic Tilt Method for pour point of
petroleum products.
ASTM D 5985Rotational Method for pour point of
petroleum products.

Emulsifiers and Demulsifiers


Emulsifiers are chemical compounds that enable two immiscible fluids to form an intimate raixture, known as an emulsion. Water-oil mixtures are often used as lubricants in many
industries and for a variety of applications. This is because
such lubricants are low cost, easier to dispose of, and have
fire retardant properties. Emulsions of water and mineral oil
have primary use in metalworking and hydraulic applications. To be effective, emulsions must possess a number of
desirable properties. They should be stable over long periods
of time, possess good lubricating properties, not attack seals
and metals, and be easy to demulsify for disposal.
In the presence of water, certain lubricant formulations
have an increased tendency to form emulsions. This is due to
the presence of chemical additives that act as surfactants.
Demulsifiers are added to such formulations to enhance water separation and suppress foam formation.
Emulsifiers and demulsifiers are basically surfactants and
are made up of hydrophilic and hydrophobic moieties. The
hydrophilic moiety is nitrogen, oxygen, sulfur, or phosphorus
derived polar functional group, which is attached to a hydrophobic hydrocarbon group. The hydrocarbon group must

be of sufficient chain length to provide proper solubility or


dispersibility in the oil phase.
Emulsifiers and demulsifiers can be classified as nonionic
or ionic, depending upon whether the polar part is uncharged
or charged. Ionic compounds can be subdivided further into
cationic if the charge is positive and anionic if the charge is
negative [49]. It is important to note that only the charge on
the functional group attached to the carbon chain is used in
this classification. The charge on the counterion, which is
usually inorganic in origin, is ignored. The term amphoteric
applies to a group of additives that contain both the cationic
and the anionic groups of organic origin, preferably within
the same molecule. They possess the structural features and
the properties of both the cationic and the anionic materials
grouped together. Generalized structures for emulsifiers and
demulsifiers [50] are given in Fig. 56.
Emulsifiers reduce the surface tension of water and, therefore, facilitate thorough mixing of oil and water to form an
emulsion. The efficiency of an emulsifier depends upon its
molecular weight (usually less than 2000), its HLB (hydrophile-lipophile balance) value, water pH and hardness,
the nature of the oil, and operating conditions, such as temperature. Emulsifiers with an HLB value of 3-6 are suitable
for water-in-oil emulsions and those with an HLB value of
8-18 are suitable for oil-in-water emulsions. The manner in
which these additives form emulsions is shown in Fig. 57.
Water-in-oil emulsions form when these additives associate
with water via their polar ends and with oil and other additive molecules via the non-polar ends. This is shown in part
A of the exhibit. The result is water miscibility in oil, or water-in-oil emulsion. The mechanism of oil-in-water emulsion
is similar, except that the additive molecules associate in the
reverse manner. This situation is shown in part B of the exhibit.
Demulsifiers perform the opposite function and enhance
water separation. Structurally, most demulsifiers are
oligomers or polymers with a molecular weight of up to
100 000 and contain 5-50% polyethylene oxide in a combined
form. They are commonly block copolymers of propylene oxide or ethylene oxide and initiators, such as glycerol, phenolformaldehyde resins, siloxanes, polyamines, and polyols [51].
For water-in-oil emulsions, polymers containing 20-50%
ethylene oxide are suitable. These materials concentrate at
the water-oil interface and create low viscosity zones, thereby
promoting droplet coalescence and gravity-driven phase separation. Low molecular weight materials, such as alkali metal
or alkaline earth metal salts of dialkylnaphthalene sulfonic
acids, are also useful in some lubricant-related applications.
As a general rule, nonionic emulsifiers are used in metalworking fluids based on naphthenic stocks, and fatty acid
carboxylates are used in those based on paraffinic stocks.
Polyalkylene glycols (hydroxyalkyl ethers) are sometimes
avoided because their enhanced solubility in water does not
allow clean separation for disposal. Polyethylene oxide
derivatives and salts of carboxylic and sulfonic acids are the
most commonly used emulsifiers, primarily in metalworking
fluids. Demulsifiers are used in applications where water
contamination of the lubricant is a problem and quick separation of water is desired. Automatic transmission fluids, hydraulic fluids, industrial gear oils, and some engine oils, are
examples of such lubricamts.

CHAPTER
Foam

9: ADDITIVES

AND ADDITIVE

CHEMISTRY

233

OIL

Inhibitors

Foam forms when a large a m o u n t of gas is entrained in a liquid. While foaming is desirable in certain applications, such
as flotation, washing, and cleaning, it is undesirable in others,
such as distillation and pumping of fluids. In lubricant-related
applications, foam can act as an impediment and must be controlled. Almost every lubricant application involves some kind
of agitation that encourages foam formation through air entrainment. Excessive foaming will result in ineffective lubrication and, over time, will cause oxidative degradation of the
lubricant. The viscosity and the surface tension of a lubricant
determine the stability of the foam. Low-viscosity oils produce foams with large bubbles, which tend to break quickly.
High-viscosity oils, on the other hand, generate stable foams
that contain fine bubbles and are difficult to break. The presence of surface-active materials, such as dispersants and detergents, further increases the lubricant's tendency to foam.

^^(OCW^A

OIL

(a)

Foam inhibitors control foam formation by altering the


surface tension of the oil and by facilitating the separation of
air bubbles from the oil phase. In general, these additives
have limited solubility in oil, hence they are added as very
fine dispersions. Foam inhibitors are effective at very low levels (3-150 parts per million).
Silicones (polysiloxanes), poly(alkyl acrylates), and
poly(alkyl methacrylates) are the commonly used foam inhibitors, with silicones being more popular. The ASTM D 892
and D 6082 Tests are used to assess a lubricant's foaming tendency. The structures of the two common types of additives
are shown in Fig. 58.

H2O

v^0

O^^^

H2O

Other Additives
In addition to the major classes of additives described above,
lubricants contain a n u m b e r of other additives. These include
seal-swell agents, dyes, biocides, and couplers. Seals are used
in m o d e m machinery for a variety of reasons. In lubrication
systems, their functions are to:
Isolate various lubrication environments from harmful elements.

H2O

FIG. 57A representation of (a) water-in-oil emulsion,


(b) oil-ln-water emulsion.

Non-ionic
CH2CH2OH
RN

RO{CH2CH20)xCH2CH20H
NH(CH2CH20)xH
N-Hydroxyalkylamide

CH2CH2OH
Poiyethoxylated Alcohol
(HydroxyalkyI Ether)

DIettianolamlne

R"

RC

^CpNa

1
1

R"
Sodium
Carboxylate

Anionic

(b)

Trialkylammonium
Salt

R'
RNCH2CH2 C,
1
1
R"
Tetraalkylammonium
Carboxylate

Cationic
FIG. 56Emulsifiers and demulsifiers.

Amplioteric

234 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


CHa

CH,

- 0 - S I - OSI0--SI
I
CH,
CH,
CHa
DImethylslloxane
Polymer

CH3

CH,
-CH2-

-C
I
COOR

Alkyl Methacrylate
Polymer

FIG. 58Common types of foam Inhibitors.

Help maintain hydraulic pressure.


Allow removal and replacement of the malfunctioning
parts without the need to totally dismantle equipment.
Minimize contamination and the loss of lubricant.
Seals are commonly made from polymeric materiails such
as fluoroelastomers, nitrile rubber, polyacrylates, and silicones. Lubricants containing certain basestocks and additive
systems can cause shrinkage, brittleness, and deterioration of
seals, and impair the performance of the lubricating system.
Seal-swell agents are additives that maintain the integrity of
these seals. Additives belonging to this class include
polyesters, some phosphorus derivatives, and proprietary
chemicals. Seal-swell agents are commonly used in transmission and hydraulic fluids.
Dyes are used to color-code lubricants to ensure their use
in the proper application and as a leak detection aid for the
consumer. ATFs contain a red dye, and the two-stroke cycle
oils contain a blue or a purple dye. These dyes are oil-soluble
organic compounds, mostly with an azo structure (contains
nitrogen-nitrogen double bond). To a limited extent, dyes are
also used to impart color or fluorescence to lubricants that
were historically perceived to indicate good performance.
This is because today's refining processes remove compounds that imparted this characteristic.
In general, mineral oil based lubricants resist microbial attack because of their high-temperature operation and the
presence of additives, many of which have biocidal action.
High water-based lubricants, such as certain metaJworking
fluids and hydraulic fluids, are easily attacked by microbes
and fungi. The control of bacterial and fungal growth is essential to minimizing product deterioration and possible
health hazards. This is done by the use of water-soluble triazine, morpholine, imidazoline, and thiazoline derivatives,
which possess biocidal properties. Triazines, which owe their
biocidal action to their formaldehyde-releasing ability, find
extensive use in this application. Couplers are additives used
in water-based lubricants to help stabilize microemulsions.
Glycol and its derivatives are commonly used for this purpose.
Metalworking fluids use a number of other additives.
These include alkalinity buffers, odor masks, and antimisting
agents. Alkalinity agents and odor masks are used to control
acidity and odor in water-based systems. Acidity and odor results from the breakdown of oil and additives due to bacterial
and fungal attack. Amines and inorganic bases are used to
control acidity and natural and synthetic aromatic materials
are used to control odor. Antimisting agents are used to suppress mist formation, primarily in oil-based fluids, which if
not controlled can be harmful to workers. Polymers of various types are used for this purpose.

MULTIFUNCTIONAL NATURE OF
ADDITIVES
A number of additives perform more than one function. Zinc
dialkyl dithiophosphates, known mainly for their antiwear
action, are also potent oxidation and corrosion inhibitors.
Polyacrylates and styrene-ester polymers can act as viscosity
modifiers, dispersants, and pour point depressants. Basic
sulfonates, in addition to acting as detergents, perform as
rust and corrosion inhibitors. They do so by forming protective surface films and by neutralizing acids that arise from
fuel combustion, lubricant oxidation, and additive degradation.

ENVIRONMENTAL IMPACT OF ADDITIVES


ATC (the Technical Committee of Petroleum Additive Manufacturers in Europe) carried out a study that traced engine oil
additives across nineteen OECD (Organization for Economic
Cooperation and Development) countries from cradle to grave
perspective. The objective was to assess the impact of additives on the consumer and the environment. The report [52]
reviews the nature, development, health and safety aspects,
benefits to the consumer, and the ultimate fate of engine lubricant additives. An accompanying report [53] examines the
same for fuel additives.

THE INTRODUCTION OF A NEW ADDITIVE


The development of a new additive is initiated after a new
product (lubricant) need is identified. The need for a new
product is usually expressed by the OEMs and the end-users
and relates either to the inadequate performance of the existing products in the current equipment or the perceived needs
of the equipment under development. To fulfill this need, various organizations, such as the SAE, API, ASTM, AGMA, and
OEMs, initiate the development of new performance specifications and test methods.
Additive companies, either alone or in collaboration with a
lubricant supplier, try to satisfy the performance requirements established for the new product. If the additive company is unable to develop the additive system using their existing technology base, they initiate a project to develop and
test a new additive.
Newly developed additives are blended with other additives
in a customer's base oil and are screened in a number of proprietary bench tests. Bench tests, also called screen tests, are
accelerated tests that are devised to closely simulate conditions the lubricant is likely to experience in actual service. This
kind of testing is quite common because it allows the evaluation of a large number of additives quickly and inexpensively.
Once a lubricant satisfies the performance criteria of the
bench tests, full-fledged testing using actual equipment is carried out. This may be done in a laboratory or in collaboration
with an end-user. For additives used in automotive products,
field trials may also be necessary. The costs associated with
the development and testing of the new additives can be phenomenal. The performance package that has successfully met
all the performance requirements is ready to be marketed either through factory-fill or service-fill lubricant blenders.

CHAPTER

PERFORMANCE TESTING
Reliable lubricant performance is a function of the quality of
its components. This implies both the base oil quality and
that of the performance package. Because most additives are
reactive components, their quality is assessed both individually as well as in an additive package, which comprises a collection of additives.

9: ADDITIVES

AND ADDITIVE

CHEMISTRY

235

1500), flash point (ASTM D 92 and D 93), volatility (ASTM D


1078 and D 5800), melting point, boiling point, odor, clarity
a n d water content (ASTM D 1744, D 4928, and D 4377).
While some ASTM standards are designed to analyze only
low quantities of the described elements, in many instances
these methods can be used and are used to analyze larger
concentrations via dilution.
Tests for F i n i s h e d F o r m u l a t i o n s

Tests for Individual Additives


The first and foremost concern after an additive is manufactured is to establish its structural identity and purity. This is
essential both from the perspective of conserving testing resources and for developing chemicals with optimal performance. Structural identity can be established by the use of
analytical techniques available to a chemist. These include elemental analysis, wet chemical methods, functional group
determination, molecular weight determination, and spectroscopic techniques. Some of the methods are provided in
the ASTM standards while others are not. Elemental analysis
is used to determine the amount of certain elements in the
additive, the finished lubricant, or the used lubricant. Such
elements include chlorine (CI), bromine (Br), nitrogen (N),
sulfur (S), phosphorus (P), and boron (B), and metals, such
as sodium (Na), potassium (K), calcium (Ca), magnesium
(Mg), barium (Ba), zinc (Zn), copper (Cu), and molybdenum
(Mo). The m e t h o d s to analyze these are provided in the
ASTM Standards D 4951, D 5185, D 4927, D 5291, D 4047,
D 1091, D 129, D 874, D 2622, D 808, D 4628, D 6443, and D
6481. Functional group analysis involves the use of both the
wet chemical m e t h o d s a n d the spectroscopic techniques.
Commonly used wet chemical methods include neutralization n u m b e r determination (ASTM D 974, D664, D 3339,
D4739, D2896), saponification n u m b e r (ASTM D 94),
bromine n u m b e r (ASTM D 1159 and D 2710), iodine value,
acetylation reaction, reaction with Grignard reagent, and
Kjeldahl method. The neutralization numbers and saponification n u m b e r provide information on acidic functional
groups, such as sulfonic acid, carboxylic acid, and phosphoric acid. The neutralization numbers also provide information on basic functional groups, such as amino groups and
inorganic bases, and metal oxides, hydroxides, and carbonates. Bromine n u m b e r and iodine value are used to assess unsaturation in additives and lubricants. Acetylation and reaction with Grignard reagent are used to determine the
hydroxyl content of additives. Grignard reagent is primarily
used for situations, for example in the case of hindered phenols, where steric crowding does not allow a complete reaction with the acetylation reagent. Kjeldahl method (ASTM D
3228) is used to determine elemental nitrogen. Spectroscopic
methods include infrared (IR), nuclear magnetic resonance
(NMR), and mass spectrometry (MS). These techniques are
well established and are aptly covered in many publications
[54]. Purity is determined by gas liquid-phase chromatography (GLC or GC), thin layer chromatography (TLC), liquid
chromatography (LC), and gel permeation chromatography
(GPC). Additional tests include molecular weight determination by vapor phase osmometer (VPO) and MS, oil solubility/package compatibility (ASTM D 501), copper strip activity
(ASTM D 130), viscosity (ASTM D 445), color (ASTM D

As mentioned earlier, lubricant additives are supplied as


packages, especially for automotive applications, which are
blended in mineral oil or synthetic basestocks to yield finished lubricants. The additives, being reactive chemicals, can
react with one another in the package either synergistically
or antagonistically [55]. The formulator's challenge is to deliver the intended performance by minimizing antagonistic
effects and maximizing synergistic effects through careful
balancing.
The viscosity modifier and the performance package are
usually sold separately. This is because the two are not always compatible in the concentrate form [45]. For applications needing a viscosity modifier, the viscosity modifier is
blended in the base fluid, along with the performance package, to formulate the finished lubricant. Lubricant additive
suppliers develop general-purpose performance packages
that meet industry specifications using widely available basestocks and may fine tune them for an individual company's
use in its basestocks. Table 2 shows classes of additives used
to formulate engine lubricants, and Table 3 contains classes
that are used to formulate non-engine lubricants. It is important to note that all formulations do not contain all classes of
additives identified in these tables.
The quality of the additive package is determined by its
ability to meet established performance standards. Examples
of such standards include:
SAE's viscosity classification system
API's, ILSAC's, ACEA's, and U.S. Military's engine oil standard for gasoline engine and diesel engine lubricajits
GM's DEXRON standard and Ford's MERCON standard
for automatic transmission fluids
API's standard for gear lubricants.
The standards result from the joint efforts of many organizations. In the United States, such organizations include the
Society of Automotive Engineers (SAE), American Petroleum
Institute (API), American Society of Testing and Materials
(ASTM), American Automobile Manufacturers Association
(AAMA), Engine Manufacturers Association (EMA), U.S.
Original Equipment Manufacturers (OEMs), the U.S. Military, and Chemical Manufacturers Association (CMA). In Europe, the organizations include ACEA (Association des Constructeurs E u r o p e e n s de I'Automobiles), CEC (Conseil
Europeens de Coordination pour les Developments des Essais de Performance des Lubrifiants et des Combustibles
pour Moteurs), ATC (Technical Committee of Petroleum Additive Manufacturers), and ATIEL (Association Technique de
I'lndustries Europeenne des lubrifiants). The ILSAC (International Lubricant Standardization and Approval Committee) standard is a result of a collaborative effort of the American Automobile Manufacturers Association of the United
States, Inc. (AAMA) and the Japan Automobile Manufactur-

236

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

ers Association, Inc. (JAMA). It is important to note that


many OEMs and end-users have performance requirements
that are over and above those prescribed in these standards.
The testing of packages involves prehminary testing and
full scale testing. Preliminary tests include physical, chemical, and machine tests. Full scale testing entails testing in a
laboratory via accelerated tests in real world equipment and
simulating actual service conditions. That is, the tests eire carried out using actual engines, transmissions, axles, hydraulic
pumps, and so on. These tests usually eveJuate more than one
lubricant property at a time. The equipment is disassembled
and its parts cire rated based on different criteria. Laboratory
tests, performed under standard conditions, ascertain that
lubricants meet the performance requirements established
by various organizations. Standardized test methods for lubricants are published in Federal Republic of Germany's DIN
standards, the USA's ASTM standards, the Britain's IP Standards, and the France's NF Standards. The equivalent test
methods for important lubricant properties in different standards are available elsewhere [4c,56]. In the U.S., such tests
are run according to procedures prescribed by ASTM and
OEMs. The lubricants that pass these tests are sometimes
tested under field conditions as well.

D 4741, and D 4684), emulsion-forming tendency, foaming


characteristics (ASTM D 3427, ASTM D 892, and ASTM D
3825), refractive index (ASTM D 1218), flash point (ASTM D
3828, ASTM D 93, and ASTM D 92), cloud point (ASTM D
2500), pour point (ASTM D 97), volatility (ASTM D 6417),
and evaporation loss (ASTM D 972). Standard ASTM test
procedures are used to evaluate these properties (See individual additive testing section). Chemical tests, in conjunction with spectroscopic methods, are used to characterize the
lubricant. Important chemical tests are:
Structural analysis.
Hydrolytic stability.
Tests to determine carbon residue, water content, sulfur,
and ash content. The carbon residue test help determine
the coke-forming tendency of the lubricants.
Acidity, alkalinity, and alkaline residue.
Corrosion and corrosion protection tests.
Seal compatibility tests.
Tests to determine a lubricant's aging characteristics to
predict its service life.
Machine tests help assess a lubricant's performance in laboratory tests that are designed to simulate actual service conditions. Machine tests, such as SAE #1, Four-Ball, Falex, FZG
(ASTM D 4998), and Ryder gear tests, evaluate a lubricant's
effectiveness u n d e r mixed-film a n d b o u n d a r y lubrication
conditions [4a]. The details of the test are provided in Chapter 18, Metalworking and Machining Fluids.

Physical tests, commonly used for finished lubricants, include those relating to density (ASTM D 1298), viscosity
(ASTM D 445), viscosity index (ASTM D 2270), shear stability (ASTM D 1298, D 4624, D 5481, D 5133, D 2603, D 4683,

TABLE 2 -- C o m m o n additive types for engine lubricants.

Additive

Gasoline
Engine Oils

Diesel Engine
Oils

Dispersant
Detergent
Antiwear/EP Agent
Oxidation Inhibitor
Corrosion Inhibitor/Metal Deactivator
Friction Modifier
Pour Point Depressant
Foam Inhibitor
Viscosity Modifier
Other'

Stationary Gas
Engine Oils

Two-stroke
Cycle Engine
Oils

Aviation
Engine Oils

'Other additive include couples, dyes, diluents, and emulsifiers.

TABLE 3Common additive types used in non-engine lubricants.

Additive
Dispersant
Detergent
Antiwear/EP Agent
Oxidation Inhibitor
Corrosion Inhibitor/
Metal Deactivator
Friction Modifier
Pour Point Depressant
Foam Inhibitor
Viscosity Modifier
Other^

Automatic
Transmission
Fluids

Gear Oils
Automotive
Industrial
Gear Oils
Gear Oils

'Other additives include couplers, dyes, diluents, and emulsifiers.

Hydraulic Fluids
Tractor
Hydraulic Fluids

Industrial
Hydraulic Fluids

Metalworking
Fluids

Greases

CHAPTER
Viscosity Tests
Viscosity plays a crucial role in forming effective lubricating
films, which makes it one of the most important properties of
a fluid [57]. Viscosity, defined as a fluid's resistance to flow,
is mainly a consequence of the internal friction of the fluid
[4]. Viscosity requirements or specifications are therefore
prescribed for almost all lubricants. Meeting these is absolutely critical for automotive lubricants, such as engine oils,
transmission fluids, and tractor hydraulic fluids.
For automotive engine oils, viscosity requirements are described in the SAE Standards J300 [58] and J1536 [59]. The
SAE Standard J300 deals with the viscosity of lubricants for
four-stroke cycle engines, of both compression ignition (CI)
and spark ignition (SI) types, and two-stroke cycle CI engines.
The SAE Standard J1536, on the other hand, specifies viscosity of oils for two-stroke cycle SI engines only. The SAE Standard J1536 describes the miscibility and fluidity grades for
two-stroke cycle engine oils. The basic viscosity grade categories for engine oils are determined by the Crankcase Classification System devised by the SAE, which uses test methods
approved by the ASTM. For transmission fluids and tractor
hydraulic fluids, the SAE grades are the same as those used
for engine oils. However, for automotive gear oils, these are
different and are described in the SAE Standard J306 [60].
Viscosity of non-automotive lubricants, such as industrial
gear lubricants and industrial oils, is described by the American Gear Manufacturers Association (AGMA) and International Standardization Organization (ISO) Standards, respectively.
ACEA uses SAE viscosity classification system, described
in SAE J300. However, it has additional requirements relating to shear stability, evaporation loss, elastomer compatibility, sulfated ash, foaming tendency, and changes in viscosity
due to high shear and high temperature. Special laboratory
test procedures are used to determine if a lubricant meets the
desired performance requirements in these areas. These procedures are described in the SAE J2227 report [61].
The ASTM D 445 method is used to determine kinematic
viscosity of a lubricant at 40C and 100C. This procedure employs a capillary viscometer. The ASTM methods D 2602,
D2983, D 3829, D 4684, and D5293 are used to determine low
temperature viscosity of lubricants. ASTM D 2602 uses cold
cranking simulator to determine apparent viscosity at 0 to
- 4 0 C range. The ASTM D 3829 and D 4684 procedures use
mini-rotary viscometer and are used to measure borderline
pumping temperature (BPT) and apparent yield stress and apparent viscosity, respectively. ASTM D 5133 is scanning
Brookfield technique that is used to measure gellation point,
point at which sample viscosity reaches 30,000 cP. ASTM D
2983 is also a Brookfield procedure that is used primarily for
low temperature properties of automotive gear oils, automatic transmission fluids, torque and tractor fluids, and hydraulic fluids. The measurement is carried out at a constant
temperature in the range of 0 to 40C. The ASTM procedures
D 5624, D 4683, D 4741, and D 5481 are used to measure high
temperature/high shear viscosity (HTHS). The ASTM D 5624
procedure uses a capillary viscometer where force is applied
to a lubricant that is at 150C to generate a high shear rate (10
s"'). The ASTM D 1092 procedure, used to measure viscosity
of greases, also uses pressure [57b]. The ASTM D 4683 and

9: ADDITIVES

AND ADDITIVE

CHEMISTRY

237

D 6616 methods, on the other hand, use tapered bearing simulator to determine HTHS viscosity. Two procedures that are
used to measure grease viscosity are ASTM D 1092 and ASTM
D 4693. The first measures apparent viscosity and the second
measures pumpability. The procedures ASTM D 2270 and D
2161 do not directly measure viscosity but are used for conversion purposes. ASTM D 2270 or D 39 B is used to calculate
viscosity index (VI) from 40C and 100C kinematic viscosities
and ASTM D 2161 is used to convert viscosities measured in
now obsolete units of Saybolt Universal Seconds (SUS) and
Saybolt Furol Seconds (SFS) into centistokes (cSt).
For two-stroke cycle SI engine oils, viscosity grades are
based on miscibility with fuel and fluidity. This is to ensure
that the lubricant is miscible with fuel and that the blend
meets the low-temperature viscosity requirements. The rationale behind these requirements is that two-stroke cycle SI engines usually do not have an oil sump, and the lubricant is
mixed with the fuel in the fuel tank. The testing involves mixing lubricant with fuel and determining its pour point (ASTM
D 4682). The performance of the new oil is compared with
that of the reference oils to assign a viscosity grade. Transmission and tractor hydraulic fluids, like engine oils, have
low t e m p e r a t u r e and high t e m p e r a t u r e viscosity requirements. Low temperature requirements are base upon ASTM
D 2983 (Brookfield test) and ASTM D 445 is the basis for 40C
and 100C kinematic viscosities.
Performance Tests
As mentioned earlier, each tjrpe of lubricant must meet certain performance requirements prior to use. Such requirements are described in service classifications or specifications (ASTM D 4485). The following section describes these
based on the lubricant type.
Engine

Oils

Engine oil performance requirements for North America are


based on standard tests and are described by the API Engine
Service Classification System, which was first introduced in
1969/1970 [62]. The system comprised separate performance
classes for gasoline engine lubricants and diesel engine lubricants. The system has been revised many times. At present, classes for gasoline engine lubricants range from SA to
SL and for diesel engine lubricants they range from CA to CI4. Of these, SA to SG categories for gasoline engine oils and
CA to CE categories for diesel engine oils are obsolete and
their r e q u i r e m e n t s are satisfied by API SH a n d CF (and
higher service classes), respectively [63]. However, at present, the use of SH designation is limited to lubricants recommended for both the heavy-duty diesel and the gasoline
engines, such as those designated as CF/SH.
The ILSAC's performance categories, GF-1 and GF-2, issued in 1992 and 1996, use the API SH performance criteria
but include a fuel economy ASTM Sequence VI Test. A new ILSAC category, ILSAC GF-3, was introduced in the year 2001.
This category incorporated a n u m b e r of new tests that use engines of current design and operate on unleaded fuel, so as to
conform to the growing trend towards the use of unleaded
gasoline. The tests include ASTM Sequence IIIF for oxidation,
ASTM Sequence IVA for valve train wear, ASTM Sequence VG
for sludge, varnish, and deposits, ASTM Sequence VII for

238

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

bearing corrosion, and ASTM Sequence VIII for rust and corrosion [74]. API has stopped licensing GF-2 passenger car oils
since April 2002 [64]. The work on the next ILSAC upgrade,
GF-4, has already started. The new category will require oils
that are emission system catalyst compatible, have better fuel
economy, and provide better engine protection [65].
For diesel engine oils, API CF, CF-2, CF-4, CG-4, CH-4, and
CI-4 categories are active. API CF-2 is for severe-duty twostroke cycle engines. API CF is for four-stroke cycle engines
that are either turbocharged or use high sulfur fuel. Such engines are often for off-highway use. API CF-4 and CI-4 categories are for four-stroke cycle engines for on-highway use.
API CF-4 is for 1991 low emissions engines, API CG-4 is for
1994 low emissions engines, and API CH-4 is for 1998 low
emissions engines. API CI-4, the 2002 upgrade of the diesel engine oil standard, is suitable for use in engines that are
equipped with exhaust gas recirculation and other exhaust
emissions control mechanisms/components. Such engines are
designed to meet the 2004 exhaust emissions standard. In general, oils meeting higher service requirements are suitable for
use in the lower service class within the same category. New
proposed category, PC-8, for next generation heavy-duty
diesel engine oils has been under consideration for some time.
It is designed to address the Japanese OEM concerns over the
ability of the API CH-4/CI-4 qualified oils to protect their engines that use slider followers. The American engines use
roller followers. The CI-4 category includes eight fired engine
tests and seven bench tests [66]. The diesel engine tests include
Caterpillar IR, Cummins M i l , MackTSE (ASTM D 5967) and
T-10, and GM 6.5L Roller Follower Test (ASTM D 5966). This
category accommodated two major OEM specifications,
Cummins CES 20076 and Mack EO-M Plus, both of which require performance beyond that delivered by API CH-4.
In addition to API, two other organizations actively participate in establishing engine oil performance. These are U.S.
Military and original equipment manufacturers (OEMs). The
needs of the U.S. Military are different from those of the commercial users. Its fleets consist of vehicles that not only vary
in size (ranging from 2 to over 1000-hp), but they also operate under a variety of conditions. U.S. Military specifications
are designated by the prefix MIL. While largely similar to API
service designations, there can be subtle differences. Similarly, certain OEMs have additional requirements to qualify
oils for use in their equipment. Mack EO-M and Cummins
CES 20076 specifications are examples of such requirements.
ACEA establishes oil quality for use in Europe and JASO
and Bureau of Indian Standards (BIS) establishes oil quality
for use in Japan and India, respectively. ACEA specifies the
use of tests developed by the ASTM and CEC (Conseil Europeen de Coordination pour les Developments des Essais de
Performance des Lubrifiants et des Combustibles pour Moteurs; Coordinating European Council). ACEA 2002 Standard consists of four lubricant classes for gasoline engines,
Al-02, A2-96 (issue 3), A3-02 and A5-02; five lubricant classes
for light-duty diesel engines, Bl-02, B2-98 (Issue 2). B3-98
(Issue 2), B4-02, and B5-02; and four lubricant classes for
commercial diesel engines, E2-96 (Issue 4), E2-96 (Issue 4),
E4-99 (Issue 2), and E5-02. Current Japanese specifications
include JIS K 2215 for gasoline engine oils and JASO DH-1
for diesel engine oils.
Each active category has associated tests. These tests pri-

marily pertain to frictioucJ characteristics, oxidation resistance, deposit controlling ability, corrosion and wear preventing ability, and fuel efficiency of the oil. The current engine
and bench tests for gasoline engine lubricants are as follows.
U.S. and European Tests
Rust and corrosionCRC L-38, ASTM Sequence VIII
(ASTM D 6709), ASTM Sequence IID (ASTM D 5844), and
Ball Rust Test (ASTM 6557)
OxidationASTM Sequences HIE (ASTM D 5844) and
IIIF, CRC L-38, and Peugeot TU-3M High-temperature
Thermal and Oxidative StabilityThermo-oxidation Engine Oil Simulation Test (TEOST; ASTM D 6335), Hightemperature Deposit Test
Sludge, varnish, deposits, and v\;earCRC L-38, ASTM Sequence HIE (ASTM D 5533), ASTM Sequence VE (ASTM D
5302), and VG (ASTM 6593), M-B Ml 11 Black Sludge, VW
1302, and Peugeot TU-3M High-temperature
Valve Train WearASTM Sequence IVA and Peugeot TU3M Wear
Fuel EfficiencyASTM Sequence VI, VIA (ASTM D 6202),
and VIB (For GF-3), and M-B M i l l Fuel Economy
Extended drain capabilityVW T-4
Japanese and Indian Tests
Rust and corrosionCRC L-38/Petter Wl, ASTM Sequence
IID (ASTM D 5844)
OxidationToyota. IG-FE, CRC L-38/PetterWl, and ASTM
HID and HIE (ASTM D 5533)
Sludge, varnish, deposits, and wearToyota IG-FE, Nissan
VG-20E, Nissan SD22 (JASO 336-90), Nissan TD25 (JASO
336-97), CRC L-38/Petter Wl, CLR LTD, ASTM HID and
HIE, ASTM VD and VE (ASTM D 5302)
Valve train wearToyota 3A, Toyota 3E, Nissan KA-24E
The current diesel engine tests are as follows. These tests
are devised to measure protection against rust, varnish, deposits, sludge, wear, high-temperature oil-thickening, ring
sticking, fuel economy, and foaming tendency.
U.S. and European Tests
Piston deposits, ring sticking, oil consumption, and piston
liner and ring distressCaterpillar IK, IM-PC (ASTM D
6618), IN, IP (ASTM D 6681), and IR; Detroit Diesel 6V
92TA (two-stroke cycle engine; ASTM D 5862)); Mack T-6;
VW 1.6TC Diesel Intercooler and VW Direct Injection; Peugeot XUDl 1 ATE and XUDl IBTE; MAN 5305; and M-B OM
364A/LA and M-B OM 441LA
Roller follower wearRoller Follower (lifter pin wear), GM
6.2L and GM 6.5L (ASTM D 5966)
Soot thickeningMack T-6, T-7, T-8/T-8E (ASTM D 5967),
T-9 (ASTM D 6483), and T-10.
Engine oil corrosiveness^ASTM D 5968
Oxidative stability/Viscosity increaseVW Direct Injection
and Peugeot XUDl lATE and XUDl IBTE
Sludge, varnish, and wear/cleanlinessM-B OM 602A, M-B
OM 364A/LA, M-B OM 441 LA, and Cummins M-11
Fuel EconomyM-B M i l l Fuel Economy
Foaming tendencyNavistar 7.3L EOAT [Hydraulically Actuated Electronic Controlled Unit Injector (HEUI)]
Bore PolishingMAH 5305, M-B OM 364A/LA, M-B OM
441 LA

CHAPTER
Indian Tests
Piston deposits, sludge, varnish, and
wearCaterpillar
1H2/MWM-B, Caterpillar 1G2/MWM-B, M-B OM 364A, MBOM616
Soot ThickeningMack T-7
Bore PolishingM-B OM 616
Service classifications for two-stroke cycle engine oils are
described in the SAE Standard J2116 [67]. The API designations for oils approved for use in two-stroke cycle engines are
TA and TC, and NMMA (National Marine Manufacturers Association) designations are TC-W, TC-WII, and TC-W3. TA
oils are designed for use in low performance engines and TC
oils are designed for use in high performance engines, except
outboard engines (ASTM D 4859). TC-W, TC-WII, and TCW3 oils, on the other hand, are intended for use in watercooled outboard engines. The quality of two-stroke cycle oils
is assessed on the basis of their ability to prevent piston scuffing, exhaust system blocking, ring sticking, and deposit-induced pre-ignition ASTM D 4857 and D 4858). JASO and ISO
based two-stroke cycle categories are at present being developed. These will be based upon oil's lubricity and detergency,
and its ability to control exhaust smoke and exhaust system
blocking. The engine test requirements for NMMA's most recent category TC-W3 are listed below.
Piston varnish, deposits, and ring stickingOMC 40-hp,
OMC 70-hp
Scuffing, bearing stickiness, and compression
lossMercury 15-hp
Tightening and lubricityYamaha CE50S
Preignition^Yamaha CE50S
Many changes have occurred for water-cooled engine specifications since writing this article. NMMA's categories TCW, TC-WII, and TC-W3 are now obsolete and a recertified
TC-W3 category was introduced. At present, the availability
of the OMC 70-hp and OMC 40-hp engine test parts is in question.
Transmission

Fluids

The important functions of these fluids are lubrication, cooling, and to act as a hydraulic medium to transmit power.
These fluids are of three types: automatic transmission fluids, manual transmission fluids, and power transmission fluids. There is no official API classification system for these fluids. Performance requirements for transmission fluids are
established by the OEMs [68]. The most important features
of these fluids are their frictional consistency (durability) and
frictional compatibility with the transmission's components.
In a u t o m a t i c transmissions, such c o m p o n e n t s include
clutches and bands; in manual transmissions and manual
transaxles, they include cone or plate type synchronizers. Unlike automatic transmissions, which use transmission fluids
recommended only by the OEMs, manual transmissions use
a variety of fluids. Such fluids include automatic transmission fluids, engine oils (5W-30), some gear lubricants, and
specialty fluids. In addition to frictional properties, certain
OEMs require transmission fluids for their equipment to
have improved shear stability, low-temperature fluidity, and
other specific characteristics.
Automatic Transmission FluidsThe frictional compatibility
of automatic transmission fluids (ATFs) with the transmis-

9: ADDITIVES

AND ADDITIVE

CHEMISTRY

239

sion's clutch and band system is their most important feature. DEXRON and MERCON are the two major types of
a u t o m a t i c transmission fluids that are presently in use.
DEXRON fluids meet General Motors' performance specifications and are primarily designed for use in their transmissions. MERCON fluids meet Ford's performance requirements and are used in its transmissions. DEXRON-III,
MERCON , and MERCON-V fluids are the most current
specifications for transmission fluids. DEXRON-III, introduced in 1994, is suitable for use in GM transmissions that
were designed to improve fuel economy and emissions [69].
Design changes and operating environment for these transmissions called for fluids with good low-temperature properties, good thermo-oxidative stability (ASTM D 5579), and
frictional durability. DEXRON-III specification was designed to improve shift-feel smoothness, antiwear characteristics, low-temperature fluidity, and oxidation resistance of
the fluid. DEXRON-IV specification, proposed but not yet
in use, will require fluids of lower kinematic and Brookfield
viscosities so as to minimize energy losses and further improve fuel efficiency. Tests and evaluation criteria for automatic transmission fluids are provided below.
Friction and wearASTM D 2882, Band Clutch, Plate
Clutch Friction
Thermo-oxidative stability4L60 Transmission, ABOT Oxidation
Frictional consistency and durabilityCycling
(ASTM D
5579)
Smooth shifting of gearsShift Feel
Power Transmission
FluidsPower
transmission fluids
(PTF) aire used in heavy-duty automatic transmissions and
torque converters in off-highway equipment. Such equipment is commonly used in agriculture and construction industries. Viscosity and frictional properties of these fluids are
critical to their performance. Just like ATFs, the SAE and
OEM performance specifications are used to describe these
fluids [70]. Power transmission fluids are classified on the
basis of their performance in Allison C-4 and Caterpillar TO4 friction tests. Fluids meeting Allison C-4 requirements are
designed for equipment that has both torque conversion and
automatic transmission features.
Gear Oils
Gear oils are primarily formulated to provide extreme pressure protection for gears and axles to prevent fatigue, scoring, and wear under boundary lubrication conditions. Gears
are used in automobiles and industry to perform a number of
diverse functions. Because of differences in design, each gear
type places different demands on the lubricant.
Automotive Gear OilsPerformance
specifications for automotive gear oils are established by the API, U.S. Military, and
the OEMs. The API service designations for automotive gear
oils range from GL-1 to GL-6, specifying oils in increasing order of load-carrying capacity [71,72]. The abbreviation "GL"
stands for gear lubricant. The GL-6 classification, which was
previously used to describe antiscoring performance over
and above that provided by the GL-5 lubricants, is technically
obsolete. The GL-4 and GL-5 categories correspond to U.S.
Military specifications MIL-L-2105 and MIL-L-2105D, respectively, and define oils for service-fill only. The specifica-

240

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

tion MIL-PRF-2105E, issued in 1995, combines the GL-5 requirements of MIL-L-2105D and thermal oxidation stabihty,
antiwear, and seal compatibility requirements of the newly
released API specification MT-1. The new specification defines lubricants for nonsynchronized manual transmissions
used in buses and heavy-duty trucks. Factory-fill oils are defined by major car and truck manufacturers. Such oils have
performance characteristics that are critical to the satisfactory operation of a particular drive train and may include
break-in, bearing preload, and limited slip durability. Mack
GO-G/S and GO-H/S are examples of such specifications.
European OEMs use API GL-5 and MIL-L-2105D to define
minimum performance requirements for oils used in their
equipment. They have additioned requirements pertaining to
surface fatigue, component cleanliness, synchromesh durability, and viscometrics, depending upon their specific need/s.
Japanese OEMs recommend API GL-5 lubricants for vehicles
fitted with h3rpoid and spiral bevel axles and API GL-3 and GL4 lubricajits for cars and trucks equipped with manual transmissions. Most modem cars use transaxle drive train arrangement and hence do not need rear axle lubricants. A new
performance specification, PG-2, for automotive geetr oils is
presently under consideration [73]. It is a temporary designation for axle lubricants to be used in heavy-duty truck and bus
final drives that employ spiral bevel and hypoid gears. This
category is designed to qualify lubricants with higher thermal
durability, seal compatibility, and surface fatigue performance than the existing GL-5 lubricants.
The API and the military specifications have associated
bench and axle tests [74]. These include tests to evaluate the
oil's ability to protect gears and axles against fatigue, scoring,
and wear. Additional tests deal with a gear oil's oxidative stability, foaming tendency, and the ability to protect against
rust and corrosion. Axle tests are run according to methods
established by the American Coordinating Research Council
(CRC). Bench and axle tests used to qualify automotive gear
oils (ASTM D 5760) are given below.
Scoring resistance under high-speed shock load conditions
CRC L-19 and FTM 6504T, CRC L-42, Vehicle Rear Axle
Score
Resistance to gear distress under high-torque low-speed conditionsCRC L-20, CRC L-37 (ASTM D 6121)
Antiwear propertieskSlU D 5182, FZG (A/8.3/90), and
(A/10/90)
Gear surface fatigueMack Spalling
High-temperature stability of lubricantASTM D 5763,
Mack Transmission Test T-2180, CRC L-60, and CRC
L-60-1
Lubricant stability in motored axle testFord BJ 15-1
Corrosion resistance in the presence of waterCRC L-13 or
FTM 5313.1 and CRC L-21, CRC L-33
Copper corrosion^ASTM D 130
Oil seal compatibilityASTM D 471, ASTM D 5662
Foaming tendencyASTM D 892, CRC L-12
Transmission cyclic durabilityASTM D 5579
Material separated on centrifugation after 30 day storage at
room temperatureFTM 3440, modified
Channeling characteristics of lubricantFTM 3456.1, modified
Compatibility with existing gear lubricantsSS & C FEDSTD-791 Method D 3430 and D 3440

Industrial Gear OilsService requirements of industrial gear


oils are established by AGMA, DIN, and a variety of other organizations, such as U.S. Steel, Cincinnati Milacron, and Alcoa [74]. The important function of these lubricants is to reduce friction and wear. Tests pertaining to these include
Timken (ASTM D 2782), Four-Ball EP (ASTM D 2783), FourBall Wear (ASTM D 4172), U.S. Steel S-205, and FZG
(A/8.3/90). Additional tests deal with rust and yellow metal
corrosion protection (ASTM D 665, IP 135, and ASTM D 130),
demulsibility (ASTM D 1401, IP19, and ASTM D 2711), oxidation resistance (ASTM D 2893, U.S. Steel S-200), foaming
tendency (ASTM D 892 and IP 146), and air release time (DIN
51381, IP313).
Hydraulic

Fluids

The primary function of these fluids is to transmit power efficiently and control wear. Hydraulic fluids are of two general
types: those used to lubricate tractor hydraulics and those
used to lubricate industrial hydraulic equipment.
Tractor Hydraulic FluidsTractor hydraulic fluids (THFs)
are multipurpose lubricants that are used to lubricate transmissions, final drives, hydraulic systems, wet brakes, and wet
clutches [75]. To perform these functions properly, THFs
must combine hydraulic and transmission properties with
extreme-pressure properties. Their function as a transmission fluid and as a lubricant for wet brakes and wet clutches
requires them to possess proper frictional characteristics.
Tractor hydraulic fluids differ widely in performance requirements because OEMs can not agree on common specifications for a universal tractor hydraulic fluid. The specifications for these fluids, in general, deal with extreme
pressure (EP) and antiwear properties, and with matching
the frictional requirements of the equipment. The quality of
these fluids is assessed on the basis of their ability to meet individual OEM specifications as well as API GL-4 (for EP) and
Allison C-4 (for friction, oxidation, and wear) performance
requirements. There are eight major OEM specifications and
most tractor fluids are formulated to meet them. These specifications are:
JI Case MS 1207
John Deere J20C/D, and J27
New Holland FNHA-2-C-201.00 and M2C159B/C
AGCO Massey-Ferguson Ml 135, Ml 139, and Ml 141
Tests associated with these specifications include:
Wear and Extreme-pressure TestsDenison T-50 Vane
pump and P-46 Piston Pump; Vickers 35VQ-25 Vane and
Vickers V104C Vane Pump, Constant Volume Vane Pump
(ASTM D 2882); FZG EP/antiwear [DIN 51354 (Part 2)];
Four-Ball EP (ASTM D 2783); and Four-Ball Wear (ASTM
D4172)
Oxidation TestsTnrbme Oil (ASTM D 943); Sludge
(ASTM D 4310); and Rotary Bomb (ASTM D 2272); Universal Oxidation Test (ASTM D 5846)
Corrosion TestsTurhins Oil Rust (ASTM D 665) and Copper Strip (ASTM D 130)
Miscellaneous TestsTurbine Oil Demulsibility (ASTM D
1401); Hydrolytic Stability (ASTM D 2619); Cincinnati Milacron Thermal Stability (ASTM D 2070); Denison TP
02100 Filterability; Foam ASTM D 892; Air Separation
(DIN 51381); and Seal Compatibility [DIN 53538 (Part 1)]

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY

241

In addition to a hydraulic fluid, farm tractors and related


equipment need an engine oil and a transmission fluid. In order to reduce the number of lubricants handled by the farmer,
the concepts of Universal Tractor Transmission Oil (UTTO)
and Super Tractor Oil Universal (STOU) were developed. UTTOs have the ability to lubricate transmissions, wet brakes,
and hydraulic systems. STOUs have the additional ability to
be used as engine oils and meet major performance criteria of
the leading equipment manufacturers. Such oils must therefore pass additional tests. For UTTO oils, these include L-20
High Torque Low-speed Test, Vane and Piston Pump Test,
and Vickers 35VQ25 Test. For STOU oils, these include engine
oil tests, such as ASTM Sequence IID, HID, VD, CRC L-38,
Mack T-6, and T-7; L-20 High Torque Low-speed Test; Vane
and Piston Pump Test; and Vickers 35VQ25 Test.
Industrial Hydraulic FluidsThese lubricants help transmit
and control power in equipment used in industries, such as
automotive, manufacturing, material handling, construction,
chemical, mining, textile, food, rubber, and agriculture.
These fluids fall under three categories: antiwear hydraulic
fluids, rust and oxidation-inhibited oils (R & O oils), and fireresistant fluids. Performance criteria for industrial hydraulic
fluids are defined by OEMs. Each hydraulic pump manufacturer has its own performance requirements that pertain to
lubricant viscosity, antiwear properties, demulsibility, and
ability to inhibit rust, oxidation, corrosion, foam, and filter
plugging. Tests for these fluids include:

every other aspect, they resemble soluble oils. Because of the


lower oil content, these fluids appear clear. However, some
high semisynthetic fluids contain >3.0% oil and are translucent. Their appearance is a function of the particle size.
The performance specifications of metalworking fluids are
established by the OEMs and end-users. Test methods to
evaluate performance of these fluids are not well standardized. Tests that are presently used or can be used to judge the
suitability of metalworking fluids include:
Corrosion TesteCopper Strip (ASTM D 130), Turbine Oil
Rust (ASTM D 665), Aqueous Cutting Fluid (IP125), Filter
Paper Chip Breakpoint (IP287), Aluminum Cup Stain, Humidity Cabinet Rust (ASTM D 1748), Salt Spray (MIL-B117-64), Cleveland Condensing Humidity Cabinet (ASTM
D 2247)
Extreme PressureFour-Ball Wear (ASTM D 4172),
Timken (ASTM D 2782), Four-Ball EP (ASTM D 2783),
Falex EP (ASTM D 3233)
Stability~oam Tendency/Stability (ASTM D 892, IP312),
Panel Coker, Demulsibility (ASTM D 1401), Emulsion Stability (IP263), Aquarium Biostability
MiscellaneousColor (ASTM D 1500), GM Quenchometer
(ASTM D 3520), Thread Tapping (Lubrizol test). Pipe
Threading (Lubrizol test). Stick-slip (Cincinnati Milacron
test), Bijur Filtration, Falex #8, SLT (Draw Bead Simulator), Reichert Test, and Tapping Torque Test (ASTM D
5619)

Wear and Extreme-pressure TestsDenison T-50 Vane


pump and P-46 Piston Pump; Vickers 35VQ-25 Vane and
Vickers V104C Vane Pump; FZG EP/antiwear [DIN 51354
(Part 2)]; Four-Ball EP (ASTM D 2783); and Four-Ball
Wear (ASTM D 4172)
Oxidation JesfsTurbine Oil (ASTM D 943); Sludge
(ASTM D 4310); and Rotary Bomb (ASTM D 2272)
Corrosion TesfsTurbine Oil Rust (ASTM D 665) and Copper Strip (ASTM D 130)
Miscellaneous TestsTurbine Oil Demulsibility (ASTM D
1401); Hydrolytic Stability (ASTM D 2619); Cincinnati Milacron Thermal Stabihty; Denison TP 02100 Filterabihty;
Foam ASTM D 892; Air Separafion (DIN 51381); and Seal
Compatibility [DIN 53538 (Part 1)]

Miscellaneous Industrial Oils


Compressor oils, refrigeration oils, turbine oils, circulating
oils, slideway lubricants, and rock drill lubricants make up
this group. Compressor and refrigeration oils are used in compressors to reduce friction and act as a seal separating low and
high-pressure areas. Turbine and circulating system oils are
used to lubricate steam and gas turbines for marine and stationary applications. Circulating oils are used in systems
where large quantities of heat must be removed and where
heavy contamination of oil occurs. As a result, these oils must
possess excellent air and water separation properties and
good oxidative stability over the duration of their use. Slideway and drill lubricants are used to lubricate guiding surfaces
on the bed of a machine along which a table or a carriage
moves and to lubricate pneumatic equipment. These oils must
perform under extreme temperatures, high loads, moisture,
and poor ambient air quality. They therefore possess both the
EP activity and the rust and corrosion-inhibiting properties.
ISO viscosity grades and U.S. Military and OEM performance
requirements usually specify these lubricants.
Turbine oils are classified as R & O oils, non-EP oils, and
EP oils. R & O oils are formulated to provide rust and oxidation protection and EP oils are formulated to provide EP protection, depending upon the intended end use. EP oils contain R & O packages enhanced with antiwear additives. R &
O oil performance specifications are established by OEMs,
such as U.S. Steel, Cincinnati Milacron, Denison, General
Electric, and organizations, such as U.S. Military, AFNOR
(Association Francais Petroles de Normalisation) and DIN
(Deutsche Industrie Norm). Specifications for non-EP oils
are established by General Electric, British Government, and
DIN and for EP oils the OEM Brown Boveri plays an active
role [74]. Common tests for these oils are as follows.

Metalworking

Fluids

Metalworking fluids are used to convert metal into a component or a piece. These fluids are of four basic t3^es, straight
oils, soluble oils, semisynthetic fluids, and synthetic fluids. Soluble oils, semisynthetic fluids, and synthetic fluids are waterbased and differ from one another, mainly in their oil content
and emulsion type [76]. Straight oils are devoid of water.
They are mineral oil-based (primarily hydrotreated naphthenic basestocks) and usually contain sulfur, chlorine, and
phosphorus-derived additives. Soluble oils are water emulsions of mineral and/or fatty oils. An emulsifying agent or
surfactant is used to form these emulsions. Synthetic fluids
are oil-free and are simply solutions of additives in water.
Since most organic materials are hard to dissolve in water,
high polarity of the additives is necessary for solubility.
Soaps or other surfactants are sometimes added to help in
this regard. Semisynthetic fluids are in between soluble oils
and synthetic fluids as far as their oil content is concerned. In

242

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

R & O Oils
Wear TestsVane P u m p (ASTM D 2882), Denison P-46 Piston Pump, Four-Ball Wear (ASTM D 4172)
Oxidation TestsRotary Bomb (ASTM D 2272), Turbine
Oil (ASTM D 943), 1000-hour Sludge (ASTM D 4310),
Cincinnati Milacron Heat, FTMS 5308.6
Corrosion TestsRust (ASTM D 665), Copper Strip (ASTM
D 130)
Miscellaneous TestsTurbine Oil Demulsibility (ASTM D
1401), Neutralization N u m b e r (ASTM D 974 and D 664),
Foam (tendency/stability) (ASTM D 892), and Air Release
(DIN 51381, ASTM D 3427)
Turbine Oils
Oxidation TesfsTurbine Oil (ASTM D 943), 1000-hour
Sludge (ASTM D 4310), IP280 TOP, IP280 Sludge, Rotary
Bomb (ASTM D 2272), FTMS 5308.6, and Universal Oxidation Test (ASTM D 5846)
Corrosion TestsRust (ASTM D 665), Copper Strip (ASTM
D130)
Wear TestFZG (A/8.3/90), a n d Four-Ball EP (ASTM D
2783), Falex (ASTM D 2670), Ryder gear tests to fulfil U.S.
Military requirements.
Miscellaneous
TestsViscosity
Index (ASTM D 2270),
Flash Point (ASTM D 93), Pour Point (ASTM D 97), Neutralization N u m b e r (ASTM D 974 and D 664), Air Release
(DIN 51381, ASTM D 3427), F o a m (tendency/stability)
(ASTM D 892), Demulsibility (ASTM D 2711), and Turbine
Oil Demulsibility (ASTM D 1401)
Greases
The use of this lubricant goes back to ancient times [62]. Lubricating grease is defined as a "solid-to-semifluid products
of dispersion of a thickening agent in a liquid lubricant.
Other ingredients imparting special properties may be added
(ASTM D 288)." Such ingredients include additives that impart other desirable properties, such as EP, water resistance,
etc. The lubrication function is carried out by the small
amount of oil that is released during equipment operation.
Because of their semisolid nature, greases are used when
fluid lubricants are inefficient, the need for lubrication is infrequent, and/or the lubricant is required to maintain its original position in a mechanism.
Greases are formulated from both synthetic and mineral
oil basestocks by using a thickening agent and selected additive packages. The thickener, usually a metal soap (a carboxylic acid salt) and sometimes a gelled basic sulfonate,

serves to immobilize the lubricant until service application


causes it to be released. The lubricant contains additives
which reduce friction and prevent wear. Greases perform
the same basic functions as their fluid counterparts but, in
view of their high viscosity, they do not perform cooling and
cleaning functions efficiently. Based on thickener, greases
can be classified as simple-soap, complex-soap, and nonsoap. Simple-soap greases contain lithium (Li), sodium
(Na), calcium (Ca), barium (Ba), or aluminum (Al) fatty
acid carboxylates. Complex-soap greases contain metal salts
of fatty and nonfatty acid mixtures. Nonsoap greases may
contain either inorganic compounds or orgeinic compounds
as thickeners.
Greases are described by the National Lubricating Grease
Institute (NLGI) consistency grades and NLGI Service Classification System for automotive use, first implemented in
1991 [77], Consistency grades are 000, 00, 0, and 1-6 and are
based on degree of hardness and ASTM Worked penetration
rcinge @ 25C. NLGI service classifications are LA and LB for
chassis use and GA, GB, and GC for use in wheel bearings.
Prior to this classification, the SAE recommended practice,
published in the SAE information report J310, was used for
this purpose. The report, first introduced in 1951, had several
revisions, the most recent of which occurred in 1993 [78].
Tests associated with NLGI Service Classes, provided in the
ASTM 4950 Automotive Grease Specification, are listed below.
Shear StabilityMukistroke
Penetration (ASTM D 217),
Roll Stability (ASTM D 1831), Wheel Bearing Leakage
(ASTM D 4290 and D 1263)
Oxidation ResistanceBomb
Oxidation (ASTM D 942),
High Temperature Life (ASTM D 3527), High-Temperature
Performance (ASTM D 3336)
Water ResistanceWater Washout (ASTM D 1264), Water
Spray-off (ASTM D 4049)
Bleed ResistanceOil Separation, static (FTM 321.3), Pressure Oil Separation (ASTM D 1742)
Extreme Pressure/ AntiwearFour-ball EP (ASTM D 2596),
Timken Method (ASTM D 2509), Four-ball Wear (ASTM D
2266), Fretting Protection (ASTM D 4170), SRV Test
(ASTM D 5706 and D 5707)
CorrosionRust Test (ASTM D 1743), E m c o r (IP 220),
Copper Corrosion (ASTM D 4048)
PumpabilityLow-temperatu
re Torque (ASTM D 4693)
Mobility (US Steel LT37)
Msce/ZaneoMSElastomer Compatibility (ASTM D 4289)
Dropping Point (ASTM D 566 or D 2265)

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY

243

ASTM AND OTHER STANDARDS


ISO No.
2592:1973
2719:1988
6293:1983
3016:1994

IP No.
36/84 (89)
34/88
136/89
15/95

2160:1985

154/95

D 217-97
D 445-01

2137:1985
3104:1994

50/88
71/97

D 482-00
D 566-97
D 664-95 (2001)

2176:1995
6619:1988

132/96
177/96

D 665-99

7120:1987

135/93

D
D
D
D

808-00
874-00
892-01
942-90 (1995)

3987:1994
6247:1998

163/96
146/82 (88)
142/85 (92)

D
D
D
D

943-99
972-97
974-01
1078-95

4263:1986

280/96

6618:1997

139/93
195/90

3839:1978

130/92

D 1298-99

3675:1993

160/96

D
D
D
D

6614:1994
2049-1996

412/96
196/97

D
D
D
D
D
D

ASTM No.
92-01
93-00
94-00
97-96a
129-00
130-94(2000)

D 1091-00
D 1092-99
D 1159-01
D 1218-99
D 1263-94 (1999)
D 1264-00

1401-98
1500-98
1742-94 (2000)
1743-01

D 1744
366/84

D 1748-00
D 1831-00
D 2070-91 (2001)
D 2161-93 (1999)
D 2265-00

239/97

D 2266-91 (1996)
D 2270-93 (1998)
D 2272-98

2909:1981

226/91 (95)

D 2500-99
D 2509-93 (1998)

3015:1992

219/94
326/83 (88)

D 2596-97
D 2602-86
D 2603-01

Test
Test Method for Flash and Fire Points by Cleveland Open Cup
Test Method for Flash Point by Pensky-Martens Closed Cup Tester
Test Method for Saponification N u m b e r of Petroleum Products
Test Method for Pour Point of Petroleum Products
Test Method for Sulfur in Petroleum Products (General B o m b Method)
Test Method for Detection of Copper Corrosion from Petroleum Products by the
Copper Strip Tarnish Test
Test Method for Cone Penetration of Lubricating Grease
Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (the
Calculation of Dynamic Viscosity)
Test Method for Ash from Petroleum Products
Test Method for Dropping Point of Lubricating Grease
Test Method for Acid Number of Petroleum Products by Potentiometric Titration
Method
Test Method for Rust Preventing Characteristics of Inhibited Mineral Oil in the
Presence of Water
Test Method for Chlorine in New and Used Petroleum Products (Bomb Method)
Test Method for Sulfated Ash from Lubricating Oils and Additives
Test Method for Foaming Characteristics of Lubricating Oils
Test Method for Oxidation Stability of Lubricating Greases by the Oxygen B o m b
Method
Test Method for Oxidation Characteristics of Inhibited Mineral Oils
Test Method for Evaporation Loss of Lubricating Greases and Oils
Test Method for Acid and Base Number by Color-Indicator Titration
Test Method for t h e Determination of Distillation Characteristics of Volatile
Organic Liquids (ASTM Procedure Now Obsolete)
Test Method for Phosphorus in Lubricating Oils and Additives
Test Method for Measuring Apparent Viscosity of Lubricating Greases
Test Method for B r o m i n e N u m b e r s of Petroleum Distillates and Commercial
Aliphatic Olefins by Electrometric Titration
Test Method for Refractive Index a n d Refractive Dispersion of Hydrocarbon
Liquids
Test Method for Leakage Tendencies of Automotive Wheel Bearing Greases
Test Method for Determining the Water Washout Characteristics of Lubricating
Greases
Practice for Density, Relative Density (Specific Gravity), or API Gravity of Crude
Petroleum and Liquid Petroleum Products
Test Method for Water Separability of Petroleum Oils and Synthetic Fluids
Test Method for ASTM Color of Petroleum Products (ASTM Color Scale)
Test Method for Oil Separation from Lubricating Grease During Storage
Test Method for Determining Corrosion Preventive Properties of Lubricating
Greases
Test Method for Determination of Water in Liquid Petroleum Products by Karl
Fischer Reagent (Discontinued 2000)
Standard Test Method for Rust Protection by Metal Preservatives in the Humidity
Cabinet
Test Method for Roll Stability of Lubricating Grease
Test Method for Thermal Stability of Hydraulic Oils
Practice for Conversion of Kinematic Viscosity to Saybolt Universal Viscosity or to
Saybolt Universal Viscosity
Test Method for Dropping Point of Lubricating Grease Over Wide Temperature
Range
Test Method for Wear Preventive Characteristics of Lubricating Grease (Four-Ball
Method)
Practice for Calculating Viscosity Index from Kinematic Viscosity at 40 and 100C
Test Method for Oxidation Stability of Steam Turbine Oils by Rotating Pressure
Vessel
Test Method for Cloud Point of Petroleum Products
Test Method for Measurement of Load-Carrying Capacity of Lubricating Grease
(Timken Method)
Test Method for Measurement of Extreme-Pressure Properties of Lubricating
Grease (Four-Ball Method)
Test Method for Apparent Viscosity of Engine Oils at Low Temperature Using
Cold-cranking Simulator (Replaced in 1993 with D 5293)
Test Method for Sonic Shear Stability of Polymer-Containing Oils

(Continues)

244 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


ASTM No.

ISO No.

IP No.

D 2619-95
D 2622-98
D 2670-95 (1999)
D 2710-99
D2711-01a
D 2782-01
D 2783-88 (1998)

293/97

D 2882-00
D 2893-99
D 2896-01

3771:1994

D 2983-01

276/95
267/84

D 3228-96
D 3233-93 (1998)
D 3336-97
D 3339-95 (2000)

7537:1989

BS7393

3679:1983
3680:1983

303/83 (88)

4265:1986

149/93

D 3427-99
D 3520-88 (1998)
D 3527-95
D 3825-90 (2000)
D 3828-98
D 3829-93 (1998)
D 4047-00
D
D
D
D

4048-97
4049-99
4170-97
4172-94 (1999)

293/97

D 4289-97
D 4290-94 (1999)
D 4310-98
D 4377-00
D 4485-01
D 4624-93 (1998)

356/93

D 4627-92

287/94
125/82

D 4628-97
D 4682-87 (1996)
D 4683-96
D 4684-99
D 4693-97
D 4739-96
D 4741-00
D 4857-Ola
D 4858-00

276/95
417/96

Test

Test Method for Hydrolytic Stability of Hydraulic Fluids (Beverage Bottle Method)
Test Method for Sulfur in Petroleum Products by Wavelength Dispersive X-Ray
Fluorescence Spectrometiy
Test Method for Measuring Wear Properties of Fluid Lubricants (Falex Pin and Vee
Block Method)
Test Method for Bromine Index of Petroleum Hydrocarbons by Electrometric
Titration
Test Method for Demusibility Characteristics of Lubricating Oils
Test Method for Measurement of Extreme-Pressure Properties of Lubricating
Fluids (Timken Method)
Test Method for Measurement of Extreme-Pressure Properties of Lubricating
Fluids (Four-Ball Method)
Test Method for Indicating Wear Characteristics of Petroleum and Non-Petroleum
Hydraulic Fluids in Constant Volume Vane Pump
Test Method for Oxidation Characteristics of Extreme-Pressure Lubricating Oils
Test Method for Base Number of Petroleum Products by Potentiometric Perchloric
Acid Titration
Test Method for Low-Temperature Viscosity of Automotive Fluid Lubricants
Measured by Brookfield Viscometer
Test Method for Total Nitrogen in Lubricating Oils and Fuel Oils by Modified
Kjeldahl Method
Test Method for Measurement of Extreme Pressure Properties of Fluid Lubricants
(Falex Pin and Vee Block Methods)
Test Method for Life of Lubricating Greases in Ball Bearings at Elevated
Temperatures
Test Method for Acid Number of Petroleum Products by Semi-Micro Color Indicator Titration
Test Method for Air Release Properties of Petroleum Oils
Test Method for Quenching Time of Heat-Treating Fluids (Magnetic Quenchometer Method)
Test Method for Life Perforraance of Automotive Wheel Bearing Grease
Test Method for Dynamic Surface Tension by the Fast Bubble Technique
Test Method for Flash Point by Small Scale Closed Tester
Test Method for Predicting the Borderline Pumping Temperature of Engine Oil
Test Method for Phosphorus in Lubricating Oils and Additives by Quinoline
Phosphomolybdate Method
Test Method for Detection of Copper Corrosion from Lubricating Grease
Test Method for Determining the Resistance of Lubricating Grease to Water Spray
Test Method for Fretting Wear Protection by Lubricating Greases
Test Method for Wear Preventive Characteristics of Lubricating Fluid (Four-Ball
Method)
Test Method for Elastomer Compatibility of Lubricating Greases and Fluids
Test Method for Determining the Leaking Tendencies of Automotive Wheel
Bearing Grease Under Accelerated Conditions
Test Method for Determination of the Sludging and Corrosion Tendencies of
Inhibited Mineral Oils
Test Method for Water in Crude Oils by Potentiometric Karl Fischer Titration
Specification for Performance of Engine Oils
Test Method for Measuring Apparent Viscosity by Capillary Viscometer at HighTemperature and High-Shear Rates
Test Method for Iron Chip Corrosion for Water-Dilutable Metalworking Fluids
Test Method for Analysis of Barium, Cadmium, Magnesium, and Zinc in Unused
Lubricating Oils by Atomic Absorption Spectrometry
Specification for Miscibility with Gasoline and Fluidity of Two-Stroke Cycle Gasoline Engine Lubricants
Test Method for Measuring Viscosity at High Shear Rate and High Temperature by
Tapered Bearing Simulator
Test Method for Determination of Yield Stress and Apparent Viscosity of Engine
Oils at Low Temperature
Test Method for Low-Temperature Torque of Grease-Lubricated Wheel Bearings
Standard Test Method for Base Number Determination by Potentiometric
Titration
Test Method for Measuring Viscosity at High Temperature and High Shear Rate by
Tapered-Plug Viscometer
Test Method for Determination of the Ability of Lubricants to Minimize Ring
Sticking and Piston Deposits in Two-Stroke-Cycle Gasoline Engines Other Than
Outboards
Test Method for Determination of the Tendency of Lubricants to Promote Preignition in Two-Stroke-Cycle Gasoline Engines

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY


ASTM No.
D 4859-97

ISO No.

IP No.

D 4863-00
D 4927-96
D 4928-00
D 4950-95 (2000)
D 4951-00
D 4998-95
D 5133-99
D 5182-97
D 5185-97
D 5291-96
D 5293-99a
D 5302-01

D 5480-95 (1999)
D5481- 96
D 5533-98
D 5579- 01
D 5 6 1 9 00
D 5662
D 5706- 97
D 5707.
D 5760- 95
D 5763- 95
D 5800 00a
D 5844. 98
D 5846- 99
D 5862- 99a
D 5949- 96
D 5950- 96
D 5966- 99
D 5967- 99a
D 5968 00a
D 5985- 96
D 6082- 00
D6121- 01
D 6202 -01
D 6335
D 6375 99a
D 6417 99

334/93

245

Test
Specification for Lubricants for Two-Stroke-Cycle Spark-Ignition Gasoline
Engines-TC
Test Method for Determination of Lubricity of Two-Stroke-Cycle Gasoline Engine
Lubricants
Test Methods for Elemental Analysis of Lubricant and Additive Components
B a r i u m , Calcium, P h o s p h o r u s , Sulfur, and Zinc by Wavelength-Dispersive
X-Ray Fluorescence Spectroscopy
Test Methods for Water in Crude Oils by Coulometric Karl Fischer Titration
Classification and Specification for Automotive Service Greases
Test Method for Determination of Additive Elements in Lubricating Oils by Inductively Coupled Plasma Atomic Emission Spectroscopy
Test Method for Evaluating Wear Characteristics of Tractor Hydraulic Fluids
Test Method for Low T e m p e r a t u r e , Low Shear Rate, Viscosity/Temperature
Dependence of Lubricating Oils Using a Temperature Scanning Technique
Standard Test Method for Evaluating the Scuffing Load Capacity of Oils (FZG
Visual Method)
Test Method for Determination of Additive Elements, Wear Metals, and Contaminants in Used Lubricating Oils and Determination of Selected Elements in Base
Oils by Inductively Coupled Plasma Emission Spectroscopy (ICP-AES)
Test Methods for Instrumental Determination of Carbon, Hydrogen, and Nitrogen
in Petroleum Products and Lubricants
Test Method for Apparent Viscosity of Engine Oils Between - 5 and 35C Using
the Cold Cranking Simulator
Test Method for Eveduation of Automotive Engine Oils for Inhibition of Deposit
Formation and Wear in a Spark-Ignition Internal Combustion Engine Fueled
with Gasoline and Operated Under Low-Temperature, Light-Duty Conditions
(Sequence VE)
Test Method for Engine Oil Volatility by Gas Chromatography
Test Method for Measuring Apparent Viscosity at High-Temperature and HighShear Rate by Multicell Capillary Viscometer
Test Method for Evaluation of Automotive Engine Oils in Sequence IIIE, SparkIgnition Engine
Test Method for Evaluating the Thermal Stability of Manual Transmission Lubricants in a Cyclic Durability Test
Test Method for Comparing Metal Removal Fluids Using the Tapping Torque Test
Machine
Test Method for Determining Automotive Gear Oil Compatibility with Typical Oil
Seal Elastomers
Test Method for Determining Extreme Pressure Properties of Lubricating Greases
Using a High-Frequency, Linear-Oscillation (SRV) Test Machine
Test Method for Measuring Friction and Wear Properties of Lubricating Greases
Using a High-Frequency, Linear-Oscillation (SRV) Test Machine
Specification for Performance of Manual Transmission Gear Lubricants
Test Method for Oxidation and Thermal Stability Characteristics of Gear Oils
Using Universal Glassware
Test Method for Evaporation Loss of Lubricating Oils by the Noack Method
Test Method for Evaluation of Automotive Engine Oils for Inhibition of Rusting
(Sequence IID)
Test Method for Universal Oxidation Test for Hydraulic and Turbine Oils Using the
Universal Oxidation Test Apparatus
Test Method for Evaluation of Engine Oils in Two-Stroke Cycle Turbo-SuperCharged 6V92TA Diesel Engine
Test Method for Pour Point of Petroleum Products (Automatic Pressure Pulsing
Method)
Test Method for Pour Point of Petroleum Products (Automatic Tilt Method)
Test Method for Evaluation of Engine Oils for Roller Follower Wear in Light-Duty
Diesel Engine
The Method of Evaluation of Diesel Engine Oils in T-8 Engine
Test Method for the Corrosiveness of Diesel Engine Oil
Test Method for Pour Point of Petroleum Products (Rotational Method)
Test Method for High Temperature Foaming Characteristics of Lubricating Oils
Test Method for Evaluation of the Load Carrying Capacity of Lubricants Under
Conditions of Low Speed and High Torque Used for Final Hypoid Drive Axles
Test Method for Automotive Engine Oils on the Fuel Economy of Passenger Cars
and Light Duty Trucks in t h e Sequence VIA Spark Ignition Engine
Test Method for Determination of High T e m p e r a t u r e Deposits by ThermoOxidation Engine Oil Simulation Test
Test Method for Evaporation Loss of Lubricating Oils by Thermogravimetric
Analyzer (TGA) Noack Method
Test Method for Estimation of Engine Oil Volatility by Capillary Gas Chromatography
(Continues)

246 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


ASTM No.

D 6443-99
D 6481-99
D 6483-99
D 6557-00
D 6593-00

D 6616-01
D 6618-00
D 6681-01
D 6709-01

ISO No.

IP No.

Test

Test Method for Determination of Calcium, Chlorine, Copper, Magnesium, Phosphorus, Sulfur, and Zinc in Unused Oils and Additives by Wavelength Dispersive
X-ray Fluorescence Spectrometry (Mathematical Correction Method)
Test Method for Determination of Phosphorus, Sulfur, Calcium, and Zinc in
Lubrication Oils by Energy Dispersive X-ray Fluorescence Spectrometry
Test Method for Evaluation of Diesel Engine Oils in T-9 Engine
Test Method for Evaluation of Rust Preventive Characteristics of Automotive
Engine Oils (Ball Rust Test)
Test Method for Evaluation of Automotive Engine Oils for Inhibition of Deposit
Formation in a Spark-Ignition Internal Combustion Engine Fueled with
Gasoline and Operated Under Low-Temperature, Light Duty Conditions
(Sequence VG)
Test Method for Measuring Viscosity at High Shear Rate by Tapered Bearing
Simulator Viscometer at 100C
Test Method for Evaluation of Engine Oils in Diesel Four-Stroke-Cycle SuperCharged IM-PC Single Cylinder Oil Test Engine
Test Method for Evaluation of Engine Oils in a High Speed, Single-Cylinder Diesel
EngineCaterpillar IP Test Procedure
Test Method for Evaluation of Automotive Engine Oils in the Sequence VIII SparkIgnition Engine (CLR Oil Test Engine)

REFERENCES
[1] Obert, E. F., "Lubrication," Ch. 16, Internal Combustion Engines
and Air Pollution, Intext Educational Publishing, NY, 1968, pp.
633-677.
[2] Modler, R., Anderson E., and Yoshida Y., "Lubricant Oil Additives," Specialty Chemicals, Strategies for Success, Vol. 9, SRI International, December 1996.
[3] Rizvi, S. Q. A., "Additives: Chemistry and Testing," Tribology
Data HandbookAn Excellent Friction, Lubrication, and Wear
Resource, CRC Press, Boca Raton, FL, 1997, pp. 117-137.
[4] Klamann, D., Lubricants and Related ProductsSynthesis, Properties, Applications, International Standards, Verlag Chemie,
Hamburg, 1984. (a) "Analysis and Testing," Ch. 10, pp. 218-247.
(b) "Additives," Ch. 9, pp. 177-217. (c) Appendix A, pp. 437-442.
[5] Gergel, W. C, "Lubricant Additive Chemistry," Presented at the
International Symposium on Technical Organic Additives and
Environment, Interlaken, Switzerland, 24-25 May 1984.
[6] Ford, J. F., "Lubricating Oil Additives^A Chemist's Eye View,"
Journal of the Institute of Petroleum, Vol. 54, July 1968, pp.
188-210.
[7] Schilling, A., Motor Oils and Engine Lubrication, Scientific Publications, Great Britain, 1968.
[8] Ingold, K. U., "Inhibition of Autoxidation of Organic Substances
in Liquid Phase," Chemical Reviews, Vol. 61, 1961, pp. 563-589.
[9] Johnson, M. D., Korcek, S., and Zinbo, M., "Inhibition of Oxidation by ZDTP and Ashless Antioxidants in the Presence of Hydroperoxides at 160C," Lubricant and Additive Effects on Engine
Wear, SP-558, Fuels and Lubricants Meeting, San Francisco, CA,
31 Oct.-3 Nov., 1983, pp. 71-81.
[10] Al-Malaika, S., Marogi, A., and Scott, G., Journal ofApplied Polymer Science, Vol. 33, 1987, pp. 1455-71.
[11] Abou El Naga, H. H. and Salem, A. E. M., "Effect of Worn Metals on the Oxidation of Lubricating Oils," Wear, Vol. 96, 1984,
pp.267-283.
[12] Vijh, A. K., "Electrochemical Mechanisms of the Dissolution of
Metals Eind the Contaminants Oxidation of Lubricating Oils Under High-temperature Friction Conditions," Wear, Vol. 104,
1985,pp.l51-158.
[13] HambUn, P. C, Kristen U., and Chasan D., "A Review: Ashless
Antioxidants, Copper Deactivators, and Corrosion Inhibitors,
Their Use in Lubricating Oils," Lubrication Science, Vol. 2, 1990,
pp. 287-318.

[14] Kreuz, K. L., "Gasoline Engine Chemistry as Applied to Lubricant Problems," Lubrication, Vol. 55, 1969, pp. 53-64.
[15] Lachowicz, D. R. and Kreuz, K. L., "Peroxynitrates. The Unstable Products of Olefin Nitration with Dinitrogen Tetroxide in
the Presence of Oxygen. A New Route to a-Nitroketones," Journal of Organic Chemistry, Vol. 32, 1967, pp. 3885-3888.
[16] Kreuz, K. L., "Diesel Engine Chemistry as Applied to Lubricant
Problems," Lubrication, Vol. 56, 1970, pp. 77-88.
[17] Covitch, M. J., Graf, R. T., and Gundic, D. T., "Microstructure of
Carbonaceous Diesel Engine Piston Deposits," Lubricant Engineering, Vol. 44, 1988, p. 128. (b) Covitch, M. J., Richardson, J.
P., and Graf, R. T., "Structural Aspects of European and American Diesel Engine Piston Deposits," Lubrication Science, Vol. 2,
1990, pp. 231-251.
[18] Kombrekke, R. E., Personal Communication, Research and Development, The Lubrizol Corporation, Wickliffe, OH.
[19] Boner, C. J., "Theory of Action and Performance," Ch. 8, Gear
and Transmission Lubricants, Reinhold Publishing Company,
NY, 1964.
[20] Bhushan, B. and Gupta, B. K., "Physics of Tribological Materials," Ch. 3, Handbook of Tribology; Materials, Coatings, and Surface Treatments, McGraw-Hill, Inc., NY, 1991. (c) Buckley, D.
H., "Properties of Surfaces," CRC Handbook of Lubrication,
(Theory and Practice of Tribology), Vol. II, Theory and Design,
Richard E. Booser, Ed., CRC Press, Boca Raton, FL, 1983, pp.
17-30.
[21] Lansdown, A. R., "Extreme Pressure and Anti-wear Additives,"
Ch. 12, Chemistry and Technology of Lubricants, R. M. Mortier
and S. T. Orszulik, Eds., VCH Publishers, Inc., NY, 1992, pp.
269-281.
[22] O'Brien, J. A., "Lubricant Additives," CRC Handbook of Lubrication, (Theory and Practice of Tribology), Vol. II, Theory and Design, Richard E. Booser, Ed., CRC Press, Boca Raton, FL, 1983,
pp. 301-315.
[23] "Engine Service Classification System and Guide to Crankcase
Oil Selection," API Publication 1509, American Petroleum Institute, Washington, D.C., 1996.
[24] Oliver, C. R., Renter, R. M., and Sendra, J. C, "Fuel Efficient
Gasoline-Engine Oils," Lubrication, Vol. 67, 1981, pp. 1-12.
[25] Jayne, G. J., Matthews, B. M., and Thomas, A. S., "Hypoid Gear
Oils for the 1980s," Ch. 19, Performance and Testing of Gear Oils
and Transmission Fluids, R. Tourret and E. P. Wright, Eds.,
Heyden and Son, 1981, pp. 307-319.

CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY


[26] Feng, I. M., Perilstein, W. L., and Adams, M. R., "Solid Film Deposition and Non-Sacrificial B o u n d a r y Lubrication," ASLE
Transactions, Vol. 6, 1963, pp. 60-66.
[27] Schiemann, L. F. and Schwind, J. J., "Fundamentals of Automotive Gear Lubrication," SAE Paper 841213, Fuels and Lubricants Technology: An Overview, SP603, Society of Automotive
Engineers, Warrendale, PA, October 1984, pp. 107-115.
[28] Jones, R. B. and Coy, R. C , "The Thermal Degradation and EP
Performance of Zinc Dialkyl Dithiophosphate Additives in
White Oil," ASLE Transactions, Vol. 24, 1981, pp. 77-90. (b)
Jones, R. B. and Coy, R. C , "The Chemistry of Thermal Degradation of Zinc Dialkyl Dithiophosphate Additives," ASLE Transactions, Vol. 24, 1981, pp. 91-97.
[29] Brazier, A. D. and EUiot, J. S., "The Thermal Stability of Zinc
Dithiophosphates," Journal of the Institute of Petroleum, Vol. 53,
1967, pp. 63-76.
[30] Bateman L. and Moore, C. G., "Reaction of Sulfur with Olefins,"
Ch. 20, Organic Sulfur Compounds, Vol. 1, N. Kharasch, Ed.,
Pergamon Press, NY, 1961, pp. 210-228.
[31] T h o m , G. D. and Ludwig, R. A., The Dithiocarbamates and Related Compounds, Elsevier Publishing Company, NY, 1962.
[32] Gerrard, W. and Hudson, H. R., "Organic Derivatives of Phosphorous and Thiophosphorous Acids," Ch. 13, Organic Phosphorus Compounds, Vol. 5, G. M. Kosolapoff and L. Maier, Eds.,
Wiley Interscienee, NY, 1973, p. 21.
[33] Cherbuliez, E., "Organic Derivatives of Phosphoric Acid," Organic Phosphorus Compounds, Vol. 6, G. M. Kosolapoff and L.
Maier, Eds., Wiley Interscienee, NY, 1973, p. 211.
[34] Fein, R. S., "Boundary Lubrication," CRC Handbook of Lubrication, Theory and Practice in Trihology, Vol. II, Theory and Design,
Richard E. Booser, Ed., CRC Press, Boca Raton, FL, 1983, pp.
49-67.
[35] Forbes, E. S. and Battersby, J., "The Effect of Chemical Structure
on the Load-carrying and Adsorption Properties of Dialkyl Phosphites," ASLS Transactions, Vol. 17, No. 4, 1974, pp. 263-270.
[36] Dorinson, A., "The Additive Action of Some Organic Chlorides
and Sulfides in the Four-Ball Lubricant Test," ASLE Transactions, Vol. 16, No. 1, 1973, pp. 22-31.
[37] Forbes, E. S. and Reid, A. J. D., "Liquid Phase Adsorption/Reaction Studies of Organo-sulfur Compounds and Their Load-Carrying Mechanism," ASLE Transactions, 1973, Vol. 16, No. 1, pp.
50-60.
[38] Plaza, S., "Some Chemical Reactions of Orgsinic Disulfides in
B o u n d a r y Lubrication," ASLE Transactions, Vol. 30, No. 4,
1987, pp. 493-500.
[39] Kawamura, M., Moritani, H., Esaki, Y., and Fujita, K., "The
Mechanism of Synergism Between Sulfur- and Phosphorus-type
EP Additives," ASLE Transactions, Vol. 29, No. 4, 1986, p p .
451^56.
[40] Rounds F. G., "Additive Interactions and Their Effect on the
Performance of a Zinc Dialkyl Dithiophosphate," ASLE Transactions, Vol. 2 1 , No. 2, 1978, pp. 91-101.
[41] Rounds, F. G., "Some Effects of Amines on Zinc Dialkyl Dithiop h o s p h a t e Antiwear Performance as Measured in Four-Ball
Wear Tests," ASLE Transactions, Vol. 24, No. 4, 1981, p p .
431-440.
[42] Speller, F. N., CorrosionCauses and Prevention, McGraw-Hill
Pubhshing, Columbus, OH, 1935.
[43] Cooper, A. R., "Molecular Weight Determination," Concise Encyclopedia of Polymer Science and Engineering, J. I. Kroschwitz,
Ed., Wiley Interscienee, NY, 1990, pp. 638-639.
[44] R a w e , A., "Molecular Weights of Polymers," Organic Chemistry
of Macromolecules, Marcel Dekker, NY, 1967, pp. 39-54. (b)
Deanin, R. D., Polymer Structure, Properties, and Applications,
Cahner Books, NY, 1972, p. 53.
[45] Baczek, S. K. and Chamberhn, W. B., "Petroleum Additives,"

247

Encyclopedia of Polymer Science and Engineering, Second Edition, John Wiley and Sons, NY, 1988, Vol. 11, p. 22.
[46] MuUer, H. G., "Mechanism of Action of Viscosity Index Improvers," Tribology International, June 1978, pp. 189-192.
[47] Watson, R. W. and McDonnell, T. F., Jr., "AdditivesThe Right
Stuff for Automotive Engine Oils," Fuels and Lubricants Technology: An Overview, SP. 603, Society of Automotive Engineers,
Warrendale, PA, October 1984, pp. 17-28.
[48] Stambaugh, R. L "Viscosity Index Improvers and Thickeners,"
Chemistry and Technology of Lubricants, R. M. Mortier and S. T.
Orszulik, Eds., VCH Publishers, Inc., NY, 1992, pp. 124-159.
[49] Becher, P., Emulsions: Theory and Practice, American Chemical
Society Monograph Series, Ch. 6, Reinhold Publishing Corporation, NY, 1957, pp. 209-231.
[50] Karsa, D. R., "Industrial Applications of Surfactants," Industrial
Applications of SurfactantsAn Overview, D. R. Karsa, Ed., Published by Royal Society of Chemistry, Cambridge, England,
1987.
[51] Hancock, R. I., "Macromolecular Surfactants," Surfactants, T. F.
Tadros, Ed., Academic Press, San Diego, CA, 1984, pp. 287- 321.
[52] Lubricant Additives and the Environment, CEFIC, Brussels, Belgium, 1993, an ATC (Technical Committee of Petroleum Additive Manufacturers) Technical Publication.
[53] Fuel Additives and the Environment, CEFIC, an ATC (Technical
Committee of Petroleum Additive Manufacturers) Technical
Publication, Brussels, Belgium, 1994,
[54] De Hoffmann, E., Charette, J., and Stroobant, V., Mass Spectrometry: Principles and Applications, John Wiley & Sons, NY,
December 1996. (b) Colthup, N. B., Daly, L. H., and. Wiberley,
5. E., Introduction to Infrared and Raman Spectroscopy, 3rd edition. Academic Press, San Diego, CA, September 1990. (c) Macomber, R. S., A Complete Introduction to Modem NMR Spectroscopy, John Wiley & Sons, NY, December 1997. (d) Derome,
A. E., "Modem NMR Techniques for Chemistry Research," Vol.
6, Tetrahedron Organic Chemistry Series, J. E. Baldwin and P. D.
Magnus, Eds., Pergamon Press, Oxford, 1993.
[55] Hsu, S. M. and Cummings, A. L., "Interactions of Additives and
Lubricating Basestocks," Lubricant and Additive Effects on Engine Wear, SP - 558, Fuels and Lubricants Meeting, San Francisco, CA, 31 Oct.-3 Nov. 1983, pp. 61-70.
[56] Annual Book of ASTM Standards, ASTM International, West
Conshohocken, PA, 1998, and the later revisions.
[57] Rein, S. W., "Viscosity-I," Lubrication, Vol. 64, No. 1, 1978, pp.
1-12. (b) Rein, S. W., "Viscosity-II," Lubrication, Vol. 64, No. 1,
p p . 13-32, 1978. (c) "Viscosity," Lubrication, Vol. 52, No. 3,
1966, pp. 2 1 ^ 8 .
[58] SAE J300: "Engine Oil Viscosity Classification," Society of Automotive Engineers, Warrendale, PA, 1995, and the later revisions.
[59] SAE J1536: "Two-stroke Cycle Engine Oil Miscibility/Fluidity
Classification," Society of Automotive Engineers, Warrendale,
PA, 1995, and the later revisions.
[60] SAE J306: "Axle and Manual Transmission Lubricant Viscosity
Classification," Society of Automotive Engineers, Warrendale,
PA, 1985. (b) "Revision to SAE J306 Approved," Lubrizol
NewsLine, Vol. 16, No. 3, June 1998.
[61] SAE J2227: "International Tests and Specifications for Automotive Oils," Surface Vehicles Information Report, Society of Automotive Engineers, Warrendale, PA, July 1998. (b) "ACEA Issues
New Engine Oil Specification," Lubrizol NewsLine, Vol. 16, No.
3, June 1998.
[62] Rizvi, S. Q. A., "History of Automotive Lubrication," SAE Technical Paper 961949, Presented at Fuels and Lubricant Meeting,
San Antonio, TX, 14-17 Oct. 1996, Society of Automotive Engineers, Warrendale, PA.
[63] SAE J183: "Engine Oil Performance and Engine Service Classification (Other Than "Energy Conserving")," SAE 1995 Hand-

248 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK

[64]
[65]
[66]
[67]

[68]

[69]

[70]

book, Society of Automotive Engineers, Warrendale, PA, 1995,


and the later revisions.
Sullivan, T., "API Snuffs out GF-2," Lube ReportIndustry News
from Lubes-n-Greases, Vol. 2, No. 14, 2002.
McFall, D., "GF-4 Oil Due in One Year," Lube
ReportIndustry
News from Lubes-n-Greases, Vol. 2, No. 14, 2002.
McFall, D., "CI-4 Diesel Oil: On Time, On Target," Lubes-nGreases, Feb. 2002, p p . 6-12.
SAE Standard J2116: "Two-stroke-Cycle Gasoline Engine Lubricants: Performance and Service Classification," Approved July
1993, Society of Automotive Engineers, Warrendale, PA, 1994.
Deen, H. E. and Ryer, J., "Automatic Transmission Fluids
Properties and Performance," Fuels and Lubricants Technology:
An Overview, SP. 603, Society of Automotive Engineers, Warrendale, PA, October 1984, pp. 117-127.
Artman, D. M. and Copes, R. G., "ATF From Performance Challenges to Market Opportunities," Presented at the 1994 NPRA
National Fuels and Lubricants Meeting, 3-4 Nov. 1994.
Graham, R. and Oviatt, W. R., "Automatic Transmission FluidsDevelopments Toward Rationalization," Presented at CEC
1985 International Symposium,
Wolfsburg, Germany, 7 J u n e
1985.

[71] "Lubricant Service Designations for Automotive Manual Transmissions a n d Axles," API Publication No. 1560, American
Petroleum Institute, Washington DC, 1981.
[72] Sutherland, J. M., "Proposed Automotive Gear Lubricant Categories: Their Impact on the Industry," Presented at NPRA National Fuels and Lubricants Meeting, Houston, TX, 2-3 Nov. 1989.
[73] "Progress is Slow on PG-1 and PG-2," Lubrizol NewsLine, Vol.
11, No. 1, January 1993.
[74] (a) "Ready Reference for Lubricant and Fuel Performance,"
Publication 1288 240-94R1, The Lubrizol Corporation, Wickliffe, OH, 1999/2002. (b) Reference Library, Lubrizol web site,
www.lubrizol.com.
[75] "Tractor Wet Brake and Wet Clutch Friction Properties," W. K.
S. Cleveland, NLGI Sopkesman, July 1987, p p . 135-138.
[76] Laemmle, J. T., "Metalworking Lubricants," American Society
of Metals Handbook, Friction, Lubrication, and Wear Technology, S. D. Henry, Ed., ASM International 1992, Vol. 18,
pp. 139-149.
[77] "NLGI Lubricating Grease Guide," National Grease Institute,
Kansas City, MO, 1987.
[78] SAE J310; "Automotive Lubrication Greases," SAE 1995 Handbook, Society of Automotive Engineers, Warrendale, PA, 1995.

MNL37-EB/Jun. 2003

Synthetic Lubricants
Non Aqueous
Thomas F. Buenemann,
and Ian Thompson^

^ Steve Boyde, ^ Steve Randies, ^

POLYOL AND DIESTERS

Chemistry and Manufacturing


General Features

ALTHOUGH THE DEVELOPMENT OF SYNTHETIC ESTER LUBRICANTS is

In addition to their good properties at extreme temperatures, synthetic esters have other desirable characteristics including good lubricity, high viscosity index, low volatility,
and compatibility with s t a n d a r d lubricant additives a n d
basefluids. The fundamental chemistry is flexible and a wide
range of raw materials is available, which means that ester
base fluids can be designed having a wide raxige of viscosities.
Other key properties such as biodegradability can also be
controlled by molecular design [3]. Consequently, synthetic
esters have found use in many applications outside aviation.
Examples include automotive crankcase a n d gear oils, 2stroke lubricants, industrial gear oils, hydraulic fluids, textile
yarn lubricants, metal cutting and rolling fluids, air compressor lubricants, and refrigeration compressor lubricants
[4].

Raw

' Senior Application Manager and ^ Technology Manager, Uniqema


Lubricants, P.O. Box 2, 2800 AA Gouda, Buurtje 1, Gouda, BE 2802,
Netherlands.

Materials

The raw materials used in the manufacture of synthetic esters


for lubricant applications are derived from a variety of sources,
both natural and synthetic. Aromatic acids or anhydrides are
manufactured by the oxidation of the corresponding hydrocarbons [6,7]. Alpha, omega diacids are also generally produced by oxidation. The diacids used most widely to synthesize ester lubricant fluids are adipic, azelaic, sebacic, and
dodecanedioc acids, as well as C36 dimer acid. Adipic and dodecanedioc acids are derived from petrochemical feedstocks.

249
2003 by A S I M International

Groups

Esters are defined as the class of chemical compounds containing the ester functional group. They are normally manufactured by reaction of a carboxylic acid with an alcohol (Fig.
1), optionally in the presence of an esterification catalyst, and
with elimination of water [5].
The properties of the product esters can be controlled by
appropriate selection of the raw materials used. The final
product properties are mainly dependent on the molecular
weight, the n u m b e r of ester groups per molecule, and the degree of branching in alkyl substituent groups. A mixture of
raw materials may be used to deliver the precise combination
of properties required.
There are three main classes of synthetic esters currently in
use as lubricant base fluids: aromatic esters, aliphatic diesters,
and polyol esters. Aromatic esters, shown in Fig. 2, are manufactured by the reaction of an aromatic di or poly acid or anhydride, such as phthalic anhydride, tiimellitic anhydride, or
pyromeUitic anhydride, with a monoalcohol or mixture of
monoalcohols. Diesters, shown in Fig. 3, are manufactured by
the reaction of an aliphatic alpha, omega diacid with a monoalcohol or mixture of monoalcohols. Polyol esters, shown in Fig.
4, are manufactured by reaction of a diol or polyol having the
neopentyl structure, such as neopentyl glycol, trimethylol
propane or pentaerythritol, with a monoacid or mixture of
monoacids. Oligomeric esters, generally known as complex esters, can be manufactured by reaction of a diol or polyol with
a di or polyacid/anhydride, with a monoacid or monoalcohol
to act as capping reagent. This allows preparation of materials
having higher average molecular weights and consequently
higher viscosities, than can be achieved with simple diesters or
polyol esters. However, complex esters also have a distribution
of molecular weights, which means that their volatility characteristics are not as good as simple esters of the same number
average molecular weight.

relatively recent, the use of esters as lubricating fluids is as


old as h u m a n technology. Before suitable mineral oils became widely available as a b3^roduct of the petroleum based
fuels industry, lubricants were based on natural fats or oils,
which are either triesters of glycerine with natural fatty acids,
e.g., tallow and olive oil, or long chain monoesters of fatty
acids with fatty alcohols, e.g., sperm whale oil.
The use of synthetic esters as high performance lubricating fluids was originally driven by the development of the
gas turbine or jet engine in aviation. Aviation turbines have
a higher operating temperature than the piston engines that
preceded them, and jet aircraft are capable of operation at
m u c h higher altitudes, where the ambient temperature is
very low. Consequently, lubricants for aviation turbines are
required to have both very good high temperature stability
and good low temperature flow properties. It was found
that mineral oils and synthetic hydrocarbons did not deliver
the required combination of properties, and diesters were
adopted as the lubricant base fluid of choice for early aviation turbines [1]. As gas turbine technology developed, the
operating temperatures increased further, and diesters have
been largely substituted in aviation applications by polyol
esters, which have even better thermal stability [2]. Despite
intensive research into alternative chemistries, polyol esters
remain the base fluid of choice for aviation turbine lubricants.

Copyright'

and Product

www.astm.org

250

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

whereas azelaic, sebacic, and C36 dimer acids are derived from
natural fatty acids [8]. The monoalcohols used in diesters are
mainly manufactured by carbonylation of olefin feedstocks.
These alcohols are also used in the manufacture of plasticizers
and ethoxylate surfactants. They are generally commercially
available as a mixture of isomers and/or carbon chain numbers. Exceptions include 2-ethylhexanol, a derivative of butanol, which is a single isomer, and the linear C-even alcohols
(eg Cg, Cio alcohol), which are manufactured by chemical reduction of naturally occurring fatty acids [9],
The mono acids (fatty acids) used in polyol esters may be
derived either from petrochemical or natural sources. Naturally occurring fatty acids are almost always linear and have
an even number of carbon atoms. Lower carbon numbers

Polyol esters

R'"

R"-

CK

O ^

R = C4-C17linearor
branched aikyi
groups

^R

R"
PE; Pentaerythritol; R' = R" = R'" = CH20COR
TMP; Trimethylol propane; R" R" = CH20C0R, R" = Et
NPG; Neopentyl glycol; R' = CH20C0R, R" = R" = Me
FIG. 4Examples of polyolesters.

Acid

st(^r:'

OH Fsterififaqtion ^ ^ ' t ^ R'


n

nWater

FIG. 1Chemistry of esteriflcatlon.

Aromatic esters
o

I ^ I

II
Phthalate O

Trimellitate

II

R = C8 - CI8 linear or branched alkyl groups


FIG. 2Examples of aromatic esters.

Diesters

R'

>^'
% C
( ^ " 2 > n - \
. /

0 ~ R '

n = 4 - adipates
n = 7 - azelates
n - 8 - sebacates
n = 10 - dodecanedioates
R' - C8 - C13 linear or branched alkyl groups
FIG. 3Examples of diesters.

(CsCift) are normally fully saturated, while higher carbon


numbers (CigC22) have olefinic unsaturation. Petrochemical fatty acids may be either linear or branched. Linear
petrochemical acids are manufactured by the oxidative carbonylation of linear olefins, which are themselves derived
from ethylene and are therefore C-even (an even number of
C-atoms/molecules). Carbonylation adds a single carbon
atom, so linear petrochemical acids are normally C-odd (an
odd number of C-atoms/molecules) [8].
The neopentyl polyols used in polyol esters are manufactured by reaction of an aldehyde with formaldehyde, followed by chemical reduction [10]. As noted below, the
neopentyl structure confers superior thermal and oxidative
stability as compared to other polyols, such as butane diol or
glycerol, and neopentyl polyol derived materials are preferred in lubricant applications for this reason.
The only significant exception to this rule is for glycerol esters, which are also widely used in lubricating applications,
though only those where thermal and oxidative stability is not
a key performance requirement. Some of these glycerol esters
are simply purified vegetable oils, which are not normally
classified as synthetic esters. Others, known as mid-chain
triglycerides (MCTs), are produced by chemical reaction of
purified short chain natural fatty acids with glycerol. The oxidative stability of MCTs is inferior to that of neopentyl polyol
esters, but they are used in applications where very high
biodegradability is required, or where products are required
to be manufactured only from renewable raw materials.
Manufacturing
Technology
Esters are manufactured by reacting the desired acid and
ailcohol with an esterification catalyst, if required, and reacting at an elevated temperature [11]. The esterification reaction is reversible, and consequently it is necessary to drive the
equilibrium over to the desired product by removal of water.
The reaction temperature and pressure are therefore selected
so that water can be removed by distillation as it is formed.
High temperatures also increase the rate of reaction, but very
high temperatures may lead to undesirable side reactions or
discoloration. Esterification reactions are, therefore, normally conducted at a temperature in the range 200-250C.
For diesters and aromatic esters, the reaction is generally
conducted in the presence of an excess of the monoalcohol.
ASTM D 974-97 Standard Test Method for Acid and Base

CHAPTER 10: SYNTHETIC


Number by Colorimetric Titration (DIN 51 559 Part 1) is used
to measure the acid value, and when the acid value of the reaction mixture has reached the target value, implying that all
of the acid groups have reacted, the excess monoalcohol is removed by distillation.
For polyol esters, the reaction is usually carried out in the
presence of an excess of the monoacid. In this case, the
progress of the reaction is controlled by monitoring the hydroxy] value according to ASTM E 326 Standard Test Method
for Hydroxyl Groups by Phthalate Esterification. When the
target value is achieved, the excess monoacid is removed by
distillation.
Esterification catalysts are normally used to accelerate the
rate of the esterification reaction. Conventionally used homogeneous catalysts include complexes of transition metals,
especially titanium and tin, and strong acids, e.g., toluenesulfonic acid. Heterogeneous catalysts such as acid ion exchange resins may also be used [11].
The fact that acids catalyze the esterification process can
be exploited in the manufacture of polyol esters, where the
mono acid reagent, present in excess, may itself serve as the
catalyst. The crude ester produced by chemical reaction and
distillation of excess raw materials normally requires further
processing to render it suitable for use as a lubricant base
fluid. It is particularly important to remove all traces of the
esterification catalyst, since the esterification catalyst is also
capable of acting as a hydrolysis catalyst, which would have
a detrimental effect on the hydrolytic stability of the product.
Where titanium catalysts are used it is normal to wash the
crude ester with water, which hydrolyzes the catalyst to form
insoluble titanium oxide, which can be removed by subsequent filtration. Further treatments may be applied to reduce
acid value; reduce water content, which is determined by
ASTM E 1064, Standard Test Method for Water in Organic
Liquids by Coulometric Karl-Fischer Titration (DIN 51 777
Part 1); or to remove color, which is measured by ASTM D
1209-97, Standard Test Method for color of clear liquids
(Platinum-Cobalt scale) formed during reaction. Finally, the
product is filtered to remove particulate impurities.
Physical Properties
Viscosity
Probably the most important characteristic of a lubricant
base fluid is the viscosity measured by ASTM D 445-97, Standard Test Method for Kinematic Viscosity of Transparent and
Opaque Liquids (DIN 51 550). The ester group does not significantly increase viscosity as compared to a hydrocarbon
chain. Consequently, esters typically have viscosities similar
to those of hydrocarbons of comparable molecular weight and
degree of branching [12]. The viscosity of ester fluids can be
controlled over a wide range by appropriate choice of molecular structure, and current commercially available materials
cover the range of viscosities at 40C from 5 cSt for simple diesters up to >1000 cSt for complex esters [13,14].
As for all fluids, the temperature dependence of viscosity
(Viscosity Index, VI) is calculated by ASTM D 2270-93, Practice for Calculating Viscosity Index from Kinematic Viscosity
at 40C and 100C (DIN/ISO 2909) which is a function of the
extent and type of branching in the molecule. VI can be controlled by molecular design as for viscosity [12],

LUBRICANTSNON

AQUEOUS

251

Low Temperature Characteristics


The low temperature properties of esters, as for all lubricating
fluids, depend on the VI, and on the tendency to form waxy
solids [15], As noted above, the VI can be controlled by appropriate molecular design. Linear substituents are desirable
to give a high VI and therefore control the increase in viscosity with increasing temperature. Wax formation tendency is
dependent on the presence of saturated linear hydrocarbon
chains above a critical chain length. Linear saturated hydrocarbon substituents containing approximately eight or more
carbon atoms will generally lead to tendency to wax formation
in the temperature region of interest, i.e., 50C to 0C. Ester
base fluids intended for low temperature applications generally have a balance of linear and branched substituents to
achieve both performance criteria which is measured by
ASTM D 97-96a, Standard Test Method for Pour Point of
Petroleum Products (DIN 51 597).
Volatility
The ester group carries a permanent electric dipole. This
means that an intermolecular force due to dipolar interaction
exists between the ester molecules, in addition to the normal
molecular van der Waals forces which are present between
hydrocarbon groups. Consequently, intermolecular forces
are stronger in ester fluids, and esters have significantly
lower vapour pressure, and therefore higher flash points than
hydrocarbons of similar molecular weight and viscosity [4]
determined by ASTM D 92-97, Standard Test Method for Fire
and Flash Point by Cleveland Open Cup (DIN 51 376).
Chemical Characteristics
Thermal Stability
Sjmthetic esters all show very good thermal stability as compared to mineral oil, but diesters are significantly less stable
than polyol esters. This is because diesters can decompose
via a /3-elimination reaction, which forms an acid and an
olefin. This pathway is not possible for polyol esters due to
the neopentyl structure, which has no hydrogen atoms, attached to the /3 carbon of the alcohol residue [4].
Hydrolytic Stability
As noted above, the esterification reaction is reversible, and
esters can, in principle, react with water to regenerate the
acid and alcohol raw materials. This reaction is known as hydrolysis. The rate of hydrolysis under normal service or storage conditions is very low, and hydrol3?tic stability is rarely an
issue in practice. However, it can be a cause of concern in
some applications as the acids produced by hydrolysis could
potentially act as corrosive agents. Test methods have been
developed to characterize the rate of hydrolysis, i.e., ASTM D
2619, Standard Test Method for Hydrolytic Stability of Hydraulic Fluids. In this test, 75 g of fluid and 25 g of water eire
sealed in a beverage bottle with a copper strip present for 48
h at 93C (200F). At the end of the test, the oil and water layers are separated and insolubles are weighted. Viscosity and
acid numbers are also determined.
However, these test methods must be used with caution as
the rate of hydrolysis depends on factors such as the
structure and purity of the ester, reaction conditions, and the
nature of additives present. An understanding of these rela-

252

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

tionships can be used to select appropriate ester lubricant


formulations for a given application [16].
Biodegradability
Esters generally exhibit higher aerobic biodegradability than
corresponding hydrocarbons, because microorganisms produce lipase enzymes which catalyze ester hydrolysis. This
converts the ester into alcohol and acid, which have higher
water solubility and can be further degraded by enzyme catalyzed oxidation reactions. The degree of initial biodegradability of ester fluids is highly correlated with the hydrolytic
stability. Ultimate biodegradability is also dependent on the
linearity of the hydrocarbon subsituents. Esters derived from
reactants containing fully linear alkyl substituents (and in
particular those containing olefinic unsaturation) such as
polyol esters derived from natural fatty acids, e.g., trimethylolpropane oleate (TMPO), generally biodegrade particularly
rapidly. In contrast, a r o m a t i c esters, particularly those
containing highly branched alkyl groups, biodegrade more
slowly. However, even some branched aromatic esters can
meet the criteria for ready biodegradabilitiy according
to OECD 301B [17]. OECD 301B is currently the most
widely used test method for ready biodegradability of waterinsoluble organic substances [18]. However, another closely
related test m e t h o d is ASTM D 5864-95, S t a n d a r d Test
Method for Biodegradability of Organic Substances, which is
less stringent in that the latter allows for preacclimation of
the microbial inoculum, and therefore represents a less severe test regime.

Application and Performance Characteristics


Although slightly more polar, most esters are fully miscible
with mineral oils or synthetic hydrocarbons. Due to their
higher polarity, they are generally better solvents for polar
materials, such as many standard lubricant additives used in
mineral oil based formulations. Consequently, esters are frequently used as a component of mixed base fluids containing
polyalphaoleflns, which are poor solvents for polar additives.
However, the relatively higher solvency of esters may be a
disadvantage in formulations containing polar additives,
such as antiwear and EP agents which are required to adsorb
on the metal surface. The additive treat rate in an ester-based
fluid may need to be higher than in a mineral oil formulation
in order to ensure an effective surface concentration of the
additive [19].
The miscibility of esters with more polar materials also allows their use as mixtures with other polar synthetic basefluids, e.g., poly alkylene glycols, which are not generally
miscible with mineral oil.
The inherent oxidative stability of esters is similar to that
of synthetic hydrocarbons. They therefore require the use of
antioxidant additives to limit the rate of oxidation in service.
However, esters generally show very good response to standard antioxidants and can easily be formulated to give good
oxidative stability [4].
Four stroke cycle crankcase formulations require good
thermal and oxidative stability, low volatility, and good low
temperature pumpability. These requirements can be met by
the use of mixed poly (alphaolefin)/ester base fluids. Diesters

and polyol esters are typically used. The more polar ester
serves to enhance solubility of less polar additives in PAO,
and confer seal swelling properties, as well as superior thermal stability. PhthaJate esters have been used where a low
cost seal swellant is required.
Diesters based on C36 dimer acid and polyol esters are frequently used in two stroke cycle formulations to provide low
smoke properties and biodegradability for spilled or uncombusted oil, particularly in marine applications.
Hydraulic fluids are formulated using synthetic polyol esters or diesters where a combination of good oxidative stability and biodegradability is required. Organic esters also
have better flame retardancy than mineral oils, although not
as good as phosphate esters.
As noted above, polyol esters remain the lubricant base fluid
of choice for aviation turbine lubricants, even in military applications. Polyol ester- derived aviation turbine lubricants
are generally formulated containing aminic antioxidants and
ashless phosphate ester antiwear agents. There is continuing
interest in increasing the upper temperature limit for aviation
turbine lubricants, but the thrust of current research has
moved away from investigation of alternative base fluids towards optimization of ester chemistry.
The relatively recent development of hydrofluorocarbon
(HFC) compatible refrigeration compressor lubricants has
led to increased demand for polyol esters [20].
Concern over the environmental impact of the ozone
depleting chlorofluorocarbons (CFCs) previously used as refrigerant fluids has led to international legislation prohibiting
their use. This has resulted in a change to alternative refrigerants including the zero ozone depletion potential HFCs. The
HFCs are not miscible with the hydrocarbon lubricants that
were generally used in CFC systems. Lubricant immiscibility
was found to cause poor oil return leading to lubricant starvation in the compressor and fouling of low temperature heat
exchange surfaces. Consequently, it has been necessary to develop new HFC-miscible synthetic lubricants. Polyol esters
have been generally adopted as the preferred basefluid for
most HFC compatible refrigeration applications.

POLYALKYLENE GLYCOLS
Polyalkylene glycol (PAG) is a generic name used to describe
a family of products formed from the polymerization of one
or more alkylene oxides. Such products are also known as
polyethers, polyoxyalkylene glycols, polyalkylene glycol
ethers, polyglycols, and PAGs [21,22]. PAGs are an extremely
versatile family of products, which can exhibit a wide range of
physical and chemical properties. They are excellent lubricants in their own right [22-25], which makes them the fluid
of choice for a large n u m b e r of engineering and lubricant
applications.
The history of PAGs is a long one. The earliest reported
polymerization of ethylene oxide dates back to 1863 [26],
with the first commercial products (polyethylene glycols)
available in 1939 [27]. The range of viscosities now covered
by PAGs is vast, making these products suitable as lubricants
in their own right, but also as thickeners and lubricity improvers in water based systems.

CHAPTER 10: SYNTHETIC LUBRICANTS~NON AQUEOUS 253

4.5

log (molecular weight)

FIG. 5^Typical molecular weight distribution for a


polyalkylene glycol.
Chemistry and Manufacturing
PAGs are linear or branched chain polymers, which contain
ether linkages in their main polymer structure. They are produced by the polymerization of one or more alkylene oxides,
such as ethylene oxide (EO, C2H4O) cind propylene oxide (PO,
CsHgO), though butylene oxide (BO, C4H10O) and higher oxides can also be used. They can be considered to consist of
three parts: the initiator, the alkylene oxide or polyether section, and the terminal or end group as shown below.
initiator

polyether section
(CH2-CH(R)-0)

end group
-

R2

(R is H or alkyl; R' and R^ are H, alkyl, acyl, etc; X is O, N, S,


etc; n is an integer 1, 2, 3, etc.) The three distinct parts of the
polymer are variable, and it is therefore possible to produce
an infinite n u m b e r of different products, each with its own
unique properties. The skill in making PAGs is to select the
appropriate combination of initiator, polyether section and
terminal group to give the desired properties. Since the PAG
is in fact a "statistical polymer," the product will contain a series of polymers w i t h a distribution of polyether chain
lengths, centered around "n," and distribution of molecular
weights, as shown in Fig. 5. The molecular weight distribution is measured by the modified ASTM D 5296-97, Standcird
Test Method Gel Permeation Chromatography (GPC). As "n"
and the length of the polymer increases, so does the viscosity,
thus giving access to a wide range of viscosity. The R group is
H for EO, CH3 for PO, etc.
The initiator must be an "active hydrogen" containing compound R ' X H ; thus X must be an atom of the type O, N, S, etc.
Alcohols are the most extensively used initiators, and include
monohydric alcohols (i.e., containing 1 OH group), such as butanol, or polyols (i.e., containing two or more OH groups), such
as ethylene glycol, glycerolwater can be considered as a dihydric alcohol. Increasing the functionality of the initiator is
particularly useful when trying to build high molecular weight,
as there are more reactive OH ends for addition, and thus the
reaction rate is increased. The higher OH concentration also
increases the polarity of the polymer, which is useful for particular applications; the OH value is typically measured using
ASTM E326, Standard Test Method for Hydroxyl Groups by
Phthalate Esterification. Lower polarity can be achieved by the
use of long chain aliphatic or aromatic alcohols; this is an option for achieving mineral oil miscibility of PAGs [28].

The polyether section may contain one or more alkylene


oxides. Single oxide derived PAGs ("homopolymers") are
widely used and relatively simple to manufacture. When two
or more alkylene oxides are used"copolymers"these will
be incorporated as blocks ("block copolymers," e.g.,
EOEOPOPOEOEOEO, by sequential reaction
of the oxide), or r a n d o m l y ("random copolymers," e.g.,
POEOEOPOEOEOPOEO, by the reaction of a
mixture of oxides). These different polyether configurations
lead to somewhat different properties. For example, blocks
copolymers tend to have worse low temperature properties
than r a n d o m copolymers.
The principle benefits from including EO are increased water solubility, reduced solubility with non-polar species (e.g.,
hydrocarbons), and increased stability. The principle benefits
from including PO are improved low temperature performance, reduced polarity, and thus increased solubility of lubricant additives a n d nonpolar species.
In most PAGs, the end group is a hydrogen atom, and this
is adequate for most applications. Reacting this active hydrogen further (endcapping), by etherification or esterification, can yield beneficial effects. Typical end groups of this
form include aliphatic and aromatics (by etherification) and
alipathic ester groups [29].
Nuclear magnetic resonance (NMR) spectroscopy is a key
analytical technique for the chemical structural analysis of
PAGs, including the determination of EO/PO ratio, initiator
and end group analysis, polymerization sequencing (random/block), and molecular weight [30,31].
Synthesis
Most PAGs are manufactured via a three step process involving: catalyzation of the initiator; reaction with the alkylene
oxide(s) ('alkoxylation'); and post-treatment to remove the
catalyst or adjust the p H (see Fig. 6), the reaction of a n alcohol (ROH) with EO.
The initiator is typically reacted with a catalytic amount of
a base, such as potassium hydroxide, to produce the alcoholate, RO K + . The water produced may either be left in at this
stage, or may be removed under vacuum. The oxide addition
Catalyzation:
R-O-H + KOH-

- * R-O-K+ + H2O

Reaction with oxide:

R-OK* + CH2-CH2"

R-0-CH2-CH,-0-K+

AK
R-O-CH2 - CH2 - O- K+ + n-1 (CHj - CH2 )
Post-treatment:
R-(0-CH2 - CHj ) - O - K+ + 'H+'

R-(0-CH2-CH2)-0-H
FIG. 6Reaction scheme for PAG production.

254

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

reaction is normally carried out in a stainless steel reactor at


elevated temperatures (tjrpically 80-150C) and at high pressures (up to 10 bar). The alcoholate is a strong nucleophile,
and this approaches the carbon adjacent to the ring oxygen of
the alkylene oxide. An OC bond is formed, and the epoxide
ring is opened; the ring oxygen then acts as the nucleophile for
the next alkylene oxide addition. As the oxide is consumed in
forming the polymer, more oxide is fed into the reactor, generally at a rate to maintain reactor pressure.
A key side reaction that occurs during propoxylation is the
formation of unsaturation by the isomerization of the PO
unit. This reaction limits the viscosity attainable with pure
propoxylates. In terms of reactivity, EO has a higher reaction
rate than PO and higher oxides, and reactivity is enhanced by
the use of more basic catalysts.
Depending on the requirements of the final application,
when the poljTiierization reaction is complete, the final product may be subjected to a catalyst removal step. This is achieved
by demineralization, using a magnesium silicate, and neutralization with an acid, both of which are followed by filtration.
Both techniques work by replacing the metal ion (in this example K"*") with a hydrogen ion (H"*"). Sometimes the catalyst is
left in the product, and the product is treated with an acid to adjust its acid value, which is measured by ASTM D 974, Standard
Test Method for Acid and Base Number by Colorimetric Titration (DIN 51 559 Part 1); here, no filtration is then used.
Typical quality control measurements, carried out during
production of PAGs, include determination of viscosity by
ASTM D 445, Standard Test Method for Kinematic Viscosity
of Transparent and Opaque Liquids (DIN 51 550), density by
ASTM D 70, Test Method for Density of Semi-Fluid Bituminous Materials (Pycnometer method), flash point by ASTM D
97, Standard Test Method for Fire and Flash Point by Cleveland Open Cup (DIN 51 376), pour point by ASTM D 92, Standard Test Method for Pour Point of Petroleum Products (DIN
51 597), OH value by ASTM E326, Standard Test Method for
Hydroxyl Groups by Phthalate Esterification, and water content by ASTM E 1064, Standard Test Method for Water in Organic Liquids by Coulometric Karl-Fischer Titration (DIN 51
777, Part 1).

PAGs show a broad viscosity range, from a few mm^/s at


40C up to a few hundred thousand, as a result of the build
in molecular weight from a few hundred to several tens of
thousands. Over the wide range of PAG viscosity (for a consistent structural t3^e), the trends in the other physical
properties tend to vary in a fairly linear fashion. Their key
properties are water solubility, and excellent viscosity index
(VT) determined by ASTM D 2270, Practice for Calculating
Viscosity Index from Kinematic Viscosity at 40C and 100C
(DIN/ISO 2909) together with very good pour point and
flash point. The main route to adjusting the physical properties is by adjusting the initiator and the EO/PO ratio, as
shown in Table 1.
For example, by changing the initiator from a diol, to a
mono hydric alcohol (compare products a and b in Table 1),
there is an increase in viscosity index. Likewise, increasing
the EO/PO ratio also results in an increase in VI. This is important in applications relying on little change in viscosity
over a range of temperatures (e.g., worm gear lubrication).
Excellent pour and flash points are maintained across a wide
viscosity range, but are again influenced by EO/PO ratio. Increasing the molecular weight leads to increased VI and flash
point, but also increased pour point.
PAGs may be either water soluble or water insoluble depending on their structure. Increasing the EO content increases the water solubility. Linked with water solubility is
the so called "cloud point," (or inverse solubility temperature), which is measured by ASTM D 2024, Standard Test
Method for Cloud Point of Petroleum ProductsPAGs show
inverse solubility in water. Below the cloud point, normal solubility is observed, but at the cloud point, the PAGs come out
of solution and eventually separate. The solubility and the
cloud point increase as the EO content increases, and
decrease with increasing molecular weight. PAGs tend to be
soluble in relatively polar materials and their excellent solubility in the ozone benign hydrofluorocarbons, such as Rl 34a
(1,1,1,2-tetrafluoroethane), has considerably aided the transition from the chlorofluorocarbons in automotive air conditioning systems [32].
Chemical Characteristics

Physical Properties
The physical properties of a selection of commercially available PAGs are shown in Table 1, to illustrate the range of
physical properties.

Compared to mineral oils, PAGs have good thermal stability,


but poor oxidative stability as shown by thermal gravimetry
(23,25,28,30). However, one of the key characteristics of
PAGs is that when they decompose, the final decomposition

TABLE 1Typical physical properties of PAGs (with ASTM methods).

VI

Mol
Weight

Density
(g/cm^)
@20C

Cloud
Point
CC)

Flash
Point
Open Cup
ASTM D 92
(C)

D2270
103
204
184
242
157
225
287
408
489

350
1900
2000
2600
1200
1650
4500
12500
25000

D70
0.9573
0.9940
1.0035
1.0031
1.0951
1.0564
1.0574
1.0908
1.0905

D2024
insol
insol
insol
insol
>100
59
53
81
76

D92-97
80
225
230
232
254
230
230
240
240

Viscosity
(mm?/s)

Functionality
of Initiator

EO/PO
Ratio

40C

100C

ASTM Method
Mono
Mono (a)
Di(b)
Di
Tri (c)
Mono (d)
Mono
Di
Tri

0:1
0:1
0:1
0:1
3:1
1:1
1:1
3:1
3:1

D445
11
126
142
387
127
132
1050
19500
45000

D445
3
22.5
22.2
65
18
25
180
2400
6500

NOTE: the molecular weight is calculated from Mol Weight = functionality of initiator * 56100/OH value.

Point
Pour
Point
CO
D97
-53
-36
-36
-23
-28
-42
-28
4
7

CHAPTER 10: SYNTHETIC


products are all volatile, with the result that there is no carbonaceous solid or liquid residue, which can be proven by
ASTM D 189-97, Standard Test Method for Conradson
Carbon Residue of Petroleum Products. This is a major advantage in many functional fluid applications such as high
temperature chain oils and compressor fluids.
In the absence of air, PAGs are stable up to around 250C.
At this point polymer chain scission occurs, which releases
free radical ends, which further decompose by depolymerization to produce volatile components (eddehydes, ketones,
alcohols, alkenes, alkanes, CO2) and lower molecular weight
polymers [30]. In the presence of air, PAGs are stable up to
around 180C. Decomposition is initiated by an oxygen
molecule attaching itself randomly along the polymer chain.
A radical is then formed, which rearranges, causing the polymer chain to break and lose its end group. This again leads to
a reduction in molecular weight and production of similar
volatile components to the thermal breakdown.
By adjusting the chemical composition and by the use of
antioxidants, the stability of the PAG can be improved significantly. Increasing the EO content (compare the flash points
of product "c" and "d" in Table 1) and increasing the molecular weight of the polymer tend to increase its stability.
Aminic and phenolic antioxidants, especially in combination,
provide significant increase in stability to PAGs [33].
PAGs have good hydrolytic stability, which is measured by
ASTM D 2619-88, Standard Test Method for Hydrolytic Stability of Hydraulic Fluids, since they do not contain hydrolytically labile chemical groups.
When released into the environment, PAGs tend to slowly
biodegrade, helped by their affinity for water (and thus ability to disperse in the environment) and their ability to oxidize
and fragment into smaller and more biodegradable structures [22]. Rapid biodegradability of PAGs, as measured by
such tests as the OECD 301 and 302, is not inherent across
the range, but, is achievable by careful structural modification, especially towards the lower viscosity end of the range
[34]. In general, biodegradability is favored by linear components (i.e., EO rather than PO), and by reduction in molecular weight.
In terms of general toxicity, PAGs are generally classified
as low hazard, and some have approvals as indirect food contact lubricants [35].
Due to their highly polar nature, which gives them a very
strong affinity for metal surfaces, PAGs have excellent inherent lubrication properties [23]. The lubricating film formed
between moving metal parts remains intact even during very
difficult operating conditions, such as high temperatures and
loads.
However, their polar nature does require that care must be
taken in the choice of compatible materials, particularly
paints and some elastomers [25], which is determined by
ASTM D 471-98el, Standard Test Method for Rubber Property-Effect of Liquids. Formulations using standard additive
chemistry can also be hampered by solubility problems and
potential reduction in activitythe PAG may compete for the
metal surface with the additive. Increasing the molecular
weight and the PO content does improve this situation by reducing the polarity. Their hygroscopicity requires care to be
teiken regarding ferrous metal corrosion, which is measured
by ASTM D 665-99, Standard Test Method for Wear Preven-

LUBRICANTSNON

AQUEOUS

255

tive Characteristics of Inhibited Mineral Oil in the Presence


of Water. Anti-corrosion agents are available.
Application and Performance Characteristics
Due to the flexibility in their chemical structure and properties, and their inherent lubricity, PAGs are used in a wide
range of application areas, as illustrated by Fig. 7.
Very high viscosity PAGs are used extensively in HFC (Hydraulic Fluid C type) water based fire resistant hydraulic fluids [36,37] where they perform the function of thickening the
water, suppressing its pour point, and providing lubricity
determined by ASTM D 2882, Standard Test Method for Indicating the Wear Characteristics of Petroleum and NonPetroleum Hydraulic Fluids in Constant Volume Vane
Pumps. The water provides the fire protection [38]. The key
parameter is fire resistance and the performance standards
are developing apace [39,40].
A similar lubricity improving function is delivered by PAGs
in water based metal working fluids, which additionally use
the cloud point phenomenon of the PAG to boost lubricity: as
lubricity of the fluid begins to fail, metal-metal contact
causes the temperature to increase, which heats the solution
above the cloud point of the PAG, which is determined by
ASTM 2024-65, Standard Test Method for Cloud Point of
Nonionic Surfactants. This temperature rise results in the
PAG coming out of solution and being released into the contact to provide enhanced lubricity.
The low coefficient of friction and excellent viscosity/temperature or VI characteristics of the PAG lend it to the lubrication of the gecirs and bearings, particularly to heavily loaded
worm gears used within the plastics, rubber and paper industries [41-43]. Tests for gear oil performance include the FZG
Test [DIN 51 354] and ASTM D 2782-94, Standard Test
Method for Measurement of Extreme-Pressure, better known
as the Timken Test. The efficiency of the worm gear is related
to the friction between the wohn drive and the gear wheel.
Contact between these involves a high level of sliding resulting in increases in operating temperaturesideal operating
conditions for the PAG. Combining this with their high level
of tolerance for water ingress delivers excellent performance.
The compression of process gases presents a unique technical challenge [44]. Due to the intimate contact between lubricant and gas, there can be dissolution of the gas into the lubricant, resulting in a reduction in viscosity of the lubricant,
and as a worst case, washing of the lubricant from the metal
surfaces requiring lubrication. Owing to the polar nature of
PAGs, they perform extremely well in the lubrication of compressors for low polarity process gases (e.g., methane, ethylene, nitrogen). Since there is very little dissolution of the gas
into the lubricant, the viscosity and lubricity is maintained
[44].
PAGs are also suitable for use as air compressor lubricants,
especially when combined with esters [46,47]. Since any
build up of sludges or deposits in the compressor can lead to
ignition of the lubricant (for the proof of low carbon residues
ASTM D 189-97 Standard Test Method for Conradson Carbon Residue of Petroleum Products can be used), the clean
decomposition characteristics of the PAG (ASTM D 189)
make this a very attractive alternative to mineral oil based air
compressor lubricants.

256 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK

.2
(0

o
a.

"Q.
(S

I
I
3

o
o
(0

a>

I
(3
<
E
o

I
f
CO

o
a
#
o
CO

.2
(0

'a.
a

CO
a

CO

u
4)
E

v
oa

LL

CHAPTER 10: SYNTHETIC LUBRICANTSNON AQUEOUS 257


POLY (ALPHA-OLEFINS)

/-I

Polyalphaolefiin fluids, or PAOs, are synthetic, saturated hydrocarbons that are manufactured by a two-step process from
hnear alpha-olefins, that are themselves manufactured form
ethylene. These synthetic hydrocarbons are generically described by their viscosity at 100C. The most common commercially used PAOs are 2, 4, 6, 8, and 10 cSt and the higher
viscosity grades 40 and 100 cSt. PAOs have excellent physical
properties when compared with conventional mineral oils, a
wide operating temperature range, including high flash and
firepoints, high viscosity indices and low volatilities. When
compared with certain natural and synthetic esters, PAO fluids have excellent thermal, oxidative, and hydrolytic stability.
Since the mid 1980s PAOs have quickly gained market share
in the synthetic lubricant base fluid market, particularly in
Europe [48]. The major application area was and continues to
be the automotive sector for crankcase oils answering the
quest for tighter specifications for lower oil volatility. Today,
automotive crankcase lubrication is still the main application
area for PAOs globally. Other automotive application sectors
are now two-stroke cycle engine oils, automatic transmission
oils, gear oils (multigrade), and greases. Industrial applications include: hydraulic oils, compressor oils, heat transfer
fluids, and food grade oils and greases.
The milestones of the technical history are marked by three
patents, one by Brennan [49] at Mobil Oil in 1968 and two by
Shubkin [50,51] of Ethyl Corporation in 1973. Brennan first
described a process for oligomerization of alpha-olefins
using a BF3ROH catalyst system [49] whereby the combination of the selected process conditions and the catalyst system yielded a product consisting of a mixture of oligomers
with a high concentration of trimers. Shubkin showed that
instead of ROH as a co-catalyst, H2O [50] or alcohols and
carboxylic acids [51] could be also used in combination with
BF3 to produce oligomers of uniform quality.
The U.S. Army and U.S. Navy took an early interest in this
new synthetic base fluid. In July 1970 the MIL-H-83282 specification for fire resistant hydraulic fluids based on PAOs was
established in cooperation with the industry [52].
Chemistry and Meinufacturing
As the name implies, Polyalphaolefines are synthesized up
from alphaolefines. The starting material of the chemical

CH2 = CH2

Catalyst
>

BF3

Unsaturated

R-CH=CH2

>

ROH

Unsaturated Oligomers + H2

aigomeric
Mixture

Dimer
Trimer
Tetramer
Pentamer
Higher

NIorPd

DIstilatlon

Oligomers

DImer
Trimer
Tetramer
Pentamer
Higher

Saturated Paraffinic Hydrocarbons

Viscosity
Grades

FIG. 8Chemistry of PAO manufacture [55].

Qimsr

FIG. 9Typical PAO components [55].

synthesis is ethylene as shown in Fig. 8. The reaction products of the first step are linear unsaturated alphaolefins
(LAO). These LAOs are used for the manufacture of a variety
of chemicals, mainly as detergents. For the synthetic lubricant base fluids (PAOs 2-10 cSt), mainly 1-Decene is
oligomerized with the catalyst BF3 and a protic co-catalyst
such as water or an alcohol. For the higher viscosity PAO 40
and PAO 100 Ziegler-Natta (Aluminium chloride based), catalysts are used. The unsaturated oligomer mixture is hydrogenated using either Nickel or Palladium catalysts. Finally, a
distillation step is applied to remove unreacted monomers
and to separate the various product grades. Sometimes the
distillation step is carried out prior to hydrogenation [54].
The tjrpical molecular structures of a dimer, trimer and a
tetramer of 1-decene are shown in Fig. 9. Every oligomer is
branched and is present as a number of different isomers.
Though 1 -decene is the pre-dominantly used alphaolefine for
PAO manufacturing, shorter or longer chain length olefines
may also be used. In particular, 1-dodecene has recently
gained importance for the synthesis of PAO 5 and PAO 9 [57].
Tailor made products can also be obtained by changing
reaction vsiriables such as temperature, time, catalyst concentration, co-catalyst t3^e, and concentration and distillation conditions [57].
Physical Properties
The physical properties of the common commercially available PAOs are shown in Table 2. The given properties are typical values and do not represent values for PAOs from a
particular supplier. The low viscosity PAOs 2-10 have
excellent low temperature properties which make them very
suitable for applications in cold climate. The average viscosity index (VI) calculated by ASTM D 2270, Practice for Calculating Viscosity Index from Kinematic Viscosity at 40C and
lOOX (DIN/ISO 2909) for PAOs is 135. This has the advantage
that the viscosity changes much less with increasing temperature compared to a product with low VI. For PAO 2 no VI is
given because VI is undefined for fluids having a kinematic
viscosity ofless than 2.0 cSt at 100C. The advantage of a high
VI is that addition of viscosity index improvers is not required
for the formulation of lubricants for many applications. Also,
the addition of pour point depressants is often not necessary
as the pour points for PAOs are very low. In Table 2 some other
physical properties are given which are important to the lubricant formulator. The flash point is important for safety reasons and the given flash points in Table 2 are at least as high

258

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

TABLE 2Properties of polyalphaolefines.


Parameter

Test Method"

PA0 2

PA0 4

PA0 6

PAO 10

PAO 40

PAO 100

KV @ 100 C cSt
KV @ 40 C cSt
KV @ - 4 0 C cSt
Viscosity Index
Pour Point, C
Flash Point, C
Noack, % Loss

ASTM D445
ASTM D445
ASTM D445
ASTM D2270
ASTM D79
ASTM D92
DIN 51581

1.80
5.5
310

3.90
16.8
2540
122
-69
215
12.0

5.90
31.0
7800
137
-63
225
6.7

9.60
45.8
19000
134
-54
264
2.0

40.0
395

100
1250

150
-34
280
0.8

170
-20
290
0.6

-63
>155
99

"ASTM D 6375 and D 5800 are alternate procedures.

TABLE 3The oxidative stability of motor oil qualities studied


using High Pressure Differential Scanning Calorimetry (PDSC).
Additive-free Base Oils

Mineral oil based lube


Synthetic lubricants
Polyalphaolefin
Polyolester
Diester 1
Blends of synthetic lubricants
Polyalphaolefin/polyolester 80/20 blend
Polyalphaolefin/diester 80/20 blend
Base oils with additive
Mineral oil based lube
Mineral oil/polyalphaolefin based lube
55% mineral oil/22% PAO
Mineral oil based diesel engine lube
Polyalphaolefin/esteroil 80/20 blend

T (onset) [C]

187
187
210
198
196
196
254
260
262
274

as those of mineral oil of the same viscosity. Volatility is measured by the standard NOACK volatility test at 250C for 1 h.
Except for PAO 2, all other PAOs have very low volatility,
which makes them very suitable for high temperature applications and engine oils to reduce the need for "topping-up."
Low volatility is also an important property for a fluid to retain the original viscosity during its working life.
The highly viscous PAO 40 and PAO 100 hsted in Table 2
are similar to low viscosity PAOs and have good viscometric
properties and allow operation over a broad temperature
range. New PAOs with m e d i u m viscosity grades 5, 7, and 9
and very high viscosity grades, u p to 3000 cSt, and have recently been developed as custom-synthesized products [56].
Chemical Properties and Performance
Characteristics
Oxidation stability is one of the most important properties of
automotive lubricants, which are mainly responsible for the
oil renewal time. Essiger [57] investigated the oxidation stability of different motor oil qualities with High Pressure Differential Scanning Calorimetry (PDSC) as shown in Table 3.
PAO without anti-oxidants is as stable as mineral base oil,
blends with synthetic ester, a n d shows superior oxidation
stability. In the presence of anti-oxidants, such blends were
significantly more stable than mineral oil based engine lubes.
The use of PAO is also c o m m o n today in high performance
greases. The lifetime of such greases is said to be three to five
fold c o m p a r e d to mineral oil based products. Wunsch
recommends operating temperatures of u p to 150-160C for
Lithium-12-hydroxystearate greases based on PAO [57].

Low toxicity in general, and biodegradability of the low


viscous PAOs according to the CEC L-33-A-93 test, are
other important benefits making these products versatile
for incidental food contact and environmentally acceptable
lubricants

OTHER SYNTHETIC BASE STOCKS


Although mineral oils and the synthetic base fluids described
in the sections above, together with solid lubricants, satisfy
the performance requirements of the majority of lubricating
applications, there r e m a i n m a n y applications where a
different combination of properties would be desirable. A
wide variety of other chemical classes have been proposed as
candidate synthetic base fluids to cover the real or perceived
shortcomings of more established fluids. Many of these developments have been targeted towards high performance
aerospace applications, e.g., military aircraft and satellites,
where satisfactory performance under extreme conditions of
t e m p e r a t u r e , high vaccuum, a n d high radiation m a y be
required, and unit cost is less significant [3]. Most of the proposed chemistries, e.g., silicate esters, silahydrocarbons, titanate esters and phosphazines, appear not to have found any
real application. However, others, in particular silicones, perfluoroalkyl ethers, polyphenyl ethers and cycloaliphatic hydrocarbons have found significant niche applications and are
discussed briefly in this section.

Silicones
Silicones are polymers containing the siloxane (SiOSi)
backbone structure with pendant alkyl side chains, normally
methyl groups. The chemistry is well established and silicone
fluids have been commercially available since the 1940s
[59,60]. They are manufactured by hydrolysis of dialkyldichlorosilane themselves p r e p a r e d by reaction of
methyl chloride (or other alkyl chlorides) with silicon metal.
Trialkyl monochlorosilanes are introduced into the reaction
in controlled stoichiometry to act as end capping reagents
and control the molecular weight.
Silicone fluids can be prepared with viscosities ranging
from < 1 to > 500 000 cSt. They are characterized by low pour
points, low surface tension, high compressibility and little
change in viscosity with temperature. The standard viscosity
index calculation is not appropriate for silicones and other
materials with such low temperature coefficients of viscosity.
Methyl groups m a y be substituted by other functional
groups to modify the inherent properties of the basefluid.

CHAPTER 10: SYNTHETIC


These substituents include phenyl groups (for improved oxidative stability) and trifluoropropyl or tetrachlorophenyl
groups (for lubricity)
Silicones are highly fire resistant and have very low
volatility, good thermal stability, and very good chemical resistance. This makes them well suited to some highly demanding functional fluid applications, e.g., heat transfer oils
and transformer dielectric fluids. However, the load bearing
characteristics of poly (dimethyl siloxane) Eire very poor and
metal contacts lubricated by silicones tend to seize under
boundary lubrication conditions [59]. For this reason, simple
silicones are rarely used as base fluids, except in some speciality greases where they serve as stable carriers for additives and solid lubricants. Such greases are used in aviation
and automotive industries to lubricate linkages, bearings and
bushings, and instrument components [3].
Silicones are also used in textile applications as fibre,
thread and yam lubricants, and modified silicones are used
as textile treatments for improved resistance to staining.
Traditional lubrication applications of silicones are further
limited by the fact that they are not generally miscible with
mineral oils, or other synthetic base fluids. This does, however, make them suitable for use as both profoaming and antifoaming additives in more conventional base fluids.
Use of silicone fluids or additives in some manufacturing
environments where goods are painted or coated is discouraged because minute traces of silicones can interfere with the
spreading and adhesion of paints.
Silicone fluids are essentially non biodegradable and although of low toxicity, they are likely to be persistent in the
environment. Consequently, the environmental impact of
dispersive applications is a cause of some concern.
Perfluoroalkyl Ethers (PFAEs)
PFAEs have structures basically similar to those of PAGs, but
with all the hydrogen atoms replaced by fluorine. They were
originally developed in the 1960s for aerospace applications
and have subsequently found some use in other applications,
particularly where resistance to oxidation or other chemically aggressive environments is required.
Four different classes of PFAEs have been commercialized,
for which the abbreviations D, K, Y, and Z have become generally accepted. These differ somewhat in their chemical
structure, and consequently show slight differences in performance, but all show broadly the same characteristics as
compared to other classes of base fluids.
PFAE-K and PFAE-Y have quite similar structures, consisting of a (CFaCF(CF3)O) repeat unit, although with
different manufacturing routes, which lead to some
differences in properties. PFAE-K is prepared by anionic polymerization of hexafluoropropylene oxide, whereas PFAE-Y is
prepared by polymerization of hexafluoropropene in the presence of oxygen. PFAE-Z contains a (CF2CF2)O) repeat unit and is prepared similarly to PFAE-Y, using tetrafluoroethene, rather than hexafluoropropene. PFPE - D contains
a (CF2CF2CF2O) repeat unit, and is manufactured
by ring-opening polymerization of tetrafluorooxetane, followed by exhaustive fluorination to convert the remaining
CH bonds to CF bonds.

LUBRICANTSNON

AQUEOUS

259

All types are manufactured as poly disperse polymers,


which are then fractionated to give the molecular weight and
viscosity ranges of interest.
PFAEs are available with viscosities ranging from about 5
to about 500 cSt 40C. Viscosity indices vary according to the
chemical type, with the K and Y types having lower VT than
the D and Z types. Pour points are generally low. High temperature volatilities depend on the molecular weight spread
of the particular grade, but are generally low [60].
The main chemical characteristic of PFAEs is outstanding
resistance to oxidation by air. They are also resistant to
chemical attack by corrosive chemicals including strong
acids and alkalis and oxidants such as fluorine and hydrogen
peroxide. As oxidative degradation is one of the most frequent limiting factors for lubricant life, this means that
PFAEs can have very long lifetimes in service, and are well
suited for sealed for life applications.
Like silicones, PFAEs have a tendency to exhibit seizure under boundary conditions, and, also like silicones, they are not
miscible with standard lubricant additives, so the problem
cannot be alleviated by formulation with conventional
antiwear agents [3]. Thermal stability of PFAEs under ideal
conditions in contact with glass is very good, but the benefit
is often not realized in real life applications as thermal decomposition is catalyzed at lower temperatures by metcil fluorides, particularly those of aluminium and ferrous metals.
Metal fluorides are apparently produced by reaction of PFAEs
with metal oxides under conditions of tribological contact.
The same effect can lead to oxidative corrosion of some metals by PFAEs under air. Both thermal decomposition and oxidative corrosion are inhibited in the absence of oxygen [59].
The very high cost of PFAEs has restricted their use to high
value applications where their properties are essential or
where greatly extended oil life can justify their use on economic grounds. The initial applications were in spacecraft,
where the very high chemical resistance of PFAEs was required. The largest current application is in specialty vacuum
pump oils for use in contact with reactive chemicals in electronics manufacture. PFAEs are cJso used in formulation of
greases for some sealed for life bearings.

Polyphenyl Ethers
Polypheny] ethers (PPEs) consist of benzene rings joined by
ether links, with the ether links in bridging monomer units
being arranged in meta geometry. They were developed during the 1950s for high thermal, oxidative, and radiation
stability [61].
PPEs are manufactured by reaction of phenols and halides.
The simplest member of the family is diphenyl oxide; longer
chain analogues are available up to six benzene rings and are
coded according to the number of benzene rings and ether
groups they contain; thus 5P4E contains five benzene rings
and four ether linkages.
PPEs have very high pour points and most are not liquids
at room temperature. For example, the only example which
is currently commercially available, 5P4E, crystallizes at
43C in the pure state, and therefore must be mixed with
other fluids to extend the liquid range and inhibit
crystallization, or used only in applications where it will re-

260

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

main at elevated temperature [62]. In addition, PPEs have


very low viscosity indices, so it is necessary to accept high viscosity at lower temperatures in order to have adequate viscosity at the elevated temperatures of operation. [3]
PPEs are also characterized by high surface tension (ca. 50
dyn/cm, as compared to 30 dyn/cm for typical mineral oil).
This means that they do not wet metal surfaces, or migrate
from the point of application. Thermal stability of PPEs is
good, but oxidative stability is not outstanding.
PPEs have been used as aviation gas turbine lubricants for
supersonic military aircraft [61]. The main current application for PPEs is as ultra-high vacuum diffusion pump fluids,
where lubricity is not important and the good high temperature characteristics can be exploited. They are also used in
formulation of radiation-resistant greases.
Alkylated Cyclopentanes
Multiply-alkylated cyclopentanes (MACs) were introduced
as candidate lubricating fluids during the 1980s. MACs are
manufactured by reaction of cyclopentadiene, in the form of
dicyclopentadiene, with an alcohol, followed by catalytic reduction of alkylated cyclopentadiene initial product [63,64].
A wide range of MACs have been reported, although
apparently only one member of the class, tris(octyl dodecyl)
cyclopentane, has been commercialized.
Viscometric properties are typical for hydrocarbons and
similar to those of PAOs. The main distinguishing characteristic of MACs is that they are essentially monodisperse and
their volatility is therefore substantially lower than mineral
oil or PAO of similar viscosity.
Viscosity and viscosity index can be adjusted by appropriate selection of the chain length and degree of branching of
the alcohol raw material, and by the degree of substitution
obtained. MACs are miscible with mineral oil and with standard lubricant additives. Tris(octyl dodecyl) cyclopentane
has a particularly low pour point and low volatility, and is
used in spacecraft applications [63].
Cyclohexane Derivatives
The cyclohexane derivatives are a class of fluids which are
targeted, not at high temperature applications, but rather at
automotive transmission applications requiring high traction. A range of such fluids were commercialized during the
1970s, although only one such material is currently available
[65], namely 2,4-dicyclohexyl-2-methylpentane, which is
manufactured by catalytic hydrogenation of the linear dimer
of alpha methyl styrene [63].
In most respects, the cyclohexane derivatives behave similarly to other synthetic hydrocarbons of similar molecular
weight, but have the distinctive characteristic that they exhibit high traction coefficients under the very high pressures
experienced in an elastohydrodynamic (EHD) contact [63]. It
is believed that the rigid regular structure of the cyclohexyl
component leads to a very high volume change on melting,
and consequently a very strong pressure dependence of the
temperature of solidification. Thus, under extreme pressure,
these fluids transiently solidify in the contact, forming a solid
pad in the contact, which readily transmits lateral force and
resists formation of shear slip planes.

SUJVIMARY
Synthetic lubricants possess superior performance capabilities compared to mineral oils. There are three main reasons
why synthetic lubricants are selected in preference to mineral
oils:
improved stability, usually oxidative,
improved lubricity, usually at very high or very low temperatures and
reduced environmental impact, usually high biodegradability or reduced toxicity.
Oxidative

Stability

The superior oxidative and thermal stability of synthetics


over mineral oil is historically the main reason why they are
used. It is very difficult to give precise figures for the exact
temperature at which decomposition for a synthetic lubricant occurs as this is affected by several variables, the main
ones being:
exposure time
tj^e and amount of additives present (antioxidants, metal
passivators/chelators etc.)
availability of oxygen (air)
ability of the lubricant to remove heat
which metals the lubricant is in contact with (catalysis and
potential deposit formation at metal surfaces) and
the presence of system contaminants (e.g., acidic components)
There are several different ways of measuring the oxidative
stability of a lubricant:
Decomposition temperature as measured by a change in:
viscosity, acid value, hydroxyl value (ASTM D 943, Turbine
Oil Stability Test), amount of oxygen consumed (ASTM D
2272, Rotary Bomb Oxidation Test), heat flow change (Differential Scanning Calorimetery), etc., under specified conditions
Temperature and nature of deposit formed on decomposition (e.g.. Panel Coker FTM3462 or Wolf strip tests UK 359,
ASTM D 189, Conradson Carbon Residue, DIN 51 551,
Pneurop DIN 51352-2)
Volatility of a lubricant at set temperature and times (e.g.,
ASTM D 5800, Noack test, Thermogravimetric Aneilysis)
The life of oil at a particular temperature depends on the
amount and type of degradation, which is acceptable,
which in turn depends on how much performance can be
allowed to deteriorate. Any chart comparing the relative
stability of synthetic lubricants will therefore be quite arbitrary and highly dependent on the specific oil, test conditions, and application [65]. For example, oxidation tests on
pure basestocks can show that esters have an oxidative stability similar or slightly worse than that of mineral oil. The
reason for this is that mineral oil contains impurities that
can act as anti-oxidants. Esters tend to only show their remarkably better stability when compared to mineral oil,
provided the oils are formulated with antioxidants. Figure
10 gives an indication of oil life versus temperature for a
range of formulated synthetic lubricants. Useful lifetimes
are based on filed experience from a range of applications
and should only be used as a crude approximation of actual
service life in a specific application. As the previous dis-

CHAPTER 10: SYNTHETIC LUBRICANTSNON AQUEOUS 261


cussion has shown, oil hfe will change dependent on the exact temperature regime.
Table 4 gives a useful qualitative overview of the volatility
a n d deposit forming tendencies of various oils. Depositforming tendencies of synthetics can be highly dependent on
several p a r a m e t e r s not necessarily connected with chemistry. For example, lubricants with a high polarity can help
solubilize and disperse decomposition products leading to
lower deposits. Polymers should have a narrow dispersion of
molecular weight to avoid the lower molecular weight component volatilizing. Polymers such as Polyalkylene Glycols
(PAGs) and Poly Iso Butylene (PIBs) tend to be very stable u p
to a certain t e m p e r a t u r e a n d then rapidly degrade. The
volatility and deposit forming tendencies can be highly dependent on the presence of metals. Metals act as a catalyst
a n d therefore aid decomposition for specific chemistries.

Their volatility is therefore highly dependent on the test temperature. The types of additives used also play an important
role. Therefore, the table should only be used as a rough
guideline.
The generation of heat from friction causes the temperature of the oil film to increase. This higher temperature reduces the viscosity of the oil. As the oil's ability to remove
heat is increased, this may lead t o lower operating
temperatures. A lower temperature will reduce the decrease
in viscosity of the lubricant and also reduce the oxidative
degradation of the lubricant, potentially increasing the life of
other components in the system. The heat transfer of various
lubricants can be compared by using a simplified version of
the Sieder and Tate equation given below [69]. This equation
is applicable to areas of turbulent flow. The equation can be
further simplified for areas of laminar flow.
LrO.bl pO.8^0.33

ha
snnHEtic HnmocAfaoNS
Where:
h =
K =
p =
X=
Cp =

SUGON^

too

aoo

300

TEMPERA-niRE ' C
FIG. 10A comparison of oil lifes for a range of synthetic lubricants [66].

TABLE 4An overview of the volatility and depo forming


tendencies of a range of synthetic lubricants evaluated using a
variety of tests.
Lubricant
Mineral oil WON
PA0 6
Alkyl benzene 150
Esters
PAGs
PIBs
Silicones
Fluorocarbons

Volatility
at 250 "C
Poor
Good
Fair
Very good
Poor
Very poor
Excellent
Good to excellent

Deposit Formation
at 250C
Poor
Fair
Fair
Excellent
Very good
Good
Very good
Very good

heat transfer coefficient of lubricant components


thermal conductivity
density
viscosity
specific heat capacity at constant pressure

Lubricants with good heat-transfer characteristics generally


have high specific heat capacity, high thermal conductivity,
high density, and a low working viscosity. T5rpical data for
several lubricant classes are given in Table 5. PAGs and
polyol esters, due to their polar nature and their superior lubricity, should be able to lubricate the system at lower bulk
viscosities than their mineral oil equivalents, improving heat
transfer still further [69].
Lubrication
As with oxidation, the lubricity of a synthetic lubricant is
highly dependent on the operating regime. Most wear tends
to occur during; start-up, slow-down to stop, overheating, or
overloading. Polar lubricants such as esters have greater
affinity for metal surfaces than mineral oil and are less likely
to drain to the sump [69]. Such lubricants are therefore more
likely to maintain a lubricant film on start-up. Low temperature viscosity is also an important technical criterion. Cold
starts, for instance, is the prime cause of engine wear and an
effective lubricant film can be only be maintained by immediately effective lubrication circulation. Lubricants that have
poor low temperature flow properties can take a significant
time to reach the parts that require lubrication. For automotive applications, this can be evaluated using the cold crank

TABLE 5-

Lubricant Type

Specific Heat Capacity


at100C
Calg-' C^'
(ASTM E 1269)

Thermal Conductivity
at 100C
m W m " ' C"'

Density at 100C
gcni~^
(ASTM D 70)

Viscosity at 100C in cPs


(ASTM D 445)

Lube Heat
Transfer Coeft.

Mineral Oil
PAO 6 [67]
Polyol ester [68]
PAG

0.52
0.55
0.55
0.46

127
144
150
185

0.82
0.77
0.93
1.02

6.49
4.54
5.58
7.75

7.33
9.14
9.91
9.21

262 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


simulator test (ASTM D 2602). An example of the benefits
synthetics can bring is given in Table 6.
The viscosity of a lubricant has a marked effect on wear
(viscosity being related to film thickness). Viscosities of lubricating oils are often quoted at 40C (ISO grade) or 100C
(ASTM D 445). In reality the viscosity u n d e r operating
conditions is the controlling factor. Provided the stability of
the lubricant is sufficient, the ability of the lubricant to resist
viscosity dilution is dependent o n the Viscosity Index (ASTM
D 2270) and the ability of the lubricant to remove heat. The
viscosity index provides a measure of the rate of reduction of
viscosity with temperature. The viscosity pressure coefficient
measures the rate of viscosity increase with increased load.
The ability of the lubricant to resist overloading is therefore
highly dependent on the viscosity pressure coeffecient of the
lubricant. Table 7 gives an overview of the viscosity indices
and viscosity pressure coefficients for a range of synthetic lubriccints.
In certain compressor applications, a proportion of the gas
u n d e r compression can become dissolved in the lubricant
(e.g., refrigerants, hydrocarbons), thereby reducing the lubricant viscosity below the recommended viscosity required for
lubrication. This problem can be solved to a certain degree by
using high viscosity grade lubricants (up to ISO 680 mineral
oil). However, at low temperatures these lubricants are difficult to p u m p . In addition, gas streams may wash the lubricant off the cylinder walls, resulting in wear. PAGs and PIBs
have been used in hydrocarbon applications because of their
ability to resist this dilution. Where good solubility of the
lubricant is required, e.g., refrigeration applications, the excellent lubricity of PAGs and polyol esters has been used to
compensate for the reduction in viscosity. Table 8 gives Ein
TABLE 6Review of cold crank simulator viscosities for fluids
with a viscosity of 4cSt fluids at 100C.

Lubricant

Viscosity at 100C
icSt)
(ASTM 445-97
DIN 51550)

Cold Crank Simulator


Viscosity at -25C (MPa.s)
(ASTM D 2602)
DIN 51377)

Mineral Oil SN 100


PA0 4
Polyol Ester

3.8
3.9
4.5

1300
500
550

TABLE 7^Viscosity indices and viscosity pressure coefficients for


a range of synthetic lubricants.
Viscosity

Type of
Lubricant

Index
(ASTM 2270)

Naphthenic Mineral oils


Parafflnic Mineral oils
PAO
DI & Tri esters
Polyol esters
PAGS
Alkyl benzenes

0-80
80-120
120-150
50-150
50-170
150-280
<0-110

Viscosity Pressure
Coefficients (GPa~"
18.0 -is.ot^" -10.5^"] -5.3[] -5.3^=5 _7 7[72] _11.8--

36.0^^"
23.0C72]
12.6
19.9
21.1
19 jpo]
33.4

TABLE 8Field experience on the suitability of synthetic


lubricants with a variety of gases.
Lubricant

Mineral Oil
PAOs
Esters
PAGs

Suitable

Air, Hydrocarbons, CFC


Air, Hydrocarbons
Air, CFC, HFC, HCFC, CO2
Air, Ammonia, HFC, CO2

Not Suitable

HFC/HFCs, CO2
HFCs
Ammonia
Hydrocarbon

overview of the suitability of a variety of gases in a range of


synthetic lubricants.
The polarity of the lubricant can also be very important.
Recent work suggests that when a small amount of a high
viscosity polar lubricant (ester) is added to a low viscosity
non-polar base fluid (PAO), the polar component will preferentially stick to the surface [76]. When the two metal surfaces
are far apart, the bulk viscosity is controlled by the PAO.
When the surfaces come closer together, the PAO is squeezed
out of the contact zone. The polar ester sticks to the surface
and stays in the contact area. As the ester has high viscosity,
the bulk viscosity of the oil will increase as the surfaces come
closer together.
As viscosity of the lubricant is reduced, or if shear rate or
load is increased, the chance of boundary lubrication is increased. This is especially true under conditions of start-up
where the lubricant film may not yet have formed [77]. The
general properties of the lubricant that affect boundary lubrication are: the degree of branching/aromaticity, molecular
weight, polarity, a n d additives present in the lubricant.
Polar molecules are very effective boundary lubricants as
they tend to form physical bonds with metal surfaces (i.e.,
they stick to the surface better than mineral oil). Because of
these different interactions, the lubricity of a polar lubricant
in a fully formulated fluid is not always easy to predict. Poleir
synthetics such as esters and PAGs can compete with antiwear or EP agent for the metal surface. When polar basefluids are used they can cover metal surfaces in preference to
the antiwear additives. This can result in higher wear characteristics because, eJthough esters have superior lubricity
properties to mineral oil, under high load conditions they are
certainly less efficient than antiwear additives. It is therefore
very important to choose the cortect additive and to optimize
its concentration to get the full lubricity benefit of using polar basestocks. Often, more polar antiwear agents or the same
antiwear agent at a higher dose rate is used to offset this factor. Alternatively, the lubricant can be modified to decrease
its polarity.
The use of bench tests is an attractive approach to wear
testing. Their low cost, short duration, and ease of operation
make them a desirable research tool. Many wear tests only
evaluate a particular wear regime. For example, the Shell
four ball (ASTM D 4172) and Falex (ASTM D 2670/D 3233)
tests measure the boundary weeir while the FZG (CEC L-071-71) and four ball (ASTM D 2783) tests look at failure load.
Due to this narrow assessment, there has been justifiable reluctance to rely on lubricant performance data obtained from
the use of bench wear tests. Nevertheless, they are useful as
an initial screening tool to spot crude trends that can later be
checked by system trials.
Environmental

Acceptability

In 1985, some 4.5 million tons of lubricants were used in the


EEC. Of these, some 2.5 million tons were consumed in service, leaving 2.0 million tons of waste oil. Of this waste oil, 0.7
million tons were re-used as a fuel supplement and 0.7 million tons were recycled, leaving 0.6 million tons or 13% unaccounted for [79]. This loss is the equivalent of one Exxon
Valdez disaster per m o n t h [80]. Increasing interest is therefore being taken in the ultimate environmental impact of the
lubricant.

CHAPTER
Eco-labels for lubricant applications are starting to appear
in both the United States and Europe. Initially these have
been focused a r o u n d hydraulic fluids (Blue Angel in Germany, Nordic Swan in Scandinavia, and ASTM D 6046 in the
U.S.) but this is likely to be extended to other application areas in the future. The schemes are voluntary and have been
set u p to allow products to be differentiated using an agreedupon environmentally friendly labelling classification. The
biodegradability of the lubricant is an important part of the
legislation and can be measured by a variety of different test
methods (CEC-L-33-A-94, OECD 301B, ASTM D 5864, etc.).
The biodegradability of a variety of synthetic lubricants is
shown in Table 9. Even within a class of synthetics, the
biodegradability can cover a large range. Different
biodegradability tests can also give very different results for
the same chemistry. Results can also be highly dependent on
where the activated sludge used in the tests is obtained from.
However, in general high viscosity, aromaticity, and a high
degree of branching all have a negative impact on biodegradability. ASTM D 6006 and D 6384 are useful guidelines to
biodegradability testing and the terminology used to describe
the results.
Food and Drug Administration (FDA) approved low toxicity lubricants are required increasingly for applications connected to the food industry. The FDA food approval system is
undergoing major changes and will be replaced shortly by a
new system. However, the old FDA classification system is
still being used. See Table 10. The cost of registration of a
new lubricant for food use can be considerable.
For many of the lubricants, several limitations of use are
listed, such as maximum dose rate or effect (e.g., can only be
used at a dose rate of bellow 0.5% in another FDA approved
oil).
Relative

Cost of

Synthetics.

Synthetic lubricants are made from a range of relatively expensive raw materials via a whole range of chemical interacTABLE 9Biodegradability of synthetic lubricants.
Lubricant Type

% Biodegradability
by CEC-L-33-A-94 Test
After 21 Days

% Biodegradability
by OECD 301B Test
After 28 Days

Mineral oil
PAOs
Diesters
Aromatic Esters
Polyol Esters
Alkyl Benzenes
PAGs
Polybutenes

10-45
20-80
75-100
0-95
0-100
5-20
5-70
5-20

10-40
5-60
25-80
5-45
0-80
0-20
5-80
0-20

TABLE 10An overview of FDA incidental food contact approval


(CFR 178.3570).
Lubricant
Mineral oil
PAD
Ester
PAG
Polybutene

FDA Registered
No
Yes
Glycine ester (CAS No 110-25-8) and
Isopropyl oleate
Several water soluble and insoluble PAGs >
RMM = 1000
Hydrogenated polybutenes listed under
178.3740

10: SYNTHETIC

LUBRICANTSNON

AQUEOUS

263

TABLE 11Relative cost of synthetic lubricants


versus mineral oil.
Lubricant
Mineral oil
PAOs
Esters
PAGs
PIB
Alkyl benzene
Silicones
Polyphenylethers
Fluorocarbons

Relative Cost to Mineral Oil


1
2-5
2-10
2-6
2-4

2-3
10-50
50-250
75-300

tions and transformations. Synthetics will therefore always


cost more than mineral oil. Their relative prices as opposed
to mineral oil are given in Table 11.
Although more expensive than mineral oil, synthetics can
lead to a major reduction in system production and running
costs and thereby quickly repay their initial costs. For example, synthetics can lead to reduced lubricant consumption,
lower maintenance and less plant downtime, reduced disposal costs, and longer equipment lifetimes.
The growth of mineral oil has been stagnating over the last
few years. The higher performance, reduced environmental
impact, and the increasing potential to reduce costs using synthetics has allowed them to show strong year on year growth
in many sectors. In short, the commercial importance of synthetic lubricants is set to increase significantly in the future.

ASTM STANDARDS
No.
D70
D86
D91
D92
D93
D94
D97
D 130
D 189
D445
D471
D524
D664
D665
D873
D892
D 892 (Option A)
D943
D972
D974
D
D
D
D

1209
1218
1298
1401

Subject
Density
Distillation
Precipitation n u m b e r (Sludge Formation)
Flash Point - Cleveland Open Cup
Flash Point - Pensky-Martins
Saponification Number
Pour Point
Copper Strip Corrosion
Carbon Residue - Conradson
Viscosity - Kinematic
Elastomer Seal Compatability
Carbon Residue - Ramsbottom
Acid Number, Potentiometric
Rust Prevention
Potential Residue
Foaming Characteristics (Sequence IHI)
Foaming Characteristics (Sequence IIII) (Option A)
Turbine Oil Stability Test (TOST)
Volatility - Evaporation loss
Acid/ Base N u m b e r by Color Indicator
Titration
Color - APHA
Refractive Index
Density
Emulsion Characteristics

264 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


D 1500
D 1744
D 1748
D2070
D2270
D2272
D2500
D2602
D2619
D6375
D2670
D2711
D2780
D2782
D2783
D2983
D3233
D3427
D3827
D4052
D4172
D4739
D4742
D5001
D5133
D5185
D5191
D5481
D5800
D6079
D6082
D 6082 (Option A)
E326
E 1064
E 1269

Color - ASTM
Water Content by Karl Fisher
Rust Protection
Thermal Stability
Viscosity Index
Rotating B o m b Oxidation Test
Cloud Point
Cold Cranking Simulator
Hydrolytic Stability (93C)
Volatility - NOACK at 250C / TGA
method
Falex PinA^ee
Demulsibility Characteristics
Gas Solubility
Timken OK Load
EP, 4-Ball E P
Viscosity -Brookfield
Falex Pin/Vee
Air release
Gas Solubility
Specific Gravity
Four ball wear
Base N u m b e r
Thin Film Oxygen Uptake Test
Ball on Cylinder Lubricity Evaluation
Brookfield - Scanning
Elemental Analysis
Vapour Pressure, Reid
Viscosity - High T e m p e r a t u r e High
Shear by capillary
Volatihty - NOACK at 250C / TGA
method
High Frequency Reciprocating Rig
Foam, High Temperature
Foam, High Temperature (Option A) TMC Certified
Phthalate Esterification
Coulometric Karl-Fischer Titration
Specific Heat Capacity

OTHER STANDARDS
No.
D I N 51 5 5 0
DIN/ISO 2909
D I N 51 5 9 7
D I N 51 3 7 6
D I N 51 5 5 9 P a r t 1
DIN 51 777 Part 1

Subject
K i n e m a t i c Viscosity
K i n e m a t i c Viscosity Index
P o u r P o i n t of P e t r o l e u m P r o d u c t s
Cleveland Open C u p
Calorimetric Titration
Coulometric Karl-Fischer Titration

REFERENCES
[1] Barnes, R. S. a n d F a i n m a n , M. Z., Lubrication
Engineering,
1957, p. 454.
[2] Smith, T. G., "Neopentyl Polyol Esters," Synthetic Lubricants, R.
C. Gunderson and A. W. Hart, Eds., Reinhold, NY, 1962, p. 388.
[3] Randies, S. J., "Esters," Synthetic Lubricants and High Performance Functional Fluids, R. L. Rudnick and R. L. Shubkin, Eds.,
Marcel Dekker Inc., NY, 1999, p. 63.

[4] Randies, S. J., "Refrigeration Lubes," Synthetic Lubricants and


High Performance Functional Fluids, R. L. Rudnick and R, L.
Shubkin, Eds., Marcel Dekker, NY, 1999, p . 563.
[5] Randies, S. J., "Esters," Synthetic Lubricants and High Performance Functional Fluids, R. L. Rudnick and R. L. Shubkin, Eds.,
Marcel Dekker, NY, 1999, p . 63.
[6] Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 18, 4th
Edition, John Wiley & Sons, Inc., NY, 1991, p. 991.
[7] Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 18, 4th
Edition, John Wiley & Sons, Inc., NY, 1991, p . 991.
[8] Johnson, R. W., "Dibasic Fatty Acids," Fatty Acids in Industry, R.
W. Johnson and E. Fritz, Eds., Marcel Dekker, NY, 1982, p. 327.
[9] Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 1, 4th
Edition, John Wiley & Sons, Inc., NY, 1991, p . 893.
[10] Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 1, 4th
Edition, John Wiley, NY, 1991, p . 913
[11] Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 9, 4th
Edition, John Wiley, NY, 1991, p . 755.
[12] Briant, J., Denis, J., a n d Pare, G., Rheological Properties of
Lubricants, Editions Tecnip, Paris, 1989.
[13] Emkarate Esters for Synthetic Lubricants, Product Brochure, ICI
Performance Chemicals, Middlesbrough, UK, 1997.
[14] Lubricant Esters, UnichemaBV, Gouda, Netherlands, 1997.
[15] Boyde, S., Journal of Synthetic Lubrication, Vol. 18, 2001, p . 99.
[16] Boyde, S., Journal of Synthetic Lubrication, Vol. 16, 1999, p . 297.
[17] Scholz, N., Diefenbach, R., Rademacher, 1., and Linnemann, D.,
"Biodegradation of DEHP DBF DINP," Bulletin of Environmental Contamination and Toxicolology, Vol. 58, 1997, p. 527.
[18] OECD Guideline for t h e Testing of Chemicals, Ready
Biodegradability, OECD 301, Organisation for Economoic Cooperation a n d Development (OECD), Paris, adopted 17 July
1992.
[19] Boyde, S., Randies, S. J., and Gibb, P., "The Effect of Molecular
Structure on Boundary and Mixed Lubrication by Synthetic
Fluidsan Overview," Lubrication at the Frontier, D. Dowson, et
al., Eds., Proceedings of the 25th Leeds-Lyon Symposium on
Tribology, 1998, Elsevier, NY, 1999, p. 799.
[20] Randies, S. J., "Refrigeration Lubes," Synthetic Lubricants and
High Peformance Functional Fluids, L. R. Rudnick and R. L.
Shubkin, Eds., Marcel Dekker, Inc., NY, 1999, p. 563.
[21] Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed., Vol.
6, John Wiley & Sons, Inc., NY, 1991, pp. 225-269.
[22] Matlock, P. L. a n d Clinton, N. A., in 'PAGs' in Synthetic Lubricants and High Performance Functional Fluids, R. L. Shubkin,
Ed., Marcel Dekker, Inc., NY, 1999, pp. 101-124.
[23] Klamann, D., Lubricants and Related Products, Verlag Chemie,
Weinheim, Germany, 1984.
[24] Emkarox Physical Properties, ICI Corp., London, 1997.
[25] Polyalkylene Glycols, Properties and Applications, ICI Corp.,
London.
[26] Wurtz, A., Annales de Chimie et Physique, Vol. 69, 1863, p. 330.
[27] McClelland, C. P. and Bateman, R. L., Chemical Engineering
News, Vol. 23, No. 3, 1945, p . 247.
[28] Thompson, R. I. G., Eastwood, J., and Stroud, P. M., "The Development of High Performance Carrier Fluids for Detergent
Fuel Additive Packages," Proceedings of the 11th International
Colloquium, Technische Akademie, Esslingen, Germany, 1998,
p. 2485.
[29] Briant, J., Denis, J., and Pare, G., Rheological Properties of Lubricants, Editions Technip, Paris, 1989, pp. 155-163.
[30] Yang, L., Heatiey, F., Blease, T., and Thompson, R. I. G., "A
Study of the Mechanism of the Oxidative Thermal Degradation
of Poly(ethylene oxide) a n d Poly(propylene oxide) Using ' H and '^C-NMR," European Polymer Journal, Vol. 32, No. 5, 1996,
pp. 535-547.
[31] Headey, F., Luo, Y.-Z., Ding, J.-F., Mobbs, R. H., and Booth, C ,
Macromolecules, Vol. 21, 1988, p . 2713.

CHAPTER 10: SYNTHETIC LUBRICANTSNON AQUEOUS 265


[32] Sanvordenker, K. S., "Materials Compatibility of R134a in Refrigerant Systems," presented at The American Society of Heating, Refrigeration and Air-Conditioning Engineers, Winter Meeting, Jan. 1989.
[33] Hamblin, P., "Oxidative Stabilisation of Synthetic Fluids and
Vegetable Oils," Journal of Synthetic Lubrication, Vol. 16, No. 2,
1999, pp. 157-181.
[34] Moxey, J. R., "Process for the Preparation of Polyoxylalkylene
Block Copolymers," European Patent 0 570 121B1, Europena
Patent Office, Munich, Germany, 10 Feb. 1999.
[35] Chapter I, Food and Drug Administration, Department of
Health and H u m a n Services (Continued), Part 178Indirect
Food Additives: Adjuvants, Production Aids, and Santizers
S u b p a r t DCertain Adjuvants a n d P r o d u c t i o n AidsSec.
178.3570, Lubricants with Incidental Food Contact, Food and
Drug Administration, U.S. Government Printing Office via GPO
Access, Pittsburgh, PA, April 2002.
[36] ISO 6743: Industrial Oil Class L Classification Part 4: Family H
(Hydraulic Systems), International Organization for Standardization, Geneva.
[37] Hodges, P., Hydraulic Fluids, John Wiley & Sons, Inc., NY, 1996.
[38] Doc. No. 4746/10/91 EN, Requirements and Tests AppUcable to
Fire-Resistant Hydraulic Fluids used for Power Transmission
and Control, 7th ed., Comite Europeen des Transmissions Oleohydrauliques et Pneumatiques, Luxembourg, 1994.
[39] Bock, W., "Moderne Schwerentflammbare u n d Umweltschonende Hydraulikflussigkeiten in Industrie und Bergbau," Tribologie und Schmierungstechnik,
Vol. 46, 1999, pp. 22-28.
[40] Test Standard for Specification Test Standard for Flammability
of Industrial FluidsClass Number 6930, Factory Mutual Research Corporation, Johnston, RI, 2000.
[41] Kussi, S., "Eigenschaften von Basisflusigkeiten fur Synthetische
Schmierstoffe," Tribologie und Schmierungstechnik,
Vol. 33,
1986, pp. 33-39.
[42] MoUer, U. J., "Grenzen and Moglichkeiten fur Syntheseole und
Konventionelle Oele," Erdoel und Kohle, Vol. 23, 1970, p p .
667-673.
[43] Moller, U. J. a n d Boor, U., Lubricants in Operation, Verlag,
Duesseldorf, 1986.
[44] Lilje, K. C , Short, G. D., and Miller, J. W., "Compressors and
Pumps," Synthetic Lubricants and High Performance Functional
Fluis, R. L. Shubkin, Ed., Marcel Dekker, Inc., NY, 1999, pp.
539-562.
[45] Short, G. D., "Development of Synthetic Lubricants for Extended Life Rotary-Screw Compressors," Lubrication Engineering, Vol. 40, 1984, pp. 463-470.
[46] Carswell, R. and McGraw, P. W., "Rotary Screw Compressor Lubricants," U.S. Patent 4,302,343, granted to the Dow Chemical
Company, Midland, MI, 1981.
[47] Ward, E. L., McGraw, P. W., and Appleman, T. J., "Lubricants
for Reciprocating Air Compressors," U.S. Patent 4,751,012,
granted to the Dow Chemical Company, Midland, MI, 1988.
[48] Benda, R., BuUen, J., and Plomer, A., "Base Fluids for High-Performance Lubricants," Journal of Synthetic Lubricants, Vol. 13,
No. 1, 1997, p. 41.
[49] Brennan, J. A., "Polymerisation of Olefins with BF3" U.S. Patent
3,382,291, to Mobil Oil, Washington DC, 1968.
[50] Shubkin, R. L., "Process for Producing a Ce-Cie N o r m a l
ALPA-Olefin Oligomer Having a Pour Point Below About 50F," U.S. Patent 3,763,244, to Ethyl Corp., Washingotn DC,
1973.
[51] Shubkin, R. L., "Synthetic Lubricants by Oligomerisation and
Hydrogenation," U.S. Patent 3,780,128 to Ethyl Corp., Washington DC, 1973.
[52] Szydywar, J., "Synthetische Kohlenwasserstoffe, Speziell
Polyalphaolefine," Schmiertechnik
+ Tribologie, Vol. 28, No. 4,
1981, p. 124.

[53] Plomer, A., Senior Scientist, Personal communication, BP


Amoco Chemicals, Feluy, Belgium, October 1999.
[54] Benda, R., Market Development Manager, Personal communication, BP Amoco Chemicals, Feluy, Belgium, October 1999.
[55] Rudnick, L. R. and Shubkin R. L., "Lubrication at the Frontier,"
D. Dowson et al., Eds., Proceedings of the 25th Leeds-Lyon Symposium on Tribology, 1998, Elsevier, NY, 1999, p. 10.
[56] "PAO a n d Synthetic Esters," Product Literature, Mobil Chemicals, Chemical Products, Edison, NJ, 1998; "Polyalphaolefins,"
Product Literature, BP Amoco Chemicals, Chicago, IL, 1987.
[57] Wunsch, F., "Synthetische Schmierstoffe - Heute und Morgen,"
Proceedings of the 9th International Colloquium, Technische
Akademie Esslingen, 1996, p. 2271.
[58] Randies, S. J., Lubrication Engineering, Vol. 22, 1957, p. 82.
[59] Quinn, C , Traver, F., and Murthy K., "Silicones," Lubrication at
the Frontier, D. Dowson et al., Eds., Proceedings of the 25th
Leeds-Lyon Symposium on Tribology, 1998, Elsevier, NY, 1999,
p. 267.
[60] Bell, G. A., Howell, J., and DelPasco, T. W., "Perfluoroalkyl
Polyethers," Synthetic Lubricants and High Performance Functional Fluis, R. L. Rudnick a n d R. L. Shubkin, Eds., Marcel
Dekker, Inc., NY, 1999, p. 215.
[61] Joaquim, M., "Polyphenyl Ether Lubricants," Synthetic Lubricants and High Performance Functional Fluis, R. L. Rudnick and
R. L. Shubkin, Eds., Marcel Dekker, Inc., NY, 1999, p. 239.
[62] "OS 124, Polyphenyl Ether Fluid by Santovac," Commecial Literature, Santovac Fluids, St Charles, MO, 1999.
[63] Casserly, E. W. and Venier, C. G., "Cycloaliphatics," Synthetic
Lubricants and High Performance Functional Fluis, R. L, Rudnick and R. L. Shubkin, Eds., Marcel Dekker, Inc., NY, 1999,
p. 325.
[64] Venier, C. G. and Casserly, E. W., Lubrication Engineering, 1991,
Vol. 47, p. 586.
[65] "Santotrac Traction Lubricants," Commercial Literature, Findett Corporation, St Charles, MO, 1999.
[66] Landsdown, A. R., High Temperature Lubrication, Mechanical
Engineering Publications Ltd., London, 1988.
[67] M. J. Neale, Ed., Tribology Handbook, Butterworth, London,
1973.
[68] Shubkin, R. L., "Polyalphaolephins," Presented at the Advanced
Synthetic Lubricants Education Course, STLE National Meeting,
Calgary, Alberta, Canada, May 1993.
[69] "Midel 7131," Transformer Fluid Brochure, M & I Materials,
1993.
[70] Randies, S. J. and Whittaker, A. J., "Compressor Fluids^Value
Creation Using Synthetics," International Conference on Compressors and Their Systems, Paper C542/029/99, ImechE Conference Transactions, 1999, p . 127.
[71] Aderin, M., Spikes, H. A., and Caporiccio, C , "The Elastrohydrodynamic Properties of S o m e Advanced Non-Hydrocarbon
Based Lubricants," Lubrication Engineering, Vol. 48. No. 8, August 1992, pp. 633-638.
[72] CRC Handbook of Lubrication, Vol. 2, CRC Press, Boca Raton,
FL, 1988, p. 235.
[73] Guangteng, G. and Spikes, H. A., "Boundary Film Formation by
Lubricant Base Fluids," Paper 95-NP-7D-3, Presented at The
50th Annual Meeting, STLE, Chicago, IL, 14-19 May 1995.
[74] Chang, H. S., Spikes H. A., and Bunemann, T. F., "The Shear
Stress Properties of Ester Lubricants in Elastrohydrodynamic
Contacts," Journal of Synthetic Lubricants, Vol. 8, No. 3, 1991, p.
258.
[75] Gunsel, S., Lockwood, F. E., and Westmorland, T., "Engine Oil
OxidationCorrelation of ASTM III-D and III-E Sequence Engine Tests to Bench Tests" Presented at the SAR International
Fuels and Lubricants Meeting and Exposition, Baltimore, MD,
1989, SAE Paper No. 892164, Society of Automotive Engineers,
Warrendale, PA.

266 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


[76] Gunsel, S. and Pozebanchuk, M., "Elastrohydrodynamic Lubrication with Polyester Lubricants and HFC Refrigerants," The
Air Conditoinaing and Reirigeration Technology Institute, Project No. 670-54400, Report No. DOE/CE/23810-102, April 1999.
[77] Smeeth, M. and Spikes, H. A., "The Formation of Viscous Surface Films by Polymer Solutions: Boundary or Elastrodynamic
Lubrication?," Paper 95-NP-7D-2, Presented at the 50th Annual
Meeting, STLE, Chicago, IL, 14-19 May 1995.
[78] Summers-Smith, D., An Introduction to Tribology in Industry,
The Machining Publishing Co., Brighton, England.
[79] CONCAWE (Conservation of Clean Air and Water Europe), "The
Collection, Disposal and Regeneration of Waste Oil and Related
Materials," Report 85/33, The Hague, 1985.
[80] Betton, C. I., "Lubricants and Their Environmental Impact," Ch.
13, Chemistry and Technology of Lubricants, 2"^ Edition, R. M.

Mortier and S. T. Orszulik, Eds., Blackie Academic and Professional, London, 1997.
[81] Smeeth, M. and Spikes, H. A., "The Formation of Viscous Surface Films by Polymer Solutions: Boundary or Elastrodynamic
Lubrication?," Paper 95-NP-7D-2, Presented at the 50th Annual
Meeting, STLE, Chicago, IL, 14-19 May 1995.
[82] Summers-Smith, D., An Introduction to Tribology in Industry,
The Machining Publishing Co. Ltd., Brighton, UK, 1969.
[83] CONCAWE (Conservation of Clean Air and Water Europe), The
Collection, Disposal and Regeneration of Waste Oil and Related
Materials, Report 85/33, The Hague, 1985.
[84] Betton, C. I., "Lubricants and Their Environmental Impact,"
Chemistry and Technology of Lubricants, 2nd Edition, R. M.
Mortier and S. T. Orszulik, Eds., Blackie Academic and Professional, London, 1997.

MNL37-EB/Jun. 2003

Environmentally Friendly Oils


Hubertus Murrenhoff^ and Andreas
Remmelmann^

A
Cs

d
FM

g
P
Q
T
V
V

P
DIN
EP
HEES
HEPG
HETG
HFA
HFC
NZ
ppm
TMP

VI
WGK
C
CI
CO2
H
H2O
N
O
VCI

Units
,2
m
area
J/(kgK)
heat capacity
mm
diameter
N
force
gravity
m^/s
bar (lO^N/m^)
pressure
flow
m^/s
C
temperature
m^
capacity
Ns/m^
dynamic viscosity
mm'^/s
kinematic viscosity
kg/m^
density
Deutsches Institut fiir Normung
Extreme Pressure
Hydraulic-Environmental group ES (synthetic
ester)
Hydraulic-Environmental group PG (polyglycol)
Hydraulic-Environmental group TG (tri-glycerid)
Hydraulic-Fire-resistant group A (water-based)
Hydraulic-Fire-Resistant group C (water glycol)
Neutralization N u m b e r
Parts-Per-Million
tri-methylol-propan
Viscosity-Index
Water Hazard Class
Carbon
Chlorine
Carbon Dioxide
Hydrogen
Water
Nitrogen
Oxygen
Verband Chemischer Ingenieure

Pressure Media
In a variety of technical systems, hydraulic drives are the preferred alternative because of their versatility and efficiency.
To perform the drive functions over the life of the system, the
hydraulic fluid must be considered as a system component
during the design stage. Due to a societal increase in
' Executive Director, Institute of Fluid Power Transmission and
Control, IFAS, University of Teciinology Aachen, Steinbachstr. 53, D52074 Aachen, Germany.
^ Product Engineering Hydraulics, John Deere Works Mannheim,
Windeckstr. 90, 68163 Mannheim, Germany.

environmental consciousness in the late 1980s, regulatory


agencies began d e m a n d i n g that these fluids be rapidly
biodegradable and nontoxic. This excluded mineral oil from
consideration. Currently vegetable oils, some synthetic esters,
and polyglycols are being used for these applications [1-10].
Since the properties of those base fluids differ substantially
from those of conventional mineral oils, extensive testing is
required. To qualify the fluids for the intended applications,
special laboratory tests are required to ensure that they will
withstand the pressures and t e m p e r a t u r e s encountered.
Many of the chemical and physical test procedures were developed for mineral oils and aren't applicable for these new
types of hydraulic fluids.
Parallel to the development of base fluids, new additives
are being developed. This is necessary for two reasons:
1. Existing additives used so far in mineral oil based pressure
media lead to a deterioration of the performance properties in rapidly biodegradable oils.
2. Existing additives contain toxic substances leading to a
significant deterioration of the biodegradability of the
fluid [11,12-14].
Functions and Requirements
In a hydraulic system, the pressure media has many functions. Fig. 1. Transmitting the hydraulic power is the main
function. For this purpose, the pressure media connects the
generator (pump) and the motor (cylinder) via the enclosed
volume and carries the pressure that is determined by the
load [15].
This main function of a pressure media can be accomplished in principle with any fluid; but additional requirements result in a substantial limitation of the fluids to be
used. To ensure a long lifetime of the hydraulic components,
wear protection is of central importance. Moreover, the fluid
must protect the component surfaces against corrosion and
it must be compatible with the elastomers used as sealing
material.
Based on the above-mentioned tasks, a variety of demands
are m a d e on hydraulic fluids, see Fig. 2. To transmit hydraulic power and guarantee high load stiffness, the fluid
must exhibit a high bulk modulus. This is another prerequisite for optimal control in open and closed loop hydraulic
systems [14].
The task of protecting hydraulic components against wear
and corrosion creates very high demands on the fluid [33]. It
must exhibit a high increase of viscosity vs. pressure, thus
producing a self-enhancing effect in the tribological contact

267
Copyright'

2003 by AS'I M International

www.astm.org

268

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

FIG. 1Functions of hydraulic fluids.

FIG. 2Demands on hydraulic fluids.

for high loads [16]. In addition, the fluid must provide good
lubricating film wetting between surfaces moving relative to
each other that reduce wear and stick slip. Materials used in
hydraulic components such as bronze or other alloys are susceptible to corrosion. Consequently, the fluid should contain
only a m i n i m u m a m o u n t of free acid, if any. The by-products
created by the aging process must be neutralized or adsorbed
by additives contained in the fluid to eliminate any acid
build-up. In addition, the fluid properties must vary only
slightly over extended time [31].
Elastomers and other non-metal components may also
be attacked by these by-products. Increased elastomer
swelling may result in complete decomposition and sealing
failure.
Mechanical and volumetric losses in hydraulic units are responsible for heat generation. This heat is partially released
to the environment by convection. The pressure media itself,
however, accounts for the major part of the heat loss. To limit
the temperature increase of the fluid, it must possess high
heat capacity and thermal conductivity.
These demands are directly related to the use of the pressure media in a hydraulic system. The development of fluids
is significantly influenced by external requirements. For ex-

ample, fluids used in underground mining or in steel mills


must be fire resistant to reduce the dcuiger of fire. An additional requirement is environmental compatibility, which
has led to the development of another pressure media group
[19,22,35,38].
Types of Pressure Media
Different types of hydraulic fluids are shown in Fig. 3. Each
one is developed for a specific application. The most comm o n type in use today is based on mineral oil.
Fluids are blended with additives to inhibit aging, weeir and
to reduce friction and corrosion. For special application requirements, additives with detergent and dispersent characteristics are used to suspend solid particles as well as water,
in some cases u p to 5% water.
By utilizing special refining methods, it is possible to improve the viscosity t e m p e r a t u r e performance of the base
stock. Group II API Base Oils can be blended to produce good
tribological characteristics and long-term stability. State of
the art refining technology ensures constant production of
prime quality base stocks. The technology to develop additives is readily available.

CHAPTER 11: ENVIRONMENTALLY

FRIENDLY OILS

269

FIG. 3Different types of hydraulic fluids [24,25].

TABLE 1Groups of biologically fast degradable


pressure media.
Fluid

Base Fluid

Saturation

Origin

HETG
HEES

Native ester
Synthetic ester

Unsaturated
Unsaturated
Saturated

HEPG

Poly-glycol

Native materials
Native materials
Chemical industry
Chemical industry

New groups of fluids have been developed to provide good


fire resistance, rapid biodegradability, and low toxicity.
Mineral oils are classified based on their performance,
which is different from readily biodegradable pressure media, which are classified according to base fluid composition.
There are three groups of biodegradable fluids: natural esters
(type HETG), synthetic esters (type HEES), and poly-glycols
(type HEPG) as listed in Table 1.
HETG base stocks are derived from vegetable oils such as
rapeseed and sunflower. These base fluids have a limited
temperature range. New additives have been developed to
meet the expected application temperature ranges. Their
poor thermal stability is due to the amount of unsaturated
carbon containing acids found in these natural esters.
HEES base stocks can be produced from various materials
including natural esters. The use of natural esters usually
leads to unsaturated synthetic esters. Performance of the fluids is superior to HETG fluids due to a more uniform molecular structure and the use of different alcohols. Using completely saturated esters, the resulting fluids exhibit very
stable aging characteristics. Additives used speciflcally for
this type of fluid have also been developed.
Based on the many choices of acids and alcohols available

for the production of synthetic esters, a wide variety of technical performance properties is possible. Early synthetic esters possessed a chemical structure similar to rapeseed oil.
HEPG fluids is the third fluid type and is the only type that
is water-soluble. This can be an advantage for the biological
degradation in water. On the other hand, there is the danger
of fluid-contaminated water penetrating more deeply into the
soil layers, thus reaching ground water. For that reason, in
some countries, polyglycols are not considered environmentally friendly fluids.

CHEMICAL B A S E S O F N A T I V E A N D
SYNTHETIC ESTERS
Functional Groups and Elementary Compound
Pressure media based on native and synthetic esters consist
of carbon-hydrogen bonds as do mineral oils. However, the
structure differs significantly from that of mineral oil, which
explains the different properties and performance characteristics exhibited by these fluids. Examples of the different
functional groups can be seen in Fig. 4.
The characteristic group for an alcohol is the hydroxy
group (OH-group). In a case where the OH-group of aliphatic
alcohols is connected to a carbon-atom, the alcohol is described as primary alcohol. In a case where the OH-group is
connected to a carbon-atom in the center of the molecule, it
is considered secondary alcohol. Tertiary alcohols are those
with an OH-group connected at a branch site in the molecule.
The hydroxy group of alcohols is responsible for their
higher boiling points compared to those of the comparable

270

MANUAL

37: FUELS AND LUBRICANTS


hydroxyl-group

carbonyl-group

HANDBOOK

alkyl-group

Mechanism of Esterification

CH

OH

H
carboxyl-group

aldehyde
O

CH

COH

ketone
0

II

carboxylic acid

R1-CR2

alcohol

ester

R 2 - C OH

R^-OH

R^-OC R2

FIG. 4Important functional groups of organic chemistry.

R^
\

-.1

OH

R'
OH

In Fig. 8, the general equation of a reaction for the production of esters is shown. This chemical reaction produces ester and water. Water must be removed during reaction to
achieve a complete conversion of the alcohol reaction with
the acid to produce a n ester (by shifting the equilibrium to
the right).
The equilibrium constant (K) for the ester producing reaction is [30]:

-.1
R'
+\ *
OH - - 0 H

FIG. 5Hydrogen bond of alcohols, [22-30].

alkanes, because of the shared hydrogen bond of the hydroxyl groups. A strong polarity of the OH-connection is
based on the electro-negativity of oxygen. The result is a positive shifting of the hydrogen a t o m so that the hydrogen
bonding connection shown in Fig. 5 becomes feasible.
The possibility for hydrogen bonding is the reason for the
still unlimited miscibility of simple alcohols with water.
However, with increasing size of the non-polar organic alcohol residue, this characteristic decreases.
The abbreviation R used in Fig. 5 represents a n alkylgroup. This is a n acylic saturated carbon-hydrogen compound, called an aJkane, from which a hydrogen molecule is
split off. According to their bonding capability, alcohols are
considered to be monovalent, bivalent, or trivalent.
To produce a synthetic ester hydraulic fluid with good performance properties, carboxylic acids are used. The carboxy
g r o u p COOH is the functional g r o u p of carbon acids. Its
nomenclature is based on the combination of the carbonyl
and hydroxy group. Carboxylic acids with long-chain Rgroups attached are called fatty acids. The capability of carbon acids to hydrogen bond as with alcohols, is based on
their chemical structure. This is the reason for their relatively
high boiling point, which is comparable to alcohols due to its
dimeric structure resulting from the hydrogen bonds shown
in Fig. 6.
Small carbon acids like the corresponding small alcohols
are still soluble in water. However, the solubility diminishes
with increasing molecular size. When carboxylic acids contain only single bonds, they are considered saturated.
Unsaturated acids contain at least one double bond. The
n u m b e r of double bonds influences chemical properties. Furthermore, carboxylic acids are distinguished by different isomers resulting in different chemical and physical properties
(Fig. 7).

[ester] [water]
[acid] [alcohol]

Where: "[ ]" indicates the concentration of the reactants (acid


and alcohol) or products (ester and water) in mole/liter. It is
desirable to maximize the concentration of ester and to minimize the concentration of acid and alcohol. One way to do
this is to remove water during the reaction. Thus, to maintain
equilibrium, more water must be produced, which decreases
the concentration of acid and alcohol resulting in increased
water production. Similarly, increasing the alcohol concentration will decrease the acid and increase the desired ester
content.
The rate of reaction is increased by the increasing temperature or by the addition of an acid catalyst such as H2SO4
(typically 5-10% based on the weight of the acid carboxylic).
Other, even stronger, acids may also be used. The rate of the
esterification reaction increases with increasing catalyst concentration
The objective of ester production is to quantitatively complete transition of acid into ester. This means that the concentration of ester should be as high as possible.
The removal of water from the reaction mixture may be facilitated by the addition of a solvent such as toluene. In this
case, water is removed from the reaction mixture by
azeotropic distillation.
H O

R ' - Cy
.

+
O H

,0HO
C R^

R^ - C

CR^
OHO

FIG. 6Hydrogen bond of carbon acids.

cis-configuration

trans-configuration

C=C

H
FIG. 7Isomers of carboxylic acids, cis and trans structure.

carboxylic acid

aicohd

ester

water
H

O
R^-C OH

R} - O H

R' - O C R 2

FIG. 8Chemical reaction of ester production.

OH

CHAPTER 11: ENVIRONMENTALLY


The mechanism of the acid catalyzed production of ester
from carboxyhc acids and primary or secondary alcohols is
based on the addition of a proton to the oxygen of the carboxyl
group. Producing a mesomer-stabilized cation and the Catom of the carboxyl group becomes positive. By adding the
nucleophilic oxygen of the alcohol to this carbon atom, the ester is finally produced by separation of water and protons; see
Figs. 9a and 9b.
Tertiary zJcohols are not esterified in this way because the
hydroxyl group will undergo acid catalyzed elimination producing undesirable alkenes, as shown in Fig. 10.

FRIENDLY OILS

271

1. step: alcohol protonation


H
R3C-OH

R3C-O

2. step: carbenium formation


H
R3C-0

- >

R3C

H2O

H
3. step: electrophilic carboxyl group attack
1. step: carbonyl oxygen protonation

o
1 II

OH'

R^ - C

^
H

1 II
*

R^ - C O H

~*'

R^ - C O H

4. step:proton migration
0^CR,

OH*

OH

R^ - G

R 2 --OH

R^- - c 0

~*

R^ - C O *

- C = 0 H " '

OCR3

OCR3

R^-C=O

R^1 - CI O R 2

Alcohol Bonds

L V
4. step: water split off
OH
R1
^ - CI O R^

Ri

FIG. 10Ester synthesis with tertiary-alcohols.

OH

OCR3

5. step: proton removal

R^-C=OH'

3. step: proton shifting


OH

R1^ - CII O H

FIG. 9aEster synthesis with primary and secondary alcohols under acid conditions [22-30].

OR""
R,1' - C

H.O

II .
OH
5. step: proton split off
0 R-"
1

R^ - C

//

\
OH

Rfi^

I
OH

2. step: alcohol addition

R' - C

"^

R^ - C

OH

o'^CRj

OR"

FIG. 9bEster synthesis with primary and secondary alcohols under acid conditions.

By variation of the acid and ester reagents, a vast array of


possible ester products and a wide variety of chemical properties is achievable. These varieties, however, are limited by
the demand for a good biological degradability as well as by
other technical requirements with regard to viscosity, viscosity temperature dependence, and its stability under hydraulic
load. The different alcohols depicted in Fig. 11 are used for
the production of hydraulic fluids.
Trimethylolpropane is a colorless, crystalline substance
easily soluble in water. This is the stacking material used for
polyols by reaction with ethylene oxide and propylene oxide,
which are other reacted to form polyurethanes. By esterification with carboxylic acids, ester lubricants with a high viscosity index (VI) are produced.
Glycerin is also a trifunctional alcohol and is very soluble
in water. This is the main reason for its wide use in drugs and
cosmetics. When esterified with carboxylic acids, ester-based
lubricants with a high VI are produced as well. These esters
can also be produced from natural materials such as rapeseed oil through a pressing process.

272

MANUAL 37: FUELS AND LUBRICANTS

trimethylolpropane
HH

ditives. Mono and glycerin esters, however, exhibit limited


chemical stability at high temperatures and low temperature
performance.
High temperature stability and low temperature performance properties can easily be achieved with di-carboxylic
acid and polyol ester. Carbon-6 to carbon-12 di-carboxylic
acid esters are increasingly important as engine and compressor lubricants. Polyol-esters are used in huge quantities
as turbine oils for aviation applications where they are exposed to extreme temperatures. Good oxidative stability is

glycerin
OH

OH

C H

HC H
H

H-CC
H

HANDBOOK

-C O H

-OH

H
HCH

HCH

OH

OH

trimethylolethane

pentaerythritol
OH

OH

vinegar acid

H C H

stearic acid

HC H

O
H

-C OH

-c-

OH-C-

-OH

OH
neopentylglycol

-C

I
C

CH

"*^17'^35

oleic acid 1x unsaturated cis-configuration


O

OH-CC^H,-^H

-c-

HCH

II

OH

H0CCH

"T"

-CH

H
H CH

"^8^17

linoleic acid 2x unsaturated cis-configuation


O

OH-CC,H;

OH

For esterification of those alcohols to lubricants, carboxylic


acids of vegetable and animal origin are used. Examples of the
different acids used in hydraulic fluids are illustrated in Fig. 12.
Ester basestocks, which are suitable as lubricants or pressure media typically possess a carbon number of about
18-30. These may be derived from natural sources. Achievable viscosities are within the range of about 22-100 mm'^/s.
For this application, esters based on fatty acids are considered. They can be divided into five ester groups: mono, glycerin, dicarboxylic, polyol, and complex, as shown in Fig. 13.
Mono-esters are prepared from linear monocarboxylic
acids, which are reacted with branched or linear alcohols.
The main applications of monoesters are in metaJ working
such as for lubricants for cold and hot rolling. Of special importance within the group of mono-esters are the unsaturated methyl esters from which extreme pressure (EP) additives may be produced by reaction with sulfur or
sulfur-containing functionality. Glycerin esters of rapeseed
oils, particularly when the rapeseed oil has a high iodine
number (high unsaturation), are used to synthesize such ad-

'^5^n

FIG. 11Survey of alcohols for lubricants.

Carboxylic Acids

-CC^C-

Pentaerythritol is a tetrafunctional alcohol with five carbon


atoms. The four primary hydroxyl groups allow a relatively
easy esterification with different acids. These esters are very
stable against biological degradation in an aqueous solution.

FIG. 12Survey of acids for lubricants.

dicarboxylic acid ester

mono aster

II

II-

II

R1-0CR2

R1-0CR2-C0R3

polyol ester (TMP-ester)


O

glycerin ester
0

II

II

CHj-OCR1

CHj-OCR1

C,H,-C*

Q[_|__Q

HC

-R1

CI H j - O C R 1

CJ H j - O C R 1
complex ester
0

0
II
II
CH^-O0R1

C^riy - 0 - - C R 2
0

C,H,-( ; C H j - o c -R1

C,Hg<

II

-CH,- 0 C R 2

CH,-0CR1 - C O C H ,

II

FIG. 13Different ester types for lubricants [30].

CHAPTER 11: ENVIRONMENTALLY FRIENDLY OILS 273


achieved because of the unsubstituted beta-carbon atom and
the primary hydroxyl groups.

CHEMICAL PROPERTIES OF NATURAL AND


SYNTHETIC ESTERS
Properties of esters are determined by the alcohol and acids
from which they are derived. Various polyol-esters have been
prepared by using alcohols for the production of lubricants
similar to the triglycerides of rapeseed oil.
Viscosity and Viscosity Properties
Viscosity properties are important when esters are used as
lubricants. The acid being esterified does not only determine
the viscosity of an ester molecule. The viscosity of esters
products increases with increasing molecular weight of the
alcohols or their number of hydroxyl groups. This is due to
the increasing structural possibilities for carboxylic acid
components (Fig. 14).
Pour points for these esters exhibit the same dependency
as observed with viscosity. Lowering the pour point requires
a short-chain branching of the alcohol with tertiary carbon or
hydrogen-atoms. On the other hand, those molecular structures lead to a decreased oxidative stability of the alcohol.
Therefore, neo-pentyl-polyols are especially advantageous
for the production of lubricants, since they contain exclusively primary hydroxyl groups and they are branched.
Acids used for the production of lubricants may also be the
same as those of natural oils and fats with 16-18 carbon
atoms, which produce the required classes of hydraulic fluid
viscosity ISO VG 22 to 68. To obtain high oxidation stability,
unsaturated acids are not desirable, since they represent a
preferred point of attack for reaction with oxygen. However,
double bonds also create a distortion of the ester molecule.
This distortion positively influences the cold flow properties
of the ester. The ester produced from acid with a monofunctional alcohol and acids containing double bonds will still
flow at a temperature of 5C, whereas completely saturated
ester become solid at a temperature of 75C (Fig. 15).

The position of the double bond within the fatty acid has
no significant influence on the pour point. However, slight
differences can be observed depending on the degree of distortion imparted by the double bond of the molecule. Depending on the position of the double bond, the distance between molecules increases, resulting in slightly different
pour points (Fig. 16).
Besides the number of double bonds, their steroconfiguration has a decisive influence on the viscosity properties. Ester with cis- double bonds will flow at low temperatures,
whereas fluids with trans- double bonds exhibit pour point at
comparable temperatures.
Branching exerts similar influence as double bonds. With
increasing branching at a constant carbon number, the cold
flow behavior of the ester increases and viscosity decreases.
In contrast, an increased chain length with the same structure results in an increase of viscosity.
Reduction of the pour point is also obtainable by using esters with acid mixtures. These mixtures do not crystallize as
readily thus leading to a decreased pour point.
With the more complex esters there is no correlation between viscosity and carbon number, since the viscosity increase is compensated by branching, due to increasing carbon number.

g 60"o
Q.
3
O

ziU

-40 -

6:0

8:0

10:0 12:0 14:0 16:0 18:0 18:1 18:2 18:3


fatty acid
[C-number: double bond]

FIG. 15Pour-point of different esters with the same alcohol


[20].

45
40

"

'*

^>

< - -

4*

''

35
B

O 30

cis

.e 25
o
a.
S 20
o
- 15
10

pentaerithritol

trimethylolhexane

trimethylolpropane

trimethylolethane

glycerin

neopentylglycol

FIG. 14Viscosity of different polyol-esters with the same


acid [46].

D5

D7

D9

D11

D13

position of the double bond

FIG. 16Influence of double bonds on the Pour-point [20].

274

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Hydrolysis
The chemical reaction for ester production is an equihbrium
reaction. Consequently, all esters-based fluids cleave into
their alcohol and acid components upon hydrolosis. This directly influences the ester bond. This reaction, also called
"hydrolytic splitting," which continues until the chemical
equilibrium is restored. Thus, hydrolytic stability of an ester
is influenced by its chemical structure.
Steric hindrance of the ester bond improves hydrolj^ic stability. This protection is due to the presence of methyl groups
instead of hydrogen atoms relative to the ester group. Those
methyl groups sterically protect the ester bond against water
attack. Depending on the n u m b e r of methyl groups positioned around the ester group, the reaction rate may be reduced many times. Table 2 provides a survey of the reaction
rate as a function of the amount of branching.
With mono-esters, hydrolytic stability is primarily increased using linear short-chain alcohols. Even short alkyl
chains in these alcohols yield a significant increase of hy-

TABLE 2Influence of a-carbon branching of


the oxygen ester on reaction speed [13].
Alkyl-substitution
CH3
CH3CH2
(CH3)2CH
(CH3)3C

Relative Reaction Speed


30
1
0,03
0

drolytic stability. Only when using branched alcohols larger


than C8, does resistance increase to the level of saturated linear mono-alcohols. With glycerin esters, the saturated esters
are more stable than unsaturated esters. Their stability can
be compared to the stable mono-esters.
In general, di-carboxylic acid esters are very stable against
hydrolysis. Their stability is almost independent of the chain
length, branching, and the alcohol components used. Saturated polyol-esters also achieve a comparably good stability.
The stability of unsaturated polyol-esters is comparable to
unsaturated glycerin esters. Figure 17 depicts hydrolytic stabilities of different ester structures. Low hydrolytic stability
corresponds to a high acid n u m b e r in the figure.
Molecular features that improve hydrolytic stability also
reduce the biodegradability rate. This is of special importance since hydrolosis is the starting reaction for biological
degradation. It follows that protecting an ester bond might be
a disadvantage with regard to the ecotoxicologiccd properties.
In any case, the formulation of rapidly biodegradable pressure media requires a confirmation of the ecotoxicologic
properties of the fluid.
Oxidation Stability
Oxidation stability of synthetic esters is decisively influenced
by their structure. With alcohols, especially short-chain
branched structures with tertiary H-molecules as they occur
in rapeseed oil, which is a triglyceride, results in a significant
decrease of oxidation stability. The degree saturation of the
ester molecule, however, has a much larger impact on oxida-

FIG. 17Hydrolytic stability of different ester structure [15].

CHAPTER
tion stability. As a rule, saturated alcohols are used for the
production of lubricants and pressure media. For that reason, the oxidative stability is mainly determined by the degree saturation of the carboxylic acids. In general, the tendency of an ester molecule towards oxidation continually
increases with increasing amounts of unsaturated carboxylic
acids. Figure 18 shows this for three different saturated
polyol-esters a n d rapeseed oil. The oxidation stability of
those fluids was determined by the viscosity increase after an
aging process according to the Baader-test (DIN 51587).
The dependency of the oxidation time for vegetable oils can
be taken from Fig. 19. These results were obtained by the
R a n k i m a t method, which provides a significant improvem e n t in the precision of the test. Rapeseed oils, which are low
in euricic-acid content and sunflower oils, which are high in
oleic acid content were used as hydraulic fluids. Mixing those
oils provided the required degrees of saturation. The strong
dependency of the stability on the a m o u n t of double bonds is
evident.
Oxidative stability may be enhanced by sterically protecting the double bond, e.g., by branchings. The effects of steric
b r a n c h i n g on oxidative stability are comparable to the

180
160
140
10

'1
F
>

120

rapseed oil
unsaturated polyol-ester
partial saturated polyolestsr
saturated polyol-ester

10(1

+ j

(A
O
O

an

ID

3
4
5
aging time [days]

FIG. 18Influence of saturation on oxidation stability [34].

^\l

le" 1R
(1>

14 -

19 IZ -

o T"
o o
5
fi0
O
.E 4
O

03

3.25

3.5

3.75

4.25

4.5

4.75

FRIENDLY

OILS

275

amount of increased hydrolytic stability obtained. In addition to the amount of unsaturated carboxylic acids (relative
to s a t u r a t e d esters), the n u m b e r of double bonds in carboxylic acid also influences oxidative stability. In general, increasing the number of soluble bonds in a carboxylic acid (increasing unsaturation) decreases oxidative stability.
The foregoing discussion provides only an overview of
structure-performance consideration of ester base stock.
However, the generalizations m a d e t h u s far will aid the
reader in understanding lubricant formulation to provide
high load capacity and good chemical and physical properties. The summary of the effects is illustrated in Fig. 20.

PRODUCTION OF ENVIRONMENTALLY
FRIENDLY FLUIDS BASED ON NATURAL
AND SYNTHETIC ESTERS
Native Esters
Oil is removed from rapeseeds by milling, pressing, or extraction. These seeds contain approximately 40% oil and
8-10% water by weight. In the milling process the seeds are
fed into rollers to break down the cells so the oil can be released. Next, the milled seeds are conditioned by heating to
80-90C to control the humidity to a m a x i m u m of 8% (Fig.
21). By this procedure, the vegetable oil becomes lighter and
thinner. The seeds are then squeezed in a screw press under
a pressure of 200 bcir. This procedure yields between 40-60%
of oil. A higher yield can be obtained by either a finishing or
by solvent extraction. The finishing process removes 90-96%
of the oil. For economic reasons the extraction method is the
procedure of choice.
A higher oil yield can be obtained either by another pressing process, the finish pressing, or by extracting the prepressed coarse-ground grain. By finish pressing, the oil concentration decreases to values between 4 and 10%. An
extraction reduces the residual oil contents to below 2% in
the seeds. The individual production steps are shown
schematically in Fig. 22.
For extraction, a solvent is used to dissolve the glycerides
from the seeds, not the undesirable accompanying substances like gums or resins, slime, and dye materials. Moreover, the solvent must not contain any toxic substances that
are nonvolatile and thus unremovable. The solvent also must
be separated from the extracted material. Aliphatic hydrocarbons are used for this purpose, especially n-hexane, which
can, due to its boiling point of 55-70C, be separated easily
from the coarse-ground grain. After those steps, the extracted
raw material contains between 1 and 2% free fatty acids as
well as 300 p p m phosphatides and 0.35 to 0.5% sterines. To
achieve the desired quality of the vegetable oil, a refining process follows the extraction of the crude oil. Refining serves
the purpose of reducing the contents of free fatty acids to
0.05% and that of the phosphatides to 0.02 ppm. The following refining steps are necessary:

60

>

11: ENVIRONMENTALLY

double compound amount [mmol/g]


FIG. 19Oxidation stability vs. amount of double bonds with
Rankimat method [34].

1. Precleaning to remove phosphatides (desliming).


2. Deacidizing and neutralization.
3. Decolorization (bleaching) by means of absorbents, e.g.
bleaching earth.
4. Filtration and deodorization.

276

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

branching of branching of saturation of molecule


alcohol
acid
acid
weight

hydrolysis
staWlity

viscosity

low
temperature
viscosity
oxidation
stability

viscosity
index

air release
property

L
,\

linearity

11

1,

. I

i,

i,

1,

, 1

1 I

1 1

It

FIG. 20Summarized table of the influence of structure on chemical and


physical properties.

Synthetic Esters
Raw materiaJs for the production of synthetic esters are derived mainly from petro-chemistry. However, it is also possible to use natural raw materials or their transformation products. In any case, this requires re-esterification or an
additional chemiced treatment, e.g., hydrogenation. Besides
the esterification procedure described previously, ester synthesis can be subdivided into the production of different alcohols and acids. The great majority of those products originate from other applications. The systematic production of
lubricants can be considered rather insignificant at this time.
Quantitatively, the largest portion of esters is the softener
sector. Long-chain alcohols and fatty acids cire mainly used
for the production of washing and cleaning agents, surfactants, and detergents. The fundamental path of synthesis will
be explained using a few examples.
MultifunctioncJ alcohols are produced using the so-called
"aldol condensation". This is a catalytic addition of carbanions by bases to the carbonyl group of aldehydes or ketones.
The carbanions are produced from activated methylene
groups. After this reaction step, water is eliminated. Figure
23 shows this process for the alcohol pentaerythritol. The
production process for trimethylol propane is very simple except when formaldehyde and n-butanal are used.
For the production of neopentyl glycol, the aldol reaction

is conducted in a slightly different way utilizing formaldehyde and i-butanal. However, as a catalytic agent, sodium hydroxide is used (Fig. 24).
The production of carboxylic acids can be divided into two
major processes. On the one hand, from natural oils and fats
the corresponding fatty acids can be generated directly by hydrolysis. On the other hand, an alternative process is to direct
re-esterification of natural oils with synthetic alcohols. In addition to those two possibilities, acids may also be produced using chemical processes. Figure 25 shows this process for adipic
acids being used for the production of di-carboxylic acid esters.
Large-scale production of synthetic esters are typically
batch processes. Depending on the desired degree of esterification, different catalysts are added to the process, leading to
an accelerated conversion. During esterification, undesirable
water is continuously removed from the alcohol and fatty acid
reactants to optimize the conversion process. The reaction is
stopped once the desired acid number, a measure for the completeness of the esterification, has been attained. To achieve
very low acid numbers (<0,5), another refining step is necessary. Undesired substances are eliminated from the ester by a
subsequent bleaching earth treatment. Finally, a filtration
step is required to eliminate the bleaching earth from the ester. A survey of the ester production process can be taken
from Fig. 26.

CHAPTER 11: ENVIRONMENTALLY

FRIENDLY OILS

277

seeds

milling

u.1

f steam ^

conditioning

squeezing

pelletextraction

n-hexane

j r
drying

n-tiexane

9^i:r^.':''i-'^'-''''-' -.y'-^wl

Vi

misceiia

.i a

filtration

L_n_
steam ^

toasting

D used n-hexane

drying

cooling

h'

vaporization

"P

filter
backlog

disposal

feeding stuff

FIG. 21Production of rapeseed crude oils.

LOADS O N P R E S S U R E MEDIA IN
OPERATION
Oxidation
During operation, the pressure media goes through a continuous change of its chemical properties due to the hydraulic load
in the system. Over the long service life of the pressure media,
its properties should change very slowly; this requires aging
stability. During operation, the hydraulic load parameters
such as pressure and temperature as well as shear stress affect
the fluid. During operation, different types of contamination
influence the service life of the pressure media. These can be
liquids such as water or foreign oils, and solid particles such
as abrasive materials or environmental dust. Those loads can
affect the fluid chemically as well as physically.
Of special importance for the stability of a pressure
medium is its resistance against oxidative attack. Oxidative
stability problems are aggravated by contact of the fluid with
the ambient air in the tank of the system or with the air dissolved in the fluid, leading to a change of the chemical and
physical properties.
For the stability of lubricEints based on natural or sjmthetic
esters, their resistance against the so-called autoxidation processes is of importance, since those reactions already start at

very low temperatures as they occur in hydraulic systems.


Moreover, autoxidation represents the initial stage for polymerization processes leading to surface films such as varnish
or lacquer [27,28].
Autoxidation starts with an induction period where the
first carbon-radicals are initiated. To make this possible, activation is required, e.g., by mechanical supply of power
through shearing or by a temperature increase. Furthermore,
different catalytic agents, such as hydro-peroxides, peroxides
or heavy-metal ions, accelerate this process, since these
molecules undergo bond scission to produce free radical initiators. The necessity of a good fluid filtration is necessary because heavy-metal ions produced from the metallic wear debris produce those free radicals. When hydro-peroxides are
subsequently produced from peroxide and another carboxylic acid, then a free C-radical is created. This radical reacts with the oxygen in the air to form peroxides, thus starting a chain reaction (initiation). The hydro-peroxide
produced by this reaction is chemically unstable. It transforms easily into epoxides, keto-bonds, di-carboxylic acids,
or other polymerization products. The reaction mechanism
of autoxidation can be taken from Figs. 27 and 28. The autoxidation mechanism stops once the radical concentration
exceeds a threshhold concentration, starting a reaction between the radicals (Fig. 28).

278 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK

NaOH )

Jp^ slime removal


(90C)

neutralisation

Tt.
H3P04 (75%

ik

rotational
separation

separation

i r
H?n

H-RBntnnil

crude oil

M .iiJ 1

washing

l ' " ' . - y vacuum drying


'
steam-V| iombar/90C

HCI active

bleaching

soapy contents ^

H2SO4(30%)j
& steam I

fatty acid
raffination

H
steaming

filtration

H
I

steam J

P(

L ^ desodoration
2mbar/250C

drying

filter backlog
disposal

bleach
disposal

PI

refined oil

FIG. 22Refining process of rapeseed oil.


CHj-OH
+ Ca(0H)2
HCH

CH3-CH

OH-CH2-CCH
+ NaOH

9^3 O
formaldehyde

9^30

acetal
HCH

HCCH

CH2-OH

HO-CH^CC-

CH,
formaldehyde

CH,

i-butanal

CHj-OH
+ HCHO, H2O
O
OH-CH2-CCH

-HCOOH

CH2-OH
OH-CH2-CCH2-OH
CHj-OH

CH2-OH

pentaerythrltol

FIG. 23Synthesis of alcohols by aldol condensation.

9H3O
HO-CHj-CCH
CH,

+ H,

CH,
HO-CHj-CCHj-OH
CH,

FIG. 24Synthesis of neopentylglycol.

CHAPTER

11: ENVIRONMENTALLY

FRIENDLY

OILS

279

H2O

1. Start

Hydrolysis
Hydrolj^ic cleavage of the pressure media based on natural
and sjTithetic esters represents a reaJ danger for the fluid,
since the reaction to produce synthetic esters is an equilibrium reaction producing water. Since equilibrium reactions
may proceed in either the forward or reverse directions, esters exposed to water cleave again into their alcohol and acid
components. At room temperature and without mechanical
load, this reverse reaction proceeds very slowly with synthetic esters so that no direct damage of the fluid contaminated with water is expected. However, u n d e r mechanical
load and increased temperatures such as the t5rpical conditions that occur in a hydraulic system, the hydrolysis process
is accelerated. In general, hydrolosis may follow two different paths: saponification or acid catalyzed hydrolysis [17].
Alkali saponification starts by adding a hydroxide ion to
the carbonyl carbon atom of the ester. The hydroxide ion can
be added to the reaction, e.g., by mixing sodium or potassium
hydroxide to it. The reaction intermediate produces a very

-> XH

2. Chain building

-> ROO

ROD

RH

-> ROOH

RO

RH

-> ROH

RO

3. Chain splitting

ROOH
ROOH

cyclohexanol

RH

-> RO
+

ROOH

OH
ROO

adipic acid

FIG. 27Autooxidation process of ester based fluids.

^CH,
CH-OH

HNO, or

o.

II

I
I

I
I

I I II
CCCOH
I I

HOCCC
H

CH,

4. Chain termination
adipic acid

cyclohexanone
^CH,
CH,

HN03or

o,

II

II

>

R-R

ROO

- ROOR

HOCCC CCCOH

FIG. 25Synthesis of adipic acids.

FIG. 28Termination of oxidation process.

alcohol
alcohol synthesis

carbon acids
acid synthesis
bleaching
mineral acid

FIG. 26Schematic ester synthesis.

280

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

1. step: hydroperoxide ion addition


O

R1-COR2

R1-COR2

OH

HO
2. step: all^oxide ion formation
0~

R1-COR2

~*"

R1-COH

-h

OR2

HO
3. step: alkoxide deprotonation
O
-h
_
II _
' OR2
R1-CO
FIG. 29Alkalic saponification of esters.

R1-COH

1. step: ester protonation


0R2

R1-C

-f-

R2-0H

0 R2
+

R1 - c

II .

OH

0
2.step: water addition

H-- O H

0 R2
R1-C

HP

-h

il .

OH

OH

R1 - C 0 R2

R1-CO*

OH

OH

R2

3. step: alcohol split off


OH H
R1-CO*

1 1
OH R2

OH
1
1
R1-C

R2-0H

II .
OH

4. step: hydrogen split off


OH

R1-C
M

-f

R2-0H

R1-COH

R2-0H

OH
FIG. 30Ester splitting under acid conditions.

basic cJcoxide ion during the subsequent elimination step.


This alcoxide ion reacts with the carboxyhc acid instantly to
ydeld a non-reactive carboxylate ion. This reaction is called
saponification, and is shown in Fig. 29.
During use, the precondition of the acid catalyzed hydrolosis of ester-based fluids is met because the acidity of the fluid
increases during use due to fluid oxidation. However, con-

trary to saponification, acid catalyzed hydrolosis is reversible


unless the water produced during hydrolosis is removed from
the systems.
Figure 30 shows the process steps of acid catalyzed hydrolosis. The proton of an acid is necessary to catalyze the
addition of water. Following a very fast and reversible proton displacement, splitting of the alcohol takes place. Acid

CHAPTER
is produced after a H^-ion is removed. The H"^-ion is then
available again for hydrolyzing another ester bond. The reaction continues until the chemical equilibrium of the four
components is restored again.
In a pressure medium, free fatty acids represent the basic
material for chemical reactions. They react with metallic
abrasive particles contained in the fluid. From this reaction,
so-called metallic saponification agents arise, leading to a
possible functional i m p a i r m e n t of the hydraulic system.
Metallic saponification agents deposit on the surfaces of the
hydraulic components leading to a premature blockage of the
filters.

ALTERNATION OF TECHNICAL AND


CHEMICAL PROPERTIES BY AGING
PROCESSES
Oxidation Stability
The aging stability of pressure media based on natural a n d
synthetic esters is influenced by its oxidation stability. Oxidation stability is a fundamental quality used to differentiate
between the different performance classes of pressure media.
For a precise rating, different laboratory test procedures are
available.
Laboratory

Aging

The following describes different tests to evaluate oxidation


stability which are performed with the modified Rotary Pressure Vessel Test (RBOT) according to ASTM D 2272. The
RBOT test is conducted to determine the time necessary to
react with a certain a m o u n t of oxygen. This test is illustrated
in Fig. 31.
The test fluid and a copper coil are put into a breaker and
sealed in a steel container. The copper coil performs as a catalytic agent to accelerate the oxidation reaction. Thus, in the
pressure vessel, metal catalytic oxidation takes place (see the
Alcohol Bonds section above). The pressure vessel is filled
with a specified a m o u n t of oxygen and put into a heated bath.
Temperature control equipment provides for an adjustment
between 40and 150C.
The temperature is maintained at 1C. An electronic sen-

11: ENVIRONMENTALLY

FRIENDLY

OILS

281

sor connected to a computer for data storage measures the


pressure in the steel container. For hydraulic fluids based on
esters, no water is added to the pressure vessel, since hydrolysis could occur. Oxidation stability is defined by the time required for maximum pressure to decrease 1.75 bar. This pressure drop depends on the amount of oxygen with which the
lubricant reacts as a result of the oxidation process. To differentiate between the different fluids, tests are conducted at
a temperature of 150C.
Three different base oils were evaluated. They are distinguished mainly by their degree of saturation and the alcohol
used. Figure 32 depicts the test results for these three base
fluids.
Fluid G S l , an unsaturated trimethylolpropane ester, reacts
quickly with the oxygen in the test vessel, showing only an extremely low resistance against oxidation. Continuous improvement of the oxidation stability is achieved by using
partly a n d completely saturated esters. This can be read from
the test results for the fluids GS2 and GS3. Each of these base
fluids represents the next developmental phase of synthetic
esters. Although the first generation of esters contained unsaturation, the next generation of fluids were saturated. The
current generation of hydraulic (GS4) fluids are saturated,
but they are produced by more economical procedures. For
comparison, a mineral oil without any additives was also
tested. Its oxidation stability is comparable to that of saturated synthetic esters. However, the test times exhibited by
those fluids are not sufficient for use as pressure media.
Therefore, the use of additives is necessary to increase aging
coxidative stability. Corresponding improvements by using
additives can be observed in Fig. 33.
Results are shown for the oxidation of the base fluids with
additives according to their special requirements. The fluids
SI to S4 are each formulated from base fluids GSl to GS4,
respectively. The mineral oil HLP is a formulated fluid with
the base of the fluid "H." The low oxidation stability of the
fluid GSl is improved significantiy by using additives. However, in comparison to HLP mineral oil and to the partly and
fully saturated synthetic esters, the oxidation stability obtained is too low for use in high performance hydraulic systems. Adequate oxidation stability is provided with a test
time above 200 min. Used oils should show a test time of at
least 180 min. to provide adequate oxidation stability.
Further development of the base fluids and especially the

11

i.
2

'1,75 bar

Z3
W
CO

oxidationstability

a.
TQ
copper coii
FIG. 31Rotary bomb test rig.

time [min] T,

282

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK
test parameter

40

35

35
30
25
20
15
H 10
o
5
0

20

20

1
11
3

GS1

1
1
1
1
GS2

1
1
1
11
11
11

temperature:

1
1

II 1

t
20

1
1

GS3

t
0
0

150 iC

GS4

base oil

atmosphere:
6,25 bar
oxygen

limit:

1,75 bar
pressure
drop

catalyst:
^ g copper, 3m
S 1,5 mm

FIG. 32Oxidation stability of different base fluids (ASTM D 2272).


test parameter

300'
!= 250!& 200-

1 150 | 100"

500-

267
220

tn
HLP

1
1
1
1
1
1

fr

213

1
T

temperature:

24

150iC

atmosphere:
/ * ^ 6,25 bar
\^Joxygen

70

limit:
^ T ^ 1,75 bar
^ ^ pressure
x^P^drop
catalyst:

SI

S2
nuid

S3

S4

^
^

copper, 3m
1,5 mm

FIG. 33Oxidation stability of different ester formulations (ASTM D 2272).

use of fully saturated synthetic esters results in a significant


increase of oxidation stability. However, fully saturated base
fluids are relatively expensive raw materials.
Oxidation stability is also influenced by temperature. Oxidation stability decreases by one hcilf with every 10C temperature rise. This rule of thumb is roughly confirmed for the
examined fluids. Fluids with additives exhibit a slightly
greater increase of reaction rate with increasing temperature
than the base fluids (Fig. 34).
Besides temperature, the catalyst being in contact with the
fluid also influences oxidation stability. In hydraulic systems,
many different materials are used for different tasks for a variety of hydraulic components. To evaluate the usability of a
fluid, the influence of those materials on the aging performance of the fluid is important. In hydraulic systems, iron and
copper alloys and different coated materisils are used as construction materials. Oxidation is significantly accelerated by
the presence of certain metallic catalysts, as shown in Fig. 35.
The very strong influence of copper on the oxidation sta-

bility compared to the remaining tested materials can easily


be recognized. For the pure metals that were tested, these results coincide very well with the position of the different metals in the periodic systems. The position in the periodic system gives preliminary information on the reactivity of the
metals. With decreasing periodic number, the catal5tic effect
of the metals diminishes. Material coating and their base materials exhibit a very positive influence on the oxidation stability in comparison to the standard construction materials.
For the use of rapidly biodegradable pressure media based on
synthetic esters, a significant improvement in oxidative stability with increasing temperature is obtained by exchanging
traditional construction materials with newly developed material coatings.
Test Stand Aging
Laboratory tests cire conducted to evaluate oxidation stability
and the effects of aging pressure media. In a hydraulic system, different parameters that affect oxidation stability usu-

CHAPTER 11: ENVIRONMENTALLY


ally occur in combination, thus accelerating the overall aging
process. Therefore, to evaluate the fluid performance, custom aging test stands are required, which model a hydraulic
system as precisely as possible. To obtain test results within
a reasonable period, fluid loads in such test stands are greater
than those of practical applications. The primary task of the
test stand consists of examining fluid properties, thereby, the
test stand design should be very simple. Figure 36 shows a
test rig circuit fulfilling this requirement [8].
The hydraulic test rig circuit is operated as an open circuit.
Test stands are constructed using mass-produced hydraulic
components to model the loads activating the pressure media
in a real system as accurately as possible.
Variations of the pressure media are determined by analyzing fluid samples taken periodically. Acid number (AN)
and viscosity are very important characteristic parameters to
describe the aging condition. The load during operation is
primarily responsible for the production of free acids. Those

FRIENDLY OILS

acids can attack non-ferrous metals, thus endangering the


hydraulic system during use.
In addition, viscosity is an excellent indicator of fluid quality. The molecular structure of the fluid influences its viscosity and its viscosity temperature performance. Depending on
the reactions occurring in the fluid, viscosity increases or decreases. As a lifetime criterion for rapidly biodegradable
pressure media derived from esters, a viscosity increase of
20% is applicable [8,23].
Results of the Test Stand Aging Studies
For the test stand aging studies, the same fluids were used
that were already tested with regard to their oxidation stability. The influence of different loads on the fluid was realized
by a variation of system pressures and temperatures. The influence of those system parameters on the aging behavior is
determined by the variation of acid number and viscosity at
40C, after an aging time of 1000 h as shown in Fig. 37 [8].

test Darameter
10000

i
1

GS1

temperature:

QS1

t.

variable

1 0 0 0 - ^^^^^^^=
atmosphere:

10"

1 -

90 j C

Z * ^ 6,25 bar

\jjl

oxygen

limit:

^H

^H

^^^^^1

^^^1

^ - 1 ^ 1 , 7 5 bar
^ S f j pressure
>_>'drop

1H H

120jC
temperature [\C]

catalyst:
^ p copper, 3m
^ ^ 1,5 mm

15C>iC

FIG. 34Temperature influence on oxidation stability.

test parameter

150

temperature:

S1

-.125
E

110

>!ioo
75

64

1 50
a
"S
o
25

84

77

.a

150 iC

atmosphere:

RH

6,25 bar
oxygen

46
limit:

24

1,75 bar
pressure
drop

catalyst:

Cu

Fe

283

Cr
CrN
Ti
TiN
materials and coatings

without

FIG. 35Catalyst influence on oxidation stability.

^S variable

284

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

FIG. 36Oil aging test rig [8].

test parameter:
temperature:
variable

pressure:
S y\ variable
volume flow:

300 bar 300 bar 150 bar 300 bar 300 bar 150 bar
90C 60C eO-C 90C 60C 60C

GS1

GS1

GS1

S1

SI

20 l/min

water content:
^ < 0,03 %
4 HaO
test duration:

S1

1000 hrs

FIG. 37Change of TAN and viscosity after aging test runs.

The influence of high temperature and pressure indicates


a high specific load on the fluid. Comparing the aging influence of pressure and temperature shows that the temperature exhibits the greatest influence on the aging. The influence of pressure is evidently less, at least as determined
from tests performed at reservoir temperatures of 90C and
60C.
Decreasing the reservoir temperature by 30C reduces the
aging process four-fold in the fluid as indicated by viscosity
change. On the other hand, a 50% reduction of pressure yields
only a very small reduction of the aging processes and rates.
Absolute variation of fluid properties during tests are greater
than conventional mineral oil based fluids.

Test runs on the aging test bench confirmed the very good
oxidation stability of the more advanced fluids formulations
(Fig. 38). Fluid S3, in particular, exhibits an aging stability
comparable to mineral oils. The excellent stability is indicated by the constant viscosity throughout testing time.
A comparison of results of the formulated fluids with their
base fluids shows that the additives used and the base fluid
correlate well with each other. Additives increase the aging
resistance of the base fluid significantly.
Table 3 illustrates the effect of additional fluid characteristics. Variations of these characteristics are only of minor importance with respect to the aging performance. Therefore, a
graphical presentation is not shown.

CHAPTER

Aging

Rapidly biodegradable pressure media are primarily used in


mobile hydraulic equipment, since they are often used in ecologically sensitive environments. These machines are often
exposed to atmospheric influences so that there is always the
danger of water ingression into the hydraulic system. Due to
their chemical structure, synthetic esters tend to be hydrolytically unstable in the presence of water (see the Hydrolysis
section above). Thus, evaluation of hydrolytic stability is of
central importance for the assessment of the usability of
rapidly biodegradable pressure media.

28

test parameter:

temperature:
90 C

viscx3sity

24

EBAN
5
X

IV.

g20

CO

12
>,

1^-

^g.

1 8

o_

FRIENDLY

O 00_

lOCM

1^

o
o"

GS1 GS2 GS3 S1 S2 S3


fluid generations

S4

pressure:
300 bar

0)

volume flow:

(0

o>
c

I 4

z
<

20 l/min

water content:
^ <

0,03 %

H,0

test duration:

HLP

1000 hrs

FIG. 38AN and viscosity changes of different fluid generations after aging test runs.

TABLE 3Important fluid properties.


Property

Density
Viscosity
@40X
Viscosity
@ 100C
Viscosity
index
Pour-point
Flash-point
FZG-test
Vickers
pump test
AN

Corrosion
Steel

Alternative Test
Methods'"
ASTM^
ISC^

Unit

HEES 46

HLP 46

DIN
Standard"

kg/m3
nim2/s

ca. 920

ca. 880
46

51 757
51562T1

D 1298
D445

3104

7,1

51562T1

D445

3104

100

ISO 2909

D 2270

2909

-27
220
12
<120
<30

ISO 3016
ISO 2592
51 354 T2
51389T1
51 389 Tl
51 558
D 664

D92
D97
D5182
D 2882

3016
2592
14635
20763'*

D 974
D 664
D 5770

3371
6618
7537

46

mm2/5

["C]
[C]
Load level
[mg] ring
[mg] vane
[mg KOH/g]

9,3
184
-42
290
12
<120
<30
1.2

0,3

D 665A
7120
D665B
7120
1-100A3 1-100 A24
D130
2160
Copper
51759
"The DIN test procedures shown here were used to obtain the values shown.
* Although DIN test procedures were used for this work, equivalent ASTM tests may
also be used.
'' In some cases, the ASTM tests are not truly equivalent but the ASTM procedures
cited may be used.
'' This ISO Standard is still under development and has not yet been published.
0-A

OILS

285

The effect of hydrolytic stability was evaluated using the


same procedure described above for oxidation stability in a
laboratory test procedure. A procedure developed at IFAS
(Institute of Fluid Power Transmission and Control, Aachen,
Germany) is used. A scheme of the test equipment is provided
in Fig. 39. In this case, a pressure-proof and lockable stainless steel container is used. The container features a stirring
device that mixes the oil turbulently with the water used to
contaminate the system. The container is heated by a heating
bath so that the tests are run u n d e r actual operating conditions.
During the test, a defined amount of test oil is mixed over 72
h together with a specified amount of water. Metallic catalyst

Hydrolysis Stability
Laboratory

11: ENVIRONMENTALLY

0-A

51 585

286

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

test fluid
(150 g)
+
catalyst
(iron or copper)
+

fluid analysis

(variable)

FIG. 39Hydroiytic stability test.

3,0

test parameter:

^^^^1,5% iron |^

temperature:

32,5

Br 90C

2,0
E
ft. "I-5
en
c
n
u1.0
z
<
0.5

fluid:
GS1
test duration:
72hrs
catalyst:

0,0
0,0

0,2

0,4

0,6
0,8
1,0
water content [%]

1,2

1,4

1,6

^
p

iron,
1,5%

FIG. 40Hydroiytic stability of the GSI ester fluid vs. water content.

is added in the form of pulverized copper or iron to accelerate


the hydrolosis reaction. Thereafter, the AN of the fluid is measured and the deposited hydrolysis products are investigated
by means of SEM and element determination. Viscosity measurement is not helpful because it doesn't provide reproducible results due to the hydrolysis byproducts and deposits.
Figure 40 provides the test results obtained with varied water content. It is evident that water contents below the saturation point only causes hydrolysis. As free water appears in
the fluid, an accelerated attack on the fluid occurs. At water
contents above 1.5%, the effect no longer increases linearly
with increasing water content.
Like the oxidation processes, hydrolysis is also strongly influenced by the presence of metallic particles. In addition,
with this reaction, the effectiveness of the individual elements is different. Figure 41 shows the influence of the
metallic catalysts on the hydrolysis of the GSI ester. Adding
iron or copper chips considerably accelerates the reaction
process. Iron exhibits the greatest effect relative to copper.
Increasing the temperature also accelerates the hydrolosis
reaction. The effect is exponential. Above 110C, oxidation

processes also occur since the reaction vessel was not purged
with nitrogen. Contrary to the oxidation tests reported earlier, the oxygen supply is very low since the container is only
filled with atmospheric pressure air.
Besides the determination of AN, deposit formation during
the tests was determined. This was done by SEM microscopy
to determine structure as shown in RBOT tests reported earlier, Fig. 42. The structure of the deposited particles differs
most with regard to particle size. The particle size of the deposits was significantly smaller. The medium particle size of
the contaminants measures about 10 ^i,m vs. about 60 /xm for
the iron test dust of the laboratory investigations.
After ultrasonification, there was no significant difference
in the particle size and amount between those generated in
the test rig cind those generated in the RBOT laboratory tests.
In addition, the compositions of the deposits from the two
tests were essentially the same. In addition to iron and copper, the deposits taken from the test rigs contained small
amounts of tin and zinc, which are alloying elements of the
non-porous materials used for construction of the test rig system components. The presence of phosphorous or sulfur.

CHAPTER
which would be attributable to the additives used for fluid
formulation, was not observed, which indicates that the data
obtained from the test rigs correlates well with results obtained from laboratory tests such as RBOT.
The analyses techniques, however, were unable to detect
hydrogen. Based on the chemical reactions occurring, the
presence of hydrogen would be expected, since metal
saponification occurs with the metal catalyzed hydrolysis.
Ester hydrolysis follows the reaction process described earlier. The faster hydrolytic reaction of iron vs. copper is due
to the stronger acidity of iron relative to copper.
Hydrolytic

Stability

Test With Test

Stands

Further assessment of the hydrolytic stability of different ester-based fluids was conducted using the test stand. These

5
X
04

11: ENVIRONMENTALLY

FRIENDLY

test parameter:
temperature:

variable

fluid:

GSi
0,8 % H2O

to O
O)

test duration

10

72lirs

^1

catalyst:

40

287

studies were performed with significantly lower loads relative to those used for the studies discussed previously to prolong the use lifetime of the hydraulic components used for
the test stand. Initially, the first generation of ester-based fluids (vegetable oils), were evaluated using varying water content u p to a maximum of 0.1%, which is the maximum allowable value r e c o m m e n d e d by VDMA (Association of
German Machine Manufacturers) [36,37]. (This is an empirical recommendation, which was not derived experimentally.)
For this work, the water contaminant was injected slowly
into the suction pipe of the p u m p on the test stand. Excellent
mixing of the fluid a n d water c o n t a m i n a n t was obtained
from the "whirling" action of the oil flow in the p u m p and the
subsequent turbulent motion of the fluid on the pressure re-

- C ^ 1,5% iron
-0 1,5% cxDpper

20

OILS

60
80
temperature [C]

100

120

140

variable

FIG. 41Hydrolytic stability influence of a catalyst on the hydrolysis of the GSI ester fluid.

ultra sonic
treatnmnt
latoratory
test

?m*

I
FIG. 42Hydrolytic splitting products.

':"|l

288 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK
test parameter:
temperature:
60-0

I
0;

pressure:
150 bar

volume flow:

20 l/min

water content:
^ ^ variable
%0 see figure

0,03%
GS1

0,1%
GS1

0,5%
GS1

0,03%
SI

0,1%
SI

0,5%
SI

test duration:
1000 lirs

FIG. 43AN and viscosity changes after aging tests in the test rig with water contamination.

test parameter:
temperature:
60 C

pressure:

0-

isobar

volume flow:

20 l/min

water content:

GS1

GS2

GS3

S1

S2

S3

o.syoHjO

test duration:
1000 hrs

FIG. 44AN and viscosity changes after aging tests in the test rig with water contamination and using different generations of fluid development. The oldest was GSI and the most
recent fluid candidate is S3.

lief valve. Water content was determined at 24 h intervals and


corrected, if necessary, to maintain the water content in the
fluid for the duration of this test.
Figure 43 shows the results of the investigations conducted
with the fluids GSI and 81. The influence of the water content
during the aging (hydrolysis) of the fluid is clearly evident
from the variation of the AN of the fluid during the test. All the
tests using these base fluids always showed a decrease of AN,
whereas the tests in which water was added for the first time
exhibited an increase of AN. This is an indication of increased
hydrolysis of the fluid into alcohol and acid components.
Figure 44 illustrates the results obtained for different fluids, which were evaluated at 0.5% water. The fluids shown in
the figure vary in order from the earliest candidate (GSI) to

the most recently developed fluid candidate (SI). The results


showed that the susceptibility to hydrolysis decreases with
increasing advances in ester-base stock fluid structure.
The observed improvement in hydrolytic stability is due to
the greater stability offered by the saturated versus unsaturated structure and the improvement of the additives used.
For example, fluids S2 and S3 exhibit significantly better
demulsifying characteristics (ASTM D 2711) relative to the SI
fluid, which causes the water to separate to the bottom of the
fluid in a short time. This reduces the amount of water available for hydrolytic degradation throughout the test, thus reducing the overall hydrolysis rate.
Varying the viscosity and AN of water contaminated fluids
is relatively unimportant compared to the impact of the effects

CHAPTER
of increased system pressure and reservoir temperature. In addition, it is also important to consider system component
compatibility. For example, water is soluble in the ester-based
fluid u p to 0.1% b.w. and 60%. Under these conditions no deleterious system effects were observed. However, water contents
of 0.5% b.w. are insoluble in the fluid and significant attack on
the system is observed. Although an oil-water emulsion is
formed initially, phase separation does subsequently occur depending on the demulsification properties of the fluid.
The extent of fluid hydrolysis was greatest with the GSI
fluid, which contained no additives. All of the fluid candidates contained emulsifies deposits at the b o t t o m of the
reservoir and the filter elements during the test run.
These deposits are formed due to the emulsification of the
fatty acids, which react with the corrosion metals from the
system components. This process may result in filter plugging even after only a few hours of operation during the test.
This occurs because the filter elements are equipped with a
by-pass valve that opens once a preset differential pressure is
exceeded at which time the fluid invades the system without
filtration. This results in an increase of solid abrasion particles (contamination) in the system.
The tests didn't show any impairment of the lubricating
properties of the fluids caused by the water as contaminant.
However, indirect consequence of water contamination is
that 3-body-abrasion causes increased wear on the hydraulic
components. The improved hydrolytic stability of more recently developed fluids produces smaller amounts of deposits
on the bottom of the reservoir.
A comparison of the composition of these deposits relative
to those found in laboratory tests was discussed earlier.

LOW TEMPERATURE PROPERTIES OF


ESTER BASED FLUIDS
For the use of pressure media in mobile applications, the performaiace at low temperatures is of great importance to prevent failure on the hydraulic system during cold weather operation (such as in the winter).
Viscosity Properties
To evaluate the viscosity properties of a pressure media at low
temperatures, two characteristically different rates of cooling
can be distinguished. In a case of fast cooling, the change of
viscosity with respect to temperature is important. This also
determines the viscosity class that can be used to fill the hydraulic system (ASTM D 6080). The low temperature behavior
during slow cooling, exposure to low temperatures, a prolonged time is important, since esters often show a time-dependent solidification. This starts with a separation of paraffin crystals, such as that which occurs in diesel fuel. These
crystals may cause clogged filter elements.
Figure 45 shows the viscosity-temperature dependence as
well as the viscosity index (VI) of different fluids. Viscosity index is measured at the variation of viscosity with temperature. The greater the VI, the less sensitive the fluid viscosity
is to variation in temperature. Comparison to a mineral oil is
provided. Synthetic esters show significantly better viscosity
properties due to their higher VI. At low temperatures, the

11: ENVIRONMENTALLY

FRIENDLY

OILS

289

viscosity of synthetic esters is considerably lower than mineral oil, providing a safe operation of a hydraulic system after changing over from a mineral oil to a synthetic ester of the
same viscosity class. At high temperatures, viscosity of the
same ISO viscosity class (ISO 3448, ASTM D 2422) is significantly higher, so that oil of the next lower viscosity class
might be used. Consequently, synthetic esters perform like a
multi-grade oil. ASTM D 6080 provides a procedure for esterbased hydraulic oil as a function of use temperature.
Crystallizing P r o c e s s e s With Slowly Decreasing
Temperatures
With very slowly decreasing temperatures a first formation of
crystals may occur at approximately - 2 0 C in synthetic esters. As experienced with vegetable oils, the degree of crystallization is dependent on time [8,23,26,32]. For the fluid GSI,
the completely crystallized condition is achieved after a four
day storage time at a temperature of 45C.
Consequently, the temperatures necessary for crystallization are about30C lower than those for rapeseed oils and
are below the temperatures where mineral oils are no longer
able to flow. Thus, a safe operation of hydraulic systems operated with synthetic esters instead of mineral oil is guaranteed at low temperatures.
From Fig. 46 the start of crystallization can be taken for
the generations of fluids for the fluids SI, S2, and S3, which
are branched, saturated diester-based fluids. Moreover, different filterability tests were conducted to assess the low
temperature performance. Good filtering properties of the
pressure media are a precondition for a safe operation of
the hydraulic system because if the fluid is excessively viscous, the p u m p will be starved for fluid and cavitation will
result. If the fluid viscosity is too low inadequate lubrication
will result. For the filterability tests the experimental system
shown in Fig. 47 was used that was developed at IFAS. The
fluid volume enclosed in the cylinder is pressed through a
membrane filter by means of compressed air at different
temperatures. Measures for filterability are either the time
necessary for a certain volume to pass the filter or the volu m e flow through the filter element in dependence of time.
The diagram shows the filterability properties of fluid GSI,
since no significant differences were found between the individual fluids based on synthetic esters. Compared to mineral
oil HLP 46, those fluids show a considerably better filterability. In the case of mineral oil, the filter m e m b r a n e clogs at
temperatures of 10C after a test time of only 60 s. The volu m e flow of fluid GSI through the filter element diminishes
within the same time by only 25%. However, when the SJTIthetic ester is contaminated with 0.5% water, the good filtering properties are lost, causing the filter element to clog after
a very short time. Since the water is no longer dissolved, but
finely dispersed in the Quid, ice crystals can form resulting in
clogged filter elements.
ECOLOGICALLY TOXIC PROPERTIES
Test Methods
For the investigation and development of environmentally
friendly, biologically fast degradable pressure media discussed above, various methods currently in use in Europe

290 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


test oarameter:
10^

'

^^\*-

'

'

'

'

''''

A.^

SN
VkV
m

\ ',
\^
KX
^
^3

GS1

S2

f-

GS3

P3

HLP46

fluid

^fe

? \ \

slope

1 i
3.34

S2

VI

^M WM i
^ in

80 .

^
%

63,550
40
31,5.

>

25 .
20
15,81

12,5-

^
\

in _

u
-W

^\
6 5-60

-zto

-2 0

(3

20

A0

60

80

100

temi:jera ture [iC]

FIG. 45Viscosity vs. temperature of ester fluids.

-10

aging parameter:
temperature:
90 C

i Hi ni 11 Mq HI I I
MM nl I ! I 111

pressure:

/ * ^ 300 bar
volume flow:

water content:
/ ^ < 0,03 %

new fluid
1000 h aging
GS1

GS2

GS3
fluid

S1

20 l/min

W
S2

S3

H,0

aging time:
1000 h

FIG. 46Crystallization of esters at low temperatures. (Crystallization properties are determined by IFAS lab test procedure).

CHAPTER 11: ENVIRONMENTALLY FRIENDLY OILS 291


test parameter:
temperature.:

GS1
GS1 0,5% HP
X - -HLP46

20

~~~~-J

,,___^

-10 C

compressed air
(6 bar) "^

"i
5 10.
o
5=

-~

50

<

100

150
time [s]

200

ZO
filter [5|jm]

FIG. 47Filtering properties of esters at low temperatures. (Flexibility was determined by


IFAS lab test procedure)

were employed. The examination of the toxicological properties of rapidly biodegradable fluids is a critically important
parameter in evaluation of the use-properties of these fluids.
This includes the self-classification of the test fluids into water hazard classes [40], since exclusively finished products
and no individual components were tested. These properties
were determined for this work using both new and used fluids. Aged fluids were evaluated to determine impact of aging
on biodegradability and toxicity. The VCI (Verband Chemischer Ingenieure) classification system [6,29,32] comprises
the tests shown in Fig. 48 and Table 4.
Test Results
Table 4 provides an insight into the test-substance specific investigations, results, and (preliminary) WGK-classifications
(WOK = water hazard class) [40].
ASTM International has developed various standards to
provide guidance in determining the biodegradability and
ecotoxicity properties of hydraulic fluids. A brief summary of
the slope of these tests will be provided here and more detailed discussion is provided in Chaper 34, Environmental
Characteristics of Fuels and Lubricants. Biodegadability is
one of three characteristics that are assessed when evaluating
the environmental impact of a hydraulic fluid. The other two
characteristics are ecotoxicity and bioaccumulation.
D 6006Guide for Assessing Biodegradability of
Hydraulic Fluids
This guide provides information to assist in planning a laboratory test or series of tests that would provide information
about the degradability of an unused fully formulated hydraulic fluid in its original form. Biodegradability may be
considered by type of environmental compartment: aerobic
fresh water, aerobic marine, aerobic soil, and anaerobic media. Test methods for aerobic fresh water, aerobic soil, and

anaerobic media have been developed that are appropriate


for each compartment and aire reviewed here.
D 5864Test Method for Determining the Aerobic
Aquatic Biodegradation of Lubricants or Their
Components
This test method covers the determination of the degree of
aerobic biodegradation of fully formulated lubricants or
their components on exposure to an inoculum under laboratory conditions. This test method is intended to specifically
address the difficulties associated with testing water insoluble materials and complex mixtures such as are found in
many lubricants.
D 6046Classification of Hydraulic Fluids for
Environmental
Impact
This classification covers all unused fully formulated hydraulic fluids in their original form. Classifications for categories for the impact of hydraulic fluids in different environmental compartments is provided. Fresh water and soil
environmental compartments are addressed.
D 6384Terminology Relating to Biodegradability and
Ecotoxicity of Lubricants
Terminology relating to biodegradability and ecotoxicity of
lubricants is provided in this standard.

SUM]VIARY AND OUTLOOK ON FUTURE


DEVELOPMENTS IN THE FIELD OF
PRESSURE MEDIA
The overall broad grouping of esters offers a variety of different fluids from which pressure media can be produced,
making a uniform description impossible. However, due to
their basic structure, ester-based fluids differ substantially

292 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

WGK
classification

r
pre test

.
J'"flS'Ctlr,nV-,l
compulsory

i--.taxids-.i'J

daphni=<:>-.'*'/

mm^
test of
components

special case

additional
toxicidy tests

biodegradability
& mobility

FIG. 48Ecological test for German water hazard classification [18,19,39,41-45].

Germ-toxic
Test method
Unit
GS2 Unused
GS2 1000 h Aging
S2 Unused
S2 1000 h Aging

TABLE 4Ecological properties of a formulation and the base fluid.


Biodegradability
Fish-toxic
Mammal-toxic
Biodegradability

DIN 38412 T 8

OECD 203

ECio [mg/L]
> 10.000
> 10.000
>10.000
> 10.000

LC50 [mg/L]
> 10.000
> 10.000
> 10.000
> 10.000

OECD 401
Limittest
LD50 [mg/L]
>2.000 78
>2.000 84
>2.000 89
>2.000 89

CEC L-33-A-93
Depletion [%]
N/A
N/A
76
64

BODIS ISO/DIN
10708
Depletion [%]
0
0
0
0

transfer of triboligical properties from the


fluids to the materials

OH
complete
addrtive
package

strategy
- coatings
- eccological acceptable fluids
- data bases & simulation tools
- examinations on trSbological modells
- examinations on machines

FIG. 49Strategies for future fluid and material developments [21].

Oil less
addrtivs

Biodegradability WGK
VCI-strategy

CHAPTER 11: ENVIRONMENTALLY FRIENDLY OILS 293


from mineral oil-based lubricants. The different basic structures and their physical and chemicEil properties were explained in detail.
When examining their fluids, properties of the esters were
found to be both similar and different to those of mineral
oils. Esters offer considerable improvement relative to mineral oils with respect to low temperature properties and lubricity. Oxidation stability, hydrolytic stability and, in general, aging stability were deficiencies relative to mineral oil,
especially for unsaturated fluids. However, the use of completely saturated fluids eliminated those deficiencies. All tests
distinctly demonstrated the application-related advantage of
completely saturated fluids in high-load hydraulic systems.
The direct assessment of the different developmental stages
of the fluids allowed an excellent coordination of the additives with the respective basic fluid.
Future development in the field of lubricants will increasingly consider the entire tribological system with the aim of
making it ecologically more compatible. This will require the
development of environmentally compatible lubricants as well
as the use of materials complementing those lubriccints with
regard to their tribological properties, to provide increasingly
more tribological functions of the lubricants. For example, a
further reduction in the toxicological properties of biodegradable hydraulic fluids is necessary. Additional improvements in
ester-basestocks chemistry is also important to provide further
improvement in film-forming and antiweeir properties.
It's likely that the focus will remain on ester-basestock development in view of their overall excellent biodegradable
and toxicological properties. However, further and substantial improvement is needed in their oxidation properties for
t h e m to rival those exhibited by mineral oil. These functions
may potentially be provided by additive development.
Calculation or simulation of friction and wear are still not
possible. Therefore, work will continue to model tribological
systems by analogy to those already known, using laboratory
tests. Of course, this process necessitates subsequent validation in actual hydraulic systems.

D 665

D 974
D 1298

D 15 3 3
D 2270
D 2422
D 2619
D 2882

D5182

D 5770

D 5864

D 6006
D 6046
D 6080
D 6158
D 6384

ASTM STANDARDS
No.
D 2272

D 92
D 95

D 97
D 130

D 445

D 664

Title
Standard Test Method for Oxidation Stability
of Steam Turbine Oils by Rotating Pressure
Vessel
S t a n d a r d Test Method for Flash a n d Fire
Points by Cleveland Open Cup Tester
Standard Test Method for Water in Petroleum
Products and Bituminous Materials by Distillation
S t a n d a r d Test Method for Pour Point of
Petroleum Products
Standard Test Method for Detection of Copper
Corrosion from Petroleum Products by the
Copper Strip Tarnish Test
Standard Test Method for BCinematic Viscosity
of Transparent and Opaque Liquids (the Calculation of Dynamic Viscosity)
S t a n d a r d Test Method for Acid N u m b e r of
Petroleum Products by Potentiometric Titration

E 203

S t a n d a r d Test Method for Rust-Preventing


Characteristics of Inhibited Mineral Oil in the
Presence of Water
Standard Test Method for Acid and Base Number by Color-Indicator Titration
Standard Practice for Density, Relative Density (Specific Gravity), or API Gravity of Crude
Petroleum and Liquid Petroleum Products by
Hydrometer Method
Standard Test Methods for Water in Insulating
Liquids by Coulometric Karl Fischer Titration
Standard Practice for Calculating Viscosity Index from Kinematic Viscosity at 40 and 100C
Standard Classification of Industrial Fluid Lubricants by Viscosity System
Standard Test Method for Hydrolytic Stability
of Hydraulic Fluids (Beverage Bottle Method)
Standard Test Method for Indicating the Wear
Characteristics of Petroleum and Non-Petrole u m Hydraulic Fluids in Constant Volume
Vane P u m p
S t a n d a r d Test Method for Evaluating the
Scuffing Load Capacity of Oils (FZG Visual
Method)
S t a n d a r d Test Method for Semiquantitative
Micro Determination of Acid Number of Lubricating Oils During Oxidation Testing
Standard Test Method for Determining Aerobic Aquatic Biodegradation of Lubricants or
their Components
Standard Guide for Assessing Biodegradability
of Hydraulic Fluids
Standard Classification of Hydraulic Fluids for
Environmental Impact
Standard Practice for Defining the Viscosity
Characteristics of Hydraulic Fluids
Standard Specification for Mineral Hydraulic
Oils
Standard Terminology Relating to Biodegradability and Ecotoxicity of Lubricants
Standard Test Method for Water Using Volumetric Karl Fischer Titration

OTHER STANDARDS
International Organization for Standardization
(ISO)
Title
Petroleum products; determination of flash and fire points: Cleveland open cup method
Petroleum products; determinaISO 3016
tion of pour point
Petroleum p r o d u c t s and bitumiISO 3733
nous materials; determination of
water, distillation method
ISO 6743/4 -1982 Part 4: Lubricants, industrial oils and related products (class L); classification. Family H (hydraulic systems)
No.
ISO 2592

294

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

D e u t s c h e s Institut fur N o r m u n g (DIN)


No.
DIN 51 354 Part 2

DIN 51 381

DIN 51 389 Part 2

DIN 51 502

DIN 51 517 Part 1


DIN 51 519
DIN 51 524 P a r t i
DIN 51 550
DIN 51 558 P a r t i

DIN 51 561

DIN 51 562 Part 1

DIN 51 566

DIN 51 569

DIN 51 585

DIN 51 587

DIN 51 592

DIN 51 599

DIN 51 757

Title
Testing of lubricants: mechanical testing of lubricants by the FZG gear test
rig method; gravimetric m e t h o d for
A/8, 3/90 lubricating oils
Testing of lubricants a n d hydraulic
fluids; d e t e r m i n a t i o n of air release
properties; impinger method
Testing of lubricants; mechanical testing of hydraulic fluids by the vanep u m p method: m e t h o d A for anhydrous hydraulic fluids
Lubricants a n d related materials;
designation of lubricants and marking
of lubricant containers, lubrication
equipment and lubrication points
Lubricants; lubricating oils; C lubricating oils; m i n i m u m requirements
Lubricants; ISO viscosity classes for industrial liquid lubricants
Pressure fluids; hydraulic oils; HL hydraulic oils: m i n i m u m requirements
Viscometry; determination of viscosity; general principles
Testing of mineral oils; determination
of neutralization number; color indicator titration
Testing of mineral oils, liquid fuels
and related liquids; measurement of
viscosity using the Vogel-Ossag viscometer: temperature range: approximately 10 to 1 50C
Viscometry; determination of kinematic viscosity using the standeird design Ubbelohde viscometer
(at present at the stage of draft) Testing of lubricating oils: determination
of foaming characteristics
Testing of mineral oils, liquid fuels
and related liquids; measurement of
viscosity using the Vogel-Ossag viscometer: t e m p e r a t u r e range: 55 to
approximately + 10C
Testing of lubricants; testing of corrosive effect of steam turbine oils and
hydraulic oils containing additives
Testing of lubricants: determination of
aging behavior of steam turbine oils
and hydraulic oils containing additives
(at present at the stage of draft) Testing
of lubricants; determination of the
content of u n dissolved matter in lubricating oils; membrane filter method
Testing of lubricating oils; determination of demulsification capacity by the
stirring method
Testing of petroleum products and related materials; determination of density

DIN 51 759

DIN 51 848 Part 1

DIN 53 505
DIN 53521

DIN 53 538 Part 1

Testing of liquid hydrocarbons; determination of the effect of corrosion on


copper; copper strip test
Testing of petroleum products; precision of test methods; general introduction; concepts and their application to
petroleum s t a n d a r d s specifying requirements
Testing of elastomers; Shore A and D
hardness testing
Testing of rubber and elastomers: determination of their resistance to liquids, vapours and gases
Standard reference elastomers; peroxide-cross-linked acrylonitrilelbutadiene rubber (NBR) for characterizing
service fluids with respect to their action on NBR

REFERENCES
[1] Backe, W., The Present and Future of Fluid Power, Proceedings of
the Institution of Mechanical Engineers, Institution of Mechanical Engineers, Milwaulkee, WI, Dec. 1993.
[2] Backe, W. and Busch, C, "Biologisch Schnell Abbaubare Hydraulikflilssigkeiten," Tribologie + Schmierungstechnik, No. 1,
1995, pp. 30-35.
[3] Becker, R. and Knorr, A., "Antioxidantien fiir Pflanzliche Ole,"
Tribologie + Schmierungstechnik, No. 5, 1995, pp. 232-240.
[4] Bongardt, F., Einfluji der Chemischen Struktur aufdas Luftabscheidevermogen und die Hydrolytische Stahilitdt von Estem, Teil
1, Fat Science Technology, No. 12, 1990, pp. 607-613.
[5] Bongardt, F., Einfluji der Chemischen Struktur aufdas Luftabscheidevermogen und die Hydrolytische Stabilitat von Estem, Teil
2, Fat Sci. Technology, No. 12, 1990, pp. 614-619.
[6] Bongardt, F., "Native Ester: Basisole fiir leistungsfahige und
Umweltvertragliche Hydraulikfliissigkeiten," Tribologie 2000
Band 1, TAE, Esslingen, 1992.
[7] Busch, C, "Biologisch Schnell abbaubare Hydraulikfliissigkeiten," Tribologie und Schmierungstechnik, Vol. 41, No. 1,
1994, pp. 23-31.
[8] Busch, C, "Untersuchung und Analyse der Eigenschaften und
Eigenschaftsanderungen einer Rapsolbasischen Druckfliissigkeit in ihrer Funktion als Druckiibertragungsmittel," Dissertation RWTH Aachen, Aachen, Germany, 1995.
[9] Busch, C, Rapsol auf dem Priifstand - Alterungsstabilitat und
VerschleiySschutzvermogen, 10th AFK, Aachen, Germany, 1992.
[10] Dimming, T., Hartmann, J., Wunderwald, U., and Schafer, V.,
"Additivkomponenten auf Basis nativer Ole," Tribologie +
Schmierungstechnik, No. 6, 1994, pp. 375-380.
[11] Feldmann, D. G. and Remmelmann, A., Biologisch Schnell Abbaubare HydraulikfliissigkeitenErgebnisse von Priifstandstests
und Folgerungen fiir die Anwendung, 12th AFK, Aachen, Aachen,
Germany, 1996.
[12] Feldmsinn, D. G. and Hinrichs, J., Biologisch Schnell Abbaubare
Hydraulikfliissigkeitenein Neuartiges Konstruktionselement fiir
Hydrostatische Getriebe, Konstruktion, VDI Verlag, Dusseldorf,
Germany, 1995.
[13] Fessenbecker, A. and Korff, J., "Additive fiir Okologische Unbedenklichere Schmierstoffe," Tribologie + Schmierungstechnik,
No. 10, 1995, pp. 623-629.
[14] Mang, T., Umweltvertragliche Hydraulik, 12th AFK, Aachen,
Germany, 1996
[15] Fessenbecker, A., "New Additive for the Hydrolytic Stabilisation

CHAPTER 11: ENVIRONMENTALLY FRIENDLY OILS 295


of Ester Lubricants," Tribology Solving Friction and Wear Problems, Technische Akademie Esslingen, Ostfildern, Germany,
1996.
[16] Gold, P. W., "Tribologie 1," Umdrucke zur Vorlesung, RWTH,
Aachen, Germany, 1996.
[17] Francke, W. and Walter, W., Lehrbuch der Organischen Chemie,
23, S. Auflage, Ed., Hirzel Verlag Stuttgart, Leipzig, Germany,
1998.
[18] Hund, K. Fabig, W., and Btinemann, T. F., "Biologische Abbaubarkeit von Synthetischen Schmierstoilkomponenten," Tribologie + Schntierungstechnik,
No. 1, 1993, pp. 48-56.
[19] Freitag.R., "Gesetzliche VorschriftenfiirdieEntsorgungvonAltol," Okologische und Okonomische Aspekte der Tribologie Band
1, Technische Akademie Esslingen, Ostlildem, Germany, 1994.
[20] Hart, H., Organische Chemie, ein Kurzes Lehrbuch, VCH Verlag,
Weinheim, Germany, 1989.
[21] Holderich, W. F., "Umweltvertragliche Tribosysteme," Entwicklung Neuartiger Schmierstoffe und Druckiibertragungsmedien
mit
Hilfe Chemischer Methoden, Teilprojekt Al im SFB 442 RWTH,
Aachen, Germany, 1997.
[22] Ihrig, H., "Umweltvertragliche Schmierstoffe in den 90er
Jahren," Tribologie + Schmierungstechnik,
No. 3, 1992, p p .
103-110.
[23] Kempermann, C. and Remmelmann, A., Umweltschonende Hydraulikflussigkeiten, o +p. No. 1, 1996, pp. 67-73.
[24] Mang, T., "Schmierstoffe u n d Druckiibertragungsmedien im
Maschinenbau," Umdruck zur Vorlesung, RWTH, Aachen, Germany, 1998.
[25] Murrenhoff, H., "Grundlagen der Fluidtechnik, Teil 1 Hydraulik," Umdruck zur Vorlesung, RWTH, Aachen, Germany,
1998.
[26] Murrenhoff, H. and R e m m e l m a n n , A., "Environmentally
Friendly Pressure Media Based on Synthetic EstersNew
Changes for Mobile Hydraulics," SAE International Paper
98185, Presented at t h e Earthmoving Industry Conference,
Peoria, IL, 1998, Society of Automotive Engineers, Warrendale, PA.
[27] Paetzold, P., Einfiihrung in die Allgemeine Chemie, 2, Auflage
Friedrich Vieweg & Sohn, Braunschweig, Wiesbaden, Germany,
1988.
[28] Schmitt, H.-G., "Komplexester aus Pflanzlichen Olen," Tribologie -h Schmierungstechnik,
No. 1, 1994, pp. 38-43.
[29] Schiilert, G., Bernhard, U., Ude, G., a n d Geiger, G., "Alterungsverhalten von Umweltschonenden Hydraulikfliissigkeiten," Okologische und Okonomische Aspekte der Tribologie
Band 1, Technische Akademie Esslingen, Ostfildern, Germany,
1994.
[30] Schwetlick, K. U. A., Organikum, 20, Auflage, Johann Ambrosius Barth Verlag Heidelberg, Leipzig, Germany, 1996.

[31] Spilker, M. and Bock, W., Die Umwelt als Ideologietrdger, FluidTechnik,No. 4, 1995.
[32] Vetter, J., "Synthetische u n d Nachwachsende GrundolkomponentenProduktsicherheit, Eigenschaften, Gesundheits- und
Umweltaspekte," Biologisch Schnell Abbaubare
Schmierstoffe
und Arbeitsfliissigkeiten, Technische Akademie Esslingen, Ostfildern, Germany, 1995.
[33] Wendorf, J., "Daueruntersuchung von Hydraulikolen auf Rapsolbasis in Mahdreschem und Selbstfahrenden Feldhackslem,"
Biologisch Schnell Abbaubare Schmierstoffe
und Arbeitsfliissigkeiten, Technische Akademie Esslingen, Ostfildern, Germany, 1995.
[34] Streitwieser, H. and Heathcock, J., Organische Chemie, 1. Auflage VCH-Verlag, Weinheim, Germany, 1990.
[35] DIN 51 524 T1-T4 Hydraulikole, Mindestanforderungen,
Deutsches Institut fur Normung e. V., Beuth Verlag, 06.1985,
Berlin, Germany.
[36] VDMA-Einheitsblatt 24 568: Biologisch Schnell Abbaubare HydraulikfliissigkeitenTechnische Mindestanforderungen, 3,
Beuth Verlag, Berlin, 1994.
[37] VDMA-Einheitsblatt 24 569: Biologisch Schnell Abbaubare HydraulikfliissigkeitenUmstellungsrichtlinien, Beuth Verlag,
Berlin, 1994.
[38] Bundes Imimissionsschutz-Gesetz, Law of the Federal Republic
of Germany, 1998.
[39] AbschluySbericht zum Forschungsvorhaben, "Synthetische Ester," VDMA, Frankfurt, Germany, 1997.
[40] KBwS: Bewertungsmuster zur Stoffeinstufung in Wassergefahrdungsklassen im Sinne von 19 Wasserhaushaltsgesetz;
Chemiereport VCI, 1989.
[41] OECD: Guidelines for Testing of Chemicals; OECD 203, OECD
401, Organization for Economic and Co-operation and Development, Paris 1981 (adopted 1983, 1984, 1986, 1987, 1989 und
1992).
[42] DIN 38412 T 8: Testverfahren mit Wasserorganismen L8,
Beuth-Verlag, Berlin, 1993.
[43] ISO/DIS 10708: Water QualityEvaluation in an Aqueous
Medium of the "Ultimate" Aerobic Biodegradability of Orgsinic
BondsMethod by Determining the Biochemical Oxygen Demand (two-phase closed bottle test). International Organization
for Standardization, Geneva, 1995.
[44] CEC L-33-A-93: Biodegradability of Two-Stroke Cycle Outboard
Engine Oils in Water; Commission for Environmental Cooperation, 1995.
[45] DIN 51828-2: B e s t i m m u n g der Schnellen Biologischen AbbaubarkeitInfrarotspektrometrisches Verfahren; Gelbdruck,
Beuth-Verlag, Berlin, 1995.
[46] UUmanns Enzyklopddie der Technischen Chemie, Vol. 11, Auflage Verlag Chemie, Weinheim, Germany, 1976.

MNL37-EB/Jun. 2003

Turbine Lubricating Oils and


Hydraulic Fluids
W. David Phillips^

back or outsourced. Operators are trying to extend the time


between overhauls and are therefore seeking longer component lives. This review of turbine oils and fluids is therefore
set against a background of significant technological change.
Perhaps, not surprisingly, the same pressures that are changing the commercial landscape are also driving developments
in lubricant and hydraulic fluid technology.

T H E POWER GENERATION INDUSTRY IS CURRENTLY UNDERGOING

the most radical changes it has seen in its relatively short history. The very conservative, slow moving industry dominated
by state utilities has, in the last ten years, seen a major transition for both political and commercial reasons. Many areas
of what used to be a highly regulated market have become
very competitive with the privatization of large, governmentowned power generators and a developing global energy market [1,2].
With the break-up of the state monopolies, smaller, independent power producers have appeared seeking to install
plant at the lowest cost and to make a rapid return on their
investment [3]. At the same time, intense competition in the
turbine industry has resulted in the development of equipment with substantially increased efficiency as the participants seek to increase their meirket share.
On the political front, apart from the decision to deregulate
the power industry, there has been environmental pressure to
halt the construction of, and even replace, nuclear power stations and to reduce the effect of emissions on global warming
by switching from coal and oil to gas and 'green' energy such
as wind power. In Europe, safety of machinery legislation [4]
has been introduced which, although not specifically directed at the p o w e r industry, nevertheless imposes constraints upon it.
As might be expected, such changes, while determining the
commercial shape of the industry well into the next century,
also have a major impact on its technical requirements. For
example, increased competition has driven improvements in
equipment efficiency. This, in turn, has resulted in turbines
operating at ever higher temperatures [5]. According to one
report, for each increase of 100F in firing temperatures of
gas turbines, the output is increased by 10-13% with a gain
of 2-4% in simple cycle efficiency [6]. This has the effect of
placing greater thermal stress on the system components
including the lubricantand an adverse impact on operating
life. Such pressures have forced the steam turbine builders to
consider technology previously used only in aero-derivative
gas turbines, w h i c h operate at the highest t e m p e r a t u r e s
found in the industry [7].

TURBINE TYPES
The source of the kinetic energy for conversion into power
depends on the turbine type. In a steam turbine it is the
rapid expansion of high-pressure steam, and in a gas turbine, the expansion of fuel combustion products. With wind
emd water turbines, the movement of a mass of air, or water under pressure, is the energy source. To convert the rotational energy into a more useful form of power, turbines
are coupled to alternators for electricity generation or to a
pump, compressor, or fan when used as a mechanical drive
[8]. Depending on the speed of the turbine rotation it may
be necessary to introduce a reduction gear between the turbine and driven equipment for steam, industrial gas, and
wind turbines.
Aero-engine gas turbines are not directly coupled to other
equipment, but instead the energy of the expanding gases is
used to provide forward motion, as in aviation usage, or to
drive a second turbine wheel, sometimes called a power turbine, which is independent of the power source and attached
to an alternator or compressor.
To summarize, turbines are manufactured in a wide variety of sizes and for several different applications as follows:
For power generation, where they may drive a generator,
either directly or indirectly via a gearbox.
As a direct mechanical drive for p u m p s and compressors.
As gas generators for propulsion (in the aircraft industry),
or when used with an independent power turbine, for driving p u m p s and compressors.
Steam Turbines

At the same time commercial pressures on the utilities to


lower operating costs have resulted in a reduction of personnel (some units are now operating with a third of staff originally employed). Where possible, maintenance has been cut

Steam turbines are currently manufactured in the following


approximate ranges:
Small (0.5-80 MW) units, which are used for mechanical
drive and industrial power applications. As these turbines
normally operate at high speed (2800-16000 rpm), they are
used together with reduction gears and, for power generation, with air-cooled generators or alternators.

' Marketing and Technical Manager, Great Lakes Cliemical Corporation, Performance Additives and Fluids, Tenax Road, Trafford
Park, Manchester M17 IWT, England.
297
Copyright'

2003 by A S I M International

www.astm.org

298

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Medium size units (100-300 MW) with rotor speeds of


1500-3600 rpm directly driving air/water-cooled generators.
Large sets of up to 1500 MW, also with direct drive and
normally used with hydrogen-cooled generators. These are
favored by the large utilities for base-load powerparticularly for nuclear operations.
Gas Turbines
In the past gas turbines were so-called because of their sole
use of gas as a fuel, but developments in design now enable
"gas" turbines to operate on volatile liquid fuels such as
kerosene or naphtha. They are perhaps more correctly, and
less confusingly, known as combustion turbines, but for the
purposes of this chapter will be referred to as gas turbines.
Gas turbines can be also be subdivided into three categories:
Micro-turbines of 25-300 kW output, which are currently
of current interest to the automotive industry, in small
power generation packs and as a mechanical drive [9].
Industrial (heavy duty) units of 5-300 MW used for power
generation either in simple cycle or combined cycle operation (see below) and driving all designs of alternators either
via a reduction gear, as is the case with small units up to
about 70 MW output, or directly for larger sets. Small industrial sets up to 15 MW are also used for mechanical
drive applications, e.g., gas pumping.
Aero-gas turbines with outputs of 2000-6000 lb thrust
(turbo-propeller types) and 11000-110000 lb thrust (turbofan and turbojet types) for aviation applications. In industrial and marine applications a reduced range of engines is
used and their power output is slightly lower (13-51 MW)
than when used in aviation applications. The non-aviation
uses require, of course, an independent power turbine to
convert the energy generated by the combustion gases into
power or for use as a mechanical drive.
When gas turbines are used alone for power generation or
for the production of both heat and power (combined heat
and powerCHPor co-generation applications [6,10]),
they are said to be used in 'simple' cycle operations with operating efficiencies of 35-50%. A demand for higher efficiency has resulted in combining the operation of gas and
steam turbines in what are known variously as combined
cycle units (CCGT) or "steam and gas" (STAG) or, in Germany, as Gas und Dampf ("GuD"). In this application the
waste heat from the gas turbine is used to raise steam for
the steam turbine via a heat recovery steam generator
thereby raising the overall efficiency of the process to
50-60% [11-13]. This is currently the most popular method
of installing new utility or independent power production
(IPP) capacityproviding there is a source of gas available.
As the investment required is lower than for a single steam
turbine of the same total output and installation more
rapid, the financial return is faster.
The latest developments in this field have been to design
the steam, gas turbine and generator (possibly also a pump
or compressor) on a single shaft [14]. This has the advantage of lower capital costs, a simpler design, and a layout
with a smaller footprint. This is, however, at the cost of flex-

ibility of operation unless a clutch is used between the


steam turbine and the generator. In this development a
common lubrication system for all components may be
used which means that the oil has to withstand the extremes of operation required by the individual pieces of
equipment, that is wet operation in the steam turbine and
high temperatures in the combustion turbine. A typical lubricating oil system for a single shaft CCGT unit is shown
schematically in Fig. 1.
Water Turbines
Water or hydro-turbines are available in several different designs, such as the Francis or Kaplan turbines, and selection
of the most appropriate design depends largely on the available head of water. A fixed blade propeller (Francis) or a variable pitch propeller (Kaplan) uses the hydrostatic head to
drive a generator. For high heads (e.g., of 30-300 m) the
Francis turbine is preferred while for heads of 15-30 m the
Kaplan design is normally used.
The power output for water turbines is almost as wide as
for steam turbines with a current range of about 1-800 MW.
The function of the turbine oil system is to lubricate the bearings of the turbine and the generator, which normally sits
above the turbine on the same shaft. A forced lubrication system can be used with the main oil pump driven from the rotor shaft. In such cases an auxiliary pump is necessary to provide adequate oil pressure during start-up and shutdown. An
alternative technique is self-lubrication by the suitable design
of the bearing pads and pad supports.^
Oil pressures vary between 2-10 bar and the lubrication
system capacities vary from 1-10 m^ for turbines of 10-300
MW.
In addition to the lubrication system, there is a hydraulic
circuit for operating the governor and inlet valve system. In
the past the same oil was used for both the hydraulics and
bearing lubrication with hydraulic pressures of 20-25 bar.
However, pressures in the hydraulic system have increased
over the years to their current levels of 100-160 bar with a
consequent reduction in system volume from about 3-4 m^ to
0.8-1.5 m^. Today, where hydraulic pressures are >60 bar,
separate hydraulic and lubrication systems are used.
Where the design involves separate systems, conventional
turbine oils of ISO viscosity grades (VG) 32-68 are used for
bearing lubrication and hydraulic oils of ISO VGs 32 and 46
for the hydraulic system-except for low temperature environments where oils of ISO VGs 10 and 22 may be used in
the gate hydraulic control. (ISO Standard 3448 or ASTM D
2422, Standard Classification of Industrial Fluid Lubricants
by Viscosity System, classify industrial lubricants by viscosity grade. The grade number corresponds to the mid-point
of a viscosity range extending to 10 % of the mid-point
value and is measured in centistokes at 40C.) Bulk oil temperatures are in the range of 40-55C for the lubrication
system. Under these conditions the stress levels in the system are low and the oil normally lasts the life of the turbine.

^ Private communication with H. Moeller, Elsam, Nordjyllandsvaerket, Denmark.

CHAPTER

12: TURBINE

LUBRICATING

AC main AC auxiliary DC emergency


iube oil lube oil pump lube oil pump
pump

OILS AND HYDRAULIC

FLUIDS

299

Oil
purifier

FIG. 1Lubricating oil system for a single-shaft combined-cycle turbo generator.


Removal of excess water by centrifuge takes place every six
months.
Wind Turbines
Wind turbines are a relatively recent development in which
the rotation of a propeller is coupled to a generator either directly or via a gearbox. The power output currently varies according to location. Typically, land turbines have an output
of 300-1000 kW while offshore turbines are larger with a capacity of u p to 2-3 MW [15]. Units of 5 MW output are currently under development [16].
Two basic types of propeller design are in use: those with a
horizontal axis (otherwise k n o w n as p i t c h turbines) a n d
those with a vertical axis (stall turbines). The former type
uses one (or even two) gearbox(es) [17] and a generator. The
gearbox is oil lubricated while the roller bearings of the generator are grease lubricated. A separate hydraulic system
containing a conventional ISO VG 46 hydraulic oil (40-60 L
capacity with a pressure of about 60 bar) for altering the
pitch of the propeller may also be included. Some designs
have demonstrated it is possible to avoid the use of a gearbox,
and with these the propeller directly drives a multi-pole generator.
The early gearboxes on machines of < 5 00 kW had a capacity of about 125 L and relied on splash lubrication with a n
ISO VG 220 gear oil at temperatures of 80-90C. For turbines
with an output of >500 kW, forced lubrication systems are
used a n d system capacities for the larger machines have
since risen to about 200 L.

Problems initially arose with the use of conventional turbine oils in t e r m s of reduced oil life, deposit formation,
micro-pitting and bearing failure and led to the use of polyalphaolefin (PAO)-based oils owing to their better high temperature stability. In spite of this the average life of the gearbox oil in the small units was still only about 1-2 ycctrs. The
oil life has increased since temperatures were reduced to
<70C but the problems of micro-pitting smd bearing failures
have not yet been totally eliminated. However, all new gear
oils for this application are required to pass an FZG micropitting test (FVA test 54/I-IV, Test Procedure for the investigation of the Micro-Pitting Capacity of Gear Lubricants).
Higher viscosity products (ISO VG 320) are also used in an
attempt to further minimize the problems. Even with these
changes, the current oil life expectations are, as yet, only 3-5
years. With additional research on the effects of oil cleanliness, moisture, and metal contamination, further improvements are thought possible.'^
As well as the operating problems mentioned above, other
factors have to be taken into consideration during operation,
for example the inaccessibility of the equipment in the event
of a failure (especially if located offshore). Power generation
without producing carbon dioxide can also have a higher
profit margin, so downtime losses/MW output are also higher
for this tjrpe of equipment.
As well as the gearbox, almost all wind turbines have a
small hydraulically operated braking system of 2-4 L capacity and working at about 100 bar pressure. Since conventional turbine oils are not used in wind turbines there will be
n o further discussion of this application.

300 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


THE FUNCTION OF THE LUBRICATING OIL
AND HYDRAULIC FLUID
The primary function of the turbine oil is to lubricate the turbine and generator bearings. However, it may also fulfill the
following secondary functions:
Acting as a hydraulic fluid in steam/gas valve operation and
in the jacking systems for the rotor shaft and gear wheel
Lubricating the reduction gear (if used)
Lubricating the exciter bearings
Acting as a shaft seal for hydrogen-cooled generators
Lubricating the coupling between the turbine and the alternator
In addition, the oil acts as a coolant for the lubricated surfaces, minimizes friction and wear; removes any wear particles to the filters, and protects the system from rust and corrosion.
The hydraulic control or governor oil system controls the
rate at which steam is admitted to the turbine cylinders eind
hence the turbine rotational speed. The hydraulic fluid is also
used to operate emergency stop valves.

THE OPERATING ENVIRONMENT FOR


LUBRICATING AND HYDRAULIC OILS
Although the equipment varies considerably in its size and
complexity, the basic design of the hydraulic and lubricating

oil systems is essentially the same across the range of turbine


types. With the exception of totcil loss systems in some military aviation applications, the lubrication systems are closed
circuits involving a reservoir, a pump train with main, auxiliary, and emergency pumps, filters, a cooler and possibly a
centrifuge or purifier (on a bypass to the oil tank) to remove
excess water and dirt. The oil is supplied under a slight pressure to the bearings. Fig. 2 shows, in diagrammatic form, the
supply of lubricating oil to a steam turbine generator. In high
pressure hydraulic systems there may additionally be accumulators to "store" the higher pressure until it is needed for
valve displacement. When using fire-resistant hydraulic fluids, the oil purifier's prime function is to remove acid that
would otherwise catalyze further degradation of the fluid.
Where mineral oil is used, which is still the most common
situation, lubricating and hydraulic oil systems are normally combined with lubricating oil system supply pressures at about 3-4 bar and a pressure at the bearing inlet of
about 1-2 bar. Hydraulic pressures are somewhat higher at
7-20 bar and both the hydraulic system and lubricating oil
for the turbine, gearbox (if used), and generator are fed
from the same tank. Exceptionally, there are separate hydraulic systems containing mineral oil where the pressure is
high at 160 bar.
In modern large turbines, with steam temperatures now
reaching 600C, the presence of mineral oil in the hydraulic
system presents a major fire hazard. The escape of mineral
oil and contact with steam pipes in the vicinity of the control

- EXCITER

ELECTHIC GENERATOR AND

B" LOW PRESSURE TURBINE

" A ' X O W PRESSURE TURBINE

HIGH PRESSURE AND


REHEAT TURBINE
MAIN SHAFT OIL PUMP

GRAVITY
DRAIN AND
GUARD PIPE
PRESSURIZED
OIL PIPES
OIL VAPOR EXTRACTOR
OIL RETURN
SCREENS

OIL
COOLERS

OIL RESERVOIR AND


OILE.IECTORS

FIG. 2Shaft driven lubrication system of a steam turbine generator. Reproduced by permission of the Electric Power
Research Institute, Palo Alta, CA.

CHAPTER

12: TURBINE

(Eh

Fluid returns

>

'^-r

LUBRICATING

OILS AND HYDRAULIC

FLUIDS

301

4x}

-|J_yent

z
Fluid conditioning

^M%

Cooling water>

llling using
loling pump

C( Dllng water

-M-

Emptying>

illing using
^ s n ianual pump

FIG. 3Typical steam turbine control fluid system.


valves has caused many turbine fires [18,19]. As a result the
industry, as long ago as the mid-1950s, introduced the concept of a separate hydraulic system containing a fire-resistant
fluid [20]. Although there are alternative ways of reducing the
fire hazard, e.g., by providing pipe-in pipe systems, fire-resistant hydraulic fluids are now widely used in electro-hydraulic
governor control and emergency stop-valve systems. In order
to reduce the volume of fluid used and the capital cost of a
separate system, the pressures in these circuits are normally
m u c h higher than when oil is used. Currently 160 bar is the
m a x i m u m found, but an increase to 200 b a r is being considered. A typiccJ hydraulic control circuit diagram is shown in
Fig. 3.
Fire-resistant hydraulic fluids based on triaryl phosphates
are now used in over 1000 large steam turbines worldwide.
More recently the same fluids have been developed for use as
a combined hydraulic fluid and main bearing lubricant for
both small and large steam turbines u p to 1000 MW and the
operating experience obtained since the early 1980s has
shown them to be highly successful in this application [21].
Although most industrial gas turbines use mineral oil or
synthetic hydrocarbons as the hydraulic fluid and lubricant
in a single system, there are applications where fire-resistant
hydraulic fluids are used in a separate system (in mediumlarge sized units) or as the operating media for both hydraulic and lubrication systems. As an example of the latter,
their use in gas pipeline turbo-compressors has provided in-

creased safety and reduced downtime since 1958 and they are
now widely used in this application in North America [22]. In
the 1970s they were introduced for use in the control and lubrication systems of 70 MW sets for power generation [23]. A
t5rpical lubrication system for an industrial gas turbine is
shown diagrammatically in Fig. 4.
Aero-derivative gas turbines were introduced during the
Second World Weir and, while mineral oils were initially used
for lubrication, it was soon realized that both the low temperature properties and the high temperature stability of the
oils then available were inadequate for the more powerful engines that were being developed. Synthetic ester fluids were
therefore introduced a n d have remained the most widely
used type of fluid in this equipment for both aviation and industrial applications where they function as a combined hydraulic fluid and lubricant for the turbine [24]. Mineral oils
are still used in some of the older or smaller aero-engines for
military aviation, and in industrial applications where the
thermal/oxidative stresses are lower.
Where aero-derivative units are used for mechanical drive
applications, the hot exhaust gases drive a power turbine that
is attached to a compressor or a gearbox/generator, etc. In
this application, a synthetic ester product lubricates the engine, while the power turbine and the "driven" equipment are
normally lubricated with mineral oil in a separate system.
When used for pumping natural gas, the power turbine cind
compressor Eire often lubricated with a fire-resistant fluid.

302

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

IEGBO):

A
A
A
H

Mr

mm
MSuwIlF
DfMn

->

Q
)f>RESSUnE
'TRANSMITTEfl

TgwlflCSTiKfOMAt

FIG. 4Typical lubrication system for an Industrial gas turbine. Reproduced with permisson of Solar Turbines, Inc., San Diego, CA.

There has also been some limited use of fire-resistant fluids


in the hydraulic systems of aero-derivative gas turbines, but
as yet there is no significant experience with these fluids as
lubricants for this equipment.
The severity of lubricating oil service (and hence operating
life) varies considerably and depends on a number of factors
including:
System design
The duty cycle, for example continuous or intermittent operation
Oil stability
The quality of system maintenance
The quality of oil or fluid maintenance
Top-up rates.

The system design determines the degree of thermal and


oxidative stress to which the fluid or oil is subjected. In most
turbines the thermal loading on the lubricant Eirises through
heat conducted along the rotor to the bearings (shaft temperatures in large steam turbines can reach 320C at the
bearings), as a result of the heat generated through frictional
and viscous losses in the bearings, and during compression in
the pumps.
Additionally, in gas turbines, Icirge quantities of sealing air
at temperatures of 200-350C [26] are drawn into the bearing
and form an aerated mixture with the lubricating oil as it
drains back to the tankan ideal environment for promoting
oxidation and foaming. The inlet temperatures of industrial
gas turbines have risen over the years from around 700C in

CHAPTER 12: TURBINE LUBRICATING


1950 to 1500C in 1998 [27,28], as shown in Fig. 5 [28], while
compressed air temperatures have also increased with the
trend toward higher compression ratios. Together this would
suggest a significant increase in the heat being dissipated via
the engine structure. Certainly gas turbine bearings are now
operating at high stress levels. For example, temperatures of
up to about 115C are found for plain bearings and up to
about 300C for roller beeirings. The various sources of heat
and its removal for a t5rpical gas turbine bearing are shown in
Fig. 6.
Unfortunately, although the heat input at the bearings has
steadily increased, the volume of fluid available for heat removal has not. If anything, oil volumes have been reduced as
a consequence of reducing the size and therefore the cost of
the system. This has been achieved by increasing circulation
rates (with an adverse effect on aeration) and, where possible, by more effective cooling. In most cases however, the result has been an increase in oil return line temperatures, in
the case of recent estimates for steam turbines, by 10-15C
[29]. As oxidation rates approximately double with every ten
degrees rise in temperature, it is hardly surprising that tur-

1940

1950

1960

OILS AND HYDRAULIC FLUIDS

303

bine oil lives, particularly for gas turbines, are now giving
cause for concern.
Since the thermal/oxidative stress on the oil or fluid is a
factor of temperature, time and the extent of air contact, the
faster the oil temperature (and the air content) can be reduced, the lower the amount of resulting fluid degradation. A
cooler in the return line is therefore preferred. The presence
of air depends to a large extent on tank design (including the
location of return lines, baffles, and sieves to remove entrained air), but it also depends on fluid circulation rates, the
level of fluid/oil in the tank, etc., Guidance on the basic system design parameters of turbine lubricating oil systems (including the use of suitable materials of construction; design
features of the reservoir and pump train; the appropriate use
and location of coolers, valves and filters, etc.) is available for
steam and industrial gas turbines when using conventional
turbine lubricating oil. This appears in such standards as
ASTM D 4241, Standard Practice for the Design of Gas Turbine Generator Lubricating Oil Systems, ASTM D 4248, Standard Practice for Design of Steam Turbine Generator Oil Systems, and the American Petroleum Institute (API) Standard

1970
Year

1980

1990

2000

FIG. 5Development of gas turbine capacity, inlet/outlet temperature


and efficiency. Reproduced by permission of Verelnigung der
Grosskraftwerk Betreiber, Essen, Germany.

304

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

614, Lubrication, Shail-Sealing, and Control-Oil Systems for


Special-Purpose Applications, b u t is t h e n sometimes ignored. In fact, tank residence times have decreased in recent
years in the pursuit of lower costs, making it more difficult
for the air to be released and with an adverse effect on oxidative stability [29].
The duty cycle is important where the turbine experiences
frequent stops and starts or where the unit is used at maxim u m power for only a short period, as in aviation applications. If aircraft gas turbine oils were continually subjected to
the same stress as found on take-off, the oil life would be substantially reduced. By contrast, the long periods of continuous operation in base-load thermal or nuclear power generation are less demanding. The stability of the oil or fluid will
obviously play an important peirt in determining its operating
life and may help identify the most appropriate type of product for the application.
Depending on the quality of fluid maintenance (which is
discussed in more detail later) and also system maintenance,
for example minimizing air and water leeiks into the oil, the
life of the lubricant can be extended considerably. The importance of reguleir, planned, maintenance cannot be overemphasized in the pursuit of trouble-free operation.
Lastly, top-up rates will determine the rate at which new
fluids, and therefore additives, are replenished. Normally,
top-up rates are fairly lo\? for steam turbines (about 3-10%
per year), but much higher veJues have been reported in the
past (up to 27%) and the beneficial effects of such high topu p rates in extending oil life have been investigated [30]. In

industrieJ gas turbines with some mineral oil types, top-up


rates can rise to as high as 3 3 % per year while aero-engines
in aviation consume on average about 0.25 L per hour or a
complete replacement charge in about 24-130 h of engine operation. In industrial operation the c o n s u m p t i o n may be
lower due to the fitting of more efficient oil demisters.
In the past, an oil change normally took place when equipment builders' recommendations on used fluid performance
were exceeded. These would normally include limits on acidity, water, viscosity increase, and dirt levels. When these values were reached or exceeded, the oil or fluid was considered
too degraded or contaminated for continued use. Today, filtration techniques are available which can readily reduce the
levels of some contaminants, e.g., water and particulates.
This improvement, together with the possibility of monitoring the depletion of additives and then re-inhibiting when
necessary, makes it possible to extend life substantially in
some applications.
The volume of oil used in t u r b i n e lubrication systems
varies considerably. While a figure of 270 L per MW used to
be quoted as typical, steam turbine lubrication systems today
contain in the region of 1 0 0 ^ 0 0 L per Megawatt for turbines
of <200 MW and from about 50-80 L per Megawatt for sets
in the range 250-1500 MW. There is considerable variation as
the builders frequently use one size of tank for a range of turbine outputs and the configuration of the unit, i.e., the type
of driven equipment, will also influence the volume required.
Such large volumes of oil are used to provide adequate
time for the release of air from the bulk liquid in the tank.

Heat from shaft/bearing housing


(power output/duty cycle)

Lube oil inlet temperature

Lube oil vapour/air to


secondary breather

i
i

Heat from seal air


(on external housing
and internally into bearing)
- compression ratio
- take-off point in compressor

Lube oil outlet temperature


hot air to drain
- flow rate
- thermal conduction
- specific heat
- density

Heat transferred along


shaft or via housing
FIG. 6Heat input and removal for a gas turbine bearing.

CHAPTER 12: TURBINE LUBRICATING

OILS AND HYDRAULIC FLUIDS

305

TABLE 1Typical operating conditions for turbine lubricating oils.


Turbine Type

System Property

Medium-Large Steam
(250-1500 MW)

Small Industrial Gas


(1-14 MW)

Medium-Large
Industrial Gas
(30-300 MW)

Lube system capacity (m^.)


Circulation rate (changes/hour)
Bulk e u i d temp. (C)
Bearing oil return temp. (C).

19-115
5.5-10
60-65
70

1-3
17-21
50-70"
60-115

15-34
6-10
45-80"
55-85

Aeroderivative-Gas
Aviation
Industrial
(11 000-110 000 lb. thrust)
(31 MW)
0.006-0.02
60-240
60-70
120-130

0.9
5
ISO""
150-180

Marine
(4MW)
0.11
60
70
150

''The bulk fluid temperature In the tank may be similar to bearing return oil temperature if the cooler is placed on the pressure side of the pump. In this case
the bearing oil supply temperature will be significantly lower than that in the tank.

Much smaller volumes and higher circulation rates are found


in small industricd and aero-derivative gas turbines (Table 1)
because of restrictions on space and weight.
The volume of hydraulic fluid in steam turbines similarly
varies from about 1 m^ to 20 m^ depending on system design
and pressure and is substantially smaller in gas turbines. With
the emphasis on reducing costs, the size and volume of hydraulic systems have been steadily decreasing, but at the expense of increasing pressure. Today, system pressures range
from 40-160 bar, but are starting to increase to 200 bar.
Some of the operating conditions under which lubricating
oil is used in the different tjqjes of equipment are given in
Table 1. The data given is representative of the major applications and equipment but cannot possibly encompass all the
equipment variations currently available. However, with respect to the impact of these conditions on fluid life, the following generalizations can be made:
For steam turbines, the life of mineral oil and synthetic hydrocarbon ranges from 5-25 years (up to the life of the turbine) while currently averaging about 12 years.
For industricd gas turbines, the lives vary between 1.5-6
years, but for new generation combined cycle gas turbine
(CCGT) applications, operating lives to date are in the region
of about 4-5 years. In aviation gas turbines, the synthetic ester oil is continually made up and therefore the whole charge
is not normally replaced. In industrial applications it may be
changed annually or after 8000 operating hours.
For both fire-resistant hydraulic fluids and lubricants the
latest data suggests lives of 5 years to more than 20 years
depending on the type of in situ conditioning or purification used.

TURBINE OIL TYPES AND THEIR


FORMULATION
While the turbine oil market used to be almost exclusively the
domain of solvent-refined paraffinic mineral oils, the changing technical requirements have resulted in a move to other
types of lubricants, both hydrocarbon-based and sjrnthetic.
For example, in industrial gas turbines and combined cycle
units, the high operating temperatures have resulted in a reduced life for products based on solvent-refined oils. Lives of
a "few thousand" hours for such oils in high stress situations
have been reported [31,32] and replacement by special "GT"
oilsin reedity hydrocracked oilsincreases the operating
life up to 50000 h [31].
In turbines operating with high temperature steam
(>500C), mineral hydraulic oil has been almost completely

replaced by fire-resistant fluids based on triaryl phosphates


in order to avoid fires arising from oil escaping at high pressure and coming into contact with steam pipes.
The following is a brief summary of the basestock types
and additives currently in use and their advantages/disadvantages. A more detailed account of the different oil types
used in hydraulic fluids and their properties, which is also
largely applicable to turbine oils, is available from other references [33].
BASESTOCKS
Hydrocarbon Oils
Petroleum oils are complex mixtures of many different chemicals and their relative amounts vary considerably from one
crude source to another. The components do, however, fall
into a limited number of categories, principally straight- and
branched-chain saturated hydrocarbons (also known as
paraffins), cyclic saturated hydrocarbons (also known as cycloparaffins or naphthenes), and unsaturated cyclic hydrocarbons (otherwise known as aromatics), examples of which
are shown in Fig. 7. Additionally, small amounts of impurities, consisting mainly of cyclic derivatives of nitrogen, sulfur
and oxygen, and polar materials such as naphthenic acids,
may be present. Fig. 8 shows typical examples of such heterocyclic compounds.
Each hydrocarbon component influences the properties of
base oil to an extent dependent on its concentration (Table 2
[34]). The above impurities are present in solvent-refined oil
in small quantities, typically 0.1-0.5 %, but occasionally in
much larger amounts, and they can also impact the performance of the fluid particularly in terms of stability and lubrication. Much lower amounts of impurities, if any, are present in the hydro treated oils.
The need to quantify the different components in lubricating oils has resulted in the development of several analj^tical
test procedures. Currently these include ASTM D 2425, Standard Test Method for Hydrocarbon T5rpes in Middle Distillates by Mass Spectrometry; ASTM D 3238, Standard Test
Method for Calculation of Carbon Distribution and Structural Group Analysis of Petroleum Oils by the n-d-M Method;
and ASTM D 5443, Standard Test Method for Paraffin, Naphthene, and Aromatic Hydrocarbon Type Analysis in
Petroleum Distillates Through 200C by Multi-Dimensional
Gas Chromatography. While the D 3238 method is easiest to
apply, being based on refractive index, density and molecular
weight, it is more restrictive in its application with limits on
the total ring content and the ratio of aromatics to naph-

306

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Type

n-paraffin

Viscosity index

Structure

high

^Ho

high

CH,
CH,

iso-paraffin

CH,
CHo

CH,

CH

naphthene

moderate

aromatic

low

FIG. 7Typical hydrocarbon structures.

^ - - ^

Dibenzothiophene

^"^^

(High T e m p e r a t u r e Method); ASTM D 2622, Standard


Test Method for Sulfur in Petroleum Products by X-Ray
Spectrometry; or ASTM D 4927, Standard Test Method for
Elemental Analysis of Lubricant and Additive Components
Barium, Calcium, Phosphorus, Sulfur a n d Zinc by Wavelength-Dispersive X-Ray Fluorescence Spectroscopy.
In order to provide general guidance on the identification
and selection of lubricants, ASTM has issued D 6074, Standard Guide for Characterizing Hydrocarbon Lubricant Base
Oils. This document recommends methods for analyzing the
composition of base oils, describes their important chemical
properties, and discusses the toxicological requirements, including regulations covering the presence of undesirable
components such as polynuclear aromatics.

Conventional Solvent-Refined Types


Pyrrole

1,7- phenanthrone

FIG. 8Impurities typically present in solvent refined mineral oils.


thenics. The levels of impurities such as nitrogen and sulfur
are not available from these tests and this information has to
obtained from other procedures, e.g., ASTM D 3228, Standard Test Method for Total Nitrogen in Lubricating Oils a n d
Fuel Oils by Modified Kjeldahl Method and ASTM D 1552,
S t a n d a r d Test Method for Sulfur in Petroleum Products

In order to produce oils that meet industry requirements it is


necessary to remove or substantially reduce the level of those
components that adversely affect performance, and this has
been achieved by various refining techniques. As indicated
above, the oil produced by the solvent refining of a crude
paraffinic basestock (Fig. 9 [34]) is still in major use for both
steam and industrial gas turbine applications. In this basestock, about 45-60% of hydrocarbons are in the form of saturated straight- or branched-chain paraffins and monocycloparaffins, but there is still a significant a m o u n t of

CHAPTER 12: TURBINE LUBRICATING OILS AND HYDRAULIC FLUIDS 307


TABLE 2Effect of composition on base stock properties.
Chemical Component
n-Paraffin
Iso-Paraffin
Naphthene
Aromatic
Polar compounds

Viscosity
Index
Very High
High
Low
Low
Low

Pour Point
(High/Low)
High
Low
Low
Low
Low

Response to
Antioxidants
Good
Good
Good
Some poor
Poor

Oxidative Stability
Good
Good
Average
Average/poor
S is antioxidant; N and O
are pro-oxidants

Volatility
(High = Poor,
Low = Good)
Good
Good/average
Average
Poor
Poor

ReprintedfromHandbook for Hydraulic Fluid Technology, 2000, p. 716, courtesy of Marcel Dekker Inc., NY.

Crude oil

Dewaxing

Solvent extraction

Atmospheric/vacuum
distillation

Conventional
base oil

Gas oil

Wax

Extract

FIG. 9Solvent refining process. Reproduced with permission of Petro-Canada


Lubricants, Mississauga, Canada.
TABLE 3Chemical composition of lubricant base oils.
Oil Reference

API Category

II

II

II

III

III

Description

I
Solvent
Refined

Solvent
Refined

Hydro-Cracked

Hydro-Cracked

Hydro-Cracked

Dewaxing

Solvent

Solvent

Solvent

Solvent

Iso-

Solvent

Iso-

Mass Spec. Analysis


Paraffins, n- & isoMonocycloparaffins
Polycycloparaffins
Aromatics
Thiophenes
Paraffins -1Monocycloparaffins

25.7
20.8
27.9
24.9
0.7
46.5

29
25
31.7
14.2
0.1
54

23.7
30.8
39.1
6.4
0.0
54.5

21.6
32.8
37.6
8
0.0
54.4

30.2
30.5
35.3
4
0.0
60.7

32.6
34.2
32.9
0.6

76.1
14.7
9.2

66.7

90.8

Severely
Hydro-Cracked

Severely
Hydro-Cracked

Reprinted with permission of Petro-Canada, Mississauga, Canada


unsaturated ring structures (Table 3 [35]). The refining process removes wax (mainly high molecular weight paraffinic
compounds), most of the aromatic hydrocarbons, as well as
some of the polar compounds containing oxygen and nitrogen, products that would otherwise have significantly reduced the stability of the oil. However, small amounts of sulfur-containing c o m p o u n d s , e.g., thiophenes, r e m a i n and
these can be beneficial in terms of increasing the stability of
the base.
These basestocks are classified as Group 1 products by the
API Classification of Base Oils according to their viscosity index, sulfur content and the content of saturated hydrocarbons (Table 4 [36]).

Hydrocracked/Hydrotreated Basestocks
In view of the demand from industry for oils with better oxidation stability, as operating conditions become more severe,
attention has turned to processes that can remove yet more

TABLE 4American Petroleum Institute classification


of base-stocks.
Base Stock
Sulphur,
Saturates,
Viscosity
Group
(wt%)
(wt.%)
Index
Group I
>0.03
and/or
<90
80-120
Group II
<0.03
and
>90
80-120
Group III
<0.03
and
a90
>120
Group IV
All Poly-Alphaolefins (PAOs)
Group V
All Basestocks not included in Groups I-IV
of the aromatic content and the residual impurities. Since the
mid-1980s, therefore, oils produced by hydrotreating, hydrocracking or hydro-refining processes, involving the reaction
of hydrogen with the feedstock in varying degrees of severity,
have resulted in the availability of much purer basestocks
(Table 3 [35]). Using the API Classification [36] these fall into
Group II (mildly hydrocracked) or Group III (severely hydrocracked or hydrotreated) depending on the low sulfur levels
and increasing viscosity indices (Table 4).
In addition to the hydrogenation of the lubricant feedstock.

308

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

the process m a y also include hydro-isomerization of the


straight-chain paraffinic components of the wax removed
during solvent refining or hydrotreating (Fig. 10) [37]. This
process involves a molecular rearrangement and converts the
straight chain hydrocarbons to branched-chain or iso-paraffins that are then blended into the hydrotreated basestock to
give better low temperature properties.
As a result of the different processes, a range of improved
basestocks is currently available with which to formulate turbine oils. These are sometimes referred to as High Viscosity
Index (HVI) oils, which are classified as Group II products;
Very High Viscosity Index (VHVI) oils (Group III); or Ultra
Pure Base Oils (also Group III products). Levels of aromatics,
sulfur, etc., decrease significantly on moving from Group I to
Group III products but significant variability in composition
still exists within these groups [35]. Group II products appear
currently favored for formulation purposes but with a slight
trend towards Group III.
The technical advantages of the new basestocks [32,38] include:
Excellent oxidation stability when formulated
High thermeJ stability
Very low deposit-forming tendency
Improved demulsibility
Reduced volatility
Very low toxicity
Environmentally "friendly"
There are few technical disadvantages of these new basestocks but, depending on the level of hydrotreating, they m a y
be less oxidatively stable compared with solvent-refined products in view of the removal of small amounts of sulfur and aromatic compounds that act as naturally occurring stabilizers.

This is, however, more than compensated for by better response to antioxidants when carefully selected [32,37]. The
loss of aromatics also results in reduced additive solvency necessitating a careful choice of stabilizers emd the continued
presence of small amounts of aromatics may be beneficial in
such cases [39]. The loss of sulfur also reduces the antiwear/extreme-pressure properties of these oils although these
can easily be improved by incorporating suitable additives.
These base materials vary in price from a level which is
comparable to that of solvent refined stocks to about three
times their price, depending on material type a n d local availability. As a result of the favorable price/performance characteristics it is likely that their use in conventional turbine oil
formulations will spread.

Polyalphaolefins (PAOs)
These synthetic fluids are normally m a n u f a c t u r e d by the
oligomerization of Eilpha-olefins, particularly a-decene, but
also by a-octene and a-dodecene and, until recently, were
available in a range of viscosities u p to the ISO 100 grade. The
latest development [40] reports the availability of very high
viscosity products ranging from 150-3000 cSt at 100C and
intended mainly as blending components for other hydrocarbon oils. They are currently more expensive than other hydrocarbon types.
PAOs are free of aromatic hydrocarbons, sulphur, oxygen,
and nitrogen compounds, and show excellent response to antioxidants [41], although they are now being challenged by
some of the severely hydro-cracked oils [42]. They also have
high viscosity indices (as assessed by ASTM D 2270, Standard Practice for Calculating Viscosity Index from Kinematic

H,
I

Atmospheric/vacuum
distillation

n.,,i

H2
I

- >
Ultra pure
base oils
Crude
oil

Atmospheric/vacuum
distillation

HTU = hydrotreatment unit

"Wax

HTU2

Hydro
Isomerization

FIG. 10Hydrotreatment plus hydroisomerizatlon process. Reprinted with permission


of Petro-Canada Lubricants, Misslssauga, Canada.

CHAPTER 12: TURBINE LUBRICATING OILS AND HYDRAULIC FLUIDS

309

TABLE 5A comparison of some physical properties of 6.0 cSt PAOs with solvent-refined and hydrocracked oils of similar viscosity.
Parameter

Test Method

API Group
Viscosity, cSt
at 100C
at 40C
at - 4 0 C
Viscosity Index
Pour Point (C)
Flash Point (C)
Evaporation Loss
(NOACK), %

ASTM
D445

ASTM D 97
ASTM D 92
DIN 51581

PAO
IV
5.98
30.9
7830
143
-64
235
6.1

160
Hydro-Treated

240
Neutral

200
Solvent Neutral

II

5.77
33.1
SoUd
116
-15
220
16.6

6.98
47.4
SoUd
103
-12
235
10.3

6.31
40.8
Solid
102
-6
212
18.8

Very High Viscosity


Index Oils
III
III
5.14
24.1
Solid
149
-15
230
8.8

5.9
NA
127
-12
225
6

NOTEReprintedfrom:Synthetic Lubricants and High Performance Functional Fluids, 1992, p. 13, courtesy of Marcel Dekker Inc., NY.
Viscosity at 40C and 100C) and flash points (by ASTM D 92,
Standard Test Method for Flash and Fire Points by Cleveland
Open Cup); very good low temperature viscosities (ASTM D
445, Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids) and p o u r points (ASTM D 97,
Standard Test Method for Pour Points of Petroleum Products), and a wide operating temperature range [42]. A comparison of the physical properties of PAOs with other hydrocarbon products of the same viscosity is given in Table 5 [43].
In view of the lack of aromaticity, additive solubility can be
a problem. PAOs also have limited dispersency and do not
penetrate rubber seals to cause swelling (as assessed by FEDSTD-791, methods 3604 and 3633, or by ISO 6072). As aresult,
it is necessary to blend PAOs with small a m o u n t s of a sealswelling agent (usually a carboxylate ester) to avoid leakage.
PAO-based gas turbine oils have been available for many
years [39] where the higher prices could be justified in terms
of smaller volume and better stability. They have not, as yet,
m a d e a n y significant penetration of the steam turbine oil
market [41].

Synthetic Ester Fluids


Apart from the very early days of operation, carboxylate or
synthetic esters (possibly in c o m b i n a t i o n with polyglycolether thickeners) have been the only products used for the
lubrication of aero-derivative gas turbines in aviation applications. This market, like the others, is fragmented into different applications, this time in terms of the lubricant requirements of the turbopropeller, turbofan (civil) or turbojet
(principally military) engines (Table 6) and into the different
technical requirements of civil and military aircraft operation. The turbopropeller engine, for example, employs a reduction gear to accommodate the propeller. This necessitates
the use of a higher viscosity fluid to provide a thicker lubricating oil film with the ability to reduce wear at heavy loads.
At the other end of the spectrum, the military requirement to
start an engine quickly at low temperatures requires the use
of "lower" viscosity oils for turbojet engines. As a result, specifications for these oils currently cover four viscosity levels: 3,
4, 5, and 7.5 cSt at 100C.
Diesters, the lowest viscosity oils used in this application,
were introduced after the World War II, initially for military
applications. They were also used for the early commercial
turbo-jets and in blends with polyglycolethers, for turbopropeller aircraft [24,26]. Diesters are produced by the reaction
of an alcohol and an acid [44], viz

TABLE 6^Aviation lubricant types currently


commercially available.
Engine Type
Turbo-propeller
Turbofan
Turbojet

Engine Lubricant Composition


Diester -I- Thickener
'High' Viscosity Polyol Ester
'Low-Medium' Viscosity Polyol Ester

TABLE 7A comparison of minersil oil and


carboxylateester properties.
Mineral

Mineral
Lubricant

Oil

Ester

Oil

Kinematic viscosity
(cSt)at210F
2.5
3.3
-40F
3000
1700
-65F
25 000
11000
Viscosity Index
75
154
Pour Point ("F)
<-75
-80
Vapor Pressure
(psi) at
250F
0.15
350F
<0.01
1.3
400F
3.5
0.016
0.52
550F
Ryder gear machine
600
2000
failure load lb/in.
tooth face width
Flash point
295
430
(COC, ''F)

20.1
Solid
Solid
95
0

<0.01
0.065
-3000

485

Ester
7.5

12 000
Solid
150

-65

<0.01
0.28
3200
465

NOTEReproduced with permission of Elsevier Science, Oxford, UK.

2ROH -1^ HOOC(CH2)nCOOH


alcohol
diacid

ROOC(CH2)nCOOR
diester

where, for aircraft turbine oils, n = 7-8 and R = Cs-g straight


or branched chain
The resulting diesters have a viscosity of about 3 ^ . 5 cSt at
100C (ASTM D 445). In comparison with a well-refined mineral oil these products have a similar thermal and oxidative
stability, better load-carrying performance, lower volatility
(ASTM D 972, Standard Test Method for Evaporation Loss of
Lubricating Oils and Greases) and a m u c h wider operating
temperature range (see Table 7 [45]). They are also very responsive to the addition of antioxidants. They do, however,
slowly hydrolyze in the presence of water and, like most esters, are not compatible with n e o p r e n e seals, w h i c h are
widely used with mineral oil.
The introduction of more highly-powered engines operating at higher temperatures and the requirement in com-

310

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

mercial applications for extended drain intervals necessitated the development of more stable products, and the socalled "polyol" or "hindered" esters were introduced at the
beginning of the 1960s [24]. These esters, based on the reaction products of neopentylglycol, trimethylolpropane, or
pentaerythritol with monobasic acids as shown in the reaction scheme below, have thermal degradation temperatures
about 40C higher than the diesters and are more oxidatively stable [46]. They have since been the basis for all commercial engine lubricants and an increasing proportion of
military requirements where low temperature limitations
permitted.
C2H5

I
C2H5
3RCOOH + HOH2CCCH2OH -^
I
I
RCOOH2C CCH2OOCR
CH2OH
I
CH2OOCR
monoacid
trimethylopropane
ester
CH2OH
I
CH2OOCR
4RCOOH + HOH2CCCH2OH +
I
I
RCOOH2CCCH2OOCR
CH2OH
I
monoacid
pentaerythritol
CH2OOCR
ester
where R = C5_^9
The continual pressure on equipment builders to increase
engine power in both military and civil applications has resulted in a need to periodically review and, where necessary,
improve the stability (oxidative and thermal) and deposition
performance of these oils. New versions of specifications, normally calling for improvements in these areas, have appeared
at intervals of a few years, particularly in the military arena.
That continual improvements in oil performance have been
possible is due to the skills of the formulators and the availability of more effective additives [47]. The impact of changes
in additive and basestock composition on oil stability is
shown in Fig. 11 [48]. In the oxidation test from which the
data has been taken, the B^^'^ temperature is the temperature
at which the insoluble content of the oil exceeds 0.5mg/g over
an 8-day test period when the oil is oxidized in the absence of
metals, and is used as a measure of bulk oil stability. The data
shows the initial performance level of diesters in the 1950s followed by improvements to the stabilizer package; the development of more stable fluids (the hindered or polyol esters)
followed by yet more additive developments. More information on the various additive t3^es in use and their function is
given in the following section.
Long chain polyol esters have also been promoted as "less
flammable" hydraulic fluids for steam turbine control systems on account of their relatively high flash and fire points.
The esters used in this application are normally reaction
products of trimethylolpropane and oleic acid (a C18 unsaturated monobasic acid) and in some respects, are significantly
different to the short-chain products used in aviation gas turbines oils. For example, they are far less stable due to the unsaturation (or the presence of double bonds) in the molecule
and their low temperature properties are inferior. When sold

as fire-resistant fluids they contain a polymeric thickener


(also known as a viscosity-index improver), which increases
the droplet size in a spray. This reduces the surface area accessible to oxygen and renders the fluid more difficult to ignite under spray test conditions (combustion is an oxidation
process). However, as the polymer breaks down due to the
shearing action in p u m p s and gears, this advantage is lost
and the viscosity (and hence fire-resistance) tends toward
that of the basestock. This temporary improvement in fire-resistance is limited to spray flammability and has no impact
on the ignitability of the fluid under other hazard conditions,
e.g., when it contacts a hot surface [49]. This is therefore an
artificial approach which, to date, has been rejected by the
major turbine builders for new large steam turbines, although small amounts are used in industrial units and in refurbished equipment. A comparison of the fire resistance
properties of mineral oil, polyol esters, and phosphate esters
is given in Table 8.

Tiiaryl Phosphates
In common with the other two groups of fluids there are variations in the chemistry of triaryl phosphates that have led to
the commercial availability of different products. In this
case, however, it has been the past limitations on suitable
raw materials that has resulted in the diversity of products
available. Traditionally, phosphate esters were manufactured
from the distillation products of coal tar, which were mixtures of cresols and xylenols and known collectively as "cresylic acids." The phosphate esters produced from these feedstocks were referred to as "natural" products and were chiefly
tricresyl and trixylyl phosphate (TCP/TXP). When natural gas
became widely available, the distillation of coal tar rapidly
declined and attention turned to the production of phosphate
esters from synthetic feedstocks, specifically those based on
alkylated phenols [50]. The reaction scheme for the manufacture of triaryl phosphates, is given below:
ArOH +

POCls^

a phenol

phosphorus
oxychloride

(ArOsPO

3HC1

a triaryl
phosphate

The reaction of propylene or butylene with phenol produces mixtures of alkylated phenols and these became the
feedstocks for a range of "synthetic" phosphates with viscosities falling into ISO VGs 22-100. Since their introduction, the
raw material supply position for the production of the "naturcil" fluids has eased with the introduction of synthetic processes for the production of cresols and xylenols. As a result
the distinction between "natural" and "synthetic" phosphates
has become blurred but the terms are still used today to distinguish between TCP/TXP and the synthetic products based
on isopropylphenols and tertiarybutylphenols.
Although manufactured to the same viscosity level, commonly ISO VG 32 or 46, commercially available fluids do
have somewhat different levels of performance relative to one
another as indicated in Table 9. Therefore, depending on the
requirements of the application, one type of phosphate may
be preferred. For example, in steam turbines where contact
with water is most likely, the phosphate that is most hydrolytically stable, trixylyl phosphate, may be preferred. In

CHAPTER 12: TURBINE LUBRICATING OILS AND HYDRA ULIC FLUIDS 311

Ester limit?

Additional additive effect

Additive effect

1950

1960

1970

1980

1990

2000

year
FIG. 11Developments In the stability of gas turbine lubricants. Reprinted with permission of B. Rayner, consultant.

TABLE 8^A comparison of the fire-resistance properties of mineral turbine oil, polyol ester, and phosphate ester fluids.
Phosphate Ester
Polyol Ester
Mineral Oil
Property
Test Method
ISO VG 46
ISO VG 68
ISO VG 46
270
258
ASTM D 92
220
Flash point-COC (C)
ASTM D 92
245
316
350
Fire point ( X )
ASTM D 2155
340
425
580
Autoignition temperature (C)
Hot manifold ignition (C)
AMS 3150C
350
430
>800
ISO 14935
Fail
Fail
Pass
Wick ignition
MIL-PERF-19457D
Compression ignition
-Ignition ratio
10
>42
Spray ignition
-Persistence of burning
F.M. Std 6930
Fail
Pass
Pass
Group 3 (worst)
Group 1-2
Group 1
F.M. Std 6930
- S p r a y Flammability Parameter
-Persistence of burning
ISO 15029-1
Fail
Pass
Pass
Class H (worst)
Class H
Class D/E
ISO 15029-2
-Ignitability Parameter

312 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 9Impact of chemical composition on phosphate ester
performance.
Phosphate Type
Trixylyl
phosphate
Tritertiarybutyl
phenyl
phosphate
Triisopropyl
phenyl
phosphate

Fire
Resistance

Oxidation
Stability

Good

Good

Good
Moderate

Hydrolytic
StabiUty

compares the principal physical properties of an ISO VG 46


mineral turbine oil and triaryl phosphate ester.

Air Release
Excellent

Excellent

GoodExcellent
Poor

Moderate

Moderate

Moderate

Moderate

TABLE 10^A comparison of some typical properties of an


ISO VG 46 mineral turbine oil and phosphate ester
hydraulic fluid/lubricant.
Mineral
Phosphate
Oil
Ester
Test Method
Property
Kinematic viscosity
ASTM D 445
(cSt) at
100C
6.7
5
40''C
46
43
0C
450
1700
-9
Pour point (C)
ASTM D 97
-20
0.15
Acid number
ASTM D 664
0.05
(mg KOH/g)
Specific gravity
0.87
ASTM D 1298
1.135
(20/20C)
Air release (min)
ASTM D 3427
3
1
Foaming tendency/
250/0
ASTM D 892
30/0
stability at
24C (ml)
Water content (%)
ASTM D 1744
0.001
0.06
Rust preventing
Pass
ASTM D 665
Fail
characteristics
(distilled water)
Thermal conductivity
0.134
0.134
(W/mK)
Specific heat at 20C
(J/gK)
1.76
1.69

gas turbines, high oxidative stability is needed and hence a


tertiarybutylphenyl phosphate could be selected. These latter
fluids are at least as oxidatively stable as the best hydrocarb o n oils available and do not normally require antioxidants
[27].
The m a i n reason for selecting phosphates is, of course,
t h e i r fire resistance. While they are n o t completely nonflammable (most organic materials will ignite in the presence
of sufficient energy) they do require a substanticilly greater
energy input for ignition than hydrocarbons and most other
non-aqueous fluids in commercial use, and they are self-extinguishing once they have moved away from the ignition
source. Additionally they are excellent lubricants as demonstrated in p u m p tests, e.g., ASTM D 2882, Standard Test
Method for Indicating the Wear Characteristics of Petroleum
and Non-petroleum Hydraulic Fluids in a Constant Volume
Vane Pump, and have very low volatility in the ASTM D 972
test procedure. Viscosity/temperature properties are, however, poor [51]; they have a significantly higher density than
oil and require more power for circulation. As with all esters
they are sensitive to moisture and require different seals and
paints to those used with conventional turbine oils. Table 10

ADDITIVES AND THEIR EVALUATION


Additives play an important part in improving the performance
of all the above fluid types, but no more so than with the aviation esters. As the composition of the aviation lubricant basestocks has remained stable for many years, the improvements in
performance have arisen principally as a result of developments in additive technologyparticularly in oil stabilization.
In comparison, major improvements in hydrocarbon oil stability have been due to improvements in refining techniques and
additive response rather than to breakthroughs in additive
technology. The move from Group I to Group III has, for example, resulted in a substantial increase in oxidation stability
for the same level of antioxidant (Table 11 [52]).
While some additives, for example stabilizers, can be of
benefit in phosphates, these fluids are also used uninhibited.
As will be seen later, in situ conditioning techniques are used
with phosphates to remove degradation products as they are
formed and this can remove the need for stabilizers. However, corrosion and rust inhibitors are normally highly polar
products that would be removed by the conditioning medium
(tj^ically an activated clay) and therefore cU"e not usually recommended. Fortunately phosphates, as polar materials, have
some inherent rust preventative performance as they tend to
be adsorbed on to the metal surface and there form a "barrier" to water. Some of the acidic degradation products are
also effective inhibitors. As a result rusting of the system is
not normally a problem except where wetting of the surface
does not occur.
Phosphate esters are good lubricants and are widely used
as antiwear additives in hydrocarbon oils. It is therefore not
usually necessary to improve this aspect of the performance
of fire-resistant fluids.
Typical additive packages designed to meet turbine lubricating and hydraulic oil specifications, whether for hydrocarbon or synthetic ester-based fluids, are less complicated
than, for example, automotive engine oils and would contain
a balanced mixture of antioxidants, metal passivators, rust,
and corrosion inhibitors, anti-wear and/or extreme pressure
additives, and possibly an antifoam. These types and the various methods used for their evaluation in turbine oils and fluids are now considered in more detail.

Antioxidants
The actual mode of oxidative decomposition of both hydrocarbon a n d synthetic oils is a complex process involving
many different mechanisms a n d a variety of intermediate
products depending largely on the temperature and the structure of the substrate. Fig. 12 [52] is a model of lubricant
breakdown at high temperatures, concisely illustrating the
different processes involved.
Antioxidants are chemicals that extend the life of the fluid
by interrupting the oxidation process, e.g., by decomposing
hydroperoxide intermediates (ROOH, where R is an alkyl
chain) and scavenging free radicals [52]. In the past the dominant stabilizer type for hydrocarbons in both automotive

CHAPTER 12: TURBINE LUBRICATING OILS AND HYDRAULIC FLUIDS 313


TABLE 11Comparison of oxidation stability of turbine oils formulated with two different antioxidants
in a hydrotreated and solvent neutral base stock.
Test fluids

H O / ( ^ V - R-S-R1

0.25%

0.25%

mw = 492

0.25%

HO/QV-CH3

0.05%
balance

Corrosion inhibitor
Mineral oil
Oxidation stability
TOST (ASTM D 943)
(95C; water, Fe and Cu catalysts; 3 L air/hour)
- t i m e to total acid n u m b e r of 2.0 mg KOH/g oil
-sludge (mg) (ASTM D 4310)
Basestock characteristics
ISOVG
CA (aromatic hydrocarbon)
Sulfur

4300
6

0.05%
balance

2400
39

0.25%

0.05%
balance

2200
28

hydrotreated
32
0
0

%
%

1100
47
solvent neutral
32
6.5
0.54

NOTEReprinted from: Chemistry and Technology of Lubricants, courtesy of Kluwer Academic Publishers, Dordrecht, The Netherlands.

volatile low molecular


weight hydrocarbons

- volatile low molecular


weight oxidation products
- carbon dioxide
- carbon monoxide

volatile
hydrocarbon
fragmentsi

0.05%
balance

air (with/without metal)

polycondensation
polymerisation
(with/without metal)

high molecular
products

polycondensation
polymerisation

sludge

FIG. 12Model of lubricant degradation under high temperature conditions. Reprinted


with permission of Kluwer Academic Publishers, The Netherlands.

314

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

and industrial oils has been a zinc dihydrocarbyl diphiophosphate (Fig. 13). This is a multi-functional additive in that
it also possesses antiwear/extreme pressure properties and
under certain conditions can provide protection against "yellow" metal corrosion. Different types of zinc dialkyldithiophosphates (or diaryl) are available depending on the alcohol
or phenol used in their manufacture, and the hydrocarbyl
group present strongly influences their activity; the greater
the thermal stability of the product, the lower the antioxidant
activity [33]. There is, however, a move away from this tj^e
of antioxidant in turbine oils and hydraulic oils as the thiophosphates are sensitive to moisture and the hydrolysis products, (zinc oxide and hydroxide), can precipitate. Some tur-

RO

bine builders are therefore placing strict limits on the zinc


content of approved oils, and so-called "ashless" antioxidants
are being used in their place. These are either hindered phenols or aromatic amines (Fig. 13) that are used separately or
in combination [53].
The antioxidant most widely used in turbine oils in the past
was 2,6-ditertiarybutyl-p-cresol (also known as BHT). While
it is still featured in some turbine oil formulations on account
of its relatively low cost and good efficiency, its high volatility and solid form has lead to its replacement by higher
molecular- weight products, preferably those that are liquids
for ease of blending. Although, in general, aromatic amines
tend to be more active than hindered phenols across the tem-

OR

where R is typically C3 - Cg

\ .
Zn

OR

zinc dialkyldithiophosphate

2, 6 - ditertiarybutyl - 4 - methylphenol (BHT)

O
CH2CH2C OR

where PL is Cg-Cig

long-chain esters of substituted hydroxybenzenepropionic acid

where R is C4-C9

dialkyldiphenylamine
FIG. 13The structure of some common turbine oil antioxidants.

CHAPTER

12: TURBINE

perature spectrum [52], there are exceptions. Some hindered


phenols are excellent high t e m p e r a t u r e antioxidants, but
even these can be outperformed by certain amines or S3Tiergistic mixtures of amines and phenols [52]. However, radical
scavenging efficiency is not the only criterion used in selecting an antioxidant. Cost is obviously important as are the tendencies of amines to color the basestocks in which they are
used and also because they are more likely to form deposits
during oxidation. The type of mineral oil basestock, e.g..
Group 1 or Group 2, etc., can also influence the choice of antioxidant as hindered phenols are preferred in oils with a low
aromatic and low sulfur content.
Synergism is also displayed between radical scavengers
and hydroperoxide decomposers, for example a r o m a t i c
amines are used with phenothiazine derivatives (a sulphurcontaining antioxidant) in aviation turbine oils. Table 12
shows the synergism between an amine antioxidant and an
organosulfur hydroperoxide decomposer [52].
The superior performance of aromatic amines, particular
the alkylated derivatives [52], at high temperatures has resulted in their exclusive use in aviation gas turbine oils. Here,
in addition to their efficiency in reducing fluid viscosity increase and acidity development (which are the two most
c o m m o n parameters used in assessing oxidation stability),
they have been able to control deposit formation on hot surfaces. This is important because it is more likely that an engine failure would take place as a result of deposits them as a
consequence of a rise in viscosity and acidity, especially as
the aero-engine oils are topped-up so frequently.
Other stabilizers, for example phosphites, which are used
in some oil applications as sjTiergists with hindered phenols,
are not used widely in general industrial turbine oils, possibly because these materials are usually very sensitive to the
presence of moisture with the resulting development of acid.
They have been used in aviation gas turbine oils where the
temperatures would limit the water level in the fluid, but as
extreme pressure additives rather t h a n as antioxidants.
The activity of antioxidants is normally assessed, as indicated above, by their effect in minimizing the physical
changes that occur in oil on oxidation, i.e., an increase in viscosity and the development of acidity and sludge. In tests
where metals are present, either to catalyze the oxidation or

TABLE 12Oxidation stability of a lubricant stabilized with a


synergistic antioxidant combination.
Test Fluid
Alkylated diphenylamine
S(CH2CH2COOR)2
Rust inhibitor
Basestock

Oxidation Stability
TOST (ASTM D 943)
(95C; water; Fa and Cu
catalyst 3 L air/h) time (h)
to total acid number of
2 mg KOH/g
sludge (mg) (ASTM D 4310)
Basestock characteristics

0.25%
0.05%
balance

0.25%
0.05%
balance

2000

200

0.2%
0.05%
0.05%
balance
3300

172

>5000
89
ISO VG 32
CA (aromatic carbon) = 6.5%
S = 0.54%

NOTEReprinted from Chemistry and Technology of Lubricants, courtesy of

Kluwer Academic Publishers, Dordrecht, the Netherlands.

LUBRICATING

OILS AND HYDRAULIC

FLUIDS

315

to represent the materials of construction of the system, measurements are also made of the weight changes of the metal
specimens. Oxidation is accelerated by holding the fluid at a
high temperature in the presence of air, which is usually bubbled through the sample at a fixed rate. In some tests, particularly for steam turbine oils, water is also present to represent the effect of c o n t a m i n a t i o n t h a t is a fairly c o m m o n
occurrence in this application. The use of water can limit the
temperature of the test in order to avoid loss due to volatility.
It can also preferentially solubilize acids that are generated in
the oil on oxidation and, if present as a separate layer, may
remove t h e m from the oil so reducing their impact o n oil oxidation and acidity measurements. On the other hand the water will promote rusting and the generation of sludge and
may also result in the partition of some additives into the water layer.
The oxidation tests that are used to assess stability of turbine oils fall into two categories; those which use water to accelerate the testing and/or make the test more representative
of service, and those where the fluid is tested "dry." In spite
of the fact that gas turbine oils are used at higher temperatures than steam turbine oils and that service conditions are
generally drier, "wet" tests are also used for evaluating the
stability of these productsthough sometimes in combination with a dry test. The two principal tests used today for assessing the stability of inhibited turbine oils are indicated below.
1. ASTM D 2272, Standard Test Method for Oxidation Stability of Steam Turbine Oils by Rotating BombIn this
test (also known as the RBOT test), the fluid, water and a
copper catalyst are contained in a glass vessel. This is
placed in a pressure vessel equipped with a gauge or other
means of monitoring the change in internal pressure. The
"bomb" is charged with oxygen to a pressure of 6.2 bar (90
psi) and heated to 150C. The time taken for the pressure
to fall by 1.75 bar (25.4 psi) is monitored and recorded as
the life of the sample. Fig. 14 shows the b o m b and it's component parts while Fig. 15 shows a typical pressure chart
after a test. This is a highly accelerated test that is normally
completed well within 24 h. It does not represent what
happens in practice as the pressure prohibits the antioxidant (and water) from volatilizing. However, it is maintained that it shows good correlation with service [54]. It is
also widely used in fluid development as a screening test
for quality control purposes and in monitoring the stability of used fluid. Typical limits on mineral turbine oil
would be >350 m i n for ISO 32 or 46 grade products
(ASTM D 4304). Higher values, e.g., > 4 5 0 min are required
by some turbine builders.
2. ASTM D 943, Standard Test for Oxidation Characteristics
of Inhibited Mineral Oils, also known as the TOST (turbine
oil stability) test, is the second principal test for steam turbine oils. This involves heating the fluid together with water at 95C in the presence of iron and copper catalysts,
while air is passed through. At regular intervals the acid
n u m b e r in the fluid is measured and the test terminated
when the level reaches 2.0 mg KOH/g. In contrast to the
RBOT procedure, and depending on the base stock and activity of the stabilizers, this test can take several thousand
hours to complete. Minimum requirements for ISO 32/46
viscosity grades are normally 2000-2500 h. Fig. 16 shows

316 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

FIG. 14A view of the ASTM D 2272 pressure vessel, recorder, and sample container with catalyst.

FIG. 15Typical chart recording pressure changes in the RBOT test.

CHAPTER 12: TURBINE LUBRICATING


the arrangement of fluids and metal specimens in the oxidation cell used for this test.
As the length of the D 943 method can make product development with this procedure a very time-consuming process, some specifications (e.g., MIL-L-17331) have reduced
the duration to 1000 h but added limits on metal content and
sludge. To meet the requirements for a procedure in which
sludge was determined, ASTM introduced D 4310, Standard
Test Method for Determination of the Sludging Tendencies of
Inhibited Mineral Oils. This procedure utilizes the apparatus
of the D 943 method but after 1000 h the test is concluded
and the fluid filtered through a 5-fim filter in order to determine the weight of sludge produced. Optionally, the change
.'S'^ia
k^

OILS AND HYDRAULIC FLUIDS

317

in weight of the catalyst coil may be measured and, of course,


the increase in acidity may be determined.
Another goal of test method development in this Eirea has
been to find a method that could be used for both steam and
gas turbine oils. Although the FED-STD-791 oxidation test
methods are quite widely used (see below), they are regarded
primarily as tests for aviation oils in view of the types of
metal catalysts used and the high temperatures normally
specified. When these conditions are used with mineral oils,
the results are regarded as "somewhat inconsistent" [54]. For
these reasons, it was eventually decided to specify a dry test
procedure, which involved passing air through the oil or fluid
in the presence of copper and iron catalysts, but at the lower
temperature of 135C. This formed the basis for ASTM D
5846, Universal Oxidation Test for Hydraulic and Turbine
Oils. In this case the acidity and sludge are monitored and the
test is terminated when the acid number reaches 0.5 mg
KOH/g or the level of sludge (determined by rating the deposits left on a filter paper after placing a drop of used fluid
at its center), becomes unacceptable. Since its introduction,
the test has been of particular interest for gas turbine oil development in view of the availability of more stable basestocks.
The stability testing of gas turbine oils, particularly aeroengine oils, has traditionally been at much higher temperatures than for steam turbine oils in view of their more severe
operating environment. Most of the tests used in this area
have been variations on the FED-STD-791, Method 5308,
Corrosiveness and Oxidation Stability of Light Oils, which, in
its original version, involved oxidizing the fluid in the presence of six different metal specimens for 164 h at 120C. A
modified version of this test still features in U.S. Navy specification MIL-PRF-23699F in which test conditions of three
days at 175C, 204C, or 218C are required. Although initially used in the U.S. Air Force specification MIL-L-7808 it
was later replaced by FED-STD-791 method 5307, which has
a test duration of four days and possible temperatures of
248-680F (120-360C) in the presence of seven metal specimens. The test (slightly modified) also features in the latest
USAF specification, MIL-L-27502, for a high temperature engine oil in which conditions of two days at 220C and 232C
are specified. Unlike the 5308 test in which the fluid and catalyst coupons are evaluated only at the end of the test, in the
5307 procedure, fluid samples are taken during the test and
monitored for viscosity and acidity increase. ASTM D 4636,
Standard Test Method for Corrosiveness and Oxidation Stability of Hydraulic Oils, Aircraft Turbine Engine Lubricants,
and Other Highly Refined Oils, was later issued as a combined 5307/5308 method offering three alternative procedures and the ASTM method is now also specified as an alternative to the 5307 procedure in MIL-PRF-7808L.

FIG. 16Metal catalyst, fluid, and water


arrangement in the
ASTM D 943 oxidation
test.

The metal specimens used in the oxidation tests are normally (but not cJways) in electrical contact as this is how they
are found in the system and corrosion is frequently accelerated by bringing together metals of different electrical potential. The arrangement of the metal specimens in the FEDSTD-791, method 5308 and Alternative Procedure 2 in ASTM
D 4636 is shown in Fig. 17.
Mineral gas turbine oils are also tested by a modification of
the 5308 procedure. General Electric, for example, specifies
this method for its high temperature gas turbine oil specifi-

318

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK
bine oils meeting ISO VGs 32 and 46. To increase the test
severity the duration was extended from 3-9 days for most
oils. This resulted in the mineral oils starting to degrade significantly.

Rust and Corrosion Inhibitors

FIG. 17Metal catalyst arrangement used in the FEDSTD-791 method 5308 oxidation test.

cations, GEK 32568 and GEK 101941, which call for a temperature of 175C while reducing the duration to three days.
Because of the importance of deposit formation in aircraft
lubricants, the accurate measurement of the amount of dirt
or sludge produced during the high temperature oxidation
tests is as important a feature of these tests as the generation
of acidity and increase in viscosity.
Oxidation test conditions for phosphate esters tend to fall
between those of mineral oil axid synthetic esters though, because of their tendency to hydrolyze, the tests specified are
dry tests. Typical test conditions are 164 h at 120C in the
presence of copper and iron catalysts (ISO 15595) or three
days at 175C (FED-STD-791, m e t h o d 5308 modified) as
found in b o t h ASTM D 4293, S t a n d a r d Specification for
Phosphate Ester Based Fluids for Turbine Lubrication and
the General Electric specification GEK 28136 for phosphate
ester fire-resistant gas turbine lubricants. Table 13 [27] compares the oxidation stability under stemdard and more severe
FED-STD-791 test conditions of uninhibited butylatedphenyl
phosphate esters and commercially available mineral gas tur-

Rust is a continuing problem in turbines when carbon steel


is present because water contamination of steam turbine oils
and fluids is very difficult to avoid. Acid is also invariably present in degraded oils and this can attack certain metals. Although the engine in aero-gas turbines is usually constructed
of stainless steel or exotic alloys, carbon steel can still be present in the auxiliary equipment and the oil tank.
In order to avoid rusting and corrosion, certain chemicals
have been found to protect the metal surfaces. For steel, such
inhibitors are usually highly polar materials, e.g., organic
acids, esters or amides (Fig. 18), which form an adsorbed
film on the surface of the metal that physically hinders the
transfer of water to the metal surface. This necessitates careful formulation to avoid interaction with other surface-active
materials, such as antiwear additives, and to minimize the
impact on foaming/air release properties. In view of the fact
that many turbines operate in saline environments, rust protection is frequently required against salt water. This is a
more severe requirement than distilled water protection.
Rust inhibitors may also be used in polyol and phosphate
esters. However, the polarity and film-forming tendency of
the latter when uninhibited already offer some protection
against rusting, which is enhanced by acidic degradation
products. If the phosphate is used in conjunction with adsorbent media for controlling the level of acidic degradation
products, careful selection of the inhibitor is required as the
adsorbent solids can remove both acidic and basic additives.
The most widely used procedure for evaluating rust inhibitors is ASTM D 665, Standard Test Method for Rust Preventing Characteristics of Inhibited Mineral Oil in the Presence of Water. This involves stirring together 300 mL of the
fluid and 30 mL of either distilled or synthetic seawater for
24 h at 60C. A cylindrical test specimen of carbon steel is immersed in the mixture and, at the conclusion of the test, is assessed for the amount of rust produced. Ratings vary from a
"pass" where no rust is found, through light rust (<6 spots)
to moderate rust ( < 5 % of the surface is covered by rust), and
to heavy rust ( > 5 % covered). If rusting is going to occur it is
thought that it will appear within the first 4 h of the test and
proposals are currently being considered by ASTM to reduce
the test duration to this period.
In addition to steel, there are other metals that can be attacked by degraded oils and by some additives, such as sulfur-containing extreme-pressure additives. Of these, copper
is by far the most important, not only because of its common
use in system construction but also because it may catalyze
the breakdown of oils and fluids when present as soluble salts
at concentrations of < 4 0 p p m [52]. The mechanism normally
involves acid attack on the metal with the formation of metal
salts, which then dissolve in the oil. However, copper is also
susceptible to attack from sulfur either present in the oil or,
more commonly, released from extreme-pressure additives
as they degrade. This can result in the formation of sulfidecontaining deposits. Fortunately certain types of chemicals

CHAPTER 12: TURBINE LUBRICATING

OILS AND HYDRAULIC FLUIDS

319

TABLE 13--Comparison of the oxidation stability of mineral gas turbine oil with butylated phenyl phosphates
under extended FED-STD-791 test conditions.
Test
Duration
(days)

Viscosity
Increase

ISO VG 32 phosphate
(TBPP)

3
6
9

ISO VG 46 phosphate
(TBPP)

3
6
9

Gas turbine oil A


(ISO VG 32)

3
6
9

3
4.4
3.8
6
6.4
7.3
3.6
4.2
25

Gas turbine oil B


(ISO VG 46)

3
6
9
3
6
9

Fluid

Gas turbine oil C


(ISO VG 46)
Gas turbine oil D
(ISO VG 46)
Turbine industry limits
ASTM D 4293 limits

3
6
3
3

(%)

18.3
24.3
49.5
23.4
28.6
80.6
13.4
21.2
- 5 to +15
- 5 to +20

Acidity
Increase
(mg KOH/g)
0.11
0.37
0.85
0.27
0.33
1
0.44
0.8
5.3
2.2
3.1
5
3
4.5
7
2
5.1
2.5 max
3.0 max

C12H22CH C O O H

Metal Weight Change (mg/cm^)


Fe

Cu

Cd/Fe

Al

Mg

-0.11
0.02
-0.01
-0.01
0.11
-0.04
0.0
0.03
0.14
0.03
0.21
0.56
0.02
0.04
0.18
0.06
0.24

-0.17
0.04
0.1

-0.03
0.02
0.03
-0.01
0.17
0.18

-0.07
0.0
0.0
-0.11
0.08
-0.11
0.0
0.0
0.09

-0.03
0.02
-0.02
-0.02
0.13
0.07

where R, is

0.03
0.29
-0.02
0.02
0.04
0.01
0.08
0.13
0.04
-0.03
-0.1
-0.47
0.02
-0.13

0.05
-0.05
-11.7

0.03
0.03
0.05

0.01
0.03
0.06
0.06
0.07
0.33
0.02
0.01
0.04

-0.04
0.02

0.0
0.52

0.01
0.35

-0.04
0.02
-0.15
-0.1
0.07
0.96

0.05
0.02
0.32

+-CH2CH2O-J-H

I
CH2COOR1

C12H22CH C O O H

where R2 is a polyamine residue

CH2CONHR2
FIG. 18Typical structures for turbine oils rust inhibitors.

can protect the metal from either type of attack by the formation of a protective layer of up to 5000A thick [55]. These
products, known as metal passivators are, for turbine oils
and fluids, chiefly of the triazole family (Fig. 19), and the effect of their activity is to substantially extend the life of fluids
in copper-catalyzed oxidation tests. Their effectiveness is
readily demonstrated in oxidation tests such as ASTM D 2272
and ASTM D 943. Apart from their performance in these and
other metal-catalyzed oxidation tests, the corrosive tendencies of oils towards copper is most frequently assessed by
ASTM D 130, Standard Method of Test for Detection of Copper Corrosion from Petroleum Products by the Copper Strip
Tarnish Test. In this test, a copper strip is normally immersed
in the oil for 3 h at lOO'C, but more severe conditions are also
used depending on the application. Following the immersion
period the strip is solvent cleaned cind visually rated for corrosion by comparing the surface color or tarnish with the
ASTM Copper Strip Corrosion Standards, which represent
increasing levels of tarnish axid corrosion. Normally turbine
oil specifications call for a maximum rating of lb, which is
slight tarnish.

Unfortunately, triazole derivatives titrate as acid and therefore contribute slightly to the acidity of the fresh fluid, a factor that has to be considered when meeting specification limits on fresh fluid.
Antiwear and Extreme-Pressure Additives
Antiwear additives are compounds added to an oil to reduce
the wear occurring between the surfaces in sliding contact.
They are normally effective at light to medium loads, for example in pump operation. These additives, of which neutral
triaryl phosphates are perhaps the most well known examples, initially form strongly adsorbed layers on the surface.
As the temperature increases due to the relative movement
of the surfaces, a chemical reaction takes place with the surface. The mechanism early suggested involved the formation
of a lower melting eutectic of iron and iron phosphide,
which flowed into the gaps between the asperities and therefore helping to provide a greater surface area to cany the
load. This idea was later rejected in favour of a metal phosphate layer that assisted lubrication [56]. The latest work,

320 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

methylene-bis-benzotriazole

tolutriazole

N
N

I
CH2NR2

N-alkylated benzotriazole

N-alkylated 1,2,4, triazole

FIG. 19Structures of some metal passivators used in turbine oils and fluids.
however, suggests the formation of a self-regenerating
polyphosphate layer possibly in the presence of amorphous
carbon [57].
As the temperature increases still further a point is reached
where the phosphate film breaks down and cannot prevent
metcil to metal contact. In order to sustain even greater loads,
for example to provide adequate gear lubrication, it is necessary to generate higher melting films, which are normally
achieved by adding extreme pressure (EP) additives, particularly sulfur in the form of a sulphur carrier, e.g., ZDTP, sulfurized fats or olefins. Combinations of phosphorus and sulfur are also widely used and cover a wider temperature range
than each element individually, providing both antiwear
properties and EP performance over a wide range of applied
loads. Figure 20 shows the structures of some typical antiwear and extreme pressure additives.
Most specifications for hydrocarbon turbine oils do not require antiwear performance. There are also normally no
load-carrying requirements for steam turbine oils except for
extreme pressure steam turbine oils, e.g., in marine applications, but they do exist for gas turbine oils, and where the oil
is used for the lubrication of both a steam and gas turbine as
in some combined cycle applications. These requirements
are not particularly onerous, typically lying between FZG
failure load stage values of 5-8 while EP turbine oils require
a failure load stage of 12 + . Micro-pitting resistance may aJso
be required for this more severe application and is also ceirried out on the FZG gear rig using the Forschungsvereinigung Antriebstechnik (FVA) method 54/I-IV.
The other application to require gear testing is aero-engine

lubrication. These oils have traditionally required performance on the Ryder Gear Tester (ASTM 1947now discontinuedor FED-STD-791, method 6508). Increasingly, because of better precision, the test devised by the German
Forschungsinstitut fiir Zahnrad und Getriebe (FZG) is being
used and this method has been standardized by ASTM as D
5182, Standard Test Method for Evaluating the Scuffing
Load Capacity of Oils. Both the FED-STD 791 method and
the FZG procedure involve "a recirculating power loop principle, also known as a four square configuration, to provide a
fixed torque (load) to a pair of precision test gears." A
schematic is shown in Fig. 21. The drive gearbox and the test
gearbox are connected through two torsional shafts. Shaft 1
contains a load coupling used to apply the torque through the
use of known weights hung on the loading arm. The procedure involves operating the machine at a constant speed
(1450 rpm) and oil temperature (90C) for a fixed period at
successively increasing loads until the failure criteria are
reached. This is "when the summed total width of scuffing or
scoring damage from all 16 teeth is estimated to equal or exceed one gecir tooth width." The FVA micro-pitting test referred to above is in two parts. First, a load stage test is carried out in which the test oil is run at each load stage between
5 and 10 for a period of 16 h. This is followed by endurance
test involving 80 h at Load Stage 8 followed by 5 periods of 80
h at Load Stage 10. An assessment is made of the amount of
pitting or profile deviation on each tooth at the end of each
test period.
For aviation applications, the Ryder Gecir Test is still used
with the MIL-PRF-23699F specification in accordance with

CHAPTER 12: TURBINE LUBRICATING


FED-STD-791 method 6508, in which the performance of the
test oil is evaluated in comparison with reference oils giving
known failure loads. In this case the load-carrying ability is
defined as the "gear tooth load at which the average percent
of tooth area scuffed is 22.5 %." The variability of the results
on this equipment requires eight determinations of the reference oil and six determinations of the test oil. The performance is judged acceptable if the average of the six results is
not less than 102% of the reference oil. In the MIL-PRF7808L standard, however, it is now possible also to use the
ASTM D 5182 method where a minimum load stage failure of
5 is required. Only an average of two tests is required on this
equipment.

OILS AND HYDRAULIC FLUIDS

Antifoams
The inhibition of foaming is essential to ensure the correct lubrication of pumps and bearings and, in hydraulic systems,
the transmission of power. Foam can also result in a rapid
loss in oxidation stability of the oil or fluid and, under the
worst conditions, can cause fluid loss from the tank. It is
therefore important that air is lost quickly from the fluid and
this can be assisted by the addition of very small quantities
(usually a few parts per million) of specific chemicals known
as antifoams that reduce the surface tension on the bubble
envelope [58]. The most widely used of these are the silicone
fluids. Chemically, these are polydimethylsiloxanes, which

where R is typically CjjCj orC4

triaryl phosphate

dialkyl phosphite
where R is C4-C8

triphenylphosphorothionate

RO^

OH.HNR'2

321

R'zNH.HO'

OH.HNR'2

amine phosphates
FIG. 20Structures of typical antlwear/extreme pressure additives used in turbine oils
and fluids.

322

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

are available in a range of viscosities, b u t the most active


products are those that are not soluble but dispersible in the
oil or fluid. Soluble siloxanes do not have the same activity at
the air/fluid interface. Other problems associated with these
additives include the difficulty in obtaining a homogenous
dispersionthe polymers tend to accumulate at the surface
and then deposit on the walls of the tank so that over time the
efficiency of the additive is lost. At "high" concentrations they
can also have an adverse effect on air release properties and,
if the turbine oil escapes into the turbine, there have been reports of the build u p of silicon on the turbine blades. As a result, the trend in mineral turbine oils is away from the use of
silicones and towards other products such as polyglycolethers and polyvinylethers, but larger quantities of these are
normally needed.
The laboratory test procedure (ASTM D 892, Standard Test
Method for the Foaming Characteristics of Lubricating Oils,
or the ISO equivalent method, 6247) involves passing air at a
fixed rate through either a spherical crystalline alumina diffuser or a cylindriccd sintered steel diffuser immersed in the
oil or fluid contained in a measuring cylinder (Fig. 22). These

1 != pinion
2 = gear wheel
3 = drive gears
4 = load clutch

diffusers produce bubbles of a known and consistent size. After passing air through the fluid for 5 min at 24C (TS^F), the
volume of foam (tendency) is noted immediately and then
also after 10 min (stability). The test is repeated at 93.5C
(200F) and then again at 24C to check if the foaming behavior has changed (possibly due to loss of cintifoam) as a result of the exposure to high temperature. The results are
quoted in terms of the tendency/stability values obtained at
each of the three temperatures. Values are normally much
lower at the higher temperature and hence limits under this
condition are more severe.
Because of the importance of foaming and its related topic,
air release, it is further discussed in the section on Performance Requirements, Their Significance and Evaluation.
The performance of the oil is usually retained as long as the
additives remain in solution a n d are not depleted owing to removal from the fluid as volatiles, by partitioning into any free
water, by precipitation, or by natural usage. If the additive is
removed by any of these means, the rate of degradation, for
example, can suddenly accelerate. If the oil monitoring is not
adequate it can result in the oil exceeding its operating limits

5 = locking pin
6 = lever arm iNWn weights
7 = torque measuring clutch
8 = temperature sensor

Schematic section of FZG Test Rig


torque measuring
clutch

shaft 2

test gears

drive motor

drive gears
load clutch
shaft 1
FIG. 21Diagram of the FZG Test Rig.

CHAPTER 12: TURBINE LUBRICATING OILS AND HYDRAULIC FLUIDS 323


suggested a quantity of about 360000 tons of turbine oils, excluding aviation eind marine gas turbine requirements, were
sold worldwide. Obviously, with a global market of this size
there are a large n u m b e r of suppliers including both multinational companies and smaller, national oil companies.
One of the "problems" associated with the supply of mineral turbine oil is that the are produced in different parts of
the world from different crude sources. Although attempts
have been made by the oil industry to minimize these differences by introducing "formula numbers" or product identification numbers that identify the product by certain physical
characteristics, e.g., viscosity, flash point and pour point,
etc., it is still possible for the base material to vary in its composition. As a result there may be variations in the performance, particularly stability, of finished products sold under
the same trade name. This has caused some turbine builders
to abandon formal approval lists in order to avoid liability
claims and to rely on the local supplier to convince the end
user that a product is available that meets the specification
requirements.

FIG. 22The development of foam in the


ASTM D 892 test procedure.
unnoticed. It is n o w widely accepted that with m o d e m turbine oils, condition monitoring is important; this aspect will
be examined in more detail later.

THE CLASSIFICATION OF TURBINE


LUBRICANTS AND HYDRAULIC FLUIDS
In order to clarify the different applications for turbine lubricants and hydraulic fluids a n d hence ensure that the
correct type of oil or fluid is used, ISO Standard 6743-5, Lubricants, Industrial Oils And Related Products (Class L)
ClassificationFamily T (Turbines), has been issued. This
classifies the type of turbine, e.g., steam or gas, and then subdivides the application according to whether the requirement
is for normal service or for a special application as, for example, in high temperature service or high load carrying ability. A further subdivision is according to viscosify. Table 14
shows the current classification and typical applications. At
present the classification does not extend to lubricants for
water, wind, or aviation gas turbines although the standard is
currently under revision.

TURBINE OIL AND FLUID STANDARDS


The turbine oil market is one of the largest segments of the
industrial oil market. An estimate of consumption in 1998^
^ Private communication, D. J. Whitby, Pathmaster Marketing
Ltd., Woking Surrey, UK.

In order to ensure that the quality of the turbine oil supplied


meets certain minimum standards, and to form the basis for
purchasing agreements, performance specifications have
been issued by international and national standards organizations as well as by the turbine builders and some end users.
ASTM, for example, publishes D 4304, Specification for Mineral Lubricating Oil Used in Steam and Gas Turbines. As a result, the industry is now one of the most heavily specified. The
major specifications currently used by industry are listed in
Tables 15 and 16 for the main turbine applications. While past
practice was for separate specifications on hydrocarbonbased steam and gas turbine oils, the current trend is to issue
a combined document as, for example, in D 4304. At present
there are n o separate specifications for water turbine oils, but
requirements are sometimes included in standards for steam
and gas turbine lubricants, e.g., ISO 8068, Petroleum Products and Lubricants-Petroleum Lubricating Oils for Turbines
(categories ISO-L-TSA and ISO-L-TGA)-Specifications.
Although there has recently been significant consolidation
within the power generation industry, some of the specifications listed are still published under the n a m e of the previous
builder. Some simplification of the list is therefore to be expected.
When seeking approval, the oil or fluid supplier would first
approach the turbine builder or end user with a request for
their product to be examined against the specification. Tests
would be carried out by the specifier (in-house or at an independent laboratory) to ensure that the product was technically acceptable. If successful, approval for field trials or
commercial use would be given. In the former case it might
be necessary to obtain several years of operating experience
before full approval was given. Where no formal approval
process existed, the supplier would have to convince the user
that the product met the requirements, normally by providing the results of independent laboratory tests.
Although most specifications are primarily concerned with
the quality of new fluid as delivered, some manufacturers
also specify the quality of any flushing fluid to be used and
cilso the limits on fluid performance in use. The latter aspect
will be referted to in more detail in the discussion on monitoring used fluid quality.

324 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 14Classification of lubricants for turbines (ISO Standard 6743-5).
Application
Steam, direct coupled
or geared to the load

Gas, direct coupled or


geared to the load

Control system

Specific Application

Composition and Properties

Symbol ISO-L-

Typlcal Applications

Normal service

Highly refined petroleum oil


with rust protection and
oxidation stability

TSA

Special properties

Synthetic fluids with n o


specific fire-resistant
properties

TSC

Fire-resistant

Phosphate ester lubricant

TSD

High load-carrying
ability

Highly refined petroleum oil


with rust protection,
oxidation stability, and
enhanced load-carrying
abilityoxidation stability,
and enhanced load-carrying
ability

TSE

Power generation and industrial


drives and their associated
control systems. Marine drives
where improved load-carrying
ability is not required for the
gearing
Power generation and industrial
drives and their control systems
where special properties of the
fluid are advantageous, for
example oxidation stability, low
temperature properties.
Power generation and industrial
drives and their associated
control systems with need for
fire- resistance
Power generation and industrial
drives; marine geared drives and
their associated control systems
where the gearing requires
improved load-canying ability.

Normal service

Highly refined petroleum oil


with rust protection and
oxidation stability

TGA

Higher temperature
service

Highly refined petroleum oil


with rust protection and
improved oxidation stability

TGB

Special properties

Synthetic fluids with no


specific fire-resistance
properties"'*

TGC

Fire-resistant

Phosphate ester lubricant

TGD

High load-carrying
ability

Highly refined petroleum oil


with rust protection,
oxidation stability and
enhanced load-carrying
ability

TGE

Fire-resistant

Phosphate ester control fluid

TCD

Aircraft^
Hydraulic"

Power generation and industrial


drives and their associated
control systems. Marine drives
where improved load-carrying
ability is not required for the
gearing
Power generation and industrial
drives and their associated
control systems where high
temperature resistance is
required due to hot spot
temperatures
Power generation and industrial
drives and their control systems
where special properties are
advantageous, for example
oxidation stability, low
temperature properties.
Power generation and industrial
drives and their associated
control systems with need for
fire-resistance
Power generation and industrial
drives; marine geared drives and
their associated control systems
where the gearing requires
improved load-carrying ability
Steam, gas, hydraulic turbine
control mechanisms where the
fluid supply is separate from the
lubricant and fire-resistance is
needed

TA
TH

"These products may not be compatible with petroleum-based products.


'This category Includes synthetic hydrocarbons as well as other chemical types.
"Classifications for these categories have not been established.
Reproduced with permission of the International Organization for Standardization, Geneva, Switzerland.

Specifications typically include r e q u i r e m e n t s o n b o t h the


c h e m i c a l a n d p h y s i c a l c h a r a c t e r i s t i c s of t h e l u b r i c a t i n g oil o r
h y d r a u l i c fluid. T h e y a l s o i n c l u d e ( b u t o f t e n fail t o differentiate b e t w e e n ) the so-called "type" tests t h a t identify a general
level of p e r f o r m a n c e a n d r o u t i n e t e s t s u s e d for r e g u l a r q u a l ity c o n t r o l . T h e f o r m e r r e q u i r e m e n t c o u l d i n c l u d e l o n g t e r m

o x i d a t i o n t e s t s (for e x a m p l e t h e A S T M D 9 4 3 o x i d a t i o n t e s t
referred to above) o r large-scale fire-resistance tests t h a t are
clearly impossible and/or u n n e c e s s a r y to evaluate on a b a t c h
p r o d u c t i o n b a s i s . A n e x c e p t i o n t o t h i s s i t u a t i o n is for m i l i t a r y
a v i a t i o n s p e c i f i c a t i o n s , e.g., M I L - P R F - 2 3 6 9 9 F w h e r e t h e Ryd e r G e a r T e s t is p e r f o r m e d o n t h e first b a t c h of e a c h c o n t r a c t

CHAPTER 12: TURBINE LUBRICATING


awarded and the bearing test performed on the first three
full-scale production batches of any newly qualified oil.
The co-existence of both international and national standards together with those of the individual turbine builders
and end users is, perhaps, surprising. Although the publication of a European (EN) Standard requires the withdrawal of
any competing national standcird, this is not the case for ISO
(International Organization for Standardization) standards.

OILS AND HYDRAULIC FLUIDS

325

ISO/EN/national standards are also minimum requirements


and, in some cases, may not be severe enough to meet the
manufacturer's or user's requirements. In such cases the latter's specifications may still be used. National and international standards also require considerable time for revision,
a process that may be inadequate for manufacturers seeking
to make rapid changes in technical requirements to respond
quickly to the concerns of industry.

TABLE 15International and national specifications for turbine oils and hydraulic fluids.
International or
National Specifications
International Standards
Organisation
International Electrotechnical
Commission
European Standard
Canada
China
France
Germany
Japan
India
Russia
UK
USA

Steam Turbines

Industrial Gas Turbines

ISO 8068

Fire-Resistant
Hydraulic Fluid

Aero-Derivative Gas

ISO 8068

CD 10050
lEC 61221
EN61221

3-GP-357Mb
DL-571

DL/T 571-95
AIR 3514A AIR 3517

DIN 51515
nS-K-2213
IS 1012
Tp-22CTU 38.101821
Tp-22BTU 38.401-58
BS489
ASTM D 4304
ASTM D 4293

In preparation
JISK-2213
IS 1012

DIN 51518
COST 12245-66
COST 13076-86

ASTM D 4304
ASTM D 4293

TABLE 16Turbine builders and utility specifications for lubricating oils and hydraulic fluids.
Turbine Builder/Utility
Alstom Power
(France/UK)
Alstom Power Mannheim
(Germany)
Alstom Power (Switzerland)
Alstom Power (Sweden)

Alstom Energy Lincoln, (UK)


Alstom Power (Germany)
Ansaldo
BHEL
EDF
Fuji Electric
General ElectricMedium & Large Steam
Turbines
General Electric-Industrial
Steam Turbines
Hitachi
Kawasaki
Mitsubishi Heavy Industries

Steam Turbine
Oil Specification

Industrial Gas
Turbine Oil Specification

Aviation Gas
Turbine Oil Specification

NBAP50001A

SBVPRlOOl C

DIN 51515

HTGD 690149 VOOOIK

H G T D 9 0 117V001Q
812101
812102
812106
812107

HTGD 690 149 VOOOIK


81 23 00

812101
812102
812106
812107
65/0027

QM44-101/B
IS 1012
HN 20-S-30
JISK-2213
GEK 46506D

QM44-100/B
602W917
ST 22007
HN20-S-41
Siemens TLV 9013.04
GEK 32568C
GEK 101941
GEK-28136A*

D50TF1-S4

Solar
Toshiba
Siemens Westinghouse

GEK 46357E

165A974CE
JISK-2213
GEK 4506D
JISK2213
769 45192
JISK2213

GEK 32568 (mod)


GEK 101941 (mod)
H T G D 9 0 117(ABB)
JISK2213

GEK 46357E

STM-1840

National Power (UK)


Pratt and Whitney
Siemens

Fire-resistant Hydraulic
Fluid Specifications

Procurement Specification
207001, Part 9
521CTypell
TLV9013/04
TLV 9016 03/02
(hydraulic oil)
JISK-2213
55125Z3

TLV 9013/04

TLV:9012 01/05

ES 9-224
GEK 32568C
55125Z3

GEK 46357E
53740AL

326

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

TABLE 17Military specifications for turbine oils and hydraulic fluids.


Country

Steam Turbine Oil

Belgium

BN-PO-175A

Canada
France

3GP-357-Mb
STM 7220B

Italy
UK

MM-O-2001
Def Stan. 91-25/3

USA

MIL-L-17331H

Industrial Gas
Turbine Oil

Aviation Gas
Turbine Oil

BA-PO-lOeA"
BA-PO-115A
BA-PO-103B''
BA-PO-109C
AIR3514/A
AIR3515/A-B''
AIR3516/A"
Def. Stan 91-93
Def.Stan 91-94
Def.Stan 91-97/1"
Def.Stan 91-98/1
Def.Stan 91-99/1"
Def.Stan 91-100
Def.Stan 91-101
MIL-L-aOSlC
MIL-PRF-7808L
MIL-PRF-23699F

' Denotes a mineral oil-based product. The remainders are synthetic-based lubricants.

Table 17 lists some of the current military specifications


for turbine oils. Where no standard is listed for a specific
country it is probable that one of the standards developed by
other countries (particularly the USA and the UK) is adopted
for use. As can be seen, there are no military standards available for industrial gas turbines or fire-resistant turbine hydraulic fluids. The reason is that few industrial gas turbines
are used in this application because of limitations on size and
weight. There are military applications for fire-resistant fluids but these are not in turbines.
One other complication in the chart is that there are several specifications available for aviation turbine lubricants.
These are divided between mineral oil (extreme pressure and
non-extreme pressure grades) and synthetic-based products.
The latter are further subdivided according to the different
fluid viscosities.

PERFORMANCE REQUIREMENTS, THEIR


SIGNIFICANCE AND EVALUATION
As might be expected in an application that may be using
the latest technological advances, the technical requirements can be extensive and severe. This is also a result of
providing a resource on which industry and the consumer
totcdly depend and on which the safety of large numbers of
the traveling public rely. Table 18 illustrates the technical
requirements for:
1. A steam or industrial gas turbine oil without additional
load carrying capacity (T5^e 1 oils listed in ASTM D 4304,
Standard Specification for Mineral Lubricating Oil Used
in Steam or Gas Turbines).
2. An aero-derivative gas t u r b i n e lubricant (MIL-PERF23699F, Lubricating Oil, Aircraft Turbine Engine Oil,
Synthetic Base, NATO Code N u m b e r 0-156, standard
grade).
3. A fire-resistant turbine control fluid (lEC 61221, Petroleum
Products and Lubricants-Triaryl Phosphate Ester Turbine
Control Fluids (Category ISO-L-TCD)Specifications.

In each case the data in the table is given on one viscosity


grade only as all these specifications contain multiple requirements. These would include, for example, a range of different viscosities; applications with additional load-carrying
requirements; or, in the case of the aviation lubricant, grades
with corrosion inhibiting or thermal stability requirements.
For information on the grades not mentioned, reference
should be made to the appropriate specification.
As will be seen, there is commonality in some physiccd and
chemical tests but considerable differences exist as far as
"performance" or "type" tests (for example, stability a n d
load-carrying requirements) are concerned. The following
comments explain the background to the incorporation of
the different performance requirements into the specifications and outline the procedures available for their determination. Table 19 lists the common ASTM, Federal Standard
Method, or ISO standard tests used in turbine oil specifications; however, not all standards for the same property are
identical.
Viscosity
The viscosity of a liquid can be regarded as its resistance to
flow, but is more precisely a measure of the interned friction
as the molecules move relative to one another. The property
is important as it enables us to rank oils and fluids in terms
of their relative "thickness" and to define the appropriate
"level of thickness" necessary to ensure the presence of an adequate lubricating film in the p u m p , bearings, or gears
throughout the operating temperature range of the equipment, including low temperature start-up capability. It was
noted earlier, for example, that military requirements necessitate the use of a low viscosity lubricant for engine start-up
in very cold climates. At the other extreme, when using mineral oils in turbines operating in high temperature environments, it may be necessary to use higher viscosity products to
achieve adequate lubrication. However, if a lubricant has too
high a viscosity, cavitation will occur while too low a viscosity can result in p u m p slippage and internal leakage (Fig. 23

CHAPTER 12: TURBINE LUBRICATING OILS AND HYDRAULIC FLUIDS 327


[59]). Also related to viscosity are volatility and, to a limited
extent, flash point properties.
The most c o m m o n procedure for measuring kinematic viscosity (ASTM D 445, Standard Test Method for Kinematic
Viscosity of Transparent and Opaque Liquids) involves measuring the time for a fixed volume of liquid to flow under
gravity through a calibrated glass capillary viscometer. Although in the past, 100F and 210F were standard tempera-

tures for measuring viscosity, the most widely-used temperatures are now 40C and 100C, and these are cJso the basis for
the determination of viscosity index and viscosity classifications (see below). The former temperatures, however, are still
frequently quoted and care is needed to avoid confusing the
different data. It is possible to measure viscosity over a wide
temperature retnge using this method and Fig. 24 illustrates
the viscosity/temperature relationships for the major fluids

TABLE 18A comparison of the technical requirements for turbine oils and fire-resistant hydraulic fluids.
Test Method
Property

Viscosity Grade
Appearance (20C)
Kinematic Viscosity (cSt)
at 40X

Steam/Industrial
Gas Turbine Oil

Aero-Derivative
Gas Turbine Oil

Fire-Resistant
Hydraulic Fluid

ASTM

32
Clear and bright

22

46

D2422

3448

D445

3104

28.8-35.2

41.4-50.6

-6
180

>23
4.9-5.4
13000
6
-54
246

D97
D92

3016

Report

1.0

100C

-40X
Vise. Change after 72 h at -40C (%)
Pour point (C)
Flash Point (X)
Density at 15C
Total Acid No (mg KOH/g)

max
mEix
max
min
max
max

-18
1.2
0.1

FED-STD-791 etc.

ISO etc.

3675
6619

D974
SAE ARP 5088

Foaming Tendency/Stability
Sequence 1
Sequence 11
Sequence 111
Air Release at 50C
Chlorine Content (mg/kg)
Water Content (%)
Volume Resistivity at 20C (Mfim)
60247
Emulsion Characteristics at 54C
min. to 3 ml emulsion
Evaporation Loss (%)
Rust Preventing Properties
Procedure A
Rubber Compatibility (% swell)
Corrosiveness to Copper Rating
Fluid Compatibility-sediment (mg/L)
Trace Metal Content (ppm)
Shear Stability-Viscosity Loss
at 100F (%)
Bearing Deposition-demerit rating
Thermal Stability & Corrosivity
at 274C
-Viscosity Change (%)
-Acid Number Change (mg KOH/g)
-Metal Weight Change (mg/cm^)
Oxidation Stability h to acid
number 2.0
Oxidation Stability-min. to
175kPa drop
Oxidation Stability
Viscosity change (%)
Total Acid Number Change
Sludge Content (mg/100 mL)
Wt. change (mg/cm^)-Fe
Wt. change (mg/cm^)-Cu
Wt. change (mg/cm^)-Ag
Wt. change (mg/cm^)-Mg
Wt. change (mg/cm^)-Ti
Wt. change (mg/cm^)-Al
Oxidation Stability
Acid number increase (mg KOH/g)
Wt. loss-Fe (mg)
Wt. loss-Cu (mg)

D892
max
max
max
mix
max
max
mm

6247

150/0
25/0
150/0
6
50
0.1
40

D3427

9120
15597
760
lEC

30

15

D 1401

6614

50/0

25/0
25/0
25/0

10

D972
D665

25-May

D6546
D 130

Pass

3604/3433

6072

3403
Atomic Emission
Spectr.

max
max

20
Various (1-11)

max

max

80

max
max
max
min

5.0
6.0
4.0
2000

D943

min

350

D2272

D2603
3410
3411

5308
max
max
max
max
max
max
max
max
max
max
max
max

- 5 to + 25
3.0
25/50
0.2
0.4
0.2
0.2
0.2
0.2
15595
1.5
1.0
2.0

328

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 19A summary of the principal test methods for evaluating turbine oil properties.
Property

ASTM Method

ISO Procedure

Color
Kinematic Viscosity
Low Temperature Viscosity
and Viscosity Stability
Viscosity Index
Viscosity Classification
Density-hydrometer method
Density-digital density meter
Acid Number-Colorimetric
Potentiometric

D 1500
D445
D2532

3104

D2270
D2422
D1298
D4052
D974
D664

2909
3448
3675
12185
6618
6619

Water Content

D 1744

Pour Point
Evaporation Loss
Flash/Fire Points-Open Cup
Autoignition Temperature
Spray Ignition

D97
D972
D92
D2155/E659

760
12937
3016

Hot Manifold Ignition


Wick Ignition
Foaming
Air Release
Demulsification
Shear Stability-Oxidation Stability

D5306
D892
D3427
D 1401
D2711
D943
D2272
D5846

2592
3988
15029
20823
14935
6247
9120
6614

Others (FED-STD-791
Unless Specified)
102
305
307
9111

5105
5106
SAE ARP 5088
3253
201
351
1103
1152
Factory Mutual
Std. 6930
6053
3213

5307/5308
Hydrol5^ic Stability
s h e a r Stability-diesel injector
Shear Stability-sonic oscillator
Shear Stability-tapered bearing
Thermal Stability
Particle Contamination-optical
Particle Contamination-microscopic
Particle Contamination-gravimetric
Sizing particles
Trace Sediment
Copper Corrosion
Rust Preventing Characteristics
Corrosion prevention
Seal Compatibility
Fluid Compatibility
Electrical Resistance
4-Ball Wear Test
Vane P u m p Test
Gear Test-Ryder
Gear Test-FZG
Bearing Test
Deposition Test

D2619

15595
15596
CETOPRP 112H

D2603/D5621
D2070
F661
F313
D4898
D2273
D 130
D 665/D 3603
D 1748

CEC L-45-A-99
2508/3411
4402
4407/8
4405
4406
2160
4404
6072

D 1169
D4172
D2882
D 1947
D5182

used in turbine fluids and lubricants. Very low temperature


viscosities (which are required for aviation gas turbine lubricants in view of their potential operation in very cold environments) are measured by a slightly different procedure.
This involves not only a determination of viscosity at - 4 0 or
-65F but also a cold "soak" to check whether the fluid
changes viscosity on prolonged exposure to low temperatures
(ASTM D 2532, Standard Test Method for Viscosity and Viscosity Change After Standing at Low Temperatures of Aircraft Turbine Lubricants). This test is in addition to a requirement for stability at -18C for six weeks without
crystallization, separation, or gelling.

3009

3004/3010
5325
4011
3604/3432
3403
lEC 60247
CETOP RP 67H

20763
14635

6508
DIN 51354
3410
5003

Other ASTM standards that involve the measurement of


viscosity include the determination of viscosity index (ASTM
D 2270, Standard Practice for Calculating Viscosity Index
from Kinematic Viscosity at 40 and 100C). Viscosity Index is
a way of representing the change in viscosity of an oil or fluid
with temperature relative to two reference mineral oils arbitrarily assigned viscosity indices of 0 and 100. The lower the
change of viscosity, the higher the Viscosity Index. Additionally, the classification scheme ASTM D 2422, Standard Classification of Industrial Fluid Lubricants by Viscosity System,
(equiveJent to ISO 3448) enables fluids and lubricants to be
classified according to their viscosity at 40C (in centistokes)

CHAPTER

12: TURBINE

in a series of eighteen grades. These range iirom 2-1500 cSt


and the width of each band is 1 0 % of the mid-point. This
scheme is widely used to identify the level of viscosity required for different applications. The ASTM D 4304 turbine
oil standard, for example, has limits on fluids u p to an ISO
150 viscosity grade while at least one major steam turbine
builder specifies an ISO VG 100 hydraulic oil. However, the
common viscosity grades for both hydraulic cind lubricating
oils in industrial steam and gas turbines Eire 32 and 46 while
products with ISO viscosity grades 10 and 22 are found in
aero-engine oil applications.
Pour Point/Low Temperature Storage Stability
In addition to avoiding thickening at low temperatures, either in use or in storage, it is also important to ensure that the
fluid in service does not solidify or precipitate. Such behavior could lead to pumping problems or operational failure.
Conventional solvent-refined mineral oils tend to precipitate
wax at low temperatures; the hydrocracked products m u c h
less so and not at all with PAOs. In comparison, the synthetic
esters may, if wet, become turbid at low temperatures and
also more viscous on storage. Phosphates normally solidify
without precipitation b u t may also become turbid in the
presence of water.
Additive incompatibility at low temperatures can also adversely influence the low temperature behavior of the oil or
fluid and it is mainly for this reason that aviation gas turbine
lubricants are tested for extended storage stability. The qualification sample for approval against MIL-PRF-23699F, for
instance, is stored at temperatures ranging from - 4 0 C to
+60C for a period of three yeeirs. If at any time during this
period the fluid fails to meet any of the technical criteria, the
approved is withdrawn.
The normal procedure for determining p o u r point (ASTM
D 97, Standard Test Method for Pour Point of Petroleum

(mm2/sec)
10 000
5000 Cavitation

2000 4Jpp6^viscosity limit


1000
500 Slow respoRse-

X3

(0
>

,g
'Jam

ro
E

(D
C

7)

100
50
20
10
5

Low efficieaiey=

<D
O
O

a> 3
S 3
5' CD
3

Q.
CD
O.

3
CO
(D

Reduced volumetRelfticiency
-4i^3lv3Q0S

1
FIG. 23Significance of viscosity for tlie operation of a typical hydrostatic system. Reproduced from "Hydraulic Fluids,"
with kind permission of Butterworth-Helnemann, Oxford, UK.

LUBRICATING

OILS AND HYDRAULIC

FLUIDS

329

Products) involves cooling a fixed volume in a cylindrical


container with a thermometer inserted just below the surface. As the t e m p e r a t u r e is lowered, the flow behavior is
noted by holding the container horizontal for 5 s and watching for movement in the meniscus. The pour point is that
temperature w h e n the fluid ceases to flow under these conditions and to which three degrees centigrade has been added.
Typical limits for Type 1 turbine oils (of all viscosities) given
in ASTM D 4304 are - 6 C maximum.
Acid N u m b e r
The acidity present in the new oil or fluid arises from two
sources:
1. Residual acidity from manufacture (in the case of the ester-based products),
2. From the presence of additivesusually acidic rust inhibitors and/or metal passivators, but also some antioxidants.
A high level of acid in a n unused, inhibited, fluid is therefore not necessarily indicative of a poorly processed product
or one that has aged significantly on storage. The latest version of MIL-PRF-23699, for example, has a limit of 1.0 mg
KOH/g. On the other haind the presence of a high level of
acidity cem be disadvantageous to surface active properties,
for example foaming (ASTM D 892) and air release (ASTM D
3427). It may cause corrosion (ASTM D 665) and promote oxidation (ASTM D 2272). The level of acid in new, uninhibited,
phosphate esters is tighfly controlled because this may contain strong acid, with a p H of < 4 , which can catalyze the hydrolytic degradation process. A low initicd acidity in esterbased products therefore ensures good storage stability, a
satisfactory condition on filling into the system and a longer
operating life. As will be shown later, the acidity level is a n
important indicator of fluid "health." Monitoring this parameter is therefore essential to ensure the trouble-free operation
of the system.
Two techniques are used for the measurement of acidity or
acid n u m b e r of turbine oils and fluids. Both involve neutralizing the acid by a base (potassium hydroxide) of known
strength in a measured quantity of fluid. One procedure uses
indicators that change color when the sample is neutralized
(ASTM D 974, Standard Test Method for Acid and Base Number by Color Indicator Titration). The other method measures the acid n u m b e r by plotting the changes in the potential of a glass electrode as the alkali is added. The amount
required to produce an inflexion point on the graph is taken
as the neutralization point. Where inflexion points are not
readily defined, a predetermined end point, for example a p H
of 11, is frequently used (ASTM D 664, Standard Test Method
for Acid N u m b e r of Petroleum Products by Potentiometric
Titration). While b o t h procedures give similar results on
fresh fluids, their accuracy, peirticularly reproducibility, is
acceptable rather t h a n good. For example, in the colorimetric technique where the initial acidity lies below 0.1 m g
KOH/g, the reproducibility is 0.04 m g KOH/g. More difficult
still is the accurate determination of used fluid acidity where
the fluid color has darkened or when the fluid has been dyed.
This makes indicator end points more difficult to detect and
precision may suffer with increasing acidity. The trend is
therefore towards the use of the potentiometric method for

330 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


5.0

(0

o
.52
"c
<u
o
to

ou
CO
>

(U

200

10

20

40

55

65

75

85

degrees farenheit
FIG. 24Viscosity/temperature data for different turbine oil and fluid.

100

CHAPTER 12: TURBINE LUBRICATING


fluids in service. For aviation lubricants a potentiometric
method has been developed by the Society of Automotive Engineers (SAE-ARP 5088) which is now included in MIL-PRF23699F.
In the past, determination of acidity was traditionally carried at the close of an oxidation test. However, because the
major criterion for failure in the D 943 method was the time
taken to reach a certain level of acidity, it was necessary to
follow the development of this parameter throughout the
test. This required regular sampling of up to 20 g of fluid per
determination. For long-term tests this could significantly reduce the fluid volume in the test and would therefore disturb
the relationship between catalyst surface area and the fluid
and also between water and the fluid, making it difficult to
compare test results. To reduce the effect of sampling on the
oxidation test conditions, methods of measuring acidity on
much smaller samples were developed. Currently ASTM D
3339, Standard Test Method for Acid Number of Petroleum
Products by Semi-Micro Indicator Titration, and D 5770,
Standctrd Test Method for Semi-quantitative Micro Determination of Acid Number of Lubricating Oils During Oxidation
Testing, are used. The former method uses up to 5 g of fluid
while the latter uses only "drops" of fluid. The D 5770 procedure is regarded as less precise than D 974 or D 664 and is not
recommended for monitoring oils in service. Its principal use
is therefore likely to be product development and the method
advises that "each laboratory shall develop its own criteria
for determining when to switch from this method to a more
precise test method for acid number."
Figure 25 shows typical automatic titration equipment
used for determining total acid number on a series of samples. Specifications vary considerably in their requirements

OILS AND HYDRAULIC FLUIDS

331

on initial acidity. ASTM D 4304 has no limits but values are


to be reported. Some turbine manufacturers also have no requirement while others call for a limit of 0.2 mg KOH/g maximum for non-geared units and 0.3 mg KOH/g for geeired turbines. Higher limits are found for the ester-based aviation
lubricants. MIL-PRF-7808L, for example, specifies 0.3 or 0.5
mg KOH/g max. while at the other extreme, the specification
limit on fire-resistant control fluids is typically 0.1 mg KOH/g
maximum.
Water Content
Water is a problem contaminant for all tjrpes of fluid. It can
be present in either dissolved or dispersed form and, in the
case of major contamination, may form a completely separate layer. When the main reservoir contains mineral oil, free
water normally falls to the bottom of the tank owing to the
different density and requires removal by means of the vaJve
on the tank base or via a sediment drain to the tank side. If
the fluid has a density greater than that of water, as in the
case of phosphate ester, the free water layer will be on top of
the fluid in the tank and should be skimmed or siphoned off.
Other methods used for free water removal include centrifugal separation and water absorbing filters. To remove dissolved water, vacuum dehydration is recommended. The latter technique may take the form of an extractor on the tank
encouraging the flow of a stream of dry air across the surface
of the oil or fluid. Alternatively, a vacuum dryer may be used
on a by-pass to the main oil tank in which a thin film of the
oil or fluid is exposed to a counter-current of dry air. This
technique reduces the water level more rapidly. Although water contamination is more likely on steam turbines, it can

FIG. 25Equipment for the measurement of acid number by automatic titration.

332

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

also occur on gas turbines as these are occasionally washed


to remove deposits forming on blades, etc.
The solubility of water in turbine oils is very lowabout
30-100 mg/kg at ambient temperatures, and excess water in
new mineral oils can usually be detected visually as it causes
turbidity. With esters, the solubility is m u c h higher, in the
range of 2000-2500 mg/kg at ambient temperatures although
levels in service are normally in the region of 500-1500
mg/kg. Small amounts of water can normally be tolerated,
and are common in used steam turbine oils. While dissolved
water can cause a reduction in viscosity, hydrolysis of additives (or even of the ester fluids themselves) and hence a loss
of stability, etc., it is dispersed or free water that is the usual
cause of emulsification, rusting, and possible extraction of
additives. With ester fluids, hydrolysis is the normal form of
degradation and the acid formed can promote further degradation. Monitoring the water content of oils or fluids is therefore a n essential part of any fluid maintenance program.
The procedure used for detecting water has to be capable
of accurately measuring very small amounts and the technique used is to titrate a measured a m o u n t of fluid or oil with
standard Karl Fischer reagent to an electrometric end point.
The most c o m m o n method is ASTM D 1744, Standard Test
Method for the Determination of Water in Liquid Petroleum
Products by Karl Fischer Reagent. Precision has been established for levels between 50 and 1000 mg/kg, but the method
is frequently used for detecting m u c h higher values, peirticularly on used ester fluids. Limits are not frequently specified
for new mineral turbine oils in view of the low solubility of
w a t e r a n d the reliance on visual appearance (free w a t e r
causes turbidity). Occasionally limits of 0.01-0.02% w/w
(100-200 mg/kg) are quoted while, for fire-resistant control
fluids and aviation esters, the values are significantly greater
(0.1 % w/w or 1000 mg/kg), reflecting the higher solubility
and the hygroscopic (water absorbing) nature of these fluids.
Density
Measurement of density or specific gravity is one way of identifying the use of the correct fluid and ensuring that the correct volume of fluid is purchased if the product is supplied by
weight. It is also a n important factor for designers in determining the p o w e r required for p u m p i n g the oil or fluid
around the system and in arranging for removal of free water. Phosphate esters, for example, have densities about 30%
greater than mineral oils and require more power for circulation. Also, ciny free water in the tank will accumulate on top
of the phosphate. This fluid t3rpe will hold more dirt in suspension than other fluids, which necessitates better filtration
initiedly, but offers the possibility of a cleaner system in operation.
Density or relative density (specific gravity) values for both
transparent and opaque liquids Ccin be obtained either by the
use of a hydrometer (ASTM D 1298, Standard Practice for
Density, Relative Density (Specific Gravity) or API Gravity of
Crude Petroleum and Petroleum Products by Hydrometer
Method, or the ISO 3675 equivalent), or by a digital densitometer (ASTM D 5002, Standard Test Method for Density and
Relative Density of Crude Oils by Digital Analyzer, for which
the ISO equivalent method is 12985). Values are normally
measured at 15 or 20C, but can be calculated at other tem-

peratures from knowledge of the values at these or two other


temperatures.
API Gravity is a special function of relative density, and is
obtained by hydrometer measurement carried out at 60F
(15.6C). This test is not normally applied to non-hydrocarbon oils and gives values that are numerically significantly
higher than the other procedures mentioned. Density limits
featuring in specifications depend on the type of fluid being
used. Mineral oils, for example, are typically quoted at 0.9
kg/1 maximum at 15C while the API gravity for an ISO 32 gas
turbine oil is 29-33.5. Triaryl phosphates have a substantially
higher density and limits on this fluid would typically be 1.17
kg/1 maximum for an ISO VG 46 product.
F o a m i n g a n d Air R e l e a s e
Air is a "contaminant" of every turbine oil and fluid. Whether
or not it causes problems it depends largely on whether it is
soluble in the oil, or present as dispersed bubbles. System design, circulation rates, fluid cleanliness, etc., are also factors
to be considered. Dissolved air is not normally a concern but
if it comes out of solution when pressure is reduced locally it
may cause p u m p cavitation. Dispersed air tends to be a problem if it is not readily released from the bulk of the fluid in
the tank and compression of the bubbles by the p u m p does
not cause their dissolution. Under such conditions dispersed
air can cause a loss of control due to a change in the compressibility of the fluid, result in increased oxidation, and
may have an adverse effect on lubrication. Foam is the accumulation of air bubbles surrounded by a thin film of oil and
occurs at the surface of the liquid. Air release measurements,
by contrast, are made in the bulk of the liquid where a relatively thick film of oil separates the air bubbles.
There are a n u m b e r of factors relating to fluid properties,
system design and use that can influence foam formation.
These include tank design and circulation rates [60], fluid viscosity, surface tension, vapor pressure, contamination, bubble size [61], air leaks on suction lines, or simply too low an
oil level in the tank. Some foam is inevitable as air is released
from the oil or fluid when the pressure returns to ambient. In
most systems the presence of a small a m o u n t of foam can be
tolerated without any significant adverse effect on fluid/system performance. In extreme cases, excess foam may reduce
lubrication performance, induce bearing vibration, cause
fluid oxidation or loss of fluid, and create m u c h inconvenience to maintenance staff.
In hydraulic systems operating at high pressures, the presence of dispersed air will depend on the system pressure, the
size of the air bubbles, fluid temperature, and the compression time in the p u m p . Where the bubble is small, the compression time relatively slow, Eind the pressure Eind temperat u r e high, there is only a slight chance of bubbles being
circulated that could affect the compressibility of the fluid
euid hence the response time of the system. Conversely, if the
bubbles do not readily dissolve under pressure, not only is
there a risk of a loss of control but there may also be a n associated lubrication failure, fluid oxidation, and also the possibility of "dieseling." This is a phenomenon where compression/ignition takes place inside the bubble with resulting
fluid degradation [62]. In turbine lubrication systems, pressures are normally too low for this phenomenon to occur but

CHAPTER 12: TURBINE LUBRICATING


it is occasionally found in high pressure hydrauHc systems resuUing in a rapid darkening of the fluid, an increase in acidity, and the development of a "humt" odor.
In addition to the D 892 foam test method discussed above,
military aviation lubricant specifications also call for the use
of a dynamic foam test, FED-STD 791, method 3214 in which
the oil is heated and circulated around a loop consisting of a
pump, oil heater, air injection orifice, foam test cell, and associated instrumentation. As the oil is circulated at a temperature of 80C or 110C, the sample is aerated for a period of
30 min at a fixed rate with measurements being taken of the
foam, etc., every five minutes. At the end of the test, the foam
level, oil pressure and oil volume are noted together with the
time taken for the first patch of clear surface to appear or the
foam remaining after 5 min. The test is then repeated with a
different air-flow rate or at a higher temperature. The equipment is able to operate at low pressures thereby simulating
the effect of high altitude flight.
Typical foam limits for mineral turbine oils vary significantly and can also depend on whether the application is in a
steam or gas turbine. Limits in the latter application are usually stricter in view of the high aeration of the gas turbine oil
as it leaves the bearings. For both steam and gas turbines.

OILS AND HYDRAULIC FLUIDS

therefore, foaming tendency/stability values of 50/0 mL. for


all conditions (as defined in the ASTM D 892 test described
above) are required in ASTM D 4304 while, for steam turbines, the builder's requirements can be as high as 450/10,
50/10, and 450/10 mL for the three test sequences. In gas turbines, some equipment memufacturer's limits are 10/0, 20/0,
and 10/0 mL. For fire-resistant control fluids, limits are also
usually fairly severe at 50/0 ml. (all sequences) ranging up to
150/0, 50/0, and 150/0 mL. For aviation gas turbine oils, limits are also severe with the MIL-PERF-23699 requiring 25/0
mL metximum at all temperatures.
Unfortunately, the laboratory test cannot simulate the conditions that are found in the turbine; such is the influence of
system design. As a result, the test data should be treated as
indicative of a trend in fluid behavior and any significant
change, particularly the generation of stable foam, be initially
confirmed by investigating the behavior in the tank itself.
Air release properties (ASTM D 3427, Standard Test
Method for the Air Release Properties of Petroleum Oils, or
ISO 9120) are similarly measured by saturating the fluid
(normally at 50C, but other temperatures are also possible)
with air bubbles and then measuring the time it takes for the
fluid to return to an air content of 0.2%. Figure 26 shows the

c
(D

Group 1
mineral
oil

Groups
mineral
oil

333

ISOVG32
polyol ester

ISOVG46
PAO

ISOVG46
phosphate ester

FIG. 26The effect of temperature on air release values for different turbine oils and
fluids.

334

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

air release properties over a range of operating temperatures


for various turbine oils and fluids.
Typical specification requirements for mineral oils, e.g., as
required by ASTM D 4304, vary from 5 min (ISO VG 32),
through 7 min (ISO VG 46) to 17 min (ISO VG 150) for nonEP oils and up to 25 minutes for products with improved
load-carrying capacity. As would be expected, air release values increase with viscosity and this is reflected in these limits. Turbine manufacturers tend to have more severe requirements with 3-5 min m a x i m u m frequently specified for both
steam and gas turbines. The air release properties of phosphate esters vary significantly with chemical type. The "natural" phosphates such as trixylyl phosphates tend to have very
low air release values of about 1 min while the synthetic types
(ISO VG 46 grade) are in the region of 5-8 min, hence specification limits for fire-resistant control fluids are frequently
of the latter order. It is probable that m a n y
fluid-related
problems could be avoided if there was a greater awareness
of the impact of system design on air entrainment.

Chlorine Content
Limits on chlorine content are required with phosphates in
order to avoid servo-valve erosion [63]. In fact it is the chloride ion (CI ) level that is critical and this can arise either
as a trace contaminant from the manufacturing process
(from the use of phosphorus oxychloride) or by air-bom
contamination. Another source is the incorrect use of chlorinated solvents for cleaning system components. Although
the chlorine in solvents is not initially present in ionic form
it is thought that the solvents break down thermally in the
system to release chloride ion. While limits are placed on
new fluid levels (normally 50 ppm), the content of chlorine
in fresh fluid is usually significantly lower (typically 20-30
p p m ) . In spite of the importance of the level of chloride ion
in the fluid, it is rarely specified for new fluid and the limits that have appeared in the past are at much lower levels,
e.g., 0.5-2 ppm.
The accurate measurement of very low levels of chlorine is
not easy and the standard b o m b calorimeter tests are not sufficiently accurate, as the combustion of phosphates by macro
techniques is usually incomplete. ASTM D 808, Standard
Test Method for Chlorine in New and Used Petroleum Products (Bomb Method), a typical bomb calorimeter process, for
example, is only valid for chlorine levels of 0.1-50%. Instead,
microcoulometry (e.g., IP proposed method AK99), a combustion process which uses very small amounts of sample is
preferred, or possibly X-ray fluorescence (ISO 15597). The
basis of all the calorimeter methods is the titration with silver nitrate of the chloride ion produced by combustion. Due
to the purity of phosphates in commercial production this
parameter is rarely a problem today and, as will be shown
later, is controlled in use by special filtration techniques.

Fire-resistance Tests
These properties are the most important requirements for the
phosphate esters and for the small quantities of polyol esters
that are supplied as hydraulic fluids into this application. The
origins of fires in turbines are divided almost equally between
the lubricant and hydraulic fluid [64] and are normally a re-

sult of contact with a hot surface. An obvious example of this


would be a hot steam pipe, where temperatures are now
reaching 610C. However, there are other potential sources of
ignition such as bearing housings and gas turbine exhausts
that may be hot enough to ignite oil vapor, if not the liquid itself [65].
Unfortunately, there is no single test that can satisfactorily
predict fire behavior and several tests are necessary to obtain
a more complete assessment of performance. Much depends
on the form in which the fuel (in this case the oil or fluid) is
present. For example, it is easier to ignite the fluid in the vapor state as the access to oxygen is greater (combustion is an
oxidation reaction with the release of heat in the form of a
flame). The evaluation of fire resistance by tests that simulate
the hazard is therefore of crucial importance. While many
tests have been devised to assess this property, three types are
widely used: 1) Spray ignition behavior, 2) Hot surface ignition, and 3) The flammability behavior when the fluid is absorbed onto a substrate [66].
Simple flash and fire points (ASTM D 92, Standard Test
Method for Flash and Fire Points by Cleveland Open Cup) are
used to identify very flammable (and volatile) materials but,
for products of low volatility such as are used as fire-resistant
fluids, flash and fire points do not necessarily relate to the
performance of these fluids in other, more hazard-related,
tests. A high fire point, for example, does not automatically
mean good performance in spray or hot surface ignition tests
(see Table 8 and [66]). Today, flash and fire point tests are
used more for quality control purposes rather than for measuring fire resistance [66].
As indicated above, in turbines, the main hazard is a hot
surface. Where the surface is lagged, the risk increases in
view of exposure of thin films of oil or liquid to oxygen in the
lagging. The wick test (below) does not properly simulate this
condition as the oil film in the lagging (unless saturation is
reached) is thinner and the access to oxygen is greater. However there is currently no standard method that accurately reproduces this condition.
The test methods that are most widely used to assess fire
resistance include the following:
Spray Ignition

Tests

These are of two types: 1) Those that attempt to ignite the


fluid by spraying at elevated t e m p e r a t u r e and pressure
through a n open flame, noting whether ignition occurred
and, if so, whether burning continued once it had moved
away from the ignition source (ISO 15029, Parts 1 and 3,
Petroleum and Related ProductsDetermination of Spray
Ignition Characteristics of Fire-resistant Fluids). 2) Measuring the heat emitted by the burning fluid (Factory Mutual
Test Standard 6930 for the Flammability of Industrial Fluids
and ISO 15029-2). It might seem strange to assess the fire resistance of so-caJled fire-resistant fluids by deliberately igniting them, but "fire-resistant" in this context does not mean
non-flammable. Most, if not cdl, fire-resistant fluids will combust if contacted by a high-energy source for a sufficient period of time.
Past spray tests tended to be pass/fail methods with poor
precision but the latest methods, such as ISO 15029-2 and the
new Factory Mutual procedure, are able to rank fluid behavior with acceptable precision and generally in the same or-

CHAPTER

12: TURBINE

LUBRICATING

OILS AND HYDRAULIC

FLUIDS

335

exhaust channel
anemometer
exhaust gas
thermocouple (Tp/Tex)

nozzle

\_

ambient air
thermocouple

atomising air
hydraulic fluid

FIG. 27Schematic representation of the test chamber used for the ISO 15029-2 Spray
Ignition Test. Reprinted with permission of the Health and Safety Laboratory, Sheffield,
UK.
der. Figures 27 and 28 are diagrammatic representations of
the equipment used to carry out the above tests.
Hot Surface
Tests
Although the latest spray ignition tests can indicate the relative fire resistance of fluids, the results tell us nothing about
the temperature at which the fluid would ignite on contact
with a hot surface. It is therefore important to obtain some
idea of this aspect from appropriate procedures. Currently
only one test is specified for turbine fluids, the determination
of autoignition or s p o n t a n e o u s ignition t e m p e r a t u r e , by
ASTM D 286 or D 2155 (both now obsolete) or by E 659, Standard Test Method for Autoignition Temperature of Liquid
Chemicals. In each of these procedures a small, measured
a m o u n t of the test fluid is inserted into a heated glass container (conical or round-bottomed flask). The temperature at
which the fluid ignites with the production of a visible flame
was the result recorded in the two earlier tests while the most
recent variant also observes the production of "cool flames,"
which occur at lower temperatures than conventional hot
flames.
The recent procedures have resulted from attempts to obtain a more even temperature distribution throughout the
container, while replacing the original molten lead bath,
which was a health hazard. Major differences are found between the results of the three tests with the trend towards
lower values with the later methods [66]. The reason for the
differences in results is mainly due to the increased size of
the container and therefore to the increased oxygen concentration present [67]. Unfortunately, the reduction in autoignition temperature values with recent methods has occasionally led the user to believe that an inferior product was
being supplied and as a result data is still quoted on the earlier methods, sometimes together with the figures from the
latest test. A further hot surface ignition method (The Hot
Manifold Test), based on FED-STD-791 Method 6053, is currently being developed by ISO as Standard 20823 and may be
preferred to autoignition temperature in the future as the
conditions more obviously simulate a n industrial hazard.
Wick Tests
The flammability behavior of the fluid when it is absorbed
into a substrate (or wick) can be assessed by ASTM D 5306,

S t a n d a r d Test Method for the Linear Flame Propagation


Rate of Lubricating Oils and Hydraulic Fluids, which, as the
title suggests, measures rate of flame travel along the wick.
Alternatively, ISO 14935 records the time it takes for the
burning fluid to self-extinguish after removal of the ignition
source. I n the case of the ISO standard, the ignition source is
an oxy-propane flame while in the ASTM method, matches
are used to ignite the wick. Such a test might simulate the ignition of the fluid when soaked into cloth waste. In both tests,
the unused fluid is usually evaluated whereas in reality the
fluid may have been in contact with the absorbent over a period of time allowing volatile components, such as water, to
escape. This could significantly alter the behavior of the fluid.
Obviously where such tests are required it is expected that
the fluid would meet the criteria for a "pass" irrespective of
its condition. Figures 29 and 30 show the equipment required
for the two tests.
Water Separability/Demulsibility Tests
As noted earlier, water is a common contaminant of steam
turbine oils. It may arise as a result of the penetration of seals
by steam, from cooler leaks, condensation in the tank or from
steam valves dripping onto hydraulic actuators, etc. Although
gas turbines are normally drier due to the absence of steam
and the higher operating temperature, they also use waterfilled coolers and may be periodically washed with water to
reduce the build-up of deposits within the turbine. The oil
tanks for some gas turbines are also located out-of doors and
may not be protected from the elements. Consequently, undesirable levels of water in turbine oils and hydraulic fluids
can occasionally build u p . Free water is found more frequently with mineral oils because of its m u c h lower solubility in this medium.
Water can affect turbine oil in m a n y ways: it promotes
rusting and subsequent wear, causes a reduction in the oil
stability^possibly by partition of the additives into the waterand, in the event of the formation of an emulsion, has
a n adverse effect on lubrication performance and may cause
filter blockage [68]. The effects of water can be enhanced by
the presence of other contaminants such as oxidation products, dirt, rust and other additive-treated mineral oils [69].
With both phosphate and polyol esters, the effect of water is

336

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

fire products
collector

1.25 m

nozzle

^ y - / ^

flexible
^/connectors

1.4 m

propane
burner
floor

MdNn
'

sample
pressure
vessel

propane

load cell

/7777Z
FIG. 28Factory Mutual Research spray ignition test equipment. Reprinted with permission of Factory IVIutual Research, Norwood, MA.

to cause hydrolysis and acidity generation with a potential


adverse effect on stability, rusting and corrosion performance, and surface active properties like emulsification. A
high water content in the long chain polyol ester hydraulic
fluid has also been found to promote bacterial growth
which, in severe cases, has resulted in fluid gelatification
[70].
Water must therefore be removed from the fluid or oil as
quickly as possible. In steam turbine systems free water can
be removed using a centrifuge and by filters coated with water-adsorbing polymers. Dissolved water is removed using either chemiccd adsorbents, for example a molecular sieve, or

by applying a vacuum to the fluid. Physical methods for drying used oil and fluid are practiced widely but currently the
use of chemical adsorbents is only found with fire-resistant
fluids.
Although the behavior of the fluid in use is more critical
due to the likely presence of contaminants and fluid degradation products, new fluid is tested to ensure that emulsification does not initially occur as a result of the use of surfaceactive products such as corrosion inhibitors.
The method most widely used to assess this aspect of performance is ASTM D 1401, Standard Test Method for Water
Separability of Petroleum Oils and Synthetic Fluids, (ISO

CHAPTER 12: TURBINE LUBRICATING OILS AND HYDRA ULIC FLUIDS 337

ceramic
fibre cord

chart recorder
50 g weight

50 g weight

FIG. 29Diagram of apparatus for determining linear flame propagation.

reservoir

wick

stop holes for


adjustment
<

TF5^
burner position for
setting flame height
r

|l
|l
|l
burner may
be raised and
lowered in
clamp

stop bar
from propane
regulating valve
FIG. 30Equipment used for the ISO 14395 wicl( flame persistence test.

338 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

6614) where the fluid at 40C is stirred with an equal volume of water and the time taken for separation of the resulting emulsion (if formed), is noted. Typical limits for separation to a residue of 3 mL emulsion are 30 min maximum
(mineral oils) and 15 min maximum for phosphate esters.
Stability Characteristics
Oxidative Stability
All fluids are assessed for their oxidative stability as their service lives depend to a large extent on this property, and the effects of fluid degradation in terms of acidity generation, viscosity increase, and the production of deposits can have an
important impact on the system performance. The principal
methods used for evaluating oxidative stability were indicated earlier in the discussion on the testing of antioxidants.
These methods are additionally used to assess the effects of
other additives, e.g., rust inhibitors on oxidation stability and
assessing the performance of complete formulations.
In addition to the Universal Oxidation Test designed to
overcome the long test duration associated with the ASTM D
943 test, other approaches have been or are being evaluated.
These include a dry version of the TOST and, for research
and development, quality control and residual life assessments, high pressure differential scanning calorimetry
(ASTM D 6186, Standard Test Method for Oxidation Induction Time of Lubricating Oils by Pressure Differential Scan-

50

ning Calorimetry (PDSC), [71]) and voltammetric techniques


[72,73]. The PDSC method involves heating a known (small)
quantity of the oil or fluid under pressure in oxygen at a fixed
temperature until an exotherm or release of heat occurs. The
time to the onset of the exotherm is reported as the induction
time at the specified temperature. Although it is an extremely
rapid test, "no correlation has yet been established with service performance."
The Remaining Useful Life of a Lubricant Evaduation Technique (RULLET) has recently been developed to assist the
maintenance of military aircraft engine oils. In order to determine the remaining useful life, it is first necessary to thermally and oxidatively stress a fresh oil in the laboratory at
150-175C and monitor the chemges in acidity and viscosity
as the test proceeds. When the changes in these values start
to deviate from a steady increase, this point is taken as the
end of the useful life in service and intermediate data on the
oil are used to predict the percentage remaining life in service
(Fig. 31 [73]). This method has good repeatability and apparently correlates well with RBOT and PDSC tests.
Cyclic voltammetric techniques can be used to quantify the
remaining antioxidant concentration in used oil or fluid [73].
This technique involves the extraction of the antioxidants by
a solvent containing a dissolved electrolj^te. The solvent/electrolyte system will vary depend on the type of fluid and antioxidant being analyzed. Using the solvent/electrolyte, a voltage is applied across an electrode system consisting of a

Hours of stressing time


100
150
I
l__

200

250
1-22

21

--20

--19
(^
o
18 b
To

178
' '

in

--16

-Lis
200

150

100

IHours of remaining useful life


FIG. 31Percent remaining useful life (RUL), viscosity (40C) and total acid number
against h of stressing time and remaining useful life at 175C for a typical aircraft engine
oil. Reproduced with permission of STLE, Park Ridge, IL.

CHAPTER 12: TURBINE LUBRICATING


"glassy" carbon electrode, a platinum reference electrode,
and a platinum auxiliary electrode. The voltage of the auxiliary platinum electrode is scanned from 0 to 1.5 V at 0.2
V/sec. Data is produced by measuring the current through the
cell as a function of the applied potential and the different antioxidants produce a typical "signature" from which the composition can be deduced. Comparison of the current produced for each antioxidant with reference data on solutions
containing known amounts of the stabilizer will reveal the
level of the antioxidant in the used oil. It was found possible
to correlate the remaining oil life with the residual antioxidant concentration, and both techniques can be of benefit in
applying predictive maintenance.
The importance of avoiding deposits in aviation gas turbine lubricants is such that an additional full-scale bearing
test that simulates engine behavior is specified for these oils.
Details of the test used to assess this aspect of performance
are given in FED-STD-791 method 3410 and involve lubricating a heated 100 mm diameter roller bearing with the test
fluid at an elevated temperature (between 300-400F or
149_204C) for 100 h. At the end of the test the bearing is assessed for deposits against a "demerit rating scale" while the
weight of filter deposits and changes in oil viscosity and acidity are also measured.
Thermal Stability
Tests for this parameter fall into two categories:
1. Those carried out in the absence of air, e.g., FED-STD-791
method 3411 (despite the fact that it is almost impossible
to find a condition where the oil or fluid is heated in the
complete absence of air).
2. Those where oxygen is present and may cause further
degradation over and above the physical and chemical
changes resulting from the thermal degradation of the oil.
An example of this type of test is ASTM D 2070, Standard
Test Method for Thermal Stability of Hydraulic Oils.
The Federal standard method is currently only used in aviation turbine oil specifications, e.g., MIL-PRF-23699F, probably for historical reasons and to provide additional support
for the oxidation stabihty data in applications where the temperatures are very high. This procedure involves sealing a
portion of the fluid together with a steel specimen in a glass
ampoule under vacuum, heating for 96 h at 274''C and then
determining the changes in viscosity, acidity, and the weight
of the metal catalyst. Limits of 5% on viscosity change and
6.0 mg KOH/g on acidity increase are called for in the above
specification.
The ASTM method involves heating the fluid (200 ml) in an
open beaker together with iron and copper catalyst rods for
168 h at 135C. At the completion of the test the color of the
rods, which is the principal evaluation criterion, is assessed
and the amount of sludge produced, determined. This procedure is used primarily to evaluate the stability of mineral hydraulic oils and is strongly influenced by the presence of additives. However, the standard notes, "No correlation of the
test to field service has been made." By contrast the FEDSTD-791 method could be used to discriminate between ester
types that display different levels of stability depending on
their chemical structure. Diesters, for example, are able to
find a decomposition path at lower temperatures due to their
ability to more readily form a cyclic intermediate [74].

OILS AND HYDRAULIC FLUIDS

339

Hydrolytic Stability
This property assesses the fluid stability in the presence of
moisture. Normally the effect of water is to generate the acid
and alcohol (or phenol) from which the ester was originally
formed. All esters are sensitive in varying degrees to water
and, since hydrolysis is the normal mode of breakdown, it is
an important factor in determining the Hfe of both phosphates
and the polyol ester fluids used in hydraulic and aero-engine
lubricant applications. In steam turbine systems particularly,
water contamination of the hydraulic fluid and lubricant is often found and requires regular monitoring. As noted earlier
(Table 9) the structure of phosphates affects their hydrolytic
stability and may influence the selection of product for use in
steam (wet) or gas (dry) turbine applications.
The test procedure most commonly used for assessing hydrolytic stability is ASTMD 2619, Standard Test Method for
Hydrolytic Stability of Hydraulic Fluids (Beverage Bottle
Method). In this test the fluid and water are mixed together
in a rotating sealed container for 48 h at 93C in the presence
of a solid copper catalyst, followed by measurement of the
acidity level in both the fluid and the water layers and the
metal weight change. Procedures are available for fluids that
are more or less dense than water and Fig. 32 shows the bottle with oil, water, and catalyst coupon.

n
li

FIG. 32The ASTM D 2619


beverage bottle container
with oil sample (upper layer),
water, and copper catalyst.

340

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

For steam turbine control fluids, ISO 15596 is used. It is a


static procedure that is uncatalyzed and the acidity increase
of both fluid and water layers is measured. In this test, a limit
on total acidity increase of 0.5 mg KOH/g is specified.
Shear Stability
Shear stability is an additional requirement that is part of
some specifications for non-hydrocarbon oils. This is the resistance of the fluid to shear stress as the fluid is forced
through a neirrow aperture and which can result in the breakdown of long-chain molecules into smaller units. It is of particular importance for hydraulic applications in view of the
high pressures and very fine tolerances involved in pumps and
valves, particularly when the fluid contains a high-molecularweight polymer, as is the case with polyol ester fire-resistant
hydraulic fluids [66]. However, no specification requirements
yet exist for the shear stability of these fluids in steam or industrial gas turbine applications. Limits do exist, however, for
some aero-gas turbine oils, e.g., in the MIL-PRF-23699F specification. This requirement is thought to date back to the submission of thickened diester lubricants against early versions
of the specifications. The instability of these fluids resulted in
the addition of a limit on this parameter. Turbine oils (of all
t5rpes) are themselves quite shear stable.
Specifications for fire-resistant fluids based on phosphate
esters have, for many years, stipulated that polymeric thickeners are not to be used as additives. This was due to their removal by the conditioning media (usually fullers earth) with
the resulting blocking of filter cartridges and a marked reduction in fluid viscosity.
Shear stability has traditionally been measured by two
techniques viz resistance to high-frequency sound and circulation under pressure through an orifice.
Sonic Shear
The technique specified in MIL-PRF-23699F requires exposure under prescribed conditions to vibrations from a sonic
oscillator followed by a measurement of the change in viscosity (ASTM D 2603, Standard Test Method for Sonic Shear
Stability of Polymer-Containing Oils or ASTM D 5621, Standard Test Method for the Sonic Shear Stability of Hydraulic
Fluid). The scope of the early version of this method, which
was last reviewed in 1998, indicated that while useful for
quality control purposes, it did not show good correlation
with the service behavior of polymer-containing oils and may
rate different types of thickener in a different order to the
diesel injector test. The latest method however, states, "Evidence has been presented that a good correlation exists between the shear degradation that results from sonic oscillation and that obtained in a vane pump test procedure."
The principle of the test is first to degrade a reference fluid
with a sonic probe at 0C using sufficient power for 12.5 min
to produce a viscosity decrease at 40C of about 15%. Then,
using the same power setting that gave the above level of viscosity change, to irradiate the test fluid at 0C for 40 min followed by a determination of viscosity. The initial and irradiated viscosities at 40C are reported.
Resistance to Shear in a Diesel-Injector Nozzle
The second procedure involves measuring the viscosity loss
at 100C after the fluid has been circulated through a diesel

injector nozzle set at a predetermined lifting pressure, for example 17.5 MPa (175 bar) for 30 cycles, (ASTM D 3945, Standard Test Method for Shear Stability of Polymer-Containing
Oils Using a Diesel Injector Nozzle). More recently, ASTM D
5275, Standard Test Method for Fuel Injector Shear Stability
for Polymer-Containing Fluids has been published. The latter
method was originally Procedure B of the D 3945 method but
was separated after tests showed that the two procedures in
the earlier method often gave different results. Although the
principle of the two methods is the same, the equipment differs and the latest test uses conditions of 20.7 MPa (207 bcir)
and 20 cycles. In both cases, reference fluids are required to
calibrate the equipment prior to evaluating the test samples.
A concern over the lack of field correlation with the results
from the diesel injector rig has recently led to the proposal in
Europe to use a tapered roller bearing as the means for shearing the fluid. This is Co-ordinating European Council (CEC)
method L-45-A-99, "Viscosity Shear Stability of Transmission Lubricants" that promises improved precision and better correlation with field data.
Rusting and Corrosion Behavior
The requirement for an oil or fluid to prevent rusting (of ferrous metals) and corrosion (of non-ferrous metals) is an existing part of nearly all hydrocarbon turbine oil specifications. While most rust tests are carried out at typical bulk
fluid temperatures of 35-60C, high temperature corrosion
performance requires evaluation either by oxidation/corrosion tests or by specific high temperature tests in non-oxidizing conditions such as those specified by the aviation turbine
builders. Some tests, e.g., gas turbine "hot end corrosion"
cannot be satisfactorily simulated in the laboratory and require evaluation in an engine test.
The most widely-used test for assessing rusting characteristics was reported earlier as ASTM D 665, Standard Test
Method for Rust Preventing Characteristics of Inhibited Mineral Oil in the Presence of Water. In spite of the title, the
method is also used for non-hydrocarbon oils and there is provision for the testing of products such as phosphate esters,
which are heavier than water. Although it may be difficult to
distinguish between the ratings for "moderate" and "heavy"
rusting in this test, this is largely academic, as specifications
normally call for a "Pass," that is, the absence of rust.
One of the limitations of the D 665 method is that it evaluates rusting on vertical surfaces only. In reality, horizontal
surfaces that can retain droplets of water are more prone to
rusting. A method has therefore been devised "to indicate the
ability of oils to prevent rusting and corrosion of all ferrous
surfaces in steam turbines." This is ASTM D 3603, Standard
Test Method for Rust-Preventing Characteristics of Steam
Turbine Oil in the Presence of Water (Horizontal Disk
Method). The test involves immersing a horizontal steel disk
and a vertical steel cylinder in a stirred mixture comprising
275 mL of the oil and 25 mL of distilled water for 6 h at 60C.
At the end of this period the specimens are washed and inspected for rust. The test is carried out in duplicate and no
rust must be seen in either of the two tests for the oil to be
considered a pass.
The above procedures only consider rusting in fluid contact with the metal surface whereas vapor-phase rusting is

CHAPTER

12: TURBINE

also possible, for example above the liquid layer in the tank.
This condition is simulated in ASTM D 5534, Standard Test
Method for Vapor-Phase Rust-Preventing Characteristics of
Hydraulic Fluids. With the exception of cin additional steel
specimen, which is located in the vapor space above the liquid, the apparatus and test conditions are identical to those
found in ASTM D 3603. The method is divided into two parts,
the first relating to fluids where water is the continuous
phase and the second to fluids where oil or other water-free
fluids (except phosphates) are in the continuous phase. In the
latter case the water necessary to cause corrosion is contained in a bcciker located below the specimen for assessing
vapor-phase corrosion. Results are reported as a pass or fail.
The introduction of a corrosion-inhibited grade of fluid in
the MIL-PRF-23699 specification has also resulted in the incorporation of a humidity cabinet test (ASTM D 1748, Standard Test Method for Rust Protection by Metal Preservatives
in the Humidity Cabinet.) This procedure involves immersing steel plates in the fluid, allowing them to drain and then
exposing t h e m to water vapor in the cabinet. The time tciken
for the production of rust is monitored.
In use, metals of different t3rpes may be in contact with one
another and the potential difference of the metal couple in
these conditions can influence gcJvanic corrosion, particularly with water-based fluids. An attempt to simulate this
condition for non-aqueous fluids is found in the CETOP
Method RP 48H, which is also being published as ISO 4404
Part 2. In this test, selected metal pairs in electrical contact,
after cleaning and pre-weighing, are half immersed in the
fluid for 28 days at 35C in a covered beaker. At the end of the
test period the weight change is measured and examination
made of the specimens for signs of corrosion, including the
surface above the liquid layer, which will indicate whether
vapor-phase corrosion has tciken place.
Hydraulic or lubricating oil systems containing phosphate
esters can be made from either mild or stainless steel and,
while rusting can occur with these fluids, it is not a common
occurrence and is normally limited to the area above the liquid layer in the tank where condensation occurs. If the tcink
interior is coated with phosphate, this forms a protective
layer and reduces the possibility of rusting. In cases where
the mild steel surface does not come into contact with the
fluid, condensation may be prevented by maintaining w a r m
fluid in the tank and/or passing dry air over the surface of the
liquid in the reservoir. As a result it is now standard practice
to leave the interior surfaces of hydraulic systems unpainted
when using phosphate esters. In the past, epoxy coatings
were recommended, but unless the coating can be cured in
position, the long-term resistance of this type of paint cannot
be guaranteed. However, due to the reduced risk of rusting
with these fluids in turbine applications, the frequent use of
stainless steel systems and the possible removal of inhibitors
by the adsorbent solids used in fluid conditioning to maintain low levels of acidity, there is normally no rusting requirement in the specification for this type of fluid.
With regard to non-ferrous metals, the corrosion of copper/brass as is found, for example, in turbine oil coolers, can
be a problem for all oil types, as the dissolution of this metal
will catalyze oil oxidation. The potential for oils to cause corrosion of copper and its alloys and the use of ASTM D 130 for
assessing this condition was mentioned above. While metal

LUBRICATING

OILS AND HYDRA ULIC FLUIDS

341

passivators can minimize this problem, use of stainless steel


or titanium coolersor even dry coolingis now possible.
Lead, silver, a n d magnesium, which are also prone to
acidic corrosion, may need special protection when used.
These metals have been used in aero-engine systems as
lightweight casings for components (magnesium) and in solder (lead a n d silver). To prevent magnesium corrosion the
surface is painted and propyl gallate has been used as an inhibitor for lead. A test for lead corrosion still features in MILPRF-7808L. This is FED-STD 791, method 5321, which involves immersing lead and copper specimens in the fluid for
1 h at 325F (162C) during which time air is passed through.
At the conclusion of the test the weight change of the lead
panel is measured. The same specification also requires a
corrosion test to be carried out on silver and bronze using
FED-STD-791, method 5305. This is a high temperature test
carried out at 450F (232C) in which strips of each metal cire
immersed in the oil for 50 h followed by an assessment of the
weight change.
In systems using phosphate esters, a l u m i n i u m surfaces
need to be hard anodized to prevent attack by acidic degradation products.
Lubrication
The lubrication performance of a n oil or fluid can be regarded as its ability to reduce weeir on metal surfaces sliding
relative to one another under load. It is a combination of the
performance of the fluid base stock and the additive package.
All the finished fluids discussed so far are acknowledged to
have good lubrication performance and for most steam and
gas turbine applications there are no additional lubrication
performEince requirements. Occasionally there is a call for a
4-ball wear testASTM D 4172, Standard Test Method for
Wear Preventative Characteristics of Lubricating Fluid. This
involves measuring the wear produced on three ball bearings
held stationary in a cup containing the test fluid. A fourth ball
is rotated in contact with the stationeiry bccirings while a load
(normally 40 kg) is applied for a period of 1 h (see Fig. 33).
For oils needing extreme pressure performance, a gear-test
failure load may be specified. As indicated above, this is now
carried out according to ASTM D 5182, S t a n d a r d Test
Method for Evaluating the Scuffing Load Capacity of Oils
(FZG VisucJ method), or in aviation oils by the Ryder Gear
Test.

Cleanliness
The importance of clean oil, to ensure that small orifices in
valves remain clear, that bcciring surfaces cire undamaged,
and that p u m p s and motors r u n smoothly, is now well accepted. Dirt can EJSO play a part in catalyzing oil and fluid
degradation by stabilizing foam and increasing oxidation. It
may also promote emulsification in the presence of water
and increase the conductivity of the fluid. Limits on cleanliness have therefore become steadily tighter over the years. At
the same time the variety Eind efficiency of filters has improved [53]. Today, turbine lubrication systems use 6 fim
(j8 = 200) filters while hydraulic systems generally have finer
filtration, typically 3 jam (jS = 200) filters to remove particles
as small as 3.0/im "absolute" in view of the use of fine toler-

342

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Top ball turned


by drive motor

3 lower balls
clamped

Thermocouple

A/V\AAAA^

Heater

FIG. 33Schematic of the four-ball wear test apparatus.

ance valves, such as servo-valves, where clearances can be of


the order of 3-5 microns.
Several methods are available for the determination of particulate levels. These fall into the categories of automatic
counting by light interruption techniques, manual counting
of particles deposited on a filter paper, and gravimetric procedures.
Light interruption methods are probably the most widely
used of the above and involve the passing of a fixed volume of
the fluid across a light beam. When a particle interrupts the
beam a record is made and the size is registered depending
on the extent to which the beam has been blocked. The particle counters will automatically allocate the reading to one of
several pre-programmed size ranges depending on the range
required by the specification, for example, to a range of,
>5)U,m, 5-15)am, 15-25jam, 25-50Atm, 50-100/j.m, etc. While
it is a relatively quick way of counting particles, it is not the
most precise. It presupposes that the sample is homogenous,
i.e., the particles are evenly dispersed and that they are regularly shapedassumptions that are entirely theoretical. Light
interruption techniques can also count products dispersed in
the fluid, e.g., antifoams. The ASTM method using this technique is F 661, Standard Practice for Particle Count and Size
Distribution Measurement in Batch Samples Using an Optical Particle Counter, while the equivalent ISO standard is
4402.
The membrane filtration methods are more accurate. In
the manual counting method, e.g., ASTM F 312, Standard
Test Method for Microscopical Sizing and Counting Particles
from Aerospace Fluids on Membrane Filters, a known volume of fluid is filtered through a membrane filter, the surface
of which is divided into squares of known and equal size. The
number of particles in a representative selection (at least 10)
of these squares is then counted manually and sized and
scaled-up to produce an approximate total number on the filter pad. (ISO 4407/4408 are similar manual counting methods.) This procedure is very time-consuming and is also

based on the assumption that the deposit is distributed


evenly over the filter. Potentially the most accurate procedure, and sometimes used as a referee method in cases of dispute, is the gravimetric method in which a known volume of
fluid (usually 100 mL) is passed through a filter disk with a
pore diameter of 0.45^lm or 0.80/Am and the weight of the deposit accurately determined (ASTM D 4898, Standard Test
Method for Insoluble Contamination of Hydraulic Fluid by
Gravimetric Analysis). ISO 4405 is based on the same technique. Again the method does not indicate the size of the particles, a factor that can be of use in determining the possibility of damage to equipment and may also suggest the source
of the contamination. For example, the presence of sub-micron sized particles can be indicative of "dieseling" in the hydraulic system.
The ability of the light interruption technique to size particles in bands or ranges allows the development of a classification system based on the maximum number of particles in
each band. Original attempts to rank the contamination levels of hydraulic fluids were published as ASTM, SAE, and
NAS standards. However the distributions used were largely
geometric progressions that were unrelated to the actual pattern of particle distribution found in hydraulic fluids [76]. As
an alternative, ISO subsequently published a standard, 4406,
Hydraulic Fluid Power-Fluids-Method For Coding Level of
Contamination by Solid Particles, the latest version of which
(1999) classifies particles into ranges of >4 ^m, >6 ^m, and
> 14 ^tm, respectively and, depending on the numbers of particles in each range, allocates a "scale number." This makes
possible a numerical description for the particulate levels in
both new and used fluids. For example the scale number 15
corresponds to 160-320 particles/mL and scale number 12 to
between 20 and 40 particles/mL.
Most turbine oil and fluid specifications still have to be updated and are using the previous version of the ISO classification based on the number of particles >5 /i,m and >15 yam
in size. They typically call for scale numbers of 17/14 or 18/15

CHAPTER 12: TURBINE LUBRICATING


for turbine lubricants and 15/12 for the control fluids. However, such is the pace of change that the SAE 749D classification procedure, which was disowned by SAE in 1971, is still
occasionally specified.
In order to obtain meaningful data from any of these tests
it is essential that the correct sampling procedure, in terms of
where and how to take a sample from the system or container,
be used. ISO 4021, for example, indicates how samples should
be taken from the lines of an operating system. ISO 3170 details suitable sampling procedures from containers while ISO
3722 details how containers should be cleaned before use, a
point that is frequently overlooked and can invalidate particle
count data. It is also important to ensure that the sample bottle is compatible with the fluid being sampled.
Trace Metals
The introduction of trace metal analysis into turbine oil specifications is now found quite widely, but for different reasons.
In mineral turbine oils the trend to ashless products, and
particularly away from the use of zinc dialkyldithiophosphate as an antioxidant/extreme pressure additive, has led to
the introduction of limits on zinc content. Current specification limits can be very low (about 2 ppm meix.) or somewhat
higher levels (100 ppm max.).
In aviation gas turbine lubricants, limits of 2-10 ppm, depending on the metal concerned, have long been in place.
This is to minimize contamination, to avoid a possible catal5^ic effect on oxidative breakdown, and because certain
organo-metallic additives, used in the past as extreme pressure additives, precipitated on storage. Today, the data also
functions as baseline or reference information for the spectrographic oil analysis programs (SOAP), which are used to
monitor the condition of used military aviation gas-turbine
lubricants. With phosphate esters, the final processing step in
manufacture may involve contact with alkaline media to
lower the acid number and the resulting presence of soluble
metal salts can promote foaming and an increase in air release properties [77]. In use, phosphate esters are normally
treated by an adsorbent medium to remove acidic degradation products. However, the most widely used adsorbents,
fullers earth and activated alumina, contain compounds that
react chemically with the acids to form soluble metal salts
[78]. These salts can adversely the surface-active properties
of the fluid and therefore need occasional monitoring. One
method used for measuring low levels of metal contaminants
in hydrocarbon oils is ASTM D 4951, Standard Test Method
for Determination of Additive Elements in Lubricating Oils
by Inductively-Coupled Plasma Atomic Emission Spectrometry. With phosphate esters, this method can give incorrect
results on certain metals (e.g., sodium) and for this medium
at least, atomic absorption spectrometry (AAS) is preferred.
The ASTM procedure for AAS (D 4628) is currently targeted
towards the analysis of barium, calcium, magnesium, and
zinc but can easily be adapted to detect other metals.
Volume Resistivity
One requirement that is specific to phosphate ester control
fluids is the measurement of volume resistivity. This param-

OILS AND HYDRAULIC FLUIDS

343

eter, which is the reciprocal of conductivity, has been found


to relate to the tendency of the fluid to produce servo-valve
erosion [63]. This is an electrochemical process caused by the
development of a "streaming current" close to the valve surface arising from fluid flow across the valve. As well as being
influenced by the chemical structure of the fluid, it also depends on the presence of contaminants such as water, acid,
chloride ions, dirt, and metal soaps. Even polar additives can
reduce the resistivity.
The problem initially arose when polychlorinated biphenyls
were used as fire-resistant fluids in turbine control systems
and investigators linked the phenomenon with chlorine content and low resistivity. A minimum limit on resistivity of 5 or
10 by 10' ohm.cm. (50 or 100 Mi2m) was therefore introduced
and is now part of all fire-resistant control fluid specifications.
This property is measured by ASTM D 1169, Standard Test
Method for Specific Resistance (Resistivity) of Electrical Insulating Liquids. Internationally, the method specified is lEC
60247, Measurement of Relative Permittivity, Dielectric Dissipation Factor, and d.c. Resistivity of Insulating Liquids.
Both procedures involve measuring the resistance between
the terminals of a test cell when a specified voltage is applied.
Accurate measurement of the test temperature is important as
resistivity is very sensitive to this property. While the lEC
method precisely specifies the voltage gradient, the ASTM
procedure allows considerable latitude in this key aspect. In
order to improve the correlation between the methods, the
voltage gradient along with other test variables such as electrode gap and test temperature should be the same. In view of
the effect of small amounts of impurities on the results, it is
important that no additional contamination of the sample
takes place. Consequently, the sampling of the fluid and the
cleanliness of the sample container are very important when
evaluating this parameter. Figure 34 shows a general view of
the test equipment used for determining volume resistivity,
while Fig. 35 is a diagram of a typical test cell.
Compatibility with System Materials
In selecting system components for use with both mineral
and synthetic turbine oils, it is important to ensure that the
fluid is compatible with the constructional materials, that is
contact with the fluid should not result in significant changes
to the physical or chemical properties of the material. Small
changes are to be expected in some materials and, indeed,
may be beneficial. For example, the controlled swelling of a
seal will help it fill the cavity and maintain its performance at
high pressures.
The main concerns in this area are the behavior of seals,
paints, and gasket materials in the presence of the operating
fluid. Inadequate compatibility with a seal, for example, may
cause the swelling or softening of the rubber due to penetration by the oil or fluid, with subsequent fluid leakage. The use
of unsuitable paints could cause softening, flaking and subsequent filter blockage, perhaps leading to pumping problems. Occasionally there are incompatibility problems with
metals. Phosphate esters do not "wet" the surface of aluminium and therefore this metal is unsuitable as a bearing
material for these fluids.
Hydrocarbons are generally less searching than synthetic
fluids in this area although the PAOs are problematic owing

344

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

to their lack of seal swelling and necessitate the use of a cocomponent (usually a carboxylate ester) as a seal-swelling
agent.
The high operating t e m p e r a t u r e s experienced in a n increasing n u m b e r of applications, for example aviation gas
turbine lubricants, place severe stress on conventional elastomers. Consequently, the use of fluorocarbon (and, to lesser
extent, perfluoroelastomer) seals is now widespread. Phosphates eire also very selective with regard to seals and paints,
but fortunately a suitable range of materials is now available.
Examples of suitable elastomers for turbine oils and fluids
are given in Table 20. A general procedure for testing for the
compatibility of seals in non-aerospace applications is detailed in ISO 6072, Hydraulic Fluid Power-Compatibility between fluids cind standard elastomeric materials, while the
aero-gas turbine oil specifications require performance
against FED-STD-791 methods 3604 and 3433 or procedures
listed by the equipment manufacturers. An ASTM standard
entitled "Standard Test Methods and Suggested Limits for
Determining the Compatibility of Elastomer Seals for Industrial Hydraulic Fluid Applications" is currently in development. Table 21 illustrates the conditions recommended for
testing different elastomers in the ISO 6072 standtird. The list
indicates the principal types of elastomers used with the different fluids, but is not exhaustive.
All the procedures involve suspending a rubber specimen
of known volume in the oil or fluid u n d e r fixed conditions of
temperature and test duration. This is followed at the end of
the test by a second measurement of the volume to determine
the percentage swell that has occurred. Additional measurements may be made of the chemges in elongation at break and

tensile strength. Depending on the rubber type and application, the test temperature may vary significantly. Fluorocarbon and perfluorocarbon rubbers are, for example, evaluated
at higher temperatures than nitrile and neoprene. However,
tests at high temperatures, e.g., 150C as currently appear in
the latest draft ISO 6072 standard, may not be representative
of practice since, at this temperature, the basestocks and additive packages may not be stable and could give erroneous
results.
Until recently, all methods specified relatively short periods of immersion, usually u p to one week. It is now accepted
that this period may be too short for the degree of swell to
have stabilized, and in the latest version of ISO 6072, tests of
1000 h in length are now proposed in addition to the shorterterm exposure.
No s t a n d a r d m e t h o d s in turbine oil specifications are
known for evaluating paint compatibility and this aspect is
generally left to the paint manufacturers w h o u n d e r t a k e
long-term tests.
The aspects of compatibility discussed above relate only to
the fluid/constructional material interface. There is EJSO the
aspect of the compatibility of different oils and fluids with
each other. Should fluids from different manufacturers be
mixed? This aspect is viewed differently by different industries. On the one h a n d it is a condition of militciry aviation oil
specifications that all approved products should be compatible with one another. If this were not the case it could impair
the combat readiness of aircraft. In the industrial power generation market some equipment builders specify that a new
fluid must be compatible with the residue of the previous
charge without any adverse effect on the new oil. However,

FIG. 34A general view of the test equipment for measuring d.c. resistivity.

CHAPTER 12: TURBINE LUBRICATING

OILS AND HYDRAULIC FLUIDS

345

090
1

1 = inner elecrode
2 = outer etecrode
3 = guard ring
4 = inner elecrode
5 = silica washer
6 = silica washer
7 = minimum level
of liquid

Volume of liquid is about 45 cm^


All surfaces in contact with liquid have a mirror finish
Dimensions in millimetres
FIG. 35Example of a three-terminal resistivity cell. Reprinted with
permission of the International Electrotechnical Commission, Geneva,
Switzerland.

nothing is indicated regarding topping-up an existing fluid


with a product from a different supplier, probably because
such an occurrence is unusual. Obviously, mixing fluid tjrpes
that are not completely miscible should be avoided. Some
concern has also been expressed regarding the mixing of
products that have the same base material but different additive packages. This is because of possible interaction of the
different additives resulting in a reduction in performance.
Very often, the attitude of the turbine builder is not to allow
the use of a second oil (for top-up) during the warranty period of the turbine. Afterwards this would only be accepted if

the builder had investigated the compatibility of the two fluids cmd/or the user had accepted the risk associated with mixing. In some cases oils can be mixed without problems but
laboratory tests are advisable to check the effects of physical
and chemical (in)compatibility, e.g., the impact on stability
and the surface active properties (e.g., foaming and air release). The test used by the aviation turbine oil industry,
FED-STD-791 method 3403, Compatibility of Turbine Lubricating Oils, involves checking the miscibility with reference
ester-based lubricants. Mixtures of the test oil and the reference lubricants at three concentrations are heated in an oven

346

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

for 1 week at ZZl^F (105C) followed by a determination of


the sediment produced.
Volatility
In military aviation applications where a low viscosity oil is
used in a high temperature environment, for example the 3
cSt oils specified in MIL-PRF-7808L, it is necessary to ensure
that the oil is not too volatile. This is determined in ASTM D
972, Standard Test Method for Evaporation Loss of Lubricating Greases and Oils. This procedure involves passing air
at 400F (205C) over the surface of a weighed quantity of oil
heated to the same temperature and held in a test cell of specified dimensions. After 6'/2 h the weight loss of the sample is
determined. In order to ensure that the equipment is providing the appropriate level of severity, a test is carried out with
a reference liquid and, if necessary, a correction factor applied. The test limit is 10% maximum.
Assuming that the new fluid meets all the requirements
laid down in the specifications it may still be necessary to arrange trials in the turbine builder's equipment. These can require several years of satisfactory operation and be very
costly to arrange and carry out.
TABLE 20Elastomer compatibilities of different
turbine oils and fluids.
Phosphate
Mineral Oil
Seal/Hose Material
and PAOs
Ester
Neoprene
Nitrile
Chlor-sulphonated
polyethylene
Epichlorhydrin
Styrene-butadiene
Ethylene-propylene
Butyl
Fluorocarbon
Perfluoroether
PTFE

Polyol
Ester

Yes
Yes
Yes

No
No
Yes''

No
Yes"
Yes

Yes
No
No
No
Yes
Yes
Yes

No
No
Yes"
Yes
Yes*
Yes
Yes

No
No
No
No
Yes
Yes
Yes

"Variations in the composition of these elastomers in particular can cause


differences in fluid compatibility and the seal manufacturers should be
consulted before use.
^Fluorocarbon rubbers are compatible with aryl phosphates, but not with
alkyl phosphates.

THE IMPORTANCE OF SYSTEM


CLEANLINESS
One emphasis in this chapter has been on ensuring the cleanliness of the oil or fluid. However, there is no advantage in
having a clean fluid only to fill it into a dirty system. The performance advantages of fresh fluid would soon disappear in
these circumstances.
There are two situations where attention to the system
cleanliness is most important. The first is during commissioning of the new equipment or after major overhauls when
the system is flushed. This procedure will remove dirt,
preservative oils and greases, cleaning solvents, and other
residual matter from cleaning and assembly operations, e.g.,
welding slag and cleaning rags. Effective flushing may involve removing or blanking-off system components and separately cleaning them while dividing the pipework into sections and circulating a flushing fluid through each section,
preferably under turbulent flow conditions to remove as
much debris as possible.
Some builders remove rust by "pickling" the pipework by
circulating a dilute solution of acid followed by a water wash
and then dry with a current of warm air.
In the past, chlorinated solvents have been used to remove
oil films on components during assembly and residual product in the hydraulic system has subsequently caused servovalve erosion [63]. As a result, use of this tjrpe of solvent is
now banned and has been replaced by hydrocarbons or, in
some cases, by water-based products. Preservative oils containing inhibitors that prevent rust during the transportation
and storage of the equipment can cause foaming of the operating charge if they are not adequately removed.
The second important use of a flushing charge is when replacing badly degraded fluid, which, in addition to containing acid, may have resulted in deposit formation. In this case
it is important to remove all but traces of the previous fluid
and any associated deposits by a thorough flush and, if necessary on examination, a manual cleaning of components including the tarrk interior.
More detailed guidance on the cleaning and flushing of lubrication systems is given in ASTM D 6439, Standard Guide
for the Cleaning, Flushing and Purification of Steam, Gas

TABLE 21Conditions recommended for testing the compatibility of elastomers with different turbine fluids.
Suitable
Temperature
ISO
Duration of
Test Elastomer
C 1
Test" h 2
Fluid
Classification
HH, HL
HM, HR
HV

NBRl, 2
HNBRl
FKM2

100
130
150

Aryl phosphate esters

HFDR

FKM2
EPDMl

Polyol esters

HFDU

Mineral oils

Synthetic hydrocarbon

HEPR

168

1000

150
130

168

1000

NBRl, 2
HNBRl
FKM2

100

168

1000

HNBRl
FKM2

130
150

168

1000

"The test duration of 1000 h is recommended for evaluation of elastomer compatibility with highly critical fluids.
NBR = nitrile (acrylonitrile butadiene)
HNBR = hydrogenated nitrile
EPDM = ethylene propylene
FKM = fluorocarbon
Reprinted courtesy of the International Organization for Standardization, Geneva, Switzerland.

CHAPTER 12: TURBINE LUBRICATING


and Hydroelectric Turbine Lubrication Systems and, for hydraulic systems, in ASTM D 4174, Standard Practice for the
Cleaning, Flushing and Purification of Petroleum Fluid Hydraulic Systems. Both documents relate specifically to hydrocarbon oils and discuss the types of contamination found
in practice, how they can be controlled, guidance on suitable
flushing procedures, oil sampling techniques, and condition
monitoring. For non-hydrocarbon fluids, information is to be
obtained from the fluid manufacturers or other appropriate
standards, e.g., lEC 60978, Maintenance and Use Guide for
Triaryl Phosphate Ester Turbine Control Fluids, which provides similar information except for recommendations on
flushing.
The fluid used for flushing is often the operating charge,
but this is expensive if a second charge of fluid is used for
normal operation. If only small amounts of the flush fluid are
left in the system after flushing and draining, the use of a
chemically similar material, usually the base stock for the operating charge may be considered. However, if significant
quantities of the flush fluid remain in the system when the
operating charge is filled-in, the use of a cheaper fluid could
be counter-productive. The use of flush fluids that are a different chemical type to the operating charge is to be avoided
in view of concerns with regard to their compatibility with
system components and the fact that it is very difficult to remove residues from the system.
Depending on the level of contamination acquired during
the flush, it may be possible to re-use the flushing fluid several times.

TURBINE OIL AND FLUID MAINTENANCE


EPRI Report CS-4555 [79] comments that "failures of steam
turbine bearings and rotors cost the utility industry an estimated $150 million/year" and "one third of these failures involve contaminated lubricants or malfunctioning lubricant
system supply." It is unfortunately the case that many of the
operating problems found with turbine oils and hydraulic
fluids are due to poor maintenance, occasionally compounded by inadequate system design. As operating conditions become more severe, the importance of regular maintenance (both system and fluid) increases. This comes at a
time when utilities are achieving cost reductions by shedding jobs and trying to increase equipment availability. As a
consequence, there is a distinct possibility that non-essential
maintenance will suffer and the improvements in oil performance available as a result of recent technical developments
will not be fully utilized.
An essential part of all planned maintenance is the ability
to carry out regular fluid monitoring. This involves taking
representative samples from the system under strictly defined conditions as indicated, for example, in the above
ASTM and ISO Standards and then evaluating critical parameters to determine the current condition of the material.
Implicit in such a scheme is the availability of limits on these
parameters and recommendations on appropriate action
should they be reached. Also important is the frequency
of sampling. This will vary depending on the particular
parameter involved, the stress on the fluid in use, whether

OILS AND HYDRAULIC FLUIDS

347

or not the system is being commissioned, and if operational problems are being experienced. Using the data produced to establish trends in performance can assist in identifying the source of problems and when action may be
needed [80].
Unlike the extensive range of specifications available on
fresh oil or fluid, the situation with regard to the used oil is
less complicated. Many, but not all, of the turbine builders incorporate used oil requirements into their new oil specifications. A few have separate standards and some of the oil or
fluid suppliers offer guidance in the absence of information
from the turbine manufacturers. Where no builder recommendations exist, guidance is also available from national/international standards. For mineral turbine oils there are
ASTM D 4378, Standard Practice for In-service Monitoring of
Mineral Turbine Oils for Steam and Gas Turbines; the lEC
Standard 60962, Maintenance and Use Guide for Petroleum
Lubricating Oils for Steam Turbines; and the very detailed
EPRI report referred to earlier [79]. For fire-resistant hydraulic fluids, lEC 60978 and ISO 7745, Hydraulic Fluid
Power-Fire-resistant Fluids-Guidelines for Use, are available, while for aero-engine oils there are recommended limits on acidity and viscosity increase from the turbine
builders, but otherwise no published requirements. The
rapid rate of top-up of oil in this applicationeven in industrial applicationsmeans it is unlikely that the physical
changes in fluid quality would normally reach values of concern.
The above industry guides are comprehensive documents
which typically examine the reasons for fluid degradation
and its impact on fluid performance, identify fluid sampling
techniques, give appropriate tests for monitoring both new
and used oil behavior, as well as a proposed schedule for
their use. Table 22, which is taken from ASTM D 4378, identifies the turbine properties of gas and steam turbine oils
that are monitored in service, their warning limits and appropriate action to be taken in the event that these limits are
exceeded. Quite a wide range of tests can be used to monitor
fluid degradation, etc. These can be divided into primary
tests that check for specific degradants or contaminants and
secondary tests, the results of which are influenced by the
degradant or contaminant. An example would be the measurement of water, which can be determined directly and in
esters, its presence may be implied from a reduction in viscosity or a rapid increase in acid number.
Acidity is probably the most important property monitored on a regular basis, but is the parameter most frequently disputed. As indicated earlier, of the two techniques
used for determining the acid number of both new and aged
fluid or lubricant, only the potentiometric method is really
suitable for aged fluid [81]. This is because the fluid darkens
on ageing and it becomes more difficult to estimate the endpoint in the colorimetric method. Some fire-resistant fluids
are also dyed to ensure that they are not confused with mineral oils and for such fluids this technique is also unsuitable,
particularly when new.
Other important properties that are routinely measured
for all Quids include viscosity, water content, and particulate
levels. In addition, rapid changes in color and appearance
can be indicative of developing problems. A measure of the
residual life or stability of the product may also be advanta-

348 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

Test

TABLE 22Interpretation of test data and recommended action for mineral turbine oils.
Steam (S)
Oil Life
Warning Limit
or Gas (G)
(Running Hours)
Interpretation

Action Steps

up to 20 000 h
up to 3000 h

This represents above normal


deterioration
Possible causes are:
a) system very severe
b) antioxidant depleted
c) wrong oil used
d) oil contaminated

Investigate cause.
Increase frequency of
testingcompare with
RBOT data.
Consult with oil supplier for
possible reinhibition.

0.3-0.4 mg KOH/g

S, G

at any time
during life of
oil charge

Oil at or approaching end of


service life, c) or d) above
may apply

Look for signs of increased


sediment on filters and
centrifuge. Check RBOT. If
less than 2 5 % of original,
review status with oil
supplier and consider oil
change. Increase test
frequency.

RBOT

less than hcJf value


on original oil

up to 20 000 h

Above normal degradation

Investigate cause.
Increase frequency of testing.

RBOT

less than half value


on original oil

up to 3000 h

Above normal degradation

Investigate cause.
Increase frequency of testing.

RBOT

less than 2 5 % of
original oil

S, G

at any time

Together with high acid no.


indicates oil at or
approaching of service life.

Resample and retest. If same,


consider oil change.

Water content

exceeds 0 . 1 %

at any time

Oil contaminated.
Potential water leak.

Investigate and remedy cause.


Clean system by suitable
method.'' If still
unsatisfactory, consider oil
change or consult oil
supplier.

Cleanliness

exceeds accepted
limits"

at any time

Source of particulates may


be: a) make-up oil; b) dust
or ash entering the system;
or c) wear condition in
system.

Locate and eliminate source


of particulates. Clean
system oil by filtration or
centrifuge or both.

Rust test D 665,


procedure A*

light fail

up to 20 000 h

a) the system is wet or dirty


or both
b) the system is not
maintained properly (e.g.,
water drainage neglected,
centrifuge not operating.)

Investigate cause and make


necessary maintenance
changes. Check for rust.
Consult oil supplier
regarding reinhibition if test
result unchanged.

Rust test D 665,


procedure A*

light fail

S, G

after 20 000 h

Normal additive depletion in


wet system. Maintenance

Consult oil supplier regarding


reinhibition.

Appearance

hazy

S, G

at any time
solids or both

Oil contains water, and


remedy. Filter.

Investigate cause or centrifuge


oil or both.

Color

unusual and rapid


darkening

S, G

at any time

This is indicative of:


a) contamination
b) excessive degradation.

Determine cause and rectify.

Viscosity

5% from original
oil viscosity

S, G

at any time

a) Oil is contaminated,
b) oil is severely degraded, or
c) higher or lower viscosity
oil added.

Determine cause. If viscosity


is low, determine flash
point. Change oil if
necessaiy.

Flash point

drop 30F or more


compared to new
oil

S, G

at any time

Probably contamination.

Determine cause. Check other


quality parameters.
Consider oil change.

Foam test D 892

exceeds following
limits
tendency: 450
stability: 10

S, G

at any time

Possibly contamination or
antifoam depletion. In new
turbines residual rust
preventatives absorbed by
oil may cause problems

Rectify cause. Check with oil


supplier regarding
reinhibition.
NOTE: plant problems often
mechanical in origin.

Acid no.
Increase over
new oil

0.1-0.2 m g K O H / g

Acid no.
Increase over
new oil

Sequence 1

S, G

"Definition of suitable cleanliness levels depends on turbine and user requirements.


^Satisfactory for land turbines.
'^Appropriate methods may include centrifuging, coalescence, or vacuum dehydration.

CHAPTER

12: TURBINE

geous. This can be obtained either by determining the RBOT


value, an indication from analytical methods of the level of
antioxidant concentration, or by the use of voltammetric
techniques. For phosphate esters, volume resistivity may additionally need to be monitored in order to avoid the possibility of servo-valve erosion.
One basic difference between the use of fire-resistant fluids/lubricants ajid hydrocarbon oils and synthetic esters is
that, in order to remove the acid that is normally formed as
a result of fluid hydrolysis or oxidation, the fire-resistant fluids are purified or reconditioned in situ. This involves passing the fluid on a by-pass loop from the m a i n reservoir
through an adsorbent solid that removes acid and chloride
from the fluid and also acts as a fine particle filter. For many
years fullers earth has been used for this purpose but has often resulted in the formation of soluble calcium and magnesium soaps, which have h a d an adverse effect on fluid foaming a n d air release properties a n d w h i c h eventually
precipitate in the form of gels in filters and in parts of the
system where the fluid is cooled [80]. In an attempt to avoid
this problem, other treatments have been used, notably activated alumina and blends of purified activated eJumina with
alumino-silicates. The latter is a definite improvement but
can still eventually result in the dissolution of sodium and
aluminium in the fluid unless the acidity is kept very low
[80]. More recently, the use of ion-exchange media h a s
shown great promise a n d now enables the life of the fluid to
be extended almost indefinitely [78] with a very positive effect on fluid maintenance costs and almost eliminating the
need for fluid disposal.

FUTURE TRENDS
Many of the developments discussed in the course of this
chapter will continue to influence the development and availability of turbine lubricating oils. Some of t h e m were the subject of presentations at an ASTM Symposium entitled "Turbine Lubrication in the 21st Century." The papers presented
are now published and serve as a useful reference to the subject [82].
Where possible, the turbine builders will continue in their
sccirch for higher operating efficiencies that will result in even
higher operating temperatures and greater thermal and oxidative stress on the lubricant. This, in turn, will accelerate the
move from solvent refined oils towards severely hydrocracked
oils and synthetic hydrocarbons. It may also accelerate a
move toward fire-resistant lubricants particularly as the dcingerous "cocktail" of higher temperatures and reduced staffing
could result in an increase in the frequency of oil fires.
The d e m a n d for greater e q u i p m e n t availability and reduced outages in order to improve the financial returns to the
IPPs will also result in a demand for longer oil/fluid lives. The
increase in operational severity will place even greater emphasis on stability, but the advent of in-service monitoring of
stabilizer levels, re-inhibition of the existing charge, the possibility of in situ reclamation by better filtration, and removal
of developed acidity by by-pass treatment will extend oil life
still further.
As a result of the anticipated longer oil life there will be increased competition for the initial fill. This will substantially

LUBRICATING

OILS AND HYDRAULIC

FLUIDS

349

reduce the operating margins for new business cind encourage the suppliers to provide "cradle-to-the-grave" service
agreements whereby they maintain the fluid throughout its
life, supply top-up material as needed, and eventually dispose
of the degraded product. The development of in situ condition-monitoring techniques will assist station staff in determining the level and timing of necessary fluid maintenance.
The trend to environmentally friendly fluids, where required, may also develop^particularly for water turbine applications, where some experience has been obtained with
biodegradable fluids [83].
One recent development not previously mentioned that
may have a future impact on the lubrication of gas turbines
has been the successful evaluation in a static engine test of a
vapor-phase lubricant based on a tertiarybutylphenyl phosphate [84,85]. Very small amounts of the lubricant are vaporized and react with the metal surface of a ceramic bearing
to form a polymeric film that can sustain a load. The immediate interest appears to be for missiles and other unmanned
aero-space vehicles because of the reduced weight penedty
with the smaller volume of liquid required, b u t wider use in
the longer term may be possible.
Acknowledgments
The author gratefully acknowledges the kind assistance (and
patience) of R. Coombes and G. N. Kay of Alstom Power, M.
Dennis of Rolls Royce, D. Irvine of Petro-Canada Lubricants,
G. Jones of G.E. Energy, E. Letterman of General Electric
Power Systems, H. Moeller of Elsam, M. Morris, Consultant,
Dr. T. Okada of ExxonMobil, Dr. L. Quick of Siemens A. G.,
J. Pankowiecki of Siemens Westinghouse a n d B. Rayner,
Consultant. Lastly, thanks are cJso due to Alan Holt of Great
Lakes Chemical Corp. for the photographs and to Alan Watson for editorial assistance.

REFERENCES
[1] Smith, D. J., "Private Ownership of Electric Power is More Efficient and Reliable than Public-Owned Plants," Power Engineering International, March/April 1995, pp. 25-28.
[2] Kurtz, D., "Great Expectations," Power Engineering International, May 1999, pp. 33-37.
[3] Lane, J., "IPPs Open Up New Markets," Power Engineering International, April 1998, pp. 27-30.
[4] Council Directive 89/392/EEC, Official Journal, L183 of 29th
June 1989, Office for Official Publications of the European
Community, Luxembourg.
[5] Dodman, K., "Efficiency Will be the Greatest Issue," International Power Generation, September 1997, pp. 51-53.
[6] Collins, S., "Gas Turbine Power Plants," Power, June 1994, pp.
17-31.
[7] Paterson, A. N., Simonin, G., and Neft, J. G., "Turbine Blading
Materials Boost," International Power Generation, July 1996, pp.
65-67.
[8] Curtis, T., "GE 2500+ Power Turbines," Turbomachinery International, May/June 1995, pp. 42-44.
[9] Anon., "Micros-a New Gas Turbine Market," Turbomachinery
International Handbook, 1997, pp. lli-lS.
[10] Ashmore, C, "Power, Light and Cheap Heat," International
Power Generation, September 1997, pp. 54-57.
[11] Makansi, J., "Combined-Cycle Powerplants," Power, June 1990,
pp. 91-126.

350 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


[12] Smith, D. J., "Combined-Cycle Gas Turbines: The Technology of
Choice for New Power Plants," Power Engineering
International,
May/June 1995, pp. 21-26.
[13] S w a n e k a m p , R., "Gas-Turbine/Combined Cycle Power Systems," Power, June 1995, pp. 15-26.
[14] Swanekamp, R., "Single-Shaft Combined Cycle Packs Power in
at Low Cost," Power, January 1996, pp. 24-28.
[15] Anon., "Two Prototypes for Large-Scale Wind Turbines," International Power Generation, May 1995, pp. 37-38.
[16] Anon., "Towards the 5 MW Turbine," Supplement to Modem
Power Systems, October 2000, p. 36.
[17] Lakkenborg, J. "Understanding the Mechanisms," International
Power Generation, November 1996, p. 45.
[18] Hall, D. T., "Turbine Generator Fire Protection Overview," presented sX American Power Conference, Chicago, IL, April 1986.
[19] "Evaluation of Fire-Retardant Fluids for Turbine Bearing Lubricants," Electric Power Research Institute Report NP-6542,
Palo Alto, CA, 1989, pp. 2-1 to 2-7.
[20] Schober, J., "Fire-Resistant Hydraulic Fluids," The Brown
Boveri Review, Vol. 53, No. 1/2, 1966, pp. 142-147.
[21] Schenck, K., Hoxtermann, E., and Hartwig, J., "Operation of
Turbines with Fire resistant Fluids, Including the Lubricating
System," VGB Kraftwerkstechnik, Vol. 77, No. 6, 1977, pp. 412416.
[22] Dufresne, P. D., "14 Million Hours of Operational Experience
with Phosphate Ester Fluid in a Gas Turbine Main Bearing
App.lication," Proceedings of the 11th International Tribology
Colloquium, Esslingen, Germany, January 1998, pp. 1447-1452.
[23] Smith, A. N., "Fire Resistant Lubricants," General Electric Publication GTU-5 78, 1978.
[24] Knipple, R. and Thich, J., "The History of Aviation Turbine Lubricants," SAE Paper 810851, Society of Automotive Engineers,
Warrendale, PA, 1981.
[25] Anon., "Turbine Lubricants for Steam, Gas, Wind and Water
Turbines," Industrial Lubrication and Tribology, September/October 1994, pp. 8-15.
[26] Byford, D. C. sind Edgington, P. G., "The Development of Special
Oils for the Power Plants of Supersonic Transports," Proceedings
of the Eighth World Petroleum Congress, 1971, pp. 101-110.
[27] Phillips, W. D., "Triaryl Phosphates-The Next Generation of
Lubricants for Steam and Gas Turbines," ASME Paper, 94JPGC-PWR-64, American Society of Mechanical Engineers, NY,
1994.
[28] Hoxtermann, E. and Richter, P., "Failures of and Damage to Gas
Turbine Components," VGB PowerTech, Vol. 80, No. 10, 2000,
pp. 51-54.
[29] Kondo, H., " Recent Trends in Turbine Oils," Japanese Journal
of Tribology, Vol. 35, No. 9, 1990, pp. 969-979.
[30] DenHerder, M. J., "Control of Turbine Oil Degradation During
Use," Lubrication Engineering, Vol. 37, No. 2, 1981, pp. 67-71.
[31] Moeller, H., "Lubricants for Gas Turbines," Proceedings of the
11th International Tribology Colloquium, Technische Akademie
Esslingen, Germany, January 1998, pp. 379-382.
[32] Ashman, L. A., Vetrone, J., Curts, L., and Johnston, A., "Advantages of Turbine Fluids Blended with Hydro-treated Base Oils:
Exceptional Oxidative Resistance, Filterability, Air and Water
Separation," presentation at the 54"" Annual Meeting of the Society of Tribologists and Lubrication Engineers (STLE), Las Vegas, May, 1999.
[33] McHugh, P., Stofey, W. D., and Totten, G. E., "Mineral Oil Hydraulic Fluids," Handbook of Hydraulic Fluid Technology, G. E.
Totten, Ed., Marcel Dekker, NY, 1999, pp. 711-794.
[34] Hoo, G. H. and Lewis, E., "Base Oil Effects on Additives Used to
Formulate Lubricants," Adv. Prod. Appl. Lube., Proceedings of
the International Symposium,
H. Singh, P. Rao, and T. S. R.
Tata, Eds., McGraw-Hill, New Delhi, 1994, pp. 326-33.
[35] Henderson, H. E., "Base Oils for Engines and Drivetrains of the

[36]

[37]

[38]

[39]

[40]

[41]

[42]

[43]

[44]

[45]
[46]

[47]

[48]
[49]

[50]

[51]

[52]

[53]

[54]

[55]

[56]

Future," Supplement to Proceedings of the 12''' International Tribology Colloquium, Esslingen, Germany, Jan 2000, pp. 41-53.
"Engine Oil Licensing and Certification System," American
Petroleum Institute Publication 1509, 14* ed.. Appendix E, Section E.1.3, Washington, D.C., Dec 1996.
Ashman, T., "Advantages of Turbine Oils Blended with Hydrotreated Base Oils," Presented at the 54"' Annual STLE Meeting, Las Vegas, May 1999.
Galiano-Roth, A. S. and Page, N. M., "Effect of Hydroprocessing
o n Lubricant Base Stock Composition a n d P r o d u c t Performance," Lubrication Engineering, Vol. 50, No. 8, pp. 659-664.
Deckman, D. E., Lohuis, J. R., and Murphy, W. R., "HDP for Industrial Lubricants," Hart's Lubricants World, September 1997,
pp. 20-26.
Zielinski, J., "Supersyn Polyalphaolefins-a New Generation of
Synthetic Fluids," Presented at the 54"' Annual STLE Meeting,
Las Vegas, May, 1999.
Benda, R., BuUen, J, V., and Plomer, A., "Polyalphaolefins-Base
Fluids for High Performance Lubricants," Journal of Synthetic
Lubrication, Vol. 13, No. 1, 1996, pp. 41-57.
Fefer, M., Henderson, H. E., Legzdins, A., and Ruo, T., "Oxidation of Polyalphaolefins and Severely Hydro-Cracked : Kinetics
of Peroxide Formation-Part III," presented at the 54''' Annual
STLE Meeting, Las Vegas, May, 1999.
Rudnick, L. R. and Shubkin, R. L., "Poly(a-olefins)," Synthetic
Lubricants and High Performance Functional Fluids, L. R. Rudnick and R. L. Shubkin, Eds., Marcel Dekker Inc., NY, 1999.
Randies, S. J., "Esters," Synthetic Lubricants and High-Performance Functional Fluids, L. R. Rudnick and R. L. Shubkin, Msircel Dekker, NY, 1999, pp. 63-101.
Fowler, B. T., "Diesters as High Temperature Lubricants," Wear,
Vol. 15, 1970, pp. 97-104.
"Aviation Gas Turbine Lubricants-Military and Civil Aspects,"
SAE Special Publication 633, Proceedings of the Aerospace Technology Conference, California, October 1985, Society of Automotive Engineers, Warrendale, PA.
Markson, A. J., "Future Gas Turbine Lubrication-A Formulators
View," Proceedings of the 10th International Tribology Colloquium, Esslingen, Germany, January 1996.
Rayner, B. R., Private presentation to Rolls-Royce pic, Derby,
UK, 17 May 2000.
Phillips, W. D., "A Comparison of Fire-resistant Hydraulic Fluids for Hazardous Industrial Environments -Part 1," Journal of
Synthetic Lubrication, Vol. 14, No. 3, 1998, p p . 211-235.
Phillips, W. D., "Phosphate Esters," Handbook of Hydraulic
Fluid Technology, G. E. Totten, Ed., Marcel Dekker, NY, 1999,
pp. 1025-1093.
Marino, M. P. and Placek, D. J., "Phosphate Esters," CRC Handbook of Lubrication and Tribology, Vol III, Monitoring, Materials, Synthetic Lubricants and Applications, E. R. Booser, Ed.,
CRC Press Inc., Boca Raton, FL, 1994, pp. 269-285.
Rasberger, M., "Oxidative Degradation and Stabilisation of Mineral Oil Based Lubricants," Chemistry and Technology of Lubricants, R. M. Mortier and S. T.Orszulik, Eds., Kluwer Academic
Publishers, Dordrecht, The Netherlands, 1997, pp. 98-142.
Graham, J. and Leonhardt, H., "Development of Lubricating
Oils for Combined Cycle Applications," Proceedings, 11''' International Tribological Colloquium, Technische Akademie Esslingen, Germany, January 1998, p p . 1487-1500.
"Lubricating Oil Recommendations for Gas Turbines with Bearing Ambients Above 500F (260 C)," General Electric Specification GEK 32568C, July 1993.
Chadwick, D. and Hashemi, T., "Adsorbed Corrosion Inhibitors
Studied by Electron Spectroscopy; Benzotriazole on Copper
and Copper Alloys," Corrosion Science, Vol. 18, 1978, p p . 39-51.
Godfrey, D., "The Lubrication Mechanism of Tricresyl Phosphate on Steel," ASLE Preprint 64 LC-1, Park Ridge, IL, 1964.

CHAPTER 12: TURBINE LUBRICATING OILS AND HYDRAULIC FLUIDS 351


[57] Forster, N. H., "High Temperature Lubrication of Rolling Contacts with Lubricants Delivered from the Vapor Phase and as
Oil-Mists," WL-TR-97-2003, 1997.
[58] Tourret, R. and White, N., "Aeration and Foaming in Lubricating Oil Systems," Aircraft Engineering, May 1952, pp. 122-130,
137.
[59] Hodges, P. K. B., Hydraulic Fluids, Arnold, Great Britain, 1996,
p. 46.
[60] Staniewski, J. W. G., "The Influence of Mechanical Design of
Electro Hydraulic Steam Turbine Control Systems on Fire-Resistant Fluid Condition," Lubrication Engineering, Vol. 52, No. 3,
1996, pp. 255-258.
[61] Backe, W., and Lipphardt, P., "Influence of Dispersed Air on the
Pressure Medium," Proceedings of the Institute of Mechanical
Engineers, paper 091116, London, 1976, pp. 77-84.
[62] Hatton, D. R., " Some Practical Aspects of Turbine Lubrication,"
Canadian Lubrication Journal, Shell Canada Products Co., Vol.
4, No. 1, 1984, pp. 3-8.
[63] Phillips, W. D., "The Electrochemical Erosion of Servo Valves
by Phosphate Ester Fire-Resistant Hydraulic Fluids," Lubrication Engineering, Vol. 44, No. 9, 1988, pp. 758-767.
[64] Kaspar, K., "Einsatz von synthetischen schwerbrennbaren Hydraulikflilssigkeiten im Schmier- u n d Steuerkreislauf von
Dampfturbosatzen," Der Maschinenschaden, Vol. 50, No. 3, p p .
87-92, 1977.
[65] Schenck, K,, Hoxtermann, E., and Hartwig, J., "Operation of Turbines with Fire-Resistant Fluids, Including the Lubricating System," VGB Kraftwerkstechnik, Vol. 77, No. 6, 1997, pp. 412-416.
[66] Phillips, W. D., "Fire Resistance Tests For Fluids and LubricantsTheir Limitations and Misapplication," Fire Resistance of Industrial Fluids, ASTM STP 1284, G. E. Totten, and J. Reichel, Eds.,
ASTM International, West Conshohocken, PA, 1996, pp. 78-101.
[67] Howells, P., "Measurement of Autoignition Temperature," BP
Technical Report 31 737/M, British Petroleum Company, Sunbury-on-Thames, UK, 31 January, 1976
[68] Reichardt, H. U., Fischer, R., a n d Schiilert, G., "Wasser im
Turbinenol-Einfluss, Eigenschaften und Bestimmungsmoglichkeiten," Schmierungstechnik,
Vol. 18, No. 11, 1987, pp. 335338.
[69] Li, T-D. and Mansfield, J. M., "Effect of Contamination on the
Water Separability of Steam Turbine Oils," Lubrication Engineering, Vol. 51, No. 1, 1995, pp. 81-85.
[70] Rockwell, J., "The Slime Intermission," Herald Tribune, 27 May
1992.
[71] Bowman, W. F. and Stachowiak, G. W., "New Criteria to Assess
the Remaining Useful Life of Industrial Turbine Oils," STLE
Pre-print 96-NP-4F-1, STLE Annual Meeting, Cincinnati, 1996.
[72] Kaufmann, R. E., "Rapid, Portable Voltammetric Techniques
for Performing Antioxidant, Total Acid Number (TAN) and Total Base N u m b e r (TBN) Measurements," Lubrication Engineering, January 1998, pp. 39-46.

[73] Kauffman, R. E., "Remaining Useful Life Measurements of


Diesel Engine Oils, Automotive Engine Oils, Hydraulic Fluids,
and Greases Using Cyclic Voltammetric Methods," Lubrication
Engineering, Vol. 51, No. 3, 1995, pp. 223-229.
[74] Critchley, S. W. and Miles, P., "Synthetic Lubricants-Selection
of Ester Types for Different Temperature Environments," Proceedings of the Industrial Lubrication Symposium,
London,
March 1965.
[75] Anon, "Oil Filters and C o n t a m i n a n t Control,"
Industrial
Lubrication
and Tribology, November/December 1993, p p .
14-19.
[76] SAE J1165: "Reporting Cleanliness Levels of Hydraulic Fluids,"
SAE Recommended Practice, Society of Automotive Engineers,
Wareendale, PA, July 1979.
[77] Staniewski, J. W. G., "Operating Experience with Fire-Resistant
Phosphate Esters in Steam Turbine Electro-Hydraulic Control
Systems," presented at the EPRI/NMAC Lubrication
Workshop,
Cleveland, OH, June 1994.
[78] Phillips, W. D. and Sutton, D. I., "Improved Maintenance and
Life Extension of Phosphate Esters using Ion Exchange Treatment," Proceedings of the 10th International Tribology Colloquium, Technische Akademie, Esslingen, Germany, January
1996, pp. 405-432.
[79] "Guidelines for Maintaining Steam Turbine Lubrication Systems," Electric Power Research Institute Report No. CS-4555,
Palo Alto, CA, 1986.
[80] Brown, K. J. and Staniewski, J. W. G., "Condition Monitoring
and Maintenance of Steam Turbine-Generator Fire Resistant
Triaryl Phosphate Control Fluids," STLE Special Publication SP27, Proceedings of the 1989 Condition Monitoring and Preventative Maintenance Conference, May 1989, pp. 91-96.
[81] Christopher, S. a n d Marson, A. J., "Development of a Test
Method for the Determination of the Total Acidity in Polyol Ester and Diester Gas Turbine Lubricants by Automatic Potentiometric Titration," Proceedings of the 11th International Tribology
Colloquium, Technical Akademie, Esslingen, Germany, 1998,
pp. 121-127.
[82] Turbine Lubrication in the 21" Century, ASTM STP 1407, W. R.
Herguth and T. M Warne, Eds., ASTM International, 2001.
[83] Boehringer, R. H. and Ness, F., "Lubrication of Hydroelectric
Turbine Thrust Bearings with a Diester-Based Synthetic Lubricant," Journal of Synthetic Lubrication, Vol. 6, No. 4, 1989, pp.
311-323.
[84] Rao, A. M. N., "High Temperature Vapour Phase Lubrication,"
Proceedings of the 11th International
Tribology
Colloquium,
Technische Akademie, Esslingen, Germany, January 1998.
[85] Van Treuren, K. W., Barlow, D. N., Heiser, W. H., Wagner, M. J.,
and Forster, N. H., "Investigation of Vapor-Phase Lubrication in
a Gas Turbine Engine," ASME Transactions, Journal of Engineering for Gas Turbines and Power, Vol. 120, April 1998, pp.
257-262.

MNL37-EB/Jun. 2003

Hydraulic Fluids
W. A. Givens^ and Paul W. Michael^

T H E PRIMARY PURPOSE OF A HYDRAULIC FLUID is to

Where:
K = Bulk modulus
Vo = Original volume
AP = Pressure change
Ay = Change in volume

transfer

power. The concept of fluid power is based on a principle articulated by Blaise Pascal, which is usually given as follows:
"Pressure applied to an enclosed fluid is transmitted undiminished to every portion of that fluid and the walls of the
containing vessel" [1]. Within the context of fluid power,
pressure is related to the force acting on a confined fluid as
illustrated in Fig. 1 [2]. This principle has given rise to mode m hydraulics, which entails highly engineered systems for
efficiently controlling fluid flow to transfer energy and accomplish work.
The heart of any hydraulic system is the pump, which pulls
in fluid from a reservoir by creating a vacuum at its inlet and
then forces the fluid through its outlet, usually against pressure created by flow controllers and/or actuators downstream of the p u m p . Pumps, actuators, and other system
components have surfaces that move relative to each other,
often at high speeds, pressures, and temperatures. These
components require cooling and lubrication for efficient performance and durability. Consequently, hydraulic fluids not
only must transmit power, they serve critical functions as lubricant and heat transfer medium.

Heat Transfer
Heat is generated as a by-product of normal operation of a
hydraulic circuit. Friction between the moving parts of a
p u m p or hydraulic motor, as well as friction between the
fluid and surfaces of valves, pipes, and other circuit devices
generates heat. In addition, heat is generated in a hydraulic
system as a result of the dissipation of the potential energy of
pressurized fluid [8]. As a hydraulic fluid is circulated
through a system, heat is transferred from high temperature
areas to coolers, reservoirs, and other regions of the circuit
where it is dissipated. As can be seen in Table 1, typical specific heat and thermal conductivity values for hydraulic oils
are a fraction of that of water [4]. These factors are an important consideration in sizing hydraulic system coolers because the inherent cooling efficiency of petroleum based hydraulic fluid is less than that of water. ASTM D 2717, Test
Method for Thermal Conductivity of Liquids and ASTM D
2766, Test Method for Specific Heat of Liquids and Solids are
used to determine these properties of fluids.

P o w e r Transfer
To transfer power efficiently, a hydraulic fluid must exhibit
minimal compressibility. Low compressibility allows all of
the pressure applied to the fluid to be available for direct
and effective transmission to system components such as
motors, cylinders, or other actuators. The compressibility of
a fluid is generally discussed in terms of its "bulk modulus,"
which describes the change in fluid volume as a result of applied pressure [3]. The bulk modulus of a fluid, which is the
reciproccd of compressibility, is described by Eq 1. There
are a n u m b e r of m e t h o d s available for estimating the
isothermal secant bulk modulus of a fluid based upon its
viscosity and density characteristics [4,5]. As depicted in
Fig. 2, the bulk modulus for oil also varies with temperature
[6]. For petroleum oils, compressibility is often assumed to
be 0.5% for each 1000 psi pressure increase u p to 4000 psi
[7].
Bulk modulus {K) = -Vo

(\PI\V)

Lubrication
The durability of hydraulic equipment depends to a large extent upon the lubricating properties of the fluid. As a lubricant, the key function of the hydraulic fluid is to reduce friction between contact surfaces. A reduction in friction lowers
contact t e m p e r a t u r e s a n d wear. This is accomplished
through a combination of hydrodjoiamic and boundary lubrication mechanisms. The hydrodynamic lubricating properties of a fluid are governed by its physical properties while
boundciry lubrication is a function of fluid chemistry. A discussion of hydraulic fluid wear testing is presented in the
Wear Protection section of this chapter.

(1)

TRENDS

* Exxon Mobil Research & Engineering, Paulsboro Technical Center, 600 Billingsport Rd., Paulsboro, NJ 08066.
^ Benz Oil, 2724 West Hampton Avenue, Milwaukee, WI 53209.

A brief outline of major trends in the motion control industry, particularly with respect to hydraulic equipment design
and fluid requirements, is presented as a backdrop for the
discussion of hydraulic fluids test methods. As motion con-

353
Copyright'

2003 by A S I M International

www.astm.org

354 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK

Force

Area

F = force in pounds
p = pressure in pounds / sq. incli (psi)
A = sq. in.

FIG. 1Relationship of force, pressure, and area in fluid power. Any one of the parameters equals the other two in the relationship depicted by the triangle.
TABLE 1Thermal conductivity and specific
heat values for oil and water.

40

30

M
Q.

Oil
Water

z
CO

Thermal
Conductivity
Btu/h/ft^/F/Ft
@ 212F

Thermal
Conductivity
W/m-K
@373K

Specific
Heat
BTU/lbF
@68F

Specific
Heat
J/kg K
@293K

0.08
0.39

0.14
0.67

0.47
1.0

1966
4184

20

I
10
3

m
100

200

300

FIG. 2- -Effect of temperature on the bulk modulus of petroleum


fluid.

trol technology advances, there is a trend towards higher performance and efficiency. For hydraulic equipment, this
translates into a concentration of horsepower in smaller
components. There are a n u m b e r of reasons for such a trend.
Equipment manufacturers are looking for ways to minimize
raw material usage and cost. Users of the equipment demand
smaller systems for better space utilization in industrial environments cind compact multifunctional capabilities in mobile equipment. These advancements in mechanical design
along with e n c r o a c h m e n t of environmental, health, and
safety regulations fuel the following trends:
Hydraulic equipment builders will continue to push comp o n e n t manufacturers to design parts to a c c o m m o d a t e
high pressures a n d t e m p e r a t u r e s . F o r example, hoses,
valves, and other fittings will continue to evolve in terms of
materials used as well as actual functional design.

Smaller c o m p o n e n t s will m e a n smaller p u m p displacements [cubic inches or cc per p u m p revolution]. To maintain flow rates at present or higher levels, p u m p speeds will
be increased [cubic inches/minute = displacement X speed
(rpm)]. Smaller reservoir sizes will mean shorter fluid residence times and will therefore dictate use of hydraulic fluids with improved air release characteristics.
Smaller dimensional clearances will be required. These
smaller clearances will dictate more stringent fluid cleanliness requirements to prevent abrasive wear from particulate c o n t a m i n a n t s a n d failure of servo or proportional
valves.
Fluid cleanliness will increasingly be emphasized as an effective way of increasing equipment durability and controlling warranty costs. As a result, users will move to finer
filtration and specify pre-filtered hydraulic fluids [9]. Consequently, the filterability of the hydraulic fluid will continue to grow in significance. (Filterability is described in
section 4.6.)
Quieter hydraulic systems will be required in order to meet
workplace noise restrictions and compete with electric motors. Reduction of noise levels in hydraulic equipment has
been attained by the insulation that absorbs the noise. This
insulation results in higher system temperatures, as heat is
not as readily dissipated.
Components and actuators, such as cylinders, will be designed with tighter seals to increase efficiency and reduce

CHAPTER

13: HYDRAULIC

FLUIDS

355

leakage. The effects of this trend include increased stress


on seal materials and cylinder chatter resulting from reduced lubrication between seal and cylinder wall. In addition, certain applications will require fill-for-life systems
that translate into lower maintenance and disposal costs.
Consequently, fluids will remain in a system for longer periods, since meike-up fluid is not required.
A growing awareness of the environmental impact of
chemicals will lead to further restrictions on performance
additives eind base stocks used in lubricants. As a result,
lubricant p r o d u c e r s are required to address such issues through alternative (usually more costly) chemistry
and the development of environmentally friendly (nontoxic/biodegradable) lubricants.
The hydraulic fluid industry has evolved from the use of
plain water in hydraulic systems to the use of advanced
fluid technologies that continue to evolve as performance
requirements become more stringent and equipment designs become more sophisticated [10]. Due to environmental health and safety issues, hydraulic systems are once
again being designed to employ pure water as hydraulic
fluid [11].

Solvent refining yields base oils that fall into Group I while
hydroisomerization and deep hydrogenation processes yield
low sulfur, high paraffin content Group II a n d Group III
base stocks. Because of their lower aromatic and sulfur content, hydraulic fluids formulated from Group II and Group
III base stocks typically have superior oxidation stability.
However, more highly refined stocks tend to be less effective
at dissolving additives. Not only is additive solubility a concern, additive chemistries and their functional mechanisms
may be b o t h synergistic a n d antagonistic. Thus, additive
chemistry must be ceirefully balanced to achieve optimum
performance. In the following section, test methods for evaluating key fluid properties such as oxidation stability, wear
prevention, and corrosion inhibition are discussed. These
methods have been developed to measure characteristics of
hydraulic fluids that are thought to correlate to performance
in "real-life" applications as well as gage additive response
for the fluid formulator. In order to provide a link between
fluid tests and additive chemistry, a description of the generally accepted functional mechanisms of additives is also
included.

PETROLEUM BASE STOCKS

FLUID CHARACTERISTICS AND


PERFORMANCE

Most hydraulic fluids consist of a base fluid and additives


that are designed to i m p a r t chemical characteristics and
functionality to the finished product. Operating conditions
and equipment builder specifications generally dictate the
type of fluid that is needed and thus, the kind of base stocks
and additives employed. In petroleum based hydraulic fluids
the typical concentration of additives is less than 3.0% by
weight. Paraffinic oils are the primary base stock utilized in
hydraulic fluids but other materials, from polyglycols to vegetable oil, serve as the basis for formulating hydraulic fluids.
From a historical standpoint, solvent reflned paraffinic oils
have been the most widely used base stock for hydraulic applications. In recent years alternative refining processes such
as catalytic isomerization and deep hydrogenation have been
developed to yield higher purity base oils that are better
suited to withstand severe operating conditions [12]. These
base stocks are categorized by the American Petroleum Institute (API) according to their composition and viscosity index
[13]. Groups I through III consist of crude derived base oils
while Group IV is reserved for synthetic polyalphaolefins.
Low viscosity index naphthenic oils and other base stocks
that do not meet Group I through IV criteria are classified
as Group V. The API Base Oil classification is described in
Table 2.
TABLE 2API base oil classifications.
Category
Group I
Group II
Group III
Group rV
Group V

Composition
< 9 0 % Saturates or
> 1 0 % aromatics
9 0 % Saturates or
< 1 0 % aromatics
> 9 0 % Saturates or
< 1 0 % aromatics
All polyalphaolefins (PAO)
All others not included in
Groups 1,11, m or IV

Suli^ir
>0.03%

Viscosity
Index
80-120

<0.03%

80-120

<0.03%

>120

Oxidation a n d Thermal Stability


An important characteristic of a hydraulic fluid is its ability
to withstand high temperatures. This is because horsepower
losses in hydraulic systems directly result in transfer of heat
to the fluid. Resulting high temperatures can cause hydraulic
fluids to react with oxygen. The rate of this reaction accelerates exponentially with increasing temperatures and is further catalyzed by metals like copper and iron, especially at
temperatures above 200F [14]. Rate constants for the oxidation of saturated hydrocarbons at 125C are as much as 40
times higher than rate constants at 60C [15]. Thus, fluid oxidation is highly dependent upon hydraulic system operating
temperatures. Lubricants expected to operate in high temperature environments are tjrpically fortified with additives
known as antioxidants, which are discussed in the Antioxidants section. Oxidative stabilization of the fluid translates
directly into extended oil service life. Failure to resist oxidation can result in thickening of the oil (viscosity increase),
formation of acidic byproducts, and subsequent deposit formation.
Not only can heat cause oxidation, fluids may thermally degrade upon exposure to high temperatures with litde or no
oxygen present. The thermal stability of a hydraulic fluid is
dependent mainly on the intrinsic ability of the base fluid or
its components to resist decomposition at high temperatures.
Unlike oxidation, controlled thermal degradation of certain
types of additives [such as Zinc Dialkyldithiophosphate
(ZDTP)] is desirable, because it is the very mechanism by
which they react with the metal surfaces they are designed to
protect [16]. Similar to oxidation however, the negative effects of thermal degradation may include increased acidity,
thickening of the oil, and deposit formation. Therefore, good
control of thermal degradation results in the retention of desired fluid properties.

356

MANUAL

37: FUELS AND LUBRICANTS

High Temperature/Oxidation

HANDBOOK

Tests

One of the most commonly sited methods for measuring the


abihty of a fluid to resist oxidation is ASTM D 943, Standard
Test Method for Oxidation Characteristics of Inhibited Mineral Oils (also known as the Turbine Oil Oxidation Stability
Test - TOST). In this test, 300 ml of fluid a n d 60 ml of distilled
water are placed in a large test tube together with coils of
copper and iron wire (Fig. 3). The fluid is heated to 95C
(203 F) and oxygen is bubbled through the fluid at a controlled rate. The test is complete when the Total Acid Number (AN) of the fluid reaches 2.0 mg KOH/g. As can be seen
from the reaction scheme in Fig. 5, cJdehydes eire among the
chemical by-products of hydrocarbon oxidation. These aldehyde compounds are readily converted to carboxylic acids in
the hydraulic system [17,18]. Since carboxylic acids are corrosive to yellow metals and agglomerate to form deposits,
they have a detrimental effect upon fluid performance when
their concentration becomes excessive. The concentration of
acidic oxidation debris present in a fluid can be determined
by titration with potassium hydroxide. For the D 943 test, a
variation on ASTM D 664 Acid N u m b e r of Petroleum Products by Potentiometric Titration is used. This method, ASTM
D 3339, Test Method for Acid N u m b e r By Semi-Micro Color
Indicator Titration is utilized because it permits a 0.2-1.0 g
sample size for total acid numbers in the 0.5-3.0 mg KOH/g

OXYGEN
DELIVERY
TUBE

range. The hours to form 2.0 m g of KOH equivalents of acidic


oxidation products per gram of some typical fluids are shown
in Table 3. In general, turbine oils provide longer TOST oxidation life t h a n antiwear hydraulic fluids because turbine
oils typically do not contain zinc dialkyldithiophosphate
(ZDTP). Zinc dialkyldithiophosphate r e d u c e s the t i m e it
takes for a fluid to reach 2.0 mg KOH/g because it is acidic
and its mere presence raises the acid n u m b e r of the fluid. In
addition ZDTP is subject to hydrolysis and forms acidic compounds as it degrades. Ester based fluids such as rapeseed
oils are also subject to hydrolysis, which accounts for their
poor performance in the D 943 test. When the D 943 test is
run without water (dry method), the oxidation life of a synthetic ester can be extended by nearly a factor of 100.
The a m o u n t of sludge produced in the TOST test may be
measured by ASTM D 4310, Test Method for Determination
of the Sludging Tendencies of Inhibited Mineral Oils. In this
test, the fluid is subjected to D 943 test conditions for 1000 h.
At the end of this time, the sludge produced is determined
gravimetrically by filtration of the oxidation tube contents
through 5-/u,m pore size cellulose acetate filter disks. To a certain extent the D 943 and D 4310 tests evaluate different
mechanisms of high temperature degradation. In the D 943
test, acidity is measured and this acidity is predominantly
due to formation of carboxylic acids by the conventional liquid phase oxidation mechanism shown in Fig. 4. In essence
D 943 measures the stability of the base oils and the effectiveness of oxidation inhibitors. Sludge formation in hydraulic oils is to a greater extent due to theimal degradation
of the ZDTP antiwear additive. Consequently, the result of a
D 4310 test is an indication of the thermal stability of ZDTP.
Figure 5 shows a model for the mechanism of sludge formation by zinc dialkyldithiophosphate [19].
Another method for measuring the sludging tendency of
hydraulic fluids is the Cincinnati Machine Heat Test [20].
This test has been adopted as an ASTM procedure and is designated ASTM D 2070, Standard Test Method for Thermal
Stability of Hydraulic Oils. In this test, polished pre-weighed
copper and steel rods are placed in a beaker containing 200
cc oil and heated to 135C (275F) for 168 h. At the end of the
test, the copper and steel rods are examined for discoloration
due to corrosion caused by carboxylic acids and sulfur compounds formed by thermal degradation. Sludge content and
viscosity increase are also measured (Table 4).
Antioxidants

CATALYST
COILS

Oxidation inhibitors, commonly referred to as antioxidants,


are chemicals that reduce the rate at which oxidative degradation of a lubricant occurs. Degradation begins with the reaction of hydrocarbon molecules at elevated temperatures to
form unstable reactive species known as free radicals. These
TABLE 3D 943 turbine oil oxidation test life of
typical hydraulic fluids.

FIG. 3Oxidation cell and sampling tube for


ASTM D 943 apparatus.

Fluid Type

Hours to TAN of
2.0 by D 943 Method

Synthetic ester without antioxidant


Mineral oil without additives
Antiwear hydraulic oil. Group I base stock
Antiwear hydraulic oil, Group 11 base stock
Synthetic ester with antioxidant, dry method
R & O hydraulic oil

65
300
2016
5040
5500
>10,000

CHAPTER 13: HYDRAULIC FLUIDS 357


Temperature
Light, catalyst

Initiation

RH

Propagation

R + O2

ROO*

Peroxy radical

ROO + RH

ROOH + R*

Hydroperoxide

ROOH

-*

RO + OH

Alkoxy radical

RO + RH

->

ROH + R

Alcohol

OH + RH

->

H2O + R

Water

Branching

Termination

Alkyl radical

R + ROO

Alcohols

RO + ROO

Aldehydes

ROO + ROO

Ketones

RO + R

Acids

R + R

Longer chain
hydrocarbons

FIG. 4Reaction scheme for liquid hydrocarbon oxidation.

Hydraulic Oil
RO

RO

SZnS

OR

OR

Base Oil
(Paraffinic)
and
Additives

Machines
and Outside
Environment

T
Reaction withi

Thermal P^''^^
Deterioration
Degradation
witii Water
ZnSq
RO

Decomposition
Oxidation
Reaction with
l\^etai Ions

Polyphosphates
0

OR

0- -Zn0

OR

\ ^
RO

Oxidation
Products
and
Metal Soaps

Wear Particles,
Dust, Rust, Water
andOtliers

Sludge
FIG. 5Mechanism of sludge formation by zinc dialkyldithiophosphate.

358 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 4Cincinnati machine thermal stabihty
test performance requirements.
Property

Condition of steel rod


Visual
Deposits
Corrosion
Condition of copper rod
Visual
Corrosion
Condition of fluid
Viscosity
Sludge
Total acid number

Requirement

No discoloration
3.5 mg maximum
1.0 mg maximum
5 rating maximum
10.0 mg maximum
5% change maximum
25 mg/100 mL max
50 % maximum

species react with oxygen and non-oxidized oil to form additional free radicals, which propagate the oxidation process.
This generally accepted mechanism is described as free radical chain reaction and is illustrated by the steps shown in
Fig. 4.
Antioxidants interrupt this chain reaction and thus, reduce
the rate of oxidation and the resulting viscosity increase and
acid and deposit formation. There are two general mechanisms by which these additives inhibit oxidation. The antioxidants are therefore categorized as primary or secondary, depending u p o n the m e c h a n i s m of oxidation inhibition.
Primary antioxidants, commonly referred to as "free radical
scavengers," react with the peroxy radicals and hydroperoxides to form inactive compounds (Fig. 6) [21]. Examples of
primary antioxidants include hindered phenols and aromatic
amines. Secondary antioxidants, commonly referred to as
"peroxide decomposers," react with hydroperoxides or peroxy radicals to form less reactive compounds. Examples of
secondary antioxidants include sulfur a n d / o r p h o s p h o r u s
c o m p o u n d s a n d metal dithiophosphates (Fig. 7). Antioxidants genereilly function in the bulk lubricant and are consumed as they do their job [22].

Detergents

IDispersants

Detergents and dispersants are used to delay formation and


subsequent deposit of insoluble oil degradation species. The
terms detergent and dispersant are often used interchangeably, but are generally differentiated by their composition
and primary functionality. Detergents are metallo-organic
compounds that neutralize acidic deposit precursors, while
dispersants are predominantly organic chemicals that keep
insoluble materials dispersed a n d suspended in the lubricant.
The t e r m "ashless" dispersants, m e a n i n g non-metallic, is
used to further differentiate dispersants from detergents.
Some detergents have the ability to disperse and suspend insolubles, while some dispersants are capable of neutralizing
precursors of deposits. Typical lubricant detergents include
barium, calcium, and magnesium phenates, phosphates, salicylates a n d sulfonates. Ashless dispersants are typically
alkyphenol-based or alkyl succinimides.

(R0)3P?-0O3
(R0)3P + R'OOH
H
(R0)3P=0 + HOR'
FIG. 7Secondary antioxidants such as the phosphite compound depicted above inhibit oxidation by decomposing hydroperoxides. This prevents the oxidation process from progressing beyond the branching stage In the reaction
mechanism.

o
+ R00
ROO^^R
FIG. 6Reaction scheme for primary antioxidants. Primary or freeradical trapping antioxidants work by donating a hydrogen radical H* to
the peroxy radical formed during mineral oil oxidation. Due to steric hindrance, the antioxidant radical does not attack mineral oil molecules,
i.e., R-H bonds. Consequently, the radical chain is terminated.

CHAPTER 13: HYDRAULIC FLUIDS


Wear Protection
Reduction of friction and prevention of wear is the fundamental purpose of a lubricant. Lubricants reduce friction in
machine components by producing a physical or chemical
barrier between surfaces that slide or roll past each other. Depending on equipment design and function, lubricants function within three commonly recognized regimes: hydrodynamic, mixed-film, and boundary lubrication (Fig. 8) [23].
Hydrodynamic lubrication is often the dominant lubrication regime under conditions of moderate temperatures and
loads. According to the ASM Handbook on Friction, Wear
and Lubrication Technology, [24] hydrodynamic lubrication
is "a system of lubrication in which the shape and relative
motion of the sliding surfaces causes the formation of a fluid
film that has sufficient pressure to separate the surfaces." In
this regime, viscosity is the most important fluid characteristic because it, in combination with sliding speed, contact geometry and load, determines the thickness of the lubricating
film, and determines whether or not the surfaces will contact
each other.
Fluid viscosity plays an important role in hydraulic applications. A hydraulic fluid that is too low in viscosity will
cause low volumetric efficiency, fluid overheating, and increased pump wear. A hydraulic fluid that is too high in viscosity will cause poor mechanical efficiency, difficulty in
starting, and wear due to insufficient fluid flow [25]. Since
viscosity is a function of fluid temperature, the temperature
operating window (TOW) for a particular viscosity grade of
hydraulic fluid is a function of temperature. Figure 9 depicts

the TOW for straight grade mineral oil based hydraulic fluids. The viscosity grade indicated in the TOW corresponds to
ASTM D 2422, Classification of Industrial Fluid Lubricants
by Viscosity System. For example, ISO 32 hydraulic oil generally will provide satisfactory performance in a temperature
window of - 8 to 64C.
There are several methods for measuring the viscosity of
hydraulic fluid. The most widely utilized method is the ASTM
D 445, Standard Test Method for Kinematic Viscosity of
Transparent and Opaque Liquids. In this test, the time is
measured for a fixed volume of liquid to flow under gravity
through the capillary of a calibrated viscometer at a closely
controlled temperature. The kinematic viscosity is the product of the measured flow time and the calibration constant of
the viscometer. Based upon D 2442 and ISO 3448, the standard temperature for measuring hydraulic fluid viscosity is
40C [26]. Typically, the viscosity of a hydraulic fluid is 15-68
mm^/s (centistokes) at 40C. ASTM D 446, Standard Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers, describes more than 15 types of viscometers that may be employed in performing a D 445 viscosity
test. With the exception of invert-emulsion type fluids, hydraulic fluids are generally transparent. Consequently, a tube
suitable for transparent liquids such as the popular CannonFenske viscometer may be used. For opaque liquids, a reverse-flow tube is required because it is difficult to see the
meniscus as the fluid flows by the timing marks on a standard viscometer. Cannon-Fenske tubes for viscosity measurement of transparent and opaque liquids are depicted in
Fig. 10.

1
MIXFn FN M

LUBRICA-|ON
B OUNDARY
LIJBRICATION
0.1

c
o
o
c
g>
o

0.01

^
O

o
0.001

0.001

0.01

359

0.1

hULL-hlLM
LUBRICATION
1
1

10

Sommerfeld number, (rjA// P) x 10"^


FIG. 8Stribeck Curve of coefficient of friction versus Sommerfeld Number (S), where
S = r}N/P. N shaft speed; P, average pressure between shaft and bearing due to applied
load; 7), lubricant viscosity.

360 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


100

212

90

94 194

80

o
<D

176

84

70

158 LL.
140

73

60

64

5 50
-I

55

122

104 CO
CD
86 O.

44

I" 30

32

j5^20

CO

+10

10

+4
-2

-23

-4

-30 3 3

-22

-40
10

50

14

-15

-20

E
.<!>

32

-8

-10

CD
V

15

22

32

46

68

100

-40

ISO Viscosity Grade


FIG. 9^Temperature Operating Window (TOW) for 100 VI mineral oil based hydraulic fluids. Based upon survey of viscosity requirements for hydraulic pumps and motors, fluids
will generally provide satisfactory performance at the temperature range that corresponds
to 13 to 860 cSt.

FIG. 10Cannon-Fenske standard and reverse flow kinematic viscosity tubes, respectively.

Frequently in high-pressure hydraulic applications, the


loading conditions are sufficient to rupture hydrodynamic
lubricating films. Consequently, boundary and mixed-film
lubrication regimes play an important role in controlling
wear in hydraulic applications. In boundary lubrication, friction cind wear between two surfaces in relative motion are de-

termined by the properties of the surfaces and by properties


of the surfaces and lubricants other than viscosity [27 ]. In hydraulic equipment, these surfaces are typically composed of
ferrous or yellow metals. Under magnification, tribologicsJ
surfaces in hydraulic components reveal the presence of surface asperities. High load conditions cause these aperities to

CHAPTER
make contact, resulting in friction and weeir. In most cases,
mixed-film lubrication takes place and some hydrodynamic
lubrication occurs, even as "asperity contact" creates boundary conditions. Depending upon the extent of asperity contact, scuffing or adhesive wear may occur. A schematic description of the various wear processes specific to hydraulic
p u m p s is shown in Fig. 11. When cavitation, corrosion, or
scuffing wear processes generate particles that are the same
approximate size as p u m p clearances, synergistic wear may
take place. Sjmergistic wear ultimately leads to failure that
may appear to be abrasive in origin [28].
Wear protection under conditions of boundary lubrication
may be enhanced through the use of additives that interact
with surfaces to form protective chemical films. (See the Antiwear Performance Testing section for description of the
boundary lubrication additives utilized in hydraulic applications.) These chemical films reduce friction by decreasing the
shear strength of the surface relative to the underlying material. Thus, surface interaction under boundary lubrication
conditions is primarily between the low-shear strength chemical films rather than the metal substrate. Good wear protection and friction reduction result in enhanced equipment
durability, reduced heat generation, improved energy conservation, and many other operational advemtages.
Antiwear

Performance

13: HYDRAULIC

FLUIDS

pressures, and entry angles in a functioning hydraulic system


[29,30].
One of the more c o m m o n bench tests used for screening
the antiwear performance of a hydraulic fluid is the FourBall Method. There are two versions of the test for liquid lubricants: ASTM D 2783, Standard Test Method for Measurement of Extreme-Pressure Properties of Lubricating Fluids
(4-Ball Method) and ASTM D 4172, Standard Test Method
for Wear Preventive Characteristics of Lubricating Fluids (4Ball Method). The former method is generally used for evalu a t i n g extreme pressure gear lubricants while the latter
method is used for evEiluating antiwear hydraulic fluids. In
the 4-Ball Wear Test (D 4172), three half-inch diameter steel
balls are clamped together and covered with the lubricant to
be evaluated. A fourth ball of equal diameter is pressed with
a force of 1 5 ^ 0 kg into the cavity formed by the three stationary balls making a three-point contact (Fig. 12). Lubricants are evaluated by rotating the top ball under load at 1200
r p m for 60 min and measuring the average scar diameters
worn in the three lower balls.
In cooperative testing of fluids performed by members of
ASTM D02.L on Industrial Lubricants, the addition of zinc
dithiophosphate to 46 cSt mineral oil decreased the scar di-

Testing

The majority of hydraulic fluids are formulated with antiwear additives because surface loads associated with highpressure p u m p operation necessitate the use of fluids with
enhanced wear protection. There are a variety of test methods available for assessing the antiwear performance of hydraulic fluids. These tests may either be bench-top or fullscale tests employing high-pressure piston and vane pumps.
Bench tests are generally less expensive to perform t h a n
p u m p tests. However, translating bench test data into realworld performance can be problematic because of the complexity involved in simulating all of the materials, velocities.

(a)
FIG. 12The four-ball test:
(a) perspective view, (b) plan view.

EXTEERNAL
PAR"riCLE
INGREESSION
\Air:Ap

CAVITATION JElr

ASPERITY
CONTACT

FATIGUE
WEAR

ADHESIVE
WEAR

VVtArl

DEBRIS

WEAR
DEBRIS1

>

ABRASIVE
WEAR

TOTAL
WEAR

ELECTROLYTE
(WATER)

361

CORROSIVE
WEAR
WEAR

WEAR DEBRI S

DFRRI.q

FIG. 11Synergistic view of pump wear process. Fatigue, adhesive, and corrosive wear
can be triggered Independently. Resulting wear debris generation leads to abrasive wear.

362

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

ameter in 4-ball wear tests from 0.72 m m to 0.42 m m at 40kg


[31]. These results are tjpical of a mineral oil based antiwear
hydraulic fluid where average scar diameters of less than 0.50
m m are the norm (P. W. Michael, unpublished data).
While four-ball tests are effective in screening antiwear additive response, they do not directly correlate with p u m p
tests [32]. This is in part due to the fact that loads in the fourball tests are constant and do not pulsate in the same way
that a hydraulic p u m p does as sliding surfaces transition
from high pressure to low pressure regions of the pump. In
an effort to enhance the correlation between the four-ball test
and full-scale p u m p eveJuations Penn State University has
performed investigations involving sequential four-ball wear
tests. In the sequential four-ball test, wear scars are evaluated
at 10 and 40 kg and 600 r p m and the diameter of the scar is
measured after the fluid has been replaced by white oil in order to measure the durability of the antiwear film [33,34].
This method yields better correlation with vane p u m p tests.
The FZG Test is another bench test used for screening hydraulic fluids. FZG test equipment consists of two gear sets
arranged in a foursquare configuration (Fig. 13). The FZG
p r o c e d u r e is described in ASTM D 5182 S t a n d a r d Test
Method for Evaluating the Scuffing (Scoring) Load Capacity
of Oils. In this test, pre-examined gears are immersed in 1600

mL of oil that is heated to 90C (194F). The test gear set is r u n


in the test fluid for 15 min at successively increasing loads
until the failure criteria is reached. According to the ASTM
procedure, failure criteria are reached when the summed total width of scuffing wear damage from all 16 teeth is estimated to equal or exceed one gear tooth width. In DIN 51524,
Part 2, a m a x i m u m weight loss of 0.27 mg/kW h for antiwear
hydraulic oil is specified as well as a m i n i m u m damage stage
of 10. While Reichel reported a correlation between FZG Test
results and hydraulic fluid performance in vane pumps, correlation with piston p u m p performance has proven difficult
to establish [35].
The most widely referenced vane p u m p wear test for hydraulic fluids is ASTM D2882, Standard Test Method for Indicating the Wear Characteristics of Petroleum and NonPetroleum Hydraulic Fluids in a Constant Volume Vane
Pump (Vickers 104C). In this test, a hydraulic fluid is circulated through a rotary vane p u m p for 100 h at a p u m p speed
of 1200 r/min and a p u m p outlet pressure of 2000 psi. The
fluid temperature is controlled to 150F at the p u m p inlet for
most fluids. Petroleum based fluids with a viscosity greater
than 46 mm'^/s and some synthetic fluids must be evaluated
at 175F. At the end of the test, the total cam ring and vane
weight losses are measured and reported. Based upon ASTM

Drive gear case

Test gears with


long addenda

FIG. 13The Neimann (FZG) Four-Square Gear Test Rig.

CHAPTER
D 6158, Standard Specification for Mineral Hydraulic Oils,
less than 50 mg of total wear is expected from properly formulated petroleum based antiwear hydraulic oil. For invertemulsion type fluids, higher wear rates in the 100-200 mg
range are c o m m o n while water glycol fluids routinely generate less than 50 mg wear in the D 2882 test.
While the D2882 test is a popular benchmark for evaluating hydraulic fluids, this method is not without its problems.
First of all, Vickers has discontinued production of the
V104C p u m p . This will ultimately necessitate the use of substitute hardware or abandonment of the test procedure. Second, rotor and bushing failures are common in the first few
hours of the test. This may be due to the fact that the p u m p
was originally designed for a m a x i m u m pressure of 1000
psig. Fluid performance in the V104C p u m p is evaluated at
1000 psi using the ASTM D 2271, Standard Test Method for
Preliminary Examination of Hydraulic Fluids (Wear Test). In
this procedure, the p u m p stand is operated for 1000 h, which
provides an extended evaluation of p u m p wear behavior under normal operating conditions. Xie et al. provide a detailed
discussion of the D 2882 Test Method in the Handbook of Hydraulic Fluid Technology [36].
For higher pressure a n d mobile applications Vickers
prefers their 35VQ25 vane p u m p for screening hydraulic
fluid wear performance (Table 5). In the 35VQ25 test, three
50-hour tests are conducted on the same charge of test oil.
For each 50-hour test a new p u m p cartridge is used. The test
rig is operated at 3000 psi and 200F with a p u m p speed of
2400 rpm. Vickers limits the amount of wear on each test kit
to 90 mg: 75 mg ring, 15 mg vanes. In addition there must be
no sign of scuffing on the cam ring.
The Denison T6C vane p u m p test is a variable pressure
vane p u m p test. In this test, a Denison T6CSH 020 p u m p cycles between 7 b a r (100 psi) and 250 bar (3600 psi) at onesecond intervals for 300 h [37]. The p u m p speed is nominally
1700 r/min a n d fluid t e m p e r a t u r e is m a i n t a i n e d at 80C
(176F) for mineral oil based fluids a n d 45C (113F) for
those based on water. The test is r u n in two 305-hour sequences. Each 305-hour test consists of a 5-hour break-in period followed by 300 h of high pressure cycling. After the first
305-hour test, the p u m p cartridge is removed for inspection
and a new cartridge is installed for the second sequence. The
second 305-hour sequence is r u n with 1% distilled water
added to the fluid. The first stage of the T6C test serves as an
aging mechanism and increases the susceptibility of the fluid
to the deleterious effects of water contamination. After the
second 305-hour sequence the p u m p cartridge is again removed for inspection. As with the 35VQ25 test, weight loss of
cam ring and vanes, vane tip profile, and visual appearance
of all components are all reported. In addition, a wet filterability test is performed on the fluid to determine if water
contamination will lead to filter blinding. (See the Filterability section for a discussion of filterability tests.)
Although the V104C and 35VQ25 vane p u m p tests have
served the industry well for many years, these tests are not
sufficient to screen hydraulic fluids that will be used in highpressure piston p u m p s applications [38]. Thus, piston p u m p
tests have been to qualify the antiwear capabilities of hydraulic fluids. Komatsu, Rexroth, and S u n d s t r a n d piston
p u m p tests are described below.
K o m a t s u developed a piston p u m p test to evaluate

13: HYDRAULIC

FLUIDS

363

biodegradable vegetable oil based hydraulic fluids [39]. This


test is based on a Komatsu HPV35+35 twin-piston p u m p using cycled pressure test conditions. In this test p u m p efficiency change, wear and surface roughness, formation of lacquer and varnish, a n d hydraulic oil deterioration are
evaluated.
Rexroth has proposed a three-stage piston p u m p test based
on the Brueninghaus A4VSO piston p u m p [40]. Stage one is
conducted at the m a x i m u m operating pressure and temperature and at the m i n i m u m viscosity specified for the fluid being tested. The test duration is 250 h at which time the p u m p
is dismantled and inspected. The second stage of the test is
pulsed pressure test at the m a x i m u m displacement of the
p u m p . This stage is operated for one million cycles. When
this stage is complete, the p u m p is dismantled and inspected.
The third stage is a variable displacement stage at maximum
pressure, maximum temperature, and m i n i m u m fluid viscosity. The test duration is 280 h at which time the p u m p is dismantled and inspected again. The final pass/fail assessment
is made with reference to a standard damage catalog.
The Sundstrand Water Stability Test Procedure test originally employed a Sundstrand Series 22 piston p u m p at a constant pressure [41]. Currently, this test procedure is conducted using a Sundstrand Series 90 piston p u m p with a 55-cc
displacement. The objective of the test is to determine the effect of water contamination on mineral oil hydraulic performance and yellow metal corrosion. However, other fluids, including water-containing fluids such as HFB and HFC fluids,
may also be evaluated using this test. The test duration is 225
h, at which time it is disassembled and inspected for wear,
corrosion, and cavitation. If the flow degradation is equal to
or greater than 10%, the test is considered to be a "fail."
Antiwear

and Extreme

Pressure

(EP)

Additives

Antiwear and EP additives prevent wear of metal surfaces by


forming a protective chemical film between moving parts.
These additives have traditionally been labeled as antiwear or
extreme pressure (EP), depending on the mechanism of protection. Antiwear additives are generally considered to form
protective films that adsorb on the metal surface and function effectively under relatively mild conditions of load and
t e m p e r a t u r e . Extreme pressure additives form protective
films by reacting with the metal surfaces at localized high
temperatures to form low shear strength films that are relatively insoluble in the bulk oil. In either case, tribological
contact is between the surface films rather than the metals.
Various types of chemistry are employed in the prevention
of wear in hydraulic applications. Typical compounds include zinc dialkyldithiophosphates (ZDTP), tricresylphosphates (TCP), sulfur compounds, amine phosphates, dithiocarbamates, and other chlorinated, phosphorus/sulfur, and
molybdenum compounds.
Water Content a n d Hydrolytic Stability
In many hydraulic systems, the lubricant is susceptible to
contamination with water. Contamination with water can
lead to a host of problems including loss of lubricity, corrosion, additive degradation, and filter plugging. Consequently,
machine builders and equipment users often attempt to limit
the amount of water that enters their hydraulic systems. At
the same time, fluid formulators endeavor to manufacture

364 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


TABLE 5Machine builder specifications for antiwear hydraulic oil.
Properties
Method(s)
ISOVG
Kinematic Viscosity, cSt
D445
0C max., calc. D 5133
40Cmax.
40C min.
100Cmin.
Flash Point C min.
D92
Fire Point, C min.
D 92
Pour Point, C, max
D97
Color, max
D 1500
ISO Contam. Code, max
ISO 4406
Density @15C
D1298
TAN, mg KOH/g, max
D664/ D974
Rust Test A
D665 A
Rust Test B (Salt Water)
0665 B
Cu Rating (3 hr, 100C), max. D130
TOST Oxidation, Hours to 2.0 ,^^,
TAN
"*^
Air Release @ SOX, minutes Q J ~ ,
(max)
Foam tendency/statxiity
D892
Seq 1
max
Seq II
max
Seq III
max
DemulsilJility @ 54C
D1401
FZG Fail Stage
D 5182
Change in Hardness
NBR1,168hrs@100C
Change in Volume (%)
NBR1,168hrs@100C
Viscosity Index, min
D 2270
Aniline Point C min.
D 611
CM Thermal Stabtity
D 2070 A
Viscosity Change, % max
TAN Variation, % max *
Comparative IR Scan
Sludge, mg/100 ml max
Cu metal removed, mg/200 ml, max.
Copper rod appearance, rating (max.)
Steel deposits, mg/200 ml, max
Steel metal removed, mg/200 ml, max
Steel rod appearance, rating (max)
Oxidation (1000 h)
D4310
AN, mgKOH/g max
Total sludge, mg max.
Copper, mg max
Iron, mg max
Hydrolytic Stability
D 2619
Copper wt loss, mg/cm^ max
Water layer TAN. mgKOH max
V104 C Pump
mg wear, max
D 2882
Vickers 35 VQ 25 Pump Test
Vane Wear, mg max
Rir^ Wear, mg max
Denison P-46 (100 h)
DenisonTBC, vane wear
TP-30283
Cam ling wear
Denison Fnterability Test, sec TP 02100
Dry, max
Wet, max

Denison HF-0

Vickers

Requirements

Requirements

6 M LS-2

Cincinnati iWachine
.

P68
32

P70
46

P69
68

35.2
28.8

50.6
41.4

74.8
61.2

188
215

196
218

196
218

LH-02
22

LH-03
32

LH-04
46

LH-06
68

300
24.2
19.8
4.1
175

420
35.2
28.8
5
190

780
50.6
41.4
6.1
190

1400
74.8
61.2
7.8
195

-21

-18

-15

-12

10

10

19/16/13
0.84 - 0.90
<1.S>
Pses

Pass
Pass

Pass
<1b>
<1500>
5

<:50/0>
<SO/0>
<50/0>
Timeto40/40)(O/W/E)
<30>
<10>

-10
-/O
-10

90
100

<90>

Oto-7

Oto-7

Oto-6

OtolS

0to12
<95>

0to12

OtolO

<5>
<50>
Record
< 25 mg. /100ml >
<10>
<5>

<5>
<50>
100
10
Report

Oto-8

< 25 mg. /100ml >


<10>
<5>
<3.5>
<1>
<1.5>

<1.5>

2
200
50
SO
(1)
0.2
4.0

<0.2>
<4>
I-2S6-S
SO
M-2950^
15
75

Satisfactory
Satisfactoiy

600
2xdry

(1) Rqmnt. Sut>ject to Denison discretion (based on other pump/fietd history)


(2) D 2882 mn at 79,4C (higher temp.) for ISO 68 and higher grade.

< 50 >

(2)
<10>
<50>
no smear, scratch, etc
< 0.01 >
No distress
<600>
< 2 X dry >

CHAPTER 13: HYDRAULIC FLUIDS


hydraulic fluids that resist chemical degradation or hydrolysis in the presence of water and heat. Several ASTM methods
are used to monitor water content of hydraulic fluids as well
as their ability to resist hydrolytic degradation.
Distillation, Centrifuge and Karl Fisher Titration Tests
In ASTM D 95, Standard Test Method for Water in Petroleum
Products and Bituminous Materials by Distillation, the material to be tested is diluted with a water-immiscible solvent
such as toluene and heated under reflux conditions. The resulting distillate is condensed and separated in a trap. The
amount of water present in the sample is determined by observing the volume of water settled in the graduated section
of the trap.
Centrifuge tests such as ASTM D 96, Standard Test Method
for Water and Sediment in Crude Oil by Centrifuge Method,
can also be used for un-emulsified or insoluble water contamination in fluids. While distillation and centrifuge methods provide reasonably accurate results for samples that contain free water contamination, these methods are generally
not sensitive enough for hydraulic applications. A more accurate method for quantifying water in hydraulic fluid is the
Karl Fischer test (ASTM D 1744, Standard Test Method for
Determination of Water in Liquid Petroleum Products by
Karl Fischer Reagent) [42]. In this test, the fluid is dispersed
in a solvent such as methanol and titrated with standard Karl
Fisher reagent to an electrometric endpoint (Fig. 14). The
endpoint of the titration, at which free iodine is liberated.

365

may be registered either potentiometricly or by color indication. Although this method has the capability to be more accurate than distillation or centrifuge techniques, the Karl
Fisher Test is susceptible to chemical interference. Calcium
sulfonate, magnesium sulfonate, ZDTP and other oil additives react with iodine and have been known to interfere with
the titration [43].
Hydrolytic Stability Testing
Hydrolytic stability refers to the lubricant's resistance to
chemical interactions with water that result in undesirable
changes to fluid properties. Certain chemical components
may react with water to decompose or form undesirable
byproducts of hydrolysis. Heat and catalysts such as copper
can accelerate the process of hydrolysis. Hydrolytically unstable oils form insoluble contaminants and acidic compounds that create hydraulic system malfunctions similar to
those produced by oxidation and thermal degradation of fluids. Furthermore, antiwear additives and corrosion preventatives that are susceptible to hydrolysis are likely to lose their
ability to perform their critical functions in the presence of
heat and water.
ASTM D 2619, Standard Test Method for Hydrolytic Stability of Hydraulic Fluids (Beverage Bottle Method) is used to
measure this fluid property. In this test, 75 g of fluid and 25
g of water are sealed in a beverage bottle with a copper strip.
The test bottie is rotated in an oven for 48 h at 93C (200F).
At the end of the test, the oil and water layers are separated

FIG. 14The Karl Fisher apparatus (a) titrant solution, (b) burette, (c) titration cell with
electrode, (d) solvent, (e) waste.

366

MANUAL

3 7 ; FUELS AND LUBRICANTS

HANDBOOK

and insolubles are weighed. Viscosity a n d acid numbers are


also determined. Based upon the Denison HF-0 specification
(see Table 5 for details of this specification), t h e weight
change of t h e copper specimen should b e less t h a n 0.20
mg/cm^ a n d the water layer acidity should be less than 4.0 mg
KOH. Since exposure to water can be expected throughout
the life of a fluid, hydrolytic stability is a n important design
characteristic of hydraulic fluids.
In genereJ, there are no additives specifically used to improve hydrolytic stability. Instead, hydrolytic stability is
achieved by appropriate selection of stable components that
maintain effectiveness even in t h e presence of water. Hydrolytic stability is also a key factor in the wet filterability behavior of hydraulic oils (see the Filterability section) [44].
Demulsibility
Demulsibilty is the term used to describe a fluid's ability to
separate from water. As discussed above in the Water Content
and Hydrolytic Stability section, water contamination of the
hydraulic oil may lead to various problems that adversely affect both fluid a n d equipment durability. Thus, it is desirable
for hydraulic oil and water to separate as quickly as possible.
In many industricJ applications, water is drained from the
hydraulic oil reservoirs as it separates and settles on the bottom. For fluids with poor demulsibility, the separation is either very slow or unlikely to occur to any significant degree.
Demulsibility

Testing

levels, entrained air is visible to the h u m a n eye as larger bubbles and can cause the oil to become cloudy. Uncontrolled air
contamination results in a n u m b e r of undesirable consequences. Entrained air increases the compressibility of the
fluid and can adversely affect its response to hydraulic control mechanisms or devices, especially in high-pressure systems. Dissolved or entrained air expands into larger bubbles
as its solubility in the fluid decreases as a result of exposure
to vacuum conditions at the p u m p inlet. This leads to noise
and cavitation, which is the dynamic process of gas cavity
growth a n d collapse in a liquid [47]. Several studies of this
p h e n o m e n o n have suggested theoretical m e c h a n i s m s a n d
documented experimental evidence of wear a n d increased
oxidation due to cavitation [48].
Foaming is very much rooted in the fundamentcJ problem
of air contamination and consequently, results in many of the
same negative effects of air entrainment. It is characterized
by the formation of a mass of relatively large bubbles on the
surface of the fluid and is usually brought about by turbulent
return of oil to the reservoir or migration of entrained air to
the surface. It is desirable to have fluids with a low tendency
to form foam in the first place a n d have the foam collapse
quickly once formed. For effective foam control, the rate of
foam collapse must be faster t h a n the rate at which entrained
air migrates to the surface to form the foam. Otherwise, the
foam layer will continue to increase and air may eventually
be re-dispersed in the bulk fluid [49]. In severe cases, oil that
produces a significant amount of foam may bubble out of hydraulic reservoir breathers, creating a fluid spill.

The speed at which water is separated from oil and the tendency of an oil to form a cuff of emulsified oil at the interface
between the oil and water phases may be measured by ASTM
D 1401, S t a n d a r d Test Method for W a t e r Separability of
Petroleum Oils and Synthetic Fluids. In this test, a 40 ml sample of oil a n d 40 ml of distilled water are stirred for 5 min at
54C (130F) in a graduated cylinder. The time required for
the emulsion to separate into water a n d oil phases is
recorded. An oil with good demulsibility will completely separate in 30 m i n or less without a "cuff' of emulsified oil between the phases [45].

Air entrainment has increasingly become a concern due to


a trend toward smaller reservoir sizes. Shorter fluid residence times therefore dictate use of hydraulic fluids with improved air release characteristics for the reasons discussed
above. Several studies have shown that fluid viscosity is a
critical factor influencing air release properties. Within a
given class of fluids, higher viscosity and lower oil temperatures translate into slower air release characteristics. While
different classes of base fluids have demonstrated unique air
release advantages, there has been little success in identifying
additives that improve air release properties of a base fluid.

Demulsifiers

Foam and Aeration

Demulsifiers are chemicals used to alter the surface tension


at the oil/water interface to accelerate separation. T3rpical
demulsifiers include alkylphenol ethers, low molecular
weight synthetic sulfonates, and polyoxyalkylate resins.

Because of the importance of properly managing air contamination in hydraulic fluids, there are a n u m b e r of standardized test methods for evaluating this feature of fluid performance. The foaming tendency a n d stability of oil may be
measured by ASTM D 892, Standard Test Method for Foaming Characteristics of Lubricating Oils. In this test, an oil
sample is equilibrated at 24C (75F). Air is bubbled through
oil for 5 min, and then the oil is allowed to settle for 10 minutes. The volume of foam is measured at the end of both periods. The test is repeated at 93.5C (200F) and again at 24C
(75F) after the foam breaks. Various levels of foaming tendency are permitted by industry standards, but stable foam is
generally not tolerated [50,51].
Not only must a hydraulic fluid resist the tendency to form
stable foam, it also must allow air to rapidly rise and separate
from the fluid. The Waring blender test is one test method
that may be used to measure the air release properties of fluids [52]. In ASTM D 3519, Standard Test Method for Foam in
Aqueous Media (Blender Test), 200 ml of the fluid is stirred

Aeration a n d Foam
Under normal conditions there is always air present in a hydraulic fluid. By volume, it is present at about 7-9% at room
temperature a n d atmospheric pressure [46]. In this state, it is
not visible to the h u m a n eye and thus referred to as dissolved
air. Higher temperatures and/or lower pressures (such as vacu u m conditions) lead to lower dissolved air levels. (See chapter on compressor lubricants for detailed discussion on gas
solubility and methods of measuring gas solubility.)
Fluid circulation through hydraulic systems and reservoirs
may cause mecheinical introduction of air into hydraulic fluids, particularly if reservoir size or design does not allow sufficient residence time for air separation to occur. At elevated

Tests

CHAPTER
at an agitation rate of 4000 to 13000 r p m for 30 s. The meixim u m total height at zero time, at 5 m i n a n d 10 m i n is
recorded in order to assess the foaming and aeration tendency of a fluid under high shear conditions.
Air release properties of a hydraulic fluid may also be
quantified by IP 313, DIN 51381 or ASTM D 3427, Standard
Test Method for Air Release Properties of Petroleum Oils. In
these tests, the time in minutes for finely dispersed air in oil
to decrease to 0.2% under standard test conditions is measured using a density balance. Air release times and specifications typically vary with oil viscosity.
Defoamants
Antifoam additives, generally referred to as defoamers or defoamants, are materials that destabilize the liquid film that
surrounds air bubbles. The most commonly used defoamants
are silicone polymers (particularly polydimethylsiloxanes),
which function as finely dispersed marginally soluble liquid
particles. Since silicon defoamants have very low surface tensions, they tend to accumulate at air/oil interfaces. When the
larger bubbles rise to the surface and join other bubbles to
form foam with only very thin films separating them, silicone
defoamants cause these films to rupture, thus accelerating
collapse of the foam. While silicone defoamants reduce the
foaming tendency of a fluid, they may also tend to increase
air entrainment (Fig. 15) [53].
Besides affecting air entrainment in hydraulic fluids, silicone defoamants tend to have poor filterability and storage
stability due to their marginal solubility in oil. Non-silicone
defoamants are increasingly used to address these disadvantages. Polyalkylacrylate additives are the most common class
of non-silicone defoamants recognized in the industry. Although they do not possess the disadvantages of the silicone
types, these polyalkylacrylates must be used at higher concentrations to deliver equivalent performance.

13: HYDRAULIC

It is widely recognized that beyond proper fluid selection,


good fluid maintenance is the key to reliability and durability
of hydraulic equipment. Fluid maintenance is closely linked
to fluid cleanliness and filtration. Filtration devices, therefore, are critical tools for maintaining hydraulic fluids and
system components. Hydraulic fluid "filterability" is concerned mainly with the appropriate flow characteristics of
the fluid through filter media. For proper operation, the fluid
should readily flow with m i n i m u m pressure drop across the
filter and with negligable depletion of additives. The viscosity
and chemistry of the lubricant will affect filterability. Therefore, filter size and materials should be compatible with the
circulating fluid. The drive to increase hydraulic system reliability through the use of fine filtration magnifies the importance of this performance parameter.
Filterability

Tests

Due to the likelihood of water contamination in many hydraulic systems and its potential impact on fluids, most of the
filterability tests are designed to r u n dry and wet (with water
added). Hydraulic fluid filterability tests generally consist of
filtering a specified quantity of fluid t h r o u g h a standard
medium while monitoring changes in flow rate (Table 6). The
results are tj^pically reported in terms of a ratio between flow
rates with and without water added to the fluid. This approach attempts to account for changes in filterability behavior independent of viscosity. In Denison TP 02100 the
time required for complete flow of a standard volume of fluid
through a specified filter is evaluated. In the Pall Filterability
Test the differential pressure across a specified filter assembly is monitored over the duration of the test and cin appropriate limit is established to discriminate between fluids with
good and poor filterability behavior. While key equipment

OIL WITH
SILICONES

O
O
eg
<

h-

SETTLING OR
"TRANQUIL PHASE"

BLOWING OR
TURBULENT PHASE"

367

Filterability

AIR RELEASED DURING


BLOWING PHASE

VOLUME OF AIR
BLOW IN

FLUIDS

>

TIME
FIG. 15Impact of silicone defoamer on foaming tendency and air release. Silicone defoamer decreases the tendency of the oil to generate foam while increasing the tendency
of the fluid to retain air below its surface.

368

MANUAL

37: FUELS AND LUBRICANT

Method

TABLE 61Filterability tests.


AFNOR
Pall"
0.8jU.M
0.2
70 h
70C

Medium pore size


Percent water added
Aging time
Temperature

HANDBOOK

Denison

3/LiM
1.0
24 h
70C

1.2 ^M
2.0
None
25C
"Parkhurst, H., Pall Filterability Index Test for Paper Machine Oils, SLS Report No. 5669, April 1995.

builders and industrial manufacturers may require fluids to


meet certain filterability criteria as measured by these tests,
global hydraulic oil specifications (i.e. ASTM D 6158, ISO
11158, DIN 51524) have not yet incorporated these procedures.
Filterablility

Additives

From a formulation standpoint, identifying and replacing additives with potential filterability problems (i.e., filter material incompatibility, gel-forming tendency, hydrolytic instability, etc.) has been the primary method of improving fluid
filterability. Recently, dispersants have been identified that
enhance filterability by preventing agglomeration of insoluble species present in the fluid. These dispersants are typically alkyphenol-based or alkyl succinimide polymers of
varying molecular weights.

Corrosion Protection
Chemical contaminants and corrosive by-products of fluid
degradation can cause surface attack of metallic hydraulic
system components. Ferrous metal corrosion in a hydraulic
system is most often caused by water contamination, while
copper and its alloys are susceptible to attack by the products
of high temperature fluid degradation. Rusting of ferrous
metal is an electrochemical reaction that occurs between the
parent metal and the thin oxide layer on the metal surface
formed as a result of exposure to the atmosphere [20]. Rust,
which is hydrated iron oxide, compromises the integrity of
the metaJ surface and adversely affects other important fluid
properties w h e n it contaminates the bulk fluid. Ferrous
metal corrosion protection in hydraulic systems is usually accomplished by incorporating surface-active additives such as
rust inhibitors. There are several ASTM methods for evaluating the corrosion inhibition properties of hydraulic fluids.
Corrosion

and Rust

Testing

The ability of fluids to prevent rusting of ferrous parts due to


water c o n t a m i n a t i o n m a y be m e a s u r e d by ASTM D 665,
Rust-Preventing Characteristics of Inhibited Mineral Oil in
the Presence of Water. In Part A of this test, 10% distilled water is added to oil that has been heated to 60C (140F).
Round steel rods are polished to remove their oxide coating
and immersed in the oil. The oil-water mixture is continuously stirred to avoid separation while the temperature is
maintained at 60C. At the end of 24 h the specimens are inspected for rust (Fig. 16).
In Part B of the method, the same procedure is used, except
synthetic seawater is substituted for distilled water. As described in Part B, synthetic seawater is made by the addition

of sodium chloride, magnesium chloride, calcium chloride,


and several other ionic compounds to distilled water. Part B
is particularly pertinent to maritime hydraulic fluid applications where seawater, rather t h a n fresh water or condensation, is a likely source of contamination.
The standard test method for measuring vapor phase corrosion inhibition of hydraulic fluids is ASTM D 5534, Test
Method for Vapor-Phase Rust-Preventing Characteristics of
Hydraulic Fluids. In this test, a steel specimen is attached to
the cover of an ASTM D 3603 test apparatus that contains hydraulic fluid maintained at a temperature of 60C (140F).
ASTM D 3603 is the Horizontal Disk Method for Rust-Preventing Characteristics of Steam Turbine Oils in the Presence
of Water. The specimen is then exposed to water and hydraulic fluid vapors for a period of 6 h. At the end of this time,
the specimen is inspected for evidence of corrosion and results are reported on a pass-fail basis. The ASTM D 5534 test
is particularly relevant for water-glycol and invert-emulsion
hydraulic fluids because corrosion of the underside of reservoir covers has been observed in systems that use these fluids.
Accelerated corrosion can also occur when dissimilar metals are in electrical contact in the presence of an electrolyte
(i.e., conductive solution). This corrosion mechanism,
known as galvanic corrosion, has been found to be particularly relevant for certain biodegradable oils [54], The ability
of a fluid to prevent galvanic corrosion may be measured by
ASTM D 6547, Test Method for Corrosiveness of a Lubricating Fluid to a Bi-Metallic Couple. In this test, a brass clip is
fitted to the oil coated surface of a steel disk. The bi-metallic
(brass/steel) couple is then stored in 50% relative humidity
for ten days. At the end of the ten-day period, the surfaces are
inspected for evidence of staining like that depicted in
Fig. 17. The steel disks are rated on a pass-fail basis.
Sulfur containing additives such as zinc dithiophosphate,
sulfurized olefins, organic polysulfides, and carbamates may
be used as antiwear and extreme pressure additives in hydraulic fluids [55]. Depending u p o n the chemical activity of
these sulfur compounds, hydraulic fluids exhibit varying degrees of corrosiveness to copper when activated by high temperatures. ASTM D 2070, Standard Test Method for Thermal
Stability of Hydraulic Oils is one of the most effective methods for predicting the corrosiveness of a hydraulic fluid to
copper and its alloys. The ASTM D-2070 test measures the
aggressiveness of chemical constituents in the fluid toward
yellow metals when aged under high temperature conditions.
(See the section on High Temperature Oxidation Tests)
In some cases, such as when a hydraulic fluid is contaminated with sulfur containing metalworking fluid, the fluid
may exhibit corrosivity to copper without requiring thermal
degradation. The standard test method for measuring the copper corrosion properties of oil is ASTM D 130, Standard Test
Method for Detection of Copper Corrosion from Petroleum
Products by the Copper Strip Tarnish Test. In this test, a polished copper strip is immersed in oil and heated for a predefined period of time. At the end of the test, the copper strip's
appearance is compared to a standard. The rating system used
for the D 130 test appears in Table 7. The rating system is on
a scale of one to four. The higher the copper strip rating, the
greater the degree of copper corrosion. Color standards are
also available from ASTM for rating copper strips [56].

CHAPTER 13: HYDRAULIC FLUIDS

369

FIG. 16ASTM D 665 passing vs. failing rod.

FIG. 17Galvanic corrosion: staining on test specimen by vegetable oil.

Corrosion Inhibitors, Rust Inhibitors, and Metal


Passivators
Corrosion Inhibitors, Rust Inhibitors, and Metal Passivators
are designed to prevent deterioration of metal surfaces that
are in contact with the lubricant. Corrosion inhibitors are polar molecules that are surface active. They adsorb on the
metal surface and inhibit the electrochemical reaction that
produces rust. Some hydraulic fluids, particularly those used
in applications that require enhanced fire resistance, are for-

mulated with water. Such fluids have entirely different corrosion inhibition requirements. For instance, water glycol
hydraulic fluids must prevent corrosion in the vapor phase
above the liquid due to evaporation. Thus they are formulated with vapor phase corrosion inhibitors such as morpholine. Typical classes of rust inhibitors include metallic sulfonates, amine phosphates, simple fatty acids, and succinic
acid esters. Triazoles, or derivatives thereof, are commonly
used metal passivators.

370

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

TABLE 7Copper strip classifications.


Rating

Designation

la

Slight tarnish

lb
2a
2b
2c

Slight tarnish
Moderate tarnish
Moderate tarnish
Moderate tarnish

2d
2e
3a
3b

Moderate tarnish
Moderate tarnish
Dark tarnish
Dark tarnish

4a

Corrosion

4b
4c

Corrosion
Corrosion

Light orange, almost the same as


freshly polished strip
Dark orange
Claret red
Lavender
Multicolored with lavender blue or
silver overlaid on claret red
Silvery
Brassy or gold
Magenta overcast on brassy strip
Multicolored with red and green
showing (peacock), but no gray
Transparent black, dark gray or
brown with a trace of peacock
Graphite or lusterless black
Glossy or jet black

Seal Compatibility
Very critical to the successful operation of a hydraulic system
is the ability to prevent leakage and accidents that are a result
of failed seals. Leaks can lead to contamination, loss of pressure, loss of lubricating fluid, and environmental damage depending on the severity of the spill. In extreme temperature
and pressure operations, sudden failure of seeds may have life
threatening consequences, considering the potential for explosions, fires, etc. [57]. Hydraulic fluids and elastomeric
seals are composed of complex chemical components that
can interact as they come into contact. Depending on the
chemistries involved, time, t e m p e r a t u r e , a n d mechanical
stresses cause fluid interactions with the seal material, resulting in swelling or shrinkage of the elastomer compound.
It is desirable to select seal materials that exhibit minimal
change in hardness, volume, tensile strength etc. in service.
Slight swelling of seals is preferable to shrinkage as indicated
in Table 8. This is because a reduction in seal volume may result in leakage of fluid due to failure of the seal to fill the
gland that retains it in place.
Seal Compatibility

TABLE 8Recommended property change limits for


determining compatibility of elastomer seals for
industrial hydraulic fluid applications.

Description

Testing

In general, industry recognized seed compatibility tests entail


exposure of the elastomer material to the test fluid for a specified duration and at a standard temperature u n d e r static
conditions. Familiar industry seal compatibility tests include
ISO 7619, ISO 6072, DIN 53 538, and ASTM D 6546-00, Standard Test Methods for and Suggested Limits for Determining
Compatibility of Elastomer Seals for Industrial Hydraulic
Fluid Applications. Other major organizations such as ASTM
and SAE also have related specifications for sealing devices.
Due to variations in elastomer chemistry, it is necessary to
perform compatibility tests on the specific materials being
used. While most standard tests measure changes in hardness, stress/strain properties, and volume changes after exposure to the test fluid, translation of these results to a practical application m a y be difficult, since geometry and
mechanical conditions of the targeted application profoundly impact the elastomer. It is therefore recommended
that seal materials be tested u n d e r conditions that closely
simulate the actual application [58].

Maximum
Volume
Swell,

Time in
Hours
24
70
100
250
500
1000

Seal Swell

Maximum
Vol.
Shrinkage,

Hardness
Change,
Shore A
Points

15
15
15
15
20
20

-3
-3
-3
-4
-4
-5

7
7
8
8
10
10

Maximum
Tensile
Strength
Change, %
-20
-20
-20
-20
-25
-30

Agents

These chemicals react with the elastomeric materials to


cause slight swelling or softening to counteract the typical effects of temperature and mechanical stress. Seal swell agents
are typically used with base fluids having very low aromatic
content. Aromatic derivatives or phosphate esters are typically used to enhance the seal swell characteristics of a fluid.
Coolant Separability
Hydraulic systems used in machine tool operations are susceptible to contamination by aqueous cutting fluids, which
contain components with poor oxidation resistance, high deposit forming tendency, and/or high corrosivity. In metcdworking applications, the hydraulic fluid may be considered
a contaminant of the cutting fluid that alters its effectiveness
in metal removal operations. Regardless of the perspective, a
mix of these two categories of fluids is undesirable, especially
if they have not been designed to be compatible. In this case,
compatibility is defined as the ability of either fluid to complement, enhsince, or at least have no impact on the performance of the other w h e n mixed. The lubricant's ability to
readily separate from coolants is highly desirable in most
cases. However, the variety and complexity of coolant
chemistries makes it difficult to ensure good separability of
the hydraulic oil from all metalworking fluids [59].
There are generally n o additives specifically designed to
improve coolant separability, since coolant chemistries vary
so widely. The t3?pical approach is to formulate a lubricant to
have good demulsibility (water separability) and then test its
compatibility with specific coolants with which it is expected
to come into contact.
Coolant

Separability

Testing

A standard industry test method for assessing lubricant compatibility with coolants has not yet been established. However, some Icirge industrial manufacturers and lubricant suppliers do have in-house test procedures designed to simulate
oil contamination by a low percentage of coolant, as well as
coolant contamination by a low percentage of oil (typically
referred to as tramp oil). In general, these procedures consist
of mixing the lubricant with the coolant at a specified ratio
a n d t e m p e r a t u r e for a s t a n d a r d duration. The fluid container, t5^ically a graduated cylinder, is then allowed to sit
while the degree of separation between the coolant and the
lubricant is observed at specific time intervals. Properties
such as additive leaching and foam stability may also be ob-

CHAPTER
served. Rapid separation, implying absence of a stable emulsion or cuff (the layer between way oil and coolant) at the interface, is very desirable (Fig. 18).
Shear Stability
Mobile hydraulic equipment such as excavators, farm tractors, cranes, and timber harvesters frequently are required to
operate under extreme high and low temperature conditions.
To accommodate wide-ranging environmental conditions,
hydraulic fluids with enhanced viscosity - temperature properties are often employed. These fluids t3^ically contain viscosity index improving polymers that thicken oil at high temperatures, while having little impact u p o n their low
temperature fluidity. Viscosity index (VI) is a common means
for expressing the variation of viscosity with temperature.
The viscosity index of an oil is calculated from the measured
viscosity of the fluid at 40 and lOOX using ASTM Method D
2270, Standard Practice for Calculating Viscosity Index from
Kinematic Viscosity at 40 and 100C. A high VI indicates less
relative change in viscosity for a given change in temperature. Vl-improved oils are commonly referred to as multigrade oils, because they meet both the low temperature requirements of low viscosity oils and the high temperature
requirements of higher viscosity oils. Conceptually, an SAE

Good

13: HYDRAULIC

FLUIDS

371

lOW-30 multigrade oil consists of a lOW base oil and sufficient polymer to thicken the oil at 100C to a viscosity equal
to that of an SAE 30 weight oil (Fig. 19).
Viscosity Index Improvers are typically subjected to mechanical degradation due to shearing of the molecules in high
stress areas such as between gear teeth in gear pumps and
vane-ring interface in vane p u m p s . High pressures generated
in hydraulic systems subject fluids to shear rates up to 10^ s~'
[60]. Not only does hydraulic shear cause fluid temperature
to rise in a hydraulic system, but shear may bring about permanent viscosity loss in hydraulic fluids [61]. Permanent viscosity loss results from mechanical scission of polymer
molecules in multigrade hydraulic fluids and often occurs after a relatively short period of time (<24 hours of operation).
The polymer (as opposed to the base oil) is susceptible to mechanical shear because it has a higher molecular weight and
therefore a larger molecular volume. As a result, with polymer-containing multigrade hydraulic fluids, the functional
viscosity of an oil may differ from that predicted from kinematic viscosity measurements of new oil [62].
Shear Stability

Tests

It is desirable to formulate hydraulic fluids with shear-stable


VI improvers so that the fluid retains its viscosity properties
throughout its service life. Several laboratory test methods are

Fair

FIG. 18Good vs. Bad coolant separability.

Poor

372 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Multigrade Oils
100,000
10,000
1,000

of resistance to mechanical shear, as well as their chemical


and thermal stability. For a given polymer type, shear stability decreases with an increase in molecular weight. Shear is
indicated by a loss in fluid viscosity (Fig. 20). The "thickening
efficiency" of the viscosity modifiers generally increases with
an increase in molecular weight for a given polymer type. Selection of the best VI Improver must entail consideration of
viscosity requirements, shear stability, and thermal and oxidative stability in actual equipment operation.
Low Temperature Pumpability

2-i
-40

.
^40
100
150
Temperature, C
FIG. 19Impact of VI improver on lubricant viscosity.
-20

designed to stress multigrade oils so that they produce a permanent viscosity loss such as would take place in service. The
two methods generally used are mechanical shearing with a
Bosch diesel fiiel injection pump and sonic shearing with a
high frequency sonic oscillator. In ASTM D 6278, Test Method
for Shear Stability of Polymer Containing Fluids Using a European Diesel Injector Apparatus, the polymer-containing
fluid is passed through a diesel injector nozzle at a shear rate
that causes polymer molecules to degrade. Under standard
test conditions, the kinematic viscosity of the fluid is measured after 30 to 250 cycles through the injector pump to determine the extent of permanent viscosity loss that has taken
place. In ASTM D 5621, Standard Test Method for Sonic
Shear Stability of Hydraulic Fluid, the polymer-containing oil
is irradiated with a sonic oscillator for 40 min and changes in
kinematic viscosity are measured. Based upon data from
Kopko and Stambaugh, the Fuel Injector Shear Stability Test
lacks the necessary severity to predict permanent viscosity
loss produced by hydraulic equipment [62]. However, 40 min
of irradiation with a high frequency sonic oscillator produced
viscosity changes that closely correlate to that experienced in
the ASTM D 2882 Vane Pump Test. Consequently, this test
method has become the basis for ASTM D 6080, Practice for
Defining the Viscosity Characteristics of Hydraulic Fluids.
Viscosity Index Improvers
Viscosity Index Improvers (also referred to as viscosity modifiers) are high molecular weight poljTuers that reduce the
magnitude of viscosity change as a function of temperature.
They function by enabling the oil to retain thickness at higher
temperatures while having minimal impact on viscosity at
lower temperatures. In general. Viscosity Index Improvers
are oil-soluble organic polymers with molecular weights
ranging from about 10000 to 1 million. The oil temperature
controls coiling of the polymer molecules, which in turn controls the degree to which the polymer increases viscosity. The
higher the temperature, the less the coiling and the greater
the "thickening" effect of the polymer. Therefore, as temperature increases, there is less thinning of the lubricant compared to non-polymer-containing oils.
The performance of VI Improvers is also described in terms

Paraffinic mineral oils, which comprise the bulk of hydraulic


fluids, contain some amount of wax that forms crystalline
structures at low temperatures. As these structures form, the
oil becomes more viscous. At very low temperatures the fluid
may become gel-like or even solid. For hydraulic systems,
poor low temperature flow characteristics can result in catastrophic failures. During start-up at very low temperatures, significant pump cavitation can occur due to inadequate oil flow.
Low Temperature Pumpability Tests
A number of bench tests are commonly used to evaluate low
temperature flow characteristics of lubricants. One of the
most common tests specified for this purpose is ASTM D 97,
Standard Test Method for Pour Point of Petroleum Products,
which measures the lowest temperature at which a lubricant
will flow. ASTM D 6351, Test Method for Determination of
Low Temperature Fluidity and Appearance of Hydraulic Fluids is used for evaluating the pour characteristics of
biodegradable oils. While this test gives an indication of low
temperature flow characteristics of the fluid, it does not necessarily address fluid performance in many applications subjected to very low temperatures. Pumps, motors, engines, and
many types of lubricated machinery require that the lubricant be pumped or circulated effectively at start-up. As a result, several tests have been developed to determine fluid viscosity at low temperature. For hydraulic systems, tests such
as Brookfield (ASTM D2 983), Scanning Brookfield SBV
(ASTM D 5133), and Mini Rotor Viscometer MRV (ASTM D

Multigrade Oils and Shear Stability


Quiescent Polymer Coil in
Oil Solution

Reversible/
Orientation of Coil
Under Shear Forces

Temperature
Viscosity Loss

sNonreversible
Rapture of Coil and
Subsequent Orientation
Under Shear Forces

Permanent
Viscosity Loss

FIG. 20Impact of shear stress on VI improver molecule.

CHAPTER 13: HYDRAULIC FLUIDS 373


TABLE 9Low temperature viscosity
grades for hydraulic fluid classifications.
Viscosity
Grade

Min.

Max.

L5
L7
LIO
L15
L22
L32
L46
L68

-49
-41
-32
-22
-14
-7
-1

-50
-42
-33
-23
-15
-8
-2
4

that will crystallize at low temperatures and cause the fluid to


solidify. These additives do not entirely prevent wax from
crystallizing in the oil. Rather, they lower the temperature at
which large wax crystal structures are formed. By reducing
the size of the crystal matrix, pour point depressants permit
lubricants to flow at lower temperatures.
Two widely used types of pour point depressants are alkylaromatic polymers, which adsorb on wax crystals to inhibit
growth and adherence of crystals to each other, and polymethacrylates (PMA), which co-crystallize with wax to minimize growth of crystals. Depending mainly on the type of
base fluid, the pour point of oil can be lowered typically by
20-30F (I1-17C).

4684)all of which include specified cooling cycle and low


shear rates simulating field conditionscan be used to assess
fluid pumpability. Performance specifications that include
low temperature pumpability requirements, such as ASTM D
6080, Standard Practice for Defining the Viscosity Characteristics of Hydraulic Fluids, typically specify a temperature
range for different viscosity grades. In Table 9 (from Standard D 6080) the temperature range for a given L-grade is approximately equivalent to that for an ISO grade of the same
numerical designation and having a viscosity index of 100.
For instance, the temperature range for the L32 oil is approximately the same as an ISO VG 32 grade with a Viscosity
Index of 100.
Pour Point

Depressants

Pour point depressants are additives designed to reduce formation of rigid wax crystals in the lubricant at low temperatures. Conventionally refined mineral oils typically require
the use of pour point depressants because they contain wax

TYPES OF HYDRAULIC FLUIDS


The major compositional categories of hydraulic Quids are
Petroleum Based, Synthetic Based, Water Based, Vegetable
Oil Based, and Water (Fig. 21). As expected, these different
categories have properties that make them especially desirable in particular applications. In this section, the types of
hydraulic fluids will be discussed in terms of their defining
functionality rather t h a n composition. For example, fire resistant fluids, which are typically water-based or ester-based
fluids having high flash points, are used extensively in the basic metals industry where the risk of ignition is high, while
"environmentally acceptable" fluids are used in environmentally sensitive areas.
Hydraulic system hardware is usually designed and formally rated to work with mineral oils, since they are the
predominant hydraulic fluid in use. Systems may have to

HVDRMjuc mxs

Pelrolaum 8al

R&OlfWbHed

SynlHtBc Ba9Cl

AnCweartAW)

MuBgrade

Witer Baaed

SynttieBc Hydiocarfcona (SHC)

PoW/'}

EMere

Phosphale Eaan

SMeones

PololEgre

Rapwwed

Polyalphaolat>i8(PAO)

wsot 0 ^

Polyaloxarwa

EWare

HatoaanalKl Cemiiounds

Polyetherg

Aryieftera

ScBean
SynHiellc SoluUon

Water-h-QI (hvBrt)

O U n - W W f ;So>i>le OB

Ghlorinatad Hydrocarbons
Raflutor

Silanas

FluowEstere

V 9 a * f c b 0 1 Based

WiiBd Haloflan Coropounds

FIG. 21Schematic of hydraulic fluid types.

Mcra Emulalm

374

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

be modified to accominodate alternative types of hydraulic


fluids.

precipitates that can cause hydraulic valve sticking and filter


plugging [65].
HM

Mineral Hydraulic Oils


The majority of hydraulic fluids in service are mineral oil
based because they generally provide excellent performance
at a relatively low cost. Within the mineral hydraulic oil category there is a wide range of viscosity grades and fluid types.
The International Organization for Standardization (ISO) established a classification system for hydraulic fluids that is
designated ISO 6743-4: 1999, Lubricants, Industrial Oils and
Related Products (Class L)-Classification-Part 4: Family H
(Hydraulic Systems). Using this classification system as a
foundation, ASTM created ASTM D 6158, Standard Specification for Mineral Hydraulic Oils, which defines the physical
properties and performance r e q u i r e m e n t s of mineral hydraulic fluids. Table 10 provides a list of mineral oil based
fluids listed in ASTM D6158.
HH
Type H H fluids are straight base oils without any additives.
They may be used in air-over-oil hydraulic systems such as is
found in car lifts at automotive service centers. They are also
used in manual hydraulic pumps, jacks, and other low-pressure hydraulic systems. While type H H fluids are able to perform the primary function of a hydraulic fluid, which is to
transmit power, they are unable to withstand high temperatures and have limited lubricating capabilities. Thus these
fluids find limited application in industry.
HL
Type HL fluids are also mineral oil based, but they contain
rust and oxidation inhibitors to protect equipment from the
detrimental effects of water contamination and chemical deterioration due to heat. These fluids are also known as R & O
oils because they contain rust and oxidation inhibitors. Type
HL fluids are often recommended for use in machine tool applications where system pressures are limited to 2000 psi or
less. They are also recommended for some piston p u m p applications. For example, type HL fluids are the preferred fluid
for Denison piston p u m p s [63]. This is because some ZDTP
containing oils can be aggressive to yellow metal (brass and
bronze) and silver alloyed components in piston pumps.
R & O oils often are formulated using a rust inhibitor
chemistry that contains succinic acid derivatives [64]. These
additives may be incompatible with metallic sulfonate or
phenate rust inhibitors or ZDTP antiwear additives used in
many antiwear hydraulic fluids, resulting in formation of

TABLE 10Mineral oil based hydraulic fluid classifications.


Symbol

Classification

HH
HL

Non-inhibited refined mineral oils


Refined mineral oils with improved
rust protection and oxidation
stability
Oils of the HL type with improved
anti-wear properties
Oils of the HM type with improved
viscosity index properties

HM
HV

Commercial
Designation
Straight base oils
R&O oils
Antiwear oils
Multigrade oils

Type HM fluids contain antiwear additives in addition to the


rust and oxidation inhibitors found in HL fluids. They are the
most widely used mineral oil based hydraulic fluids because
antiwear additives provide enhanced performance in highpressure hydraulic applications. The requirements for HM
oils are listed in Table 11. While early versions of HM oils
lacked the thermal stability necessary for satisfactory piston
p u m p performance, modern fluids are able to perform quite
well in piston p u m p applications.
Zinc dialkyldithiophosphate is the most widely used antiwear additive for hydraulic applications. In recent years, concerns about the environmental effects of ZDTP have led to development of zinc-free or ashless antiwear hydraulic fluids.
These products utilize sulfur and phosphorus compounds to
achieve satisfactory antiwear performance. Thus, a type HM
fluid may contain zinc or some other type of antiwear additive chemistry.
HV
Type HV fluids contain the same basic chemistry as HM fluids plus a viscosity index (VI) improver. (See the Shear Stability section.) Viscosity index improvers impart multigrade
functionality to type HV fluids. While a wide range of polymers may be used for VI enhancement, these additives all
function in the same basic manner. At low temperatures, VI
improvers have a minimal effect upon fluid viscosity and at
high temperatures they have a thickening effect. This enables
the fluid to provide satisfactory performance at a wider operating temperature range [66].
T r a c t o r F l u i d s , ATF, a n d E n g i n e O i l s
Tractor fluids are unique in that they are formulated to lubricate transmissions, final drives, wet brakes, clutches, and
hydraulic systems from a c o m m o n fluid reservoir on the tractor [67]. Consequently, tractor fluids are often used in agricultural equipment, off-highway machinery, backhoes, and
turf applications where a multifunctional hydraulic fluid is
required. To lubricate gears, wet brakes, and hydraulic systems, tractor fluids typically utilize phosphate ester based
friction modifiers and ZDTP.
Automatic transmission fluids (ATFs) are similar to tractor
fluids in that they are designed for multiple functionality,
however, they generally utilize ashless antiwear additives
r a t h e r t h a n ZDTP. ATFs tend to be used in applications
where superior low temperature performance is desired because they are designed to remain fluid at temperatures as
low as 40C. Years ago it was common to use lOW engine
oils in hydraulic applications. Until recently lOW diesel engine oil was the primary hydraulic fluid recommendation for
Caterpillar equipment because lOW diesel engine oil contains ZDTP antiwear additives and is compatible with engine
oil [68]. The disadvantage of using ATFs and engine oils in
hydraulic applications is that they tend to have poor water
separation properties, which reduces wet filterability performance due to hydrolysis of the metallic sulfonates and phenates. Consequentiy, fluids designed specifically for hydraulic
performance are generally more desirable.

CHAPTER

13: HYDRAULIC

FLUIDS

375

TABLE 11International specifications for antiwear hydraulic oil.


DIN 51524 Part 2

ISO 11158
ASTM
Properties
ISOVG
Kinematic Viscosity, cSt
D445
40'C max.
40C min.
D92
Flash Point, C min.
Flash Point, C min.
093
Brookfield Vis < 750 cP, Max
D2983
D97
Pour Point, C, max
Visual
Appearance
D1744
Water Content, wt%
01298
Density @1SC
TAN, ma KOH/g, max
0664 or 0974
D665A
Rust Test A
Rust Test B (Salt Water)
06658
Cu Rating (3 hr, 100C), max. 0130
TOST Oxidation, hours
0943
AN after 1000h, max.
Air Release @ 50C, minutes
D3427
(max)
Foam tendency/stability
0892
Seql
max
max
SeqII
max
SeqIII
Demulsibility @ 54C
01401
Minutes to 37 mL water .
0 5182
FZG Fail Stage
Ctiange in Hardness
0 471
NBR1,168 hrs @ 100C
ISO 7619
Change in Volume (%)
NBR1,168hrs@100C
Viscosity Index, min
0 2270
CM Thermal Stab.
02070A
Sludge, mg/100 ml max
Copper rod appearwice, rating (max.)
0 4310
Oxidation (1000 h)
AN, mgKOH/g max
Total sludge, mg max.
Total Metals in oil/water/sludge
Vickers 104C mg. wear max.
0 2882

HM (Antiwear)
32
46

22

S8

22

68

24.2
19.8
165

35.2
28.8
175

50.6
41.4
185

74.8
61.2
195

24.2
19.8
165

35.2
28.8
175

50.6
41.4
185

74.8
61.2
195

-18

-15
< Report >

-12

-12

-21

-18

-15

-12

-15
-21

-8
-18
<C&B>

-2
-15

4
-12

2
1000

< Report >


< Report >
<Pass>
< Pass>
2
1000

2
1000

2
1000

10

13

30

30

Oto-7

Oto-6

<-ao5->

< Report >


< Report >
< Report >
<Pass>

< Report >


< Report >
<Pass>

10

13

10

10

<15Qro>
<7SI0>

<i5ao>
<75/Q>
<150)>
30
10

<15C/0>
<70>
<150)>

<i5oro>
30
10

30
10

30
10

40

40
10

40
10

60
10

< Report >

Oto-8

Oto-7

Oto-7

Oto-6

< Report >


< Report >

0to15

0to12

0to12

OtolO

2
< Report >

HFAE

Oil-in-water emulsions containing


typically >80% water
Chemical solutions in water
containing typically >80% water
Water-in-oil emulsions containing
approximately 45% water
Water-polymer solutions containing
approximately 45% of water
Synthetic fluids containing no water
and consisting of phosphate esters
Synthetic fluids containing no water
and of other compositions

< 150 in exterxled test>

Commercial
Descriptions

Soluble oils
High water based
fluids
Invert emulsions
Water-glycols
Phosphate esters
Polyol esters

30

30

r288 hrs. f 000)


Oto-8
Oto-7
Oto15

0to12
<-90->

0to12

OtolO

< Report >


< Report >

25
5

25
5

25
5

200

200
< Report >
50

200

200

50

50

: Report >

Classification

HFDU

HM (Antiwear)
32
46

74.8
61.2
180
168

Symbol

HFDR

22

50.6
41.4
180
168

TABLE 12ISO designations for fire resistant


hydraulic fluids.

HFC

68

35.2
28.8
160
148

Fire resistant hydraulic fluids are used in the basic metals industry, die casting, military, and foundry applications. They
may be found in any application where a ruptured hydraulic
line presents a potential fire hazard. Fire resistant hydraulic
fluids are formulated with materials that have a lower BTU
content than mineral oils, such as polyol esters, phosphate esters, and water-glycol solutions. As a result, they b u m with
less heat generation than mineral hydraulic oils. As with mineral hydraulic fluids, the International Organization for Standardization has established a classification system for fire resistant fluids based upon composition. Table 12 provides a list

HFB

ASTM D6158

24.2
19.8
140
128

Fire Resistant Fluids

HFAS

Requirements
32
46

50

of the ISO designations for fire resistant hydraulic fluids [69].


While power transmission, heat transfer, and lubrication
are essential requirements for all types of hydraulic fluids, it
is sometimes necessary to compromise these properties to
accommodate a critical fluid characteristic. This is especially
true of fire resistant hydraulic fluids. Fire resistant fluids differ from mineral hydraulic fluids in density, compatibility,
and lubricating properties. As a result, hydraulic systems are
often modified when utilizing a fire resistant fluid. To optimize the performance of fire resistant fluids, the National
Fluid Power Association and ISO have published guides for
their use [70,71]. These NFFA and ISO documents detail the
operational characteristics of fire resistant fluids and provide
suggestions for storage, use, and handling of these fluids.
Table 13 provides a comparison of the properties of common
fire resistant hydraulic fluids.
HFA
HFA fluids contain greater than 80% water. These products
are sometimes referred to as 95:5 fluids, because 5% concentrations are commonly employed. The ISO 6743-4 classification divides HFA into two sub-categories: HFAE and HFAS.
HFAE fluids are oil-in-water emulsions. HFAS fluids are
chemical solutions or blends of selected additives in water.
Typically these products are sold as concentrates and diluted
prior to use in service. Because of the high vapor pressure of
water, the m a x i m u m recommended bulk fluid temperature
for HFA fluids is 50C [72]. The antiwear properties of these
fluids are inferior to mineral hydraulic fluids because the vis-

376

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 13Comparison of c o m m o n fire resistant fluid properties.


Property
ISO Designation
Heat of Combustion"
Autoignition Temp, "F*
Maximum" Temperature
Vapor Pressure, m b a r
Specific Gravity
Viscosity @ 40C, cSt
Water
Content
Vane p u m p rating"
Compatible Seals

Antiwear Hyd.
Oil

Invert
Emulsion

Water
Glycol

Phosphate
Ester

Polyol
Ester

HM
29.1 kJ/g
650
150F
0.001 @ 50C
0.85-0.88
32-68
0.05%

HF-B
16.3 kJ/g
830
120F
NA
0.91-0.93
80-100
43%

HF-C
5.3 kJ/g
830
120F
80 @ 50C
1.05-1.10
40
43%

HF-DR
19.0 kJ/g
1100-H
150F
< 1 @ 150C
1.02-1.16
22-100
0.05%

HF-DU
21.1 kJ/g
750"
150F
NA
0.91-0.96
46-68
0.1%

100%
Buna-N, Viton

33%
Nitroxyl, Buna-N

67%
Buna-N

67%
Butyl, EPR

100%
Viton, Buna-N

"Roberts and Brooks Flammability Data, NFPA T2.13.8-1997, a calculated estimate was used for HFDU.

cosity of HFA fluids is comparable to water, approximately 1


cSt. Performance is satisfactory with HFA fluids when suitable components are used but is apt to be poor if used in conventional hydraulic systems. Special precautions also are required in the selection of filter construction materials and
plumbing of p u m p inlets. Thus, it is necessary to work closely
with fluid a n d c o m p o n e n t suppliers w h e n utilizing HFA
fluids.
HFB
HFB fluids are water-in-oil emulsions consisting of
p e t r o l e u m oil, emulsifiers, selected additives, and water.
They are commonly referred to as invert emulsions. In an invert emulsion the oil phase, which provides lubricity and rust
protection, encapsulates the water phase, which provides fire
resistance. The water content of an HFB fluid is normally in
the 4 3 - 4 5 % range (w/w). When water content of these fluids
drops below 38% due to evaporation, the fire resistance of the
invert-emulsion deteriorates. Maintenance of invert emulsions is complicated by the fact that when these fluids lose
water through evaporation, a high-shear mixing device is
normally necessary for proper addition of make-up. The viscosity properties of invert emulsions are u n u s u a l in that
evaporation of water results in a viscosity decrease.
Several ASTM methods have been developed specifically
for invert emulsion hydraulic fluids. ASTM D 3709, Standard
Test Method for Stability of Water-in-Oil Emulsions Under
Low to Ambient Temperature Cycling Conditions, is used to
evaluate the freeze-thaw stability of invert emulsions. ASTM
D 3707, Standard Test Method for Storage Stability of Waterin-Oil Emulsions by the Oven Test Method is used to determine if the emulsion has a propensity to separate after 48 h
at 85C. As with HFA fluids, special precautions also are required in the selection of filter construction materials and
plumbing of p u m p inlets. Thus, it is necessary to work closely
with fluid and c o m p o n e n t suppliers w h e n utilizing HFB
fluids.
HFC
HFC Fluids are solutions of water, glycols, additives, and
thickening agents. They are commonly referred to as waterglycol hydraulic fluids. Typically, water-glycol fluids are formulated with diethylene glycol or propylene glycol and a
polyalkylene glycol based thickening agent [73]. The low
molecular weight glycol reduces the vapor pressure of tlje

fluid (relative to water) while high molecular weight


polyalkylene glycol acts as a thickening agent, much like a
viscosity index improver. This combination thickeners and
glycols enhance the lubricating properties of a water-glycol
and reduces the propensity of the fluid toward cavitation erosion. Nonetheless, operating temperatures for water-glycols
are limited to a maximum of 50C because of the effect of
temperature on vapor pressure [74].
Water glycol fluids are highly alkaline due to the presence
of amine based corrosion inhibitors. As a result, these fluids
can attack zinc, cadmium, magnesium, and non-anodized
aluminum, forming sticky or gummy residues. Consequently,
these metals should be avoided when selecting system components. Special precautions also are required in the selection of filter construction materials and plumbing of p u m p
inlets. Thus, it is necessary to work closely with fluid and
component suppliers when utilizing HFC fluids.
HFD
HFD Fluids are non-water containing fire resistant fluids.
The first edition of International Standard ISO 6743-4 classification (1982) divided HFD into four sub-categories:
HFDR, HFDS, HFDT, and HFDU. In 1999 the standard was
revised, deleting the HFDS and HFDT fluids from the classification system. HFDS and HFDT fluids are no longer
commercially viable because they were based upon chlorinated materials such as polychlorinated biphenyls (PCBs)
or other chlorinated aromatic compounds. Environmental
concerns associated with chlorinated hydrocarbons led
to withdrawal of these products from the market. On the
other hand, HFDR and HFDU fluids continue to be widely
used in a variety of commercial and military hydraulic applications.
HFDR fluids are composed of phosphate esters. The majority of phosphate ester type hydraulic fluids used in industrial applications are based upon triaryl phosphate [75].
Trialkyl and mixed alkylaryl phosphate esters are used in
aviation because of their lower density [76]. Phosphate esters are difficult to ignite because they are non-volatile and
chemically stable. The stability of p h o s p h a t e esters is
demonstrated by the fact that they do not propagate a flame
in the Standard Test Method for Linear Flame Propagation
Rate of Lubricating Oils and Hydraulic Fluids (ASTM D
5306-92). The principal reason they do not propagate a
flame is that the chemical reactions that take place during

CHAPTER
combustion of phosphate esters are endothermic. Thus,
phosphate esters generate less heat when burned relative to
other HFD fluids. In addition, because their Are resistance
is not dependent upon the presence of water or mist suppressing additives, the fire resistance of HFDR fluids does
not degrade in service.
HFDR fluids have been used in hydraulic applications for
more than forty years and are known for excellent inherent
lubricating properties [77]. In fact, aryl phosphate esters
serve as antiwear additives in mineral oil based hydraulic fluids [78]. However, phosphate esters have a steep viscosity
temperature curve, which makes their temperature operating
window rather narrow [79]. Hydrolysis is the most c o m m o n
form of degradation in HFDR fluid, and can occur in the
presence of a small amount of water and heat. When hydrolysis takes place, phosphate esters break down into their constituent acids and alcohols. Due to the frequent presence of
water in hydraulic applications, the sensitivity of phosphate
esters to water has limited their use and significantly reduced
their service life.
Phosphate esters are compatible with all common metals
except aluminum. Phosphate esters do not "wet" the surface
of aluminum and thus aluminum should not be used in tribological contacts such as bearings [80]. Phosphate esters
should never be added to systems containing mineral oil or
water-based fire resistant fluids. Not only are these materials
chemically incompatible with each other, in all probability
preexisting gaskets, seals, hoses, and coatings are also incompatible. Special precautions also are required in the selection of filter construction materials and plumbing of
p u m p inlets. Thus, it is necessary to work closely with fluid
and component suppliers when utilizing HFD fluids.
HFDU fluids typically are composed of polyol esters although other materials such as polyalkylene glycols are included in the HFDU category. Trimethylol propane oleate,
neopentyl glycol oleate, and pentaerythritol esters are the
most c o m m o n of the synthetic polyol esters. Triglycerides
derived from soybeans, sunflower, and rapeseed plants are
naturally occurring polyol esters that also are used in HFDU
fluids. Polyol esters derive their fire resistance from a combination of factors. First, polyol esters have a relatively high
flash, fire, and autoignition point. Second, they b u m with
less energy than oil because of the presence of oxygen in the
molecule. And finally, polyol ester fire resistant fluids employ antimist additives that enhance their spray-flammability resistance [81]. Depending upon the shear stability of the
polymer, the fire resistance of the fluid may deteriorate in
service.
Like phosphate esters, polyol esters have excellent lubricating properties but are prone to hydrolysis in the presence
of water [82]. In addition, they are vulnerable to oxidation because of unsaturation irl the fatty acid portion of the ester.
These factors tend to limit their service life relative to mineral
oils. Most common metals used in hydraulic applications are
compatible with polyol ester hydraulic fluids, with the exception of lead, zinc, and cadmium. Unlike other fire resistant
fluids, polyol esters performance is satisfactory with comm o n filter construction materials and system designs. Thus it
is relatively easy to convert a hydraulic system that operates
on mineral oil based hydraulic fluids to HFDU fluids.

13: HYDRAULIC

FLUIDS

377

Environmentally Acceptable Hydraulic Fluids


Environmentally acceptable hydraulic fluids have found
their way into hydraulic applications where there is risk of
fluid leaks and spills entering the environment (especially
waterways) affecting aquatic and terrestrial life. Some examples of these niche markets include forestry, construction,
locks a n d d a m s , heavy-duty lawn equipment, a m u s e m e n t
parks/entertainment industry, offshore drilling, and maritime. Most environmentally acceptable hydraulic fluids
exhibit two key environmental characteristics: virtual nontoxicity to aquatic life a n d aerobic biodegradability. Organizations such as the Organization for Economic Co-operation
and Development (OECD), the Co-ordinating E u r o p e a n
Council (CEC), and the U.S. Environmental Protection
Agency (EPA) have developed standard test methods to determine the toxicity a n d biodegradability of substances.
More recently ASTM has developed a Guide for Assessing
Biodegradability of Hydraulic Fluids (ASTM D 6006) and a
Classification of Hydraulic Fluids for Environmental Impact
(ASTM D 6046) based on the above organizations' methods.
Utilizing the methodology from these organizations, standard classifications and performance requirements for environmental fluids have also been established by the International Organization for Standardization (ISO) and regional
environmental organizations t h a t a w a r d Eco Labels (i.e.,
German Blue Angel, Nordic Swan, Japanese EcoMark). ISO
environmental hydraulic fluid classifications are described in
Table 14.
HETG
Type HETG fluids are based on naturally occurring vegetable
oils or triglyceride esters. Without the addition of a thickener, vegetable oils are limited to a narrow viscosity range between ISO 32 and 46. While HETG fluids biodegrade rapidly,
have excellent natureil lubricity and have a natural VI in excess of 200, they are unsuitable for use at high and low temperature extremes. This is because they tend to gel at low
temperatures and oxidize at high temperatures. The practical
temperature limits for uses HETG fluids is 25F to 165F.
HEES
Type H E E S fluids are based on unsaturated to fully saturated
synthetic esters. Common ester chemistries utilized for hydraulic fluids consist of TMP oleates, neopentylglycols, pentaerythritol esters, adipate esters, and complex esters. The
synthetic esters provide better performance over HETG t5T3e
hydraulic fluids with wider operating temperature ranges,
broad range of ISO viscosity grades, and better oxidation stability while still maintaining biodegradability.

TABLE 14ISO environmental hydraulic fluid classifications.


Symbol

Classification

Commercial Designation

HETG
HEES

Vegetable oil types


Sjmthetic ester types

HEPG
HEPR

Polyglycol types
Polyalphaolefln types

Vegetable oils and natural esters


Polyol esters, neopentylglycols,
syntiietic adipate esters
Polyglycols
Polyalphaolefins (PAO) or
synthetic hydrocarbons (SHC)

378 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


HEPG
Type HEPG fluids are polyethyleneglycols (PEG), which possess good oxidation stability and low temperature flow characteristics. At molecular weights of up to 600-800, HEPG
type fluids are ecotoxicologically harmless and readily
biodegradable (>90% in 21 days) [83]. Some disadvantages
of this class of fluids include miscibility with water, incompatibility with mineral oils, and aggressiveness toward some
common t5^es of elastomer seal materials.
HEPR
HEPR type fluids are polyalphaolefins (PAO) or synthesized
hydrocarbon (SHC) base fluids, which have significantly better viscometric properties over a wider range of temperatures
than mineral base fluids with the same standard viscosity
classification. Some low viscosity PAOs have shown acceptable primary biodegradability, though not as rapid as vegetable or synthetic ester base fluids (Fig. 22). Additional advantages claimed for synthetic lubricants over comparable
petroleum-based fluids include improved thermal and oxidative stability, superior volatility characteristics, and preferred
frictional properties.

Another challenge that comes with the various hydraulic


applications is that of developing test methods that are truly
representative of performance in actual systems. Bench-top
tests are to be used as logical indicators of a fluid's response
to expected conditions of temperature, pressure, contamination, etc. A significantly higher number of variables concurrently influence the fluid more than any single bench test can
simulate. Therefore, standards and specifications consist of
multiple bench tests as well as more realistic full-scale test
stands that use actual pumps in typical hydraulic circuits.
Test methods will continue to evolve as more sophisticated
techniques are developed to predict field performance of hydraulic fluids.

ASTM STANDARDS
No.
D 92
D 95
D 96
D 97
D 130

CONCLUSIONS
A well formulated hydraulic oil consists of a properly selected
base fluid and the appropriate balance of additives, optimized to provide the best possible overall performance required for the targeted application. The versatility of hydraulics makes fluid power advantageous in a wide variety of
industrial and mobile applications. With this versatility
comes the challenge of developing fluids that function appropriately in a wide range of conditions, even as environmental health and safety requirements become more and
more stringent. New fluid technologies continue to emerge to
meet these challenges.

D 287
D 445
D 446
D 471
D 664

Title
Test Method for Flash and Fire Points by Cleveland
Open Cup
Test Method for Water in Petroleum Products and
Bituminous Materials by Distillation
Test Method for Water and Sediment in Crude Oil
by Centrifuge Method
Test Method for Pour Point of Petroleum Products
Test Method for Determination of Copper Corrosion from Petroleum Products by the Copper Strip
Tarnish Test
Test Method for API Gravity of Crude Petroleum
and Petroleum Products (Hydrometer Method)
Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (the Calculation of Dynamic Viscosity)
Specifications and Operating Instructions for Glass
Capillary Kinematic Viscometers
Test Method for Rubber Property-Effect of Liquids
Test Method for Acid Number of Petroleum Products by Potentiometric Titration

Polypropylene glycols

I Mininnum
Maximum

Mineral oils

Hydro-treated
mineral oils
Polyethylene glycols
1 Vegetable oils

Synthetic esters
20

40

60

80

100%

FIG. 22Chart comparing primary biodegradation of base fluids by CEC


method.

CHAPTER
D 665
D 892
D 943
D 974
D 1298

D 1401
D 1744
D 2070
D 2270
D 2271
D 2272
D 2422
D 2619
D 2717
D 2766
D 2783
D 2882

D 2983

D 3339
D 3427
D 3519
D 3603

D 3707
D 3709

D 4172
D 4310
D 4684

D 5133

D 5182

Test Method of Rust-Preventing Characteristics of


Inhibited Mineral Oil in the Presence of Water
Test Method for Foaming Characteristics of Lubricating Oils
Test Method for Oxidation Characteristics of Inhibited Mineral Oils
Test Method for Acid and Base Number by ColorIndicator Titration
Test Method for Density, Relative Density (Specific
Gravity), or API Gravity of Crude Petroleum Products by Hydrometer Method
Test Method for Water Separability of Petroleum
Oils and Synthetic Fluids
Test Method for Determination of Water in Liquid
Petroleum Products by Karl Fischer Reagent
Test Method for Thermal Stability of Hydraulic Oils
Practice for Calculating Viscosity Index from Kinematic Viscosity at 40C and 100C
Test Method for Preliminary Examination of Hydraulic Fluids (Wear Test)
Test Method for Oxidation Stability of Steam Turbine Oils by Rotating B o m b
Classification of Industrial Fluid Lubricants by Viscosity System
Test Method for Hydrolytic Stability of Hydraulic
Fluids (Beverage Bottle Method)
Test Method for Thermal Conductivity of Liquids
Test Method for Specific Heat of Liquids and Solids
Test Method for Measurement of Extreme-Pressure
Properties of Lubricating Fluids (Four-Ball Method)
Test Method for Indicating the Wear Characteristics of Petroleum a n d Non-Petroleum Hydraulic
Fluids in a Constant Volume Vane Pump
Test Method for Low-Temperature Viscosity of Automotive Fluid Lubricants Measured by Brookfield
Viscometer
Test Method for Acid N u m b e r of Petroleum Products by Semi-Micro Color Indicator Titration
Test Method for Air Release Properties of Petroleum
Oils
Test Method for Foam in Aqueous Media (Blender
Test)
Test Method for Rust-Preventing Characteristics of
Steam Turbine Oils in the Presence of Water (Horizontal Disk Method)
Test Method for Storage StabiHty of Water-in-Oil
Emulsions by the Oven Test Method
Test Method for Stability of Water-in-Oil Emulsions
Under Low to Ambient Temperature Cycling Conditions
Test Method for Wear Preventive Characteristics of
Lubricating Fluid (Four-Ball Method)
Test method for Determination of the Sludging and
Corrosion Tendencies of Inhibited Mineral Oils
Test Method for Determination of Yield Stress and
Apparent Viscosity of Engine Oils at Low Temperatures
Test Method for Low temperature. Low Shear Rate,
Viscosity/Temperature Dependence of Lubricating
Oils Using a Temperature Scanning Technique
Test Method for Evaluating the Scuffing Load Ca-

D 5306
D 5534
D 5621
D 6006
D 6046
D 6080
D 6158
D 6278

D 6351
D 6546

D 6547

13: HYDRAULIC

FLUIDS

379

pacity of Oils (FZG Visual Method)


Standard Test Method for Linear Flame Propagation Rate of Lubricating Oils and Hydraulic Fluids
Test Method for Vapor-Phase Rust-Preventing
Characterisitics of Hydraulic Fluids
Test method for Sonic Shear Stability of Hydraulic
Fluid
Guide for Assessing Biodegradability of Hydraulic
Fluids
Classification of Hydraulic Fluids for Environmental Impact
Practice for Defining the Viscosity Characteristics
of Hydraulic Fluids
Specification for Mineral Hydraulic Oils
Test Methods for Shear Stability of Polymer Containing Fluids Using a European Diesel Injector Apparatus
Test Method for Determination of Low Temperature Fluidity and Appearance of Hydraulic Fluids
Test Methods for and Suggested Limits for Determining Compatibility of Elastomer Seals for Industrial Hydraulic Fluid Applications
Test Method for Corrosiveness of a Lubricating
Fluid to a Bi-Metallic Couple

OTHER STANDARDS
AFNOR NF E48-690: Hydraulic Fluid Power. Fluids. Measurement of Filtrability of Mineral Oils
AFNOR NF E48-691: Hydraulic Fluid Power. Fluids. Measurement of Filtrability of Minerals Oils in the Presence of
Water
ANSI/(NFPA) S t a n d a r d T2.13.7R1-1996: Hydraulic Fluid
Power - Petroleum Fluids - Prediction of Bulk Moduli
ISO 6743/4 Part 4: Family H (Hydraulic Systems), Lubricants, Industrial Oils and Related Products (Class L ) : Classification Part 4: Family H (Hydraulic Systems)
ISO 12922: Lubricants, Industrial Oils, and Related Products
(Class L)Family H (Hydraulic systems)Specifications
for categories HFAE, HFAS, HFB, HFC, HFDR and HFDU
ISO/DIS 15380: Lubricants, Industrial Fluids and Related
Procedures (Class L), Family H (Hydraulic Systems)-Specifications for Catagories HETG, HEPG, HEES and HEPR

REFERENCES
[1] Halliday, D. and Resnick, R. Physics, 3rd ed., John Wiley &
Sons, NY, 1978, p. 376.
[2] Henke, R., Diesel Progress, Fluid Power Buyer's Guide, Diesel
and Gas Turbine Publications, Waukesha, WI, 1994, p. 4.
[3] Vickers Industrial Hydraulics Manual, Ch. 3, Vickers, Inc.,
Rochester Hills, MI, 1992, p. 3-1.
[4] Booser, E. R., Handbook of Lubrication, Volume II Theory and
Design, CRC Press, Boca Raton, FL, 1987, pp. 242-244.
[5] NFPA Standard T2.13.7R1 - 1997: Hydraulic Fluid Power Petroleum Fluids - Prediction of Bulk Moduli, National Fluid
Power Association, Milwaukee, WI, 1997.
[6] Lightening Reference Handbook, 7th ed., Paul-Munroe Hydraulics, Whittier, CA, 1990, p.l22.
[7] Totten, G. E., Webster, G. M., and Yeaple, F. D., "Physical Prop-

380 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


erties and Their Determination," Handbook of Hydraulic Fluid
Technology, G. E. Totten, Ed., 2000, Marcel Dekker, NY, p. 253.
[8] Esposito, A., Fluid Power with Applications, Prentice Hall, Englewood Cliffs, NJ, 1988, p. 478.
[9] Michael, P. W. and Wanke, T. S, "Surgically Clean Hydraulic
Fluid - A Case Study," Proceedings of the 47th National Conference on Fluid Power, National Fluid Power Association, Milwaukee, WI, 1996, pp. 129-136.
[10] Esposito, A., Fluid Power with Applications, Prentice Hall, Englewood Cliffs, NJ, 1988, p.3.
[11] Ruble, L. R., "The Expanded Focus, Use, and Future of Water
Powered Rotary Actuators," Proceedings of the 48th National
Conference on Fluid Power, National Fluid Power Association,
Milwaukee, WI, 2000, pp. 567-574.
[12] Perrier, R., "Lubricant Basestocks," Speech, STLE Chicago
Lube School, Downers Grove, IL, 17 Mar. 1999.
[13] Engine Oil Licensing and Certification System, 14th ed.. Publication 1509, American Petroleum Institute, Washington DC,
1996.
[14] Wills, J. G., Lubrication Fundamentals, Mobil Oil Corporation,
Fairfax, VA, 1980, p. 30.
[15] Denisov, E., Handbook of Antioxidants, CRC Press, Boca Raton,
FL, 1995, p. 19.
[16] Lubricant and Fuel Additives, Advanced Lubrication Education
Program, Report 1525, May 1992.
[17] Rasberger, M., "Chemistry and Technology of Lubricants," Oxidative Degradation and Stabilisation (Sic) of Lubricants,
Blackie and Academic Professional, London, 1992, pp. 83-123.
[18] Igarashi, J., "Oxidative Degradation of Engine Oils," Japanese
Journal of Tribology, Vol. 35, No. 10, 1990. p. 1098.
[19] Saxena, D., Mookken, R. T., Srivastava, S. P., and Bhatnagar A.
K., "An Accelerated Aging Test for AW Oils," Lubrication Engineering, Vol. 49, No. 10, 1993, pp. 801-809.
[20] Approved Lubricants Manual, Cincinnati Machine P u b No.
lO-SP-95046, Cincinnati Machine, Cincinnati, OH, 1995,
pp. 2-40.
[21] Reyes-Gavilan, J. L. and Odorisio, P., "A Review of the Mechanisms of Action of Antioxidants, Metal Deactivators and Corrosion Inhibitors," NLGI Spokesman, Vol. 64, No. 11, Feb. 2001,
pp. 22-33.
[22] Gatto, V. J. and Grina, M. A., "Effects of Base Oil Type, Oxidation
Test Conditions and Phenolic Structure on the Detection and
Magnitude of Hindered Phenol/Diphenylamine Synergism," Lubrication Engineering, Vol. 55, No. 1, Jan. 99, pp. 11-20.
[23] Pike, R. and Conway-Jones, J. M., "Friction and Wear of Sliding
Bearings," ASM Handbook, Volume 18, Friction, Lubrication,
and Wear Technology, 1992, ASM International, Materials Park,
OH, p. 519.
[24] Blau, P. J., "Glossary pf Terms," ASM Handbook, Friction, Lubrication, and Wear Technology, Volume 18, 1992, ASM International, Materials Park, OH, p. 11.
[25] Michael, P. W., Herzog, S. N., and Marougy, T. E., "Fluid Viscosity Selection Criteria for Hydraulic Pumps and Motors" Proceedings of the 48th National Conference on Fluid Power,
Chicago, National Fluid Power Association, Milwaukee, WI,
2000, pp. 313-325.
[26] ISO 3448: Industrial Liquid Lubricants-ISO Viscosity Classification, International Organization for Standardization, Geneva,
1992.
[27] Michael, P.W., "Lubrication Basics," Plant Services, Vol. 14, No.
5, May 1993, pp. 19-22.
[28] Silva, G., "Wear Generation in Hydraulic Pumps," presented at
the SAE International Off Highway Congress, Milwaukee, WI,
1990, Paper 901679, Society for Automotive Engineers, Warrendale, PA.
[29] Voitik, R. M., "Realizing Bench Test Solutions to Field Tribology Problems Utilizing Tribological Aspect Numbers," Tribol-

ogy - Wear Test Selection for Design and Application, ASTM


STP 1199, A. W. Ruff and R. G. Bayers, Eds., ASTM International, West Conshohocken, PA, 1993, pp. 45-59.
[30] Hogmak, S. and Jacobson, S., "Hints and Guidelines for Tribotesting and Evaluation," Lubrication Engineering, Vol. 48,
No. 5, May 1992 p. 401.
[31] ASTM Round Robin Test Program RR: D02-1152, ASTM International, West Conshohocken, PA, 1994.
[32] Xie, L., Bishop, Jr., R. J., and Totten, G. E., "Bench and P u m p
Testing of Hydraulic Fluids," H a n d b o o k of Hydraulic Fluid
Technology, G. E. Totten, Ed., Marcel Dekker, NY, 2000, p. 526.
[33] Perez, J. M., Klaus, E. E., and Hansen, R. C , "Comparative Evaluation of Several Hydraulic Fluids in Operational Equipment, A
Full-scale Pump Stand Test and the Four-Ball Wear Tester. Part
II - Phosphate Esters, Glycols and Mineral Oils," Lubrication
Engineering, Vol. 46, No. 4, April 1990, p. 249.
[34] Perez, J. M., Weller, D. E., and Duda, J. L., "Sequential Four-Ball
Study of Some Lubricating Oils," Lubrication Engineering, Vol.
55, No. 9, 1994, pp. 28-32.
[35] Reichel, J., "Importance of Mechanical Testing of Hydraulic
Fluids," Tribology of HydrauUc P u m p Testing, ASTM STP 1310,
George E. Totten, Gary H. Kling, and Donald J. Smolenski, Eds.,
ASTM International, West Conshohocken, PA, 1996.
[36] Xie, L., Bishop, Jr., R. J., and Totten, G. E., "Bench and P u m p
Testing of Hydraulic Fluids," H a n d b o o k of Hydraulic Fluid
Technology, G. E. Totten, Ed., Marcel Dekker, NY, 2000, p. 526.
[37] Denison Test E q u i p e m e n t and Instructions, Consigne TP30283, Denison Hydraulics, Marysville, OH, 1999.
[38] Kling, G. H., Totten, G. E., and Ashraf, A., "Strategies for Developing Performance Standards for Alternative Hydraulic Fluids,"
in Lubricants for Off-Highway Applications, SAE SP-1553, Society for Automotive Engineers, Warrendale, PA, 2000, pp. 1-9.
[39] Ohkawa, S., Konishi, A., Hatano, H., Ishihama, K., Tanaka, K.,
and Iwamura, M. "Oxidation and Corrosion Characteristics of
Vegetable-Base Biodegradable Hydraulic Oil," SAE Technical
Paper Series, Paper N u m b e r 951038, Society for Automotive
Engineers, Warrendale, PA, 1995.
[40] Melief, H. M., Totten, G. E., and Bishop, R. J., "Overview of the
Proposed Rexroth High-Pressure Piston P u m p Testing Procedure for Hydraulic Fluid Qualification," Fluid Power for OffHighway Applications, SAE SP-1380, Society for Automotive
Engineers, Warrendale, PA, 1998.
[41] "Sundstrand Water Stability Test Procedure," Sundstrand Bulletin No. 9658, Sauer-Danfoss Corp., Ames, lA.
[42] Hodges, P. K.B., Hydraulic Fluids, John Wiley, NY, 1996, p. 116.
[43] Karl Fischer Applications, Mettler-Toledo AG., CH-8606
Griefensee, Switzerland, 1992.
[44] Lloyd, B. J., "Water Water Everywhere," Lubes-N-Greases,
Vol.11, No. 3, 1997, pp. 44-53.
[45] Tsong-Dsu, L. and. Mansfield, J., "Effect of Contamination on
the Water Separability of Steam Turbine Oils," Lubrication Engineering, Vol. 51, No. 1, 1995, pp. 81-85.
[46] Barber, A. R. and Perez, R. J., Air Release Properties of Hydraulic Fluids, The Lubrizol Corporation, Wickliffe, OH.
[47] Totten, G. E., Sun, Y. H., Bishop, R. J., and Lin, X., "Hydraulic
System Cavitation: A Review," SAE 982036, Society for Automotive Engineers, Warrendale, PA, 1998.
[48] Brew, D., Khonsari, M., and Ball, J. H.,"Current Research in
Cavitating Fluid Films," STLE Special Publication SP-28, Society of Tribologists and Lubrication Engineers, Park Ridge, IL,
1990, pp. 63-65.
[49] "Foaming and Air Entrainment in Lubrication and Hydraulic
Systems," Mobil Technical Bulletin, Mobil Oil, Fairfax, VA,
1989.
[50] HVLP HydrauUc Oils, Minimum Requirements, DIN 51524 Part
II, Deutsche Norm, Beuth Verlag GmbH, BerUn, 1990.
[51] Denison Fluid Standard HF-0: Hydraulic Fluid-For Use in Axial

CHAPTER 13: HYDRAULIC FLUIDS 381

[52]
[53]
[54]

[55]

[56]
[57]

[58]
[59]

[60]

[61]

[62]

[63]
[64]

[65]

[66]

Piston Pumps and Vane Pumps in Severe Duty Applications,


Denison Hydraulics, Marysville, OH, 1995.
Claxon, P. D., "Aeration of Petroleum Based Steam Turbine
Oils," Tribology, Februaiy 1972, pp. 8-13.
Hatton, D. R., "Some Practical Aspects of Turbine Lubrication,"
The Canadian Lubrication Journal, Vol. 4, No. 1, 1984, p. 4.
Rhee, I., Velz, C , and Von Bemewitz, K., Evaluation of Environmentally Acceptable Hydraulic Fluids, Technical Report No.
13640, U.S. Army Tank-Automotive Command, Research Development and Engineering Center, Warren, MI, March 1995.
Rizvi, S. Q. A., "Lubricant Additives and Their Functions," ASM
Handbook 10th ed., Vol. 18, Friction, Lubrication, and Wear
Technology, ASM International, Materials Park, OH, 1992, pp.
98-112.
Available from ASTM International Headquarters, 100 B a r r
Harbor Drive, PO Box C700, West Conshohocken, PA.
F a i n m a n , M. Z. and Hiltner, L. G., "Compatibility of Elastomeric Seals and Fluids in Hydraulic Systems," Lubrication
Engineering, Vol. 37, May 1980, pp. 132-137.
Ashby, D. M., "O-ring Specifications - Some Important Considerations," Hydraulics & Pneumatics, August 1999, pp. 53, 54, 90.
Leslie, R. L. Sculthorpe, H. J., "Hydraulic Fluids Compatible
with Metalworking Fluids," Lubrication Engineering, Vol. 28,
May 1970, pp. 165-167.
Carpsjo, C , Proceedings of International Symposium on Performance Testing of Hydraulic Fluids, Institute of Petroleum,
London, 3-6 Oct 1978.
Stambaugh, R. L. a n d K o p k o , R. J. "Behavior of Non-Newtonian
Lubricants in High Shear Rate Applications," SAE Transactions
82, Paper 730487, Society of Automotive Engineers, Warrendale, PA, 1973.
Stambaugh, R. L., Kopko, R. J., and Roland, T. F., "Hydraulic
P u m p Performance - A Basis for Fluid Viscosity Classification,"
SAE International Off Highway Congress, Milwaukee, WI, Paper
901633, Society of Automotive Engineers, Warrendale, PA, 1990.
Hydraulic Fluids Information, Denison Corp., Marysville, OH,
1995, p. 2.
Rizvi, S. Q. A., "Lubricant Additives and Their Functions," ASM
Handbook Volume 18 Friction, Lubrication, and Wear Technology, ASM International, Materials Park, OH, 1992, p. 106.
Sharma, S. K., Snyder Jr., C. E., Gschwender, L. J., Lang J. C ,
and Schreiber, B. F., "Stuck Servovalves in Aircraft Hydraulic
Systems," Lubrication Engineering, Vol. 55, No. 7, July 1999.
Michael, P. W. and Webb, S., "Future Fluids - What's Coming
Down the Hydraulic Line," OEM Off-Highway, January 1998,
pp. 34-36.

[67] Lubrizol Ready Reference for Lubricant and Fuel Performance,


The Lubrizol Corporation, Wickliffe, OH, 1998, p. 111.
[68] Colver, R., Chek-Chart Publications, Simon & Schuster, NY,
1995, p. 45.
[69] ISO 6743-4: Lubricants, Industrial Oils and Related
Products (Class L) - Classification - Part 4: Family H (hydraulic
systems). International Organization for Standardization,
Geneva, 1999.
[70] NFPA/T2.13.1: R3-1997, R e c o m m e n d e d Practice - Hydraulic
Fluid Power - Use of Fire Resistant Fluids In Industrial Systems,
NFPA, Milwaukee, WI, 1997.
[71] ISO 7745: Hydraulic Fluid Power - Fire Resistant (FR) Fluids Guidelines for Use, International Organization for Standardization, Geneva, 1999.
[72] Vickers Guide to Alternative Fluids, Eaton Corp., Southfield,
MI, November 1992.
[73] Totten, G. E. and Sun, Y., "Water-Glycol Hydraulic Fluids,"
Handbook of Hydraulic Fluid Technology, G. E. Totten, Ed.,
Marcel Dekker, NY, 2000, pp. 917-982.
[74] NFPA/T2.13.1: R3-1997, Recommended Practice - Hydraulic
Fluid Power - Use of Fire Resistant Fluids in Industrial Systems,
NFPA, Milwaukee, WI, 1997.
[75] Phillips, W. D., "Phosphate Ester Hydraulic Fluids," in Handbook of Hydraulic Fluid Technology G. E. Totten, Ed., Marcel
Dekker, NY, 2000, pp. 1025-1027.
[76] Parker O-Ring H a n d b o o k Y2000 Edition, Parker Hannifin
Corp., Cleveland, OH, 1999, pp. 3-18.
[77] O'Connor, J. and Boyd, J., Standard Handbook of Lubrication
Engineering, McGraw-Hill, NY, 1968, pp. 2-16.
[78] MIL-H-5606G Military Specification: Hydraulic Fluid,
Petroleum Base, Aircraft, Missile and Ordinance, NATO code
n u m b e r H-515, U.S. Department of Defense, Fort Belvoir, VA,
1994.
[79] Parker O-Ring H a n d b o o k Y2000 Edition, Parker Hannifin
Corp., Cleveland, OH, 1999, pp. 3-18.
[80] Phillips, W. D., "Phosphate Ester Hydraulic Fluids," Handbook
of Hydraulic Fluid Technology, G. E. Totten, Ed., Marcel
Dekker, NY, 2000, pp. 1025-1027.
[81] Gere, R. A. and Hazelton, R. A., "Polyol Ester Fluids," Handbook
of Hydraulic Fluid Technology, G. E. Totten, Ed., Marcel
Dekker, NY, 2000, pp. 983-1022.
[82] Hohn, B. R., Michaelis, K., and Dobereiner, R., "Load Cjirrying
Capacity of Fast Biodegradable Gear Lubricants," Lubrication
Engineering, 1999, Vol. 55, p. 37.
[83] Bartz, W. J., Environmentally Acceptable Hydraulic Fluids,
Technische Akademie Esslingen, Ostfildern, Germany.

MNL37-EB/Jun. 2003

Compressor Lubricants
Desh Garg, ^ George E. Totten, ^
and Glenn M. Webster^

Charle's Law states that at a constant pressure, the volume


of a gas increases in proportion to the temperature:

COMPRESSORS ARE VITALLY IMPORTANT IN MANY INDUSTRIAL TECH-

NOLOGIES. For example, compressors are used in nearly every


industry including steel, automotive, petroleum, mining,
food, gas production, and storage and energy conversion [1].
The purpose of the compressor lubricant is to reduce friction
and wear of the working parts of a compressor such as bearings, gears, and pistons; reduce internal leakage; and if the oil
is compressed in the compression zone, to provide heat
transfer to reduce the temperature of the gas being compressed [2]. In addition, a properly formulated compressor
lubricant should provide corrosion protection and be sufficiently stable to minimize the potential for deposit formation
on hot surfaces within the system [3].
The following topics will be discussed in this chapter: a basic tutorial on gas compression, the classification, operation
and lubrication of typical gas compressors, lubricant types
and classifications, solubility of common gases, and a review
of recommended compressor lubricant testing. The chapter
will not discuss refrigeration compressors applications. See
Chapter 15.

II
V2

T2

In addition, if the temperature of a gas increases as the pressure increases when the volume is held constant then Amonton's Law states that:
Pi_
P2

T2

For these calculations, all temperatures are in reference to


absolute zero. Therefore, if temperature in degrees Fahrenheit (F) is used, absolute temperature in degrees Rankine
(R) is calculated from:
"Rankine = F 4- 460
Similarly, if the temperature is in degrees Celsius (C), the absolute temperature in degrees Kelvin is calculated from:
"Kelvin = "C + 273

DISCUSSION

Charle's Law and Boyle's Law are combined to form the wellknown Ideal Gas Law which states:

Gas Laws

PxV,
P2V2
Ty
T2
Avogadro's Law states that the equal volumes of gases at the
same temperature and pressure contain the same number of
molecules:

The objective of this section is to provide a basic background


of the behavior of gases with respect to pressure, temperature, and volume. For example, Boyle's Law states that at a
constant temperature, the product of a pressure and volume
of a gas is constant:

PV = nRT

PiFi = P2V2
When performing these calculations, the reference value used
to determine the pressure must be indicated. If the reference
value is a vacuum, then the pressure is absolute {Pa) However,
if the reference level is atmospheric pressure {Patm), then it is
called gauge {Pg) pressure. They are related by:

Where n is the number of moles, R is the so-called gas constant that is selected to be consistent with the units of temperature, pressure, and volume used in the calculation (see
Table 1).
Dalton's Law states that the total pressure (Py) of a mixture
is the sum of the partial pressures of the constituent gases
(a,b,c,
) in the mixture:
PT = Pa + Pb + Pc+

Absolute pressures must be used for the gas law relationships


to be discussed here.

Similarly, the total volume of a gas is equal to the sum of the


partial volumes of the constituent gases (Amagat's Law):
VT=Va + Vb+V,+
If the temperature of a gas decreases or if the pressure increases sufficiently, the gas will undergo a change of state to
a liquid. Further decreases in temperature or increases in
pressure will convert the liquid into a solid. If the tempera-

' Desh Garg Consulting, 14 Carlson Terrace, Flshkill, NY 12524.


^G.E. Totten & Associates, LLC, P.O. Box 30108, Seattle, WA
98103.
3 63 Rockledge Rd., Hartsdale, NY 10530.

383
Copyright'

2003 by A S I M International

www.astm.org

384 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


ture is increased indefinitely, a point will be reached where
the gas can no longer be liquified by increasing pressure. The
highest temperature at which a gas can be liquified by increasing pressure is called the critical temperature of the gas.
The pressure required to liquefy a gas at the critical temperature is called the critical pressure of the gas. A summary of
physical constants for selected gases is provided in Table 2.
When pressure, temperature, and volume variation of a gas
follows the ideal gas law, it is referred to as an ideal gas. However, as the pressure increases, the behavior of a gas deviates
from that predicted by the ideal gas law. This is due to the
compressibility of the gas and is accounted for in the ideal
gas calculation by using the compressibility factor (Z);
PiV,
TiZ,

PV curve as shown in Fig. 2 [4]. For isothermal compression,


temperature is held constant during compression by removal
of the heat of compression, and the work performed corresponds to:
PrVr = P2V2

Adiahatic (isoentropic) compression occurs when there is no


heat added or removed during compression:
PiVf

Where k is the ratio of specific heats.


Comparison of the work required for an isothermal process
(ADEF) and an adiahatic process (ABEF) shows that less
work is required for an isothermal process. However, an
isothermal process is impossible to achieve, although compressors are designed for as much heat removal as possible.
Similarly, adiahatic compression is also impossible since

P2V2
T2Z2

Values for the compressibility factor are obtained from reference charts called general compressibility charts such as
those available in Ref. 4.

The Gas Compression Cycle


PV Curves
The product of pressure (P) X volume (V) is work. Work is
equal to force X distance where pressure corresponds to
force and volume corresponds to distance. The horizontal
line shown in the PV curve of Fig. 1 corresponds to the distance, for example, the distance a piston moves and the vertical line corresponds to force on the cylinder of a piston, for
example. The area under the curve is P X y and is equal to the
work performed during the cycle.

Pd

I'".'" .--' - V'. -'13

-J,-;

IJJ
Isothermal versus Adiahatic Operation
Theoretically, there are two ways that a positive displacement compressor can be operated; either isothermally or adiabatically. These modes of operation are illustrated using a

WORK

-h ;:v.

'"^"/t-i-'i-r'

Ps

TABLE 1Ideal gas law


constants (R).
8.3143
8.3143
1.9872
82.054

P2V'2

VOLUME INCREASES

X l O V gs/deg mole
joules/d eg mole
cal/deg mole
cc atm/deg mole

FIG. 1Illustration of a PV diagram that d o e s not include


clearance volume.

TABLE 2 --Physical constants of natural gas components.

Gas
Methane
Ethane
Propane
i-Butane
n-Butane
i-Pentane
n-Pentane
Hexane
Carbon Dioxide
Hydrogen Sulfide
Nitrogen
Oxygen

Chemical
Formula
CH4
C2H6
CjHg
C4H10
C4H10
C5H12
C5H12

CeHn
CO2
H2S
N2
O2

Critical
Temperature
(R)
344
550
666
735
766
830
846
915
548
673
227
278

Critical
Pressure
(psia)
673
708
617
529
531
483
489
440
1073
1306
492
732

Molecular
Weight
(g/mole)
16
30
44
58
58
72
72
86
44
34
28
32

Density @
60F, 14.7 psia
Specific
Gravity
Air= 1.0
Lbs/ft^
0.554
1.038
1.523
2.007
2.007
2.491
2.491
2.975
1.519
1.176
0.967
1.105

0.0424
0.0799
0.1180
0.1578
0.1581
0.190
0.190
0.227
0.1166
0.0897
0.0738
0.0843

Specific Heat @
60F, 14.7 psia
Cp
Cv
BTU/lb/F
BTU/lb/F
0.527
0.410
0.388
0.387
0.387
0.383
0.388
0.386
0.199
0.238
0.248
0.219

0.403
0.344
0.343
0.353
0.353
0.355
0.361
0.363
0.154
0.180
0.177
0.157

Cp/Cv
1.308
1.192
1.131
1.097
1.097
1.078
1.076
1.063
1.293
1.325
1.400
1.346

CHAPTER 14: COMPRESSOR


^E

AB - ADIABATIC
AC - POLYTROPIC
AD - ISOTHERMAL
.
\

[4]:

THEORETICAL
NO CLEARANCE

Tjv = 100 - CiR^'") - 1)

0}
W
Ul
DC

where R is the compression ratio which is defined as the absolute discharge pressure divided by the absolute inlet pressure of a compressor and C is the cylinder clearance (%). This
is a theoretical value and equation must be modified to account for inefficiencies such as internal leakage, gas friction,
pressure drops through valves, etc. This is done by introducing the factor "L."

Q.

..A

VOLUME

FIG. 2PV diagram illustrating theoretical compression cycles.

some heat is always added or emitted. Actual compression is


referred to a polytropic cycle:
Where n is experimentally determined for each type of compressor and usually not equal to k. Thermodynamically,
isothermal and adiabatic processes are reversible but polytropic processes are irreversible, steady-state processes.
The value of n may also be calculated from:
(n-l)/n

Ti

385

Leeikage past valves and piston rings,


Slight increase of gas volume due to heat rise from the
warm cylinder.
Theoretical volumetric efficiency (TJV) is calculated from

D CB

UJ

LUBRICANTS

7)^ = 100 - C(i?^* - 1) - L


The value of L is variable depending on the compressor, lubricant and the gas. For a moderate pressure air compressor
with a petroleum oil lubricant, the value of L may be approximately 5%.
Power Requirement
To properly size a compressor and its components, it is necessciry to determine the amount of power required to drive
the system. To do this, it is necessary to determine the
amount of brake horsepower required to compress a given
volume of gas from the incoming inlet pressure to the desired
discharge pressure [5]. Brake horsepower is defined as the
ideal isoentropic (theoretical) horsepower plus any fluid
(valve, fluid flow, and other leakage) or mechanical friction
losses [5]. Theoretical horsepower may be calculated from:

Pi

Gas Compression Cycle


Consider the situation where a gas is compressed in a piston
cylinder from the inlet pressure, Ps, to the discharge pressure, Pd, along the lone 1-2 in Fig. 3a. Since it is impossible to
discharge all of the gas due to the volume of space not covered by the piston stroke, there will be a residual value referred to as clearance volume. This is typically the area between the cylinder and the head of the piston illustrated in
Fig. 3a. Typically, clearance volumes range from 4-20%.
Figure 3fo illustrates the completion of the compression
stroke along the path 2-3. When the piston reaches point 3,
the discharge valve closes and the piston undergoes the expansion stroke 3-4 (Fig. 3c) until the pressure drops below
the inlet pressure at point 4. At point 4, the inlet valve opens
and the gas fills the cylinder as shown in Fig. 3>d and the process is repeated.
Volumetric Efficiency
Piston displacement represented by the line 5-1 on the PV
curve shown in Fig, 4. The actual capacity is less than that
represented by the piston displacement, line 4-1. The ratio of
the actual capacity to the total displacement is referred to as
the volumetric efficiency. The volumetric efficiency is always
less than that that derived theoretically because:
The re-expansion of the gas trapped in the cylinder clearances,
Entrance losses due to the pressure drop at the inlet.

(B)

FIG. 3The compression cycle. A. Compression Strol<e, B.


Discharge Stroke, C. Expansion Strolce, and D. Suction Stroke.

386 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


Gas Compressors
Compressors are used in many industrial operations to compress a variety of gases, such as natural gas, ethylene, air, and
ammonia. There are several major compressor designs that
may be selected to suit a variety of application needs. The selection of a particular type of compressor depends on such application requirements as the gas being compressed, flow rates,
pressures involved, and downstream considerations. In this
section, the classification of compressor types will be discussed.
This will be followed by an overview of the most commonly encountered compressor types and their lubrication demands.
Compressor types can be classified into two basic categories as illustrated in Fig. 6 [7 ] reciprocating and rotary. Reciprocating compressors are used for compressing natural
gases and other process gases when desired pressures are
high and gas flow rates are relatively low. They are also used
for compressing air.
Reciprocating

Piston Displacement-

TABLE 3Effect of cylinder clearance and valve area on


compression ratio.

FIG. 4Illustration of the determination of volumetric efficiency from the PV diagram using piston displacement and actual capacity

Compression Ratio

Very high
High
Moderate
Low
144
33000 \ k - 1

Compressors

Reciprocating compressors compress gas by physiccilly reducing the volume of gas contained in a cylinder using a piston. As
the gas volume is decreased, there is a corresponding increasing in its pressure (as indicated by the gas laws discussed earlier). Therefore, this type of compressor is also referred to as a
positive displacement type. An illustration of a reciprocating

More Important Factor

10-30 (vacuum pumps)


8-10 max.
5 max.
2 or less

Clearance
Clearance principally
Balanced
Valving

(k-l/k)

R - 1

(PsVs)

Where: 144 is in'^ per ft.^, 33000 foot-pounds per minute = 1


horse power, k = k-value of the gas, Ps = inlet pressure in
PSIA, Vs = inlet volume in ft^/min, and R is the compression
ratio. The relative effect of cylinder clearance and valving
(cylinder valve area) on the compression ratio is shown in
Table 3.
Compressors may also be characterized by specific power
consumption (Pspec) [6]:

300
O

^spec = power consumption (kW)/volume flow (m^/min)


For example, Pspec for a compressor lubricated with a poly a - olefin or synthetic ester may exhibit a 1-3% advantage relative to a petroleum oil [6].
Temperature
As indicated by the gas laws, gas compression occurs with a
rise in temperature. The greater the amount of gas compression, the higher the final temperature. If high discharge pressures are required, this process is conducted with cooling in
two or more stages, which improves efficiency and reduces
power consumption [9]. The temperatures actually encountered in these compression processes must be considered in
lubricant selection since it affects fluid viscosity, oxidation,
and potential deposit formation. An illustration of the temperature rise of air due to compression in a Broomwade
2050H reciprocating compressor is shown in Fig. 5 [8].

2 200
E

<a
\-

100
1
50

1
100

1
150

200

Air Delivery Pressure (psi)


FIG. 5Air temperature rise versus delivery pressure for a
Broomwade2050H reciprocating compressor

CHAPTER 14: COMPRESSOR


compressor is provided in Fig. 7 [7 ]. Reciprocating compressors are typically "once-through" processes. That is, gas compression and lubricant separation occurs in a single pass.
Reciprocating compressors may be further classified as
single acting or double acting. Single acting compressors,
also classified as automotive compressors or trunk piston
units [3], compress gas on one side of the piston, in one direction. Double acting compressors compress gas on both
sides of the piston, bidirectional.
Figure 7 is an illustration of a typical double-acting reciprocating compressor, which consists of a crankshaft, connecting rods, cross-heads, piston rods, pistons, cylinders and
liners, and piston rings, which are all mounted onto a suitable frame. As the crankshaft turns, the connecting rod converts the rotation to a reciprocating linear motion via the
cross-head. The cross-head transfers this motion to the piston via the piston rod. The gas contained in the cylinder is
compressed and discharged through the discharge valve. The
piston rod packing, also known as cylinder packing, seals the
high-pressure gas from the low-pressure crankcase.

LUBRICANTS

To consider the lubrication process, it is convenient to divide the parts that need to be lubricated into two categories;
namely cylinder parts and running parts. Cylinder parts include pistons, piston rings, cylinder liners, cylinder packing,
and valves. All parts associated with the driving end (i.e., the
crankcase end), cross-head guides, main bearing and wristpin, crankpin, and cross-head pin bearings are running parts.
An equation recommended by Scales for estimating the
amount of oil to inject into a cylinder for lubrication is [3]:
Q

BXSXNX

62.8

10 000 000

Where: B is the bore diameter size (in.), S is the stroke (in.),


N is the rotational speed (rpm), and Q is the usage rate in
quarts per 24-hour day. The constant 62.8 is used to convert
the numerator into the amount of cylinder bore area swept
clean per day and is calculated from ITT X 10. The value TT
(3.14) is multiplied by 2 (6.28) since the pump cycle is in two
directions. The 6.28 value is multiplied by 10 because it is as-

COMPRESSOR TYPES
RECIPROCATING

ROTATING

FIG. 6Classification of compressor types. Reprinted with permission from Universal Compression,
Inc.

Cylinder
Liner

Crosshead
Guide

Crosshead

Piston Rod
pamnq

Water Jacketed
Cylinder

Variable VOIURK

Clearance Pocket

FE 6501

Piston
Rod
Valve

Frame

Crankshaft

387

Connecting

Counter
Wght

FIG. 7Cross section of a reciprocating compressor. Reprinted with permission from Universal Compression, Inc.

388 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


sumed that ten cycles are required for the total cylinder area
to be swept clean. The 10000000 value converts an average
assumed film thickness in microns to inches (in.) and also
converts in^/day to quarts/day.
The lubricant is then generally fed directly to the cylinders
and packings using a mechanical p u m p and lubricator arrangement. Single-acting machines, which are usually open
to the crankcase, usually utilize splash lubrication for cylinder lubrication. Compressor valves are lubricated from the
atomized gas-lubricant in the system.
Compared with cylinder part lubrication, the lubrication of
running parts is typically m u c h simpler because there is no
contact with the gas. The required viscosity grade is specified
by the equipment manufacturer.
Since gas temperature increases with increasing pressure,
if heat is not removed, the lubricant will be exposed to high
temperatures and undergo severe decomposition. Therefore,
compressor cylinders are equipped with cooling jackets. The
coolant is usually water or a water-glycol refrigerant. One of
the most important roles of the compressor cylinder lubricant is as a coolant. Although the same lubricant can be used
to cool both the cylinder and the running parts, there are
many cases where different lubricants are used because the
cylinder lubricant is exposed to compressed gas at high temperatures. Table 4 provides a comparison of illustrative compressor operation temperatures [15]. Therefore, the lubricant
should also exhibit thermal and oxidative stability.
Rotary

Compressors

Rotary compressors are further classified as positive displacement or djTiamic type compressors. A positive displacement type of compressor utilizes gas volume reduction to increase gas pressure. Examples of this type of compressor
include: rotary screw, lobe, and vane compressors that are illustrated in Fig. 8 [10,12,14], Fig. 9 [9] and Fig. 10 [9].
The rotary screw compressor illustrated in Fig. 8 consists
of two intermeshing "screws" or rotors that trap gas between
the rotors and the compressor case [13]. One rotor is the male
rotor and is driven by the motor. The outer rotor is the female
rotor and is driven by the male rotor. Both rotors are encased
in a housing provided with gas inlet and outlet ports. Gas is
drawn through the inlet port into the voids between the rotors. As the rotors rotate, the volume of trapped gas is successively reduced and compressed by the rotors coming into
mesh.
These compressors are available as dry or wet (oilflooded) screw types. For the dry-screw type, the rotors run
inside of a stator without a lubricant (or coolant). The heat
of compression is removed outside of the compressor, limiting it to a single-stage operation. For oil-flooded screw
type compressors, the lubricant is injected into the gas that
is trapped inside of the stator. The functions of the lubricant include cooling, sealing, and lubrication. The gas is removed from the compressed gas-lubricant mixture in a separator. As opposed to reciprocating compressors, which are
once through processes, rotary compressors, such as the
screw compressor, continuously recirculate (1-8 times a
min) the lubricant-gas mixture to facilitate gas cooling and
separation [13].
In a rotary screw compressor, the lubricant is injected into
the compressor housing. The rotors are therefore exposed to
a mixture of the gas and lubricant. In addition to providing a

thin film on the rotors to prevent metal-to-metal contact, the


lubricant also provides a sealing function to prevent gas recompression. It also serves as a coolant by removing heat that
is generated during gas compression. For example, for rotary
screw air compressors, the air discharge temperature may be
80-110C (180-230F), rapid oxidation is favored due to turbulent mixing of the air and lubricant [15].
In addition to these functions, the bearings at the inlet and
outlet of the compressor must be lubricated. With rotary
screw compressors, the lubricant is in contact with the gas
being compressed at high temperatures and experiences high
shearing forces between the intermeshing rotors. This creates very demanding use-conditions for the lubricant with respect to both lubrication and stability.

TABLE 4Comparison of the operational temperature


ranges for different compressor types.
Operating
Temperature Range
Compressor
Lubrication Problems
Deposits block filter,
Rotary screw
80-115C(180-240F)
separator elements
Varnish on bearings
Deposits block filters
Vane
80-150C (180-300F)
Vane wear increases
filter deposits and
varnishing
Single stage to:
Varnish and carbon
Reciprocating
270C (500F)
deposits on exhaust
(and inlet) valves
Multi-stage to:
Piston ring wear
160-210C
increases leakage
and deposits
(325^25F)

FIG. 8Cross section of a rotary screw compressor.

CHAPTER

.y Impeller^

Labyrinth Seal-,
Oil Pump

14: COMPRESSOR

LUBRICANTS

389

Impeller

'Roller
Bearing

Timing
Gears

(a)

(b)
FIG. 9Cross section of a rotary straight lobe compressor.

i INLET

DISCHARGE

-THRUST PIN
SLOT
VANE
PACKING
STRIP

ROTOR

FIG. 10Cross section of a rotary sliding vane compressor.

A simplified diagram for lubricant flow in a typical rotary


screw compressor is shown in Fig. 11 [12]. The lubricant and
gas mixture from the compressor discharge line goes into a
gas/lubricant separator where the compressed gas is separated from the lubricant. After separation, the lubricant is
cooled and filtered, then p u m p e d back into the compressor
housing and bearings.
A schematic diagram for rotary lobe compressor is provided in Fig. 9 [9]. The principle of operation is analogous to
the rotary screw compressor. As the lobe impellers rotate, gas
is trapped between the lobe impellers and the compressor
case where the gas is pressurized through the rotation of

lobes and then discharged. The bearings and timing gears are
lubricated using a pressurized lubricating system.
A rotary vane compressor schematically illustrated in Fig.
10 [9]. Rotary cane compressors consist of a rotor with multiple sliding vanes that are mounted eccentrically in a casing.
As the rotor rotates, gas is drawn into areas of increasing volu m e (A) and discharged as compressed gas from areas of
small volume (B).
As with reciprocating compressors, lubrication of rotary
vane compressors is also a once through operation. The lubricant is injected into the compressor casing and it exits
with the compressed gas and is usually not recirculated. The
lubricant provides a thin film between the compressor casing
and the sliding vanes and also provides lubrication within the
slots in the rotor for the vanes. The sliding motion of the
vanes along the surface of the compressor housing requires a
lubricant that can withstand the high pressures within the
compressor system.
A dynamic compressor, such as the centrifugal compressor
shown in Fig. 12 [9], operates on a totally different principle.
Energy from a set of blades rotating a high speed is transferred to a gas that is then discharged to a diffuser where the
gas velocity is reduced and its kinetic energy converted to
static pressure. One of the advantages of this type of compressor is the potential to handle large volumes of gases.
In a centrifugal, the lubricant and gas do not come into
contact with each other which is a major distinction from reciprocating, rotary screw and rotary vane compressors. The
lubricant requirements are therefore simpler and usually a
good rust and oxidation-inhibited oil will provide satisfactory
lubrication of the bearings, gears and seals.
Compressor Lubricants
Performance

Demands

The choice of a compressor lubricant is dependent on: type


a n d construction of the compressor, the gas being com-

390

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

LUBRICANT SCAVENCER LINE

-AIR
DISCHARGE

FIG. 11Oil-flooded rotary screw compressor lube system.

BACKPLATE
DIFFUSER
PACKING BOXLABRINTH
SEAL
SLEEVE
BEARING

FIG. 12Illustration of a centrifugal compressor.

pressed, the degree of compression and the final outlet temperature. Piston compressors provide the highest gas pressures and are among the most difficult from the standpoint
of cylinder lubrication. Rotary compressors with final pressures below 1 MPa are less difficult to lubricate. Because of
the potential for vane-on-ring contact, rotary vane compressors require the use of an antiwear oil [17], whereas an R &
O oil is often sufficient for the crankcase splash lubrication

of a reciprocating compressor. Therefore, the selection of the


proper compressor and application-dependent lubricant
with the appropriate physical-chemical properties is vital to
a successful process [2]. A classification procedure (ISO
6743-Part 3A) for compressor lubricants based on the type of
equipment and operating conditions is provided in Table 5.
Some of the most commonly reported oil-related service
problems with compressors include [22]:

CHAPTER 14: COMPRESSOR LUBRICANTS

391

TABLE 5ISO 6743-Part 3A: Family D-Compressor lubricant classification oil-lubricated air compressors.
Particular Application
Positive
displacement
air compressors
with oil-lubricated
compression
chambers

More Specific
Application
Reciprocating
(crosshead and
trunk pistons or
Rotary drip feed
(vane)

Rotary oil-flooded
(vane and screw
compressors

Positive displacement
air compressors with
oil-free compression
chambers

Dynamic compressors

Symbol ISO-L
DAA

Typical
Applications
Light duty

Product Type and/or


Performance Requirements
Intermittent operation

Continuous operation

DAB

Medium duty

Intermittent operation

DAC

Heavy duty

Intermittent or
continuous operation

DAG

Light duty

DAH

Medium duty

DAJ

Heavy duty

Liquid ring
compressors
and w a t e r flooded vane
and screw
compressors
Reciprocating oilfree compressors
Rotary oil-free
compressors
Radial and axial
turbo
compressors

'Under favorable conditions, light-duty oil may be used at discharge pressures higher than 800 kPa (8 bar).

Remarks
Sufficient time to allow cooling
between periods of operation
Compressor stop and start
Variable discharge capacity
a. discharge pressure >10^kPa
(lobar)
discharge temperature >160C
stage pressure ratio >3:1 or
b. discharge pressure >10^ kPa
(lobar)
discharge temperature >140C
stage pressure ratio >3:1
Sufficient time to allow cooling
between periods of operation
a. discharge pressure >10^kPa
(lobar)
discharge temperature >160C
or
c. discharge pressure > 10^ kPa
(lobar)
discharge temperature >140''C
or stage pressure ratio >3:1
As for "medium," when
conditions a, b, or c above are
fulfilled and where severe coke
formation in a discharge
system might be anticipated as
a result of previous experience
with a medium-duty oil.
Air and air/oil discharge
temperature <90C
Discharge pressure
<800 k P a ' ( < 8 bar)
Air and air/oil discharge
temperature <100C
Discharge pressure
800-1500 kPa (8-15 bar)
or
Air and air/oil discharge
temperature 100-110C
Discharge pressure
<800 k P a ' ( < 8 bar)
Air and air/oil discharge
temperature > 100C
Discharge pressure
<800 k P a ' ( < 8 bar)
or
Air and air/oil discharge
temperature f l O O X
Discharge pressure
800-1500 k P a ' ( 8 - 1 5 bar)
or
Discharge pressure
> 1500 b a r (>15 bar)
Lubricants suitable for gears,
bearings and transmissions

Lubricants suitable for bearings


and gears

392

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Increase in oil viscosity and total acidity


Copper corrosion (oil turns green)
Sludge deposits
Substantial oil entrainment in discharge gas (air) due to
decreased efficiency of the demister element
Oil strainer plugging
Bearing failure
For successful operation, a compressor oil must exhibit: oxidation resistance, wide operating temperature range (high
flash point, low pour point, high viscosity index), low volatility,
superior jmti-wear performance, good demulsibility, adequate
corrosion resistance, thermal/oxidative stability, rust and corrosion inhibition, hydrolytic stability, material compatibility,
non-sludging performance, minimal oil loss to the system,
non-foaming potential behavior, and m u s t be non-toxic
[8,10,24]. The successful development of a compressor lubricant will depend on how well the oil meets these technical requirements. Testing procedures that may be used to develop
and maintain compressor lubricants will be discussed here.
Lubricant

Basestocks

Mineral OilsAlthough it is more c o m m o n for naphthenic


mineral oils to be used as a basestock for compressor fluid
formulation, paraffinic oils may be used as well [15,23,26].
The composition of two illustrative examples is provided in
Table 6 [15]. In either case, the basestock is formulated with
additives to provide the desired stabilization to oxidation and
sludge formation, rust and corrosion control, foam control,
demulsibility, and antiwear behavior [23,26]. The response of
the base oil to these additives is dependent on the composition of the oil [23].
Although the performance of these oils is generally good,
there is a temperature and pressure limit, beyond which a
mineral oil-based compressor lubricant should not be used.
This is particularly critical for air compressors due to the relatively poor oxidation resistance and sludge-forming characteristics of mineral oils in the presence of air at high temperatures. Figure 13 illustrates the guidelines recommended by
Matthews, et al. for the use of mineral oil lubricants for air
compressors [23].
The oxidative stability and sludge (coke) forming properties exhibit a significant impact on both the operation and
the explosion and fire h a z a r d of compressor oil in use
[20,27,28]. As with other basestocks, mineral oil oxidation as
represented by the autoignition temperature is further exacerbated by the presence of corrosion metals such as iron oxide as illustrated in Fig. 14 [1].
The poor fire-resistance, oxidative instability and other deficiencies of mineral oil compressor lubricants often limit
their use. In these cases, a synthetic oil-based lubricant may
be selected. However, one approach to this limitation of the
use of mineral oil-based compressor lubricants is to further
refine the mineral basestock using a two-stage hydrotreating
process. In this process [15] and others that have been reported [12,14], polycycloparaffins are broken u p and aromatic compounds are converted into saturated cycloparaffins. In addition, sulfur, nitrogen, and oxygen-containing
compounds are completely decomposed. Table 6 provides a
comparative illustration of the chemical composition of a
two-stage hydrotreating process to a conventionally refined
paraffinic and a naphthenic oil [15]. Data reported by Cohen

TABLE 6T3q5ical composition of mineral oil basestock used for a


32 centistoke compressor oil lubricant formulation.
Solvent
Refined
Paraffinic
ISO viscosity grade
Ave. molecular weight
Total saturates (%)
Paraffins (iso+ normal)
Cycloparaffins (total)
Monocyclo
Dicyclo
Tricyclo
Tetracyclo
Pentacyclo
Hexacyclo
Total aromatics (%)
Monoaromatics
Diaromatics
Triaromatics
Tetraaromatics
Pentaaromatics
Total thiophenes (%)
Total polar compounds (%)
S, ppm
N, ppm

32
395
84.14
17.74
66.40
(24.46)
(15.24)
(9.10)
(10.58)
(4.67)
(2.35)
14.37
(10.49)
(2.60)
(0.48)
(0.13)
(0.67)
0.19
1.30
500
30

Solvent
Refined
Naphthenic
32
330
58.22
12.22
45.00
(15.69)
(12.82)
(8.21)
(6.01)
(2.45)
(0.82)
31.06
(12.28)
(12.58)
(2.72)
(2.28)
(1.20)
9.09
1.64
13,400
160

Two-Stage
Hydrotreated
32
405
99.97
32.60
67.37
(30.81)
(19.52)
(8.87)
(4.75)
(2.56)
(0.86)
0.03
(0.03)
Nil
Nil
Nil
Nil
Nil
Nil
2
1

showed a significant improvement in oxidative stability when


evaluated in an air compressor test relative to normally refined basestocks [15].
Synthetic BasestocksIn addition to exhibiting improved oxidative stability relative to mineral oil, synthetic basestocks
also are used in compressing gases that may react with conventional mineral oils. These reactive gases include: methyl
chloride, sulfur dioxide, hydrochloric acid, ammonia, and
other process gases such as carbon dioxide (which may be
c o n t a m i n a t e d with acids, hydrogen sulfide, or other oxidants), chlorosiloxanes, chlorinated hydrocarbons, and gases
containing trace mineral acids. In many chemical plant processes, mineral oil based lubricants are not allowed due to
potential catalyst contamination [14].
In these applications, an appropriate synthetic oil-based
lubricant must be selected. In this section, a brief overview of
the more commonly encountered synthetic lubricant basestocks will be provided. The basestocks to be discussed here
include: polyalkylene glycol (PAG), ester, phosphate ester,
polyalphaolefin (PAO), silicones, fluorocarbons, and alkylbenzenes. Compressor fluids formulated from these basestocks are the most commonly encountered in the industry
[16].
Polyalkylene Glycol-PAGCompressor
lubricants formulated
with polyalkylene glycols are being used increasingly as compressor lubricants, particularly in hydrocarbon gas compression applications because of their resistance to hydrocarbon
dilution [12,19]. The poor solubility of hydrocarbon gases in
PAGs also assists in preventing the washing away of the lubricant that would result in metal-to-metal contact (dry running) [16]. However, at high operating pressures, hydrocarbon gases may continue to condense, leading to a build-up of
a hydrocarbon-rich phase in the lubricant separation tank.
This problem is easily remedied even though the lubricanthydrocarbon phases do not readily separate by gravity. If
such problems do occur, the hydrocarbon gas may be re-

CHAPTER 14: COMPRESSOR

LUBRICANTS

393

350r

Aryl Ester Based Product

..Operating Envelope for Many


Reciprocating Air Compressors

100

200

300

PRESSURE (bar)
FIG. 13Recommended guideline for the use of mineral oil lubricants for air compressors.

Phosphate Ester
- _ ^ Phosphate Ester
_
w/ Iron Oxides
Polyol Ester
Diester, 100ISO
Polyalphaolefin
Mineral Oil #1
Mineral Oil #2
Mineral Oil #2
w/ Iron Oxides
90
120 150 180
PRESSURE (PSIG)
FIG. 14Autoignition of various synthetic and mineral oils compared
to discharge pressures and temperatures. A. single stage, B. two stage,
and C. three stage.

moved using a flash still unit such as the one shown schematically in Fig. 15 [19].
PAG polymers exhibit excellent viscosity-temperature behavior (high viscosity index) as shown in Fig. 16 [ 14] and they
may usually be used up to compression temperatures of
200C [16] However, they have been reported to degrade at
compression temperatures of 230C which would make them
unsuitable for high temperature air compressor applications
[23]. Other reported advantages include low pour point, high
flash point, and low vapor pressure. PAG-based compressor
lubricants have been used with success in natural gas, nitrogen, carbon dioxide, hydrogen, and helium compression [29].
Ethylene compression for low-density polyethylene (up to
50000 psig) has also been reported [29].
Blends of PAGs with other basestocks have been reported
to offer properties superior to either basestock itself. For ex-

ample, it has been reported that a polypropylene glycol with


a pentaerythritol ester can be used for air compression in a
rotary screw compressor (where the oil is recirculated) with
excellent long service life [11].
Polyalphaolefin (PAO)Polyalphaolefins are also used extensively as a synthetic basestock for compressor lubricant formulation. In addition to good viscosity properties relative to
mineral oil, as illustrated in Fig 16, PAOs exhibit excellent
thermal and oxidative stability, and are hydrolytically stable,
as shown in Fig. 17 [19], and are not attacked by reactive gases
such as ammonia [30]. These factors have led to their growth
in usage in rotary screw compressor applications [12].
In some cases, compressor oils are used in the food industry and may come in contact with food. They may also be used
to compress gasses that are used in food applications, such as
CO2 [2]. For these applications, a food-grade compressor lu-

394

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK
COMPRESSED
-GAS
DISCHARGE

Gas
Refrigerant

r0cCOOLER

MOTOR
OMPRESSOR
1 I LUBE
Gas + Lube +
i r SEPARATOR
H.C. Condensibles Z

Condensibles

_F;

fe 3

(fn

Lube + H.C.
Condensibles

Recycle Stream^<^ 1
H.C. Vapors
IFILTER

SUCTION
TANK

-Or

HEATER

FLASH
DISTILLER

LUBE
PUMP
COOLER

FIG. 15Flooded rotary screw gas compressor system equipped with a flash still unit.

bricant must be used, which may be a white mineral oil [2] or


a food-grade PAO [25]. Figure 18 illustrates the substanticJ
improvement in fluid lifetime for the food grade PAO compared to the white mineral oil used as a reference [25].
EstersEster basestocks used in compressor oil formulations
include: diesters, polyols, phthalates, and trimellitates [21]
Esters are often used as low-cost basestocks for compressor
fluids used in air compressors because of their improved oxidative resistance as shown in Fig. 14 [1]. Furthermore, esters
have been used increasingly as cylinder lubricants for reciprocating compressors due to their high-temperature stability
and solvency properties [12]. The use of ester basestocks, such
as diesters and polyol esters, results in minimal deposit formation on hot pistons and discharge valves [12].
SiliconesSilicones, including dimethyl, alkylmethyl, and
fluorinated polymers are EIISO used to formulate compressor
fluids. These polymers are relatively inert to almost all chemicals except pure oxygen, and other strong oxidizing agents.
They are tj^Dically used to formulate compressor fluids used

100,000
20,000
(0
u
E
CO
O

1,000
300

75
40
15
PAG
PAO
Semi-Synfhetic
Mineral Oil

>

-30

50

100

150 200

250 300 350

TEMPERATURE (F)
-17.8

37.7

93.9

148.9

TEMPERATURE (C)
FIG. 16Comparative viscosity-temperature relationships
for different compressor lubricants.

100
90
80

9
3
X
UJ

>
UJ

in

Polyalphaolefin
"Fluid

70
60

/C

50

DIester
Fluid

403020
10-

'

500

Jt-L

1000

- 1 ^iOO

' ' _ ' ' ' ' '

2000

2500

3000

3500

WATER CONCENTRATION (PPM)


FIG. 17Comparison of the hydrolytic stability of a compressor lubricant formulated using a PAO and an ester basestock.

CHAPTER

"0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17

WEEKS
FIG. 18Comparison of the oxidative stability of a food
grade Poly(Alphaolefin) (PAO) with a hydrocarbon white oil.

for HCl and chlorine compression [14]. Some silicones have


exhibited outstanding corrosion protection on metal surfaces
and have even been used as a corrosion inhibiting additive
for the formulation of PAO compressor fluids [14].
Dimethylsilicones exhibit excellent viscosity-temperature
characteristics and are hydrolytically stable and, if used with
an effective antiwear additive, exhibit acceptable lubricating
characteristics and exhibit excellent oxidative stability [19].
Fluorinated BasestocksThere
are three classes of fluorinated fluids that are used for lubricant formulation. These include: chlorofluorocarbons, perfluoroalkylpolyethers, and
fluorosilicones. All are very expensive a n d are only used
where their outstanding chemical inertness, even to liquid
oxygen and chlorine, is demanded [19].
Phosphate SstersPhosphate
esters are used primarily for
their fire-resistance properties, particularly in the mining industry [20], relative to mineral oil as illustrated in Fig. 14 [1].
In addition, they exhibit high flash points, excellent resistance to aging, and minimal coke formation. They eire used in
high-pressure multistage compressors and other applications. However, if the lubricant degrades, by-products with
poor material compatibility may be formed. In some cases, it
has been reported that there may be problems with boundary
lubrication between aluminum and cast iron cylinders.
AlkylbenzenesAs illustrated in Fig. 13, the thermal-oxidative
stability of mineral oils, particularly solvent refined naphthenic oils, is somewhat limited, particularly in air compression operations. In such applications, it has been shown that
selected, well-refined alkylbenzenes do not exhibit carbonaceous sludge formation in reciprocating compressors with final compression temperatures of 220C and 0.8-1.0 MPa [20]
Alkylbenzenes m a y also be used to formulate a m m o n i a
compressor fluids although they do exhibit slightly greater
ammonia solubility than paraffinic oils and PAOs [30]. However, vapor pressure is lower than solvent refined naphthenic
oils, but greater than PAOs or hydrotrated oils. Alkylbenzenes
also exhibit relatively poor viscosity-temperature properties.
Gas Solubility

in the

Lubricant

The solubility of natural gas and other hydrocarbons is m u c h


higher in petroleum oils. That is expected because both hy-

14: COMPRESSOR

LUBRICANTS

395

drocarbon gas and petroleum oils are very similar molecules


consisting of primarily CH bonds. The solubility of hydrocarbons is m u c h less in some synthetic lubricants, especially
PAGs. This is because, in a typical PAG molecule, each third
atom in the polymer backbone, is an oxygen atom, which
makes it quite polar. Therefore, hydrocarbons are less soluble in PAGs.
In reciprocating and rotary screw compressors, the gas being compressed and the lubricant come into contact with
each other. Hydrocarbon gases are infinitely soluble in mineral oil-based compressor lubricants, and the solubility of hydrocarbon gases increases with increasing pressure at a constant temperature in a less compatible fluid such as a ISO 220
polypropylene glycol, as illustrated in Fig. 19 [14]. Figure 20
illustrates that increasing the temperature at a constant pressure will result in lower gas solubility. [14]. At some point, if
the viscosity reduction of the compressor lubricant is sufficient, lubrication failure may result because of loss of hydrodynamic lubrication [2].
The solubility of various gases in lubricants has been measured and reported [8,14,29]. The solubility was measured in
a fixed volume apparatus. A known a m o u n t of gas and lubricant was allowed to reach equilibrium at a given temperature. Gas solubility was calculated using the gas laws. The lubricant was stirred to facilitate equilibrium.
Solubility of methane at pressures u p to 5000 psig is compared at 50C for three lubricants: PAG, PAO and a petroleum
oil in Fig. 21. The m e t h a n e gas solubility in PAG is roughly
one half of that for a PAO and petroleum oil and that the solubility was nearly as high in the PAO as in the petroleum oil.
Gas solubility exhibits a significant effect on lubricant viscosity. The greater the solubility of the gas in the oil, the
greater the viscosity loss (viscosity dilution). A lubricant viscosity-dilution chart is shown in Fig. 22 for methane at 50.
Similar gas solubility comparisons for nitrogen, hydrogen,
ethylene, propane, c a r b o n dioxide, are provided in Figs.
23-27, respectively. [29]

300
j f

<

Q^ 200
LU

DC
i/>

Uj 100

a:

crfSs-

^5^=^

Q.

10

20

30

% GAS
FIG. 19Hydrocarbon gas solubility in an ISO 220 polypropylene oxide at constant temperature.

396

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

o
o
>

2000
3000
4000
PRESSURE (PSIA)

500
1000
500i

5000

FIG. 23Nitrogen gas solubility comparison in a PAG versus


a PAO at 50C.

20

40

60

80 100

TEMPERATURE (C)
FIG. 20Effect of hydrocarbon gas dilution on viscosity with
increasing temperature of a hydrocarbon gas in an ISO 220
polypropylene oxide fluid.

"0

1000

2000

3000

4000

Pressure (PSIA)
FIG. 24Hydrogen solubility comparison in a PAG.
2000

3000

PRESSURE (PSIA)

FIG. 21Methane gas solubility comparisons for a polyalkylene glycol, Poly(Alphaolefin) and petroleum oil at 50C.

Lubricant Solubility in the Gas


The lubricant solubility in the gas should be minimized to reduce carryover by absorption of the lubricant in the gas. The
absorption of the lubricant in natural gas was evaluated by
Matthews using a constant pressure flow through a load
(gravimetric) cell [8]. The results of this work, shown in Fig.
28 indicated that there was an appreciable absorption of the
mineral oil in the gas. The PAG lubricant showed no appreciable loss.
Test Procedures

2000

3000

PRESSURE (PSI)

FIG. 22Viscosity dilution comparison for methane in a


Poly(Alkyleneglycol) (PAG) and a petroleum oil at 50C.

Kinematic Viscosity (ASTM D 445)


Compressor fluid viscosity is important with respect to lubrication of bearings, gears, and other moving surfaces within
the pump and for providing adequate sealing within the compressor. Typically, fluid viscosity at 40C and 100C is determined [8,25,32,34] and, if low-temperature use is expected,
the viscosity at 0C is determined [11,34]. Higher fluid viscosities result when the fluid is oxidized. Therefore, viscosity

CHAPTER 14: COMPRESSOR

LUBRICANTS

397

^ 0.5
(

lU 0.4t

>

CD 0.3

0.2

^ ^ s * ^ ^

0.1 -{"4f

1000

2000

(a)

3000
4000
5000
PRESSURE (PSIA)

6000

7000

(O

(
l

i""-i
1

i S J PAG
t

10

20

30

40

50

60

70

80

90 100 110 120

TEMPERATURE C O
FIG. 27Solubility of carbon dioxide in a PAG at SOX.

Specific Gravity (Test Methods D 287 and D 729SJSpecific


gravity depends on the chemical composition of the base
stock used to formulate a compressor, such as the naphthenic/paraffinic ratio of a mineral oil. Test Methods D 287
and D 1298 for specific gravity require the use of both a hydrometer and an accurate thermometer or a thermohydrometer. Because specific gravity is temperature dependent, the
temperature of the oil at the time of measurement, typically
25C or 77F, must be determined precisely [11,31,34].
2000

1000

(b)

3000
4000
5000
PRESSURE (PSIA)

6000

7000

FIG. 25Ethylene solubility comparison at 50C of: A. a PAG


versus a petroleum white oil and B. a PAG versus a polybutene.

-^ 0.5

o
E 0.4
.^.PJAG

^ 0.3
5 0.2
O

0.1

48

i
!
60
72
84
TEMPERATURE (C)

i
96

108

FIG. 28Solubility of propane in a PAG at SOX.

is also an important fluid maintenance procedure and is useful for comparison with the viscosity of a fresh fluid. Viscosity measurement by various tests, including Test Method D
445, is discussed in detail in Chapter 32Flow Properties
and Shear Stability, and will not be discussed further here.
The viscosity-temperature relationship (viscosity index) of
a compressor fluid is another important physical property
that may be determined according to ASTM D 2270.

Pour Point (Test Method ASTM D 97)


Pour point is used to characterize the suitability of a lubricant for use at low temperatures. Pour point is defined as the
lowest temperature at which the movement of the fluid is observed.
Water Content (Test Methods D 95, D 1744, D 4007)
The presence of moisture in a compressor fluid, particularly
with hydrocarbon gas compression, is important because hydrocarbon gases may form a "cold sludge" in the presence of
moisture [6]. (If the compressor fluid contains trace amounts
of water, it must be operated above the dew point of the fluid
[10].) Also, water may condense in the system under conditions of low temperature and high humidity [11]. The presence of large slugs of water may lead to fatigue failure of
bearings. Fluids that are susceptible to hydrolysis may then
react with the residual water upon heating, thus reducing
their lifetime and possibly leading to corrosive system damage.
The presence of water in a compressor fluid may be determined by titration of the oil with Karl Fisher chemical
reagent to an electrometric endpoint (Test Method D 1744).
This test is recommended for water levels of 50-1000 ppm
(less than 0.1%). Higher levels of water contamination may
be quantified by distillation (Test Method D 95) or centrifugation of the sample and measurement of the volume of separated water according to Test Method D 4007.
Demulsibility (Test Method D 1401 or D 2711)
The ability of a fluid to separate from water is called "Demulsibility." Demulsibility properties of a compressor fluid
may be determined using Test Method D 1401 where a 40
mL sample of the fluid and 40 mL of distilled water are

398

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

PRESSURE 340 bar


TEMPERATURE 100 "C
I

I MINERAL OIL (ISO 680)

^ ^ 2 0 0 est PAG

a.
O 40
OT 30

o
o
W 20

hOGAS
ATMOSPHER C PRE

URE

340 bar N,

SATURATED WITH
METHANE

FIG. 28Effect of pressure and gas dilution on the viscosity of a mineral oil and a PAG cylinder lubricant.

stirred for 5 min at 54.4C (130F) in a graduated cylinder


[10,26,31,32,34,35]. The time for separation of the emulsion
that is formed is determined. Test Method D 2711 is recomm e n d e d for evaluating the demulsibility properties of
medium to high-viscosity lubricating oils.
Hydrolytic

Stability

(Test Method

2619)

Some compressor lubricants hydrolyze in the presence of water at elevated temperature such as those based on ester basestocks [8]. Therefore, it may be important to determine the
hydrolytic sensitivity of a compressor fluid to water. Conducting Test Method D 2619, the Beverage Bottle Method,
can do this.
Test Method D 2619 covers the determination of the hydrolytic stability of synthetic or petroleum-base hydraulic
fluids b u t is as applicable to compressor fluids. In this
method, 75 g of the compressor fluid and 25 g of water and a
copper test specimen are sealed in a pressure-type bottle. The
bottle is rotated, end for end, for 48 h in an oven at 93C
(200F). Layers are separated, and insolubles are weighed.
The weight change of copper is measured. Viscosity and acid
numbers and the acidity of the water layer are determined.
This method differentiates the relative stability of compressor lubricants in the presence of water under the conditions of the test. Hydrolytically unstable fluids form acidic
and insoluble contaminants, which may cause compressor
system malfunctions such as corrosion, valve sticking, or
change of viscosity of the fluid.
Foaming

Tendency

(Test Method

D 892)

The assessment of a wet or dry fluid to foam is important for


various reasons. One is that foaming fluid may fill the separator and saturate the filter element, leading to severe fluid
loss with the compressed gas. A "bubbly fluid" may cause lubrication failure, poor sealing properties and reduced efficiency [11]. As described in Test Method D 892, the foaming
tendency of a fluid should be determined at 24C and 93.5C
[26]. This test is conducted by equilibrating the test fluid at
24C (75F) at which point air is blown through the fluid at a
constant rate for 5 min, then allowed to settle for 10 min. The
foam volume is measured at the end of both periods. The test
is repeated on a second sample at 93.5C (200F), and then after collapsing the foam at 24C (75F).

Air Release

(Test Method

3427)

In addition to foaming, it is important to monitor the ability


of a fluid to release entrained air because excessive air entrainment may reduce fluid delivery rates to the compressor
rotors. This has the same effect as operating the compressor
below recommended fluid levels [25,32].
Air entrainment may be determined using Test Method D
3427 where compressed air is blown through the test fluid
which has been heated to 25, 50, or 75C. After the air flow is
stopped, the time required for the air entrained in the fluid to
reduce in volume by 0.2% under the conditions of the test
and at the test temperature is measured.
Corrosion

(Test Method

4310)

A well-formulated compressor fluid will contain additives to


provide adequate copper and iron corrosion protection
[10,11,15,22,32]. A build-up of corrosion metals in the separator could block the lubricating lines and impede fluid flow
through the filter. Furthermore, if not properly inhibited,
corrosion metals such as copper and iron will catalyze the oxidation of many fluids [11].
Copper Corrosion (Test Method D 130)~ASTM Test Method D
130 (Copper Strip Corrosion Test) will evaluate the corrosiveness of a compressor lubricant toward copper. In this
test, a polished copper strip is immersed into the test fluid
and heated at a temperature a n d for a length of time that is
characteristic of the fluid being tested. At the conclusion of
the test, the copper strip is removed, washed, and compared
with ASTM Copper Strip Corrosion Standards.
Iron Corrosion (Test Method D 665)Iron corrosion, or "rust"
potential of a compressor fluid is evaluated by Test Method D
665, which is also known as the Turbine Oil Rust Test. This
test evaluates the ability of a compressor fluid to inhibit rusting of ferrous parts should water become mixed with the
compressor fluid. The test is conducted by mixing 300 mL of
distilled water (or synthetic sea water) at 60C (140F) with a
cylindrical steel test rod completely immersed into the
fluid/water mixture. The test is usually run for 24 h at which
time the steel test rod is inspected for rusting.
Flash and Fire Points (Test Methods D 92)
The fire resistance and safety properties of a compressor
fluid are t5rpically determined from its flash and fire point

CHAPTER
[10,11,25,26,31,32,34,35]. The flash point is the lowest temperature, corrected to a barometric pressure of 101.3 kPa
(760 m m Hg), at which the application of an ignition source
causes the vapors of a fluid being tested to ignite under the
specified conditions of the test. The test usually cited for
compressor fluids is the so-called Cleveland Open-Cup flash
point. This test procedure is described in detail in Chapter
25Volatility.
The fire point is the lowest temperature, corrected to a
barometric pressure of 101.3 kPa (760 m m Hg), at which the
application of an ignition source causes the vapors of a fluid
being tested to ignite and continue to b u m for 5 s under the
specified conditions of the test.
Autoignition

(Test Method

E 659)

Compressor fluids should not be used above their autoignition temperature. Autoignition temperature is the temperature at which the fluid will ignite spontaneously in contact
with air and may be determined by Test Method E 659. No
sparks or open flame need be present. Hydrocarbon fluids
absorbed on porous surfaces can ignite at temperatures more
t h a n 50C (approximately 100F) lower t h a n indicated by
Test Methods E 659.
Evaporation
Increasing volatility of the compressor fluid will result in increasing carbon build-up in the discharge system of a compressor [27]. This will occur if the oil fractions are sufficiently volatile to r e m a i n in the vapor state of the hot
discharge zone where the oil can break down into carbon.
Evaporation Loss (Test Method D 972)Oil volatility can be
measured by Test Method D 972. In this test, a weighed sample of the compressor oil is placed in a bath maintained at the
desired test temperature, typically 100-150C (210-300F).
Heated air is passed over its surface for 22 h. The evaporation
loss is calculated from the loss of mass of the sample.
NOACK Evaporation Loss (Test Methods D 5800 and D
6375)The NOACK test method is a method of measuring
evaporative loss of an engine oil during use, but can be related to any set of conditions. It was recently applied to measuring the evaporative loss of compressor fluids [35]. This
test is conducted using the NOACK Evaporative Tester illustrated in Fig. 29. In this test, a measured quantity of the compressor fluid is placed in an evaporation crucible, which is
then heated to the desired temperature with a constant flow
of air drawn through it for 60 min. The loss in mass of the oil
is determined. In this test, Wood's metal, which contains
lead, bismuth, antimony, a n d cadmium, is used. These components have been found to be health hazards. Therefore, if
it is possible. Test Method D 6375 should be used (see following discussion).
An automated, smaller scale variant of Test Method D 5800
is Test Method D 6375, the "TGA NOACK Method." This
method is applicable to lubrication oils that exhibit NOACK
evaporative losses of 0-30%. In this test, a sample of the desired compressor fluid to be tested is placed in an appropriate Thermogravimetric Analyzer (TGA) specimen pan. The
pan is placed on the TGA p a n holder and quickly heated to
between 247-249C under a stream of air and then held for
an appropriate time. Throughout the process, the TGA monitors and records the mass loss experienced by the specimen

14: COMPRESSOR

LUBRICANTS

399

due to evaporation. The NOACK evaporation loss is subsequently determined from the specimen weight percent loss
versus time curve (TG Curve) as the mass percent lost by the
specimen at the NOACK reference time determined under
the same TGA conditions. This procedure requires m u c h
smaller test specimens and is m u c h faster when multiple
samples are sequentially analyzed; it is also safer than the
NOACK Test Method D 5800.
Carbon

Residue

One of the greatest problems encountered when using a compressor fluid is the formation and accumulation of sludge,
which can lead to a safety problem, possibly even an explosive situation if coupled with overheating. This will occur if
sufficient quantities of c a r b o n a n d sludge are formed to
cause the valves to stick open (Reference ISO 5388 part
6.6.1). Therefore, it is desirable to determine the sludgeforming potential of a compressor fluid.
Conradson Carbon Residue (Test Method D189)One method
of quantifying the sludge-forming potential of a compressor
fluid involves determination of the Conradson carbon residue
(Test Method D189) [31 ], which measures the amount of polymeric material remaining in the oil after heating to elevated
temperatures in the absence of sufficient oxygen to burn off
all of the organic compounds present. The Conradson carbon
residue is determined by placing a weighed sample in an iron
crucible. The crucible is heated with a Meeker-type gas burner
to a sufficiently high temperature to evaporate and b u m the
oil. The sample is further heated until the bottom and sides of
the crucible are cherry red and is held at this temperature for
30 min. The crucible is then cooled and weighed. The amount
of tar remaining in the crucible relative to the original amount
of the oil define the Conradson carbon residue value. Test
Method D 189 may be affected by some additives used to formulate the compressor fluid.
Ramsbottom Carbon Residue (Test Method D 524)Another
test that is used to determine the tendency for a compressor
lubricant to form carbonaceous residues is Test Method D
524, the Ramsbottom Carbon Residue test [15]. In this test,
the sample, after being weighed into a special glass bulb, is
placed in a metal furnace and heated to 550C. In this way,
the sample is quickly heated to the point where all volatile
material is evaporated out of the bulb, with or without decomposition, while the remaining residue undergoes cracking and coking reactions. After the test, the bulb is cooled and
weighed. The residue remaining is reported as % of original
sample and is called the Ramsbottom Carbon Residue.
"Micro Method" for Carbon Residue (Test Method D 4530)In
the "micro method," a weighed sample of the fluid is heated
in a 2 mL glass vial at 500C under an inert atmosphere (nitrogen) in a controlled manner for a specific time. The sample undergoes coking reactions a n d the volatiles that are
formed are swept away by the nitrogen. The carbonaceous
residue formed is reported as % of original sample as "carbon
residue (micro)." This test method is reported to be equivalent to the Conradson Carbon Residue.
Precipitation

Number

(Test Method

D 91)

Sludge formation in a compressor oil is caused by oxidation of


various components, leading to polymerization and crosslinking reactions. These cross-linked and polymerized byprod-

400

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK
~N

Manometer

Thermometer

j ~ To Pump

FIG. 29Schematic illustration of the NOACK Evaporative Tester (ASTM Test Method D 5800).

ucts are sufficiently fiigfi in molecular weight to cause them to


be Insoluble in the oil. As indicated above, sludge can lead to
valve sticking, creating an unsafe condition (ISO 5388). Increasing sludge formation often indicates increasing oil oxidation. The amount of sludge can be quantified by adding
naphtha solvent to the compressor fluid sample and determining the volume of precipitate (sludge) after centrifuging.
Acid Number (ASTM D 664 and D 974)
The acid number (AN) measures the acidity of the fluid, acidity produced when the fluid is oxidized. Fresh, oxidation inhibited, compressor fluids tjrpically exhibit AN values of approximately 0.15 or less [22,26]. The AN value may be
determined by Test Method D 664, which covers lubricants
soluble or nearly soluble in mixtures of toluene and isopropanol. It is applicable for determination of acids whose
dissociation constants in water are larger than 10"'. Extremely weak acids whose dissociation constants are smaller
than 10~' do not interfere. Salts react if their hydrolysis constants are larger than 10~'. For Test Method D 664, the compressor fluid is dissolved in a mixture of toluene and isopropanol containing a small amount of water and titrated
potentiometrically with alcoholic potassium hydroxide, using a glass electrode and a calomel reference electrode. Test
Method D 974 is similar except the sample is titrated colorimetrically using a p-naphtholbenzein as the indicator.
Infra-Red Spectroscopy
An alternative method that is being used increasingly to identify and quantify oil oxidation, even in the presence of additives, is infra-red (IR) spectroscopy [22]. Figure 30 provides
an illustration of the use of IR spectral analysis to identify oil
oxidation [36]. Mang and Jiinemann monitored the IR

stretching vibrations ofC = O a t l 7 1 0 cm ', for carboxylic


acids contained in oxidized oil. IR analysis has been used to
detect and quantify other carbonyl-containing compounds
[37]:
Metal carboxylate salts-1600 and 1400 cm"'
Carboxylic Acids-1710 cm"'
Metal sulfates-1100 and 1600 cm"'
Esters-1270 and 1735 cm "'
Fluid Oxidation
The severity thermal and oxidative stresses that a compressor
fluid is subjected to are compressor dependent. For example,
thermal and oxidative stresses on a fluid in a rotary vane and
rotary screw compressor are considerably more moderate
thcin a fluid would encounter in a reciprocating compressor.
However, although the thermal and oxidative stress is
greater/cycle in a reciprocating compressor, it is only a "once
through process," whereas the expected lifetime of a fluid for
a rotary vane or rotary screw compressor would be expected
to last for several thousands of hours [23].
Various tests have been proposed to determine relative lifetimes of a compressor fluid under rigorous thermal and oxidative conditions. The tests that have gained greater acceptance as reasonably predicting actual production experience
in a compressor will be reviewed here.
Turbine Oil Stability Test - TOST (Test Method D 943)Sugiura, et al. [23] has reported some success with the Test
Method D 943 to determine the long term oxidative stability
of a compressor oil. Test Method D 943 evaluates the oxidative stability of a lubricant with a specific gravity less than
water, which contains rust and oxidation inhibitors in the
presence of oxygen, water, copper, and iron at an elevated
temperature. In this test, the sample is contacted with oxygen

CHAPTER
in the presence of an iron-copper catalyst at 95C. The test is
continued until the measured acid n u m b e r is 2.0 mg KOH/g
or above. The n u m b e r of hours required for the test fluid to
reach 2.0 mg KOH/g is the "oxidation lifetime." Sugiura,
however, utilized a m u c h lower critical AN value of 0.4 mg
KOH/g since his work indicated that the oxidation rate of the
compressor oils he examined increased dramatically above
0.4 mg KOH/g [22].
Rotating Bomb Oxidation Test-RBOT (Test Method D 2272)
Various workers have reported the use of RBOT as an accelerated test to evaluate compressor fluid lifetime [11,23,26].
This test m e t h o d utilizes an oxygen-pressurized vessel to
evaluate oxidation stability of new and used compressor fluids in the presence of water and a copper catalyst at 150C.
For this test, the compressor fluid, water, and copper catalyst
coil, contained in a covered glass container, are placed in a
vessel equipped with a pressure gauge. The vessel is charged
with oxygen to a gauge pressure of 620 kPa (90 psig, 6.2 bar),
placed in a constant-temperature oil bath set at 150C, and
rotated axially at 100 r p m at an angle of 30 from horizontal.
The n u m b e r of minutes required to reach a specific drop in
gauge pressure is the oxidation stability of the fluid.
Indiana Stirring Oxidation Test-ISOT (Test Method JIS K
2514)~The ISOT, although developed in the U.S., has only
been standardized in Japan as JIS K 2514 and has been reported to provide superior correlation with actual results for
actual industrial compressor use [22,26]. This test cell for
this method is illustrated in Fig. 3 1 . This modified version of

14: COMPRESSOR

LUBRICANTS

401

the ISOT test reported by Sugiura [22] involves blowing dry


air at 10 L/h through 300 mL of the test fluid held at 165.5C
(329.9F) in the presence of a copper and iron catalyst. The
n u m b e r of hours to reach a AN of 0.4 mg KOH/g is determined.
Wolf Strip Oxidation Test [8]Matthews has reported excellent correlations with carbon and sludge forming tendencies
of a compressor fluid in an air compressor using the Wolf
Strip Test [8,23]. This is a 12 h test that is conducted by
pumping a fluid sample over an inclined steel plate test strip,
which is heated to 250C. The oil is removed from the plate
by solvent washing at the conclusion of the test and the steel
test strip is air dried. The weight of the residue adhering to
the test strip is measured and the evaporative loss of the total
volume of the oil after the test completion is recorded. This is
very similar to the hot panel coking test which utilizes an alum i n u m test plate [38] and has been used in the automotive
lubricants industry for many years [23].
Liquid Heptane
Resistance
f8]

Washing

Test for Oil Film

Wash-Off

Matthews has devised a test to indicate the resistance of an oil


film to be removed by heavier hydrocarbons (C7 or higher),
which may be present in natural gas [8]. This test is conducted
by pre-weighing dry steel plates that are dipped into the test
lubricant and then suspended for 1 h to allow the excess oil to
drain off from the surface of the steel. The steel plates are
reweighed to determine the weight gain due to the oil film and

Wave Number (cm'^)


FIG. 30Infra-red spectral identification of oxidation of a used compressor oil (mineral
oil-derived fluid).

402

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Dry Air
10 1 Mir.

fr
Oil Bath
Temperature = 170 "C

4-5Sample
4J.44

^ ^
Dimensions in miilimeters (mm)

FIG. 31Illustration of the test cell for


the Indiana Stirring Oxidation Test
(ISOT).

[15] or 1 h at 40 kgf, 1500 rpm [8]. In both cases, the wear


scar at the completion of the test is measured. Matthews also
reported the weld load, which is a determination of the load
carrying (extreme pressure-EP) properties of the fluid using
Test Method IP 239. The weld-load is the lowest applied load,
in kilograms, under the conditions of the test at which the rotating ball welds to the three stationary balls, indicating that
the extreme - pressure level of the lubricant-force has been
exceeded. ASTM Test Method D 2783 can be used to determine the EP properties of a lubricant and it is conducted, after properly preparing the test machine, at the desired starting temperature: 18.33-35C (65-95F), 1760 40 rpm, and
a series of tests of 10 s duration are made at increasing loads
until welding occurs. This is called the "weld point."
FZG Visual Method (Test Method D 5182)This test method,
the Forschungstelle fiir Z a h n r a d e r u n d Getriebebau (Research Site for Gears and Transmissions) is commonly referred to as the FZG Visual Method. This method is intended
to measure the scuffing load capacity of oils used to lubricate
hardened steel gears. Scoring, is included as a failure criteria
in this test method. The FZG Gear Test Machine is operated
at a constant speed (1450 rpm) for a fixed period (21700 revolutionsapproximately 15 min) at successively increasing
loads until the failure criteria is reached. The initial oil tem100

Liquid Heptane
Wasiiing Test

then the plates are dipped into a bath of heptane for 5 s. After
ten dipping cycles, the steel plates are suspended in air to allow the h e p t a n e to evaporate and then the plates are
reweighed to determine the a m o u n t of oil film removed. An illustration of the relative weight loss of two different compressor oils subjected to this test is provided in Fig. 32 [8].
Antiwear

Properties

If possible, it is desirable to determine the lubrication properties of every compressor oil in every compressor. However,
in addition to being prohibitively expensive and requiring
enormous amounts of time, industrial equipment is not designed with the precision required for ideal laboratory test instruments. Therefore smaller scale lubrication testing is performed as a laboratory fluid development tool and while very
useful, these data must, at some point, be confirmed by infield testing in actual compressor units and processes where
the use of the fluid is contemplated. Although any test could
conceivably be used if properly correlated with compressor
operation, there are two bench tests that are encountered
most often in the published literature: FZG [23,32,35] and 4ball [8,15,25]. These tests will be discussed here.
4-BaU EP and Wear Test (Test Methods D 2783, D 4172 and IP
239)Test Method D 4172 is used to measure the relative
wear preventive properties of lubricating fluids under sliding
contact conditions using a Four-Ball EP and Wear Test Machine. Although Test Method D 4172 calls for test loads of 15
or 40 kgf at 1200 r p m and 75C, any load condition can be
used, if more appropriate. Some test conditions that have
been reported include: 1 h at 40 kgf, 1800 rpm and 54.4C

Cycles
FIG. 32Comparison of the liquid heptane
wash-off results for a 200 cSt PAG and a mineral
oil compressor lubricant.

CHAPTER 14: COMPRESSOR LUBRICANTS


perature is 90C beginning at load stage 4. The test gears are
examined initially and after the prescribed duration at each
load stage for cumulative damage (scuffing) to the gear tooth
flanks. Generally, it is expected that compressor fluids will
pass at least ten load stages in this test [32].
Compressor Tests^As with any machinery lubricant, the best
test is to evaluate it in the machine of interest. However, just
as bench tests do not necessarily correlate with machinery results, it is also true that performance in one machine does not
necessarily predict performance in a different m a c h i n e .
Matthews has reported the development of two compressor
tests where tests with different compressor fluids do seem to
correlate well with other compressors in the field. These two
tests will be outlined here, although they are not national or
international standard tests at this time.
Broomwade 2050H Compressor Rig Test [8]The Sebe (Compare) Broomwade 2050H is a single-stage, air-cooled, beltdriven, twin-piston air compressor that is mounted on an air
receiver tank as shown in Fig. 33. A gear p u m p is used to
splash-lubricate the bearings a n d cylinder walls using a
rapid, 825 rpm, crankcase movement in the sump. The operating conditions are summarized in Table 7.
The compressor rig was modified as follows:
1. The air discharge t e m p e r a t u r e is controlled by a miniether operating a magnetic on/off valve which regulates
the delivery pressure in response to a thermocouple located in the air outlet stream.
2. The discharged air is passed through an air-cooled heat exchanger to reduce the temperature to an acceptable level
during continuous operation.
Before each test is performed, the compressor is fitted with
new inlet and delivery valves, seals, gaskets, and filters and
the cylinder head is ultrasonically cleaned and solvent
washed between tests. The compressor is run continuously
with visual inspections at 100 h intervals. At the conclusion
of the test, the piston ring gap is measured in addition to the
visual inspection.
Reavell VHP 15 Compressor Rig Test [8]The Reavell VHP 15
is a 4-stage, single acting, air compressor that is driven by an
electric motor, illustrated in Fig. 34. The cylinder, V-form

403

compressor is mounted on the crankcase at 90. Multi-stage


water inter-coolers are filtered after each compression stage.
Each compression valve combines both suction and delivery.
The conventional trunk-type first and second stage pistons
utilize splash lubrication generated by the rotating (1450
rpm) crankshaft in the sump. The crossheads and guides for
the third and fourth stage pistons are lubricated separately
using a mechanical lubricator. The operating conditions are
summarized in Table 8 and Table 9.
The test stand was fitted with transducers to monitor the
inlet and outlet temperatures and pressures at each stage. A
water-flow control valve operated by a thermocouple located
in the air delivery stream at Stage 4 was used to control the
air delivery temperature. Over-pressure relief valves were
used on each stage to prevent overheating.
New valves were used for each test and seals replaced as
necessary. The compressor was run continuously with periodic inspection of the valves and cones. Valve removal should
not be performed since this process would disturb the accumulated carbon deposits that would falsely indicate an apparent increase in the lifetime of the lubricant. Therefore, the
valves should be left in position and the pressures and temperatures, which are continuously monitored, would be used
to indicate compressor malfunction that would typically be:
1. Lifting of the inter-stage relief valves that would be indicative of a leaking inlet valve.
2. Unacceptably low inter-stage delivery pressures that
would indicate a delivery valve failure.
3. Rapid rise in air delivery temperature indicating possible
internal combustion.
4. Very high oil consumption indicating worn piston rings.

TABLE 7Operating conditions for the Broomwade


2050H compressor.
Electric Motor Output

7.5 k W

Speed
Maximum oil deliveiy pressure
Oil capacity
Free air delivered
Air discharge temperature

825 rpm
10bar(150psig)
4.5 L
15.2L/sat lOOpsig

H.P. AIR DELIVERY (t')

MANUAL REGULATING
VALVE

CONDENSATE DRAIN

FIG. 33Schematic of the Broomwade 2050H compressor rig test.

300-325C

404

MANUAL 37; FUELS AND LUBRICANTS

HANDBOOK

<i>
LP AIR T O
ATMOSPHERE

<I>

C/W RETURN

"mERMOCOUPLE
(STAGE 4)

Sr^ ^-

RECIRCULAtORY
COOLING WATER - FLOW

H.P.AIR

<i>'

^-^

&

REAVELL VHP15
4 STAGE AIR
COMPRESSOR

10

LPAIR1. Non-retum valve


2. Pressure reHef
3. Manual blow-down
4. Over-pressure switch
5. Pressure-maintaining valve
6. Manual cooling water valve
7. Motorized cooling water valve
8. Temerature controller
9. Pressure storage vessel
10. Pressure storage vessel

DRIVE
MOTOR
22 Kw
CONDENSATE
DRAINS

FIG. 34Schematic of the Reavell VHP 15 compressor rig test.

Coalescer Blocking Tendency (CBT) Test [32]As discussed


earlier, compressor fluids are recycled through a rotary compressor, such as a rotary screw compressor. To this, the residual gas that is being compressed must be removed from the
compressor fluid before it can be sent back to the reservoir.
This is done using a coalescer for gas removal. During use,
compressor fluids will contain degradation by-products that
will adhere to or block the coalescer filter. This will create an
increase in differential pressure across the filter that may
lead to machine stoppage. Therefore, coalescer blocking tendency is an important parameter since it defines the useful
life of a compressor fluid in a compressor.
As indicated in Table 10 [32], although there are various
bench tests to evaluate fluid oxidation, carbon and sludging
tendencies, and filterability, no single test correlates well
with actual compressor usage. The best test still is a compressor test. One test developed by Mills, et al. will be outlined here [8,32].
The CBT test is conducted using an oil-flooded 22 kW (30
Hp) rotary screw compressor with a free air delivery rate of
42 L/s (93 ft^/min) was used. The specifications for the compressor are summarized in Table 11 [32].
The following modifications were made to the compressor
to construct the test stand illustrated in Fig. 35
1. Oil temperature was controlled by using a control system
that maintained the inlet oil temperature at 40-170C
2C.
2. The compressor's 5-10 micron air filter was proceeded by
two in-series foam air filters, each rated as 99.5 % efficient
at 5 microns. The purpose of this modification was to minimize the day-to-day variation in air dust on the severity of
the test.
3. An oil flow rate meter was placed in the oil feed circuit to
monitor oil flow rate and an oil removal filter was fitted to
the discharge air to give a maximum oil content of 0.01
ppm. The purpose of this modification was to minimize oil
carryover.

TABLE 8Operating conditions for the reavell VHP 15


air compressor.
Electric Motor Output

22 kW

Speed
Maximum delivery pressure
Free air delivery rate
Sump oil capacity 23.1 L

1450 r p m
350 b a r (5000 psig)
13.3 L/s

TABLE 9Stage temperatures and pressures.


Stage
Delivery pressure (bar)
Delivery temperature (C)

3.1
140

19.6
179

84.5
146

310
180

4. A high-resolution Bourdon gauge was used to monitor the


pressure differential across the coalescer.
5. The working discharge pressure of the compressor was established using a gate valve in the discharge main area.
6. The inlet oil temperature, air/oil outlet temperature, and
air delivery temperature of the compressor was continuously monitored on a chart recorder.
Before each test, the compressor was flushed using a flushing fluid of the same type being tested. (Mill called for using
a mineral oil compressor fluid but this would not be appropriate if it we not compatible with the fluid type being tested.)
The flushing conditions are; oil charge 22.5 L (6 gal), outlet
air pressure 690 1 5 kPa, inlet oil temperature 70 2C for
24 h. When the flushing is complete, the flushing fluid is
drained hot from the reclaimer, compressor unit, and oil
cooler for 15 min.
A new 85% masked coalescer and new oil filter are installed, the unit is charged with 22.5 L (6 gal) of the test fluid
and the soluble catalyst system. The catalyst system is 20 g
each of copper and iron as a naphthenate in a hydrocarbon
solvent. This will provide approximately 60 ppm of copper
and iron in the test fluid.

CHAPTER 14: COMPRESSOR LUBRICANTS


TABLE 10-Performance of commercial mineral oil-based compressor fluids in various bench tests.
Test l*"
Test 3'
Test 4''
% Viscosity
Filtration
Filtration
%
%
Carbon
Evaporation
Increase
TAN Increase
Time
Time
%
Residue
Loss
at 40C
(mg KOH/g)
Sludge
(min)
(min)
0.48
3.0
0.44
7.4
0.11
17.6
Blocked
0.40
0.25
Blocked
0.5
2.0
0.83
Blocked
Blocked
1.5
1.6
0.06
0.06
0.98
16
0.37
0.21
4.3
1.0
10.0
0.49
Blocked

405

Test 1

Compressor
Fluid
A
B
C
D

Field
Rating
(1 = Best)
3
4
1
2

"Test 1: DIN 51352 Fart 1 (PNEUROF Oxidation Test-Conradson carbon residue.


^Test 2: Modified DIN 51352-Same as Test 1 but 120C, 100 h with 50 ppm Fe catalyst as iron naphthenate.
''Test 3: Beaker Filtration test-300 mL oil, 120C, 168 h, filtered at ambient temperature through 47 mm diameter, 1.2 /xm Millipore filter under 88 kPa
(26 in. Hg) pressure.
''Beaker Filtration test-100 mL oil, 120C, 28 days,filteredas described for Test 3.

TABLE 11Specifications for compressor used for the


coalescer blocking tendency test.
Minimum 70 psi (5 bar)
Air Delivery Pressure
Normal 100 psi (7 bar)
Maximum 150 psi (10 bar)
Free Air Delivery
42 L/s (93 hVmin)
Unit 40 L (10.6 gal)
Oil Capacity (nominal)
Reclaimer 32 L (8.5 gal)
Compressor
Single stage, oil injected, asymmetric
screw
22 kW (30 Hp)
Motor
Compressor-Air/oil cooled
Cooling
Air Cooler-Thermostatically controlled
updraft fan
Inlet air 5-10 micron paper cartridge
Filters
Oil 15 micron paper cartridge
Coalescer 1-2 micron

Air Flow
ON Flow
Alr/OII Flow
Water Flow

5M
Air
Filter

The compressor is then started under the test conditions:


outlet air pressure 830 1 5 kPa, inlet oil temperature 100
2C until a pressure differential across the coalescer of 207 kPa
is obtained. At this point, the coalescer is defined as "blocked."
Every hour the coalescer pressure differential is measured
and recorded. Every 24 h, the compressor is shut down for
2-5 m i n for a 60 m L sample to be removed from the reclaimer. (A 100 m L presample is taken to flush the sampling
system.) The oil carryover filter bowl contents are measured
and discarded during the shut down period.
No attempt is made to top-off the compressor fluid since
losses should be very small. If the fluid level drops sufficiently
for air entrainment to occur (as indicated by the oscillating
outlet air pressure), or any other malfunction occurs in the

Differential
Pressure
Gauge

5-10 M
Air
Filter

Motor

Oil Cooler
Drain Valve
FIG. 35Schematic illustration of compressor test circuit used for coalescer blocking tendency test.

406

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

system, then the test is invalidated.


Gas Solubility into the
Lubricant
Knowledge of gas solubility is of vital importance when considering compressor lubrication. It is particularly important
in b o u n d a r y lubrication, where sudden release of the dissolved gas may cause lubricating film collapse or even cavitation. There are various tests that can be conducted for gas
solubility determination. These test procedures will be discussed here.
Gas Solubility in Petroleum Oils at Atmospheric Pressure (Test
Method D 2779)Tesi Method D 2779 may be used to estimate the solubility of several common gases in hydrocarbon
liquids. These include petroleum fractions with densities that
range from 0.63-0.90 at 288 K (59F). The solubihties can be
estimated over the temperature range of 228 K( 50F) to 423
K(302F). The test method is based on Henry's Gas Law and
the Perfect Gas Law. This test is conducted as follows:
Step 1Determine the density of the compressor fluid by
Test Method D 1298 if it is not already available.
Step 2Determine a value of "L" for the gas of interest at
the desired temperature from Fig. 36 if it is shown. If it is
not shown, then it may be calculated from the following
equation and the value of Lo taken from Table 12.

100

-SO

90

L = 0.300 exp
Where T =
for a liquid
273 K for a
ent density

o.639m;^

/H3.333LO

temperature in K, L = Ostwald coefficient at T


of density 0.85 and LQ = Ostwald coefficient at
liquid of density 0.85. For liquids with a differ(d), calculate Lc from:
L, = 7.70L (0.980 - d)

Where Lc = the Otswald coefficient at T for a liquid of the


specified density.
Step 4Calculate the Bunsen Coefficient (B) from:
B = 2697

(P-Pv)L

Where: P = pressure of the gas in Mpa, Py = vapor pressure


of the liquid at the specified temperature (T).
Step 5Calculate the solubility of the gas, which is sometimes expressed as part per million by weight, using the following equation:
1 - 0.000595

0.224

TEMPERATURE,-F
200
30O

100

tSO

200

eso

T E M P E R ATURE.'C

FIG. 36Solubility of gases in petroleum liquids witii a density


(d) = 0.85.

r - 288 - 2

CHAPTER
TABLE 12Ostwald coefficients at 0C for
petroleum liquids with d = 0.85.
Gas

Ostwald
Coefficient (LQ)

Helium
Neon
Hydrogen
Nitrogen
Air
Carbon monoxide
Oxygen
Argon
Methane
Krypton
Carbon dioxide
Ammonia
Xenon
Ethylene
Hydrogen sulfide

0.012
0.018
0.040
0.069
0.098
0.12
0.16
0.18
Use Fig. 36"
0.60
1.45"
1.7"
3.3
Use Fig. 36"
5.0"

// =

Estimation of Gas Solubility in Petroleum and Other Organic


Liquids (Test Method D 3827)This test method provides a
procedure for estimating the equilibrium solubility of several c o m m o n gases in petroleum oil and synthetic lubricants at temperatures between 0 and 488 K. This method is
limited to systems in which polarity and hydrogen bonding
are not strong enough to cause serious deviations from ideal
behavior. Specifically excluded are gases such as HCL, NH3
and SO2 and hydroxy liquids such as alcohols, glycols, and
water. Also the estimation of CO2 in non-hydrocarbons is
excluded.
The calculation procedure is as follows:
Step 1Determine the value of Si (solubility parameter of
the liquid in (Mpa)''^ by one of the following procedures:
a. Procedure 1If the liquid is a non-hydrocarbon, determine 5i from Table 13. If the fluid is not listed in Table
13 and the structure is known, use the method of Fedors
provided in Ref. 39.
b. Procedure 2If the liquid is a refined petroleum or a
synthetic hydrocarbon, then determine the density of
the fluid p by Test Method D 1218. If the fluid density p
is 0.885 g/mL or less, calculate 5i as follows:
Si = 12.03p + 7.36
c. Procedure 3If the liquid is a refined hydrocarbon or a
synthetic hydrocarbon with p = 0.886 or greater, or a
nonhydrocarbon of unknown structure, determine the
refractive index, nn, by Test Method D 1218 and calculate as follows:

IlD

B = 2697

Step 5For hydrocarbon oils, calculate the density of the


liquid at a specified temperature px as follows:
1 - 0.000595

r-288.2

Alternatively, the density may be determined experimentally by Test Method D 1298 or it may be obtained from the
fluid supplier. Another method of density temperature correction is to use the value dp/dT from Table 13 and calculate as follows:

MG

Where ML = the moles of liquid and Mo = the moles of gas.


Henry's Law constant (H) is calculated from:

407

Step 2Obtain the value of the equivalent solubility parameter of the gas, S2, (MPa)''^ from Table 14.
Step 3Calculate the Ostwald coefficient (L) for a lubricant from:
L = exp[(0.0395 (Si - 82)^ - 2.66) - 3.03Si
- 0.0241 (17.60 - 82^ + 5.731]
To calculate the Ostwald coefficient for a distillate fuel or
a halogenated liquid, multiply by the fuel factor from Table
14.
Step 4Calculate the Bunsen coefficient (B) as follows:

PT-

X= 10"

LUBRICANTS

Si = 8.63 2 + 0.96

''Do not use this method for these gases in highly


aromatic liquids

Where: 0.0224 is the molar volume at 273 K and 101.3 kPa


in liters/mole, and 0.000595 and 1.21 are the empirical constants for correcting d to a specified temperature, T.
Step 6Calculate the gas solubility as mole fraction from:

14: COMPRESSOR

p^ = p-(T-

288.2) - ^

Step 6Calculate the gas solubility G in mg/kg using the


value of M2, the molecular weight of the gas (g/mole), from
Table 14 and the following equation:
G = 44.6G^
Pi

Step 7Determine the value of the molecular weight of the


liquid. Ml, by:
a. For synthetic non-hydrocarbons, use the value of Mi
from Table 13, or calculate it directly.
b. The value of Mi for refined hydrocarbons or sjrnthetic
hydrocarbons may be determined experimentally using
Test Method D 2502.

TABLE 13Constants for synthetic hydrocarbons.


Compound

Di-2-ethylhexyl adipate
Di-2-ethylhexyl sebacate
Trimethylolpropane
pelargonate
Pentaerythritol caprate
Di-2-ethylhexyl phthalate
Diphenoxy diphenylene
ether
Diphenoxy triphenylene
ether
Polychlorotrifluroethylene
Polychlorotrifluroethylene
Polychlorotrifluroethylene
Dimethyl silicone
Methyl phenyl silicone
Perfluoro polyglycol
Tri-2-ethylhexyl phosphate
Tricresyl phosphate

S,

dp/dT

M,

18.05
17.94
18.48

370
427
459

0.928
0.916
0.962

0.00075
0.00073
0.00070

18.95
18.97
23.24

540
390
440

1.002
0.986
1.178

0.00065
0.00075
0.00079

23.67

520

1.205

0.00076

15.47
15.55
15.71
15.14
18.41
14.30
18.27
18.82

600
700
1000
10000
5000
1000
467
368

1.925
1.942
1.998
0.969
1.063
1.914
0.923
1.158

0.00166
0.00154
0.00152
0.00093
0.00080
0.00180
0.00090
0.00090

408

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 14Solubility parameters of gaseous solutes.


Gas

He
Ne
H2
N2

Air
CO
O2

Ar
CH4

Kr
CO2

M,

52 at 298 K

Fuel Factor

4
20
2
28
29
28
32
40
16
84
44

3.35
3.87
5.52
6.04
6.67
7.47
7.75
7.71
9.10
10.34
14.81

1.27
1.37
1.27
1.70
1.44
1.37
1.28
1.37
1.42
1.37
1.14

c. The value of Mi for non-hydrocarbons of u n k n o w n


structure may be determined experimentally using Test
Method D 2503.
7. Step 8Calculate the gas solubility as a mole fraction
from:
X= 10"

M2

8. Step 9Calculate Henry's Law constant (H) as:


(P - Pv)
H =
X
Experimental Determination of Gas Solubility in Liquids (Test
Method 2780)This procedure covers the experimental determination of the solubility of gases in liquids and is suitable
for gas/liquid mixtures that do not react with each other. This
method also permits the determination of the concentration
of gases in solutions that are not saturated with the gas.
In this test, the liquid is saturated with the gas of interest
under specified temperature and pressure conditions. (The
apparatus for ambient pressure is illustrated in Fig. 37 and
for gas solubility experiments conducted at elevated pressures, the apparatus illustrated in Fig. 38 is used.) If the objective is to determine gas concentration, the saturation step
is eliminated. A portion of the solution is then transferred to
a gas extraction apparatus shown in Fig. 39 where the gas is
quantitatively removed from the liquid. The separated gas is
transferred to a gas burette in which its volume is determined.
Viscosity of Gas/Liquid Mixtures Under PressureIt is not
only important to determine the solubility of a gas a compressor fluid, but it is also important to determine the impact
of dissolved gases on fluid viscosity. This is of particular importance in determining the lubricating ability of the compressor fluid during gas compression.
Measurement of viscosity of lubricants saturated with gas
at elevated pressures is done in a fixed volume apparatus.
Typically a Parr reactor (or other high-pressure autoclave)
equipped with a stirrer, pressure transducer, thermocouples,
and heating and cooling devices is used to conduct these experiments at desired temperatures. The vessel is fitted with a
viscosity measurement probe suitable for measurements at
high pressure. Viscosity probes that can operate u p to 5000
psia (340 Bars) are readily available. Viscosity and gas solubility data at a given temperature and pressure can be obtained from the same experiment.
The Parr reactor is charged with a known mass of lubricant

and gas at the desired temperature. Gas is typically transferred to the Parr reactor from a gas-charging vessel. The lubricant is stirred to obtain equilibrium as indicated by reaching a constant pressure. Viscosity of saturated lubricant at
final pressure is measured with a viscosity probe and it's associated electronics. Gas solubility can be calculated from
initial and final pressures using gas laws and compressibility
factors. It can also be obtained by weighing the gas-charging
vessel before and after equilibrium.
Absorption of the Lubricant into the Gas PhaseThis is the
test procedure published previously by Matthews, which was
performed to determine the amount of lubricant lost into the
gas being compressed [8]. The test is conducted by weighing
the test oil into a small aluminum container of about 25 m m
diameter which was then placed into a 50 mL stainless steel,
high pressure reactor which was then heated to 100C. The
test gas is then pressurized to 400 bar and fed through stainless steel tubing into the stainless steel reactor containing the
test oil. The pressure is maintained by releasing the gas
through a needle valve and the total volume of the gas being
discharged is metered. At the end of the test, the aluminum
container is re-weighed and the weight loss is recorded.
Heat Transfer

Efficiency

Thermal Conductivity (Test Method D 2717) and Specific Heat


(Test Method D 2766)These thermal conductivity and specific heat tests are difficult to carry out, facilities for performing them are few, and the precision data is yet to be es-

Gos Inlet

g.

>v

Gas Outlet

1000-ml Seporotory
Funnel (peor-shopedl
Control
ThecTnocouple

Test Liquid

Healing Mantle

Ts" \

,
Cos Dispersion
Element

PTFE Stopcock A

Boll Joint B
i 12/2
FIG. 37Schematic illustration of an ainblent pressure saturator.

CHAPTER

14: COMPRESSOR

LUBRICANTS

409

tablished. Values can be estimated for design use from the


general chemical composition. The VEilues for thermal conductivity and specific heat may be available from the fluid
supplier.

Pressure Goge

Tube Connection
A"

Elastomeric

Seals Compatibility

(Test Method

D 471)

Seals may degrade in use. As an oil deteriorates in service, additional tests may be required to assure that seals remain
compatible with the degraded oil. Mills et. al, have reported
the determination of seal compatibility by a short term test
by immersion of 50 m m X 25 m m X 2 m m test specimens of
the elastomer (most often a nitrile rubber) into the compressor fluid of interest at 120''C for 168 h [32]. Volume swell was
d e t e r m i n e d according to the procedures outlined in Test
Method D 471 and the hardness was determined according to
Test Method D 1415. The authors recommended setting the
volume swell limits at 5 to -1-15% and the change in hardness to -t-20%. Although an accelerated test may be performed, it is preferable that the temperature ranges of the
tests should correspond to temperatures to which seals will
be exposed in service and the tests should be conducted for at
least 1000 h.

Thermocouple

2500-ml
Stainless
Steel \fe$sel

Thermostotic
Control

Jacket

Paint Compatibility

; 12/2 Stoinless Steel


BaH Joint B
FIG. 38Schematic illustration of an elevated pressure saturator.

Test

[32]

Paints are used to protect metal surfaces of the compressor


components and machinery. However, they may be attacked
readily by the compressor fluid being used. The paint may
then be removed and become a contaminant in the fluid,
causing great damage. Therefore, it is important that the
paints that are used be compatible with the compressor fluid.
A simple test used to determine paint compatibility is to

To Condenser K
14/35

Solid Broce

stopcocks
L,M,N, ore
2-woy

'^E-0.5 mm Cleoronce
60mn(i 0.0.
SOmmO.D.

Lewting
Bulb
(Mercury)

Co pillory
Monometer
(Opin-Endl

(a)

Boiler-1

To Leveling
BulbH-

J 12/2
to Boiler I

FIG. 39Gas extraction system: A. schematic illustration of the entire apparatus and B: Illustration of the gas extraction chamber.

(b)

410

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

paint a small steel test specimen with the paint of interest and
let it dry [32]. The painted surface is then scratched in the
form of a cross and then immersed into the compressor fluid
at 120C for 168 h. If the paint is lifted or removed by the
fluid, it fails the test.

D 445

D 471
D 524

Filter Bowl Compatibility

Test

[32]

A filter bowl is used to retain the compressor fluid after it is


removed from the compressed gas by an absorbent filter. A
commonly reported field problem is that compressor fluid attacks the filter bowl, whcih is often constructed from a plastic such as polycarbonate. A simple test that is used by many
compressor manufacturers is to pressurize a filter bowl containing the compressor fluid being tested to 6900 kPa (100
psig). The test is considered to be a pass if the filter bowl does
not fail within 100 h.

D 664
D 665
D 892
D 943
D 972
D 974

SUMMARY
In this chapter, an overview of basic compressor fluid technology has been provided. This discussion included a description of the gas laws and how they applied to gas compression. Also provided was a short tutorial on how c o m m o n
types of compressors operate. This was followed by a summary of the properties of the most common classes of compressor fluids in current use in the market place. Finally,
there includes an extensive listing of various test procedures
that have been applied to the analysis of the expected performance of compressor fluids such as water content, oxidative
stability, carbon and sludge formation, gas solubility and lubrication properties.
However, it is must be realized that there is no one single
bench test that will best predict the performance of a particular compressor fluid, in a given compressor, in a given industrial process. This is illustrated in Table 10, which shows
that no one single test predicts the actual relative performance of a compressor fluid in an industrial process. It is
therefore recommended that groups of tests be performed
and overall ranking be used. Of course, whatever the bench
tests indicate, whether individually or collectively, final compressor machine performance validation is necessary.

ASTM STANDARDS
No.
D 91
D 92
D 95
D 97
D 130

D 189
D 287

Title
Test Method for Precipitation Number of Lubricating Oils
Test Method for Flash and Fire Points by Cleveland Open Cup
Test Method for Water in Petroleum Products and
Bituminous Materials by Distillation
Test Method for Pour Point of Petroleum Products
Test Method for Determination of Copper Corrosion from Petroleum Products by the Copper
Strip Tarnish Test
Test Method for Conradson Carbon Residue of
Petroleum Products
Test Method for API Gravity of Crude Petroleum
and Petroleum Products (Hydrometer Method)

D 1298

D 1401
A 1415
D 1744
D 2270
D 2272
D 2502

D 2503

D 2619
D 2711
D 2717
D 2766
D 2779
D 2780
D 2783

D 3427
D 3827
D 4007

D 4172
D 4530

Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (the Calculation of Dynamic Viscosity)
Test Method for Rubber Property-Effect of Liquids
Test Method for Ramsbottom Carbon Residue of
Petroleum Products
Test Method for Acid N u m b e r of Petroleum Products by Potentiometric Titration
Test Method of Rust-Preventing Characteristics
of Inhibited Mineral Oil in the Presence of Water
Test Method for Foaming Characteristics of Lubricating Oils
Test Method for Oxidation Characteristics of Inhibited Mineral Oils
Test Method for Evaporation Loss of Lubricating
Greases and Oils
Test Method for Acid and Base Number by ColorIndicator Titration
Test Method for Density, Relative Density (Specific Gravity), or API Gravity of Crude Petroleum
Products by Hydrometer Method
Test Method for Water Separability of Petroleum
Oils and Synthetic Fuels
Test Method for Rubber Property-International
Hardness
Test Method for Determination of Water in Liquid Petroleum Products by Karl Fischer Reagent
Practice for Calculating Viscosity Index from
Kinematic Viscosity at 40C and 100C
Test Method for Oxidation Stability of Steam Turbine Oils by Rotating Pressure Vessel
Test Method for Estimation of Molecular Weight
(Relative Molecular Mass) of Petroleum Oils from
Viscosity Measurements
Test Method for Relative Molecular Mass (Molecular Weight) of Hydrocarbons by Thermoelectric
Measurement of Vapor Pressure
Test Method for Hydrolytic Stability of Hydraulic
Fluids (Beverage Bottle Method)
Test Method for Demulsibity Characteristics of
Lubricating Oils
Test Method for Thermal Conductivity of Liquids
Test Method for Specific Heat of Liquids and
Solids
Test Method for Estimation of Solubility of Gases
in Petroleum Liquids
Test Method for Solubility of Fixed Gases in Liquids
Test Method for Measurement of Extreme-Pressure Properties of Lubricating Fluids (Four-Ball
Method)
Test Method for Air Release of Petroleum Oils
Test Method for Estimation of Solubility of Gases
in Petroleum and Other Organic Liquids
Test Method for Water and Sediment in Crude Oil
by the Centrifuge Method (Laboratory Procedure)
Test Method for Wear Preventive Cheiracteristics
of Lubricating Fluid (Four-Ball Method)
Test Method for Determination of Carbon
Residue (Micro Method)

CHAPTER 14: COMPRESSOR LUBRICANTS


D 5182
D 5800
D 6375

E 659

T e s t M e t h o d for E v a l u a t i n g t h e Scuffing L o a d Cap a c i t y of Oils ( F Z G V i s u a l M e t h o d )


T e s t M e t h o d for E v a p o r a t i o n L o s s of L u b r i c a t i n g
Oils b y t h e N o a c k M e t h o d
T e s t M e t h o d f o r E v a p o r a t i o n L o s s of L u b r i c a t i n g
O i l s b y T h e r m o g r a v i m e t r i c A n a l y z e r (TGA)
Noack Method
T e s t M e t h o d f o r A u t o i g n i t i o n T e m p e r a t u r e of
Liquid Chemicals

OTHER STANDARDS
No.
DIN 51352

DIN 51352

IP 239

ISO 5388
I S O 6743-3A

JIS K 2514

Title
P a r t 1 D e t e r m i n a t i o n of A g i n g C h a r a c t e r i s t i c s
of L u b r i c a t i n g O i l s . I n c r e a s e i n C o n r a d s o n
c a r b o n residue after aging by passing air
t h r o u g h t h e l u b r i c a t i n g oil.
P a r t 2 D e t e r m i n a t i o n of A g i n g C h a r a c t e r i s t i c s
of L u b r i c a t i n g O i l s . I n c r e a s e i n C o n r a d s o n
c a r b o n residue after aging by passing air
t h r o u g h t h e l u b r i c a t i n g oil i n t h e p r e s e n c e of
iron(III) oxide.
D e t e r m i n a t i o n of E x t r e m e P r e s s u r e a n d Antiw e a r P r o p e r t i e s of L u b r i c a n t s - F o u r Ball M a chine Method
Stationary air compressors-Safety rules a n d
c o d e of p r a c t i c e
L u b r i c a n t s , i n d u s t r i a l oils, a n d r e l a t e d p r o d u c t s (Class L ) - C l a s s i f i c a t i o n - P a r t 3A: F a m i l y
D (Compressors)
T e s t i n g M e t h o d of O x i d a t i o n C h a r a c t e r i s t i c s
of E n g i n e Oils

REFERENCES
[1] Lilje, K. C , Short G. D., and Miller, J. W., "Compressors and
Pumps," Ch. 4, Synthetic Lubricants and
High-Performance
Functional Fluids, 2"'' ed., L. R. Rudnick and R. L. Shubkin,
Eds., Marcel Dekker Inc., NY, 1999, pp. 539-558.
[2] Patzau S. and Szchawnicka, E., "Oils for Air and Technical Gas
Compressors," Trybologia, Vol. 20, No. 4, 1989, pp. 18-21.
[3] Scales, W., "Air Compressor Lubrication," Ch. 19, Tribology
Data Handbook, E. R. Booser, Ed., CRC Press, Boca Raton, FL,
1997, pp. 242-247.
[4] Bloch, H. P., A Practical Guide to Compressor Technology, McGraw-Hill Inc., NY, 1996.
[5] "Unit Course 2-For Natural Gas Compressors-Considerations
for Sizing a Reciprocating Gas Compressor Package," Weatherford Compression, Corpus Christi, TX.
[6] Istvan, V., "Interplant Tests of Chemical Plant Lubricants: - Part
2-Compressor Oils and Heating System Oils and Their Application: Grease Lubrication," Magyar Kemikasok Lapja, Vol. 53,
No. 3, 1998, pp. 139-144.
[7] "Unit Course 1-For Natural Gas Compressors-An Introduction
to the Basic Function and Components of a Gas Compressor
Package," Weatherford Compression, Corpus Christi, TX.
[8] Matthews, P. H. D., "Lubrication of Reciprocating Compressors," Journal of Synthetic Lubricants, Vol. 6, No. 4, 1990, pp.
292-317.
[9] Wills, J. G., "Compressors," Ch. 14, Lubrication
Fundamentals,
Marcel Dekker, Inc., NY, 1980, pp. 365-394.

411

[10] Short, G. D., "Development of Synthetic Lubricants for Extended Life in Rotary-Screw Compressors," Lubrication Engineering, Vol. 40, No. 8, 1983, pp. 463-470.
[11] Carswell, R., McGraw, P. W., and Ward, E. L., "A Blend of a
Polyglycol and a Trtra Ester as a Lubricant for Rotary Screw Air
Compressors," Lubrication Engineering, Vol. 39, No. 11, 1982,
pp. 684-689.
[12] Miller, J. W., "Synthetic and HVI Compressor Lubricants," Journal of Synthetic Lubricants, Vol. 6, No. 2, 1989, pp. 107-122.
[13] Kist, K. R. and Doperalski, E . J . "Brief Introduction to the Screw
Compressor," Paper 68E, AIChE 8 6 * National Meeting, 1979.
[14] Tolfa, J. C , "Synthetic Lubricants Suitable for Use in Process
and Hydrocarbon Gas Compressors," Lubrication
Engineering,
Vol. 47, No. 4, 1990, pp. 289-295.
[15] Cohen, S. C , "Development of a "Synthetic" Compressor Oil
Based on Two-Stage Hydrotreated Petroleum Basestocks," Lubrication Engineering, Vol. 44, No. 3, 1987, pp. 230-238.
[16] Kajdas, C , "Industrial Lubricants," Ch. 8, Chemistry and Technology of Lubricants, 1992, pp. 196-222.
[17] Arbocus, G., "Synthetic Compressor Lubricants-State of the
Art," Lubrication Engineering, Vol. 34, No. 7, 1977, pp. 372-374.
[18] Chen, C.-I., "Typical Lubricating Oil Properties," Tribology Data
Book, E. R. Booser, Ed. CRC Press, Boca Raton, FL, 1997, pp. 333.
[19] Miller, J. W., "Synthetic Lubricants and their Industrial Applications," Journal of Synthetic Lubricants, Vol. 1, No. 2, 1984, pp.
136-152.
[20] Klamann, D., Ullmann's Encyclopedia of Industrial
Chemistry,
5"" ed.. Vol. A15, VCH Verlagsges mbH, 1990, pp. 423-518.
[21] Randies, S. J., "Esters," Ch. 3, Synthetic Lubricants and HighPerformance Functional Fluids, 2"^ ed., L. R. Rudnick and R. L.
Shubkin, Eds., Marcel Dekker Inc., NY, 1999, pp. 63-102
[22] Sugiura, K., Miyagawa, T. and Nakano, H., "Laboratory Evaluation and Field Performance of Oil-Flooded Rotary Compressor
Oils," Lubrication Engineering, Vol. 38, No. 8, 1982, pp. 510518.
[23] Matthews, P. H. D., Walkden, R. H., and Williams, G. C , "Current and Future Developments of Lubricants for Industrial Air
Compressors," Paper N u m b e r C477/023/94, ImechE Conference, Proceedings of the Institute of Mechanical Engineers, 1994,
pp. 175-183.
[24] Van Ormer, H. P., "Trim Compressed Air Cost with Synthetic
Lubricants," Power, 1987, pp. 43-45.
[25] Miller, J. W., "New Synthetic Food-Grade Rotary-Screw Compressor Lubricant," Lubrication Engineering, Vol. 40, No. 7,
1983, pp. 433-436.
[26] Takashima, H., "Gas Compressor Oils," Toraiborojisuto, Vol. 38,
1993, pp. 135-139.
[27] Hampson, D. F. G., "Reducing the Risk of Fires in Large Reciprocating Air Compressor Systems," Wear, Vol. 34, 1975, pp. 399407.
[28] McCoy, C. S. and Hanly, F. J. "Fire-Resistant Lubes Reduce
Danger of Refinery Explosions," The Oil and Gas Journal,
November 10, 1975, pp. 191-197.
[29] Garg, D. R., "Polyalkylene Glycol-Based Compressor Lubricants," presented at the Sixth Annual Reciprocating Compressor
Conference, Salt Lake City, UT, 23-26 Sept. 1991.
[30] Oberle J. and Rajewski, T., "The Development of Lubricants for
Ammonia Refrigeration Systems," presented at the 11AR 19'*'
Annual Meeting, 23-26 March 1997, New Orleans, LA.
[31] Whiting, R., "Monitoring Energy Savings of Diester Compressor
Oils," 6 * International Colloquium, Technische Akademie Essligen, 1998, pp. 14.41-14.43.
[32] Mills, A. J., Tempest, M. A., and Thomas, A. S., "Performance
Testing of Rotary Screw Air Compressor Fluids in Europe," Lubrication Engineering, Vol. 42, No. 5, 1986, pp. 278-286.
[33] Blackwell, J. W., BuUen, J. V., and Shubkin, R. L., "Current and
, Future Polyalphaolefins," Proceedings of the Conference on Syn-

412 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


thetic Lubricants, A. Zakar, Ed., Hungarian Hydrocarbon Institute, Szazhalombatta, Hungary, 1989, p p . 36-68.
[34] Witts, J. J., "Diester Compressor Lubricants in Petroleum and
Chemical Plant Service," Journal of Synthetic Lubricants, Vol. 5,
No. 4, 1989, pp. 319-326.
[35] Legeron J-P. and Beslin, L., "Rotary-Vane Compressors: Some
Technical Aspects for Long-Life Lubricants," Journal of Synthetic Lubrication, Vol. 6, No. 4, 1990, pp. 299-309.
[36] Totten, G. E., Bates, C. E., and Clinton, N. A., "Quench Bath
Maintenance," Ch. 6, Handbook of Quenchants and Quenching

Technology, ASM International, Materials Park, OH, 1993, pp.


191-238.
[37] Mang T. and Jiinemann, H., "Erdol kohle-Erdgas-Petrochem,"
vemeigt Brennstoff-Cheniie, Vol. 25, No. 8, 1972, pp. 459-464.
[38] Rounds, F. G., "Coking Tendencies of Lubricating Oils," Paper
570097, Presented at the SAE National Fuels and Lubricants
Meeting, Cleveland, OH, 1957.
[39] Fedors, R. F. "A Method for Estimating Both the Solubility Parameter and Molar Volume of Liquids," Polymer Engineering
and Science, Vol. 14, 1974, p. 147.

MNL37-EB/Jun. 2003

Refrigeration LubricantsProperties and Applications


H. Harvey Michels^'^ and Tobias H. Sienel^

additives have been developed to improve the properties of a


lubricant [7]. These include acid neutralizers, extreme pressure (EP) agents (for startup and compressor break-in operation), and anti-oxidants. The diminishing use of chlorinated
refrigerants such as CCI3F, CCI2F2, and CHCIF2, mandated by
the Montreal Protocol of 1987 to help reduce ozone depletion
in the atmosphere, has put new requirements on refrigerant
lubricants. The intrinsic lubricity characteristics of chlorinated refrigerant molecules are not found in the newer replacement refrigerants, such as the hydrofluorocarbons
(HFCs). Further, many of the newer lubricants that have
been formulated to be compatible with HFCs exhibit lubrication cheiracteristics that differ from the older mineral oils, especially in mixtures with HFC refrigerants. Such lubricants
often depend heavily on additive properties to improve lubricity and anti-wear characteristics.

T H E PRIMARY FUNCTION OF A LUBRICANT IS TO REDUCE FRICTIONAL

LOSSES. This is achieved by interposing a film between the


moving sohd surfaces that reduces or ehminates direct sohd
to sohd contact [1]. In h y d r o d y n a m i c lubrication (HD),
where contact surfaces conform geometrically, only the lubricant viscosity governs friction and lubricant film thickness
[2]. In this region, which is typical of many bearing and piston surfaces, the contact surfaces are completely separated
by the lubricant film and nominal contact pressures are low
(<50 MPa). The lubricant film thickness varies with the same
dependence on operating parameters, such as speed, shear
rate, and applied force, as the viscosity for this region. This
makes the correct choice of lubricant viscosity become an
important issue in the HD region. Low viscosity may lead to
solid contact, while too high viscosity leads to an increase in
frictional losses resulting in increased motor loading a n d
higher p o w e r c o n s u m p t i o n . In regions of elastohydrodyn a m i c lubrication (EHD), such as bearings or gears with
high-pressure loadings, additional lubricant properties such
as the pressure-viscosity coefficient and limiting shear stress
come into play [3,4]. Temperature plays a critical role in both
the HD and EHD regions because of its strong effect on the
viscosity of a lubricant. In typical air conditioning (A/C) or refrigeration systems, both of these regions of lubrication may
be encountered. The m a x i m u m pressure attained in a refrigeration system can be as high as 2.5 GPa, indicating operation well into fully developed elastohydrodynamic or boundary lubrication regions. Here, the thermophysical properties
of the lubricant that become important are molecular conformability and resistance to physical degradation [5].

The proper choice of refrigerant lubricant also depends on


the design of the A/C or refrigeration system and the choice
of compressor. Since the compressor and evaporator are usually at the coldest region of the refrigeration system, migration of the refrigerant to these parts of the system during
shutdown can cause dilution of the lubricant, resulting in a
large decrease in solution viscosity. Several compressor designs have significant storage of lubricant in the sump region,
thereby making the dilution of the lubricant from the condensed refrigerant a major start-up issue. This is often addressed by adding a strip heater and associated controls to
boil off the more volatile refrigerant before starting the compressor cycle. Alternatively, additives are added to the lubricant to prevent direct metal to metal contact during start-up
with a reduced viscosity lubricant/refrigerant mixture.

Secondary functions of a lubricant include: the transfer of


heat from one region to another; to act as sealants, especially
in pressurized systems; to protect surfaces from corrosion;
and to capture and suspend system debris. Refrigerant lubricants often require compatibility with the system refrigerant
in terms of solubility, miscibility, and chemical stability [6].
The solubility issue of lubricants with refrigerants is especially critical since dilution of the lubricant results is a
dramatic reduction in the solution viscosity and a parallel reduction in the lubricant film thickness and lubrication properties. These characteristics have brought about a complex
array of lubricants designed for specific system requirements, including the operating ranges of temperature and
pressure, and the duty cycle. In addition, many chemical

A further consideration for proper choice of lubricant depends on whether the system is of the hermetically sealed
type, such as that found in window rack or other portable A/C
installations, or is designed to be serviced periodically, such
as outdoor residential and commercial units. In hermetically
sealed systems, the motor windings are exposed to the refrigerant/lubricant mixture. This mixture must have both good
electric insulating properties a n d chemical compatibility
with seals, materials of construction, and residual contaminants. A hermetically sealed system is charged with refrigerant and lubricant and sealed only once, with an expected
maintenance-free life of fifteen years or more. The older lubricants, such as mineral oil or synthetic alkylbenzene formulations, were mainly non-polar and did not dissolve and
hold significant amounts of residual materials of construction, assembly cleaning solvents, and the like in suspension.
The solubility of such compounds is much higher in many of

^ United Teciinologies Research Center, East Hartford, CT 06108.


^ Present address: Physics Department, University of Connecticut,
Storrs, CT 06269.

413
Copyright'

2003 by A S I M International

www.astm.org

414

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

the newer polar lubricants, such as the polyolesters. Further,


the polar nature of several of the newer lubricants results in
a hygroscopic characteristic whereby any residual water in
the system is dissolved in the lubricant as well as carried
about the system in the circulating vapor. This can permit insoluble residues to form, especially in additized lubricants,
which then deposit in capillary tubes or other expansion devices, causing plugging and loss of performance [8]. In systems with service ports, a change of lubricant is possible after compressor break-in, which allows removal of insoluble
system debris. In hermetically sealed systems, this residue
problem must be addressed in the original system design.
Complex lubricant additive packages and the use of filter driers to remove excess water and trap insoluble deposits are
among current solutions being tested.
A separate characteristic of refrigerant/lubricant mixtures
that m u s t be considered is their foaming tendency. With
most of the older chlorofluorocarbon/mineral oil mixtures, a
dense, slowly collapsing foam is generated in the compressor,
leading to good noise suppression and little carry-over to the
condenser. The newer more polar refrigerant/lubricant mixtures exhibit rapidly collapsing foam characterized by initial
large bubble formation. Such mixtures are less effective in lubrication of inlet ports in compressors and can result in excessive lubricant carry-over out of the compressor during
start-up. Lubricant manufacturers often add small amounts
of compounds, such as the polysiloxanes, that modify the
mixture surface tension. The chemical stability and longterm behavior of these compounds are not well known.
In addition to the chemical stability characteristics of refrigerant lubricants, there are equipment design and operational issues associated with the choice of lubricants for use
with the newer hydrofluorocarbon refrigerant blends, such
as R-410A, R-407C, and R-404A. The standard notation for
single component refrigerants and refrigerant blends is given
in ANSI/ASHRAE 34-2001. The designations are a function of
the refrigerant atomic composition and, for blends, are chosen as ASHRAE industry standards. Miscible lubricants dissolve in the refrigerant and are circulated to a small extent
throughout the system, returning to the compressor by either
gravity or the drag force of the circulating refrigerant. Several of the new refrigerant blends, such as R-407C, exhibit
fractionation owing to the different volatilities of the components of the blend [9,10]. The solubility characteristics of a
lubricant may therefore be different in a compressor sump
than in the evaporator or condenser. Regions of limited lubricant miscibility may therefore be encountered in the evaporator, for example, resulting in lubricant holdup and insufficient oil r e t u r n to the compressor. The required vapor
velocity to insure good lubricant return can usually be obtained by proper sizing of the return lines [11]. For cooling
mode operation, typical of an air conditioner (A/C), the worst
lubricant return conditions are likely to be at the evaporator
exit, where the vapor refrigerant line feeds into the accumulator. For heat p u m p operation, the worst lubricant circulation condition is usually found in the vapor line leaving the
compressor, where the evaporator now serves as the system
condenser. These equipment design issues associated with
proper lubricant circulation and the elimination of excess
holdup have been the subjects of several recent experimental
studies.

Very recently, the use of immiscible lubricants, such as mineral oils, in systems using hydrofluorocarbon refrigerants, has
been the subject of renewed discussion in the Heating, Ventilation, and Air Conditioning, (HVAC) and refrigeration industry. The initial decision of the HVAC industry to use
polyalkylene glycol (FAG) and polyolester (POE) lubricants in
conjunction with the new hydrofluorocarbon refrigerants was
based on the assumption that high mutual solubility and miscibility between a lubricant and refrigerant were required for
proper lubricant circulation and compressor operation. Thus,
lubricants such as POEs were chosen because their polar
characteristics are similar to hydrofluorocarbons, resulting in
good mutual solubility and an assumed system behavior similar to the older hydrochlorocarbon and mineral oil mixtures.
Recent lubricant circulation studies have shown, however,
that except for low temperature refrigeration applications,
immiscible lubricant (alkyl based)/refrigerant mixtures can
be used in systems where return lines have been properly
sized [12,13]. The potential for significant cost reductions due
to the use of lower cost lubricants, such as mineral oils, rather
than the more expensive synthetic lubricants, has generated
renewed interest from HVAC system manufacturers. However, there are many issues associated with proper lubricant
circulation, mixture chemical stability, and compressor lubrication that must be addressed before there will likely be a
significant industry movement toward the use of immiscible
lubricant/refrigerant mixtures.
In the sections below, the properties of mineral oil based
and synthetic refrigerant lubricants will be described. These
lubricants differ in their chemical stability, solubility characteristics in different hydrohalocarbons, and viscosity and lubricity properties. There is extensive literature on the natural
mineral oil based lubricants [14,15]. This review will focus
more on the properties of the newer synthetic lubricant structures. The critical system issues such as oil holdup and compressor compatibility are also reviewed.

CHEMICAL STRUCTURE OF
REFRIGERANT LUBRICANTS
Mineral oil based lubricants used in refrigeration are generally of three types: paraffinic, which consist of both straight
and branch chain saturated hydrocarbons; napthenic, which
are saturated hydrocarbons that mainly consist of cyclic or
ring structures; and aromatics, which are comprised mainly
of unsaturated cyclic hydrocarbons. Typically, the crude oil
sources from which these lubricants are distilled and refined
contain a mixture of these mineral oil types. For this reason,
it is c o m m o n to identify mineral oils in terms of the number
of carbon atoms associated with each of the structures, paraffinic (Cp), napthenic (CN), and aromatic (NA): the carbon-type
composition is usually expressed in terms of weight percent.
Since this type of identification requires a time consuming
laboratory analysis, more qualitative methods of analysis
based on refractive index and photoabsorption have been introduced and standardized as ASTM D 2140, ASTM D 2549,
and ASTM D 2008. In general, paraffinic oils have a higher
percentage of paraffin wax (saturated straight chain
molecules) than napthenic oils, which results in high pour
points (ASTM D 97), the temperature at which the oil will flow

CHAPTER

15: REFRIGERATION

LUBRICANTSPROPERTIES

AND APPLICATIONS

415

TABLE 1Typical properties of refrigerant lubricants.


Mineral Oil
Property

Naphthenic

Parafflnic

0.92
33
12

Density @ 15C (g/cc)


Viscosity @ 40C (cSt)
Viscosity Index
Pressure Viscosity
Coefficient @ 6 0 X (GPa"')
Average Molecular Weight
Pour Point (C)
Flash Point (C)
Lower Critical
Solution Temperature
withR-134aorR-22'"(X)

0.86
34
95

25
300
-43
170

30
378
-18
200
52*

0*

Alkylbenzene

0.87
32
27
25
320
-46
178
-70*

Polyalkylene
Glycol

0.99
30
210
14
750
-46
200

Polyolester

Polyvinylether

0.97
30
90

0.92
30
69

15-18
500-600
-48
234

20
500-600
-45
212

<34

S50

" Solutions witli mineral oil or alkylbezene.

CH3

CH3

I
CH3 CH CH2 - C -

I
CH3

I
/ ^

[CHCH2]CH CH3

'
CH3
n = 2-5 branched alkyl groups

CH3 - CH - CH2
I
[CHd^
I
CH3

CH - CH2 - CH2
I
I
[CHz]^
[CHj],
I
I
CH3
CH3

FIG. 1Structure of a commercial branched


chain alkylbenzene.

FIG. 2Structure of an oligomer of 1decene.

under gravity at prescribed conditions. Parafflnic oils, however, exhibit a m u c h higher viscosity index (ASTM D 2270) a
measure of the viscosity change with temperature, t h a n
napthenic oils. Owing to concerns about expansion valve and
capillary line plugging, and oil trapping in evaporators, typical mineral oil formulations that have been in use in refrigeration have low wax content. Mineral oils are formulated in a
fixed range of viscosity by adjusting the refining process. Specific system requirements, such as high resistance to oxidation, are mainly addressed by the use of additives.
Synthetic lubricants are produced by chemically combining
base stock hydrocarbon components in fixed proportions to
form a mixture with the desired lubrication characteristics.
Unlike mineral oils, which may consist of hundreds of different hydrocarbon molecules and whose composition varies
with the source of the crude oil, synthetic lubricants are tailored from a small number of different molecular weight starting components that are reacted to yield a final mixture of
compounds with the desired viscosity properties. These manmade lubricants can be classified by the type of base stock used
in their manufacture. The following synthetic types are commonly used in A/C and refrigeration systems: alkylbenzenes,
olefin oligomers (poly-a olefins), dibasic acid esters, polyolesters, and polyalkylene glycols [16,18]. Other synthetic lubricants such as the phosphate esters, silicones, monocarbonates, and fludrocarbon lubricants have not met with wide
usage due either to their poor thermal stability, their viscosity
and/or solubility characteristics with refrigerants, or their high
cost of manufacture. Typical properties for several of the comm o n refrigerant lubricants are given in Table 1.

group can be either a straight chain or branched chain paraffin, usually containing 10-20 carbon atoms. A typical structure of a commonly used branched chain alkylbenzene is
shown in Fig. 1.
Alkylbenzenes have excellent low temperature fluidity and
low pour points. Their viscosity indexes are somewhat lower
than those of typical mineral oils. They are stable against
oxidation, high temperature decomposition, and hydrolysis,
and are completely compatible with mineral oils [19]. Alkylbenzenes have found widespread use with refrigerant systems using R-22 and R-502, but have had limited use to date
with hydrofluorocarbon refrigerants owing to their immiscibility with these more polar molecules. However, since alkylbenzenes are man-made compounds, there have been several
recent studies directed toward changing the typical balance
of low, intermediate, and high molecular weight compounds
that are formed in the synthesis process [12,13]. If the percentage of high molecular weight components could be kept
low, the resulting alkylbenzene blend may have sufficient
fluidity to be carried by the vapor stream back to the compressor with m i n i m u m holdup in the evaporator, for example. These newer alkylbenzene formulations are sometimes
referred to as hard alkylbenzene lubricants (HAB). They are
currently under evaluation for use in hydrofluorocarbon systems using rotary compressors, where vane wear is a serious
issue with several of the synthetic lubricants.

Alkylbenzene (AB)
These synthesized hydrocarbon molecules are formed by the
alkylation of an aromatic compound, usually benzene, in the
presence of a catalyst such as aluminum chloride. The alkyl

Poly-a Olefins (PAO)


These compounds are formed by combining a low molecular
weight unsaturated material, such as ethylene, into a specific
olefin. The olefin structure is then polymerized to form a
branched hydrocarbon structure, usually consisting of three
or more repeating units. An example of this type of comp o u n d is shown in Fig. 2; it is formed by the polymerization
of the olefin 1-decene.

416

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK
thesized that exhibit similar physical properties [23]. These
polybasic esters have tetrahedral character about a central
carbon atom, similar to several of the polyolesters. They can
be formed by the reaction of acrylate esters with malonate esters to form, for example, estrs of 1,3,3,5-pentanetetracarboxylic acid. Dibasic esters are used in the formulation of
sjTithetic automotive lubricants and in jet engine oils. They
are not highly miscible with the new hydrofluorocarbon refrigerants but their use in some refrigeration systems has
been reported. However, this class of synthetic lubricants has
not yet found widespread usage in new A/C and refrigeration
systems.

Poly-a olefins are similar to paraffinic mineral oils but


since they are m a n - m a d e , their c o m p o n e n t structure and
composition are reproducible. By varying the pendant chain
lengths and degree of branching, different viscosity formulations can be achieved. These compounds exhibit very high
viscosity indexes and low pour points resulting in good low
temperature fluidity [20]. They are often used in the formulation of synthetic automotive lubricants. Poly-a olefins have
excellent thermal and oxidative stability and are compatible
with mineral oils. They have found use in severe service refrigeration systems that employ screw compressors, using R22 as the refrigerant, and in ammonia systems. Like mineral
oils, they exhibit good miscibility with several chlorofluorocarbons, such as R-12, but the use of this class of refrigerants
is phasing out u n d e r the Montreal protocol. Poly-a olefins
have limited miscibility in both R-22 and ammonia and typically are not used in light service A/C or refrigeration applications [21]. They are immiscible in hydrofluorocarbons due
to their non-polar nature.

Polyolesters (POE)
Polyolesters are the condensation product of an alcohol with
two or more hydroxyl groups (polyhydric alcohol or polyol),
and a monobasic (carboxylic) acid. In these structures, the
carboxylic acid links to all available hydroxyls in the polyol,
splitting off water molecules at each linkage. A typical polyolester is shown in Fig. 4.
Similar to the dibasic esters, the polyolester structure can
be varied by changing the carboxylic acid and by the use of
one or more polyols [22]. Typically, neopentyl glycol, pentaerythritol, and dipentaerythritol are chosen as the polyols.
Dipentaerythritol is used mainly to form polyolesters of
higher viscosity but is typically found as a significant (12%)
by-product in commercial grades of pentaerythritol. Upon esterfication with a carboxylic acid, the result is a compound of
high molecular weight and high viscosity. Such compounds
are desired for high viscosity lubricant formulations but can
lead to plugging and waxing in certain low temperature systems. Generally, pentaerythritol is reacted with two or more
carboxylic acids to form an ester mixture with desired properties. Owing to the tetra-hydroxy structure of pentaerythritol, the use of two carboxylic acids results in the formation of
five different esters. The number of possible esters increases
rapidly if more carboxylic acids (or alcohols) are used resulting in complex chemical mixtures of the possible esters.

Dibasic Acid Esters (Diesters)


This class of molecules is formed by combining a dibasic
acid, such as adipic acid, with an alcohol that contains only
one reactive hydroxyl group. The esterfication process joins
the alcohols at the end of the dibasic acid, splitting off two
water molecules to form the final ester compound [16,22]. An
example of this type of ester molecule is shown in Fig. 3.
Dibasic acid esters typically have very low pour points and
excellent low temperature fluidity. Their viscosity indexes are
tjTjically lower than poly-a olefins and they exhibit good thermal and oxidative stability. As with most ester structures,
they exhibit a lower hydrolytic stability t h a n mineral oils
since the double bonded oxygens have an affinity to hydrogen
bond with water molecules. The viscosity of dibasic ester lubricants is determined by both the dibasic acid chain length
and the type of alcohol employed in the esterfication process.
A wide range of viscosities is possible by changes in the acid
and alcohol structures. Polybasic esters have also been syn-

O
CH3 [CH2]3 CH CH2

O -

C -

O
[CH2]4 -

C -

0 -

CH2 - C H

[CHzls - C H 3

I
CH2

CH2

CH3

CH3

FIG. 3dibasic acid ester of adipic acid and 2-ethyihexanoi.

O
CH3 -

(CH2)4 -

C -

O
O -

CH2 ^

CH2 -

O -

C -

(CH2)4 -

CH3

CH2 -

O -

C -

(CH2)4 -

CH3

c
CH3 -

(CH2)4 -

C -

O -

CH2 /

II

11

FIG. 4Polyolester of pentaerythritol and n-hexanoic acid.

CHAPTER

15: REFRIGERATION

LUBRICANTSPROPERTIES

AND APPLICATIONS

417

Ri O [CH2 CH 0 ] n R2

I
CH3
n = # of branched [CH2 CH O] groups

I
CH3
Rl ,R2 = alkyl end groups
FIG. 5Polyalkylene glycol derived from propylene oxide.

The viscosity a n d solubility properties of polyolesters


can be modified by the use of different polyols and, more frequently, by the use of carboxylic acids t h a t are either
branched or straight chain in character. Straight chain acids
lead to esters with good lubricity, but these structures often
suffer from limited miscibility and solubility characteristics
with hydrofluorocarbon refrigerants. Similarly, b r a n c h e d
chain acids lead to esters with good miscibility and solubility
characteristics but poorer viscosity characteristics. Typically,
a balance of acids (mixed acid POE) is used to formulate a
polyolester blend with the specific properties required by the
refrigeration equipment [1,24]. Ceu-boxylic acids that are in
c o m m o n use in forming polyolester blends are n- and ipentanoic, n- and i-hexanoic, and 3,5,5-trimethylhexanoic.
Blends using both straight and (n) branched (i) chain acids
up to nonanoic (C9) structures have been foimulated [25].
Polyolesters have good high temperature stability and with
proper acid (or polyol) choice, can be formulated with good
low temperature fluidity and low pour point. They are chemically compatible with the hydrofluorocarbons that have
been identified as replacement refrigerants for the chlorofluorocarbons. However, they exhibit several negative features
in comparison with tj^ical mineral oils. Polyolesters have
lower pressure-viscosity coefficients than mineral oils and
alkylbenzenes. The pressure viscosity coefficient is defined as
(3 In Tj/a p)x. This is a measure of how the viscosity of a lubricant increases with pressure at a constant temperature.
See Table 1 for typical values for different lubricants. A lower
pressure viscosity coefficient translates into reduced lubricant film thickness u n d e r high pressure loading such as
would be encountered, for example, in rotary compressors.
Polyolesters formulated with long, straight chain acids exhibit somewhat better pressure viscosity coefficients than
those formulated with b r a n c h e d chain acids. Perhaps the
most serious problem with polyolesters is their low hydrolytic stability. Hydrolysis of all polyolesters is thermodynamically similar with a small positive Gibbs energy change
(10 kJ/mol). Although this suggests that these compounds
may hydrolyze at higher temperatures, the presence of a high
energy activation barrier normally prevents their reaction
back to form an organic acid. This activation barrier is larger
(= 40 kjol/mol) for polyolesters formed from a-branched carboxylic acids, where the branching nature of the alkyl chain
hinders hydrogen bonding of water at the unsaturated 0 = C
linkage in the ester. The carboxlyic acid, 2-ethyl (AG^ a 50
kv/mol) hexanoic, has been used extensively in Japan in polyolester formulations since it results in a very effective steric
h i n d r a n c e against hydrolysis [26]. These polyolesters are
generally referred to as hydrolytically stabilized polyolesters

(HSPOE), but their stability against hydrolysis is a function


of all other acids used in their formulation [27]. This hydrolysis problem is of major concern since the resulting organic
acids may initiate a chain of reactions with additives, metals,
process fluids that are present in a system as contaminants,
and even react with polyolester components in a process
known as transesterfication that can result in ester modification. To minimize hydrolysis effects in hydrofluorocarbon
systems, it is c o m m o n practice to incorporate a filter drier in
the system to keep the water content to very low values (< 100
p p m ) . Despite the hydrolytic stability concern of polyolesters, they have emerged as the major lubricants in hydrofluorocarbon A/C and refrigeration systems. It is clear
that their optimum formulation is dependent on the system
application and compressor type.
Polyalkylene Glycols (PAG)
Polyalkylene glycols are sometimes referenced as polyglycols, polyethers, or polyglycol ethers. They are synthesized
typically from ethylene or propylene oxides that are subjected to a polymerization process initiated using an alcohol
or water [28]. The polymerization process can result in either
monoether or diether types of structures, usually as a mixture
with a range of molecular weight c o m p o u n d s . A typical
polyalkylene glycol is represented in Fig. 5.
Owing to their polar nature, polyalkylene glycols are completely miscible with most hydrofluorocarbon refrigerants.
They have very good lubricity properties and exhibit large
viscosity indexes. Polyalkylene glycols have good low temperature fluidity and low pour points, typical of naphthenic
mineral oils [29]. They are not miscible with mineral oils and
are somewhat less stable chemically than other synthetic lubricants, especially at high temperatures [30]. For many applications, thermal stability is not a major problem since the
decomposition products are typically volatile, resulting in little sludge buildup. Thermal and chemical decomposition stabihty can be analyzed using the ANSI/ASHRAE 97-1989 test
procedure. The major disadvantage is that these compounds,
like all ethers, are very hygroscopic, due to hydrogen bonding
of water at the ether linkages. This reduces the electrical resistivity of these lubricants to the point where they usually
cannot be safely used in hermetically sealed or closed systems in which the motor windings are directly exposed to the
refrigerant. Typical PAG formulations exhibit a volume resistivity of ~ 1 0 ' ^ fl cm in contrast to mineral oil and alkybenzene lubricants that typically exhibit values > lO^"* Cl cm. Volu m e resistivity can be measured using the ASTM D 1169 test
procedure. This problem could be circumvented by care-

418 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


ful water control in the system, but their use in these applications has been replaced by polyolesters that are m u c h less
hygroscopic. Polyalkylene glycols can be effectively used in
systems using external motor drives for the compressor and
have found significant acceptance in the automobile A/C
market that has adopted R-134a as the replacement refrigerant for R-12.
Polyvinylethers (PVE)
Recently, a polyvinylether (PVE) structure has been synthesized at Idemitsu Kosan in Japan. This new ether-type
structure is chemically similar to typical polyalkylene glycol
structures with the exception that the ether linkages are in
the branched hydrocarbon segments instead of being located
in the backbone chain of the molecule [31]. A typical molecular structure for a poljrvinylether lubricant is given in Fig. 6.
The groups indexed by n and m are adjusted to control lubricity and refrigerant solubility characteristics. Lubricity
characteristics Eire discussed in ASTM F2161. A standard test
procedure is available as ASTM D2670.
Similar to polyalkylene glycol structures, and in contrast to
polyolesters, polyvinylethers do not hydrolyze to form organic acids. However, because of the ether groups, they are
hygroscopic. Tests indicate somewhat better stability against
water pickup than is exhibited by many polyalkylene glycols.
Polyvinylethers exhibit high pressure-viscosity coefficients
that are nearly comparable to those measured for mineral
oils. They are somewhat less thermally stable than the polyolesters. Poljrvinylethers are very miscibile in most hydrofluorocarbon refrigerants and exhibit a viscosity reduction in
refrigerant/polyvinylether mixtures that is comparable to
refrigerant/polyolester mixtures. Miscibility is usually described as the temperature at which a second liquid phase is
formed, measured as a function of the refrigerant/lubricant
composition. A lower temperature for phase separation indicates better miscibility. Their oxidation characteristics are
somewhat poorer than mineral oils and alkybenzenes, and
they are not as stable as polyolesters with regard to this property. The potential oxidation and hygroscopic characteristics
exhibited by polyvinyl ethers have been addressed by the use
of additives. This is a new class of refrigerant lubricants and
will likely undergo extensive industry tests before decisions
are made for its potential application in residential or commercial equipment [32].
In refrigerant system applications of these lubricants,
some of the undesired properties can be modified by the addition of a small a m o u n t of an additive. The modification of
the oxidation properties of a lubricant by the addition of an
oxidation inhibitor is one of the oldest examples of this approach.

[Ri CH2 CHJn CH2 CH R3


0

0-[R4-0]m-R5

R,
Rx (x = 1-5) = alkyl groups
FIG.
6General
polyvinylethers.

molecular

structure

for

REFRIGERANT LUBRICANT ADDITIVES


Additives are chemical compounds added to lubricants to deliver specific properties such as moisture control, lubricity
improvement, antioxidant character, etc. [7,33]. Standard industry test procedures are ASTM E 203 and D 6304 (moisture)
and ASTM D 664 (total acid). Oxidation test include ASTM D
943 and ASTM D 5846. They can act chemically with system
components or react with water and system debris to modify
the break-in characteristics of an A/C or refrigeration system.
Additives can also act to modify the physical properties of a
lubricant such as its pour point or viscosity index. Most additives contain large hydrocarbon groups that often have a heteroatom, such as P, N, O, or S for functionality or to impart
polar character. The solubility properties of additives in lubricants can be modified by changes in the hydrocarbon chain
length or, in the case of additives used in synthetic lubricant
formulations, by changes in the polarity of the molecule. Additives that are chemically active, in the sense that they can react with metals in the system or with contaminants in the lubricant, include dispersants, oxidation inhibitors, extreme
pressure agents, corrosion inhibitors, and detergents. Additives that change physical property characteristics include
pour point modifiers, anti-foam agents, viscosity improvers,
and emulsifiers. Test procedures include ASTM D 97 (pour
point), ASTM D 892 (foam tests), and ASTM D 445 (viscosity).
The functionality of additives can be time dependent, such as
those used for system break-in, or they can be expected to provide protection for the life of a system. In general, additives
are more chemically reactive than the base stock lubricant or
the refrigerant, and their formulation and dosage must be
carefully examined. Excessive use of additives can lead to reactions that produce unwanted products that are insoluble or
corrosive. Unfortunately, many lubricant manufacturers are
reluctant to disclose additive formulations and it is often a hit
or miss situation in formulating an additive package that provides the necessary protection for a system. It is often the case
that an additive, such as an extreme pressure agent, can function properly in its role as added bearing protection during
compressor break-in. However, it can also react with water
and organic acids that may be present in the system to form
insoluble compounds that can cause blockage in capillary
tubes or expansion devices. The chemical formulation and required quantity of additives that are optimum for a given system design are difficult choices for both the lubricant supplier
and the compressor or system manufacturer.
The formulation of additives for use in synthetic lubricants
is especially challenging since the possible chemistry with the
more polar refrigerant and lubricant molecules is complex.
Additive formulations that have been successfully used in
chlorofluorocarbon/mineral oil systems have often proved to
exhibit detrimental reactions in hydrofluorocarbon/synthetic
lubricant systems (see [7] and references thereir). This has
caused some HVAC equipment manufacturers to avoid the
use of additive packages altogether, relying on system design
changes for reliability. In general, less is better in the rule
adopted for the use of additives in m o d e m equipment design.
The functionality of lubricant additives include pour point depressants, viscosity index improvers, anti-foaming agents, detergents and dispersants, oxidation and corrosion inhibitors,
rust inhibitors, and antiwear agents. There is a large literature

CHAPTER

15: REFRIGERATION

on the chemistry and properties of these additives (see [7] and


references therein). This review will focus on problems that
have been addressed by the use of additives in hydrofluorocarbon/s5mthetic lubricant systems.
Anti-Oxidants
All lubricants, since they are hydrocarbon in character, have
some thermal limit against reaction with oxygen. Mineral
oils have some natural anti-oxidant properties due to sulfur
or nitrogen based components that are found in petroleum
feedstocks. Synthetic lubricants that are used in high temperature applications, such as heat pumps, generally require
the use of an anti-oxidant to modify their chemical reaction
rate with oxygen [34]. Their chemical role is to modify the
radical chain mechanism of the oxidation process, slowing
it to a rate that is consistent with long term stability against
significant decomposition [35]. Alkyl phenols, such as
dibutylhydroxytoluene, are often used to protect polyolester
lubricants against oxidation. Nitrogen containing inhibitors,
such as the arylamines and phenols, that are often found in
petroleum feedstocks and are effective anti-oxidants in mineral oil formulations, have been found to exhibit unwanted
reactions in some synthetic lubricants. The typical amount
of anti-oxidant that is used is 0.1-0.5 weight percent, depending on the potential exposure of the system to air in
servicing operations.

Anti-Wear Additives
Lubricants that are used in A/C and refrigeration systems
suffer from dilution effects of the refrigerant with a corresponding decrease in viscosity. In systems that employ chlorofluorocarbon refrigerants, the refrigerant can react with
the bearing metal under pressure, and the resulting frictional
heat generated by sliding metal surfaces forms a metal chloride coating that protects against direct metal to metal contact. Hydrofluorocarbon refrigerants do not offer this protective feature and anti-wear additives are tj^ically added to the
synthetic lubricants that are used in these newer systems.
These additives can be classified into two categories: those
that are formulated to provide protection under normal operating conditions (anti-wear agents) and those that are formulated for use during system break-in and extreme operating conditions (extreme pressure agents) [36]. Extreme
pressure (EP) agents can be evaluated using the ASTM D
3233 test procedure. Both anti-wear and extreme pressure
agents function by thermally activated chemical reactions,
forming compounds that react with the metal surface to form
a protective layer. Thiophosphates have t3TDically been used
as anti-wear agents. Extreme pressure agents include aryl
disulfides, thiocarbamates, and several classes of organic
phosphorous compounds [37,38]. Extreme pressure agents
react at higher temperatures than anti-wear agents. At higher
temperatures (>200 C) and under heavy loads, these agents
modify the structure of sliding surfaces by lowering the
height of aspertites and forming a protective film. In effect,
they act as polishing agents that reduce the high level of friction that may be encountered during system break-in.
Experience with the use of anti-wear and extreme pressure
agents in hydrofluorocarbon/synthetic lubricant systems has

LUBRICANTSPROPERTIES

AND APPLICATIONS

419

uncovered several severe problems. Since most of these


agents are designed to chemically react with metals, insoluble reaction products have been encountered that cause capillary and expansion device restrictions. Reaction of these
agents with several types of synthetic lubricants has also been
observed. Tricresyl phosphate, a particularly effective extreme pressure agent, is known to produce undesired reaction p r o d u c t s when used with some synthetic lubricants.
Polyolester lubricants can absorb sufficient water to cause,
under high temperature conditions, a series of reactions leading successively to diaryl phosphate, monoarylphosphate
and phosphoric acid, which then reacts with iron bearing
surfaces to form a protective iron phosphate surface coating.
The problem is that these intermediate reaction products
have limited solubility in hydrofluorocarbon/polyolester systems and typically deposit as metallic soaps rather than continuing in the reaction chain to form the desired ferrous
phosphate coating. The use of oversized filter driers and careful control of moisture in a system are typical measures taken
to circumvent this problem. Typically, 1.0 weight percent of
extreme pressure agents are used in synthetic lubricant based
systems, but values as high as 3.0 percent have been used in
some polyolester based systems.

Acid Catchers
The use of compounds to control acid levels is especially important in synthetic lubricant systems. In contrast to mineral
oil lubricants, polyolester and polyalkylene glycols can adsorb (by hydrogen bonding), significant amounts of water. In
some cases, the lubricant or system processing fluids can react with water, forming organic acids that can result in wear
and corrosion. Tjrpical compounds that are used to control
acid level are the alkanolamines, long chain amides and
imines, carbomates, and epoxides. This latter class of compounds has found extensive use in polyolester based systems.
T5rpical concentrations of 0.1-0.5 weight percent are used for
water and acid control in hydrofluorocarbon systems. A potential disadvantage in the use of acid catchers is their reactivity with other additives such as anti-weeir agents. Control
of water and acid by proper system design, cleanliness in system assembly, and proper maintenance are preferred strategies.

Anti-Foaming Agents
Foaming in a refrigeration system is caused by mechanical
mixing of the lubricant and the refrigerant, by the sudden release of refrigerant gas from the lubricant when pressures are
reduced, and by outgassing that can occur at system start-up.
The type of foam that is formed in chlorofluorocarbon/mineral oil systems is persistent and undergoes a slow collapse.
In hydrofluorocarbon/synthetic lubricant systems, foam typically forms and collapses rapidly with the potential of lubricant transport out of the compressor sump zind ineffectiveness in its action to modify compressor noise. Compounds
that have been used to control foaming characteristics include the poly dimethyl siloxanes, polyalkoxyamines, a n d
polyacrylates. These compounds act to modify the surface
tension of the lubricant/refrigerant mixture. They are typically employed at the 100-1000 p p m level. Their disadvan-

420 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

tage is that other chemical compounds in the system can often react with foaming agents rendering them ineffective.
Their chemical stabihty under severe system operating conditions is also uncertain.
Other additives that have been considered for use in A/C
and refrigeration systems are copper deactivators to protect
connecting lines and components, viscosity improvers, sealswell agents, detergents, and emulsifiers/demulsifiers. Such
additives have the potential of creating more problems than
are solved by their usage. Proper system design and choice of
lubricant are more fundamental to long life system operation
than the use of additives with their potential for adverse
chemical reactions.

PURE LUBRICANT AND REFRIGERANT


PROPERTIES
The most important lubricant property from an A/C or refrigeration system application viewpoint is its viscosity. Viscosity
is defined as the ratio of shear stress/shear rate and is a measure of the resistance of a fluid to flow. This property is often
expressed in units such as Saybolt Seconds Universal viscosity (SSU), which are derived from a calibrated instrument
used to measure flow resistance. The common metric unit for
measuring absolute (djTiamic) viscosity is the poise or centipoise (cP). An alternate measure is called kinematic viscosity, which is measured in centistokes (cSt). These different viscosity measures are related by the density of the lubricant:
McP) = p(g/cc) X T7(cSt)

(1)

The viscosity of a lubricant decreases as its temperature is


increased. This viscosity decrease results in a thinning of the
protective film that a lubricant forms on moving surfaces and
is of critical concern in the choice of the viscosity grade of a
lubricant. High viscosity lubricants can result in increased
compressor requirements owing to fractional drag, while too
low a viscosity can result in equipment failure. The temperature impact on the viscosity of a lubricant is often referred to
as the viscosity index (see ASTM D 2270). An empirical relationship between kinematic viscosity and temperature is
given by:
ln[ln(T7 + 0.7] = a -I- b InT

(2)

where 77 is the kinematic viscosity given in cSt, T is the absolute temperature in Kelvin degrees and a and b are constants
derived from experimental data. A more rigorous model for
describing the temperature dependence of viscosity is the extended Andrade equation [39]:
lnfi = A + YB + CT + DT^

(3)

where fji. is the absolute viscosity and A, B, C, and D are constants fitted to experimental data. This form is often more
useful for modeling viscosity at the lower temperatures encountered in refrigeration. Eq 3 has been applied to model
the temperature dependence for both refrigerant and lubricant viscosity.
Pure refrigerant density is often represented by the
equation:
ft.(T) = a -I- bX -I- cX^ -t- dX^ + eX''

(4)

where T is absolute temperature, p in g/cc and X = (1


T/Tc)^'^, where Tc is the refrigerant critical temperature, the
temperature above which a substance cannot exist in the liquid state regardless of the pressure [40]. For lubricant density, the simpler polynomial form is often used:
/L(T)

a -F bT -(- cT^

(5)

where T is absolute temperature, p in g/cc.


For refrigeration and other low temperature applications,
a property known as the pour point is often important. The
pour point of a lubricant is defined as the lowest temperature
at which a lubricant will flow under gravity when tested by a
prescribed method such as ASTM D97. The pour point is a
complex function of viscosity, lubricant type, wax content
(high molecular weight components) and additives [33]. It is
of less value in A/C and refrigeration systems where the lubricant is diluted to some extent by the presence of the refrigerant but is of some value in the choice of lubricants that
are immiscible with the refrigerant, such as carbon dioxide
and ammonia systems. Other lubricant and refrigerant properties that are often measured are the flash and flame points.
These are used to evaluate if a lubricant could decompose
(coking) under extreme operating conditions. Vapor ignition
points (lower flammability limits) have become of greater
concern with the increased use of hydrofluorocarbon refrigerants. These data have been used to screen refrigerants and
refrigerant mixtures to assure that they will not support
combustion when exposed to air under normal system operating conditions. Flammability limits of refrigerants can be
determined using ANSI/ASHRAE 34-1992 and ASTM G 125
test procedures.
The models chosen to represent thermophysical properties of pure lubricants and refrigerants must be extended or
modified to include the composition dependence of lubricant/refrigerant mixtures. The density of a lubricant/refrigerant mixture can be expressed from a rigorous thermodynamic analysis but requires mixture experimental data that
are generally not available. The viscosity of lubricant/refrigerant mixtures is less well defined but several recent studies
have resulted in useful (and accurate) models for A/C and
refrigeration temperature and composition conditions
[49,51]. The most difficult property of mixtures to model is
the solubility of a refrigerant in a lubricant. Solubility effects are very important since the addition of a refrigerant
to a lubricant lowers its viscosity [41,42]. This does not
stand on its own but is described in detail in the following
section.

SOLUBILITY AND VISCOSITY MODELING


OF LUBRICANT/REFRIGERANT MIXTURES
The role of refrigerant lubricants in A/C and refrigeration
systems is complex. Their primary function is for compressor lubrication, but they also must function as coolants to
remove heat from bearings and to transfer heat from the
compressor shell to the exterior. Lubricants also minimize
gas leakage at gaskets and fittings in the system and can act
to reduce noise generated by the compressor. The principal
differences between refrigerant lubricants and those used,
for example, in automotive applications are the solubility ef-

CHAPTER

15: REFRIGERATION

LUBRICANTSPROPERTIES

fects arising from a dilution of the lubricant with refrigerant. Under normal system operating conditions, the lubricant in the compressor crankcase may be diluted by a few
percent of the refrigerant. Upon start-up, however, if the
ambient temperature at the compressor location is cold, the
lubricant in the compressor sump can be highly diluted
(30%) with refrigerant that has migrated to this cold point
in the system. In most A/C and refrigeration applications,
some lubricant is carried out of the compressor and circulates with the refrigerant. Typically, the percentage of circulating lubricant is small, especially for systems with scroll
design compressors, but can be as high as 3% for systems
with reciprocating compressors that have seen extensive
service. This circulating lubricant-rich mixture can impact
system performance in several ways. Refrigerant/lubricant
miscibility limitations may result in a two-phase liquid region under certain conditions of temperature and pressure.
The most serious effect is the possible development of a
highly viscous phase in the evaporator section that may result in decreased heat transfer rates.
In the case of refrigerant blends, such as R-407C, a new
problem arises since the individual system components may
exhibit different solubilities in the lubricant [9,10]. These different component solubilities can give rise to fractionation
(distillation) effects in the evaporator, condenser, or compressor sump that result in different vapor-liquid equilibrium
conditions and corresponding composition shifts. The effects
of these refrigerant/lubricant interactions may impact both
cycle analysis and system performance. If these chemical interactions are significant (non-ideal solution behavior), they
may result in detrimental performance and lower system operating efficiency. Several models have been developed to analyze the solubility effects of lubricant/refrigerant mixtures.
The thermophysical properties, density, viscosity and vapor
pressure, must be modeled to include the effects of mixture
composition.

Density
The molar volume of a lubricant/refrigerant mixture can be
written as:
V

U L V L + nRVR

(6)

where UL and n^ refer to the n u m b e r of moles of lubricant


and refrigerant in the mixture, and VL = (3V/3nL)T,p,nR; VR =
(c)V/c)nR)T,p,nL are the partial molar specific volumes of lubricant and refrigerant in the mixture, respectively [43]. Equation 6 can be cast into density form as:
1
Pmixture

Vmixture ^ L V L + X R V R

(7)

where vmixture is the volume of one mole of the mixture and XL


and XR represent the mole fractions of lubricant and refrigerant, respectively. It is often assumed that the specific volumes
of the lubricant and refrigerant in the mixture are equal to
their values as pure components: VL = VL and VR - VR. This
simplification is useful if the lubricant and refrigerant
components are chemically alike and are similar in size. Unfortunately, this is often not the case for synthetic refrigerant/lubricant mixtures, such as R-32/POE combinations,
where the mixture exhibits significant non-ideal behavior.

AND APPLICATIONS

421

Assuming ideal behavior, Eq 7 becomes:


1
Pmixture

Vmixture X L V L +

XRVR

(8)

or recasting as mass fractions:


1
Pideal mixture

xf
PR

(9)

where x*" now represents mass fraction and p"" represents


mass density in g/cc. Empirical corrections to Eq 8 have been
suggested in the form: Pmixture = pideai mixture/A, where A is a
density correction factor that can be as large as 6% for high
temperatures and high lubricant dilution. If the molecular
weights of the refrigerant and lubricant are known (typical),
Eq 6 can be used to extract partial molar volume data directly
from measured mixture densities. This approach permits a
cortelation of the deviations from ideal behavior with the individual component properties. The measurement of liquid
densities to high accuracy is difficult (see ASTM D 891 for
general methods).

Viscosity
Viscosity models based on empirical polynomial expansions
in temperature and composition have often been used to describe mixture behavior. Almost all models assume or require
that values for the viscosity of the p u r e components be
known. Thus, the primary feature for judging the validity of
viscosity models for mixtures is their utility in interpolating
data from the extreme composition limits of pure refrigerant
and pure lubricant. It is known that the viscosity of liquid
mixtures is not a simple function of composition. The viscosity of mixtures may exhibit a maximum, a minimum, or both
over a specified composition range. For the pure components, the extended Andrade [39] equation, a polynomial in
temperature, is often used to represent the temperature dependence of viscosity. Studies show that a four or five term
expansion can accurately represent viscosity for pure comp o n e n t s over the n o r m a l operating range of interest,
20C-80C, for both refrigerant and lubricant.
Difficulties can arise in developing reliable models to cover
mixtures ranging from pure lubricant to high refrigerant dilution levels. Owing to the large size differences between refrigerant and lubricant molecules, a reliable model must account
for both the difference in molar volumes of refrigerants and lubricants a n d for differences in molecular interaction
strengths. Most studies of the viscosity of liquid mixtures have
focused mainly on systems of molecules of nearly equal size
and have been restricted mainly to near-ideal mixtures. An
ideal mixture is one that undergoes zero volume change and
zero heat exchange upon mixing. For such mixtures, Arrhenius [44] proposed that mixture viscosity should be an additive
property, linearly connected to the viscosity of the pure components. Mixtures that exhibit this type of behavior are typiCcJly non-polar. Examples are hydrocarbons and halogenated
hydrocarbons, such as CFCs. The introduction of HFCs as refrigerants, which are m u c h more polar, has led to the use of polar polyolester lubricants to improve solution solubility and
miscibility. However, these new refrigerant/lubricant mixtures exhibit significant non-ideal character with very Icirge
molecular size differences between refrigerant and lubricant.

422 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


If 4>i is taken as the volume fraction of component i, we can
represent the viscosity of a binary lubricant/refrigerant mixture as:
In rj

Data
Arrhenius:
Kendall:
Frenkel:

(10)

= (f>i In 171 + 4)2 In 172

Grunberg-Nissan:
Yokozeki:

Equation 10 is commonly referred to as the Arrhenius [44]


equation for ideal binary mixtures. It is useful for mixtures
where there are no strong intermolecular forces (non-polar)
and where there is n o volume change upon mixing. A variation of Eq 10 was proposed by Kendall [45], where composition is measured using mole fraction instead of volume fraction. Mixture equations of this additive type have b e e n
extended by adding terms with one or more disposable constants. An example is the Grunberg-Nissan [46] equation,
which for binary mixtures can be written as:
lm7

01 In TJi -I- <^2 In T?2 + 24>i(l>2Gi2

(11)

For binary polar mixtures, Irving [47] finds that the Grunberg-Nissan equation has the smallest average error when
tested with nearly 1000 data points, taking 4>i as the mole
fraction of component i and optimizing the value of the adjustable parameter, G12, using mixture data. A variation of Eq
11, based on a kinetic model involving binary pair activation
energies, is due to Frenkel [48]:
In T7ix,ure = xf In Tji + xl In 172 + 2x1X2 In 1712

(12)

In Eq 12, Xi refers to the mole fraction of component i, and In


TJ12 is a n interaction parameter between unlike molecules,
usually determined experimentally from mixture data. Irving
finds that Eqs 11 and 12 have comparable accuracy, comparing both polar and non-polar mixtures.
Recently, Yokozeki [49] has proposed a mixture viscosity
model in the form:
mfxi
5^ ^i In Tji;

In rjn

McAllister 3-Body Model:


McAllister 4-Body Model:
Q Michels-Sienel:

0.3

0.4
0.5
0.6
Mass Fraction Refrigerant

0.7

0.8

FIG. 8Viscosity fits for R134a/POE-68. (POE-68: polyolester


of viscosit y 68 cP at 40C.)

temperature. Yokozeki finds that k ~ 0.58 for many refrigerant mixtures but finds that k must be treated as an adjustable parameter for refrigerant/lubricant mixtures. For k
= 0, the Yokozeki model reduces to the model proposed by
Kendall. For k = 1, the concentration measure becomes
weight fraction rather t h a n mole fraction. A genereilized
definition of the concentration measure, ^i, can be shown to
be related to the familiar q-ratio (the ratio of the van der
Waals surface area for lubricant and refrigerant) in UNIFAC and other solution theory models [50,51]. In Figs. 7
and 8, the viscosities of R-22/AB150 and R-134a/FOE-68
mixtures are compared against several models that have
been proposed [51]. In general, one- or two-parameter models are required to quantitatively represent experimental
mixture data.

(13)
Solubility

In Eq 13, Xj and m^ refer to the mole fraction and molecular weight of component I, respectively, and k is an empirical parameter, often modeled as a simple polynomial in the

Data
-Airheimis: [44]
-Kendall: [45]
-Frenkel [48]
-Grunberg-Nissan: [46]
-Yoko2Eld: [49]
- McAllister 3-Body Model: [47]
- McAllister 4-Body Model: [47]
-Michels-Sienel: [51]

The solubility of a refrigerant in a lubricant has been modeled using several different approaches. The older literature
solubility data on mineral oil/CFC mixtures have mainly been
analyzed using empirical correlations in temperature and
composition [52]. Models that are thermodynamically more
rigorous have been developed that are applicable to the
more polar hydrofluorocarbon/synthetic lubricant mixtures
[9,43,49,53]. These models have been based either on a n
equation of state approach or on non-ideal solution theory. A
comparison of the features of these different approaches is
given in Table 2.
Empirical correlations are usually polynomial fits of the
mixture vapor pressure as a function of temperature (T) and
composition (x).
P = X aioT' + x X a i i P + x^ a i 2 r + .
(14)
P = bio/P + X X b/T> + X2 X b i 2 / r +.

0.1

0.2

0.3

0.4
0.5
0.6
Mass Fraction Reffigerant

0.7

0.8

0.9

FIG. 7Viscosity fits for R22/AB 150. (AB 150: allcylbenzene


of viscosity of 150 cP at 40C.)

InP = C(x)

D(x)
T + constant

C(x) = Yi CiXi;

(Antoine form) [54]


D(x) = 5^ diXi

CHAPTER 15: REFRIGERATION LUBRICANTSPROPERTIES AND APPLICATIONS 423


TABLE 2Approaches to modeling solubility of
refrigerant/lubricant mixtures.
Empirical correlations:
mathematically simple models (+)
often thermodynamically inconsistent ()
applicable to limited composition ranges ()
not useful for evaluating blend fractionation effects ()
limited to bubble point predictions (-)
limited to two component (refrigerant/lubricant) composition
analysis (-)
Equation-of-state (EOS) approach:
mathematiccJly more complicated ()
thermodynamically rigorous for pure components (+)
requires vapor phase properties of lubricant ( - )
all thermodynamic properties derived from single EOS (+)
EOS mixture rules are often arbitrary and thermodynamically
inconsistent ()
Non-ideal solution theory:
mathematically more complicated ()
models are often thermodynamically inconsistent ()
applicable to multi-component mixtures over entire compo-sition
range {+)
obviates need for vapor properties of the lubricant (-I-)
applicable to both bubble and dew point predictions {+)
not useful in the vicinity of the critical point ()
difficult to model temperature dependence ()
most accurate modeling approach for mixtures, except in the
vicinity of the critical point (-I-)

These forms are convenient for fitting to experimental data


for mixtures. They often yield very inaccurate predictions if
used outside of the fitting range and typically do not accurately represent the vapor pressure of the pure refrigerant.
The non-ideal behavior of the liquid and vapor phase is
lumped together in the expansion coefficients of these models. In general, there is n o thermodynamic basis for these
functional forms. The Antoine form, for example, is developed from the Clausius-Clapeyron equation only for a pure
fluid.
In the equation-of-state (EOS) approachmodels for mixtures are based on extension of the theory of corresponding
states for pure substances using empirical mixing rules. Generally, cubic EOS are required for any quantitative treatment
of mixtures:
a) van der Waals model
b) Soave modification of Redlich-Kwong equation (SRK)
c) Peng-Robinson equation (PR)
These EOS are described in detail by Prausnitz, et al. [43].
Yokozeki [49] and Morrison et al. [56] have independently
developed EOS models that have been used to describe the
solubility behavior of hydrofluorocarbon/polyolester lubricant mixtures. These models involve the difficult task of describing the pressure-volume-temperature (PVT) behavior
for mixtures of two substances with vastly different vapor
pressures. The usual mixture rules for combining the EOS fitting parameters for pure components are not applicable for
refrigerant/lubricant mixtures without complicated modifications and inherent difficulties in fitting experimental data.
The primary advantage of EOS models is their usefulness
near the critical region of these mixtures.
The most reliable solubility models are generally those that
are developed from the thermodynamics of non-ideal solution theory [43]. The vapor-liquid equilibria of a mixture can

be formally described in terms of the component fugacities in


the liquid and vapor phases. At equilibrium, we have
fr = yiPT<^i' = f i = Xi7iPr</.*F}

(15)

where
yi = vapor phase molar composition of component i,
PT = total system pressure at temperature T,
4>i = vapor phase fugacity coefficient which, for moderate
pressure, can be estimated from second virial coefficient data,
Xi = liquid phase molar composition of component i,
Yi = liquid phase activity coefficient,
P,^ = vapor pressure of pure component / at temperature T,
4)* = fugacity coefficient for pure i at the system T and P,
Fi = pointing factor for compressibility of the liquid
phase.
J , * ^= T7?
(f)*
F | = 1.0, this analysis reduces to an idea
solution description and is representative of Raoult's Law.
Combining the fugacity coefficients and Poynting factor into
a correction term, F the vapor-liquid equilibria for component i in solution can be written as:

F o r 4>}'

iVc!
yiPr = Xi7iPrFS

(16)

The correction term, Fu can be evaluated from liquid density


and second virial coefficient data for pure refrigerants. One
convenient source is the tabulation given in the NIST REFPROP [57] database. The difficult part of this modeling approach is the representation of the liquid phase activity coefficients, 7,, w h i c h are formally connected to the excess
(non-ideal) Gibbs energy. These liquid activity coefficients
may be extracted from experimental data or estimated using
group additivity models such as UNIFAC [50]. The latter approach is difficult at present due to limited knowledge of the
chemical formulations of the synthetic lubricants and the
lack of reliable functional group interaction parameters.
Preliminary evaluation of the non-ideal behavior of HFC32/POE, HFC-125/POE, and HFC-134a/POE binary mixtures
has indicated b o t h positive and negative deviations from
ideal solution behavior [9,58]. Many of the proposed forms
for liquid phase activity coefficients cannot mathematically
represent such behavior. The Wilson [59] model for the excess Gibbs energy, for example, is not applicable over the
entire refrigerant/lubricant composition range. Various modifications of the Wilson model have been proposed [60] including those described in the literature as the Heil [61],
NRTL [62], and T-K [63] equations. All of these equations
represent local composition models in an attempt to incorporate effects of molecular size as well as mixture concentration. Their derivations, however, are mainly empirically
based, and can lead to computed solution parameters that
lack physical meaning. Recent studies have shown that the
Wohl [3]-suffix expansion [64] for representing the excess
Gibbs energy, written in terms of an effective volume measure of composition, yields reliable results for many lubricant/refrigerant mixtures. A comparison of experimental vap o r pressure data and calculations based on the Wohl
[3]-suffix model is shown in Figs. 9 and 10 for R-134a/POE68 and R-410A/POE-68 refrigerant/lubricant mixtures [9].
The theory is somewhat better for modeling single component refrigerants, such as R-134a. Solution theory models, in

424 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

T=60C.--

T-OfC

surements but can be formally located through an analysis of


the Gibbs excess energy for the mixture [43].

-T=20fC

- T=40 C
- T=60 C

c
o

0.2

0.4

0.6

0.8

T=0Cdata

T= 20 C data

T= 40 C data

T=60Cdata

R-134a liquid mass fraction

FIG. 9Vapor pressure of R-134a/POE-68 mixture.

_ .

- T-OPC
-T=2ff'C

- T=40 C
- T=60 C

0.2

0.4

0.6

T=0Cdata
T= 20 C data
T- 40 C data
T- 60 C data

0.8

R-410A liquid mass fraction

FIG. 10Vapor pressure of R-410A/POE-68 mixture.

general, do not universally apply to liquid-liquid equilibria


such as is required for studies of immiscibility. An advantage
of a solution theory approach is that there is no need for vapor phase lubricant properties since it is a good assumption
that the concentration of lubricant in the vapor phase is negligible. A disadvantage of this approach is that solution theory models are most useful for T < Tc.
A very useful method to determine the kinematic viscosity
of lubricant/refrigerant mixtures is based on combining viscosity and solubility data as shown by Daniel [20]. In this representation, the kinematic viscosity of refrigerant/lubricant
mixtures is plotted against temperature with mixture isobars
as parameters. These plots are now universally adopted by lubriccmt manufacturers to display the solubility characteristics of their lubricants. A typical Daniel plot for R-41OA and a
22 cSt mixed acid polyolester is shown in Fig. 11. The rapid
decrease in mixture viscosity that results from refrigerant dilution of a lubricant is apparent for the lower temperature
mixtures shown in Fig. 11. This is of critical concern for compressor design, especially for those conditions encountered
at system start-up. Figure 11 also indicates the temperature/composition regions (gray shaded) where liquid phase
immiscibility is encountered. This refrigerant/lubricant pair
exhibits both a lower consolute temperature of 25 C and an
upper consolute temperature of ~ 15 C. Within the shaded region, two liquid phases are present for this mixture. This immiscibility region is usually located from experimental mea-

LUBRICANT CIRCULATION
The purpose of the lubricant in the HVAC system is to lubricate, cool, seal, and otherwise protect the compressor in the
system from failure. In the course of executing these functions, some lubricant is captured in the compression process
and carried by the refrigerant out of the compressor. Within
the remainder of the system, the lubricant serves little to n o
useful function, and acts as a detriment to system performance u n d e r most conditions. The challenge to the system
designer is to ensure that the lubricant returns to the compressor satisfactorily u n d e r all operating conditions, as a prolonged migration of the lubricant from the compressor into
the system will result in performance degradation and eventually compressor failure due to lack of lubricant. The design
considerations influencing adequate lubricant return consist
of line sizing, lubricant and refrigerant selection, system operational envelope, and transient effects, each of which will
be described in further detail. Measurement of the circulation in these systems is also a challenge, particularly when
transient phenomena occur, and this will be considered in
further detail as well.
HVAC Cycle
Vapor compression systems, in basic form, consist of a compressor, a heat rejecting heat exchanger (typically referred to
as a condenser), an expansion device, and a heat absorbing
heat exchanger (t5^ically referred to as an evaporator). The
cycle begins with the refrigerant as a high pressure vapor at
the exit of the compressor. It next flows through the condenser, rejecting heat, cooling, and condensing to become a
liquid at the discharge of the condenser. Next, the pressure of
the refrigerant is dropped as it flows through the expansion
device, which can be as simple as a kink in the refrigerant line
or as sophisticated as a microprocessor-controlled, electronically-actuated stepper motor connected to a needle valve. At
the exit of the expansion device, the refrigerant has typically
entered into the two phase region again and enters the evaporator. The evaporator absorbs heat from the environment and
uses it to evaporate the refrigerant back to vapor form. Finally,
the vapor refrigerant enters the compressor, where it is compressed and heated to begin the cycle again. This process is
shown schematically in Figs. 1 2 a n d l 3 , which depict the pressure-enthalpy and temperature-entropy diagrams of the cycle.
This cycle is important to understand as it influences all of the
design considerations impacting lubricant transport.
In addition to the basic components, many systems are
equipped with additional components serving a variety of
functions. Charge storage devices, such as accumulators and
receivers, are used in systems that have large operational envelopes and, due to the density differences of the refrigerant at
the different operational temperatures, require significantly
different amounts of refrigerant at different conditions. Receivers are employed where liquid flows through the lines, typically in the high pressure part of the system between the exit
of the condenser and the expansion device. The liquid flowing
into the expansion device is drawn from the receiver and, be-

CHAPTER 15: REFRIGERATION LUBRICANTSPROPERTIES AND APPLICATIONS 425


400

10

20
Temperature (C)

60

30

FIG. 11Daniel plot of R-410A/POE-22 mixture.

10000
Liquid
>

1000

i
I

100

10
50

250
450
Enthalpy (kj/kg)

1.5

1
1.5
Entropy (kJ/kg-K)

FIG. 12R-134a P-h diagram.

FIG. 13R-134a T-s diagram.

cause there is a reservoir of liquid to draw from, a system


equipped with a receiver is more tolerant to transients in the
condenser. Accumulators, on the other hand, are applied
where refrigerant vapor flows, typically between the exit of the
evaporator and the inlet of the compressor. The purpose of the
accumulator is twofold; it stores excess charge and also prevents liquid (which can damage the compressor) from entering the compressor. Accumulators act as effective oil separators, and m u s t b e equipped with a m e c h a n i s m to allow

lubricant to return to the compressor, as they would otherwise


simply absorb all of the oil from the compressor. Because the
refrigerant density is substantially higher in the high-pressure
part of the system, receivers Eire preferred when the size of the
equipment becomes a concern. All cheirge storage devices can
trap substantial amounts of lubricant, particularly when the
refrigerant-lubricant combination is not fuUy miscible.
Other components utilized in HVAC systems include filter/dryers, reversing vtJves, and secondary heat exchangers

426

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

such as liquid suction heat exchangers. Filter/driers, as the


name imphes, serve the two functions. The fiUering of
particulates, which can plug the expansion device or damage
the compressor, is usually accomplished by screens, meshes,
or felts. Moisture can react with lubricants in the system to
decompose them back to acids and alcohols, and the dryer
section of the filter/dryer is designed to remove any residual
moisture from the system. Filter/dryers can be applied in the
vapor or liquid portions of the system, but are usually found
in the liquid flow due to pressure drop concerns. Reversing
valves are used in heat pump systems, where the system operates part of the time as an air conditioner and part of the
time as a heater. They simply reverse the flow through the
heat exchangers, so that the condenser becomes the evaporator and visa-versa. The lubricant in the system aids the valve
actuation process, but usually does not impact this component in any other way. Liquid suction heat exchangers act to
further cool refrigerant exiting the condenser (to lower the
entheJpy at the inlet of the expansion device) at the price of
heating the suction vapor to the compressor.
Finally, oil separators are sometimes employed to ensure
adequate lubricant return to the compressor. These devices
are tj'pically applied at the exit of the compressor, and use a
variety of methods to separate and return the lubricant to the
compressor.
Equipment Line Sizing
The system components are connected by lines, which cdlow
the flow of refrigerant (and lubricant) from component to
component. The pressure drop through these lines, and also
through the heat exchangers, has a considerable impact on
system performance and the tradeoff between system performance and cost is made in sizing the diameter of these lines
[65,66]. For optimal performance, these lines would be sized
to ensure minimum pressure drop, and this would be a valid
philosophy if the lubricant were not present. In the liquid
line, the lubricant flows in suspension (in the case of an immiscible lubricant-refrigerant combination) or as a fully soluble part of (when fully miscible) the refrigerant. There is
typically no lubricant transport issue in liquid lines. In vapor
lines, lubricant transport becomes much more of an issue, as
the lubricant does not vaporize along with the refrigerant.
Lubricant transport in vapor lines occurs by two primary
mechanisms: mist flow and annular flow. In mist flow, the lubricant is atomized into small droplets that are carried in suspension with the vapor refrigerant. In annular flow, the lubricant builds up along the perimeter of the line and is
dragged along by the velocity of the vapor flow. Mist flow
dominates when the lubricant viscosity is low while annular
flow is more prevalent when the lubricant viscosity is high
(when the annular flow becomes laminar).
As pressure drop is a function of Reynolds number, (Re =
, where D = tube diameter, v = velocity, fi = viscosity) if
the velocity of the vapor flow is decreased, the pressure drop
will also decrease. However, as the velocity is reduced, the
shear forces eventually become insufficient to drag the annular flow of lubricant, and the droplets in the mist flow succumb to gravity forces and drop out of suspension from the
vapor flow. This condition essentially stops lubricant transport through the system, and is referred to as the minimum

100 -|

Insufficient Velocity

r 3

Sufficient Velocity

90 80 .

- 2.5

70 &
^
a

60 50 -

40-

-2

- 1-5 Q

^y>

30 -

-0.5

Measured Line Flooding

10 0

r 1

IS
s

OH

20 0 i

-5%
o.

^ ,

- 0
2

Vapor Velocity (m/s)


FIG. 14Minimum velocity for R-410A/POE 68.

velocity condition. The relationship between the pressure


drop, velocity, and flooding (or lubricant holdup) is shown in
Fig. 14 for the combination of R-410A and POE-68. A number of correlations have been devised to predict when this
condition is reached in practice [67,68]. Under this condition, the lubricant will build up in the section of the system
experiencing minimum velocity, typically in traps or along
the bottom of lines. This buildup of lubricant in the system is
referred to as holdup, and can have severe consequences on
system performance. As this buildup continues, the area
available for flow will contract, and thus the velocity will increase again. Due to pressure and surface tension effects, the
transition from a less than adequate velocity to a sufficient
velocity is often dramatic. The pressure buildup behind the
lubricant obstruction, coupled with the transition to adequate transport velocity, causes a slug of lubricant to burst
from the trap and to be carried to another part of the system
[69]. When the lubricant obstruction has been cleared, the
flow velocity again drops and lubricant again becomes
trapped. This cycle repeats on a frequency dictated by the line
size, vapor velocity, and characteristics of the refrigerant-lubriccint pair. In some cases, the slug transport never occurs
due to the amount of available surface area, such as in a horizontal line, or due to extremely high lubricant viscosity.
Refrigerant/Lubricant Selection
The selection of the refrigerant is based on the operational
performance given the envelope of operating conditions, as
well as, increasingly, the environmental effects of the refrigerant. The lubricant selection follows the refrigerant selection, as in most cases, it is based on the refrigerEint selection.
The specific compressor type will dictate a minimum operational viscosity for adequate lubrication given the operational characteristics. The solubility of the lubricant with the
chosen refrigerant, at the most severe operational conditions,
determines the viscosity grade of the chosen lubricant. Other
considerations for lubricant selection are related to the operational envelope of the system, particularly for refrigeration
systems.
If the refrigerant-lubricant combination exhibits regions of
immisciblity, these must be carefully considered in system
design, particularly for charge storage components. The re-

CHAPTER
80
60
40
20
0
E
u -20
w -40
H
-60
-80

15: REFRIGERATION

Immiscible
Lower CST
Miscible
Upper CST
Immiscible

20

40

60

80

Oil Concentration (%)


FIG. 15Critical solution temperatures for R410A/POE-68.

gions of immiscibility are usually defined by the critical (consolute) solution temperature, as shown in Fig. 15 for R-410A
and POE-68. In the immiscible region, two liquid phases will
form, one lubricant rich and one refrigerant rich. These two
phases will have different densities, and in an actual system,
stagnant liquid will tend to separate according to these density differences. If the lubricant rich phase is less dense than
the refrigerant rich phase, it will float above the refrigerant
dense phase. This is the preferred arrangement for most of
the system lines, as the lubricant rich phase can still be entrained into the vapor flow. If the situation were reversed, the
lubricant rich phase could become trapped below the refrigerant rich phase, leading to poor lubricant return to the compressor. On the other hand, for receivers the situation can be
reversed, as liquid flow to the expansion valve is generally
drawn from the bottom of the device. If the lubricant rich
phase floats above the refrigerant rich phase in this case, it
will not be drawn into the remainder of the cycle and will essentially become trapped. For accumulators, where vapor
flows from the exit and only a small a m o u n t of liquid becomes entrained into this vapor flow through an oil return
mechanism, an immiscible system in combination with system geometry can also produce a situation where lubricant
does not flow back to the compressor. Experiences with this
situation have led to accumulator designs where the contents
are continuously agitated so as to reduce or eliminate stratification. Flooded heat exchangers are also a concern for lubricant holdup. These typically shell and tube heat exchanges
are used in chiller or other liquid heat transfer systems
where, if the lubricant rich phase is less dense than the refrigerant rich phase, oil holdup can occur in portions of the
heat exchanger.

System Operational Envelope


As the temperature of the lubricant is reduced, its viscosity
will increase. The degree of solubility of the lubricant with
the refrigerant, coupled with the viscosity index of the lubricant, combine to determine the mixture viscosity. This is
shown in Daniel plots, such as the one in Fig. 11. For refrigeration conditions, the evaporation temperature can be very
low, and the corresponding viscosity in the vapor phase can

LUBRICANTSPROPERTIES

AND APPLICATIONS

427

be extremely high. Newer refrigerant-lubricant combinations, such as HFC-POEs, have tended to exhibit higher viscosities than the older combinations, such as CFC-MOs that
have been used for these applications. When the lubricant
viscosity becomes sufficiently high, it becomes similar to
wax, and transport becomes difficult, if not impossible. As lubricant continues to build u p in the low temperature portion
of the system (evaporator), this will have a noticeable effect
on heat transfer and pressure drop in the heat exchanger and
thus on performance. The saving grace for these conditions is
often system transients, such as defrost cycles or slugs of relatively w a r m refrigerant, which sufficiently decrease the viscosity of the lubricant to allow transport back to the system.
At the same time, due to the high pressure differences in the
system, compressor discharge temperatures are higher than
at low lift conditions. Both of these conditions lead to contradictory requirements: the desire for a low viscosity lubricant at low temperature, refrigerant dilute conditions; and a
relatively high viscosity lubricant at high temperature, refrigerant rich conditions. This is, of course, the same lubricant,
and must be chosen carefully.

Lubricant Circulation Rate


The circulating lubricant concentration has an effect on performance and the design of system components; knowledge
of this concentration (referred to as oil concentration rate, or
OCR) can be quite important. The basic methods for determination of OCR can be broken down to invasive and non-invasive techniques.
The easiest method for determination of OCR is by use of
a sampling volume, as outlined by ASHRAE [70]. A sample of
liquid refrigerant is c a p t u r e d in a volume (previously
weighed), which is then weighed. The refrigerant in the
volume is next slowly released with care taken not to allow lubricant to escape with the refrigerant. After refrigerant evacuation, the sample volume is weighed again to determine the
residual oil weight. This system determines the instantaneous OCR in the liquid line of the system. This information
is of limited vaiue and may be very misleading when significant transients, such as lubricant slugging, are occurring.
This method, by its nature, is also quite invasive to the system
and will result in a loss of charge every time a measurement
is taken. A less invasive technique employs oil separators to
ensure little or no residual CEirryover to the remainder of the
system [71]. The separated oil flowrate is measured and compeired to the flowrate in the remainder of the system to determine OCR. This technique requires two flowmeters and
will only work in the vapor region of the system (such as at
the compressor discharge). It is still invasive as it disrupts the
normal flow of lubricant through the system and may mask
slugging trouble spots in the system.
There have been a n u m b e r of minimally invasive or non-invasive OCR measurement systems developed recently, which
are much better at identifying problems with system design.
Coriolis flow meters can provide bulk flow density information. Knowledge of the pressure and temperature at the density measurement point coupled with refrigerant and lubricant properties, which are used to d e t e r m i n e p u r e fluid
density at the measurement point, can lead to a determination of the OCR [72]. However, liquid refrigerant and lubri-

428

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

cant densities tend to be quite similar, requiring the density


measurement accuracy to be high. In some cases, the error
band associated with the instrumentation accuracy obscures
the entire range of measured oil concentrations, although
some authors have reported success with this technique. A
commercially available unit for measurement of OCR by ultraviolet (UV) absorption has been on the market for some
time, and some success has been reported in the use of this
device [73]. Several researchers have been working on index
of refraction type OCR measurement systems, although none
have yet been commercialized [74]. Acoustic velocity and direct fluid viscosity measurement have also been proposed as
the basis for determining OCR, once again by comparing the
known pure fluid properties to the measured bulk property
values [72]. Both the UV and index of refraction measurements cire optical techniques, and cire thus fully non-invasive,
while the density m e a s u r e m e n t technique typically introduces a pressure drop in the liquid line. All of the above mentioned measurement systems work only in the liquid line of
the system cind are severely influenced by system transients,
which bring two-phase flow (bubbles) to the measurement
points. In addition, the capability of these devices to measure
OCR in immiscible mixtures is also in doubt.

formance cheiracteristics of the system. This is generally only


of concern when the ratio of lubricant to refrigerant is high.
Finally, careful consideration of edl of these system variables
is the challenge given to designers of m o d e m HVAC and refrigeration equipment.

ASTM STANDARDS
No.
D 97
D 445
D 664
D 891
D 892
D 943
D 1169
D 2008

PERFORMANCE EFFECTS
D 2140
The lubricant in the HVAC system has distinct performance
impacts on the compressor, the heat exchangers, and working fluid, all of which combine to affect system performance.
The compressor requires a certain lubricant viscosity for adequate protection. If the fluid viscosity drops below this limit,
damage to the compressor may occur due to bearing failure.
On the other hand, if the lubricant is too viscous, the drag on
the bearings as weU as any sealing surfaces will increase, resulting in an increase in consumed power and a reduction in
performance.
For the heat exchangers, many of the lubricant impacts
have already been discussed. Some studies have suggested
that trace amounts of lubricant actually aid in heat transfer
properties and thus system performance [75]. However, anything above trace amounts (typically 0.1% OCR) has generally
been reported to have a negative performance impact. Lubricant in the vapor phase of the heat exchanger introduces a
contact resistance, which detracts from the overall heat transfer coefficient. The degree to which this impacts performance
is a function of the amount of OCR and lubricant hold up.
Studies have suggested that the degree of performance degradation caused by the lubricant can be related to the lubricant
viscosity at the exit of the evaporator [76]. Under refrigeration
conditions, the holdup can have a severe performance impact
as the holdup also influences pressure drop.
Finally, the fluid performance is also impacted due to the
displacement of refrigerant from the flow. The lubricant does
not aid substantially in the transfer of heat from the heat absorbing heat exchanger to the heat rejecting heat exchanger.
Thus, for every percent lubricant flowing in the bulk flow, a
corresponding percent drop in performance can be expected.
For multi-component refrigersint mixtures (ctny of the R-400
series of refrigerants), differential solubility effects can cause
the circulating composition to fractionate, changing the per-

D 2270
D2549

D 2670

D 3233

D 5846

D 6304

E 203
F2161
G 125

Title
S t a n d a r d Test Method for Pour Point of
Petroleum Products
Standard Test Method for Kinematic Viscosity of
Transparent and Opaque Liquids
S t a n d a r d Test Method for Acid N u m b e r of
Petroleum Products by Potentiometric Titration
Standard Test Method for Specific Gravity, Apparent, of Liquid Industrial Chemicals
Standard Test Method for Foaming Characteristics of Lubricating Oils
Standard Test Method for Oxidation Characteristics of Inhibited Mineral Oils
S t a n d a r d Test Method for Specific Resistance
(Resistivity) of Electric Insulating Fluids
Standcird Test Method for Ultraviolet Absorbance
and Absorptivity of Petroleum Products
Standard Test Method for Carbon-Type Composition of Insulating Oils of Petroleum Origin
Standard Practice for Calculating Viscosity Index
from Kinematic Viscosity
S t a n d a r d Test Method for Separation of
Representative Aromatic and Nonaromatic Fractions of High-Boiling Oils by Elution Chromatography
Standard Test Method for Measuring WeEir Properties of Fluid Lubricants (Falex Pin a n d Vee
Block Methods)
Standzird Test Method for Measurement of Extreme Pressure Properties of Fluid Lubricants
(FeJex Pin and Vee Block Methods)
Standard Test Method for Universal Oxidation
Test for Hydraulic a n d Turbine Oils Using the
Universal Oxidation Test Apparatus
S t a n d a r d Test Method for Determination of
Water in Petroleum Products, Lubricating Oils,
and Additives by Coulometric Karl Fischer Titration
Standard Test Method for Water Using Volumetric Karl Fischer Titration
S t a n d a r d Guide for I n s t r u m e n t and Precision
Bearing LubricantsPart 1 Oils
S t a n d a r d Test Method for Measuring Liquid
and Solid Material Fire Limits in Gaseous Oxidants

ANSI/ASHRAE STANDARDS
34-1992

Determination of Refrigerant Lower Flammability Limit in Compliance with Proposed Addend u m p to Standard 34.

CHAPTER 15: REFRIGERATION LUBRICANTSPROPERTIES AND APPLICATIONS 429


97-1989

34-2001

Sealed Glass T u b e M e t h o d to Test the Chemical


S t a b i l i t y of M a t e r i a l s for U s e w i t h i n R e f r i g e r a n t
Systems
D e s i g n a t i o n a n d S a f e t y C l a s s i f i c a t i o n of Refrigerants

REFERENCES
[1] 'Wills, J.G.,LubricationFundamentals,MarcelDekker,NY,
1980.
[2] Cameron, A., Basic Lubrication Theory, 3'''^ ed., Ellis Honvood,
Ltd., NY, 1981.
[3] Evans, C. R. and Johnson, K. L., "The Rheological Properties of
Elastohydrodynamic Lubricants," Proceedings of the Institute of
Mechanical Engineers, Vol. 200C, 1986, p. 303.
[4] Gunsel, S., Korcek, S., Smeeth, M., and Spikes, H. A., "The Elastohydrodynamic Friction and Film Forming Properties of Lubricant Base Oils," Tribology Transactions, Vol. 42, 1999, p. 559.
[5] Akei, M. and Mizuhara, K., "The Elastohydrodynamic Properties of Lubricants in Refrigerant Environments," Tribology
Transactions, Vol. 40, 1997, p. 1.
[6] Henderson, D. R., Rajewski, T. E., Speich, C. F., and Greig, B.,
"Lubricants in Refrigerant Systems," Chapter 7, ASHRAE Handbook-Fundamentals,
ASHRAE Publications, Atlanta, 1997.
[7] Rizvi, S. Q. A., "Lubricant Additives and Their Functions," ASM
Handbook, ASM International, Materials Park, OH, Vol. 18,
1992, pp. 98-112.
[8] DeVos, R., "R-134a Qualification-Industry Refrigerator Capillary Data," ASHRAE Transactions, BN-97-7-4, 1997, p. 1.
[9] Michels, H. H. and Sienel, T. H., "Solubility Modeling of Refrigerant/Lubricant Mixtures," Proceedings of the 1995 International
CHC and Halons Alternatives Conference, Alliance for Responsible CFC Policy, Frederick, MD, 1995.
[10] Biancardi. F. R., Sienel, T. H., Pandy, D. R., and Michels, H. H.,
"Modeling and Testing of Fractionation Effects with Refrigeration Blends in an Actual Residential Heat P u m p System,"
ASHRAE Transactions, Vol. 103, Pt. 1, 1997, pp. 1-14.
[11] Biancardi, F. R., Michels, H. H., Sienel, T. H., and Pandy, D. R.,
"Study of Lubricant Circulation in HVAC Systems," ASHRAE
Proceedings, GRA19715, 1997, p. 940.
[12] Sunami, M., Takigawa, K., Suda, S., and Sasoki, U., "New Immiscible Refrigeration Lubricant for HFCs," ASHRAE Transactions, SD-95-8-3, 1995, p. 940.
[13] Sunami, M., Taldgawa, K., and Suda, S., "New Immersible Refrigerant Lubricant for HFCs," Proceedings of the ASHRAEPurdue CFC Conference, Purdue University, West Lafayette, IN,
1994, p . 129.
[14] Godfrey, D. and Herguth, W. R., "Physical and Chemical Properties of Industrial Mineral Oils Affecting Lubrication," Lubrication Engineering, Vol. 51, No. 5, 1995, p . 397.
[15] Van Nes, K. and Weston, H. A., Aspects of the Constitution of
Mineral Oils, Elsevier, NY, 1951.
[16] Gunderson, R. C. and Hart, A W., Synthetic Lubricants, Reinhold, NY, 1962.
[17] Sanvordenker, K. S. and Larime, M. W., "A Review of Synthetic
Oils for Refrigeration Use," ASHRAE Lubricants Symposium,
ASHRAE Jandbook-Fundamentals, Atlanta, GA, 1972.
[18] Komatsuzaki, S. and Honama, Y., "Lubricants of HFC Refrigerant Compressors," Sekiyu Gakkaishi, Vol. 37, No. 3,1994, p. 226.
[19] Glova, D. J., "High Temperature Stability of Refrigerants in Lubricating Oils," ASHRAE Transactions, Vol. 90, No. 4, 1984, p.
806.
[20] Daniel, G., Anderson, M. J., Schmid, W., and Tokumitsu, M.,
Performance of Selected Synthetic Lubricants in Heat Pumps,
Heat Recovery Systems, Vol. 2, Pergamon Press, Oxford, 1982, p.
359.

[21] Shubkin, R. L., Polyalphaolefins in Synthetic Lubricants and


High Performance Functional Fluids, Marcel Dekker, NY, 1993.
[22] Short, G. D., "Synthetic Lubricants and their Refrigeration
Applications," Lubricants Engineering, Vol. 46, No. 4, 1990,
p. 239.
[23] Lilji, K. C , Sabahi, M., and Hamid, S., "Polybasic Esters: Novel
Synthetic Lubricants Designed for Use in HFC Compressors,"
ASHRAE Transactions, SD-95-8-2, 1995, p. 935.
[24] Komatauzaki, S., H o m m a , Y., Itok, Y., Kawashima, K., and
lizuka, T., "Polyolesters as HFC-134a Lubricants," Lubrication
Engineering, Vol. 10, 1994, p. 801.
[25] Sunami, M., Takigawa, K., and Suda, S., "Optimization of POE
Type Refrigeration Lubricants," Proceedings of the Purdue Refrigeration Conference, Purdue University, West Lafayette, IN,
1994, p. 153.
[26] Newan, M. S., "Some Observations Concerning Steric Factors,"
Journal of the American Chemical Society, Vol. 72, 1950, p. 4783.
[27] Suda, S., Sasaki, U., Takigawa, K., Okada, M., and Sunami, M.,
"Optimization of Polyester Type Refrigeration Lubricants-Balance of Hydrolytic Stability and Wear Prevention," Proceedings
of the International Tribology Conference, Japan Air Conditioning Society, Yokohama, Japan, 1995.
[28] Geymayer, S., "Polyalkyllenglykote in Synthetic Lubricants and
Operational Fluids," 4 * International Colloquium, Technische
Akademie Esslingen, Vol. 3, No. 1, 1984.
[29] Aderin, M. E., Johnson, G. L., Spikes, H. A., Babson, T. G., and
Emery, M. G., "The Film-Forming Properties of Polyalkylene
Glycols," Journal of Synthetic Lubricants, Vol. 10, 1993, p. 23.
[30] Kussi, S., "Chemical, Physical and Technological Properties of
Polyethers as Sjnithetic Lubricants," Journal of Synthetic Lubricants, Vol. 2, 1985, p. 63.
[31] Takagi, M., "New Type Refrigeration Lubricants for Alternative
Refrigerants," Energy Resources, Vol. 16, 1995, p. 497.
[32] Hiodoski, S., Matsuura, H., Kanayama, T., Nishikawa, F., and
Nomura, M., "Practical Evaluation of Polyvinylethers as a Lubricant for Alternative Refrigerant Compressor and Systems,"
ASHRAE Transactions, Vol. 103, 1997, p. 15.
[33] Baczek, S. K., and Chamberlin, W. B., "Petroleum Additives,"
Encyclopedia of Polymer Science and Engineering, 2"^ ed.. Vol.
11, John Wiley NY, 1988.
[34] Scott, G., "New Developments in the Mechanistic Understanding of Antioxidant Behavior," Journal of Applied Polymer Science-Applied Polymer Symposium, Vol. 35, 1979, p. 123.
[35] Ingold, K. U., "Inhibition of Autoxidation of Organic Substances
in the Liquid Phase," Chemical Reviews, Vol. 61, 1961, p. 563.
[36] Feng, I. M., Perilstein, W. L. and Adarms, M. R., "SoUd Film Deposition a n d Non-Sacrificial B o u n d a r y Lubrication," ASLE
Transactions, Vol. 6, 1963, p. 60.
[37] Kharasch, N., Organic Sulfur Compounds, Vol. 1, Pergamon
Press, NY, 1961.
[38] Gerrard, W. and Hudson, H. R., "Organic Derivatives of Phosphorous Acid and Thiophosphorous Acid," Organic Phosphorous Compounds, Vol. 5, G. M. Kosolopoff and L. Maier, Eds.,
Wiley Interscience, NY, 1973, pp. 21-329.
[39] Andrade, E. N. "DaC, Viscosity of Liquids," Proceedings of the
Royal Society (London), Vol. 214A, 1952, p. 36.
[40] Yen, L. C. and Woods, J. J., "A Generalized Equation for Computer Calculation of Liquid Densities," Journal of the American
Institute of Chemical Engineers, Vol. 12, 1966, p. 95-99.
[41] Parmelee, H. M., "Viscosity of Refrigerant-Oil Mixtures at Evaporator Conditions," ASHRAE Transacftons, Vol. 70, 1964,p. 173.
[42] Spauschus, H. O. and Speaker, L. M., "A Review of Viscosity
Data for Oil-Refrigerant Mixtures," ASHRAE Transactions, Vol.
93, 1987, p. 667.
[43] Prausnitz, J. M., Lichtenthaler, R. N., a n d deAzevedo, E. G.,
Molecular Thermodynamics of Fluid Phase Equilibria, 2nd ed..
Prentice Hall, NJ, 1986.

430 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


[44] Arrhenius, S., "The Viscosity of Aqueous Solutions," Zeitschrift
filr Physikalische Chemie, Vol. 1, 1887, p. 285.
[45] Kendall, J., "Viscosity of Solutions," Meddelelser
VentenskapsakadNobelinst, Vol. 2, 1933, p. 25.
[46] Grunberg, L. and Nissan, A. H., "Mixture Law for Viscosities,"
Nature, Vol. 164, 1949, p. 799.
[47] Irving, J. B., "Viscosities of Binary Liquid Mixtures: The Effectiveness of Mixture Equations," Report ISSN 03051439, National Engineering Laboratory, East Kilbride, Scotland, 1977.
[48] Frenkel, Y. I., Kinetic Theory of Liquids, Oxford University Press,
London, 1946.
[49] Yokozeki, A. M., Solubility and Viscosity of Refrigerant-Oil Mixtures, Proceedings of the International Refrigeration Conference, Purdue University, West Lafayette, IN, July 1994.
[50] Fredenslund, A., Gmehling, J., and Rasmussen, P., Vapor-Liquid
Equilibrium Using UNIFAC, Elsevier, Amsterdam, 1977.
[51] Michels, H. H. and Sienel, T. H., "Viscosity Modeling of Refrigerant/Lubricant Mixtures," Proceedings of the CFC and Halons
Conference, Washington, DC, 1997.
[52] Bambach, G., "Das Verhalten von Mineralol-F12 Gemischen in
K a l t e m a c h i n a n Abhandlung," P u b . No. 9, des Deutschen
Kaltetechnischen Vereins, C. F. MuUer, Karlsruhe, 1955.
[53] Spauschus, H. O., "Thermodynamic Properties of RefrigerantOil Solutions, Part 1," p. 47; "Thermodynamic Properties of Refrigerant-Oil Solutions, Part 2," ASHRAE Journal, Vol. 5, 1963,
p. 63.
[54] Antoine, C , "Tensions des Vapeurs: Nouvelle Relation Entre les
Tensions et les Temperatures," Comptes Rendus, Vol. 107, 1888,
p. 681.
[55] Sandler, S. I., Models for Thermodynamic and Phase Equilibria
Calculations, Marcel Dekker, NY, 1993.
[56] Morrison, J. D., Barley, M. H., Murphy, F. T., Parker, T. B., and
Wheelhouse, R. W., "The Use of an MHV2 Equation of State for
Modeling the Thermodynamic Properties of Refrigerant fixtures," International Journal of TherTnophysics,\o\.
16, 1994, p.
1165.
[57] Gallagher, J., McLinden, M., Morrison, G., and Huber, M.,
"NIST Thermodynamic Properties of Refrigereints and Refrigerant Mixtures (REFPROP)," NIST, Standard Reference Database
23, Version 5.1, 1997.
[58] Martz, W. L., Burton, C. M., and Jacobi, A. M., "Vapor-Liquid
Equilibria for R-22, R-134a, R-123 and R-32/R-125 with a Polyolester Lubricant: Measurements and Departure from Ideality,"
ASHRAE Transactions, Vol. 102, 1996, p. 367.
[59] Wilson, G. M., "A New Expression for the Excess Free Energy of
Mixing," JACS, Vol. 86, 1964, p. 127.
[60] Martz, W. L., Burton, C. M., and Jacobi, A. M., "Local Composition Modeling of the Thermodynamic Properties of Refrigerant
and Oil Mixtures," International Journal of Refrigeration, Vol. 19,
1996, p. 25.

[61] Heil, J. F., and Prausnitz, J. M., "Phase Equilibria in Pol3'mer


Solutions," AIChE Journal, Vol. 12, 1966, p. 678.
[62] Renon, H. and Prausnitz, G. M., "LOCEJ Compositions in Therm o d y n a m i c Excess Functions for Liquid Mixtures," AIChE
Journal, Vol. 14, 1968, p. 135.
[63] Tsuboka, T. and Katayama, T., "Modified Wilson Equation for
Vapor-Liquid and Liquid-Liquid Equilibria," Journal of Chemical Engineering of Japan, Vol. 8, 1975, p. 181.
[64] Wohl, K., "Thermodynamic Evaluation of Binary and Ternary
Liquid Systems," Transactions of the AIChE, Vol. 42, 1946
p. 215.
[65] O'Donnell, T. K. and Ward, D. F., "Liquid Overfeed Systems,"
Ch. I, ASHRAE Handbook-Refrigeration, ASHRAE Publications
Atlanta, GA, 1998, p. 1.
[66] Jones, R. A., "System Practices for Halocarbon Refrigerants,"
Ch. 2, ASHRAE Handbook-Refrigeration, ASHRAE Publications
Atlanta, GA, 1998, p. 1.
[67] Wallis, G. B., One-Dimensional Two-Phase Flow, McGraw Hill,
NY, 1969.
[68] Macken, N. A., Scheideman, F. C , Jacobs, M. L., and Kazem, S.
M., "An Experimented Study of Pressure Drop and Liquid Transport of Oil-Refrigerant Mixtures," Final Report, ASHRAE Project RP-109, Atlanta, GA, 1976.
[69] Biancardi, F. R., Michels, H. H., Sienel, T. H., and Pandy, D. R.,
"Study of Lubricant Circulation in HVAC Systems," Final Report, ARTI MCLR 665-53100, Ariington, VA, 1996.
[70] ANSI/ASHRAE Standard 41.4-1996: Standard Method for Meas u r e m e n t of Proportion of Lubricant in Liquid Refrigerant,
ASHRAE Pubhcations, Atlanat, GA, 1996.
[71] Hewitt, N. J., McMuUan, J. T., Mongey, B., and Evans, R. H.,
"From Pure Fluids and Azeotropic Mixtures: The Effects of Refrigerant-Oil Solubility on System Performance," International
Journal of Energy Research, Vol. 20, 1996, pp. 57-67.
[72] Baustian, J. J., Pate, M. B., and Bergles, A. E., "Properties of OilRefrigerant Liquid Mixtures with Applications to Oil Concentration Measurement," AS//i?AE TmniacfioMs, Vol. 92, lA, 1986,
p. 55.
[73] Katsuna, K., Inoue, I., Mizutsini, T., Sudo, E., and Araga, T.,
"Real Time Oil Concentration Measurement in Automotive Air
Conditioning by Ultraviolet Light Absorption," SAE Paper
910222, Society for Automotive Engineers, Warrendale, PA,
1991.
[74] Newell, T. A., "In Situ Refiractometry for Concentration Measurements in Refrigeration Systems," International Journal of
HVAC&R Research, Vol. 2, No. 3, 1996, pp. 247-256.
[75] Worsoe-Schmidt, P., "Some Characteristics of Flow Patterns and
Heat Transfer of Freon-12 Evaporating In Horizontal Tubes," International Journal of Refrigeration, Vol. 40, 1960, pp. 40-44.
[76] Sienel, T. H., and Michels, H. H., "Lubricant Effect on Performance," presented at the ASHRAE Seminar 12, Dallas, TX, 2000.

MNL37-EB/Jun. 2003

Gear Lubricants
Vasudevan Bala^

FUNCTION OF GEAR LUBRICANTS

GEAR DESIGN AND THE LUBRICANTS USED FOR THEIR APPLICATION

have evolved continuously over the last 200 years [1]. These
improvements were largely attributed to advances in gear design, metallurgy, lubricant additives and base oil refining
[1,2]. Global trends in improved end user satisfaction, fuel
economy, lower down time, cheaper maintenance, and improved equipment durability have provided the necessary
motivation for increased competition among Original Equipm e n t Manufacturers (OEMs) [1-3]. As a result of these
trends, gear lubricants currently are formulated to meet exacting standcirds required to lubricate gear boxes and automotive drivelines. The following sections cover the basics in
gear lubrication and provide information in the selection of
proper gear lubricants depending on their end application.

EARLY GEAR LUBRICANTS


The history of gear lubrication dates back to Aristotle around
330 B.C. [4]. Since then application of gears in precursors to
m o d e m timepieces, windmills, and p u m p s were quite common. Table 1 summarizes early gear applications and theorists. The early gears were predominantly made of wood that
precluded the use of lubricants until cast iron was used to
fabricate gears [5]. In examples recorded during the building
of the p5Tamids, animal fats were used to lubricate wooden
rollers that were used to move massive stones [5]. It was,
however, with the introduction of spiral-bevel gears primarily for increased load-carrying capacities in the mid-1800s
that gear lubrication become severe. This led to the development of extreme pressure (EP) additives and the first patent
issued in 1869, describing the use of lead soap and active sulfur [6]. The first commercieil gear lubricants were mixtures of
animal fats and mineral oils. F r o m the late 1800s to the
1970s, the demands of the gear industry were met with additives based on lead, chlorine, zinc, sulfur, and phosphorus.
The use of lead oleates, napthenates, dithiocarbamates, and
sulfurized olefins provided the necessary anti-score and corrosion protection. During the 1930s, these additives were
found to be inadequate for jixles that operated under heavy
loads and high temperatures. This led to the combined use of
lead soaps, chlorinated paraffins, zinc dialkyldithiophosphates, and sulfurized olefins. By the 1960s, gear additives
were predominantly based on zinc, chlorine, and sulfur that
met Military, OEM, and industry standards. Table 2 illustrates EP gear chemistry used [7].

' Cognis Corporation, 4900 Este Ave., Cincinnati, OH, 45232.

The basic function of a gear lubricant is to reduce friction


between the gear teeth under contact, which reduces tooth
wear and prolongs its life. Another critical function of the
gear lubricant is to dissipate heat generated in the contact
zones. In automotive applications, the gear lubricant can reduce shock and noise emanating from reeir axles, hence providing s m o o t h a n d quiet operation during acceleration.
Other important functions of the gear lubricant during service are removal, and prevention of corrosion and pitting,
while prolonging gear life.
These functions collectively define the properties of gear
lubricants in automotive and industrial applications (described later). Gear lubricants meeting viscosity requirements, depending on their application, can assist in proper
start-up and the normal operation of gear boxes and axles.
Gear lubricants with very low viscosities can promote premature seizure of gear teeth, while those with high viscosities affect the efficiency and operating temperatures in gear
boxes and axles. In automobiles, the combined effects of
aesthetically pleasing aerod5Tiamics for improved fuel economy and installation of high performance engines, capable
of achieving higher peak torques at lower revolutions per
minute, collectively have increased sump operating temperatures and power densities transmitted by the gears used in
transmissions and axles. As a result of these effects, gear lubricants must resist oxidation and be thermally stable under normal and severe service. Gear lubricants can contain
dispersants that can disperse high molecular weight oxidation by-products or sludge, promoting clean operation of
the gear boxes. In some instances, build-up of sludge can
affect the performance of wheel-end and axle shaft lipseals, thus preventing loss of gear lubricant. The use of EP,
antiwear additives (AW), and friction modifiers (FM) can
protect the gear and bearing surfaces under boundary lubrication. The resulting drop in friction can reduce sump
temperatures, t h u s prolonging lubricant and equipment
(gears, bearings, seals) life. In high-speed operations (in paper and steel mills) or driving, gear lubricants are pumped
and splashed incessantly. As a result, foam suppression by
gccir lubricants is critical to prevent loss of lubricant delivery, cavitation, or implosion at the metal contact zones. In
certain industrial operations, water separation for regular
maintenance and lubricant top-off is desired. Other functions of gear lubricants include storage stability during
transportation and fuel economy benefits under most driving conditions.

431
Copyright'

2003 by AS'I M International

www.astm.org

432

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 1Early gear inventors and theorists.


Early Gear Information
Approximate
Date

Name
Aristotle

Item
Explained gear wheel drives in windlasses; pointed out that the direction of rotation
is reversed when one gear wheel drives another gear wheel.
Made water clocks and water organs using gears.
Made rack and pinion devise to raise water.
Made devices to multiply force or torque many times; studied spiral.
Described the first real use of power gearing in mill drives.
Described gears (cogwheels) for many uses; ceJculated actual gear ratios; devised
distance (cyclometer) eind angle (dioptra) measurements using gears.

330 B.C.
250
230
220
27
60

Otesibius (Greek)
Philo of Byzanitum
Archimedes
Vitruvlus
Hero

B.C.
B.C.
B.C.
B.C.
A.D.

Gear Theorists
Name

Approximate
Date

Nicholas of Cusa
Albert Durer
Girolamo Cardano
Philip de la Hire

1451
1525
1557
1694

French
German
Swiss
French

Charles Camus

1733

French

Leonard Euler

1754

Swiss

Abraham Kaestner

1781

German

Robert Willis
Edward Sang

1832
1852

English
Scotch

Nationality

Contribution
Studied cycloidal curve.
Discovered epicycloids.
Developed first mathematics of gears in print.
Developed full mathematical analysis of epicycloids; recommended involute
curve for gearing (involute not used in practice until about 150 years later.
Expanded on work of la Hire; developed theories of mechanisms; studied
lantern pinion and gear, crown gears, and beveled gears.
Worked out design principles and rules for conjugate action some consider
him the "father of involute gearing."
Wrote practical methods for computing tooth shapes of epicycloid and
involute gear teeth; considered 15 degrees to be a minimum pressure angle.
Wrote and taught extensively in gear fielda pioneer in gear engineering.
Developed generaJ theory of gear teeth; provided theoretical basis on which
all gear tooth generating machines are based.

TABLE 2Early EP gear oil additives.


S:2
1943

S:3

S:4

Date

S:l
1935

1948

1957

Cliemistry Type

S, CI

S, CI, P

Pb, CI, S*

Zn, S, CI, P*

Chlorine, %
Sulfur, %
Phosphorus, %
Lead, %
Zinc, %
Performance Level
Dosage, Wt %
Application

34
10

26
8
0.5

4.6
4.9

15
13
4

7.55
5-10
Automotive

GL-4'"
5-10
Automotive

GL-4*
28
Automotive

3.5
GL-4, GL-5*
5-10
Automotive

"Some versions of S-3 and S-4 contained limited slip additives.


'API gear oil classification system, Publication 1560.

GEAR TYPES
Gears can be classified according to their tooth profile,
shape, loading, and direction of torque transfer [8a]. The
choice of these different gear types depends on these factors
and is seen in automotive and industrial applications. The
basic function of gears is to transmit power along with increasing or decreasing shaft speed. Gears can also be used to
deliver the required torque and, depending on the gear design
used, can be used to change the direction or axis of rotation.
In specific automotive applications, gears are used to synchronize shaft speeds in transmissions and change torque
transfer in front and rear axles.
There are different gear types used in automotive and industrial applications. The c o m m o n gear types are spur, helical, herringbone, w o r m , straight, and spiral-bevel a n d
hypoid. Spur gears come in straight, helical, and herringbone
designs. The most c o m m o n type is the straight spur gear type
that sees no axial forces a n d uses simple bearing design.

Helical gears are used in applications when higher peripheral


speeds and quieter operations are needed. The resulting eixial
forces require more complex bearing design. With herringbone gears, axial forces are eliminated, but the tooth width is
generally twice as large compared to the helical design. Bevel
gears have intersecting axes, line contact and low slide/roll
ratios. Cylindrical w o r m gears also have crossed axes, line
contact, but large slide/roll ratios. They permit the transmission of high ratios under quiet, smooth, and low-vibration
operation. The hjrpoid gear design is predominantly used in
automotive axles. They have a high center off-set with
crossed axes, elliptical contact, and large slide to roll ratios.
Figure 1 illustrates the different types of gears and provides
information on their uniqueness and operation. These comm o n gears are used in automotive and industrial gear boxes.
The proper selection of gear sets is dependent on gear size allowed, load bearing limit, desired gear ratio for torque and
speed transfer. Table 3 provides additional information
on the selection of gear sets based on their gear ratio,

CHAPTER 16: GEAR LUBRICANTS

433

HELICAL GEARS

WORM GEARS

Teeth In Spiral Plane To


The Axis
Smoother Than Spur
Gears
Higher Load Capability
Multiple Tooth Contaot

Extreme Case Of Hypoici @ear

Hardened Steel And Bronze


Quiet
Smooth Operation
High Load Capability

SPUR GEARS
Teeth In Parallel Plane To The
Axis
Oast Iron Or Steel
Noisy
Rough Operation
simple And Economical To
ManufQeture
single Tooth Contaot
Rolling And Sliding Motion

HERRINGBONE GEARS

Expensive To Manufacture
Quiet
Smoom Operation
Used For High Speed
Gearing

HYPOID GEARS
BEVEL GEARS

Form Of Spiral Bevel Gear


Pinion Axis Does Not Intersect
Ring Gear Axis
Smooth Running
Light Weight And Cempoet
Severe Sliding Action
Sleel Due To High Tooth
Loading

Axis Centers Intersect

Noisy
Rough Operation
Limited To Low Siseeds
Greater Load Capabiltly
With Spiral Bevel

FIG. 1Different types of gear sets [8].

TABLE 3- Performance comparison of various types of gear sets.


Position of Axes
Parallel

Intersecting

Gear Type
Spur
Straight
Helical

Bevel
Straight
Skew

Maximum
Transmission
Ratio

Maximum
Peripheral
Speed

Maximum
Output
(kN)

Maximum
Torque
(kNm)

10
10
10
10

5
25
200

2250
7500
22500
22500
22500

9000
2300
600

375
3750
3750

90
90
45

750
75
750

300
170

7
7
7

2.5
2.5
60

Crossing at 90

Worm
Crossed Helical
H5^oid

50
50
50

60

Crossing at 80-100
(not 90)

Worm
Crossed Helical

50
50

50

115
170

434 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


peripheral speed, load, and torque [9]. The selection of the
proper gear lubricant for these c o m m o n gear sets is dependent on the application and requirements set forth to meet
certain gear box or axle performance criteria. This is further
elaborated later in this chapter under Classification of Gear
Lubricants for automotive and industrial applications.

METHODS OF GEAR LUBRICATION


The c o m m o n modes of gear lubrications are [8a]:
manueJ application with brushes
drip feed from reservoir or tubes
intermittent or continuous lubrication under pressure or
splash
In the selection of gear lubrication, consideration has to be
given to the end application and the prevention of gear failure.
Manual application or drip feed is used for open gear sets
where the temperature rises and load and wear on the gear
teeth are all low due to the operation, and where the gears can
be lubricated easily by a single application or repeated applications at long intervals [9]. Gears that demand longer service
life operate continuously with high peripheral speeds (0.8-3
m/s) under moderate loads during operation re- quire intermittent lubrication. Continuous lubrication via splash, p u m p assisted or pressure fed is generally provided for power transmission with closed housings. Oil splash lubrication is by far
the most c o m m o n method of lubricating gears. It combines
the advantages of efficiency, continuous lubrication, and
cooling over a wide range of speeds and loads. Effective splash
lubrication where one of the gears dips into the reservoir and
provides lubrication to the other gears is seen in industrial applications, automotive transmissions, and axles where closed
gear housings are predominantly used [5].

nation within the lubricating system [8a]. Failures resulting


from these effects cem lead to serious tooth surface damage
such as pitting, spalling, wear, and scuffing. Table 4 provides
the basic failure modes encountered in gear lubrication
[10,11a].
Descriptions of common lubrication related failures in pitting, micropitting, adhesive wear, abrasive wear, polishing
wear, and scuffing and their prevention follow.
Pitting is a fatigue phenomenon and occurs when a surface
initiated crack propagates into the metal before turning towards the surface [10,lla,12]. In some instances, pitting can
also be initiated from a subsurface defect or inclusion, usually impurities (Fig. 2). When several pits grow together, the
large pit is referred to as a spell. The recommended guidelines to prevent the onset of pitting and/or spalling in gear
sets are [11a]:
reduce contact stresses by reducing loads
improve material strength of gear metal
increase specific film thickness (defined as film thickness/surface roughness)
Micropitting, as the name suggests, is similar to pitting except that the pit sizes are several orders smaller [10,lla,12].
Other names used to describe micropitting are gray staining

GEAR FAILURE MODES


C o m m o n gear failures usually can be traced to lack of
lubrication, improper lubrication for the hardware, use of
incompatible lubricant and/or additives, or possible contami-

FIG. 2Example of common gear failure


pitting. Courtesy of AGMA from Standard ANSI/AGMA
1010-E95.

TABLE 4 -Basic failure modes of gear teeth.


Non-lubrication-related Failures
Overload
Bending Fatigue

Brittle fracture
Ductile fracture
Plastic deformation
Cold flow
Hot flow
Indention
Rolling
Bruising
Peening
Brinelling
Rippling (fish scaling)
Ridging
Bending (3aelding)
Tip-to-root interference

Low-cycle fatigue
(scycles to failure)
High-cycle fatigue
( a 1000 cycles to failure)

Lubrication-related Failures
Hertizan Fatigue

Wear

ScuiBng

Pitting
Initial
Superficial
Destructive
Spalling
Micropitting
Frosting
Gray staining
Peeling
Subcase fatigue
(case crushing)

Adhesion
Running-in
Mild
Moderate
Severe
Excessive
Abrasion
Scoring
Scratching
Plowing
Cutting
Gouging
Corrosion
Fretting corrosion
Cavitation
Electrical dischsirge damage
Polishing (burnishing)

Scoring
Galling
Seizing
Welding
Smearing
Initial
Moderate
Destructive

CHAPTER
and frosting [8a] (Fig. 3). The specific film thickness has been
identified as a key parameter that influences micropitting [8].
The recommended guidehnes to prevent the onset of micropitting in gear sets are [11a]:
use smooth tooth surfaces produced by grinding or honing
use adequate amount of gear lubricant of the highest viscosity possible
use of high speed
use of carburized steel
Adhesive wear can be classified as mild or severe depending
on the cimount of wear seen on the gear tooth [10,11 a, 12]. Mild
adhesive wear generally occurs during break-in when the tooth
surface asperities are removed to improve the specific film
thickness. Severe wear has occurred when there is a significant
change in the tooth profile. The recommended guidelines for
preventing the onset of adhesive wear in gear sets are [11a]:
use smooth tooth surfaces
run-in new gear sets at 1/2 the load before use
Use higher speeds when possible. Under slow-speed high
loads, use nitrided gears combined with highest viscosity
lubricants
Abrasive wear is usually caused by foreign contamination
or wear debris from run-in of the gear sets [8a, 10,11a, 12]
(Fig. 4). Contamination can originate from inherently unclean gear boxes during build-up, ingressed through breather
valves a n d seals. Proper m a i n t e n a n c e of the gear box by
regular visual inspections and analyses of the lubricants can
reduce abrasive wear. The recommended guidelines for preventing abrasive wear in gear sets are [11a]:
1. Remove contamination during build-up with proper flushing and draining of the lubricant.
2. Refill with fresh lubricant and filter where applicable.
3. Use smooth surface hardened gears in combination with
high viscosity lubricants
4. Adopt regular maintenance schedules
5. Use filtrating systems with circulating oils
6. Follow OEM recommended drain intervals
7. Conduct used oil analyses to m o n i t o r condition of the
lubricant
Polishing wear is believed to be caused by continuous removal of the reactive boundary layer by fine abrasive material

FIG. 3Example of common gear failure


micropitting. Courtesy of AGMA from Standard
ANSI/AGMA 1010-E95.

16: GEAR LUBRICANTS

435

FIG. 4Example of common gear failureabrasion.


Courtesy of AGMA from Standard ANSI/AGMA
1010-E95.

FIG. 5Example of common gear failure


polishing. Courtesy of AGMA from Standard
ANSI/AGMA 1010-E95.

in the lubricant [8a,10,lla,12] (Fig. 5). The use of EP and


antiwear additives can alleviate this type of wear. The recommendations for reducing polishing wear in gear sets are [11a]:
Use of lubricants with the properly selected gear additives
Continuous filtration to remove fine abrasive debris present in lubricant
Scuffing is defined as localized welding between mating
metal surfaces. This genereJly occurs when the gears operate
under boundary lubrication [8a, 10,11 a, 12] (Fig. 6). Gears are
prone to scuffing, especially during start-up. It is not uncomm o n to use gears coated with phosphorus-maganese (lubrited), copper, or silver to prevent scuffing during run-in. Gear
lubricants containing sulfur-phosphorus additives are formulated to reduce scuffing. The following guidelines are
recommended to reduce scuffing [11a]:
1. Use gears with smooth surfaces that were honed.
2. Use gears with coatings to reduce propensity to scuff.
3. Use high viscosity lubricants containing sulfur-phosphorus additives.
4. Use heat exchanger to cool the lubricant sump.
5. Use nitrided gears.
Several references [4,5,10,1 la,13] provide further details
that elaborate on gear failure modes. The American Gear

436

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Manufacturers Association Standard ANSI/AGMA 1010-E95


[12] provides a common language to describe gear weeir and
failure and serves as a guide to uniformity and consistency in
the use of its language. It describes the appearance of gear
tooth failure modes and mechanisms to facilitate the
identification of gear wear and failure.

GEAR LUBRICATION
The conforming surfaces of gear teeth in mesh can operate
under three different modes of lubrication: boundary, mixed,
and elastohydrodynamic. Boundary lubrication occurs
during start-up or stopping conditions. In certain conditions of heavy loads and slow speeds e.g., towing, boundary

FIG. 6Example of common gear failurescuffing.


Courtesy of AGMA from Standard ANSI/AGMA
1010-E95.

condition persists between the pinion and ring gears in automotive hypoid axles. Under boundary conditions, the additive system present in the gear lubricant prevents scuffing,
metal adhesion, and wear.
Under higher speeds and/or lighter loads, the gears operate
under mixed lubrication. Under mixed lubrication, gear surface asperities still come in contact and wear occurs at a
slower rate than under boundary lubrication. Both the viscosity of the gear lubricant and the additive system can influence
optimum gear performance under mix lubrication. ElastohydrodjTiamic (EHD) lubrication provides the optimum condition under which separation of gear teeth occurs, minimizing
wear. The lubricant's viscosity is important under EHD lubrication and is affected by proper selection of the lubricant viscosity grade. Table 5 provides the necessary equations that describe the calculation of film thicknesses under EHD for spur
and bevel gears with straight and helical teeth [9].
Figure 7 shows the typical contact between gear teeth for
spur, helical, and bevel gears [14]. The contact starts with
high sliding and some rolling. The sliding reduces to pure
rolling at the center of the gear tooth or pitch line after which
rolling decreases with increasing sliding. Generally, under
these conditions, the gear teeth undergo boundary to EHD
and back to boundary lubrication. Mixed and boundary lubrications generally persist for hypoid gear sets. EHD theory
has shown that film thicknesses of ~1 micron can prevent
surface asperities from coming in contact [15]. Under the
conditions of high pressure, the lubricant can exhibit viscosity increases that maintain film thickness. Increases in the
relative velocities of the gear tooth surfaces, gear lubricant
viscosity, and in the radius of curvature at the point of contact, can lead to gear oil film thicknesses more dramatically
than proportionate reductions in unit tooth load, or elastic
modulus of the gear metal [9].

Table 5Symbols used in elasto-hydrodynamic film thickness calculation [9].


Gap parameter
P
Load parameter
Ep

^ = "4
G'=^aE

^mia

^O

a
= ! ( , + uj)

p^

PI

Pi +
E

PI

PJ

X ,

^^>
2(1 - <^i) + (! - 'I)

T ffj

w'^FIb

Velocity parameter
Material parameter
Minimum film thickness between surfaces
Operating viscosity at atmospheric
pressure
Pressure coefficient of viscosity
Effective peripheral
velocity of two surfaces
Effective radius of curvature of the
two surfaces
Effective modulus of elasticity
of the two materials
Poisson's ratio for the two materials
Normal tooth force per unit tooth
width

CHAPTER 16: GEAR LUBRICANTS

437

pinion pitch cSroie

(to) Pitch point

(} First point of contact


(c) L t point of contact

FIG. 7Relative motion of meshing gear tooth surfaces. Reprinted with permission of CRC Press, Boca
Raton, FL. [14].
Table 6Calculation of the effective radius of curvature [9].
I l l
2
i
- = + = -r-r-x
p />! P2 sin/J ' V"0.
Spur gear
Straight teeth

p =

Helical teeth

Pn =

1 = pinion;

"0. 2 /

Bevel gear (90 degrees)

ai sin p

p = /! sin P,

( 1)'
ai sin ^
CDS'* Y{i 1)^

2 = gear;

'yAi' + iJ

4- = external teeth;

p radius of curvature
d^ = pitch diameter
a centre distance
A - cone distance

Table 5 provides the description of the symbols used in


m i n i m u m film thickness equation. The effective values for
velocity, load, modulus of elasticity and curvature are determined first. Tables 6-8 contain information for calculating
the effective radius of curvature, peripheral velocity, and specific normal tooth force, respectively. The viscosity-temperature and pressure-viscosity coefficient of the lubriccint at the
operating temperature are determined. These are obtained
by the following equations.

= internal teeth

t = transmission ratio
P = mesh angle
Y = helix angle

The methodology for performing m i n i m u m film thickness


calculations applicable to gear pairs (spur and bevel gears) is
provided next [9]. The m i n i m u m film thickness equation is

log log (v + 0.7) = A - B log T

A
~ cos*

"

a=1.030+3.509(logvo)^
+ 2.412*10-'*mgi'^(logvo)1.5976
-3.387 (logVo)^'V"".
where:
a =
mo =
vo

p =

pressure-viscosity coefficient, [10~*Pa~']


viscosity-temperature property from the ASTM
Walter equation and equal to (ASTM slope)/0.2
atmospheric kinematic viscosity at the temperature of interest, [mm^/S]
atmospheric density at the temperature of interest, [lO^kg/m^]

These values are used to calculate the minimum film thickness. Table 9 provides the variation for the different paired
gears of spur and bevel types.

where:
log
V

T
AandB

logarithm to base 10
kinematic viscosity, [cSt] or [mm^/s]
Temperature, [K] or [R]
dimensionless constants

TYPES OF GEAR LUBRICANTS


Most commonly available gear lubricants are blended from
petroleum basestocks. The following categories briefly de-

438

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Table 7Calculation of the effective peripheral velocity [9].

At pitch point: u = u, KJ p,tOi = Pico^


Spur gear
Straight teeth = ^
Helical teeth

Bevel gear (90 degrees)

( j sm ^.

= - ^

u= ^

(^-A.) 3i ^

>t sin ^

= __^^^sin^

1 = pinion; 2 = gear; + = external teeth; = internal teeth


n = rotational speed
i = transmission ratio
A = cone distance
p = mesh angle
a = centre distance
Y = helix angle
u = peripheral velocity

Table 8Calculation of the specific normal tooth force [9].

F
w= F
F = ^;
cos fit,
P=
^
w
F
b
Fu

straight teeth

F
T-^
77:; hehcal teeth
(cos ^ i , cos y,)
2M

= specific normal tooth force


= normal tooth force
tooth width
= peripheral force

M = torque
dy, = pitch circle diameter
^ = mesh angle
7 = helix angle

Table 9Calculation of elasto-hydrodjmamic film thickness [9].

ft, = 2.65 X a^'^lnowf >***-*'*'*w-^


Spur gear
Straight teeth
,

2.65 X,

'miB

0.54 /

_ \0.7

rO.*S

0.03

Helical teeth
2.65 X a-^* /
nnj^y
(a sin ^ J " ^
i*'
'mi- 0.03^0.13 ^^'^o 3 Q J X c o s " y ( i l ) '
Bcpc/ gear
Straight teeth
2.65 X ' * /

nn,Y\

"mi- = 0.03^0.13 ( ''O -^j

i^m Sm P)

'13

0.27
'

(,2 + j)0.43

Helical teeth
2.65 X a '* /
'''"

"H''''M''*'

nnX''
30;

i^m sn ^ , 1.13
) " ' , 0 . 2 7
cos''*y
(F + l ) * '

CHAPTER
scribe the Vcirious types of gear lubricants and their general
applications [14,15]. Gear lubricants can fall under any one
of these categories and their fined application, whether industrial or automotive, is predicated on the meeting of specific performance requirements that will be discussed later in
the chapter.
R u s t a n d O x i d a t i o n I n h i b i t e d ( R & O) O i l s
R & O oils are mineral oils containing rust and oxidation inhibitors, antifoamants, and/or antiwear additives. The rust inhibitors prevent corrosion of the metal surfaces by slowing the
formation of acids and free radicals that are the by-products
formed at the onset of oxidation. Without oxidation inhibitors,
these acids and free radicals can form high moleculeir weight
sludge and deposits manifesting as viscosity increase [26]. Inhibited oils are used in gear application under light to moderate loads. This type of gear lubricant can be used to lubricate
bearings and gears operating between - 2 0 to 120C. Inhibited
oils can be reconditioned with filters to ensure cleanliness even
with wear debris and contaminants are present.

16: GEAR LUBRICANTS

439

cation in w o r m gear drives where high sliding speeds between the gear teeth requires lubricity additives to reduce
friction and improve torque efficiency. Compounded oils are
required to operate in the temperature range of 5-120C.
Constant relubrication of the gear teeth is recommended due
to the unique gear mesh that wipes off the oil from the teeth
after contact. Reconditioning of the oil similar to inhibited
oils is quite common.
Open Gear Compounds
These oils are used in large gear sets t h a t move at slow
speeds. These lubricants contain tackifiers that adhere to the
gear teeth that resist being thrown-off or squeezed out of the
mesh. Solvents are sometimes used to help in the application;
they then evaporate leaving behind a thick lubricant film.
The normEd operating temperature range for these lubricants
is 5-120C. This type of lubricant does not offer any advantage that circulating lubricants do for cooling and heat
removal.
Greases

E x t r e m e P r e s s u r e Oils
Extreme pressure oils contain additives predominantly of the
sulfur & phosphorus type to reduce destructive wear and
scoring. These additives combine with the metal surface under frictional heating and provide a sacrificial boundary film
that is easily sheared. EP oils can also contain other surface
active non-sulfur/phosphorus based additives. Examples include graphite, molybdenum disulfide, potassium triborate,
and additives containing bismuth. EP oils are used to lubricate spur, helical, and spiral-bevel gears u n d e r loads too
heavy for inhibited oils. EP oils with the addition of dispersants and detergents can b e used in hjrpoid axles that are exposed to heavy loads or shock loading. Shock loading occurs
under sudden heavy accelerations and decelerations that can
promote scoring at the gear surfaces. These automotive applications will be elaborated later in the chapter. The useful
temperature range for EP oils is generally - 2 0 to 120C. It is
not u n c o m m o n to see automotive gear lubricants subjected
to temperatures from 54 to 170C.

C o m p o u n d e d Oils
These oils contain fat or tallow as lubricity agents in heavy
cylinder basestocks to reduce friction. These oils find appli-

Greases are usually mineral lubricants that are thickened with


soaps to a gelatinous consistency. The thickener holds the liquid lubricant and releases it when in use. The advantage of
greases is that they do not have to be added continuously.
Greases can act as sealants to keep contaminants out. Packed
wheel bearings and small gear boxes in household appliances
are typical examples where greases are used. Greases are restricted to gears or bearings that operate at slow-speeds and
more importantly, light loads. The useful operating temperatures for greases are 30 to 120C, depending on the base oil
and soap used. Table 10 summarizes the various types of gear
lubricants and their application [15].

ADDITIVES USED IN GEAR LUBRICANTS


As stated before, the purpose of gear lubricants is to reduce
friction and wear between gear teeth, dissipating frictional
heat (not referring to greases), removal and reduction of
sludge and deposits, and prolonging gear tooth life. The additives used in gear lubricants impart and enhance the lubricating properties of mineral and/or synthetic base oils in
which they are blended. The general properties of mineral
and synthetic base oils are described later in the chapter.

TABLE 10Types of gear lubricant used with various gear applications.


Gear Types
Lubricant
R & O oil (non-EP)

Spur
Normal loads

Helical
Normal loads

EPoil

Heavy or shock
loading
Not normally
used
Slow-speed
Open gearing
Slow-speed
Open gesiring

Compounded oil
(ca. 5% tallow)
Heavy-bodied
open gear oils
Grease

Bevel
Normal loads

Hypoid
Not recommended

Heavy or shock
loading
Not normally
used
Slow-speed
Open gearing

Worm
Light loads
Slow speeds only
Satisfactory for most
applications
Preferred by most
gear manufacturers
Slow-speeds only
EP additive desirable

Heavy or shock
loading
Not normally
used
Slow-speeds
Open gearing

Slow-speed
Open gearing

Slow-speeds only
EP additive desirable

Slow-speeds
Open gearing

Required for most


applications
For light loading
only
Slow-speeds only
EP additive
required
Not recommended

440

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

Gear lubricants can be referred to as nonengine lubricants


used in noncombustible environments. The additives in gear
lubricants can be classified as chemically active or inert. Examples of chemiccilly active additives are dispersants, detergents, antiwear, EP, oxidative inhibitors, friction modifiers,
rust, and corrosion inhibitors. These additives generally
interact, via adsorption and/or decomposition and/or rearrangement, with surfaces and with polar oxidation bi-products. Examples of chemically inert additives are emulsifiers,
demulsifiers, p o u r point depressants (PPDs), seal swell
agents, antifoamants, a n d polymeric thickeners. These
additives alter the physiccJ properties of the finished gear
lubricant.
Most gear additive systems consist of all or most of the following additives components:
extreme pressure agents
detergents
dispersants
friction modifiers
oxidation and corrosion inhibitors
antiwear agents
demulsifiers and emulsifiers
foam inhibitors
pour point depressants
These additives and their currently understood mechanism
of activity are described in the following section. There, it will
become apparent that some of these additives Eire multifunctional and understanding their S5Tiergistic and antagonistic
properties towards each other collectively in the gear lubricant will allow formulators the ability to meet their performance targets.
Extreme Pressure (EP) Agents
The purpose of EP agents is to reduce metal wear from scoring, cold welding, and seizure under conditions of high loads.
Typical c o m p o n e n t s t h a t provide E P properties are zinc
dialkyldithiophosphates (ZDDP), alkyldithiophosphates, sulfurized olefins, alkylpolysulfides, sulfurized fats, potassium
triborate, and chlorowaxes. Other examples are lead, bism u t h , and molybdenum dithiocarbamic and organic acid
derivatives. Lead Etnd chlorine containing EP agents are becoming less popular due to their potential environmental and
hazardous impact. Most sulfur and some phosphorus containing components can function as good EP agents.
ZDDPs are formed by reacting organic alcohols with phosphorus pentasulfide to form dialkyldithiophosphoric acids,
which are subsequently reacted with zinc oxide to form zinc
salts. Organic dialkyldithiophosphates are made without the
last reaction. Sulfurized olefins are m a d e by reacting elemental sulfur with olefins at high temperatures forming a
mixture of sulfur containing compounds. Chlorowaxes are
manufactured via a similar process using chlorine and fatty
paraffins. Zinc, bismuth, emd molybdenum salts of dithiocarbamic acid are made by reacting the acid derived from reacting dialkylamine and carbon disulfide with the metal oxide.
Polysulfides are generally prepared by oxidizing alkyl mercaptans. EP agents are relatively surface active and adsorb on
metal surfaces. Frictional heat derived from sliding u n d e r
high loads provides enough energy for bond scissation to occur, forming a sacrificial boundary film of lower yield stress

than the metal itself. The boundary film prevents scoring,


colding, welding, and seizure of gear surfaces.
Antiwear Agents
The purpose of antiwear agents is also to reduce frictional
wear, but under conditions of low loads. Typical components
t h a t provide antiwear properties are zinc dialkyldithiophoshates, alkyl phosphates and phosphites, aryl phosphates
and phosphites, p o t a s s i u m triborate, a n d chlorowaxes.
Phosphates and phosphites are manufactured by reacting
alcohols with phosphorus pentoxide, or trichloride, respectively. Generally, alkyl p h o s p h a t e s a n d phosphites are
neutralized with amines for enhanced surface adsorption.
Their function to reduce wear is similar to EP agents via surface adsorption and decomposition under frictional heating
to form a sacrificial b o u n d a r y film. Generally, antiwear
agents are more surface active than EP agents. Thus, their
content in gear lubricants is generally lesser than EP agents
by comparison.

Detergents
Detergents keep metal surfaces clean of deposits. Tjrpical
types of detergents are alkali earth metal (sodium, calcium,
magnesium) sulfonates, phenates, salicylates, and carboxylates. These additives neutredize organic acids from lubricant
oxidation and also associate with precursors that form sludge
and varnish. This has the overall effect of keeping metal surfaces clean of deposits. Consequently, the m a n n e r in which
detergents react with oxidation byproducts can result in prolonging the use of gear lubricants and maintaining clean
working gear boxes. Neutral and basic metal sulfonates are
formed by reacting alkylbenzenesulfonic acids with metal hydroxides or oxides (calcium, magnesium, sodium types) to
form salts. Neutral salts are formed with correct stoichiometry and overbased salts are formed in the presence of carbon
dioxide. Neutral and overbased metal phenates and carboxylates are prepared similarly to sulfonates except cJkylphenols
and alkylsalicylic acids, respectively, are used instead of
alkylbenzenesulfonic acids.

Dispersants
Dispersants keep insoluble contaminants dispersed in the
bulk lubricant. Typical examples of dispersants used in gear
lubricants are of the alkenylsuccinimide, succinate ester,
Mannich derived, and alkenylphosphonic acid derivatives.
The latter is seldom used as the other three types see dominant use in crankcase engine lubricants. In manufacturing
alkenylsuccinimides, succinic anhydride is prepared first by
reacting polyalkenes with mzJeic anhydride. The most comm o n polyalkene used is polyisobutene. The resulting polyisobutene succinic a n h y d r i d e is then neutralized with
aJkylenepolyamines to form polyisobutene succinimides.
In some instances, further reaction of polyisobutene
succinimides with m e t a b o r i c acid is commonly used to
impEirt seal compatibility and enhance deposit and Vcimish
control. Alkenylsuccininate esters are formed by reacting
polyisobutene succinic anhydride with polyhydric alcohols. Mannich derived dispersants are formed by reacting

CHAPTER
formaldehyde, pol}dsobutenyl, and alkylenepolyamines. Disp e r s a n t s associate with p r e c u r s o r s of insolubles, t h u s
controUing deposit formation. The presence of a long hydrocarbon chain in polyisobutene helps in suspending the precursors of insolubles in the bulk lubricant.

16: GEAR LUBRICANTS

441

are edkylated naphthalene and phenolic polymers and polymethacrylates. Alkylated naphthalene is formed by the reaction of napthalene with chlorowax or olefins in the presence
of aluminum chloride. Alkylphenolic polymers are also prepcired in similar fashion. These pour point depressants all act
in similar fashion by hindering the formation of wax from the
base lubricant by adsorption on wax crystals.

POLYMERIC THICKENERS
Polymeric thickeners are also c o m m o n l y referred to as
viscosity modifiers a n d viscosity index improvers. They
function to reduce the lubricant viscosity's dependence on
t e m p e r a t u r e . Typical examples of these include polyisobutene, polymethacrylates, and copolymers of st5Tene and
butadiene. Isobutylene is polymerized to desired molecular
weights in the presence of a Lewis acid. Polymethylacrylates
are prepeired by free radical polymerization of alkyl acrylates
and methacrylates. Styrene butadiene polymers are formed
by free radical polymerization of styrene-butadiene mixtures
in the presence of vanadium based catalysts. Similjir process
is used in the polymerization of olefin block copolymers. This
latter type of poljTner is not commonly used due to its high
manufacturing cost. The molecular weight of these polymers
vary greatly. Due to shear stability constraints imposed by viscosity classification for gear lubricants, the molecular weights
(MW) generally range from 5000-50 000, depending on polym e r type. The most c o m m o n tj^e of viscosity modifier used
for gear lubricants is polyisobutene, whose MW is around
5000. All viscosity modifiers act in similar fashion. At low temperatures, the polymers are tightly coiled cind their effects on
the viscosity are low. As temperature increases, the polymer
uncoils and occupies more space. This has the overall effect of
not reducing the lubricant's viscosity at high temperatures.

F o a m Inhibitors
Foam inhibitors act to deter the formation of foam in applications where there is substantial a m o u n t of churning and
p u m p i n g , e.g., automotive axles. Typical c o m p o u n d s are
polydimethylsiloxanes a n d polyalkylmethacrylates. These
compounds effectively reduce the surface tension of the airlubricant interface, thereby facilitating their collapse.
Polydimethylsiloxanes a n d alkyl methylacrylates are prep a r e d by polymerization of dimethylsiloxane a n d alkyl
methylacrylates.
Friction Modifiers
Friction modifiers are c o m p o u n d s that act to reduce the
coefficient of friction. Certain antiwear and EP agents such
as long chain edkyl phosphates and molybdenum compounds
can be used as friction modifiers. Other examples of friction
modifiers are graphite, fatty alcohols, acids, and amides.
Friction modifiers adsorb on the metal surfaces with their
polar ends, thus forming a b o u n d a r y film with desired
properties.
Pour Point Depressants
These compounds enable the gear lubricant to flow at low
temperatures. Tjqjical examples of p o u r point depressants

Oxidation Inhibitors
Oxidation inhibitors function to inhibit the oxidation and
decomposition of the gesir additives and lubricant. Examples
of oxidation inhibitors are ZDDPs, polysulfides, hindered
and sulfurized phenols, and aromatic amines. The preparation of ZDDPs and polysulfides has been described. Hindered
phenols are made by Lewis acid catalyzed alkylation of phenol or aJkylphenol with poljdsobutylene. Sulfurized phenols
are formed by reacting alkylphenol with sulfur monochloride. Arylamines are prepared by alkylating diphenylamine
with a n olefin in the presence of aluminum chloride. Oxidation inhibitors function to decompose hydroperoxides and
radicals formed during oxidation. The reduction in hydroperoxides and radicals slows down the rate of oxidation of
the gear lubricant.

Corrosion Inhibitors
Corrosion inhibitors function to prevent corrosion and rusting of metal peirts in contact with the gear lubricant. Comm o n examples of these are ethoxylated phenols, sulfonate
based detergents, triazoles, and thiadiazoles. Polyethoxylated phenols and amines are formed by reacting ethylene
oxide, alkylphenols, a n d amines. Benzotriazole is m a d e
from diazotization reaction with nitrous acid. Dimercaptothiadiazole (DMTD) derivatives are made of sodium salt
of DMTD with Ein alkyl halide. Corrosion inhibitors adsorb
on the metal surface via their polcir ends. Some of these,
such as DMTD derivatives, can be used to prevent corrosion
against yellow metals s u c h as synchronizers and brass
washers.

Demulsifiers and Emulsifiers


Demulsifiers enhance water separation from the gear lubricant c o n t a m i n a t e d with water. Emulsifiers promote the
mixing of water and oil to form an emulsion. Examples of
demulsifiers cire block polymers of ethylene oxide, or propylene oxide and glycerol, siloxanes, polyamines, and polyols.
Common examples of emulsifiers are hydroxyalkylamines,
amides, a n d ethers. Demulsifiers function oppositely of
emulsifiers. They migrate to the water-lubricant interphase
to create low viscosity zones, thus promoting the cocdescencing of water or lubricant. On standing, gravity drives the
separation of water from oil. Emulsifiers reduce the surface
tension of water, thus promoting its mixing with oil.
Tables 11-18 [ 8 a , b , l l b ] provide a s u m m a r y of additive
tjrpes and their function, with examples given for each type.
These tables also provide details on their chemical structure
and the general mode of sjmthesis. The additives described
are collectively formulated into mineral cind/or synthetic base
oils. Table 19 summarizes typical properties of base oils that

442 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 11Chemically active additives and their function.
Additive Class
Antiwear and extreme
presure (EP) agents

Purpose
Reduce Mction and Wear,
and prevent scoring and
seizure

Typical Compounds
Zinc dialkyl dithiophosphates, di or
tri-alkyl and atyl phosphites, alkyl
phosphoric acid esters and salts,
organic sulfides and polysulfides,
sulfurized fats, dithiocarbamic acid
derivatives, and chlorowaxes."

Mechanism of Performance
These additives react with the metal
surface to form a sacrificisil
chemical film with lower shear
strength than the metal itself.
This not only inhibits welding of
two surfaces in contact but also
minimized metal removal due to
friction.

Corrosion and rust


inhibitors

Prevent corrosion and rusting


of metal parts in contact
with the lubricant

Ethoxylated phenols, neutral and basic


metal sulfonates, alkanolamines,
alkenylsuccinic acids, and heterocyclic
compounds, such as alkyltriazoles
and dimercaptohiadiazole (DMTD
and their derivatives.)*

These chemicals adsorb on the


metal surfaces via their polar
ends"^ and at the same time
associating with the lubricant via
their hydrocsirbon groups. This
allows the formation of a durable
lubricant film that acts as a
barrier against corrosion-causing
materials. Some of these are
basic and have the ability to
neutralize corrosive acids as well.

Detergents

Prevent metal attack by acidic


byproducts of combustion
and oxidation and keep
metal surfaces free of
deposits

Neutral and basic (contain base reserve,


usueilly as metal carbonate sodium
calcium and magnesium sulfonates,
phenales, and carboxylates.)

These additives perform by two


mechanisms. (1. They neutralize
organic acids that result from
lubricant oxidation. (2. They
associate with sludge and
varnish precursors and keep
them dissolved in oil. Both
these mechanisms prevent
deposit formation, thereby
keeping meteil surfaces clean.

Dispersants

Keep insoluble contaminants


dispersed in the lubricant

Alkenylsuccinimides and succinate


esters, Mannich products, and
alkenylphosphonic acid derivatives

These chemicals, like detergents,


associate with deposit precursors
and prevent their agglomeration
to insolubles. The presence of
long hydrocarbon chains in
dispersants help in suspending
these precursors in the bulk
lubricant.

"Tlieir use is being discontinued due to perceived negative impact of chlorine on the environment.
^Heterocyclic compounds are useful in controlling yellow metal corrosion.
A11 additives except some viscosity modifiers and pour point depressants have a polar end and a non-polar hydrocarbon chain.
Polarity is due to the presence of a nitrogen, oxygen, sulfur, or phosphourus-containing functional group.

are used to blend automotive and industrial gear lubricants.


The two categories of base stocks shown are mineral and
synthetic. Mineral base stocks typically are solvent refined
from crude and have viscosities ranging from approximately
4-30 cSt at 100C. Synthetic base stocks are chemically different and cein range widely in viscosities. The selection of
these various base stocks (mineral and/or synthetic) is
dependent on the cost, application, and performance of the
gear lubricant. There are no definite rules to follow except
that any combination of base stocks can be used to meet the
viscosity and performance targets, e.g., oxidation of the formulated gear lubricant.

well [16-18]. The purposes of defining service designations


and classifications cire:
to promote a uniform practice for use by marketers of gear
lubricants and by OEMs in identifying and recommending
these lubricants by service designations [16-18].
to assist the users of automotive and industrial equipment
in the selection of gear lubricants for field use [16-18].
The following sections cover specifications to meet comm o n automotive and industrial gear lubricant requirements.
A glossary of test methods covered is provided following this
section.
Automotive Gear Lubricants

CLASSIFICATION AND PERFORMANCE


TESTING OF GEAR LUBRICANTS
This section covers some commonly used requirements for
qualifying automotive and industrial gear lubricants. Even
though the purpose for developing SAE J308 was its application to automotive and manual transmission lubricants,
the requirements apply to industrial gear lubricants as

The evolution of gear lubricants to their present composition


and service requirements began with the introduction of hypoid gears by Gleason Works in 1925 [5]. This design was
adopted because it provided automobile manufacturers the
advemtages of a lower center of gravity, lower weight, quieter
operation, and greater load carrying capabilities. However,
the lubrication of h5rpoid geeirs proved challenging. They required gear lubricants with enhanced EP performance. At the

CHAPTER 16: GEAR LUBRICANTS

443

TABLE 12Chemically inert additives and their function.


Additive Cass

Purpose

Typical Compounds

Functions
These materials have the ability to
complex with metal ions to make
them inactive. This inhibits the
oxidation-promotion action of
metal salts.

Metal deactivators

Reduce catal5'tic effect


of metcils and their
salts on the rate of
oxidation

Complexing agents, such as


ethylenediaminetetraacetic acid (EDTA
and diseJicylidene-propanediamine)

Oxidation inhibitors

Inhibit oxidative
decomposition of
lubricant and
additives

Zinc dialkyl dithiophosphates, organic


sulfides and polysulfides, sulfur-coupled
phenols (phenol sulfides and hindered
phenols, and aromatic amines)

These additives have the ability to


decompose hydroperoxides and
to make radicals innocuous. Both
these species promote oxidation.
Their removal from the reaction
sequence results in a slowdown
of oxidation.

Emulsifiers

Promote mixing of
water and oil to
form an emulsion"

Nonionic surfactants, such as hydroxyalkyl


amines, amides and ethers, and ionic
surfactants, such as sodium carboxylate
and trialkyl-ammonium halides and
carboxylates

These materials facilitate emulsion


formation by lowering surface
tension of water and allowing its
through mixing with oil.
For oil-in-water emulsions, these
chemicals encapsulate oil using
their non-polar ends and keeping
it in solution by associating with
water via their polar ends. For
water-in-oil emulsions, these
additives perform in a reverse
msinner. That is, they associate
with water via their polar ends
and keep it in solution by
associating with oil via their
non-polar ends.

Demulsifiers

Enhance water
separation from
oil contaminated
with water

Block polymers of ethylene oxide or


propylene oxide and glycerol, siloxanes,
polyamines, or polyols

Demulsifiers have a function


opposite to that of emulsifiers.
They facilitate water separation
from a water-contaminated
lubricant. They concentrate at
the water-oil interface to create
low viscosity zones, thereby
promoting drop coalescence and
gravity-driven phase separation.

Foam inhibitors

Prevent lubricant
from forming a
persistent foam

Silicone polymers, such as


polydimethylsiloxane, and organic
polymers, such as poly (sJkyl
methaciylates)

These additives reduce surface


tension of air or gas bubbles,
thereby facilitating their
collapse.

Friction modifiers

Alter coefficient of
friction

Organic fatty alcohols, acids, and amides,


linear alkyl phosphites and phosphates
esters and their salts, molybdenum
compounds, and graphite

These materials associate with


metal surfaces via their polar
ends and with lubricant via their
hydrocarbon chains. The result
is the formation of a durable
lubricant film of desired frictional
characteristics.

Pour point
depressants

Enable lubricant to
flow at low
temperatures

Alkylated naphthalene and phenolic


polymers, polymethacrylates

These compounds adsorb


themselves onto wax crystals and
prevent the formation of
undesirable crystalline networks
that can adsorb leirge quantities
of oil and hinder its flow.

Seal swell agents

Swell elastomer seals

Organic phosphates and aromatic


hydrocarbons

These additives are adsorbed by the


elastomer seal material causing
it to swell. This not only assures
the integrity of the seals but it
also prevents them from
cracking and deterioration.

Viscosity modifiers

Reduce the rate of


viscosity change
with temperature

Poly (alkyl methaciylates, polyolefins, and


copolymers of styrene and butadiene

The key to the performance of these


additives is their differential
association* with lubriceint at
different temperatures. At low
temperatures, this association is
low, and at high temperatures, it
is high. The result is a lower loss
in viscosity at high temperatures.

"Desired for some hydraulic and metalworking lubricants tiiat use such emulsions.
''The term solubility is often used to describe this phenomenon. However, the term association may be more appropriate.

444

MANUAL 37: FUELS AND LUBRICANTS

Table 13^Antiwear and extreme pressure (EP) additives.


Structure
Methods of Synthesis

Compound
Zinc dialkyl
dithiophosphates

Phosphites and
phosphates

HANDBOOK

These materials are made by reacting alcohols with


phosphorus pentasulfide to form dialkyl dithiophosphoric
acids. These acids react with zinc oxide to form zinc salts.

(RO),E^

Phosphites result when alcohols or phenols are reacted with


phosphorus trichloride or a lower alcohol phosphite, such as
trimethyl phosphite or dimethyl hydrogen phosphite.

O
(RO)2P^
H
Dialkyl Hydrogen
Phosphite
o

Triaryl Phosphite
o

R O P a RNHj

ROpff

OR

RNHj

OH

Amine Salts of Dialkyl and Mono-alkyI

Amine phosphates are obtained from amine salting of


monoalkyl and dialkyl phosphoric acids. These acids are
usually made by reacting alcohols with phosphorus
pentoxide.

Phosphoric Acids

Organic sulfides and


polysufides

CHj
HjC-

I
-css- - C C H ,
CH,

CHj

:cssscCH,

GH,

CHJ

Dialkyl Disulfide

CHJ

Dialkyl Trisulfide

Disulfides can be made by oxidative coupling of


mercaptans, which can react with sulfur to form higher
polysulfides. Polysulfides can also be made by a one step
process involving olefin-hydrogen sulfide-sulfur reaction.

RCH=CH-CH;

Sulfiirized olefins

Sa

s/

s.

R-CH2-CHCH2
RCH2'

R-CH2-CHCHJ

These products are salts of dithiocarbamic acid. The acid,


made from dialkylamine and carbon disulfide, is salted
using zinc oxide.

R2Nc:^

Dithiocarbamates

Olefins can be sulfurized using sulfur at 125''C or higher.


Usually, a mixture containing a variety of products is
obtained.

Zinc Dithiocarbamates

N O T E : R and R2 represent alkyl groups.

Compound
Neutral and basic
metal sulfonates

Neutral and basic


metal phenates

Table 14Detergents.
Structure
Methods of Synthesis
Alkybenzenesulfonic acids are reacted with stoichiometric
S0j)M^003
S05)2M
amount of lime (calcium hydroxide) or magnesium oxide to
form neutral salts. One can use excess of these reagents if
Neutral Metal
Basic Metal
carbon dioxide is used as a co-reactant. The materials thus
Sulfonate
Sulfonate
M = Ca or Mg
obtained, called basic or overbased salts, contain excess
base as metal carbonate.

<r

'<r

oyn^ooj

.0J2M

Basic Metal
Phenate

Neutral Metal
Phenate

Neutral and basic


metal carboxylates

M = Ca or Mg

-CCs - -ex,..
o
o
Neutralc Metal Salicylate
,QH

Basic Metal Salicylate

M=Ca or Mg

The process for making these materials is the same as that


for metal sulfonates, except that the starting acid is an
alkylphenol instead of an alkylbenzenesulfonic acid.

The process for making these compounds is the same as


that for metal sulfonates and phenates. The starting
material for these products is alkylsalicylic acid. This acid
results when a phenol is reacted with a strong base, such as
sodium or potassium hydroxide, and carbon dioxide
(Kolbe's process).

CHAPTER

16: GEAR LUBRICANTS

Table 15Dispersants.
Compound

Methods of Synthesis
These materials are made by reacting alkylenepolyamines
with polyisobutenylsuccinic anhydride. Succinic
anhydride is an ene reaction product of polyisobutylene
and maleic anhydride.

Structure

Alkenylsuccinimides

./
\

NCHjCHjNHCHjCHiN

Polyisobutenvlsyccinimtde

Alkenylsuccinate esters
L

Polyisobutenylsuccinic anhydride is reacted with


polyhydric alcohols, such as neopentyl glycol and
penterythritol, to form these esters.

Polvisobutenytsuccinate Ester

Mannic products

1^
"^1^5^

Alkenylphosphonic acid
derivatives

These products result from the condensation of an


alkylphenol, formaldehyde, and alkylenepolyamines.
When these products are designed for use as dispersants,
the alkyl group in alkylphenol is polyisobutenyl.
These materials can be obtained by reacting olefinphosphorus pentasulfide adduct with polyhydric alcohols.
Usually, the adduct is first hydrolyzed using steam and
then reacted with an alkylene oxide, such as propylene
oxide, to form these esters.

CHjNHCHjCHNHCHjCHzN
Polyamtnomethylalkylphenol

PIBPOCHjCH-CW
OCHiCH-OH
CH,
Bis-hydroxypropyl
Alkenvlohosohonate

Table 16Oxidation inhibitors.


Compound

Methods of Synthesis
These materials are made by reacting alcohols with
phosphorus pentasulfide to form dialkyl dithibphosphoric
acids. These acids are reacted with zinc oxide to form
zinc salts.

Structure

Zinc dialkyl
dithiophosphates

Organic sulfides and


polysulfides

CH,
H,CCSSCHj

HjCCSSS-

CHj

CH,

CH,

Dialkyl Trisulfide

Dialkyl Sulfide

Sulfur-coupled phenols
(phenol sulfides) and
hindered phenols

Monosulfides can be obtained by reacting a mercaptan


with an olefin. Disulfides can be made by oxidative
coupling of mercaptans, which can react with sulfur to
form higher polysulfides. Polysulfides can also be made
by a one step process involving olefm-hydrogen sulfidesulfur reaction.
Sulfur-coupled phenols, or phenol sulfides, can be
prepared by reacting an alkylphenol with sulfiir
monochloride.
Hindered phenols are made by Lewis acid-catalyzed
alkylation of phenol or alkylphenol with an olefin, usually
isobutylene.
Diphenylamine is aklylated with an olefin in the presence
of a Lewis acid, such as aluminum chloride, to yield these
products.

Aromatic amines
Arylamine

445

446

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

Table 17Viscosity index improvers.


Compound

Methods of Synthesis

Structure
CH,

Polyolefins

CHj-C
CH,

^3 J n

Isobutylene polymerizes in the presence of Lewis acids to


form these polymers. Higher olefins also polymerize to
yield analogous materials.

Polyisobutylene

Olefin copolymers
CH,
-fCH2-CH2^

-CHCHj-

Ethyiene-propylene Copolymer

Styrene diene
copolymers

CH3
CH-CH2-

-CH2CH=C-CH2-

Styrene-diene Polymer

Alkyl methacrylate
polymers

CH,
CH2-C-

COORJj,
Alkyl Methacrylate Polymer

Styrene ester
polymers

RO^

-C^o

-CH-CHj-CH-CH

0=0

RO

These polymers are prepared from mixtures by vanadiumbased Ziegler-Natta catalysis. In these polymers, the ratio
of different olefins in the monomer mixture determines
the polymer's low and high temperature properties. Two
common polymers of this type are EPRs and EPDMs.
EPRs are made fi^om ethylene-propylene mixtures.
EPDMs, on the other hand, contain butadiene or isoprene
as the third monomer. These materials result from free
radical polymerization of styrene-butadiene mixtures.
Because of the presence of unsaturation (double bond),
these polymers are more susceptible to oxidation. Their
oxidation resistance can be improved by removing the
double bonds through hydrogenation.
Free radical polymerization of alkyl acrylates and
methacrylates results in these polymers. In addition to
being good viscosity modifiers, these polymers have the
ability to lower pour point. Hence, they are also used as
pour point depressants.
These esters are prepared by reacting styrene-maleic
anhydride polymer with alcohols. Styrene reacts with
maleic acid in the presence of fi-ee radical initiators to
yield this polymer.

Styrene Ester Polymer

automobile manufacturers request, b o t h t h e additive a n d


petroleum industries initiated the development of gear lubricants to meet hypoid gear performance. Gear lubricants
based on sulfur-chlorine additives were then developed for
passenger car rear axles for high speed a n d moderate loads.
Chlorinated paraffins, sulfurized fatty acids, a n d olefins are
examples of sulfur-chlorine additives used for this purpose.
As the popularity of hypoid axles increased into t h e mid1930s, they were incorporated into trucks, which operated at
low speeds a n d higher loads. This led to the development of
sulfur-phosphorus-chlorine based gear lubricants for both
passenger cars and light duty truck applications. This was evident during World War II, where gear lubricants designated
by MIL-L-2105 were plagued with persistent problems associated with truck axles operating under high torques and low
speeds. These problems were relieved with the use of phosphorus containing additives in zinc dithiophosphates, alkyl
phosphates, a n d phosphates. After World W a r II, MIL-L2105 gear lubricants were becoming inadequate in meeting
the requirements of new hypoid axles, which were subjected
to higher torques.
By the 1950s, the U.S. Military, working closely with the
Coordination Research Council (CRC) a n d t h e American

Petroleum Institute (API), developed test methods a n d


service designations for qualifying gear lubricants under low
speed, high torque a n d high speed-shock load conditions.
This led to the development of MIL-L-2105A. These tests and
service designations were able to differentiate the loadcarrying capacities of automotive gear lubricants.
The 1960s, with improved aerodynamics a n d demand for
further increases in load-carrying requirements of hypoid
axles, led to increasing thermal and oxidative problems in the
field. This along with environmental concerns over lead and
chlorine use prompted the use of advemced sulfur-phosphorus and later, borate based additives (in the 1970s), which are
still in use today. The U.S. Military revised their specifications to incorporate thermal and oxidative requirements into
MIL-L-2105B. Later, other tests for power divider, fatigue
spalling, a n d corrosion were incorporated by the industry
from the 1970s to 1980s. Table 20 highlights some of the important milestones affecting automotive gear lubricants.
The corroborative efforts of API, ASTM, SAE, Military, and
CRC led to the complete description of gear lubricants meeting viscometrics and performance requirements for various
service designations. ASTM a n d CRC were responsible for
defining the different service categories, while SAE defined

CHAPTER 16: GEAR LUBRICANTS

447

Table 18Miscellaneous additives.


Structure

Compound

Methods of synthesis
CH2CH2OH

Corrosion and rust


inhibitors

RN^

Ca

Neutral Calcium Sulfonate

CH2CH2OH

Diethanolamine

Neutral and basic calcium sulfonates are made by reacting


alkylbenzenesulfonic acids with lime in the absence or the
presence of carbon dioxide. In basic detergents, the reserve
base is usually in the form of calcium carbonate.

O
SO3

RCHCOH

^f

CaxCaCOs

CHCOH

II

O
Basic Calcium Sulfonate

Alkenylsuccinic Acid
0(CH2CH2)xCH2CH20H

^ ^ ^

Alkenylsuccinic acid is a hydrolysis product of alkenylsuccinic


anhydride.
Dimercaptothiadiazole (DMTD) derivatives are made either by
reacting sodium salt of DMTD with alkyl halide or by reacting
DMTD with mercaptans in the presence of an oxidizing agent.
DMTD is manufactured by reacting hydrazine with carbon
disulfide.

Polyethoxvlated Phenol

SR

RS.

Polyethoxylated phenols and amines result from the reaction


of ethylene oxide with alkylphenols and amines.

NN
Oimercaptothiadiazole

Alkylbenzotriazole

Derivative

Benzotriazole is usually made from o-phenylenediamine via a


diazotization reaction (reaction with nitrous acid).

CH2OOOH
N=CHCH2CX30H

Metal deactivators

Ethylenediaminetefraacetic acid is made from base-catalyzed


reaction of ethylenediamine and chloroacetic acid.

-CH2COOH
W

HO

CH2COOH

Emulsifiers and
demuisiflers

N, N-Disalicylidene-1,2Propanediamine

Ettivlenediaminetetraacetic
Acid

R0(CH2CH20)xCH2CH20H

NH(CH2CH2);P
Polymhoxylated Alcohol
IHydraxyalkyI Etherl

N-Hydroxyalkvlamide
CH2CH2OH

RN'^

CH2CH2OH
Diethanolamine
R'

R'
I
RNH X

OSi-

I
CH;

CH,

R"

R"
Trialkylammonium
Salt
CH3

Sodium
Cartoxylate

RN^-CHjCHjC

Foam inhibitors

ONa'*'

Tetraalkylammonium
Carboxylate
1 CH,

CH3

Hydroxyalkyl and polyhydroxyalkyl derivatives are prepared


by reacting amides, amines, and alcohols with alkylene oxides.
Ethylene oxide is most often used for this purpose.
Sodium carboxylate is prepared by reacting a carboxylic acid
with sodium hydroxide.
The reaction of amines with mineral acids yield
alkylammonium salts. When amines are reacted with organic
halides, quatemary ammonium salts are obtained.
Tetraalkylammonium carboxylate is a product of chloroacetic
acid with trialkylamines.

Siloxane polymers are products obtained from the reaction of


dimethylsilyl chloride with water.

OSiO-j-SiCH,

Sahcylaldehyde reacts with 1,2-propanediamine to form the


salicylidene.

CHj-C
COORj n

CH,

Alkyl Methacrylate
Polymer

Dimethylsiloxane
Polymer

OH

Pour point
depressants

Alkyl methacrylate polymers result from free radical


polymerization of alkyl methacrylates.

Alkylnaphthalenes form when naphthalene is reacted with


chlorowax and or olefins in the presence of a Lewis acid, such
as aluminum chloride.

R'

Alkylnaphthalene

CH,

Alkylphenol

Alkylphenols are products of Lewis acid-catalyzed reaction of


phenol with waxy olefins and or chlorowaxes.

-CH2-C

COORj
AlkylMethacrylate
Polymer
R, R' Waxy Alkyl Groups

Alkyl methacrylate polymers result from free radical


polymerization of alkyl methacrylates.

4 4 8 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

TABLE 19Physical properties: mineral oils versus synthetic base stocks [8b].

Type
90
100
200
350
650
150

Neutral
Neutral
Neutral
Neutral
Neutral
Bright Stock

Kinematic
40C
17,40
20,39
40,74
65,59
117,90
438,00

Alkylated aromatic
Olefin oligomer
Dibasic acid ester
(Dioctyl sebacate)
Trimethylolpropane
Ester (C7 Acid)
Polyglycol

Viscosity, cSt
100C
3,68
4,11
6,23
8,39
12,43
29,46

(A) Mineral Oils


Dynamic Viscosity,
at -40C (cP)

Solid
Solid
Solid
Solid
Solid
Sohd
(B) Synthetic Base Stocks

26,84
16,77
18,2

4,99
3,87

9047
2371
3450

13,94
45,69

3,4

2360

Viscosity
Index

Pour Point
(X)

92
101
99
97
96
95

-15
-13
-20
-18
-18
-18

190
192
226
252
272
302

119
126
176

-18,3
-43,0
-15,6

224
221
232

-18.3

232
177

150

TABLE 20Chronological changes in automotive gear lubricants.


Year

Performance Demands

Reasons and Consequences

1925

Hypoid Axle introduced

1940s
1950s

Service Classification
MIL-L-2105A updated

1962

MIL-L-2105B revised

1975

Mack GO-G

1976

MIL-L-2105C

1987
1994

MIL-L-2105D
MT-l/PG-1

1995

MIL-PRF-2105E

1996

Extended Service

1998
2001

SAE J306
MIL-PRF-2105E
Modified

Lower center of gravity,


weight, quieter operation
By API and Military
Wear and EP limits
incorporated
Oxidation & thermeJ stability
limits incorporated
Power divider & Spalling
Tests introduced
Low temperature, crossgrades, corrosion limits
incorporated
Quality issues: MSDS
HD transmission specification
introduced
MIL-L-2105D + MTl/PG-1
introduced
OEM specifications by Eaton,
Mack, Meiitor
Revised viscosity classification
Extended field testing

TABLE 21API gear oil service designations [5,8,17,21].


API
Classification
Type
Applications
GL-1

Straight mineral oil.

GL-2

Usually contains fatty


materials.
Contains mild EP
Additives.

GL-3
GL-4

GL-5

GL-6
MT-I

viscosity grades and service designations for axle cind manual


trEinsmission lubricants. Today's automotive gear lubricants
are classified by several designations:
API Service Designation
SAE Viscosity Classification (SAE J306)
US Military MIL-PRF-2105E and SAE J2360 [19,20]
OEM Specifications
These different classifications will be discussed next.

API SERVICE DESIGNATION


There are six service designations defined by API, summarized in Table 21. API GL-1 designates the type of service
t3rpical of manual trEmsmissions operating under mild conditions of low unit pressures and minimum sliding velocities.
Mineral oils treated only with oxidation smd rust inhibitors.

COC Flash
Point (C)

Equivalent to obsolete
MIL-L-2105; usually
satisfied with 50%
GL-5 additive level.
Virtually equivalent to
present MIL-L-2105D;
primary field service
recommendation of
most passenger car
a n d truck builders
worldwide.
Obsolete.
Contains t h e m a l
stability and EP
additives

Truck manual
transmissions.
Worm gear drives.
industrial gear oils.
Manual transmissions
and spiral bevel
final drives.
Manual transmissions
and spiral bevel a n d
hypoid gears in
moderate service.
Moderate and severe
service in hypoid
and other types of
gears. May cdso be
used in manual
transmissions.
Severe service
involving high
offset hypoid gears
Nonsynchronized
manual
transmissions in
heavy-duty service.

defoamants, and PPDs may be used under this service


category. Use of EP, emtiwear, or friction modifiers are not
permitted.
API GL-2 designates the type of service typical of automotive worm gear axles operating under conditions of load,
temperature, and sliding velocities, which lubricants satisfactory for API GL-1 service will not suffice. Use of antiwear
and very mild EP additives are permitted under this service
category.
API GL-3 designates the type of service typical of manual
transmissions and spiral-bevel axles operating under mild to
moderate to severe conditions of speed cmd load. These conditions require the gear lubricant to have greater load carrying capabilities required for GL-1 and GL-2, but not meeting the requirements for GL-4. Generally, gear lubricants

CHAPTER

16: GEAR LUBRICANTS

449

TABLE 22Proposed light duty manual transmission fluid standard [22].


Test Method

Characteristic

Conditions/Modifications

Synchomesh SSP 180


Wear
Thermal Oxidation

CEC L-66-X-96
ASTMD5182
GFC Procedure A

Under development
90C, 3600 rpm
160C, 192 hours

Viscosity after shear


loss
Pour Point
Brookfield Viscosity
Cold Crank Simulator
Foam

CEC-L-45-T-93

20 hrs, 60C, 5000 N

ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM

Rust Prevention
Copper Corrosion
Seal Compatibility

D
D
D
D
D
D
D
D

97
2983
5293
892
6082
665 (Method A)
130
5662

TABLE 23API GL-5 tests [21,23].


Test
Designation

Type

L-33

Gear test using axle


components.

L-37

Gear test using


complete axle
assembly.

L-42

Gear test using


complete axle
assembly.

L-60
ASTM D 892

Bench test using


spur gears.
Bench test.

ASTMD 130

Bench test.

Characteristics
Measured

Resistance to
corrosion in the
presence of
moisture.
Resistance to
gear distress
under the
conditions of
low speed high
torque.
Resistance to
gear distress
(scoring) under
conditions of
high speed and
shock loads.
Thermal oxidation
stability.
Foaming
tendencies.
Stability in the
presence of
copper alloys.

meeting this service category 2U"e not intended for hypoid


axles.
API GL-4 designates the type of service typical of spiralbevel and hypoid gears in axles operating under moderate
speeds and loads. Gear lubricants under this service designation m a y be used in selected m a n u a l transmissions and
transaxles. While this service category is commercially used,
some original equipment for qualifying against this service
designation is n o longer available. ASTM is currently investigating the possibility of redefining this service designation
using m o d e m test equipment. This service category is called
Passenger Manual Transmission (PM-1). A summary of the
proposed tests for PM-1 is given in Table 22.
API GL-5 designates the tjrpe of service typical of hypoid
gears, operated u n d e r high-speed and/or low speed with
high-torque conditions (see Table 23). Lubricants formerly
qualified u n d e r MIL-L-2105D satisfy the requirements for
API GL-5 service category. Details of API GL-5 performance
tests [21] are contained in the following publications:
ASTM STP-512A: Laboratory Performance Tests for Automotive Gear Lubricants intended for API GL-5 Service.

-40^
-30C
Seq I, II, III
SeqIV
3 hrs, 1 2 r C l

Limits
No clash at 100 000 cycles
10 load stage pass
50% vis inc. max
2.5 m g KOH/g
25% max
5.8 cSt m i n at lOOX
Less t h a n - 3 9 C
50 000 cP max
5000 cP max
20,50,20/0 ml
100/0 ml
Pass
lb max
Pass

SAE J2360 Lubricating Oil, Gear Multipurpose Military


Use
Or equivalent MIL-PRF-2105E
API GL-6 designates the tjrpe of service characteristic of
gears designed with very high pinion offset. Such designs require score protection in excess of that required by GL-5.
This service category is almost obsolete, as equipment required for testing is no longer commercially available.
The API GL-5 service category is currently the most
popular worldwide. In 1994, a new category for service in
non-synchronized manual transmissions used in buses and
heavy-duty trucks was approved (API MT-1). Gear lubricants
meeting API MT-1 were approved against performance tests
for improved deposit control, oxidation and thermal stability,
and seal compatibility beyond those required by lubricants
meeting GL-1 through GL-5. Comparisons between API GL4, GL-5, and MT-1 are given in Table 24.
SAE J306 Viscosity Classification
Axle a n d m a n u a l transmission lubricants were originally
classified by their viscosities described in SAE J306c - Recommended Practice, published in 1978. In this classification
system the ' W designates 'Winter' operation and defines low
temperature viscosity limits for 75W to 85W grades. This was
to alleviate pinion bearing failures when axles operated at
temperatures when viscosities were greater than 150 000 cP.
From 1996 through 1998, the following changes were made
to SAE J306:
Title change to "Automotive Gear Lubricant Viscosity
Classification"
Labeling requirements similar to SAE J300 in format and
content
Viscosity grade must be preceded by "SAE"
W grade precedes non-W grade
Only the lowest W grade satisfied to be used
Two additional grades added (SAE 80 and SAE 85) with
viscosity limits at 100C
Footnote regarding low temperature performance of manual transmission lubricants
Incorporation of stay-in-grade shear stability requirement
using CEC-L45-T93
The requirement for shear stability was incorporated because m o d e m gear lubricants may contain high molecular
weight polymers that may shear, resulting in a loss in viscos-

450

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

TABLE 24API GL-4, GL-5 and MT-1 performance comparisons (5,23).


Performance

API GL-4 (MIL-L-2105)

Scoring resistance u n d e r
high speed shock load
conditions
Resistance to gear
distress under high
torque, low speed
conditions.
Corrosion resistance in
the presence of water.

CRC L-19'' test or FTM


6504T; equal to or better
t h a n RGO-105.
CRC L-20 test; no tooth
disturbance such as
rippling, ridging, pitting,
or severe wear.
1. CRCL-13 or FRM 5313.1
2. CRCL-21
No evidence of rusting.

Thermal and oxidation


stability/component
cleanliness.

No requirement.

Antiwear

No requirement.

No requirement.

High temperature
lubricant stability.

No requirement.

No requirement.

Antifoaming
characteristics

CRC L-12 test: readings


taken immediately
after 5 min. aeration;
Sequence 1 -23.9C,
650 mL; Sequence
2 -93.3C, 650 mL
ASTMD130:3bmax.
after 1 hr. at 1 2 r C .
No requirement.

ATSM D892: readings taken


immediately after 5 min.
aeration; Sequence 1 20 mL
max; Sequence 2 - 5 0 mL max;
Sequence 3 - 2 0 mL max.

Cooper corrosion
Channeling
characteristics

API MT-1
No requirement.
No requirement.

L-33 test: n o evidence of rusting


after 7 day's exposure on any
working surface; m a x i m u m
0.5 in.^ rust on cover plate
( 1 % surface area).
L-60-1 test; 100% max. viscosity
increase; 3 % max. pentane
insolubles; 2% max. toUuene
insolubles.

No requirement.

L-60-1 test; 100% max. viscosity


increase; 3 % max. pentane
insolubles; 7.5 min. carbon/
varnish ration on large gear;
9.4 min. sludge rating on all
gears.
FZG (A/8.3/90); minimum 10
stage pass.
Mack Transmission Test
T-2180: equal to or better
than reference
ATSM D892: readings taken
immediately after 5 min.
aeration; Sequence 120 mL
max; Sequence 250 mL;
Sequence 3 - 2 0 mL max.

ASTM D130: 3 max. after 3 hr.

ASTM D130: 2A max. after 3 hr.


at 1 2 r C .
No requirement.

at 12rc.

FTM 3456.1 Modified: SAE 75,


- 4 5 ^ max; SAE 80W90, - 3 5 C
max; SAE 85W-140, - 4 0 C max.
SS&CFED-STD-791

SS&CFED-STD-791

Compatibility with
existing gear
lubricants
Solubilitymeasure
separated material
after centrifuging oil
stored for 30 days at
room temperature
(29.4 9.5C).
Compatibilitysame
solubility except
mixed 50/50 with each
of six reference oils.

API GL-5 (MIL-L-2105D)


L-42 test: gear/pinion coast side
scoring equal to or better
thanRGO-110
L-37 test; no tooth disturbance
such as rippling, ridging,
pitting, or severe wear.

SS&CFED-STD-791

FTM 3430: 0.25 wt. %


max of original
nonpetroleum
material in sample

FTM 3430: 0.25 wt. % max of


original nonpetroleum
material in sample

FTM 3430: 0.25 wt. % max of


original nonpetroleum
material in sample

FTM 3440: 0.50 wt. %


max of original
nonpetroleum
material in SEimple.

FTM 3440: 0.50 wt. % max of


original nonpetroleum
material in sample.

FTM 3440: 0.50 wt. % max of


original nonpetroleum
material in sample.

"Equipment no longer available; impossible to conduct test per original procedure.

TABLE 25Viscosity classifications for SAE J306 and MIL-PRF-2105E [18,19,23].


SAE Viscosity Classification
Properties
Vis at 100C
Min (cSt)
Max (cSt)
Vis of 150,000 cP
Max Temp, C

70W

75W

SOW

85W

80

85

90

140

250

4.1
None

4.1
None

7.0
None

11.0
None

7.0
<11.0

11.0
<13.5

13.5
<24.0

24.0
<41.0

41.0
None

-55

-40

None

None

None

None

Properties
Viscosity at 100C
Min (cSt)
Max (Cst)
Vis of 150,000 cP
Max Temp, C
Channel Point, min. "C
Flash Point, min C

-26

-12
None
iUilitary Specification
75W
80W90
4.1

85W140

-40

13.5
<24.0
-26

24.0
<41.0
-12

-45
150

-35
165

-20
180

CHAPTER

16: GEAR LUBRICANTS

451

TABLE 26Chemical and physical property requirements of MIL-PRF-2105E [19].


Property

SAE 75W

SAE 80W-90

SAE 85W-140

As per SAE J306


-45
150
Report
Report
Report
Report
Report
Report
Report
Report
Report
Report
Report
Report
Report

As per SAE J306


-35
165
Report
Report
Report
Report
Report
Report
Report
Report
Report
Report
Report
Report
Report

As per SAE J306


-20
180
Report
Report
Report
Report
Report
Report
Report
Report
Report
Report
Report
Report
Report

ASTM Method

Viscosity
Channel Point, C, max
Flash Point, "C, min
API Gravity
Viscosity Index
Pour Point, "C
Pentane Insolubles, wt%
Sulfur, wt%
Sulfur from Additive, wt%
Phosphorus, p p m
Chlorine, p p m
Nitrogen, p p m
Zinc, p p m
Boron, p p m
Potassium, p p m
Organo-metals, ppm

D445
FTM 3456
D92
D287
D2270
D97
D893
D1552
D 1552
D 1091
D808
D3228
D4951
D4951
D4951
D4951

ity. In order to ensure that the designated high temperature


viscosity grade is retained during use, gear lubricants must
meet viscosity limits at 100C after shear. The permanent loss
in viscosity may be detrimental to the gears and bearings as
film thicknesses may decrease.
U.S. Military MIL-PRF-2105E
In August 1995, MIL-L-2105D was superceded by MIL-PRF2105E. Most of the requirements needed for API MT-1 were incorporated into MIL-L-2105E. In 1998, at the U.S. Mihtary's
request, SAE adopted the SAE J2360 Standard equivalent to
MIL-PRF-2105E. The viscosity requirements are shown in
Table 25 along with the SAE J306 Standard. The requirements
for stay-in-grade also apply to the military viscosity grades. Tables 26-29 summarize key performance tests as required by
MIL-PRF-2105E. Field tests using light duty trucks or passenger cars and heavy duty Class 8 trucks are also required to
demonstrate no heirm performance in light and heavy duty
axles and heavy duty non-synchronized manual transmissions. The gear lubricants covered by MIL-PRF-2105E or SAE
J2360 are intended for automotive gear units, heavy-duty industrial type enclosed gear units, steering gear units, heavy
duty non-s3rnchronized Class 7 and 8 manual transmissions,
and fluid lubricated universal joints of automotive equipment.
The lubricants covered by this specification are intended for
use as defined by appropriate lubrication orders when ambient temperatures are above -54C. In addition, API GL-5/MT1 tests, field tests in both light emd heavy-duty vehicles, are required for meeting MIL-PRF-2105E. Axles from the light and
heavy-duty vehicles along with the transmissions from the
heavy-duty vehicles are inspected for cleanliness, surface distress to gears, bearings, and shifting mechanisms. The gear lubricant's condition is also monitored at periodic intervals.

OEM Specifications
Many OEMs have developed their own performance classifications for standard and extended drain services. These factory and service fill requirements generally meet API GL-5
performance requirements [1,24]. In addition, performance
considerations for these lubricants meet specific performance targets in the areas of improved fuel economy, temperature reduction, improved fatigue performance, enhanced

TABLE 27Bench and rig test requirements for


MIL-PRF-2105E [19].
Passing Requirements

Test Method
Copper Corrosion,
ASTM D 130,
12rC, 3 h

Not to exceed 2a rating

Foam Tendency,
ASTM D 892

Seq

Max Vol. at end of Blowing

I
II
III

20 ml
50 ml
20 ml

Oxidative and
Thermal Stability,
ASTM D 5704,
50 hrs, 163C
(L-60-1)

Viscosity Incr. at 100C


Pentane Insolubles
Toluene Insolubles
Carbon Varnish Rating
Sludge Rating

Gear Wear Test,


ASTM D 6121,
24 h, 275F,
Green and
Lubrited Gears
(L-37)

No severe surface distress to gears

Cyclic Durability
Test, ASTM 5579

Better than reference oil

Seal Compatibility,
ASTM D 5662

<100%
< 3 wt%
< 2 wt%
>7.5
>9.4

Polyaciylate, 150C, 240 h


Parameters
Elongation change, %
Hardness change, points
Volume change, %

Min
No limit
-35
-5

Max
-60

+5
+ 30

Fluoroelastomer, 150C, 240 h

API L-33 Gear


Corrosion
API L-42 Gear
Scoring Test

Parameters

Min

Max

Elongation change, %
Hardness change, points
Volume change, %

No limit
-5
-5

-75
+ 10
+ 15

No rust on ages, < 1% on cover plate"


Lower % scoring than reference on gears.

"Rating being modified for better consistency.


yellow metal corrosion, frictional durability for limited slip
axles, and power divider transaxles [25-47].
Other enhanced performance considerations include improved oxidative stability, reserve performance for extreme
pressure [2], and wear. These requirements ensure that the
axles and transmissions are protected under the increased

452 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 28Light and heavy-duty field test requirements of MIL-PRF-2105E [19,20].
Field Test Type

Number of Vehicles Needed

Test Mileage

Sampling Interval

Heavy Duty Service


(Axles and Transmissions)
Light/Moderate Duty Service

Minimum of three Class 8


Trucks
Minimum of five light
trucks and/or sedans

100 000 miles (previous)


200 000 miles (current)
50 000 miles (previous)
100 000 miles (current)

4 oz, every 20 000 miles


4 oz, every 10 000 miles

TABLE 29Field test oil analyses requirements of


MIL-PRF-2105E [19].
Property

ASTM Method

Viscosity at 40 and 100C, cST


Phosphorus, p p m
Sulfur, wt%
Chlorine, ppm
Nitrogen, p p m
Zinc, p p m
Boron, p p m
Potassium, p p m
Organo-metals, p p m
Total Acid Number
Total Base Number
Insolubles, wt%

D445
D 1091
D1552
D808
D3228
D4951
D4951
D4951
D4951
D664
D4739
D983

TABLE 30Current/future OEM axle specifications [1]."


OEM
Mack

SAE Viscosity
Grades

Specification
No.
GO-J

80W-90, 85W-140

GO-J Plus

Performance Requirements

Recommended Drain Period (miles)

Mil-PRF-2105E
Seal immersion test
Mack spalling test(*)
500 000 mile field test
100 h o u r L-60-1
Extended Mack cycling testC)

250 000

500 000

500 000

Eaton/Dana

PS-163/
SHAES-256

75W, 80W-90, 85W-140

Mil-PRF-2105E
Copper & bronze corrosion tests
Dynamic seal tests
Spalling test
500 000 mile field test
Wet L-37 Test

ArvinMeritor

076-D & A

80W-90, 85W-140

MiL-PRF-2105E

100 000 miles without p u m p and filter


to 500 000 miles with p u m p , filter
a n d appropriate additives

Mercedes Benz

235

90, 85W90, 85W140

API GL-5
In-house axle tests

60 000 (long haul)


for all without flexible service system
(FSS)
220 000 for FSS

Mercedes Benz

235.6

80W90
85W90,90

API GL-5
In-house axle tests

60 000 (long haul)


for all without flexible service system

Dynamic seal tests


50 p p m CI max.

Volvo

MAN

97 310
97 312

75W, SOW, 90, 85W140, API GL-5


80W140
API GL-5/Pitting test/field test
75W90

342N
342ML

90
80W90

342SL

75W90
80W90

Iveco
ZF

TEML05

API GL-5
API GL-5
FZG PITS field test
API GL-5
FZG PITS field test

(FSS)
220 000 for FSS
75 000 (long haul)
110 000 current (long haul)
250 000 target
50 000
100 000 (long haul)
200-250 000

90
85W140

API GL-5

75 000

90

API GL-5
In-house axle and FZG tests

50 000

"This oil is used for axles and transmissions.


^Test currently not available.

CHAPTER 16: GEAR LUBRICANTS


driving durability they are currently being subjected to. Certain OEMs rely on extended versions of the L-60-1 test to define improved performance for oxidation [1]. Gear lubricants
are also required to perform in power dividers. Interaxle and
interwheel power dividers transfer torque between front-rear
axles and wheels, respectively. Most conventional sulfurphosphorus and borate based gear lubricants are not capable
of providing improved frictional durability required for
performance in power dividers. These require the use of
friction modifiers for enhancing the proper lubrication of
gears, cams, and bearings found in power dividers. Similar
frictional performance for light-duty vehicles is seen in
limited-slip axles. These serve to transfer torque equally
between the rear wheels. The friction plates of these limitedslip clutch packs are made of steel plates that are manganesephosphate, molybdenum, or paper coated. The frictional
requirements for power dividers and limited slip axles allow
for conventional sulfur-phosphorus and borate chemistries
to be compatible with friction modifiers with no compromise
to the gear lubricant's GL-5 performance. Table 30 summarizes several major U.S. and European heavy-duty OEM current and future specifications [1].

INDUSTRIAL GEAR LUBRICANTS


In general, industrial gear lubricants are used under conditions of moderate loading. These lubricants are applied in enclosed and open gearboxes. Industrial gear sets are more
diverse than automotive gear sets and are generally lubricated by manual application, drip feed, spray, and splash lubrication. Typical uses of industrial gear lubricants are in
steel mills, construction and mining sites, kilns, and
furnaces. The main function of industrial gear lubricants are
to prevent corrosion of rust and yellow metcJs, EP, as antiwear agents, for foam suppression, to prolong oxidation, to
demulsify, and to be able to lubricate under some level of
contamination. Examples of specifications for industrial
gear lubricants cire:
AISE 224 (formerly known as U.S. Steel 224)
American Gear Manufacturers Association 9005-D94 [16]
General Motors LS-2
David Brown ET 33/80
DIN 51517/3
Flenders
Cincinnati Milacron P-35, P-59, P-63, P-74, P-77, P-78
The two most common industrial specifications among the
ones hsted are AISE 224 and AGMA 9005-D94. AGMA
formed the lubrication committee in 1938 to study gear
lubrication problems. This committee was responsible for
the adoption of the standard AGMA 250.01Lubrication of
Enclosed and Open Gearing in 1946. Several revisions culminated in the standard AGMA 250.04 pubhshed in 1981, which
eliminated lead napthenate as an EP additive and modified
the AGMA lubricant numbering to coincide with the viscosity ranges in ASTM 2422 and the British Standard Institute
(BS.4231) and International Standards and Organization
(ISO 3448). The elimination of open gearing where bearings
were lubricated separately led to the adoption of AGMA Standcird 251.01 approved in 1963. This standard was revised
again in 1974. The current AGMA standard 9005-D94 again

453

TABLE 31^AISE 224 requirements lead free EP gear oil [16].


Test
API Gravity, ASTM D 287
Viscosity Index, ASTM D 567
Precipitation Number, ASTM D 91
Pour Point, ASTM D 97
Flash Point, ASTM D 92
ISO Grade 150 and higher
ISO Grade 68 and 100
Copper Corrosion, ASTM D 130
Rust Test (A & B), ASTM D 665
S-200 Oxidation312 hrs, 121.1C
Viscosity Increase, 98.9C
Precipitation N u m b e r after test
Demulsibility, ASTM D 2711
Free Water
Emulsion
Water in Oil
4 Ball EP, ASTM D 2783
Load Wear Index
Weld Point
4 Ball Wear, ASTM D 2266
20 kg, 1800 rpm, 1 hr
Timken Load Arm Test, ASTM D 2782
FZG Four Square Test

Limits
25 min
95 min
Trace
- 9 C max (based
on viscosity)
232.2C min
203.4C min
l b max
Pass
6% max
0.1% max
80 ml min
1.0 ml max
2.0% max
45 kg min
250 kg m i n
Scar Diameter of
0.35 m m max
O.K. 60 lbs min
1 1 * Stage min

combines enclosed and open gearing superceding AGMA


standards 250.04 and 251.02. It also covers the use of
synthetic industrial gear lubricants. Specifications of EP oils
have been upgraded to reflect advances in additive technology. Table 31 summarizes requirements for U.S. Steel 224
(AISE 224). Table 32 compares several industrial requirements for EP gear lubricants. Tables 33-35 are specifications
for compounded, EP, and synthetic gear lubricants, respectively, from AGMA 9005-D94. Table 36 specifies the viscosity ranges for AGMA gear lubricants.'^
T E S T IMETHODS F O R EVALUATING G E A R
LUBRICANTS
Precipitation Number ASTM D 91
This test method covers the determination of precipitation
number of lubricating oils including steam cylinder stocks
and black oils. Fully refined petroleum oils normally contain
no naphtha insoluble material. Semi-refined or black oils frequently contain some naphtha insoluble material, sometimes
referred to as asphaltenes. This test measures the amount of
naphtha insoluble material in oil. This quantity is reported as
the precipitation number. The ASTM precipitation number,
n, is the number of milliliters of precipitate formed when 10
mL of lubricating oil are mixed with 90 mL of naphtha and
centrifuged between 600-700 rpm.
^ The original material is printed with permission of the copyright
holder, the American Gear Manufacturer's Association, 1500 King
Street, Suite 201, Alexandria, Virginia 22314. Statements presented
are those of the author and may not represent the position of the
American Gear Manufacturer's Association.

454 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 32Comparison of industrial gear oil specifications [23].
Tests

AGMA 9005-D94 E P

DN 51517 Part 3 (CLP)

Timken OK Load, ASTM D 2782


FZG A/8.3/90, Pass Stage, min
4 Ball EP, ASTM D 2783
Weld Point
Load Wear Index
4 Ball Wear, ASTM D 2266
120 kg, 1800 rpm, 1 hr
Corrosion Protection
ASTM D 130, 3 hrs/100C
ASTM D 665, min
Oxidation Stability
ASTM D 2893 (121C), % Vis Incr
S 200, % Vis Incr
Precipitation Number
Foam Suppression, ASTM D 892
Seq I Tendency/Stability, ml max
Seq II Tendency/Stability, ml max
Seq III Tendency/Stability, ml max

60 lbs min
12

11

AISE 224

60 lbs min
11
250 kg min
45 min
Scar Diameter0.35
max

lb max
PassB

Pass A

lb max
Pass A & B

6 max
6 max
0.1 max
75/10
75/10
75/10

Table 33Minimum physical and performance specification for inhibited and compounded gear lubricants.
Courtesy of AGMA from Standard ANSI/AGMA 9005-D94.
Property

Viscosity
Viscosity
Index
Oxidation
Stability

Rust
Protection
Corrosion
Protection
Foam
Suppression

Demulsibility

Cleanliness

Criteria for Acceptance

Test Procedure

ISO 3104
ASTM D 445
ISO 2909
ASTM D 2270
ISO 4263
ASTM D 943

ISO 7120
ASTM D 655B
ISO 2160
ASTM D 130
ASTM D 892

ASTM D 2711

None

Must be as specified in Table 36


90 minimum
Hours to reach a neutralization number of 2.0 ")
AGMA Grade
Hours (minimum)
0,1,2
1500
3,4
750
5,6
500
No rust after 24 h with synthetic sea water
#lb strip after 3 h at 12rC (250F)
Must be within these limits:
Max volume of foam (ml) after
Temperature
n. blow
Sequence I
24C (75F)
75
Sequence II
9 3 . 5 ^ (200F)
75
Sequence III
24C (75''F)
75
*Must be within these limits:
Max percent water in the oil after 5-hour test
Max cuff after centrifuging
Min total free water collected during entire test
Must be free of visible suspended or settled contamination.

10 min. rest
10
10
30.0 ml
0.5%
2.0 ml
30.0 ml

"The criteria for acceptance indicated for oxidation stability and demulsibility is not applicable to compounded gear oils.

Flash a n d Fire Points b y Cleveland O p e n Cup


ASTM D 92
This test method describes the determination of flash and fire
point of petroleum products by a m a n u a l or a u t o m a t e d
Cleveland open cup apparatus. Approximately 70 mL of the
test specimen is filled into the test cup. The temperature of
the specimen is increased rapidly at first and then at a slower
rate as the flash point is approached. At specified intervals a
test flame is passed across the cup. The flash point is the lowest liquid temperature at which the vapors from the specimen
will ignite. To determine the fire point, the test is continued
until the test flame causes the specimen to ignite a n d sustain
burning for a m i n i m u m of 5 s.

Pour Point ASTM D 97


This test m e t h o d m e a s u r e s the lowest t e m p e r a t u r e of a
petroleum specimen to determine its utility in certain low
t e m p e r a t u r e applications. After preliminary heating, the
sample is cooled at a specified rate and examined at intervals
of 3C for flow characteristics. The lowest temperature at
which movement of the specimen is observed is recorded as
the pour point.
Copper Strip Tarnish Test ASTM D 130
The sulfur from the base oil and EP additives can have a corroding action on various metals but is not related to the total

CHAPTER 16: GEAR LUBRICANTS

455

Table 34Minimum physical and performance specification for ep gear lubricants.


Courtesy of AGMA from Standard ANSI/AGMA 9005-D94.
Test Procedure

Property
Viscosity
Viscosity
Index
Oxidation
Stability
Rust
Protection
Corrosion
Protection
Foam
Suppression

Demulsibility

Criteria for Acceptance

ISO 3104
ASTM D 445
ISO 2909
ASTM D 2270
ASTM D 2893

Must be as specified in Table 36


90 minimum (applies to viscosity grades 2 EP thru 8 EP only)
Increase in kinematic viscosity of an oil sample at 121C (250F)
should not exceed 6%)
No rust after 24 hours with synthetic sea water")

ISO 7120
ASTM D 655B
ISO 2160
ASTMD 130
ASTM D 892

# l b strip after 3 hours at 100C (212F)


Must be within these limits:
Max volume of foam (ml) after:
Temperature
Sequence I
2 4 ^ (75F)
Sequence 11
93.5C (200F)
Sequence III
2 4 X (75F)
*Must be within these limits'):

ASTMD 271IMOD

5 min. blow
75
75
75

10 min. rest
10
10
10

AGMA Grades
2EPto7EP
8 EP to 13 EP
2.0%
2.0%

Cleanliness
Load carrying property

None
ASTM D 2782 (Timken Test)
and DIN 51 354 (FZG Test)

Filterability

None

Max percent water in the oil


after 5-hour test
Max cuff after centrifuging
1.0 ml
4.0 ml
Min total free water collected
80.0 ml
50.0 ml
during entire test (start with
90 ml of water)
Must be free of visible suspended or settled contamination.
An oil must meet both; a 60 pound Timken OK lad, and fail stage
greater t h a n 12 on the FZG machine with A/8.3/90C parameters
for acceptance").
Must be filterable to 25u (microns) (wet or dry) without loss of EP
additive (b25 = 200 fiher rating)

"Acceptance criteria has been upgraded.

Table 35Minimum physical and performEince specification for synthetic gear lubricants.
Courtesy of AGMA from Standard ANSI/AGMA 9005-D94.
Property
Viscosity
Viscosity Index
Oxidation Stability
Rust Protection
Corrosion Protection
Foam Suppression

Demulsibility

Cleanliness
Mciximum Pour Point

Test Procedure
ISO 3104
ASTM D 445
ISO 2909
ASTM D 2270
ASTM D 2893
ISO 7120
ASTM D 665B
ISO 2160
ASTMD 130
ASTM D 892

ASTMD 2711 MOD

Load Carrying Property

None
ISO 7120
ASTM D 665
DIN 51 354

Filterability

None

Criteria for Acceptance


Must be as specified in Table 36
120 minimum "
Increase in kinematic viscosity of oil sample at 121C (250F)
should not exceed 6%
No rust after 24 h with synthetic sea water.
# l b strip after 3 h at 1 2 r c (250F)
Must be within these limits:
Max Volume of foam (ml) after:
Temperature
5 min. blow
Sequence I
24C (75F)
75
Sequence II
93.5C (200F)
75
Sequence III
2 4 X (75T)
75
Must be within these limits*).
Max percent water in the oil after 5 hour test
Max cuff after centrifuging
Min. total free water collected during entire
test (start with 90 ml of water)
Must be free of visible suspended or settled contaminants.
- 3 2 C (22F)

10 min. test
10
10
10
1.0%
2.0 ml
60.0 ml

An oil must meet 11 stage fail (10 stage pass) on FZG machine with A/8.3/90C
parameters for acceptance.
Must be filterable to 25/i (microns) wet or dry without loss of additives
(/325 = 200 filter rating).

" Esters having a lower viscosity index and meeting all other requirements of this specification may be used in specific applications where proper viscosity at
operating temperature has been verified.
* Polyglycols which will not pass the demulsibility test, but meet all other requirements of this specification, may be used in specific applications where there
is no danger of water contamination.

456

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Table 36Viscosity ranges for AGMA gear lubricants. Courtesy of AGMA from Standard ANSI/AGMA 9005-D94.
Rust and Oxidation
Inhibited Gear Oils,
AGMA Lubricant No.

0
1
2
3
4
5
6
7, 7 Comp''
8, 8 Comp''
8A Comp''
9
10
11
12
13
Residual compounds'^
AGMA Lubricant No
14R
15R

Viscosity
Range " mm'^/s
(cSt) at 4000

Equivalent
ISO Grade"

28.8-35.2
41.4-50.6
61.2-74.8
90-110
135-165
198-242
288-352
414-506
612-748
900-1100
1350-1650
2880-3520
4140-5060
6120-7480
190-220 cSt at
100C (212F)
Viscosity ranges"
cStatl00C(212F)
428.5-857.0
857.0-1714.0

32
46
68
100
150
220
320
460
680
1000
1500

Extreme Pressure
Gear Lubricants *
AGMA LubricEint No.

2EP
3EP
4EP
5EP
6EP
7EP
8EP
8AEP
9EP
10 EP
11 EP
12 EP
13 EP

Synthetic Gear Oils


AGMA Lubricant No.

OS
IS
2S
35
4S
5S
6S
7S
85
95
10 S
US
12 5
13 S

"per ISO 3448, Industrial Liquid Lubricants - ISO Viscosity Classification, Also ASTM D 2422 and British Standards Institution B.S. 4231.
''Extreme pressure lubricants should b e used only w h e n recommended b y the gear manufacturer.
"Synthetic gear oils 9S -13S are available but not yet in wide use.
''Oils marked Comp are compounded with 3 % to 10-% fatty or synthetic fatty oils.
"Viscosities of AGMA Lubricant N u m b e r 13 and above are specified at 100C (212F) as measurement of viscosities of these heavy lubricants at 40C (lOOT)
would not be practical.
l i e s i d u a l compounds - diluent type, commonly knows as solvent cutbacks, are heavy oils containing a volatile, no-flammable diluent for ease of applications.
The diluent evaporates leaving a thick film of lubricant on the gear teeth. Viscosities listed are for the base compound with diluent.
CAUTION: These lubricants may require special handling and storage procedures. Diluent can be toxic or irritating to the skin. Do not use these lubricants
without proper ventilation. Consult lubricant supplier's instructions.

sulfur level in the gear lubricant. The effect varies pending on


the activity of sulfur. This test is designed to assess the relative degree of corrosivity of lubricants. A polished copper
strip is i m m e r s e d in a specified quantity of sample a n d
heated at a temperature for a specified time. At the end of this
period the copper strip is removed, washed, and compared
with ASTM Copper Strip Corrosion Standards. Generally, industrizJ and automotive gear lubricants are tested at 100 and
121C for 3 h, respectively.
A P I Gravity A S T M D 2 8 7
This test covers the determination by means of a glass hydrometer of the API gravity of crude petroleum products.
Gravities are m e a s u r e d at 60F (15.56C) or converted to
values at 60F, by means of standard tables. This test method
relies on the principle that gravity of a liquid varies directly
with the depth of immersion of the floating API hydrometer.
Kinematic Viscosity ASTM D 445
This method specifies a procedure for determining the kinematic viscosity of lubricants by measuring the time of flow
under gravity through a calibrated glass capillary viscometer.
The viscometer is placed in a heated bath at typically 40 and
100C. The kinematic viscosity is the product of the measured
flow time and the calibration constant of the viscometer. The
correct operation of equipment, such as gearboxes, axles and
transmissions, depends on the appropriate viscosity of the
gear lubricant.

Acid N u m b e r ASTM D 6 6 4
This method determines the acidic constituents in gear lubriceints that are present as additives or as degradation products during service. It is applicable for the determination of
acids whose dissociation constants in water are Isirger than
10~^; extremely weaJs acids whose dissociation constants are
smaller t h a n 10~^ do not interfere. Salts react if their hydrolysis constants are larger than 10"*. The sample is dissolved in
a mixture of toluene a n d propan-2-ol containing a small
amount of water and titrated potentiometrically with alcoholic potassium hydroxide (KOH). The acid n u m b e r is reported as mg KOH/g of sample. Since a variety of oxidation
products contribute to the acid n u m b e r and the organic acids
vary widely in corrosion properties, this test method cannot
be used to predict corrosiveness of the geeir oil u n d e r service.
Rust Inhibition ASTM D 6 6 5
This method evaluates the ability of oils to prevent rusting of
ferrous parts if water mixed with the oil. A mixture of 300 mL
of the oil under test is stirred with 30 mL of distilled water
(Method A) or synthetic seawater (Method B) at 60C in the
presence of a completely immersed cylindrical steel rod. The
duration of the test is 24 h. At the end of 24 h, the test rod is
inspected for signs of rust.
F o a m Characteristics ASTM D 892
This method covers the determination of foaming characteristics of oils at 24C and 93.5C. The tendency of oils to

CHAPTER
foam can be serious in systems such as high-speed gearing,
high volume pumping, and splash lubrication. Inadequate
lubrication, cavitation, and overflow loss of oil can lead to
m e c h a n i c a l failure. The s a m p l e is m a i n t a i n e d at 24C
while air is blown into it at a constant rate for 5 m i n a n d
allowed to settle for 10 min. The volume of foam is measured at the end of both periods. The test is repeated on a
second sample at 93.5C a n d t h e n after collapsing the
foam, at 24C.
Insolubles in U s e d Oils ASTM D 8 9 3
This m e t h o d covers the d e t e r m i n a t i o n of p e n t a n e a n d
toluene insolubles in used oils. Procedure A covers the
determination of insolubles without the use of coagulant in
pentane. Procedure B determines insolubles of oils containing detergents and employs a coagulant for both the pentane
and toluene. In both procedures, a representative amount of
sample is mixed with pentane and centrifuged. The solution
is decanted and washed with either pentane and/or toluene.
The "wet" insolubles are dried and weighed.

16: GEAR LUBRICANTS

457

Water Content ASTM D 1744


This method covers the determination of water in the concentration from 50-1000 mg/kg in oil. The new or used oil is
titrated with standard Karl Fischer reagent to an electrometric end point. Knowledge of the water level can be used to
predict performance and quality of oils, especially used oils.
High levels of water of > 2 wt% cem cause equipment failure
and may necessitate an oil drain.
F o u r BaU W e a r ASTM D 2 2 6 6
This method covers the determination of the weetr chciracteristics in sliding steel on steel applications only. This test Ccin
be used to determine the antiwear properties of industrial
gear lubricants relative to each other. No correlation has
been established between this test and field service. A steel
bcdl is rotated under load against three stationary balls. The
diameters of the wear scars on the stationeiry balls are measured at the end of the test.
Viscosity Index ASTM D 2270

Chlorine Level ASTM D 808


This method covers the determination of chlorine in new and
used oils in the rzinge of 0.1-50 wt%. The procedure assumes
that compounds containing halogens other than chlorine are
not present. Knowledge of the level of chlorine in oils CEin be
used to predict performance or handling of gear oils. The oil
is oxidized by combustion in a b o m b containing oxygen under pressure. The liberated chlorine c o m p o u n d s are absorbed in a sodium carbonate solution. The level of chlorine
present is determined gravimetrically by precipitation as
silver chloride.
Phosphorus Level ASTM D 1091
This test method determines the level of phosphorus in unused and used oils and is independent of the type of phosp h o r u s compounds. This is because of the conversion to a n
aqueous solution of orthophosphate ion by oxidation of
the sample during the course of the analysis. Knowledge of
the phosphorus level can be used to predict performance
a n d quality of oils. The organic material in oils is destroyed and the p h o s p h o r u s is converted to phosphate ion
by oxidation with sulfuric acid, nitric acid, and hydrogen
peroxide. The residual hydrogen peroxide is removed by
diluting with water and evaporation. The level of phosphor u s is t h e n d e t e r m i n e d by p h o t o m e t r i c or gravimetric
methods.
Sulfur Level ASTM D 1552
This method covers three procedures for determining total
sulfur content in oils and is applicable to samples boiling
above 177C and containing not less than 0.06 wt% sulfur.
One procedure uses infrared detection following pyrolysis.
The other two procedures use iodate detection followed by either a n induction furnace or resistance furnace following pyrolysis. Knowledge of the sulfur level can be used to predict
performeince and qucdity of oils.

This method specifies the procedures for calculating the Viscosity Indices (VI) of oils from 40C and 100C. Described
Procedures A and B determine the VI of oils u p to 100 and
greater than 100, respectively. The VI is a widely accepted
measure of the variation in kinematic viscosity due to the
changes in temperature. The higher the VI of the oil is, the
less the dependence of viscosity on temperature. JCnowledge
of a gear lubricant's VI can be used to predict performance
and quality.
T i m k e n M e t h o d for E P ASTM D 2 7 8 2
This method covers the determination of the load-carrying
capacity of oils by means of the Timken EP Tester. The tester
is operated with a steel test cup rotating against a steel test
block. The rotating speed is 123.71 0.77 m/min or 800
rpm. Oil samples Eire preheated to 37.8C before starting the
test. Two determinations are made: the minimum load (score
value) that will compromise the lubricant film between the
rotating cup and stationary block and cause seizure or scoring; and the maximum load (OK value) at which the rotating
cup will not compromise the lubricant film.
Four Ball E P ASTM D 2 7 8 3
This method also determines the load carrying properties of
lubricating oils. This method differentiates between lubricating oils having low, medium, emd high level of EP properties.
The tester is operated with one steel ball under load rotating
against stationary three balls. The rotating speed is 1760 40
r p m . The test lubricant is b r o u g h t between 18.33-35C
(65-95F) and a series of 10 s durations are made at increasing loads until welding occurs.
DemulsibUity ASTM D 2711
This method determines the ability of oil and water to separate from each other. It is intended for oils with medium and
high viscosity. The test provides a guide for determining the

458

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

demulsibility of gear lubricants that are prone to water contamination and may encounter the turbulence of pumping
and circulation capable of producing water-in-oil emulsions.
The ability to separate water is desired in applications where
it is relatively easy to perform maintenance without draining
the oil sump completely.
Oxidation of EP Oils ASTM D 2893 (S-200)
This widely used method determines the oxidation characteristics of EP gear oils. The oil sample is subjected to a
temperature of 95C in the presence of dry air for 312 h. The
oil is then tested for precipitation number and viscosity
increase.
Low Temperature Brookfield Viscosity ASTM D
2983
This test method describes the use of the Brookfield viscometer for the determination of the low-shear rate viscosity
of gear lubricants in the temperature range from - 5 to
-40C. The viscosity range is 1000-1 000 000 cP. A lubricant
sample is cooled in an air bath at test temperature for 16 h. It
is carried in an insulated container to a nearby Brookfield
viscometer where its viscosity is measured at the temperature
of the bath. The low temperature properties of gear lubricants are critical for equipment starts that may be subjected
to low temperatures. The lack of lubrication can cause severe
catastrophic distress to the gears and bearings.

oils and additive packages. A small portion is weighed and


diluted with solvent such as xylene. Internal and calibration
standards are weighed into the test specimen. The mixture is
then fed into an ICP instrument. By comparing the emission
intensities of the elementals against the calibrated standards,
the concentrations of elements in the sample oil are
calculated. This test method can be used to confirm whether
the additive packages or oil meet specifications with respect
to elemental composition.
FZG Scuffing Test ASTM D 5182 or DIN 51354
This test method, developed by the Forschungstelle fur Zahnrader und Getriebebau (Research Site for Gears and
Transmissions), is commonly referred to as the FZG Visual
Method. It is intended to measure the scuffing load capacity of oils used to lubricate hardened steel gears. High EP
gear lubricants that meet API GL-4 and 5 easily exceed the
capacity of the test rig. An FZG Gear Test Machine is operated at constant speed (140 rpm) for a fixed period (15
min.) at successively increasing loads (12 max) until the
failure criteria is reached. The test gears are examined initially and after each load stage for cumulative damage
(scuffing) to the gear tooth flanks. This test method can be
used to screen the scuffing load capacity of oils used to lubricate spur and helical gear units. The FZG Four Square
Test is required for AISE 224 that stipulates no greater than
10 mg between stages.
Cold Crank Simulator ASTM D 5293

Nitrogen Level (Kjeldahl Method) ASTM D 3228


This test method determines the level of nitrogen for concentrations between 0.03 and 0.1 wt%. The sample is digested in
a mixture of concentrated sulfuric acid, potassium sulfate,
mercuric oxide, and copper sulfate. After digestion, sodium
sulfate is added to the mixture to precipitate the mercury,
and the mixture is made alkali with caustic. Nitrogen in the
form of ammonia is then titrated to determine the level of nitrogen present. The concentration of nitrogen is a measure of
the presence of nitrogen containing additives. Knowledge of
nitrogen levels can be used to predict performance.
Base Number ASTM D 4739
This method covers a procedure to determine the basic components in oils. This method resolves these components into
groups having weaJi-base and strong-base ionization properties. Base numbers of up to 70 are covered by this method.
The sample is dissolved in a mixture of toluene, isopropyl alcohol, chloroform, and water. The mixture is then titrated
potentiometrically with alcoholic hydrochloric acid. The end
point is selected from a titration curve and used to calculate
a base number in units of mg KOH/g sample. The base number can provide information on the performance and quality
of new and used oils.
Elemental Content ASTM D 4951
This method quantifies the levels of barium, boron, calcium,
copper, magnesium, phosphorus, sulfur, and zinc in unused

This test method provides the determination of the apparent


viscosity of a lubricating oil at temperatures between 5 and
-30C at shear stresses between 50 000 to 100 000 Pa and
shear rates of iC10^ sec^ An electric motor drives a rotor
that is closely fitted inside a stator. The space between the rotor and stator is filled with the test oil. The test temperature
is measured near the stator inner wedl. The speed of the stator is calibrated against viscosity. The test oil's viscosity is determined from this calibration and measured motor speed.
Thermal and Oxidation (L-60-1) ASTM D 5704
This test method determines the oil-thickening, insolubleformation and deposit-formation cheiracteristics of axle and
transmission oils, especially when subjected to high temperature oxidation. A sample of the oil is placed in a heated gear
case containing two spur gears, a test bearing, and a copper
catalyst. The test oil is heated to 163C for 50 h. Air is bubbled
through the test oil at a constant rate. Parameters used to
evaluate oil degradation after testing are: viscosity increase,
insolubles, and gear cleanliness. The deterioration of the oil
in the transmission or axles can lead to serious seal failures
with deposit formation at the seal-shaft interface.
Cyclic Durability Test ASTM D 5579
This test method evaluates the thermal stability of heavy-duty
gear transmission lubricants when operated under high
temperatures. The gear lubricant's performance is measured
by the number of shifting cycles that can be performed with-

CHAPTER 16: GEAR LUBRICANTS


out failure of synchronization when the transmission is
operated while continuously cycling between high and low
ranges. Field correlation with truck transmission service has
not been established, however, this method has shown to
discriminate between satisfactory and unsatisfactory transmission lubricants in the one petrticular transmission. After
the transmission is rebuilt emd flushed with the test lubricant,
it is started and operated at low range until the sump temperature reaches 250F. This temperature is maintained
throughout the duration of the test. The transmission is
automatically cycled between low and high range until two
unsynchronized shifts occur or the desired length of time is
reached. At the conclusion of the test, parts are rated for
wear.
Seal Compatibility ASTM D 5662
This method evaluates the compatibility of nitrile, fluoroelastomer, and polyacrylate seals in lubricants. Seal failure in
gearboxes, axles, and transmissions is caused by excessive
seal hardening, elongation loss, and volume swelling. This
method tests the likelihood of premature seal failure caused
by the lubricant's effect on seals. The seal materials are
placed in the test oil and subjected to the specified duration
and temperature. At the end of the test, changes in elongation, volume, and hardness are determined.
High Temperature Foam Inhibition ASTM D 6082
This method describes the procedure for determining the
foaming characteristics of oils at 150C. By comparison,
ASTM D 892 determines foaming characteristics of up to
93.50C. A measured quantity of oil is heated to 49C for 30
min and allowed to cool to room temperature. The oil is
transferred to a 100 mL graduated cylinder and heated to
150C and aerated at 200 mL/min with dry air for 5 min. The
amount of static foam at the end of aeration and the stability
after specific times are recorded.
L-37 Low S p e e d High Torque Hypoid Test ASTM
D6121
This test evaluates the load carrying capacity of gear lubricants under low speed and high torque conditions. The gears
are conditions for 100 min at 440 wheel r/min and 394 Ibf-ft
wheel torque, maintaining the sump at 297F. The gears are
inspected and the second phase is commenced. The duration
of the second phase is 24 h and the sump temperature is controlled at 275F. The wheel r/min and wheel torque are 80 and
1742 Ibf-ft, respectively. The gears are inspected for wear and
various forms of other distress. This test measures the gear
lubricant's ability to protect final drives from abrasive wear,
adhesive wear, plastic deformation, and surface fatigue. Lack
of protection can lead to premature gear or bearing failure,
or both. This test procedure is followed for both coated and
non-coated gears to evaluate gear lubricants against MILPRF-2105E requirements. The Wet L-37 test differs in the
temperature during the second phase: a specified amount of
water is added and the axle is motored for 12 h at temperatures below 175F. The axle is then motored for another 12 h
at a temperature of 325F.

459

GFC Oxidation
This test method measures the oxidative stability of gear lubricants under high temperatures. A quantity of sample
placed in a flask is heated at a specific temperature with air
bubbled throughout the duration of the test. At the end of the
test, the viscosity increase, wt% insolubles, and acid number
are reported.
Synchronizer SSP 180 Test
This test measures the ability of a transmission lubricant to
provide proper synchronized shifts at a specified temperature and synchronizer friction material. The test rig uses
cone t)rpe synchronizers of several friction types. The industry is currently conducting round robin testing to formulize a
test procedure for PM-1.
Shear Stability CEC-L45-T-93
The test procedure eveJuates the shear stability of lubricants
containing polymeric additives. Polymeric additives are usually used for thickening and improving low temperature flow
properties. A specified quantity of oil is placed in a tapered
roller bearing fixture that is motored by the Four Ball Machine. The temperature is controlled at 60C for 20 h with a
load of 5000N. At the end of this duration, the percent change
in viscosity at 100C is determined. SAE J306 has shear stability requirements for gear lubricants to not shear out of
grade. Loss in viscosity can caused compromise to lubricant
films for proper bearing and gear performance.
FZG (Forschungsstelle fur Zahnrader und
Getriebebau) Pits C 180 TS
This test procedure evaluates the influence of oil aging on the
pitting life of gears under conditions of variable load, speed,
and high temperature. The results are compared to a reference oil in the same test. The failure criterion is to report less
than 4% of the active flank area of one single tooth at the
end of the test. The pitting performance of gear lubricants is
critical
Channel Point FTM 3456
This test method is used to determine the channeling characteristics of oils at low temperature. The test consists of storing the oil sample for 18 h at the temperature required by the
specification, cutting a channel in the oil with a metaJ strip,
and determining whether the lubricant flows together to
cover the bottom of the container within IDs. The ability of
a lubricant to resist channeling at low temperatures provides
adequate lubrication at startup conditions.
Gear Scoring Test L-42
This test method evaluates the anti-scoring characteristics of
a gear lubricant under high-speed and shock loading conditions using a hypoid axle. The axle is driven by a 5.7 liter V8 engine that drives the test axle, a 4-speed truck transmission, and
two inertia dynamometers at a rate to simulate hard acceleration to approximately 100 mph. After break-in, the axle is ac-

460

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

celerated through the gears to a speed of lOSOrpm, then decelerated to 530 rpm. This cycle is repeated five times. The highspeed sequence is followed by ten shock loadings. The gear lubricant is required to equal or better the scoring on the coast
side of the pinion Eind ring gears of a passing reference oil.
Gear Corrosion Test L-33
This test evaluates the rust and corrosion inhibiting properties of a gear lubricant when subjected to water contamination and elevated temperatures. The test utilizes an unloaded
hypoid axle unit mounted on a test stand, which enables the
unit to be motored over with heat lamps. The axle is filled
with 1200 mL of oil and 30 mL of water and motored for 4 h
at 82.2C. On completion of this motoring phase, the axle is
stored for 162 h for 51.7C in an environmental oven. At the
end of storage, the axle is disassembled and rated for corrosion, sludge, and other deposits.
Dynamic Seals Test
This test method evaluates the seal compatibility during operation at a specified temperature and high shaft speed of
2500 r p m for 1000 h. The lip shaft seals are inspected for wear
and deviations from original dimensions at the end of test.
Modifications to this test specific to OEM seal materials and
shaft diameters can be made. This test attempts to simulate
seal performance and the gear lubricant's effect in the field.
Compatibility of Gear Lubricants FTM 3430
This test procedure is used to determine the compatibility of
gear lubricant when blended with a reference gear lubricant
by observing for precipitation of additive matericd after storage. The test consists of storing the blended oils for 30 days

at room temperature and centrifuging thereafter to quantify


the level of incompatibility from the amount of insolubles.
Storage Solubility of Gear Lubricants FTM 3440
This method is used for determining the storage stability
characteristics of gear lubricants. The gear lubricant is
heated at 120C for 20 min and observed for separation of additive material after storage at room temperature for a period
of 30 days. The level of incompatibility is determined from
the amount of insolubles weighed at the end of storage.
Air R e l e a s e A S T M D 3 4 2 7 o r D I N 5 1 3 8 1
This method covers the ability of the gear oil to separate
entrained air. Compressed air is blown through the test oil,
which has been heated to 25, 50, or 75C. After the air flow is
topped, the time required for the entrained air in the oil to
reduce in volume to 0.2% is recorded as the air bubble
separation time.

FUTURE TRENDS IN GEAR LUBRICANTS


Automobile manufacturers are competing for consumers by
claiming improved vehicle performance. Promoting vehicle
performance in the areas of "Fill for Life" or extending drain
intervals, seamless shifting, aerodynamic changes for aesthetics, and improved fuel economy are some examples. Tables 37 Eind 38 summarize the consequences of these trends
to automotive gear lubricants.
As a result of these trends, automotive gear lubricants are
required t o have improved performance in fatigue, seal
compatibility, oxidative and thermal stability, reduced chlorine, lower friction, lower cross grades in SAE 75W-90, EP,

Table 37^Axle trends and consequences [1].


Trend

' Consequences

Extended Drain

Improved Component
Durability

> Reduced Airflow


Use of Retarders
Reduced Noise
(Use of insulation)
Higher Unit Power/Wt
Ratio

Higher Bulk Oil


Temperatures

Improved Efficiency Improved Shiftability

Lower Oil Viscosity at


Start and Lower
Temperatures Under
Normal Operation

Lubricant Effect
Improved
Pitting
Performance
Improved
Synchronizer
Performance
Improved Seal
Compatibilty
Better
Thermal/Oxidative
Stability

Lower Viscosity Grades


- Increased Use of
'Synthetics'
Lower Friction
Additive
Technology

CHAPTER 16: GEAR LUBRICANTS

461

Table 38Transmission trends and consequences [1].

Trend
Extended Drain

Lubricant Effect

Consequences
Improved Component
Durability
Use of Filters?

improved Pitting
Performance
Improved Seal
Compatibilty

I Higher Speeds
< Reduced Airflow
I increased Unit Loading

> Higher Bulk Oil Temperatures

I iVIore Environmentally
Friendly

Easier Disposal

Improved
Thermal/Oxidation
Stability

Reduced Chlorine
(Target 50 ppm Max)

< improved Fuel Economy

' Improved Axle


Efficiency

Lower Friction Additive


Technology
Lower Viscosity Grades
80W-90 and 75W-90

Component Cost Reductioi

I Simplified
Technology

IMore Robust
Performance

< Hypoid Axle With


Heavier Loadings
< Reduced Noise

Improved EP
Performance

I Reduction in Use of Doubl<


Reduction Axles

antiwear, and cost effectiveness. E n d users of industrial gear


lubricants are requesting reduction in inventory and cost. It
is not u n c o m m o n to see the use of advanced gear additive
chemistries to rationalize or minimize inventory. Gear additive systems capable of meeting both industrial (low treats of
1.4 to 2.5 wt%) and automotive (treat levels of 4.0 to 15.0
wt%) performances are being used today. Other trends for industrial gear lubricants are improved oxidative stability, improved demulsibility, and lower additive treat cost.
It is becoming more evident, as these trends for gear
lubricants are materializing, that the additive and lubricant
industries are meeting these challenges with improved technology in refinement, additive development, and formulation.

mance requirements. Last, a section on future trends for gear


lubricants was dedicated to acknowledge the industry's intention to constantly upgrade gear lubrication specifications
to meet its changing needs.

ASTM STANDARDS
Unless otherwise indicated all of the following standards are
current.
No.
D 91
D 92

CONCLUSIONS
D 97
This chapter described gear lubricants and summarized their
requirements for automotive a n d industrial gear applications. Lubricating gears in axles or gearboxes is challenging,
as gear lubricants are required to provide efficient operation
with minimized maintenance. Gear lubricants collectively
provide various attributes such as: scuffing resistance, extreme pressure (EP), antiwear, corrosion resistance against
ferrous and yellow metals, compatibility with various elastomeric seals, oxidative and thermal stability, possession of
varying degrees of demulsibility depending on application,
low and high temperature film strength, good low temperature fluidity, cost effectiveness, and environmental safety.
Commonly used gear sets were described in this chapter
along with some tj^ical gear failure modes. A list of typical
additives used to formulate gear lubricants were also given.
Current classifications for automotive and industrial gear lubricants were compared along with their testing and perfor-

D 130

D 287
D 445

D 664
D 665
D 808
D 892

Title
Test Method for Precipitation Number for Lubricating Oils
Test Method for Flash and Fire Points by Cleveland
Open Cup
Test Method for Flash Point by Pensky-Martens
Closed Cup Tester
Test Method for Detection of Copper Corrosion
from Petroleum Products by the Copper Strip Tarnish Test
Test Method for API Gravity of Crude Petroleum
and Petroleum Products (Hydrometer Method)
Test Method for JCinematic Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity)
Test Method for Acid N u m b e r of Petroleum Products by Potentiometric Titration
Test Method for Rust-Preventing Characteristics of
Inhibited Mineral Oil in the Presence of Water
Test Method for Chlorine in New a n d Used
Petroleum Products (Bomb Method)
Test Method for Foaming Characteristics of Lubricating Oils

462 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


D 893
D 1091

Test Method for Insolubles in Used Lubricating Oils


Test Method for Phosphorus in Lubricating Oils
and Additives
D 1552 Test Method for Sulfur in Petroleum Products
(High-Temperature Method)
D 1744 Test Method for Determination of Water in Liquid
Petroleum Products by Karl Fischer Reagent
D 2266 Test Method for Wear Preventive Characteristics of
Lubricating Grease (Four-Ball Method)
D 2270 Practice for Calculating Viscosity Index from Kinematic Viscosity at 40 and 100C
D 2 7 1 1 Test Method for Demulsibility Characteristics of
Lubricating Oils
D 2893 Test Method for Oxidation Characteristics of Extreme-Pressure Lubricating Oils
D 2983 Test Method for Low-Temperature Viscosity of Automotive Fluid Lubricants Measured by Brookfield
Viscosmeter
D 3228 Test Method for Total Nitrogen in Lubricating Oils
and Fuel Oils by Modified Kjeldahl Method
D 3427 Test Method for Air Release Properties of
Petroleum Oils
D 4739 Test Method for Base N u m b e r Determination by
Potentiometric Titration
D 4951 Test Method for Determination of Additive Elements in Lubricating Oils by Inductively Coupled
Plasma Atomic Emission Spectrometry
D 5182 Test Method for Evaluating the Scuffing Load Capacity of Oils (FZG Visual Method)
D 5293 Test Method for Apparent Viscosity of Engine Oils
Between-5 and-30C Using the Cold-Cranking
Simulator
D 5579 Test Method for Evaluating the Thermal Stabihty of
Manual Transmission
Lubricants in a Cyclic Durability Test
D 5662 Test Method for Determining Automotive Gear Oil
Compatibility with Typical Oil Seal Elastomers
D 5704 Test Method for Evaluation of the Thermal and Oxidative Stability of Lubricating Oils Used for Manual Transmissions and Final Drive Axles
D 6082 Test Method for High Temperature Foaming Characteristics of Lubricating Oils
D 6121 Test Method for Evaluation of the Load Carrying
Capacity of Lubricants Under Conditions of Low
Speed and High Torque Used for Final Hypoid
Drive Axles

OTHER STANDARDS
AGMA 9005-D94Industrial Gear Lubrication
Federal Test Method 3456Channel Point of Federal Test
Method Std. No. 791
FZG-PITS Test C 180 TSTest Method for Evaluating the
Influence of Oil Ageing on the Pitting Load Capacity of
Lubricants
GFC (Groupement Francais De Coordination) or CEC L-48-A00Oxidative Stability of Lubricating Oils Used in Automotive Transmissions by Artificial Ageing (Laboratory Test)
MIL-PRF-2105E or SAE J2360Lubricating Oil, Gear Multipurpose (Metric) Military Use
SAE J308Axle and Manual Transmission Lubricants

SAE J306Automotive Gear Lubricant Viscosity Classification


SSP 180 or CEC L-66-T-99Evaluation of the Sychromesh
E n d u r a n c e Life using the FZG SSP 180 Synchromesh
Test Rig

REFERENCES
[1] Bala, v., MacPherson, I., and Walters, D. K., "Gear Additive
Technology for Extended Drain Commercial Driveline Requirements," NLGI Paper No: 9719, Presented at The 64th Annual
Meeting of National Lubricating Grease Institute, Carlsbad, Oct.
1997.
[2] MacPherson, I., Kuhlman, R. E., Carlson, J. W., and Taylor, J. M.,
"Gear Additive Considerations for the Next Decade," NLGI Paper
No: 9719, Presented at The 62"^ Annual Meeting of National Lubricating Grease Institute, Ponte Vedra Beach, Oct. 1995.
[3] Norman, S., Kovitch, G. H., and Klein, R. M., "Industry Requirements for a New Generation of Automotive Gear Oils,"
NLGI Spokesman, Vol. 53, 1989, pp. 183-196.
[4] Drago, R. J., Fundamentals of Gear Design, Butterworth Publishers, Boston, 1988.
[5] NLGI Gear Education Course Material, Presented at The 65"'
Annual Meeting of National Lubricating Grease Institute, Naples,
1998.
[6] Hendrick, E. E., "Improved Compound for the Manufacture of
Lubricating Oils," U.S. Patent No. 90,100, Washington D.C.,
May 1869.
[7] Papay, A. G. and Dinsmore, D. W., "Advances in Gear Additive
Technology," Presented at The 30th ASLE Annual Meeting, Atlanta, GA, May 1975.
[8] a. Ethyl Petroleum Additives Specialties Gear Training Manual,
Ethyl Petroleum Additives, Inc., Richmond, VA, 1996. b. Lubrizol Corporation's Additive Ready Reference for Lubricant and Fuel
Performance. Lubrizol, Wickliff, OH, 1998.
[9] Bartz, W. J., Lubrication of Gearing, Mechanical Engineering
Publications, Ltd., London, 1993.
[10] Benedict, G. H., "Gears," Ch. 20, Standard Handbook of Lubrication Engineering, McGraw-Hill, NY, 1968.
[11] American Society of Metals Handbook on Friction, Lubrication
and Wear Technology, Vol. 18, Oct. 1992. a) Errichello, R., "Friction, Lubrication, and Wear of Gears," pp. 535-545; b) Rizvi, S.
Q. A., "Lubricant Additives and Their Functions," pp. 98-112.
[12] ANSI/AGMA 1010-E95: Appearance of Gear TeethTerminology of Wear and Failure, AGMA, Alexandria, VA.
[13] Ludema, K. C, Friction, Wear, LubricationA Textbook in Tribology, CRC Press Ltd., Boca Raton, FL, 1996.
[14] Stucker, J. B., "Rear Axle and Gear Box Lubricants," CRC Handbook of Lubrication, Vol. I, CRC Press, Boca Raton, FL, 1992.
[15] Radovich, J. L., "Gears," CRC Handbook of Lubrication, Vol. II,
CRC Press, Boca Raton, FL, 1992.
[16] AGMA 9005-D94: Industrial Gear Lubrication, AGMA, Alexandria, VA, August 1994.
[17] SAE J308: Axle and Manual Transmission Lubricants, Society
of Automotive Engineers, Warrendale, PA, 1989.
[18] SAE J306: Automotive Gear Lubricant Viscosity Classification,
Society of Automotive Engineers, Warrendale, PA, 1998.
[19] MIL-PRF-2105E: Lubricating Oil, Gear Multipurpose (Metric)
Military Use, U.S. Military, Aug. 1995.
[20] SAE J2360: Lubrication Oil, Gear Multipurpose Military Use,
Society of Automotive Engineers, Warrendale, PA, 1998.
[21] Laboratory Performance Tests for Automotive Gear Lubricants intended for API GL-5 Service, ASTM STP 512A, ASTM International, West Conshohocken, PA, 1991.
[22] Proposed Specification for Passenger Manual Transmission,
Minutes of ASTM Committee D02.B0.003 Meeting, Nashville,
TN, Nov. 2000, ASTM International, West Conshohocken, PA.

CHAPTER 16: GEAR LUBRICANTS


[23] Ethyl Petroleum Additives Lubrication Specification
Handbook,
Ethyl Petroleum Additives, Inc., Richmond, VA, June 2000.
[24] Goodhead, J. W. and Cook, S. P., "High-Temperature PerformEince
Needs of Gear Oils: A Comparison of Current and Future Technologies," 4th CEC Symposium, Birmingham, UK, May 1993.
[25] Bala, V. and Saathoff, L., "Oxidative Stability of Automotive
Gear Lubricants," NLGI Paper No: 9821, Presented at The 65"'
Annual Meeting of National Lubricating Grease Institute, Naples,
Oct. 1998.
[26] Bala, V., Hartley, R. J., and Lawrence, J. H., "The Influence of
Chemical Structure on the Oxidative Stability of Organic Sulfides," Presented at The 1995 STLE Annual Meeting, May 1995.
[27] Bala, V. and Pietras, J. M., "Enhanced Performance Considerations for Automotive Gear Lubricants," Presented at the 2"'' International Symposium on Fuels and Lubricants, New Delhi, 2000.
[28] Pinkus, O. and Wilcock, B. K., "Strategy for Energy Conservation Through Tribology," Presented at the 33rd ASLE Annual
Meeting, Dearborn, April 1978.
[29] Bartz, W. J., "Fuel Economy Improvement by Engine and Gear
Oils," 5th CEC International Symposium on the Performance
Evaluation of Automotive Fuels and Lubricants, Goteborg, Sweden, May 1997.
[30] Bartz, W. J., "Some Considerations Regarding Fuel Economy
I m p r o v e m e n t s by Engine and Gear Oils," presented at t h e
ASLE/ASME Conference, New Orleans, LA, Oct. 1981.
[31] Chamberlin, W. B. and Sheahan, T. J., "Automotive Fuel Savings Through Selected Lubricants," SAE Paper No. 750377, Society of Automotive Engineers, Warrendale, PA, 1975.
[32] Richardson, L. P., Schiemann, L. F., and O'Connor, B. M., "Economic and Energy Benefits through use of Multigraded Gear
Oils," presented at the NPRA Fuels and Lubricant Meeting, Houston, Nov. 1977.
[33] O'Connor, B. M., Graham, R., and Glover, I., "European Experience with Fuel Efficient Gear Oils," SAE Paper No. 790746, Society of Automotive Engineers, Warrendale, PA, 1979.
[34] Naman, T. M., "Automotive Fuel EconomyPotential Improvement through Selected Engine and Gear Lubricants," SAE Paper No. 800438, Society of Automotive Engineers, Warrendale,
PA, 1980.
[35] Stambaugh, R. L., Galluccio, R. A., and KoUer, R. D., "Multigrade Gear Lubricants in Truck Fleet Testing^Analysis for Fuel
Economy Effects," SAE Paper No. 818178, Society of Automotive Engineers, Warrendale, PA, 1981.

463

[36] Moat, N. W., "Canadian Experience with Multigrade Gear Oils,"


SAE Paper No. 811204, Society of Automotive Engineers, Warrendale, PA, 1981.
[37] Watts, R. F. and Willette, G. L., "Newtonian Multigrade Gear
Lubricants: Formulation and Performance Testing," SAE Paper
No. 821180, Society of Automotive Engineers, Warrendale, PA,
1982.
[38] Adams, J. H., Frost, K. A., Hartmann, L. M., and Painter, L. J.,
"The Effect of Gear Lubricant on Fuel Economy as Measured in
a Line Haul Truck Fleet," SAE Paper No. 810179, Society of Automotive Engineers, Warrendale, PA, 1981.
[39] Greene, A. B. and Risdon, T. J., "The Effect of Molybdenum
Containing Oil Soluble Friction Modifiers on Engine Fuel Economy and Gear Oil Efficiency," SAE Paper No. 811187, Society of
Automotive Engineers, Warrendale, PA, 1981.
[40] Devlin, M. T., Naumann, J. K., Saathoff, L. D., and Walters, D.
K., "Predicting the Fuel Economy Properties of Gear Oils Using
Laboratory Friction Tests," GFC Conference, Paris, Nov. 1999.
[41] Adamo, R. and Corso, S., "Frictional and Antiwear Behavior of
Fuel Efficient Gear Lubricants," presented at the 36th ASLE Annual Meeting, Pittsburgh, May 1981.
[42] Porrett, D., Miles, S., Werderits, E., and Powell, D., "Developm e n t of a Laboratory Axle Efficiency Test," SAE Paper No.
800804, Society of Automotive Engineers, Warrendale, PA,
1980.
[43] Bala, V., Brandt, G., a n d Walters, D. K., "Fuel Economy of
Multigrade Gear Lubricants," presented at the 12th International Colloquium Tribology, Esslingen, Germany, 2000.
[44] Bala, V., RoUin, A. J., and Brandt, G., "Rheological Properties affecting the Fuel Economy of Multigrade Automotive Gear Lubricants," SAE Paper No. 2000-01-2051, Society of Automotive
Engineers, Warrendale, PA, 2000.
[45] Bala, V., Guidry, K. L., and Kuhlman, R. E., "Fuel Economy
Considerations of Multigrade Automotive Gear Lubricants,"
NLGI Paper No: 0016, Presented at 67th Annual Meeting of National Lubricating Grease Institute, Asheville, NC, Oct. 2000.
[46] Bala, V. and Pietras, J. M., "Fuel Economy Evaluation of Multigrade Automotive Gear Lubricants," Presented at the PetroTech
Conference, New Delhi, January 2001.
[47] Bala, V., Guidry, K. L., and Kuhlman, R. E., "Enhanced Performance Properties of Multigrade Automotive Gear Lubricants,"
NLGI Paper No: 0131, Presented at the 68'^ Annual Meeting of
National Lubricating Grease Institute, Palm Beach, Oct. 2001.

MNL37-EB/Jun. 2003

Automotive Lubricants
Shirley E. Schwartz, ^ Simon C. Tung,^ and Michael L. McMillan'

LUBRICANT TYPES
MANY TYPES OF LUBRICANTS ARE USED IN A VEHICLE. Engine oil

and transmission fluid, on a volume basis, provide a major


portion of the lubricants in a typical car or truck, and a great
n u m b e r of standard tests are associated with these fluids.
Greases provide a variety of highly specialized functions and
are found in many locations within a vehicle (for example, in
door locks, gears for seat adjustments and windshield wipers,
bearings, electrical contacts, and numerous other places).
For some automotive lubrication applications, standard
tests are not available. An example is automotive air conditioning systems, which require a specialized lubricant that
can be transported by the air conditioning medium. Those
who use lubricants for which standard tests are not available
must devise their own procedures to ensure that the lubricant
performs acceptably.
Functions of Automotive Lubricants
Various issues influence the choice of lubricant composition
for optimum performance in automotive applications. The
lubricant must protect the automotive components that it lubricates. In some cases this protection is in the form of a fluid
film that keeps opposing surfaces separated. In other cases,
the lubricant provides weair protection by forming a wearresistant fllm on a surface, to generate boundary lubrication
protection.
During exposure of a lubricant to high temperature in the
presence of oxygen, there is a risk that the lubricant will react with the oxygen to form organic acids, which can be corrosive and can cause varnish to form on engine components.
Automotive lubricants eire protected against this oxidation by
virtue of antioxidant additives, which are sacrificial agents
that react with oxygen and thus reduce the probability of oxygen attacking the oil's base stock.
In addition, alkaline additives (detergents) in the oil neutralize acids that may be formed. Detergents are chemicals
consisting of a hydrocarbon tail and a polar head, such that
the polar head will be attracted to the products of oil oxidation and nitration and will inhibit the formation of varnish or
deposits, which otherwise could build u p on engine surfaces.
' Materials Engineer, General Motors Powertrain, 3003 Van Dyke
Ave., Warren, MI 48090-9060.
^ Senior Staff Research Engineer and Principal Research Engineer,
respectively. Chemical and Environmental Sciences Laboratory,
General Motors Research and Development and Planning, 30500
Mound Road, Warren, MI 48090-9055.

Defoamers are agents that spread over a fluid surface and


reduce surface tension, so that air bubbles can easily escape.
Viscosity index (VI) improvers are long-chain chemical
c o m p o u n d s t h a t change shape u n d e r various conditions.
When the oil is hot, the VI improvers stretch out and, in the
process of stretching out, they make the oil behave as if it was
more viscous. When the oil is cold, the VI improvers fold in
upon themselves, and as a consequence, they exhibit lower
viscosity than would be the case if they didn't curl up.
The lubricant base stock has the important function of
transporting the various protective chemical additives to the
sites in which they are needed and transporting waste products away from the sites in which the waste is generated. For
example, engine oil t r a n s p o r t s anti-wear surface-active
agents to the nose of the cam on a camshaft, a region in
which chemical agents are essential for wear protection
when a lifter slides over a cam nose. Protective anti-wear
agents are not as critical when a roller follower is used, rather
than a sliding contact.
The wearing surfaces in a newly manufactured vehicle may
have burrs or rough spots, which are smoothed during use.
The lubricant transports these burrs or residues away from
the rough spots in which they originated. The burrs can then
be transported to a filter, or they may be dropped to the bottom of the oil reservoir.
The diversity of function of automotive c o m p o n e n t s
strongly influences the characteristics of the lubricant required for use with the component. That is, different vehicle
components require different lubricant base stocks, fluid viscosities, and type and quantity of additive treatment for the
component to function properly. Thus, a variety of specialized lubricants are required for automotive applications.
Engine oil must remain effective despite the fact that fuel
and combustion products can condense in the oil under conditions such as short trips and cold starts in a winter climate,
during which fuel and water may accumulate in engine oil at
concentrations greater than five percent [1,2]. During high
temperature operation, engine oil must not evaporate or degrade excessively. Transmission fluid must withstand high
temperatures and loads. Various types of bearings require
the presence of a fluid film that separates a rotating shaft
from its opposing bcciring surface. Brake fluid must continue
to provide appropriate braking force, even if the vehicle
drives through pouring rain or encounters puddles or slush
on the road.
During high load, high temperature conditions, such as the
those experienced by piston rings at the top of the cylinder
under the influence of the burning fuel, fluid film lubrication

465
Copyright'

2003 by A S I M International

www.astm.org

466

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

may not be sufficient to provide complete wear protection. In


such cases, the lubricant must contain additives that interact
with r u b b i n g surfaces to form chemical anti-wear films.
These protective chemical films form on hot iron surfaces
during vehicle operation as long as the lubricant has not degraded excessively. However, these chemical films may be
partially removed during severe engine service [3]. Once the
additives that provide this chemical film (typically, zinc dialkyl dithiophosphate, ZDP, and other anti-wear agents) are
sufficiently degraded during use, the engine oil needs to be
changed; otherwise engine wear can accelerate.
In addition to providing a fluid film and a chemical surface
film, automotive lubricants must also inhibit corrosion. For
example, partially burned fuel can be acidic, and these fuelderived acids can condense in engine oil, especially during
very short trips in exceedingly cold weather. An example of
this effect is shown later in this chapter in the section on test
methods for automotive lubricants. Engine oil itself, when
exposed to hot spots in the presence of oxygen, can also form
acids (due to oil oxidation) that promote varnish formation
and engine corrosion, especially if the oil's alkaline anticorrosion additives have been degraded as a consequence of
extended use without an oil change.
A lubricant typically reduces friction, but in some cases an
automotive lubricant is designed to provide a desired amount
of friction, as is the case for proper clutch engagement in automatic transmissions. A desired amount of traction may be
needed, as is the case for traction fluid in a continuously
variable transmission. Traction fluids have a chemical structure that, under stress, forms a three-dimensional network
that resists flow [4,5].
The lubricant associated with air conditioning fluid must
be sufficiently compatible with the air conditioning medium
that the air conditioning fluid can transport the lubricant to
the wearing surfaces. In addition, the mixture of lubricant
and air-conditioning fluid must have sufficient lubricating
properties to protect the air-conditioning p u m p , b u t the
fluid/lubricant combination must not become aggressive to
hoses or to other materials in the air-conditioning system.
These examples illustrate the complexity of the issues that
must be addressed when attempting to provide adequate automotive lubrication. In some cases, standard test methods
document whether a lubricant provides appropriate protection to the hardware. In other cases, vehicle, component, or
lubricant manufacturers designate the lubricant that, in their
estimation, best fits a given application.

COMPOSITION OF AUTOMOTIVE
LUBRICANTS
In general, automotive lubricants consist of a base stock and
various additives. The choice of base stock depends on the
function of the lubricant. In the case of engine oil, various
types of organic oils may be used: paraffinic, naphthenic, and
synthetic. Paraffinic hydrocarbons consist of hydrogen and
carbon atoms that are chemically bonded together in the
form of branched chains. Naphthenic hydrocarbons contain
carbon atoms that are bonded together in the form of rings.
Paraffinic and naphthenic hydrocarbons are typically derived by refining oil from oil wells. Synthetic hydrocarbons

are formed by combining small hydrocarbon building blocks


to form longer chains of a desired composition that tends to
be more resistant to chemiccd attack than is the case for oils
produced by a refining process.
Additives are blended into a base stock to provide desirable
properties such as optimum friction characteristics for the
desired application, anti-wear and antioxidant capability, defoaming capability, and corrosion inhibition. The chemical
nature of the additives for a given application are chosen on
the basis of their ability to perform their desired function,
withstand the conditions u n d e r which they must operate,
and be compatible with the base stock in which they are used.
Test M e t h o d s for Automotive Lubricants
A variety of tests are needed to guarantee that a given automotive lubricant performs as it should. These tests include:
Engine and component tests that mimic different driving
or operating styles under a variety of test conditions,
Physical and chemical properties of the lubricant,
Corrosivity of a used lubricant,
Wear protection provided by the lubricant,
Remaining effectiveness of the lubricant's additive package.
Additional desired information with regard to lubricant
characterization includes: tendency to form deposits, rate
and extent of oil oxidation, fuel efficiency, and emission system protection, including limits on phosphorus in engine oil,
since phosphorus can adversely affect the performance of the
catalyst that reduces automotive emissions [6-9].
For some lubrication functions, standard test methods are
available to ensure that the various products in the marketplace provide the desired protection. For other lubrication
functions, there are no standard tests, but a vehicle manufacturer may require that the lubricant of choice must pass
the memufacturer's (or some other) designated tests.
Each different type of automotive lubricant has its own
unique test methods that address the issues relevant to the
service needs of that particular lubricant. For example, engine tests are used to determine whether a new candidate
engine oil formulation meets current certification requirements. These certification requirements must be passed before an oil container is allowed to show the "starburst" label
that indicates the oil is acceptable for use in current vehicles.
Bench tests can often be used to indicate whether certain
fundamental lubricant properties are within a desired range
(for example, tests for viscosity, pour point, volatility, shear
stability, wear rate, wear depth, etc.). Chemical and physical
tests measure the composition and properties of a lubricant,
the changes that occur as the lubricant ages, and the characteristics of any contaminants or wear debris that may have
entered the lubricant.
The following sections describe issues relative to various
types of automotive lubricants and test methods that have
been developed to address those issues. As is t5?pically the
case, older test methods are periodically upgraded, and new
methods are developed. Thus, some of the tests described in
any given list of standard methods may be out of date. An example of this evolutionary process is seen with regard to a lowtemperature engine test, ASTM D 5844, Test Method for Evaluation of Automotive Engine Oils for Inhibition of Rusting
(ASTM Sequence IID). This engine test has recently been re-

CHAPTER
placed by a bench test, ASTM D 6557, Standard Test Method
for Evaluation of Rust Preventive Characteristics of Automotive Engine Oils, also known as the "BEJI Rust Test." During
the creation of the Ball Rust Test, extensive testing was conducted to identify appropriate chemiccJ reagents and test conditions to ensure that the bench test would provide the same
useful information as was gleaned from the engine test.
AUTOMOTIVE E N G I N E OILS
Introduction
Identifying appropriate test methods for engine oils represents one of the most difficult challenges facing automobile
and lubricant manufacturers. The reason for the difficulty is
not because of any inherent characteristic of engine oil. The
challenges in the development of test methods for engine oil
arise because the environment in which engine oils must operate can be exceedingly harsh and difficult to control. Combustion gases, fuel and water in the oil, and outside contaminants (dirt, sand, other airborne materials) accelerate oil
degradation, cause unique filtration problems, and result in
m u c h shorter change intervals compared to other typical automotive lubricants. Engine oil properties and composition
also affect vehicle fuel economy (as is the case for transmission fluids and rear axle lubricants). Engine oil influences
vehicle emissions as a consequence of emission system contamination and catalyst poisoning. Engine oil can escape
from the engine via mist exiting the exhaust system. In addition, small amounts of engine oil or oil mist can b u m when
exposed to a flame front, which can create particulate emissions containing charred hydrocarbons and degraded oil additives.
It is for these reasons that engine oil is the focus of much
attention in the technical literature as well as in the standard
test-development arena. The following sections describe
standard test methods for evaluating engine oil performance
(including both engine and bench tests) and the terminology
used to describe engine oil performance, from both historical
and current perspectives. The discussions are limited primarily to performance designations a n d associated test
methods commonly used in North America. Oils described by
other means and defined by different test methods are used
in various other areas of the world, for example Europe and
Japan. However, these international test methods are not addressed in detail in this chapter.
E n g i n e Oil P e r f o r m a n c e S t a n d a r d s - - P a s t
and Present
Over the years, many organizations have contributed to the
development of engine oil performance standards. Among
these organizations are ASTM International (ASTM), the
American Petroleum Institute (API), the Engine Manufacturers Association (EMA), the Coordinating European Council
(CEC), the Japan Automobile Manufacturers Association
(JAMA), and the International Lubricant Standardization and
Approval Committee (ILSAC). ILSAC includes automotive
and engine builders JAMA, EMA, and the former American
Automobile Manufacturers Association (AAMA, whose members were General Motors, Ford, and Chrysler). When AAMA

17: AUTOMOTIVE

LUBRICANTS

467

was dissolved in 1999, it was replaced by a new organization


the Alliance of Automobile Manufacturers (the Alliance),
which includes the former members of AAMA plus six other
manufacturers. The Alliance, however, is not actively involved
in development of automotive lubricant standards.
An early attempt at classifying engine oils was initiated in
1911, when the Miscellaneous Division of the Society of Automotive Engineers (SAE) introduced Specification No. 26,
which specified that specific gravity, flash and fire points,
carbon residue, and viscosity (resistance to flow at a given
temperature) should be used to describe oil properties. In
1923 the specification was expanded to include specific
ranges for the various measured properties of the engine oils.
The designation of engine oils on the basis of performance
began in 1947. API (American Petroleum Institute) adopted a
classification system based on the intended use of the oil.
Three types of oil were defined: Regulcir (termed ML), Prem i u m (MM), and Heavy Duty (MS). The performance categories for gasoline engine oils (ML, MM, and MS) imply motor oil ("M" in the designation) suitable for light (L in the
designation), moderate (second M in the designation), and
severe (S in the designation) service. Regular oils generally
were straight mineral oils. Premium oils contained some oxidation inhibitor (but no other performance additives), and
Heavy Duty oils were blended with oxidation inhibitors and
detergents/dispersants. This system was modified in 1952 to
create different performance requirements for diesel oils
than those for gasoline engine oils and to rank the severity of
the service.
Performance categories for diesel engine oils were DL, DM,
and DS, where D stands for diesel, and M, L, and S are the
same as for gasoline engine-oil categories.
Even though these designations (ML, MM, MS, DL, DM,
and DS) indicated the quality of the engine oil, many vehicle
and engine manufacturers found it necessary to add additional performance requirements to ensure adequate protection for their engines. This led to the development of lubricants tailored to a given manufacturer, and complicated
the manner in which engine manufacturers informed their
customers which oils were currently recommended. Finally,
in 1969 three organizations, API (American Petroleum Institute), ASTM (was American Society for Testing and Materials, now called ASTM International), and SAE (Society of
Automotive Engineers, now called SAE International), cooperated to establish a performance designation system, which
is still being used. In this system, two series of engine oil
performance and service categories were established. The "S"
series, in which S designates service, is used with gasoline-fueled, 4-stroke-cycle, spark ignition engines. The "C" series denotes commercial, intended for use in compression-ignition
diesel engines, both 2-stroke-cycle and 4-stroke-cycle).
Table 1 shows the evolution of light-duty gasoline engine
oil performance designations. The "~" symbol means that
the terminology for API SA and API SB oils was created after
those oils were no longer considered adequate for current vehicles. A similar evolution occurred for heavy-duty diesel engine oil performance. A detailed description of the history of
both gasoline and diesel engine oil performance categories
can be found in SAE (Society of Automotive Engineers)
Standard J183, "Engine Oil Performance and Engine Service
Classification."

468

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

TABLE 1Historical evolution of engine oil performance designations.


Performance Designation
Period of Use
ML, MM, MS
~1950s and later
API SA (designation created after this oil was already obsolete)
-1900-1930
API SB (designation created after this oil was already obsolete)
-1931-1964
APISC
1964-1967
APISD
1968-1971
APISE
1972-1979
APISF
1980-1988
APISG
1988-1992
API SH / ILSAC GF-1
1993-1996
API SJ / ILSAC GF-2
1996-2001
API SL / ILSAC GF-3
2001 and beyond

The API SA through API SD designations Hsted in Table 1


were adopted in 1971 to describe oils that had been available
previously. API Category SA was adopted to describe oils generally available in North America between 1900 and 1930.
These oils contained no performance additives. Such oils had
previously been designated as "Regular" or "ML." API SA and
SB oils can still be found in some retail establishments,
where a n uninformed customer (who may need to add makeu p oil) may purchase an SA oil that is sadly deficient with regard to engine protection.
API Category SB was adopted to describe oils for gasolinefueled engines that were generally available in North America between 1931 and 1963. These oils were comparable in
performance to oils known as "Premium" or "MM" prior to
1971. They contained a minimal level of performance additives. API Category SC described oils typically available between 1964 and 1967 in North America. These oils were probably the first oils to contain a full range of performance
additives. They had been designated "MS" prior to 1971. API
Category SD described oils of the performance level generally
available in 1971. Although these oils were also described as
"MS" prior to 1971, they generally contained a higher additive treatment level than API SC oils.
API "S" categories (API SE through API SL) were developed
as needs arose for greater engine protection. API SE oils addressed high-temperature engine oil thickening problems in
the field. API SF oils addressed customer concerns related to
engine wear. API SG oils addressed oxidation and sludge formation concerns that had arisen in the field. Throughout this
period (1972-1992), automotive engines had undergone
tremendous changes to accommodate increasingly more stringent emission control requirements, both nationwide and in
California beginning in 1972, and U.S. Corporate Average Fuel
Economy (CAFE) requirements originating in 1978.
The desire of vehicle manufacturers to specify oils which
might help them address these requirements, as well as their
desire to have a greater voice in establishing engine oil performance specifications, led to the formation of ILSAC (International Lubricant Standardization and Approval Committee) in 1987. Originally a u n i o n between the Motor
Vehicle Manufacturers Association (MVMA) and the Japan
Automobile Manufacturers Association (JAMA) for the purpose of establishing lubricant standards, ILSAC expanded to
include the Engine Manufacturers Association (EMA).
MVMA later became the American Automobile Manufacturers Association (AAMA), and subsequently became the Alliance of Automobile Manufacturers (the Alliance) in 1999.
However, only the original three members of AAMA (General

Motors, Ford, and DaimlerChrysler) retained membership in


ILSAC when AAMA was dissolved.
The first ILSAC engine oil standard (ILSAC GF-1, where
GF stands for gasoline-fueled engines) was published in
1993, as indicated in Table 1. ILSAC standards apply only to
certain viscosity grades, namely SAE OW-XX, 5W-XX, and
lOW-XX viscosity grades, in which "XX" represents a viscosity designation such as 20, 30, 40, etc. ILSAC standards also
include m i n i m u m levels of fuel economy performance and
contain other requirements (most notably a maximum phosphorus level) to address emission system compatibility and
other issues. Even though API (American Petroleum Institute) engine-oil categories apply to all viscosity grades and do
not include fuel economy requirements, an ILSAC GF-1 oil is
roughly equivalent to an API SH quality oil, but in addition
the GF-1 engine oil also meets requirements allowing the GF1 oil to be classified as energy conserving. The ILSAC GF-2
standard for engine oils is roughly equivalent to API SJ, but
also includes fuel economy requirements. The ILSAC GF-3
standard is similar to API SL, but again, GF-3 oils must satisfy fuel economy requirements, which GF-2 and API SLquality engine oils are not required to meet. A well-stocked
automotive supply store may have a dozen different brands
of engine oil, many choices of viscosity grades, and several
choices of oil quality from which a customer may select the
oil of his choice.
The ML, MM, a n d MS Categories, as well as API SA
through API SG, have been declared technically obsolete by
SAE (Society of Automotive Engineers). This was done because many of the engine tests necessary to demonstrate that
oils meet the performance requirements of these categories
cannot be conducted, since reference fuels, reference oils,
and engine parts for these tests are no longer available. In addition, oils with recent designations (API SH, SJ, and SL) can
be used in applications for which earlier oil designations (SA
through SG, which are now considered technically obsolete)
were required. API SH, while not technically obsolete, is generally not used except in combination with a "C" Category, to
describe oils intended for mixed fleet (that is, diesel and gasoline) service. In such cases, the "C" Category designation usually precedes the "SH" designation on a label.
E n g i n e Oil P e r f o r m a n c e T e s t s
Beginning with oils designated as API SB, all of the oil performance categories described in Table 1 were or are defined
by a series of engine dynamometer performance tests (usually termed engine sequence tests) and bench tests. The com-

CHAPTER
plete description of each of these performance categories
(both the current categories and those declared technically
obsolete) is provided in SAE Standard J183, Engine Oil Performance and Engine Service Classification. Only the tests
used to define the current performance categories (API SJ
and ILSAC GF-2) and the tests used in the categories effective
in 2001 (API SL and ILSAC GF-3) are discussed in this section. Some of these tests have been developed into ASTM
Standard test methods, and others are in the process of being
developed into ASTM Standards. It is not a requirement that
all tests used to define a n engine performance category be
ASTM Standards. However, those tests that are not ASTM
Standards are usually advanced to ASTM Standards during
the lifetime of a given category. ASTM Subcommittee D02.B0
on Automotive Lubricants maintains a section devoted exclusively to converting test methods developed for new lubricant performance categories into ASTM Standards.

Issues Addressed in Test Method Development


Examples of the types of questions that need to be addressed
to ensure that a given engine oil will protect an engine in various t5rpes of service are as follows:
1. If the engine is run at high engine speed and high oil temperature,
Will the engine oil thicken excessively?
Will there be sufficient wear protection?
Will harmful deposits form?
2. If the engine is driven in city service, will the oil provide
sufficient sludge protection?
3. If the engine is driven in extreme short trips in a winter climate, will the oil provide adequate corrosion protection
when water, fuel, and fuel oxidation products condense in
the engine oil?
Each numbered item in the previous paragraph represents
a different driving style: high temperature high-load, city service with oil fully warm, and extreme short trip service in
which the engine oil never warms completely. Each of these
driving styles is associated with a specific ASTM standard
test method to ensure that an engine oil provides sufficient
protection for that particular type of service. An engine oil
must pass all of these tests before its manufacturer is allowed
to display a label indicating that the oil meets current specifications. Freeway driving (an additional driving style) is considered to be mild on engine oil and is not represented in a
standard test, since it is assumed that the tests representing
the other driving styles are sufficient to characterize lubricant properties.
A test method must mimic the oil degradation and engine
damage that occurs as a consequence of a given style of driving. That is, a test must exhibit the same fundamental mechanisms that occur during real-world operating conditions. A
given engine test environment must be related to real-world
driving conditions in at least three ways:
The chemical changes that talce place in the test should be
comparable to those that occur in real-world driving.
The materials used in the test (for example, engine, piston
rings, seals, bearing materials) should not create an environment that might cause a test to provide misleading information.

17: AUTOMOTIVE

LUBRICANTS

469

The temperatures and loads of the test should be appropriate for the tjrpe of service being emulated.
For a given test method, a desired chemical environment is
created by utilizing an appropriate fuel (including its degradation products) and generating oil degradation products
that are similar to those generated in the driving style of interest. A desired materials environment is created by using
engine and hardware materials that are representative of the
engines that the test method is designed to protect. In addition, hardware should be chosen for the test such that interactions between hardware surfaces and chemicals used or
generated in the tests (such as fuels, lubricants, and their
degradation products) are similar to those in the real world.
A desired t h e r m a l environment m e a n s that test temperatures, even if they are severe, are not so severe that fundamental mechanisms of damage have changed.
Creating an appropriate test environment, but also finding
test conditions such that the test does not require an inordinate a m o u n t of test time, is often difficult to achieve. An example of this difficulty is as follows. If a lubricant test
method is designed to determine the corrosive effects of fuel
degradation products on engine materials, the test must be
conducted at a temperature such that those corrosive fuel oxidation products will not boil off, but will remain in the engine oil to create corrosive conditions. If a test temperature
differs significantly from operating temperatures, an investigator must determine whether or not any apparent correlation is accidental. In addition, leaded fuel tjrpically contains
chlorine and bromine compounds that can contribute to engine corrosion. If leaded fuel is used in an engine test that
simulates a given type of vehicle operation, but current vehicle operation uses unleaded fuel, one m u s t determine
whether any correlations observed between the leaded-fuel
test and actual vehicle operation are real or accidental. That
is, the investigator must determine whether the chemical environment in the engine test simulates an accelerated version
of reality. Such correlation is often difficult to prove.
Thus, chemical, thermal, and materials properties all influence the outcome of a test, and it is important to ensure
that these properties, as utilized in a given test, are providing
a realistic representation of actual operating conditions. In
addition, when bench tests are used in place of engine tests to
measure a given performance parameter, great care must be
taken to ensure correlation between the bench test and engine effects.
Gasoline Engine-Oil Performance Categories and
Associated ASTM Standard Test M e t h o d s
As of the year 2001, only four designations were widely used
to describe gasoline engine oil performance: API SJ and SL,
and ILSAC GF-2 and GF-3. As stated previously, the engine
test and bench test performance requirements for API SJ and
ILSAC GF-2 are similar with regard to engine test methods,
but in addition ILSAC GF-2 oils must meet the stricter Energy Conserving fuel efficiency requirements. Similarly, API
SL requirements as well as Energy Conserving requirements
must be passed before an engine oil can be designated as
ILSAC GF-3.
The appropriate test methods for engine oils must be conducted in accordance with the requirements outlined in the

470

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

American Chemistry Council (ACC) Product Approval Code


of Practice. These requirements include test registration of
all tests and use of only calibrated equipment and facilities.
These requirements were implemented when API SH and ILSAC GF-1 designations for engine oil were adopted in 1993.

ILSAC GF-2 A N D API SJ STANDARD TESTS


H i g h T e m p e r a t u r e Oil O x i d a t i o n a n d E n g i n e
Wear, ASTM S e q u e n c e HIE
During high speed, high load service, an engine oil becomes
very hot. Engine deposits may form. The oil's viscosity may
increase excessively as a consequence of any or all of the following: evaporation of the lighter ends of the oil, base stock
polymerization, oxidation, and nitration of the oil. In addition, engine c o m p o n e n t s m a y exhibit unacceptable wear.
These issues are addressed in ASTM D 5533, Standard Test
Method for Evaluation of Automotive Engine Oils in the
Sequence HIE Spark-Ignition Engine. In this test a 3.8L V-6
engine and a specified fuel are used, test preparation and operation are described in great detail, engine components are
measured before and after a test, and oil samples are taken
every 8 h and checked for viscosity increase. After a break-in
period, the test is conducted for 64 h at an engine speed of
3000 revolutions per m i n and an oil temperature of 149C.
Additional operating parameters are also specified. At the
end of the test, oil properties and engine components are
rated for viscosity increase, sludge, varnish, deposits, lifter
sticking, scuffing, ring sticking, and wear.
Terminology used in ASTM D 5533 is defined in ASTM D
4175, Standard Terminology Relating to Petroleum, Petroleum
Products, and Lubricants, in which the standard's test number
and ASTM committee associated with the test are also listed.
Limiting values for this and other tests are provided in
ASTM D 4485, Standard Specification for Performance of
Engine Oils. For SJ quality engine oil, limiting values indicate that kinematic viscosity increase at 40C should not be
more than 375% after 64 h of testing. There should be n o
stuck lifters and no oil-related ring sticking. There should be
n o c a m or lifter scuffing. Combined cam plus lifter wear
should average less than 30 fim, with a maximum of no more
than 64 |xm. Engine sludge is rated according to CRC (Coordinating Research Council) Sludge Rating Manual No. 12.
Piston skirt varnish and oil ring land deposits are rated by
comparing the engine components to CRC Varnish Rating
Manual No. 14. These merit rating measurements should be
higher t h a n a specified limiting value.
In addition, a homogeneity and miscibility test. Federal
Test Method Standard No. 79IC, Method 3470, is used to determine whether an engine oil is compatible with standard
test oils. This test ensures that if a vehicle owner adds a liter
(quart) of make-up oil to a different oil that is already in the
oil pan, n o adverse effects will occur, assuming both oils
meet current specifications.
High Temperature
CRC L-38

Copper-Lead

Bearing

Wear,

An additional high temperature engine test method is ASTM


D 5119, Standard Test Method for Evaluation of Engine Oils

in the CRC L-38 Spark-Ignition Engine. This test evaluates


bearing weight loss and oil deterioration under high-temperature, high-load service conditions. According to Section 1.4
of the test method, "correlation of test results with those obtained in automotive service has not been established."
Test operating conditions include an engine speed of 3150
revolutions per min, fuel flow of 2.15 kg/hour, and gallery oil
temperature of 143.5C for SAE 20, 30, 40, 50, and multigrade oils. There is a 4-hour run-in period and a half-hour
flush at the start of the test, followed by four 10-hour test segments. Any fuel that has entered the engine oil during the test
is stripped (removed) before viscosity is determined. Stripping is accomplished by heating the oil at 120C under vacu u m in a nitrogen a t m o s p h e r e for 1 h after the oil has
warmed to the test temperature. ASTM D 445, Standard Test
Method for Kinematic Viscosity of Transparent and Opaque
Liquids (the Calculation of Dynamic Viscosity), is used to
evaluate the viscosity stability of multiviscosity oils such as
SAE lOW-40.
The change in acidity of the engine oil is determined, since
oil acidity increase is a measure of oil degradation. Acidity
may be evaluated either by ASTM D 974, S t a n d a r d Test
Method for Acid and Base N u m b e r by Color-Indicator Titration, or by ASTM D 664, S t a n d a r d Test Method for Acid
Number of Petroleum Products by Potentiometric Titration.
The extent of varnish a n d sludge deposits is determined.
Weight loss of copper-lead bearings is determined. Bearing
weight loss should be no greater than 40 mg. Additional specifications are listed in the test method. ASTM D 974 indicates
that "the method does not measure an absolute acidic or basic property that can be used to predict performance of an oil
under service conditions. No general relationship between
bearing corrosion and acid or base n u m b e r s is known."
ASTM D 664 indicates approximately the same thing.
City Service Engine Sludge and Valve Train
ASTM Sequence
VE

Wear,

The Sequence VE test, ASTM D 5302, is titled Standard Test


Method for Evaluation of Automotive Engine Oils for Inhibition of Deposit Formation a n d Wear in a Spark-Ignition
Internal Combustion Engine Fueled with Gasoline and Operated Under Low-Temperature, Light-Duty Conditions. The
purpose of the test is to ensure that a given engine oil protects
an engine under city driving conditions.
The test is r u n in three stages. Stage 1 lasts for 120 min at
an engine speed of 2500 revolutions per min. The engine load
is listed as 33.5 brake horsepower, at an engine oil inlet temperature of 155F (note that English units are listed. 155F is
68.3C and 33.5 brake horsepower is 25 kW). Stage 2 lasts 75
m i n at 2500 revolutions per m i n at an oil temperature of
210F (98.9''C) and an engine load of 33.5 brake horsepower
(25 kW). Stage 3 lasts 45 min at an engine speed of 750 revolutions per min, a load of 1.0 brake horsepower (0.746 kW),
and an engine oil inlet temperature of 115F (46.1C). Seventy two repetitions of this four-hour test cycle are conducted, to provide a total of 288 h of test time. The fuel used
is Phillips J unleaded gasoline. Rocker arm cover, valve deck,
cylinder block, camshaft baffle, front seal housing, and the
oil pan are rated for sludge using CRC No. 12, Sludge Rating
Manual. Varnish on the piston skirt is rated using CRC Man-

CHAPTER
ual No. 14. Parts other than piston skirts are rated by comparing the engine parts to color chips. Piston undercrown deposits axid ring land deposits Etre EJSO evaluated.
The extent of clogging of vEirious components is rated: oil
screen, oil ring, PCV (positive crankcase ventilation) valve,
and camshaft lobe orifice clogging. Oil screen clogging
should be n o greater than 20%. The n u m b e r of stuck rings
and hydraulic lifter plungers is recorded. There should be no
hot-stuck compression rings. Various wear measurements
are tciken, including: camshaft lobes, rocker arm, connecting
rod bearing, and cylinder bore. Piston ring gap increase is
also used as a measure of wear. Average cam wear should be
no greater than 127 /xm. Maximum cam wear should be no
greater t h a n 380 /am. The following oil analyses are conducted: iron, copper, and silicon in engine oil, kinematic
viscosity (ASTM D 445), and pentane insolubles in oil (ASTM
D 893 B).
Short-Trip-Service

Engine

Rusting,

ASTM

Sequence

IID

ASTM D 5844, Standard Test Method for Evaluation of Automotive Engine Oils for Inhibition of Rusting, is an engine
test conducted with a 1977 5.7L Oldsmobile engine. The test
uses leaded gasoline, and a warning message is provided that
indicates "The method may not be applicable for the evaluation of engine oils if unleaded gasoline is used." In Stage I (28
h) the engine speed is 1500 revolutions per min, engine load
is 25 brake horsepower (18.6 kilowatts) at an oil temperature
of 120F (48.9 C) in the filter block. In Stage II (2 h) coolant
temperature is increased. In Stage III (2 h) the engine speed
is 3600 revolutions per min, engine load is 100 brake horsepower (74.6 kW), and the oil temperature is 260F (126.7C).
Additional operating parameters are listed in the test procedure. Various engine c o m p o n e n t s are evaluated for such
measurements as rust formation on valve lifter bodies, valve
lifter plungers, valve lifter balls, oil p u m p relief veJve, and
pushrods. Lifter plunger sticking, oil p u m p relief valve sticking, and oil consumption are also measured.
Energy Conserving
Characteristics,
ASTM Sequence
VIA
In addition to the engine performance r e q u i r e m e n t s described above, ILSAC GF-2 oils must meet fuel efficiency requirements according to the test procedure described in
ASTM Standard D 6202 (Sequence VIA). In this engine dynamometer test, the fuel consumption associated with a test
oil is measured and compared to the fuel consumption when
using a standard reference oil. For the test oil to be called
"Energy Conserving," it must exceed the fuel efficiency of the
reference oil by a given percentage, based on its SAE viscosity grade. The m i n i m u m percent improvement for ILSAC GF2 oils is 1.4% for SAE OW-20 and 5W-20 viscosity grades,
1.1% for other OW and 5W multiviscosity grades, and 0.5%
for SAE l o w multiviscosity and all other viscosity grades.
API SJ oils are not required to meet fuel efficiency requirements, although oils satisfying the above Sequence VIA requirements can be designated as "Energy Conserving" in the
bottom half of the API (American Petroleum Institute) service symbol, which appears on many oil containers. American Petroleum Institute publication API 1509 provides information on this subject.

Engine

Oil

17: AUTOMOTIVE

LUBRICANTS

471

Volatility

Engine oil volatility (evaporation loss) has been correlated to


engine oil consumption [10-12]. In ein effort to limit oil consumption, reduce its effects on emission systems, and improve customer satisfaction, volatility limits are incorporated
in both API SJ and ILSAC GF-2 categories. Volatility can be
measured by ASTM D 5800 (Noack Volatility method) or by
ASTM D 5480 or ASTM D 6417. Both of these are gas chromatography methods in which the temperature of a sample
of fluid is raised, the various components that Eire pEirt of the
fluid mixture boil off, and the composition of the components that have volatilized off is determined.
Foaming

Tendency

Oils that foam excessively can cause valve lifters in engines to


collapse and oil pumps to lose pressure. Test methods ASTM
D 892 (foaming characteristics) and ASTM D 6082 (hightemperature foaming characteristics) measure the tendency
of an oil to foam and the stability of any foam created. In
ASTM D 892 a lubricant at 24C is blown with air for 5 min,
then allowed to settle for 10 min. The volume of foam is measured at both the five-min point and the ten-min point. A second fluid sample is measured at 93.5''C, and again, after collapsing the foam, at 24C.
In ASTM D 6082, foam is generated with a diffuser. "Correlation between the amount of foam created or the time for
foam to collapse, or both, and actual lubrication failure has
not been established."
Phosphorus

Content

Phosphorus in engine oil has been shown in numerous studies [6-8] to be related to poisoning of catalytic converters and
other emissions system components. For this reason, phosphorus content of ILSAC GF-2 and certain viscosity grades of
API SJ oils must remain below a designated value. Phosphorus content is measured either by ASTM D 4951, Standard
Test Method for Determination of Additive Elements in Lubricating Oils by Inductively Coupled Plasma Atomic Emission Spectrometry or by ASTM D 5185, S t a n d a r d Test
Method for Determination of Additive Elements, Wear Metals, and Contaminants in Used Lubricating Oils and Determination of Selected Elements in Base Oils by Inductively
Coupled Plasma Atomic Emission Spectrometry.

Additional Requirements
Several additional requirements must be satisfied before an
oil can claim to be either ILSAC GF-2 or API SJ. These requirements include:
Flash Point either by ASTM D 93, Standard Test Methods
for Flash-Point by Penske-Martens Closed Cup Tester, minimum flash point of 200C or by ASTM D 92, Standard Test
Method for Flash and Fire Points by Cleveland Open Cup,
m i n i m u m flash point of 185C,
Gelation Index (a measure of low-temperature oil gelling
tendency) by ASTM D 5133, Standard Test Method for Low
Temperature, Low Shear Rate, Viscosity/Temperature
Dependence of Lubricating Oils Using a TemperatureScanning Technique,

472

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

TEOST-33 (Thermo-Oxidation Engine Oil Simulation Test,


protocol 33, a deposit control test, with a maximum deposit weight of 60 mg),
Homogeneity and Miscibility by Federal Test Method 791c
(Method 3470.1),
Engine Oil Filterability and Water Tolerance as determined by the Engine Oil Filterability Test (EOFT)
Engine Oil Water Tolerance Test (EOWTT).
As of the year 2001, the latter two tests are in the process of
being elevated to ASTM standards by ASTM Subcommittee
D02.06 (Analysis of Lubricants).
ILSAC GF-3 and API SL Standard Tests
The five new engine performance tests that define ILSAC GF3 and API SL categories, at the time of this writing, are in the
process of being advanced to ASTM Standards by ASTM
D02.B0 Committee on Automotive Lubricants. These engine
tests include the following.
Sequence IIIF
The Sequence IIIF Test replaces the Sequence HIE Test
(ASTM D 5533) and measures high-temperature engine oil
thickening and piston deposits. It also provides information
on camshaft and valve lifter wear.
Sequence VG
The Sequence VG Test is a partial replacement for the Sequence VE Test (ASTM D 5302). Sequence VG measures the
sludge and deposit control tendency of engine oils under engine conditions which simulate stop-and-go city service in vehicles.
SequenceIVA
Sequence IVA is also a partial replacement for the Sequence
VE Test (ASTM D 5302). Sequence IVA measures the ability
of an oil to provide overhead cam and slider-follower wear
protection under stop-and-go engine conditions such as are
experienced in city driving.
Sequence VIII
Sequence VIII replaces the CRC L-38 Test (ASTM D 5119). It
measures the same parameters as the L-38 Test did: copperlead bearing weight loss under high-temperature operating
conditions and permanent viscosity loss due to shearing.
However, the Sequence VIII Test utilizes unleaded fuel,
whereas the L-38 test utilizes leaded fuel.
Sequence VIB
Sequence VIB replaces the Sequence VIA Test (ASTM D
6202) for measuring the fuel-efficiency properties of an
engine oil. Like its predecessor, the Sequence VIB Test measures the improvement in fuel efficiency of a test oil compared to an ASTM standard reference oil. Unlike its predecessor, however, the Sequence VIB Test not only measures
the fuel efficiency of the oil when the oil is relatively new
(after only 16 h of aging in the engine), but also the fuel efficiency after 96 h of aging, which corresponds to approximately 4000-5000 miles (6500-8000 km) of vehicle operation. Different levels of fuel efficiency improvement are
required, depending upon the SAE viscosity grade of the en-

gine oil (the same groupings of viscosity grade as were defined in the ILSAC GF-2 requirements for the Sequence VIA
Test, as described previously). Sequence VIB fuel efficiency
requirements apply only to ILSAC GF-3 oils, not to API SL
oils, although oils satisfying the Sequence VIB requirements
for GF-2 can use the "Energy Conserving" label of the bottom
half of the API service symbol, as was previously mentioned
under the topic "Energy Conserving Characteristics," Sequence VIA.
Bench and Other Test Requirements
Most of the same bench and chemical property requirements
that exist for ILSAC GF-2 and API SJ categories also exist for
ILSAC GF-3 and API SL (although in some cases the limits
associated with the tests for ILSAC GF-3 and API SL are different from those required for ILSAC GF-2 and API SJ).
These requirements include:
Volatility loss as determined either by ASTM D 5800 or by
ASTM D 6417,
Filterability criteria as measured by the Engine Oil Filterability Test and the Engine Oil Water Tolerance Test,
Foaming tendency by ASTM D 892 and D 6082,
Homogeneity and Miscibility by Federal Test Method 791c,
Method 3470.1,
Gelation Index by ASTM D 5133, and
Maximum phosphorus content as measured either by
ASTM D 4951 or by ASTM D 5185.
There are, however, two new bench test requirements for
ILSAC GF-3 and API SL oils: the Ball Rust Test and the
TEOST MHT-4 test.
Ball Rust Test
ASTM D 6557, Standard Test Method for Evaluation of Rust
Preventive Characteristics of Automotive Engine Oils, was
developed to replace the Sequence IID Engine Test, which
measures the ability of an oil to prevent rust and corrosion in
engines operating on leaded gasoline under short-trip driving
conditions. ASTM D 6557 is also known as the Ball Rust Test,
since it uses a steel ball (lifter check ball) as a test specimen
that is representative of a typical ferrous engine component.
A ball and a measured sample of an engine oil that is to be
evaluated are placed in a test tube. If more than one oil sample is to be tested, additional test tubes, each containing a ball
and an oil sample are prepared. The test tubes are placed in
a shaker in which shaker speed and temperature are controlled. Air and a corrosive fluid are fed into the test tube to
create a corrosive environment. The corrosive fluid consists
of representative samples of the type of chemicals that can be
generated during the combustion process in short-trip winter
driving. After 18 h, the steel test specimens (balls) are evaluated for the extent of rusting, using a computerized scanning
system with optical imaging. Excellent correlation between
results obtained in the Ball Rust Test and Sequence IID has
been achieved with a wide variety of oil compositions. However, the method indicates that, in comparison with the results of ASTM D 5844 (Standard Test Method for Evaluation
of Automotive Engine Oils for Inhibition of Rusting (Sequence IID), "correlation between these two test methods
has been demonstrated for most, but not all, of the test oils
evaluated."

CHAPTER
TEOSTMHT-4
A new version of the Thermo-Oxidation Engine Oil Simulation Test (TEOST), the MHT-4, was developed for ILSAC GF3 and API SL specifications. The TEOST MHT-4 test is intended to provide additional high-temperature piston deposit
control in m o d e m engines that are designed for improved
driveability and in addition must meet federal emissions and
fuel economy requirements.
D i e s e l E n g i n e Oil P e r f o r m a n c e C a t e g o r i e s a n d
Associated ASTM Standard Test M e t h o d s
When diesel engines are operated at high temperature, the
viscosity of the engine oil can increase due to oil oxidation
and nitration, base stock polymerization, evaporation of the
lighter ends of the oil, and accumulation of soot in the oil. As
was the case for gasoline-fueled vehicles, diesel engine oil additives can degrade during long-term use. If the engine oil degrades to the point at which it becomes acidic, acidic reaction
products that form on a metal surface can be scraped off by
moving components, resulting in undesirable wear. In addition, soot accumulation can adversely affect engine wear by
two fundamentally different mechanisms. Soot can interact
with a n d sequester a n engine oil's antioxidant/anti-wear
agent so that the anti-wear capability of the engine oil becomes diminished [13]. Soot can also abrade away a protective anti-wear film that has formed on heavily loaded regions
of an iron surface [3]. These oil-related concerns are addressed using various standard tests.
At the t i m e of this writing, there were five active API
(American Petroleum Institute) diesel engine oil performance categories, designated as API CF, API CF-2, API CF-4,
API CG-4 and API CH-4. Each of these categories has at least
two engine performance tests t h a t m u s t be conducted to
demonstrate compliance with category requirements. Various bench tests are also included. A complete description of
each of these categories, including engine and bench tests, as
well as associated test limits for each requirement, is documented in ASTM D 4485, Stcindard Specification for Performance of Engine Oils and in SAE J183, Engine Oil Performemce and Service Classification. It is anticipated that these
five categories will be reduced to three: API CF-2, API CG-4,
and API CH-4. Thus, API CF and API CF-4 will no longer be
used. A description of each of these diesel engine-oil performance categories is as follows.
APICF
API CF oils are intended for use in off-road indirect-injection
diesel engines using a broad range of fuel types, including
those with high sulfur content. The only ASTM Standard
test in the performance definition of this category is the CRC
L-38 Test (ASTM D 5119), which measures bearing weight
loss a n d oil deterioration, as described previously. NonASTM tests include the Caterpillar IM-PC test (PC stands for
Pre-Chamber), which measures piston deposits and ring
sticking in a single cylinder diesel engine.
API CF-2
API CF-2 oils are intended for use in two-stroke-cycle engines, which require cylinder and ring-face scuffing resistance and deposit control. ASTM standard test requirements

17: AUTOMOTIVE

LUBRICANTS

473

include the CRC L-38 (ASTM D 5119) test, which has already
been described, and the Detroit Diesel 6V92TA test (ASTM D
5862). ASTM D 5862, Standard Test Method for Evaluation
of Engine Oils in Two-Stroke Cycle Turbo-Supercharged
Detroit Diesel 6V92TA Engine, is a two-stroke cycle diesel engine test that measures such parameters as high-temperature
stability of engine oil, cylinder liner scuffing, piston ring face
distress, plugging of liner ports, and slipper bushing distress.
Removal of tin from the cylinder liner is also eveduated. Engine components are measured before and after the test to
determine the extent of wear or degradation. The test is conducted under two different modes of operation: torque mode
and power mode. In the torque mode, engine speed is 1200
revolutions per m i n and the oil gallery temperature is 102C.
In the power mode, the engine speed is 2300 revolutions per
min, at an oil gallery temperature of 111C. Additional parameters are listed in the test procedure. A non-ASTM Standard test requirement for this category is the Caterpillar IMPC method described under the API CF category.
API CF-4
The API CF-4 category describes the tests that are used for
high-speed service in four-stroke cycle diesel engines. The
category includes tests that m e a s u r e bearing weight loss,
ASTM D 5119 (the L-38 test, which measures oil degradation
and bearing corrosionincluding a mEiximum limit of 50 mg
bearing weight loss). Piston deposits, viscosity increase, and
brake specific oil consumption are rated according to the
Mack T-6 test. Average rate of kinematic viscosity increase in
the last 50 h according to the Mack T-7 test and oil consumption and wear in the Cummins NTC-400 test ctre also
measured. In addition, the Caterpillar IK engine test is used
to measure piston and ring groove deposits, piston scuffing,
ctnd oil consumption.
API

CG-4

API CG-4 oils are intended for use in high-speed, four-strokecycle diesel engines operating in both highway and off-road
conditions, with fuels in which the sulfur content may VEiry
from less than 0.05% sulfur by weight to less than 0.5 weight
% sulfur, as described in ASTM D 4485. These oils provide
effective control of deposits and wear in engines designed to
meet 1994 exhaust emission standards. ASTM Standard tests
include the Mack T-8 engine test (ASTM D 5967), ASTM Sequence HIE engine test (ASTM D 5533), CRC L-38 bearing
test (ASTM D 5119), the roller follower wear test (ASTM D
5966), and a corrosion bench test (ASTM D 5968). Foaming
tendency according to ASTM D 892 is also included. ASTM D
5533, ASTM D 5119, and ASTM D 892 are described previously in this chapter.
ASTM D 5966, Standard Test Method for Evaluation of
Engine Oils for Roller Follower Wear in Light-Duty Diesel
Engine, was developed to address soot accumulation in engine oil, which can contribute to engine wear [3,13]. This test
is conducted at 1000 revolutions per min and a m a i n oil
gallery temperature of 120C. Roller follower shaft wear is
evaluated. Kinematic viscosity at 100C cind soot content are
also monitored.
ASTM D 5967, Standard Test Method for Evaluation of
Diesel Engine Oils in T-8 Diesel Engine (the Mack T-8 Test),
eveJuates both viscosity increase and soot accumulation in

474

MANUAL i7: FUELS AND LUBRICANTS

HANDBOOK

the engine oil of a Mack E7-350 diesel engine. Oil consumption is also monitored. The test is conducted at an engine
speed of 1800 revolutions per min, a fuel rate of 63.3 kg/hour,
an engine oil temperature of 100-107C, and an inlet manifold temperature of 43.3C. Additional test conditions are
listed in the test procedure. The viscosity should not increase
by more than 11.5 centistokes at a soot content of 3.8%.
ASTM D 5968, Standard Test Method for Corrosiveness of
Diesel Engine Oil, measures the extent to which non-ferrous
metals are susceptible to corrosion as a consequence of inappropriate engine oil formulation (rather than oil degradation
or contamination). Test coupons (lead, copper, tin, and phosphor bronze) are cleaned and placed in the test oil. Air is
allowed to flow into the oil for 168hat 121C. Test coupons
are evaluated for corrosion and discoloration, and the oil is
evaluated for the presence of metals that have entered the oil
as a consequence of corrosion of the metcil samples.
Non-ASTM tests used in defining the API (American
Petroleum Institute) CG-4 specification include the Caterpillar IN engine test, which measures piston deposits in a fourstroke-cycle, direct injection diesel engine operating on fuel
containing less than 0.05 percent sulfur by weight. API CG-4
also includes the Engine Oil Aeration Test (EOAT), which has
been correlated with oil aeration in diesel engines equipped
with hydraulically actuated, electronically controlled unit injectors.
API CH-4
API CH-4 oils are intended for use in high-speed, four-strokecycle diesel engines designed to meet 1998 exhaust emissions
standards. ASTM Standard tests include CRC L-38 (ASTM D
5119, Standard Test Method for Evaluation of Automotive
Engine Oils in the CRC L-38 Spark-Ignition Engine), ASTM
Sequence HIE test (ASTM D 5533), Mack T-8 (ASTM D 5967),
and a high temperature corrosion bench test (ASTM 5968)
were described previously.
The Mack T-9 (ASTM D 6483) is described below. The tests
use diesel fuels with sulfur content up to 0.5 weight %, as described in ASTM D 4485. Foaming tendency (ASTM D 892),
volatility (ASTM D 5800 or ASTM D 6417), and sheared viscosity (ASTM D 6278) requirements are also included.
ASTM D 6483 (Standard Test Method for Evaluation of
Diesel Engine Oils in T-9 Diesel Engines, known as the Mack
T-9 test) evaluates diesel engine oil for various performance
characteristics, including resistance to lead corrosion and
wear of piston rings and cylinder liners. The test uses a Mack
E7-350 V-MAC II diesel engine. The test starts with a onehour break-in, followed by a two-phase test that includes 75
h at 1800 revolutions per min and 425 h at 1250 revolutions
per min. Oil samples are taken during the testing and are analyzed for increase in viscosity and for weeir metals in the oil.
The extent of engine-component wear is also assessed. For
example, the maximum allowed cylinder liner wear is an average value of 25.4 \xxn at a soot content of 1.75%. The maximum allowed average-top-ring weight loss is 120 mg, and the
maximum allowed increase of lead content in the engine oil
is 25 parts per million.
Non-ASTM standard tests used in defining the API CH-4
category include the following. The Caterpillar IP engine test
measures piston and ring groove deposits in four-strokecycle, direct injection diesel engines calibrated to meet 1998

United States Federal Exhaust Emissions Standards with fuels containing less than 0.05% sulfur by weight. The Caterpillar IK engine test measures the same performance parameters as the Caterpillar IP engine test, but for engines in use
prior to 1989, using aluminum pistons and fuel that has 0.4
weight % sulfur. The Cummins Mil High Soot Diesel Engine
Test measures soot-related valve-train wear. Engine sludge
and oil filter plugging tendency are measured. The Engine Oil
Aeration Test (EOAT), mentioned in the API CG-4 specification, is also conducted.
Additional Tests Used to Describe Engine Oil
Performance and Properties
The use of a bench test, if it can be shown to correlate to an
engine test, can be considerably less labor intensive and less
costly than an engine test. Bench tests for engine oil are of
several types. Some, such as the Ball Rust Test, ASTM D 6557
(described previously), produce fundamental information
about a specific aspect of the protection provided by an engine oil. Other bench tests measure various properties of the
engine oil such as viscosity, alkalinity, acidity, extent of oil
oxidation, presence of oil additives, and the presence of oil
contaminants such as engine-wear debris or corrosion products. Many of these bench tests are included as part of the
specified analysis procedure for an engine test. In other
words, a bench test often provides necessary documentation
to evaluate the results of a dynamometer test. Various tests
that are used to ascertain the performance of automotive lubricants in general and engine oils in particular are described
in the following sections.
Engine Oil Acidity and Alkalinity
Automotive lubricants typically contain oil-soluble alkaline
agents that provide corrosion protection, since corrosion is
less likely to occur in a moderately alkaline environment.
Acids can be generated from fuel combustion or from oxidation of engine oil in hot spots. For example, if engine oil becomes acidic as a consequence of exposure to heat or if acidic
combustion by-products from the fuel condense in the engine
oil during short-trip, low temperature service, engine corrosion may occur. If oil alkalinity is too high, a lubricant or
other fluid may also become aggressive to a metal surface.
Several techniques are available to assess oil acidity and remaining alkalinity protection, for example:
ASTM D 664, Standard Test Method for Acid Number of
Petroleum Products by Potentiometric Titration
ASTM D 974, Standard Test Method for Acid and Base
Number by Color-Indicator Titration
ASTM D 1093, Standard Test Method for Acidity of Distillation Residues or Hydrocarbon Liquids
ASTM D 2896, Standard Test Method for Base Number of
Petroleum Products by Potentiometric Perchloric Acid
Titration
ASTM D 4739, Standard Test Method for Base Number Determination by Potentiometric Titration.
In each of these tests, a sample of the oil or residue of interest is titrated (that is, reacted) with the desired test
reagent. Different reagents used in the various tests yield different values for an acid number or base number. An investigator will have to determine which test best meets his needs.

CHAPTER 17: AUTOMOTIVE


For Acid Number according to ASTM D 664, the following
qualification is listed: "The test method may be used to indicate relative changes that occur in an oil during oxidizing
conditions The test method is not intended to measure an
absolute acidic property that can be used to predict performance of an oil under service conditions. No general relationship between bearing corrosion and acid number is
known." ASTM D 974 has a nearly identical notice. ASTM D
1093 indicates: "The results obtained by this method are
qualitative expressions." Thus, an investigator would be wise
to determine which type of analysis suits his needs.
An example of transient engine-oil acidification due to condensation of partially burned fuel is shown in Figure 1 (derived from information available in Ref. 2), in which an oil
sample was taken on a day when the outside temperature was
-20C. The test vehicles had been given 3-km trips three
times a day. During this interval of bitter cold, the engine oil
acidity spiked in all the vehicles that were on short-trip test
that day. Two representative examples are shown in Fig. 1.
The weather later warmed, so that the volatile fuel-derived
acids that had condensed in the oil were removed.

Entry of Water into Engine Oil


In addition to condensation of acids, water can condense in
engine oil during short-trip, winter operation. ASTM D 1744,
Standard Test Method for Determination of Water in Liquid
Petroleum Products by Karl Fischer Reagent (Discontinued
in January, 2000), has been used to determine the water content of engine oil. The amount of water that condenses in the
engine oil during very cold short-trip operation is directly related to the amount of water-per-kilometer produced by a
given fuel [2]. M85 fuel (85 percent methanol plus 15 percent
gasoline) produces approximately four times as much waterper-kilometer as gasoline. This influence of fuel type on water in oil is shown in Fig. 2 (which was derived from information available in Ref. 2). Differences in oil analysis results
due to differences in engine type and oil type are negligible in
comparison to the fuel effect. With longer trips or warmer
weather, the water is removed via evaporation.
Viscosity
Viscosity is a measure of the resistance to flow. Two types of
viscosity measurements are typically used, kinematic and dynamic. Kinematic viscosity is measured by determining the
time required for a fluid to flow past the marks on a specicd
tube at a specified temperature, assuming that the flow is
laminar, and not turbulent. Kinematic viscosity is described
mathematically in terms of mm^/s. Dynamic viscosity is
equal to kinematic viscosity multiplied by the density of the
fluid of interest.
Engine oils operate most effectively when their viscosity is
within an optimum range for a given type of engine and a
given set of driving conditions. Temperature influences
viscosity. Higher oil temperature causes a reduction in oil
viscosity, and lower oil temperature causes oil viscosity to
increase.

3.1LV-6 engine

:i=^^
200
300
400
Distance on oil, l(m

500

600

FIG. 1Condensation of volatile acids into engine


oil (per ASTM D 664), due to partial oxidation of fuel
during exceedingly cold weather, and removal of the
acids with warmer weather.
Ml

25

Percent water
In engine oil,
Karl Fischer
method

JA N

'

11

MAR

FEB

'

APR

'

MAY

A longer trip in May


caused water to
evaporate from oil

lUBSfuel65 % msthanol
+ 1 5 % gasoline

20

15
Engine

^
o
"

Fuel

Oil

3.1L MSSfuel A

'

<1
10

3.1L MBS fuel B


3.1L gasoline A

475

Corrosiveness of Diesel Engine Oil


ASTM D 5968, Standard Test Method for Coirosiveness of
Diesel Engine Oil, was described previously, under section
API CH-4.

Ambient temperature
Near -20 C, 3-km trips

100

LUBRICANTS

4.5L gasoline B
4.5L gasoline B
1

'

200

400

600

800

1000

Distance traveled, km

FIG. 2Influence of type of fuel on the amount of water that can accumulate in engine oil during short-trip, cold-start driving, according to
ASTIM D 1744.

476

MANUAL
150

37: FUELS AND LUBRICANTS

'

HANDBOOK
1

85% methanol fuel, short trips, emulsion formation


1
Evaporation of water
^ o
and methanol during
\ warm weather

Viscosity of
engine oil at
40C, cSt
100

Gasoline fuel in engine oil,


short trips, solution formation

50

___x_ '

If the viscosity vEiries significantly with sheeu", different results may be obtained from viscometers of different diameter. ASTM D 446 gives specifications and operating instructions for glass kinematic viscometers.
ASTM D 4683 measures viscosity at high temperature and
high shear a n d carries the warning, "applicability to
petroleum products other than engine oils has not been determined." Engine oil at very low temperature can become
highly viscous, per ASTM D 4684 (which carries the same
warning as is found with ASTM D 4683). In ASTM D 4684, an
engine oil is cooled from 80C at a programmed rate to a fined low temperature (between -15C and -35C). Yield stress
and apparent viscosity are measured.

SAE 10W-30, API SG-quality engine oil


I

200

400
600
Distance on oii, Icm

800

1000

FIG. 3Influence of solution-forming and emulsion-forming


fuel contamination on engine oil viscosity (per ASTIVI D 445).

In addition to the changes in viscosity due solely t o temperature effects, operation at a given high temperature will
cause the oil's viscosity to increase (in comparison to viscosity of the fresh oil at the same temperature) due to oil oxidation and to evaporation of the lighter ends of the engine oil.
Various low-temperature viscosity cheinges can also be observed. Low engine-oil temperature causes an increase in viscosity. However, at low outside temperatures, hydrocarbon
fuel can condense in engine oil, which causes a decrease in
oil viscosity. Condensation of methanol (alcohol) fuel in engine oil formed an emulsion and caused a significant viscosity increase. An example of these opposite viscosity effects is
shown in Fig. 3, which is derived from information available
in Ref. 2.
Thus, fuel-in-oil measurements can provide information
about the nature of viscosity changes and the nature of contaminants in the engine oil. However, these effects only occur
if the engine oil remains at low temperature during short-trip
operation, otherwise once the oil t e m p e r a t u r e rises sufficiently, m u c h of the fuel will evaporate from the oil, and the
oil viscosity will revert to a more typical value.
Standard ASTM viscosity tests include:
ASTM D 445, Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (the Calculation of
Djoiamic Viscosity),
ASTM D 446, Standard Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers,
ASTM D 4683, Standard Test Method for Measuring Viscosity at High Temperature and High Shear Rate by Tapered Bearing Simulator,
ASTM D 4684, Standard Test Method for Determination of
Yield Stress and AppcU^ent Viscosity of Engine Oils at Low
Temperature.
ASTM D 445 measures the time it takes for a liquid to flow
through a standard capilleiry tube. This test method has the
wzuning, "The result obtained from this test method is dependent u p o n the behavior of the sample cind is intended for
application to liquids for which primarily the shear stress
and shear rates are proportional (Newtonian flow behavior)."

EXTENT OF OIL OXIDATION


As engine oil is used in a vehicle, the ability of the engine oil
to resist oxidation becomes diminished as a consequence of
exposure to heat and to contamination from fuel and fuel reaction products. This degradation can be monitored using test
methods such as ASTM D 5483, Standard Test Method for Oxidation Induction Time of Lubricating Greases by Pressure
Differential Scanning Calorimetry. The test method indicates
that, "This test method can be used for research and development, quality control and specification purposes. However,
n o correlation has been determined between the results of this
test method and service performance." Information found in
tests such as those illustrated in Fig. 4 suggest a very useful
correlation between oil oxidation in road tests and DSC oil
analysis results as described in Refs. 14 and 15.
In this method, a small cimount of lubricant is placed in a
cup, the cup is placed in a chamber which is filled with oxygen and heated rapidly to the desired test temperature, and
held at that temperature for the duration of the test. The time
from the start of the test until the onset of rapid oxidation is
measured. An alternative procedure is to r a m p the temperature u p in a series of stages and observe the effects of elevated
temperature on oil oxidation.

1(

4I

Oxidation
induction
time by
3
differential
scanning
calorimetry,
natural
2
logarithm of
DSC

SAE 10W-30 engine oil, API SF quality

^ % v

1.

NS^ *

. No trailer

o\.
0 N

\ * ^^

o \
With trailer

NO
BP*
\ o
VNA

^-0

5000
10000
Distance on oil, km

0^^-

'

15000

FIG. 4Differences in loss of oxidative stability of engine oil


(natural logarithm of the DSC value) as a consequence of type
of service, determined using ASTM D 5483.

CHAPTER
Even though this method was developed for greases, it can
be used for other lubricants. An example is found in Figure 4,
which shows differences in the rate of engine oil oxidation
between similar vehicles, driving over identical terrain, but
two of the vehicles were not pulling a trailer (dark circles),
and one of the vehicles pulled a 1000-kg trailer (open circles)
[14,15]. As can be seen, the constant-temperature version of
the differential scanning calorimetry technique (abbreviated
as "DSC") was able to document statistically significant differences in the chemical status of the engine oil from the vehicle that pulled the trailer. The natural logarithm of the DSC
value was plotted. This figure indicates that oxidative stability can be a reliable measure of severity of service. The theoreticcil explanation for this effect is provided in Ref. 14.
The various ASTM standard test procedures described in
this section list a great n u m b e r of related test methods. Referenced Documents from these test methods are provided in
Tables 2 and 3 at the end of this chapter, so that the reader
will have a comprehensive list of the various tests associated
with engine oil.

TRANSMISSION FLUIDS
Composition and Performance of
Transmission Fluids
Transmission fluids lubricate a vehicle's transmission. They
may be composed of synthetic or mineral oil. S5Tithetic oil
typiccilly shows enhanced resistance to deterioration from exposure to heat. However, synthetic and mineral oil both contain additives that help maintain the desired friction properties, minimize wear, and provide corrosion inhibition to the
transmission components. In addition, antioxidant additives
are required to prolong the life of the transmission fluid.
Maintaining stable friction properties is highly important,
since any change in shift characteristics or generation of
shudder (objectionable vibration) after prolonged or severe
use is sure to be noticed by a vehicle owner. To provide the
desired shift properties, one of the additives present in a
transmission oil is typically a long-chain hydrocarbon that
has a polar group on one end. The polar end group of the additive is attracted to the metal surface, and the long-chain hydrocarbon portion associates with the oil, thereby forming a
durable, low-friction oil film on the metal surface. Too m u c h
friction reduction will cause transmission components to
slip, b u t too little friction reduction will not allow the transmission to shift smoothly cind will cause wear.
In addition to appropriate friction characteristics, it is also
essential to reduce wear a n d promote long transmission life.
Wear protection is provided to a great extent by oil additives.
If suitable anti-wear additives were not present, there would
likely be excessive weeir of the transmission components under severe operating conditions. Thus, fluid degradation during prolonged service should not be extensive enough to comp r o m i s e transmission performance, a n d wear rates m u s t
remain low so that excessive loss of material does not cause
shift characteristics to deteriorate.
Various standard test methods are available to ensure sustained transmission performance. Tests for automatic transmission fluids include measurement of physical eind chemical properties: viscosity, flash point, pour point, corrosion

17: AUTOMOTIVE

LUBRICANTS

477

resistance, wear resistance, friction characteristics, and resistance to foaming. Additional tests measure performance
during selected duty cycles, as defined by the manufacturer.
For example, major automotive producers in North America
have their own specifications for transmission fluids. Thus,
in retail establishments that sell transmission fluids, one can
see labels on transmission fluid bottles indicating "meets the
specifications for XXX a n d YYY", in which XXX and YYY
represent the brand names of a specific automobile manufacturer. Transmission fluid test requirements published by a
given automobile m a n u f a c t u r e r include GM-6417M for
Dexron-III (General Motors) a n d Mercon-V (Ford).
A n u m b e r of standard ASTM tests for transmission fluids
are listed in the SAE International Surface Vehicle Information Report, SAE J311 (revised 2000-02): ASTM D 130 (Copper Strip Corrosion), ASTM D 665 (Rust Preventing Characteristics), ASTM D 892 (Foaming Characteristics, as
described previously in the Engine Oil section), ASTM D
1275 (Corrosive Sulfur in ElectriccJ Insulating Oils, which is
not listed in the 2001 ASTM a n n u a l book of standards),
ASTM D 1748 (Rust Protection by Metal Preservatives in the
Humidity Cabinet), and ASTM D 2882 (Wear Characteristics
of Hydraulic Fluids in a Constant Volume Vane Pump). Additional ASTM tests are also provided in the Annual Book of
ASTM Standards. The tests listed here are described below.
Referenced d o c u m e n t s in these transmission-related test
methods are provided in Tables 4 and 5 at the end of the
chapter.

High Temperature, High Load Testing


ASTM D 5579, S t a n d a r d Test Method for Evaluating the
Thermal Stability of Manual Transmission Lubriccints in a
Cyclic Durability Test, evaluates the thermal stability of fluids used in heavy duty manual transmissions during hightemperature (121C) operation. This test measures the number of shifting cycles, between a high and a low gear, that can
be performed without failure of synchronization in a manual
transmission being operated at high temperatures. The test is
terminated when the transmission experiences two shifts in
which the clutch teeth produce a loud noise. According to
Section 1.3 of the test method, "Correlation of test results
with truck transmission service has not been established.
However, t h e procedure has been shown to appropriately
sepEirate two transmission lubricants, which have shown satisfactory a n d unsatisfactory field performance in the trucks
of one manufacturer."
ASTM D 5704, Standard Test Method for Evaluation of the
Thermal a n d Oxidative Stability of Lubricating Oils Used for
Manual Transmissions and Final Drive Axles (commonly referred to as the L-60-1 test), measures oil thickening and formation of insolubles and deposits in a manual transmission
oil and final drive axle lubricating oil.
ASTM D 5182, Standard Test Method for Evaluating the
Scuffing Load Capacity of Oils (FZG Visual Method), measures the scuffing load capacity of oils used to lubricate hardened steel gears. Scoring (abrasive wear) is also assessed. An
FZG Gear Test Machine is operated at a constant speed of
1450 revolutions p e r min. The test starts at 90C at a predetermined load. The severity of the test is increased (using a
designated test cycle) until failure occurs. The n u m b e r of

478

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

shifting cycles to failure of synchronization is determined.


Shifter fork wear is also measured. Examples of various types
of wear patterns that may be observed during the testing (polishing, abrasive wear, moderate abrasive wear, and scuffing)
are provided in the test method to help the investigator interpret test results. In the introduction, the following warning is
listed: "High EP (extreme pressure) type oils, for example,
those oils meeting the requirements of API GL-4 and GL-5,
generally exceed the capacity of the test rig and, therefore,
cannot be differentiated with this test method." "EP" in this
statement stands for "Extreme Pressure," which typically
represents extreme temperature.
ASTM D 5760, Standard Specification for Performance of
Manual Transmission Gear Lubricants, lists the methods and
performance criteria for deciding whether a lubricant exhibits acceptable behavior in nonsynchronized heavy-duty
manual transmissions. The limiting criteria are provided in
ASTM D 5704, Standard Test Method for Evaluation of the
Thermal and Oxidative Stability of Lubricating Oils Used for
Manual Transmissions and Final Drive Axles. The limits include a viscosity increase of no more than 100% (per ASTM D
445) and a pentane insolubles content of no more than 3 %
(per ASTM D 893). Limiting values for elastomer (seal) properties are also listed. For example, elastomer hardness should
not decrease by more than 20% nor increase by more than 5%.
B e n c h a n d Analytical Tests Related t o
Transmission Fluids
Various bench methods are used to help characterize transmission fluid properties a n d performance. ASTM D 130,
Standard Test Method for Detection of Copper Corrosion
from Petroleum Products by the Copper Strip Tarnish Test,
is used to determine whether a fluid of interest will tarnish
copper. In this test, a polished copper strip is immersed in the
test fluid at a temperature and for a time appropriate for the
test fluid. At the end of the test, the copper strip is cleaned
and compared to a stemdard.
ASTM D 1748, Standard Test Method for Rust Protection
by Metal Preservatives in the Humidity Cabinet, uses steel
panels which are dipped in the test lubricant, removed and
allowed to drain, and are then suspended in a humidity cabinet at 48.9C for a designated n u m b e r of hours. The size and
n u m b e r of rust spots that form on the panel are determined.
There should be n o more than three dots of rust, each of
which should be smaller than 1 m m in diameter.
ASTM D 2882, Standard Test Method for Indicating Wear
Characteristics of Petroleum and Non-Petroleum Hydraulic
Fluids in Constant Volume Vane Pump, measures the total
mass loss from the twelve vanes used in the p u m p and from
the cam ring on which the vanes ride. Good lubricants show
very little wear in this test. Fluid cleanliness before and after
the test, initial flow rate, and final flow rate are also measured to determine the extent of damage to hardware and
degradation of the fluid.
Additional tests pertinent to transmissions include measurement of the torque required to overcome the friction that
occurs between clamped clutch plates at high and low slip
speeds and assessing the tendency to shudder (which occurs
as a consequence of stick-slip motion between mating surfaces). Measurement of "shift feel" aJso provides useful information to an investigator.

ASTM D 5662, Standard Test Method for Determining Automotive Gear Oil Compatibility with Typical Oil Seal Elastomers, measures whether the properties (hardness, volume,
and elongation in a stretch test) of selected oil-seal elastomers (nitrile, polyacrylate, and
fluoroelastomer)
are
changed on exposure to automotive gear oils.
Additional transmission-related tests referenced in the
standard methods described here are listed in Tables 4 and 5
at the end of this chapter.

STANDARD TEST METHODS FOR GREASES


Introduction to Greases
Greases provide a great n u m b e r of highly specialized functions in an automobile, such as lubrication of door locks,
electrical connections, various t3rpes of bearings, gears, and
levers. There may be more than 50 different types of grease
specified by the manufacturer for use in a given vehicle.
Greases typically are composed of oil (synthetic or mineral,
representing 70 or more percent of the total composition of
the grease), a thickening agent, and various additives to provide wear protection, corrosion protection, and stability.
Thus, standard test methods for automotive greases focus on
such parameters as physical and chemical properties, separation of the thickener from the oil, oxidation resistance,
wear protection, water tolerance, and ability to retain the desired properties even after exposure to severe operating conditions such as high temperature.
Physical and Chemical Properties of Greases
Chemical

Properties,

Stability,

and

Contamination

A number of tests are available to ensure that a grease has the


appropriate composition and that its properties have not deteriorated excessively during service. ASTM D 128, Standard
Test Methods for Analysis of Lubricating Grease, describes
techniques for analyzing the chemical constituents of a conventional grease that is composed primarily of petroleum oil
and soap, a n d in addition may contain water, fatty acids,
alkaline agents for corrosion inhibition, fat, glycerin, and
insoluble c o m p o n e n t s . The method states, "Composition
should not be considered as having any direct bearing on service performance unless such correlation is established."
During hot operation, lighter components of a grease can
evaporate. ASTM D 972, Standard Test Method for Evaporation Loss of Lubricating Greases and Oils, is a test method designed to provide a quantitative measurement of the mass loss
that occurs during this evaporation process. A sample of
grease or oil is weighed a n d then maintained at a desired temperature in the range of 100-150C for 22 h. Heated air is
passed over the sample. At the end of the test the mass loss as
a consequence of exposure to heat is determined. The method
indicates that "correlation between results from this test
method and service performance has not been established."
An additional test method for evaporative loss of a grease
is also available. ASTM D 2595, Standard Test Method for
Evaporation Loss of Lubricating Greases Over Wide-Temperature Range, can be conducted at a t e m p e r a t u r e anywhere from 93-316C. Heated air is passed over a weighed
sample of grease, emd the loss of weight of the grease is mea-

CHAPTER
sured. The method indicates that "correlation between results from this test method and service performance has not
been established."
ASTM D 942 (Reapproved 1995), Standard Test Method for
Oxidation Stability of Lubricating Greases by the Oxygen
Bomb Method, measures the ability of a grease to resist oxidation in an oxidizing atmosphere at elevated temperature. A
sample of grease is oxidized in a sealed b o m b that is filled
with oxygen at 110 psi (758 kPa) at 99C. Pressure is recorded
during the test. The extent of oxidation is determined by measuring the decrease in oxygen pressure. The method carries
the notification that this test method "predicts neither the
stability of greases under dynamic service conditions, nor the
stability of films of greases on bearings and motor-parts. It
should not be used to estimate the relative oxidation resistance of different grease types."
ASTM D 1743, S t a n d a r d Test Method for Determining
Corrosion Preventive Properties of Lubricating Greases,
measures the ability of a grease to protect a bearing against
corrosion in the presence of water. A bearing is r u n for a
short time and is then exposed to water. After 48 h at 52C
and 100% humidity the bearing is inspected for corrosion.
In ASTM D 4048, Standard Test Method for Detection of
Copper Corrosion from Lubricating Grease, a copper strip is
immersed in a sample of grease and heated for a period of
time. Typical time and temperature conditions are 100C for
24 h. At the end of the test the copper strip is washed and
compared to copper strip standards to provide a measure of
the severity of corrosion. The method states, "no correlations
with actual field service, most of which are under djmamic
conditions, have been established. It does not measure either
the ability of the lubricant to inhibit copper corrosion caused
by factors other than the lubricant itself nor does it measure
the stability of the grease in the presence of copper."
ASTM D 1742, Standard Test method for Oil Separation
from Lubricating Grease During Storage, measures the tendency of a grease to separate into distinct fractions during
storage. A sample of grease is placed on a sieve and is subject
to 1.72 kPa (0.25 psi) at 25C for 24 h. The amount of matericJ that seeps into a beaker is weighed. The test represents
separation during storage rather than separation under dynamic operating conditions. The following warning is provided: "This test method is not suitable for greases softer than
NLGI No. 1 grade." In addition, the m e t h o d states, "this
method is not intended to predict oil separation tendencies of
the grease under dynamic conditions." The method does indicate oil separation that occurs during storage.
ASTM D 1404, Standard Test Method for Estimation of
Deleterious Particles in Lubricating Grease, measures the
presence of abrasive or inappropriate particles in a grease. A
small sample of grease is placed between two standard plastic plates, and pressure is applied to the plates. The presence
of inappropriate abrasive peirticles produces a characteristic
scratch pattern. The n u m b e r of such scratch patterns on the
plates is determined. "The significance of the n u m b e r of
scratches as far as correlation with field performance is concerned has not been established."
If a grease comes into contact with an elastomer, several effects may occur. Components of the grease may be sufficiently compatible with the elastomer that grease components enter the elastomer structure and cause the elastomer

17: AUTOMOTIVE

LUBRICANTS

479

to soften, swell, or to react adversely to the presence of the


grease c o m p o n e n t s . Alternatively, the grease may extract
elastomer additives such as plasticizers, which will result in
changes in the stability of the elastomer. ASTM D 4289, Standard Test Method for Elastomer Compatibility of Lubricating Greases a n d Fluids, measures the extent to which a
grease is compatible with various types of elastomeric or
polymeric materials. The hardness of a standard-sized
coupon of the elastomer to be tested is measured in the following way. Three standard sized coupons are cut out of a
sheet of elastomer of specified thickness. The hardness of the
stack of three coupons is measured with a standard indenter.
Density and volume are also determined. The coupons are
immersed in the grease of interest for 70 h at the test temperature that is designated for the elastomer of interest. After
the immersion period, the elastomer is re-tested for changes
in volume and hardness, to determine the extent of changes
in these properties. The test method carries the notice that:
"Some lubricant specifications m a y require different test
conditions, such as longer d u r a t i o n s or lower or higher
temperatures. In such instances, the repeatability and reproducibility values stated in Section 12 do not apply, and the
user and supplier should agree on acceptable limits of precision." The method also states that "the volume and hardnesschange values determined by this test method do not duplicate similar changes that occur in elastomeric seals under
actual service conditions."
Viscosity

and Penetration

Effects

The viscosity of the base oil in a grease has a significant influence on the properties of a grease. ASTM D 445 (mentioned previously) describes the measurement of the base oil
viscosity by determining the time required for the base oil to
flow through a calibrated glass tube.
The thickening agent in a grease uses surface tension and
molecular attractions to help hold the grease's oil in the place
in which it is supposed to provide protection. The thickening
agent can consist of fibers, platelets, or spheres, which are insoluble or only slightly soluble in the grease. Thickeners can
also be complex polymer-like chains such as complex
polyureas. ASTM D 1092, Standard Test Method for Measuring Apparent Viscosity of Lubricating Greases, determines
the viscosity of the grease over the range of 53 to 37.8C. A
sample of the grease is forced through a capillary, using a
floating piston that is controlled by a hydraulic system. Viscosity is calculated from the flow rate and the force developed in the system.
ASTM D 1263, Standard Test Method for Leakage Tendencies of Automotive Wheel Bearing Greases, measures the
leakage of a grease from a modified front wheel h u b and
spindle assembly. The wheel is rotated at a speed of 660 revolutions per min for 6 h at a temperature of 105C. The extent
of leakage is determined, and the condition of the bearing
surface is noted at the end of the test. The method carries the
notice that "it is not the equivalent of longtime service tests,
n o r is it intended to distinguish between wheel bearing
greases showing similar or borderline leakage."
A related leakage test is ASTM D 4290, S t a n d a r d Test
Method for Determining the Leakage Tendencies of Automotive Wheel Bearing Grease Under Accelerated Conditions. In
this test, grease is placed in a modified version of an auto-

480 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

mobile front wheel hub-spindle-bearings assembly. The hub


is rotated at 1000 revolutions per min at the same time that
the bearings are thrust-loaded to 111 N. The spindle temperature is maintained at 160C for 20 h. Leakage of the grease,
or the oil in the grease (or both), is measured. In addition, the
condition of the bearing surface is noted. The method "is not
the equivalent of long-term service tests."
ASTM D 566, Standard Test Method for Dropping Point of
Lubricating Grease, determines the temperature at which material falls through a hole in the bottom of a cup while a sample of grease is being heated. This type of test helps determine
whether a particular grease is suitable for a given application.
The following notice is given: "This test method is not recommended for use at bath temperatures above 288C."
ASTM D 2265, Standard Test Method for Dropping Point
of Lubricating Grease Over Wide Temperature Range, measures the temperature at which the first drop of material falls
from a test cup and reaches the bottom of a test tube (as corrected by a term related to the oven temperature). This test
method can differentiate between different types of thickeners such as simple soaps, complex soaps, stearate soaps, and
urea-based thickeners. The elapsed time and the temperature
that the grease withstood in the dropping-point test indicate
how well the thickener can hold the base oil within its matrix
or within its complex lattice structure before the energy from
the heat is able to weaken the internal energy of the lattice.
The information derived from this test is used to maintain
quality control of the grease and does not necessarily relate
to performance of the grease.
In ASTM D 217, Standard Test Method for Cone Penetration of Lubricating Grease, the consistency (or resistance to
flow) of a grease is measured by observing the depth to which
a cone penetrates the grease, using a device called a penetrometer. Properties of the grease may be influenced by the
manipulation that the grease has experienced. Thus, the test
method defines four test conditions: unworked penetration,
worked penetration, prolonged worked penetration, and
block penetration for grease that holds its shape.
Unworked penetration means penetration is tested at 25C
without shearing the grease beforehand. The cone assembly
of the penetrometer is released and is allowed to drop freely
into the grease for 5 s. The worked condition represents properties after the grease has been sheared during 60 double
strokes at 25C in grease-working equipment. In the condition of penetration after prolonged work, the grease has experienced more than 60 double strokes in a grease worker at
a temperature of 15-30C, plus 60 additional strokes at 25C.
Penetration is then measured immediately. The block penetration test is used for a grease that is rigid enough to hold its
shape. A cube of grease is cut from the bulk of the grease, and
penetration is measured at a grease temperature of 25C. In
each of these ASTM D 217 methods, three determinations of
penetration are conducted, and the results are averaged. This
test method is not "considered suitable for the measurement
of the consistency of petrolatums by penetration."
ASTM D 1403, Standard Test method for Cone Penetration
of Lubricating Grease Using One-Quarter and One-Half Scale
Cone Equipment, determines cone penetration for small
samples of grease, including both worked and unworked penetration. The test is conducted at 25C, and a smaller cone
than that described in ASTM D 217 is used in the test. The

test method indicates that "unworked penetrations do not


generally represent the consistency of greases in use as effectively as do worked penetrations."
Grease Performance
Some of the issues related to grease performance include the
ability of the grease to resist washout from water, effects of
low-temperature operation on grease performance, wear protection provided, and determination of the useful life of the
grease.
ASTM D 1264, Standard Test Method for Determining the
Water Washout Characteristics of Lubricating Greases, measures the resistance of a grease to being washed out of a bearing due to the presence of water. In the test, a grease is
packed into a ball bearing. Water impinges on the bearing
housing, and the amount of grease washed out is measured
by weighing the bearing before and after the test. "No correlation with field service has been established."
ASTM D 4049, Standard Test Method for Determining the
Resistance of Lubricating Grease to Water Spray, also measures the influence of water on grease. In this test grease is
applied within a scribed area on a panel. The panel is
weighed, and water is sprayed onto the grease at a pressure
of 276 kPa at 38C. At the end of the test, any grease that is
outside the scribed area is wiped off, and the panel is reweighed to determine the amount of grease that remains.
ASTM D 1478 (reapproved 1997), Standard Test Method
for Low-Temperature Torque of Ball Bearing Grease, determines the extent to which a grease retards the rotation of a
slow-speed ball bearing by measuring starting and running
torques at temperatures below 20C. In this test a ball bearing is packed completely full with the test grease. The ambient temperature is lowered to the test temperature and held
there for 2 h. At the end of this time the ball bearing is rotated, and the restraining force on the outer ring is measured
(both at starting time and after one hour). The test procedure
indicates that: "This test method has proved helpful in the selection of greases for low-powered mechanisms . The suitability of this test method for other applications requiring
different greases, speeds, and temperatures should be determined on an individual basis."
ASTM D 4693, Standard Test Method for Low-Temperature Torque of Grease-Lubricated Wheel Bearings, measures
the extent to which a grease retards the rotation of a specially-manufactured, spring-loaded, automotive-type wheel
bearing assembly when subjected to low temperatures. In the
test, a freshly stirred and worked sample of the grease is
packed into the bearings of an automotive-type spindlebearings-hub assembly. The assembly is heated, then cooled
and held at -40C (or other desired temperature). The spindle is rotated at 1 revolution per min. The torque required to
prevent rotation of the hub is measured. "It is the responsibility of the user to determine the correlation with other
types of service."
ASTM D 1831, Standard Test Method for Roll Stability of
Lubricating Grease, is a low-speed, high-surface-area tumbling procedure at low shear. Cone penetration (ASTM D
1403) is first measured, then the grease is subjected to low
shear for 2 h, and the cone penetration is again measured.
This method is used to assess shear stability of the grease.

CHAPTER
The following warning is listed, "Although this test method is
widely used for specification purposes, the significance of the
roll stability test has not been determined."
ASTM D 2266, Standard Test Method for Wear Preventive
Characteristics of Lubricating Grease (Four-Ball Method),
measures the ability of a grease to resist wear in sliding steelon-steel contacts. It does not address wear in materials other
than steel on steel, nor does it evaluate the extreme pressure
characteristics of a grease. In this test a steel ball is rotated
while in contact with three additional balls. The diameter of
the wear scar on each of the non-rotating balls is measured.
The test method indicates that "No correlation has been established between the four-ball wear test and field service."
ASTM D 2509, Standard Test method for Measurement of
Load-Carrying Capacity of Grease (Timken Method), uses a
steel cup that rotates against a steel block at a rotation speed
of 123.71 m per min. The m i n i m u m load needed to rupture
the lubricant film that lies between the rotating cup and the
block is determined. A determination is also made of the
m a x i m u m safe load such that the lubricant film will not be
ruptured by the rotating cup, and abrasion will not occur between the rotating cup and the block. The test procedure indicates that: "The test method is used widely for specification
purposes and is used to differentiate between greases having
low, medium, or high levels of extreme pressure characteristics. The results may not correlate with results from service."
ASTM D 2596, Measurement of Extreme Pressure Properties of Lubricating Grease (Four-Ball Method), determines
the load-carrying properties of lubricating grease. Two properties are measured: the diameter of the wear scar (for the
case in which welding or seizure does not occur) and the load
at which welding occurs. Two warnings are provided: 1) "The
results do not necessarily correlate with results from service"
and 2) "Lubricating greases that have as their fluid component a silicone, halogenated silicone, or a mixture comprising silicone fluid and petroleum oil, are not applicable to this
method of test."
ASTM D 3336, Standard Test Method for Life of Lubricating Greases in BeJl Bearings at Elevated Temperatures, evaluates the performance of lubricating greases operating at elevated temperatures (up to 371C) in ball bearings, at a speed
of 10 000 revolutions per min, but under light load. If the test
temperature is 149C or below, the test cycle is operated at
test temperature for 21.5 h per day, with 2.5 h of shut-down
per day in which heat is not applied. If the test temperature
is r u n at a temperature greater than 149C, the test is run for
20 h per day at the desired test temperature, with 4 h per day
of shut-down in which n o heat is applied. Tests are conducted until failure or until a specified n u m b e r of hours is
reached. The grease has failed the test when one of the following conditions has occurred:
Spindle output power increases to a value of three hundred
percent above the steady state condition at test temperature.
An increase in temperature of 15C over the test temperature occurs (but the daily start-up temperature rise is not
to be construed as a test failure).
There is loading of the test bearing or belt slippage at startu p or during the test cycle.
Hours to failure are plotted in terms of cumulative percentage of the tests conducted. Examples of these plots
(known as WeibuU plots) are provided as part of the test-

17: AUTOMOTIVE

LUBRICANTS

481

method description. F r o m such graphs, one can evaluate


product life, for example, expected n u m b e r of hours before
10% of the greases will have failed, or hours to 50% failure.
ASTM D 3337, Standard Test Method for Determining Life
and Torque of Lubricating Greases in Small Ball Bearings,
measures grease life and torque in a shorter time period than
those tests that evaluate field performance. A single row of
ball bearings, lubricated by the grease of interest, is rotated at
high speed at the desired test temperature. The end of the test
is determined when one of the following conditions occurs:
An instantaneous torque Ave times the minimum torque
occurs.
A temperature 11 C above the test temperature occurs at
the outer race of the test bearing.
There is a noise level increase that persists for more than 1
min at start-up or when running at high speed.
An example of the graphing procedure (WeibuU plot) for
cumulative life of the grease is provided as part of the test
procedure.
ASTM D 3527, Standard Test Method for Life Performance
of Automotive Wheel Bearing Grease, evaluates the life performance of a wheel-bearing grease at high temperature. A
modified automobile front-wheel hub-spindle-bearing assembly is used in the test. Bearings are thrust-loaded to 111
Newtons, the h u b is rotated at a speed of 1000 revolutions per
min, and the spindle temperature is held at 160C for 20 h.
The test is terminated when the pre-set torque limit is exceeded. The test "is not the equivalent of long-time service
tests, nor is it intended to distinguish between the products
having similar high-temperature performance properties."
ASTM D 3704, Standard Test Method for Wear Preventive
Properties of Lubricating Greases Using the (Falex) Block on
Ring Test Machine in Oscillating Motion, uses a steel test
ring oscillating against a steel test block. The test speed, load,
angle of oscillation, time, hardness, and surface finish of the
test specimen can be chosen to represent the field conditions
of interest. The width of the wear scar on the test block is determined. The method evaluates the amount of wear protection provided by a given grease. "The user of this method
should determine to his own satisfaction whether results of
this test procedure correlate with field performance or other
bench test machines."
Fretting is surface damage that results from oscillation
over a short distance. ASTM D 4170, Standard Test method
for Fretting Wear Protection by Lubricating Greases, is a test
method that documents the protection provided by a grease
that is subjected to oscillation (30 Herz) between two ball
bearings through a small arc (12). The test lasts 22 h at a
load of 2450 Newton. Mass loss of the bearings is determined.
According to the method, "Test results do not necessarily
correlate with results from other t5^es of service. It is the responsibility of the user to determine whether test results correlate with other types of service." Tables 6 and 7 show additional standard test methods related to greases.

GEAR AND AXLE LUBRICANTS


Introduction to Gear Lubricants
Gears must be designed to withstand high loads that are concentrated on gear surfaces. As a consequence, high tempera-

482

MANUAL

3 7: FUELS

AND LUBRICANTS

HANDBOOK

tures may be generated at the point of contact. Despite the


h a r s h environment, the gear lubricant must provide sufficient wear and extreme pressure protection to prevent material failure of the gears, and the gear lubricant must remain
functional for extended periods of time.
If the gear materials are not sufficiently robust and the lubricant is not sufficiently protective, irreversible damage may
occur to the gear, which typically means that the equipment
in which the gear is located will not perform as designed. Performance criteria for gear lubricants include such factors as
ability to withstand the required loads and continuing ability
to transmit power. Gear surface finish and gear tooth contour must not deteriorate. In addition, the properties of the
gear lubricant must remain stable, including oxidative stability, anti-wear protection, maintenance of appropriate friction characteristics, low-temperature viscosity, corrosion
protection, and resistance to foam formation. Various standard tests address these concerns.
Standard Tests for Gear Lubricants
ASTM D 5579, S t a n d a r d Test Method for Evaluating the
Thermal Stability of Manual Transmission Lubricants in a
Cyclic Durability Test, was described previously in the section on Transmission Lubricants. This test evaluates a gear
lubricant's performance, since a transmission cycles through
a continuing sequence of gear shifts. Shifter fork wear is
measured, and deterioration of shift performance is the criterion for termination of the test.
ASTM D 5760, Standard Specification for Performance of
Manual Transmission Gear Lubricants, was also described in
the section on manual transmissions. Performance requirements include a maximum of n o more than 100% viscosity increase and limits on the generation of insoluble contaminants
in the lubricant. Elastomers must not deteriorate excessively,
and scuffing should not occur at a specified high load.
ASTM D 2670, Standard Test Method for Measuring Wear
Properties of Fluid Lubricants (Falex Pin and Vee Block
Method), evaluates the wear-resistant properties of fluid lubricants. In this test, a rod is rotated while being squeezed between two V-shaped blocks. Load is applied to the V blocks,
and the amount of wear is determined. "The user of this test
m e t h o d should determine to his or h e r own satisfaction
whether results of this test procedure correlate with field performance or other bench test machines. If the test conditions
are changed, wear values may change and relative ratings of
fluids may be different."
The load-carrying capacity of a lubricant is the amount of
load a lubricant can withstand, without rupturing the oil
film. ASTM D 2782, Standard Test Method for Measurement
of Extreme-Pressure Properties of Lubricating Fluids
(Timken Method), measures this property. In this test a steel
test cup is rotated against a steel test block. The rotation
speed is 123.71 m per min. Fluid samples are pre-heated to
37.8C. Two measurements are obtained: the minimum load
required to rupture the lubricant film and the maximum load
at which the rotating cup will not rupture the fluid film and
cause scoring or seizure. The u s e r is notified: "This test
method is used widely for the determination of extreme pressure properties for specification purposes. Users are cautioned to carefully consider the precision and bias statements
herein when establishing specification limits."

ASTM D 5182, Standard Test Method for Evaluating the


Scuffing Load Capacity of Oils (FZG Visual Method), was described under transmission fluids. In this test, a gear test device is rotated at increasing loads until scuffing occurs. The
following statement is provided, "The test method is limited
by the capabilities of the equipment (test rig and gears), and
the performance observed may not directly relate to scuffing
performance observed with spiral bevel on hjrpoid gearing. It
is also limited to discriminating between oils with mild EP
additives or less."
ASTM D 4172, Standard Test Method for Wear Preventive
Characteristics of Lubricating Fluid (Four-BeJl Method), rotates one steel ball against three stationary steel balls that are
immersed in the test lubricant. The test method measures the
extent of the wear scar on the three stationairy balls. "The user
of this test method should determine to his own satisfaction
whether results of this test procedure correlate with field performance or other bench test machines."
ASTM D 2783, S t a n d a r d Test Method for ExtremePressure Properties of Lubricating Fluids (Four-Ball
Method), rotates one steel ball against three stationary steel
balls. Lubricant covers the stationary balls. Increasing load is
applied until welding occurs. The following notice is provided, "The user of this test method should determine to his
own satisfaction whether results of this test procedure correlate with field performance or other bench test machines."
An alternative test for measurement of extreme pressure
properties is ASTM D 3233, Standard Test Methods for Measurement of Extreme Pressure Properties of Fluid Lubricants
(Falex Pin and Vee Block Methods). A steel journal is rotated
at 290 revolutions per min against two stationary V blocks
that are immersed in the lubricant sample. Increasing load is
applied, a n d the load at which failure occurs is noted. "The
user should establish any correlation between results by either method and service performance."
An additional topic of interest is whether a given gear oil is
compatible with the elastomers it touches. ASTM D 5662,
Standard Test Method for Determining Automotive Gear Oil
Compatibility with Typical Oil Seal Elastomers, addresses
this issue. In ASTM D 5662, an elastomer test specimen is exposed to the gear oil for 240 h. The test temperature depends
on the composition of the elastomer to be tested. Nitrile is
tested at 100C. Polyacrylate and fluoroelastomers are tested
at 150C. Hardness, volume changes, and elongation are
measured and compared to the start-of-test measurements of
these same properties. The method states: "This test method
addresses only those failures caused by excessive elastomer
hardening, elongation loss, and volume swell and attempts to
determine the likelihood that a n oil might cause premature
sealing system failures in field use."
Another important characteristic of a gear lubricant is the
ability to release water rapidly, in case water should enter the
gear lubricant. ASTM D 2711, Standard Test Method for
Demulsibility Characteristics of Lubricating Oils, measures
the ability of water and oil to separate from each other. A
sample of the test oil and a designated amount of water are
stirred together for 5 min at a temperature of 82C. The extent of separation of water and oil is measured after 5 h.
ASTM D 892, which measures the amount of foam that can
form and the stability of the foam, was described previously,
in the engine oil section. ASTM D 130, which measures the

CHAPTER
extent of corrosion of a copper strip, was described in the section on transmission fluids.
Test methods for gear oils are also available from CRC
(Coordinating Research Council). The CRC L-37 method is a
24-hour dynamometer test that is conducted at high torque
and low speed and that assesses gear distress. CRC L-42 is a
24-hour dynamometer test incorporating high speed shock
loading, designed to measure resistance to gear scoring. CRC
L-33 is a 7-day motored rust test in which geeirs are exposed
to humidity in an oven. CRC L-60-1 is a test for oxidation and
deposits, using motored gears over a period of 50 h.
Viscosity characteristics of axle lubricants are measured according to ASTM D 445, Standard Test Method for Kinematic
Viscosity of Transpsirent eind Opaque Liquids (the Calculation
of Dynamic Viscosity), as described under the section on engine oils. Low temperature viscosity is measured using ASTM
D 2983, Standard Test method for Low-Temperature Viscosity of Automotive Fluid Lubricants Measured by Brookfield
Viscometer. In this test, viscosity is measured in the temperature range from 5 to 40C, using a rotating spindle.
Axle Lubricants
An additional area of concern related to gear lubricants is the
topic of axle lubricants. Requirements for axle lubricants are
described in the American Petroleum Institute API-GL-5 requirements for gear lubricants. However, two of the tests
listed in API-GL-5 (CRC L-37 and CRC L-42) are not required
for axle lubricants. Desirable properties for axle lubricants
include viscosity in an appropriate range (for example, near
14 or 15 centistokes at 100C). Performance of an axle lubricant must not degrade excessively during service. The axle lubricant must not damage metal components, nor should the
metal components accelerate an axle lubricant's degradation.
In addition, axle lubricants must not damage seals. Desirable
axle-lubricant attributes include fuel efficiency, thermal
stability, long life, and appropriate limited-slip differential
performance.
Referenced documents related to geeir and axle lubricant
test methods are provided at the end of this chapter. Tables 8
and 9.

BRAKE FLUIDS
Brake fluid typically behaves like a hydraulic fluid, since fluid
power is used to apply force to the brakes, therefore generating enough friction to slow and stop the forward motion of
the vehicle. Fifty years ago, if water got into brakes during a
heavy rain, the brakes might not work properly, and an accident might result. Today, with better technology, such occurrences are rare. However, someone who is servicing a brake
system must make sure to instcill the appropriate brake fluid
for that brake, otherwise there is risk that the brakes will not
function as they should.
Two types of braking systems are typically used in vehicles:
drum brakes and disk brakes. In a d r u m brake, a drum rotates with the wheel. Curved brake shoes are inside the drum,
separated by a slight air gap from the drum. When a driver
steps on the brake, brake fluid, acting like a hydraulic fluid to
apply force where it is needed, is sent to the braking system

17: A UTOMOTIVE

LUBRICANTS

483

such that the brake shoes are pressed onto the rotating drum.
The friction of the shoe against the d r u m stops the wheel.
A disk brake has a metal disk, and flat shoes or pads are
pressed against the disk to provide the force to stop the vehicle, using the force supplied by the hydraulic action of the
brake fluid.
Thus, the motion of a braking mechanism is controlled by
a hydraulic system that includes a pump, a fluid, and lines
(tubes) that transmit the hydraulic force to the brake components. The brake fluid must not react with components of the
brake system, and it must be able to withstand wide variations in temperature while still performing effectively.
Requirements for the brake fluid are described in the 2001
SAE Handbook, Standards Development Program, Volume
2, Parts and Components and on-Highway Vehicles (Part I),
"Motor Vehicle Brake Fluid-SAE J1703 Jan95", page 25.49,
and "Borate Ester Based Brake Fluids-SAE J1704 Jan97",
page 25.59.
SAE J1703 and SAE J1704 specify such measurements as
boiling point, fluid stability, viscosity, reserve alkalinity, corrosion resistance, low-temperature fluidity, evaporation,
water tolerance, low temperature stability, resistance to oxidation, and effect on rubber materials such as seals. A number of standard ASTM methods related to these tests are
listed at the end of this chapter.

SOLID LUBRICANTS
Solid lubricants are used where it is important for the lubricant to stay in place. Solid lubriccints are typically composed
of a solid, a binder, and additives such as corrosion inhibitors
or solvents. Examples of c o m m o n solid lubricants include
molybdenum disulfide, graphite, a n d polytetrafluoroethylene (PTFE) or other fluorine-containing polymers. Molybden u m disulfide and graphite have a chemical structure that is
like flat plates such that an upper plate can easily slip eilong
the surface of the next plate beneath it. PTFE has a chemical
structure that typically does not attract or hold a variety of
common fluids such as water or oil, as witnessed by the fact
that the fluid tends to bead u p on the PTFE surface, rather
than spreading over the surface. In contrast, if a drop of oil
touches an iron surface, the oil spreads over the surface.
Solid lubricants typically have a temperature range over
which they are effective. Above the optimum reinge, they may
degrade chemically or physically. For example, according to
information in the Tribology Data Handbook, molybdenum
disulfide has a n u p p e r t e m p e r a t u r e limit in the range of
400C, but it can withstand high loads [16]. Graphite can
withstand 650C and moderate loads.
If PTFE (polytetrafluoroethylene) is used in a high-temperature application, care must be taken to ensure that the temp e r a t u r e does not exceed the point at which PTFE is no
longer stable. On the other hand, use of low-friction materials is an advantage with regard to fuel conservation in automotive vehicles.
ASTM D 2714, Standard Test Method for Calibration and
Operation of the Falex Block-on-Ring Friction and Wear
Testing Machine, provides a test method for determination of
friction coefficient of a solid lubricant. Friction coefficient is
defined as the ratio of the friction force, F, that resists movement to the normal force, N, that presses the two bodies to-

484

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

gether. A steel test ring rotates against a steel test block. The
specimen assembly is immersed in the lubricant. A normEil
load of 65 kg is applied. The velocity of the test ring is 7.9
m/min. The test method contains the warning that "The user
of this test method should determine to his or her own satisfaction whether results of this test procedure correlate with
field performance or other bench test machines. If the test
conditions are changed, wear values can change and relative
ratings can be different."

AUTOMOTIVE AIR CONDITIONING


LUBRICANTS
In the 1930s, chlorine-containing refrigerants were introduced, since they were considered to be safer than other refrigerant fluids that had been in use prior to 1930 [17]. However, in the late 1970s it was observed that, in some places,
the protective ozone layer had been depleted as m u c h as 30
or 40% at an altitude of 40 km. As a consequence, the United
States, Canada, Norway, Sweden, and others passed legislation prohibiting the use of these chlorofluorocarbon refrigerants in spray cans [17].
In 1985 investigators found that there had been a 40% loss
of protective ozone during springtime in the antarctic. It was
also found that a chlorofluorocarbon could be thousands of
times worse than carbon dioxide in promoting global warming. Thus, a search was initiated to find a replacement for the
chlorofluorocarbons used in automotive air-conditioning
systems [17]. One of the authors of this chapter was involved
in the effort to find a replacement for the refrigerants that
had been used in automotive air-conditioning systems.
Automotive air conditioning systems require a lubricant.
However, n o standard tests h a d been created that were specific for this application. It was necessary to address several
issues relative to the search for these chlorine-containing refrigerants.
Can a lubricant be identified that is compatible with the refrigerant?
Will the lubricant that is compatible with the refrigerant
have enough lubricity to provide long life to the pump?
Will it be necessary to modify the composition of seals in
the air conditioning unit to ensure that the seals are not degraded by the new refrigerant and its associated lubricant?
Which refrigeration-system materials should be used, such
that they will not be degraded by the refrigerant or its lubricant?
Extensive testing showed that, for an air conditioning compressor to work properly, the air conditioning fluid must be
able to transport the air conditioning lubricant to the working components of the p u m p . In other words, there had to be
a chemical compatibility between the lubricant and the air
conditioning medium, in addition to the normal lubrication
requirements such as providing a protective lubricating film
and inhibiting corrosion. Thus, in order to have a viable airconditioning system, it was not sufficient to remove the original air-conditioning fluid and put another air-conditioning
fluid into the system.
This example indicates that whenever changes are made to
any component of a lubrication system, testing must be performed to ensure that no incompatibilities have arisen.

ADDITIONAL FLUIDS THAT EXHIBIT


LUBRICATING PROPERTIES
Several additional fluids within a vehicle (coolant and fuel)
must provide some lubrication, even though lubrication is
not their primeiry function. Engine coolant must not allow
excessive corrosion to occur in the coolant system. The
coolant typically incorporates a mixture of ethylene glycol
a n d water (to lower the freezing point, so that the coolant remains fluid) and corrosion inhibitors (to reduce corrosion of
the coolant system).
If engine coolant leaks from the coolant system and enters
the engine oil, the oil properties can degrade, which can damage or destroy an engine if too much coolant has entered the
engine oil. Thus, standard ASTM tests associated with effects
of the coolant on the engine lubrication system are related to
detection of coolant (ethylene glycol) in engine oil. ASTM D
4291, Standard Test Method for Trace Ethylene Glycol in
Used Engine Oil, measures the amount ethylene glycol in the
range of 5-200 parts per million by mass. A sample of oil is
mixed with water, the ethylene glycol migrates to the water
phase, and the amount of glycol present is determined by gas
chromatography.
ASTM D 2982, Standard Test Methods for Detecting Glycol-Based Antifreeze in Used Lubricating Oils, measures the
glycol content of lubricating oils by extracting the glycol from
the oil using an acid solution. The glycol is oxidized to form
formaldehyde, which is then reacted to form a colored solution that can be analyzed colorimetrically.
The fuel supply system must not wear out and must not be
excessively corroded or eroded by the fuel. Corrosiveness, lubricity, and material compatibility properties of a fuel such
as gasoline can differ significantly from those of an oxygenated fuel such as alcohol, as shown in Figs. 2 and 3. The
lower volatility and higher viscosity of diesel fuel, in comparison to gasoline, can provide greater film thickness for lubrication of injectors. Standard tests that describe relationships
between the fuel system and the engine lubrication system include measurement of fuel in oil and fuel economy.
In S t a n d a r d Test Method for Gasoline Diluent in Used
Gasoline Engine Oils by Distillation, ASTM D 322, used engine oil (which may be contaminated with fuel) is mixed with
water. Several vaporizations are conducted to separate the
fuel from the oil and from the water. The volume of fuel that
was extracted is measured.
In ASTM D 3525, Standard Test Method for Gasohne Diluent in Used Gasoline Engine Oils by Gas Chromatography, a
known amount of internal standard is placed in the engine
oil. The amount of fluid boiled off at a temperature below
that of the internal standard is used to obtain a quantitative
assessment of how much fuel was in the oil.

SUMMARY AND FUTURE DIRECTIONS


As illustrated by these examples, automotive lubrication encompasses a wide range of fluid properties, fluid functions,
and component composition and design within a vehicle. The
great diversity of vehicle lubrication requirements mandates
that many different kinds of lubricants, specifications, and
standards Eire needed.

CHAPTER 17: AUTOMOTIVE LUBRICANTS


Various issues arise on a continuing basis, with regard to
automotive lubricants:
Can further improvements be m a d e in vehicle fuel economy by developing more efficient engine oils, transmission
fluids, cixle lubricants, etc.?
Can changes in automotive design be implemented such
that power eind performance are not compromised, but energy consumption during operation is reduced?
Can suitable alternative automotive power sources (fuel
cells, hydrogen, batteries) be developed?
To w h a t extent can vehicle weight be reduced without
compromising occupant safety?
Can lighter metals such as aluminum be used in engines
to replace iron, and thus reduce energy consumption,
since less energy will be required to keep the vehicle in
motion?
What types of lubricants are effective for use with alternative materials?
Can the amount of lubriccint required for a given application be reduced, so that oil reserves will last longer?
Can the useful life of ciny given automotive lubricant be increased?
To what extent ccin automotive lubricants be recycled?
Are biodegradable automotive lubricants feasible?

485

Such issues will receive increased attention in the future.


Displacing current power sources (gasoline and diesel engines), however, will be difficult to accomplish, since current
systems have worked exceedingly effectively for m a n y
decades. Incremented improvements have occurred, but revolutionary changes in design have not yet been sufficiently
problem-free to reduce or eliminate use of the intemEd combustion engine. It will be left to future generations to find viable alternatives.

LIST OF REFERENCED DOCUMENTS


A List of Referenced Documents is included with most of the
standard test methods described previously. The referenced
documents are listed below (Tables 2 through 10), so that the
reader will have a comprehensive tabulation of standard test
methods associated with each category of automotive lubricant. In addition, abbreviations a n d terms are defined in
Table 11.
Acknowledgment
The a u t h o r s t h a n k Brent Calcut, Robert Olree, Jill Cummings, Robert Stockwell, Jim Linden, James Spearot, Colem a n Jones, John Flaherty, and Jeff Knight of General Motors
for their contributions, suggestions, and corrections.

TABLE 2Referenced documents in ASTM standard test methods related to engine oil.
ASTM No.

C 1109
D 16
D56
D86
D91
D92
D93
D97
D117
D 129
D 130
D 140
D 156
D235
D240

D287
D323
D341
D381
D445
D446
D482
D524
D525
D613
D664
D850
D873
D892
D893
D974
D 1078
D1093
D1133
D1193
D 1217
D1250

Test Method or Document Title

Analysis of Aqueous Leachiates from Nuclear Waste Materials Using Inductively Coupled Plasma-Atomic Emission
Spectrometry
Definitions of Terms Relating to Paint, Varnish, Lacquer, and Related Products
Flash Point by Tag Closed Tester
Distillation of Petroleum Products
Acidity of Hydrocarbon Liquids and Their Distillation Residues
Flash and Fire Points by Cleveland Open Cup
Flash Point by Penske-Martens Closed Tester
Pour Point of Petroleum Products
Guide to Sampling Test Methods, Standard Practices, and Guides for Electrical Insulating Oils of Petroleum Origin
Sulfur in Petroleum Products (General Bomb Method)
Detection of Copper Corrosion from Petroleum Products by the Copper Strip Tarnish Test
Practice for Sampling Bituminous Materials
Saybolt Color of Petroleum Products (Saybolt Chromometer Method)
Specification for Mineral Spirits (Petroleum Spirits) (Hydrocarbon Dry Cleaning Solvent)
Heat of Combustion of Liquid HydrocEirbon Fuels by Bomb Calorimeter
API Gravity of Crude Petroleum and Petroleum Products (Hydrometer Method)
Vapor Pressure of Petroleum Products (Reid Method)
Viscosity-Temperature Charts for Liquid Petroleum Products
Existent Gum in Fuels by Jet Evaporation
BCinematic Viscosity of Transparent and Opaque Liquids (the Calculation of Dynamic Viscosity)
Standard Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers
Ash from Petroleum Products
Ramsbottom Carbon Residue of Petroleum Products
Oxidation Stability of Gasoline (Induction Period Method)
Cetane Number of Diesel Fuel Oil
Acid Number of Petroleum Products by Potentiometric Titration
Acidity of Hydrocarbon Liquids and Their Distillation Residues
Oxidation Stability of Aviation Fuels (Potential Residue Method)
Foaming Characteristics of Lubricating Oils
Insolubles in Used Lubricating Oils
Acid and Base Number by Color-Indicator Titration
Distillation Range of Volatile Organic Liquids
Acidity of Hydrocarbon Liquids and Their Distillation Residues
Kauri-Butanol Value of Hydrocarbon Solvents
Specification for Reagent Water
Density and Relative Density (Specific Gravity) of Liquids by Bingham Pycnometer
Standard Guide for Petroleum Measurement Tables
(continues)

486 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


TABLE 2(continued).
ASTM No.
D 1266
D 1298

D1310
D 1319
D 1353
D1480
D1481
D1552
D2170
D2171
D2422
D2500
D2509
D2622
D2699
D2700
D2709
D2782
D2887
D2896
D2982
D3120
D3231
D3237
D3244
D3338
D3339
D3525
D3606
D3829
D3941
D4052
D4057
D4175
D4177
D4206
D4294
D4307
D4485
D4626
D4628
D4636
D4683
D4684
D4737
D4739
D4741
D4863
D4927
D4951
D5119
D5133
D5134
D5185
D5186
D5290
D5302
D5480
D5481
D5533
D5800
D5844

Test Method or Document Title


Sulfur in Petroleum Products (Lamp Method)
Density, Relative Density (Specific Gravity), or API Gravity of Crude Petroleum and Liquid Petroleum Products by
Hydrometer Method
Flash Point and Fire Point of Liquids by Tag Open-Cup Apparatus
Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption
Nonvolatile Matter in Volatile Solvents for Use in Paint, Lacquer, and Related Products
Density and Relative Density (Specific Gravity) of Viscous Materials by Bingham Pycnometer
Density and Relative Density (Specific Gravity) of Viscous Materials by Lipkin Bicapillary Pycnometer
Determination of Additive Elements in Lubricating Oils by Inductively Coupled Plasma Atomic Emission Spectrometry
Kinematic Viscosity of Asphalts (Bitumens)
Viscosity of Asphalts by Vacuum Capillary Viscometer
Standard Classification of Industrial Fluid Lubricants by Viscosity System
Cloud Point of Petroleum Products
Measurement of Load-Carrying Capacity of Lubricating Grease (Timken Method)
Sulfur in Petroleum Products by X-Ray Spectrometry
Research Octane Number of Spark-Ignition Engine Fuel
Motor Octane Number of Spark-Ignition Fuel
Water and Sediment in Distillate Fuels by Centrifuge
Measurement of Extreme-Pressure Properties of Lubricating Fluids (Timken Method)
Boiling Range Distribution of Petroleum Fractions by Gas Chromatography
Base Number of Petroleum Products by Potentiometric Perchloric Acid Titration
Detecting Glycol-Base Antifreeze in Used Lubricating Oils
Trace Quantities of Sulfur in Light Liquid Petroleum Hydrocarbons by Oxidative Microcoulometry
Phosphorus in Gasoline
Lead in Gasoline by Atomic Absorption Spectrometry
Standard Practice for Utilization of Test Data to Determine Conformance with Specifications
Estimation of Heat of Combustion of Aviation Fuels
Acid Number of Petroleum Products by Semi-Micro Color Indicator Titration
Gasoline Diluent in Used Gasoline Engine Oils by Gas Chromatography
Determination of Benzene and Toluene in Finished Motor and Aviation Gasoline by Gas Chromatography
Predicting the Borderline Pumping Temperature of Engine Oils
Flash Point by the Equilibrium Method with a Closed-Cup Apparatus
Density and Relative Density of Liquids by Digital Density Meter
Standard Practice for Manual Sampling of Petroleum and Petroleum Products
Standard Terminology Relating to Petroleum, Petroleum Products, and Lubricants
Standard Practice for Automatic Sampling of Petroleum and Petroleum Products
Sustained Burning of Liquid Mixtures by the Setaflash Tester (Open Cup)
Sulfur in Petroleum Products by Energy-Dispersive X-Ray Fluorescence Spectroscopy
Determination of Additive Elements in Lubricating Oils by Inductively Coupled Plasma Atomic Emission Spectrometry
Standard Specification for Performance of Engine Oils
Calculation of Gas Chromatographic Response Factors
Analysis of Barium, Calcium, Magnesium, and Zinc in Unused Lubricating Oils by Atomic Absorption Spectrometry
Corrosiveness and Oxidation Stability of Hydraulic Oils, Aircraft Turbine Engine Lubricants, and Other Highly
Refined Oils
Measuring Viscosity at High Shear Rate and High Temperature by Tapered Bearing Simulator
Determination of Yield Stress and Apparent Viscosity of Engine Oils at Low Temperature
Calculated Cetane Index by Four Variable Equation
Base Number Determination by Potentiometric Titration
Measuring Viscosity at High Temperature and High Shear Rate by Tapered-Plug Viscometer
Determination of Lubricity of Two-Stroke-Cycle Gasoline Engine Lubricants
Elemental Analysis of Lubricant and Additive Components-Bcirium, Calcium, Phosphorus, Sulfur, and Zinc by Wavelength-Dispersive X-Ray Fluorescence Spectroscopy
Determination of Additive Elements in Lubricating Oils by Inductively Coupled Plasma Atomic Emission Spectrometry
Test Method for Evaluation of Automotive Engine Oils in the CRC L-38 Spark-Ignition Engine
Low Temperature, Low Shear Rate, Viscosity/Temperature Dependence of Lubricating Oils Using a Temperature
Scanning Technique
Detailed Anedysis of Petroleum Naphthas Through n-Nonane by Capillary Gas Chromatography
Determination of Additive Elements, Wear Metals and Contaminants in Used Lubricating Oils by Inductively-Coupled
Plasma Atomic Emission Spectrometry
Determination of the Aromatic Content and polynuclear Content of Diesel Fuels and Aviation Turbine Fuels by Supercritical Fluid Chromatography
Measurement of Oil Consumption, Piston Deposits, and Wear in a Heavy-Duty High-Speed Diesel Engine-NTC-400
Procedure
Evaluation of Automotive Engine Oils for Inhibition of Deposit F o r m a t i o n and Wear in a Spark-Ignition Internal
Combustion Engine Fueled with Gasoline and Operated Under Low-Temperature, Light-Duty Conditions
Engine Oil Volatility by Gas Chromatography
Measuring Apparent Viscosity at High-Temperature and High-Shear Rate by Multicell Capillary Viscometer
Evaluation of Automotive Engine Oils in the Sequence HIE, Spark-Ignition Engine
Evaporation Loss of Lubricating Oils by the Noack Method
Evaluation of Automotive Engine Oils for Inhibition of Rusting (Sequence IID)
(continues)

CHAPTER 17: A UTOMOTIVE LUBRICANTS


ASTM No.
D
D
D
D
D
D
D

5862
5966
5967
5968
6074
6082
6202

D
D
D
D
D
D
D
E
E
E
E
E
E
E

6278
6299
6300
6335
6417
6483
6557
1
29
77
128
135
178
191

E 270
E 300
E 344
E 355
E 380
E 473
E 502
E 594
E 691
E 1119
E 1500
G 40

487

TABLE 2(continued).
Test Method or Document Title
Evaluation of Engine Oils in Two-Stroke Cycle Turbo-Supercharged 6V92TA Diesel Engine
Evaluation of Diesel Engine Oils for Roller Follower Wear in Light-Duty Diesel Engine
EvcJuation of Diesel Engine Oils in the T-8 Diesel Engine
Evaluation of Corrosiveness of Diesel Engine Oil
Guide for Characterizing Hydrocarbon Lubricant Base Oils
High Temperature Foaming Characteristics of Lubricating Oils
Measurement of the Effects of Automotive Engine Oils on the Fuel Economy of Passenger Cars and Light-Duty Trucks
in the Sequence VIA Spark Ignition Engine
Shear Stability of Polymer Containing Fluids Using a European Diesel Injector Apparatus
Applying Statistical Quality Assurance Techniques to Evaluate Anals^ical Measurement System Performance
Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products and Lubricants
Determination of High Temperature Deposits by Thermo-Oxidation Engine Oil Simulation Test
Estimation of Engine Oil Volatility by Capillary Gas Chromatography
Evaluation of Diesel Engine Oils in the T-9 Diesel Engine
Evaluation of Rust Preventative Characteristics of Automotive Engine Oils
Specification for ASTM Thermometers
Standard Practice for Using Significant Digits in Test Data to Determine Conformance with Specifications
Inspection and Verification of Thermometers
Maximum Pore Diameter and Permeability of Rigid, Porous Filters for Laboratory Use
Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
Practice for Dealing With Outlying Observations
Specification for Apparatus for Microdetermination of Carbon a n d Hydrogen in Organic and Organo-Metallic
Compounds
Terminology Relating to Liquid Penetrant Examination
Practice for Sampling Industrial Chemicals
Terminology Relating to Thermometry and Hydrometry
Gas Chromatographic Terms and Relationships
Use of the International System of Units (SI) (The Modernized Metric System)
Terminology Relating to Thermal Analysis
Selection and Use of ASTM Standards for the Determination of Flash Point of Chemicals by the Closed Cup Method
Testing Flame Ionization Detectors Used in Gas Chromatography
Conducting an Inter-Laboratory Study to Determine the Precision of a Test Method
Specification for Industrial Grade Ethylene Glycol
Installing Fused Silica Open Tubular Capillary Columns in Gas Chromatographs
Terminology Relating to Wear and Erosion

488 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


TABLE 3Referenced documents to non-ASTM methods for engine oils.
Organization
ANSI (American National
Standards Institute)
API (American Petroleum
Institute) Standard
Chemical Manufacturers
Association Code
Coordinating Research
Council (CRC) Motor Rating
Method Manuals
Deutsches Institut fiir
Normunge
Federal Test Method Standard
General Motors Corporation
Engineering Standard
lEEE/ASTM (Institute of
Electrical and Electronic
Engineers)
Institute of Petroleum
ISO

Military Specification
SAE (Society of Automotive
Engineers) Standards

U.S. Federal Test Method


Standards

Test Method or Document Title


Standard MC96.1 Temperature MeasurementThermocouples
API 1509 Engine Service Classification and Guide to Crankcase Oil Selection
CMA Petroleum Additives Product Approval Code of Practice
CRC Rust Rating (CRC Manual No. 7)
CRC Sludge Rating Manual (CRC Manual No. 12)
CRC Varnish Rating Manual (CRC Manual No. 14)
CRC Techniques for Valve Rating (CRC Manual No. 16)
DIN 51.581 Noack Evaporative Test
DIN 1725 Specification for Aluminum Alloys
DIN 12785 Specification for Glass Thermometers
No. 791b, Lubricants Liquid Fuels and Related Products, Methods of Testing
No. 791C, Method 3470
No. 791, Method 5308.7
GM9099-P Engine Oil Filterability Test (EOFT)
SI-10 Standard for Use of International System of Units (SI): The M o d e m Metric System
IP 17 Colour by the Lovibond Tintometer
IP 139 Neutralization Number by Color Indicator Titration
IP 146 Test for Foaming Characteristics of Lubricating Oil
Guide 25-General Requirements for the Calibration and Testing Laboratories
Guide 34 Quality Systems Guidelines for the Production of Reference Materials
Guide 35 Certification of Reference Material-General and Statistical Principles
3104, Petroleum ProductsTransparent and Opaque Liquids-Determination of Kinematic Viscosity and Calculation of Dynamic Viscosity
ISO 3105, Glass CapHlaiy Kinematic ViscometersSpecification and Operating Instructions
ISO 3696 Water for AnalyticEil Laboratory UseSpecification and Test Methods
ISO 9000 Quality Management and Quality Assurance Standards-Guidelines for Selection and Use
MIL-L-2104, Lubricating Oil, Internal Combustion Engine, Combat/Tactical Services
J183, Engine Oil Performance and Engine Service Classification (Other Than "Energy Conserving")
J254, Instrumentation and Techniques for Exhaust Gas Emissions Measurement
J300, Engine Oil Classification
J304, Engine Oil Tests
J726, Air Cleaner Test Code (Includes Piezometer Ring Specifications)
J1423, Passenger Car and Light-Duty Truck Energy-Conserving Engine Oil Classification
J1995, Engine Power Test Code - Spark Ignition and Compression IgnitionGross Power Rating
No. 791, Method 5308.7 Corrosiveness and Oxidative Stability of Light Oils (Metal Squares)
No. 791b Lubricants Liquid Fuels and Related Products; Methods of Testing

CHAPTER 17: AUTOMOTIVE LUBRICANTS

489

TABLE 4Referenced documents in ASTM standard test methods for transmission fluids.
ASTM No.

A108
A 109
A 240/A 240 M
B224
D91
D130
D235
D396
D412
D445
D471
D512
D516
D664
D892
D893
D975
D 1193
D1217
D 1401
D1480
D 1481
D 1655
D 1838
D2170
D2171
D2240
D2422
D3603
D4057
D4175
D4177
D5182
D5579
D5662
D5704
D5760
D6074
El
E77
E527
G40
ASTM Adjuncts

Test Method or Document Title

Specification for Steel Bars, Carbon, Cold-Finished, Standard Quality


Specification for Steel, Strip, Carbon, Cold-Rolled
Specification for Heat-Resisting Chromium and Chromium-Nickel Stainless Steel Plate, Sheet, and Strip for
Pressure Vessels
Classification of Coppers
Precipitation N u m b e r of Lubricating Oils
Detection of Copper Corrosion from Petroleum Products by the Copper Strip Tarnish Test
Specification for Mineral Spirits (Petroleum Spirits) (Hydrocarbon Dry Cleaning Solvent)
Specification for Fuel Oils
Vulcanized Rubber and Thermoplastic Rubbers and Thermoplastic ElastomersTension
Kinematic Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity)
Test Method for Rubber Property-Effect of Liquids
Chloride Ion in Water
Sulfate Ion in Water
Acid Number of Petroleum Products by Potentiometiic Titration
Foaming Characteristics of Lubricating Oils
Insolubles in Used Lubricating Oils
Specification for Diesel Fuel Oils
Specification for Reagent Water
Density and Relative Density (Specific Gravity) of Liquids by Bingham Pycnometer
Water Separability of Petroleum Oils and Synthetic Fluids
Density and Relative Density (Specific Gravity) of Viscous Materials by Bingham Bicapillary Pycnometer
Density and Relative Density (Specific Gravity) of Viscous Materials by Lipkin Bicapillary Pycnometer
Specification for Aviation Turbine Fuels
Copper Strip Corrosion by Liquefied Petroleum (LP) Gases
Test Method for JCinematic Viscosity of Asphalts (Bitumens)
Viscosity of Asphalts by Vacuum Capillary Viscometer
Rubber Property-Durometer Hardness
Classification of Industrial Fluid Lubricants by Viscosity System
Rust-Preventing Characteristics of Steam Turbine Oil in the Presence of Water (Horizontal Disk Method)
Manual Sampling of Petroleum and Petroleum Products
Terminology Relating to Petroleum, Petroleum Products, and Lubricants
Automatic Sampling of Petroleum and Petroleum Products
Evaluating the Scuffing (Scoring) Load Capacity of Oils (FZG Visual Method)
Evaluating the Thermal Stability of Manual Transmission Lubricants in a Cyclic Durability Test
Determining Automotive Gear Oil Compatibility with Typical Oil Seal Elastomers
Evaluation of the Thermal and Oxidative Stability of Lubricants Used for Manual Transmissions and Final
Drive Axles
Performance of Manual Transmission Gear Lubricants
Guide for Characterizing Hydrocarbon Lubricant Base Oils
Specification for ASTM Thermometers
Inspection and Verification of Thermometers
Practice for Numbering Metals and Alloys
Terminology Relating to Erosion and Wear
ASTM Copper Strip Corrosion Standard Engineering Drawings PCN ADJD5704

490 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 5^Additional standards or specifications related to transmission fluids.
Organization

Test Method or Document Title

ANSI/ISA (Instrument Society of America)-S7.3


DIN51354Teill
Federal Specification

Quality Stsindard for Instrument Air


FZG Zahnrad Verspannungs Priif Maschine-Allgemeine Arbeitsgrundlagen
RRS-366 (Method 5329 of W-L-791e) Test Sieve Sizes
QQ-S-698 Steel Sheet and Strip, Low Carbon
PD-680 Standard Solvent
JAN-H-792 Operations of Humidity Cabinet
Method 3430.2 Compatibility Characteristics of Universal Gear Lubricants
Method 3440.1 Storage Solubility Characteristics of Universal Gear Lubricants
Storage Solubility Characteristics of Universal Gear Lubricants
Specifications-IP Standard Thermometers, Appendix A
Specifications for IP Standard Reference Liquids, Appendix B
BS 871 Specification for abrasive papers and cloths
BS 970: Part 1: Carbon and Carbon Manganese Steels Including Free Cutting
Steels
Guide 25General Requirements for the Calibration and Testing Laboratories
3104 Petroleum Products-Transparent and Opaque Liquids-Determination of
Kinematic and Calculation of Dynamic Viscosity
3105 Glass Capillary Kinematic Viscometers-Specification a n d Operating
Instructions
3696 Water for Analytical Laboratory Use-Specification and Test Methods
4021 Hydraulic Fluid Power-Particulate Contamination Analysis-Extraction of
Fluid Samples from Lines of an Operating System
4406 Hydraulic Fluid Power-Fluids-Method for Coding Level of Contamination
by Solids Particles
9000 Quality Management a n d Quality Assurance Standards-Guidelines for
Selection and Use
Multi-Purpose (GO-H)
MIL-L-2105 and 2105D, Lubricating Oil, Gear, Multipurpose
MIL-C-15074C, Corrosion Preventive Compound Finger Print Remover
MIL-C-16173D Corrosion Preventive Compound, Solvent Compound Cutback,
Cold Application
J308, Axle and Manual Transmission Lubricants
J 405 Chemical Composition of SAE Wrought Stainless Steels
1009C Tee Reducer, Bulkhead on Side, Flareless Tube

Federal Specifications Standard No. 79IC


Federal Standard No. 791C, Method 3440.1
Institute of Petroleum

ISO

Mack Trucks Oil, Gear


Military Standard

SAE Standard

CHAPTER 17: AUTOMOTIVE LUBRICANTS

491

Table 6Referenced documents in ASTM standard tests for greases.


ASTM No.

Test Method or Document Title

D88
D95
D97
D130
D 156
D217
D235
A 240/A 240M

Saybolt Viscosity
Water in Petroleum Products and Bituminous Materials by Distillation
Pour Point for Petroleum Oils
Detection of Copper Corrosion from Petroleum Products by the Copper Strip Tarnish Test
Saybolt Color of Petroleum Products (Saybolt Chromometer Method)
Cone Penetration of Lubricating Grease
Specifications for Mineral Spirits (Petroleum Spirits) Hydrocarbon Dry Cleaning Solvent
Specification for Heat-Resisting Chromium and Chromium-Nickel Stainless Steel Plate, Sheet, and Strip for
Pressure Vessels
Rubber ProductsChemical Analysis
Specification for Acetone
Vulcanized Rubber and Thermoplastic Elastomers-Tension
BCinematic Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity)
Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers
Rubber PropertyEffect of Liquids
Sediment in Crude Oils and Fuel Oils by the Extraction Method
Dropping Point of Lubricating Grease
Specification for Isopropyl Alcohol
Rockwell Hardness of Plastics and Electrical Insulating Materials
Cone Penetration of Petrolatum
Evaporation Loss of Lubricating Greases and Oils
Distillation Range of Volatile Organic Liquids
Specification for Reagent Water
Density and Relative Density (Specific Gravity) of Liquids by Bingham Pycnometer
Flash Point and Fire Point of Liquids by Tag Open-Cup Apparatus
Nonvolatile Matter in Volatile Solvents for Use in Paints, Varnish, Lacquer, and Related Products
Cone Penetration of Lubricating Grease Using One-Quarter and One-Half Scale Cone Equipment
Density and Relative Density (Specific Gravity) of Viscous Materials by Bingham Pycnometer
Density and Relative Density (Specific Gravity) of Viscous Materieds by Lipkin Bicapillary Pycnometer
BCinematic Viscosity of Asphalts (Bitumens)
Viscosity of Asphalts by Vacuum Capillary Viscometer
Rubber Property-Durometer Hardness
Dropping Point of Lubricating Grease Over Wide Temperature Range
Cloud Point of Petroleum Oils
Evaporation Loss of Lubricating Greases Over Wide Temperature Range
Calibration and Operation of the Falex Block-on-Ring Friction and Wear Testing Machine
Practice for Rubber-Materials, Equipment, and Procedures for Mixing Standard C o m p o u n d s and Preparing
Standardized Vulcanized Sheets
Practice for Rubber-Preparation of Pieces for Test Purposes from Products
Practice for Utilization of Test Data to Determine Conformance with Specifications
Life Performance of Automotive Wheel Bearing Grease
Terminology Relating to Petroleum, Petroleum Products, and Lubricants
Elastomer Compatibility of Lubricating Greases and Fluids
Determining the Leakage Tendencies of Automotive Wheel Bearing Grease under Accelerated Conditions
Low-Temperature Torque of Grease-Lubricated Wheel Bearings
Classification of and Specification for Automotive Service Greases
Oxidation Induction Time of Lubricating Greases by Pressure Differential Scanning Calorimetry
Determining Extreme Pressure Properties of Lubricating Greases Using a High-Frequency, Linear Oscillation
(SRV) Test Machine
Measuring Friction and Wear Properties of Lubricating Grease Using a High-Frequency, Linear Oscillation (SRV)
Test Machine
Corrosion-Preventive Properties of Lubricating Greases in Presence of Dilute Synthetic Sea-Water Environments
Guide for Characterizing Hydrocarbon Lubricant Base Oils
Corrosion-Preventive Properties of Lubricating Greases Under Dynamic Wet Conditions (Emcor Test)
Oil Separation from Lubricating Grease (Conical Sieve Method)
Practice for Evaluating Compatibility of Binary Mixtures of Lubricating Greases
Specification for ASTM Thermometers
Specification for Wire-Cloth Sieves for Testing Purposes
Inspection and Verification of Thermometers
Calibration of Thermocouples by Comparison Techniques
Temperature-Electromotive Force (EMF) Tables for Standardized Thermocouples
Practice for Preparation and Use of Freezing Point Reference Baths
Specification for Sheathed Base-Metal Thermocouple Materials
Specification for Metal-Sheathed Base-Metal Thermocouples
Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
Terminology Related to Corrosion and Corrosion Testing
ASTM Adjunct: Copper Strip Corrosion Standard, Adjunct PCN 12-401300-00
Test Methods for Rating Motor, Diesel, and Aviation Fuels; Motor Fuels (Section I), Reference Materials and
Blending Accessories (Annex 2), Reference Materials (A2.7), and Table 32; (Specification for ASTM Knock Test
Reference Fuel, n-heptane)

D297
D329
D412
D445
D446
D471
D473
D566
D770
D785
D937
D972
D 1078
D 1193
D 1217
D 1310
D 1353
D1403
D 1480
D 1481
D2170
D2171
D2240
D2265
D2500
D2595
D2714
D3182
D3183
D3244
D3527
D4175
D4289
D4290
D4693
D4950
D5483
D5706
D5707
D5969
D6074
D6138
D6184
D6185
E 1
E 11
E77
E220
E230
E563
E585
E608
E691
G 15
Adjunct
ASTM

492 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


TABLE 7^Additional standards or specifications related to greases.
Organization

Test Method or Document Title

ABMA (American Bearing Manufacturers


Association)
AFBMA (Anti-Friction Bearing Manufacturers
Association)
ANSI (American National Standards Institute)

Standard 4. Tolerance Definitions and Gaging Practices for Ball and Roller Bearings

British Standards Institute


Compressed Gas Association
Federal Test Method
IP (Institute of Petroleum)

ISO (American National Standards Institute)

Military Standard
NLGI (National Lubricating Grease Institute)
SAE (Soc. Automotive Engineers) Standard

U.S. Air Force

Standard 19 1974 (available from ANSI, American National Standards Institute,


B.3.19-1975)
Specification B3.12 for Metal Balls
ANSI/AFBMA Standard 20-1987 Radial Bearings of Ball, Cyhndrical, Roller, and
Spherical-Roller Type-Metric Designs (AFBMA Code 20BCO2JO)
BS970: 1983 Part I, Section S
Booklets G-4 and G-4-1
Standard 791C, Method 3603.5, Swelling of Synthetic Rubbers
Specification for Standard IP Thermometers
Institute of Petroleum 50, Method of Testing for Cone Penetration of Lubricating
Grease
Guide 25-General Requirements for the Calibration and Testing Laboratories
3104 Petroleum Products-Transparent and Opaque Liquids-Determination of
Kinematic Viscosity and Calculation of Dynamic Viscosity
3105 Glass Capillary Kinematic Viscosmeters-Specification and Operating
Instructions
3696 Water for Analytical Laboratory Use-Specification and Test Methods
9000 Quality M a n a g e m e n t and Quality Assurance Standards-Guidelines for
Selection and Use
MIL-G-10924F, Specification for Automotive and Artillery
Grease Consistency Specification
AMS (Aerospace Materials Specification) 3217A Standard Elastomer Stocks-Test
Slabs
AMS 3217/2A Test Slabs, Acrylonitrile
AMS 3217/3A Test Slabs, Chloroprene (CR)-65-75
Butadiene (NBR-L)-Low Acrylonitrile, 65-75
Specification 539, Specification Bulletin for Standard Elastomer Stocks

CHAPTER 17: AUTOMOTIVE LUBRICANTS

493

TABLE 8^Referenced documents in ASTM stzmdards related to gear lubricants.


Test Method or Document Title

ASTM No.

B16
D96
D 130
D235
D329
D341
D396
D412
D446
D471
D484
D892
D975
D 1193
D 1217
D 1480
D 1481
D1655
D1796
D1838
D2170
D2171
D2240
D2266
D2509
D2670
D2783
D4175
D5182
D5579
D5662
D5704
D5760
D6074
E 1
E 128
G40
ASTM
Adjuncts

Specification for Free-Cutting Brass Rod, Bar, and Shapes for Use in Screw Machines
Water and Sediment in Crude Oil by Centrifuge Method (Field Procedure)
Detection of Copper Corrosion from Petroleum Products by the Copper Strip Tarnish Test
Specification for Mineral Spirits (Petroleum Spirits) (Hydrocarbon Drycleaning Solvents)
Specification for Acetone
Viscosity-Temperature Charts for Liquid Petroleum Products
Specification for Fuel Oils
Vulcanized Rubber and Thermoplastic Rubbers and Thermoplastic ElastomersTension
Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers
Rubber Property-Effect of Liquids
Specification for Hydrocarbon Drycleaning Solvents
Foaming Characteristics of Lubricating Oils
Specification for Diesel Fuel Oils
Specification for Reagent Water
Density and Relative Density (Specific Gravity) of Liquids by Bingham Pycnometer
Density and Relative Density (Specific Gravity) of Viscous Materials by Bingham Pycnometer
Density and Relative Density (Specific Gravity) of Viscous Materials by Lipkin Bicapillary Pycnometer
Specification for Aviation Turbine Fuels
Water and Sediment in Fuel Oils by Centrifuge Method (Laboratory Procedure)
Copper Strip Corrosion by Liquefied Petroleum (LP) Gases
Viscosity of Asphalts (Bitumens)
Viscosity of Asphalts by Vacuum Capillary Viscometer
Rubber Property-Durometer Hardness
Wear Preventive Characteristics of Lubricating Fluid (Four-Ball Method)
Measurement of Load-Carrying Capacity of Extreme Lubricating Grease (Timken Method)
Wear Properties of Fluid Lubricants (Falex Pin and Vee Block Method)
Measurement of Extreme Pressure Properties of Lubricating Fluids (Four-Ball Method)
Terminology Relating to Petroleum, Petroleum Products, and Lubricants
Evaluating the Scuffing (Scoring) Load Capacity of Oils
Evaluating the Thermal Stability of Manual Transmission Lubricants In a Cyclic Durability Test
Determining Automotive Gear Oil Compatibility with Typical Oil Seal Elastomers
Evaluation of the Thermal and Oxidative Stability of Lubricating Oils Used for Manual Transmissions and Final Drive
Axles
Specification for Performance of Manual Transmission Gear Lubricants
Guide for Characterizing Hydrocarbon Lubricant Base Oils
Specification for ASTM Thermometers
Maximum Pore Diameter and Permeability of Rigid, Porous Filters for Laboratory Use
Terminology Relating to Erosion and Wesir
Three Glossy Prints of Test Blocks Showing Scars (D 2780)
ASTM Copper Strip Corrosion Protection

TABLE 9Additional standards related to gear lubricants.


Organization and Test No.

ANSI (American National


Standards Institute) B3.12
DIN (Deutsch Industries Norm)
51 354 Teil (Part) 1
Federal Standard No 791 C
Institute of Petroleum Standards
IP 17
ISO

Mack Trucks, Inc.


Military Standard
SAE (Society of Automotive Engineers)

Test Method or Document Title

Specification for Metal Balls


FZG Zahnrad Verspannungs Pruef MaschineAUgemeine Arbeitsgrundlagen
Method 3430.2 Compatibility Characteristics of Universal Gear Lubricants
Method 3440.1 Storage Solubility Characteristics of Universal Gear Lubricants
Color measured using the Lovibond Tintometer
Guide 25-General Requirements for the Calibration and Testing Laboratories
3104 Petroleum Products-Transparent and Opaque Liquids-Determination of Kinematic
Viscosity and Calculation of Dynamic Viscosity
3105 Glass JCinematic Capillary Viscometers-Specifications and Operating Instructions
3696 Water for Analyticeil Laboratory Use-Specification and Test Methods
9000 Quality Management and Quality Assurance Standards-Guidelines for Selection
and Use
GO-H, Oil, Gear: Multi Purpose
MIL-L-2105, Lubricating Oil, Gear, Multipurpose
J308 Axle and Manual Transmission Lubricants

494 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 10ASTM standard test methods related to brake fluids.
D91
D260
D344
D395
D412
D445
D664
D746
D 1120
D1209
D 1364
D 1415
D2240
D3182
D3185
El
E 145
E 260-73

American Automobile Manufacturers Association


Standard Recommended Practice for General Gas Chromatography Procedure
Method of Test for Relative Dry Hiding Power of Paints
Aerospace Materials Specification
Rubber Properties in Tension
K n e m a t i c Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity)
Neutralization Number of Potentiometric Titration
Brittleness
Method of Test for Boiling Point of Engine Antifreezes
Color of Clear Liquids (Platinum-Cobalt Pigments)
Water in Volatile Solvents (Fischer Reagent Titration Method)
Method of Test for International Hardness of Vulcanized Natural Rubber and Synthetic Rubbers
Rubber PropertyDurometer Hardness
R e c o m m e n d e d Practice for Rubber-Materials, E q u i p m e n t and Procedures for Mixing S t a n d a r d Compounds a n d
Preparing Standard Vulcanized Sheets
Methods for Rubber-Evaluation of SBR (Styrene-Butadiene Rubber) including Mixtures with Oil
Specification for ASTM Thermometers
Specification for Gravity-Convection and Forced-Ventilation Ovens
Standard Recommended Practice for General Gas Chromatography Procedure

TABLE 11Definition of terms and abbreviations used in the text.


AAMA
AMS
ANSI
API
ASTM
CEC
CF, CF-2, CF-4,
CG, CG-4
CR
CRC
CRC Press
CVT
cSt
DIN
EMA
EOAT
EOFT
EOWTT
EP
FZG
GF-1, GF-2,
GF-3, GF-4
ILSAC
ISA
ISO
JAMA
MIL
NBR-L
PC
psi
rpm
SAE
SF, SG, SH,
SJ, SL
TEOST
ZDP or ZDDP

American Automobile Msinufacturers Association


Aerospace Materials Specification
American National Standards Institute
American Petroleum Institute
American Society for Testing and Materials
Coordinating European Council
"C" represents a category for engine oils that are used in compression ignition (diesel) engines. F, CF-2, CF-4, G,
and G-4 represent a particular oil quality.
Chloroprene Rubber
Coordinating Research Council
Chemical Rubber Company Press
Continuously Variable Transmission
Centistokes, a measure of viscosity
Deutsch Industries Norm (German industry standard)
Engine Manufacturers Association
Engine Oil Aeration Test
Engine Oil Filterability Test
Engine Oil Water Tolerance Test
Extreme Pressure (used for lubricants that experience high pressure or high temperature)
Fahrzeug (German word for motor vehicle)
Terms represent an engine oil quality that is defined by a series of tests that the oil must pass. GF indicates the
oils are used with gasoline fuel. GF-1 corresponds to API-SH quality engine oil.
International Lubricant Standardization and Approval Committee
Instrument Society of America
Represents a standard from the American National Standsirds Institute
Japan Automobile Manufacturers Association
Military specification
Acrylonitrile-Butadiene Rubber with Low Acrylonitrile
Pre chamber, associated with engine oil tests for diesel engines
Pounds per square inch. 550 psi equals 3.8 million N/m^
Revolutions per min
Society of Automotive Engineers
"S" represents a category for engine oils that are used in spark ignition engines. Each successive final letter
represents a more recent category. (SL is more recent than the others listed.)
Thermo Oxidation Engine Oil Simulation Test
Zinc dialkyl-dithio phosphate, an antioxidant and an anti-wear agent used as an additive in engine oil

CHAPTER 17: AUTOMOTIVE LUBRICANTS


REFERENCES
[1] Younggren, P. J. and Schwartz, S. E., "The Effects of Trip
Length and Oil Type (Synthetic Versus Mineral Oil) on Engine
Damage and Engine-Oil Degradation in a Driving Test of a Vehicle with a 5.7L Engine," SAE International Paper No. 932838,
Society of Automotive Engineers, Warrendale, PA, 1993.
[2] Schwartz, S. E., "A Comparison of Engine Oil Viscosity, Emulsion Formation, and Chemical Changes for M85 and GasolineFueled Vehicles in Short-Trip Service," SAE International Paper
No. 922297, Society of Automotive Engineers, 1992.
[3] McGeehan, J. A., Alexander, III, W., Ziemer, J. N., Roby, S. H.,
and Graham, J. P., "The Pivotal Role of Crankcase Oil in Preventing Soot Wear and Extending Filter Life in Low Emission
Diesel Engines," SAE International Paper No. 1999-01-1525, Society of Automotive Engineers, 1999.
[4] Machida, H. and Karachi, N., "Prototype Design and Testing of
a Half Toroidal CVT," SAE International Paper No. 900552, Society of Automotive Engineers, WEirrendale, PA, 1990.
[5] Hata, H. and Tsobuchi, T., "Molecular Structure of Traction Fluids in Relation to Traction Properties," Tribology Letters, Vol. 5,
1998, pp. 69-74.
[6] CuUey, S. A. and McDonnell, T. F., "The Impact of Passenger Car
Motor Oil Phosphorus Levels on Engine Durability, Oil Degradation, and Exhaust Emissions in a Field Trial," SAE International Paper No. 952344, Society of Automotive Engineers, Warrendale, PA, 1995.
[7] CuUey, S. A., McDonnell, T. F., Ball, D. J., Kirby, C. W., and
Hawes, S. W., "The Impact of Passenger Car Motor Oil Phosphorus Levels on Automotive Emissions Control Systems," SAE
International Paper No. 961898, Society of Automotive Engineers, Wcirrendale, PA, 1996.
[8] Drury, C. and Whitehouse, S., "The Effect of Lubricant Phosphorus Level on Exhaust Emissions in a Field Trial of Gasoline

495

Engine Vehicles," SAE International Paper No. 940745, Society


of Automotive Engineers, Warrendale, PA, 1994.
[9] Ueda, F., Sugiyama, S., Arimura, K., Hamaguchi, S., and
Akiyama, K., "Engine Oil Additive Effects on Deactivation of
Monolithic Three-Way Catalysts and Oxygen Sensors," SAE International Paper No. 940746, Society of Automotive Engineers,
Warrendale, PA, 1994.
[10] Deane, B. C, Choi, E., and Crosthwait, K., "The Relationship of
Base Oil Volatility to Oil Loss in Automotive Application,"
NPRA Paper No. AM 97-40, National Petroleum Refiners Association, Washington, DC, 1997.
[11] Choi, E. and Deane, B., "Base Stock Volatility and Oil Consumption," NPRA Paper No. AM-98-47, National Petroleum Refiners Association, Washington, DC, 1998.
[12] Manni, M., Gommellini, C, and Sabbioni, G., "Effect of Physical Characteristics of Lubricating Oils on Emissions, Fuel Economy and Oil Consumption in a Light Duty Diesel Engine," SAE
International Paper No. 952552, Society for Automotive Engineers, Warrendale, PA, 1995.
[13] Rounds, F. G., "Effect of Lubricant Additives on the Prowear
Characteristics of Synthetic Diesel Soots," Lubrication Engineering, Vol. 43, No. 4, 1987.
[14] Schwartz, S. E., "A Model for the Loss of Oxidative Stability of
Engine Oil During Long-Trip Service, Part I: Theoretical Considerations," STLE (Society of Tribologists and Lubrication Engineers) Tribology Transactions, Vol. 35, No. 2, 1992, pp. 235-244.
[15] Schwartz, S. E., "A Model for the Loss of Oxidative Stability of
Engine Oil During Long-Trip Service, Part II: Vehicle Measurements," STLE Tribology Transactions, Vol. 35, No. 2, 1992, pp.
307-315.
[16] Gresham, R. M., Tribology Data Handbook, CRC (Chemical Rubber Company) Press, Boca Raton, FL, 1997, pp. 600-607.
[17] Crutzen, P. J. and Ramanathan, V., "The Ascent of Atmospheric
Sciences," Science, Vol. 290, pp. 299-304.

MNL37-EB/Jun. 2003

Metalworking and
Machining Fluids
Syed Q. A. Rizvi:\

METALWORKING IS THE PROCESS OF CONVERTING BULK METAL into

a component or apart and primarily involves two types of operations: those that produce metal debris and those that produce no debris. The former type is classified as metal removal
operations and the latter type is classified as metal forming
operations. Cutting and grinding are examples of the first
type and drawing, stamping, and bending are examples of the
second type. All metalworking operations involve bringing
two solids, a tool and a work piece, together to create a new
part or a shape. The process involves high friction, high temperatures, and tool wear; and it is the job of the lubricant, or
the metalworking fluid, to control them. Metalworking fluids
accomplish this by providing cooling, lubrication, and protection against corrosion. Therefore, they improve the efficiency of the operation, and hence increase productivity.

FUNDAMENTAL CONCEPTS
Lubrication
Friction is c o m m o n to all surfaces in contact and is usually
represented by the friction coefficient, signified by the symbol /JL. The coefficient of friction (/x) is a unit-less ratio that
equals 0/N, where 0 represents the frictional force experienced by the two contacting bodies in motion and N represents the n o r m a l force pressing the same two bodies together. Its value ranges from zero (0) to one (1). The higher
the value, the higher the frictional force or the resistance of
the contacting bodies towards motion. Under boundary lubrication conditions, ^l approaches 1.
Minimizing friction is one of the fundamental functions of
a lubricant. If friction is not controlled, it can lead to wear
and surface damage, and ultimately to catastrophic failure of
the equipment. Because of a generally direct correlation between friction a n d wear [1,2], p r o p e r lubrication of the
equipment is important if its integrity is to be preserved over
its designated lifetime. However, it is important to note that
the correlation between friction and wear is a function of the
system and is not always direct [3].
In lubricant-related applications, we are concerned with
three types of friction, that is, the solid friction, fluid friction,
and internal friction [12]. The main function of a lubricant is
to minimize solid friction, which it achieves by forming a
fluid film between two contacting (often metal) surfaces.
Usually, a fluid's internal friction is not of any major concern
' Research and Development Manager, Lubricant Additives Division, King Industries, Inc., Science Road, Norwalk, CT 06852.

except at very low temperatures. At these temperatures, the


lubricant gains viscosity, w h i c h can interfere with the
smooth operation of the equipment. Internal friction is important when considering a lubricant's intrinsic properties,
such as viscosity (ASTM D 445, D 2983, D 3829, D 4684, and
D 5293) and pour point (ASTM D 97).
All metal surfaces, irrespective of their finish, contain
ridges, valleys, asperities, and depressions. When two metal
surfaces come in contact, solid friction, sometimes called
static or adhesive friction, ensues and the surfaces undergo
adhesion and cold welding. The strength of such an association depends upon the hardness of the materials, the cleanliness of the surfaces, and the electronic structure of the metals as related to their tendency to form metal-metal solutions,
or alloys [4,5]. As soon as the surfaces start to move, kinetic
friction comes into play. Kinetic friction results from the
plowing of the asperities of one surface across the other surface, plastic deformation or elastic hysteresis, and wear debris getting lodged between the moving surfaces [5]. Static
friction is larger than kinetic friction. This is because of the
extent and the duration of contact. Friction is also related to
the tjTDe of motion of the bodies. Sliding motion, for instance,
leads to higher friction than rolling motion and hence results
in more wear. This is primarily a consequence of the larger
contact zone of the sliding surfaces.
Applications that encounter metal-to-metal contact involve
either no lubrication (dry), solid lubrication, or liquid lubrication. Wear resistance in equipment designed to operate
without lubrication is introduced by the use of low-wear metals and/or surface treatment, such as hardening or coating.
Solid lubrication is c o m m o n where liquid lubrication is
u n w a n t e d or is difficult because of equipment design or
extremely high operating temperatures. Such lubricants, exemplified by graphite and molybdenum disulfide, have multilayered structures with low shear strength in some directions. Movement in such directions is therefore facilitated.
These lubricants are applied to equipment in a number of
ways such as b o n d e d dry films, sputtered films, or loose
flakes. In metalworking applications, we are primarily interested in liquid lubrication. The purpose is either to separate
contacting surfaces by introducing a liquid film or to minimize wear by delivering wear control additives to surfaces in
contact.
The relationship of coefficient of friction (/x) and the relationship of oil film thickness (p) to lubricant viscosity (Z),
equipment speed (N), and equipment load, or pressure (P), are
graphically represented in Fig. 1, Part A [6]. This graph is commonly referted to as the Streibeck Curve. As one can see, the

497
Copyright'

2003 by A S I M International

www.astm.org

498 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

Lubricant
Firm

W^Y^/.iA^^.i'V^A^lU*^

FLUID-FILIVI LUBRICATION
Surfaces well separated by
the bulk lubricartt film

LubricantFilm
MIXED-FILM LUBRICATION
Both the bulk lubricant and
the boundary film play a
role

BOUNDARY LUBRICATION
Performance essentially
depends upon the quality of
the boundary flim
(A)

RELATIONSHIP OF VISCOSITY {2),


SPEED (W), AND LOAD {P) TO
FRICTION AND FILM THICKNESS

{By GRAPHIC REPRESENTATION OF


LUBRICANT FILM THICKNESS IN
DIFFERENT LUBRICATION REGIMES

FIG. 1Lubrication regimes in mechanical equipment.

ratio of ZN/P relates directly to oil film thickness (p), but inversely to coefficient of friction (/U,). This implies that high lubricant viscosity (Z), high equipment speed (N), and low
equipment load (P) will allow the formation of a thick lubricant film, 2ind hence the equipment will encounter little or no
friction. Conversely, low lubricant viscosity, low equipment
speed, and high equipment load will create a situation where
film thickness will be inappropriate and the equipment will
encounter high friction. The initial drop in the coefficient of
friction, shown in the figure, while moving from fluid-film to
mixed-film lubrication, reflects a decrease in viscous drag due
to a decrease in lubricant viscosity and or equipment speed.
Mechanical equipment experiences three types of lubrication environments: fluid-film, boundary, and mixed-film.
These are depicted in Fig. 1, Part B [6]. Fluid-film lubrication, also known as hydrodynamic lubrication, is of the most
desirable type. This type of lubrication depends upon the viscosity of the lubricant and is effective only when the load in
the contact zone is low. Under these circumstances, the sliding surfaces are separated by a lubricant film several times
the thickness (2-100 ;nm) of the surface roughness.
Another type of hydrodynamic lubrication, referred to as
elasto-hydrodynamic lubrication or EHD [7-9], commonly
occurs in parts with rolling motion. In this type of lubrication, the lubricant is exposed to high contact pressures and
undergoes a large viscosity increase. See Viscosity section
and Fig. 4. This results in an extremely rigid lubricant film
(0.01-5.0 /xm thick), which causes elastic deformation of the
surfaces in the lubricating zone. Elasto-hydrodynamic lubri-

cation is depicted in Fig. 2. The crosshatched area in the figure indicates solid lubricant film that causes elastic deformation of the metal surfaces.
Boundary lubrication represents the other extreme of the
lubricating environment. Under this kind of lubrication, high
loads and very slow speeds produce extreme pressures that
can lead to a lack of effective lubrication, and hence promote
maximum metal-to-metal contact. The lubricant film thickness in this type of lubrication is in the order of 0.0-2.0 fjun.
If not controlled, the resulting dry metallic friction will cause
extensive wear and ultimately total seizure. Reactive chemicals, called antiwear and extreme pressure agents, provide
protection in this kind of lubricating environment. Mixedfilm lubrication falls between the two extremes mentioned
above and contains the characteristics of both the fluid-film
lubrication and the boundary lubrication. There are regions
of no metal-to-metal contact and of metal-to-metal contact.
Metalworking operations are designed to have at least
some metal-to-metal contact. This is because total separation
of surfaces will make the process inefficient. For example, in
metal removal operations, separation will lead to poor
tool-work piece contact, which will interfere in chip formation. In metal forming operations, this will lead to low friction and hence loss of control. This implies that in metalworking, the lubricant must be designed to perform in
mixed-film and boundary lubrication regimes. In general,
metal removal operations require boundary lubrication and
metal forming operations require mixed-film lubrication.
Metal removal operations, therefore, involve little or no lu-

CHAPTER

Mutually Flattened
Areas Under Load

18: METALWORKING

Metal Strip

AND MACHINING

FLUIDS

499

Elastlcally Deformed
Areas

FIG. 2Elasto-hydrodynamic lubrication.

bricant film and metal forming operations involve a fairly


thin lubricant film, as shown in Fig. 1, Part B.
Lubricant film in metal forming operations is of two types:
wedge and squeeze. Wedge type films occur when two nonparallel surfaces in motion converge and squeeze type films
occur when parallel surfaces in motion come together [10].
In forming operations, wedge type films are more common
than the squeeze type. As the lubricant enters the converging
zone, there is an increase in pressure that causes an increase
in lubricant viscosity. This is a consequence of the lubricant
molecules coming closer. The increase in viscosity changes
the nature of lubrication in the contact zone from being hydrodynamic to elasto-hydrodynamic. As the lubricant exits,
the gap widens and there is a decrease in viscosity cind an increase in velocity. This causes a reversal from elasto-hydrodynamic lubrication to hydrodynamic lubrication (Fig. 1,
Part A). The result is separation of the surfaces and minimal
metal-to-metal contact. A d r o p in viscosity is a consequence
of the widening gap that permits lubricant molecules to move
away from one another.
The quality of the lubricant film determines the metal
forming efficiency. The higher the operation speed, the
higher the film thickness; similarly, the higher the viscosity,
the higher the film thickness (Fig. 1). Both these conditions
therefore force the converging surfaces to move away from
each other (the gap widens), which improves the operation
efficiency. For example, in rolling operations, the speed of
strip determines the film thickness. Since temperature and
pressure also impact viscosity, hence lubricant film thickness, these factors also affect the efficiency of the metal forming operations. Different base fluids have differing responses
to temperature and pressure, and therefore their properties
can influence the properties of the metal forming lubricants
as well. Naphthenic basestocks are usually preferred over
paraffinic basestocks. This is because they not only experience a faster viscosity decrease with an increase in temperat u r e (have a lower viscosity index), they also u n d e r g o a
greater viscosity increase with a n increase in pressure. See
Figs. 3 and 4. These factors make lubricants derived from
these basestocks extremely effective in high-pressure applications, such as rolling.
As mentioned earlier, squeeze films form when two parallel surfaces converge, a situation that occurs in operations

t
(A
M

E
E

Naphthenic Oil

(0

o
o
(A

Paraffinic Oil
m

E
c

'2.
Temperature ( C)
FIG. 3Viscosity-temperature relationship.

such as upsetting. The film thickness increases due to fast approaching surfaces and the lubricant viscosity increases because of an increase in pressure. Both factors hinder lubricant flow out of the contact zone, which results in a squeeze
film. Deformation of the work piece during the operation results in a flatter surface, thereby making the squeeze film
thinner. The thickness of the squeeze films depends on lubricant viscosity, speed, and load (force) in the same way as that
of the wedge films, but for the reasons described.
Lubrication regime defines a lubricant's ability to support
load (modify friction and reduce metal transfer) and can be
determined by taking into account film thickness and combined surface roughness. The ratio of the two, represented by
A, equals film thickness (p) divided by the combined roughness of the surfaces (S), or p/5. The combined roughness is the
roughness amplitude of two surfaces relative to their average
levels. The value of A equal to 0.5 implies boundary regime;
the value of A between 0.5 and 3.0 implies mixed film regime;

500 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Solid

Paraffinic Oil
Naphthenic Oil
0

20

40

60

80

100

120

Pressure (1,000 psi)

140

FIG. 4Viscosity-pressure relationship.

and the value of A greater than 3 implies fluid-iilm or hydrodynamic regime [10]. Unlike metal removal operations that
primarily involve boundary lubrication regime, metal forming operations start in the boundary regime but move into
mixed-film and hydrodynamic regimes as the operation picks
up speed. Lubricant properties, such as viscosity and the
presence of film-forming additives play a role in boundary
and mixed-film regimes. Film-forming additives include friction modifiers, antiwear agents, and extreme pressure
agents. These additives protect surfaces against extensive
friction and wear. They do so by forming low shear protective
films either via physical adsorption, chemical adsorption, or
through chemical reaction. See the Film-forming Agents section for further details.
Viscosity
The role of viscosity in forming effective lubricating films
makes it one of the most important properties of a fluid [11].
Viscosity is defined as a fluid's resistance to flow and is primarily a consequence of the internal friction of the fluid [12].
The viscosity is of two tjfpes: absolute or dynamic viscosity
and kinematic viscosity. Absolute viscosity is commonly expressed in poise (P) or Pascal-seconds (Pa-s) [1 Pa-s =10^
centipoise (cP)]. Kinematic viscosity is measured under the
accelerating influence of gravity and equals absolute viscosity of the fluid divided by its density. It is expressed in centistokes (cSt), or square meters per second (m^/s) [1 m^/s =10*
centistokes (cSt)]. Absolute viscosity is often not used for
metalworking fluids, but kinematic viscosity is. Previously
used units of kinematic viscosity, Saybolt Universal Seconds

(SUS), and Saybolt Furol Seconds (SFS) are now obsolete.


The methodology to convert these units into Stokes is described in the ASTM Standard D 2161 [13].
A number of factors affect viscosity. These include temperature, pressure, time, and the structures of organic compounds present in the fluid and their response to shear forces
[12]. The two variables whose effect primarily pertains to
metalworking fluids eire temperature and pressure. Mineral
oils and synthetic oils both experience a viscosity decrease
with an increase in temperature. In general, the viscosity of
naphthenic oils decreases at faster rate than that of the paraffinic oils (Fig. 3). The viscosity-temperature relationship of a
fluid is expressed in terms of its viscosity index (VI) (DIN ISO
2909 [14], ASTM D 2270 [13]). Viscosity index, based upon
kinematic viscosities at 40C and 100C, when originally introduced had a scale ranging from 0 (zero) to 100. The two
oils that were used to establish this scale no longer exist, but
their viscosities are still used to compute viscosity indexes.
Many modem oils have viscosity indexes that extend well beyond 100. Such oils are made by isomerizing the low VI hydrocarbons in oil to high VI hydrocarbons, via a process
called hydrocracking. The process involves treating the oil
with hydrogen in the presence of a proprietary catalyst at
high temperatures. Oils whose viscosities have a high sensitivity to temperature have a low VI, and oils whose viscosities
have a low sensitivity to temperature have a high VI. Unlike
temperature, which has an inverse relationship to viscosity,
pressure bears a direct relationship. That is, when pressure
increases viscosity increases (Fig. 4). However, the effect,
which is a function of the chemical structure of the fluid, is
not as dramatic as in the case of temperature [12].

CHAPTER 18: METALWORKING


Lubricant viscosity is measured by the use of instruments,
called viscometers. Of many types that are available for this
purpose, capillary viscometers are used to measure kinematic viscosity. The lubricant is allowed to flow down a capillary and the viscosity is calculated by taking into account
flow time and the viscometer constemt. This constant is supplied by the standardization laboratory along with the instrument constant. Dynamic viscosity is determined by multiplying kinematic viscosity with fluid density. This is
described in the ASTM D 445 procedure [13].
Viscosity is critical to determining the quality of the lubricant film. In metal-forming applications, it determines the effectiveness of the film in separating the tool from the work
piece and therefore controlling friction and wear. Metal removal operations, on the other hand, have diverse lubrication
needs, and hence optimum lubricant viscosity must be estimated for each operation. This is accomplished by considering the ability of the lubricant to enter and remain in the contact zone, the durability of the lubricant film, the desired rate
of spreading, and its cooling capability. These parameters are
evaluated by the use of film-strength tests, such as the
Timken Test (ASTM D 2782), the Four-Ball Tests (ASTM D
2783 and D 4172), and the SAE #1 Test.

FLUID CLASSIFICATION BASED ON


BASE FLUID
Metalworking and machining fluids fall under three general
classes: oil-based, water-based, and solid suspensions [15].
Oil-based fluids are mineral oils with or without additives.
Water-based fluids, on the other hand, are micellar solutions
of oil and/or additives in water. These fluids are of three
types: soluble oils, semisynthetic fluids, and synthetic fluids.
The worldwide use of oil-based fluids is estimated at 45% and
that of water-based fluids is estimated at 53%; with synthetics, semisynthetics, and soluble oils, having a share of 4%,
16%, and 33%, respectively. Solid suspensions make up the
rest. The ASTM Standard D 2881 [15] and the European
Standard DIN 51 385 [14] classify metalworking lubricants
according to their nature and functions. Classes of metalworking fluids are described below. The essential difference
between various classes is that as one moves from straight oil
to semisynthetic fluid, the amount of water increases and the
amount of oil decreases. See Table 9.
Straight Oil (not dilutable)not supportive of microbial
growth.
"Soluble" Oil (oil-based emulsifiable concentrate, diluted
with water at the point of use)more likely to support bacterial growth. It primarily contains oil, emulsifiers, and
other additives. When diluted (typical dilution ratio is between 5 to 20 parts of water to 1 part of concentrate) it produces an emulsion. Oil provides lubrication and corrosion
protection and water provides cooling. In some grinding
applications, the dilution ratio can be as high as 200:1.
Synthetic Fluid (water-based solution concentrate; diluted
prior to use)more likely to support fungal growth. It contains no oil but is a solution of corrosion inhibitors and
friction reducing additives in water. These fluids provide
cooling and corrosion protection, but their lubrication
properties arise from sjrnthetic lubricity components.

AND MACHINING

FLUIDS

501

Semisynthetic Fluid (oil-in-water emulsion concentrate;


diluted prior to use)more likely to support bacterial
growth. The fluids belonging to this class contain oil and
additives emulsified in water. These preformed emulsions
when diluted further are used to provide lubrication, cooling, and corrosion protection.
Oil-based Fluids
These lubricants, commonly referred to as straight oils, are
mineral oil-based. These primarily utilize hydrotreated naphthenic basestocks and contain polyol esters and fatty oils as
lubricity agents, and sulfur, chlorine, and phosphorus-derived extreme pressure additives. However, there is a growing
trend towards the use of paraffinic basestocks because the
derived fluids have a lower tendency to produce mist. The
cooling ability of these fluids is not as good as that of the water-based systems, but it is respectable. Because of this and
their excellent lubricating ability, these lubricants are often
used in high temperature operations that involve high unit
pressures and high spot temperatures. That is, those involving slow machine speeds. These oils are labeled active if they
contain additives capable of releasing active sulfur (see discussion under extreme pressure agents). Otherwise, they
are classified as inactive. Sulfur-releasing ability is high
when sulfurized olefins and sulfurized fats used as additives
are of high sulfur content (sulfur to olefin ratio of greater
than 1). Active fluids are commonly used in machining steel.
However, some metal removal operations, such as blanking,
do employ inactive fluids. Inactive fluids contain fatty oils,
and fatty oil - mineral oil mixtures and or inactive sulfur additives.
Water-based Fluids
These fluids are emulsions consisting of an organic phase
and an aqueous phase. In emulsions, one phase is considered
a dispersed phase and the other a continuous phase (usually
the larger of the two). When the organic material (oil and/or
additives) is the dispersed phase and water is the continuous
phase, the emulsions are called normal, or oil-in-water emulsions. If, however, water is the dispersed phase and organic
material is the continuous phase, the emulsions are called invert, or water-in-oil emulsions. The two types of emulsions
are depicted in Fig. 5.
Metalworking and machining fluids are usually oil-in-water tjrpe emulsions. The emulsions are of transient stability
(ASTM D 3342, D 3707, and D 3709). Their stability depends
upon a variety of factors. These include the nature of the oil
phase, the amount and the type of emulsifier/s, the pH, the
operating temperatures (ASTM D 3707), the nature and the
amount of additives, and the impurities, either present or introduced into the system. All these factors can lead to coalescence of fine droplets into larger ones and lead to oil-water
sepciration.
In general, emulsions that are used as metalworking fluids
are kinetically stable but thermodynamically unstable (10).
This means that such emulsions maintain their integrity during use but have the tendency to phase separate when not in
use. While phase separation in bulk is undesired, the emulsions must phase separate on surfaces to release oil/additives

502

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK
HjO

HoO
OIL

"^,
.~N<00~>

IL ./wOO'^^'^^

OIL

^^2*^

'VwO

0~v

'^2*'

OIL

OIL
OIL

HoO

(a)

(b)

FIG. 5A representation of (A) water-in-oil emulsion (B) oll-in-water emulsion.

that improve lubrication. Oil availability depends u p o n its


amount being present in the formulation and the emulsion
stability. As a rule, the higher the oil content and the lower
the emulsion stability, the greater the oil availability. The
problem is that the two essential properties of emulsions,
namely lubricating ability and cooling capacity, are inversely
related. Emulsions of high oil content (lower water content)
not only have poor cooling ability, but they are also of lower
stability, which decreases their useful life. To further complicate matters, some metalworking operations, such as rolling,
tend to destabilize these high oil-based emulsions. In other
words, there is a lubrication-cooling tradeoff when emulsion
tjrpe metalworking fluids are used.
Emulsions are usually supplied as concentrates, which
need to be diluted with water prior to use. In addition to cooling and lubricity (ASTM D 2782, D 2783, D 4172, and D
5619), these fluids possess inherent rust prevention properties (ASTM D 4627), and detergency. Another attribute of
these fluids is the ability to incorporate additional performance additives. The main disadvantages are their sensitivity
towards hard water, susceptibility to microbial attack, and
skin sensitivity.
Water-based fluids cire susceptible to microbial attack, primarily because of low organic (high water) content. Bacterial
infestation of the fluid can lead to an objectionable odor due
to the formation of hydrogen sulfide, a change of color to
gray, the formation of black stains on the work piece, and
foaming. Fungal growth can produce slime and is more difficult to control than bacterial growth. The major side effect of
microbial attack is the emulsion's tendency to phase separate. Monitoring and control of emulsion quality are therefore important. The common techniques used for this purpose are summarized in Table 1. The quality of emulsions in
metalworking fluids is maintained by:
the use of biocides.
maintaining p H (bacteria are d o r m a n t at pH of greater
than 8.8; 8.8-9.2 is a good range).
controlling dissolved oxygen levels.
periodic removal of contaminants, such as tramp oil.
the use of filtration equipment.

TABLE 1Metalworking fluid monitoring techniques.


Appearance and Color PH
Odor Reserve alkalinity (ASTM
(ASTM D 1293)
D974)
Emulsion stability
Low-shear foam (ASTM D 3601)
(ASTM D 1479)
Corrosion inhibition
Microbial load (ASTM D 3946)
(ASTM D 4627)
Relative bio-resistance
(ASTM D 3946)

It is important to periodically check the organic (oil) content of the emulsion by breaking it. An acid or a salt, such as
sodium chloride, is used for this purpose. Alternatively, one
can use a refractometer to determine the oil content. If the oil
content is too low, it may be appropriate to top u p the fluid
with fresh concentrate. Since contaminants, such as tramp
oils, metal debris, and microbes, can destroy the integrity of
emulsions, they should either be removed or controlled.
Tramp oils are removed via skimming and metal debris is removed via filtration. As mentioned above, microbes are controlled by the periodic addition of the antimicrobial agents.
Foaming is another problem (ASTM D 892) with emulsions
that relates to the presence of emulsifiers. Foaming not only
leads to poor lubrication, but it also impairs the fluid's heat
transfer properties. While new emulsions are more stable
than old emulsions, the lubricating ability (ASTM D 2782, D
2783, D 4172, and D 5619) of emulsions improves with use.
This is because debris resulting from metalworking operations and the decomposition products from additives, especially EP agents, tend to destabilize emulsions via nucleation.
Ultimately, a complete breakdown of emulsion occurs and a
new batch must be used. The life of an emulsion during use
is called its "batch life." In general, less stable emulsions have
a shorter batch life.
While emulsions contain a variety of chemicals (discussed
in the Additive section), the chemical types that are critical to
their formation and stability are emulsifiers and coupling
agents. Emulsifiers are key to the formation of emulsions,
and coupling agents help improve their stability. Emulsifiers
are surfactants that reduce surface tension of the oil-water

CHAPTER
interface, thereby promoting miscibility and leading to colloidal dispersions. In many cases, a combination of emulsifiers is used and its selection depends upon the type of base
oil to be emulsified and the nature of other additives present
in the formulation [10].
Emulsions are made by mechanically mixing the organic
phase t h a t comprises additives and emulsifier/s, called a
"concentrate," with water. Since the amount of water in water-based fluids can be as high as 95%, its quality not only determines initial stability of the emulsion but also its "batch
life." The presence of greater than 200 p p m calcium or magnesium carbonate (ASTM D 511 and D 513) can lead to emulsion stability problems. And the presence of chloride and or
sulfur levels (ASTM D 512 and D 516) of greater than 150
p p m will promote corrosion, instability, and rancidity. Soft
water of less than 50 p p m hardness (ASTM D 1126), on the
other hand, leads to foaming in many formulations. While
regular water is usually acceptable, the use of distilled, deionized, or reverse osmosis water is recommended if problems are encountered.
Emulsion appearance can vary from transparent to milky
white, depending upon the droplet size. Table 2 shows emulsion appearance as a function of the droplet size. Oil-in-water emulsions with droplet sizes of approximately 0.1-0.2 um,
sometimes referred to as microemulsions, are preferred in
some metalworking applications. This is because their
smaller droplet size makes them both kinetically and thermodynamically more stable. Macroemulsions with droplet
sizes in the range of 0.2-10 u m are only kinetically stable.
This means that microemulsions prefer the dispersed form
and are therefore less likely to phase separate. Of course, the
droplet size depends upon factors such as the nature of the
oil and the amount and the type of emulsifier used. Despite
greater kinetic and thermodynamic stability, pH (ASTM D
1293), oil-water ratio, and temperature have a profound effect on the stability of microemulsions. The larger droplet
size and the tendency to coalesce are not always undesired.
Hence, m a c r o e m u l s i o n s are often used in m a n y oncethrough applications, where immediate breakdown is desired to release oil for superior lubrication. The same properties are useful for effluent treatment.
As mentioned earlier, emulsions for metalworking use are
usually produced prior to use by mechanically mixing the additive concentrate with water. The concentrate comprises oil,
emulsifier/s, and a variety of additives. The concentrate-towater ratio in such dilutions is between 1:10 (10%)-1:60
(1.5%). However, this ratio is changed if the operation requires a greater degree of cooling or more lubricity. Metalworking fluids for operations requiring more cooling contain
a higher percentage of water than those requiring more lubrication. Microemulsions are stable (ASTM D 3342, D 3707,
and D 3709), are resistant to microbial attack (ASTM D
3946), and are effective coolants. These attributes are primarily due to their low organic content and high emulsifier

18: METALWORKING

Droplet Size in Microns


>1
0.1-1
0.005-0.1
< 0.005

Appearance
Milky white
Blue white
Translucent to semi-transparent
Transparent to translucent

FLUIDS

503

levels. Despite the listed advantages, microemulsions suffer


from the disadvantages of being expensive, difficult to dispose of, and an extensive tendency to foam (ASTM D 892).
Classification of Water-based Fluids
Water-based fluids are classified as soluble oils, synthetics,
a n d semisynthetics, depending u p o n their oil content and
emulsion t3rpe. Soluble oils are macroemulsions containing
about 2-10% naphthenic or paraffinic oil. Semisynthetic fluids are microemulsions containing less than 2% oil. Synthetic
fluids contain no oil and are predominantly solutions of water-soluble organic compounds or polymers in water. The
cooling ability of each tj^De is related to its water content.
Therefore, synthetic fluids, with the highest water content,
are extremely effective in operations, such as grinding, that
generate a lot of heat. As mentioned earlier, the appeareince
of an emulsion is related to its droplet size. When the droplet
size is small, as in the case of microemulsions, the fluids appear transparent, and when it is relatively large, as in the case
of macroemulsions, the fluids appear translucent. The form a t i o n of microemulsions generally requires a higher
amount of emulsifier.
The terms S5mthetic and semisynthetic, used to describe
metalworking fluids, have a different meaning than the same
terms used to describe automotive lubricants. In the case of
metalworking fluids, these terms pertain to water-based systems, such as micellar solutions and emulsions. In the case of
automotive lubricants, however, the terms synthetic and
semi-synthetic pertain to the t3rpe of base fluid used to formulate these lubricants. Synthetic implies the use of synthetic basestocks, such as polyolefins, polyglycols, carboxylic
esters, etc., and semi-S3mthetic implies a combination of synthetic basestocks and petroleum basestocks. Despite this difference, both types of fluids meet the general definition of
synthetic as being man-made materials [20].
Soluble

Oils

(Macroemulsions)

These lubricants are emulsions of mineral and/or fatty oils in


water. An emulsifying agent or a surfactant is necessary to
form these emulsions. Fatty oil-based lubricants have excellent lubricating properties due to the friction reducing characteristics of such oils (ASTM D 2670, D 5183, and D 5619).
Because of the high oil content ( > 2.0%), these emulsions are
milky in appearance and are easily destabilized by salts, bacteria, and other materials that can deactivate emulsifiers.
Sulfur, chlorine, and phosphorus-containing additives (Fig.
16) are used to make these oils suitable for more severe metalworking operations, such as broaching, tapping, and
threading. They may also contain rust and foam inhibitors.
In view of their excellent cooling and lubricating properties,
soluble oils are used for operations that involve high speeds,
low pressures, and generate high temperatures.
Synthetic

TABLE 2Droplet size versus emulsion appearance.

AND MACHINING

Fluids

(Micellar

Solutions)

Micelles are aggregates of emulsifier molecules that occur in


water. These result from the tendency of the lipophilic portion of the molecule to avoid highly polar water solvent and
of the hydrophilic portion of the molecule to associate with
water, as is depicted in Fig. 6. Synthetic metalworking fluids
do not contain any oil, petroleum or synthetic, and are sim-

504

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Polar Group

Nonpolar Group

(Hydrophilic)

(Lipophilic)

Sodium Dodecylbenzenesulfonate - A Common Emulsifier

H,0

H,0

^im

H,0

Micelle
FIG. 6Micellar structure of emulsifier.

ply solutions of organic additives in water. Since most organic materials are hard to dissolve in water, high polarity of
additives is necessary for solubility. Soaps and other surfactants are often added to facilitate solubilization. Because synthetic fluids are oil-free, they have poor lubricating ability
but excellent cooling ability. These fluids are therefore ideal
for high speed machining (metal removal) operations that
generate a substemtial a m o u n t of heat. In these operations,
these fluids are more effective than straight oils. Synthetics
contain fatty amines, fatty amides, or fatty carboxylic acid
salts for rust inhibition (ASTM D 665) and TEFLON and
poly(alkylene glycols) for lubricity. Since these fluids are solutions and not emulsions, they do not suffer from destabilization problems and are useful for high-speed machining
applications. Higher stability is due to their small micelle size
(which also makes them appear cleeir) and low organic content. The micelle size in these fluids typically ranges between
0.005 and 0.015 um. The fluids that do not contain any metal
or amine carboxylates eire suitable for use in combination
with h a r d water.
Synthetics cem be formulated to shed t r a m p oil, i.e. undesirable contaminant oil, for easy skim-off. These fluids cire resistant to bacterial degradation (ASTM D 3946) because of
low organic content and have good work piece visibility because of clarity. The disadvantages include reduced lubricity
due to the absence of petroleum oils; tendency to leave hard
crystalline residues; a n d high alkalinity, higher cost, a n d

greater tendency to foam. The higher cost and the greater


tendency to foam relate to the higher amount of emulsifiers
and coupling agents used to formulate them. F o a m is usuEilly
controlled by the use of foam inhibitors. Sjfnthetics, in addition, are difficult to dispose of because it is not easy to separate organics from water without sophisticated sepciration
techniques. Sodium nitrite (NaN02) corrosion inhibitor in
water is a true solution. It was previously used for applications where effective cooling was the only consideration. The
use of sodium nitrite is being discontinued because of toxicity concerns. Because additives used to formulate these fluids
are synthetic in origin, these fluids are appropriately called
sjTithetic lubricants, or chemical coolants. Synthetics, like
emulsions a n d microemulsions, a r e obtained by diluting
the additive concentrate with water, typically in 1:10 to 1:50
ratio.
Semisynthetic

Fluids

(Microemulsions)

These fluids fall in between soluble oils and synthetic fluids


in terms of their oil content. In every other aspect, they resemble soluble oils. Because of the low oil content, these fluids also appecir clear. However, some semisjrnthetic fluids of
high oil content contain greater t h a n 3.0% oil and are
translucent. As mentioned earlier, emulsion appearance is a
function of the droplet size: the larger the droplet size, the
milkier the appearance. These fluids consist of fine colloidal
dispersions of organic and inorganic materials in water. The

CHAPTER 18: METALWORKING AND MACHINING FLUIDS 505


advantages of these fluids include the abihty to incorporate
both the oil-soluble and the water-soluble chemicals, good lubricity, improved wettability, and easy waste treatment/disposal.
Solid Dispersions
These lubricants contain solids suspended in water or oil.
Most solids are inorganic in origin, although at times orgEtnic
polymers are also used. Dispersions are made by mechanically agitating finely divided solids in the presence of a high
molecular weight dispersant. Common solids used to formulate these lubricants include graphite, molybdenum disulfide
(M0S2), metal powders, metal oxides, metal halides, mica,
and tetrafluoroethylene or TEFLON. Dispersions are hard
to maintain because solid particles are quite large and hence
have an increased tendency to settle. During use, these lubricants form low-shear solid films (films that are easily removed when two contacting surfaces slide) at the tool-work
piece interface, which protect surfaces against metal-tometal contact. The use of these fluids is limited to certain
metal forming operations, such as extrusion a n d forging.
They are reirely used in metal removal lubricants because of
their propensity to settle in the presence of debris. Lubricants
derived from the use of commercial passive EP (PEP) agents,
which are colloidal dispersions, can also be considered to belong to this class.

FLUID CLASSIFICATION BASED


ON END-USE
Metalworking operations generate a lot of heat, which, if not
controlled, will lead to tool damage and inefficiencies in metedworking operations. Metalworking fluids generally cool as
well as lubricate; hence, they Eire often called metalworking
coolants, or lubricant coolants. These fluids are formulated
to fulfill cooling and weeir control needs of specific operations because each differs in these requirements. This meikes
formulation or selection of a m o d e m metalworking lubricant, which meets all process and product requirements, a
complicated task. In addition to cooling a n d lubrication,
other properties sought in a metalworking fluid include appropriate viscosity (ASTM D 445), ability to wet and adhere
to surfaces (ASTM D 2782 ASTM D 5183, D 2783, a n d D
4172), and non-corrosivity to ferrous and non-ferrous metals
(ASTM D 665 and D 130). Metalworking fluids are sprayed or
poured at the metal-tool interface to dissipate heat, lubricate,
protect freshly exposed metal surfaces against corrosion, and
remove debris away from the critical areas.
Metalworking lubricants, based on the mode of their operation, can be classified as meted forming fluids, metal removal fluids, and miscellaneous others. Others include meted
protecting fluids, meted treating fluids, and slideway lubricants. Because these fluids are not directly involved in metalworking, present discussion will largely deal w i t h metal
forming and metal removal fluids, which are of the most predominant type. Metal removal fluids are lubricants that are
used in applications where metal is removed from the work
piece in order to obtain the desired shape. Such applications
include drilling, broaching, turning, grinding, milling.

threading, reaming, boring, and sawing. The primary functions of the lubricant are to cool and to facilitate debris removal. Metal forming fluids Eire lubricants that are used in
operations where metal in the work piece is plastically deformed to obtain the desired shape. Such operations involve
molding of metal by the process of bending, stretching, Eind
pounding. The primary function of a lubricant in these operations is to reduce friction. Lower friction helps in increasing
tool life and in lowering energy usage. Metal forming operations include hot rolling, cold rolling, foil rolling, forging,
wire drawing, tube drawing, deep drawing, ironing, extrusion, and spinning.
Heat removed has an effect on surface finish and cold welding of the tool to the work piece, which affects tool life. The
frictional heat generated during some metalworking operations, depending u p o n meted hardness, can reach temperatures of 1000C or higher. In addition, extensive cutting pressures at points of contact can lead to specific surface loads of
u p to 5000 N/mm'^. Both these factors can cause local welding during cutting. Shearing of welded spots will not only increase the roughness of surfaces, but it will also expose fresh
surfaces that are more prone to welding. Consequently, additional frictional heat will be generated. The function of the
fluid is to dissipate this heat and reduce the number and the
size of the welding spots. Lubrication effectiveness depends
upon the properties of the oil and the presence or absence of
the friction reducing additives. Cooling ability, on the other
hand, is a function of the amount of water present in the lubricant.

Metal Removal Fluids


Metal removing operations are of two types: those where the
work piece is moved against the stationary tool and those
where the tool is moved against the stationary work piece. In
both cases, the tool cuts into the work piece, resulting in chip
formation. These fluids, eJso called metal cutting fluids, are
utilized in operations that are used to remove excess metal on
the way to manufacturing a new part. Both oil and waterbased fluids are used for these operations. Oil-based fluids
can be of petroleum, synthetic, or biological (vegetable and
animal) origin. These fluids are designed to perform four key
functions:
cooling to prolong tool life
lubrication to minimize friction, and hence improve surface finish
facilitate removal of chips eind metal debris
protect freshly exposed surfaces against rust and corrosion.
Heat produced during metal removal is primarily frictioneJ
and the most is generated during chip formation. Additional
heat results from deformation of the metal and during travel
of the chip across the tool surface [10,16]. The primary function of the lubricant in metal removed operations is to reduce
friction as well as remove heat quickly. It must eJso remove
meted debris, resulting from cutting and grinding operations,
away from the work piece. Otherwise, extensive tool wear
will occur. While water is an excellent coolant, it lacks the
ability to reduce friction and wear. Therefore, water-based
fluids contain friction reducing and wear control additives.
Friction reducing additives primarily generate protective sur-

506

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

face films via physical interaction. Wear control additives, on


the other hand, generate such films via chemical reaction.
The former type includes fatty materials, such as vegetable
oils and animal fats, and the latter type includes sulfur, chlorine, a n d p h o s p h o r u s derivatives. The presence of these
additives also minimizes welding of the generated metal debris onto the tool edge, called the "built-up" edge. This not
only reduces blemishing, but it also improves surface finish
of the work piece.
The material used for cutting tools is selected to facilitate
metal (chip) removal. Vibration, metal feed rate, cutting
speeds, and lubricant availability (in the cutting zone) also
play a roll in this process. These factors must therefore be
taken into consideration when selecting tool material. For
high speed cutting operations, steel, special cutting alloys, ceramics, and cermets are commonly used. Cermets are composites that contain ceramics and metals bonded together.
The material hardness increases in the order listed and so
does the generated temperature, from ~ 600C to 1200C.
The geometrical shape of the cutting edge also determines
chip formation, which in turn affects the deformation and
friction zones. That is where the cutting fluid plays a roll by
providing lubrication and cooling, hence controlling wear.
The selection of a proper lubricant is therefore important because it will affect cutting speed, tool life, surface finish, and
precision of the work piece. Tool shape, the depth of cut, and
temperature are also important considerations.
A cutting fluid's ability to reduce friction can be tested by
the use of traditional film-strength test machines. These include the Almen-Wieland rig, the Falex Pin-and-vee Block
tester (ASTM D 2660 and D 3233), the Timken Wear and Lubricant Testing machine (ASTM D 2782), the Four-Ball Test
rig (ASTM D 5183, D 2783, and D 4172), and the SAE #1 Test
rig [13,17]. However, a correlation with field performance is
lacking. Thread tapping tests (ASTM D 5619), used by some
additive suppliers, may also be meaningful in assessing the
efficiency of cutting oils. For cutting operations, one can use

either straight cutting oils; which are mineral oils containing


active chemical ingredients, oil/water emulsions with or
without these ingredients; or aqueous solutions.
The test elements of the most commonly used film strength
machines are shown in Fig. 7. Machines used for these tests
measure the effect of load and temperature on the film-forming ability of the lubricant, as reflected by the friction coefficient and the wear. Results for the newly formulated oils Eire
compared with those of the reference oils to measure their
relative effectiveness.
Because of the differences in test conditions, the results
from different machines are not directly comparable. The Almen-Wieland, Falex, Timken, and Four-Ball test machines
examine the effects of sliding friction only. The SAE #1 tester,
on the other hand, evaluates a lubricant's performance both
under sliding and under rolling conditions.
The Almen-Wieland rig employs a soft steel pin that rotates
in a soft steel split bushing at a constant speed. The load is increased in stages until either seizure occurs or the maximum
load is reached. The Falex tester also uses a soft steel pin rotating at a constant speed b u t differs from the AlmenWieland machine in that the pin rotates between two hard Vshaped bearing blocks, instead of in a soft steel bushing. The
test includes a run-in stage and two stages with increasing
loads.
The Timken machine consists of a rotating cylindrical steel
ring pressed against a steel block. The machine is operated
for 10 min to determine the highest pressure at which there
is no scoring of the rotating ring or the block.
In the Four-Ball tester, a one-half inch rotating steel ball is
pressed against three stationary balls of the same size and
quality. The system of balls is in a holder that contains
enough lubricant to cover the three stationary balls. This
setup provides three small jireas of initial point contact. Because of this, high specific pressures are created at low loads,
which lead to the deformation of the contact surfaces. The
load is increased until frictional heat welds the balls together.

Lubricant

Lubricant

Timken IVIachine

Four-ball EP Machine

Lubricant

SAE Machine
FIG. 7Film-forming test machines.

CHAPTER 18: METALWORKING

AND MACHINING

FLUIDS

507

Helicai Gears

Test Geais

Hydrostatic Pressure
Hydrostatic Pressure
Spur Gears

Ryder Machine

Test Gears

I X

Locl(ed-up Torque
Coupling

Spur Gears

Gleason Machine
FIG. 8Test elements of Ryder and Gleason machines.

Weld load and wear scar diameter as a function of load are


measured. Wear-reducing additives tend to form scars of
smaller diameter, and welding occurs at higher pressures.
The SAE #1 tester consists of two cylindrical rollers that
are rotated against each other at different relative speeds.
The test oil lubricates the lower roller, which is mechanically
driven. The load is increased progressively until failure occurs. The SAE machine simulates both the rolling friction
and the sliding friction. The ratio of the two types of friction
can be changed by changing the rotating speeds of the cylinders.
These tests are the only way to assess the suitability of lubricants for equipment where mixed and boundary lubrication conditions predominate. However, the data obtained
from these tests are subjective. For slideway lubricants, the
data from these tests can be substantiated by testing in FZG
(ASTM D 5182), Gleason, and Ryder Gear Tests [17]. The test
elements of Gleason and Ryder machines are shown in Fig. 8.
Metal removal operations by their very nature (high pressures and temperatures) do not permit hydrodynamic lubrication. Hence, lubricants containing film-forming additives
are usually required. Such additives include friction reducing
agents and extreme pressure agents. The former tj?pe includes fatty acids, their metal salts (soaps), and their esters.

Extreme pressure agents used in metal removal fluids include chlorine, sulfur, and phosphorus compounds. Filmforming additives create physical and chemical protective
films. For materials of moderate hardness and for operations
involving high speeds, friction reducing agents provide the
necessary performance. These chemicals react with metal either at ambient temperature or at high temperatures to form
metal carboxylate films (see the Film-forming Agents section
for a detailed discussion). However, for difficult-to-cut materials and operations involving high pressures and slow
speeds, extreme pressure agents are needed. These additives
form protective films via chemical reaction.
The selection of a proper lubricant depends upon the nature of the metal and the severity of the cutting operation. In
general, operations that employ low cutting speeds place a
higher demand on the lubricant than those that employ high
cutting speeds. Figure 9 shows the relative severity of different cutting operations and the demand they place on the lubricant [10,18].
Tool Wear
Besides the severity of the machining operation, tool wear is
also a function of the quality of the cutting fluid and the
machinability of the metal. Cutting fluid is essential to mini-

508

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

BROACHING

TABLE 3Attributes of tool materials.


Tool Material

Attribute

TAPPING

Carbon steel

THREADING

High-speed
steel (HSS)

Short service, limited effectiveness, loses


hardness at relatively low temperatures
Maintains high cutting edge at high
temperatures, contains tungsten (W),
molybdenum (Mo), chromium (Cr),
cobalt (Co), vanadium (V)
Cobalt-based, more brittle than HSS, fills
the gap between HSS and carbide tools
Carbide-based, extremely hard, lack
strength and toughness (need good
support), not used where there is heavy
vibration or shock
Cemented metallic oxides, hardness close
to diamond, do not pick up heat, are
brittle and therefore chip easily
Hardest of all abrasives, large stones are
used in dressing tools, small stones are
used in grinding wheels

GEAR SHAPING
REAMING

Cast alloys

DRILLING

Cermets

MILLING
TURNING
FIG. 9Relative severity of metal-removal operations.

mizing wesir and equipment damage. Common types of wear


that can occur in cutting tools due to lubricant failure are as
follows.
Adhesive wearWelding between the tool surface and the
work piece surface can occur due to high local temperatures. On shear, these spots Ccin either produce metal debris or result in metal transfer from the tool to the work
piece. This kind of damage is more likely to occur at low
cutting speeds.
Abrasive wear occurs when fragments of cutting or wear
debris embedded in the chip abrade the rake face of the
tool.
Diffusive wear occurs when metal atoms from one crystal
lattice diffuse into the crystal lattice with lower atomic
density (concentration). This type of wear is likely when
tools m a d e of h a r d material are used to machine softer
metals, for example during the use of tungsten carbide
tools.
Corrosive wear results from the attack of atmospheric oxygen or of the decomposition products from antiwear and
extreme pressure additives on the tool surface. Such additives include chlorine, sulfur, and phosphorus-containing
chemicals.
Premature wear is the progressive loss of tool material at
the tool-work piece interface and occurs due to plastic flow
of metal at high temperatures.
Machinability primarily relates to metal hardness, although other factors, such as cutting speed, tool strength,
and p o w e r consumption, also play a role. In general, the
harder the metal, the greater the tool wear. It is therefore important to select proper tool material for the job at hand.
Commonly machined materiEils include steels, both alloy and
stainless; cast iron; aluminum and its alloys; magnesium and
its alloys; copper and its alloys; nickel and its alloys; heat resistance alloys that contain nickel, chromium, molybdenum,
tungsten, and titanium; and plastics. Tool materials include
carbon steel, high-speed steel, cast cJloys, ceramics, cermets,
and diamonds. The attributes of various tool materials are
provided in Table 3 and the characteristics of the metals machined are provided in Table 4.

Ceramics
Diamonds

Of the metals listed, ferrous metals such as carbon steel,


low alloy steel, and stainless steel, and eduminum are the
largest volume metals machined. Copper, brass, and titan i u m are the next group, followed by nickel-based alloys,
cobalt-based alloys, magnesium, zinc, tin, beryllium, zirconium, tungsten, molybdenum, tantalum, uranium, and vanadium. The order with respect to ease of machinability, from
the easiest to the most difficult, is as follows:
Magnesium

(Mg) and its alloys < zinc (Zn) and its alloys

< brass < aluminum

(At) and its alloys < cast iron (Fe)

< bronze < copper (Cu) < carbon steel < alloy steels
< stainless steel < nickel (Ni) alloys
< titanium

(Ti) and its alloys

Because metalworking operations involve both the p u r e


metals and the alloys, selection and use of an appropriate lubricant is a complex process.
Operation severity is a function of the cutting speed. In
general, operations with low cutting speeds, such as broaching and tapping, are more severe than those that have high
cutting speeds, such as turning and milling. Drilling a n d
reaming fall in between the two extremes in terms of severity. High severity at low speeds is because at these speeds
metal-to-metal contact is more extensive (boundary lubrication) than at high speeds, which promote hydrodynamic lubrication. Consequently, there is a greater need for extreme
pressure agents a n d anti-weld additives in the former case
than in the latter case, where either lubricant viscosity or friction-reducing additives suffice. Since good cooling and good
lubrication are not easy to obtain in the same fluid, water or
microemulsions (semisynthetic fluids) are used for operations that require more cooling. And, the use of straight oils
is preferred for operations that require better lubrication.
The majority of operations require both cooling and lubrication. Hence, macroemulsions (soluble oils) that contain
substcinticJ amounts of both organic and aqueous portions
are often employed. The operating range of these fluids is enhanced by the supplemental use of fatty additives. For a cutting fluid to perform effectively, a careful consideration of its

CHAPTER
TABLE 4Machining characteristics of machined metals.
Machined Metal

Steels
Free Machining
Alloy steels

Stainless steel
Cast Iron
Gray cast iron
Malleable cast iron
Nodular iron
White cast iron
Wrought iron
Aluminum and its alloys
Magnesium and its alloys

Copper and its alloys


Single phase alloys, such
as bronze, coppernickel, copper-silicon
Alloyed copper, leadbronze, tin-bronze,
naval brass, aluminumbronze
Alloys that contain
substantial amounts of
alloy materials
Nickel and its alloys
Pure nickel
Incone (nickel-chromiumiron alloy)
Hast alloy (nickel-copper
alloy containing small
amounts of iron,
molybdenum and
chromium)
Monel (nickel-copper
alloy)
Nickel-silver aDoy
Heat Resistant alloys
Contain nickel, chromium,
molybdenum, and
titanium
Plastics

Characteristics

Modified for machinability with added


phosphorus or sulfur
Contain chromium (Cr), cobalt (Co),
nickel (Ni), molybdenum (Mo),
tungsten (W), vanadium (V), singly
or in combination; more difficult to
machine
Difficult to machine because of high
chromium (Cr) and or nickel (Ni)
that work harden
Machines easily
Machines easily
Machines easily
Hard to machine
Hard to machine
Machine easily relative to carbon steel;
pure aluminum may be gummy
Excellent machinability; chemically
reactive hence use of water or acidic
materials in the fluid must be
avoided
Hard to machine
Medium machinability

Free machining

Good machinability

Draggy and difficult to machine


Hard to machine and hence need
heavily additized cutting fluids
Thermoplastics melt and thermosett
plastics char at low temperatures,
hence cooling is most important.
Soluble oils are often used.

cooling and lubricating requirements is essential. High-speed


cutting operations, such as turning, milling, and drilling, result in higher temperatures, hence cooling ability of the fluid
is critical. Water is an excellent coolant but has little or no lubricating ability. However, this deficiency is overcome by the
use of friction reducers and EP agents, which are entrained
into water by the use of wetting agents and emulsifiers. On
the other hand, low-speed operations such as broaching and
tapping experience high friction, and consequently lead to

18: METALWORKING

AND MACHINING

FLUIDS

509

heavy tool wear. Therefore the lubricants for these operations require the use of extreme pressure additives [19a]. A
new technique, called dry machining, is presently being explored. The purpose is to eliminate purchase, handling, use,
and disposal costs. Since this technique does not use any lubricant, it involves high temperatures. Thus far, the technique has been applied to boring operations. Efforts are underway to extend it to drilling operations [19b].
The depth of cut and surface finish are additional considerations for fluid selection. Low-speed operations where cuts
are deep and good work piece finish is important; the lubricity of the fluid is critical. The use of straight oils is therefore
appropriate. For high-speed operations that involve shallow
cuts, quick heat dissipation is desired. This makes microemulsions or micellar solutions the lubricants of choice.
In most cases, the fluid is applied under pressure into the cutting zone, which is to reduce friction, minimize metal transfer, and maximize cooling.
Metal Forming Fluids
These fluids are used for operations that depend on plastic
flow of the metal. Such operations include rolling, extrusion,
drawing (drawing tubes, tube bending, deep drawing, wire
forming), forging, and sheet metal forming. Some of these
operations involve both ambient temperatures (cold working) and high temperatures (hot working). Metal forming
processes can be distinguished as being steady-state or nonsteady-state [16], each type with different lubrication requirements. In steady-state processes, such as rolling, it is
possible to lubricate the surface of the work piece during its
approach to the deformation zone. However, in non-steadystate processes, such as sheet metal forming, the lubrication
is not usually possible because of the nature of the operation,
and one must depend upon the pre-applied lubricant film.
Some processes, such as long billet extrusion, have cheiracteristics of both; that is, n o lubricant application during certain parts of the operation and lubrication during other parts
of the operation.
The primary functions of a lubricant during metal forming
operations are to reduce friction, which lowers energy consumption; and to minimize wear, which increases tool life.
Friction reduction, in addition, facilitates the release of the
forged part from the die and improves surface finish of the
work piece. However, too m u c h friction reduction is undesired because it can lead to slippage and hence make the operation inefficient.
Common metal forming lubricants include:
mineral oilscompounded oils (blends of mineral oils and
fatty oils)
synthetic oils and estersfatty acids and their derivatives
lanolin, tallow, and paraffin waxesaqueous solutions and
emulsions
polymer
solutionsdispersions
containing graphite,
molybdenum disulfide (M0S2), salts, glass, bentonite, lime,
mica, and talc
Additives for these lubricants include fatty acids and fatty
compounds, extreme pressure agents (sulfurized and sulfochlorinated fats and oils), emulsifiers, coupling agents, inorganic solids, and dispersants.

510

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Miscellaneous Fluids
Metal Protecting

Fluids

These fluids, also called preservative oils, help protect freshly


exposed metaJ surfaces against air, water, and corrosive materials. While most of these fluids cire oil-based, the use of water-based fluids is gaining popularity because of the lower
cost, ease of disposal, environmental compatibility, and reduced volatile carbon content.
Metal Treating

Fluids

These fluids Eire used for heat-treating operations, such as


quenching and tempering. They act as heat transfer agents
and can be oil-based or water-based. The base oils to formulate these fluids can be synthetic or petroleum in origin. The
performance specifications of these fluids are established by
OEMs Eind the end-users. Synthetic fluids, due to their superior fire resistcmce and fewer disposed concerns, Eire replacing
oil-based formulations.
Slideway

Lubricants

These lubricants are used to lubricate slideways and the accompanying pneumatic equipment. Slideways are guiding
surfaces on the bed of a machine along which a table or a carriage moves. Since surfaces that slide over each other are flat,
the area of contact is large. This leads to increased adhesive
wear. These devices in addition experience motion of varying
speeds, which causes sticking and slipping of the sliding surfaces. After wear-in, opposing surfaces form an even closer
fit, which squeezes out and wipes away any lubricant that is
in the path of motion. Essentially, a boundary lubrication
condition exists. This type of lubrication to a degree is by design; otherwise, excess lubricant would form a hydrodynamic
wedge that will interfere with the motion of the plane.
BoundEiry lubricated surfaces will adhere to each other, especially during slow speed operations. Adhesion occurs when
the static friction either equals or exceeds the force of motion. If adhesion is followed by movement due to the applied
force, the p h e n o m e n o n is called stick-slip. Regular occurrence of stick-slip causes not only vibration Eind noise but
also damage to the work piece, tool, and rider and way.
Slideway lubricants perform at extreme t e m p e r a t u r e s ,
high loads, moisture, and poor ambient air quality. They
must therefore possess both the EP activity EUid the rust and
corrosion-inhibiting properties. These lubricants are formulated with friction reducers, primarily fatty carboxylic acid
derivatives that minimize stick-slip, and extreme pressure
agents that control wear damage resulting from boundary lubrication conditions. Operation at extreme t e m p e r a t u r e s
leads to oxidative breakdown of the lubricant. This must be
avoided; otherwise, poor lubrication and corrosion will result. This is accomplished by the use of oxidation inhibitors.
It is important to note that stick-slip control requires combining proper machine design and superior lubricant quality.
Since the oil is removed due to the wiping action of the
slide, lubricant is supplied at different points along the slide
route. Suspended metcJlic fines or chips in the lubricant can
lead to scratching, gouging, or abrading of the ways. The use
of a properly formulated lubricant can minimize this type of
damage, as well as control friction, chatter (noise), and stickslip. Despite the fact that lubrication is often once through.

a n oil circulating system may also b e used to deliver the lubricant at different points along the slide.

FLUID COMPOSITION
Metalworking fluids are composed of a base fluid and a collection of chemicals. While base fluid makes u p the bulk of
the formulation, it lacks the properties necessary to act as an
effective lubricant. Hence, chemical compounds, called additives, are used to either fortify the base fluid's existing properties or add new properties [20]. Because of the diversity of
lubrication requirements in metalworking operations, the
type and the quantity of additives differ from operation to operation. The quality and quantity of additives cdso depend
upon the type and properties of the base fluid.
Base Fluid
The base fluid in metalworking lubricants can be biological
(animal or vegetable) in origin, petroleum-based (mineral
oil), synthetic-based, or water. Structures of some of the
basestocks used to formulate metalworking fluids are shown
in Fig. 10. The detailed description of these basestocks is provided in Chapters 7 and 10 of this manual.
Straight oils use severely refined and hydrotreated mineral
oils and synthetics, such as polyalphaolefins (PAOs), polybutenes, ethylene oxide-propylene oxide polymers (polyalkylene glycols or PAGs), and organic esters. For water-based
fluids, naphthenic oils are preferred because of ease of emulsibility and because of their superior viscosity-pressure relationship (discussed earlier). For straight oils, however, paraffinics are the base oils of choice. Synthetic basestocks are less
popular than mineral oils, primarily due to their higher cost.
However, the use of these stocks is increasing in fluids where
tailored properties are desired and petroleum basestocks are
not effective.
Polyalkyleneglycols, prepared by polymerizing ethylene
oxide-propylene oxide (EtO/PrO) mixtures [21], are extensively used in metal removal lubricant formulations. Desirable properties Eire obtained by controlling molecular weight,
altering terminal groups, and the EtO/PrO ratio. Higher
molecular weight materials have higher viscosities a n d
higher EtO/PrO ratio products have higher water solubility.
One can even alter the EtO/PrO ratio to devise materiEils that
are water-soluble at low temperatures but are water-insoluble at high temperatures. This property is useful in formulating fluids that are clear during circulation but separate
polyalkylene glycol (and additives) at the hot tool-work piece
interface during use.
Polyisobutylenes, obtained by polymerizing isobutylene
[21], have the tendency to depolymerize at high temperatures. This makes them useful in rolling and drawing oils for
ferrous and nonferrous metals, where petroleum oil derived
lubricants cause staining during subsequent annealing process. Polyalphaolefins, often not used in metalworking fluids,
possess certain attributes that make t h e m desirable. These
include effectiveness over a wider temperature range and
lower hydrocarbon (HC) emissions t h a n petroleum oils of
similar viscosities. Polyalphaolefins are also highly resistant
to oxidative and thermal degradation.

CHAPTER 18: METALWORKING


H2
^'Cv^

H2
/C>^

H2
^C^

H2
/ ^ \

H,

H,

^C
H,

FLUIDS

511

Paraffinics

CH,

CH
H,C.

^CH,

^CH,

H,C

H3C'

H2
C^

H2

CH.

CH,

H2
,C^

H2
/^"^

AND MACHINING

CH3
H2
H2
H2
I
H2
^ C ^ ^C^
^O^
CH.
^C~^
CH
CH
CH
CH
CH
CH3
Naphthenics
CH3 HoCs. ^^''2
CH
/

H,C\

H2C

CH
\
H2C

Crl2
A
HoC

CHo
\
CH3

CH,

/
H,C

CH3
CH, C H -(-CH2 C H

-cac

CH3
Polyisobutene

-^CHj

-CH,

R = C4H11; CgH-is; C8H17


Polyalphaolefins

//

CH20C^

II

RO C(CH2)n C O R
R=C8 TO C-13

' ,

-^
CH3CH2C CH2OC R
CH2OC

Alkyl Carboxylate Ester

RO

(CH2 C H 0 ) n H

R=C5 TO C10

//
R

Polyol Ester

R = Linear or Branched Alkyl Group

R=C2 TO C3
Polyalkylene Glycol
FIG. 10Basestocks used in metalworking fluids.

Polyalkylated cyclopentanes are a new class of synthetic


hydrocarbons that are promising in terms of future formulations [10]. Their properties can be varied over a wide range
by varying the number euid the nature of the alkyl groups.
They have low pour points, high viscosity indexes, and exceptionally low volatility. Other types of synthetic basestocks
find limited use in metalworking applications.

Additives
Additives used in metalworking fluids can be broadly classified into chemically inert and chemically active. Chemically inert additives primarily alter the physical properties
of the fluid, such as lubricity and surface tension. Such additives include emulsifiers, coupling agents, friction reduc-

512

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

ers, rust and corrosion inhibitors, foam inhibitors, and antimicrobial agents. Chemically active additives, on the other
hand, alter the chemical properties of the fluid, such as oxidation susceptibility. This group of additives includes some
friction reducers, extreme pressure/antiwear agents, and
oxidation inhibitors. Common types of additives that are
typically used in metalworking fluids are provided in Table
5. Their chemistry and mode of their action are also summarized.
Emulsion

Promoters

These additives facilitate the formation of emulsions and


contribute to their stability. These include emulsifiers and
coupling agents.
Emulsifiers are chemicals that are used to emulsify (solubilize) organic additives and or mineral and synthetic oils in
water. These are used to create soluble oils, synthetics, and
semi-synthetics, all of which are water-based lubricants.
Emulsifiers contain functional groups that have the capability to associate with water as well as oil. These additives tend
to be situated at the boundary between oil and water (the
oil-water interface), where they help reduce the interfacial
tension and make the two phases miscible to form a stable
emulsion. Emulsion formation requires some kind of mixing
or stirring.

Emulsifiers are classified as nonionic or ionic, depending


upon whether the polar part is uncharged or charged. Ionic
c o m p o u n d s can be subdivided further into cationic if the
charge is positive, and anionic if the charge is negative [22].
Nonionic emulsifiers that are often used in metalworking fluids include carboxylic acid a m i d e s and esters, polymeric
ethers (polyglycol ethers), esters of polyhydric alcohols, and
alkoxylated alkylphenols. Anionic emulsifiers include metal
salts, primarily sodium, of carboxylic acids, alkyl phosphoric
acids, and sulfonic acids (both natural and sjmthetic). Because of the lower cost, these emulsifiers aire used as generalpurpose additives. Cationic emulsifiers include mineral acid
salts of amines and imidazolines. It is important to note that
only the charge on the functional group attached to the carbon chain is used in this classification. The charge on the
counterion, which is usually inorganic in origin, is ignored.
The term amphoteric applies to a group of additives, which
contain cationic and anionic groups of organic origin, preferably within the same molecule. They possess structural features and properties of both the cationic and the anionic materials grouped together. These surfactants are practically
never utilized in metalworking fluid formulations. Compounds that find extensive use as emulsifiers include:
alkali metal (primarily sodium) sulfonates, both petroleum
and synthetic

TABLE 5Metalworking fluid additives


Additive Type
Water-based fluids
Alkalinity buffers/pH
Antifoam agents
Antifungal agents
Antimicrobials/preservatives

Control
Prevent
Control
Control

Metal passivators
Couplers
Emulsifiers

Prevent staining and leaching of yellow metals


Emulsion stability
Emulsify organics in water

Extreme pressure/lubricity agents

Form heat-resistant chemical films that


reduce friction

Odor masks
Thickeners
Corrosion and rust inhibitors

Suppress odor
Improve viscosity
Control oxidative and corrosive damage to
metal surfaces and tools

Oil-based fluids
Antifoam agents
Anti-misting agents
Corrosion and rust iniiibitors
Demulsifiers
DispersEints
Extreme pressure/lubricity agents

Odor masks
Thickeners
Solid lubricants

Function
bacteria-derived acidity
foam
fungal growth
microbial growth

Prevent foam
Suppress mist formation
Control oxidative and corrosive damage to
metal surfaces and tools
Facilitate water separation and facilitate
removal of tramp oil via skimming
Prevent agglomeration of material particles
that result during cutting and grinding
Form heat-resistant chemical films that
reduce friction
Suppress odor
Improve viscosity
Improve film strength

Typical Compounds
Amines and inorganic bases
Silicones, silicates, and stearates
Sodium omadine
Triazines, omadine, phenol, oxazolidines,
and imidazolines
Triazoles
Glycols, glycol esters, and alcohols
Sodium and lithium sulfonates;
poly-ethoxylated phenols, alcohols and
acids; metal and amine carboxylates
(soaps of fatty acids)
Fatty acids, fatty amides, fatty esters, and
fatty acid salts (soaps); phosphates; sulfur
and chlorine containing compounds
Natural and synthetic aromatic compounds
Polyacrylate esters and glycol esters
Carboxylic acid salts, amides, and amines
Silicones, polymethacrylates, and stearates
Polyisobutenes and other natural and
synthetic polymers
Metal sulfonates and phosphates; organic
acids and esters; and triazoles
Cationic and non-ionic polymeric surfactants
Polyamides and metal sulfonates
Fatty acids, fatty amides, fatty esters, and
fatty acid salts (soaps); phosphates; sulfur
and chlorine containing compounds; basic
sulfonates
Natural and synthetic aromatic compounds
Polyacrylate esters
Graphite, molybdenum disulfide,
Poly(tetrafluoroethylene)-PTFE
(TEFLON)

CHAPTER 18: METALWORKING


alkali metal carboxylates
alkoxylated alcohols, phenols, fatty amines, fatty acids, and
fatty amides
sulfated fatty oils
Generalized structures of some of the common emulsifiers
are given in Fig. 11.
Emulsifiers reduce the interfacial tension of the water-organic (oil) interface therefore facilitating thorough mixing of
oil and water to form an emulsion. The efficiency of an emulsifier depends upon its molecular weight (usually less than
2000), its HLB (hydrophile-lipophile balance) value, water
pH and hardness, the nature of the oil, and the operating conditions, such as temperature. HLB scale spans zero (0) to
greater than 30. The higher numbers mean oil compatibility
decreasing and water compatibility increasing. Emulsifiers
of HLB of greater than 13 generally lead to clear water solutions. Emulsifiers with an HLB of 3 to 6 are suitable for water-in-oil emulsions and those with an HLB of 8 to 18 are suitable for oil-in-water emulsions. The manner in which these
additives form emulsions is shown in Fig. 5.
Water-in-oil emulsions form when these additives associate with water via their polar ends and with oil and other additive molecules via their nonpolar ends. This is shown in
part A of Fig. 5. The result is water miscibility in oil, or water-in-oil emulsion. The mechanism of oil-in-water emulsion
is similar, except that the additive molecules associate in the
reverse manner. This situation is shown in part B of Fig. 5.
As a general rule, nonionic emulsifiers are used in metalworking fluids based on naphthenic stocks, and fatty acid
carboxylates are used in those based on paraffinic stocks.
Polyalkylene glycols (hydroxyalkyl ethers) are sometimes
avoided because their enhanced solubility in water does not
allow clean separation for disposal. As mentioned ecirlier, alkali metal salts (soaps) of carboxylic and sulfonic acids are
among the most commonly used emulsifiers. However, metal
ion exchange with calcium and magnesium, whose salts are
present in hard water, degrade emulsions by removing these
soaps as insoluble calcium and magnesium salts. Non-ionic
emulsifiers lead to emulsions that are less sensitive to hard
water.

NON-IONIC

-P
RCs

R0{CH,CH,0),CH,CH20H

^CHjCHjOH
RN,
CH2CH2OH

Polyethoxylated Alcohol
(Hydroxyalkyl Ether)

Dialkanolamjde

,p
RC^
0(CH2CH20),CH2CH20H

CHjOH
I
CHOH

Fatty Diethanolamine

AND MACHINING

FLUIDS

Some emulsifiers show mild anti-rust performance (ASTM


D 665). Since emulsification is a liquid phase phenomenon
and the rust inhibition occurs at the liquid-solid interface,
optimizing both these properties is not easy. One can obtain
both the emulsification and the anti-rust performance by altering the hydrocarbon chain length in the emulsifier
molecule. However, in many cases, this strategy is not very
effective and it is necessary to improve the anti-rust performance by the use of supplemental additives. The common
ones include sodium nitrite, borax, boric acid amides and esters, alkanolamines, and alkanolamides. The use of sodium
nitrite is decreasing because it can form nitrosamines, which
are suspected carcinogens (cancer-inducing agents).
Coupling Agents (Couplers)
Some additives that need to be emulsified have greater solubility in water than in oil. Consequently, they are not easy to
formulate into emulsifiable oil concentrate (package) without the presence of a large amount of water (as much as
50%). Coupling agents facilitate emulsification of water into
the base oil, emulsifier system, and other additives. In the
long term, these additives maintain emulsion stability. Common coupling agents are low molecular weight alcohols, glycols, and triols, which become part of the non-oil portion of
the package. This decreases the need for the large amount of
water necessary to solubilize additives thereby improving
emulsification. It is important to note that although these
components are organic in nature, they impart little or no lubricity to the final fluid.
Structures of some of these additives are given in Fig. 12.
Also, see Fig. 11. Common examples of these additives include:
fatty alcohols, such as tridecyl alcohol
glycols, such as ethylene glycol, diethylene glycol, and
propylene glycol
glycol ethers, such as propylene glycol monomethyl ether
and hexylene glycol monomethyl ether
fatty acids, such as caprylic acid, isononanoic acid, and
neodecanoic acid
nonionic surfactants, ethoxylated alcohol, nonylphenol
ethoxylates, and polyethylene glycol esters
Film-forming Agents
This type of additives includes friction modifiers (also called
film-strength additives, oiliness additives), antiwear and extreme pressure agents (also called boundary additives, loadbearing additives), and corrosion inhibitors.

0(CH2CH2O)xCH2CH2OH

CHjOH

CH20-C-0leyl

Polyglycol Ester of a Fatty


Carboxylic Acid

Glycerol Monooleste
(GMO)

/
H3CCHI
\ OH

CHjOH
CH2OH

Alkylphenol Ethoxylate

/
HjC

Ethylene Glycol Monomethyl


Ether

ANIONIC

00

OCH3

I
.0.

Rct0
O NHECHjCHjOH],
H,C^

Sodium
Carboxylate

Trlethanolamlne Salt of a Fatty Acid

^^^^^ Alkyll^nzenesulfonate

R = Fatty Hydrocarbon Group

FIG. 11Commonly used emulsifiers.

OH

I
,0

\ ^ C ^
H H,

H,C.
OH,

\
CH,

Hexylene Glycol Monomethyl Ether

CH2OCH3

OH

Propylene Glycol

Ethylene Glycol

"^"^cPwa

513

CH,

t?

OH

Isononanoic Acid

FIG. 12Commonly used coupling agents.

514

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

Lubrication is necessary to facilitate the counter movement of two sliding surfaces. This function, which is usually
performed by the base fluid, can be enhanced by the use of
high viscosity oils, friction modifiers, or extreme pressure
(EP) and antiwear (AW) agents. Since water is a poor lubricant, the lubricity in water-based fluids is achieved by the use
of friction modifiers, also called the lubricity agents, and or
EP agents. These additives improve lubrication ability of the
metalworking fluids by forming m o n o m o l e c u l a r physical
and chemiccJ films at the tool-work piece interface, which
minimize metcJ-to-metal contact.
Film-forming agents are extremely surface active because
of a high polar-nonpolar ratio. The polar-nonpolar ratio in
additives is discussed in detail in Chapter 9 on Additives and
Additive Chemistry. These additives typically contain hydrocarbon groups of 10-18 carbon chain size and very polar
functional groups. Therefore, they, have the tendency to separate on surfaces, where they interact by a physical or a
chemical m e c h a n i s m . Modes of interaction of additive
molecules with surfaces [23] are depicted in Fig. 13.
Physical adsorption, or physisorption, is a weaker association of the additive with metal than chemical adsorption, or
chemisorption, which in turn is weaker than chemicsd reaction. During adsorption, a n additive molecule generally
keeps its structural integrity and involves no bond breakage
or bond formation. This is t5rpical of additives, such as natural fats and oils, which have a low reactivity towards metals.
However, when the temperature reaches beyond a certain
threshold temperature, these additives desorb and the fluid
loses its friction-reducing properties. The result is wear damage. Chemical adsorption, on the other hand, requires some

Additive (Molecule

Metal Surface

Physisorption

Chemisorption

o o o o o o
o o o o o o
Chemical Reaction
FIG. 13Modes of additivesurface interactions

reactivity of the additives towards metal and involves limited


bond breakage and bond formation. This situation occurs in
the case of fatty alcohols and fatty acids that react with the
metal surface to form metal alkoxides and metal carboxylates, respectively.
One c o m m o n feature of this class of additives is the presence of a fatty hydrocarbon chain (long linear chain). In addition to fatty alcohols and acids, this class includes fatty esters, natural and synthetic; fatty amides; fatty amines; and
fatty alcohol derived alkyl acid phosphates. Those used most
often include animal and vegetable oils (commonly called
triglycerides), alkyl and polyol esters of fatty acids, ethylene
oxide/propylene oxide polymers, TEFLON, alkanolamides,
and mono, di, and tri-ethanolamine salts of carboxylic acids.
The structures of these additives are shown in Fig. 14.
A greater degree of protection is needed in applications,
such as metal removal operations, which generate high temperatures. This is because physically a n d chemically adsorbed additive films are easy to remove. That is where extreme pressure/antiwear agents become important. These
additives chemically react with metal surfaces to form a more
tenacious protective film. The process involves extensive
bond breakage and bond formation via complete breakdown
of the additive. These additives are primarily organic compounds of chlorine, sulfur, and phosphorus.
The extent of EP protection in the equipment depends
upon the conjunction temperature of the two metal surfaces
in contact [2]. Figure 15 shows a direct correlation between
the conjunction temperature and the degree of EP protection
needed. Conjunction temperature is the temperature of the
two surfaces in contact and determines the type of additives
needed for protection. It is important for the activation temperature of the EP additives to match the conjunction temperature in order to provide the necessary protection. The effective t e m p e r a t u r e ranges of different tj^pes of additives
when used in metalworking applications [16] are provided in
Table 6. Equipment that operates at low speeds and high
loads generally requires more EP protection than equipment
that operates at high speeds and low loads. This is because
the former t5rpe of operation involves more metal-to-metal
contact, which generates higher temperatures as a consequence of increased friction.
As mentioned before, extreme pressure agents are primarily organic compounds of chlorine, sulfur, and phosphorus,
although sometimes boron and sulfur-nitrogen compounds
are also used. Chlorine c o m p o u n d s include chlorinated
olefins and paraffins, and chlorinated fatty acids and esters.
Sulfur c o m p o u n d s include alkyl polysulfides, sulfurized
olefins, and sulfurized fatty acids and esters of both natural
and synthetic origin. Overbased sodium and calcium sulfonates, called PEP (passive extreme pressure) agents, and
molybdenum disulfide (M0S2) are two other commonly used
sulfur-containing EP additives. Phosphorus derivatives include phosphites and aliphatic and aromatic alkyl phosphoric acids (phosphate esters) and their salts. Some EP agents
contain both sulfur and chlorine and others, such as dialkyl
dithiophosphoric acid derivatives, contain both sulfur and
phosphorus. Dithiocarbamates, on the other hand, contain
both sulfur and nitrogen. However, sulfur derived fluids suffer from being odorous and supporting biological growth.
Chlorine derived fluids, on the other hand, are unsuitable for

CHAPTER 18: METALWORKING AND MACHINING FLUIDS 515

>

,C^OCH,

Rc;

< .

\ ;cocHa

OR'

Alkyl Carboxylate
or Vegetable Oil
R' Methyl or Higher Alltyl G r o u p
R ^ Fatty Hydrocarbon Chain

H,

H,

II
C

CH2 H2C

/\

II
HO-J-CHjCHjo4-4-CH2CHojH

Ethylene Oxide - Propylene Oxide Polymer

Pentaerythritol Carboxylate

J'"
NECHjCHjOHJz

Dialkanolamide

HNECHjCHjOHh

0
Triethanolamine Salt of a CarboxylJc Acid

FIG. 14Commonly used friction modifiers.

400-

O
S_-35C

3
(U 30C

Q.

0)
I-

msm

C 250

_o
^
o
c

,3
'B20C

o
O

IJI.hBdd

150

Temperature [2]
FIG. 15Extreme Pressure (EP) protection versus conjunction temperature.
TABLE 6Effective temperature range of lubricity agents and
EP/AW agents.
Additive Type

Carboxylic acids, esters, and metal salts (soaps)


Chloropraffins and other chlorinated derivatives
Organophosphorus compounds, such as
phosphoric acids and their derivatives
Organosulfur compounds, such as polysulfides

Effective
Temperature Range

< 200C
180^50C
200-700C
600-1000C

use in working a l u m i n u m . Representative structures for


some of the compounds that are used as EP agents are presented in Fig. 16.
In all cases, active elements chlorine, sulfur, and phosphorus react with metal to form metal halide, meted sulfide, metal
phosphite, metal phosphate, and metal phosphide protective
films. These films are effective only below the eutectic point
or the decomposition temperature of these salts. Chlorine
compounds can lead to metal corrosion by hydrogen chloride,
which results from their hydrolysis. Hence, this must be taken
into account prior to their use in cutting oils. In view of their
effective range, sulfur compounds are used in heavy-duty and
extra heavy-duty cutting operations. Metal sulfide films app e a r to have a higher load-carrying capacity and shear
strength t h a n carboxylic acid soaps and metal phosphates.
Film formation by these additives occurs by a two-step
mechEinism: adsorption on the metal surface and thermal decomposition and reaction with the metal surface because of
frictional heat. The resulting metal Scilt films have low coefficients of friction and also demonstrate anti-weld properties,
both of which minimize tool wear. Metal chloride films have
a transition temperature of ~ 600C and metal sulfide films
have a transition temperature of ~ 1000C. This makes organic sulfides better extreme pressure additives than organic
chlorides, because sulfide films can endure higher temperatures before becoming soft and getting removed. Chlorinated
fats, chlorinated esters, a n d chlorinated paraffins are the
common organic chlorides used in formulating metalworking fluids. Sulfurized fats, sulfurized oils, sulfurized paraffins, dissolved sulfur, and sulfochlorinated products are the
common organic sulfides used. The sulfur in these additives
is of two types: active and reactive. Active sulfur is the dissolved or easily releasable form of sulfur, which has the tendency to corrode yellow metalsa low temperature reaction.
Because of this, the presence of active sulfur in the metcJworking fluid formulation is of concern. On the other hand,
reactive sulfur is the bound form of sulfur, for example as a
sulfide or disulfide, and is released or reacts with metal only
at high temperatures.
Because of the reactivity of sulfurized hydrocarbons towards copper, bronze, and other non-ferrous metals, and the
tendency of chloropareiffins to corrode metal via hydrolysis
or thermolysis, the need for new extreme pressure agents exists. New extreme pressure technology based on overbased
alkylbenzenesulfonates a n d carboxylates, which does not
suffer from these drawbacks, has recently become available.
Such additives, called passive EP agents, are believed to function by forming a metal carbonate film at the tool-work piece
interface. The high effectiveness of these additives in cutting,
tapping, a n d threading operations suggests a n alternative
mechanism. That is, the high pressures at the tool-metal interface convert amorphous calcium carbonate, present in basic sulfonates and carboxylates, into crystalline salts that facilitate metal removal. The films formed are of low shear
strengths and high melting points. These additives do not
contain phosphorus, reactive sulfur, or chlorine but are synergistic with sulfur-containing E P additives. In addition, they
are less corrosive, easier to dispose of after use, cause little or
no foam, and are easily removed from the work piece surface.
They can be used both for ferrous and nonferrous metals,
which is an added benefit.

516

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Dispersants

Corrosion

These additives are mainly used to suspend inorganic solids,


such as graphite and molybdenum disulfide, in specialty lubricants and include high molecular weight alkenylsuccinimides, alkylsalicylates, and alkylbenzenesulfonates. The
structures of these additives are shown in Fig. 17.

These additives are of two types: film-formers axid acid (corrosive component) neutralizers. Film-formers protect against
corrosion by forming physical films on metal surfaces. Acid
neutralizers control corrosion by neutralizing acidic species
either present in a lubricant or produced during use. The selection of these additives depends upon the fluid type and the
metal to be protected. For straight oils, overbased metal sulfonates are used to protect against iron corrosion (ASTM D
665 and D 4627).

Anti-misting

Agents

Some metalworking operations generate mist, which is not


only of concern because of worker safety, but it also leaves an
undesirable oily residue on parts and equipment. Anti-misting agents are polymeric thickeners that are used to minimize mist generation in mineral oil derived fluids. These additives control mist formation by modifying droplet size and
include ethylene-propylene copolymers, polyacrylates and
polymethacrylates, polyacrylamides, polybutenes and polyisobutenes, polystyrenes, and styrene-butadiene copolymers.
Alkalinity

Inhibitors

P1B-X^^.._
/
NCHjCHzNHCHjCHjtvr

Polyisobutenylsuccinimide

Agents

Metal Salicylate

.SOjJxM

These additives are used to impart reserve alkalinity (ASTM


D 974 and D 4739) and include alkanolamines, complex
amines, and metal hydroxides and carbonates. These not
only stabilize emulsions through a buffering action, but they
also control corrosion by neutralizing corrosive acids.

R
R

(S),

M = Ca, Ba, Na
X = 1 or2

>
Alkylbenzenesulfonate

FIG. 17Commonly used dispersants.

CH=CH

CH2COOR"
Sx

R C H r CH

Alkyl polysulfide
R = C4 and higher; n = 2-4

CHzCOOR'

Sulfurized Cairboxylic Acids and Esters


R' = H; Acid

R' = All<yl; Ester

(ROJJR:

Dlalkyl Hydrogen
Phosphite

Metal Dithiocarfoamate
M = Zn (zinc), Sb (antimony)

.^'
\.

(RO),P(OH)y- RNH2

(R0)2 P

Zn

Amine Phosphates
X, y = 1 o r 2

Zinc Dlalkyl Dithiophosphate


IVI = Na or Ca

SO,
M . M (CO3)

*" ~^ '*"' sodium and 2 for calcium


n =2 for sodium and 1 for calcium

Basic Alkylbenzenesulfonate
FIG. 16Structures of common EP agents.

CHAPTER 18: METALWORKING


Additives used to control iron corrosion in metalworking
fluids include fatty amines, neutral and basic barium and
calcium alkylaromatic sulfonates, and metal and amine salts
of carboxylic acids, boric acid, and organic acid phosphates.
Sulfonates are either alkylbenzene derived or alkylnaphthalene derived. Both the fatty acids and the high molecular
weight oxidates (oxidized hydrocarbons) are used to manufacture soaps. Alkanolamides, imidazolines, and sarcosines,
often used as rust inhibitors, are also alkaline derivatives of
carboxylic acids. Of these, amines and overbased sulfonates,
which are basic, perform by acid neutralizing mechanism.
Others perform via film formation. For yellow metal protection (ASTM D 130), benzotriazoles and dimercaptothiadiazole (DMTD) derivatives are used. Structures of these inhibitors are provided in Fig. 18.
Antimicrobial Agents
These additives, also known as biocides, are control specific.
A fluid can therefore have a combination of these: one acts as
an antibacterial and the other as an antifungal and yeast control agent. Microbial attack is undesired because it causes
buildup of acidic materials, corrosion of machinery and
tools, destruction of additives, objectionable odors, and it
produces materials that destabilize emulsions. Fungal attack
can lead to slimy material that can coat the machinery and
tools as well as clog pumps and filters. This makes monitoring for microbes a necessity. Monitoring is carried out
through commercial culture techniques. Standard practice is

AND MACHINING

R
Neutral Calcium Sulfonate

II

SO,

RCH COH
CH-COH

II

Ca. xCaCOs
2

-LR

O
Alkenylsuccinic Acid

Basic Calcium Sulfonate

II

ROPOH . R'NHj^CHjCHjOH
OR

RN,
CH2CH2OH

II

ROPOH . R'NH,"

Dlethanolamine

OH

RS.^/*\,^SR

\\

//

NN

Dimercaptothiadiazole
Derivative

517

to use two different biocides in an alternating fashion to


guard against microbes developing immunity [10].
Commonly used biocides include formaldehyde-release
agents and others. Others can be further divided into heterocyclics and organohalogen compounds. The structures of
some of the biocides are shown in Fig. 19. l,3-Di(hydroxymethyl)-5,5-dimethyl-2,4-dioxoimidazole, 2-hydroxymethylaminoethanol, hexahydro-l,3,5-tris (2- hydroxyethyl)-s-triazine, and oxazolidine are examples of formaldehyde-release
agents. These additives control bacterisJ growth by releasing
formaldehyde, an antibacterial agent. Formaldehyde results
from the hydrolysis of these additives in water-based fluids.
Heterocyclics include isothiazolone, benzisothiazolinones,
morpholine, sodium pyrithione (sodium omadine), benzotriazole, and dimercaptothiadiazole. Organohalogen compounds include 2,4,5-trichlorophenol, bis (2-chloroethyl)
ether-tetramethylenediamine copolymer, and 2,2-dibromo-3nitrilopropionamide. A variety of other compounds that are
outside these general classes are also used to control microbial infestation. These include o-phenylphenol, carbamates,
dithiocarbamates, glutaraldehyde, and nitroalcohols.
Most of these compounds destroy bacteria directly.
Sodium omadine is an effective antifungal agent. Materials,
such as 2,2-dibromo-3-nitrilopropionamide, are useful for
controlling bacteria and fungi, including yeast. These additives, by virtue of protecting against infestation from all
three, minimize worker exposure and prolong emulsion
batch life. Boron containing formulations usually do not ex-

Ca

Polyethoxylated Phenol

FLUIDS

Alkylbenzotriazole

FIG. 18Common corrosion inhibitors

AII<ylammoniun
Phosphates

518

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

perience bacterial growth. While choosing an antimicrobial


agent, one must consider its toxicity, its effect on emulsion
stability, and regulations considering its discharge into waste
streams.
Foam Inhibitors
(Antifoam Agents,
Defoamers)
These additives are used to control foam (ASTM D 892 and D
3601, IP312) in metalworking fluids. Foam in lubricants occurs because of air or gas entrainment and impairs their flow
and lubricating ability. Air entrainment is c o m m o n during
spraying and p u m p i n g of lubricants. F o a m is particularly
c o m m o n in water-based fluids because they usually contain
surfactant type water-soluble additives. F o a m is undesired
because it interferes in lubrication, inhibits cooling, and creates a problem if it overflows sumps and tanks. Foam inhibitors are readily dispersible additives, which are added to
the fluid in a low concentration, that is in parts per million or
parts per billion. They perform by reducing the surface tension of bubbles (ASTM D 1590), thereby resulting in their coalescence. Common types include amide and ester waxes, silicones and modified silicones, long-chain saturated alcohols.

certain triglycerides, water-insoluble polyglycols, ethylene


glycol-propylene glycol copoljaners, and polyacrylates.
Silicone type inhibitors can adosrb on the metal surface
and, in a subsequent operation, reduce the ability of paint or
coating to adhere to the metaJ part. Their use is also undesired because of the environmental and waste treatment concerns, plating effect or "fisheyes," and effects on cleaning and
finishing. They are h a r d to remove by washing, which may be
necessary for finishing the part via painting, varnishing, and
enameling. The structures of some of the foam inhibitors are
shown in Fig. 20.
Oxidation

Inhibitors

These additives are used in lubricants to minimize deterioration of the organic component due to oxidative attack. If not
controlled, oxidation will lead to acidic products that tend to
form sludge and corrode metal surfaces. For a more detailed
discussion on oxidation, consult Chapter 30 of this treatise.
Because many metalworking operations involve high temperatures a n d metal debris, the rate of oxidation is even
faster. This makes the need for these additives even more

FORMALDEHYDE-RELEASE AGENTS
eH,CH,OH
Hj

H2

HOHjCHjC^
2-{Hydroxymet)iylamino)ethanol

CH2CH2OH

Hexahydro-1,3,5-tris (2-hydroxyethyl)- s-triazine

CH3
H3C-C-NCH2OH

:?;>

^ N ^ O
CHjOH
1,3-dJ (hydroxymethyl)-5,5dimethyl-2,4-dioxoimidazole

Oxazolidine

OTHERS

HC

\\

NH

NH.

HC-C,

isothiazolone

BenzoisothiazoUnone

a:

/>-SH

^S

BenzotFiazole

0
Sodium pyrithione
Sodium omadine

H^N-V*"^
Br
Br

N
3

2,4,5-Trichlorophenol

2,2-Dibronio-3-nitrilopropionafnide

FIG. 19Structures of some biocides.

CHAPTER 18: METALWORKING AND MACHINING FLUIDS 519


CH,
I ^
-O-SiO
CH3

CH,
I
SiO

CH,
I ^
Si

CH3

CH3

'/<

^
CH3

Dimethylsiloxane Polymer
Arylamine

2,6-Di-t-butyl-4-niethylphenol

HO(CH2CH20)xCH2CH20[CH2CH(CH3)0]yCH2CH(CH3)OH
.CHzCOOH

N.

Ethylene Oxide - Propylene Oxide Copolymer

CH2COOH
^CHzCOOH

FIG. 20Common foam Inhibitors.

N,

'CH2COOH

Ethylenediaminetetraacetic Acid

p a r a m o u n t . Alkylated aromatic amines, alkylphenols, and


quinolines are the c o m m o n oxidation inhibitors. Sulfur compounds that are extensively used in metalworking fluids to
provide extreme pressure protection have the added advantage of acting in this capacity.
Metal ions, such as those resulting from the attack of acidic
species on metal are known oxidation promoters (see Chapter 30 on Oxidation). Metal passivators, or chelators, are used
to control oxidation by complexing with the metal ions and
making them innocuous. Chelators include triazoles, thiazoles, and organic diamines, such as ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid. Structures
of c o m m o n l y used oxidation inhibitors are provided in
Fig. 2 1 .
Dyes
These additives are used to impart color to the lubricant cind
include a n t h r a q u i n o n e s , azo c o m p o u n d s , a n d triphenylmethane.
Odor Control

Agents

These agents are used to control undesirable odors present in


lubricants or produced during use. Odor control agents include sjrnthetic sassafras, pine oil, terpenes such as teipinol
and d-limonene, and methyl salicylate.
Inorganic/Organic

FIG. 21Oxidation Inhibitors for metalworking fluids.

Lubricant Formulations
E a c h metalworking operation places a different d e m a n d
on the lubricant. A lubricant must therefore possess specific
properties to perform effectively. The properties that fulfill
the c o m m o n needs of most operations include cooling, lubrication, w e a r control, a n d protection against corrosion.
Metcdworking fluids, like other lubricants, are obtained by
blending base fluid and additives. These fluids must meet
performance specifications, which for these fluids are primarily established by OEMs and end-users. Table 7 provides
the additive composition of metal removal fluids and Table 8
provides the additive composition of metal forming fluids
and miscellaneous others. In Tables 9 and 10, additives are
listed in the form of formulations. Table 9 presents formulations based on the base fluid and Table 10 presents formulations based on the fluid function.

TABLE 7General composition of metal removal fluids.


Metal Removal Fluid
Straight cutting oil

Solids

These include graphite, M0S2, metal powders, metal oxides,


metal halides, mica, a n d tetrafluoroethylene polymer.
Tetrafluoroethylene polymer, or TEFLON, is one of the few
organic materials that are used to formulate metalworking
fluids. These solid additives are suspended in oil or waterbased lubricants by the use of high molecular weight dispersants, referred to as carriers. During use, the solid separates
at the tool-work piece interface to form a low-shear film that
provides lubrication, in a m a n n e r similar to that of the filmforming agents. These additives are generally not used in
metal removal lubricants, although some passive EP agents
that are used are colloidal dispersions. However, the use of
inorganic solids is more c o m m o n in formulating fluids for
certain metal forming operations, such as extrusion and forging. Suspension process generally involves mechanically agitating finely divided powders in oil or water, in the presence
of an emulsifier or a dispersant.

Water-soluble
cutting oil

Grinding oil
Lapping oil
Honing oil
(precision
grinding)
Punching lubricants
(emulsifiable and
nonemulsifiable
minereil, and solid
dispersion type)

Composition"
Mineral oil; friction reducer (fatty acids,
their metal salts and esters); extreme
pressure agent (chlorinated isobutylene,
dibenzyl sulfide, organic phosphates).
Water; corrosion inhibitor (sodium or
potassium nitrite; mono-, di-, or
tri-ethanolamine); emulsifier (non-ionic
surfactants; natural and synthetic fatty
acid soaps; polyalkylene glycols).
Water; mineral oil; friction modifier;
extreme pressure/antiwear agent;
anti-misting additive.
Mineral oil; dispersant; lapping agent.
Mineral oil; friction reducer (fatty acids and
triglycerides); extreme pressure agent
(chlorinated isobutylene, dibenzyl sulfide,
organic phosphates).
Mineral oil; friction reducer (fatty oils,
graphite, mos2, mica, or talc); extreme
pressure agent (organophosphorus,
organosulfur, and organohalgen
compounds).

"Not all formulations contain all the listed additives.

520 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 8General composition of metal forming and other fluids.
Lubricant

Composition"

Metal forming fluids


Hot rolling oil (emulsion type)
Cold rolling oil (straight oil type)
Cold rolling oil (emulsifiable
type)
Cold rolling oil (aqueous solution
or synthetic type)
Wire drawing lubricants (straight
oils and emulsion types)
Tube drawing fluids (straight oils
and emulsion types)
Deep drawing fluids (straight oils
and emulsion types)
Extrusion lubricants (powder,
grease, solid, and straight oil
types)
Cold forging lubricants
Metal treating fluids
Quenching oils (straight oil type)
Quenching oils (washable)
Quenching oils (emulsifiable
type)
Metal protecting fluids
Rust preventive oils straight oil
type)
Rust preventive oils (emulsifiable
type)
Slidewav lubricants

Water; mineral oil (primarily naphthenic); emulsifier; coupling agent; corrosion inhibitor
(alkanolamides); antimicrobial agent (triazines); friction reducer (fatty acid derivatives); anti-misting
additive (polyisobutylenes); and extreme pressure agent (organophosphorus compounds).
Mineral oil (kerosine cut); friction reducer (dodecanol, fatty acids and esters); and extreme pressure agent
(organophosphorus, organosulfur, and organohalgen compounds).
Water; mineral or fatty oil; friction reducer (fatty alcohols, acids and esters); emulsifier; coupling agent;
corrosion inhibitor (alkanolamides, sulfonates); foam inhibitor (ethoxylated fatty alcohols);
antimicrobial agent (triazines); and extreme pressure agent (organophosphorus, organosulfur, and
organohalgen compounds).
Water; friction reducer/EP agent ( o r g a n o p h o s p h o r u s c o m p o u n d s , polyalkylene glycols); corrosion
inhibitor (fatty amines).
Mineral oil; friction reducer (animal or vegetable oils); lubricant carriers* (phosphoric acid, oxalic acid,
lime); extreme pressure agent (organic chlorides)
Mineral oil; friction reducer (animal or vegetable oil); lubricant carrier (phosphates, oxalates, lime);
extreme pressure agent (organic chlorides);
Mineral oil; friction reducer (animal or vegetable oil); corrosion inhibitor; sdhesion improver
(polymethacrylates); extreme pressure agent (organophosphorus, organosulfur, a n d organohalgen
compounds).
Mineral oil; friction reducer (alksdi metal soaps of fatty acids, fatty animal and vegetable oils); lubricant
carrier (phosphoric acid, oxalic acid, lime); extreme pressure agent (organophosphorus, organosulfur,
and organohalgen compounds).
Mineral oil; lubricant carrier (zinc phosphate); a n d extreme pressure agent (organosulfur a n d
organohalgen compounds).
Mineral Oil; oxidation inhibitor (alkylphenol); quenching p r o m o t e r (high molecular weight hydrocarbons).
Mineral oil; emulsifier; oxidation inhibitor; quenching promoter (high molecular weight hydrocarbons).
Mineral oil; emulsifier; oxidation inhibitor; quenching promoter (high molecular weight hydrocarbons);
antimicrobial agent; corrosion inhibitor.
Mineral oil; corrosion inhibitor
Mineral oil; emulsifier; water; plasticizer (ethyl cellulose or cellulose acetate); micronized waxes;
corrosion inhibitor (alkali and alkaline earth natural metal sulfonates; fatty carboxylates; naphthenates;
and extensively oxidized hydrocarbons, both neutral and overbased, amino alcohols and triazoles)
Mineral oil; friction modifier (fatty acid derivatives); antiwesir agent; oxidation inhibitor

"Not all formulations contain all the listed additives.


''These additives, appHed through surface bonding, increase surface roughness, which improves adhesion of the lubricant/EP additives.

TABLE 9Fluid based formulations.


Fluid Type
Straight oil
Soluble oil

Semisynthetic fluid

Synthetic fluid

Approximate Fluid Composition


Mineral oil (60%), ususdly solvent-refined blends to achieve ISQ 10, 15, 22, 32, 46, 68 grades; lubricity agent
(15.3%)natural fats, synthetic esters; EP additives (20%), chlorinated paraffins, overbased sulfonates,
phosphorus, sulfur, sulfurized fats, and sulfurized olefins; corrosion inhibitor (4.7%).
Mineral oil of 40C viscosity of 15-20 cSt (53.9%); emulsifler/corrosion inhibitor (30.3%)anionic - sulfonates,
alkanolamine saltsamphoteric - a m i n o acid soapsnonionic - ethoxylates, alcohols, amines; other
additives (10.3%)foam inhibitor, bactericide/fungicide, extreme pressure agent/s; water (5.5%).
This additive package is diluted with water in 1:10 to 1:50 ratio to yield the finished fluid, which appears
opaque.
Mineral oil (14.7%); emulsifier/corrosion inhibitor (50%)anionic - sulfonates, alkanolamine soaps, boron
amides; nonionic - ethoxylates, alcohols, amines; other additives (10.3%)foam inhibitor, oiliness agent,
extreme pressure agent/s; water (25%).
This additive package is diluted with water in 1:20 to 1:60 ratio to give the finished fluid that appears almost
clear.
Corrosion inhibitor (39.7%)alkanolamines, water soluble soaps, b o r o n soaps/salts, fatty acids/esters;
wetting/lubricity agents (7.2%)polyglycols and esters; other additives (3.1%)bactericide/fungicide, foam
inhibitor, extreme pressure agent; water (50%).
This additive package is diluted with water in 1:10 to 1:100 ratio to give the finished fluid that appears
completely clear.

CHAPTER 18: METALWORKING AND MACHINING FLUIDS 521


TABLE 10^Application based formulation.
Lubricant
Mineral forming fluid
Soluble-oil forming fluid

Straight removal fluid


Soluble-oil removal fluid

Semi-synthetic removal fluid

Synthetic removal fluid

Mineral protecting fluid


Synthetic protecting fluid
Mineral treating fluid
Synthetic treating fluid

Approximate Composition
Extreme pressure agent (20.0-35%)-chlorinated wax a n d sulfurized fat mixture; corrosion inhibitor
(1.0-2.0%)-alkanolamine; lubricity agent/friction modifier (10.0-20.0%)-soap or lard oil
Extreme pressure agent (25.0-30.0%)-chlorinated wax a n d sulfurized fat mixture; corrosion inhibitor
(4.0-6.0%)-alkanolamine; lubricity agent/friction modifier (10.0-20.0%)-soap o r lard oil; foam
inhibitor (0.5-1.0%)-polyacrylate; buffer (4.0-6.0%)-diethanolamine o r triethanolamine; biocide
(1.0-2.0%)-triazine; emulsifier (4.0-6.0%)-soap.
Extreme pressure agent (10.0-20.0%)-chlorinated wax o r sulfurized olefins; corrosion inhibitor
(0.5-1.0%)-alkanolamine or triazole; friction modifier (5.0-10.0%)-carboxylic acid derivative.
Extreme pressure agent (10.0-15.0%)-chlorinated wax or sulfurized olefins; corrosion inhibitor/buffer
(4.0-6.0%)-alkanolamine; lubricity agent/friction modifier (5.0-10.0%)-carboxylic acid derivative;
foam inhibitor (1.0-2.0%)-polymethacrylate; biocide (2.0-3.0%)-triazine; emulsifier (5.0-10.0%)-soap.
Extreme pressure agent (4.0-6.0%)-chlorinated wax or sulfurized olefins; corrosion inhibitor/buffer
(5.0-10.0%)-alkanolamine; lubricity agent/friction modifier (5.0-8.0%)-carboxylic acid derivative;
foam inhibitor (1.0-2.0%)-polymethacrylate; biocide (2.0-3.0%)-triazine; emulsifier (5.0-10.0%)-soap
or petroleum sulfonate.
Extreme pressure agent (2.0-3.0%)-sulfurized olefins or zinc dialkyl dithiophosphate; corrosion
inhibitor/buffer (5.0-10.0%)-alkanolamine; lubricity agent/friction modifier (4.0-6.0%)-carboxylic
acid derivative; foam inhibitor (1.0-2.0%)-polymethacrylate; biocide (2.0-3.0%)-triazine; emulsifier
(5.0-10.0%)-soap or petroleum sulfonate.
Corrosion inhibitor (2.0-3.0%)-neutral metal sulfonate mixture.
Corrosion inhibitor (0.5-1.0%)-amine carboxylate and amine borate mixture; lubricity agent/friction
modifier (0.5-1.0%)-phosphate ester; buffer (5.0-10.0%)-alkanolamine; biocide (1.0-5.0%)-triazine.
Oxidation inhibitor (0.1-0.5%)-phenol and arylamine mixture; speed improver (1.0-10.0%)-calcium
sulfonate.
Corrosion inhibitor (1.0-2.5%)-alkanolamine; foam inhibitor (0.5-1.0%)-polyacrylate; buffer
(5.0-10.0%)-alkanolamine; biocide (2.0-3.0%)-triazine.

TABLE 11List of tests for metalworking fluids.


Oil-Base Fluids
Corrosion Tests

Water-Based Fluids
Corrosion Tests

Ferrous metals (ASTM D 665)

Ferrous Metals (ASTM


D 4627, IP 287, and IP 125
Cu and Cu alloys (ASTM D 130)
Cu and Cu Alloys (ASTM D 130)
EP-Load Carrying Tests
EP-Load Carrying Tests
Falex EP wear-Pin-on V-block(ASTM D 2670) and D 3233)
4-Ball Wear (ASTM D 4172)
4-Ball EP Weld (ASTM D 2783)
Metal Removal

Falex E P wear-Pin-on-V-block(ASTM D2670 and D 3233)


4-Ball Wear (ASTM D 4172)
4-Ball EP Weld (ASTM D 2783)
Meted Removal

Falex No. 8 Tapping Torque


Lubrizol CNC tapping torque
Lubrizol CNC drill wear/life
Lubrizol CNC milling/surface
finish
Lubrizol pipe threading test
Other Tests

Falex No. 8 Tapping Torque


Lubrizol CNC tapping torque
Lubrizol CNC drill wear/life
Lubrizol CNC milling/surface
finish
Lubrizol pipe threading test
Emulsion Stability

GM Quenchometer (ASTM
D 3520)
Cooling curve analysis (ASTM
D 6200)

Emulsion stability
characteristics-(ASTM
D 1401, IP 263)
Moderate Timken aquarium test
Lubrizol centrifuge procedure
Other Tests
Cooling curve analysis (ASTM
D 6482 and D 6549)

METALWORKING FLUID TESTS


Test methods to evaluate the performance of these fluids are
not well standardized. Some are standardized tests, such as
ASTM, IP, and DIN Tests, while others are additive supplier
or the end-user required tests. The standardized tests t h a t are
either presently used or can be used to judge the suitability of
metalworking fluids are listed in Table 11, and the p a r a m e ters they evaluate are briefly described in Table 12. Many

standards contain these tests, as summarized in Table 13. Details of these tests are available in books on ASTM, IP, and
DIN Standards [13,14,24]. It is important to point out that
the tests across standards do not always match. They may differ because of disparity in hardware, test method, or the way
they are performed.

USED LUBRICANT RECYCLING


Toxicity, safety, and environmented compatibility of chemicals are becoming a growing concern. Toxicity determines the
ability of materials to h a r m life. While h a r m to h u m a n s is a
major concern, the effect of chemicals on the environment as
a whole cannot be ignored. Unused lubricants are generally
considered less toxic t h a n used lubricants. Exposure to used
oils primarily occurs through skin absorption. Over the shortterm, the toxic c o m p o n e n t s present in t h e used oil can lead to
skin irritation; over the long-term, they can act as carcinogens. The Occupational Safety and Health Administration
(OSHA) requires all lubricant manufacturers to provide material safety data sheets (MSDSs) on their products. While
each MSDS contains a variety of information, its primary purpose is to provide physical and health hazard data on products, so as to facilitate safe handling. H u m a n exposure can be
minimized by avoiding contact with the lubricant by using
protective equipment, such as gloves, oil-impervious clothing
a n d boots, and by adopting explosion and fire prevention
measures. Environmental protection requires that neither
new nor used lubricant be released to air, water, or land. This
can be achieved only if proper procedures pertaining to storage and handling of lubricants, lubrication, equipment maintenance, and disposal of used lubricants are in place. Because
lubricant disposal is costly and is subject to a n u m b e r of federal, state, and local regulations, minimizing the volume of
the used or the leaked lubricant is highly desired.

522 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 12Metalworking fluid tests.
Test and Procedure
Corrosion
Copper (ASTM D 130) 3 h at 100C
Turbine oil rust (ASTM D 665)
A-Distilled water
B-Synthetic sea water
Aqueous cutting fluid (IP 125)
Filter paper chip breakpoint (IP287)
Aluminum cup stain 20 min at 350C
Humidity cabinet rust (ASTM D 1748)
Salt spray (MIL-B-117-64)
Cleveland condensing humidity cabinet
(ASTM D 2247)
Extreme pressure
4-Ball wear (ASTM D 2266)
40 kg, 1200 rpm, 75C,1 h average
coefficient of friction; maximum scar
diameter (mm)
Timken (ASTM D 2782)
OK Load (lb)
4-Ball EP (ASTM D 2783)
seizure (kg); Weld (kg); LWI (kg)
Falex EP (ASTM D 3233)
Stability
Foam (ASTM D 892, IP312)
tendency/stability (ml)
Panel coker
4 h at 260C, continuous splash
Demulsibility (ASTM D 1401) (mL
oil/mL water/mL emulsion)
Emulsion stability (IP263)
Aquarium biostability
Miscellaneous
Color (ASTM D 1500)
GM quenchometer (ASTM D 3520) R. C.
index
Thread tapping (Lubrizol test)
Pipe threading (Lubrizol test)
Stick-slip (Cincinnati milacron test)
Bijur filtration
Falex #8
SLT (Draw Bead Simulator)
Reichert

Purpose
Measures fluid's non-ferrous compatibility.
Measures the ability of inhibited mineral oils to aid in preventing the rusting of ferrous
metals in the presence of water.
Measures corrosion protection of aqueous cutting fluids.
Evjiluates rust inhibition properties of aqueous cutting fluids.
Cup appearsince indicates non-ferrous corrosion properties.
Measures ability of preservative oils to protect metal parts from rusting under conditions
of high humidity.
Steel part corrosion protection measured after exposure to 5% salt spray for 24 h.
Measures anti-rust properties of metal preservative fluids on steel panels. Considered more
severe than ASTM D1748 humidity test.
Evaluates anti-wear and anti-weld properties of lubricants.
Measures abrasion resistance and load carrying capacity of lubricants.
Evaluates extreme pressure and anti-weld properties of lubricants.
Measures load carrying capacity and wear properties of lubricants.
Determines foaming characteristics of lubricating oils at specific temperatures.
Determines relative stability of lubricants in contact with hot metal surfaces.
Measures separation of oil and water from emulsion over time.
Measures emulsion stability in water.
Measures foam, bacteria, fungus, and odor over time in controlled aqueous environment.
Visual determination of fluid color based on colorimetric readings.
Determines heat removal speed of a quench oil.
Evaluates fluid efficiency by measuring torque required during tapping operation in steel.
Evaluates fluid efficiency by measuring torque required during threading operation on cast
iron or stainless steel.
Measures static and dyneimic coefficients of friction in slideway lubricants.
Determines compatibility of lubricants with Bijur setup (specific to Bijur filter design)
Evaluates fluid efficiency by measuring torque required during tapping operation in steel.
Evaluates friction generated in a drawing process.
Measures load-carrying properties of lubricants.

Recycling of the used lubricant is one option. At present,


three methods are used for recycling: reprocessing, reclamation, and re-refining [25]. Reprocessing is used to make used
oil suitable for combustion as burner fuel. The simplest in
terms of treatment, this technique involves the removal of
particulates, water, and contaminants that can cause scaling
of the heat transfer surfaces and fouling of the burners and
of the fuel lines. Particulates and water are removed by the
use of settling, filtration, and or centrifugation. Sometimes
demulsifiers and heat are employed to facilitate the removal
of contaminants. Reclamation involves a higher degree of
processing and is primarily used for industrial lubricants,
such as hydraulic oils, gear oils, and metalworking fluids. It
is more effective if the feed streams are unmixed. Reclamation involves:
settling, centrifuging, and filtering to remove solids
clay and eJkali treatment to remove acidic contaminants,
followed by washing to remove the resulting soaps
mild heating or distillation to remove volatile components

clay treatment to remove polar oxygenated materials or to


improve color
aeration or biocide treatment to get rid of bacterial contamination
additive blending to make u p for the depleted additives
Some feed streams need fewer steps than others do. A commercial lubricant reclaiming company uses a host of analytical techniques to determine the degree of treatment required
to operate cost-effectively. The listed steps for reprocessing
and reclamation are shown in Fig. 22. It is important to point
out that the quality of the reclaimed lubricant is either the
same or lower than that of the lubricant prior to use.
Re-refining is the most complex of the three recycling processes and uses petroleum refining techniques, such as vacu u m distillation and hydrotreating, both of which require
specialized equipment. Because of this, only a limited number of companies are involved in this process. Re-refining,
primarily used to recycle engine oils, results in clean high
quality basestocks.

CHAPTER 18: METALWORKING AND MACHINING FLUIDS 523


TABLE 13Compsirative test standards.
Test

Standard test method for pour point


of petroleum products
Standard test method for detection of
copper corrosion from petroleum
products by the copper strip
tarnish test
Standard test method for kinematic
viscosity of transparent and opaque
liquids (the calculation of dynamic
viscosity)
Standard test method for rustpreventing characteristics of
inhibited mineral oil in the
presence of water
Standard test method for foaming
characteristics of lubricating oils
Standard test method for acid and
base number by color-indicator
titration
Standard test method for water
separability of petroleum oils and
synthetic fluids
Standard test method for emulsion
stability of soluble cutting oils
Standard test method for ASTM color
of petroleum products (ASTM color
scale)
Standard test method for rust
protection by metal preservatives
in the humidity cabinet
Standard test method for wear
preventive characteristics of
lubricating grease (four-ball method)
Standard practice for csJculating
viscosity index from kinematic
viscosity at 40 and 100''C
Standard test method for measurement
of extreme-pressure properties of
lubricating fluids (timken method)
Standard test method for measurement
of extreme-pressure properties of
lubricating fluids (four-ball method)
Standard test method for lowtemperature viscosity of automotive
fluid lubricants measured by
Brookfield viscometer
Standard test method for foam in
aqueous media (bottle test)
Standard test method for wear
preventive characteristics of
lubricating fluid (four-ball method)
Standard test method for iron chip
Corrosion for water-dilutable
metalworking fluids
Standard test method for evaluating
the scuffing (scoring) load capacity
of oils
Standard test method for apparent
viscosity of engine oils between
- 5 and -30C

ASTM Designation

ISO Designation

IP Designation

DIN Designation

D 97-96a

3016-1994

15/95

D 130-94

2160-1998

154/95

DIN- ISO
3016:1982-10
51 759

D 445-97

3104-1994

71/97

D 665-98

7120-1987

135/93

51 585 A-HE

D 892-98

6247-1998

51 566 E
Edition 12/83

D 974-97

6618-1997

146/82
312/74
139/98

D 1401-98

6614-1994

D 1479
(Discontinued)
D 1500-98

51 550

51599
290/84

2049-1996

196/97

D 1748-83

366/84

51359

D 2266-99

239/97

51 350 Part 5

226/91

DIN-ISO
2909:1997-10

D 2270-93

2909-1981

D 2782-94

51 434 Part 2
51350
Part 2

D 2783-88

293/97

D 2983-87

267/84

D 3601-88

312/74

D 4172-94

293/97

D 4627-92

287/94
125/82

51 360 Part 2

D 5182-97

334/93

51 354 Part 2

D 5293-99-

383/94

51 395-1
Dynamic Test
51 350 Part 3

524 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


Filtration

Settling

Dehydration
Reprocessed Oil

Satds and Water


Settling

Fine Solids
Fillratlon

Dehydration

/ \

^~^

Solids and Water

Fine Solids

Clay/Alkali
Treatment

Water Washing
/

-Acidic Contaminants

Water

Heating/Distillation
/

-^ Volatiles (Solvents, Fuel, Water)

Additive Blending

Clay Treatment

Reclaimed Lubricant

FIG. 22Flow schemes for lubricant reprocessing and reclamation.

REFERENCES
[1] Bartenev, G. M. and Lavrentev, V. V., "Friction and Wear of Polymers," Elsevier Publishing, NY, 1981, p. 203.
[2] Fein, R. S., "Boundary Lubrication," CRC Handbook of Lubrication,
Theory and Practice in Tribology, Vol. 11, Theory and Design, Richard
E. Booser, Ed., CRC Press, Boca Raton, FL, 1983, pp. 49-67.
[3] Samuels, L. E., Doyle, E. D., and Turley, D. M., "Sliding Wear
Mechanisms," Fundamentals of Friction and Wear of Materials,
Papers presented at the 1980 ASM Materials Science Seminar, Pittsburgh, PA, October 4-5, 1980, David A. Rigney, Ed., ASM International, Materials Park, OH, 1981, pp. 214-216.
[4] Sargent, L. B., Jr., "On the Fundamental Nature of Metal-Metal
Adhesion," ASLE Transactions, Vol. 21, 1978, pp. 285-290.
[5] Larsen-Basse, J., "Basic Theory of Solid Friction," American Society of Metals Handbook, Friction, Lubrication, and Wear Technology, Scott D. Henry, Ed., Vol. 18, ASM International, Materials
Park, OH, 1992, pp. 27-38.
[6] Schiemann, L. F. and Schwind, J. J., "Fundamentals of Automotive Gear Lubrication," SAE Paper 841213, Fuels and Lubricants
Technology: An Overview, SP603, Society of Automotive Engineers, Warrendale, PA, October 1984, pp. 107-115.
[7] Fundamentals of Tribology, N. P. Suh and N. Saka, Eds., the MIT
Press, Cambridge, MA, 1980.
[8] Wedeven, L. D., "What is EHD?" Journal of the American Society
of Lubrication Engineers, Vol. 31, June 1975, pp. 291-296.
[9] Dowson, D. and Higginson, G. R., Elasto-hydrodynamic
Lubrication: The Fundamentals of Roller and Gear Lubrication, Pergamon
Press, Oxford, England, 1966.
[10] Laemmle, J. T., "Metalworking Fluids," American Society of Metals Handbook, Friction, Lubrication, and Wear Technology, Scott
D. Henry, Ed., Vol. 18, ASM International, Materials Park, OH,
1992, pp. 139-149.
[11] Rein, S. W., 'Viscosity-I," Lubrication, Vol. 64, No. 1,1978, pp. 1-12.
[12] Klamann, D., "Tribology and Tribotechnology," Chapter 2, Lubricants and Related ProductsSynthesis. Properties. Applications. International Standards, Verlag Chemie, Hamburg, 1984, pp. 4-25.
[13] "Petroleum Products and Lubricants," Annual Book of ASTM
Standards, ASTM International, West Conshohocken, PA.

[14] DIN HandbuchMineralole


und Brennstoffe, Beuth Verlag
GmbH, Berlin, 1998.
[15] ASTM D 2881: Standard Classification of Metalworking Fluids
and Related Materials, Annual Book of ASTM Standards, ASTM
International, West Conshohocken, PA.
[16] Klamann, D., "Metal Working Fluids," Section 11.13, Lubricants
and Related ProductsSynthesis. Properties. Applications. International Standards, Verlag Chemie, Hamburg, 1984, pp. 351-383.
[17] Sargent, L. B., Jr., "Lubricant Performance," Chapter 27, Standard Handbook of Lubrication Engineering, J. J. O'Connor, Ed.,
McGraw-Hill Book Company, NY, 1968, pp. 27-1 to 27-21.
[18] Kajdas, C , "Industrial Lubricants," Chemistry and Technology of
Lubricants, Chapter 8, R. M. Mortier and S. T. Orszulik, Eds.,
VCH Publishers, Inc., NY, 1992, pp. 196-222.
[19] (a) Kajdas, C , "Additives for Metalworking Lubricants. A Review," Lubrication Science, Vol. 1, pp. 385-409. (b) Sutherlsmd, J.
W., Olson, W. W., and Bergstrom, A., "Dry Machining," Summary
of Manufacturing Research 1996-97, Department of Mechanical
Engineering and Engineering Mechsmics, Michigan Technological University, Houghton, MI.
[20] Rizvi, S. Q. A., "Lubricant Additives and Their Fimctions," American Society of Metals Handbook, Friction, Lubrication, and Wear
Technology, Scott D. Henry, Ed., Vol. 18, ASM IntemationEil, Materials Park, OH, 1992, pp. 98-112.
[21] Synthetic Lubricants and High-performance Functional Fluids,
Ronald L. Shubkin, Ed., Marcel Dekker, Inc., NY, 1993.
[22] Becher, P., Emulsions: Theory and Practice, American Chemical
Society Monograph Series, Ch. 6, Reinhold Publishing Corporation, NY, 1957, pp. 209-231.
[23] Bhushan, B. and Gupta, B. K., "Physics of Tribologicsil Materials," Chapter 3, Handbook of Tribology; Materials, Coatings, and
Surface Treatments, McGraw-HiU, Inc., NY, 1991.
[24] Standard Methods for Analysis and Testing of Petroleum and Related Products and British Standard 2000 Parts 1997, John Wiley
and Sons, NY, 1997.
[25] Becker, D. A. and Brinkman, D. W., "Recycling (Oil)," KirkOthmer Encyclopedia of Chemical Technology, Fourth Edition,
Vol. 21, Martin Grayson, Ed., John Wiley and Sons, NY, 1996, pp.
1-10.

MNL37-EB/Jun. 2003

Petroleum Waxes
G. All Mansoori, ^ H. Lindsay Barnes,^
and Glenn M. Webster^

WAXES ARE USUALLY SOLID AT ROOM TEMPERATURE because they

contain linear paraffinic hydrocarbons with carbon chains of


various lengths. Waxes can vary in consistency from easily
kneadable t o brittle. They exhibit relatively low viscosity at
t e m p e r a t u r e s slightly above their melting point. The a p pearance of waxes can vary from translucent to opaque, but
they are not glassy. The consistency (i.e., hardness) and solubility of waxes depends on the temperature at which they are
observed.
The use of waxes dates back more than 5000 years. As early
as 4200 B.C. the Egyptians extracted a waxy substance from
the honeycomb of bees and used it to saturate linen wrappings of m u m m i e s [1]. The sculptured portrait of the deceased decorating a coffin cover w a s often modeled in
beeswax and painted with pigmented beeswax. Another use
of wax was in the preparation of erasable writing tablets. Fastening together several tablets with fiber produced forerunners of the m o d e m book [2].
Waxes are classified by the matter from which they are derived: insect, vegetable, synthetic, and mineral [3]. Beeswax
is a n example of insect wax. The chemical composition of
beeswax is u n i q u e a n d its characteristics vary with t h e
species of the honeybee. Apis mellifera is the most common
cultured bee in the world and will provide a chemical generalization of composition of wax for this species [4]. Beeswax
is secreted in eight glands on the underside of the worker bee.
Bees are believed to secrete one p o u n d of wax for every eight
pounds of honey they produce. Since secreted beeswax readily absorbs color, the final color of the beeswax is influenced
by the source of the pollen. A typical composition analysis of
beeswax is provided in Table 1. Beeswax is extracted by melting or boiling the honeycomb in water and has applications
in pharmaceuticals and cosmetics, and is the primary component of religious candles.
Vegetable waxes are extracted from the leaves, bark, and
berries (seeds) of plants and trees. Almost all multi-cellular
plants are covered by a layer of wax [5]. Only a few species
grown in semiarid climates produce enough wax to be commercially viable for recovery. C a m a u b a and csmdelilla wax
are two of the most c o m m o n vegetable waxes that are commercially marketed [6]. C a m a u b a wax is removed from the
dried leaves (fronds) of palm trees grown in the northeast region of Brazil. C a m a u b a is utilized in the polish paste indus-

try as a gelling agent for organic solvents and as a raw material used in lipstick formulations for t h e cosmetic market.
C a m a u b a wax is recognized generally a s safe by the United
States Food and Drug Administration.
Candelilla wax is harvested from the shrubs Eurphorbiea
antisiphilitica, E. cerifera, and Pedilanthus pavonis in Mexico
and southwest Texas. The candelilla wax is recovered after
the entire mature plant is uprooted and immersed in acidified boiling water. During the immersion, the candelilla wax
floats to the surface and is skimmed off. The primary market
for candelilla wax is cosmetics where it is a component in lipstick formulations. The chemical composition of c a m a u b a
and candelilla wax is listed in Table 2.
Synthetic waxes are derived from either the Fischer-Tropsch process [7] or by ethylene based polymerization processes [8]. The Fischer-Tropsch (F-T) process originated in
Germany in the 1920s and is illustrated schematically in E q
1. The F-T process was developed to synthesize hydrocarbons
and oxygenated compounds from a mixture of hydrogen and
carbon monoxide. During World War II, the F-T process was
used by Germany to produce fuels from coal-derived gas. The
first commercial plant in South Africa started in 1955 at
Sasolburg, using coal as a feedstock. The so-called Sasol process is illustrated in Fig. 1 [9]. This plant produces waxes, fuels, pipeline gases (i.e., ethylene, methane), and other products using a fixed bed catalyst F-T process. During the F-T
process, carbon monoxide, which is generated from coal
gasification, is reacted u n d e r fixed-bed conditions using
high-pressure at approximately 220C in the presence of a n
iron catalyst to p r o d u c e synthetic hydrocarbon waxes, as
shown in Eq 1. Typical reaction products that may be derived
from the F-T process are listed in Table 3.
2nH2 + nCO -> C Hzn + nH20

Poly(ethylene) waxes may be produced by the industrial


polymerization of ethylene using high or low pressure ethylene polymerization technology [10], or as thermal decomposition products of the polyethylene polymers. The molecular
weights Emd melting points of the synthetic waxes as compared with the Fischer-Tropsch waxes are listed in Table 4.
The market stability of pricing a n d availability of insect
and vegetable waxes is affected by climate conditions a n d
natural disasters. With the advent of the petroleum industry,
the waxes from mineral and synthetic sources surpassed the
annual production of the combined total of the other two wax
categories. Waxes from insect and vegetable sources are mixtures of long chain fatty acids, esters of aliphatic alcohols,
and hydrocarbons. Waxes from mineral origins are chemi-

' Department of Chemical Engineering, University of Illinois at


Chicago, 810 S. Clinton Street, Chicago, IL 60607-7000.
^ CITGO Petroleum Corporation, Highway 108 South, P.O. Box
1578, Lake Charles, LA 70602.
^ 63 Rocklege Rd., Hartsdale, NY 10530.

525
Copyright'

2003 by A S I M International

(1)

www.astm.org

526

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 1Compositional analysis of beeswax.


Component

TABLE 3Products derived from t h e Fischer-Tropsch process.


Approx. Typical
Yield (wt. %)

Amount in wt. %

Monoesters, CisHjiCOOCsoHsi; C25H51COOC30H61


55-65
Diesters, triesters, hydroxy diesters
8-12
Free fatty acids, C23COOH-C31COOH
9.5-10.5
Free fatty alcohols, C34OH-C36OH
1-2
Hydroxy-monoesters, Ci4H29CH(OH)COOC26H6i
8-10
Hydrocarbons", C25H52-C31H64
12-15
Moisture and mineral impurities
1-2
"Hydrocarbons most commonly found in beeswax include nonacosane
(C29H60) and nentriacontane (C31H64).

Product
Paraffins (i.e., methane, ethane, propane,
and butane)
Olefins (i.e., methylene, ethylene, propylene,
and butylene)
Gasoline (Cs-Cn)
Diesel (C12-C18)
Ci9 to C23
Medium Wax (C24-C35)
Hard Wax (>C35)
Water soluble non-acid chemicals
Water soluble acids

7.2
5.6
18.0
14.0
7.0
20.0
25.0
3.0
0.2

TABLE 2Chemical composition of carnauba and candelilla wax.


Carnauba (wt.

Component

Monoesters
Fatty alcohols
Free fatty acids
Hydrocarbons"
Resins
Moisture and inorganic residue

%)

Candelilla (wt. %)

83-88%
2-3
3-4
1.5-3.0
4-6
0.5-1

28-30%
2-3
7-9
49-57
4-6
2-3

"Hydrocarbons commonly found in carnauba and candelilla wax are principally hentriacontane (C31H64) and tritriacontane (C33H68).

TABLE 4Comparison of Fischer-Tropsch waxes with other


synthetic waxes.
Type of Wax
Fischer-Tropsch wax
Low Pressure polyethylene
wax
High Pressure polyethylene
wax
Pyrolysis" waxes

iWolecular Weight

Melting Points, C

500-1200
900-3000

85-110
90-125

500-4000

85-130

1000-3000

90-130

"Pyrolysis waxes are derived from thermo-cracking of polyethylene.

cally inert and are primarily composed of straight chain


(paraffinic) hydrocarbons.
Petroleum wax may vary compositionally over a wide
range of molecular weight, up to hydrocarbon chain lengths
of approximately C50-C60. It is typically a solid at room
temperature and is derived from relatively high boiling
petroleum fractions during the refining process. Petroleum
waxes are a class of mineral waxes that are naturally occurring in various fractions of crude petroleum. They have a
wide range of applications that include: coating of drinking
cups; an adhesives additive; production of candles and rubber; as components of hot melts, inks, and coatings for paper;
and they can be used in asphalt, caulks, and binders. This
chapter will provide a review of petroleum waxes including
history, production, types, chemical composition, molecular
structure, and property testing.

POWER
PLANT

COAL

SIEAM
1

GASmCAHOM 4

''

OXYGEN
PLANT

AIR

AE GON N,
nrr^f

RAW CAS
FDBinCAIION

CO, + H,S-*

OSOTE
PflTAR NAPHTHA

PURE GAS

FT
PROCESS
AI.COHOLS KErroms

LA.

F T WATER
WORK-UP

WATER

SEPARATION

FHACnOHAIION

GASES
NAI>^HA

CRYOGENIC
SEPARATION

WATER

praancATioN

WAX

DISCUSSION
Classification of Crude Oils and Chemical
Structure of Ingredients

Cj/Ci

CH
EIHYL0IE
PLANT

REFORMING

on.

rt:o,

PHACnONAnON
OUCOMEBISAHON

OILS

STEAM O2

CHj

CjHj

FIG. 1Generalized Sasol Plant for hydrocarbon synthesis


by the Fischer-Tropsch Process.

Petroleum crude oil, commonly referred to as crude oil, is a


complex mixture of hundreds of compounds including
solids, liquids, and gases that are separated by the refining
process. Solid components at room temperature include
asphalt / bitumen and inorganics. Liquids of increasing viscosity vary from gasoline, kerosene, diesel oil, and light and
heavy lubricating stock oils. Also included are the major components of natural gas, which include methane, ethane,
propane, and butane [11].
An elemental einalysis of crude oil shows that it consists of
primarily two elements: hydrogen (11-14%) and carbon

CHAPTER

19: PETROLEUM

WAXES

527

TABLE 5 --Crude oil content.


Crude Type

Solvent Neutral Oil

Base Oil

Wax Content

Sulfur and Nitrogen

Asphalt

API Gravity"

ASTM Test Method

Paraffinic base
Naphthenic base
Intermediate base
Asphaltic base

Yes
No
No
No

Yes
Yes
Yes
Yes

<10%
No
<6%
0%

Low
Low
Low
High

No
No
Yes
Yes

>40
<33
33-40
<10

E-1519
D-2864
D-8
D-1079

"American Petroleum Institute gravity is an arbitrary scale expressing the density of liquid petroleum products. The measuring scale is calibrated in terms of
degree API ("API) and can be calculated in terms of the formula: "API = 141.5/(SG'-[60''F]) 131.5 where SG'' stands for liquid specific gravity with respect to water. The higher the value of API gravity, the more fluid the liquid.

(83-87%). Crude oil hydrocarbons contain long hydrocarbon


chains (saturated and unsaturated), branch structures, and
ring structures, with each having specific physical and chemical properties. Small quantities of other compounds containing sulfur, oxygen, nitrogen, carbon, and hydrogen are
frequently present in crude oils.
Crude oils are generally classified based on their predominant hydrocarbon structure type, as shown in Table 5. The
t5rpes are referred to as paraffinic, naphthenic,
intermediate
(mixture of paraffinic and naphthenic crude), and asphaltic
base crude [12].
Paraffinic hydroccirbon fractions are saturated linear or
branched alkanes. Naphthenic fractions contain five and six
carbon cyclic alkane (alicyclic) structures. Naphthenes cire
monocyclic in the lower-boiling fractions (i.e., gasoline) and
polycyclic in the higher-boiling fractions (i.e., lubricating oils)
[13]. The asphaltic crudes contain unsaturated aromatic
structures containing rings of five and six m e m b e r carbon
atoms. Aromatics are defined as those classes of organic compounds that behave chemically like benzene. They are cyclic,
unsaturated organic compounds that Cm sustain an induced
electronic ring current due to delocalization of electrons
around the ring. Aromatic base oils contain 20-25% aromatic
compounds. A constituent of asphaltic crudes is asphaltene.
Asphaltenes are defined as the high molecular weight nonhydrocarbon fraction of crude oil precipitated by a designated
paraffinic naphtha solvent at a specified temperature and solvent-oil ratio [14]. Like the naphthenic crude, the aromatic
rings are monocyclic in the lower boiling fractions and polycyclic in the higher boiling fractions. Various ASTM test
methods listed in Table 6 are used for sampling, separation,
and characterization of petroleum fractions.
Petroleum waxes are derived from both paraffinic and intermediate crude oils and are composed of three basic carbon
structures (i.e., linear, branched, and ring) that are characteristic of the crude oil.
Production, Transportation, and Refining of Waxy
Petroleum Crudes]
The majority of crude oils produced around the world contain
substantial a m o u n t s of paraffin weix. These c o m p o u n d s ,
sparingly soluble in solution components of the crude oils,
crystallize at lower temperatures and are the major contributors to petroleum Wcix deposits [15]. The wax present in
petroleum crudes primarily consists of paraffin hydrocarbons
(C18-C36), known as paraffin wax, and naphtenic hydrocarbons (C30-C60). Hydrocarbon components of WEIX can exist
in various states of matter (gas, liquid, or solid) depending on
their temperature and pressure. When these hydrocarbons
freeze, they form crystals, which are known as macrocrys-

TABLE 6ASTM test methods used for sampling, separation, and


classification of various oil samples and the procedures used.
Test Method
D 4057
D 270
D 4007
D 86
D 2007

D 2425
D 2549

D 2786
D 2887
D 3239
D 3279

Procedure and Application


Practice for manual sampling of petroleum and
petroleum products
Sampling of petroleum and petroleum products
Centrifuge method for determination of water and
sediment in crude oil
Distillation of petroleum products
Clay-gel absorption chromatography for oil samples
of initial boiling point of at least 260C (500F) into
the hydrocarbon types of polar compounds, aromatics and saturates, and recovery of representative fractions of these types
Mass spectrometry for classification of hydrocarbon
types in middle-distillate
Elution chromatography for separation of representative aromatics and non-aromatics fractions of
high-boiUng oils, between 232 and 538C (450 and
1000F)
High ionizing voltage mass spectrometry for hydrocarbon types analysis of gas-oil saturate fractions
Gas chromatography for boiling range distribution
of petroleum fractions
High ionizing voltage mass spectrometry for aromatic types analysis of gas-oil aromatic fractions
Titration for determination of the weight percent of
asphaltenes as defined by insolubility in normal
heptane solvent

talline wax. Those formed from naphtenes are known as microcrystalline wax. A hydrocarbon in pure state has definite
boiling and freezing (or melting) points, which can be measured in the laboratory [16]. Knowing the intermolecular energy parameters or critical properties cuid acentric factor
and/or refractive index of hydrocarbons, one can predict their
boiling point using vapor pressure correlations or equations
of state as discussed in Section I of this report. However, such
methods are not capable of predicting pure hydrocarbon
freezing points. There are other methods that can be used to
predict hydrocarbon and wax freezing (melting) point, which
include but are not limited to variational statistical mechanical theory [17] and cell-lattice theories [18].
Waxy Crude

Oil

A waxy crude usually consists of: (a) a variety of light and intermediate hydrocarbons (paraffins, aromatics, naphtenic,
etc.); (b) wax as defined above; and (c) a variety of other
heavy organic (non-hydrocarbon) compounds, even though
at very low concentrations they include resins, asphaltenes,
diamondoids, organometcillics, etc. When the temperature of
a waxy crude oil is lowered to its cloud point, first the heavier fractions of its weix content start to freeze out. Upon lowering of the temperature of a crude oil to its pour point al-

528 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


most all the fractions of its wax content will freeze out. A
waxy crude is characterized by its cloud point and pour
point, which are measured according to ASTM Test Methods
D 2500 and D 97, respectively, as they are discussed later in
this report.
A clean waxy crude is defined as a crude oil in which there
exists only hydrocarbons and wax as its only heavy organic
constituent. As the clean waxy crude flows through a cold
pipe or conduit (with a wall temperature below the cloud
point of the crude) wax crystals may be formed on the wall,
which could then grow until possibly the whole inner wall is
covered with the encapsulating oil inside the weix layers. As
the wax thickness increases, pressure drop across the pipe
needs to be increased to maintain a constant flow rate. As a
result, the power requirement for the crude transport will increase. The cirterial blockage problems of clean waxy crude
can be efficiently controlled by insulation and heating of the
pipe to a temperature above its cloud point. Most of the existing wax deposition problems of the clean waxy crudes are
due to the lack of proper insulation and heating systems. As
a result, application of chemical anti-foulants and frequent
use of pigging operations have become necessary [15]. Regular paraffinic or waxy crudes are widespread. The major complex systems problems related to the production, processing,
and transportation of these medium-gravity fluids is not just
crystallization of their wax content at low temperatures, but
the formation of deposits that do not disappear upon heating,
and will not be completely removed by pigging.
Regular waxy crudes are not clean and, in addition to wax,
they contain other heavy organics such as asphaltene, resin,
etc. [15]. Asphaltenes do not generjJly crystallize upon cooling
and, for the most part, they may not have definite freezing
points. Depending on their natures, these other heavy organics
will have different interactions with wax, which could either
prevent WEIX crystal formation or enhance it. Existence of
branched paraffins, aromatics, naphtenes, and resins in
petroleum, however, contribute less to these deposits, but modify their crystallization behavior. However, asphaltene presence in the crude oil could prevent or enhance wax deposition
depending in the microscopic nature of asphaltene [19,20].
The precipitation of wax from petroleum fluids during production and transportation may give rise to a veiriety of problems [17]. One of the main problems observed is deposition of
solid material on well and pipe walls as demonstrated in Fig.
2. This happens if (a) the temperature of the wall is below the
cloud point of the oil, (b) a negative radial temperature gradient is present in the flow, (c) the wall friction is high enough
for wax crystals to stick to the wall, and (d) asphaltene present
in the crude oil has already deposited and has increased the
friction of the wall (changed of wettability) and acting as mortar for the sticking together of wax crystals. Wax crystallization may cause three problems: (a) higher viscosity, which
leads to pressure losses, (b) high yield stress for restartability
of flow, and (c) fouling of petroleum flow arteries [15].
To predict wax deposition tendency of a crude oil it is important to know its composition for paraffin wax and the other
components present in, or added to, the crude oil; their composition distributions; and the pressure ctnd temperature of the
system. Thermodynamics and statistical mechanics of phase
transitions in polydisperse mixtures can be utilized to develop
predictive models for wax deposition in petroleum fluids [17].

y^'.-'

FIG. 2Pipeline petroleum transport plugging due to


wax and other heavy organics depositions (Courtesy of
Phillips Petroleum Company).

To predict the deposition as a function of time, principles of energy and mass conservation, the laws of diffusion, and the principles of phase transitions need to be considered [21,22]. In order to prevent or remediate arterial blockage/fouling and
facilitate the production of regular waxy crudes, many issues
must be underteiken: (a) detailed fluid properties characterization, (b) production scheme alternatives, (c) retrograde condensation and deposition behavior prediction, (d) onsets of deposition studies, (e) equipment and facility options, (f) design
and use of chemical anti-foulants and/or pour-point depressants and blending alternatives, (g) performance specification
and maintenance planning, and (h) transportation, storage,
and blending studies [23,24].
Petroleum Refining
Crude oil is first desalted if salty, deasphalted if asphaltenic,
and dewaxed if highly waxy, before it is distilled in an atmospheric distillation unit to separate light ends (gases), naphtha, gasoline, jet, kerosene, gas oil distillate, and residuum
(resid) (see Fig. 3). The residuum (resid) remaining after the
atmospheric distillation is then further fractionated in a vacuum distillation unit into fractions that are distinguishable
by viscosity for further processing into lubricating oil base
stocks. Wax is concentrated in the distillate stream and the
residuum fraction is used to produce the base oils for lubricant formulation. Both the distillate and residual lube fractions (stock) contain undesirable constituents such as aromatics that must be removed by extraction to jdeld base oils
that are thermally stable with a sufficiently high viscosity index'' product. The distillate fraction is extracted with a sol* Viscosity Index is defined as V.I. = (/XL ~ hiodKlJ'i. ~ MH)- wiiere /AL
is the viscosity at 100F of the zero-V.I. oil, /U-H is tiie viscosity at
100F of the 100 V.I. oil, and /itx is the viscosity at 100F of the unknown (test) oil. See ASTM D 567 and D 2270 for further detail. A
measure of the magnitude of viscosity changes in lubricating oils
with changes in temperature. The higher the viscosity index number,
the more resistant the oil is to change in viscosity.

CHAPTER 19: PETROLEUM WAXES 529


vent (such as furfural) that has a greater solubihty (selective
solvent) for the components having a low viscosity index. The
residuum fraction is extracted with propane to remove bitum e n (asphalt) and resinous material. The desirable oil and
wax component is solubilized for further processing.
The nonsoluble portion of the distillate extraction and the
soluble portion of the residuum fraction are referred to as the
raffinate phase and b o t h contain the m o r e paraffinic oil.
Wax, which typically exhibits a high viscosity index, remains
in the raffinate phase for further processing. Because the raffinate produced from the extraction process contains wax,
which crystallizes at relatively high temperatures (>15F =
-9.4C), the fluidity of the base oil that exhibits a high pour

point (i.e., the temperature where the oil ceases to be fluid) is


reduced.

Solvent Dewaxing Process


The solvent dewaxing process can be divided into three distinct sections: (a) crystallization of the wax components by dilution and chilling, (b) filtration of the wax from the solution
of dewaxed oil and solvent, and (c) recovery of the solvent
from the dewaxed oil and wax products [25]. To overcome the
high pour point, a solvent dewaxing process has been developed to remove the wax from lubricating oil basestocks, as
shown in Fig. 4. The most widely used solvent dewaxing pro-

s' X Dewaxed

iDeasphaltingp
Asphalt
FIG. 3Schematic illustration of various possible locations of wax production in
petroleum refining.

OflyWax
Receiving

Product Shipped
ik

ik

Blended
Product
Oily Wax
Storage

f .Ciystallization

Sulvent

Blending &
Packaging

Mditives

Decoloiid]^

&

Deodortdng

FntratiDn
Snlinnt
Recnwer;

Stop Tlbxnr Fnnti Oil

Wax
&
Solvrait
StmagB

PrnductllAx

FIG. 4Solvent dewaxing process for tine removal of wax from lubricating oil slacltwax basestocks.

530 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


gogo H
70

50
4030
20
100
-101
-20
-30
-401
-50
30

OaPbaaie
Spanition

40
50
60
70
80
90
% MEK Content in Dewax Solvent

100

FIG. 5Illustration of the effect of the ratio of MEK to the


petroleum fraction being dewaxed on the resulting cloud point
of the mixture.

cesses are based o n solvent mixtures of methyl ethyl ketone


and toluene, methyl ethyl ketone and methyl isobutyl ketone,
or methyl isobutyl ketone itself. Figure 5 illustrates the effect
of the ratio of MEK to the petroleum fraction being dewaxed
on the resulting cloud point of the mixture. In the dewaxing
process, the raffinate (feedstock) is diluted with solvent and
heated 15-20F ( - 8 - 1 1 C), above the cloud point of the raffinate/solvent mixture (or slurry) and chilled at controlled rates
in double-pipe scraped-surface heat exchangers and chillers.
The slurry is chilled to 5-20F ( ~ 3 - l l C ) below the desired
pour point of the oil. When the wEix/solvent solution is cooled,
wax crystals precipitate from the solution, which are then
removed by filtration using a rotary vacuum filter. The crystallized wax forms as a layer (cake) on the surface of the rotary
vacuum filter. The wax cake (filtrate) is washed with a spray
of a cold solvent to remove any residual oil before being discharged from the primary filters. At this point, the wax
contains 10-40% oil and is referred to as "slack wax" if it is derived from the distillate lube fraction, or "petrolatum" if it is
derived from the residual lube fraction. Figure 6 illustrates the
effect of solvent dilution ratio on the a m o u n t of residual oil
content in the slack wax.
To produce waxes with lower oil contents (<5%), an additional dewaxing process is performed. The wax cake from the
primary filter is diluted with additioneil solvent and filtered in
a second (repulp) rotary vacuum filter using the same operating conditions as the primary filters to obtain the desired
wax oil content.
The solvent is recovered from the dewzixed oil filtrate by
flash vaporization and distillation. The solvent is recycled for
future use in the dewaxing process. ResiducJ solvent in the
wax is recovered by flash vaporization and is recycled for future process use.
Dewaxing Process Variables
Wax production yield, oil content of the wax, and the pour
point of base oil are directly affected by variables of the

deweixing process. The major process variables include: 1)


solvent composition, 2) feedstock composition, 3) solvent dilution procedure, 4) filtration temperature, 5) filtration procedure, and 6) solvent recovery method.
1. Ketone based solvents Etre excellent solvents for oils at low
temperatures necessary to remove the wax by filtering. Diluting the raffinate with too much ketone-based solvent can
cause the oil to separate into a distinct layer. Oil phase separation will adversely affect the yield of wax and result in
the wix portion having a n undesirable higher oil content.
The likelihood of oil phase separation can be determined
experimentally by maintaining a constant solvent dilution
ratio and changing the percentage of ketone content.
2. If the raffinate feedstock contains a high proportion of
paralBnic content, it will have a high viscosity or viscosity
index. An oil phase sepeiration can occur when a ketonebased dilution solvent is mixed with the raffinate.
3. The amount of dilution with the solvent can affect the oil
content of the wax. Using a solvent dilution greater thcin 2
parts solvent to 1 part raffinate will result in a reduction of
the oil content of the wax.
4. The cooling temperature used to crystallize the wax during
the filtration process can affect the oil content of the wjix
and the desired physical properties such as melting point
and hardness. If the dilution solvent is too cold or low cooling temperatures are used, the crystal size of the wax formed
on the surface of the rotary filter will be small and will retain more oil. As the dewEixing temperature is reduced,
softer and lower melting point wax fractions will increase
the overall production yield. As illustrated in Table 7, as a

FIG. 6Illustration of the effect of solvent dilution ratio on


the amount of residual oil content in the slack wax.

TABLE 7Effect of dewax temperature on wax.


Dewax
Temperature
("F)
(C)

60
55
50

15.6
12.8
10.0

Wax
Yield

(%)

Wax Melt.Point
(ASTM D 127)
(F)
CC)

62
67
72

141
139
137

60.6
59.4
58.3

Wax Needle
Penetration
@ yy-F (25c)
(ASTM D 1321)

11
13
16

CHAPTER 19: PETROLEUM WAXES 531


lower dewEixing temperature is used, wax yield increases
and the melting point and softness change.
5. The dewaxing process is performed to maximize the recovery of the wax with the desired oil content and physical
properties such as melting point a n d hardness. This requires maintaining a uniform thickness (less than 2.5 cm)
of the wax cake on the rotary filter by controlling the process temperatures and rotational speed of the filter. Applying wash solvents (for reducing oil content) uniformly prevents cracking of the wax cake. Diluting with adequate
repulp solvent is necessary to provide a sufficiently fluid
raffinate.
The Wax Finishing Process
The last step in producing petroleum waxes is the finishing
process. This process involves the removal of odor and questionable color. In addition, the finishing process may involve
steps to reduce the polycyclic hydrocarbons to a level that
meets the Food and Drug Administration regulations for food
contact.^
Wax color removal m a y b e performed by flowing wax
through a static bed of activated clay or bauxite. There is a
production loss in the amount of wax after completing the
clay or bauxite contact process. This loss is attributed to absorption of the wax on the clay or bauxite medium and the
production loss is greater for darker colored weixes. Newer
finishing process technology is based o n hydrofinishing
(fixed bed catalj^ic process using hydrogen) and doesn't require any filtering medium. Hydrofinishing has the advantage of processing waxes with negligible product loss [26].
If the wEtx exhibits a questionable odor (such as extraction
or deweixing solvent odor), the wax may be steam stripped
(distilled) to remove traces of processing solvent. Hydrofinishing may also be used to produce odor free wjixes. After the
wax has completed the finishing process step, it can be
shipped to consumers; either in solid form (i.e., 22 kg cartons) or as a molten liquid (in specialized tanks with electrical heaters or steam coils).
Types of Petroleiun Waxes
There are two general types of petroleum waxes that are produced during the dewaxing process. WEIX that is obtained
from the distillate lubricating oil fractions is k n o w n as
macrocrystalline wax (paraffin wax), and wax derived from
the residual distillate lubricating oil fraction is referred to as
microcrystalline wax (microwax). This n o m e n c l a t u r e is
based on the crystal structure of the wax as seen through a
microscope (microstructure). A peiraffin wax can be distinguished from a microwax by its larger crystal structure.
Paraffin waxes usually exhibit plate-like crystal structures
while microwEixes exhibit needle-like crystal structures.
The composition, nomenclature, and physical properties of
petroleum are related to the refinery process used in their
production. Slack wax is a refinery term for distillate-derived
waxes that have oil contents ranging from 3-40% by weight
oil. Scale wax is a distillate wax that has an oil content be-

' FDA regulations for waxes, 21 CFR 172.886 and 21 CFR 178.3710.

tween 1 and 3 % . Petrolatums are derived from the residual


lubricant fractions with oil contents between 10 and 30%
Compositional a n d Molecular Characteristics of
Petroleum Wax
Paraffin waxes consist predominately of a mixture of straight
chain saturated hydrocarbon molecules (normal-alkanes)
with the chemical formula CnH2n+2 with n > 16 [27,28]. In
order to demonstrate the physical properties of straight chain
saturated h y d r o c a r b o n molecules. Table 8 is reported as
taken from Ref 28. In this table the molecular weights, melting points, latent heats of fusion, densities (at 20C), specific
heats in solid and liquid states, and boiling points of the normal cdkanes from Ci to Cioo, all at atmospheric conditions,
are reported. According to this table, the first four alkanes of
the series, (from methane, CH4, u p to butane, C4H10) are
gaseous at room temperature and atmospheric pressure. The
alkanes between C5 and C17 are liquids a n d alkanes with
more than 17 carbon atoms are waxy solids at room temperature. The melting points and heats of fusion of alkanes increase with their n u m b e r of Ccirbon atoms. In addition to the
n-alkanes, paraffin waxes may contain varying amounts of
iso- and cyclo-alkanes (i.e., branched chains and aliphatic
rings). Typiccdly, peiraffin weixes contain carbon atom chains
of Cis to C44. Their macrocrystalline structure is illustrated in
Fig. 7. Their plate-like crystal structures are illustrated by an
atomic force microscope image given in Fig. 8. Their molecular weights are usually less than 450 and their kinematic viscosity at 100C (212F) will usually be less than six centistokes. Being derived from distillate fractions, paraffin waxes
have distinct boiling point curves that consist of a minimum
and maximum value.
Microcrystcilline waxes contain higher proportions of isoand cyclo-alkanes (naphthenic) t h a n paraffin wEixes. MicrorystalUine waxes exhibit molecular weights between 500 and
700 with carbon atom chains ranging typically from C23 to
C85 in length. Their microcrystalline structure is illustrated
in Fig. 9. Microcrystalline waxes (microwaxes) exhibit kinematic viscosities greater t h a n 10 centistokes a t 100C
(212F). Because microcrystalline waxes are derived from
residual fractions, they do not have a distinct boiling range.
Physical properties of microcrystalline waxes vary with the
t5^e of crude oil and processing conditions used to produce
the wax. Tj^pically, microcrystalline, naphthenic waxes exhibit needle-like microstructures.
Intermediate wax properties are intermediate between
those exhibited by paraffin and microcrystalline waxes. They
generally exhibit viscosities between 6 and 10 centistokes at
100C (212F) a n d a melting point between 155-165F
(~68-74C). Intermediate waxes are derived from the highest
boiling distillate lubricating oil fraction and like paraffin
WEixes, they exhibit a distinct boiling point range.
Petrolatums are soft, unctuous products having a melting
point between 100-149F (~38-65C). The term "unctuous"
means "smooth and greasy" in texture. Petrolatums are genercJly produced from the same residual oil fraction as microcrystcJline waxes and can be prepared by controlled blending
of microcrystalline wax with mineral oil. Petrolatums generally
exhibit oil contents greater than 10% and are meirketed with
colors that vary from dcirk brown to white. Table 9 lists the general physical properties of the different petroleum waxes.

532 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 8Physical properties of n-Alkanes [28].

Alkanes

No. of
C Atoms

Mol. Wt

Melting Ft
(K)

Latent Heat
of Fusion
(kJ/kg)

Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
Nonane
Decane
Undecane
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Heptadecane
Octadecane
Nonadecane
Eicosane
Heneicosane
Docosane
Tricosane
Tetracosane
Pentacosane
Hexacosane
Heptacosane
Octacosane
Nonacosane
Triacontane
Hentriacontane
Dotriacontane
Tri triacontane
Tetratriacontane
Pentatriacontane
Hexatriacontane
Heptatriacontane
Octatriacontane
Nonatriacontane
Tetracontane
Dotetracontane
Tritetracontane
Tetrateracontane
Hextetracontane
Octatetracontane
Pentacontane
Hexacontane
Heptacontane
Hectane

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
42
43
44
46
48
50
60
70
100

16
30
44
58
72
86
100
114
128
142
156
170
184
198
212
226
240
254
268
282
296
310
324
338
352
366
380
394
408
422
436
450
464
478
492
506
520
534
548
562
590
604
618
646
674
702
842
982
1402

90.68
90.38
85.47
134.79
143.45
177.83
182.55
216.37
219.65
243.50
247.55
263.55
267.75
278.95
283.05
291.25
295.05
301.25
305.15
309.75
313.35
317.15
320.65
323.75
326.65
329.45
331.95
334.35
336.35
338.55
341.05
342.85
344.55
346.25
347.85
349.35
350.85
352.15
353.45
354.65
357.32
358.65
359.55
361.45
363.45
365.15
372.15
378.65
388.40

58
95
80
105
117
152
141
181
170
202
177
216
196
227
207
236
214
244
222
248
213
252
234
255
238
250
235
254
239
252
242
266
256
268
257
269
259
271
271*
272
273
273*
274
276
276
276
279
281*
285*

Specific Heat (/mol K)


Density at lO'C
(kg/m3)
0.658 (g)
0.124 (g)
1.834(g)
2.455 (g)
621 (1)
655 (1)
679 (1)
699 (1)
714 (1)
726 (1)
737 (1)
745 (1)
753 (1)
759 (1)
765 (1)
770 (1)
775 (s)
779 (s)
782 (s)
785 (s)
788 (s)
791 (s)
793 (s)
796 (s)
798 (s)
800 (s)
802 (s)
803 (s)
805 (s)
806 (s)
808 (s)
809 (s)
810 (s)
811 (s)
812 (s)
814 (s)
815 (s)
815 (s)
816 (s)
817 (s)
817 (s)
819* (s)
820* (s)
822* (s)
823 (s)
825* (s)
831* (s)
836* (s)
846* (s)

Solid at
298 K

485.4
514.6*
544.3
570.7*
598.1*
625.0*
651.4*
670.4*
677.8
728.1*
752.8*
777.2*
801.2*
824.5*
867.4
871.0*
887.4
916.0
937.5*
959.1*
980.4*
1001*
1022*
1062*
1085*
1102*
1140*
1177
1213*
1380*
1526*
1869*

Liquid at
353 K

Boiling Pt
(K)

0167.2
195.4
225.0
254.2
284.5
314.5
345.0
376.0
406.9
438.5
470.0
501.5
534.3
564.4
618*
658*
698*
739.0
772.0
805.0
815.9
870.0
928*
937.0
1001*
1037*
1073*
1095
1113
1149
1210*
1206
1276*
1305*
1341*
1411
1435
1465*
1495*
1553*
1595
1665*
1916*
2131*
2598*

116.6
184.6
231.1
272.7
309.0
341.9
371.6
398.8
424.0
447.3
469.1
489.5
508.6
526.7
543.8
560.0
575.2
589.5
603.1
617.0
629.7
641.8
653.4
664.5
675.1
685.4
695.3
704.8
714.0
722.9
731.2
740.2
748.2
755.2
763.2
770.2
777.2
784.2
791.2
795.2
804.2
813.2
818.2
829.2
838.2
848.2
888.2
919.2
935.2

(*)Predicted value.

(a) X 200

X 1000

FIG. 7A scanning electron microscopic illustration of a macrocrystalline structure wax


(a = 200X;b = 1000X).

(b)

CHAPTER 19: PETROLEUM WAXES

533

FIG. 8An atomic force microscope image of the spiral growth of paraffin crystal (measuring approximately 15 microns across). Inset shows orthorhombic arrangement (0.49 nm x 0.84 nm) of chain ends of one of the crystal terraces (courtesy of Professor M.J. Miles).

X 1000

(a) X200

(b)

FIG. 9A scanning electron microscopic illustration of a microstructural characterization of a refined paraffin wax (a. = 200 X; b = 1000 X).

TABLE 9 --Physical properties of petroleum waxes.


Property

Paraffin Wax

Intermediate

Microcrystalline

Petrolatum

Melt. Point (F)


Molecular Wt.
Crystal Structure
Color

110-155
320^50
Plates
White

150-165
450-550
Needles
WhiteYellow

140-195
450-700
Needles
WhiteDark Brown

110-180
450-700
Needles
WhiteDark Brown

Crystal Structure
ParafBn waxes exhibit several crystalline structures depending on their carbon chain length. Odd n u m b e r carbon chains
between C19 and C29 exhibit an orthorhombic type crystal
structure. Even numbered carbon chains between Cjg and
C26 exhibit a triclinic structure. Even n u m b e r e d carbon
chains between Cjg and C36 exhibit a monoclinic structure.
All paraffins with carbon chains between C20 and C36 have a
distinct transition point (change in crystal form) lower than
the temperature at which they solidify. The transition point

occurs when the wax crystal structure rotates from a hexagonal to o r t h o r h o m b i c form as the wax solidifies from a
molten state. Paraffins with carbon atom chains above C37 do
not exhibit a transition point due to the wax solidifying directly into a n o r t h o r h o m b i c crystal structure. Microcrystalline and intermediate type waxes do not exhibit any transition point because they contain higher a m o u n t s of
branched alkanes.
Because of the steric effects caused by the arrangement of
atoms in the molecule there is a difference between alkanes
with odd and even numbers of carbon atoms. The even-num-

534 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

bered homologs have higher latent heat than the odd-numbered homologs. Humphries [29] showed that alkanes with an
even number of carbon atoms (between 20 and 32) and alkanes with odd number of carbon atoms (higher than 7) exhibit
a lattice transition in the solid state. The even-numbered carbon atom alkanes exhibit this transition closer to their melting point than the odd-numbered alkanes, as demonstrated in
Fig. 10. The boiling point of normal-alkanes for the temperature range on the figure are sJso shown in Fig. 10.
The lattice transition in alkanes is accompanied by the release of heat of transition. Generally, lattice transition occurs

in the solid state at about 2-5K below the melting point. The
difference between the transition temperature and melting
temperature becomes smaller with increasing molecular
weight and finally disappears for alkanes with more than 36
carbon atoms [25,28] as demonstrated in Fig. 10. The heat associated with this solid-solid transition is subtracted from the
lattice heat of melting. Figures 11 and 12 show variations of
the latent heat of melting, melting point, and density of normal alkanes versus increasing number of carbon atoms in
their structure. According to these figures, while the melting
point and density versus the number of carbon atoms have

500

'

25
30
35
Number of carbon atoms

40

FIG. 10Variation of meiting point (MP), transition temperature (TrT), and boiling point
(BP) of normal alltanes with their number of carbon atoms [28].

1 .
3

_^-<TyOO-C/-

non

cS

g250 o>
I

Si
S200

O o9?fm
AAI&OO"

"O

r,

"

QRRF"^^^
)00

9NM

rtAl i t " 1

wX* *

sw-

_i
150 -

f
6

100 -

20

40

60

80
100
Number of carbon atoms

FIG. 11Variation of the latent heat of melting of normal alkanes with the number of carbon atoms in alkanes and exhibition of the steric effect [28].

CHAPTER 19: PETROLEUM

1000

400

a
u
800 11

3
>

600

400

200

20

40

60

80

^0
.100

Number of carbon atoms


FIG. 12Variation of tlie melting point and density (@ 20C)
of normal alkanes with the number of carbon atoms in alkanes
[28].

smooth variations, the latent heat of meUing goes through


fluctuations. Because of the steric effects (the solid-solid
phase transitions mentioned above) the latent heats of melting of two consecutive alkanes do not always increase with increasing number of carbon atoms, as demonstrated in Fig. 11.
Each even-numbered alkane (with eight carbon atoms or
more) exhibit a lower latent heat than the odd numbered
alkane having one carbon atom less than it. This fluctuation
of the latent heat of melting vanishes as the number of carbon
atoms approaches 40, and after that the latent heat increases
smoothly with increase of the number of carbon atoms.
As an example, the composition and thermophysical data
of a paraffin wax sample (Suntech PI 16) [30], which contains
almost 100% normal alkanes, is reported in Table 10. According to this table, the hydrocarbons with 20-32 carbon
atoms constitute 99% of the mixture and the ones with more
than 32 carbon atoms constitute the remaining 1%. Paraffin
waxes are generally polydisperse compounds for which polydisperse solution (continuous mixture) theories may be used
for characterization [31]. Figure 13 is the graphic representation of the composition data of Suntech PI 16 paraffin wax
reported in Table 10.
Wax can be crystallized out of a solution by lowering its
temperature. Varying the temperature gradient causes a transition between the growth of wax plates and growth of a treelike structure with regular branches as it is shown on Fig. 14.
Also shown on Fig. 14 is the banded growth of wax due to addition of a crystallization inhibitor.
Equations of State
In order to characterize the petroleum wax and perform various operations on weix mixtures, such as wax fractionation,

WAXES

535

it is necessary to be able to predict thermodynamic properties of wax. In this section we present five equations of state,
which are used for prediction of molar volumes, vapor pressures, and supercritical solubilities of alkanes [32].
The simplest and one of the most widely known equations
of state is that of van der Waals. However, this equation of
state is not accurate enough to predict thermodynamic properties of most fluids. Inspired by the van der Waals model, investigators have proposed several equations of state through
the years. Almost every equation of state has been claimed to
Table 10Chemical composition and
thermophysical properties of Suntech PI 16
Paraffin Wax [30].
Hydrocarbon
Weight -%
n-C-20
n-C-21
n-C-22
n-C-23
n-C-24
n-C-25
n-C-26
n-C-27
n-C-28
n-C-29
n-C-30
n-C-31
n-C-32
Melting range
Heat of fusion
Liquid specific heat
Solid specific heat
Liquid thermal conductivity
Solid thermal conductivity
Liquid density
Solid density
Liquid viscosity
Molecular weight

2.0
5.5
14.0
23.0
22.0
14.0
6.5
3.0
2.5
2.0
1.7
1.5
1.3
316-329K
266 kJ/kg
2.51kJ/kgK
2.95 kJ/kgK
0.24 W/mK
0.24 W/mK
760 kg/m^
818kg/m^
1.90kg/ms
332 g/mol

20 21.22 23 24 25 26 27 28 29 30 31 32
Number of carbon atoms
FIG. 13The distribution of n-alkanes in Suntech P116
paraffin wax as a function of the number of carbon-atoms
[28].

536

MANUAL

3 7 ; FUELS AND LUBRICANTS

A-. . " . - V

' -'i*.- T i ; : -

' >

HANDBOOK

fr^,
- . .

PR, and SRK are three-constant-parameter equations. All the


above-mentioned five equations of state can be written in the
following generalized form [32]:

2 =

'ivX

v-V yb

(2)

T%v + Tjc)(w + Ac)

where a=naaR^
Tj^-^'^ / Pc and 6 = c = rij, ^ i? T,. / P^.
Parameters {1^, ^b, y, V> and ^ ^re component-independent
constants, while a a n d j3 are component-dependent constants, and their numerical values for various equations of
states are given in Table 11. In extending the equations of
state to mixtures, parameters a, b, and c are replaced with Um,
b, and Cm with the following expressions (mixing rules):

RK. PR, SRK, RM-1: a = 5 2 :>'>'/^y


i
i

(4)

bm = 1352y3'Ay + X>''^ ) r ^rri =

'^yAi

For the RM equation there is another alternative in extending it to mixtures by replacing Tc and Pc with Tcm and Pcm as
given below:

(b)

..

FIG. 14(a) An atomic force microscope image of wax


"trees" growth in a lowering temperature solidification of wax
from solution. Varying the temperature gradient causes a transition between the growth of wax plates and growth of a
tree-like structure with regular branches; (b) An atomic force
microscope image of banded growth of wax due to addition of
crystallization inhibitors (courtesy of Prof. J.L. Hutter).

RM-2: T,m =

{^yiyiTl^pMy^yiyiT,i,pX

Rfn = YI,yiyiR%
i J

be superior in some respects to the earlier ones. The RedhchKwong (RK) equation that is a modification of the van der
Waals equation, was a considerable improvement over other
equations of relatively simple forms at the time of its introduction. In the Soave-Redlich-Kwong (SRK) equation, the
temperature-dependent term of a/T"-^ of the RK equation is
replaced by a function denoted by a that depends on the
acentric factor of the compound and temperature. The PengRobinson (PR) equation is another cubic equation of state involving acentric factor. Riazi and Mansoori [33] modified the
parameter h of the RK equation by introducing a function,
denoted by '?, that depends o n the refractive index of the compound. They showed that the resulting equation is quite accurate in the prediction of hydrocarbon densities. MohsenNia et al. [34] proposed that the 3M equation in which the
repulsive part of the RK equation is modified based on the
statistical mechanics improved the thermodynamic predictions appreciably. This equation is shown to be more accurate for heavy hydrocarbon phase behavior calculation than
most of the other equations of state. RK and 3M equations
are two-constant-parameter equations of state, while the RM,

These equations of state can be used to calculate properties


of Wcix, its components, i.e., vapor pressure, and molar volumes
of liquid at saturated-, sub-cooled and supercriticEd-conditions
as well as the solubility of wax in supercritical solvents.
To perform phase equilibrium and other saturated property calculations for WEIX in liquid and vapor states, we need
to perform equality of pressures and fugacity calculations
[32]. The fugacity coefficient of a component of the wax in a
mixture (<^r)?derived from the generalized Eq 1 is in the folTABLE 11Parameters of the generalized equation of state.
Eq. of State
Parameters 4y
iq

RK

MMM

RM

PR

SRK

0
1
0
0.5
0.42748
0.08664
1
1

1.3191
1
0
0.5
0.487480
0.064462
1
1

0
1
0
0.5
0.42748
0.08664
1

0
1 -H V2

0
0
0
0
0.42748
0.08664

1 -V2
A
0
e
0.45724
Oa
0.07780
ftfa
a
PR
CSRK
1
1
PRM
/3
apR = [1 + (0.37464 + 1.524226M - 0.26992m^)(l - T?')]^
CSRK = [1 + (0.48508 + 1.55171a) - 0.156132)(1 - T-^)T
(fe)-' = 1+ [0.02[1 - 0.92 exp(-l,000 \T, - I|)] - 0.035 (T, - 1)]{R*-1)

CHAPTER
lowing form [32]:
In <AF = (1 + y)
-InZ-

dinbmVdtii

CnRT'^^^"^

Uffj

dtli

+ XCm)

K = y [ ( l + 2fv)l(l

1 d{nc)

1 d(rp-a)

ir, - \)cRT^'^^^

WAXES 5 3 7

erence system, SG = specific gravity, Th = normal boiling


point, in degrees Rankine, a = \ - Th I T, ASG = specific
gravity correction and f = correction factor.
The critical volume (in cubic feet per pound mole) is given
by the following expressions [37]

ln(i; - bm/v)

{v + TprnXv

19: PETROLEUM

Cm

2fv)r

(8)

(6)
where

drii

fv = ^SGv [0.466590/ri'2
+ (-0.182421 + 3.0172/r^'^)ASGv]
ASGv = exp [4(SG2 - SG^)] - 1

where for RK, PR, SRK, RM-1:


1 din^Um)

^^

V? = [(0.419869 - 0.505839a - 1.5643a3 - 9481.70a'4)]-

d{nbm)

a(nc,n) L

The critical pressure (in psia) is given by the following expression [37]:

for 3M:

P, = P (r,/7^)(V?/yj[(l + 2fp)/(l - 2fp)f

1 din^dm)
n
anj

-V
=

2 >

^(nb,)
an;

(9)

where

V.77.V

fp = ASGp [(2.53262 - 4 6 . 1 9 5 5 / 7 ^ - 0.00127885 n)

M^l^yih - YLyiythj + ^

+ (-11.4277 + 252.140ITl'^ + 0.00230535 Tb)ASGp]

bu

ASGp = exp [0.5(SG - SG)] - 1


P = (3.83354 + 1.19629ai'2 + 34.8888a

and for RM-2:

+ 36.1952a2 + 104.193a^)2
J_ d{n a^)
J-

-J

^ ^ RTO-SI^Y

V T^ IP - - T

ii^xvj cfn\ -^/^^jj]^ CI}'^ CI}

T vT

IP

and where V = molar volume, in f?^/lbmole, P = pressure, in


psia and subscripts V and P refer to the volume and pressure.
The acentric factor can b e estimated with the use of the
generalized Edalat et al. vapor pressure equation [38]:

^ cm / , Yi^ cii'^ ci

'

\ /
/
d{nbm)
d(ncm)
/ o,
9/3 V v v
T- /D ^
= (-li + n - ^ j \ l l yffi TclPciij
drii
dm

In PR = (ar + br^'^ + cr^ + dr^)l{\ - T)

(10)

T=l-T/Tc,

(11)

where
To calculate liquid molar volume and vapor pressure using equations of state, t h e data of critical temperature a n d
pressure, acentric factor, a n d molar refraction are needed.
The experimental critical properties of n-alkanes u p to C24
are available in the literature [35,36], while those of n-alkanes higher t h a n C24 c a n b e estimated using correlations.
The critical temperature (in degrees Rankine) can be written as [37]:
r , = r [ ( l + 2fr)/(l - 2 / r ) ] '

(7)

where
JT = ASGr [-0.362456/7^'^
+ (0.0398285 - 0.948125/4'2)ASG7-]
ASGr = exp [5(SG - SG)] - 1
Tt = Tb (0.533272 -t- 0.191017 X 10"^ Tb + 0.77968
X 10"^ Ti -0.284376 X l O " ' " Tl + 0.959468 X 10^^ T^ " )
SG" = 0.843593 - 0.128624a - 3.3615a^ - 13749.5a'^
and where subscript T refers to t e m p e r a t u r e , subscript c
refers to the critical conditions, superscript o refers to the ref-

W= (-logP)7-^=o.7 - 1
and
a{ca) = - 6 . 1 5 5 9 - 4 . 0 8 5 5 & ;
fo(w) = 1.5737 - 1.0540(0 - 4.4365^:10^^^(0))
c(w) = - 0 . 8 7 4 7 - 7.8874W
d{(,}) = (-0.4893 - 0.9912W + 3.15510^)''
The above equation is quite accurate for calculation of vapor pressure provided the acentric factor and critical properties of a fluid a r e available. The molar refractions of wax
compounds needed in the RM equation of state are available
in Ref. 36.
The accuracy of molar volumes of saturated liquid wax
components, molar volumes in sub-cooled and supercritical
conditions a n d vapor pressures calculated using various
equations of state are reported in Tables 12-14, respectively.
According to these tables the three-constant RM equation of
state is quite satisfactory for molar volume prediction while
the SRK is accurate for vapor pressure prediction of wax.
In Fig. 15 the solubility of n-tritriacontane (n-CaaHgg) in supercritical carbon dioxide is depicted along with the predictions obtained from various equations of state. According to

538 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


TABLE 12The average deviations of various equations of state in predicting saturated liquid molar volumes of pure
compounds compared with those csilculated using the hankinson and thomson (1979) correlation.
AAD%
Compound
CO2
CH4
C2H6
C3H8
H-CAHIO
M-C5H12
n-C(,}ii4
n-CjHif,

n-CsHis
M-C9H20
n-CioH22
n-CiiH24
n-Ci2H26
"-C13H28
n-Ci4H3o
W-C15H32
"-C16H34
M-Ci7H36
H-C18H38
M-C19H40
ra-C2oH42
M-C22H46
ra-C24H5o
n-C28H58

Tr Range

RK

3M

RM

PR

SRK

0.71-1.00
0.48-0.99
0.33-0.99
0.35-0.98
0.36-0.96
0.47-0.99
0.39-0.99
0.41-0.99
0.41-0.99
0.42-0.98
0.43-0.98
0.55-0.78
0.54-0.89
0.56-0.80
0.54-0.85
0.58-0.82
0.56-0.81
0.59-0.83
0.55-0.84
0.56-0.85
0.57-0.85
0.55-0.81
0.56-0.82
0.58-0.84

19.5
4.5
10.3
11.2
13.3
16.8
19.9
22.3
24.7
26.8
29.9
31.1
35.3
37.6
42.8
45.8
49.7
56.2
59.5
63.5
67.9
57.6
66.2
62.9
36.5

8.8
13.9
11.8
10.8
9.0
7.5
6.9
7.4
6.9
7.8
10.5
10.5
14.7
16.5
21.4
24.1
26.9
32.9
35.5
39.0
42.9
31.8
39.2
36.4
19.7

19.5
4.5
6.4
3.9
3.0
2.4
2.2
1.4
1.2
0.8
0.7
0.3
0.4
0.2
1.2
1.2
1.8
3.9
4.0
4.4
4.8
4.5
2.9
11.2
3.6

4.7
8.6
6.0
5.3
3.6
3.4
2.2
2.7
4.2
5.1
7.0
7.4
10.1
11.4
15.0
16.7
19.7
24.3
26.9
29.6
32.2
25.1
31.1
27.7
13.8

14.7
4.5
9.2
9.2
10.3
12.5
14.8
16.0
17.7
18.7
20.8
21.3
24.3
25.8
29.9
31.8
35.1
40.3
43.1
46.1
49.0
40.6
47.2
43.1
26.1

Overall

TABLE 13The average deviations of various equation of state in predicting molar volumes of liquids in sub-cooled and
supercritical conditions compared with experimental data.
AAD%

Experimental Data

Compound

Tr Range

Pr Range

RK

3M

RM

PR

SRK

No. of Data Pts.

Ref

CO2
CH4
C2H6
C3H8
M-C4H10
W-C5H12
n-C6Hi4
n-C7Hi6
n-C9H2o
W-C11H24
M-C13H28
n-CnH36
W-C20H42
M-C30H62
Overall

0.7-2.2
0.5-2.6
0.3-2.3
0.2-1.9
0.3-1.7
0.4-0.7
0.4-0.7
0.6-1.1
0.5-1.0
0.5-0.9
0.4-0.9
0.4-0.8
0.4-0.8
0.4-0.8

1.0-13.6
0.0-15.2
0.0-14.3
0.0-16.5
0.0-18.5
0.0-71.3
0.0-332
1.8-183
2.2-218
2.6-259
3.0-303
4.1^10
5.0-500
6.8-682

5.0
2.0
3.8
5.9
8.4
11.2
14.7
14.5
18.8
25.1
32.3
48.5
59.9
62.7
22.3

4.8
11.1
11.2
9.6
8.4
7.6
5.8
5.6
3.1
3.1
7.9
19.8
28.6
28.9
11.1

5.0
2.0
1.7
1.8
1.6
0.8
2.0
2.3
2.2
2.6
3.2
7.2
9.9
6.8
3.5

2.9
7.4
5.6
4.2
3.8
2.5
2.5
3.3
5.1
10.4
16.7
31.0
41.1
43.5
12.8

6.1
2.4
4.1
5.9
7.9
9.4
12.6
13.5
17.1
23.1
30.1
45.9
57.1
59.8
21.0

447
459
474
533
638
880
510
70
66
70
70
60
50
50
4377

a
b
c
d
e
f
f
f.g
S
S

" Angus et al., 1976.


''Goodwin, 1974.
' Goodwin and Roder, 1976.
'^ Goodwin and Haynes, 1982.
' Haynes and Goodwin, 1976.
f Frenkel et al., 1997a.
i^Doolittle, 1964.

s
s
s
s

CHAPTER 19: PETROLEUM

WAXES

539

TABLE 14The average deviations of various equations of state in predicting vapor pressures of pure compounds
compared with the experimenteJ data.
AAD%
Compound
CO2
CH4
C2H6
C3H8
n-C4Hio

n-CsHn
n-C6Hi4
n-CyHie
n-CgHis
n-C9H2o
f3-CioH22
n-CiiH24
n-Ci2H26
n-Ci3H28
n-Ci4H3o
W-C15H32
-Cl6H34
n-Ci7H36
n-CisHss
?2-Ci9H40
n-C2oH42
ra-C22H46
n-C24H5o
n-C28H58
M-C29H60
n-C3oH62
M-C32H66
n-C33H68

Experimental Data

Tf Range

RK

3M

RM

PR

SRK

No. of Data Pts.

Ref

0.71-1.00
0.48-0.99
0.33-0.99
0.35-0.98
0.36-0.96
0.47-0.99
0.39-0.99
0.41-0.99
0.41-0.99
0.42-0.98
0.43-0.98
0.55-0.78
0.54-0.89
0.56-0.80
0.54-0.85
0.58-0.82
0.56-0.81
0.59-0.83
0.55-0.84
0.56-0.85
0.57-0.85
0.55-0.81
0.56-0.82
0.58-0.84
0.54-0.84
0.54-0.84
0.55-0.85
0.55-0.85

19.1
17.2
11.5
19.8
43.2
63.4
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
-2100

4.0
50.0
36.3
39.5
32.4
19.2
15.8
11.0
18.5
33.2
51.4
81.7
89.9
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
-650

19.1
17.2
11.9
8.3
7.0
9.9
16.5
20.7
28.9
33.3
37.4
37.7
31.7
28.8
30.3
23.4
29.3
23.9
30.2
30.4
33.0
69.1
79.4
57.9
82.5
75.8
61.5
56.9
35.4

0.8
0.7
3.0
3.0
5.6
0.8
3.1
2.4
2.7
2.1
3.1
6.6
2.9
3.3
5.8
4.0
5.6
6.2
9.2
10.4
8.8
18.6
24.7
33.9
42.5
44.5
48.9
51.8
12.7

0.5
2.9
2.6
1.9
1.9
1.5
1.9
1.2
1.2
1.5
1.2
4.4
0.4
0.5
2.5
0.6
0.9
1.6
3.0
3.6
2.4
1.2
1.5
1.7
2.7
2.7
3.2
3.9
2.0

47
84
114
101
130
91
88
80
87
82
86
27
40
27
42
27
45
43
44
42
42
21
22
23
12
12
12
12
1483

a
b,c
b,d
b,e
b,f
b,h
b,h
b,h
b,h
c,h
b,g,h
b
b,g,h
b
b,g,h
b
b,g,h
b
b,g
b,g
b,g
b,g
b,g
b,g
b
b
b
b

Overall
" Angus et al.. 1979.
'' Frenkel et al. , 1997a.
= Goodwin, 1974.
'' Goodwin and Roder, 1976.
" Goodwin and Haynes, 1982.
' H a y n e s and Goodwin, 1976.
^ Morgan and Kobayashi, 1994.
' Salerno et al. , 1986.

this figure, the 3M and RM equations aire capable of predicting supercritical solubilities accurately. In all these cases the
unlike-interaction parameter,fcy,is best fitted to experimental data. Table 15 shows the interaction parameters of various equations of state for a number of systems at various
temperatures along with the AAD%. According to this table,
the 3M equation of state gives the least value of AAD%.
Differential Scanning Calorimetry
When a solid is heated, it may absorb heat resulting in a temperature increase or a structural change (phase transition)
such as a solid to liquid or a transition from one crystalline
form to another. These transitions may be endothermic (absorb heat) or exothermic (emit heat) depending on the thermal process that is occurring. These thermal processes may
be quantitatively measured by differential scanning
calorimetry (DSC).
DSC analysis is performed by heating two small sample
pans, one containing the material being analyzed and the
other empty and used as a reference. The analysis concept is
that the two sample pans are maintained at a very small temperature difference ( 0.01C). Each pan is heated with two
heaters; a main heater and an auxiliary heater. After begin-

ning the experiment by supplying heat with the main heaters,


while heating the temperature difference (AT) between the
sample and reference pans is sensed using a thermopile (set
of thermocouples) which produces a small (0-5/xV) off-setting voltage. The auxiliary heater is then used to heat the
sample pan to keep the off-balance voltage close to zero. The
instrument displays the differential power (AP) between the
two pans as a function of temperature. The area under the
peak of differential power (AP) versus temperature (T) provides an experimental measure of the energy or total enthalpy
change (AH) of the entire process [39,40].
As described in ASTM Test Method D 4419, the melting
point can readily be determined by DSC analysis, as can heat
of fusion, which is also an important characterization parameter for waxes. Heat of fusion is defined as the increase in
enthalpy accompanying the conversion of one mole, or a unit
mass, of a solid to a liquid at its melting point at constant
pressure and temperature [43]. The heat of fusion (AATf) is obtained from the melting transition peak illustrated in Fig. 16,
by measuring the total area under the peak that is proportional to the heat flow per mass of material. Heat flow is the
heat emitted per second, therefore the area under the peak is
given in units of (heat temperature time"*) for the mass of
the sample used. As a result the area per unit mass (APUM)

540

MANUAL 37: FUELS AND LUBRICANTS


o

/tr-s-S^*-"

-5
-6
^-7

j
1

0-9
-11
-12

HANDBOOK

/
/
RK

Pr
4

/--rrQjQ.oo

-5
-6

Ss
-n
-12
-13

PR

M-~-.

Pr

Pr

FIG. 15Solubility of n-tritriacontane (n-CssHes) in supercritical carbon dioxide at 308


K as predicted by various equations of state and compared with the experimental solubility data [32].

of the sample will be


APUM

Heat X Temperature
Ttime X Mass

Q J^ ~0M

(12)

Typically, the actual units of \Hf&re (joules Kelvin seco n d s " ' g r a m s " ' ) . Typically, the APUM is divided by the
heating rate (K/s) of the DCS experiment used to collect the
data. This will simplify the expression to yield the specific
heat of melting:
Q.T
APUM
Heating Rate

e.M

X
e

Q_

(13)

Since the mass of the sample that was analyzed is known, it


is then multiplied by the heat emitted/gram of sample to 5deld
the amount of heat given off (Q) during the melting process.
(14)
%XM
=M
M
Figure 16 illustrates the DSC traces for three different
petroleum waxes; one for each wax type - paraffin (Fig. 16a),
intermediate (Fig. 16^), and microwax (Fig. 16c). The DSC

trace shown by Fig. 17 demonstrates the decrease in crystallinity as the melting point of the wax increases. The thermal analysis procedure for this work was started at - 50C for
o p t i m u m crystallization of the wax. The wax sample was
heated at a controlled rate to +150C. The point at which
there is a deflection in the base line is the temperature that
the wax begins to melt. The point at which the peak scan returned to the base line is the temperature the wax sample is
completely melted. The peak area represents the amount of
energy used to melt the wax sample and is calculated as described above. In addition, an estimate on the expected melting point can be distinguished. The experienced technologist
could tell by looking at the shape of a DSC trace if the wax is
a paraffin, intermediate, or microwax. Paraffin waxes typically exhibit sharp peaks as shown in Fig. 16a, DSC peak
shapes for intermediate waxes are less sheirp as shown in Fig.
\6b, and microwaxes exhibit even less sharp peaks, typically
like the peak shown in Fig. 16c.
It should be noted that there is a characteristic small transition peak in the DSC trace for a macrocrystalline paraffinic
wax as illustrated in Fig. 16fl. The transition that is indicated
is a solid-solid phase change (orthorhombic to hexagonal

TABLE 15 Interaction parameter (ki2) of some systems.


System
C2H6 - M-C28H58
C2H6 - n-C29H6o
C2H6 - M-C30H62
C2H6 - K-C32H66

C2H6 - ra-C33H68

CO2 - n-C28H58

C 0 2 - M-C29H60
CO2 - -C3oH62
CO2 - n-C32H66

CO2 - n-CjsHfts

AAD%

kyi

T
[K]

P
[bar]

RK

3M

RM-2

308.2
308.2
308.2
313.2
308.2
313.2
318.2
319.2
308.2
313.2
318.2
307.2
308.2
313.2
318.2
318.6
323.4
325.2
308.2
318.2
308.2
318.2
308.2
318.2
328.2
308.2
318.2
328.2

56-240
65-240
66-200
66-136
66-240
66-200
80-240
80-136
65-240
65-202
65-240
123-181
80-240
90-275
100-250
119-284
125-327
121-284
100-240
100-240
90-250
105-250
120-240
140-240
140-240
120-240
140-240
140-240

-0.4638
-0.4146
-0.4777
-0.4738
-0.5124
-0.5011
-0.5248
-0.4872
-0.4632
-0.4459
-0.4506
-0.3458
-0.3161
-0.2910
-0.2915
-0.3067
-0.2973
-0.2946
-0.2751
-0.1961
-0.3254
-0.3125
-0.4140
-0.3913
-0.3777
-0.3461
-0.3384
-0.3057

-0.2099
-0.1618
-0.2066
-0.2137
-0.2259
-0.2264
-0.2438
-0.2241
-0.1933
-0.1845
-0.1918
-0.0936
-0.0901
-0.0835
-0.0867
-0.0859
-0.0869
-0.0867
-0.0530
-0.0540
-0.1141
-0.1197
-0.1500
-0.1462
-0.1345
-0.1051
-0.1043
-0.0990

0.0807
0.1215
0.1025
0.0901
0.1020
0.1050
0.0966
0.1087
0.1100
0.1433
0.1433
0.2487
0.2477
0.2532
0.2504
0.2531
0.2552
0.2540
0.2782
0.2789
0.2481
0.2439
0.2448
0.2483
0.2596
0.2825
0.2832
0.2878

PR

SRK

RM-1

RK

3M

RM-2

PR

-0.0553
-0.0131
-0.0571
-0.0517
-0.0707
-0.0658
-0.0762
-0.0565
-0.0286
-0.0240
-0.0203
0.0110
0.0296
0.0365
0.0359
0.0347
0.0385
0.0321
0.0645
0.0818
0.0327
0.0273
-0.0162
-0.0035
0.0044
0.0262
0.0280
0.0428

-0.0189
0.0260
-0.0206
-0.0139
-0.0297
-0.0263
-0.0347
-0.0157
0.0137
0.0193
0.0228
0.0507
0.0708
0.0765
0.0746
0.0736
0.0764
0.0690
0.1075
0.1451
0.0779
0.0700
0.0316
0.0426
0.0477
0.0754
0.0872
0.0876

-0.1283
-0.0701
-0.1121
-0.1233
-0.1214
-0.1131
-0.1142
-0.1219
-0.0779
-0.0580
-0.0530
0.0211
0.0194
0.0286
0.0232
0.0278
0.0314
0.0287
0.0670
0.0672
0.0084
-0.0005
-0.0139
-0.0092
0.0104
0.0496
0.0494
0.0557

46.2
53.1
25.0
13.9
46.
24.4
45.2
23.6
50.2
39.6
45.7
51.0
52.3
46.7
64.7
53.7
62.5
64.2
71.8
81.2
69.6
67.5
59.5
67.3
57.5
68.4
65.0
67.4
60.0

27.0
29.9
22.8
30.8
43.0
34.5
17.7
37.4
34.4
21.5
24.2
7.5
18.3
25.0
13.4
8.2
5.8
7.3
21.5
22.2
17.1
8.3
8,1
6.7
9.2
25.0
22.9
18.5
20.3

14.4
23.9
57.2
29.7
56.2
40.2
22.8
39.3
50.7
28.9
28.0
34.4
35.0
44.5
31.0
33.2
28,9
22,6
12,9
6,9
28,8
28.7
24.1
22.3
27.1
11,3
4,8
3,5
28,3

38,
48.
22.
18.
41.
20.
32.
28.
43.
25.
42.
45.
49.
39.
47.
45.
53.
45.
67.
76.
66.
57.
54.
55.
40.
64.
61.
60.
46.

Overall
" Kalaga and Trebble, 1997.
' Moradinia and Teja, 1986.
" Suleiman and Eckert, 1995
' Moradinia and Teja, 1988.
" McHugh et al., 1984
^Reverchon et a ., 1993.
^ Chandler et al., 1996.

S5.0

sao
7SJ>

fata
^

TOO

2\SC
55.syc
SISJ
1316.99
2IB.99

sg s ^*'
&o1 *"35,BJM
Z5JI

"T

I
soo

-2SJ)

TSJ

IOOLO

12M

1500

Tenq>a-^iire(<0

XI

^xsrc

TS3yC
PCA
6ssn
Am I13&63
rtH 17172
H e i ^ 43Jf7

4M-

S, 4 M -

*
s

1-:

..

3W1-

-1S.0

25,0

5IU

1
7U

TemperatnTO (Q

lOOJ)

1
125,0

151

Teiiii)eratiire('C)

FIG. 16The heat of fusion (AHr) calculation from the DSC melting transition peak by
measuring the total area under the peak, (a) paraffin, (b) intermediate, (c) microwax.

542 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK

1
-50.0

-25.0

r
ao

25.0

50.0

75.0

1
lOaO

r
125.0 150.0

Temperature (Q
FIG. 17The heat of fusion (AH) calculation from the DSC
melting transition peak by measuring the total area under the
peak of several paraffins demonstrating the decrease in crystallinity as the melting point of the wax increases.
crystal structure). As the wax crystal continues to absorb energy, a larger peak is recorded and then actucil melting occurs
with a return to the base line as the temperature continues to
increase.
In addition, there is a bimodality indicated in the DSC
trace peak shapes for intermediate (Fig. 16b) and microciystalline (Fig. 16c) waxes. Bi-modal shape is related to the
breadth of the wax composition. Bimodal peak shape is not
related to transition. The apparent bimodality indicates that
the wax has not been made as a narrow distillation cut. The
melting point of wax is in the DSC area that the curve begins
to return to the base line (downward slope) as the temperature increases. The squat DSC peak shape of the microwax
shown in Fig. 16c indicates that it is less crystalline and has
a broader melting. The apparent bimodality of the microwax
is related to the different melting fractions that appear in this
particular wax.
Determination of the heat of fusion of a wax is of practical
significance for a n u m b e r of reasons. For example, the
changes of shape of a DSC trace to that of known waxes may
indicate that a wax has been contaminated or altered. This
may be confirmed by comparing the heat of fusion of a previously purchased paraffin wax with the suspect wax. For example, a historical value for heat of fusion of a wax may be
200 J/g and a newly purchased paraffin wax may have a heat
of fusion of 180 J/g. This variation confirms that the two
waxes exhibit different properties.
Another application of the heat of fusion could be for the
comparison of properties of nominally similar waxes offered
by two different suppliers. The higher the heat of fusion, the
more crystalline the wax is. For some applications, like candles, high crystallinity is desirable to aid in the mold release
properties due to shrinkage upon cooling. Low crystalline
waxes do not shrink as m u c h as high crystalline products.
ASTM Test Method D 4419 has been developed to characterize petroleum waxes and measurement of their transition t e m p e r a t u r e s by Differential Scanning Calorimetry
(DSC). Figures 16a, 16b, and 16c are DSC endothermic
scans of a paraffin, intermediate, and microcrystalline wax.

respectively. Referring again to Fig. 16a (paraffin wax), the


endotherm is started at 50C for optimum crystallization
of the wax. The wax sample is heated at a controlled rate to
-l-150C. The point at which there is a deflection in the base
line is the temperature that the wax begins to melt. The
point at which the peaik scan returned to the base line is the
temperature the wax sample is completely melted. The peak
area represents the a m o u n t of energy used to melt the wax
sample as discussed above. Figure 17 illustrates that as the
melting point of paraffin wax increases, the heat of fusion
decreases because of the higher content of less crystalline
branched alkane structures. Microcrystalline waxes have a
lower heat of fusion than paraffin wax that is directly related to the greater amount of branched alkanes (less crystalline microstructure). Listed in Table 16 are the typical
heats of fusion data for both paraffin and microcrystalline
waxes.

Effect of Additives
In the petroleum wax industry, it is often necessary to use additives to improve the processability of wax or wax mixtures
by modifying their physical properties. This may be accomplished by the addition of additives that may include stearic
acid, polyethylene, ethylene-vinyl acetate copol5'mer or a Fischer-Tropsch wax. For example, stearic acid may be added to
a paraffin weix to increase firmness, reduce melting point, aid
in mold release, prevent candles from losing their shape in
warm weather, etc. Polyethylene is another additive that may
be used. Polyethylene m a y b e added to a paraffin wax to
harden the wax structure, modify burning rate, and improve
strength and gloss. In addition to physical property modification, additives also could alter the microstructure of waxes
as demonstrated by Fig. 14.

Test Procedures for P e t r o l e u m Wax


Characterization
There are three properties used to characterize petroleum
waxes: (1) physical properties, (2) chemical properties, and
(3) functional properties.
Physical

Property

Determination

Melting Point - Test Methods ASTM D-87,D 3944, and D127


Melting point is a wax property that is of interest to the consumer and can be an indication of the performance properties of the wax being tested. The melting point of a wax is
defined as the temperature at which the melted petroleum
wax first shows a m i n i m u m rate of temperature change when
allowed to cool under prescribed conditions.
Test Method D 87 is one of the most commonly utilized
tests for melting point determination for petroleum waxes.
Paraffin waxes are often marketed based on melting point
data produced by D 87. This test method is performed by
placing a specimen of molten wax in a test tube equipped
with a thermometer as illustrated in Fig. 18a. The test tube is
TABLE 16Typical heats of fusion (J/g).
Fully Refined Paraffin wax
180-210
Microcrystalline wax
140-190

CHAPTER 19: PETROLEUM WAXES

Dimensions in inches (millimeters)

'MtanaxfabMaa Wax.

PuraRn WiuE

I
I
Tnutskkai Point-^ \ p

(b)

Time-*

. Tim*-*

FIG. 18(a) Apparatus for ASTM Test Method D 87. Cooling curve for: (b) a paraffin wax,
(c) for intermediate wax, microwax, petrolatum, or waxes containing a higfi percentage
(>50%) of branched alkanes

(c)

543

544

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

then placed in an air bath that is immersed in a water bath


and held at 16-28C (~61-82F). Temperature readings are
taken periodically until the wax solidifies u n d e r specified
conditions. During solidification, the rate of temperature decreases and produces a plateau in the cooling curve, which is
obtained by plotting the temperature versus elapsed time as,
illustrated in Fig. I8b. The temperature where the plateau occurs is defined as the melting point. (Note: The thermometer
used for this work shall conform to ASTM Specification E-1.)
Test Method D 87 is not applicable for microcrystalline
wax, intermediate wax, petrolatum, or waxes containing a
high percentage (>50%) of branched alkanes, because a temperature plateau will not occur with such type of waxes as illustrated in Fig. 18c and because these type of waxes have a
much broader melting distribution (characterized by DSC)
t h a n paraffin waxes. For non-paraffin type waxes. Test

Method D 3944, which is a "solidification point" method (Fig.


19a), can be used for melting point determination. The solidification point of a petroleum wax is: the temperature in the
cooling curve of the wax where the slope of the curve first
changes significantly as the wax sample changes from a liquid to a solid state. This is illustrated in Fig. I9b, which is a
typical cooling curve for solidification point measurement of
a petroleum wax.
Test Method D 3944 is performed by heating 50 mg of sample in a test tube above the solidification temperature. Once
the wax is melted. Fig. 20a, a thermocouple (connected to a
recorder) is placed in the sample, as illustrated in Fig. 20b,
and allowed to cool to ambient temperature. As the sample
cools, a plot of temperature versus time (Fig. 18a) is obtained. This test method is based on the same methodology
as D 87 with the exception that automated test equipment is

Iticxmo couple
Lead-

Ifi-Iluorocarbon
Boldsr Adapter
exSO nun Test Tiibe ,

Aluminum Heating
Bloek
50x50x50 nm
(2x2x2 in).

0.020 i n (H)
Metal Sheathed
Tbexnocouple Probe

r~^~^
Auotransotner
TO 110
AC
Outlet

IFE-Sluorocarbon
Disk Centering
Guide

(a)

50 mg
Wax Sample'

Temperature

solidification
Point

llOV
30-Hatt
Cartridge Heater

Heat turned off

First significant change in slope

(b)
FIG. 19(a) Apparatus for determination of melting (solidification) point (cooling curve)
of non-paraffin type waxes used in ASTM Test Method D 3944; (d) A typical cooling curve
for melting (solidification) point measurement of non-paraffin type waxes.

CHAPTER 19: PETROLEUM WAXES 545

DmKnsionsmmches(mS&r,

(a)

To Sccorder

^
6 jt SO vm
T e s t Tubs
0 . 0 2 0 I n c h O.D.
Metal Sheathed
Thermocouple
1 / 8 " Thick
I?-n.iwrc"bcm
Diak Cant-tnc
Quid*

(b)

35 X 52 ran.
Vial

FIG. 20(a) Apparatus for determination of melting point


of paraffin wax. The same methodology as Test Method D 87
with the exception that automated test equipment shown in
Fig. 20b is used; (b) Once the wax is melted (Fig. 20a), a thermocouple (connected to a recorder) is placed in the sample,
as illustrated here, and allowed to cool to ambient temperature.

Test Method D 127 is performed by depositing a sample on


two thermometer bulbs by dipping chilled thermometers into
the sample. The thermometers are then placed into test tubes
and heated in a water bath until the specimens melt and the
first drop of wax falls from the thermometers. The average of
the temperatures at which these drops fall is recorded as the
drop melting point. Other ASTM test methods for melting
and freezing point determination eire listed in Table 17.
Pour Point - Test Method D 97The pour point of a fluid is
that temperature where the fluid ceases to flow and it may be
determined by Test Method D 97 (Test Methods ISO 3016).
This test method is conducted by preheating the sample until it is sufficiently fluid to pour into a test jar. At this point
the sample is cooled at a specified rate and examined at intervals of 3C for flow characteristics. The lowest temperature at which the movement of the test specimen is observed
is recorded as the pour point. Test Method D 97 is intended
for use on any petroleum product.
Congealing Point - Test Methods D 938 and D 3944
Another important physical property for wax characterization is congealing temperature (set point), which is defined
as that temperature at which molten petroleum wax, when allowed to cool under prescribed conditions, ceases to flow or
that temperature where molten wax begins to solidify. Test
Methods D 938 and D 3944 (see above discussion for Test
Method D 3944) are used for determining the congealing
temperature. (ISO 2207 may also be used.) These tests are
more applicable for waxes with broader melting ranges, such
as microwaxes, petrolatums, and wax blends containing additives. The congealing a n d solidification point is always
lower than the recorded drop melting point.
Test Method D 938 is performed by dipping the bulb of a
thermometer to cause a droplet of wax to adhere on the therm o m e t e r bulb. The t h e r m o m e t e r is then placed in a prewarmed air jacket and cooled at a fixed rate while the thermometer is rotated in a horizontal position until the wax
sample ceases to flow (congeals). When congealing occurs,
the wax may be at the solid state or it may be at the semisolid
state, depending on the composition of the sample.
Cloud Point - Test Method D-2500The cloud point of a
petroleum product is the temperature at which a cloud of
solid crystcJs appears in a liquid when it is cooled under prescribed conditions. The cloud point is an index of the lowest

TABLE 17Other test methods for melting and freezing


point determination.
Method

used. (ISO 3841 or BS 4695 are also used for cooling curve
determination.)
Test Method D 127 may also be used to determine the
"drop melting point" of a wax. The drop melting point is defined as that temperature where the Wcix becomes sufficiently
fluid to drop from the thermometer being used for making
the determination under prescribed test conditions.
Test Method D 127 is commonly used for non-paraffin type
waxes and paraffin wax blends. These include paraffin/microcrystalline wax blends and paraffin/additive blends that
may contain polyethylene, ethylene-vinyl acetate copolymer,
or a Fischer-Tropsch wax. Test Method D 127 is used to determine the melting characteristics of petrolatums and other
high viscosity petroleum waxes.

Capillary/liquid bath
Capillary/metal block
Kofler hot bar
Differential thermal analysis & differential
scanning calorimetry
Freezing temperature

Pour point

Test Procedure

ASTM E 1
DIN 53181
DIN 53736
ASTM D 3451
ASTM E 473
ASTM E 537
BS 4633
BS 4695
DIN 51421
DIN 53175
ISO 1392
JIS K 00-65
NFT60-114
NFT20-051
ASTM D 97
ISO 3016

546

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

temperature of its utility for certain applications. The cloud


point is determined by cooling a petroleum sample in a cloud
point test apparatus illustrated in Fig. 2 1 . At a specified rate
a n d periodic examination, the t e m p e r a t u r e at which a
"cloud" is first observed at the b o t t o m of the test j a r is
recorded as the cloud point. This test method covers only
petroleum products that are transparent in layers 40 m m
thick and with a cloud point below 49C.
Oil Content - Test Method ASTM D 721Test Method D
721 describes the determination of oil in petroleum weixes
having a congealing point of 30C (86F) or higher as determined in accordance with Test Method D 938, and containing not more than 15% of oil. The test is conducted by dissolving the weix in a solvent (methyl ethyl ketoneMEK)
and chilling to a low temperature to precipitate the wax.
The wax is filtered from the solvent and the solvent soluble
residue is evaporated to determine the oil content. The oil
content of paraffin waxes is indicative of the degree of refining or processing that has been performed. Fully refined
wax generally does not have an oil content exceeding 0.5%.
Paraffin waxes having oil contents exceeding the 0.5 limit
are marketed as scale ( < 3 % oil) and slack paraffin waxes
(<40% oil). Microwaxes a n d petrolatums have a higher
affinity for oil than the paraffin waxes and are marketed
with oil contents as high as 20%.
With some t5fpes of waxes with oil contents greater than
5%, there may be an incompatibility with MEK resulting in

the formation of two liquid phases. If this occurs, the method


is not applicable to the material being tested.
Solvent Solubility - Test Method D 3235Test Method D
3235 is a solvent extraction method used to determine the total amount of wax components that are soluble in the extraction solvent. The test is performed in the same manner as
Test Method D 721 except that a different solvent composition is used.
Viscosity - Test Methods D 445, D 2669, and D 3236
Molten wax viscosity is important for determining the proper
melt flow properties for applying waxes by end use machinery under low shear conditions. Test Method D 445 for the
m e a s u r e m e n t of kinematic viscosity of t r a n s p a r e n t and
opaque liquids is used for petroleum waxes with viscosities
less than 25 centistokes at 99C.
Test Methods D 2669 and D 3236 are used for waxes that
have been c o m p o u n d e d with wax additives resulting in a
high viscosity, u p to 2000 poise at 175C (347F). Fluid viscosity is determined by placing a representative sample of the
molten wax into a thermally controlled sample chamber. Apparent viscosity is determined u n d e r thermal equilibrium
conditions using a precision rotating spindle type viscometer
as illustrated in Fig. 22. Data for several temperatures can be
plotted on appropriate semi-logarithmic graph paper and apparent viscosity at intermediate temperatures can be estimated. Although precision has not been studied. Test Method
D 3236 may be adaptable to measure fluids with viscosities

4*^-MkUk
3U-3iJ0lIlu
aiiLO- aiAU).

CORK '

OOOUWr LEVEL-

JMnr
I

MMMC

-rP ini

All dimensions in millimeters


FIG. 21Apparatus for Standard Test Method D 2500 to measure the cloud point of
petroleum products.

CHAPTER 19: PETROLEUM WAXES

547

VISCOMETER

TMEKMOMmn
auui IN HomzoNDU.
PLMC WITH C i N I U
OF SPINOLC

aoncM or luiwii
M> HTTOKOrtUMO

MCK

x_x

"

FIG. 22Viscosity measurement apparatus, side view, used in ASTIM


Test Method D 2669.

greater than present 2000 Poise limit and temperatures above


175C (347F). Equipment described in this procedure permits testing of materials having viscosities as high as 160 000
Poise and provides temperatures up to 260C (500F).
Hardness - Test Method D1321The hardness of a wax is a
measure of its consistency. Waxes can show variation in
hardness and the differences are more pronounced at higher
temperatures. For example, two waxes may have the same
hardness as measured at one temperature, but are dissimilar
at a different temperature. Hardness is determined by penetration and is defined as the depth in tenths of a millimeter to

FiG. 23Needie penetration apparatus of


Standard Test Method D
1321 used for measurement of hardness of
petroleum waxes.

which a standard needle penetrates into the wax under defined conditions using a penetrometer such as the one illustrated schematically in Fig. 23.
To measure the hardness of a wax, Test Method D 1321, the
Needle Penetration Method is commonly used. This method
is based on a standardized needle penetrating into the wax
surface at a specific temperature. The smaller the numerical
value obtained from this test, the harder the wax is. The hardness of the wax can be indicative of undesirable blocking tendency for wax-coated paper. (Note: Test Method D 1321 is
similar to Test Method D 937, which is a cone penetrometer

548 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Sample
Reference
Resistance
Thermometer
Heater

(a)

Resistance
Thermometer
Heater

AT-Signal

Nitrogen

First-Order Transition:
Apex

Second Order-Transition:
Apex - Tjj^
Onset
End

(b)

T.-^,,*..,. -r-

FIG. 24(a) Differential scanning calorimetry (DSC) experimental set up; (b) Schematic
of petroleum wax DSC curve (heating cycle) sample determined to have soiid-liquid and
solid-solid transitions. This figure is similar to Fig. 16a.

method for petrolatum, which may also be used for softer


waxes. The cone penetration value is more of a measure of
firmness or consistency rather than hardness.)
Transition Temperatures by Differential Scanning Calorimetry (DSC)-Test Method D4419Test Method D 4419 is a rapid
and convenient method for determining the temperature limits governing the change a wax undergoes from solid to liquid
or as a solid-solid transition. This test method measures the
transition temperatures of petroleum waxes, including microcrystalline waxes, by differential scanning calorimetry
(DSC) as shown in Fig. 24a. The normal operating temperature range extends from 15-150C. DSC is a technique that
measures the difference in energy inputs into a substance
and a reference material using a controUed-temperature pro-

gram. DSC can differentiate the tj^je of petroleum wax being


evaluated by its melting and crystallization property. Figure
2Ab (which is similar to Fig. 16a) is the schematic of a
petroleum wax DSC curve exhibiting solid-liquid and solidsolid transitions (Heating Cycle) and the calculation of such
temperatures. Paraffin waxes being derived from the distillation process have sharp peak shapes, while microcrystalline
waxes being derived from residual fractions have broader
peak shapes. This is shown in Fig. 16 (Note: Refer to Standard Terminology E 473 for additional information).
Chemical Property Determination
Petroleum waxes being composed of hydrocarbons Eire relatively inert but they can undergo compositional chemical

CHAPTER
changes when exposed to elevated temperatures in the presence of oxygen due to oxidation. Waxes can degrade in the
presence of heat and oxygen. The degradation process involves breaking a bond between a carbon and a hydrogen
atom to make a free radical. The free radicals quickly form
peroxides initially and further react to form acids. The
changes in composition can possibly be detected by testing
for color a n d odor. Antioxidants are added to p e t r o l e u m
waxes to chemically stabilize them from the heat degradation
process [41].
Color - Test Methods D 156 and D 1500The color of
petroleum waxes can indicate the degree of refinement or
possible contamination. Color is not always a reliable parameter for determining quality and should be used judiciously as a specification. There are two methods for determining the color of petroleum waxes: Test Methods D 156
and D 1500, and both are subjective and measure the empirical value based on visual observation of the wax in the
molten state.
Test Method D 156 is the Saybolt Chronometer Method for
quantifying the color of petroleum products such as a
petroleum wax. Saybolt color is an empirical definition of the
color of a clear petroleum liquid based on a scale of 16
(darkest) to +30 (lightest). The number is derived by finding
the height of a column that visually matches the appropriate
one of three glass standards and referring to Table 1 of Test
Method D 156. This is done using a Saybolt chronometer (see
Fig. 25), which consists of a sample and standard tubes, optical system, light source, and ASTM color standards.
While Test Method D 156 is used to determine the degree
of whiteness of a wax, Test Method D 1500 is used to measure
the color of waxes that have a tint darker than off-white. Test
Method D 1500 is conducted using a standard light source,
with liquid sample placed into a standard glass container
(sample jar) (see Fig. 26) and compared with colored glass
disks ranging in value from 0.5-8.0 with 0.5 increments.
Carbonizable Substances - Test Method D 612Test Method
D 612 is applicable to paraffin waxes for pharmaceutical use
as defined in the United States National Formulary. Molten
wax is treated with sulfuric acid and the acidic layer is compared visually with a colorimetric reference standard to determine if it passes the conformance criteria for refined wax
using the color comparator shown in Fig. 27.
Peroxide Number - Test Method D 1832Waxes are heat
sensitive and they are susceptible to the action of the oxidation process. The detection of peroxides is the first indication
that a wax has begun to deteriorate in terms of oxidation stability. Petroleum waxes should not have any measurable peroxide values. Deterioration of petroleum wax results in the
formation of peroxides a n d other oxygen-carrying compounds that will oxidize potassium iodide. Peroxide content
is reflected by the peroxide n u m b e r that is defined as the milliequivalents of constituents per 1000 g of wax that will oxidize potassium iodide.
Odor - Test Method D 1833In some end-use applications,
such as food packaging, the intensity of the odor is an important characteristic. Odors can be an indication of the degree
of refining, contamination, or oxidation. Test Method D 1833
describes how to rate the odor intensity based on a subjective
evaluation using a multiple-member test panel. This test is
conducted by preparing odor test specimens from petroleum

19: PETROLEUM

WAXES

549

wax and placing approximately 10 g of thin shavings on odorfree paper or glassine. Individual test specimens are then evaluated for odor by each panel member and assigned a number
according to the odor scale shown in Table 18 that best fits the
intensity of the odor. As an alternative procedure, the wax
shavings are placed in bottles with each panel member making an odor determination between 10 and 60 min after the
shavings are placed into the bottles. The average of the panel
ranking is reported as the odor rating of the sample.
Composition by Gas Chromatography-Test Method D 5442
Test Method D 5442 is applicable to petroleum derived waxes,
including blends of waxes. This test method covers the quantitative determination of the carbon n u m b e r distribution of
petroleum wEixes in the range of n-C17 through n-C44 by gas
chromatography using internal standardization. In addition,
the content of normal and non-normal hydrocarbons for each
carbon n u m b e r is also determined. Material with a carbon
number above n-C44 is determined by difference from 100
mass % and reported as C 45 +. (Note: Standard Practice E 260
provides further information on gas chromatography and
Standard Practice E 355 provides information relating to gas
chromatography terms and relationships.)
Test Method D 5442 is not applicable to oxygenated waxes,
such as synthetic polyethylene glycols (i.e., Carbowax), or
natural products such as beeswax or c a r n a u b a . This test
method is not directly applicable to waxes with oil content
greater t h a n 10% as determined by Test Method D 721.
Functional

Property

Determination

The following methods are for the evaluation of wax base


coatings intended for paper and paperboard. The methods
were developed in concert with the Technical Association of
Pulp and Paper Industries.
Specular Gloss - Test Method D 1834Specular gloss is
defined as the degree to which a surface simulates a mirror
in its capacity to reflect incident light. Test Method D 1834
is a method designed to determine the capacity of a wax
coated surface to simulate a mirror in its ability to reflect an
incident light beam using a glossmeter such as that illustrated in Fig. 28. Surface gloss is desirable for some waxed
paper applications. For determining the gloss of book paper, reference should be made to Test Method D 1223. For
very high gloss paper refer to Wink et al. [42].
Gloss Retention - Test Method D 2895This test is intended
to correlate with the conditions that are likely to occur in the
storage and handling of wax-coated paper and paperboard.
Test Method D 2895 is intended primarily to measure the
gloss retention, which is defined as the percent of original
gloss retained by a test specimen after aging under specified
conditions. It is calculated as the final gloss divided by the
initial gloss multiplied by 100. The initial gloss of waxed paper or p a p e r b o a r d is m e a s u r e d in accordance with Test
Method D 1834, then remeasured after aging the sample in
an oven at 40C (104F) for 1 and 7 days. The 1-day test is
conducted to observe trends while the 7-day test is the standard test duration.
Surface Wax - Test Methods D 2423, D 3521, and D 3522
Wax coatings are applied to provide a better moisture barrier, appearance, and abrasion resistance. These performance features are influenced by the amount of wax present
on the surface. Test Method D 2423 is used to determine the

550 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK

HMDU
NOTC-HiUHLE It FMTOltD T O V

0 Suae
m j

0
0
0
(i)

0
0

oouw
couM oovn
mm uiw
nacMw
(iMm
T mm
suun oi*x

WTAININt iHM

UTHADML (LTCntlfK

MUUM seMovia

0 UtlX
X) t n i m *
LS 0 WATT soil. MMTHI

SCOTIOH "A-A"

Saybolt Chromometer Tube Heater

Adapter

FIG. 25ASTM Standard Test Method D156 Saybolt Chromometer and artificial daylight
lamp.

CHAPTER 19: PETROLEUM WAXES 551


amount of wax present on the surface of the substrate, but
not the absorbed wax. Test methods that determine the applied wax by solvent extraction (such as Test Method D 3344)
do not differentiate between the wax present at the surface
and to that which penetrated the substrate.

Test Method D 3 521 also determines the a m o u n t of wax that


is present on the surface of corrugated paperboard. This
method is applicable to a board on which wax has been applied by curtain coating, roll coating, or other methods. The
substrate board may or may not contain impregnating (saturation) wax within its structure. If it is known that the specimen has coating wax only, with no internal saturating wax,
then Test Method D 3344 may determine the total coating wax
applied. Determination of the total amount of wax present by
ASTM D 3521 involves delamination of the coated facing to
obtain a ripple-free sheet, then scraping off the wax using a razor blade and calculating the amount of wax removed.
Test Method D 3522 is used to determine the amount of
wax that has been applied to the individual layers of the corrugated paperboard and the a m o u n t of the impregnating
(saturation) wax in the same facing. This is accomplished by
peeling the coated facing from the medium and then splitting
it into two layers; one bearing the coating on waxed fibers
only and the other containing waxed fibers only. The layers
are extracted separately, collecting both fibers and wax. This
will permit the calculation of the applied surface coating and
the amount of impregnating wax.

TABLE 18Odor intensity scale.


Numerical Rating
Odor Description
None
Slight
Moderate
Strong
Very strong

FIG.
26Standard
glass sample jar used
in Test Method D 1500
to measure the color of
waxes.

e-i'*Mo/es

Section

Plan

A-A.
T l 3 STOPPER

SiaTlSNECK

m
A

-i-n-j. T
Elevation

I Hi
I h !

"5

-i

i li

!l< '

$>!$

End

Elevation

ISLi
I402MM
Appnox.
CAPACITY
TO STOPPER
late TO {SA ml
145H5.0
MM 0.0.
WALL"
I.ZOIMM
AVER

TEST TUBE

FIG. 27Color comparator used in Standard Test Method D 612 for measurement of carbonizable substances in paraffin waxes for pharmaceutical use.

552

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Vacuum

'
J J t j

J J

l^L
'^-

Specimen Holder
Porou* Plate
f^\\

>.Specimen

ViU.:.v.M>'.'-.-..!.-.vA-.X!-'.J-; L

disruption occurs across 50% of the waxed p a p e r surface


when the test strips are separated. The temperature at which
the first film disruption occurs on the waxed paper when the
test strips are separated is the wax picking point. Test
Method D 1465 is used to d e t e r m i n e the t e m p e r a t u r e at
which two strips of wax-coated p a p e r will adhere to each
other. Surface disruption of wax coatings at relatively low
a m b i e n t t e m p e r a t u r e s is a performance problem for low
melting point waxes. If the surface of a waxed p a p e r is
blocked together, then surface gloss and barrier properties
will be altered. Two strips of wax-coated paper are placed on
a calibrated t e m p e r a t u r e gradient plate for 17 h and removed, cooled, and peeled apart to determine the block point
temperature. Figure 29 illustrates a Type A and a Type B
blocking plate used for these measurements.
Coefficient of Kinetic Friction - Test Method D 2534A
coated surface under load is pulled at a uniform rate over a
second coated surface. This is d o n e experimentally by
preparing a "sled" with a weight and then pulling it over the
surface to be tested using a horizontal plane and pulley assembly. The force required to move the load is measured, and
the coefficient of kinetic friction (/j-k) is calculated as follows:
fH, = A/B

rf

J ^JJ

^^*/J

FIG. 28Diagram of relative positions of essential elements


of Glossmeter used in Standard Test Method D 1834.

Total Wax Content - Test Method D 3344Many of the functional properties of a wax-treated paperboEird are dependent on
the amount of wax that is present. Test Method D 3344 determines the total amount of wax in a sample of wax-treated corrugated paperboard by extraction. It is applicable to specimens
that have been waxed by either impregnation (saturation) operations or coating operations, or combinations of the two.
Weight of Wax Applied During Coating - Test Method D
3708Test Method D 3708 is used to determine the weight of
a hot melt coating applied to corrugated board by curtain
coating. This method is intended for use as a routine process
control in the plant. The a m o u n t of wax applied is determined by attaching a folded sheet of paper to production corrugated board, running the combination through the curtain
coater, and subsequently determining the applied weight of
wax on the sheet of paper.
Blocking Point - Test Method D 1465The blocking point of
a wax is defined as the lowest temperature at which a film

(15)

Where A = the average scale reading from the electronic


load cell-type tension tester for 150 m m (6 in) of uniform sliding and B = sled weight (g). The value obtained is related to
the slip property of the wax coating. High slip property values may not be desirable for many commercial articles that
have been coated with petroleum wax.
Abrasion Resistance - Test Method D 3234This test
method is designed to help predict the resistance in change of
gloss that coatings may be subject to during the normal handling of coated paper and paperboard products. Abrasion resistance is the resistance to change in gloss when that coating has been subjected to an abrading action by an external
object. Test Method D 3234 is conducted by dropping 60 g of
sand on a very small area of a coating under fixed conditions.
The abrasion resistance test apparatus is illustrated in Fig.
30. Gloss is measured with a 20 specular glossmeter illustrated in Fig. 28 before and after the abrading action by the
falling sand.
Hot Tack - Test Method D 3706Hot tack is defined as the
cohesive strength during the cooling stage before solidification of a heat seal bond formed by a wax-polymer blend. Flexible packaging materials are formed into finished packages by
joining surfaces with heat sealed bonds. The bonding process
is performed o n high-speed packaging lines and the application pressure used to hold the surfaces together is released before the bond has completely solidified. The wax-polymer
blend must have enough hot tack while still in a molten stage
to hold the sealed areas together until the blend has cooled.
In Test Method D 3706, flexible packaging specimens are
heat-sealed together over a series of temperatures and dwell
times. Immediately after each seal is formed and before it has
started to cool, a force tending to separate the specimens is
applied by a calibrated spring. If the hot tack of the blend is
strong enough, the seal remains closed until it has solidified;
if not, the seal separates. Thus each spring force and test condition either passes or fails. The pattern of pass/fail results is
plotted to the blend characteristics.

CHAPTER 19: PETROLEUM WAXES 553


$1 nun K 30S KHX
Itey ttDck mtil Medkt 2S mm 2B RHR (1" s 1").

K S I S MDI

( r i s r K *i

7C2 MR iVty Iwit.

13 MM ^ l / r i h
(AM. Tm4l lor 13 mm d / T }

Type A Blocking Plates

Into (Mb tWRi tmiiiimd

Type B Blocking Plate


FIG. 29The two types of blocking plates used In Standard Test Method D-1465 to measure the blocking point of wax.

554 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


500 ml
Separatory Funnel

60 g of Sand
Stopcock

Size I H

Stem Cut Off from


Separator/ Funnel
U.S. Standard Sieve
No. 12

^ " ^ 2 B mm (I") I.D.

Specimen

For tscating Exact Position for


Mailing Glossmeter Readings

For Dropping 60 g of Sand

FIG. 30Apparatus for measuring abrasion resistance of wax coatings in Standard Test lUlethod D 3234.

Acknowledgments
The authors thank Dr. George Totten for his helpful advice
and guidance in the preparation of this chapter and Dr. Sony
Oyekan, Dr. Chen-Hwa Chiu, Dr. Sang J. Park, and Mr.
Adrian D'Sousa for their technical assistance.

D 721
D 937
D 938
D 1168
D 1298

ASTM STANDARDS
D 1223
No.
D 87
D 97
D 127
D 156
D 287
D 445
D 612

Title
Test Method for Melting Point of Petroleum Wax
Test Method for Pour Point of Petroleum Products
Test Method for Drop Melting Point of Petroleum
Wax Including Petrolatum
Test Method for Color, Saybolt, of Petroleum
Products
Test Method for Gravity, API, of Crude Petroleum
and Petroleum Products (Hydrometer Method)
Test Method for Kinematic Viscosity of Transparent and Opaque Liquids
Test Method for Carbonizable Substances in
Paraffin Wax

D 1321
D 1465
D 1500
D 1832
D 1833
D 1834
D 2423

Test Method for Oil Content of Petroleum Waxes


Test Method for Cone Penetration of Petrolatum
Test Method for Congealing Point of Petroleum
Wcixes, including Petrolatum
Test Method for Hydrocarbon Waxes Used for
Electrical Insulation
Test Method for Density, Relative (Specific Gravity) or API Gravity of Crude Petroleum and Liquid
Petroleum Products by Hydrometer Method
Test Method for Specular Gloss of Paper and Paperboard
Test Method for Needle Penetration of Petroleum
Waxes
Test Method for Blocking and Picking Points of
Petroleum Wax
Test Method for Color, ASTM, of Petroleum Products (ASTM Color Scale)
Test Method for Peroxide Number of Petroleum
Wax
Test Method for Odor of Petroleum Wax
Test Method for 20 Specular Gloss of Wax Paper
Test Method for Surface Wax on Waxed Coated
Paper

CHAPTER 19: PETROLEUM WAXES 555


D 2500
D 2534
D 2669
D 2895
D 3234
D 3235
D 3236
D 3 344
D 3451
D 3521
D 3522

D 3 706
D 3708
D4419

D 5442
E 1
E 260
E 355
E 473
E 537

Test Method for Cloud Point of Petroleum


Products
Test Method for Coefficient of Kinetic Friction
for Wax Coating
Test Method for Apparent Viscosity of Petroleum
Waxes Compounded with Additives (Hot Melts)
Test Method for Gloss Retention of Waxed Paper
and Paperboard after Storage at 40 C (104 F)
Test Method for Abrasion Resistance of
Petroleum Wax Coatings
Test Method for Solvent Extractables in
Petroleum Waxes
Test Method for Apparent Viscosity of Hot Melt
Adhesives and Coatings Materials
Test Method for Total Wax Content of Corrugated
Paperbocird
Standard Practices for Testing Polymeric Powders and Powder Coatings
Test Method for Surface Wax Coating on Corrugated Board
Test Method for Applied Wax Coating and Impregnating (Saturating) Wax in Corrugated
Board Facing
Test Method for Hot Tack of Wax-Polymer Blends
by Flat Spring Test
Test Method for Weight of Wax Applied During
Curtain Coating Operation
Test Method for Transition Temperatures of
Petroleum Waxes by Differential Scanning
CaJorimetry
Test Method for Analysis of Petroleum Waxes by
Gas Chromatography
Specification for ASTM Thermometers
Practice for Packed Column Gas Chromatography
Practice for Gas Chromatography Terms a n d
Relationships
S t a n d a r d Terminology Relating to Thermal
Analysis
Test Method for Assessing the Thermal Stability
of Chemicals by Methods of Thermal Analysis

OTHER STANDARDS
No.
BS 4633 & 4634

BS 4695
DIN 53175

DIN 53181

Title
Method for the determination of crystallizing point. Method for the determination of melting point and/or melting
range
Method for d e t e r m i n a t i o n of melting
point of petroleum wax (cooling curve)
Binders for paints, varnishes and similar
coating materials; determination of the
solidification point (titer) of fatty acids
(method according to Dalican)
Binders for paints, varnishes and similar
coating materials; determination of the
melting interval of resins by the capillary method

ISO 1392
ISO 2207
ISO 3016
ISO 3841
JIS K 00-64
JIS K 00-65
NFT60-114
NFT20-051

Determination of crystallizing point


General method
Petroleum waxesDetermination of
congealing point
Petroleum productsDetermination of
pour point
Method for determination of melting
point of petroleum wax (cooling curve)
Testing methods for melting points of
chemical products
Test methods for freezing point of chemical products
Petroleum productsMelting point of
paraffins
Chemical products for industrial use.
Determination of melting point. Method
for the determination of crystallizing
point (freezing point).

REFERENCES
1] Hackett, W. J., Maintenance Chemical Specialties, Chemical Publishing Co., Inc., NY, 1972.
2] Warth, A. H., Chemistry and Technology of Waxes, Reinhold Publishing Corp., NY, 1956.
3] Bennet, H., Industrial Waxes, Vol. 1, Chemical Publishing Company, Inc., NY, 1963.
4] Puleo, S. L., "Beeswax," Cosmetics and Toiletries, Vol. 102, Allured Publishing CompEiny, Inc., Chicago, 1987.
5] Warth, A. H., Chemistry and Technology of Waxes, Reinhold Publishing Corp., NY, 1956.
6] Letcher, C. S., "Waxes," Kirk-Othmer: Encyclopedia of Chemical
Technology, Vol. 24, 3'''' ed., 1984, pp. 466-481.
7] Dry, M. E., "Sasol's Fischer-Tropsch Experience," Hydrocarbon
Processing, August, 1982, pp. 121-124.
8] Erchak, Jr., M., "Process for the Oxidation of High Molecular
Weight Aliphatic Waxes and Product 880kb, U. S. Patent
2,504,400, Washington DC, April 18, 1950.
9] Haggin, J., "Fischer-Tropsch: New Life for Old Technology,"
Chemical and Engineering News, October 1981, pp. 22-32.
0] Caraculacu, A., Vasile, C, Caraculacu, G., "Polyethylene Waxes,
Structure, and Thermal Characteristics," Acta Polymerica, Vol.
35, No. 2, 1984, pp. 130-134.
1] Brooks, B. T., Boord, C. E., Kurtz, S. S., and Schmerling, L., The
Chemistry of Petroleum Hydrocarbons, Vol. 1, Reinhold Publishing Corp., NY, 1954.
2] Gruse, W. A., Chemical Technology of Petroleum, 2'' ed., McGraw-Hill Company, NY, 1942.
3] Mazee, W. M., "Petroleum Waxes," Modem Petroleum Technology, 4"" ed., 1973, pp. 782-803.
4] Vasquez, D. and Mansoori, G. A., "Identification and Measurement of Petroleum Precipitates," Journal of Petroleum Science
and Engineering, Vol. 26, Nos. 1-4, 2000, pp. 49-56.
5] Misra. S., Baruah, S., and Singh, K., Paraffin Problems in Crude
Oil Production and Transportation: A Review, SPE Production
and Facilities, Society of Petroleum Engineers, Richardson, TX,
Feb. 1995, pp. 50-54.
6] Holder, G. A. and Winkler, J., "Wax Crystsillization from Distillate Fuels," Journal of the Institute of Petroleum, Vol. 51, No. 499,
1965, pp. 228-243.
7] Mansoori, G. A. and Canfield, F. B., "Variational Approach to
Melting," Journal of Chemical Physics, Vol. 51, No. 11, 1969, pp.
4967-4972.

556 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


[18] Pourgheysar, P., Mansoori, G. A., and Modarress, H., "A SingleTheory Approach to the Prediction of Solid-Liquid and Liquid-Vapor Phase Transitions," Journal of Chemical Physics, Vol.
105, No. 2 1 , 1996, pp. 9580-9587.
[19] Park, S. J. and Mansoori, G. A., "Aggregation and Deposition of
Heavy Organics in Petroleum Crudes," International Journal of
Energy Sources, Vol. 10, 1988, pp. 109-125.
[20] Branco, V. A. M., Mansoori, G. A., De Almeida Xavier, L. C ,
Park, S. J., and Manafi, H., "Asphaltene Flocculation and Collapse from Petroleum Fluids," Journal of Petroleum Science and
Engineering, Vol. 32, 2001, pp. 217-230.
[21] Svendsen, J. A., "Mathematical Modeling of Wax Deposition in
Oil Pipeline Systems," AIChE Journal, Vol. 39, No. 8, 1993, pp.
1377-1388.
[22] Brown, T. S., Nielsen, V. G., and Erickson, D. D., "Measurement
and Prediction of the Kinetics of Paraffin Deposition," Journal
of Petroleum Technology, April 1995, p p . 328-329.
[23] Noll, L., "Treating Paraffin Deposits in Producing Oil Wells,"
Topical Report NIPPER-551 (DE92001010), Bartelsville Project
Office, U.S. Department of Energy, Bartelsville, OK, 1992.
[24] Sanchez, J. H. P. and Mansoori, G. A., "In Situ Remediation of
Heavy Organic Deposits Using Aromatic Solvents," Paper #
38966, Proceedings of the 68th Annual SPE Western Regional
Meeting, Bakersfield, CA, May 1998.
[25] Paraffin Products: Properties, Technology, Applications, G. Y.
Mozes, Ed., Elsevier, NY, 1982.
[26] Murad, K. M., Lai, M., Agarwal, R. K., and Bhattachaiyya, K. K.,
"Improve Quality of Wax by Hydrofinishing," Petroleum Hydrocarbons, Vol. 7, No. 2, 1972, pp. 144-7.
[27] Ferris, S. W., "Characterization of Petroleum Waxes Tappi,"
TAPPI Special Technical Association Publication No. 2, 1963,
pp. 1-19.
[28] Himran, S., Suwono, A., smd Mansoori, G. A., "Characterization of
Alkanes And Paraffin Wcixes for Application as Phase Change Energy Storage Medium," nergySoMrce5, Vol. 16,1994, pp. 117-128.
[29] Humphries, W. F., Performance of Finned Thermal Capacitors,
NASA TND-7690, Washington, D.C., 1974.
[30] Haji-Sheikh, A., Eftekhar, J. and Lou, D. Y. S., "Some Thermophysical Properties Of Paraffin Wax as a Thermal Storage
Medium," Progress in Astronatics and Aeronautics 86, 1983, pp.
241-253.
[31] Du, P. C. and Mansoori, G. A., "Phase Equilibrium of Multicomponent Mixtures: Continuous Mixture Gibbs Free Energy

[32]

[33]

[34]

[35]

[36]

[37]

[38]

[39]

[40]
[41]
[42]

[43]

Minimization and Phase Rule," Chemical Engineering Communication, Vol. 54, 1987, pp. 139-148.
Hartono, R., Mansoori, G. A., and Suwono, A., "Prediction of
Molar Volumes, Vapor Pressures and Supercritical Solubilities
of Alkanes by Equations of State," Chemical Engineering Communications, Vol. 173, 1999. pp. 23-42.
Riazi, M. R. and Mansoori, G. A. "Simple Equation of State Accurately Predicts Hydrocarbon Densities," Oil & Gas Journal,
1993, pp. 108-111.
Mohsen-Nia, M., Modarress, H., and Mansoori, G. A., "A Simple
Cubic Equation of State for Hydrocarbons and Other Compounds," SPE Paper No. 26667, Proceedings of the 1993 Annual
SPE Meeting, Society of Petroleum Engineers, Richardson, TX,
1993.
Nikitin E. D., Pavlov, P. A., and Bessanova, N. V., "Critical Constants of n-Alkanes with from 17 to 24 Carbon Atoms," Journal
of Chemical Thermodynamics, Vol. 26, 1994, p p . 177-182.
Frenkel, M., Gadalla, N. M., Hall, K. R., Hong, X., and Marsh, K.
N., TRC Thermodynamic
Tables-Hydrocarbon;
Non-Hydrocarbon, R. C. Wilhoit, Ed., Thermodynamic Research Center, The
Texas A & M University System, College Station, TX, 1997.
Twu, C. H., "An Internally Consistent Correlation for Predicting
the Critical Properties and Molecular Weights of Petroleum and
Coal-Tar Liquids," Fluid Phase Equlibrium, Vol. 16, 1984, pp.
137-150.
Edalat, M., Mansoori, G. A., and Bozar-Jomehri, R. B., "Vapor
Pressure of Hydrocarbons, Generalized Equation," Encyclopedia of Chemical Processing and Design - 61, Marcel Dekker, Inc.,
NY, 1997, pp. 362-365.
Letoffe, J. M., Claudy, P., Garcin, M., and Voile, J. L., "Evaluation of Crystallized Fractions of Crude Oils by Differential Scanning Calorimetry, Correlation With Gas Chromatography,"
Fuel, Vol. 74, No. 1, 1995, pp. 92-5.
Braun, R., "Limits in Differential Thermoanalysis of Wsixes,"
Fette Seifen Anstrichm, Vol. 82, No. 2, 1980, pp. 76-81.
Handbook on Antioxidants and Antiozonants, Goodyear Chemicals, Akron, OH, 1977.
Wink, W. A., Delevanti, C. H., and Van den Akker, J. A., Instrumentation Studies LXXVII, Study on Gloss I, A Goniophotometric Study of High Gloss Papers, TAPPI, Technical Association of
the Pulp and Paper Industry, Vol. 35, December 1953, p. 163A.
Tomsic, J., Dictionary of Materials and Testing, 2"^ ed., SAE International, Warrendale, PA, 2000, p. 205.

MNL37-EB/Jun. 2003

Lubricating Greases
Thomas M. Verdura, ^ Glen Brunette, ^ and Rajesh Shah~

tremely small, uniformly dispersed, and capable of forming a


relatively stable, gel-like structure with the liquid lubricant.
Greases are distinct from lubricating pastes that can appear grease-like. Pastes are mostly solids; generally about
70-95% solids, but sometimes merely wetted solids. The solid
thickener concentrations of greases range from about 3-30%,
tjrpically about 10%. Also, for pastes, affinity between the
solid and liquid phases is not essential; neither is it necessary
that a stable, gel-like structure be formed. The manufacturing methods also differ. Pastes are simply solid-liquid mixtures formed using low-shear mixing. Grease manufacturing
requires considerably m o r e processing, usually including
synthesizing the thickener in the fluid. A strict time, temperature, a n d mixing profile must be followed to properly synthesize the thickener. Next, thorough mixing and blending in
the desired additives at the proper time and temperature has
to be done prior to the final finishing a n d processing. Included in the finishing a n d process steps is homogenization,
where t h e grease is passed through a mill to disperse the
thickener and additives, or deaerating, to remove entrained
air or both where needed.

T H E ESSENTIAL FUNCTION OF ANY LUBRICANT is to prolong the life

and increase the efficiency of mechanical devices by reducing


friction and wear. Secondary functions include heat dissipation, corrosion protection, power transmission, and contaminant removal. Generally, fluid lubricants are difficult to retain at t h e point of application a n d m u s t be replenished
frequently. If, however, a fluid lubricant is thickened, its retention is improved, a n d lubrication intervals c a n b e extended. A lubricating grease is simply a lubricating fluid
which has been gelled with a thickening agent so that the lubricant can be retained more readily in the required area.
This is not to say that the thickener does not play a part in the
lubrication. Depending on the type of thickener being used
and the lubricating regime, some thickeners will contribute
in the lubrication.
Lubricating greases have a n u m b e r of advantages over lubricating fluids. Some of these are:
Dripping and spattering are nearly eliminated
Less frequent applications are required
Greases are easier to handle
Less expensive seals can be used
Greases can form a seal in many cases and keep out contaminants
They adhere better to surfaces
They reduce noise and vibration
Some grease remains even when relubrication is neglected
Grease was previously defined as a gelled lubricating fluid.
Although this simplistic definition conveys the general concept of a grease, a more extensive discussion is required to
provide a fuller understanding of just what constitutes a lubricating grease. A lubricating grease is a semi-fluid to solid
product of a dispersion of a thickener in a liquid lubricant.
Additives, either liquid or solid, Eire usually included to improve grease properties or performance.
By definition, grease is a lubricant. It is also essentially a
two-phase systema liquid-phase lubricant into which a
solid-phase finely divided thickener is uniformly dispersed.
The liquid is immobilized by the thickener dispersion that
must remain relatively stable with respect to time and usage.
At operating temperatures, thickeners are insoluble or, at
most, only slightly soluble in the liquid lubricant. There must
be some affinity between the solid thickener and the liquid lubricant in order to form a stable, gel-like structure. The thickener can be constituted of fibers (such as various metallic
soaps), or plates or spheres (such as certain non-soap thickeners). The essential requirements are that the particles be ex-

' Retired, General Motors NAO Research and Development, Warren, MI.
^ CITGO Petroleum Corporation, Oklahoma City, OK.
^ Koehler Instrument Company Inc., Bohemia, NY.

COMPOSITION
Greases are composed of a lubricating fluid, a thickener, and
usually performance enhancing additives. A complete discussion of the many variations of grease formulations and manufacturing process would require far more space than allotted for this work. Extensive discussion on grease chemistry
and manufacturing process has been published [1-4]. Therefore, only a n overview of the most common grease types and
methods has been presented.
The lubricating fluids t h a t c a n b e thickened to form
greases vary widely in composition and properties and are a n
extremely important component of the grease. Lubricating
fluids can account for as m u c h as 95% of a grease. By iar, the
largest volume of greases in use today consists of those made
with petroleum oils thickened with soaps. Many types of
petroleum oils are used, including naphthenic, paraffinic, hydrocracked, and hydrogenated. The viscosity of the oil used
also varies. Oil blends with a viscosity between an ISO 100
and 220 are most common, however, for specialized greases,
the oil viscosity can be lighter or much heavier. In addition to
petroleum oils, other lubricating fluids such as vegetable oils,
silicones, synthetic hydrocarbons, and others can be used. Of
the synthetic fluids used in grease manufacturing the most
common type is poly(alpha)olefin (PAO). Because it is more
expensive, its usage is small compared t o petroleum oil.
Greases made with PAO as the lubricating fluid can provide
good performance over a wide-temperature range.
Many products have been used as thickeners for grease.
Soaps were the first thickeners used and still have the widest

557
Copyright'

2003 by A S I M International

www.astm.org

558 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK

S Lithium soaps
0 Calcium soaps
H Aluminum soaps
H Sodium and other
soaps
g^o m Clay & other non-soaps
B Polyurea
FIG. 1Worldwide grease production by thickener type
(1999 NLGI Survey).
application (see Fig. 1). Some of the other thickeners that
have been employed include polymers, clays, silica gel, and
pigments.
Soaps are present in greases in the form of fibers. The
structure and size of these fibers, i.e., thickness and length,
depend on the metallic moiety and the conditions u n d e r
which they are formed. In general, soap fibers can vary from
about l-100^lm in length with about a 10 t o l length-to-diameter ratio. Large, coarse fibers do not absorb fluids as well
as fine, closely knit fibers. Thus, a higher percentage of thickener is required for coarse fiber soaps to make greases having the same consistency as those made with fine fiber soaps.
Non-soap thickeners are generally smaller, even colloidal,
and have either a spheroidal or plate like structure.
Soap thickeners are formed by neutralization reaction of
an acid and base to form a salt and water as a byproduct.
When the acid is a fatty acid, its salt is called a soap, and the
reaction is Ccilled saponification. If the acidic component has
a narrow range of moleculcir weight, as in fatty acids, a simple soap is made, e.g., lithium stearate. Reacting the metallic
base with two dissimilar acids of widely different molecular
weight will form a complex soap, e.g., calcium stearate acetate. Mixed-base greases consist of a mixture of two or more
different thickener systems, such as sodium-calcium or alum i n u m complex-clay.
The natural fatty materials used for soap formation can be
of animed or vegetable origin. Beef tallow and its derivatives
are the major source of animal fatty materials. The reaction
product with beef tallow derivatives Eind lithium hydroxide is
lithium stearate soap. Castor oil derivatives are the m a i n
source of vegetable oil fatty materials. Because the acids derived from castor oil have a hydroxyl group (OH) on the 12'''
carbon of the acid molecule, the reaction product with castor
oil derivatives and lithium hydroxide is lithium 12-hydroxystearate soap. Although the resulting soap is named according to the acid most prevalent, the natural occurring fatty
acids are actually mixtures of similar acids (in the form of a
glyceride) with slightly different molecular weights. The type
of fatty materials used affects the properties of the soap and
the grease. Greases made from castor oil derivatives Eire more
work stable and have higher dropping points than greases
made from beef tallow derivatives due to the hydrogen bonding at the hydroxyl group. The use of mixtures or blends of
fatty materials can obtain improved cost, oil separation,
worked stability, or other properties.

The most common basic components used to neutralize


the fatty acids are hydroxides of lithium, calcium, and
sodium. The resulting greases are named according to the basic component and the acidic component used to form the
soap, e.g., calcium stearate grease, lithium 12-hydroxystearate grease, etc.
Grease Selection
When selecting a grease for a particular application, one
should first determine the type and viscosity of the lubricating fluid required because the fluid has a major influence in
grease lubrication. The properties of greases are determined
by the characteristics of the thickener system, by the viscosity and type of the fluid component, and by the performance
additives used. Similar criteria as is used for selecting industrials oils can be used when determining the type and viscosity of the lubricating fluid needed in a grease for a particular
application. In general, heavily loaded and slow speed applications require higher oil viscosity Eind lightly loaded high
speed applications require lower oil viscosity. E a c h thickener
system has its own unique characteristics. Additional discussion of the properties of the various soap type greases will be
provided in subsequent paragraphs.

GENERAL CHARACTERISTICS
Describing the general characteristics of a grease based on
the thickener type is difficult because the base oil components and the performance additives used effect the characteristics of the grease as m u c h or more than the thickener
type. Therefore, assigning characteristics to a grease based
on thickener t5^e has limited value, however, some characteristics inherent to the thickener tjfpe are discussed below.
The reader should be aware that some of the weaknesses of a
thickener type can be improved and some of the strengths of
a thickener type can be degraded with the inclusion of performance additives.
Aluminum Soap Greases
Aluminum soap greases are usually made with preformed
soap unlike most other thickeners that Eire made in situ. Alum i n u m distearate is the m o s t c o m m o n conventional alum i n u m soap used to make grease. It is dissolved in hot oil in
a mixing grease kettle, and the hot mixture is poured into
pans to gel and cool. The cooling rate affects the final consistency. The final product is a smooth, transparent grease with
a tendency to thin when worked but with excellent water resistance. Aluminum soap greases are used as thread and way
lubricants. The poor work stability of aluminum-soap
greases is used to advantage in electrically conducting conveyers of electroplating systems; the grease thins down during use, allowing good electrical contact in the track rollers
while still providing good lubrication.

Calcium Soap Greases


The Ccirliest known greases were made with calcium soaps.
Greases thickened with hydrated calcium soaps (usually cal-

CHAPTER 20: LUBRICATING


cium stearate) are water resistant, work stable, and inexpensive. The name hydrated calcium comes from the fact that a
small amount of water (about 0.1% wt.) is required to stabilize the grease. The water associates with the calcium soap
and provides the molecular cohesion needed for efficient
thickening. These calcium greases are also known as conventioneJ calcium, calcium cup, or lime soap greases. The greatest shortcoming of a hydrated calcium soap grease is its low
dropping point, typically about 95C (200F). This limits conventioneJ calcium soaps to use in only low temperature applications.
Anhydrous calcium soaps (usually calcium 12-hydroxystearate) are not as temperature limited because they do not
need water to hold the soap together due to the stabilizing effect of the hydroxyl group (OH). With a dropping point of
about 150C (300F), they are somewhat more temperature
resistant. Anhydrous calcium greases have the same advantages as hydrated calcium greases, but are slightly more expensive cind do not run the risk of drying out and softening.
They can be used as multi-purpose greases within their temperature limitations. Historically, the greatest usage for Einhydrous calcium grease has been in a low temperature grease
made with a low-viscosity base oil designed to meet earlier
versions of the military specification MIL-G-10924 for applications where operation over a wide range of climatic conditions is essential.

GREASES

559

thermal limitations of the oils and additives they contain.


Aluminum complex greases have excellent water tolerance
characteristics as well as high-temperature resistance, consequently, they are widely used in steel mills and other wet applications. The soap used for aluminum complex grease is
usually eJuminum benzoyl stearoyl hydroxide. This soap can
be formed by reacting aluminum isopropylate with stearic
acid, benzoic acid, and water. To limit or avoid the isopropyl
alcohol byproduct, other aluminum compounds can be used.
Compatibility with other greases can be a problem with aluminum complex greases.
Calcium Complex Soap Greases
Calcium complex greases Eire usually made by reacting acetic
acid and a fatty acid with lime. The resulting grease has inherent EP (extreme pressure) properties and provides good
friction and wear performance. Thickening efficiency is not
very good with this soap, therefore, a relative high soap concentration is required. As a result, the low-temperature performance is not as good as other complex soap greases, and
they tend to harden in long-term storage or under pressure in
lubrication systems. Used within its limitations, calcium
complex greases are cost effective but are not compatible
with most other grease types.
Lithimn Complex Soap Greases

Sodium Soap Greases


Sodium (soda) soap greases have higher dropping points
[about 175''C (350F)] than calcium greases and form a very
fibrous grease. They Eire not water resistant and emulsify in
the presence of water, yet, they have inherent rust protection
properties. The soap can be made by reacting sodium hydroxide cind tallow, therefore, is a very inexpensive thickener.
In earlier times, when calcium and sodium greases made up
most of the market, these greases were the most temperature
resistant. They are still used in moderately high temperature
applications, such as electric motor bearings. Sodium soap
greases are not normally compatible with other greases.
Lithium Soap Greases
Lithium greases were the first so-called multipurpose
greases. They provide both good water resistance, similar to
calcium soap greases, and even higher-temperature properties than sodium soap greases. The soap is usually manufactured in a portion of the lubricating oil using lithium hydroxide and a fatty material of either animal or vegetable
origin. Lithium 12-hydroxystearate greases have dropping
points of about 190C (375F). They also have good work stability; that is, they do not soften much when worked. Lithium
greases have good over-all performance and are cost effective. In North America more lithium grease is made them all
other tj^es combined.
Aluminum Complex Soap Greases
Complex soap greases are noted for their high-dropping
points [230C (450F) and higher], although most are
not recommended for use up to the dropping point due to

Lithium complex grease performance is generally like that of


lithium greases except dropping points are about 50C
higher. Lithium complex is a misnomer used to describe high
dropping point lithium greases. Because, lithium is mono-valent (mccining it can only react with one acid per ion) it cannot form a traditional complex soap where two or more acids
are reacted with one basic ion. However, there are severed
components that can be used to enhance the molecular interactions of the soap molecules and increase the dropping
point enough to call the resulting grease a "lithium complex."
The most common method is by forming a lithium salt of a
dibasic acid (usually azelaic or sebacic) in situ with lithium
12-hydroxystearate soap. Lithium complex greases provide
good low-temperature performance and excellent high-temperature life performance in tapered roller bearings. It is the
most populcir of the complex greases and has wide-spread
application.
Polyurea Greases
Polyurea greases are similar to the complex soap greases with
respect to high-temperature performance; dropping points
are about 245C (475F). The reactants (isocyanates and
amines) are hazardous but the resulting thickener is considered quite safe. Polyurea greases can be made by various
methods resulting in various strengths and weakness. Most
have good oxidation resistance, water resistance, pumpability, and high temperature performemce. Wesiknesses generally associated with poljoirea greases include poor shear stability, poor storage stability, and incompatibility with other
greases, however, some of these weaknesses have been overcome with more recent formulations [5]. Although used in all
types of bearings, they have proved especially useful for the

560

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

lubrication of sealed-for-life, ball bearings used in electric


motor bearings where superior oxidation resistance and
high-temperature life is essential.
Organo-Clay Greases
Clay thickened greases are made with a modified clay design
to have some affinity for the lubricating oil. The process can
be as easy as mixing the modified clay thickener with the lubricating oil and providing enough shear to disperse the
thickener. They have been referred to as non-melting greases
because they tend to decompose before reaching their dropping point. They usually have poor work stability properties
as compared to soap greases. Because many of the common
additives used in grease will soften clay thickened greases,
they are more difficult to inhibit with extreme pressure additives. Although water resistant, they can be susceptible to severe degradation from other contaminants, such as brine.
Low-temperature performance could be considered satisfactory, but many clay greases are formulated with high-viscosity base oils for high-temperature applications; such greases
will have poor low-temperature properties. Clay greases are
not normally compatible with other greases.

CLASSIFICATION AND SPECIFICATIONS


Over the past six decades, efforts to develop a grease classification system were frustrated by seemingly insurmountable
difficulties. Until recently, the American grease industry had
not developed grease specifications for industry-wide applications. However, in 1989, after about 15 years of development, ASTM D4950, Standard Classification and Specification for Automotive Service Grease, was published.
Development of this standard was a cooperative effort by
ASTM International, NLGI (National Lubricating Grease Institute), and SAE (Society of Automotive Engineers). It is the
first and only cooperatively-developed grease specification
accepted by American industry. Development of this standard was made possible only because several grease performance tests were developed specifically for automotive applications. These performance tests (D 3527, D 4170, D 4289,
D 4290, and D 4693) are discussed subsequently.
D 4950 classifies automotive service greases into two chassis grease and three wheel bearing grease categories based on
the performance needs of several service conditions. A guide
to the requirements of these categories is given in Table 1.
The NLGI has established a licensing procedure for greases
qualifying for ASTM D 4950, categories GC and LB. In conjunction with licensing, three certification symbols can be
used only with the highest-performance categories of chassis
and wheel bearing greases. NLGI specifically prohibits the
use of the symbols with lesser-performance grease categories.
Industry response to the licensing system has grown over
the last decade and containers of grease bearing the certification symbols are commonly available in the aftermarket,
and their availability is expected to expand. Beginning with
the 1992 model year, most U.S. automakers began recommending the use of NLGI Service Greases GC, LB, and GCLB for scheduled maintenance of chassis and wheel bearings
of passenger cars and light-duty trucks.

TABLE 1Guide to requirements for grease categories


(ASTM D 4950).
Test

Description

LA

LB

GA

GB

GC

D-217
0-566"
D-1264
D-1742
D-1743
D-2266
D-2596
D-3527
D-4170
D-4289
D-4290
D-4693

Penetration
Dropping Point
Water Washout
Oil Separation
Rust Protection
4 Ball Wear
4 Ball EP
High Temperature; Life
Fretting Wear
Elastomer Compatibility
Leakage
Low Temperature Torque

/
/

/
/

/
/

/
/
/
/
/
/
/

/
/
/

/
/
/
/
/
/
/

'^D-2265 may be substituted.

TEST METHODS AND THEIR


SIGNIFICANCE
Greases are used for particular lubrication applications because of their intrinsic properties. Users and producers alike
need a common means to describe the properties required
for grease performance for particular applications. Test
methods are devised to describe the requisite properties.
When the usefulness of some test becomes known throughout the industry, it is developed, through cooperative effort,
into an industry standard such as an ASTM standard. The
standard tests used to determine the properties of petroleum
oils Eire commonly applied to grease base stocks, as well. Few
among these are kinematic viscosity (D 445), flash and fire
points (D 92), pour point (D 97), and aniline point (D 611),
etc. The significance of these tests are discussed elsewhere
throughout this book.
There are no standard tests for the evaluation of grease
thickeners, per se, because most thickeners (soaps) are
formed in situ and are not used independently of the grease.
Consequently, there is little need for standard tests to evaluate neat thickeners. However, work is currently in progress,
including an ASTM Round Robin using the Penn State Microoxidation test, to study oxidation characteristics of
greases, which helps lend limited insight to the evaluation of
the thicker system.
ASTM and IP (Institute of Petroleum) have developed and
standardized a number of tests to describe the properties and
performance characteristics of lubricating greases. Because
these tests are conducted in laboratories under well-defined
conditions, they are used primarily as screening tests. Some
of the grease tests do indicate how a grease might perform in
service, but direct correlation between laboratory and field
performance is often unattainable because the tests never
precisely duplicate service conditions.
Consistency
Consistency can be defined as the degree to which a plastic
material, such as a lubricating grease, resists deformation
under an applied force. It is a measure of the firmness or
rigidity of the thickener structure of the grease. The standard
method for measuring grease consistency is the penetration
test. Consistency is reported in terms of ASTM cone penetration, NLGI Consistency Number, or apparent viscosity. Cone

CHAPTER 20: LUBRICATING


penetrations and NLGI number are discussed in the following paragraphs. Apparent viscosity is included in the Shear
Stability section.
Cone Penetration
ASTM D 217 (IPSO) Test Methods for Cone Penetration of Lubricating Grease is the universal standard for the determination of the penetration of a normal grease sample. (In this
context, normal greases are those that are neither too soft nor
too hard to be measured by this method.) In this method, a
double-tapered cone of prescribed construction sinks under
its own weight into a sample of grease at 25C (77F) for 5 s.
The depth of penetration, measured in tenths of a millimeter,
is the penetration value. (It is common practice to omit the
units when reporting or specifying penetration vEilues.) Firm
greases have low-penetration values, whereas soft greases
have high-penetration values.
Full-scale penetration tests require about 500 g (1 lb) of
sample. The penetration number for smaller samples of
grease can be determined by using ASTM D 1403 (IP310),
Test Methods for Cone Penetration of Lubrication Grease Using One-Quarter and One-Half Scale Cone Equipment. The
one-quarter and one-half scale tests require about 5 and 50 g
samples, respectively. As might be expected, the reducedscale tests are not as precise as the full-scale tests. Reducedscale penetration values are not normally used as such; instead, equations are given to convert the reduced-scale
penetrations to equivalent full-scale values. Recent advances
in instrumentation, such as automatic and digital Penetrometers, have helped improve the precision of this test method.
The following paragraphs describe the several types of penetration measurements.
Unworked PenetrationThis value is obtained when a penetration measurement is made on a grease transferred from
the original container to the standard grease worker cup,
with only a minimum amount of disturbance. This result is
not always reliable, because the amount of disturbance cannot be controlled or repeated exactly. This measurement may
be significant to indicate consistency variances in transferring grease from container to equipment.
Worked PenetrationWorked penetration is the standard
penetration measurement for a grease. It is measured after a
grease has been worked for 60 double strokes in the standard
grease worker. This method is more reliable than unworked
penetration, because the disturbance of the grease is standardized by the prescribed working process. A significant difference between unworked and worked penetration can indicate poor shear stabilityand indicate a need for further
evaluation by prolonged working or roll test (see the Shear
Stability section).
Prolonged Worked PenetrationThis value is obtained after
a sample has been worked for a prolonged period in the
grease worker, i.e., 10000, 50000, 100000, etc., double
strokes. After prolonged working, the sample and worker are
brought back to penetration test temperature 25C (77F) in
1.5 h. It is then worked for 60 double strokes and the penetration is measured. This test is significant because it can indicate the degree of shear stability of a grease.
Block PenetrationIf a grease is firm enough to hold its
shape, it is not transferred to a worker cup container for test.

GREASES

561

Instead, the penetration is determined on three faces of a


freshly-cut, 50-mm (2-in.) cube of grease.
Undisturbed PenetrationUndisturbed penetration is that
measured on a grease sample in a container as received, without any disturbance. This measurement was formerly a requirement in D 217, but because of the uncertainty of repeatable sample handling, it now is included merely as an
information item. Such measurements can be used for consistency control in grease manufacture, and to assess the degree to which a grease develops false body or set with prolonged storage.
NLGI Consistency NumbersOn the basis of worked penetrations, the NLGI has standardized a numerical scale as a
means of classifying greases in accordance with their worked
consistency. This scale is shown in Table 2 in order of increasing hardness. The majority of greases used in automotive and industrial applications fall in the range of NLGI No.
1 to NLGI No. 3.
Consistency Stability
The consistency of a grease may change with its history.
Some greases may harden with age; others may change due
to wide fluctuations in temperature. Evaluation of these
changes needs to be on an individual basis. That is, the test
grease needs to be subjected to controlled aging or temperature fluctuations, with penetration measurements taken periodically.
The consistency of greases may also change in service due
to changes in the size and dispersion of thickener particles resulting from mechanical shearing. The ability of a grease to
resist changes in consistency during mechanical working is
referred to as consistency stability, shear stability, work stability, or mechanical stability. Two test methods have been
standardized to evaluate the stability of a grease resulting
from two degrees of low-shear working.
Prolonged Worked Penetration & Low Temperature
Penetration
ASTM D 217 (IP50), described previously, is used before and
after prolonged working in a grease worker to determine the
change in grease consistency. Because shear rates are low,
evaluation of shear stability by prolonged working is time
consuming (working 100000 strokes takes nearly 28 h). Mechanical grease workers with cut off timers help make this a
little more manageable task, however, this test is not extensively used anymore.

TABLE 2NLGI consistency classification.


NLGI
Consistency No.

ASTM Worked
Penetration at 25C

000
00
0
1
2
3
4
5
6

445-475
400-430
355-385
310-340
265-295
220-250
175-205
130-160
085-115

562

MANUAL

Roll

Stability

37: FUELS AND LUBRICANTS

HANDBOOK

Results can be obtained more quickly with the roll stability


test, which operates at somewhat higher shear conditions.
Roll stability is determined by ASTM D 1831, Test Method for
Roll Stability of Lubricating Grease. It is used in conjunction
with the reduced-scale penetration test [D1403 (IP310)].
After a worked penetration has been measured on a grease
sample, 50g of the worked grease is transferred into a horizontally-mounted cylinder containing a 5-kg (11-lb) steel
roller. The cylinder is rotated at 165 r p m for 2 h. The inner
roller rolls over the grease, working it during the test. After
the test, the penetration of the grease is once again measured
by D 1403, and the change between before and after penetrations gives a n indication of shear stability. Recent trend (last
few years) has been to run the roll stability tests at elevated
temperatures, often even above 100C, instead of the conventional room temperature tests, to help evaluate the roll stability of greases at a higher temperature.
Roll stability tests are widely used in specifications. Test results are significant insofar as they can show a directional
change in consistency that could occur during service. No accurate correlation between roll-test results and actual service
performance has been established.
In both shear stability tests, the change in consistency is reported as either the absolute change in penetration values or
the percent change as outlined in ASTM D 1831. If absolute
values are to be reported, the quarter-scale values are first
converted to full-scale values.

Flow Properties
The consistency of a grease is a critical p a r a m e t e r which
helps define the ability of a grease to perform under given operating conditions. Consistency, as measured by penetration,
is affected by temperature. But the penetration test is not
suitable for determining the minor, yet sometimes significant, changes in consistency as the grease approaches temperatures at which phase changes in the thickener occur.
Penetration is basically a flow measurement; in addition,
there are other flow-measurement tests that can be utilized to
evaluate this property at other conditions.
Flow Properties

at High

Temperatures

ASTM Test Method D 3232, Measurement of Flow Properties


of Lubricating Greases at High Temperatures, can be used to
evaluate flow properties of lubricating greases under hight e m p e r a t u r e , low-shear conditions. Using this method, a
grease sample is packed into a n annular channel in an alum i n u m block. The packed block is placed on a hot plate capable of attciining temperatures in excess of 315C (600F) at
a heating rate of 5 r C (102F)/min. A special trident
probe spindle, attached to a Brookfield-RVF viscometer, is
lowered into the grease sample, and the hot plate is turned
on. Simultaneously, the spindle is rotated at a constant 20
rpm, and torque measurements are read from the viscometer
every minute. Readings are continued until the reading drops
below 0.5 on the viscometer scale or until the maximum sample temperature of interest is attained. With these data and
a n appropriate conversion equation, a plot of apparent viscosity versus temperature is prepared.

The trident probe test gives information not obtained with


the dropping point test. The dropping point test (to be described subsequently) determines the temperature at which
the first drop of material drops from the orifice of the standard cup. That first drop may be "melted" grease or leeiked
fluid. For example, if a grease becomes so fluid that it drops
from the cup, the trident probe test will show a low viscosity
at the same temperature. In another case at the same temperature, where it is only oil that drops from the cup, the trident probe will show a higher viscosity than the first case, indicating that the grease is still firm.
The results of this test provide a n indication of the flow
properties of a grease between room a n d elevated temperatures. Although the test does not give actual flow rates, as in
a pipeline, it provides a means for obtaining some indication
of this property. This test is used more for grease development, rather than for specifications.
Apparent

Viscosity

Grease is by nature a non-Newtonian material. It is characterized by the fact that flow is not initiated until stress is
applied. Increases in shear stress or pressure produce disproportionate increases in flow. The term apparent viscosity
is used to describe the observed viscosity of greases; it is
measured in Poises in D 1092, Test for AppEirent Viscosity of
Lubricating Greases. Since apparent viscosity varies with
both temperature and shear rate, the specific temperature
and shear rate must be reported along with the measured
viscosity.
In this test, a sample of grease is forced through a capillary
tube by a floating piston actuated by a hydraulic system using a two-speed gear p u m p . From the predetermined flow
rate cind the force developed in the system, the apparent viscosity is CcJculated using the classic Poiseuille equation. A series of eight capillaries and two p u m p speeds provide 16
shear rates for the determination of apparent viscosities. The
results are expressed in a log-log graph of apparent viscosity
as a function of shear rate at a constant temperature, or apparent viscosity at a constant shear rate as a function of temperature.
This apparatus also has been used to measure the pressure
drops of greases u n d e r steady-flow conditions at constant
temperature. Such information can be used to estimate the
pressure drop or required pipe diameters in distribution systems. Also, apparent viscosity data are useful for evaluating
the ease of handling or pumping at specified temperatures of
dispensing systems; it is often used to evaluate pumpability
at low temperatures. (The NLGI can provide a group of
charts that relate pressure drop, apparent viscosity, shear
rate, and pipe-flow data.) Apparent viscosity also is used to
provide an indication of the directional value of starting and
running torques of grease-lubricated mechanisms. Specifications may include limiting values of apparent viscosity for
greases to be used at low temperature.
Currently an ASTM Round Robin is being conducted to
rewrite the U.S. Steel Grease Mobility test method under the
aegis of ASTM. The Low Temperature grease mobility test
method utilizes only one capillary tube, maintained at various temperatures. The amount of grease collected in a specific time (gms/minute) is measured and used as an indication of the mobility of the grease. The test is easier to conduct

CHAPTER
t h a n ASTM D 1092, and uses axi apparatus similEir to the apparent viscosity test method.
Low-Temperature

Torque

(Ball

Bearings)

Greases designed for low-temperature applications must not


stiffen or offer excessive resistance to rotation. However,
greases harden emd become more viscous as the temperature
is lowered. Sometimes the grease can become so rigid in the
bearing t h a t excessive torque is required for rotation. In
extreme cases, the grease can solidify to the point of bearing
lock-up. Two standard test methods are available to measure
bearing torque at low temperatures. Both operate on the
same principlethe restraining force or torque is measured
while grease-lubricated test bearings are r u n at low speed.
The tests differ in the size and types of bearings, the intended
applications, and types of greases (i.e., in viscosity characteristics).
ASTM D 1478, Test Method for Low-Temperature Torque
for Ball Bearing Greases, measures the starting and running
torque of lubricating greases packed in small ball bearings at
temperatures as low as 54C (65F). In this procedure,
fully packed bearings are installed on a spindle that can be
rotated at 1 rpm. The assembly is inserted in a cold box. The
outer race is connected by a cord assembly to a spring scale,
which measures the restraining force. When the m o t o r is
started, the initial, peak restraining force is recorded. After
running for 10 min, the restraining force is recorded again.
The force values are multiplied by the length of the lever arm,
and the products are reported as the starting and running
torque in gram-centimeters (g-cm). [Because the cgs (centimeter-gram-second) metric unit, g-cm, is nearly universally
used in grease specifications, it is the standard unit of torque
measurement for this test; some newer specifications require
the SI torque unit, N-m (Newton-meter).] In the past several
years, advances in data acquisition techniques have helped in
making these test methods easier to r u n and have improved
precision and reliability.
Because this method was developed using greases with extremely low-torque cheiracteristics at - 5 4 C (-65F) it may
not be applicable to other greases, speeds, or temperatures. If
a machine has significantly more power available than is actually required, torque is not an important consideration. On
the other hand, it can be very i m p o r t a n t in low-powered
equipment. This test is significant because it provides a
means of comparing the low-temperature torque effects of
widely different greases. It is useful in the selection of greases
for low-powered mechanisms, such as instrument bearings
used in aerospace applications. The suitability of this method
for other applications requiring different loads, speeds, and
temperatures should be determined on an individual basis.
Usually, test conditions are substantially different from those
found in service, so test results may not correlate with actUcJ
service performance.
Low-Temperature

Torque

(Tapered Roller

Bearings)

For applications using larger bearings or greater loads,


D 4693 Test Method for Low-temperature Torque of GreaseLubricated Wheel Bearings, is better suited than D 1478.
D 4693 can be used to predict the performance of greases
in automotive wheel bearings operating at low temperatures. It will differentiate among greases having distinctly

20: LUBRICATING

GREASES

563

different low-temperature characteristics. It is used for


specification purposes, a n d it is one of the automotive
grease performance tests required by D 4950. It is not
known to correlate with other types of service. It should be
noted that greases having such characteristics that permit
torque evaluations by either D 1478 or D 4693 will not give
the same values in the two test methods (even when converted to the same torque units) because the apparatus and
test bearings are different.
D 4693 determines the extent to which a grease retards the
rotation of a specially-manufactured, tapered roller bearing
assembly. The test unit is a model device that closely duplicates an automotive wheel bearing assembly. Additionally, it
employs a spring-loading m e c h a n i s m to improve test repeatability; and it is not intended to simulate any service-load
condition. Although the test assembly cind torque-measuring
transducer are necessarily inside the cold-test chamber, the
drive mechanism can be either inside or outside.
In this test, a sample of test grease is stirred and worked,
and a specified a m o u n t is packed into the two test bearings.
The test assembly is heated to mitigate the effects of grease
history; it is then cooled at a specified rate to 40C (40F).
A drive m e c h a n i s m rotates the spindle at 1 rpm, a n d the
torque required to prevent rotation of the h u b is measured by
a strain gage load cell at precisely 60 s after start of rotation.
The results are recorded on a strip chart or using a data acquisition system that can be displayed and stored via computer. (Starting torque was found to be less repeatable, as
well as a redundant measurement, and is not determined in
this test.)
Heat Resistance
Heat affects greases in several ways. As the temperature increases, greases soften and flow more readily (see description
of D 3232); oxidation rate increases (see description of D
942); oil evaporation increases (see descriptions of D 972 and
D 2595); the thickener melts or loses its ability to retain oil
(see descriptions of D 566 and D 2595). Sometimes these phen o m e n a are all involved simultaneously (see descriptions of
D 3336, D 3337, and D 3527).
Dropping

Point

The dropping point of a grease is the temperature at which it


passes from a semi-solid to a liquid. Although a thickener can
have a definite melting point, the resulting grease does not.
Rather, the thickener loses its ability to function as a grease
thickener as the temperature is increased. As the temperature
is raised, the grease softens to the extent that it loses its selfsupporting characteristic, the structure collapses, and the
grease flows under its own weight. When this phenomenon
takes place in a standard cup under standard conditions, it is
called the dropping point.
Two similar procedures are used to determine the dropping point of grease. In both methods, a prescribed layer of
grease is coated on the inner surface of a small cup whose
sides slope toward a hole in the bottom. With ASTM D 566
(IP132), Test Method for Dropping Point of Lubricating
Grease, the sample is heated at a prescribed rate until a liquid drop falls from the cup. In ASTM D 2265, Test Method for
Dropping Point of Lubricating Grease Over Wide Tempera-

564 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

ture Range, the sample is introduced into a preheated environment so that the heating rate is controlled more uniformly. In both tests, the difference in temperature between
the grease in the cup and the environment are taken into account when calculating the dropping point of the grease.
Some greases containing non-soap thickeners may not separate oil or melt.
Cooperative testing indicates that dropping points by
Methods D 566 and D 2265 generally agree up to about 260C
(500F). In cases where results differ, there is no known significance.
The dropping point is useful (1) in establishing bench
marks for quedity control, (2) as an aid in identifying the type
of thickener used in a grease, and (3) as an indication of the
maximum temperature to which a grease can be exposed
without complete liquefaction or excessive oil separation.
(For simple soap greases, the maximum usable temperature
is about 20-30C lower than the dropping point. For complex
soap grease, the maximum usable temperature is limited by
the base oil characteristics, and under dynamic conditions
seldom exceeds 175C. Some complex soap greases will tolerate intermittent operation at higher temperatures, and although they may liquefy somewhat, their structure will reform as the temperature is reduced.)
Greases normally do not perform satisfactorily at temperatures near or above the dropping point; other factors are involved. High-temperature performance can depend on the
application method and frequency, whether a softened
grease is retained at the point of application by proper seals,
and whether the high temperature is continuous or intermittent. High temperature stability and evaporation properties
of the grease also can affect performance.
Dropping point is most useful as a quality-control tool. Unless correlation has been established, dropping point has no
direct bearing on service performance. Performance at high
temperature would be better evaluated with one of the performance-type tests or by actual experience.
Evaporation Loss
Exposure of a grease to high temperatures can cause evaporation of some of the liquid lubricant, thus causing the remaining grease to become drier and stiffer or leading to other
undesirable changes in the grease structure. Greases containing low-viscosity oils for good low-temperature performance may be susceptible to evaporation losses at higher
temperatures. Evaporation also can cause problems where
vapors may be hazardous or combustible, or interfere with
operations. In most applications, even high-temperature applications, evaporation is not a serious problem because of
effective sealing. However, when it is necessary to evaluate
evaporation loss, two ASTM test methods are available.
Evaporation Loss of Greases and Oils
D 972, Test Method for Evaporation Loss of Lubricating
Greases and Oils, determines mass evaporative losses from
greases or oils at any temperature in the range of 100-150C
(210-300F). A weighed sample of lubricant is placed in an
evaporation cell in an oil bath at the desired test temperature.
Heated air at a specified flow rate is passed over the sample
surface for 22 h, after which, the loss in sample mass is determined.

Evaporation Loss Over Wide Temperature Range


D 2595, Test Method for Evaporation Loss of Lubricating
Greases over Wide Temperature Range, augments D 972,
which is limited to 150C (300F), and was developed because
of higher service temperatures. D 2595 can be used to determine the loss of volatile materials from a grease over a temperature range of 93-316C (200-600F). This test uses the
same sample cup as D 972, but the rest of the apparatus is
markedly different. It uses an aluminum block heater, instead
of an oil bath, to achieve much higher temperatures. The other
test conditions, i.e., air flow rate and test duration, remain the
same. Laboratories equipped with D 2595 do not need D 972;
the results will be similar, but not necessarily identical.
Within their respective temperature constraints, both tests
can be used to compare evaporation losses of greases intended for similar service. All other factors being equal,
greases having the least evaporative losses will probably perform longer in high-temperature service. Results of these
evaporation tests may not be representative of volatilization
that can occur in service.
Oil Separation (Static Bleed Test)
Nearly all greases will separate some oil during storage, but
they differ markedly in the amounts that are liberated. If a
grease separates too much oil, the grease could harden to the
extent that lubrication will be affected. Opinions differ on
whether or not lubrication depends on oil bleeding; greases
that do not separate some oil during operation can be noisy
in service. However, excessive liberation of free oil during
storage is to be avoided. Oil can be released from a grease at
varying rates depending on the gel structure, the nature and
viscosity of the lubricating fluid, and the applied pressure
and temperature.
ASTM D 1742, Test Method for Oil Separation from Lubricating Greases During Storage, is used to determine the tendency of lubricating greases to separate oil when stored at
25C (77F) at an applied air pressure of 1.72kN/m^ (0.25psi).
It gives an indication of the oil retention characteristics of lubricating greases stored in both normally-filled and partiallyfilled containers. This test is not suitable for use with greases
softer than NLGI No. 1 consistency because of a tendency for
the grease to seep through the screen.
The test is useful because the results correlate directly
with oil separation, which occurs in 16-kg (35-lb) containers
of grease stored at room temperature. Storage in other containers gives similar results. This test should not be used to
predict the oil separation of grease under dynamic service
conditions. (See Standards Under Development, Cone Test,
for a description of an elevated-temperature, static bleed
test.)
Oil Separation (Centrifuge Test)
ASTM D 4425 describes a procedure for determining the tendency of lubricating grease to separate oil when subjected to
high centrifugal forces. The results can be related to grease
performance in shaft couplings, universal joints, and rolling
element thrust bearings subjected to large or prolonged centrifugal forces. Results correlate well with actual service performance.
In this test, pairs of centrifuge tubes are charged with test
grease and placed in a high-speed centrifuge. The grease sam-

CHAPTER 20: LUBRICATING


pies are subjected to a centrifugal force equivalent to a relative centrifugal acceleration, G value, of 36000 at 50C. (The
units for the G value are awkward and not used, but they have
acceleration dimensions of length/time'^.) The normal test
duration is 24 h, but it can be extended to 48 or 96 h. At these
specified time intervals, the centrifuge is stopped, and the
amount of separated oil is measured and the volume percent
calculated. The resistance-to-separation index, called the
K36 value, is reported as the volume percent of separated
oil/total test hours (both actual values are reported as a fraction; the fraction is not to be reduced).
Leakage from Wheel Bearings
There are two tests to evaluate leakage of grease from wheel
bearings at high temperatures. The older test, D 1263, Test
Method for Leakage Tendencies of Automotive Wheel Bearing Greases, utilizes a modified automotive front hub assembly (1940s vintage design and bearings). The two bearings are
packed with a specified amount of test grease, and an additional 85g is distributed in the hub. The assembly is run at
660 rpm for 6 h at 104C (220F). After the test, the amount
of grease that leaked into the hubcap and collector is
weighed. The bearings are washed and examined for varnish,
gum, and lacquer-like materieJ.
ASTM Test D 1263 provides a means to differentiate among
grease products with distinctly different leakage characteristics. In addition, skilled operators can observe significant
changes in other grease characteristics that may have occurred during the test. However, these observations are subject to differences in personal judgment and cannot be used
for quantitative ratings. The test does not distinguish between
wheel bearing greases having similar or borderline leakage.
Accelerated Leakage from Wheel Bearings
ASTM D 4290, Test Method for Determining Leakage Tendencies of Automotive Wheel Bearing Grease Under Accelerated Conditions, uses the same principle of operation as does
D 1263. It is, however, a more modem test that uses a model
front wheel-hub-spindle assembly employing current production, tapered roller bearings. The test apparatus is identical to that used in D 3527 (however, the test conditions are
markedly different). In D 4290, the test temperature, 160C
(320F), is significantly higher, and the duration, 20 h, is
much longer than that of D 1263.
D 4290 was developed to evaluate wheel bearing leakage of
greases intended for use in vehicles equipped with disk
brakes, which involve much higher operating temperatures.
It is used in grease specifications for such applications, and
it is one of the performance tests required by D 4950. This
test is not known to correlate with any other type of service.
Oxidation Stability
Bomb Oxidation Test
The Standard Test Method for Oxidation Stability of Lubricating Greases by the Oxygen Bomb Method, D 942 (IP142),
determines the resistance of lubricating greases to oxidation
when stored statically in an oxygen atmosphere in a sealed
system at an elevated temperature. In this test, five glass
dishes are filled with 4g of grease, each, for a total of 20g.
These dishes are then racked and sealed in a bomb, which is

GREASES

565

then pressurized to 758kPa/cm^ (llOpsi) with oxygen. The


bomb is heated in a bath at 99C (210F) to accelerate oxidation. The amount of oxygen absorbed by the grease is
recorded in terms of pressure drop over a period of 100 h and,
in some cases, 500 or 1000 h. The pressure drop is a net result of the consumption of oxygen by oxidation of the grease
and the gain in pressure due to any gases or volatile by-products released from the grease.
Care must be exercised in the interpretation of data derived
from the oxidation bomb test. Additives incorporated into the
grease can produce misleading results because they can also
react with oxygen. As an example, sodium nitrite is sometimes added to grease to serve as a rust inhibitor. In the oxidation bomb test, this material consumes oxygen to form
sodium nitrate. In this instance, the drop in pressure is not
indicative of the amount of oxidation of the grease alone.
Also, greases containing excess carbonate can release CEirbon
dioxide gas whose vapor pressure will tend to offset the pressure decrease due to oxygen absorption.
The bomb oxidation test was originally designed to predict
shelf storage life of greases in prepacked bearings. Whatever
its original intent, experience has shown little correlation
with the stability of grease films in bearings or on other parts.
It predicts neither the stability of greases stored in containers
for long periods nor those used under dynamic conditions.
Its primary usefulness is for quality control to indicate batchto-batch uniformity. It can be used to estimate relative oxidation resistance of greases of the same type, but it should
not be used to compare greases of different types.
Although widely used for specification purposes, it is important to note that D 942 has been severely criticized for its
potential for misleading results and for having no relation to
oxidation in service. There are no standard, dynamic oxidation tests. For dynamic tests that are influenced to a greater
or lesser extent by the oxidation resistance of the grease, see
descriptions of D 3336, D 3337, and D 3527.
PDSC Oxidation Test
A number of grease test methods have recently been developed by the ASTM grease committee, one of them being the
PDSC (pressure differential scanning calorimetry) technique
for evaluating oxidation stability. In this test, a few mg of
grease is placed in a sample pan in a bomb, which is pressurized to 3.5MPa (500psi) with oxygen and regulated at that
pressure until an exothermic reaction occurs. From a plot of
heat as a function of test time, the oxidation induction time
(called extrapolated onset time) is determined. This method
of evaluating oxidation stability has two significant advantages over D 942: 1) It is considerably faster, generally less
than an hour, vs. 100 h or more, and 2) unlike D942, this
method is not subject to false values from greases that give off
carbon dioxide or other gases during heating. The disadvantages are that the apparatus is expensive, and like D942 the results are not known to correlate with service performance.
Another test being developed is the thin film microoxidation test, which has been shown in literature to provide a
good indication of the oxidation stability of a grease sample.
Greases in Ball Bearings at Elevated Temperatures
ASTM D 3336, Test Method for Performance Characteristics
of Lubricating Greases in Ball Bearings at Elevated Temper-

566

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

atures, is used to evaluate the performance characteristics of


lubricating greases in ball bearings operating u n d e r light
loads at high speeds cind elevated temperatures for extended
periods. Correlation with actual field service cannot be assumed. This method has been criticized for having two test
spindles qualified that purportedly do not necessarily give the
same results.
In this test, the lubricating grease is evaluated in a 20-mm,
SAE No.204, heat resistant, steel ball bearing rotated at
10000 r p m under light loads of 22-67N (5-151bf) at a specified elevated temperature u p to 370C (700F). The test is r u n
on a specified, test-temperature-dependent, operating cycle
until lubrication failure or completion of a specified time.
(Unless automatic controls Eire used, a 72-h weekend shutdown is required.) With superior greases, tests can last u p to
several thousand hours. Multiple tests need to be r u n because
the results follow Weibull, rather than normal, distributions.
Greases in Small

Bearings

The computer and aircraft industries have used miniature


bearings for many years. As the trend toward miniaturization increased in other industries, a suitable test was needed
to evaluate lubricating greases in small bearings. ASTM D
3337, Test Method for Evaluation of Greases in Small Bearings, was developed to serve this purpose. Although this test
is not the equivalent of long-term service-performance tests,
it can be used to predict relative grease life at high temperature in a reasonable test period. Also, this test can measure
running torque at both one r p m and 12000 r p m if this property is significcmt for the intended application. The method
will not differentiate among greases of closely related characteristics.
ASTM D 3337 determines grease life and torque in a small
(6.35mm bore) R-4 ball bearing. In this test the bearing is run
at 12000 r p m with a 2.2N (1/2-lbf) radial and a 22N (51bf) axicJ load. While a test temperature of 250C (or 500F) may be
typiccJly specified, the equipment is capable of testing u p to
315C (600F) if high-temperature bearings are used.

Extreme Pressure and Wear


A lubricant functions by separating bearing surfaces. If the
separation was always complete, parts would never wear.
However, the integrity of the lubricant film cannot be maintained u n d e r all conditions, and contact occurs to varying degrees. Such contact depends on operating conditions (such as
load and speed), lubricant properties (such as fluid viscosity
and grease consistency), and lubricant chemistry (such as the
presence of wear inhibitors and extreme pressure additives).
Several tests are available for evaluating the antiwear and
load-carrying properties of greases.
Extreme

Grease

Life

With the advent of automotive disk brakes in the 1960s, then


c u r r e n t test m e t h o d s proved inadequate for evaluating
greases for this high-temperature application. A specific, correlating test method was needed, and after several yeeirs of
development, one was standardized. ASTM D 3527, Standard
Test Method for Life Performance of Automotive Wheel
Bearing Greases, evaluates grease life in a tapered roller,
wheel bccirings in a model, front wheel assembly r u n at 1000
rpm, under a thrust load of 11 IN, at 160C, using a cycle of
20 h on and 4 h off. The test apparatus is the same as that of
D 4290, b u t the operating conditions a n d measured peirameters are quite different.
Motor torque is monitored, and the test is terminated at a
calculated, preset torque vEilue. Grease life is indicated by the
n u m b e r of "on" hours (or n u m b e r of cycles) to failure. This is
a severe test; the results are influenced by a combination of
grease properties, such as oxidation stability, shear stability,
and volatility. As with D 3336, multiple tests need to be r u n
because the results follow Weibull distributions. This test
method is used for specification purposes and is required by
D 4950.

Timken

Method

ASTM D 2509, Test Method for Measurement of Extreme


Pressure Properties of Lubricating Grease (Timken Method),
can be used to determine the load carrying capacity of a
grease at high loads. Non-stemdard techniques have been devised to measure wear at lighter loads, but they are not discussed.
In the Timken test, a tapered roller bearing cup is rotated
against a stationary, hardened steel block. Both parts are lubricated with the test grease prior to starting the test. During
the test, the p a r t s are continuously lubricated with fresh
grease by means of a feed mechanism. Using a lever system
with a ten-fold mechanical advantage, fixed weights apply a
force to the block in line contact with the rotating cup. Loads
are applied step-wise until lubrication failure occurs, as evidenced by inspection for scoring or welding. The "OK Value"
is the m a x i m u m load the lubricant film will withstand without rupturing and causing scoring in the contact zone after a
10-min. run.
This test is a rapid method that can be used to differentiate
between greases having low, medium, or high levels of extreme pressure properties. It is widely used for specification
purposes; however, the results may not correlate with service
performance.
Extreme

Wheel Bearing

Pressure

Pressure

Four-Ball

Test

ASTM D 2596, Test Method for Measurement of Extreme


Pressure Properties of Lubricating Grease (Four-Ball
Method), is another test used to determine the load-carrying
properties of lubricating greases. With this procedure two
evaluations are made: (1) the Load-Wear Index (formerly
called Mean-Hertz Load), and (2) the Weld Point.
This test was developed to evaluate the extreme pressure
and antiweld properties of a lubricant. The tester is operated
with one steel bcdl rotated under load against three like bsJls
held stationary in the form of a cradle. The grease under test
covers the contact area of the four balls. Loads u p to 800 kgf
(7845N, 17601bf) can be applied to the balls to achieve unit
pressures u p to 6.9 X lO^kPa (1 000 000 psi).
The procedure involves the running of a series of 10-second
tests over a range of increasing loads until welding occurs.
During a test, scars are formed in the surfaces of the three
stationary balls. The diameter of the scar depends on the
load, speed, test duration, and lubricant. The scars are measured under a microscope having a calibrated grid. From the
scetr measurements, the Load-Wear Index is calculated. The
lowest load at which the rotating ball seizes and then welds
to the stationary balls is called the weld point; it indicates

CHAPTER
that the load carrying capacity of the grease has been exceeded.
The significance of this test is that it is a rapid method that
can be used to differentiate a m o n g greases having low,
medium, or high levels of extreme pressure properties. It is
widely used for specification purposes, b u t the results may
not correlate with service performance. Because of their poor
lubricity, some lubricating greases containing a silicone or a
halogenated silicone fluid component are not suitable for
testing by this test method.
Wear Preventive

Characteristics

of

Grease

ASTM D 2266, Test Method for Wear Preventive Characteristics of Lubricating Grease (Four-Ball Method) is used to determine the wear-preventive characteristics of greases in sliding steel-on-steel applications. This test does not distinguish
between EP and non-EP greases.
As in D 2509, a four-ball configuration is used, but there
are few other similarities as the apparatus and operating conditions are conspicuously different. Wear prevention qualities are evaluated from the diameters of the wear scars that
occur on the stationary balls during the test.
The test is significant because it can be used to determine
the relative wear-preventing properties under the test conditions, so it is useful for grease development. D 2266 is widely
used in grease specifications, but its actual usefulness is suspect because of the following limitations. If test conditions
are changed, the relative ratings may change.
1. Wecir characteristics are not predicted for metal combinations other than AISI (American Iron and Steel Institute)
E52100 steel unless non-stcindard balls of other materials
are used.
2. No differentiation can be made between extreme pressure
and non-extreme pressure greases.
3. No correlation can be inferred between the results of the
test and field service unless such correlation has been established.
Fretting

Wear

Fretting wear is a form of attritive wear caused by vibratory


or oscillatory motion of small amplitude. It is characterized
by the removal of finely-divided particles from the rubbing
surfaces. Air can cause immediate loccil oxidation of the
wear particles produced by fretting wear, and moisture can
hydrate the oxidation product. In the case of ferrous metals,
the oxidized wear debris is abrasive iron oxide (Fe203) having the appearance of rust, which gives rise to the nearlysynonymous terms, fretting corrosion and friction oxidation.
Fretting is a serious problem in industry. If severe enough,
it can cause destructive vibrations, premature failures, and
pcirts seizure. No grease can give total protection if fretting
conditions exist, but greases vary significcintly in their ability
to mitigate fretting wear. ASTM D 4170, Test Method for
Fretting Wear Protection by Lubricating Grease, evaluates
grease performance in a proprietary test machine (Fafnir
Friction Oxidation Tester) which oscillates two grease-lubricated, ball thrust bearings, u n d e r specified conditions of
load, speed, and angle. Fretting wear is determined by measuring the mass loss of the bearing races (the balls Eind retainers are not included).

20: LUBRICATING

GREASES

567

A related, but somewhat different, phenomenon often accompanies fretting wear. False brinelling is localized fretting
wear that occurs when the rolling elements of a bearing vibrate or oscillate with small amplitude while pressed against
the bearing race. The mechanism proceeds in stages: 1) asperities weld, are torn apart, and the wear debris which is
subsequently formed is oxidized; 2) due to the small-amplitude motion, the oxidized detritus cannot readily escape, and
being abrasive, the oxidized wear debris accelerates the wear.
As a result, wear depressions are formed in the bearing race.
These depressions are often polished and appear similar to
the Brinell depressions obtained with static overloading,
hence the term, false brinelling. D 4170 cannot distinguish
between false brinelling and fretting wear. If false brinelling
does occur, it is included in the determination of fretting
wear when bearing race mass losses are measured.
This test correlates with the fretting performance of
greases in wheel bearings of passenger cars shipped long distances. D 4170 also has been used to predict grease performance in automobile drivelines. It is used for specification
purposes and is one of the performance tests required by D
4950.
Oscillating

Motion

There is another wear test involving oscillatory motion,


namely, ASTM D 3704, Test Method for Wear Preventive
Properties of Lubricating Greases Using the Block on Ring
Test Machine in Oscillating Motion. Ring and block parts,
similar to those of the Timken Tester (D 2509), are operated
u n d e r varying conditions of load, speed, oscillation angle,
time, temperature, and specimen surface finish and hardness
to simulate service conditions. This test can distinguish
among greases of low, medium, and high wear preventive
properties and can be used for grease development. The user
should determine whether test results correlate with service
performance or results from other bench test machines.
Oscillating

Wear (SRV)

Test

A high load, high frequency, low amplitude, high speed reversal test, using the SRV (Schwingung, Reibung, Verschleiss) a p p a r a t u s simulates high-speed vibrational or
start-stop motions that occur in many mechanisms. Two procedures, using a ball-on-disk configuration, have been developed: [ASTM D 5706 (EP Test) and ASTM D 5707 (Wear)]
one to measure wear-protection qualities and coefficient of
friction, and the other to measure the ability of a grease to
carry loads under extreme pressure. (This apparatus can use
other configurations to suit different applications.) Both procedures have been correlated with grease performance in automotive driveline mechanisms and are used in grease specifications for these applications. These procedures can be
used to evaluate lubricants and materials for other applications of similar motion.
Corrosion
Copper

Corrosion

Lubricated parts that contain copper alloys, such as copper


or brass electrical components or bronze gears and bearings,
m a y be susceptible to the corrosive effects of formulated
greases. For example, such corrosion can cause high resis-

568 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

tance in electrical contacts, or premature bearing failure


from chemical attack.
D 4048, Test Method for Detection of Copper Corrosion
from Lubricating Grease by the Copper Strip Tarnish Test, is
the grease analog of the more familiar D 130 used to evaluate
oils. In this test, a prepared copper strip is totally immersed
in test grease and heated at specified conditions, usually
100C (210F) for 24 h. At the end of the test period, the strip
is removed, washed, and compared with the ASTM Copper
Strip Corrosion Standards.
Although this method is used in specifications, the user
must establish correlation between test results cind actual service performance. This test does not determine the ability of
a grease to inhibit copper corrosion caused by factors other
than the grease itself; neither does it determine the stability of
grease in the presence of copper. The sole determination is the
chemical staining of copper by lubricating grease.
Rust Prevention
Greases must not be corrosive to metals they contact and
should not develop corrosion tendencies with aging or oxidation. A method for assessing rust prevention by greases is
ASTM D 1743, Test Method for Corrosion Preventive Properties of Lubricating Greases.
In this method, a tapered roller bearing is packed with
grease, and following a short run-in period, dipped into distilled water and stored above the water in 100% relative humidity at 52C (125C) for 48 h. The bearing is then cleaned
and examined for corrosion. Either a Pass or Fail result is reported.
The significance of this test is that it indicates those greases
capable of preventing rust and corrosion in static or storage
conditions. This test is widely used in grease specifications.
The correlation with service conditions, particularly under
static conditions, is considered to be quite good.
Accelerated Corrosion Tests
Two test methods were recently worked on to evaluate the
corrosion protection properties of greases under severe conditions. These are: 1) a version of D 1743 using synthetic sea
water now called ASTM D 5969, and 2) two procedures of the
IP220/DIN51802 dynamic rust test [commonly known as the
EMCOR test (ASTM D 6138)], one using distilled water and
another using salt water.
Effect of Water
Contamination by water can affect greases and grease performance in several ways. Corrosion or rust protection, previously discussed, is one. Other effects include change in consistency, texture, or adhesiveness. An emulsion can be
formed, which will probably be an inferior lubricant, or it
could be washed away. Attempts to standardize means of
evaluating these effects have had mixed success. Two standard tests do exist, however: the water washout test and the
water spray-off test.
Water Washout
The ability of a grease to resist washout under conditions
where water may splash or impinge directly on a bearing is an
important property in the maintenance of a satisfactory lu-

bricating film. ASTM D 1264, Test for Water Washout Characteristics of Lubricating Greases, evaluates the resistance of
a lubricating grease in a bearing to washout by water.
This test method uses a standardized bearing, available
from ASTM. It is a 204K Conrad-type, ball bearing equipped
with shields but without seals. The bearing is packed with 4g
of test grease then rotated at 600 rpm while a jet of water, at
either 38C (100F) or 79C (175F), impinges on the bearing
housing for 1 h. The bearing is then dried, and the percent
grease loss by weight is determined.
This test method serves only as a relative measure of the resistance of a grease to water washout. It should not be considered the equivalent of a service evaluation unless such correlation has been established. Test results are affected by
grease texture and consistency. Test precision is poor, especially with soft greases. Although widely used, this test can
give misleading results. Even comparative results between
similar greases may not predict the relative performance of
the two greases in actual service.
Water Spray-Off
ASTM D 4049, Test Method for Resistance of Lubricating
Grease to Water Spray, is used to evaluate the ability of a
grease to adhere to a metal panel when subjected to direct
water spray. Test results correlate directly with operations involving direct water impingement, such as steel mill roll neck
bearing service and certain automotive body hardware applications.
In this test, a 0.79 mm (1/32 in.) film of test grease is uniformly coated onto a stainless steel panel; then water, at 38C
(100F), is sprayed directly on the panel for 5 min. The spray
is controlled by specified spray nozzle, pump, and plumbing.
After the spraying period, the panel is dried, weighed, and the
percentage of grease spray-off is determined.
Miscellaneous
Contamination
ASTM D 1404, Test Method for Estimation of Deleterious
Pcirticles in Lubricating Grease, defines a deleterious particle
as one which will scratch a polished plastic surface. The test
is applicable to all greases, even those containing fillers. In
fact, it can be used to test fillers, such as graphite, if they are
dispersed into a grease (or petrolatum) that is known to be
free of deleterious particles. It can be used also to test other
semi-solid or viscous-liquid substances.
With this method, the test material is placed between two
clean, highly polished acrylic plastic plates held rigidly and
parallel to each other in metal holders. The assembly is
pressed together by squeezing the grease into a thin layer between the plastic plates. Any solid particles in the grease
larger than the distance of separation of the plates and harder
than the plastic will become embedded in the opposing plastic surfaces. The apparatus is so constructed that one of the
plates can be rotated about 30 with respect to the other
while the whole assembly is under pressure. This will cause
the embedded particles to form characteristic arc-shaped
scratches in one or both plates.
The relative number of such solid particles is estimated by
counting the total number of arc-shaped scratches on the two
plates.

CHAPTER
The test has significcince because it is a rapid means for estimating the n u m b e r of deleterious particles in a lubricating
grease. However, a particle that is abrasive to acrylic plastic
m a y not be abrasive to steel or other bearing materials.
Therefore, the results of this test do not imply performance
in field service.
Elastomer

Compatibility

Nearly all grease-lubricated mechanisms have elastomeric


seeds to retain lubricant zmd exclude contaminants. In order
for these seals to function properly, the grease must be compatible with the rubber-like elastomer seal. ASTM D 4289,
Test Method for Compatibility of Lubricating Grease with
Elastomers, is a simple total immersion test designed to evaluate the compatibility of grease with elastomer specimens
cut from standard sheets. It also can be used as a guide to
evaluate compatibility of greases with rubber products not in
standard sheet form.
Unlike other standard compatibility tests, which are designed to evaluate elastomers in standard fluids, the emphasis of D 4289 is the evaluation of the greases. Elastomer specimens are cut from s t a n d a r d ASTM sheets (D 3182) a n d
immersed in test grease for 70 h at either 100 or ISO'C. Compatibility is evaluated by determining the changes in volume
and DurometerA hardness (D 2240). (Volume is determined
by the water displacement method, D 471.)
The volume and hardness change values determined in this
test do not duplicate the changes that occur in rubber seals in
actual service conditions. However, they can be correlated in
many instances. For example, the volume-change values correlated very well (r^ = 0.99) with those that occurred in a vehicle test. Because of wide variations in grease and elastomer
formulations and service conditions, correlations between
this test and particular applications should be determined on
an individual basis.
This method provides for optional testing with two Reference Elastomers to evaluate relative compatibility. The results CcUi be used to judge a service characteristic of lubricating greases; in this respect, the test m e t h o d is useful for
specification purposes. ASTM D 4950 requires testing with
Reference Elastomer CR (polychloroprene) cind Reference
Elastomer NBR-L (acrylonitrile-butadiene).
Compatibility
Mixing of two different grease types often occurs when a
mechanism is service lubricated with a type of grease different from that already in the bearing. If the two greases
are incompatible, the likelihood is that lubrication will be
inadequate and/or the lubrication life will be greatly shortened.
The problem of incompatible grease mixtures has long
been known. Foreknowledge of the chemistry of the greases
is not often reliable in predicting compatibility. Compatibility needs to be judged on a case-by-case basis. In light of this
need, a standard practice was developed Eind is now our new
ASTM method ASTM D 6185.
There are several non-standard means worthy of consideration, however. One such practice involves the preparation of
three binary mixtures in concentrations of 10:90, 50:50, and
90:10 mass ratios. These three mixtures and the two neat
greases are then tested for dropping point (D 566 or D 2265),

20: LUBRICATING

GREASES

569

shear stability (either by prolonged working or by the roll


test, D 1831), oil separation (D 1742), and storage stability
(cheinge in consistency after prolonged storage, such as one
to six m o n t h s ) . Other tests, s u c h as D 3527 (life performance), D 4290 (leakage), water spray-off (D 4049), etc. EJSO
should be r u n if the application warremts such. Incompatibility is indicated if any mixture tests worse t h a n the poorer
of the neat greases. The repeatability of the test methods
must be tciken into consideration when making such determinations.
Static Bleed (Cone)

Test

Federal Test Method (FTM) 791C, Method 321.3, static bleed


test (also known as the cone test), was developed as ASTM
Standard D 6184. In this method, a 10-g sample of grease is
placed in a 60-mesh wire cone, which is then suspended in a
covered bejiker and placed in a n oven at 100C (212F) for 30
h (some specifications may require different temperatures or
durations). The amount of oil that bleeds from the grease collects in the bejiker is weighed, and the percentage of separated oil is calculated. Some specifications require the cone
and residual grease to be weighed also, and the additional
weight loss is reported as evaporation.

Chemical Analysis
D 128, Test Methods for Analysis of Lubricating Grease, is
the premier standard for grease analysis. This procedure
gives flow diagrams and details for the analysis of conventioneJ greases, i.e., those made of soap-thickened petroleum
oils. The constituents that can be determined are soap, unsaponifiable matter (petroleum oil, etc), water, free alkalinity, free fatty acid, fat, glycerin, a n d insolubles. A supplementary test method is provided for application to greases
that cannot be analyzed by conventional methods because of
the presence of nonpetroleum oils or nonsoap thickeners.
These test procedures can be used to identify and estimate
the a m o u n t of some of the constituents of lubricating
greases. The methods are applicable to many, but not all,
greases. Composition should not be considered as having a
direct bearing on service performance unless such correlation has been established.
D 128 references several useful, but nonstandard, methods
that can be used for grease analysis. Infrzired Spectroscopic
(IR) analysis is commonly used for research purposes, quality control, and specification purposes. But, a n IR method
has not been standardized because the technique frequently
must be adapted to the specific grease being analyzed.
Although D 128 is the general analytical method for
greases, t h e r e are other test m e t h o d s for specific constituents. These include the following:
D 95Test Method for Water in Petroleum Products and
Bituminous Materials by Distillation
D 129Test Method for Sulfur in Petroleum Products
(General B o m b Method)
D 808Test Method for Chlorine in New a n d Used
Petroleum Products (Bomb Method)
D 1317Test Method for Chlorine in New and Used Lubricants (Sodium Alcoholate Method)
D 3340^Test Method for Lithium and Sodium in Lubricating Greases by Flame Photometer.

570

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

DISCONTINUED STANDARDS
Severed standards have been discontinued since the 5th edition of the Manual on Significance of Tests for Petroleum
Products. Unless otherwise noted, the reason for discontinuance of the following test methods was lack of interest, i.e.,
the standcirds were no longer being used or supported by the
industry:
D 1262Test Method for Lead in New and Used Greases
(Discontinued 1991)
D 1402Test Method for Effect of Copper on Oxidation
Stability of Lubricating Greases by the Oxygen Bomb
Method (Discontinued 1985)
D 1741Test Method for Functional Life of Ball Bearing
Greases (Discontinued 1991)
D 3428Test Method for Torque Stability, Wear, and
Brine Sensitivity Evaluation of Ball Joint Greases (Discontinued 1990). (D 3428 was withdrawn because the ball joint
used as the test piece was no longer available and a suitable
substitute was not found.)

STANDARDS UNDER DEVELOPMENT


Ignition Test
Because grease fires in steel mills are a common occurrence,
there is a need for a standard method for evaluating the ignition and flammability characteristics of greases used in such
applications. Techniques for evaluating these cheiracteristics
are being developed. The procedure most likely to be evaluated in round robin testing consists of placing a shaped sample of grease on a metal ramp; a methenamine tablet is inserted in the grease and ignited. If the grease burns, the
characteristics of the fire (time to grease or oil ignition, bum
time, fire size, self-extinguishing, etc.) are compared with referenced descriptions and assigned a rating.

ISO STANDARDS
In 1987, ISO (International Standards Organization) published ISO 6743-9, which is an international classification
system for grease. About 75% of commercial greases can be
described by this standard. This standard classifies lubricating greases according to the operating conditions of the use
unlike most other ISO product standards, which are classified according to specific end-use. The nature of greases
allows a specific grease to be used in many applications. This
makes it impractical to classify greases by end-use, and a
properties description is a reasoned alternative. Consequently, users are advised to use ISO 6743-9 to define the requisite grease properties, but are they cautioned not to rely
solely on the standard for grease selection for a particular application. Rather, users are advised to consult with the grease
supplier, as well.
In this classification system, each grease will have one symbol only. This symbol should correspond to the most severe
conditions of temperature, water contamination, and load in
which the grease can be used. Grease products are designated
in a uniform manner, with each character having its own sig-

nificance. The line call-out code will have the following format:
ISO-L-XSiS2S3S4N
where:
ISO
L
X
Si
52
53
54
N

=
=
=
=
=
=
=
=

identification of the standards organization


designator for class (lubricants)
designator for family (grease)
symbol for Lower Operating Temperature
symbol for Upper Operating Temperature
symbol for Water Contamination
symbol for EP
NLGI consistency number

Symbols (letters) are used to designate the four operating


conditions. The Lower Operating Temperature is defined
by symbols representing requirements at 0, -10, -20, 30,
40, and <40C; the Upper Operating Temperatures is defined by symbols representing seven temperatures from 60 to
>180C. Nine symbols are used to define the effects of water,
which include both water contamination and antirust requirements. Only two symbols are used for the EP or load
carrying requirement.
Limits have been tentatively established for the operating
conditions. But, full implementation of IS06743-9 depends
on the development of ISO standard test methods. National
standards must be converted to ISO format and approved by
the ISO community. The national standards proposed to ISO
are as follows:
Lower Operating
Temperature
Upper Operating
Temperature
Water Effect

EP (load carrying
capacity)

NFT60-171 (France), a lowtemperature penetration test.


ASTM D 566 and D 3336
ASTM D 1264 for Water Contamination and DIN 51802 (Germany)/
IP220 (United Kingdom) for Rust
Protection
ASTM D 2596

ASTM STANDARDS*
No.
D 217
D 566
D 942
D 972
D 1092

Title
Test Methods for Cone Penetration of Lubricating
Grease
Test Method for Dropping Point of Lubricating
Grease
Test Method for Oxidation Stability of Lubricating
Greases by the Oxygen Bomb Method
Test Method for Evaporation Loss of Lubricating
Greases and Oils
Test Method for Apparent Viscosity of Lubricating
Greases

' Analytical standards not included.

CHAPTER
D 1263
D 1264
D 1403

D 1404
D 1478
D 1742
D 1743
D 1831
D 2265
D 2266
D 2509

D 2595
D 2596

D 3232
D 3336

D 3337
D 3527
D 3704

Test Method for Leakage Tendencies of Automotive Wheel Bearing Greases


Test Method for Water Washout Characteristics of
Lubricating Greases
Test Methods for Cone Penetration of Lubricating
Grease Using One-Quarter and One-Half Scale
Cone Equipment
Test Method for Estimation of Deleterious Particles in Lubricating Grease
Test Method for Low-Temperature Torque of Ball
Bearing Greases
Test Method for Oil Separation from Lubricating
Grease During Storage
Test Method for Corrosion Preventive Properties
of Lubricating Greases
Test Method for Roll Stability of Lubricating
Grease
Test Method for Dropping Point of Lubricating
Grease Over Wide Temperature Range
Test Method for Wear Preventive Characteristics
of Lubricating Grease (Four-Ball Method)
Test Method for Measurement of Extreme Pressure Properties of Lubricating Grease (Timken
Method)
Test Method for Evaporation Loss of Lubricating
Greases Over Wide-Temperature Range
Test Method for Measurement of Extreme-Pressure Properties of Lubricating Greases (Four-Ball
Method)
Test Method for Flow Properties of Lubricating
Greases at High Temperatures
Test Method for Performance Characteristics of
Lubricating Greases in Ball Bearings at Elevated
Temperatures
Test Method for Evaluation of Greases in Small
Bearings
Test Method for Life Performance of Automotive
Wheel Bearing Grease
Test Method for Wear Preventive Properties of Lu-

D 4048

D 4049
D 4170
D 4289
D 4290

D 4425
D 4693
D 4950
D 5483

D 5706

D 5707

D 5969

D 6138

D 6184
D 6185

20: LUBRICATING

GREASES

bricating Grease Using the (Falex) Block on Ring


Test Machine in Oscillating Motion
Test Method for Detection of Copper Corrosion
from Lubricating Grease by the Copper Strip Teirnish Test
Test Method for the Resistance of Lubricating
Grease to Water Spray
Test Method for Fretting Wear Protection by Lubricating Greases
Test Method for Compatibility of Lubricating
Grease with Elastomers
Test Method for Determining the Leakage Tendencies of Automotive Wheel Bearing Grease Under
Accelerated Conditions
Test Method for Oil Separation from Lubricating
Grease by Centrifuging (Koppers Method)
Test Method for Low-Temperature Torque of
Grease-Lubricated Wheel Bearings
Classification and Specification for Automotive
Service Greases
Test Method for Oxidation Induction Time of Lubricating Greases by Pressure Differential Scanning Calorimetry
Test Method for Determining Extreme Pressure
Properties of Lubricating Greases Using a HighFrequency, Linear-Oscillation (SRC) Test Machine.
Test Method for Measuring Friction and Wear
Properties of Lubricating Grease Using a High-Frequency, Linear-Oscillation (SRV) Test Machine.
Test Method for Corrosion Preventive Properties
of Lubricating Greases in the Presence of Dilute
SjTithetic Sea Water Environments
Test Method for Determination of Corrosion Prevention Properties of Lubricating Greases Under
Dynamic Wet Conditions (EMCOR Test)
Test Method for Oil Separation from Lubricating
Grease (Conical Sieve Method)
Standard Practice for Evaluating Compatibility of
Binary Mixtures of Lubricating Greases

OTHER STANDARDS^
Standard No.
ISO

DIN

2176
2137

51801
51804/1-2

132
50

51805
51802
51811
51803

220
112
5

51809/1-2
51813

37/137/139
134

51807/2
51807/1
51808
51817

215

2160

51814
51815

IP

FTM791b

COST

Characteristic/Property

102
132

1421
311

6793
5346

135

40001.2
5309.4

5757

Determination of Dropping Point


Determination of Cone
Penetration
1/1 - 1/2 - 1/4 Cone
Determination of Flow Pressure
Corrosion Preventing Properties
Corrosive Effects on Copper
Determination of Ash of
Greases (Incl. Sulfate)
Neutralization Number
Content of Solid Foreign Matters
Effect of Water
Water Washout Test
Static Test
Oxidation Stability
Oil Separation

NF-T 60

M 07-037

1461
6474

133/112

142
121
M 07-38

571

3005.3

6370

3453
321/2

5734
7142
1631

Content of Base Oil and Soap


Content of Li/Na/Ca by Atomic

Absorption Spectroscopy
(continues)

572 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


Standard No.
ISO

DIN

IP

FTM 791 b

NF-T 60

COST

Characteristic/Property

9270

Determination of Li/Na by Flame


Photometer
Determination of Solids
(Graphite or M0S2)
Determination of Particle Size of
Solid Lubricants
Density
Evaporation Loss
Content of Water

199
51831

3720/22

51832
59
183
74

3733

9566
1044
2077

113

51816/1
51816/2

139
51350-4/5

6503.2

239
326

331.2/333.1

51806
168
266
(51821/2)
(51821/1)
186
R868
1817

53505
53521

3104
3016
2592
2977

51562
51597
51376
51775/51787
51820 E

3603.3
71
15
36
2

Pumpability Properties
SheU-DeLimon Rheometer
Decompression Characteristics
Apparent Viscosity
Roll Stability
Extreme Pressure Properties
Shell-Four-Ball Test
Timken Test
Mechanical Dynamic Testing
SKF-R2F
Roller Bearing Performance
Churning
FAG-FE 8 (EP Greases)
FAG-FE 9
Wheel Bearing Leakage
Low Temperature Torque
Elastomer Compatibility
Hardness Change (Shore A)
Volume Change
Tests on Base Oil
Viscosity
Pour Point
Flash Point
Aniline Point
Infrared-Analysis

^ Reprinted with permission from The Lubrizol Corporation, Wickliffe, OH.

REFERENCES
[6]
[1] Polishuk, A. T., A Brief History of Lubricating Grease, Llewellyn
& McKane, Inc., Wilkes-Barre, PA, 1998.
[2] Boner, C. J., Manufacture and Application of Lubricating Grease,
Reinhold PubUshing Corp., NY, 1954.
[3] Boner, C. J., Modem Lubricating Greases, Scientific Publications
(G.B.) Ltd, Broseley, Shropshire, England, 1976.
[4] Lubricating Grease Guide, 4 * ed.. National Lubricating Grease
Institute, Kansas City, MO, 1996.
[5] Ward, C. E., "Polyurea Greases," National Lubricating Grease

[8]

[9]
[10]

Institute (NLGI) Grease Education Advanced Course, Kansas


City, MO, 1998.
"Lubricating Greases," Ch. 9, Manual on Significance of Tests for
Petroleum Products, 5th ed., G. V. Dyroff, Ed., ASTM International, West Conshohocken, PA, 1989.
Federal Test Method Standard No. 79IC: Lubricants, Liquid Fuels, and Related Products: Methods of Testing, Available from
Global Engineering Documents, Irvine, CA, Sept. 30, 1986.
"Index of the NLGI Spokesman," Compact Disk, National Lubricating Grease Institute, Kansas City, MO, 2000.
Annual Book of ASTM Standards, Volumes 05.01, 05.02, 05.03,
ASTM International, West Conshohocken, PA.

MNL37-EB/Jun. 2003

Mineral Oil Heat Transfer Fluids


John Fuhr, ^ Jim Oetinger, ^ George E. Totten,^ and Glenn M. Webster^

The focus of this chapter will be on mineral oil derived heat


tremsfer fluids. This discussion will include a basic overview
of the heat transfer coefficient as a fluid chciracterization parameter followed by a discussion of fluid chemistry and the
impact on properties. An overview of various test procedures
used in the selection and maintenance of mineral oil heat
transfer fluids will be provided. System maintenance, operation, and design will be discussed toward the closing.

BECAUSE OF COST AND POTENTIAL FOULING PROBLEMS, indirect

process heating designs are usually preferred over direct,


fuel-fired heating or individual electrically heated units [2].
For indirect process heating, heat transfer is usually
accomplished by steam or by using a h e a t transfer fluid
(HTF). Examples of HTFs include: petroleum based mineral
oils, glycols, silicones a n d various S3Tithetic fluids such as
alkyleated aromatics, terphenyls, a n d mixtures of bi and
diphenyls and their oxides. Selected physical properties for a
n u m b e r of illustrative tj^pes of heat transfer fluids are
provided in Table 1. These data show that there are notable
differences in the physical properties of different classes of
different fluids within a class.

DISCUSSION
Heat Transfer Coefficient

Steam is one of the most economical, since it is generated


easily and it possesses excellent heat transfer properties, due
to its relatively high heat of vaporization and high thermal
conductivity. However, steam suffers frora a n u m b e r of disadvantages such as corrosion and the fact that it must be
used in high-pressure equipment. It is often most suitable for
temperatures of <300F [3].
In some cases, reactors must not only be used for heating,
but also for cooling. In these cases, a secondary coolcint may
be used such as a n aqueous glycol coolant like those illustrated in Table 2 [3]. In these situations, the use of steam and
cooling water in separate loops reduces the available heat
treinsfer cirea and increases the amount of piping required. It
also increases the thermal stresses arising from the alternating flow of chilled water and steam. In general, glycol water
solutions are most applicable for applications requiring moderate heating and/or temperatures to 0F.
Above 500F, mineral oil and synthetic eiromatic based heat
transfer fluids are often used because of the cost of using
steam at the corresponding temperatures. Furthermore, heat
transfer fluids are often the better choice for intermediate
temperatures above 300F, particularly for the single process
user who cannot justify a steam boiler and also for systems
requiring both heating and cooling. Some mineral oil heat
transfer fluids may be used above 600F although the most
c o m m o n use range for these fluids is 300-570F. The ISO
6743-12 fluid classifications for mineral oil based heat transfer fluids is shown in Table 3. For higher temperatures u p to
700F, fluids such as modified terphenyls may be used cind
biphenyl emd other fluids such diphenyl oxides may be used
u p to 750F [3].

For heat transfer fluid selection, a n u m b e r of fluid-related


factors m u s t be considered including fluid performance,
thermal stability, and safety. Several physiccd properties of a
heat transfer fluid directly affect fluid flow, a n d thus heat
transfer performance, which are quantitatively illustrated using the classic Seider and Tate equation for the fluid-film
heat transfer coefficient (h) for fully turbulent flow in a tube
[1,4,20]:
hdA = 0.027 (Jvp/M)* (.Cpfi/kf-^^ (fc)"-*^ (M/MW)"'^
Where: h is the fluid-film heat transfer coefficient, d is the inside diameter of the tube, k is thermal conductivity, v is velocity, p is fluid density, Cp is the specific heat capacity, fi is
the absolute viscosity at the bulk fluid temperature, and /AW is
the absolute fluid viscosity at the wall temperature. Seider
and Tates correlation analysis showed that there was little
variation between /x and /xw in the region of turbulent flow
fluids seldom exhibit large temperature coefficients of viscosity and because heat transfer rates are high, there are less
high temperature differences. W h e n the exponent of the viscosity gradient (;U//AW) was 0.14 for fully turbulent flow, (see
above equation for hd/k), the viscosity gradient was equal
to 1. Therefore, the simplified equation for h, the fluid-film
heat transfer coefficient is obtained [1].
h = 0.027 id)'"-^ (v) (p)0 (Cp)0" ikf"

The Seider and Tate equation shows that higher heat transfer is favored by: increasing fluid density, increasing heat capacity, increasing conductivity, increasing fluid velocity and
turbulence, and decreasing fluid viscosity [2]. Rates of heat
transfer are also affected by system heat sources and heat
sinks, geometry, and temperature gradients [2].
Heat transfer properties of two fluids can be compared by
assuming they are flowing through the same pipe. Therefore,

' Paratherm Corporation, Consholiocken, PA 19428.


^ G.E. Totten & Associates, Inc., LLC, PO Box 30108, Seattle, WA
98103.
^ 63 Rockledge Rd., Hartsdale, NY 10530.
573
Copyright'

2003 by A S I M International

(/x)-o-47

www.astm.org

574

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 1Comparison of typical heat transfer fluid properties.

Type of
Fluid

Fluid
Caloria
HT43
Dowtherm
A
Dowtherm
G
Therminol
66
Dowtherm
J
Dowtherm
Q
Mobiltherm
603
Paratherm
NF
Syltherm
800
Syltherm
XLT

Comparison
Inside Film Coefficients
(BTU/Hr) (ft^) (F) 2"
Sched 40 Pipe @ 87Sec
400^
500F
eoo-F

Max"
Bulk
Temp
F

Max"
Film
Temp
F

Flash
Point
(coc)
F

Fire
Point
(coc)
F

Auto
Ignition
Temp
F

Coefficient
of Thermal
Expansion
%rF

Pour
Point
"F

Vapor
Pressure
@600F
psia

Vise
100C
cSt

236

267

302

600

660

406

453

632

0.0483

10

15

5.0

492

547

590

750

800

236

245

1139

0.0642

53

45.34

0.13

350

404

449

685

750

266

275

1083

0.0525

-40

22

0.29

332

397

449

650

705

363

414

705

0.046

-25

449

428

384

600

650

136

140

788

0.105

-100

Diphenyl

417

451

465

625

675

249

255

773

0.0569

-30

Paraffinic
mineral oil
Napthenic
hydrocarbon
Polydimethylsiloxane
Polydimethylsiloxane

304

354

399

550

625

380

375

670

0.0531

25

317

388

464

600

650

345

385

690

0.0304

-45

239

265

279

750

800

320

380

725

0.0813

-76

87

0.46

329

298

242

500

550

116

N/A

662

0.1143

-168

163.4

0.09

Paraffinic
hydrocarbon
Diphenyl oxide/
biphenyl blend
Di- a n d triaryl
ether
Modified
terphenyl
Diethyl benzene

3.8

7.47

0.07

174
37.74

0.14

2.9

4.0

4.72

3.686

' Manufacturer's recommended maximum temperatures.

TABLE 2Comparison of selected secondary coolants.


Coolant
Aqueous Glycol Solutions
Propylene Glycol: 30%
Ethylene Glycol: 30%
Propylene Glycol: 50%
Ethylene Glycol: 50%
Other Coolants
Synthetic Hydrocarbon''
Silicone Oil''
Alkylated Benzene''
Water

Pumping Limit
("F)"

Temperature for 10 cP
Viscosity'' (F)

Corrosion Inhibitor
Required"

Normal Boiling
Point (F)

5(FP)
6(FP)
141
-31

17
< 6 (FP)
51
20

Yes
Yes
Yes
Yes

212
212
223
224

<-120
<-120
- 1 0 0 (FP)
32 (FP)

-52
-85
-100
32

No
No
No
Yes

378
347
358
212

"Pumping (fluidity) limit is defined as the point where coolant is at the freezing point (FP) or 2000 cP viscosity [3].
^Possible limit to efficient heat exchange, below which turbulent flow is not effectively obtained in economic heat exchangers.
'When in contact with metal equipment.
''Data shown tor typical commercial grades in coolant service.

velocity and tube diameter are equal and the ratio of the two
heat transfer coefficients is dependent only on the ratio of the
fluid densities, specific heat capacities, thermal conductivities, and absolute viscosities raised to the appropriate power
[1].
From this equation and the above expressions for heat
transfer coefficient, it is evident that h is a good summary parameter that incorporates all of the important fluid properties as they relate to their effect on heat transfer.

Pressure Drop
An i m p o r t a n t p a r a m e t e r used by process designers in the
analysis of heat transfer systems is pressure drop (/IP). The
pressure drop of a system is related to the energy required to
move the heat transfer fluid through a stem at a given pressure and it is related to the physical properties of the fluid.

This is illustrated with the following equation for pressure


drop in r o u n d pipe that is expressed in lbs/100 ft of pipe:
AP =

(62.3292)(p)(V)^

0.0001906 +

0.01171
(927.4777)(fi,)(p)(V)\o-381

where:
di = I.D. of pipe in inches
p = Fluid density in lb/gal
K = Thermal conductivity in BTU/hr-ft2 F/ft
fi = Viscosity in cPs
V = Fluid velocity in feet per second
Cp = Specific heat in BTU/lb F
NOTE: p, K, u, and Cp at average fluid temperature

(2)

CHAPTER
Many manufacturers supply computer programs that are
m o r e easily used to perform such calculations. These
programs are available upon request, or many fluid and hardware suppliers make such softweire available on the Internet.
Selected examples of such p r o g r a m s that are currently
available at a web site are provided in Table 4.
M i n e r a l Oil F l u i d C o m p o s i t i o n
Crude petroleum oil is a complex mixture of petroleum
hydrocarbons as well as nitrogen, oxygen, and s u l f u r containing compounds, which are separated into fractions
by refining. Solid components include petroleum coke, asphalt bitumen, and inorganics. Liquids of increasing viscosity vary from gasoline, kerosene (paraffin oil), diesel oil, engine crankcase oil, light a n d heavy m a c h i n e oil, a n d
cylinder oil. Also included are methane, ethane, propane
and butane, the major components of natural gas, which
are gases at room temperature [6]. Aromatic aspheilt com-

21: MINERAL

OIL HEAT TRANSFER

FLUIDS

575

pounds are classified as resins, asphaltines, or carbenes, depending on their solubility [6]:
Resinspentane or heptane soluble
Asphaltenespentane or heptane soluble
Carbenes^benzene insoluble, carbon disulfide soluble
Crude oils eire classified as paraffinic, naphthenic, intermediate (mixed), or asphaltic as shown in Table 5. Paraffinic
fractions are saturated linear or b r a n c h e d alkanes. Naphthenic fractions contain cyclic alkane fractions. Also included are aromatic (pol5ainsaturated cyclic) chemical structures derived from benzene. Aromatic components exhibit a
greater tendency to form sludge and varnish than paraffinic
or naphthenic derivatives [7]. Generic examples of typiceil
structures are illustrated in Fig. 1 [8,9]
In addition to paraffinic, n a p h t h e n i c , a n d aromatic
derivatives, petroleum oils also contain heterocyclic (cyclic
derivatives of nitrogen, sulfur and oxygen), and other polar
c o m p o u n d s such as carboxylic acids, usually saturated
aliphatic or cycloaliphatic (naphthenic) acids, and aldehy-

TABLE 3ISO 6743 classification of fluids for lieat transfer.


More
Specific
Application

Code
Letter

General
Application

Particular
Application"

Heat
Transfer

Maximum
Measured
Temperature
<250C

Open circuit

Maximum
Measured
Temperature
<300C

Product Type
and Performance
Requirements

Symbol
ISO-L

Typical
Application

Refined mineral
oil or synthetic
fluid mechanical
or with stability
To oxidation

QA

Open oil containers


For heating of
electrical
components

Closed circuit
with/or
without
forced
circulation

Refined mineral
oil or synthetic
fluid with
thermal stability

OB

-Heat transfer fluid


heating system
-Closed-circuit
water bath

Maximum
Measured
Temperature
>300 C and
<320C

Closed circuit
with forced
circulation

Refined mineral oil


or synthetic fluid
with thermal
stability

QC

Maximum
Measured
Temperature
<320C
Maximum
Measured
Temperature
>-30Cand
<200C

Closed circuit
with forced
circulation

Synthetic fluid
with particularly
high thermal
stability
Refined mineral oil
or synthetic fluid
with low viscosity
at low temperatures
and with thermal
stability

QD

Heat transfer fluid


heating systems

QE

Unit with hot flow


and/or cold flow

Cooling
circuit

Remarks

The fire risk for the


particular application
shall be a consideration.
including the system,
operating environment
and the fluid itself
1) Units with heat
transfer fluid heating
systems should be
fitted with efficient
expansion tank, vent
and
filtrationsystems.
2) For units with heat
Exchangers for heating
of foodstuffs the heattransfer fluid shall
comply with applicable
national hygiene and
safety regulations.

"Temperatures indicated in the column are of the bulk of the oil, measured in the discharge line from the heater. They are not the temperatures of the film of
oil contact with the heater, which may reach higher values.

TABLE 4Sources and web site addresses for computer programs to calculate heat transfer coefficients.
Company

Program Name

Web Site Address

Dow Chemical Company


Paratherm
Solutia Inc.
Engineering Process Tools
K & K Thermal Connection

FLUIDFILE
PARACALC

http://www.dow.com/heattrans/index.html
http;//www.paratherm.com
http://www.therminol.com
http://www.processassociates.com/process/tools.htm
http://www.tak2000.com

576

MANUAL 37: FUELS AND LUBRICANTS

Crude Type

Solvent Neutral
Base Oil

Pciraffinic base
Naphthenic base
Mixed base
Asphaltic base

Yes
No
No
No

HANDBOOK

TABLE 5Crude oil content and suitability.


Base
Specialty
Wax
Oil
Oil
Content
Yes
Yes
Yes
Yes

No
Yes
No
No

Yes
No
Yes
No

S&N
Content"

Asphalt

Low
Low
Low
High

No
No
Yes
Yes

API
Gravity''
>40
<33
33-40

"S is sulfur and N is nitrogen.


''API gravity is scale in degrees adopted by the American Petroleum Institute where: "API = [141.5/specific gravity] 131.5.

NmmaiclatnTg

Viscosity
Index

n-Panffins

Very high

iso-Paraffins

m^

Low

Moderate

Low

Low

Low

Naphthenes

Anunatics

-^

T^Y^

^ I

Pour
Point
High

FIG. 1Typical organic structures present in


mineral oil.

Dibenzothiophene

1,7-Phenandirone

Furan

Pynole

Thitqihene
FIG. 2Examples of heterocyclic
derivatives typically present in a
petroleum oil.

des. Selected examples of polar derivatives that may be found


in petroleum oils are illustrated in Fig. 2 [6-8]. Traces of phenolic and furan derivatives may also be present. A summary
of the overall effect of these different derivatives on physical
and chemical properties is provided in Table 6 [7].
Yoshida has shown that the pro-oxidant effect of nitrogen
heterocyclic compounds is a function of the basicity of the nitrogen in the compound. Generally, only the more basic nitrogen heterocyclic compounds, pyridine and quinoline

derivatives, exhibit a pro-oxidant effect; this effect is


accelerated in the presence of copper [10].
ParafHnic base oils contain 45-60% paraffinic compounds.
Naphthenic base oils contain 65-75% of naphthenic compounds and aromatic base oils contain 20-25% aromatic
compounds [8]. Table 7 provides a summary of the effect of
paraffinic, naphthenic, and aromatic content of base oils on
fluid density [6].
Base oil composition affects physical and chemical
properties of the oil. Base oil properties may be estimated
from aromaticity (aromatic carbon content), which is
primarily dependent on the degree of refining [11,12]. The
degree of aromatic compound content of a base oil may be
determined from the aniline point and is determined by
ASTM D 611. The aniline point is determined by mixing specified volumes of the base oil, aniline, and heptane and then
the mixture is heated at a controlled rate until it becomes
miscible. The mixture is then cooled at a controlled rate and
the temperature where two phases separate is recorded as the
aniline point. Aromatic hydrocarbons exhibit the lowest
value and paraffinic hydrocarbons the highest value.
Cycloparaffins and olefins exhibit intermediate aniline
points.
Another parameter that is reflective of base-oil quality is
sulfur content since sulfur-containing polar compounds may
exhibit significant antioxidant activity. Therefore, a determination of both the aniline point and sulfur content are necessary to determine base oil type, which is reflective of its
resistance to oxidation.
API has developed a classification system for petroleum oil
base, which can be used as an aid in selecting basestocks that
exhibit improved oxidative stability. These classifications are
[27]:
Group IBase oils with a viscosity index of 80-120, and
containing less than 90% saturated hydrocarbons and/or
more than 0.03% elemental sulfur.
Group IIBase oils with a viscosity index of 80-120, and
containing > 90% saturated hydrocarbons and/or ^ 0.03%
elemental sulfur.
Group IIIBase oils with a viscosity index of s 120, and
containing a 90% saturated hydrocarbons and/or 0.03%
sulfur.
Group IV^All polyalphaolefins
Group VAll other base stocks not included in Groups I,
II, III, or IV.
A reduction in the overall composition of aromatic derivatives and polar compounds of a petroleum base stock may be
accomplished by high-temperature catalytic hydrogenation.
This will produce a base stock with improved color and
oxidative stability [13,14],

CHAPTER 21: MINERAL OIL HEAT TRANSFER FLUIDS


There are various methods for the determination of the
composition of petroleum oil derived heat transfer fluids.
These methodologies, many of which have not been developed into ASTM or other national standards, have been
reviewed previously. One such review is provided in Ref. 28.
ASTM methods for petroleum oil compositional analyses
are classified by Drews into: correlative, chromatography,
a n d spectrometric methods [21]. Correlative methods are
those that are derived by statistical analysis of a measured
composition-dependent property. It is important to note that
correlative carbon-type data are not directly comparable to
data obtained by molecular structural analysis. However,
correlative analysis data are often an effective means of monitoring the effect of a process change, such as oxidative
stability, with variations in the composition of the oil.
Examples of ASTM correlative methods are provided in
Table 8. Test Method D 2140 utilizes a correlation between

577

the viscosity-gravity constant (VGC) and refractivity to determine oil composition in terms of aromatic carbon (%CA),
naphthenic carbon (%CN), and paraffinic carbon (%CP). The
VGC parameter is derived from kinematic viscosity and density and is dependent on the saturated/aromatic hydrocarbon
ratio. The equation to calculate VGC from kinematic
viscosity at 100C (V') and density at 15C (G) is:
VGC-

G - 0.108 - 0.1255 Log ( V ' - 0.8)


0.90 - 0.097 Log (V - 0.8)

Aromatic (RA) and naphthenic (RN) ring distribution of


the so-called "average molecule" is determined using ASTM
Test Method D 3238.
Naphthenic content of a petroleum oil can be determined
by ASTM D 2159 using the refractivity intercept which is
defined as: Refractivity Intercept = n - {d/2) where n is the

TABLE 6Effect of composition on base stock properties.


Property

n-Alltane

Napthene

Aromatic

Polar Compounds

Viscosity Index
Pour point (high/low)
Oxidative Stability

Very high
High
Good

High
Low
Good

iso-Alkane

Low
Low
Average

Low
Low
Average/Poor

Response to
Antioxidants
Volatillity
(high = poor)
(low = good)

Good

Good

Good

Some poor

Low
Low
S is antioxidant;
N and 0 are pro-oxidant
Poor

Good

Good/Average

Average

Poor

Poor

TABLE 7Relationship between molecular carbon type and density.


Base Oil Type

Paraffinic Carbon

Naphthenic Carbon

Aromatic Carbon

Density (kg/L)

Paraffinic
Naphthenic
Mixed
Aromatic

65-70
50-60
48-57
21-35

25-30
30-40
24-33
20-30

3-8
8-13
17-22
40-50

0.800-0.812
0.834-0.844
0.850-0.872
0.943-1.005

ASTM No.

D 1319
D2007
D2140
D2425
D2501
D2502
D2549
D2786
D3238
D3239
D3524
D3525
D4291
D4808
D5186
D5291
D5292

TABLE 8--ASTM test methods for determining petroleum oil composition used for heat transfer fluid formulation.
Standard Test Method for
Separation Type

Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption


Characteristic Groups in Rubber Extender and Processing Oils and Other PetroleumDerived Oils by the Clay-Gel Absorption Chromatographic Method
Carbon-Type Composition of Insulating Oils of Petroleum Origin
Hydrocarbon Types in Middle Distillates by Mass Spectrometry
Calculation of Viscosity-Gravity Constant (VGC) of Petroleum Oils
Estimation of Molecular Weight (Relative Molecular Mass) of Petroleum Oils From
Viscosity Measurements
Separation of Representative Aromatics and Nonaromatics Fractions of High-Boiling
Oils by Elution Chromatography
Hydrocarbon Types Analysis of Gas-Oil Saturates Fractions by High Ionizing Voltage
Mass Spectrometry
Calculation of Carbon Distribution and Structural Group Analysis of Petroleum Oils by
the n-d-M Method
Aromatic Types Analysis of Gas-Oil Aromatic Fractions by High Ionizing Voltage Mass
Spectrometry
Diesel Fuel Diluent in Used Diesel Engine Oils by Gas Chromatography
Gasoline Diluent in Used Gasoline Engine Oils by Gas Chromatography
Trace Ethylene Glycol in Used Engine Oil
Hydrogen Content of Light Distillates, Middle Distillates, Gas Oils, and Residua by
Low-Resolution Nuclear Magnetic Resonance Spectroscopy
Determination of Aromatic Content and Polynuclear Aromatic Content of Diesel Fuels
and Aviation Turbine Fuels by Supercritical Fluid Chromatography
Instrumental Determination of Carbon, Hydrogen, and Nitrogen in Petroleum Products
and Lubricants
Aromatic Carbon Contents of Hydrocarbon Oils by High Resolution Nuclear Magnetic
Resonance Spectroscopy

Chromatography
Chromatography
Correlation
Spectrometry
Correlation
Correlation
Chromatography
Spectrometry
Chromatography
Spectrometry
Chromatography
Chromatography
Chromatography
Spectrometry
Chromatography
Spectrometry
Spectrometry

578

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

refractive index at 20C and d is the density at 20C. The


naphthene content in percent by volume is determined from
a plot of refractivity intercept and density as shown in Fig.
3. Polycyclic naphthenes, if present, will cause a high value
for total naphthenes to be indicated. Although basic data for
this correlation compensate, in part for the presence of dicyclic naphthenes, results may be high by as m u c h as 1%
for each 1 volume % dicyclic naphthenes present. Thus, the
n a p h t h e n e content indicated for stocks with end points
greater than 163C (325F) should be considered "equivalent
naphthenes."
The chemical composition of a petroleum base oil may also
be calculated from physical properties such as refractive index {ni) at 20C, density at 20C (df), percentage sulfur (S)
concentration, and average molecular weight (M) by ASTM D
3238, which describes the "n-d-M Method" (refractive index,
density and molecular weight method).
Chromatographic methods for determining the composition of p e t r o l e u m oil are s u m m a r i z e d in Table 8. These
methods include gas chromatography and open-column separations on silica gel or clay-silica gel columns. Moleculartype analyses are conducted using open-column separations
such as those outlined in ASTM D 2007. ASTM Test Method
D 2007 may be used to classify petroleum oil samples with an
initial boiling point of at least 260C (500F) into the hydrocarbon types of polar compounds, aromatics, and saturates
and recovery of representative fractions of these types.
ASTM D 2007 is conducted by diluting the sample with solvent and then charging it to a glass-percolating column containing clay in the upper section and silica gel plus clay in the
lower section. n-Pentane is then charged to the double-colu m n until a definite quantity of eluent has been collected.
The upper (clay) section is removed from the lower section
and washed with n-pentane. A toluene-acetone mixture is
t h e n charged to the clay section for desorption a n d a
specified volume of eluent is collected. The lower (silical) gel
column may be desorbed by recirculation of toluene. After
solvent removal, the aromatics are collected by difference.
This is a useful procedure for classifying petroleum oils into
structural groups that may be related to their inherent ther-

1.047

'
^^ - -^

mal/oxidative stability properties. This test method is not directly applicable to petroleum oils of greater than 0.1 mass %
pentane insolubles. The hydrocarbon types and structural
groups measured by this method include:
Asphaltenes, or n-pentane insolubles that are defined as insoluble matter that precipitates from a solution of oil in npentane under specified conditions.
Polar compounds that are material retained ion adsorbant
clay after percolation of the same in n-pentane eluent under specified conditions.
Polar aromatics, which is a synonym for polar compounds.
Aromatics that are materials that, o n percolation, pass
through a column of adsorbant clay in a pentane eluent but
adsorb on silica gel u n d e r the conditions specified.
Saturates which are materials that, on percolation in an npentane eluent, is not adsorbed on either clay or silica gel
under the conditions specified.
In addition to ASTM D 5186, which utilizes supercriticcJ
fluid chromatography (SFC), a n u m b e r of additional methods have been reported for use with petroleum oils including
thin layer chromatography (TLC) and high pressure liquid
chromatography (HPLC) [21,22-25].
There are various spectrometric methods for petroleum
compositional analysis, which are summarized in Table 8.
Non-ASTM methods for the use of infra-red (IR) spectroscopy for quantitative analysis of hydrocarbon t5^es have
been reported. Fourier trzmsform (FT) IR methods have also
been reported for the analysis of degradation by-products
present in used oils [21,26]. Nuclear magnetic resonance
(NMR) spectroscopy methods have been developed including
ASTM D 4808 and D 5292.
There are three spectrometric test methods for petroleum
analysis based on mass spectroscopy (MS): ASTM D 2549, D
2786, and D 3239. ASTM D 2786 yields information on the
relative amounts of paraffins, 1-through 6-ring naphthenes
and alkyl naphthenes. ASTM D 3239 determines eighteen
aromatic t3^es and three aromatic thiophene structures [21].
Both methods require the use of Test Method D 2549 for
prior separation of the paraffinic a n d aromatic fractions.
ASTM D 2425 may be applicable for petroleum oils in the
lower molecular weight range [21].
M i n e r a l Oil F l u i d P r o p e r t i e s

\
^ ~>-N

0.B2

It has been shown that heat transfer fluid performEuice is dependent on the physical properties of the fluid including:
thermal conductivity, density, specific heat capacity, and viscosity. It has also been shown that the physical and chemical
properties of a mineral oil are dependent on its composition
a n d degree of refining. However, Table 1 showed that the
physiced properties of heat transfer fluids of a given type, including mineral oil-derived fluids, varied with respect to each
other. This is illustrated in Table 9 where the physical properties of two commercially available mineral oil heat transfer
fluids are compared. One fluid is a hydrotreated pEiraffinic
base and the other is a napthenic base. It is essential that the
engineer obtain the actual data he requires for the fluid being
considered. This data is available from the fluid supplier.

FIG. 3Naphthene content by volume percent using the refractivity intercept.

A s u m m a r y of ASTM test procedures r e c o m m e n d e d in


ASTM D 5372 for mineral oil-based heat treinsfer fluids is
provided in Table 10.

0^

^^
.o\

IM

>
N

e
j

i-

'^

' ^
^
,\
^
y
"^
y
><
y
%
>
fP ^
\
\A
"'>,

ec

sMN

/'

iO<]

\
'

* rf)N

jPN

,^

1.033

0.64

/ >
, / -" /
/ ' ^'
/'

0.66

0.6B

0.70

OTZ
0.74
0cflsityaf2OC

0.76

07B

0.60

CHAPTER 21: MINERAL

OIL HEAT TRANSFER FLUIDS

TABLE 9Comparison of the physical properties of two different commercially


available heat transfer fluids.
ASTM Test
Procedure
Fluid 1
Physical Property
Napthenic
Feedstock Base
Viscosity (cSt)
300F
400F
500F

Density (lb/gallon)
300F
400F
500F
Specific Heat (BTU/lb-F)
300F
400F
500F
Thermal Conductivity (BTU/hr-ft^-F
300F
400F
500F
Vapor Pressure, psia @
300F
400''F
500F
Coefficient of Thermal Expansion

Viscosity
TABLE 10Summaiy of ASTM D 5372 recommended test
procedures for mineral oil heat transfer fluids.
Recommended Test
Mineral Oil Fluid Properties
Flash Point, Closed Cup
Pour Point
Viscosity
Specific Viscosity
Water Content
Safety
Autoignition Temperature
Flash Point, Open Cup
Flash Point, Closed Cup
Effect on Equipment
Rubber and Elastomeric Seals
Corrosion
Efficiency
Thermal Conductivity
Specific Heat
Service Life
Thermal Stability Laboratory Tests"
Precipitation Number
Insolubles
Flash Point, Open Cup
Flash Point, Closed Cup
Carbon Residue

"
"
Viscosity
Distillation

"
"

Neutralization Number
Water Content

ASTM Test Procedure


D93
D97
D445
D1298
D95
E659
D92
D93
D471
G4
D2717
D2766

D91
D893
D92
D93
D189
D524
D4530
D445
D86
D 1160
D2887
D664
D95

"At present no suitable method has been approved for heat transfer fluids.
Test method D 2160 is of limited value due to limitation in testing small noncirculatory samples in glass containers.

Fluid 2
Paraffinic

1.96
1.16
0.74

2.79
1.52
0.98

6.82
6.64
6.45

6.51
6.22
5.92

0.56
0.61
0.66

0.56
0.61
0.66

0.072
0.069
0.067

0.071
0.069
0.066

0.0003
0.1470
0.9670
0.000304/F

579

0.00039
0.00970
0.13500
0.000592/F

(ASTM D 445)

Viscosity is important in determining Reynolds and Prsindtl


numbers for heat transfer systems, to estimate fluid turbulence, h e a t transfer coefficients, and heat flow. Viscosity
measurement by various tests, including ASTM D 445, is discussed in detail in Chapter 32, Flow Properties and Shear Stability, and will not be discussed here.

Pumpability
Pumpability refers to the ease of pumping a fluid in a heat
transfer system. According to ASTM D 5372, if the fluid viscosity is greater than 200 cS, it is difficult to p u m p . If a heat
transfer fluid is subjected to temperatures below its minim u m p u m p i n g t e m p e r a t u r e w h e n not in use, the system
should be heat traced to w a r m the fluid start-up. The p u m p
and system design will determine the viscosity limit required
for pumping, and therefore the minimum pumping temperature. The construction of a viscosity/temperature curve using
measured viscosities in the temperature range of interest can
be used to estimate m i n i m u m pumping temperature.
It should be noted that the "pumpability" concept of ASTM
D 5372 is not the same concept as "pumping limit" used by
Green and Morris [3] and cited in Table 2. The Green and
Morris concept refers to those conditions defined by freezing
point of the fluid or a viscosity of 2000 cP as conditions where
a fluid is n o longer p u m p a b l e . In the ASTM approach,
"pumpability" refers to that fluid viscosity (200 cS) above
which the fluid would be difficult to pumpwhich is a consensus value.

Thermal

Stability

Thermeil stability (cracking) is defined as the resistance of a


heat transfer fluid to permanent physical changes caused by
exposure to heat (themiEil cracking). Depending on the composition of the oil, these changes can become noticeable at

580

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

temperatures as low as 250C while rapid changes in composition (thermal cracking or pjrolysis) begin around 350C.
These changes include evolution of solid carbon particles
(coke) and lower boiling point components (light ends). If
there are substantial a m o u n t s of asphaltenes and polar
residues in the fluid, the coke may adhere to the heater surfaces, causing fouling, which in t u r n reduces heat transfer
rates. The lower boiling point components will cause the
overall system pressure to increase and m a y result in vaporous cavitation at the p u m p section. These components
will also tend to depress the Flash Point of the fluid. Thermal
cracking is often accompanied by color change [19] however,
color change is more c o m m o n when oxidation is present.
While higher viscosity oils are generally more susceptible to
cracking than lower viscosity, the main cause is due to overheating. Overheating typically results from flame impingement and/or low velocity through the tubes of fired heaters.
In forced circulation electric immersion heating systems, satisfactory fluid life has been obtained with heat flux of 15-22
watts per square in., and in free convection systems (no circulating pumps), 5-12 watts per square in.
Thermal
Under

Stability (New ASTM


Development)

Test

Method

Although it is true that there are few tests that directly assess
the thermal stability of a heat transfer fluid, there is one test
currently being balloted within ASTM, Standard Test Method
for Thermal Stability of Organic Heat Transfer Fluids [ 1 ]. This
test is conducted by adding the heat transfer fluid to be analyzed into a test cell that is purged with nitrogen and tightly
sealed to remove and preclude the introduction of oxygen and
water from the atmosphere. The fluid is then heated in the test
cell for a prescribed time and temperature. The boiling range
of the fluid after themicJ stressing is then determined by gas
chromatography (using Test Method D 2887) and compared
to the unused fluid. This portion of the thermally stressed
fluid that has a boiling point outside of the boiling range of
new, unused fluid is defined as "degradation."
Guffey has introduced the concept of "overall degradation
rate" [1], where components exhibiting boiling points above
or below the original boiling point range are assumed to be
degradation products. To determine the overall degradation
rate, it is assumed that 99% of the fluid volume is equally distributed at the heater-outlet, heater-inlet, and the heater-inlet
temperature minus a selected amount such as 50F (which
accounts for the fluid in the system expansion tank). The remaining 1% is assumed to be at the fluid-film temperature.
Degradation rates are then taken from the test at various temperatures. This data is then used to calculate the "overall
degradation rate" [1].
Oxidative

increase in the amount of air contact (foaming air entrainment, fluid turbulence) will also affect the rate of oxidation.
Oxidative stability is a function of the base stock selected.
For example, paraffinic oils exhibit better oxidative stability
than naphthenic oils, but they exhibit poorer "solvency"
poorer ability to dissolve byproducts [17]. The presence of
alkylaromatic derivatives a n d some polar components further increases the susceptibility of a petroleum oil to oxidation, and other derivatives such as some sulfur-containing
compounds may exhibit a stabilizing effect [18].
Carbon Residue

(ASTM D 189, D 524, and D

4530)

"Carbon residue" is defined as the residue formed by evaporation and thermal degradation of a carbon containing material, which provides an indication of the fluid's tendency to
form carbonaceous deposits.
One test that is used to determine carbonaceous residues is
Test Method D 189 the Conradson Carbon Residue. In this
test, a sample is added to a crucible and subjected to destructive distillation. The residue formed undergoes cracking
and coking during the fixed period of severe heating. At the
conclusion of the test, the crucible is cooled and weighed.
The Conradson Carbon Residue is the % of residue remaining at the conclusion of the test. This test provides a rough
approximation of the tendency of the heat transfer fluid to
form deposits when heated and the formation of volatile byproducts is possible.
Another test that is used to determine the tendency for a
heat transfer fluid to form carbonaceous residues is Test
Method D 524, the Ramsbottom Carbon Residue test. In this
test, the sample is weighed into a special glass bulb and
placed in a metal furnace where it is heated quickly to 550C.
All volatile material is evaporated out of the bulb, with or
without decomposition, while the remaining residue undergoes cracking and coking reactions. After the test, the bulb is
cooled and weighed. The residue remaining is reported as %
of original sample and is called the R a m s b o t t o m Carbon
Residue.
Test Method D 4530 is a "Micro Method" for determination
of carbon residue. In this test, a weighed sample of the fluid
is heated in a 2 mL glass vial at 500C under an inert atmosphere (nitrogen) in a controlled manner for a specific time.
The sample undergoes coking reactions and the volatiles that
are formed are swept away by the nitrogen. The carbonaceous residue formed is reported as % of original sample as
"carbon residue (micro)." This test method is reported to be
equivalent to the Conradson Carbon Residue (ASTM D 189).
Specific

Gravity

(ASTM D

1298)

Hydraulic shock during p u m p i n g has been predicted via the


use of a combination of density and compressibility data.

Stability

Oxidation occurs when the hot fluid comes into contact with
air (oxygen). Oxidation rates double every 10C (18F) increase temperature. The principal oxidation byproducts are
organic acids which can undergo further reaction to form extremely high molecular weight components that are soluble in
the fluid and increase the viscosity of the fluid [15]. Above
200C these components will precipitate out on hot surfaces
and become insoluble. Insoluble byproducts will lead to fouling of heater surfaces, filter plugging, and sticking valves. Any

Metal

Content

Transition metals (0.1-50 ppm), capable of a one electron


transfer process, will act as a catalyst for hydrocarbon oxidation. Homolytic peroxide decomposition occurs by:

RCOOH + M"+ -> RO + M<"+"+ + H O "


RCOOH + M<"+'>+ ^ RCOO + M"+ + H^
2 RCOOH M"^/M<-^"^ ^ j^QQ ,+ R o + H2O

CHAPTER
These free radical processes, a n d others not shown, are
strongly affected by temperature. This is illustrated in Table
11 where it is shown that if both water and the metal are present, the oil degradation rate was 10-fold (iron) to 30 fold
(copper) that of the uncontaminated oil [16]. There are numerous test procedures that are discussed in detail in Chapter 26, Elemental Analysis, cind therefore will not be discussed
further here.
Thermal PropertiesThermal
Conductivity
2717) and Specific Heat (ASTM D 2766)

(ASTM

Thermal conductivity a n d specific heat tests are difficult to


carry out, facilities for performing them are few, Eind the precision data is yet to be established. Since thermal conductivity and heat capacity are temperature dependent, to be of use
to the designer, they m u s t be determined at different
temperatures. Values can be estimated for design use from
the general chemical composition. The values for thermjd
conductivity and specific heat may be available from the fluid
supplier.
Autoignition

(ASTM E

659)

It is important to note that while heat transfer fluids are routinely used above their flash a n d fire points, they should
never b e used above their autoignition t e m p e r a t u r e . Autoignition is the temperature at which the fluid will ignite
spontaneously in contact with air. It is recommended that the
fluid supplier be consulted for standard recommended safe
practices. The autoignition temperature of a heat transfer
fluid is determined according to ASTM D 659.
Effect on Rubber

or Elastomeric

21: MINERAL

OIL HEAT

TRANSFER

FLUIDS

581

by the fluid supplier or contract laboratory. The following


are some simple tests that should be performed in the plant
weekly or biweekly.
Listen to the

System

Minered oil heat transfer fluids exhibit various characteristic


sounds that may indicate potential problems. For example:
snapping, crackling, Eind popping noises indicate that water
may have entered the system. Loud noises in the circulation
p u m p may indicate potential cavitation, which is a significant problem and should be dealt with immediately. Sources
of excessive vibration of any p a r t of the system should be
identified and eliminated.
Visual System

Inspection

When the system is operating, smoke ciround piping indicates


that fluid is oozing through gaskets or valve or p u m p seals.
Eventually, a black carbon crust will form at the leak. Unless
there is an external source of ignition, these leaks are not normally a safety hazard, but more of a housekeeping issue and
should be corrected as soon as possible. During each inspection, examine the expansion tank, vent and overflow catchcontainer. Steam coming from the vent may indicate water in
the system. The presence of a n oil mist may indicate that the
heat transfer fluid is oxidizing. Both situations require immediate attention. The catch-container should be closely inspected. If there is heat trzinsfer fluid in the container, the
cause must be identified. Whether the fluid in the container
is water, oil, solvent or another liquid, it is a safety hazard
and must be removed. Always keep the catch container clean
and dry.

Seals (ASTM D 471)

Heat exchange equipment typically utilizes mechanical seals


fabricated from steel or other metal. If elastomeric seals are
present, it is desirable that they exhibit rubber swelling in the
range of 1-5% to prevent leakage because of poor seal contact. Seals may degrade in some fluids. As an oil deteriorates
in service, additiontJ tests may be required to assure that
seeds remain compatible with the altered oil. The temperature ranges of the tests should correspond to temperatures to
which seals will be exposed in service and the tests should be
conducted for at least 1000 h.
Fluid MaintenanceIn-plant Tests
Well-maintained, unabused mineral oil heat transfer systems may be smooth running and trouble-free over many
yccirs of use. To assure long-term and trouble-free operation, it is recommended that periodic maintenance be performed. Some of these tests are simple and may be performed by the user. Other tests may need to be performed

TABLE 11Effect of water and catalysts on oil oxidation.


Catalyst

Water

Hours

Final Acid Number

None
None
Iron
Iron
Copper
Copper

No
Yes
No
Yes
No
Yes

3500
3500
3500
400
3000
100

0.17
0.9
0.65
8.1
0.89
11.2

Unusual

Odors

A burning oil odor is usually indicative of a leak. Identify the


source of the leak and repair, if necessary.
Fluid

Appearance

With the heater off, start the circulating pump(s) and wait ten
or fifteen minutes. Open a low-point valve, edlowing a small
amount of fluid to drain into a clear glass container. Put the
container on a bench and let it sit. Color may range from light
yellow to dark brown or black. Darker colors do not necessarily indicate that the fluid has become unusable. A hazy
fluid suggests water contamination or oxidation. If there are
particles on the b o t t o m (or floating in the liquid), fluid
"coking" may be indicated or mill scale or other hard contaminants may be present. Either condition should be investigated before problems escalate.
Fluid Sampling
Recommended locations from which to remove a fluid sample include a low-point drain near the p u m p or heater or the
blow-down valve mounted on the Y-strainer. The Y-strainer
is usually located in the return line just upstream of the p u m p
suction. Fluid samples should b e taken when the p u m p has
been running so that the sample is representative of the fluid
in the system. Ideally, the fluid should be removed from the
system between 180 and 280F and put directly into the sample container. If the fluid sampled is too hot, it will not only
smoke, but the acid n u m b e r may indicate artificially high

582

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

acid levels due to oxidation during the sampling process. The


sample container must be sealed tightly as quickly as possible after filling to minimize contact with air (oxygen). Samples taJcen from the expansion tank, or from a "dead leg," are
not representative of fluid in the system.
The fluid supplier should supply a suitable sample container. Contract laboratories typically require approximately
one quart (750 mL) of sample to properly conduct the
analysis.

. . fion
o

Fluid MaintenanceLaboratory Tests

(1)

550

High Boilers-

I-*

500

450

a)
CL

10)-

c 400
o
m

4-*

350

Laboratory analysis of the fluid should be performed at set intervals to ensure that abnormal degradation is not occurring.
Abnormal degradation can result from contamination that
catalyzes the breakdown, oxidation, or overheating. The condition of the fluid can be accurately established by three basic
tests, which determine the amount of thermal cracking and/or
oxidation that has occurred. Additional tests may be required
to identify specific contaminants such as water and solids.
Acid Number (ASTM D 664 and D 974)
Acid number (AN) measures the acidity produced when the
fluid is oxidized. Unless the expansion tank is maintained under inert gas blanket, some increases in AN are unavoidable
over time. The higher the operating temperature, the more
critical the AN becomes since the ensuing fluid degradation
is temperature dependant. In general an increase of 0.5
should be viewed as a warning sign, with immediate fluid replacement at an increase of 1.0. The increase in AN with increasing time is illustrated in Fig. 4 [19].
Test Method D 664 is conducted by dissolving a sample of
the HTF to be analyzed into a solution of toluene and isopropanol containing a small amount of water and titrated potentiometrically with alcoholic potassium hydroxide and a
saturated calomel reference electrode. The meter readings
are plotted manually or automatically against the respective
volumes of KOH titrant and endpoints are taken only at welldefined inflections of the resulting curve. This titration may
be performed colorimetrically according to Test Method D
974. Alternatively, infrared analyses may be used, which provides a more reliable method of detecting oxidation.

1.4
#n

5> 1.2
X

Oxidized Fluid

1.0
o>

e
3 0.6

D
B 0.4 -

|0 0.2 0

...U ....

1. n

Increasing Fluid On-Stream Time >


FIG. 4Illustration of the increasing solids content
present in a mineral oil based heat transfer fluid with
increasing time after the onset of degradation.

o 300
a>

_ Low

Boilers

<

Fresh Fluid

- - Thennally Degraded Fluid

JO 250
3

CO 200

10 20 30 40 50 60 70

80

_i_

90 100

Amount Distilled (%)


FIG. 5Gas chromatographic distillation (GCD) comparison of a new and used mineral oil based heat transfer fluid.

Distillation (ASTM D 1160, and D 2887)


The distillation test compares the boiling temperatures of
standard fractions of new fluid with those for a used fluid.
This is illustrated graphically in Fig. 5 [19]. When a heat
transfer fluid undergoes thermal or oxidative degradation
(overheated) it generates lower boiling and/or higher boiling
components, which in turn causes a change in the boiling
temperatures of the various fractions. The percentage shift in
temperatures versus new fluid collectively determines how
much degradation had occurred. Typically, a shift of 10% indicates that the fluid has been severely damaged.
In Test Method D 1160, 100 ml of fluid sample is distilled
in a single stage equivalent apparatus under vacuum. The
temperature readings and volumes of condensate are
recorded along with the volume of residue and any vapor
losses. The data is converted to atmospheric equivalent temperatures in a table.
Test Method D 2887 is a gas chromatographic procedure that
simulates distillation. It is conducted by injecting a quantity of
the fluid sample on to a nonpolar packed or open (capillary) gas
chromatographic column. The hydrocarbon components are
eluted in order of increasing boiling point. The column temperature is raised at a reproducible linear rate and the area under the chromatogram is recorded throughout the analysis.
Boiling points are assigned from a calibration curve obtained
under the same conditions of a known mixture of hydrocarbons covering the boiling range expected for the sample.
Viscosity (ASTM D 445)
While viscosity is not the most critical test for fluid
maintenance, it does provide useful information and also
confirmation of other test results. Viscosity is of import in
determination of Reynolds and Prandtl numbers for heat
transfer systems, to estimate fluid turbulence, heat transfer
coefficients and heat flow. In general, viscosity increases as
the result of oxidation and decreases due to thermal cracking.
Changes in viscosity may also be the result of contamination
by a different fluid. Fluid viscosity is compared with that of
new fluid in Table 12. Viscosity measurement by various

CHAPTER 21: MINERAL OIL HEAT TRANSFER FLUIDS


TABLE 12Comparison of a new and used mineral oil fluid.
Physical Property
Flash Point, Open Cup
(F)
Viscosity (cS)
AN (mg KOH/g)
Solids Content, (%)
Iron (ppm)
GCD Low Boilers, (%)

ASTM Procedure

Fresh Fluid

D92

450

D445
D664

25.0
0.05
0.0
0.0

D2887

Used Fluid
392
94.5
2.12
7.6
700
4.7

TABLE 13Correlation of base stock aromatic content and color


generation during oxidation.
Fluid

N
(ppm)

S
(ppm)

Wt. %
aromatics

ASTM Color
After Heating
in Air

A
B
C

27
1
<0.2

6200

26"
4
1

>8
5.5
2.5

92
1

tests, including Test Method D 445, is discussed in detail in


Chapter 32, Flow Properties and Shear Stability and will not
be discussed further here.
Open Cup and Closed Cup Flash Points (ASTM D 92
and D 93)
Because the majority of systems operate safely above the
Flash Point of the fluid, periodic determination is usually unnecessary. A reduction in flash point does indicate the presence of low boiling components, which result from thermal
cracking. A rapid decrease in flash point may indicate that severe overheating has occurred. The presence of volatile components can be determined by ASTM D 92, Cleveland Open
Cup Flash Point and/or ASTM D 93 Pensky-Martens Closed
Cup Flash Point Test. As determined by these methods, the
flash point is the lowest temperature, corrected to barometric pressure of 101.3kPa (760 mm Hg), where the application
of an ignition source causes the vapors of the fluid being
tested to ignite, either in an open cup (D 92) or closed cup (D
93). These test procedures are described in detail in Chapter
25, Volatility.
Water Content (ASTM D 95 and D 1744)
Heat trsinsfer systems operating at temperatures of 120C or
greater must, for reasons of safety, be dry, because destructive high pressures are generated when water enters the high
temperature sections of the system. If water is not removed,
the vapor will cause pump cavitation and possible fluid discharge through the expansion tank vent
Test Method D 95 is a classic distillation procedure for water content. It is conducted by heating the fluid under reflux
with a water immiscible solvent that codistills with water in
the fluid. Condensed water and solvent are continuously separated in a trap, the water settles in the graduated section of
the trap. The amount of water is reported as % by volume of
the original sample. However, distillation is only suitable for
relative high levels of water content. In most well-maintained
heat transfer systems, the actual water content is lower than
that necessary for distillation. A more suitable procedure for
determination of water content is Test Method D 1744, a Karl
Fischer method where the sample is titrated to an electrometric end point [19].

583

Safety
Mineral oil heat transfer fluids are hydrocarbons, and therefore are combustible with the associated safety risks. However, mineral oil based heat transfer systems have been in
safe operation for over 100 years.
System Leakage
Unlike hydraulic systems, mineral oil heat transfer systems
are not generally pressurized. The leaks that do occur are
found mostly in threaded fittings, joints, valves, and pumps
the fluid will slowly weep rather than gush or spray. Leaking
heat transfer fluid will tjrpically smoke rather than bumeven
at temperatures in excess of their flash and fire points. However, hot mineral oil fluid vapors can also be highly flammable
if allowed to accumulate in a poorly ventilated area.
Insulation Fires
All organic heat transfer fluids are capable of spontaneous
combustion when leaks occur into porous insulation (such as
fiberglass or calcium silicate). The exact mechanism of the
autoignition has not been established. One possibility is that
partial oxidative decomposition occurs in the insulation
(similar to the way heat is generated in a pile of oily rags or
wood chips). The heat produced adds to the system heat and
ultimately exceeds the autoignition temperature of the fluid.
An alternate mechanism is that the autoignition temperature
of the fluid decreases as it degrades in the insulation. In either case, if air enters the insulation at this point and contacts the degraded fluid, spontaneous combustion will occur.
Automatic Shutdown Controls
Although rare, fires have occurred in heaters when fluid circulation is interrupted (due to pump failure or blockage) and
the high temperature shutdown fails. In this situation, the
fluid temperature rapidly increases above the autoignition
temperature while the increasing thermal stress eventually
causes either the heater tube or housing to fail. All systems
should incorporate automatic shutdown controls for high
fluid outlet temperature and loss or reduction of fluid flow
through heater.
Design and Construction
Like any other industrial system, the proper design and installation of heat transfer fluid systems is critical to their
smooth functioning and extended operating life. In this section, an overview of recommended practices to minimize the
potential of system fires will be provided.
Component Selection
In designing and constructing a thermal oil system, attention
must be paid to the selection of appropriate components. If
care is not taken, poor operation, system failure, and fires
can result. In this section, an overview of various system design considerations for mineral oil heat transfer fluids will be
provided.
Piping
Schedule 40 seamless carbon steel piping is recommended.
Schedule 80 piping is recommended for threaded installations up to 1 in. Threaded fittings are not recommended for

584

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

piping greater than 2 in. Pipe should be free of mill scale,


wedding flux, quench oils, and lacquers. The use of copper
should be minimized.
Flanges and

Fittings

Flanges and fittings must be 300 lb forged steel, Yu in. raised


face. Studs and nuts should be continuous threaded, alloy
steel with heavy hex nuts.
Valves should be 300 lb cast or forged steel, or nodular
(ductile) iron with steel or stainless steel trim. For o p t i m u m
service, bellows may be considered. The use of cast iron in
thermal oil systems is not recommended.
Suggested gasket and packing materials include:
Flange gasketsSpiral wound graphite filled or filled PTFE
(maximum temperature 450F)
Valve stem packingRings of die formed graphite foil
Pump packingEnd (nonextrusion) rings of braided carbon yeim
Mechanical SealsCarbon versus silicon or tungsten carbide for continuous service. Silicon Ccirbide versus tungsten carbide for intermittent service.
Elastomers
Fluoroelastomer r e c o m m e n d e d to 450F, perfluoroelastomers recommended to 600F. Compatibility of other elastomers should be evaluated using tests such as ASTM D 471.
Insulation
Heat loss should not exceed 80 btu/ft at operating temperature. Nonporous (closed cell foam glass type) insulation is
recommended. Porous insulation(such as glass fiber and calcium silicate) can be used on straight piping runs where leakage is unlikely. In such installations, nonporous insulation
should be installed around leak prone areas such as valve and
instrument taps and extended 18 in. m i n i m u m on either side.
Weep holes should be drilled in the b o t t o m of insulation
around veJves. If possible, flanges should be left uninsulated.
Metal covers with weep holes can be installed for personnel
protection.
Pumps
P u m p s should be cast carbon steel. Positive displacement
p u m p s should be of the "gear within a gear" design. Canned
or magnetic drive p u m p s are typically not required since
fugitive emissions regulations do not apply for mineral oils.
It is recommended that the alignment be rechecked after the
system is operating at temperature. Flex hose should be installed on the inlet and outlet.
Pressure

Gauges

Y-strainers
One-quarter to Ys in. opening is recommended. A 60 mesh element should be instcJled for start-up only.
Flow

Protection

Many systems utilize a pressure differential switch to provide


a method of shutting the system down when fluid flows drop
below set limits. Some systems are equipped with flowmeters
in addition to the pressure differential switches. However,
since flowmeters can fail in the open position, they are typically not recommended for use as a flow switch.
Installation
During installation or construction, four areas should be addressed:
system cleanliness
component orientation
system tightness
allowance for thermal expansion and contraction
System

Cleanliness

Care must be taken to assure that the system is clean and dry.
Both the "hard" and "soft" contamination must be removed
as the system is being assembled. Hard contamination such
as mill scale, weld spatter/slag, and dirt can cause premature
failure of p u m p and vzJve seals. A startup strainer should be
monitored continuously during initial system circulation.
Soft contamination such as quench oil, welding flux, and
protective lacquer coatings can potentially dissolve in the
fluid. Although this would be expected to exhibit only a minimal effect in most cases, such contaminants may be carried
through the heater where they may degrade at much lower
temperatures than the fluid itself, and can cause fouling of
heater surfaces.
Component

Orientation

Expzinsion tanks should be located far enough away and piped


so that the temperature is n o greater than 1 SOT for vented systems. Design the expansion tank for twice the expansion volu m e of the system where the tcink is % full cold and M full when
the system is at operating temperature. Valves should be
m o u n t e d system sideward so that leakage from the stem or
from bonnet gasketing drips away from the piping.
System

Tightness

The system should be chcirged with an inert gas once construction is completed. Not only will corrosion be prevented,
but the system can be pressure-tested using simple soap-bubble detection methods at potential leak points.

Pressure gauges should be rated to 100 psi, 650F (343C) at


a temperature range of 300-600F; Thermometers should be
calibrated according to ASTM E l to provide accurate readings in this range [6].

ASTM STANDARDS

Expansion

No.
D 91

Joints

For expansion joints, it is recommended that the HTF system


be designed for an expansion growth of 4 in. per 100 ft, mini m u m . Both loops and joint expansion devices are acceptable. Either m u s t be high-temperature rated and must be
considered part of the piping system.

D 92
D 93

Title
Test Method for Precipitation Number of Lubricating Oils
Test Method for Flash and Fire Points by Cleveland
Open Cup
Test Method for Flash Point by Pensky-Martens
Closed Cup Tester

CHAPTER
D 97
D 130

D 189
D 445
D 471
D 524
D 611

D 664
D 877
D 893
D 1160
D 1169
D 1298

D 1319
D 1500
D 1744
D 1747
D 2007

D 2140
D 2425
D 2501
D 2502

D 2549

D 2717
D 2766
D 2786

D 2887
D 3238

D 3239

Test Method for Pour Point of Petroleum Products


Test Method for Detection of Copper Corrosion
from Petroleum Products by the Copper Strip Tarnish Test
Test Method for Conradson Carbon Residue of
Petroleum Products
Kinematic Viscosity of T r a n s p a r e n t a n d Opaque
Liquids (The Calculation of Dynamic Viscosity)
Test Method for Rubber Property-Effect of Liquids
Test Method for Ramsbottom Carbon Residue of
Petroleum Products
Test Method for Aniline Point and Mixed Aniline
Point of Petroleum Products a n d H y d r o c a r b o n
Solvents
Test Method for Acid N u m b e r of Petroleum Products by Potentiometric Titration
Test Method for Dielectric Breakdown Voltage of
Insulating Liquids Using Disk Electrodes
Test Method for Insolubles in Lubricating Oils
Test Method for Distillation of Petroleum Products
at Reduced Pressure
Test Method for Specific Resistance (Resistivity) of
Electrical Insulating Liquids
Test Method for Density, Relative Density (Specific
Gravity), or API Gravity of Crude Petroleum and
Liquid Petroleum Products by Hydrometer Method
Hydrocarbon Types in Liquid Petroleum Products
by Fluorescent Indicator Adsorption
Test Method for ASTM Color of Petroleum Products
(ASTM Color Scale)
Test Method for Determination of Water in Liquid
Petroleum Products by ICarl Fischer Reagent
Test Method for Refractive Index of Viscous
Materials
Characteristic Groups in Rubber Extender and Processing Oils and Other Petroleum-Derived Oils by
the Clay-Gel Absorption Chromatographic Method
Carbon-Type Composition of Insulating Oils of
Petroleum Origin
Hydrocarbon Types in Middle Distillates by Mass
Spectrometry
Calculation of Viscosity-Gravity Constant (VGC) of
Petroleum Oils
Estimation of Molecular Weight (Relative Molecular Mass) of Petroleum Oils F r o m Viscosity
Measurements
Separation of Representative Aromatics a n d
N o n a r o m a t i c s Fractions of High-Boiling Oils by
Elution Chromatography
Test Method for Thermal Conductivity of Liquids
Test Method for Specific Heat of Liquids and Solids
Hydrocarbon T5rpes Analysis of Gas-Oil Saturates
Fractions by High Ionizing Voltage Mass Spectrometry
Test Method for Boiling Range Distribution of
Petroleum Fractions by Gas Chromatography
Test Method for Calculation of Carbon Distribution
and Structured Group Analysis of Petroleum Oils by
the n-d-m Method
Aromatic Types Anedysis of Gas-Oil Aromatic Fractions by High Ionizing Voltage Mass Spectrometry

21: MINERAL
D 3524
D 3525
D 4291
D 4530
D 4808

D 5186

D 5291
D 5292

D 5372
D 6546

D 6743
E 659
G4

OIL HEAT TRANSFER

FLUIDS

585

Diesel Fuel Diluent in Used Diesel Engine Oils by


Gas Chromatography
Gasoline Diluent in Used Gasoline Engine Oils by
Gas Chromatography
Trace Ethylene Glycol in Used Engine Oil
Test Method for Determination of Carbon Residue
(Micro Method)
Hydrogen Content of Light Distillates, Middle Distillates, Gas Oils, and Residua by Low-Resolution
Nuclear Magnetic Resonance Spectroscopy
Determination of Aromatic Content and Polynuclear
Aromatic Content of Diesel Fuels and Aviation Turbine Fuels by Supercritical Fluid Chromatography
Instrumental Determination of Carbon, Hydrogen,
and Nitrogen in Petroleum Products and Lubricants
Aromatic Ccirbon Contents of Hydrocarbon Oils by
High Resolution Nuclear Magnetic Resonance
Spectroscopy
Guide for Evaluation of Hydrocarbon Heat Transfer Fluids
Stcindard Test Methods for a n d Suggested Limits
for Determining Compatibility of Elastomer Seals
for Industrial Hydraulic Fluid Applications
Test Method for Thermal Stability of Organic Heat
TrEinsfer Fluids
Test Method for Autoignition Temperature of liquid
Chemicals
Method for Conducting Corrosion Coupon Tests in
Plant Equipment

OTHER STANDARDS
ISO 6743-12: 1989 (E) International Standard, "Lubricants;
Industrial Oils and Related Products (Class L)"-Classiication-Part 12: Family Q (Heat Transfer Fluids)

REFERENCES
[1] Guffey, G. E., "Sizing Up Heat Transfer Fluids and Heaters,"
Chemical Engineenng, Vol. 104, No. 10, 1997, pp. 126-131.
[2] Green, R. L., Larsen, A. H., and Pauls, A. C, "The Heat Transfer
Fluid Spectrum," Chemical Engineering, Vol. 96, No. 2, 1989, pp.
90-98.
[3] Green, R. L. and Morris, R. C, "Heat Transfer Fluids-Too Easy
to Overlook," Chemical Engineering, Vol. 102, No. 4, 1995, pp.
88-92.
[4] Seider, E. N. and Tate, G. E., "Heat Transfer and Pressure
Drop," Industrial Engineering and Chemistry, Vol. 28, 1936, pp.
1429-1436; b. Kern, D. Q., "Chapter 6-Counterflow: Double Pipe
Exchangers," Process Heat Transfer, McGraw Hill Inc., NY,
1950, p. 103.
[5] ASTM E 1, "Specification for ASTM Thermometers," Annual
Book of ASTM Standards, Vol. 14.03.
[6] Anon. "Product Review: Oil Refining and Lubricant Base
Stocks," Industrial Lubricatoin and Tribology, 1997, Vol. 49, No.
4, pp. 181-188.
[7] Singh, H., "Characterization of Lube Oil Base StockApproach
and Significance," Advances Production & Application of Lubricant Base Stocks, Proceedings, International Symposium, H.
Singh, P. Rao, and T. S. R. Tata, Eds., McGraw-Hill, New Delhi,
1994, pp. 303-310.

586 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


[8] Hoo, G. H. and Lewis, E., "Base Oil Effects on Additives Used to
Formulate Lubricants," Adv. Prod. Appl. Lube Base Stocks, Proceedings, International Symposium, H. Singh, P. Rao, and T. S.
R. Tata, Eds., McGraw-Hill, New Delhi, 1994, pp. 326-333.
[9] Prince, R. J., "Base Oils from Petroleum," Chemistry and Technology Lubricants, R. M. Mortimer a n d S. T. Orszulik, Eds.,
Blackie, Glasgow, 1992, pp. 1-31.
[10] Yoshida, T., Watanabe, H., and Igarashi, J., "Pro-Oxidant Properties of Basic Nitrogen Components in Base Oil," Proceedings of
the 11''' International Colloquium of Industrial and Automotive
Luhrication-Vol.
1, W. J. Bartz, Ed., Technische Academie
Esslingen, Esslingen, 1998, pp. 433-444.
[11] Adhvatyu, A. and Singh, I. D., "FT-NMR and FT-IR Applications
in Lubricant Distillation and Base Stock Characterization," Tribotest Journal, Vol. 3, No. 1, 1996, pp. 89-95.
[12] Singh, H. and Singh, I. D., "Use of Aromaticity to Estimate Base
Oil Properties," Advances Production & Application of Lubricant
Base Stocks, Proceedings International Symposium, H. Singh,
P. Rao, and T. S. R. Tata, Eds., McGraw-Hill, New Delhi, 1994,
pp. 288-294.
[13] Al-Bamwan, M., "Base Stocks Properties/Characteristics,
Additive Response and Their Interrelationship," Advances Production & Application of Lubricant Base Stocks, Proceedings International Symposium, Proceedings, International
Symposium,
H. Singh, P. Rao, and T. S. R. Tata, Eds., McGraw-Hill, New
Delhi, 1994, pp. 303-310.
[14] Al-Sammerrai, D., "Study of Thermal Stabilities of Some Heat
Transfer Oils," Journal of Thermal Analysis, 1985, Vol. 30, No. 4,
pp. 163-110.
[15] Jones, C , "Properties of Hydraulic Fluids," Mechanical World
Engineering, January 1964, pp. 3-5.
[16] Farris, J. A., "Extending Hydraulic Fluid Life by Water and Silt
Removal," Field Service Report 52, Industrial Hydraulics Division, Pall Corporation, Glen Cove, NY.
[17] Godfrey, D. a n d Herguth, W. R., "Physical and Chemical Properties of Industricil Mineral Oils Affecting Lubrication-Part 4,"
Lubrication Engineering, Vol. 51, No. 12, 1995, pp. 977-979.
[18] Adhvaryu, A., Pandey, D. C , and Singh, L. D., "Effect of Composition on the Degradation Behavior on the Decomposition of

[19]
[20]
[21]

[22]

[23]

[24]

[25]

[26]

[27]

Base Oil," Symposium on Worldwide Prospectives on the Manufacture, Characterization, and Application of Lubricant Base Oils,
Division of Petroleum Chemistry, Inc., 213 National Meeting of
the American Chem. Society, 1997, pp. 227-228.
Fuchs, H. C. G., "Understand Thermal Ansdysis Techniques,"
Chemical Engineering Progress, Vol. 93, No. 12, 1997, pp. 39-44.
Kern, D. Q., Process Heat Transfer, McGraw-Hill Book Company, NY, 1950, pp. 99, 103.
"Chapter 3-Viscous Oils," Manual on Hydrocarbon Analysis, 6'*^
Edition, A. W. Drews, Ed., 1998, ASTM International, West Conshohocken, PA, p p . 25-30.
B a r m a n , B. N., "Hydrocarbon-Type Analysis of Base Oils
and Other Heavy Distillates by Thin Layer Chromatography
with Flame-Ionization Deection and by the Clay-Gel Method,"
Journal of Chromatograpic
Science, Vol. 34, No. 5, 1996,
pp. 219-225.
Sassiat, P., Machtalere, G., Hui, F., Kolodziejczyk, H., and Rosset, R., "Liquid Chromatographic Determination of Base Oil
Composition and Content in Lubricating Oils Containing Dispersants of the Polybuteneylsuccinimide Type," Analytical
Chimica Acta, Vol. 306, No. 1, 1995, pp. 73-79.
Kagdiyal, V., Joseph, M., Sastry, M. I. S., Satapathy, S., Basu,
B., Jain, S. K., et al., "Estimation of Polycyclic Aromatic Hydrocarbons of Base Oils by HPLC and by UV Spectroscopic
Technique: A Comparison," Proceedings of the Advances Production & Application of Lubricant Base Stocks, Proceedings
International Symposium, H. Singh and T. S. R. Prasada Rao,
Eds., Tata McGraw-Hill, New Delhi, India, 1994, pp. 295-302.
Jain, M. C , Bansal, V., Jain, S. K., Srivastava, S. P., and Bhatnagar, A. K., "The Role of Thermal and High Temperature Gas
Chromatographic Techniques in the Characterization of Base
Oils Blends," Proceedings Adv. Prod. Lube Base Stocks, H. Singh
and T. S. R. Prasada Rao, Eds., Tata McGraw-Hill, New Delhi,
India, 1994, pp. 272-279.
Powell, J. R. and Compton, D. A. C. "Automated FT-IR Spectrometry for Hydrocarbon-Based Engine Oils," Lube Engineering, Vol. 49, No. 3, 1993, pp. 233-239.
Anon., "Characterizing Base Oils," Lubrizol Newsline, Lubrizol
Corporation, Wickliffe, OH, December 1996, pp. 5.

MNL37-EB/Jun. 2003

Non-Lubricating Process Fluids:


Steel Quenching Technology
Bozidar Liscic, ^ Hans M. Tensi, ^ George E. Totten, ^
and Glenn M. Webster^

THIS CHAPTER WILL FOCUS ON QUENCHING TECHNOLOGY FOR STEEL

HEAT TREATING APPLICATIONS. Quenching is the process of cooling metal parts to achieve the desired microstructure, hardness, strength or toughness. Quenching can produce both desirable and undesirable residual stresses and distortion in
addition to cracking. Steel, for example, is heated to the
austenitizing t e m p e r a t u r e , that t e m p e r a t u r e where the
austenite m i c r o s t r u c t u r e is formed. To obtain o p t i m u m
hardness, strength, and toughness, the maximum amount of
martensite transformation microstructure is desired. The
primary function of the quenching medium is to control the
rate of heat transfer from the surface to optimize the microstructure while minimizing undesirable features such as
cracking and distortion [1].
The selection of a quenching medium is dependent on the
composition of the alloy, the desired final microstructure and
the surface to volume ratio of the part. The most c o m m o n
quenchant media are usually liquids or gasses. Liquid quenchants include: mineral oils, water, water that may contain
salt or caustic additives, and aqueous polymer solutions. The
most c o m m o n gasses, which may or may not be pressurized,
include nitrogen, helium, and argon.
Various aspects of quenching technology will be discussed
in this chapter. This includes: hardenability, fundamentals of
quench processing, description of c o m m o n quench media,
cooling curve analysis, and quench bath maintenance. Included in this discussion is the current status of international
standards development for quenchant characterization. This
discussion will be limited to steel quenching technology.
Quenching of non-ferrous alloys are not discussed here
although the basic surface cooling principles involved are
the same.

DISCUSSION
Steel Transformation
Properties such as hardness, strength, ductility, and toughness are dependent on the microstructure and grain size. The
first step in the process is to heat the steel to its austenitizing
temperature. The steel is then cooled rapidly to avoid the formation of ferrite and maximize the formation of martensite,
which is a relatively hard transformation product, to achieve
the desired as-quenched hardness.
' University of Zagreb, Zagreb, Croatia.
^ Technical University of Munich, Munich, Germany.
^ G. E. Totten & Associates, Inc., LLC, Seattle, WA.

The most common transformation products that may be


formed in quench-hardenable steels from austenite in order of
formation with decreasing cooling rate: martensite, bainite,
peeirlite (which is a mixture of ferrite and cementite), and
pearlite/ferrite. Each of these microstructures provides a
unique combination of properties, and especially the relationship between ferrite and cementite in pearlitedepending on
the carbon content and the cooling velocitystrongly influences the mechanical properties. These transformation products have been described by J.R. Davis (in order of their formation with increasing cooling velocity) [2]:
1. AusteniteA microstructural phase characterized by a
face-centered cubic iron (gamma iron) crystallographic
structure. It is the desired solid solution microstructure
produced prior to hardening. An austenite microstructure is illustrated in Fig. lA [2].
2. Ferrite^A near carbon-free solid solution of one or more
elements in a body-centered, cubic arrangement in which
alpha iron is the solvent. Fully ferritic steels are only obtained when the carbon content is very low. Ferritic grain
boundaries, as illustrated in Fig. IB [2] is the most obvious microstructural feature
3a. PearliteA microstructural phase characterized by its
body-centered crystallographic structure which is a
metastable lamellcir aggregate of ferrite and cementite (or
with an extremely low cooling rate, a mixture of globular
cementite in ferrite) whose microstructure is shown in
Fig. 1C [2] resulting from the transformation of austenite
at temperatures above the bainite range.
3b. CementiteBrittle compound of iron and carbon, which
is known as iron carbide with the approximate chemical
formula FesC and is characterized by an orthorombic
crystal structure. When it occurs as a phase in steel, the
chemical composition will be affected by the presence of
m a n g a n e s e a n d other carbide-forming elements. The
highest cementite contents are observed in white cast
irons (Fig. ID) [2].
4. Bainite^A metastable aggregate of ferrite and cementite
resulting from the transformation of austenite at temperatures below the pearlite transformation temperature,
but above the start of martensite transformation (Ms).
Upper bainite is an aggregate that contains parallel lathshape units of ferrite and carbides and produces a feathery appearance in optical microscopy, as shown in Fig.
IE [2]. It is formed above approximately 350C (660F).
Lower bainite exhibits an acicular appearance similar to
t e m p e r e d martensite, as shown in Fig. I F [2] a n d is
formed below approximately 350C (660F).

587
Copyright'

2003 by A S I M International

www.astm.org

588 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK

i>6-

(a),(b)

^.>fl

'"-*-.^

:>..>'^

vs?i.

.v^>

-^y-.
/*

(d),(e)

- -

mA
f^-i-ii

(c)

i^-M'S

(g),(h)
FIG. 1Illustrations of microstructural transformation products:
a) Equiaxed austenite grains and annealing twins in an austenitic stainless steel. 250X; ASM Materials and Engineering Dictionary, ASM International, Materials Park, OH 44073-0002, Fig. 20, p. 26. b) Low-carbon ferritic sheet steel
etched to reveal ferrite grain boundaries-. 100X; ASM Materials and Engineering Dictionary, ASM International, Materials Park, OH 44073-0002, Fig. 25, p. 30. c) Pearlite structure in high-carbon steel (Fe-0.5C). The cementite lamellae
are white; the ferrite is dark: 500X; ASM Materials and Engineering Dictionary, ASM International, Materials Park, OH
44073-0002, Fig. 26, p. 30. d) White cast iron contains massive amounts of cementite (white) and pearlite (dark): 500X;
ASM Materials and Engineering Dictionary, ASM International, Materials Park, OH 44073-0002, Fig. 64, p. 66. e) Upper
bainite in 4360 steel; ASM Materials and Engineering Dictionary, ASM International, Materials Park, OH 44073-0002,
Fig. 173, p.156. f) Lower bainite (dark plates) in 4150 steel; Reprinted from Ref. 3, p. 67 by courtesy of Marcel Dekker,
Inc. g) Microstructure of lath martensite; 500X; Reprinted from Ref. 3, p. 68 by courtesy of Marcel Dekker, Inc. h) Microstructure of plate martensite; light shading is retained austenite; 500X; Reprinted from Ref. 3, p. 69 by courtesy of
Marcel Dekker, Inc. i) Microstructure of tempered martensite; 500X; ASM Materials and Engineering Dictionary, ASM
international. Materials Park, OH 44073-0002, Fig. 365, p. 308.

(f)

CHAPTER

22: NON-LUBRICATING

PROCESS

5. MartensiteA generic term for microstructures formed


by a diffusionless phase transformation in which the parent and product phases have a specific crystallographic
relationship. Martensite in steel is characterized by its
body-centered tetragonal crysteJlographic structure. The
a m o u n t transformation from austenite to martensite depends on the cooling rate and on the lowest temperature
attained since there is a distinct t e m p e r a t u r e where
martensitic transformation begins (Ms) and ends (Mf).
Three microstructural forms of martensite are: lath (Fig.
IG [3]), plate (Fig. I H [3]) a n d t e m p e r e d (Fig. 11[3])
martensite.
The formation of these products and the proportions of
each are dependent on the austenitization time (because of
increasing solution of elements in austenite with increasing
time), the time and temperature cooling history of the particulcir alloy, and composition of the alloy. The transformation products formed are typicEilly illustrated with the use of
transformation diagrams, which show the temperature-time
dependence of the microstructure formation process for the
alloy being studied. Two of the most commonly used transformation diagrams are TTT (time-temperature-transformation) a n d CCT (continuous cooling transformation) diagrams.
TTT

Diagrams

TTT diagrams, which are also called isothermal transformation (IT) diagrams, are developed by heating small samples of
steel to the t e m p e r a t u r e where austenite transformation
structure is completely formed i.e., austenitizing temperature, and then rapidly cooling to a temperature intermediate
between the austenitizing and the Ms temperature, and then
holding for a fixed period of time until the transformation is
complete, at which point the trcinsformation products are determined. This is done repeatedly until a TTT diagram is constructed such as that shown for a n unalloyed steel (AISI
1045) in Fig. 2A. TTT diagrams can only be read along the
isotherms.

FLUIDS:
CCT

STEEL

QUENCHING

TECHNOLOGY

589

Diagrams

Alternatively, seimples of a given steel may be continuously


cooled at different specified rates and the p r o p o r t i o n of
tremsformation products formed after cooling to various temperatures intermediate between the austenitizing temperature and the Ms determined to construct a CCT diagram,
such as the one shown for an unalloyed carbon steel (AISI
1045) in Fig. 2B. CCT curves provide data on the temperatures for each phase trzmsformation, the amount of transformation product obtained for a given cooling rate with time,
and the cooling rate necessary to obtain mEirtensite. The critical cooling rate is dictated by the time required to avoid formation of pearlite for the particular steel being quenched. As
a general rule, a q u e n c h a n t m u s t produce a cooling rate
equivalent to, or faster than, that indicated by the "nose" of
the pearlite transformation curve in order to maximize
mEirtensite transformation product. CCT diagrams can only
be read along the curves of different cooling rates.
Caution: Although it is becoming increasingly common to
see cooling curves (temperature-time profiles) for different
cooling media (quenchants) such as oil, water, air, and others superimposed on either TTT or CCT diagrams, this is not
a rigorously correct practice and various errors are introduced into such analysis due to the inherently different kinetics of cooling used to obtain the TTT or CCT diagrams versus the quenchants being represented. A continuous cooling
curve can be superimposed on a CCT, but not on a TTT
diagram.
Hardenability
Hardenahility has been defined as the ability of a ferrous material to develop hardness to a given depth after being austenitized and quenched. This general definition comprises two
subdefinitions, the first of which is the ability to achieve a
certain hardness [4]. The ability to achieve a certain hcirdness
level is associated with the highest attainable hardness,
which depends on the carbon content of the steel and more

Austenite Temperature = 880 C

ill
m

800 A3
700 A l

T Fe rite

5 - BOO
2

III

Austenite Temperature = 880 Q,

T] LUpea rlite - StartI


li Pea lite- End
-Sta

500
Bajnite - >ta 1

2 m
Q.

Bainite

fc m ^ I v i d r i i

site^

1-

eoo

1 II

700
n
7

7(7'

Seconds

(a)

-Time-

B]pi0'
T l

End

1
1 II

10*
10^
h 15 30 ffb
Minutes
7 d t SB
Hours

7
1Sl*

-Time-

S f B 75 30
Minutes
T S ifB8 1BSt
l-lours

FIG. 2a) Time-Temperature-Transformation (TTT) diagram of an unalloyed steel containing 0.5% carbon; b) ContinuousCooling-Transformation diagram of an unalloyed steel containing 0.6% carbon.

(b)

590

MANUAL

3 7: FUELS

AND LUBRICANTS

HANDBOOK

specifically on the amount of carbon dissolved in the austenite after austenitizing.


This is illustrated by considering the problem of hardening
of high-strength, high-carbon steels. The higher the concentration of dissolved c a r b o n in the austenitic phase, the
greater the increase in mechanical strength after rapid cooling and transformation of the austenite in the metastable
martensite phase. Martensitic steels typically exhibit increasing hardness and strength with increasing carbon content, as
shown in Fig. 3, but they also exhibit relatively low ductility.
However, with increasing carbon concentration, martensitic
transformation from austenite becomes more difficult, resulting in a greater tendency for retained austenite and correspondingly lower strength.
The second subdefinition of hardenability refers to the
hardness distribution within a cross section from the surface
to the core under specified quenching conditions. It depends
on the carbon content, which is interstitially dissolved in
austenite and the a m o u n t of alloying elements substitutionally dissolved in the austenite during austenitization. Therefore, as Fig. 3 shows, carbon concentrations in excess of 0.6%
do not yield correspondingly greater strength [7]. Also, increasing carbon content influences the Mf temperature relative to Ms during rapid cooling as shown in Fig. 4 [8]. In this
figure, it is evident that for steels with carbon content above
0.6%, the transformation of austenite to martensite will be
incomplete if the cooling process is stopped at 0C or higher.
The depth of hardening depends on the following factors:
Size cmd shape of the cross section
Heirdenability of the materiEd
Quenching conditions
The cross section shape exhibits a significant influence on
heat extraction during quenching and therefore, on the hardening depth. Heat extraction is dependent on the surface area
exposed to the quenchant. Bars of rectangular shape achieve

^600

S.400
E

\M,

o
ro 200
CO

I 0

0.5
1.0
Carbon Content (wt. %)

1.5

FIG. 4Influence of the carbon content in steels on


the temperature of the start of martensite formation
(Ms) and the end of martensite formation (Mf).

Equivalent bar diameter. In.


1
175
E
E 150
m

4
5
6
1
Round Dars-

Squ are bi jrs

in

<o

= 125

_o

E.
t 100

1
Plates

0)

c
o

*0)
-

I 75

<u

't

(0
TJ

3
T3
O

150

"^N^

<D

\-

50

*-^
u

25

D
O

0
25
50
75 100 125 150 175
Equivalent bar diarneter, mm
100

FIG. 5Correlation between rectangular cross sections and


their equivalent round bar and plate sections.

D)
C

w
^

>-

50

0.2
0.4
0.6
0.8
Carbon Content (wt. %)
I

30

25
20
Nickel Content (wt. %)

FIG. 3Influence of the carbon content in steel on


the yield strength {ao.e) after quench hardening. The
yield strength values were obtained from compression tests; the additional variation of nicltel content
causes a negligible solid-solution-hardening and was
selected to obtain a constant Ms temperature for the
start of martensitic transformation.

less depth of hardening than round bars of the same cross


section size. Figure 5 can be used to convert square and rectangular cross sections to equivalent circular cross section
sizes [6].
The effect of steel composition on hardenability may be
calculated in t e r m s of the "ideal critical diameter" or Di,
which is defined as the largest b a r diameter t h a t can be
quenched to p r o d u c e 50% martensite at the center after
quenching in an "ideal" quench, i.e., under "infinite" quenching severity. The ideal quench is one that reduces surface
temperature of a n austenitized steel to the bath temperature
instctntaneously. Under these conditions, the cooling rate at
the center of the bar depends only on the thermal diffusivity
of the steel.

CHAPTER 22: NON-LUBRICATING

PROCESS FLUIDS: STEEL QUENCHING

The ideal critical diameter may be calculated from:


Di = Di Base (carbon concentration and grain size)
X fmn X f s i ^ f c r ^ fiVIo X /V X f c u X /"NI X f^

Where fx is a multiplicative factor for the particular substitutionally dissolved alloying element. The base Dj Base value and
one set of alloying factors are provided in Table 1 [6] (Note:
This is not an exhaustive listing of alloying factors but these
are commonly encountered and they permit calculations to
illustrate the effect of steel chemistry variation on hardenability.)
Grain size refers to the dimensions of grains or crystals in
a polycrystalline metal exclusive of twinned regions and subgrains when present. Grain size is usually estimated or measured on the cross section of an aggregate of grains. Common
units are: (1) average diameter, (2) average area, (3) number
of grains per linear unit, (4) number of grains per unit area,
and (5) number of grains per unit volume.
Grain size may be determined according to Test Method E
112. The test methods covered in Test Method E 112 describe
the measurement of average grain size and include the comparison procedure, the planimetric (or Jeffries) procedure,
and the intercept procedures. Standard comparison charts
are provided. These test methods apply chiefly to single phase
grain structures but they can be applied to determine the average size of a particular type of grain structure in a multiphase or multiconstituent specimen.
In addition, the test methods provided in E 112 are used to
determine the average grain size of specimens with a unimodal distribution of grain areas, diameters, or intercept
lengths. These distributions ire approximately log normal.
These test methods do not cover methods to characterize the
nature of these distributions. Characterization of grain size
in specimens with duplex grain size distributions is described
in Test Method E 1181. Measurement of individual, very
coarse grains in a fine-grained matrix is described in Test
Method E 930. These test methods deal only with determination of planar grain size, that is, characterization of the twodimensional grain sections revealed by the sectioning plane.

TECHNOLOGY

591

Determination of spatial grain size, that is, measurement of


the size of the three-dimensional grains in the specimen volume, is beyond the scope of these test methods.
The test methods described in E 112 are techniques
performed manually using either a standard series of graded
cheirt images for the comparison method or simple templates
for the manual counting methods. Utilization of semiautomatic digitizing tablets or automatic image analyzers to
measure grain size is described in Test Method E 1382.
The ASTM grain size number (G), referred to in Table 1, is
a grain size designation bearing a relationship to average intercept distance at 100 diameters magnification according to
the equation:
G = 10.00 - 21og2L
Where L = the average intercept distance at 100 diameters
magnification. The smaller the ASTM grain size, the larger
the diameter of the grains.
The effects of quenching conditions on the depth of hardening are not only dependent on the quenchant being used
and its physical and chemical properties, but also on process
parameters such as bath temperature and agitation.
Hardenability Measurement
There are numerous methods to estimate steel hardenability.
However, perhaps the two most common are: Jominy curve
determination and Grossmann hardenability. These two procedures will be discussed here.
Jominy Bar End-Quench Test
The most familiar and commonly used procedure for measuring steel hardenability is the Jominy bar end-quench test.
This test has been standardized and is described in ASTM A
255, SAE J406, DIN 50191, and ISO 642. For this test, a 100
mm (4 in.) long by 25 mm (1 in.) diameter round bar is
austenitized to the proper temperature, dropped into a fixture, and one end rapidly quenched with 24C (75F) water
from a 13 mm (0.5 in.) orifice under specified conditions, as

TABLE 1Hardenability factors for carbon content, grain size and selected alloying elements in steel.
Carbon
Content (%)
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
1.00

Carbon Grain Size No.

Alloying Element

Mn

Si

Ni

Cr

Mo

0.0814
0.1153
0.1413
0.1623
0.1820
0.1991
0.2154
0.2300
0.2440
0.2580
0.273
0.284
0.295
0.306
0.316
0.326
0.336
0.346

0.0750
0.1065
0.1315
0.1509
0.1678
0.1849
0.2000
0.2130
0.2259
0.2380
0.251
0.262
0.273
0.283
0.293
0.303
0.312
0.321

0.0697
0.0995
0.1212
0.1400
0.1560
0.1700
0.1842
0.1976
0.2090
0.2200
0.231
0.241
0.251
0.260
0.270
0.278
0.287
0.296

1.167
1.333
1.500
1.667
1.833
2.000
2.167
2.333
2.500
2.667
2.833
3.000
3.167
3.333
3.500
3.667
3.833
4.000
4.167
4.333

1.035
1.070
1.105
1.140
1.175
1.210
1.245
1.280
1.315
1.350
1.385
1.420
1.455
1.490
1.525
1.560
1.595
1.630
1.665
1.700

1.018
1.036
1.055
1.073
1.091
1.109
1.128
1.146
1.164
1.182
1.201
1.219
1.237
1.255
1.273
1.291
1.309
1.321
1.345
1.364

1.1080
1.2160
1.3240
1.4320
1.54
1.6480
1.7560
1.8640
1.9720
2.0800
2.1880
2.2960
2.4040
2.5120
2.62
2.7280
2.8360
2.9440
3.0520
3.1600

1.15
1.30
1.45
1.60
1.75
1.90
2.05
2.20
2.35
2.50
2.65
2.80
2.95
3.10
3.25
3.40
3.55
3.70

592 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

illustrated in Fig. 6 [3]. The austenitizing temperature is selected according to the specific steel alloy being studied, however, most steels are heated in the range of 870-900C
(1600-1650OF).
In the Jominy end-quench test, a cylindrical specimen is
heated to the desired austenitizing temperature and welldefined time, which is material composition dependent, and
then it is quenched on one end with water. The cooling velocity decreases with increasing distance from the quenched
end. After quenching, parallel flats are ground on opposite
sides of the bar and hardness measurements are made at 1/16
in. (1.6 mm) intervals along the bar, as illustrated in Fig. 7
[6]. The hardness as a function of distance from the
quenched end is measured and plotted and, together with
measurement of the relative areas of the martensite, bainite,
and pearlite that is formed, it is possible to compare the hardenability of different steels using Jominy curves. As the slope
of the Jominy curve increases, the abiUty to harden the steel
(hardenabihty) decreases. Conversely, decreasing slopes (or
increasing flatness) of the Jominy curve indicates increasing
hardenabihty (ease of hardening).
The Jominy end-quench is used to define the hardenabihty
of carbon steels with different alloying elements like
chromium (Cr), manganese (Mn), molybdenum (Mo) and
has different critical coohng velocities. Jominy curves for different alloy steels are provided in Fig. 8 [9]. These curves illustrate that the unalloyed, 0.4% carbon steel exhibits a relatively small distance for martensite (high hardness)
formation. The 1% Cr and 0.2% Mn steel, however, can be
hardened up to a distance of 40 mm. Figure 8 illustrates that
steel hardenabihty is dependent on the steel chemistry, that
unalloyed steels exhibit poor hardenabihty, and that Jominy
curves provide an excellent indicator of relative steel hardenabihty.
The Jominy test provides valid data for steels having an
ideal diameter from about 25-150 mm (1-6 in.). This test can
be used for Di values less than 25 mm (1 in.), but Vickers or
microhardness tests must be used to obtain readings that are
closer to the quenched end of the bar and closer together
than generally possible using the standard Rockwell "C"
hardness test method [4].
The austenitizing time and temperature, extent of special
carbide solution in the austenite and extent of oxidation or
surface decarburization during austenitizing, care and consistency of surface flat preparation, and bar positioning prior

... iwith increasing


Pearlite fdistance ofttie

I Cemenlite Lamella
Probi
WaterNozzlei

200 400 600 800


Hardness (H,)

FIG. 6Schematic illustration of the Jominy end-quench test


and microstructural variation with increasing distance from the
quenched end.

270 70 18 5-6
4B9-\Z4'-32.3"1<y
y.6 V,. y. 'V,,

-rr- 1

r,i}cooling rates
Distance from quenched end., in.

^
"a
\U

60
50

S 40
I

230
o
0

^ M

'

to

'

'

1.0
'

25

'

2.0
-^I
50

3.0 in.
I

I
75 mm

Distance from quenched end


FIG. 7Measuring hardness on the Jominy test specimen
and plotting hardenability curves.
to making hardness measurements are important factors that
influence test results. Therefore, all tests should be conducted in compliance with the standard being followed [4].
Grossmann

Hardenability

Grossmann's method of measuring hardenability uses a


number of cylindrical steel bars of different diameters hardened in a given quenching medium [6]. Aftier sectioning each
bar at mid-length and examining it metallographically, the
bar that has 50% martensite at its center is selected, and the
diameter of this bar is designated as the critical diameter D^^f
Other bars with diameters smaller than Dent will have more
martensite and correspondingly higher hardness values and
bars with diameters larger than D^^it will attain 50% martensite only up to a certain depth as shovro in Fig. 9 [4]. The D^^^
value is valid only for the quenching medium and conditioiTs
used to determine this value.
To determine the hardenability of a steel independently of
the quenching medium, Grossmann introduced the term
ideal critical diameter, Di, which as discussed previously, is
the diameter of a given steel bar that would produce 50%
martensite at the center when quenched in a bath of quenching intensity H = oo. Here H = co indicates a hypothetical
quenching intensity that reduces the temperature of heated
steel to the bath temperature in zero time.

CHAPTER

22: NON-LUBRICATING

PROCESS

To identify a quenching medium and its condition, Grossm a n n introduced the Quenching Intensity (Severity) factor
"H". Table 2 provides a summary of Grossmann H-Factors
for different quench media and different quenching conditions [1]. Ahhough this data has been pubhshed in numerous
reference texts for many years, it is of relatively limited quantitative value. One of the most obvious reasons is that quenchant agitation is not adequately defined and is often unknown, yet it exhibits enormous effects on quench severity.
The Grossmann value "H" is based on the Biot (Bi) number, which interrelates the interfacial heat transfer coeffi-

FLUIDS:

STEEL

QUENCHING

TECHNOLOGY

593

TABLE 2Effect of agitation on quench severity as indicated by


Grossmann quench severity factors (H-factors).
Grossmann H Factor
Agitation

Oil

Water

Caustic Soda or Brine

None
Mild
Moderate
Good
Strong
Violent

0.25-0.3
0.30-0.35
0.35-0.4
0.4-0.5
0.5-0.8
0.8-1.1

0.9-1.0
1.0-1.1
1.2-1.3
1.4-1.5
1.6-2.0
4

2
2-2.2

cient (a) thermal conductivity (A) and the radius (R) of the
round bar being hardened:
Bi = a/\-R
H = al{2-

0
10
20
30
40
50
Distance from the Quenched Front Side (mm)
FIG. 8Jominy curve comparison of the hardenability of one
unalloyed and a number of other different alloy steels. All alloy
concentrations are weight %.

i 40

r-i-

-HRC .,s50%M

i/i

a>

Cfll

"I 20

-?c^t^

o
I

'm
FIG. 9Determination of critical diameter Dcrit according to
Grossmann.

H-D
X)

Since the Biot number is dimensionless, this expression means


that the Grossmann value, H, is inversely proportional to the
b a r diameter. This method of numerically analyzing the
quenching process presumes that heat transfer is a steady
state, linear (Newtonian) cooling process. However, this is seldom the case and almost never the case in vaporizable quenchants such as oil, water, and aqueous polymers. Therefore, a
significant error exists in the basic assumption of the method.
Another difficulty is the determination of the //-value for a
cross section size other than one experimentally measured.
In fact, //-values depend on cross section size. Values of H do
not account for specific quenching characteristics such as
composition, oil viscosity, or temperature of the quenching
bath. Tables of //-values do not specify the agitation rate of
the quenchant either uniformly or precisely (see Table 2).
Therefore, although //-values are commonly used, more current and improved procedures ought to be used when possible. For example, cooling curve analyses a n d the various
methods of cooling curve interpretation that have been reported [1,5] are all significant improvements over the use of
Grossmann Hardenability factors.

Q u e n c h i n g F i m d a m e n t a l s a n d C o o l i n g Curve
Analysis
Steel Wetting

GO

Kinetics

Hardening of steels (so cedled Martensitic- or Bainitic- Hardening) requires preheating (austenitizing) of the steel to temperatures in the range of 750-1100C, from which the steel is
quenched (cooled) in a defined way to obtain the desired mechanical properties such as hardness a n d yield strength.
Most liquid vaporizable quenchants used for this process exhibit boiling temperatures between 100 and 300C at atmospheric pressure. When parts are quenched in these fluids,
the wetting of the surface is usually time dependant, which
influences the cooling process and the achievable hardness.
G. J. Leidenfrost described the wetting process about 250
years ago [10]. The Leidenfrost Temperature is defined as the
surface temperature where the vapor film collapses and the
surface is wetted by the liquid. Literature describes temperature-values for this event for water at atmospheric pressure
between 150 and 300C [11-14]. It is apparent that the Leidenfrost Temperature is influenced by a variety of factors,
part of which cannot be quantified precisely even today.

594 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


For a nonsteady state cooling process, the surface temperature at all parts of the workpiece is not equal to the Leidenfrost Temperature. When the vapor blanket (or film boiling)
collapses, wetting begins by nucleate boiling due to the influence of lateral heat conduction (relative to the surface) [15].
This is due to the simultaneous presence of various heat
transfer conditions during vapor blanket cooling (or film
boiling [FB]), nucleate boiling [NB], and convective heat
transfer [CONV] with significantly varying heat transfer coefficients apB (100 to 250 W/irn^K)); aNB (10 to 20 kW/{m^K)y,
and ttcoNv (ca. 700 W/(m'^K)). Figure 10 schematically illustrates the different cooling phases on a metcJ surface during
an immersion cooling process with the so-called "wetting
front," w, (separating the "film boiling phase" and the "nucleate boiling phase") and the change of the heat transfer coefficients, a, along the surface coordinate, z, (mantle line). In
most cases during immersion cooling, the wetting front ascends the cooling surface with a significant velocity, v,
whereas during film cooling the wetting front descends in the
fluid direction [13,16].
An example of wetting heated cylindrical and prismatic
specimens which are submerged in water is shown in Fig.
1 l a and fo [13,17]. Because of the different wetting phases on
the metal surface (and the enormous differences of their values of apB,ttNB,and acoNv). the time dependant temperature
distribution within the metal specimens will also be influenced by the velocity and geometry of the wetting front (for
example, circle or parabolic-like) as well as geometry of the
quenched part.
Figure 12 illustrates different types of wetting behavior under different conditions [17]. By changing a quenching parameter, for example the chemical composition of the fluid,
the period of wetting (tw) can be reduced over more than one
order of magnitude. The time interval, t^^, when the wetting
front appearsusually at the lower end of the specimen^up
to the time the wetting front has moved across the entire
specimen surface; sometimes two wetting fronts appear as illustrated in Fig. l i d . In addition to explosive-like wetting
(fw ~ 0), a foam may appear in the fluid neeir the specimen

Immersion cooling
Wetting front

surface, which will depress the heat flux from the specimen
into the fluid.
Factors Influencing

Film

Boiling

To quantitatively define the change of the wetting behavior,


for example, to ascertain the cooling process or to develop or
aneJyze quenching fluids, the measurement of the electrical
conductance between the submerged sample and a counter
electrode is helpful [13]. During the film boiling phase, the
hot metal is largely insulated by the vapor film surrounding
the metal and conductance between the metal a n d the
counter electrode is low. When the vapor blanket (film boiling) ruptures on the metal surface, localized wetting begins
and conductance increases. The increase in conductance of
the wetted metal is proportional to the amount of the metal
surface wetted by the quenchant. When the metal surface is
completely wetted, conductance is at its highest value.
Figure 13a schematically illustrates a normal electrical
conductance, (G) increase corresponding to the percentage
of the wetted surface (compare Fig. 11A or 1 IB). Three other
possibilities of wetting are also shown. Figure I3b shows a
rapid rewetting process (or "explosive" wetting) similar to
that shown in Fig. 12. Figure 13c illustrates rapid wetting followed by insulation by bubbles adhering to the metal surface
and Fig. I3d illustrates rapid wetting with repeated new formation of film boiling, a process which occurs with many
aqueous polymer quenchant solutions. In all four diagrams,
the temperature, Tc, is shown, which is measured in the center of the probes. The time, ts, characterizes the time (and the
corresponding temperature value from the Tc (t) slope, the
temperature Ts) when wetting begins. This shows that temperature measurements in the center of probes provide poor
information about the real quenching process that is insufficient to adequately characterize the hardening process. This
is also illustrated in Fig. 14 [19] by T(t) slopes, measured in
the center and the surface of cylindrical probes, quenched in
water with t^v + 0, and in an aqueous poljTner solution with
a short ty^ time.
To obtain a better definition of the wetting kinematic, the
starting time, ts, of wetting, the finishing time, tf, of wetting
and the difference between tf and ts as the wetting time fi^
should be used. The effect of vEiriation of these parameters on
the quenching process is summarized in Table 3.

Film boiling

Impact of the Wetting Process o n Cooling


Behavior

Nucleate boiling
Convective beat
transfer
Heal transfer
coefficient at

Film cooling
Film of liquid
Convection boiling

Fluid drops
Wetting front ir

FIG. 10Wetting behavior and cliange of heat transfer coefficient a along the surface [13,16].

An illustration of the influence of a wetting process occurring


over a long time (a so-called "non-NEWTONIAN wetting") on
the temperature - time cooling curves, measured near the
surface at different distances from the lower end of the
probe, is illustrated in Fig. 15 [17]. The wetting front requires
about 18 s to arrive at a height of Z = 80 m m taken from the
discontinuities of the curve "0" (ca. Is) and curve "80" (ca.
19s). If there is an explosion-like wetting of the probe (a so
called "NEWTONIAN wetting"), these five t e m p e r a t u r e
slopes cire congruent. If the temperature was measured (like
usucJ) in the center of the probe, the large differences in wetting behavior would not be observed.
The temperature distribution within the probe during
quenching (indicated by isotherms at different times after

CHAPTER 22: NON-LUBRICATING

(a)

(b)

(c)

4.0 s

3.8 s

4.3 s

7.0 s

5.7 s

8.3 s

PROCESS FLUIDS: STEEL QUENCHING

TECHNOLOGY

595

10 s

6.9 s

12,3

3^2 s

4,92 s

5,97 s

7,38 s

(d)

FIG. 11Process of transition between tlie three cooling phasesfilm boiling (FB), nucleate boiling (NB) and convective cooling (CONV) during immersion cooling of CrNi -steel specimens with a cylindrical geometry 25 mm dia x 100
mm), a. Wetting process of a cylindrical CrNi-steel specimen being quenched from 850C into water at 30C with an agitation rate of 0.3 m/s b. prismatic geometry (15 x 15 x 45 mm) in water of 60C without forced convection; Immersion
temperature of 860C, c. CrNi-steel probe (25 mm dia. x 100 mm) in oil at 60C without agitation, d. hollow cylinder (60
od X 30 id X 60 mm long) quenched into oil at 60 and no agitation. Note: there are two wetting fronts.

beginning the quenching process), having a "non-NEWTONIAN wetting" is shown in Fig. 16a. where there is a great
difference relative to that of the "NEWTONIAN wetting"
(Fig. 166). In the second case, the temperature gradient, T,
is radial whereas in the case 'a it is axial. Of course the
hardness distribution in the probes must be extremely different. In the case of "a," a strong axial hardness distribution (accompanied by a very low radial hardness distribution); in the case of "b," a very strong radial hardness
gradient is observed.

Cooling Curve Data Acquistion and Analysis


Data Acquistion and Analysis
The need to acquire sufficient data to adequately define a
cooling curve for subsequent analysis has long been recognized. Special data acquisition devices, including hardware
such as oscillographs, were used for work reported by Jominy
[20], French [21], and others [21,22]. However, this equipment is difficult to calibrate, which has inhibited widespread
use of cooling curve analysis. Currently, sufficient data ac-

596

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

quisition rates can be achieved with personal computers


equipped with analog-to-digital (A/D) converter boards.
Although computer hardware is available, there are no
published guidelines for selecting the proper data acquisition
rate, which varies with probe alloy, size, and quench severity.
Perhaps the best method for selecting the required acquisition rate is to determine it experimentally. This can be done
by repeatedly quenching a probe in cold (25C, or 77F) water, one of the more severe quenchants, and collecting data at

1000
O
o

!
*

750

(0
ki.
ID
Q.

; a

c_

JO

r",

(b)

(a)

500

2 \
"* \

1
/Water

AK

250 polymer ^

10

/3

X.

20

30

3
2
1

1-3

40 0

10

15

20

Time in s

Time in s

FIG. 14Comparison of cooling curves measured at different positions in a cylindrical CrNi-steel probe (25 dia. x 100
mm) during slow wetting (water) and sudden wetting (aqueous
polymer solution) at (a) center and (b) close to the probe surface at three indicated heights (1,2, and 3).

TABLE 3"Effect of fluid and metal property variation


on quench severity.

6.35 s

Effect on Property Variation


Increasing, 4- =Decreasing)

7.65 s

(t ==

FIG. 12Transition from film boiling (FB) to nucleate boiling (NB) during immersion of cylindrical silver
specimen (15 mm dia x 45 mm) quenched from 850C
into a 10% aqueous polymer quenchant solution at
25C without agitation [18] In comparison with the
tw-values of Fig. 13 a and b, the wetting time is extremely short [18].

iIk (a)
i^

0)
1

ts.tf

Atw

n
Ti
i

ti
Ti
i

ti
ti

".Parameters: ts'. time when wetting starts; tf. time when wetting is finished;
Atw- time interval of wetting [s]; a: heat transfer coefficient.

m
<o
o.

E
0)

Fluid Property
Type of quenchant
Addition of additives
Increasing agitation (v)
Increasing bath
Temperature (Tt)
Metal Property
Increasing thermal
Diffusivity (a)
Increasing cross
section Size
Increasing surface
Roughness
Increasing surface
Oxidation

^ ^
timet

ts = tf

timet

timet
FIG. 13a-d): Temperature decrease, Tc, and increasing electrical conductance, G, (proportional to
the wetted surface) during quenching in different
quenchants; a) slow wetting, b) rapid (explosive-like)
wetting; c) rapid wetting followed by isolation of bubbles adhering to the metal surface; d) rapid wetting
with repeated formation of film boiling after this process (see also Figs. 14 and 15) [13,18].

various acquisition rates. For example, a 13 mm X 100 mm


(1/2 in. X 4 in.) cylindrical Inconel 600 probe with a tjqje K
thermocouple inserted at the geometric center was quenched
into 25C (77F) water with data acquisition rates of 1, 2.5,
and 5 Hz. (A "hertz" value is equivalent to a data point per
second.) The corresponding cooling time and rate curves are
shown in Fig. 17 [5]. These results show that for this particular probe, a data acquisition rate of at least 5 Hz was required
to obtain a smooth cooling rate curve in the maximum cooling rate region. Smooth curves are required to minimize errors in determining the maximum cooling rate in this critical
region of the quenching process.
In data acquisition, the proper A/D converter card must be
selected to match the thermocouple being used. The thermocouple output is nonlinear with respect to temperature. If
software for data analysis is being written for this use, this
nonlinearity must be taken into account. One method is to
create a data file that will convert thermocouple electromotive force (emf) values to the appropriate temperature.

CHAPTER 22: NON-LUBRICATING

PROCESS FLUIDS: STEEL QUENCHING TECHNOLOGY

597

Tj^ical data acquisition errors were found to be 0.5C


(0.9F) within the temperature range of 0-900C
(32-1650F). Another source of error is the algorithm used to
calculate cooling rates. In general, however, it was found that
the error obtained was primarily a result of an error in the
data.
Most data have some background noise; consequently,
most data acquisition techniques employ data averaging or
smoothing to minimize the noise. One method is a five-point
"running" average [24]:

r = {-%5Tn^2) + (%r_i) + (%rj


+ (%rn+i)-e/35j+2)

15
20
Quenching time
FIG. 15^Temperature drop on the surface of a cylindrical
steel probe (25 mm dia x 100 mm) at various distances zfrom
the lower end [16].

where T is the temperature at the n,n - \,n + l,n - 2, and


n + 2 groups of points being averaged. A running average
means that after T^ is calculated, the average of the next (n +
1) point is then averaged. This process is continued until all
of the data points have been averaged.
Another feature of the A/D converter card that must be considered is ice-junction compensation. Because thermocouples are only able to measure temperature differences, to obtain accurate temperature measurements, it is important to
calibrate to a reference temperature, typically ice water.
Cooling Time and Rate Parameters

/=5s

-825'C

-775"C
t=5s

/=10s

/=11s

/=15s

FIG. 16a and b) Time-dependant temperature distribution


during cooling of cylindrical steel probes (25 mm dia x 100
mm) in the case of slow non-Newtonian wetting and explosive Newtonian wetting.

Zhu [23] analyzed computer data acquisition for cooling


curve analysis and reported the following sources of error:
Thermocouple voltage to temperature conversion
A/D signed conversion
Preamplifying circuit and signal transmission circuits
Electronic component instability
Error caused by signal interference

In recent years, several rate- and time-dependent parameters


have been suggested to quantify the severity of various quenchant media. Some of these parameters include the cooling
rates at 705 and 205C (1300 and 400F), maximum cooling
rate, and time to the cooling rate at 730-260C (1350-500F)
[48]. It is generally desirable to maximize the cooling rate at
705C (1300F) to avoid the pearlite transformation region. It
is desirable to minimize the cooling rate at 205C (400F),
which is in the region of the Ms transformation temperature
for many steels, to minimize cracking. It is also desirable to
minimize the time to cool from 730-260C (1350-500F) in
order to optimize the potential hardness by avoiding pearlite
formation.
Tensi and Steffen [25] have prepared a set of critical cooling parameters for cooling curve characterization as shown
in Fig. 18:
Full-film boiling (vapor blanket cooling) to nucleate boiling transition time, temperature, and rate,i?DHmin- These
parameters characterize the transition from A- to B-stage
cooling.
Maximize the rate of cooling, i?max. and the temperature
where this occurs, TRmax- GenereJly, it would be desirable
to maximize i?max and minimize ?Rmax Rate of cooling at temperatures such as 200C (i?2oo) and
300C, (i?3oo)- In order to minimize cracking and distortion, it is desirable to minimize cooling rates in this region.
Although the dimensions for cooling rate most typically
used throughout the heat treating industry are [C/s], this
is physically incorrect. The correct units for cooling rates
are [K/s].
One problem with this approach is the potential misinterpretation of low cooling rates in the Ms transformation region. Traditionally, it has been thought that minimizing the
cooling rates in the Ms transformation region is essential for

598 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


Dana collected at 1 HZ

60 Time (sec.)
40

20

80

60

100

120

140

Cooling rate (C/sec.,

Data collected at 2.5 HZ


800

_^^
^ 600 w
3

13
w 400
Q.
E
V

1-

200

n
0

-
*

11

10

2G

20

40

30

60

80

40

100

50
120

60 Time (sec.)
140

Cooling rate rc/sec.j

Daita collected at 5 HZ

60 Time (sec.)
0

20

40

60

80

100

120

140

Cooling rate fCsec.)

FIG. 17Effect of data acquisition rate on cooling rate curve smoothness.

CHAPTER 22: NON-LUBRICATING

PROCESS FLUIDS: STEEL QUENCHING

minimizing cracking and distortion. This is desirable, but not


necessarily a sufficient, condition for reduction of quench
cracking. Zhelokhovtseva [26] has shown that uniformity of
cooling in the Ms region is also critical parameter. It seems
reasonable, therefore, that minimal and uniform cooling
rates to minimize stresses that occur due to thermal gradients are probably the necessary and sufficient conditions for
optimizing quenchants in the Ms temperature region.

TECHNOLOGY

599

Hardening Capability (Power)


Segerberg [27] has developed an empirical approach for determining of hardening power (HP) of quench oils without
agitation. Segerberg's hardening power approach utilized
cooling curves obtained with the Wolfson probe shown in
Fig. 19 (see ASTM D 6200). After the cooling curve was determined according to ASTM D 6200 (or ISO 9950), statistical correlation of hardness and cooling rate data provided the
following regression equation:
HP = 3 . 5 4 C R F -1- 12.30 CRM -

168

Where: CR^ is the cooling rate at 550C (990F) which is the


at, or at least near, the nose of the pearlitic transformation
for many steels and CRM is the cooling rate at 330C (595F),
which is near the Ms temperature for many steels [5].
Segerberg [27] used this procedure to predict the asquenched hardness achievable with a commercial quench
system, by strategically placing a series of instrumented steel
probes throughout a typical quench load. The hardening
power at these various positions was calculated from the
above regression equation. Using the correlation curve for
the steel of interest (e.g., the curve for the AISI 1045 steel
shown in Fig. 20, it is possible to predict the hardness for
steel bar with a 16 mm Dia. (0.6 in.) cross section. A similar
procedure can be used for other alloys and different cross
section sizes.
Shock Film Boiling
Time
FIG. 18Critical cooling curve parameters.

-30mm

30mm-

Full-film boiling, nucleate boiling, and convective cooling


heat transfer modes have been studied by various authors

M6mm

9.5mm
13mm (12.5mm after
- f
finish grinding)
1.5mm tight push
fit "nominar

Not to be
center drilled
Probe details

Probe body
Details Infig.3(a^

Finish
grind

Support tube
Material - Inconel alloy 600
Tl^t fit on probe end iwith
30 angle weld allowance
Dimensions as (a)

12.5 0 . 0 1 mm

Mineral Insulated thermocouple


Type'K-CNiCr/NIAI)
Sheath materlaNlncone) alloy 600
Diametei=1.5mm; Route length190mm min; Talls-25mm
Hot iunction~lnsulated; cold seal=
epoxy resin

End support
-tube
Material Stainless steel

Termination
Standard tttermocouple
typeV(NlCf/NlAI)

General assembly
FIG. 19^Wolfson Inconel 600 probe.

600 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


Acoustical

i I

60

50
DC

-o 40
(0
X

30

HP == 3.54 CRp + 12.30 CR|y| - 168

20

200

400 600 800 1000


Hardening power (HP)

FIG. 20Quenchant classification by hardening power.

[31-34]. A m u c h less studied and understood heat transfer


process is shock-film boiling. Shock-film boiling refers t o the
initial formation of the vapor film around the hot metal upon
initial immersion. In most experiments, this cooling process
is not detected unless surface temperature-time measurements Eire made or if alternative experimental methods cire
used to detect this unstable b u t important heat transfer mode.
The cooling capacity of quenchants during full-film boiling, nucleate boiling, a n d in one-phase convection is characterized by critical heat flux density a n d by the heat transfer
coefficient (or specific heat flux) [28-29]. Nonstationary heat
processes: shock boiling, full-film boiling, transition boiling,
nucleate boiling, a n d convection heat transfer have been
readily detected by conventional cooling curve analysis
[28,30]. Except for shock-film boiling, all of these cooling
processes may occur simultaneously o n the hot metal surface
[30,31].
Determination of the first a n d second critical heat flux densities are necessary to properly explain these cooling modes,
[35,36]. Heat trzinsfer in these boiling regimes is characterized by two values. One is the first critical heat flux density
(?cri), which typically occurs within approximately 0.1 s after
initial immersion of the h o t metal (shock-film boiling). The
next step is full-film boiling. The second critical heat flux
ilcri) is the m i n i m u m heat flux at which the transition from
full-film boiling to nucleate boiling will occur. BCruzhilin has
shown that the ratio of qci2 I ^cri is a constant [37]. Kobasko
et. al. have determined that this constant is 0.204-0.207 for
water [35], If the constamt is known, the difficult to observe
qcri c a n b e calculated from t h e m o r e easily observed a n d
measured g'cr2-

Measurements

A schematic of the experimental device is shown in Fig. 21


[38]. The working firequency of the acoustical detector is 0-20
kc, which is further divided into 200 channels. The width of
each channel is 100 c/s. E a c h heat transfer mode shockboiling, full-film boiling, a n d nucleate boiling is observed
acoustically at characteristic frequencies. These are summarized in Table 4.
Note: ASTM E 131 defines frequency as "the number of cycles (c) per unit time." ASTM E 349 states "When the independent variable is time, t h e unit of frequency is the hertz.
Symbol: Hz (1 H z = P ' ) . (This unit is also called "cycle per
second c/s".) The term "kc" means kilicycles and as used in
the above discussion, 0-20 kc means 0-20 000 cycles.
Sound amplitude is proportional to the intensity of the
boiling process. High frequencies can be used to detect the
initiation of shock boiling. The time difference corresponds
to the duration of t h e full-film boiling. Knowing t h e r m o physical properties of the standard sample and duration of
full-film boiling, the second critical heat flux density can be
determined [35,36]. From the duration of the fuU-film boiling
and nucleate boiling phases a n d the second critical heat flux
density it is possible to characterize quenching capacity.
A 20 m m silver probe has been utilized, which had a soldered 0.1 m m chromel-alumel thermocouple inserted t o in
the center of the probe, as shown in Fig. 22. The thermocouple was in a 1.5 m m metal case filled with insulating materisJ.
The thickness of the case wall is 0.1 m m .
The piezoceramic sensor for acoustic noise detection was

FIG. 21Schematic illustration of acoustical noise analysis


measurement device: 1. Furnace, 2. Quenchant, 3. Probe, 4.
Thermocouple, 5. Transducer, 6. Amplifier, 7. Acoustic analyzer, 8. Glass fiber system, 9. Computer,10. Printer, 11. Time
analyzer.

TABLE 4Characteristic acoustic frequencies for


various heat transfer modes.
Heat Transfer Mode

Frequency Mode (kc)

Shock-film boiling
Full-film boiling
Nucleate boiling

9-20
0.05-1.5
0.5-4.0

CHAPTER 22: NON-LUBRICATING PROCESS FLUIDS: STEEL QUENCHING TECHNOLOGY 601


located at equal distances between probe and wall of the container with the liquid to be investigated as shown in Fig. 21.
The quenchant was placed in a container of 150 mm diameter and height of 270 mm. The signal from piezoceramic
sensor is transmitted to amplifier (6) and then to analyzer
(7)see Fig. 21of acoustic signals connected to a digital
voltmeter and computer.
With this apparatus, in addition to acoustic analysis, cooling curve temperature-time analyses are also conducted.
With this data, the duration of the full-film boiling, second
critical heat flux density, heat transfer coefficient, and the
duration of non-stationary nucleate boiling are determined.
These values are sufficient for the characterization of
quenching capacity. The results obtained by this method
are presented on Fig. 23. The silver probe was cooled from
800C in 20% aqueous solution of a poly(alkylene glycol)
quenchant. The start of full-film boiling and transition to the
nucleate boiling can be detected by conventional time-temperature cooling curve analysis. However, acoustical analysis

1.S mm

FIG. 22Illustration of cast


spherical silver probe.

9,IW

lot, 4r

i5o:

lOS

A136
100

sn

I A
2

jxi.m
iot,i

FIG. 23Comparison of quenching properties of aqueous PAG polymer quenchant (concentration 20% at 20(C). A5 and A136 correspond to 0.5 and 13.6 kc.

602

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK
was required to observe the transition from shock- film boiling via full-film boiling to nucleate boiling.
Quench Oils
Quenching oils are analogous to other petroleum-derived
products including engine oils, spindle oils, and industrial lubricating oils such as gear lubricants [39]. Although
petroleum oils are usually refined for specific applications,
they remain complex mixtures with a variety of possible compositions, which may vary even when produced by a single
refinery. The compositional complexity of quench oils affects
their quenching performance. Segerberg [40] compared a series of mineral-oil-based quenchants, which were tested by
cooling curve analysis according to ISO 9950 (ASTM D 6200)
and obtained a wide variety of cooling rates, as shown in Fig.
24. Formulated oils can produce an even wider range of cooling rates.
Quenching oils that contain substantial quantities of naphthenic derivatives usually exhibit inferior cooling characteristics, greater deposit-forming tendency, and lower flash
points than paraffinic oils. Tensi [41] has shown that the
quench severity of a particular quench oil is directly related
to its ability to wet a metal surface. The wettability of a
quench oil is quantified by measuring "rewetting" times, as
shown in Fig. 25.

O
o
3

a
E

Quench Oil Classification


For commercial acceptance, a quench oil must exhibit a
number of important properties including:
Acceptable flash and fire points,
Low sludge formation
Nonstaining of parts,
Appropriate heat removal properties.
Oxidation Resistance

Cooling R a t e . ' C
FIG. 24Potential variation of the severity of different quench oils.

10

30

50

70

90

Distance from end (mm)


FIG. 25Wetting time and surface hardness of 1045 steel as a function of distance from
the end of the specimen.

CHAPTER 22: NON-LUBRICATING PROCESS FLUIDS: STEEL QUENCHING TECHNOLOGY


Most quench oils are derived from refined petroleum-base
stocks. Higher naphthenic fractions usually result in lower
flash points and greater sludge formation. Sludge formation
reduces heat transfer efficiency, which may result in inadequately hardened parts. Increased sludging cJso reduces oil
flow t h r o u g h heat exchangers used to cool the oil during
quenching.
Ideally, a quench oil should not stain parts. High-quality
paraffinic oils impart a light gray color to quenched parts.
Sulfur-containing derivatives in the oil cause unacceptable
black stains. Some quench rate enhancing additives may also
cause staining. However, the color of a quench oil is not indicative of its staining tendency.
Since quench oils are flammable, there is always the potential to catch fire in use. The flash point of an oil is used as
an indicator of its tendency to ignite. Maximizing the flash
point minimizes the fire hazard. Increasing the naphthenic
content of an oil usually decreases the flash point.
Quench oils are selected on the basis of their ability to mediate heat transfer during the quench. Oils are classified on
the basis of quenching speed and temperature of use. ISO

Code Letter

General
Application
Heat Treatment

6743 provides a classification code for veirious quench media


including quench oils, which is shown in Table 5.
The three major quench oil classifications are [ 4 2 ^ 5 ] :
Conventional (nonaccelerated) oils, or cold oils,
Accelerated oils,
Marquenching oils, or hot oils.
Various characterization criteria for these oils are summarized in Table 6 [46]. The differences in cooling curve profiles
for typical m e m b e r s of these oils classifications are illustrated in Fig. 26 [46].
Conventional quenching oils are typically mineral oils,
which m a y contain antioxidants to reduce oxidation a n d
thermal degradation. Most of these oils have viscosities in the
range of 100-110 SUS (Saybolt Universal Seconds) at 40C
(100F), although some have viscosities u p to 200 SUS at
40C (100F).
Accelerated quenching oils are usually formulated from a
mineral oil and contain one or more additives to increase
cooling rates during the high temperature portion of the cooling process. This is accomplished by using an additive that

TABLE 5ISO 6743 Quenchant classification system.


Product Type
More Specific
Particular
and/or
Application"
Application
Performance Requirements
Oil for heat
Cold Hardening
Oil for normal hardening
Treatment
e < 8oc
Oil for quick hardening
Semi-hot hardening
8OC<0< ISCC
Hot hardening
130C<e<200C
Very hot hardening
200C<e<310C

Oil for
Oil for
Oil for
Oil for
Oil for
Oil for

normal hardening
quick hardening
normjd hardening
quick hardening
normal hardening
quick hardening

Vacuum hardening
Other cases
Aqueous Fluids
for Heat
treatment

Surface hardening

Mass hardening

Molten Salts
for Heat

Gas for heat


treatment

Other cases
150C<e<500C
500X<6><700C
Other cases

603

Water
Aqueous fluid
Aqueous fluid
Water
Aqueous fluid
Aqueous fluid

for slow hardening


for quick hardening
for slow hardening
for quick hardening

Molten salts 150C<6<500C


Molten salts 500C<e<700C
Air
Neutral Gas
Reducing Gas
Oxidizing Gas

Symbol
ISO-L
UHA
UHB
UHC
UHD
UHE
UHF
UHG
UHH
UHV
UHK

Remarks
Certain oils may be
easily eliminated by
washing with water.
This characteristic
is brought about by
the presence of
emulsifiers in the
oil formulation.
Such oils are then
known as
"washable." It is up
to the supplier at
the request of the
^^'^ user, to provide
this characteristic*

UAA
UAB
UAC
UAA
UAD
UAE
UAK
USA
USB
USK
UGA
UGB
UGC
UGD
UF
UK

Fluidized Bed
Other cases
"8 indicates the iluid temperature at the time of hardening;
''The washing solution used to remove the emulsified oil may be either detergent (soap) and water or water-borne alkaline cleaners. The cleaning conditions
shall be provided by the oil supplier.

604

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 6Quench oil physical property characteristics.


Bath Temperature

Typical GM

Typical
Viscosity at 40C
(100F) SUS

340
355
570

105
94
700

16.0
10
30

Flash Point

Type of Oil

op

Conventional
Accelerated
Marquenching

<65
<120
<200

<150
<250
<400

C
170
180
300

Time (s)

1600
1400
1200
G?

N ^^Conventional
V
quench oil
\
150F
\
\
\
Martempering oil
500 F

Fused salt
500 F

2 1000
2

800
600

High speedquench oil


150'F

400
0.7

1.0

1.5

10

"^.^ ^ > ^
'^Molten
"^.^ N.
metal
'^O'^
500 F
15

20

30

40

60

Time (sec)
FIG. 26Comparison of cooling curves for various quench media.
facilitates surface wetting, which destabilizes the film boiling
process. Examples of additives that may be used to accomplish this include: calcium naphthenate [47], alkenyl succinate [47], and sodium sulfonate [48]. Viscosities of these oils
may vary from 50-100 SUS at 40 (100F).
For some steels, quenching at an elevated temperature is
necessary to reduce thermal and transformational stresses
that may lead to cracking and increased distortion. One process that may be used to accomplish this is martempering (or
marquenching). In meirtempering, metal is usually quenched
from the austenitization temperature to a temperature just
above (see Fig. 27B) the stcirt of martensite transformation
(Ms) just long enough for the temperature to equalize between the surface and the center of the steel. The metal is
then removed from the quench bath and air-cooled. The thermal cycle for both conventional quenching Eind martempering is illustrated in Fig. 27 [1].
Martempering or hot quenching oils are used at temperatures between 95-230C (200 a n d 450F). They are usually formulated from solvent-refined mineral oils with a very high
parafBnic fraction to optimize oxidative and thermal stability.
Stability is enhanced by the addition of antioxidants. Nonaccelerated and accelerated martempering oils are available
Typical t e m p e r a t u r e ranges for m a r t e m p e r i n g oils are
shown in Table 7 [46]. Because martempering oils are used at
relatively high temperatures, a protective, nonoxidizing
atmosphere over the oil is typically used, which allows operation closer to the flash point of the oil t h a n if open-air conditions are used [49]. A protective atmosphere is any atmo-

sphere that will inhibit oxidation of the meted surface during


austenitization, prior to quenching. A protective atmosphere
may be an inert gas such as nitrogen or argon or it may be a
gas used for a heat treating furnace. These same atmospheres
Eire also used to protect the quenching oil, especially martempering oils, from the oxygen in air during use, thus reducing
the rate of sludge formation and increasing lifetime of the
quenching oil.
Classification

by GM Quenchometer

Cooling

Times

Cooling rates produced by quench oils have been classified


on the basis of the General Motors (GM) quenchometer test,
also known as the "nickel ball" test [50,51]. Details of this test
Eire provided in Test Method ASTM D 3520. This test involves
heating a 22 m m (7/8 in.) d i a m e t e r nickel ball to 885C
(1625F) and then dropping it into a wire basket suspended
in a beaker containing 200 m L of the quenching oil at
21-27C (70-80F) [52]. A timer is activated as the glowing
nickel bEJl passes a photoelectric sensor. A horseshoe magnet
is located outside the beaker as close as possible to the nickel
ball. As the ball cools, it passes t h r o u g h its Curie point
(354C, or 670F), the temperature at which nickel becomes
magnetic. When the ball becomes magnetic, it is attracted to
the magnet, activating a sensor that stops the timer as illustrated in Fig. 28 [46]. The cooling time required to reach the
Curie temperature is sometimes referred to as the "heat extraction rate" or "quenchometer time." Table 8 provides t } ^ ical GM quenchometer times for the different quench oil classifications. [46,53,54]

CHAPTER 22: NON-LUBRICATING

PROCESS FLUIDS: STEEL QUENCHING

Although the GM quenchometer test is commonly used for


evaluating quench oils, the quenchometer times are based on
a relatively limited portion of the total cooling process and
therefore are not related to as-quenched hardness or the
propensity for cracking. In fact, this test only defines a heat
removal rate, regardless of variation of cooling pathway,
over the high-temperature portion of the cooling curve.
Aqueous Polymer Quenchants
A number of polymers have been used as polymer quenchants for heat treating applications [55]. These include:
poly(vinyl alcohol) [56], poly(alkylene glycol) [56], poly (acrylamide) [58], cellulosic derivatives [59], polyvinylpyrrolidone
[60], poly(sodium aciylate) [61], and poly(ethyl oxazoline)

Surface

TECHNOLOGY

[62]. Of these, the most commonly used quenchants are


poly(alkylene glycol)PAG, poly(vinyl pyrrolidone)PVP,
and poly(ethyI oxazoline)PEOX. However, the most commonly encountered quenchant for induction heat treating applications worldwide are PAG-type quenchants.
Some water soluble polymers that are used as quenchants
undergo a phase separation as the solution temperature is increased; the hydrogen bonds break and the polymer chain
coils upon itself and separates into two phases [63]. The temperature where this occurs is the separation temperature or
cloud point. PAG pol3Tners separate as hydrates and the degree of hydration is dependent on the temperature of the solution, as shown in Fig. 29 [63]. In addition to solution temperature, the degree of polymer hydration for PAG polymers
is dependent on the ethylene oxide/propylene ratio in the

Surface

Center

Center

Time

(b)

I
o
o.
E

FIG. 27Types of quenching cycles: (a) conventional quenching and tempering, (b) martempering,
(c) isothermal quenching and tempering, and (d) austempering.
TABLE 7 --Typical use temperatures for martempering oils.
Use Temperature

Minimum
Flash Point

605

Viscosity at
40C (100F)
SUS

"C

250-550
700-1500
2000-2800

220
250
290

430
480
550

95-150
120-175
150-205

200-300
250-350
300-400

Open Air

Protective Atmosphere
F
C
95-175
120-205
150-230

200-350
250-400
300^50

606 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


polymer chain. Generally, increasing propylene oxide content in the copolymer decreases the separation temperature.
Poly(ethyl oxazoline)PEOX, a n o t h e r polymer currently
used in the heat treating industryalso exhibits a sepeu-ation
temperature [63].
Cloud point behavior of polymer quenchants can be used
as an inexpensive way to purify contaminated (by salt, or
hard metal ions from h a r d water, for example) quench bath.
Raising the temperature of the aqueous solution above its
separation temperature as shown in Fig. 29, causes it to separate into two layers. The upper layer, usually the contaminated aqueous s u p e r n a t e n t solution, is removed a n d the
lower layer of the purified polymer is then redissolved to the
required concentration [64].
Nonionic polymers are usually used since ionic polymers,
such as poly (sodium acrylate), typically precipitate in the
presence of hard metal ions. The most c o m m o n examples of
nonionic quenchant polymers are PAG, PVP and PEOX [64].
C o o l i n g Curve A n a l y s i s - I n t e r n a t i o n a l S t a n d a r d s
Cooling Curve Analysis
Test oil Nickel ball Quench
(heated)

Curie point

FIG. 28Schematic illustration of a GM Quenchometer and the principle of operation.

TABLE 8GM Quenchometer time


classification of quench oils.
GM Quenchometer
Time (s)
Classification
Fast Oil
8-10
Medium Oil
11-14
Slow Oil
15-20
Martempering Oil
18-25

Separation
temperature
"C
80
90

Water iri separated


PAG layer, %

F
(175)
(195)

70
46

Heat
100 0(212?)

Water with
contaminants
Separated
polymer
quenchant

Homogeneous
auenchant solution
FIG. 29Thermal separation of an aqueous solution
of a polyalkylene glycol quenchant.

Standards

Although numerous sizes, shapes, and metals have been,


and continue to be, instrumented for cooling curve analysis,
most national and international standards have utilized a
nickel alloy such as Inconel 600 or silver as probe materials.
One of the earliest national standards that utilized a silver
probe with a surface thermocouple was JIS K 2242,
schematically illustrated in Fig. 30 [65]. Since this probe is
very sensitive, it can sometimes be very difficult to obtain
reproducible data.
To obtain greater data stability and to provide a material
with heat transfer properties much more similar to steel, a
reusable probe based on an Inconel 600 alloy that does not
undergo phase transformation was used [66,67]. This probe
has the additional advantage of being resistEint to oxidation
and was used to develop the widely used Wolfson Heat Treating Centre Engineering Group Specification [66]. It was subsequently used as the probe for ISO 9950 and ASTM Methods
D 6200, D 6482, and D 6549 is shown in Fig. 19.
A n u m b e r of groups have traditionally not accepted the use
of either an Inconel or a stainless steel probe for cooling curve
analysis. They prefer the use of a high thermal conductivity
material that does not exhibit phase transformations such as
silver. There are currently at least two national standards that
utilize a silver probe. One is the French standard AFNOR NFT
- 60778 and the other is the Chinese standard ZB E 45003-88.
These two probes differ from each other primarily in size. The
French probe is 16 m m . dia. X 48 m m and the Chinese probe
is 10 m m dia. X 30 m m . They are illustrated in Figs. 31 and 32,
respectively [65]. Table 9 provides a comparison of the experimental requirements for relevant standards [65].
To maintain probe CcJibration and to assure interlaboratory reproducibility, it is essential that the probe be periodically calibrated during use. This process requires the use of a
calibration fluid for which there are specified cooling properties. The JIS K 2242 and the Chinese standard ZB E 4500388 utilize a JIS K6753 "standard liquor" which is: di (2-ethylhexyl) phthalate. Although available in > 9 9 % purity, the
toxicity properties of this fluid m a k e it undesirable for
widespread and routine use. The Wolfson Standard [66], ISO
9950, and the AFNOR NFT 60778 utilize a "standard" min-

CHAPTER

22: NON-LUBRICATING

PROCESS

FLUIDS:

STEEL

QUENCHING

TECHNOLOGY

Insulating lube

607

il

S i l v e r wire

Pipe made of
silver
Heat resistanl
insulator

M6 X pitch 1

Alumel wire

M> X pitch 0 . 5

Dead

M5 X pitch 0 . 5

> <

Insulating tube

FIG. 30Japanese JIS K 2242 silver probe (All dimensions are in mm).
eral oil whose physical properties are summarized in Table
10 [65].
The ASTM Test Method D 6200 is based on the Wolfson
standeird [65] and ISO 9950, except the specification limits
are controlled more tightly and were based on various statistically designed experimentation as required by ASTM
[68-70].
Development
of Cooling
with
Agitation

Curve Analyses

Methods

Many quenchants, a n d nearly all aqueous polymer quenchants, cannot be evaluated reproducibly without the use of
agitation. Such quenchants always require the use of agitation w h e n used industrially in various heat-treating processes. All of the cooling curve methods discussed d o not employ agitation and are essentially limited to analysis of
minercd oil derived quenchants.
There are two ASTM stcindards for cooling curve analysis
with agitation. One method is ASTM D 6482 and the other is
ASTM D 6549. Both test methods utilize the Wolfson probe
illustrated in Fig. 19. Test Method D 6482 uses an agitation

device, which is shown in Figs 33. [65,71] and 34A. This device is constructed from a transparent material such as Plexiglas or glass and holds approximately 1.5 L of quenchant.
Agitation is provided by a plastic impeller of 50 m m dia. and
pitch of 42 m m [72]. One of the advantages of this agitation
system is the uniformity of turbulence and flow throughout
the quench zone as shown in Fig. 35 [71]. This means that the
sensitivity to error with respect to precise placement of the
probe in the quench zone will be minimal.
Test Method ASTM D 6549 is significantly different from D
6482 in that p u m p agitation is used. This is illustrated in Fig.
34B. This p u m p agitation system is based on earlier work
performed by N.A. Hilder at Aston University [73]. Probe
placement in the fluid reservoir during quenching is illustrated in Fig. 36.
Quench Bath Mamtenance
Sampling
Flow is never uniform in agitated quench tanks. There is always variation of flow rate and turbulence from top to bot-

608

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

torn and across the tank. This means that there may be
significant variations of particulate contaminants including
sludge from oil oxidation and metal scale. For uniform
sampling, a number of sampling recommendations have
been developed:
1. Minimum Sampling TimeThe circulation pump shall be
in operation for at least 1 h prior to taking a sample from
a quench system.

pef^etofv Ofobecamg.

Thermocoupfe0l

2. Sampling PositionFor each system, the sample shall be


taken from the same position each time that system is
sampled. The sample shall be taken at the most practical
point of maximum flow turbulence. The position in the
tank where the sample is taken shall be recorded.
3. Sampling ValvesIf a sample is taken from a sampling
valve, then sufficient quenching oil should be taken and
discarded to ensure that the sampling valve and associated
piping has been flushed, before the sample is taken.
4. Sampling From Tanks With No AgitationIf samples are to
be taken from bulk storage tank or a quench tank with no
agitation, then samples shall be taken from the top and
bottom of the bulk system or quench tank. If this is not
possible and the sample can only be taken from the top,
then the Laboratory Report shall state that the results
represent a sample taken from the top of the bulk system
or quench tank and may not be representative of the total
system.
5. Effect of Quenching Oil Addition as Make-Up Due to DragOutIt is important to determine the quantity and frequency of new quenchant additions, as large additions of
new quench oil will have an effect on the test results, in
particular the cooling curve. If a sample was taken just after a large addition of new quench oil, this shall be taken
into consideration when interpreting the cooling curve of
this oil sample.
6. Sampling ContainersSamples shall be collected in new
containers. Under no circumstances sheJl beverage or food
containers be used.
R e c o m m e n d e d Test Procedures-Quench Oils
(ASTM D 6710)
Physical and Chemical Properties

FIG. 31French AFNOR silver probe (All dimensions are in


mm).

m*

' < l i

iJ

Kinematic Viscosity, (Test Method D 445)The performance


of a quench oil is dependent on its viscosity, which varies
with temperature and oil deterioration during continued use.
Increased oil viscosity typically results in decreased heat
transfer rates [74]. Oil viscosity varies with temperature,
which affects heat transfer rates throughout the process.
The flow velocity of a quench oil depends on both viscosity
and temperature. Some quench oils are used at higher temperatures, such as martempering oils, also known as hot-oils.

1B.m.4>Wi

' " "^ 'J!^ " ^ ""^ p* 4 . *fc w w * . nMk mmt mm* mmtmmm^m

s\\\\
30ia.26

mm mm i .

v'<' < ^ " ^ ^ < V '^"''"r

mmm

MiO.fi

I a
FIG. 32Chinese silver probe (All dimensions are in mm).

CHAPTER 22: NON-LUBRICATING PROCESS FLUIDS: STEEL QUENCHING TECHNOLOGY 609


TABLE 9Comparison of cooling curve standards for unagitated quench oils.
AFNOR
(NFT 60778)

Variable

ISO 9950

Probe Alloy

Inconel 600

Probe
Dimensions
Standard
Reference Oil
Vessel
Dimensions
Oil Volume
Oil Temperature

12.5 m m Dia. X
60 m m
See Table 10

Silver
99.999% pure
16 m m Dia X
48 m m
See Table 10

115 5 m m
diameter
2000 mL
40C 2C

height 138 m m X
diameter 99 m m
800 mL
50C 2C

850C 5C

800C 5 X

Probe
Temperature

JIS (IS 2242)

GB
(ZB E 45003)

Silver
99.99% pure
10 m m Dia X
30 m m
Dioctyl
phthalate
300 mL beaker

Silver
99.96% pure
10 m m Dia X
30 m m
Dioctyl
phthalate
300 mL beaker

250 mL
80''C,120C,
160C
810C 5C

250 mL
80C 2C

See Table 10
115 5 m m
diameter
2000 mL
40C 2C

810C 5C

850''C 5C

ASTM D 6200
Inconel 600
12.5 m m Dia X
60 m m

TABLE 10Physical properties of the so-called "Wolfson Oil" used as a reference for ASTM D 6200, ISO 9950,
and AFNOR NRT 60778 standards.
Institute of Petroleum Test
Minimum
Maximum
Method/ASTM Method
Value
Physical Characteristics
Value
Kinematic Viscosity at 40C, cS"
23.0
19.0
IP 71/D 445
Kinematic Viscosity at 100C, cS"
4.4
3.9
IP 71/D 445
Viscosity Index
105
IP 226/D 2270
95
Density at 15C, kg/L
IP 160/D 1298
0.855
0.870
Flash Point PMCC, "C
IP 34/D 93
210
190
5% Distillation, C
IP 123
360
330
50% Distillation, C
IP 123
420
400
' 1 cS = lO"** m^/s.

Although the viscosity of a martempering oil may not fluctuate substantially at elevated t e m p e r a t u r e s , the oil may
become almost solid u p o n cooling. Thus, the viscositytemperature relationship of a quench oil may be critically
important from the dual standpoint of quench severity and
flow velocity.
Typically kinematic viscosity determination by Test
Method D 445 is used. Viscosity measurements are made at
40C (100F) for conventional or accelerated oils and also at
100C (212F) for martempering oils.
Flash Point and Fire Point (Test Methods D92, D93, D13I0)
Use of a quench oil at a temperature near its flash point in an
unprotected environment, or near its fire point, may result in
an oil fire. General guidelines have been developed for usetemperatures of a quench oil relative to its flash point.
N o t e 2: There are various manufacturer-dependent guidelines for relating the suitability for use of a used quenching oil with respect to its flash point and they shall be
followed. In the absence of such guidelines, it is recommended that the use temperature of a quenching oil in an
open system with n o protective a t m o s p h e r e shall be
60-65C (108-117F) lower than the actual open-cup flash
point. In closed systems where a protective atmosphere is
used, the use temperature of the used quenching oil shall
be at least 35C (60F) lower than its actual open-cup
flash point.
Specific Gravity (Test Method D287)Specific
gravity depends on the chemical composition of the base stock used to
formulate a quenching oil. The oxidative stability of the
quenching oil is dependent on the chemical composition,
such as naphthenic/paraffinic ratio. Therefore, the specific

gravity of a quench oil is an indirect measure of its inherent


oxidative stability.
N o t e 3: Specific gravity is of limited value in monitoring the
quality of a formulated or used quenching oil. The Test
Method D 287 for specific gravity requires the use of both a
hydrometer and an accurate thermometer or a thermohydrometer. Because specific gravity is temperature dependent, the temperature of the oil at the time of measurement
must be determined precisely.
Aged Fluid Properties-Quench

Oils

Acid Number (Test Methods D 664 and D 974)Quench oil


oxidation results in the formation of carboxylic acids and esters. These b5fproducts are similar to compounds that may be
used as rate accelerating additives. These acids and esters significantly affect the viscosity and viscosity-temperature relationship of the oil, which in turn affect quench severity. Carboxylic acids may also act as wetting agents and increase the
quench rate by increasing the wettability of the quench oil on
the metal surface [77].
Oxidation of the oil may be monitored by tracking changes
in the neutralization number. Because the fresh oil may be either alkaline or acidic, depending on the additives present,
the absolute value of the neutralization number itself is not
indicative of qucJity. However, changes in the neutralization
n u m b e r from the initial condition may be used to indicate
the degree of oxidation. Increasing neutralization numbers
generally indicate increasing amounts of aforementioned byproducts.
The acid n u m b e r (AN) is determined by titrating the acidity of a sample of known size with a known amount of stan-

610

MANUAL

3 7: FUELS

AND LUBRICANTS

HANDBOOK
absence of such a value, it is recommended that the AN not
exceed 2.00 mg/g for a used quenching oil.
Infra-Red Spectroscopy^An alternative method that is being
used increasingly to identify and quantify oil oxidation, even
in the presence of additives, is infra-red (IR) spectroscopy.
Figure 37 provides an illustration of the use of IR spectral
cmcJysis to identify oil oxidation [77]. Mang zmd Jiinemann
monitored the IR stretching vibrations o f C B O a t l 7 1 0
c m ~ \ for carboxylic acids contained in oxidized oil. IR analysis has been used to detect and qucintify other carbonyl-containing compounds [78]:
Metal carboxylate salts-1600 and 1400 c m " '
Carboxylic Acids-1710 c m " '
Metal sulfates-1100 and 1600 cm '
Esters-1270 and 1735 cm '
Saponification Number (Test Method D 94)Oil degradation
may produce both acids and ester by-products. The acid number quantifies the amount of acidic degradation by-products in
the oil, whereas the saponification number is a measure of the
presence of esters or fatty esters in the oil. The saponification
number of an oil is determined (Test Method D 94) by heating
a sample of the oil with a known amount of basic reagent and
measuring the amount of reagent consumed. Because some
quench oils are formulated with components that also have
saponification numbers, it is necessciry to monitor trends over
time than to rely on an absolute value [81]. An increase in the
saponification number indicates an increased propensity to
sludge formation. It has been suggested that if the results of
other tests are satisfactory, that saponification numbers below
3 mg KOH/g oil may be acceptable [75,82].
Contamination-Oil

FIG. 33Schematic illustration of the Tensi agitation system


(all dimensions are in mm).

dard base (Test Methods D 664 or D 974). The test is performed by dissolving the oil in a mixture of toluene and isopropanol, then titrating it with a standard solution of potassium hydroxide (KOH). The end-point may be determined
colorimetrically with a pH-sensitive indicator. The acid n u m ber (AN) is reported in units of milligrams of KOH per g r a m
of sample (mg/g).
Note 4: The quenching oil supplier will provide a maxim u m TAN value for the quenching oil being used. In the

Quenchants

Water Content (Test Methods D 95, D 1744, D 4007)TYie


presence of water in a quench oil, which may be present due
to condensation or a leaking heat exchanger, presents a potentially serious problem. Water concentrations as low as
0.1% may cause the bath to foam during the quenching process, greatly increasing the risk of fire. Overflowing oil from
the foaming bath may result in a more serious fire than if the
flames were contained by the bath, as the oil may contact
nearby furnaces or other ignition sources. If a sufficient
amount of water accumulates in a hot bath, an explosion
caused by steam generation m a y result [53].
Note 5: The problem of water contamination in the quench
bath, with respect to foaming is illustrated in Fig. 38 where it
is shown that 1 mL of water becomes 1700 mL of vapor when
evaporated (near instantaneously).
Note 5: The amount of foaming that does occur is often
dependent on the degree of agitation. Some baths may be
agitated to the point where the quenching oil is ncEirly
splashing on the floor. In such baths, the water vapor is
released even faster causing a greater potential foEiming
problem.
The presence of water in a quench oil may also produce
variable cooling properties depending o n the nature a n d
amounts of cooling rate-accelerating additives present in the
oil. The magnitude and direction of these effects depend on
the particular quench oil and the amount of water present in
the oil. Water contamination may also result in staining of
the part being quenched, uneven hardness, and soft spots.

CHAPTER

22: NON-LUBRICATING

PROCESS

FLUIDS:

STEEL

QUENCHING

TECHNOLOGY

611

(b)
FIG. 34Illustration of commercially available quenchant agitation systems: (A) Tensi agitation system, (B) Drayton agitation
system.

FIG. 35The flow strings illustrate that the flow in the


quench zone is without bubbles or twist. A. 0.25 m/s and B is
0.6 m/s.

A quantitative test for water contamination involves titration of the oil with Karl Fisher chemical reagent to an electrometric endpoint (Test Method D 1744). This test is recommended for water levels of 50-1000 p p m (less than 0.1%).
Higher levels of water contamination may be quantified by
distillation (Test Method D 95) or centrifugation of the sample and measurement of the volume of separated water according to Test Method D 4007.
Note 6: A c o m m o n qualitative field test for water contamination is the so-called "crackle test," which is conducted
by heating a sample of the quenching oil and listening for
an audible crackling sound [77]. If the oil is contaminated
with water, a crackling sound will be heard before the
quenching oil has reached its smoke-point.
Carbon Residue (Test Method D189)One of the greatest problems encountered when using a quenching oil is the formation
and accumulation of sludge. Although the various analyses
procedures including viscosity, neutralization number, and
saponification number may indicate that a quench oil is adequate for continued use, the amount of sludge build-up in the
tank may demand that the system be drained and cleEtned.
Clccining and sludge disposal cire growing problems for the

612

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

heat treating industry. Therefore, determination of the sludgeforming potential of a quench oil prior to use is important.
One method of quantifying sludge-forming potential involves determination of the Conradson carbon residue (Test
Method D 189) measures the polymeric material remaining
in the oil after heating to elevated temperatures in the absence of sufficient oxygen to bum off all of the organic com-

pounds present. The Conradson carbon residue is determined by placing a weighed sample in an iron crucible. The
crucible is heated with a Meeker-type gas burner to a sufficiently high temperature to evaporate and bum the oil. The
sample is forther heated until the bottom and sides of the
crucible are cherry red and is held at this temperature for 30
min. The crucible is then cooled and weighed. The amount of

PLAN VIEW
FIG. 36Recommended probe placement in the Drayton centrifugal
pump apparatus shown in Fig. 34b (all dimensions are in mm).

CHAPTER 22: NON-LUBRICATING

PROCESS FLUIDS: STEEL QUENCHING

TECHNOLOGY

613

ou
c

<D

jQ

<

1600

1700

1800

Wave number, cm - ^
FIG. 37Infra-red spectral identification of oxidation of a used quenching oil.

waterquantity
FIG. 38Illustration of the volumetric expansion of
1 mL of liquid water to 1700 mL of water vapor.

tar remaining in the crucible relative to the original amount


of the oil defines the Conradson carbon residue value.
Note 7: Test Method D 189 may be affected by some additives used to formulate quenching oils.
Note 8: In some heat treating operations, steel is austenitized in air, which causes the increased formation of metal

oxide scale, which will act as a contaminant in the oil. If


this occurs, the Conradson carbon residue number may be
abnormally high and misleading.
Precipitation Number (Test Method D 91)Sludge formation
in a quenching oil is caused by oxidation of various components, leading to pol3THerization and cross linking reactions.
These cross linked and polymerized by-products are sufficiently high in molecular weight to cause them to be insoluble in the oil. Other sources that contribute to sludge are dirt,
carbon formation, and soot from the use of a furnace atmosphere with a high carbon potential.
Sludge can plug filters and foul heat-exchanger surfaces.
The loss of heat-exchanger efficiency may result in overheating of the quenchant and possibly a fire [83]. Increasing
sludge formation often indicates increasing oxidation of the
oil. In addition, sludge may adsorb on a part, causing nonuniform heat transfer during the quenching process.
It is important to maintain particulate contamination to <
1 micron to optimize quenching performance [84]. Precipitation numbers as low as 0.2% may produce staining of normally bright surfaces [46]. However, staining is more commonly observed with precipitation numbers of > 0.5%.
Note 9: These sludge levels correspond to acid numbers of
> 0.5 mg KOH/g by Test Method D 974.
Sludge formation may be accompanied by increased
volatile oxidation by-product formation that may cause a simultaneous increase in fire potential. The viscosity of a
quench bath also changes with the formation of sludge, affecting both heat transfer and quench severity. The amount

614

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

of sludge can be quantified by adding n a p h t h a solvent to the


oil sample a n d determining the volume of precipitate
(sludge) after centrifuging (Test Method D 91).
Ash Content (Test Method D 482)^Although mineral oil basestocks possess very low ash values, many formulated quench
oils contain metallic components that contribute to ash. If
the ash content in a bath filled with a formulated quenching
oil is decreasing, it is likely that an ash-containing additive is
being removed by drag-out or some other process. If the ash
content is increasing, the additive is either accumulating in
the bath or metallic contamination is increasing, perhaps in
the form of scale accumulation. Ash contents are determined
by Test Method D 482, which involves heating a quenching
oil in a muffle furnace at 775C (1425F) under conditions
that b u m off organic compounds but leave metallic species
such as metal oxides or hydroxides.
Quenching

Properties

of Oil

Magnetic Quenchometer Method (Test Method D 3520)Cooling rates produced by quenching oils are often classified on
the basis of Test Method D 3520, the magnetic quenchometer
test illustrated in Fig. 28 [46]. Table 8 provides a summary for
quench oil classification by magnetic quenchometer times
[46]. Although this is a widely used test, the quenchometer
times do not relate to metallurgical properties. This is because only a single cooling time is determined; therefore,
there is insufficient information to indicate the actual temperature-time cooling pathway that is required to determine
if a specific steel may be successfully hardened. This is illustrated in Fig. 39 [46] Therefore, this test is of limited value,
with the possible exception as a quench oil classification test.
Guisbert and Moore conducted an extensive study in an at-

tempt to identify some method of correlating a portion of a


cooling curve with GM Quenchometer times [69,70]. The results of this work showed that although some correlations
were obtained, they were not particularly good. Bates and
Totten have also been unable to find a correlation [84].
Cooling Curve Analysis (Test Method D6200 and ISO 9950)
The most c o m m o n method in use throughout the world to
evaluate the cooling properties of a quenching oil is cooling
curve analysis. Cooling curve analysis provides a cooling time
versus temperature pathway, which is directly proportional
to physical properties such as hardness, obtainable u p o n
quenching of metal. The results obtained by this test may be
used as a guide in heat treating oil selection or comparison of
quench severities of different heat treating oils, new or used.
Cooling curve analysis of a quenching oil according to Test
Method D 6200 and ISO 9950 is conducted by placing the
probe assembly illustrated in Fig. 19. into a furnace and heating to 850C (1562F). The heated probe is then immersed in
a 2000 mL volume of the quenching oil, typically at 40C, or
other preferred use temperature. Lower quenchant volumes,
as low as 700 mL, have been used for compeirative analysis.
The t e m p e r a t u r e inside the probe assembly and cooling
times are recorded at selected time intervals to establish a
cooling temperature versus time curve. From the temperature-time curve, the cooling rate is derived.
A series of cooling rate curve comparisons illustrating the effect of oil oxidation on a conventional quench oil and an accelerated quenching oil are illustrated in Figs. 40A and 40B, respectively. The effect of water contamination on a conventional
quenching oil and an accelerated quenching oil are illustrated
in Figs. 41A and 41B, respectively. The maximum cooling rate
will shift in proportion to the water content of the oil.

The GM Quenchometer time is the


time required (f- f ) to cool
" nicicei tiail from 885-354 Xi

Time (Sec.)
FIG. 39Illustration of the Inability of a single cooling time value to successfully predict the outcome of a steel hardening process where a cooling
temperature-time curve is required.

CHAPTER 22: NON-LUBRICATING PROCESS FLUIDS: STEEL QUENCHING TECHNOLOGY 615


SOO

4months'
oxidation

Smonttu'
oxidation '

L..I...I
i

ANawel
BAftarSnwntha
CMarSmonttia
PAttarOmortha

I i

SSSSSS
^^5tsp--B

amonths'
oxidation

_...4....f...f..
1 momh's
oxidation

^^.^f^^Z^^^^^
^"-""'''''^

No ox'tdatton*
Rr^

1 i i
\

Oiddation Of I ,
quendiing oii[ j
40

.
80

60

j
100

L.

Cbolbio curvM datanninad It


balhtompeisbirBof 4orc

4-1

120

20

.J

40

eo

80

100

CoollnoiataCcya)

(b)

140

Coolingrate(C/s)

(a)

FIG. 40Illustration of tlie effect of oil oxidation on tfie cooling rate curve for (A) a conventional quenching oil and (B) an
accelerated quencliing oil.

Accelerated-speed oil

' 1 " -

...|...j....

No contamination \
0.01%

water {
2%

No water
0.5% water
1 % water
water

0.05% water
0.10% water

i 0.20% water -;

J
40

(a)

60

80

^ I
100

i
120

i
140

Cooling rate (^C/s)

Cooling rate (C/s)

FIG. 41Illustration of the effect of water contamination on the cooling rate curve for (A) a conventional quenching oil and
(B) an accelerated quenching oil.

(b)

616

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Performance-Related Physical and Chemical


Properties-Polymer Quenchants (ASTM D 6666)
AppearanceContamination of aqueous polymer quenchants
by such fluids as hydrauhc or quench oils may result in a
nonuniform quench with thermal gradients sufficient to
cause cracking or increased distortion, or possible staining,
of the metal being quenched. The simplest (and an excellent)
test is to examine the visual appearance of an aqueous polymer quenchant in a clear glass container such as a bottle [86].
However, if the oil readily separates from the aqueous polymer quenchant solution, it may often be removed by skimming. On the other hand, oil may form a milky-white emulsion that is not readily reclaimed by heat treaters.
Other problems that are easy to visually identify include
carbon and sludge contamination, which often results in
cracking problems. Metal scale contamination is often identifiable by its magnetic properties by placing a magnet on the
outside of the bottle next to the scale and determining if the
scale exhibits any attraction for the magnet. Carbon, sludge,
and scale may be removed from the quenchant by filtration
or centrifugation.

1.341

10.0
15.0
QUENCHANT CONCENTRATION (%)

FIG. 42Illustration of the linear relationship between refractive index and concentration of an aqueous solution of a
polymer quenchant.

Refractive Index, (Test Method 1747)One of the most common methods of monitoring the concentration of aqueous
polymer quenchants formulated using poly(alkylene glycol)
copolymers is refractive index. As Fig. 42 [86] shows, there is
a linear relationship between quenchant concentration and
refractive index. The refractive index of the quenchant solution is determined using an Abb6 refractometer (Test Method
1747) equipped with a constant temperature bath. Although
the refractive index could potentially be used at any temperature with the control limits of the constant temperature
bath, typically either 40C or 100F is selected.
Although refractive index is a relatively simple and rapid
method for determination of polymer quenchant concentration, it is not sensitive to low levels of polymer degradation and it is often significantly affected by solution
contamination.
Note 10: Refractive index is typically unsuitable for aqueous polymer quenchants formulated with polymers with
molecular weights greater than 50000-60 000 because: 1)
The total amount of water-soluble polymer in solution is
not sufficiently different from the water diluent to provide
adequate sensitivity and 2) because the total concentration
is relatively low, small changes in polymer concentration
may result even from normal use, which imparts significant process effects. However, the corresponding variation
in refractive index may not be detectable.
Note 11: Although it is most desirable to use an Abbe refractometer because of its sensitivity, this is only practical
in a laboratory environment. In the heat treating industry,
for tankside monitoring and control, a temperature-compensated handheld refractometer similar to the one illustrated in Fig. 43a and b should be used. The hand-held refractometer is self-compensated for temperatures of 60
and 100F. Although there are various models available,
the most common models provide refractive index readings in Brix degrees over a 0-30 range. Typically, the
smallest scale that can be read directly is in divisions of
0.2 as shown in Fig. 44. A concentration-refractive index
curve obtained by a hand-held refractometer is shown in
Fig. 45 [86].

FIG. 43Typical hand-held refractometer; (A) application of quenchant solution to refractometer, (B) observation
of refractive index.

CHAPTER

22: NON-LUBRICATING

PROCESS

Viscosity, (Test Method D 445)^Aqueous polymer quenchant


viscosity depends on the quenchant concentration and temperature, as shown in Fig. 46 [86]. It is readily determined using a Cannon-Fenske tube (see Fig. 47), stopwatch, and constant temperature bath as described in Test Method D 445.
N o t e 12: Although viscosity of most water-soluble polymers is significantly affected by contaminants, particuleirly
ionic salts, the viscosity of quenchants formulated from
poly(alkylene glycol)s are not particularly affected by the
presence of contaminants. However, solution viscosity is
strongly affected by degradation.

DEGREES
BRIX
T/C
FIG. 44Illustration of the Brix refractive index scale used
for a hand-held refractometer.

3MU

FLUIDS:

STEEL

QUENCHING

TECHNOLOGY

Comparison of Concentration by Refractive Index and Viscosity^A useful procedure for monitoring variations in aqueous
polymer quenchants, particularly poly(alkylene glycol) quenchants, is to compare the difference (delta) in the quenchant
concentration values obtained by refractive index (C) and
viscosity {Cv) [87].
^ =

CR-CV

Differences in A of greater t h a n 6-8 are significant and the


source of this difference (contamination or degradation),
should be determined. Procedures for doing this follow.
Water Content (Test Methods D 95 and D
1744)Aqueous
polymer quenchants are composed of water, a water soluble
polymer, and a n additive package to provide corrosion inhibition, foam control, etc. Therefore, determination of water
content is necessary to establish the concentration of the
quenchant in a way that is relatively insensitive to poljTner
degradation.
Water content may be determined by Karl Fisher analysis
(Test Method ASTM D 1744). The advantage of Karl Fisher
analysis is that it is a direct m e a s u r e of water content,
whereas refractive index and viscosity are both indirect measurements that are substantially affected by either contamination (refractive index) or degradation (viscosity).
pH Determination, (Test Method E 70)The performance of
an aqueous polymer quench bath may be criticeJly dependent
on its pH. The p H of a quenchant solution may be determined
by Test Method E 70. There are many excellent commercially
available sources of p H meters and glass electrodes. The
choice of the instrument will be primarily affected by the desired precision of measurement. Electrodes used for pH measurement are designed for specific pH ranges and temperature; therefore the solution p H and temperature shall be
considered when the elecrodes are selected for use.

MU

'^.."
'S
^%m-

<J

om

109 zw
,, ^ ,^ .

i-'.

3.to

im

617

, - { . > :

Sio

evoo jm

-i

s.m Mm mm

, ,^ ,:fihifltaettelnfelt'|''Bpix):

FIG. 45Typical refractive index (Degrees Brix) versus quenchant concentration


relationship.

618 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

250
-

<0

a
z
o
o
u

200
(75 F, 23.9C)yC^

fsS'F,
29.4 C)

(0 150

s;ff

(6 }F, 18.3

oyy

UJ

(100 F,37.8C)

>

100
3 90

80

>:
^

70

60

50

-.
-

>
40

30
10

15

20

25

30

35

40

45

QUENCHANT CONCENTRATION (%)


FIG. 46Ouenchant viscosity as a function of concentration and temperature for an
aqueous solution of a poiymer quenchant.

FIG. 47CannonFenslce viscometer


tube.

For example, solution pH values of >10 for quenchants


used in aluminum heat treating applications may be disastrous in view of potential caustic corrosion processes that
may occur. The relatively simple determination of pH of an
aqueous polymer quenchant may provide significant insight
into potential polymer degradation, corrosion inhibitor depletion, and contamination.

Polymer degradation is t5^ically accompanied by the formation of acidic by-products, which will decrease pH. Some
polymer quenchants, particularly when containing sodium
nitrite as a corrosion inhibitor, cannot be used below pH 7.0
without increasing the polymer degradation rate.
Some aqueous polymer quenchants contain amine or
amine/fatty acid mixtures as corrosion inhibitors. If substantial decrease in the concentration of these inhibitors occurs,
a decrease in pH will result. Thus, pH determination may be
a useful indicator of corrosion protection of some quenchants.
In some cases, the quench bath may be contaminated by
ammonia, which is used in some heat treatment processes.
Clearly, pH is an excellent indicator of potential ammonia
contamination. Quench baths may be contaminated by various hydraulic and metalworking fluids, which may significantly affect the resulting pH of the aqueous polymer quenchant.
Conductance, Test Method D 2624One of the most common
and most deleterious contaminants of an aqueous polymer
quenchant is hard metal ions (Ca"^^, Mg"^^, Mn"^^, and Fe"^^).
The presence of hard metal ions will lead to corresponding
increases in cooling rates. To extend the lifetime of the quenchant, it is often recommended that either distilled or deionized water be used for initial polymer quenchant dilution or

CHAPTER 22: NON-LUBRICATING

PROCESS FLUIDS: STEEL QUENCHING

for make-up water, which must be added periodically due to


normal evaporation processes. Typically, it is recommended
that the conductivity of the water used for this purpose not
exceed 15 ^iS/cm [86].
Note 13: ASTM D 653 defines "conductance (specific)" as:
"a measure of the ability of the water to conduct an electric
current at 77F (25C). It is related to the total concentration of ionizable solids in the water. It is inversely proportional to electrical resistance." ASTM D 616 defines "conductivity" as: "the property of a substance's (in this case
water and dissolved ions) ability to transmit electricity.
The inverse of resistivity. Measured by a conductivity meter, and described in microsiemens/cm or micromhos/cm,
/LtS/cm."
Another source of ionic contamination that will result in
cooling rate increases is salts from molten salt furnaces
(baths), which may contaminate an aqueous polymer by
dragout on the part upon removal from the salt pot and subsequent immersion in the aqueous polymer quenchant. Increased ionic contamination may also result if excessive corrosion inhibitor is added to the quench system.
Since metal ions may result in increased cooling rates,
which may potentially result in cracking of the metal due to
increased thermal and transformational stresses, it is important to monitor the variation in the ionic content of an aqueous polymer quenchant. This is easily done because increasing ionic content results in increasing electrical conductance.
Any equipment capable of giving a conductivity reading almost instantaneously with the application of voltage across
the two electrodes comprising the conductivity cell as de-

FIG. 48Commercially available portable conductivity meter.

TECHNOLOGY

619

Thermal Separation Process


For PAG Polymer Quenchant

INmAL 20% SOLUTION


(WITH AGITATION)

SOtOTION IMMEDIATELY
AFTER SEPARATION
(WITH AGITATION)

REDISSOLUTION OF
SOLUTION AFTER
LAYER FORMATION

SOLUTION AFTER LAYER


FORMATION (NO AGITATION)
(LOWER LAYER IS
CONCENTRATED POLYMER)

FIG. 49Illustration of the reversible thermal separation process of an aqueous solution of a polyalkylene glycol quenchant.

scribed in Test Method D 2624 is acceptable. A typical


portable conductivity meter is illustrated in Fig. 48. The procedure followed is the same as that described in Test Method
D 2624 except that the aqueous polymer quenchant being analyzed is used.
Separation Temperature (Cloud Point)Some aqueous polymer quenchants exhibit a characteristic temperature above
which the water soluble polymer becomes mostly insoluble
in the aqueous medium [87]. This reversible process, which
is shown in Fig. 49, [87] is sometimes called the separation
temperature or cloud point.
The separation temperature is determined by heating a solution of the aqueous polymer quenchant and noting the temperature where the fluid becomes sufficiently cloudy that the
thermometer is no longer visible. Although some salts may
affect the separation temperature, oxidative degradation of
the polymer is the most common problem. Degradation that
causes the separation temperature to rise 2-4C (4-7F) over
the lifetime of the quenchant bath is not unusual. A larger increase or sudden change in separation temperature is cause
for concern.
Corrosion InhibitorBecause poljrmer quenchants are water
based, they must be formulated with a corrosion inhibitor(s).
Corrosion inhibitors protect the tank, fixtures, and parts being quenched by either surface passivation or protective film
formation. Depletion of the inhibitor during use is to be expected, and periodic replenishment of the corrosion inhibitor
is required to maintain adequate protection of the quenching
bath, parts being heat treated, and fixtures.
Many pol5TTier quenchants use sodium nitrite as the corrosion inhibitor. The concentration of sodium nitrite may be

620

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

determined according to Test Method D 3867, a cadmium reduction method that may be performed manually or by an
a u t o m a t e d procedure. Alternatively, nitrite anion m a y be
quantitatively determined by ion chromatography according
to Test Method D 4327.
Note 14: The concentration of nitrite in a quenchant may
also be determined by a relatively simple color test using a
commercially available test kit. A tablet, furnished with the
test kit, is dissolved in a specific volume of the solution,
and the resulting color of the quenchant solution is compared to a standard color chart of known concentrations of
sodium nitrite, as shown in Fig. 50.
Although sodium nitrite is a commonly used corrosion inhibitor used in the formulation of aqueous polymer quenchants, there is an increasing trend in the marketplace for socalled non-nitrite quenchants. Many of non-nitrite inhibitor
systems are based on various amines or amine-fatty acid
combinations. Due to the specificity of the required analytical procedures for determination of each non-nitrite inhibitor package that may be used, it is most common to submit samples periodically to the quenchant manufacturer for
analysis.
Foam Testing, Test Methods D 892, D 3519, and D 3601A
commonly encountered problem in production quench tanks
is excessive foaming. Excessive foaming is bad because it
may potentially lead to cracking and/or increased distortion.
Relative foaming propensity for one fresh quenchant compEired to another or a used quencheint compared to a fresh
quenchant or two used quenchant samples may be readily determined by various tests including Test Methods D 892 (using a gas diffusion tube), D 3519 (blender test), or D 3601
(bottle test).
Polymer Molecular Weight Analysis, Test Method D 5296^As a
test for pol5rmer degradation, gel permeation chromatogra-

200

150;

z
LxJ
I
Z 100
SEC trace for a polymer
from an unused aqueous
polymer quenchant solution
y
50H
CO

40

50

55

60

65

70

RETENTION TIME (sec.)


FIG. 51Size-exclusion chromatography data for a fresh and
severely degraded poly(alkylene glycol) quenchant.

phy (GPC), also k n o w n as size exclusion chromatography


(SEC), provides the most unambiguous results. This chromatography technique, described in Test Method D 5296,
separates poljrmers on the basis of their molecular size.
Note 15: Test Method D 5296 may be modified for use with
various nonionic polymers such as those based on
poly(alkylene glycol). However, many water-soluble polymers are not readily soluble in solvents other than water.
In this case, a n a q u e o u s GPC p r o c e d u r e , a procedure
where water is used as the solvent for GPC analysis, will
need to be developed.
Illustrative chromatograms for a fresh undegraded polymer from a polymer quenchant and a badlydegraded polymer
are superimposed in Fig. 51 [86].
Note 16: Another method of pol5rmer degradation analysis
is to compare, by superimposition, the GPC chromatogram
for the fresh and used polymer for the specific quenchant
of interest as shown in Fig. 51 [86]. The total area under the
pecik for the degraded polymer is normeJized to that of the
area u n d e r the fresh polymer peak. The resulting "area
shift" of the broader-peaked degraded polymer curve is a
quantitative measure of degradation. Although the area
shifts may vary widely, typically values greater than 10%
are usually cause for concern.
Biological

FIG. 50Portable color test to determine nitrite concentration.

SEC trace for a polymer


from a used aqueous
polymer quenchant solution

Stability

Fluid Biodeterioration ProcessesFluid biodeterioration involves the reaction of water with a substrate, such as the water-soluble polymer used to formulate a n aqueous polymer
quenchant, in the presence of b a c t e r i a or fungi to yield
biomass [89]. If this degradation process is not inhibited,
enormous queintities of biomass may be present in the system
in the form of sludge or microbial scum, which are composed
of dead cells, gelatinous slimes, and fungal threads. It has
been reported that a bacterial cell may double in size cind divide into two new cells every 15 min until a limiting condition
is encountered [89,90].

CHAPTER

22: NON-LUBRICATING

PROCESS

In addition to solid by-products, obnoxious gases may be


formed from the biodeterioration of certain additives acting
as microbial nutrients, such as nitrites and nitrates, which
are converted to ammonia and sulfur or sulfate, which is converted to hydrogen sulfide (H2S), which exhibits a characteristic "rotten egg" odor [91].
Biodeterioration processes that occur in the presence of air
(oxygen) are enhanced by system agitation and are designated as "aerobic" processes. However, biodeterioration processes may also occur without air (oxygen) being present.
These are called "anaerobic" processes that are inhibited by
system agitation. Most aqueous polymer q u e n c h a n t s undergo biodeterioration by an anaerobic process.
Biodeterioration Monitoring Procedures (Test Methods D 3946,
E 686, and E 979)There are four strategies for monitoring
microbial contamination: 1. gross, 2. physical, 3. chemical,
and 4. microbiological. Gross detection procedures include
visucd observation of slimes or detection of foul odors. Physical detection procedures include the observation of haze and
visible, nonmetsdlic particulate matter in the fluid. Chemical
tests that are often used include pH. Sudden decreases in p H
indicate a strong potential for microbial contamination [91].
The fourth procedure is to conduct a microbial test. One
test is to directly observe the microbial species on a glass
slide under a microscope [91]. Currently, there are three standard bench test procedures that m a y be used for monitoring
resistance to microbial growth: D 3946, E 686, and E 979. Alternatively, a commercial dip-slide test that is coated with a
microbial growth media is often used in the heat treat shop.
This is CcJled a "viable titer method," in which the population
densities of the microbial species are estimated after incubation for 24-72 h as illustrated in Fig. 52. Viable titer proce-

.':

*/

l'wf\.

STEEL

QUENCHING

TECHNOLOGY

M%

io>

FIG. 52Dip-slide test for bacteria and fungi detection.

800

U
~

600

8
3
? 400
a.

"V.

V\

,
\

5%

--

\ \
:\\

p
v. V

1 ''

3
2 400

2(

. ' ^ ,^
^<.

0)

a.
E

\ ^ -.^

^^.i

^^Zy^

,15%

10%

15%]

'^'
''

' - '

, -

5%

<-'

10%

15

Time(s)

621

dures m a y not detect microbial species that do not form


colonies and, therefore, may not correlate with biodeterioration processes.
Cooling Curve AnalysisPolymer Quenchants (Test Methods
D 6482 and D 6549)Cooling curve analysis provides a cooling time versus temperature pathway that is directly proportional to physical properties, such as hardness obtainable
upon quenching of metal. Aqueous polymer quenchants are
typically used with agitation and it is r e c o m m e n d e d that
cooling curve analysis of this class of quenchants be performed according to Test Method D 6482 (Tensi Method, see
agitation device s h o w n in Fig. 34A) or D 6549 (Drayton
Method, see agitation device shown in Fig. 34B). The results
obtained by these tests may be used as a guide in quenchant
selection or compairison of different quenchants or dilutions
of the same quenchant, whether new or used.
Cooling curve analysis of an aqueous polymer quenchant
by Test Methods D 6482 or D 6549 is conducted by placing
the probe assembly illustrated in Fig. 19 into a furnace a n d
heating to 850C (1562F). The heated p r o b e is then immersed into the agitated quenchant solution at a known agitation rate and desired temperature. The temperature inside
the probe assembly and cooling times are recorded at selected time intervals to establish a cooling temperature versus time curve.
A series of cooling rate curve compeirisons illustrating the
effect of aqueous polymer quenchant concentration and bath
temperature is illustrated in Figs. 53 and 54, respectively. The
effect of agitation is illustrated in Fig. 55. Cooling curve comparison of a fresh and severely degraded polymer quenchant
(compared to water) is shown in Fig. 56.
Advanced Cooling Curve Analysis^All of the cooling curve
analysis methods described thus far are essentially laboratory quenchant cinalysis procedure. Although they are invaluable for this use, they are of relatively limited direct value to
the heat treater, who needs to know if he can through-heirden
a part being produced in production and if he will encounter
distortion or even cracking. Therefore, there are various efforts underway at the present time to advance cooling curve
anedysis methodology to permit modeling smd simulation of
the production quenching process. In this section, one cool-

Determtnation of total alerob c bacteria

FLUIDS:

SO

100

150

200

Cooling Rate(C/s)

FIG. 53Illustration of the effect of quenchant concentration on cooling curve and


cooling rate curve performance for an aqueous polyalkylene glycol quenchant at
SOX and 0.5 m/s.

622 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


1
i ^

"^

~YN

o
o

- ^ 600

a>
a.
E
fl 200

800

\\ \ \ 1
, \ \ V40C
50C
', \
30OcX\ N \
1 /

\^^^^.
*"*-<^

jy
-

^'

---'

1-

i:

0
10

15

.^^^

50C

40C\ / ^;.--

0
S

--.

'^^ . ..=--^.
*-st,-

'

/
/

_^
100

20

150

200

Cooling Rate(C/s)

Time (s)

FIG. 54Illustration of tlie effect of bath temperature on cooling curve and cooling rate curve performance of a 15% aqueous solution of a polyalkylene glycol quenchant.
-
800 i

800 > v

\^

o
a>

O
S_

.0 m/s
( .6 m/ .}\Lo.2ni/5

3
"2 400
a>
a
E

"-1

"

0.4 m/

1 m/i;'i"
0.6

600

^^^

a2m/s

. ^

>Yr
[j I

400

(1.4 m/ "'^

a.
E

%^;-

|2

k=

'. '^

200

10

15

50

20

100

150

200

Cooling Rate (C/s)

Time (s)

FIG. 55liiustration of the effect of agitation on cooling curve and cooling rate
curve performance for a polymer quenchant.

800GPC Trace Of Fresh and


Used Polymer Quenchant

^600-

UJ
K
.3

1400
s
tu

200
-WATER

- USED POLYMER QUENCHANT


- FRESH POLYMER QUENCHANT
I I I I I I I I I I I I 1 I I I I I r I I r I I I I I I I I I I IT

20

40

60
TIME (Sec)

r - r I I I IT-T

80

> I I I I I I I

100

FIG. 56liiustration of cooling curve performance of a severely degraded aqueous polymer quenchant
compared to water and a fresh solution at the same concentration, bath temperature, and agitation.

CHAPTER

22: NON-LUBRICATING

PROCESS

ing curve analysis methodology that has been successfully


used in the heat treating shop will be described. In addition
to illustrating the overall utility of modeling and simulation
of production quenching conditions, this example also illustrated advanced techniques for investigating quenching behavior.
Temperature

Gradient

Quenchant

Analysis

BackgroundLiscic
designed a system for practical measurement, recording, and evaluation of quenching (cooling)
intensity u n d e r w o r k s h o p conditions, which expresses
quenching intensity by a continuous change in relevant therm o d j n a m i c functions during the entire quenching process.
This approach should be contrasted with the Grossmann Hfactor concept, which expresses quenching intensity with a
single value and which was shown earlier to be of limited
value in quantitatively represented quench severity when agitation is used.
All of the different cooling curve analysis methods discussed thus far utilize relatively small, usually 12.5 m m or 0.5
in diameter, round bar probes with a single thermocouple
placed at the geometric center. Such probes, while excellent
for quality control purposes, are of limited value for use under workshop conditions. The reasons include:
Because of its relatively small mass and low heat capacity,
these small probes will cool in about 10-30 s whereas an
actual workpiece of 50 m m (2.0 in) diameter will require
500-600 s to cool below 200C (392F) in the center of the
workpiece when quenched into an unagitated quench oil.
Therefore, to adequately model actual quench processes
under production conditions, a probe of similar mass and
dimensions is necessary.
The actual heat transfer coefficient during quenching of actual production parts may be simulated using a small cylindrical probe. However, the heat transfer coefficient during
nucleate boiling is heavily dependent on bar diameter [92].
The magnitude of this dependence increases with decreasing bar diameter below 50 m m (2.0 in). The dependence is
less pronounced for bar diameters greater than 50 m m (2.0
in). Therefore, for the same quenching conditions, the heat
transfer coefficient on the surface of a small diameter cylinder is quite different than that expected on the surface of
most production parts with diameters > 5 0 m m (2.0 in).
Important criteria for a cooling curve analysis system to be
utilized to model quench processes under workshop conditions should be applicable to: 1) a wide variety of quenchant
media including: water, brine, aqueous polymer solutions,
salt baths, quench oils, fluidized beds, and gas quenchants; 2)
a wide variety of quenching conditions including: different
bath temperatures, agitation rates, and fluid pressures; and
3) all quenching techniques including: direct i m m e r s i o n
quenching, interrupted quenching, martempering, austempering, and spray quenching.
The method to be reported here provides for recording of
thermodynamic functions during each test to enable the user
to ancdyze the peirticular quenching process of interest and
quenching conditions, to evaluate quenching intensity, and to
compare it with previously performed tests in other facilities
under different conditions. To do this, the user will establish
a database of quenching intensities of different systems
within the production facility. This database will provide the
user with input data for subsequent computer simulation of

FLUIDS:

STEEL

QUENCHING

TECHNOLOGY

623

the quenching process to determine optimal quenchant and


quenching conditions for every part being produced.
In addition, for optimal simulation, it is important that the
m e a s u r e m e n t m e t h o d be sufficiently sensitive to reflect
changes in each of the important quenching peirameters (specific character of the quenchant, quenchant bath temperature, in addition to mode and degree of agitation). This criterion is addressed by recording the temperature-time history
(cooling curve) at particular points within the probe used for
analysis. This requires the measurement of transient temperatures within a solid body when high thermal gradients are
involved, which requires that the following inherent effects
be considered:
Damping EffectChanges
in surface t e m p e r a t u r e are
damped in magnitude when sensed inside the body compared to their magnitude at the surface.
Lagging EffectChanges
in the surface temperature are
sensed within a finite time after they occur at the surface.
The greater the distance of the temperature measurement
point from the surface, the greater the damping and lagging effects.
Response TimeWhen working with thermocouples, it is
important to consider another effect that is inherent with
every thermocouple-response time, which is the time necessary to reach 63.2% of its total signal output when the
thermal junction is subjected to a step change in temperature [93]. The time constant of a sheathed, grounded thermocouple of 1.5 m m (0.062 in) outer diameter is 1.5 s. To
reach 99% of its full signal output when subjected to a step
change in temperature, the time constant must be multiplied by 5, which makes a 7.5 s delay. Thermocouples with
an even greater diameter will exhibit an even greater time
constant and delay in response time.
Theoretical PrinciplesBecause of all of the above described
requirements, effects, and limitations, instead of recording
only one cooling curve at the center of a small cylindrical test
probe (as in laboratory tests) the heat flux density at the surface of the quench probe has been selected as the main feature in measuring, recording, and eveduating quenching intensity. This is because changes of the h e a t flux density
during the quenching process best represent the dynamics of
heat extraction.
The method itself, known in the literature as the Temperature Gradient Method, is based on the known physical rule
that heat flux at the surface of a body is directly proportional
to the temperature gradient at the surface multiplied by the
thermal conductivity of the material of the body being
cooled:
q = \

dT
dx

Where: q is the heat flux density (W/m^), i.e., the quantity


of heat transferred through a surface unit per unit time, A is
thermal conductivity of the body material (W/mK), and dT/dx
is the temperature gradient inside the body at the body surface, perpendicular to it (K/m).
HardwareThe essential feature of the method being described here is the LISCIC/NANMAC quench probe." It is
"* The Llscic-Nanmac probe is manufactured by the NANMAC Corporation, Framingham, MA.

624

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

constructed from AISI Type 304 stainless steel, which is 50


mm (2.0 in) diameter X 200 mm ( 4.0 in ) length, instrumented with three thermocouples placed at the half-length
cross section as shown in Fig. 57. One thermocouple measures the actual surface temperature of the probe {T), another measures the temperature at a point 1.5 mm (0.06
in.) below the surface (TO, and the third one measures the
temperature at the center of the cross section. The thermocouples inside the body are standard sheath-tjrpe thermocouples. The thermocouple at the surface is of special design (U.S. Patent 2,829185), which allows continuous
measurement of the true surface temperature of a solid
body without any damping or lagging effects, in real time,
because of its extremely fast response time of about 10 /AS

/ixm (0.0036 in), is placed between a split-tapered insert and


pressed into the thermowell (body). The thermal junction is
formed by grinding and polishing across the sensing tip.
The mica insulation between the two dissimilar ribbons is
so thin that metallic whiskers of one ribbon element
bridges across the mica to the other ribbon element, and
makes hundreds of microscopic friction welded junctions,
which are parallel to one another, thus forming one composite measuring junction.
The microscopic burrs of the metal from the thermowell
(housing) bridge the thin layers of mica, thus electrically
grounding the thermal junction to the thermowell at the
sensing tip. The metal of the thermowell becomes the third
intermediate element, and since the temperature is the same
on both sides of the thermal junction, the EMF produced by
the secondary junctions on both sides of the main thermal
junction cancel each other out, leaving the EMF of the main
thermal junction as the only observed EMF (Law of Intermediate Metals in Thermocouples).
Any subsequent erosion of the surface of the thermowell
(body) simply forms new junctions while removing the old
junctions, hence its name "Self Renewing Thermocouple."
Because of its unique characteristics, this is the best type of
thermal junction to be used for heat transfer calculations because it registers all of the phenomena occurring at the surface in real time.
The temperatures recorded at the surface iT) and at 1.5
mm below the surface of the quench probe (Ti) permit the

(10-5 s)

There are two important requirements for a thermocouple


used for measuring surface temperature:
1. Its thermal junction should be two-dimensional (instead of
the usually encountered three dimensional geometry)
2. It should be flush with the surface
The unique details of the sensing tip of this thermocouple
are as follows. In the vicinity of the hot measuring junction, the round thermocouple wires are flattened into ribbons of about 38 /xm (0.0015 in) thickness. These ribbon elements are electrically insulated from each other and from
the thermowell by sheets of mica insulation of about 5 /xm
(0.0002 in) thickness. This "sandwich" of ribbon elements
and mica insulations, having a total thickness of about 91

Handle(optional
i

(19mmjO.D. stainless tube


j-(3.2mnn)O.D. s t a i n l e
sheotlied thermocouples

|.060"(1.5mm)

Adaptor

NANMAC Surface T

(990.6 mm)

(100.3 mm)

. 7.90"
(200.6 mm)

Thermocouple body

Tapered split pin

Mica insulation

Thermocouple w i r e

FIG. 57The LISCIC/NANMAC quench probe.

fiberglass
insulated leads
# 20 gage X 36."
Standard connector
attached.
(3-required-one
shown for c l a r i t y ) .

CHAPTER

22: NON-LUBRICATING

PROCESS

calculation of the temperature gradient within this surface


layer at each m o m e n t throughout the quenching process. The
role of the center thermocouple (Tc) is to indicate the timing
for heat extration from the core of the probe and to provide a
continuous measurement of the temperature difference between the surface and the core, which is essential for the calculation of thermal stresses.
Specific features of the LISCIC/NANMAC quench probe
are:
1. The size of the probe and its mass ensures sufficient heat
capacity and radially symmetric heat flow in the cross sectioned plane where the thermocouples are located.
2. The probe is constructed from austenitic stainless steel
and does not undergo microstructural change upon heating or quenching, n o r does it evolve or absorb heat because
of microstructural transformations.
3. The surface condition of the probe can be maintained for
each test by polishing the sensing tip of the surface thermocouple before each measurement.
4. Extremely fast response times of the surface thermocouple
(10~^ s), and the absence of any damping or lagging effects
allow any transient temperature at the surface to be measured and recorded exactly and in real time.
5. The heat transfer coefficient at the probe's surface, because of its sufficiently large diameter, may be used in
computer simulation of actual production parts.
W h e n the quenching intensity is to be determined, the
probe is heated to 850C (1562F) in a suitable furnace, then
transferred quickly to the quenching bath and immersed vertically. The probe is connected to a data acquisition system
including a personal computer. The data acquisition card
contains three A/D converters and amplifiers enabling digital
recording of all three thermocouple signal outputs.
SoftwareIn addition to cooling curve data, the cooling
curve analysis p r o g r a m (TGQAS - T e m p e r a t u r e Gradient
Quenching Analysis System) described here permits advanced computational modeling of production quenching
systems. The TGQAS consists of three modules:
1. Module I: zTEMP-GRAD (Temperature Gradient Method)
In each test, three cooling curves are obtained: r for the
surface of the probe, Ti for the point 1.5 m m (0.06 in) below
the surface, and Tc for the center of the probe. TypiccJ cooling temperature-time profiles for each of these points is illustrated in Fig. 58. The temperature gradient between Ti
and Tn is calculated from these cooling curves by multiplying the corresponding data by the temperature-dependent
thermal conductivity, and the heat flux density versus time,
q = fit) (see Fig. 58b) and the heat flux density versus surface temperature, q = f{T) (see Fig. 58c) are calculated.
Calculation of the differences between each thermocouple location versus time, AT f(t), provides the functions
illustrated in Fig. 59d. Calculation of the integral under the
heat flux density curve (which represent the a m o u n t of
heat extracted) from the beginning of immersion until a
predetermined time, provides the functions shown in Fig.
59e. For heat extracted from the probe, the curve designated by "(" (i.e., for the surface layer of 1.5 m m thickness)
is valid. In each point where thermocouples are located,
the cooling rate curves versus surface temperature: dT/dt =
fiT) are calculated as shown in Fig. 59f.

FLUIDS:

STEEL

QUENCHING

TECHNOLOGY

625

Calculated functions, graphically represented in Fig 58


and Fig. 59 permit comparison of the actual quenching intensity among different quenchants, quenching conditions,
and techniques. Based on these thermodynamic functions,
each quenching test m a y be evaluated with respect to:
depth of hardening, (when comparing two quenching processes), thermal stresses, a n d possible superposition of
structural transformation stresses that will occur during a
particular quenching process and delayed quenching, i.e.,
whether continuous or discontinuous cooling rates are occurring (with consequences on hardness distribution on
the cross section after hardening). These thermodynamic
functions also provide the basis for automatic control of
quenching intensity during the quenching process.
2. Module II: HEAT-TRANSF (Calculation of Heat Transfer
Coefficient and Cooling Curves)The function of this module is the calculation of the temperature distribution in the
cross section of round bars. It is based on the numerical
method of control volumes where the heat conduction in
the radial direction is solved as a one-dimensional problem. The software consists of two m a i n subroutines. The
first subroutine utilizes the measured surface temperature
as an input parameter to calculate the temperature distribution over the probe's cross section versus time and the
heat transfer coefficient between the surface and the quenchant versus time and versus the surface temperature as illustrated in Fig. 60a and Fig. (sOb.
The second subroutine utilizes the calculated heat transfer coefficient for a particular quenching test as input parameter, which permits the simulation of quenching cylindrical workpieces of varying diameters u n d e r the
conditions of each quenching test that are stored in the
users database of quenching intensities. Physical properties of the workpiece can be selected for the desired steel
grade. The cooling curve at any point within the cross section can be calculated as illustrated in Fig. 60c along with
corresponding heat transfer coefficient versus time and
versus the surface temperature.
3. Module III: CCT-DIAGR (Prediction of Microstructure and
Hardness after Quenching)This module is used to predict
the microstructure and hardness after quenching of cylindrical workpieces of different diameters. It contains a n
open data file of CCT (Continuous Cooling Transformation) diagrams in which the user may store u p to 60 CCT
diagrams of his own choice. This program enables the user
to superimpose every calculated cooling curve on the CCT
diagram of the desired steel. From the superimposed cooling curves (shown on the CRT monitor during analysis)
the u s e r can select the percentage of microstructural
phases transformed and the hardness value at the selected
point within the cross section after hardening as illustrated in Fig. 61. For a cross section of the selected diameter, cooling curves are calculated at three or five characteristic points (surface, 3/4R, 1/2R, 1/4R and center), using
the HEAT-TRANSF module. The CCT-DIAGR module enables the user to d e t e r m i n e hardness values at these
points, which will permit prediction of the hardness distribution curve.
Note 17: In the case of delayed quenching, where a
discontinuous change of cooling rates occur, the prediction of microstructural transformations and hardness

TCST2*-ncc

TCXTJi .CC

...4.--i-i-;-4
..i.j..j..j..i.4

-f-t"i"i-r-

IDO

2CX1

300

Time t

LOOO
20

Isl

(a)

SO

lOO

^^

i i u r f o c e l e m p e r o t u r e ; Ti t m p e r o l u r e l . S m m b e l o w l h s u r f o c c ;
t e m p e r o i u r e in t h e c e n t e r ot t b e probe

ZOO
Time

300
tsl

lOOO

T = s u r f a c e

f e m p e r o t u r e ; T; t m p e r o t u r e 1.5 mm b e l o w t h e s u r f a c e :
t e m p e r a t u r e in t h e c e n t e r of t h e p r o b e .

TESTzft . n c c
TCXTX-ncc

*.-.4...ii..i.^^

^^..-l-i-M.^^

^---<-t-t1

(b)

300
^oa
Time t IsJ

rc-

tc-n

Zi-r*

TCSTXC.nEC
Tttft.HCC

acoo

"e , ,
1 xooa

1 1 1 1 / 1.
..., I.. 1 ,.. .\
1 ,,,./.,

>*
^

T3
K laoo
_3

1 K.
i- l\
1
1 1 1i \
i

5.

: \

_
"o
(c)

XAJT{

1 ..l^^^^'i

too

aoa

>oo

400

9 6O

00

s=;^\ e oio f1 0 0 0 1.X00


[
TOlo s o o
Tmperolure

Tn

lac

1*01

>oo

xooo xxoo

T r o p r a t u r Tn

jiioo

I'Cl.

FIG. 58Graphical Display from Module 1 (TEMP-GRAD) when quenching the LISCIC/NANIVIAC probe into a 20C mineral oil bath
without agitation (left row, vertically) and a 25% aqueous polyalkylene glycol quenchant solution at 40C bath temperature and 0.8
m/s agitation rate (right row, vertically), (a) Measured and recorded temperature versus time, T = f{t); (b) Calculated heat flux density versus time q = f{t),; and (c) Calculated heat flux density versus surface temperature, q = f(T).

rcxTi.nee

(d)

l-^

>c-l

TE&TZtc .nee

rcsTi.ncc
oo

1 i....|.. .1.1.14-11...
0

i...-.i.-i..U.

70

1 i..4-i-4] j_,.,- '^y

"e**"

1 ::

-:

4-tiliy

-|

I--" -4"lili4i
4- ....... i..i.4.i.ii

-I-j-t'

. I

f-i-t

.^^^^.^^..Ji

*"-]-t-i

, A*o

i il

?,o

5
or-to

: : ;:

rlOO

1 j 1 iiji

i i l l ' Hi

-"J*

A
J

"j jtt'4-t-^i

to . . , . . . _ . t^Ifno

yJTi

= = * 1
i 1

.io

90

so

lOO

>t-'f!

. XOQ

Time I

(e) - .

Ul

>0
II-"

20

Jc-i

rcir.Ec
TcsTt.ncc

>3

ste>o
*

414f-

1 "1

.J

^^..

J..

...|...

\ \ J j . ....;1.....4..._..4

Z 3 . . . . .J.,..-.__ ^,., J . , _ ^,.*

"!

~"r

:"V"-r

i-

...;... - I - -\

"l "

'T'"
. . .

"'"t

-T

>o

|v-f
to

too

\ \

4- -|

\-:~-^rri^v^-'-^^Hc^^t- ...;.... -t'1

(f)

aoo

X:

-i--v

r^j^

300 ' 400

r-Lj

sod

oo

i. i

TOO OO 9OO AOOO a&oo txoo


Tempefotore T^ C*C1

1.00

too

>00

400

900

coo

700

MOO 00 lOOO llOO IXOO


T m p r o l o r e T I ' C l

FIG. 59Graphical display from Module 1 (Temp-Grad) when quenching the LISCIC/NANMAC probe into a 20C mineral oil bath
without agitation (left row, vertically) and a 25% aqueous polyalkylene glycol quenchant solution at 40C bath temperature and 0.8
m/s agitation rate (right row, vertically), (d) Calculated temperature difference versus time, AT= i(t); (e) Calculated integral of the
heat flux (heat extracted) versus time, Iqdt = f(t), and 1. Calculated cooling rates versus temperature, dT/df = 1{J,^.

628 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


2000

2000

a ^ . ^ i Z B w;mK

o, . 595 W/m'K

gi800

1800

"6
J 1600

? 1600

"UOO

", I t O O

/A

;;i200
o

-^
o 1200

olOOO
o
o

* 1000
o

I BOO

~ too
200

V,

0,1

0.01

II nil

1 1 illill

10

600

>00

.
2000

Siaoo

Sl600

S: 1600

5
_.1t00
c

, f^

ni

0 1200
glOOO
o

800

0:

(b)

800

I 600

\
\

300

too
SOO
600
Tempcrature/C

700

600

ly
Uf

/
/

N
\

"t

200

\
200

JV

-, 1 0 0 0
o

*/

100

\ -^

I 1200
o

s\

too

a:
200

K^A

1800

d itOO

1 600
lb

0:

900

900

\
100

200

300
400
500
600
Temperature/*<;

700

^..

900

^*=^K

700
o

-~ 600
at

CI

500

\\
\\
\\

e too
0/

o 500

'

Q.

V
300

200

. simulated

' m<aasured

200

\
\ ,

100

. ..1 J mm . I I I 1 liU 1 1 iiiiii U 1111.1.1


(C)

800

900

800

100

10
Time /s

2000

0.1

0.01

( 1 mm 1 1 ( i i i i i ,

1 f I I m i^ - 1 i I I t i l l

1 f ((((If

1000

Time/ s

i1
1

200'

1 1 nun

100

1 1 / I f ^ / i

/ 1 llliii

(a)

800

(A

^800

0.01

0.1

10

Timc/s

100

1 1 IIIIII
1000

,1 1 IIIUJ ...1 i i i i i i i
0.01

0,1

I I 11 U.ll

10

1 1 IIIIII
100

1 1 IIIIII
1000

Time/s

FIG. 60Graphical display from Module 2 (HEAT-TRANSF), when quenching the LISCIC/NANMAC probe into a 20C mineral oil
bath without agitation (left row, vertically) and a 25% aqueous polyalkylene glycol quenchant solution at 40C bath temperature and
0.8 m/s agitation rate (right row, vertically), (a) Heat transfer coefficient versus time, a = f(t); (b) Heat transfer coefficient versus
surface temperature, a = f(r); and (c) Comparison of measured and simulated cooling curves for the center of the quench probe
(50 mm diameter).

CHAPTER

22: NON-LUBRICATING

C
Chemicot
Composition 0.38

Si
0.23

PROCESS

FLUIDS:

STEEL

Mn
P
Cr
S
0.64 0.019 0.013 0.99

Cu
0,17

QUENCHING
Mo
0.16

TECHNOLOGY

629

V
Ni
0,08 0.01

1000

Times
FIG. 61CCT diagram of AISI4140 steel with superimposed calculated cooling curves for surface (S), three-quarter radius (3/4 R), and center (C) of a round bar of 50 mm diameter.

values after hardening ft-om an ordinary CCT-diagram is


not correct, because the incubation time consumed (at
any point on the cross section) before the coohng rate
was abruptly changed, has not been taken into account.
For a detailed explanation see Ref 94.
Hardware RequirementsFor
the system being described
here, the hardware requirements are relatively modest and
include: IBM compatible PC (286/386/486/Pentium), 640
Kbytes RAM, a color graphic system, 2 MB free hard disk
space plus additional space for files to be stored, printer port,
cind disk drive.
Example of a Quenching Process
Analysis
Two different quenching processes are illustrated in Fig. 58
and Fig. 59; Case A and Case B. Case A is a quenching process
in a mineral oil at 20C (68F) without agitation. (All associated diagrams are on the left side of the figure.) Case B is a
quenching process in a 2 5 % aqueous polyalkylene glycol
(PAG) solution at 40C (104F) and 0.8 m/s agitation rate. (All
of the diagrams for this process are on the right side of the
figure.)
By comparing the diagrams of the heat flux density versus
time in Fig. 58b, it is shown that Case B exhibits delayed
quenching because in Case A, the time required for meixim u m heat flux to occur (f^max) is only 15 s, whereas in Case B
it is 72 s (due to the thick PAG poljmer film). In Case A (oil
quenching). Fig. 59e shows that by 20 s after immersion, 34
MJ/m^ has already been extracted and by 50 s, 50 MJ/m'^ heat
has been extracted. In Case B, (quenching in a high concentration of a PAG quenchant solution), by 20 s after immersion, only 5 MJ/m^ and by 50 s, only 20 MJ/m^ has been ex-

tracted. However, immediately after that period, between 50


and 100 s, the heat extracted in Case A has increased only
from 50 to 55 MJ/m^, whereas in Case B, the heat extracted
has increased from 20-86 MJ/m^. This shows that in Case B,
the thick polymer film has prevented the heat extraction for
a relatively long time at which point the insulating polymer
film surrounding the cooling probe burst and a sudden increase of heat extraction occurred.
By comparing the time required to decrease the heat flux
density from its m a x i m u m to a low value, e.g., 100 KW/m^ as
shown in Fig. 58b, it is observed that in Case A, 45 s is necessary, whereas in Case B, only 28 s is necessary. This illustrates that Case B is a quenching process in which after the
s u d d e n burst of the thick polymer film surrounding the
probe, there is practically n o boiling, as observed in oil
quenching, but an abrupt change in the convection cooling
stage.
A discontinuous cooling change is inherent to such a
quenching regime. It is interesting to analyze cooling rate
versus surface temperature as shown in Fig. 59f. While in
Case A (oil quenching), the cooling rate at the surface of the
probe "o" exhibits a greater m a x i m u m cooling rate t h a n
the cooling rate at 1.5 m m below the surface ( ). In Case B,
the maximum cooling rate at 1.5 m m below the surface (during the period of 350C to 300C of surface temperature) is
higher than the m a x i m u m cooling rate at the surface itself!
This is also evident from the cooling curves illustrated in Fig.
58a for Case B where at 570C, a discontinuous change of
cooling curve slope of Ti occurs, and between 500C a n d
300C, this slope is greater t h a n the slope of the cooling curve
for the surface (T^). This is an experimental proof of the theoretical calculation described in Ref 95, that in delayed

630 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

quenching, cooling rates below the workpiece surface can be


higher than at the surface itself.
Another analysis, with respect to thermal stresses during
quenching (on which residual stresses and possible distortion depend), is possible by comparing Fig. 59d. This comparison shows that quenching in an aqueous PAG quenchant
solution of high concentration (Case B) compared to oil
quenching (Case A), resulted in 27% lower maximum temperature difference between the center and the surface of the
probe (o). Whereas in Case A, the maximum temperature difference between the center and 1.5 mm below the surface (A)
is higher than the maximum temperature difference between
the point 1.5 mm below the surface and the surface itself ( );
in Case B, the maximum temperature difference between the
point 1.5 mm below the surface and the surface itself ( ) is
slightly higher than the maximum temperature difference between the center and the point 1.5 mm below the surface (A),
which is reached about 20 seconds later. This analysis also
shows an abrupt heat extraction when the polymer film
bursts.
However, Figure 59d shows that in oil quenching, the maximum temperature difference between the center and the
surface (o) occurs 20 s after immersion when the surface
temperature is 450C (See Fig. 58a for Case A), i.e., above the
martensite start temperature (Ms)- In an aqueous solution of
a PAG polymer quenchant at high concentration, the maximum difference between the center and the surface (o) occurs much later, i.e., after 80 s when the surface temperature
has already decreased to 350C (see Fig. 58a for Case B). Because of this, when working with steels with high Ms temperatures, there is a greater possibility of overlapping thermal stresses with those created due to austenite - to
martensite transformation.
The probability of crack formation can be observed by
comparing the surface temperature of the probe at the moment when maximum heat flux density occurs (Tqmax,)- As
seen in Fig. 58c for oil quenching, Tqmax is 515C, while for
the aqueous PAG quenchant solution at high concentration
(Case B) this occurs at 380C. The lower the value of Tq^ax,
the greater the risk of crack formation, especially with steels
with high Ms temperature.
When comparing two different processes with continuous
cooling (for the same workpiece and the same steel grade), to
determine which will provide the greater depth of hardening,
the following analysis may be used (see Fig. 58b). The larger
the value of g^ax, and the shorter the time (fqmax), the greater
will be the depth of hardening. In the case of a quenching
process with discontinuous (delayed) quenching such reasoning is not valid.
The sensitivity of the method to variation of quenching parameters is demonstrated in Fig. 62, which shows the calculated heat flux densities versus time for the LISCIC/NANMAC
quench probe, all experiments performed in the same aqueous PAG polymer quenchant solution of 40C bath temperature and 0.8 m/s agitation rate. The only parameter that was
changed was the polymer concentration from: a) 5% to b)
15% to c) 25%. This figure illustrates how increasing polymer
quenchant concentration decreases the heat flux density, i.e.,
quenching intensity. Shifting the heat flux density maximum
to a longer time (because of increasing thickness of the insulating polymer film surrounding the probe with increasing

500

1
log t tsl

1000

10|
""

(a)

500

388

^333

J 277

o
^ 222

.^^

166

/
/

55

i - i 1 mili-f-rnm
1.01

0.1

i i i iim
10

11

iiVu

J-t-W-lIU

100

1000

(b)

log t Is)
500

_388

"e 333

I 277
o
-222
166

55

0.01

1 1 llllll

1 1 1 IIITI

0.1

1 1 llllll

10

1 1 iii!i}~t_J-llllll

,100

1000

log t Isl

FIG. 62Calculated heat flux densities versus time, when


quenching the LISCIC/NANMAC probe into an aqueous
polyalkylene polymer solution at 40C and 0.8 m/s agitation
rate, but having concentrations: (a) 5%, (b) 15%, and (c) 25%.

quenchant concentration) changes a normal quenching process to a delayed one.


This example illustrates the possibiUties that are available
for simulation of production quenching processes using advanced data acquisition and analysis techniques.
ASTM STANDARDS
No.
A 255
D 91
D 92
D 93

Title
Standard Method for Determination of Hardenability of Steel
Test Method for Precipitation Number of Lubricating Oils
Standard Test Method for Flash and Fire Points by
Cleveland Open Cup
Standard Test Method for Flash-Point by PenskeMartens Closed Cup Tester

(c)

CHAPTER
D 94

22: NON-LUBRICATING

PROCESS

Standard Test Method for Saponification Number


of Petroleum Products
D 95
S t a n d a r d Test Method for Water in Petroleum
Products and Bituminous Materials by Distillation
D 189
S t a n d a r d Test Method for Conradson Carbon
Residue of Petroleum Products
D 287
S t a n d a r d Test Method for API Gravity of Crude
Petroleum and Petroleum Products (Hydrometer
Method)
D 445
Standard Test Method for Kinematic Viscosity of
Transparent and Opaque Liquids (the Calculation
of Dynamic Viscosity)
D 482
S t a n d a r d Test Method for Ash from Petroleum
Products
D 653
Standard Terminology Relating to Soil, Rock, and
Contained Fluids
D 664
S t a n d a r d Test Method for Acid N u m b e r of
Petroleum Products by Potentiometric Titration
D 892
Standard Test Method for Foaming Characteristics
of Lubricating Oils
D 974
Standard Test Method for Acid and Base Number
by Color-Indicator Titration
D 1298 Test Method for Density Relative Density (Specific
Gravity) or API Gravity of Crude Petroleum and
Liquid Petroleum Products by Hydrometer Method
D 1310 S t a n d a r d Method for Determination of Flash
Point and Fire Point in Liquids by Tag Open-Cup
Apparatus
D 1744 Standard Test Method for Determination of Water
in Liquid Petroleum Products by Karl Fischer
Reagent
D 1747 Standard Test Method for Refractive Index of Viscous Materials
D 2624 Standard Test Method for Electrical Conductivity
of Aviation and Distillate Fuels
D 3519 Standard Test Method for Foam in Aqueous Media
(Blender Test)
D 3 5 20 Standard Test Method for Quenching Time of HeatTreating Fluids (Magnetic Quenchometer Method)
D 3601 Standard Test Method for Foam in Aqueous Media
(Bottle Test)
D 3867 Standard Test Method for Determination of NitriteNitrate in Water
D 3946 Standard Test Method for Evaluating the Bacteria
Resistcince of Water-Dilutable Metalworking Fluids
D 4007 Standard Test Method for Water and Sediment in
Crude Oil by Centrifuge Method (Laboratory Procedure)
D 4327 S t a n d a r d Method for Determination of Anions
in Water by Chemically Suppressed Ion Chromatography
D 5296 Standard Method for Determination of Molecular
Weight Averages and Molecular Weight Determination of Polystyrene by High Performance Size Exclusion Chromatography
D 6161 Standard Terminology Used for Crossflow Microfiltration, Ultrafiltration, Nanofiltration, and Reverse
Osmosis Membrane Processes
D 6200 S t a n d a r d Method for Determination of Cooling
Characteristics of Quench Oils by Cooling Curve
Analysis

FLUIDS:
D 6482

D 6549

D 6666
D 6710
E 112
E 131
E 349
E 686
E 930

E 979

E 1181
E 1382

STEEL

QUENCHING

TECHNOLOGY

631

S t a n d a r d Method for Cooling Curve Analysis of


Aqueous Polymer Q u e n c h a n t s by Cooling Curve
Analysis with Agitation (Tensi Method)
S t a n d a r d Method for Cooling Curve Analysis of
Aqueous Polymer Q u e n c h a n t s by Cooling Curve
Analysis with Agitation (Drayton Method)
Stcindard Guide for Evaluation of Aqueous Polymer
Quenchants
Standard Guide for Evaluation of HydrocarbonBased Quench Oil
Standard Test Methods for Determining Average
Grain Size
Standard Terminology Relating to Molecular Spectroscopy
Standard Terminology Relating to Space Simulation
Standard Method for Determination of Antimicrobial Agents in Aqueous Metalworking Fluids
Standard Test Methods for Estimating the Largest
Grain Observed in a Metallographic Section (ALA
Grain Size)
Standard Method for Determination of Antimicrobial Agents as Preservatives for Invert Emulsions
and Other Water Containing Hydraulic Fluids
Standard Test Methods for Characterizing Duplex
Grain Sizes
Standard Test Methods for Determining Average
Grain Size Using S e m i a u t o m a t i c a n d Automatic
Image Analysis

OTHER STANDARDS
SAE J406
DIN 50191
IP 34
IP 71

IP 123

IP 160

IP 226

ISO 642
ISO 6743

ISO 9950

JIS K2242

Methods of Determining Hardenability


of Steel
Hardenability Testing of Steel by EndQuenching
Determination of Flash Point - PenskeMartens closed cup method
Petroleum products - Transparent Eind
opaque liquids - Determination of
kinematic viscosity and calculation of
dynamic viscosity
Petroleum products - Determination of
distillation characteristics at a t m o spheric pressure
Crude petroleum and liquid petroleum
products - Laboratory determination
of density - Hydrometer method
Petroleum p r o d u c t s - Calculation
of viscosity index from kinematic
viscosity
Steel Hardenability Test by E n d
Quenching (Jominy Test)
Part 14: Family U (Heat Treatment),
Lubricants, Industrial Oils & Related
Products (Class U)
Industrial Quenching Oils-Determination of Cooling Characteristics-NickelAlloy Probe
Heat Treating Oil

632 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


JIS K6753
ZBE 45003-88
AFNOR NFT 60778

Standard Liquor
H e a t T r e a t i n g O i l s - D e t e r m i n a t i o n of
C o o l i n g Ability
Industrial Quenching Oils-Determinat i o n of C o o l i n g C h e i r a c t e r i s t i c s - S i l v e r
Probe Test Method

REFERENCES
[1] Bates, C. E., Totten, G. E., and Brennan, R. L., "Quenching of
Steel," ASM Handbook-Volume
4 Heat Treating, ASM International, Materials Park, OH, 1991, pp. 67-120.
[2] Davis, J. R., ASM Materials Engineering Dictionary, ASM International, Materials Park, OH, 1992,
[3] Sverdlin, A. V. and Ness, A. R., "The Effects of Alloying Elements
on the Heat Treatment of Steel: Chapter 2," Steel Heat Treatment
Handbook, G. E. Totten a n d M. A. H. Howes, Eds., Marcel
Dekker, Inc., NY, 1997, pp. 45-91.
[4] Liscic, B., "Chapter 3-Hardenability," Heat Treatment of Steel
Handbook, G. E. Totten a n d M. A. H. Howes, Eds., Marcel
Dekker, NY, 1997, pp. 93-156.
[5] Totten, G. E., Bates, C. E., and Clinton, N. A., "Chapter 3-Cooling Curve Analysis," Quenchants and Quenching
Technology,
ASM International, Materials Park, OH, 1993, pp. 69-128.
[6] Totten, G. E., Bates, C. E., and Clinton, N. A., "Chapter 2-Measuring Hardenability and Ouench Severity," Quenchants and
Quenching Technology, ASM International, Materials Park, OH,
1993, pp. 35-68.
[7] Winchell, P. G. and Cohen, M., "Strength of Martensite," ASM
Transactions, Vol. 55, No. 2, June 1962, pp. 347-361.
[8] Houdremont, E., "Strength of Martensite," ASM
Transactions,
Vol. 55, No. 2, June 1962, pp. 347-361.
[9] Hornbogen, E., "Strength of Martensite," ASM
Transactions,
Vol. 55, No. 2, June 1962, pp. 347-361.
[10] Leidenfrost, G. J., "De Aqua Communis Nonnullis Tractus,"
Original from 1756, in C. Waves, Inemational Journal of Mass
Transfer, Vol. 9, 1966, pp. 1153-1166 (trans.).
[11] Yamanouchi, A., "Effect of Core Spray Cooling in Transient
State after Loss of Cooling Accident," Journal of Nuclear Science
and Technology, No. 5, 1968, pp. 547-558.
[12] Duffly, R. B. and Porthouse, D. T. C , "The Physics of Rewetting
in Water Reactor Engineering Core Cooling," Nuclear Engineering and Design, Vol. 3 1 , 1973, pp. 234-245.
[13] Kunzel, T., "Einfluss der Wiederbenetzung auf die allotrope
Modifikationsanderung tauchgekiihlter Metallkorper," Dissertation, Faculty for Mechanical Engineering of the Technical
University of Munich, 1986, 138 pp.
[14] Hein, D., "Modellvorstellung zur Wiederbenetzung d u r c h
Fluten," Doctoral Thesis, Technical University of Hannover,
1980, 182 pp.
[15] Ladish, R., "Untersuchung der minimalen Filmsiedetemperaturen auf keramischen u n d metallischen Leitem," Report of
"Kemforschungsstelle Karlsruhe," KfK-2970, 1980, 96 pp.
[16] Stitzelberger-Jakob, P., "Hartevorherbestimmung mit Hilfe des
Benetzungsablaufes beim Tauchkiihlen von Stahlen," Dissertation, Faculty for Mechanical Engineering of the Technical University Munich, 1991, 160 p p .
[17] Tensi, H. M. and Lainer, K., "Wiederbenetzung und Warmeilbergang beim Tauchkiihlen in Hochleistungsolen," HTM, 1997, 52,
pp. 298-303.
[18] Tensi, H. M., "Wetting Kinematics," Theory and Technology of
Quenching, B. Liscic, H. M. Tensi, and W. Luty, Eds., SpringerVerlag, Berlin, 1991.
[19] Tensi, H. M., Stich, A., and Totten, G. E., "Fundamentals of
Quenching," Metal Heat Treating, Mar/Apr 1995, pp. 20-28.

[20] Jominy, W. E., Hardenability of Alloy Steels, ASM IntemationeJ,


Materials Park, OH, 1939, p. 73.
[21] French, H. J., "A Study of the Quenching of Steels," Transactions
ofASST, May 1930, pp. 646-727.
[22] Paschkis, V. and Stolz, G., "How Measurements Lead to Effective Quenching," Iron Age, Vol. 22, 1956, pp. 95-97.
[23] Zhu, H., "Analysis of the Algorithms for Measuring the Cooling
Rates of Quenching Media by Computer," Heat Treatment of
Metals (China), Vol. 11, 1986, pp. 26-31.
[24] Zhang, S., Liu, H., and Zhou, X., "Measurement of the Characteristic Curves of Quenching Media with a Microprocessor,"
Heat Treatment of Metals (China), Vol. 11, 1986, pp. 35-39.
[25] Tensi, H. M. and Steffen, E., "Measuring of the Quenching Effect of Liquid Hardening Agents on the Basis of Synthetics,"
Steel Research, Vol. 56, 1985, p p . 489-495.
[26] Zhelokhovtseva, R. K., "Elimination of Quenching Cracks by
Means of Optimization of Cooling Conditions," Steel USSR, Vol.
15, 1985, p p . 238-239.
[27] Segerberg, S., Oral Presentation at ASM Heat Treating Conference, Chicago, March 1990.
[28] Kovalenko, G. V. and Kobasko, N. I., "Modeling of the Unsteady
State Boiling Process in Water Quenching of Metal," Heat Transfer-Soviet Research, Vol. 20, No 1, 1988, p p . 69-78.
[29] Kobasko, N. I., "Itogi nauki I tehniki (Results of Science and
Technique)," Section: Metal Study and the Heat Treatment,
Quenchants, VINITI, Moscow, Vol. 23, 1989, p p . 127-166.
[30] Kobasko, N. I., "Technological Aspects of Cooling in Quenching:
Review," Metallovedenie Termicheskaya Obrabotka Metallov, No.
4, 1991, pp. 2-8.
[31] Tensi, H. M. and Stitzelberger-Jacob, P., "Influence of Wetting
Kinetics on Quenching and Hardening in Water-Based Polymers With Forced Convection," Proceedings of the 6'^ International Heat Treatment of Metals, ASM International, Materials
Park, OH, 28-30 Sept. 1988, Chicago, p p . 171-176.
[32] Tensi, H. M. a n d Stitzelberger-Jacob, P., "Influence of Repeated
Submerging on Quenching," Promyshlennaya Teplotehnika, Vol.
11, No. 4, 1989, pp. 57-66.
[33] Tensi, H. M., Stich, A., and Totten, G. E., "Fundamentals About
Quenching by Submerging," Proceedings of the International
Heat Treating Conference: Equipment and Processes, ASM International, Materials Park, OH, 18-20 April 1994, Shaumberg, IL,
pp. 243-251.
[34] Kobasko, N. I. and Timchenko, N. P., "Filming of Sample
Quenching in Aqueous Solution of Polymer," Metallovedenie
Termicheskaya Obrabotka Metallov, No. 10, 1986, pp. 25-29.
[35] Kobasko, N. I., Moskalenko, A. A., Totten, G. E., and Webster,
G. M., "The Determination of t h e Second Critical Heat Flux
Density on the Basis of Tests of Stsindard Samples," Promyshlennaya Teplotehnika, Vol. 17, No. 5, 1995, pp. 83-87.
[36] Kobasko, N. I., Moskalenko, A. A., Totten, G. E., and Webster,
G. M., "The Investigation of the Influence of Different Technological Factors on the Second Critical Heat Flux Density,"
Promyshlennaya Teplotehnika, Vol. 17, No. 6, 1995, pp. 57-64.
[37] Kruzhilin, G. N., "Teplootdacha ot Horizontalnoi Plity k
Kipyaschey Zhidkosti pri Svobodnoi Konvekstii," Doklady
Akademie Nauk, Vol. 58, No. 8, 1947, pp. 1657-1660.
[38] Moskalenko, A. A., Kobasko, N. I., Tolmachova, O. V., Totten, G.
E., a n d Webster, G. M., "Quenchants Characterization by
Acoustical Noise Analysis Cooling Properties of Aqueous
Poly(Alkylene Glycol) Polymer Quenchants," Conference Proceedings of the 2nd International Conference on Quenching and
Control of Distortion, G. E. Totten, K. Funatani, M. A. H. Howes,
and S. Sjostrom, Eds., ASM International, Materials Park, OH,
1996, pp. 117-122.
[39] Zhou, R. L., "The Improvement of Quenching Techniques and
the Development of New Quenching Media," Proceedings of the
4'^ Annual Conference on Heat Treatment, Institute of Chinese

CHAPTER 22: NON-LUBRICATING PROCESS FLUIDS: STEEL QUENCHING TECHNOLOGY 633


Mechanical Engineering Society, Nanjing, 25-31 May 1987,
Chinese Mechanical Engineering Society, Beijing, pp. 348-353.
[40] Segerberg, S. O., "Classification of Quench Oils: A Method of
Comparison," Heat Treating, Dec. 1988, pp. 30-33.
[41] Tensi, H. M. a n d Stitzelberger-Jacob, P., "Bedeutung des HWertes fiir die Bestimmung der Harteverteilung," HTM, Vol. 44,
1989, pp. 99-105.
[42] Furman, G. R., "Quenching IMetallurgical Aspects," Lubrication, Vol. 57, 1971, pp. 13-24.
[43] Han, S-W and Yul'Chev, R., "Conservation of Quenching Oils,"
Kong Hak Hoe lie. Vol. 2, 1989, pp. 59-65.
[44] Dicken, T. W., "Modern Quenching Oils: an Overview," Heat
Treatment of Metals, Vol. 1, 1986, pp. 6-8.
[45] Lasday, S. B., "Metal Quenching with Oils and Synthetic Media," Industrial Heating, Oct. 1976, pp. 8-19.
[46] Totten, G. E., Bates, C. E., and Clinton, N. A., "Chapter
4 - Q u e n c h i n g Oils," Quenchants and Quenching
Technology,
ASM International, Materials Park, OH, 1993, pp. 129-159.
[47] Tkachuk, T. I., Rudakova, N. Y., Sheremeta, B. K., and Novoded,
R. D., Metallovedenie Termicheskaya Obrabotka Metallov, Oct.
1986, pp. 4 2 ^ 5 .
[48] Allen, F. S., Fletcher, A. J., and Mills, A., "The Characteristics of
Certain Experimental Quenching Oils," Steel Research, Vol. 60,
1989, pp. 522-530.
[49] Boyer, H. E. and Cary, P. R., Quenching and Control of Distortion, ASM International, Materials Park, OH, 1988.
[50] Gilliland, H.-J., "Measuring Quenching Rates with the Electronic Quenchometer," Metals Progress, Oct. 1960, pp. 111-114.
[51] Bender, E. A. a n d Gilliland, H. J., "New Way t o Measure
Quenching Speed," Steel, Dec. 1957, pp. 56-59.
[52] Barley, C. A. and Aarons, J. S., The Lubrication Engineers Manual, U.S. Steel Corp., Pittsburgh, PA, 1971, pp. 56-57.
[53] F u r m a n , G. R., "Quenching 11The Oil's Role," Lubrication,
Vol.57, 1971, pp. 25-36.
[54] Blackwood, R. R., CEO, Texanol, Inc., Milwaukee, WI, personal
communication, 1987.
[55] Totten, G. E., "Polymer Quenchants: The Basics," Advanced Materials and Processes, Vol. 137, No. 3, 1990, pp. 51-53.
[56] Cornell, E. R., "Process for Quench H a r d e n i n g Steel," U.S.
Patent 2,600,290, Washington D.C., 8 Aug. 1950.
[57] Blackwood, R. R. a n d Cheesman, W. D., "Metal Quenching
Medium," U.S. Patent 3,220,893, Washington D.C., 30 November 1965.
[58] Terekhova, N. F., Tanicheva, O. N., Tiunova, N. M., a n d
Lobanova, N. M., "Quenching Medium," U.S.S.R. Patent
3,745,271, 15 Aug. 1986.
[59] Gordon, M., "Method of Quenching Metals," U.S. Patent,
2,770,564, Washington DC, 13 Nov. 1956.
[60] Meszaros, A. G., "Water-Based Quenching Composition Comprising Polyvinylpyrrolidone and Method of Quenching," U.S.
Patent 3,902,929, Washington DC, 2 Sept. 1975.
[61] Kopietz, K.-H., "Process for the Controlled Cooling of Ferrous
Metal," U.S. Patent, 4,087,290, Washington DC, 2 May 1978.
[62] Warchol, J. F., "Polyoxazolines in Aqueous Quenchants," U.S.
Patent 4,486,246, Washington DC, 4 Dec. 1984.
[63] Jarvis, L. M., Blackwood, R. R., and Totten, G. E., "Thermal Separation of Polymer Quenchants for More Efficient Heat Treatments," Industrial Heating, November 1989, pp. 23-24.
[64] Totten, G. E., Bates, C. E., and Clinton, N. A., "Chapter 5-Polym e r Quenchants," Handbook of Quenchants and Quenching
Technology, ASM International, Materials Park, OH, 1993, pp.
161-190.
[65] Totten, G. E., Webster, G. M., Tensi H. M., and Liscic, B., "Standards for Cooling Curve Analysis of Quenchants," Heat Treatment of Metals, 1997, No. 4, pp. 92-94.
[66] "Laboratory Test for Assessing the Cooling Curve Characteristics of Industrial Quenching Media," Wolfson Heat Treatment

[67]

[68]

[69]

[70]

[71]
[72]
[73]
[74]
[75]
[76]

[77]

[78]
[79]
[80]
[81]
[82]

[83]

[84]

[85]

[86]
[87]

[88]

[89]

Centre Engineering Group Specification, Wolfson Heat Treatment Centre, Birmingham, UK, 1982.
Tensi, H. M., "Methods and Standards for Laboratory Tests,"
Theory and Technology of Quenching: A Handbook, B. Liscic, H.
M. Tensi, and W. Luty, Eds, Springer-Verlag, Berlin, Germany,
1992, p p . 208-219.
Guisbert, D. A., "Precision and Accuracy of the Cooling Curve
Analysis Test Method," Proceedings of the 16th ASM Heat Treating Society Conference and Exposition, Cincinnati, OH, 19-21
M a r c h 1996, ASM International, Materials Park, OH, p p .
435^42.
Guisbert, D. A., "Correlation with Magnetic Quenchometer to
Cooling Curve Analysis Technique," Proceedings of the 16th ASM
Heat Treating Society Conference and Exposition, Cincinnati,
OH, 19-21 March 1996, pp. 4 5 1 ^ 6 0 .
Guisbert, D. A. and Moore, D. L., "Influence of Test Conditions
on Cooling Curve Test Results," The 1st International
Automotive Heat Treating Conference, R. Colas, K. Funatani, and C. A.
Stickels, Eds., ASM International, Materials Park, OH, 1998, pp.
449-455.
Tensi, H. M. and Stich, A., "Characterization of Polymer Quenchants," Heat Treating, May 1993, pp. 25-29.
One source of the "dynamic boat propeller" Part #1472, is Fa.
Robbe. D-36355, Grebenhain, Germany.
Hilder, N. A., "The Behavior of Polymer Quenchant," PhD Thesis, University of Birmingham, UK, 1988.
Tagaya, M. and Tamura, I., Technol. Rep., Osaka University, Vol.
7, 1957, pp. 4 0 3 ^ 2 4 .
Boyer, H. E. and Cary, P. R., Quenching and Control of Distortion, ASM International, Materials Park, OH, 1988, p. 169.
Totten, G. E., Bates, C. E., and Clinton, N. A., "Chapter
6-Quench Bath Maintenance," Handbook of Quenchants and
Quenching Technology, ASM International, Materials Park, OH,
1993, pp. 191-238.
Totten, G. E., Bates, C. E., and Clinton, N. A., "Chapter
6-Quench Bath Maintenance," Handbook of Quenchants and
Quenching Technology, ASM International, Materials Park, OH,
1993, pp. 191-238.
Horton, B. R. and Weetman, R., "Quench Oil Recovery," Heat
Treatment of Metals, Vol. 2, 1984, pp. 49-51.
Watanabe, H. and Kobayashi, C , Lubrication Engineering, Vol.
38, No. 8, 1978, pp. 421-428.
Hasson, J. A., "Preventative Maintenance for Quenching Oils,"
Industrial Heating, Sept. 1981, pp. 21-23.
Boyer, H. E. and Cary, P. R., Quenching and Control of Distortion, ASM International, Materials Park, OH, 1988, pp. 4 4 ^ 5 .
von Bergen, R. T., "The Control and Monitoring of Polymer
Quenchant Systems," Heat Treatment of Metals Vol. 2, 1991,
pp.37^2.
Srimongkolkul, V., "Is There a Need for Really Clean Oil in
Quenching Operations?," Heat Treating, December 1990, p p .
27-28.
Bates, C. E. and Totten, G. E., "Quantifying Quench-Oil Cooling
Characteristics," Advanced Materials & Processes, 1991, No. 3,
pp. 25-28.
Totten, G. E. and Webster, G. M., "Quenching Fundamentals:
Maintaining Polymer Quenchants," Advanced Materials and Processes, Vol. 149, No. 6, 1996, pp. 64AA-64DD.
Mueller, E. R., "Polyglycol Quenchant Cleanliness: Are There
Benefits," Heat Treating, October 1993, pp. 24-27.
Jarvis, L. M., Blackwood, R. R., and Totten, G. E., "Thermal Separation of Polymer Quenchants for More Efficient Heat Treatments,"/nrfwiina/Heafrng, November, 1989, pp. 23-24.
HiU, E. C. and Hill, G. C , "Biodegradable After Use But Not In
Use," Industrial Lubrication & Tribology, Vol. 46, No. 3, 1994,
pp. 7-9.
Hill, E. C , "The Significance and Control of Microorganisms in

634 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


Rolling Mill Oils and Emulsions," Metals Materials, No, 9, 1967,
pp. 294-297.
[90] Anon., "Microbiology of Lubricating Oils," Process Biochemistry, May 1967, pp. 54-56.
[91] Passman, F. J., "Biocide Strategies for Lubricant Rancidity and
Biofouling Prevention," Proceedings of the AISE Annual Convention, Vol. 1, Association of Iron and Steel Engineers, 1996, pp.
413-428.
[92] Kobasko, N. I., "Teplovie Procesi Pri Zakalke Stall," Metalovedenie I Termiceskaja Obrabotka Metalov, 1968, Vol. 3, pp. 2-6.
[93] Liscic, B. and Dowding, K., "Calculation and Measurement of
the Workpiece's Surface Temperature During Quenching," Heat

Treating-Proceedings of the 20th Conference Vol. 2, K. Funatani


and G. E. Totten, Eds., 9-12 October 2000, ASM International,
Materials Park, OH, pp. 688-695.
[94] Shimizu N. and Tamura, L, "Effect of Discontinuous Change in
Cooling Rate During Continuous Cooling on Pearlite Transformation Behavior of Steel," Transactions ISIJ, Vol. 17, 1977, pp.
469-476.
[95] Chen, M. and Zhou, H., "Numerical Heat Transfer Ansdysis on
the Effect of Enhancing the Thickness of the Hardened Layer by
Delayed Quenching," Jinshu Rechuli Xuebao, (Transactions of
Metal Heat Treatment), Vol. 14, No. 4, 1993, pp. 1-6. (in Chinese).

Section IV: Performance/Property Testing Procedures


Steven R. Westbrook and Rajesh J. Shah, Section Editors

MNL37-EB/Jun. 2003

Static Petroleum Measurement


Lee Oppenheim^

STATIC PETROLEUM MEASUREMENT CAN BE BEST SUMMED UP as

termine the quantity of. The measure is linear (meters, feet).


Along the way, it is necessary to determine the a m o u n t of sediment and/or water on the bottom of the tank and depending
on the product, the amount of entrained material within the
liquid to be measured. While doing so, a sample is obtained
to determine its density. A temperature of the product is also
tctken at the same time. When the basic steps are completed,
calculations side of static petroleum measurements are performed. Linear measures are converted to volumes, sediment
and water found at the bottom of a tank is eliminated from
our quantity, entrained sediment and water (S & W) mixed in
the product is subtracted, and then the product density and
temperature of the product at time of measurement is used to
produce a net volume at the specified reference temperature
(60F in the U.S.). A small error may cost either the buyer or
the seller to gain or lose much with a significcuit effect on a
company's bottom line. In a small way, this chapter will help
unravel the mystery of determining the quantity of petroleum
in a bulk container, and also provide a n understanding of the
importance of each step in the process.

the

procedures and methods used to determine the quantity of liquid in a storage tank, marine vessel, road transport vehicle, or
a rail tank car. In determining the quantity of the liquid in the
container, there may be other things in the container that detract from determining the quantity of useable petroleum or
petroleum products. They do take u p space in the container
and therefore must be desilt with as peirt of any measurement
procedure. These can include water, sediment, sludge, rust
scale, and sand to n a m e just a few. As used here, petroleum
refers to crude oil, therefore the continuous reference to
petroleum and petroleum products. Petroleum products as
used here are the liquid stocks (e.g., naphtha, kerosene, fuel
oils) derived from the refinery processes from crude oil. It is
important to know the total of the liquids and solids in a tank
to prevent a tank from overflowing during a receipt. However,
the more exacting science of static petroleum measurement is
concerned with determining a n accurate measure of the
quantity of petroleum Eind petroleum products used in the
purchase, sale, or inventory control of the commodity. This
section on static petroleum measurement will deal primary
with manual gauging techniques and the related sampling
and quality tests needed to obtain accurate petroleum and
petroleum product quantity measurements. Automatic tank
gauging, not discussed in this chapter, relies on the manued
gauging methods for calibration purposes. Newer techniques
for leak detection combine a form of static petroleum measureraent with inventory control to assure that tanks and lines
storing and moving the products are tight. Leak detection
procedures primarily combine automatic gauging methods
with computer programming. This chapter is designed to explain h o w to accurately m e a s u r e the petroleum and
petroleum products, why certain procedures are necessary,
sampling and testing processes, and the basics of converting
these measures into quantity m e a s u r e m e n t s used in the
industry.

Petroleum and petroleum products expand and contract as


the temperature changes. The rate of this expansion may vary
depending on the type of product encountered. An underlying principle used in static petroleum measurenaent is the
volume of petroleum at a specified standard temperature.
This standard temperature is a means of common reference
and helps to avoid the misunderstcuidings that occur when
comparing unlike items. It is important to understand what
temperature is being used as the reference temperature. In
using the System Internationale, sometimes referred to as the
metric system, the standard temperature is usually 15C and
sometimes 20C. Using the American measurement system,
60F is used. This does not imply that volumes at ambient
temperatures cannot be used for the sale of a product. Small
quantities such as those sold using meters at an automotive
service station or at a single user fleet dispensing location are
usually determined at the ambient (surrounding air) temperature.

The primary reference for static petroleum measurements


is the American Petroleum Institute (API) Manual of
Petroleum Measurement Standards (MPMS). Increasingly,
the s t a n d a r d s and practices are standardized with other
Standards bodies such as ASTM International (ASTM), Institute of Petroleum (IP), and the International Organization of
Standards (ISO) as well as other national standards organizations. Yet, static petroleum measurements normally do not
even measure the volume of the product we are trying to de' Chief, Quality Operations Division, Defense Energy Support Center, Ft. Belvoir, VA 22060-6222.

Storage and transport tanks have several openings from


which measurements may be taken. However, only specially
designated locations on the tank are to be used. This is because calibration of the tank volume has been made from this
point or a combination of several designated points. Smaller
transport tanks may have volume measurements scribed on
an approved measurement rod, commonly referred to as a
dipstick. These calibrated dipsticks are only for use on the
specified tanks conforming to the originjd construction of the
tanks. The majority of manual measurements are taken using

635
Copyright'

2003 by A S I M International

www.astm.org

636

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

a linear measure from a properly designated gauging point


on the tank. The linear measure is converted to a volume
measure by use of the certified calibration table (or tank capacity tables or strapping table/chart as it may be referred to)
for that tank. A strapping chart contains the official conversion of the linear measure to a volume measure within that
tank. Tank calibrations are performed using API MPMS
Chapter 2 criteria. Tajik bottoms may slope in various ways,
changing the shape of the bottom. Taking measurements
from a point not designated as the gauging point will most
likely mean a change to the linear measurement needed for
accurate quantity measurements. Tank calibrations take into
account internal structures such as supports and piping,
change in tank diameters, as well as deductions for floating
roofs. Each tank requires a certified calibration table or
strapping chart when performing static petroleum measurements. It will contain much needed information for the performance of accurate measurement and validation should
the need arise.
To begin the process of understanding how to measure and
quantify a large tank or marine vessel compartment, it is necessary to start with some basic terminology. Beginning at the
tank where the product resides, use Fig. 1 to describe the
terms. Each tank to be measured has designated a place
where gauging is to occur, or reference gauge point. Normally
a gauge hatch is designated for this purpose. Check the strapping chart for the point or points so designated. Some gauge
hatches, primarily those in stationary shore tanks, have a slot
or mark where the measuring tape can be inserted. These
slots or marks designate which side of the gauging tube is to
be used. If there is no indication on the strapping chart designating a specific location, gauging should be performed opposite the hinge on the gauging hatch for uniformity. Beneath the gauging point, there may be a datum plate,
preferably on the floor of the tank. Occasionally a datum

REFERENCE
POINT
READING

GAGING TAPE
GAGING HATCH

REFERENCE
POINT
READING

GAGING TAPE
/ GAGING HATCH

OUTAGE
TAPE
CUT
TANK
SHELL

LIQUID
LEVEL

BOB
CUT
TANK
SHELL

LIQUID
LEVEL

INNAQE

plate may be attached to the side of the tank or the bottom of


the stillpipe. The datum plate is fixed in a level position on the
floor of the tank directly underneath the reference gauge
point. It is between these two locations that we take the linear measurement. The datum plate may be raised off the
floor. In such cases a reading of zero does not indicate that
the tank is empty as product may be below the measuring
point. When this occurs, the strapping chart will have an indicated volume for a measurement of zero. It takes that much
product just to reach the zero point. If a tank does not have a
datum plate, the reference height is from the reference gauge
point to the floor of the tank. Again, this may not be the low
point of the tcink and a zero reading may account for a certain fill quantity. This is particular true of cone down type
tank bottom construction with side gauging points, but exists
in other tank styles cdso.
Between the reference gauge point and the datum plate,
the distance is called the reference gauge height. This distance
will be indicated on the strapping chart and may also be
marked on the top of the tank by the gauging point. During
the measurement process, knowing whether the sediment,
water, and product heights are accurate requires knowledge
of the reference gauge height. This will be especially true for
tanks that may contain sufficient sediment or sludge, preventing the measuring device from hitting the datum plate or
bottom of the tank.
A tape and bob combination is used to make the linear
measurement. There are several different styles of tapes and
bobs (Fig. 2). It is important that the correct combination is
used. We must therefore understand the difference between
the two measurement styles: innage and outage. Innage is the
measurement of the liquid and solids from the bottom of the
tank to the upper level of the product. Most refined products
in shore tanks, road transport vehicles, and rail tank cars are
measured in this manner. If the measurement device can get
through the sediment, sludge, and water in the tank (the reference gauging height is obtained at the reference gauge
point), then the innage method ccin be used to determine the
nonproduct or nonmerchantable part of the tank. Outage,
sometimes referred to as ullage, especially on marine vessels,
is the measurement of the void space in the tank. Most marine vessel compartments are strapped using the ullage
method. The outage method is also preferred to determine
the amount of fuel oil or heavy, viscous products. These
products may prevent the tape and bob from getting to the
bottom in a straight line, increasing the total linear distance.
It is also very messy having to clean the tape and bob after
each measurement. The innage and outage methods may be
used together for different purposes. An outage measurement
may be taken for the product, but an innage taken for sediment, sludge, and water measurements. Whether an innage
or outage gauge is taken, always remember to check the
strapping chart to determine which method to use for converting from a linear measurement to a volume measure. You
can compensate taking an innage when an outage is required
(or vice versa) by remembering the simple relationship between innage and outage.
innage height + outage height = reference gauge height

INNAGE

FIG. 1Gauging diagram.

OUTAGE

For example, take an innage gauge with a total height of


7.500 m. The Reference gauge height is 19.670 m. An outage
gauge is required when the strapping chart is used. This

CHAPTER 23: STATIC PETROLEUM MEASUREMENT

637

S t a l l T a p i tob^^ or *^t in.


w l o , O D O S lo 0.012 In. thick
Bobs l o b * mode of
coriDsion-rislstQnt m e t a l

A
r-B

II

r-ll

IS

'OUTAGE TAPE-

-H
0
U

r-ll

in

\f

\ /

10"

r-J

INNAGEtOa

SCALE
ZERO

EXTCNSION
OUTACe
SOB

PIAIM
OUTASE
SOB

DEEP
GROOVED
OUTAGE

BOS

bC^

FIG. 2Tapes and bobs.

shows that the pregauging review was not performed. Using


the formula reference gauge height innage height = outage
height or
19.670m - 7.500m = 12.170m for the outage height.
A bob is a heavy metal (usually brass) weight with linear
measurements on it. The heavy weight is designed to keep
the tape stretched in a straight line below the gauging point.
Each bob is specifically designed for various tapes. An innage bob begins at the bottom with zero and provides the
linear measure upwards towards the tape. It will have some
means for the bob to be attached to the tape. The latching
area is normally without linear gradients so measurement
should not occur in this area. The tape continues the linear
measurement up to the reference gauge point. It is important to use the corresponding bob cind tape to provide for a
continuous linear measurement. Some bobs are 6 in. with a
dead area of 2 in. between the latching area and the beginning of the linear tape gradients. Other bobs may be 10 in.
Check and validate that the measurement from the tip of
the bob up past the beginnings of the tape linear gradients
are continuous. Outage bobs can be designed to work with
either an innage tape or and outage tape. An outage bob
with an outage tape is designed so that the zero point is at

the top of the outage bob where the tape latches onto the
bob. The bob will then be graduated from the top of the bob
downwards. An extension outage bob is designed to be attached to an innage tape. Below where the zero point would
be if an innage bob was attached is a metal extension. Readings begin at the zero point and increase below the zero
point. When using an outage tape, readings on the bob below the zero point are added to the reading tciken at the reference gauge point. Treat the tape properly as the linear
measure is a critical step in getting the quantity accurate.
Kinks in the tape are to be avoided. Tapes that have been
spliced together shall not be used when gauging for custody
transfer purposes as it may change the measurement above
the splice point. A bob showing wear at the tip may affect
gauging accuracy.
Where primarily water and small amounts of soft sediment
may be the contaminant, a water gauging bar may be used to
measure the water that has settled to the bottom of the tank.
One drawback is if the bar is not attached to a corresponding
tape, it is not possible to obtain a reading of the reference
height gauge. Therefore if the bar did not hit the datum plate
or floor of the tank, the gauger will not know if the bar actually reached the datum plate or the floor.
A new tape and bob should be checked before use. Inspect

638

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

the entire length to assure that the n u m b e r s are clcEirly indicated in the correct order and the graduation meirks between
the numbers are present. Tapes should be made of steel or
corrosion resistant material. Meike sure the snaps and eyes
between the tape and the bob afford for proper fit and accuracy for measurement purposes. Tapes and bobs should be
checked daily w h e n in use. Check the tape for kinks and
splices, which would make the apparatus unsuitable for accurate gauging. The tape and bob fittings should provide for
an accurate measure. Also ensure that the bob tip has not
been worn down or damaged, which would create another
measurement error. Lastly, make sure the tape and bob Eire
fit for the purpose to be used. A tape and bob shall not be introduced into another product where the residue on the tape
and bob would contaminate the product to be measured. A
s t a n d a r d operating procedure to r e m e m b e r is t h a t crude
oil/residual fuel oil tapes should not be used to measure distillate products. Many specialty petrochemical products are
very sensitive to extremely small levels of contamination. Either separate tape and bobs may be necessary or the tape and
bob may require special cleaning before use.
There are still several items needed before a linear measurement is m a d e at the tank. Remember several other factors m u s t be accounted for to obtain accurate petroleum
measures. The first to be discussed is what is needed in determining the temperature of the product to be measured. A
thermometer or temperature measuring device is required.
The industry standard for reference is API MPMS Chapter 7,
Method of Measuring the Temperature of Petroleum and
Petroleum Products. The temperature of the product is critical to correct the measured quantity to the standcird temperature.
The temperature in a tank may vary greatly, especially for
crude oil and residual fuel oils that are heated to higher temperatures to maintain fluidity and preventing gelling of the
product. The heating coils are near the floor and heat convection helps swirl the product in the tank. It may not, however, provide for a uniform t e m p e r a t u r e within the tank.
Even distillate products in tanks have t e m p e r a t u r e variations. After distillation and condensation of the product, it
enters a storage tank. If measurements are made soon after
that, there may be a temperature gradient within the tank.
The equilibration of the product has not occurred. Another
factor affecting the temperature within a tank is the external
environmental conditions. If gauging is performed on a side
of the tank were the sun is shining, it may indicate a higher
temperature than if the gauge was taken on the shady side of
the tank. Rapid ambient temperature cheinges may also increase the t e m p e r a t u r e variation within a tank. Product
within the tank may not have h a d a chance to equilibrate. Increased temperature readings are advisable where temperature stratification is found within a tank.
The temperature within the tank is measured using a thermometer or an electronic temperature probe (thermoprobe).
Thermometers must meet ASTM E l , ASTM
Thermometers
specifications for the range of temperatures cinticipated in the
product to be measured. Thermometers shall be calibrated at
least yearly against a thermometer traceable to a certified national standard thermometer. In the U.S., the Standard body
is the National Institute of Standards and Technology (NIST).
Thermoprobes rely on electronic instrumentation to provide

a readout of the temperature. These must be calibrated o n a


yearly basis or as recommended by the manufacturer. Calibration should cdso be accomplished whenever there is reason
to doubt the accuracy of the measurement. Other temperature
measuring devices may be temperature dials placed in the
wall of the tank. These are placed strategically at various
heights, normally along the stairs going u p to the tank roof. If
a tank is not full, care must be taken only to read those thermometers on the tank side weJl that are immersed in product.
One disadvantage to the dial type is that the probe may not extend sufficiently into the tank. They would then be very sensitive to the environmental factors at the wetll surface. For example, with the sun on the tank wall, it may have warmed up
the product within 6 in. of the wall, yet the remainder of the
tank remains cooler. Using these readings would obtain a
higher temperature t h a n if a thermometer was used within
the middle of the tank. These differences could have a significant effect on the volume correction factor, resulting in
greater than anticipated quantity variations at the agreed temperature. Other temperature devices may also be used in the
tank with electronic readouts at the tank itself, or more likely
a control room.
When performing manual temperature readings using a
mercury in glass thermometer, a thermometer assembly or
holder is also required. These assemblies protect the thermometer from being broken in the course of being lowered
and raised. More importantly, they provide for a reservoir of
product to surround the thermometer bulb. Thermometers
have a tendency to react quickly to temperature changes.
Without a product reservoir, by the time the thermometer is
raised and turned to determine the reading, it would have
changed temperatures first with the variation within the tank,
but more importantly with the ambient air temperature.
Several types of assemblies are in use. Several basic t5?pes
are the cup case, flushing cup, and armored case (Figs. 3-5).
Flushing cups are not referenced in the current MPMS Chapter 7, but occasionally may be found in use. As the assembly
is lowered into the product to be measured, it quickly fills
with product. The assembly is lowered to the height required
for the temperature reading and it is allowed to equilibrate
for at least 5 min at that level. Products having viscosities
greater thein 100 Saybolt Universal Seconds may require 15
or 30 min before equilibration occurs. By raising the assembly rapidly, the p r o d u c t in the reservoir is more likely to
maintain the temperature at the level to be measured. Temperature readings therefore need to be taken as soon as possible after the assembly is raised. Conversely, temperature
probes with electronic readouts may not require any time for
equilibration. Readings may be tciken shortly after reaching
the desired level, reading when the read-out is stable.
Steps needed before going to the teink. Check that the thermometer is not broken. Make sure that the liquid in the colu m n has not separated. Do not use thermometers with these
defects. Ensure that the thermometer is within the temperature range of the product to be measured or obtain a correct
thermometer. Lastly, ensure that the assembly adequately
holds the thermometer in place and that the bulb of the thermometer is placed within the reservoir. The reservoir should
not have holes or openings that would prevent the retention
of the product in the reservoir. Replace the assembly if
defective.

CHAPTER 23: STATIC PETROLEUM MEASUREMENT

639

CLAMP.

ASTMTHERMOMETER

CORROStONRCSBTANT
METAL

CD
CUP CASE
FIG. 3Cup case Thermometer.

MAX.p
FIG. 5Armored cup
case.
ASTM
THERMOMETER

FLUSHING CASE

FIG. 4Flushing cup case.

Free water is defined as the water present in a tank that is


not in suspension or dissolved in the petroleum. To measure
free water, something is needed so that the water level after
drawing the bob or bar through the product can be observed.
To detect the free water, a water finding paste is used to distinguish between the petroleum and petroleum product layer
and the water level. For crude oils and many residual fuel
oils, the bob or bar may retain a significant coating of the
crude or product, hindering our ability to see the watermark
to be read. In these cases, a petroleum solvent may be needed
to rinse the bob or bar. Care must be taken not to disturb the
water finding paste when rinsing the bob or bar with the
petroleum solvent. This procedure also requires advance
planning so that the proper solvent can be taken to the tank
and equipment needed to preclude environmentcJ and safety
problems with the rinse are available.
It is also necessary to have a water finding paste that is suitable for the product to be measured. Some products have water soluble additives that leach out of the product into the water layer. The water paste must therefore be able to register
the water/additive mixture as well as free water. An example
of this interaction is fuel system icing inhibitor (FSII) (sometimes referred to as anti-icing additive). It is only slightly sol-

640

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

uble in aviation turbine fuel but very soluble in water. The


water finding paste for these applications must be sensitive to
a 50% water/50% FSII mixture. One way to test whether the
water finding paste is still working is to place a drop of water
on a bob with the paste. This will show a color change. Pastes
are different, some changing from pink to blue, others one
shade of pink to another, etc. By testing the paste before going u p to the tank, a new ganger will understand what is
about to be seen when gauging for water. Remember, it will
not tell if the water paste is working in water/other product
mixtures. These must be tested in a laboratory at the prescribed mixture ratios.
The measurement of sediment uses the same bob or bar
used for the detection of free water. Water should sit on top of
the sediment. While both are subtracted from the calculations
of product quantity, it is necessary to know the level of sediment in the tank. Distillate product tanks have less sediment
layering them do crude oil and residual products. Therefore,
noticing sediment building u p on the floor may indicate it is
time to clean the tank before a quality problem occurs with
the product. Crude oil and residual fuel tanks may have larger
quantities of sediment and sludge. Should the level become
too high, it could affect the ability of the p u m p s to draw product out of the tank. The other problem it creates is that shipment of the contaminates decreases the value of the product.
For most distillate products, sediment and water quickly
falls to the bottom of the tank. A visual appearance of the fuel
determines that the water and sediment have settled to the
bottom of the tank and we do not have to worry about it for
calculation purposes. However, for crude oils and residual
fuel oils, sediment and water may also be suspended or otherwise in the product to be measured. The buyer of the products may not want to pay for these contaminants and therefore require an accurate measure of them. For crude oil and
residual fuel oils, there is an anticipation that these contaminates will be received and dealing with them requires advance knowledge of the levels of each.
If not already determined, a sample for the density measurement is required. The density is necessary as product expansion and contraction is affected not only by the temperature, but the product type and its density. This relationship
will be explained later in this chapter. Crude oil and residual
fuel oils are more likely to be non-homogeneous and proper
sampling is more critical so that an accurate picture of the
product quality can be determined through the testing process. Automatic sampling is the preferred method for sampling crude oils cind residual fuel oils because of this problem. In some cases, the density, water, a n d sediment for
official custody transfer purposes will be determined based
on in-line sampling at the time of shipment. By agreement, or
to protect one of the parties, a manual sample may still be
taken in case of a failure of the automatic in-line sampler. Automatic in-line samplers are recommended for custody transfer purposes as they may better represent petroleum and
petroleum products that would normally contain suspended
(entrained) S & W. Manual sampling may not be as accurate
in sampling for these contaminants, which are present in the
product in a non-uniform manner.
Manual sampling of the tanks is covered by API MPMS
Chapter 8.1 (ASTM D 4057), Manual Sampling of Petroleum
and Petroleum Products. The object of sampling is to take a

representative sample of the product to be sampled. Distillate products and finished lubricating oils from a single
batch are normally considered to be homogenous. That is, a
sample from anywhere in the product should be uniform
and, in theory, represent the product. In reality, slight
changes in the refining or manufacturing process may cause
some variation in the product. A permitted testing variation
on specified parameters determined by prior agreement
would provide for agreement that the batch tank is deemed
homogeneous for quality and quantity procedures. Not discussed in this chapter is the automatic in-line sampling procedures covered by API MPMS Chapter 8.2 (ASTM D 4177),
Automatic Sampling of Petroleum and Petroleum Products.
While previously used to determine the quality of crude oil
and residual fuel oils in the past, they are increasingly being
used for automotive gasolines, aviation fuels and diesels
both for quality control purposes and environmental regulation compliance.
The tools needed for manual sampling include a sample
bottle(s) and sampling cage or a weighted beaker (Figs. 6 and
7). A sample receiver or receptacle is a container in which all
sample bites are collected during the sampling operation. The
n u m b e r of bottles and sample receivers needed must be determined before going out to sample. Bottles and weighted
beakers must be properly cleaned so as not to contaminate the
sample before taking the samples. Sample bottles and containers may be clear or brown glass. Ccins used must have their
seams soldered on the exterior surfaces to preclude contamination with flux used in their manufacture. Polyethylene unpigmented linear plastic bottles can be used for gas oil, diesel
oil, fuel oil, and lubricating oils. These plastic bottles should
not be used for gasoline, aviation jet fuel, kerosene, crude oil,
white spirit, medicinal white oil, and special boiling-point
products unless testing indicates there is no problem with solubility, contamination, or loss of light ends. The container closure must be clean and ensure a good tight seal. Loss of light
ends have an effect on the density of petroleum and petroleum
products, which is an important element for petroleum mea-

1-Lllre (1 qt.)
Sample Weighted Cage
(can be (abricated
to HI any size bottle)

FIG. 6Weighted bottle sampler.

CHAPTER

Copper
handle

hitah

Copper
wire
lugs

Sheet
lead

Cork arrangements

Beaker

1-Litre {1 qt) Weighted Beaker


FIG. 7Weighted beaker sampier.

surement. A sampling cage with a bottle is preferred for


volatile products to preclude the loss of light ends created by
other techniques during product transfers. Poorly taken samples provide inaccurate sediment and water results. Taking
and protecting the samples is critical both for proper sampling technique, to provide accurate data for petroleum calculations, and to prevent disputes.
What samples should be taken? An official sample is taken
at the point of custody transfer and is used for custody transfer properties. The location where this sample is taken is by
mutual agreement between the buyer and seller. The object
for obtaining accurate samples is to have a sample representing the entire contents of the tank. A representative sample is a sample representing a small portion of the tank volu m e (that is, for tanks, ships' c o m p a r t m e n t s , containers,
pipeline tenders, a n d so forth) obtained with a precision
equal to or better t h a n that of the laboratory m e t h o d by
which the sample is to be analyzed. Other samples are taken
for Vcirious process, custody, inventory, a n d quality reasons.
These samples can be taken as a single sample or as various
spot samples as agreed upon. Some of the various types of
samples that can be taken as shown in Fig. 8. A spot sample
is one taken at a single location in a tank. It represents only
material at that location. Examples of spot samples are: top,
upper, middle, lower, and outlet samples.
Top sample is one taken at spot six inches below the top
surface of the liquid.
Upper sample is one taken from the middle of the upper
third of the tank contents.
Middle sample is one taken from the middle of the tank contents and should be half the distance between the upper
and lower samples.
Lower sample is one taken at the middle of the lower third
of the tank contents.
Outlet sample is one taken at the level of the bottom of the
tank outlet, but not more than one meter from the bottom
of the tank.

23: STATIC

PETROLEUM

MEASUREMENT

641

When any sample is taken where the loss of volatile components would affect the sample result, the procedures in API
MPMS Chapter 8.4, ASTM D 5842, Standard Practice for
Manual Sampling and Handling of Fuels for Volatility Measurement, should be used. The object is to take and handle a
sample without losing the light hydrocarbons. For instance,
when a density is to be run, the loss of the light ends will increase the density (lower the API Gravity) of the tested sample. This is t u r n m a y affect the volume correction factor
(VCF) used in determining the net quantity of fuel at the standard temperature. Basic technique requires the sample container to be filled to the 80% fill level, capped quickly, kept
cool, and delivered to the laboratory for testing promptly.
Volatile samples taken from taps should use an extension
that can reach close to the bottle of the sample container.
This will preclude splashing and the generation of vapors
leading to light end loss. Brown or a m b e r bottles or sample
cans must be used when taking samples of petroleum products that are light sensitive. Failure to use the appropriate
container could cause changes to the quality of the product
before testing of the product is accomplished. This could lead
to inappropriate results that may affect the quantity determination also.
When taking spot samples to be composited for a representative sample, a standard way to take samples is as follows: For tanks over 1000 barrels that contain more than 15
ft. of oil, an upper, middle and lower sample are taken and
combined in equal volume to make a composite sample. For
tanks over 1000 barrels which contain between 10 and 15 ft
of oil, a middle sample from the top half and a middle sample from the bottom half are taken and composited. A single
sample is taken normally when the level of the oil is less than
ten feet. For tanks smaller than 1000 barrels, either a single
sample or multiple spots can be used. Again make sure the
parties involved agree on the t3rpes of samples in advance of
the sampling process. Other spot samples can be designated
or taken upon mutucd agreement for custody transfer purposes. A bottom sample is one that obtains material from the
bottom surface of the tank or container at its lowest point. A

Hatch

r
rj
TH
Tank
contents

Outlet

15 cm (6")
Top sample
Upper sample

Upper third

- Middle sample

Middle third

Lower sample
Outlet sample

Lower third

Bottom sample

NOTE 1TTie location shown tor the outlet sample appfes only to tanks with
side Qutltta. It doea not apply whaa ttn outiat comas from the tkxx of the tani( or
turns down into a sump. Bottom sample location must tie specified.
NOTE 2Samples shoiid t otitained from within solid stand pipes as the
materials normaiiy not representative of the material in the tanit at that point.
FiG. 8Sampiing terms.

642

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

bottom water sample is a spot sample of free water taken beneath the petroleum contained in a tank or marine vessel
tank. These last two samples are used as indicators of the
contamination accumulating on the bottom of a tank, to determine where water came from (process water or sea water),
or to detect bacteriological or fungal growth.
Combining agreed upon spot samples is one acceptable
method as is testing individual spot samples and averaging
the results. A composite spot sample is a blend of spot samples
mixed volumetrically proportionally for testing. For instance
a multiple-tank composite tciken from marine vessel compartment tanks is a mixture of individual samples from several
compartments, each of which contains the same grade of
petroleum material. The mixture is blended in proportion to
the volume of material in each compartment (weighted average method). API MPMS Chapter 8.3, ASTM D 5854, Standard Practice for Mixing and Handling of Liquid Samples of
Petroleum and Petroleum Products, should be used for this
process. This blending should be performed in a laboratory.
Some tests may be made on the spot samples before blending
and the results averaged.
Two types of samples can be taken that represent the column of petroleum or petroleum product in the tank. Each
has drawbacks as to its being a representative sample. They
are used primarily for homogeneous product. First is an alllevel sample. An all-level sample is taken by submerging a
stoppered bottle or beaker as near as possible to the draw-off
level, and then opening the sampler, and raising the sampler
at a uniform rate such that it is about three-fourths full as it
emerges from the liquid. A running sample is one obtained by
lowering an unstoppered beaker or bottle from the top of the
oil level to the level of the bottom of the outlet connection and
returning it to the top of the oil at a uniform rate of speed so
that the beaker or bottle is about three-fourths full when it
breaks the surface of the oil. Both a running sample and an
all-level sample may not be a true representative sample, because the tank volume may not be proportional to the depth
or because the operator may not be able to maintain the variable rate required for proportional filling. The rate of filling
is proportional to the square root of the depth of immersion
also affecting sample representativeness. The lower the
beciker or bottle, the faster liquid flows into the beeiker or bottle.
Pipeline samples can be of several t3rpes. Automatic samplers are covered by API MPMS Chapter 8.2 (ASTM D 4177),
Automatic Sampling of Petroleum and Petroleum Products.
Automatic samplers are designed to take a representative
sample from liquid flowing through a pipeline. It consists
generally of a probe, an extracting mechanism, a controller
that determines when to extract the sample bites, and a sample receiver. Flow proportioning samplers adjust to product
volume changes resulting from changes in the flow rate. This
is the best way to get a representative sample from a pipeline.
Another tj^e is a time controlled automatic sampler. It takes
a sample bite at preset time intervals. Manual samples from
pipelines, sometimes called drip samples, can be taken. A
valve is cracked leading to a sample receiver so that over the
duration of the movement, product slowly fills the sample receiver so that it fills the container over the determined period. This does not provide for a truly representative sample.
Pipeline spot samples are another tj^e of manual samples.

They represent the product at a particular moment of sampling. Several pipeline spot samples can be combined to
make a pipeline composite sample to represent the product
in question. The number of samples required should be
agreed between buyer and seller when used for custody transfer purposes. Changes in flow rates have little effect on the
amount of sample being taken. Care must be taken to preclude overfilling samples taken from a pipeline. To get a truly
representative sample from a pipeline, the product must be
flowing at a turbulent flow rate. Turbulent flow promotes
product and contaminants distributed equally throughout
the pipeline cross section. When product has a laminar flow,
there is a faster section moving above a slower section. Contaminants such as sediment and water can settle to the lower
section of the pipeline or at the low points. Samples taken at
laminar flow tend not to be representative.
Before climbing the tanks, determine if control of the volumes in the pipeline are required. For custody transfer purposes, the condition of fill of the pipelines to be used must be
known, both before and after the movement. If the pipelines
are stated as full, validate by pressure or other means that the
line is full. One reference for this operation can be found in
API MPMS Chapter 17.6, Guidelines for Determining the Fullness of Pipelines Between Vessels and Shore Tanks. If empty,
confirm as best as possible. If there is a difference in the condition of the pipeline fill before and after a movement, the differences must be accounted for in the product calculations.
It's time to climb that tank or go to the marine vessel to
take samples and to gauge the tanks. What is the proper order to perform the water cut, product gauge, temperature,
and sampling? If water cut is done first, the oil column above
the water layer may become contaminated. This would lead
to erroneous results coming from the contaminated samples.
Therefore the order should be to take the samples first.
Which samples should be taken? For the same reason, taking
the bottom water cut measurement, samples are taken starting from the highest in the tank. If a top sample is needed,
take that first. Then the upper, middle, lower, outlet, and bottom samples. If after these samples an all-level or running
sample is required, take these after the spot samples. The order of taking the samples is the same from compartments on
a marine vessel. When homogeneous product is on board a
vessel, a single middle spot sample may only be required. At
other times the individual compartment may only require an
all-level sample. However, when crude and heavy fuel oils
that contain water and sediment in a non-homogeneous
manner are sampled, several spot samples may be required
and/or a running or all-level sample. Samples are taken and
properly labeled with a marker that will not be affected
should the oil splash or be introduced onto the label. The label must be affixed to the sample bottle or containers immediately after the sample is taken. This is extremely important
when several different samples are taken from one tank. Always check that any labels, especicilly preprinted ones, are
put on the correct sample. Ensure that all relevant details are
on the sample label. No one wants to climb a tank a second
time because the results from the testing indicate a problem.
Side tap samples along the staircase can be taken either going up or going down. However, if samples are taken on the
way up, it will make the carrier weigh more as you ascend the
staircase. Recommend tEiking the samples on the way down

CHAPTER 23: STATIC PETROLEUM MEASUREMENT


after gauging is complete. When using the side taps, know
how high the product is in the tank and make a determination on which taps are needed from that information. On a
full tank, the upper, middle, and lower samples are easily
judged. When the tank is not full, the requirement for two
sets of more than five taps on a tank can be understood. By
knowing the height of the product in the tank, appropriate
level samples can be taken. Some sample taps include extensions that enable sampling from the base of the tank. When
these are encountered, make sure the tubing is flushed completely before taking samples. Otherwise, a prior batch left in
the extension tubing will be sampled.
At the top, the gauging and sampling tubes should be
clearly marked. In most cases they are the same point. Sampling and gauging tubes must be appropriately slotted in order to obtain accurate samples and gauges. The gauging
hatch or hatches should have the reference height marked on
or near the hatch. While this must be validated from the certified capacity tables, it is a good reference while on top of the
tank. Take the required number of samples in accordance
with API MPMS Chapter 8.1 and Chapter 8.4 when taking
volatile samples. After the samples are taken, go to the gauging.
When using thermometers, place them at the appropriate
levels now if they will not be in the way for the gauging operation. This will give them time to equilibrate to the surrounding temperatures. Table 3 of API MPMS Chapter 7.1,
Static Temperature Determination Using Mercury-in Glass
Tank Thermometer, provides for the minimum number of
readings required based on product height. Where the depth
is greater than 10 feet, three temperatures are required, one
each from the middle of the upper, middle, and lower sections of the tank. For depths less than 10 feet, a single temperature taken at the middle of the liquid is required. Tables
4A and 4B of Chapter 7.1 provide for the minimum immersion time for these thermometers. The immersion time is
based on the density of the product and whether the thermometer is stationary at the required level or in-motion
(raised cind lower one foot above and below the designated
level). Table 2 of API MPMS Chapter 7.3, Static Temperature
Determination Using Portable Electronic Thermometers, provides recommended immersion times for electronic thermometers. The times again vary based on the density of the
product and whether the thermometer is held stationary or
kept in-motion as described above. Check these publications
for the appropriate immersion times.
When gauging for custody transfer purposes, there is, by
necessity, an opening gauge and a closing gauge. When
standing on a roof, your weight and the weight of those
watching or helping you may depresses the roof. It is important that the same number of persons, hopefully of the same
approximate weight, accompany the gauger for each measurement. Encourage everyone to stand in the same relative
positions (at the side) to keep these factors constant. If a water gauge and product gauge will be taken at the same time,
apply the water finding paste to the bob and a thin coating of
product finding paste along the anticipated levels. When
gauging crude oils or heavy fuel oils, it may help to coat the
water finding paste and the bob with a light lubricating oil in
order to help shed the oil after its return to the top for reading. Product finding paste is not needed for heavy fuel oils.

643

crude oils, and other dark viscous products as they do not


evaporate or rise up the tape. Talc and chalk may not be used
if the product has a tendency to creep up the powdered tape
from the true reading giving erroneous readings. Place the
tape against the reference point on the gauge hatch. This releases static charge, which may build up. Lower the bob
slowly through the product. While lowering the tape and bob,
try not to disturb the liquid level greatly. Motion at the top of
the liquid level causes an inaccurate reading. The waves
caused by the disturbance or the wind can result in an increase in the total liquid height measured.
For an innage gauge, lower the tape until the length in the
tank is close, but not over, the reference height. Remember it
is most likely stenciled or written by the gauge hatch. Just
compare it to the tape reading and when they are close (that's
the point to pay close attention) be very careful, lowering the
tape until you feel the bob hit the datum plate or floor of the
tank. It is very important to come to a full stop when this is
felt. Lowering the tape any further results in the bob and the
tape arching in the tank. The bob leans to one side and more
tape goes into the product. Both measurements will have increased by some amount. If you go far enough, the bob will
actually be resting horizontally (flat on the floor or datum
plate). Maintain the tape in the stop position. Record the total height that the tape is out. This should be equal to the reference height. If it is not, then when performing the calculations, some adjustment may be needed to the product height.
The length of time the stop position must be held is dependent on the product in the tank and the amount of water.
Heavy products tend to coat the bob and water finding paste
before the bob enters the water layer. This type of product requires the bob to rest longer in position for accurate water
readings. It is appropriate for clean light products to maintain this position for 10 s. For heavy crude oils and fuel oils,
it is appropriate to maintain this position for 1-5 min.
If there is a large body of sediment and sludge on the bottom, using the innage method may be impractical as the bob
will never reach the bottom of the tank or datum plate. The
bob is unable to cut through it. More than likely, an experienced gauger will be able to discern the problem by the way
the tape feels as it hits the sediment and sludge. But more
practically, the reference height will be greater than the tape
reading at the reference point when this occurs. When there
is sediment and sludge precluding the bob from reaching the
bottom, the outage method of gauging is required. The outage
method may be required for both the product and water cuts.
However, there are occasions when a bob is unable to cut
through sediment and sludge, but a water gauging bar or rod
can. As long as the bar or rod hits the bottom, gauging using
an innage method of the total sediment and water is appropriate. One other problem occurs with tanks that have a large
bottom sediment and sludge layer. The solid material may not
be layered in the tank. Rather, pejiks and valleys may have developed due to the dynamics in the tank. Close to the inlet, the
sediment may have been pushed up forming peaks away from
the inlet. Conversely, d5mamics at the suction point results in
washing away of the sediment building up. Again a valley may
be formed here. Several measurements for sediment at various levels may be necessary to discern these anomalies.
There are several schools of thought on gauging total
height of the liquid at the same time as the free water mea-

644

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

surement. First, gauge the free water, first getting the reference height estabhshed once. This is only done once. Then
proceed on with gauging for the total height of the liquid in
the tank. SecondPerform b o t h the free water and total
height of the liquid simultaneously. Assure that an agreement
has been reached on this point between the buyer and seller
or as a company policy and then advise the ganger and/or independent surveyor of the agreed procedure.
Continuing on with the innage method using the second
school of thought, raise the tape until the product cut can be
seen. Read the location of the product, referred to as a cut, to
the nearest millimeter (or 1/8 in). Record the product cut.
Raise the tape and bring the bob to be viewed. Be careful
when bringing the bob u p and out so as not to disturb the water finding paste. Read the water cut and record it also. For
tanks with crude oil and heavy fuel oils, it may be necessary
to rinse the oil off the bob to view the water cut. Use an appropriate solvent to clean the bob. Take care in rinsing with
a solvent so as not to push the water line u p or down. Be environmentally friendly when performing these actions. Additionally, do not blow or wipe the petroleum or petroleum
products off the bob as this too may distort the water cut and
thereby give incorrect readings.
Perform the gauging actions again. They should be identical. If not try once more. If all three are within 3 m m (1/8 in)
of each other and two are identical, then the two identical
readings are reported as the official gauge. If not within 3
m m (1/8 in), continue gauging until three consecutive gauges
are within 3 m m (1/8 in) of each other. If none are identical,
averaging of the gauges m a y be permitted. Averages are to
the nearest millimeter or 1/8 in, depending on the unit being
used. Other a r r a n g e m e n t s are permitted by agreement.
Smcdler tanks or tanks gauged in windy conditions may preclude the level of accuracy desired as the product level in the
tank is unstable. Small waves are created by the wind and the
differences in the wave heights between each measurement
create the inaccuracy in measuring the product height. Once
completed it is time to return to the office to perform the calculations. However, before coming down off the tanks, if several people are gauging or witnessing the gauging, agree on
the gauges before coming down. This precludes disagreements after the fact.
Most marine measurements are not used for custody transfer purposes, but primarily for inventory control purposes.
Let us look at performing a n outage or ullage gauge. This is
used for most heavy dark oils and is the preferred method for
marine vessel gauging. The basic difference is that the bob
does not reach the bottom of the tank. When using an outage
tape and bob, ground the tape and bob to the tank. Lower the
tape and bob into the product. Lower the bob into the product only slightly. Remember, the object of a n outage tape and
bob is that the product reading is on the bob between the zero
cmd the plus side (lower end of the bob). At the reference point,
have the tape come to a whole increment, either centimeter or
inch. Note the distance the tape has been lowered into the
tank. Bring the tape back to the surface emd read the bob. If
within the correct reading zone, the bob reading is added to
the distance the tape was measured as being lowered into the
tank. Unfortunately, there are occasions when the gauger for
any n u m b e r of reasons lowers the tape too far. When you
bring the tape and bob back up, you can read a measurement

on the u p side of the tape. In this case, subtract the product


reading from total distance the tape was lowered into the tank.
Of course, if you used an extension outage bob designed for
an innage tape there is a section where n o linear measurements are encountered on the bob. Just clean the bob and redo
the measurements. As in the innage method, two consecutive
readings are required to be identical. Otherwise use the same
innage rule for obtaining gauged measurements.
Taking an outage gauge with an innage gauge and bob follows the same procedures as an outage gauge. Ground the
tape and bob to the tank by placing the tape against the tank
rim. Lower the tape and bob just barely into the product.
Lower the tape to the next whole increment on the tape. Read
and record the total tape height let out. Bring the tape and
bob back u p to the top and read the product cut on the tape
or bob. If the reading is within the eye or eye hook area where
no linear markings are, clean the tape and bob and redo the
measurement using a different lowered distance. For innage
tapes and bobs, the outage is figured by subtracting the lower
tape or bob reading from the total height the tape and bob
were lowered into the tank.
E x a m p l e 1: O u t a g e T a p e a n d B o b
a) Total height of tape p u t into the tank read at the tank
gauging point = 7.450 m
b) Measurement found o n the bob when raised = 0.090 meters. Add (a + b).
c) Outage Gauge for total liquids in the tank = 7.540 m
E x a m p l e 2: I n n a g e T a p e a n d O u t a g e B o b
a) Total height of tape p u t into the tank read at the tank
gauging point = 7.450 m
b) Measurement found on the bob when raised = 0.090 meters. Add (a + b).
c) Outage Gauge for total liquids in the tank = 7.540 m
E x a m p l e 3: Innage T a p e a n d B o b or a n Outage
Tape a n d B o b Reading above the Zero Mark or an
Innage Tape with an Extension Outage Bob
Reading above the Zero Mark o n the B o b
a) Total height of tape p u t into the tank read at the tank
gauging point = 7.450 m
b) Measurement found on the bob when raised = 0.090 m.
Subtract (a b).
c) Outage Gauge for total liquids in the tank = 7.360 m
After performing the total liquid measure in the outage
method, a measurement for water and sediment is still required. This can be done by the innage method as described
above provided the bob or rod can reach the bottom of the
tank. For tanks that may contain sediment and sludge, make
sure the bottom is reached. When the reading is tciken, estimate the level of sediment and sludge by looking for its adherence to the water finding paste. There will then most
likely be a section where the water finding paste turned the
appropriate color without any sediment. Both measurements
are important information, be it for unpumpable bottoms, or
levels that would indicate a possibility that the water and sediment would be pumped from a tank.

CHAPTER 23: STATIC PETROLEUM MEASUREMENT


However an outage measure can be performed to obtain
the height of the water cind sediment. This is a little tricky as
some trial and error may be necessary. Apply the water finding paste to the bob and if the water layer is believed to be
greater than 15 cm (6 in.), apply the water finding paste to the
tape for an appropriate distance. Ground the tape and bob to
the tank top and then lower until you believe you are in the
water layer. Remember the problems that occur if the tape
and bob hit sediment or sludge cire identical to going too far
in the innage gauge procedure. If you hit a solid layer of sediment and sludge, the bob could lean. If this happens and the
gauger shows that the tape and bob have leaned or arched,
bring the tape and bob back up, clean the equipment and
lower the tape and bob a little shorter. Lower the tape to the
next whole number on the tape and record the reading. Bring
the tape and bob up. It may be necessary to use an appropriate rinse to clear heavy oils off of the section to be read. Use
the same precautions as discussed under the innage method.
Read the water cut before the calculations as above. Depending on the tank strapping chart, this reading may have to be
converted to an innage gauge. Remember that the reference
height of the tank minus the outage gauge equals the innage
gauge.
A quick mention of automatic tank gauging is needed. API
MPMS Chapter 3.IB covers the Standard Practice for Level
Measurement of Liquid Hydrocarbons in Stationary Tanks by
Automatic Tank Gauging. These instruments require calibration before use. Manual gauging in accordance with API
MPMS Chapter 3.1 A is recommended for most calibration
procedures. Additionally, some may not have the accuracy
required for custody transfer purposes. Use of an automated
tank gauge (ATG) requires agreement by the parties prior to
their use. ATGs can have remote readouts, gauge readers at
the bottom or the top of a tank and sometimes an external
marker on the side of a tank. Even with ATGs, slotted standpipes when used are recommended. Solid stilling wells ("still"
pipes) used for environmentetl reasons are not recommended
for custody transfer purposes as they can lead to inaccuracies
of the level and temperature measurements. There are several types of ATGs in use currently. A float operated ATG contains a float, which travels along one or two wires. The floats
are designed to be buoyant at certain densities. They will
therefore remain on top of the product intended. Turbulence
in a tank can put the float out of calibration. When used in
floating roof tanks, wind can stretch the wire holding the
float cind provide inaccurate readings. A servo-operated automated tank gauge is another type that uses a small displacer
into the liquid level from a flexible cable or tape. These are
normally located at the top of a tank in a still pipe. Hydrostatic tank gauges use precision pressure measurement devices located at several levels of the tank. These gauges measure the hydrostatic head pressure at each point and use
strapping chart data to calculate the mass, density, volume,
and level within the tank. Temperatures are tcJcen and fed
into the automated calculation and readout system. This system is prone to inaccuracies caused by product stratification,
especially density stratification. Another type of ATG is the
radar tank level gauge. Radar waves are used to determine the
distance remaining in the tank. It measures the time it tcikes
for a radar wave to go to the liquid surface and return. Then
there are sonic and ultrasonic tank level gauges. These operate

645

using an acousticcJ sound. The device measures the elapsed


time of the sound and the return of its echo. These are a few
of the automated gauging types. Some ATGs are also able to
measure the water/ product interface.
To be truly accurate, at least one more measurement is
needed. The ambient air temperature just on the outside of
the tank is needed for use in the correction for steel of the
tank shell calculations. The ambient air measurement is
made at least 3 ft. off the ground on the shady side of a tank.
It should be taken by the gauger either just before or just after the tank gauges. Allow enough time for the thermometer
to equilibrate with the ambient air before reading.
Measurements on marine vessels are taken identically as on
land. There are two additional factors that are required. On
marine vessels, the vessel may not be level in two directions.
The front to back slope on a marine vessel is called trim while
the right to left tilt is called list. These are needed because the
strapping charts are prepared for vessels that are level. When
the vessels become out of level, the liquid level remains parallel to the pull of gravity, changing the gauge readings at the
point where it is normally taken. To understand this concept,
take a glass of water filled only half way. Tilt the glass in any
direction. The liquid level remains parallel to the ground. The
steeper the tilt either forward or backwards or side to side can
place a liquid surface close to the edge of at the top while the
other side gets close to the bottom of the glass. Marine vessels
have calculated values contained on the strapping cheirt for
trim and list. It is therefore necessary to determine the trim
and list. Marine vessels have markings on the side of the vessel near the bow, middle, and stem to indicate how far into the
water they are. These draft markings are used to determine
the trim. Read the draft markings as best as possible. If the
bow is higher than the stem, the vessel is down by the stem.
Should the bow be lower than the stem, the vessel is down by
the head. Note that the higher the draft, the lower the vessel is
sitting in the water at that point. The middle draft is used to
determine whether the vessel is arching or bowing in the water. Weight is not always equal at every point within the vessel and some hog or sag is expected. Additionally, the vessel
may lean to the right (starboard) or left (port). A vessel's inclinometer, usually on the bridge, is used to measure the vessel's list. If the inclinometer is not available, the list can be calculated from the midpoint port and starboard draft readings.
The measurement of the trim and list must be made at the
time the vessel gauging is performed. Otherwise the corrections applied to the actual vessel gaugings will be inaccurate.
That is one reason why gauging should occur after completion
of loading or discharge. During the transfer operations, the
trim and list may change. The corrections are added or subtracted to the observed gauges based on the instructions contained in the strapping chart.
In a marine vessel, on-board quantity (OBQ) and remaining on board (ROB) quantity must be measured. As long as
these volumes cover the entire bottom surface and all four
walls, the strapping chart applies. There are times when this
does not occur, but measurements must be tsiken. A wedge
formula is used to calculate the OBQ or ROB. Some linear
measurements of the cargo compartment are needed. For
use of the wedge formula, use API MPMS Chapter 17.4
Method of Quantification of Small Volumes on Marine Vessels
(OBQ/ROB). Where a solid or nearly immovable substance is

646

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

layered on the bottom of a marine vessel, trim and list corrections are not applied. Rather for this layer, it can be considered as layering the bottom of the vessel as a solid sheet.
Use the strapping chart to obtain this quantity as if the vessel
were on even keel.
Nov*? for the really easy pEirt, the calculations back in the
shore office or the ship's office. The calculation procedures
are governed by API MPMS Chapter 12.1, Calculation of
Static Petroleum Quantities. We will be taking the linear measurements and converting them to volumes now. In doing so,
we need to define some terms.
Total Observed Volume (TOV) is the volume found from the
measured total liquid height. It includes all petroleum liquids, water, and sediment in the product, free water, and
bottom sediment.
Free Water (FW) means all free water and bottom sediment.
This is the water cut measurement converted to a liquid
volume. It includes the bottom sediment a n d sludge, if present, as the measurement includes it. Additionally, the free
water and the sediment and sludge have different volume
correction factors from petroleum products.
Gross Observed Volume (GOV). This is the total volume of
petroleum liquids and sediment and water in the product
less the free water volume. (GOV = TOV FW).
The Volume Correction Factor (VCF) is correction for temperature of the liquid to a standard temperature. It may
also be referred to as the Correction for Temperature of the
Liquid or CTL.
Gross Standard Volume (GSV) is the GOV times the VCF
(GOV X VCF).
Net Standard Volume (NSV) is the total volume of all
petroleum liquids, excluding S & W and free water, corrected by the appropriate VCF. (G.S.V. - S & W = N.S.V.)
For sales, this is the value required. However for inventory
purposes and storage, shipping, and handling, we need to
know and understand the other definitions.
A tank may be able to contain the NSV, but not the TOV.
Remember that petroleum products expand when the temperature of the product increases. Leave enough room in the
tank for said expansion. Volumes in pipelines also expand
and contract. Static lines may not be full if several expansion/contraction cycles caused by day/night t e m p e r a t u r e
variations have occurred. Some product may have moved to
another tank through the pressure relief system.
From the laboratory tests we receive the density at 15C (API
Gravity at 60F) and the tested S & W contained in the product
as a percent reading. Performing a density or API Gravity test,
follow the procedures in API MPMS Chapter 9 Density Determination. Several ASTM test methods are D 5002 (Crude Oil
by Digital Density AnjJyzer), D 4052 (Liquids by Digital Density Meter), and D 1298 (Hydrometer Method). The basic principle for the manual method is to take the sample and place it
in a hydrometer cylinder. Make sure all air bubbles Eire eliminated from the top of the liquid. Use a hydrometer with an appropriate scale reading. Some hydrometers have a thermometer as p a r t of the hydrometer. Otherwise, a separate
thermometer is required. It is best to have the product being
measured equilibrate with the ambient temperature as it precludes temperature drift during the measurement. Especially
in the field, this may not also be possible. Lower the hydrometer into the liquid to a position close to where the hydrometer

would float. Getting liquid above this position on the hydrometer stem can result in slightly inaccurate readings as the liquid may be retained above the level of the product depressing
the hydrometer slightly. Spin the hydrometer to disperse air
bubbles on the bottom of the hydrometer. Allow the hydrometer to come to rest. Read the hydrometer to get the observed
density. As quickly as possible read the thermometer to obtain
the temperature that the observed density was taken. When using separate hydrometer and thermometer, remember to allow
the thermometer time to equilibrate in the liquid before reading it. To convert density at observed temperature to density
(API Gravity) at standard temperature, follow the procedures
in API MPMS Chapter 11.1 (ASTM D1250 or IP 200) and the
appropriate table designations. There are tables for specific
range of products. Table A is used for crude oil and naphtha
based aviation turbine fuels. Table B is used for most other
petroleum fuels. Table D is used for lubricating oils. For those
that wish to perform the coefficient of expansion tests each
time a VCF is needed for a specified product, use table C. Tests
for S & W include centrifuge method, water by distillation, water by Karl Fischer and Sediment by extraction. Round values
to the precision required as stated in API MPMS Chapter
12.1.1, paragraph 6.2 and Table 1. You can do the calculations
or a computer may be able to do them if programmed appropriately Eind the correct numbers are entered into it.
For shore tanks, take the total liquids gauged measurement
and go to the strapping chart. The volume obtained is the
TOV. For marine vessels, the trim and list factors must be applied to t h e total liquids gauged. This will b e contained
within the strapping chart. Based on the trim and list, the
strapping chart will advise you to add or subtract some linear
measurement to the observed reading. From this correct linear measurement, obtain the TOV from the strapping chart.
Whether a shore or marine tank, free water is normally obtained as an innage value. Look u p the total volume of free
water (remember this includes the b o t t o m sediment) and
record this volume as FW. There may be occasions when the
level or type of free water and sediment necessitated an outage gauge. If the chart is in innage measurements, convert
the outage gauge to a n innage gauge and look u p the FW volume. If the volume of free water and b o t t o m sediment is
great, using the outage gauge table may be appropriate. On
marine vessels, remember trim and list corrections when the
bottom layer is fluid.
For true corrections, the correction for temperature of the
shell (CTsh) is needed. This compensates for the expansion
and contraction of the tank shell caused by the temperatures
of the product and the ambient air. Tanks are strapped assuming a specified temperature range. The CTsh is used to
bring the liquid volume back into calibration. In accordance
with API MPMS Chapter 12.1.1, Section 9.1.3 the adjustment
used is CTsh = 1 - 1 - 2aA T + a^\^. The symbol a equals a linear coefficient of expansion of the tank shell, with Appendix
B-2 containing several coefficients for various metals. The AT
equals the Tank Shell Temperature Base Temperature. The
base temperature is the temperature that the strapping chart
was calibrated at. The tank shell temperature for an insulated
tank is assumed to be the temperature of the product. For
noninsulated tanks, use the formula in Appendix B of API
MPMS Chapter 12.1.1.
Calculations for a floating roof tank include a floating roof

CHAPTER
adjustment (FRA). Remember that a floating roof displaces
product due to its weight. Some strapping charts contain the
formula for this adjustment. Others just provide the weight of
the roof and the FRA must be calculated. Check this carefully
w h e n performing the CcJculations. The basic principle is that
the roof correction = weight of the roof / (density X VCF).
The displacement a m o u n t was also determined at a specified
density and part of the correction includes an adjustment for
the difference between the observed density and the density
used in the calibration, most likely 15C or 60F. Now we can
determine the GOV.
For shore tanks, the GOV is the [(TOV - FW) X CTsh]
FRA. The FW is deducted before the FRA because water and
s e d i m e n t compress differently t h a n petroleum a n d
petroleum products. For most purposes, it is assumed not to
have a compression factor and therefore is ignored in the calculations. For marine vessels the GOV = (TOV Trim/List
Corrections) FW. This now gives the total liquid volume to
be sold or moved. The next step is to convert this volume at
an observed temperature to a volume at the standcird temperature, referred to as the Gross Standard Volume (GSV).
The GSV = GOV X VCF. For distillate fuels and lubricating
oils, the trace amounts of entrained water and sediment are
accepted without adjustments to the quantity. Therefore for
distillates and lubricating oils, we also have the Net Standard
Volume (NSV). In fact for these products, we normally do not
refer to a GSV, only the NSV in the CcJculations.
However, in the case of crude oil and some heavy heating
oils, a deduction is made for the amount of S & W contained
in the product. From the laboratory, the water and sediment
value is provided as a percentage. The NSV is therefore the
GSV times a correction for the sediment and water (CSW).
To obtain the CSW, convert the sediment and water percentage into a decimal and then subtract that value from one
(1.0000). For example, if the sediment and water contained in
a crude oil is 4.25%, converting to a decimal gives 0.0425.
Then (1.0000 - 0.0425) = 0.9575 as the CSW. Then the
NSV = GSV X CSW. Conversely, use the converted sediment
and water decimal and multiply it times the GSV. This will
give a volume of sediment and water contained in the GSV.
Then the NSV = GSV minus the volume of sediment and water CcJculated. This concludes volume calculation.
Lastly, many users of this information also require the apparent mass or weight in air of the product. For this we use a
Weight Conversion Factor (WCF), which is a relationship between the density of the product and its weight in air. There
are m a n y tables contained in Volume XI a n d XII of API
MPMS Chapter 11.1 that give these relationships. There are
also numerous methods to convert from volume to weight. It
is preferable to approach the ceJculation process from the
simplest, most direct direction. Using different approaches
results in slightly different weights. It is best to obtain agreement on the conversion process as part of the agreement between buyer and seller or as a company policy for internal
use. This will preclude problems by those performing the calculations or inventory control reviews.
The order of calculation is TOV to GOV to GSV to NSV to
Weight in Air. The exception is when the tank measurement
is by a direct mass method, for example a hydrostatic tank
gauge. The reading is already in mass units and the calculations are performed within the little black box. All that is

23: STATIC

PETROLEUM

MEASUREMENT

647

needed is to confirm all the adjustments have been made for


FRA, CTsh, FW, and sediment and water. As noted earlier,
the calculation psirt of static petroleum measurement is really the easy part.
Let u s perform a sample calculation here. Information
from the tank and lab are provided:
Product Crude Oil
TOV = 10,250,500 USG
FW = 765 USG
Sediment and water = 2.25%
Product Temperature == 67F
LT/BBL
TOV
FW
minus
equals
times
equals
FRA
times

GOV
CTsh

API Gravity = 28.5


FRA = - 7 5 . 5 5 USG
CTsh = 1.00009
VCF (Table 6A) = 0.9969
WCF (Table 11) = 0.13808
10,250,500 USG
765
10,249,735 USG
X 1.00009
10,250,657 USG
- 76 USG

10,250,581 USG
VCF table 6A x 0.9969

GSV
10,218,804 USG
Note: (S = Standard temperature, in this example it is 60F)
CSW (1-0.0225)
0.9775
times

equals
NSV
9,988,881 USG
Divided by 42 USG/barrel equals
237,830.50 barrels
times
WCF (table 11)
0.13 808 long
tons/barrel
Long Tons

32,839.64 long tons

Using this information requires an understanding of the


purpose of the measurement and its relationship to other
measurements. In the petroleum industry, careful control of
quantities is expected. First, the profitability of a company
depends on accurate measures for sales and purchases.
Losses affect the company's bottom line. If you obtain a
gain, someone else has taken the loss. Second, inventory
control procedures use these quantities to determine theft
during movements or spills and leaks during storage or
movement. The accuracy of these determinations affects the
time spent in investigating the loss or gain. Losses may require an expenditure of funds in investigating the loss, some
internally m a n d a t e d , b u t m a n y regulatory mandated.
Within the industry, it is recognized that the measurements
between two points contain some vjiriation. The principle
causes of these differences are contained in the measurement precision of the methods used in determining the linear gauge, temperature, automated gauging precision, density measures, evaporation loss, and others. These slight
variations may give slightly different volumes between two
different measurements. One source of error is slowly being
displaced by the use of precision equipment. A temperature
obtained using a thermometer will have an error caused by
our ability to discern between the graduation marks. The
electronic versions provide the temperature more accurately. These changes reduce the variation expected. Agree
on the variation due to measurement errors in adveince or
have company policy clearly explain that some variation is
expected. However, losses that can be determined, such as
spills, leaks, and thefts are not contained in the variation.

648

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

These need to be identified and explained, and procedures


should be developed to eliminate them. Volatile hydrocarbon losses can be calculated. With increased attention on
the environment, environmental groups are mandating reductions in the release of volatile organic hydrocarbons.
These normally require some sort of engineering changes to
the tanks and facilities.
The true measure of successful static petroleum measurement is the care and practice of the techniques described in
obtaining the required data. The calculations are easy and
straightforward. However, with incorrect data, all that is obtained is incorrect volume eind weight measurements. Take
the time to train the samplers and gaugers to perform the required steps in accordance with the defined procedures.
Make sure they understand how important they are to the
health and financial success of your operation.

ASTM STANDARDS
No.
D 1250
D 1298
D 4052
D 4057
D 4177
D 5002
D 5842

Title
Petroleum Measurement Tables
Hydrometer Method
Liquids by Digital Density Meter
Manual Sampling of Petroleum and Petroleum
Products
Automatic Sampling of Petroleum and Petroleum
Products
Crude Oil by Digital Density Analyzer
Sampling and Handling of Fuels for Volatility
Measurement

D5854
El

Mixing and Handling of Liquid Samples of


Petroleum and Petroleum Products
ASTM Thermometers

OTHER STANDARDS
American Petroleum Institute (API) Manual of Petroleum
Measurement Standards (MPMS), Chapter 3.1
API MPMS Chapter 7, Method of Measuring the Temperature of Petroleum and Petroleum Products
API MPMS Chapter 8.1, Manual Sampling of Petroleum and
Petroleum Products
API MPMS Chapter 8.2, Automatic Sampling of Petroleum
and Petroleum Products
API MPMS Chapter 8.3, Standard Practice for Mixing and
Handling of Liquid Samples of Petroleum and Petroleum
Products
API MPMS Chapter 8.4, Standard Practice for Manual Sampling and Handling of Fuels for Volatility Measurements
API MPMS Chapter 10, Density Determinations
API MPMS Chapter 11.1, Physical Properties Data
API MPMS Chapter 12.1, Calculation of Static Petroleum
Quantities
API MPMS Chapter 17.4, Method of Quantification of Small
Volumes on Marine Vessels (OBQ/RBOB)
API MPMS Chapter 17.6, Guidelines for Determining the
Fullness of Pipelines Between Vessels and Shore Tanks International Petroleum (IP) 200, Petroleum Measurement
Tables

MNL37-EB/Jun. 2003

Hydrocarbon Analysis
James C. Fitch^ and Mark Barnes^'^

Basic Principles of NMR Spectrometry

THE AIM OF THIS CHAPTER IS TO BRIEFLY PRESENT SIX ANALYTICAL

METHODS for characterizing hydrocarbon compounds found


in fuels and lubricants. The methods presented are NMR
spectrometry, gas chromatography, liquid chromatography,
ultraviolet spectroscopy, mass spectrometry, and infrared
spectroscopy. The analysis of hydrocarbons deploying these
methods is well-founded in scientific laboratories and is the
basis of numerous ASTM standards.
Because of the large body of published work on these
methods, it is not the intention of the authors to attempt
complete coverage of all methods, but rather to provide an
overview of their use in the analysis of fuels and lubricants.
Following each section are summaries specific to ASTM D 02
standards where the analytical method is deployed in the areas of fuels and lubricants.

Absorption spectrometry works because applied electromagnetic radiation of an appropriate frequency induces a transition from one (lower) energy level to another (higher) energy
level within the molecule, causing the radiation to be absorbed by the sample. In IR and UV spectrometry, these energy levels are the vibrational and electronic energy levels of
the molecule, whereas in NMR the energy levels are associated with the nuclear spin of the nuclei that make up the
molecule. For the purpose of detailing how NMR works, we
will focus on the most commonly studied nucleus, the hydrogen nucleus 'H, which has a nuclear spin of li.
A nucleus such as 'H with a spin of 'A possesses two nuclear
spin states, +'A and 'A. Under normal circumstances, these
spin states have the same energy and are said to be degenerate. However, in the presence of a strong magnetic field (typically 2.33 tesla (T) for the ^H nucleus), the two nuclear spin
states split into two energy levels, their separation being proNUCLEAR MAGNETIC RESONANCE (NMR)
portional to the applied magnetic field as shown in Fig. 1 [1].
SPECTROSCOPY
Applying a source of electromagnetic radiation and slowly
Introduction
scanning the frequency can induce absorption when the radiation frequency matches or is in resonance with the energy
Nuclear magnetic resonance (NMR) spectroscopy is one of
separation of the two nuclear spin states under the applied
the most widely used analytical tools in chemical analysis.
magnetic field. The frequency of radiation that must be apJust like infrared (IR) and ultraviolet (UV) spectroscopy,
plied to induce such a transition is typically in the radio freNMR is a form of absorption spectrometry, whereby the
quency (rf) range. For a ^H nucleus under an applied magamount of absorbed electromagnetic radiation at a given frenetic field of 2.33 T, the resonance frequency is around 100
quency can be related to the concentration of certain chemiMHz [2]. For practical reasons, NMR spectrometers usually
cal species that absorb at that frequency. However, unlike IR
work in the opposite sense, with a fixed electromagnetic raspectroscopy, which looks at functional groups within a
diation frequency (commonly 100 MHz for ^H NMR) and a
molecule, or UV spectroscopy, which looks at the molecule as
scanning magnetic field [3]. However, the same principle apa whole, NMR is used to determine the concentration of speplies: the magnetic field is scanned until the energy separacific atoms within a sample.
tion of nuclear spin states induced by the field comes into resonance with the applied electromagnetic radiation.
It is not the mandate of this chapter to provide a detailed
quantum physical explanation of NMR or any other analytiIn reality, the magnetic field that must be applied to bring
cal method described herein. However, the basic theory bea nuclear spin transition into resonance with the applied
hind NMR spectroscopy will be outlined in this section, so
electromagnetic radiation varies slightly with the chemical
that the reader can obtain an understanding of NMR and
environment of the nuclei in question. This phenomenon is
how it can be applied to the analysis of large hydrocarbon
known as shielding and can be attributed to the effects of the
molecules typically found in fuels and lubricants.
electrons surrounding a particular nucleus, shielding the nucleus from the effects of the magnetic field [2]. Because the
electron density surrounding a particular nucleus is directly
related to the chemical structure of the molecule, the electron
distribution within the molecule gives rise to shielding ef1 Noria Corporation, 1328 E. 43''' Court, Tulsa, OK 74105.
^ Technical Editor, Practicing Oil Analysis Magazine, Tulsa, OK fects, which are typically called the chemical shift, which can
be used to differentiate between the same nuclei (for example
74105.
649
Copyright'

2003 by A S I M International

www.astm.org

650 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


will thus be split into two groupings, one associated with the
methyl hydrogen nuclei, t h e second with the aromatic hydrogen nuclei. The relative intensities of the absorption pesiks
for the two groups will be in the ratio 3:5 corresponding to
the relative ratios of the nuclei in the two environments. The
' H NMR spectrum for toluene is shown in Fig. 2 [4].
The chemical shifts reported in NMR spectrometry are
usually expressed as the pEtrts-per-million (ppm) shift from
the r e s o n a n c e frequency of a reference standard, usually
tetramethylsilane (IMS). The chemical shift c a n be calculated using the following formula [5]:

' H ) in different chemical environments. Take for example the


molecule toluene:
H

C _ H
H

Chemical shift (in p p m ) = (RFS-RFTMS)/RFTMS

Toluene h a s t w o types of protons, either as part of t h e


methyl group, or attached t o a n aromatic carbon. Because
the shielding experienced by these two different types of protons will depend on both electron density and ring current effects, the resonance frequency for interaction with the applied field will be different. The NMR spectrum for toluene

Where RFs is t h e resonance frequency of t h e sample a n d


RFTMS is t h e resonance frequency of t h e TMS reference.
Some typical chemical shifts for ' H in hydrocarbon
molecules are shown in Table 1 [5].
The key to using NMR spectrometry in t h e analysis of hydrocarbon molecules is to recognize the chemical shifts observed in the NMR spectra ind relate the relative concentrations of nuclei in these different environments to help
elucidate the bulk properties of a hydrocarbon sample, for
example the concentration of aromatic molecules in a hydrocarbon oil.
" C NMR Spectrometry
NMR spectrometry is not limited to just hydrogen nuclei. In
fact, any nucleus with a n odd s u m of protons a n d neutrons
will possess a magnetic m o m e n t and can thus be analyzed using NMR. Aside from 'H, the second most commonly studied
nucleus is '^C, which like ' H has a nuclear spin of'/. Carbon
exists in two naturally occurring isotopes ^^C a n d '^C, with
relative natural abundances of 98.9% and 1.1%, respectively.
Although '^C has a n even s u m of protons a n d neutrons a n d
thus does not possess a magnetic moment, with sufficient ex-

Magnetic
Field of
Strength

Relative
Energy

TABLE 1Typical chemical shifts for 'H nuclei in


hydrocarbon molecules.
Chemical Shift/ppm
' H Nucleus Environment
CH2 and CH3 H atoms far from
0.5-2.0
aromatic rings
2.0-4.0
CH2 and CH3 H atoms in the a
position relative to an aromatic rings
6.0-7.2
H atoms in monocyclic aromatic rings
H atoms in Polycyclic aromatic rings
7.2-9.0

Absorbed
Energy
Increasing Frequency
FIG. 1The separation of proton nuclear spin states under
an applied magnetic field.

aromatic hydrogen
resonance

methyl hydrogen
resonance

X 10*

FIG. 2^H NMR spectrum for toluene.

CHAPTER 24: HYDROCARBON


TABLE 2Typical chemical shifts for '^C nuclei in
hydrocarbon molecules.
" C Nucleus Environment

Chemical Shift/ppm

Aliphatic and naphthenic carbon atoms


Carbon atoms in terminal CHj groups
Carbon atoms in CH2 groups in the middle
of a chain
Carbon atoms in aromatic rings

10.0-60.0
14.1
29.2
110-160

perimental resolution, the NMR spectrum of samples containing ''C nuclei in natural abundance can be recorded and
analyzed, in much the same way as 'H NMR spectra can be
analyzed to determine key structural properties of the
molecules that comprise the bulk sample.
Just like ' H NMR, the resonant frequency of the ^'C nuclei
are influenced by the chemical environment in which they
are surrounded and again, chemical shifts can be calculated
in ppm relative to a calibration standard such as TMS using
the same formula used to calculate 'H chemical shifts. Chemical shifts for '^C nuclei tend to be somewhat larger than 'H
shifts in hydrocarbon molecules. Some typical chemical
shifts for '^C nuclei in hydrocarbon molecules are shown in
Table 2 [5].
Because the natural abundance of ^^C is so low, the experimental measurement of '^C NMR spectra is slightly more
difficult than 'H NMR spectra because the spectra tend to be
much weaker. To overcome this difficulty, the spectra are
recorded not by scanning the frequency as for *H NMR (a
technique often called continuous wave or CW) but by pulsing a series of short pulses of broad band radiation (of the order of 0.5-50 fjis) and monitoring the free induction decay of
the signal from the '^C nuclei. This time domain single is
then converted into the frequency domain using Fourier
Transformation [2]. This, coupled with other techniques too
advanced to discuss here, have made the recording and interpretation of '^C NMR spectra commonplace [5].
The Use of ^H and " C NMR in the Analysis of
Hydrocarbons
Because 'H and '^C are the two nuclei most commonly analyzed by NMR spectrometry, it stands to reason that NMR
has proven useful in hydrocarbon analysis. There are two
main areas where NMR has been used for hydrocarbon fuel
and lubricant aneJysis, specifically the identification of hydrogen content in aviation fuels (ASTM D 3701) and
petroleum distillates (ASTM D 4808), and in determining the
aromatic hydrogen and aromatic carbon content using 'H
and " C NMR spectrometry (ASTM D 5292).
The determination of hydrogen content is an important
property of a fuel or lubricant because it is closely related to
key performance characteristics and can be used as a measure of quality control both during and after production.
Both test methods (ASTM D 3701 and ASTM 4808) work by
taking the ratio of the total integrated hydrogen signal from
the sample NMR spectrum to a known n-dodecane standard
run on the same NMR instrument. In each case, the total hydrogen content by mass (H%) is then calculated using the
formula,
H(%)

= S/R X (WR/WS)

15.39

ANALYSIS

651

where S is the total integrated hydrogen signal from the sample, R is the integrated signal from the n-dodecane reference,
Wn is the weight of n-dodecane used, Ws is the weight of sample used, and 15.39 simply reflects the percentage by mass of
hydrogen in the n-dodecane reference standard. The accuracy of this test method is around 0.2-0.4% for a typical hydrogen content of 14% [5]. Other variations on this method
have also been used, which involve pulsed FT NMR, which
are capable of errors as low as 0.05% [6, 7].
Hydrocarbon oils made by the refining of crude petroleum
are generally classified parafHnic or naphthenic depending
on the predominant class of hydrocarbon compounds found
in the oil [8]. Despite this, most oils of this type contain a significant proportion of aromatic hydrocarbons. The aromatic
content of an oil can affect a number of physical and chemical properties such as boiling range, viscosity, stability, and
compatibility. For this reason, it is important to be able to determine to amount of aromatic hydrocarbon content in a hydrocarbon oil [9].
One way of characterizing the aromatic content is to count
the number of aromatic carbon and hydrogen atoms in a
bulk sample. Because NMR is capable of separating signals
from different atoms within molecules based on their chemical structure and environment using the concept of chemical
shifts, NMR is a natural for this type of determination: this is
the basis behind ASTM D 5292. In this case, the test method
is even simpler than measuring total hydrogen content. The
sample is analyzed using pulsed FT NMR and the total aromatic ' H and "C content determined by taking the ratio of
the aromatic carbon or hydrogen nuclei integrated signal to
the corresponding aliphatic signal. For the purpose of assigning ' H nuclear environments, peaks in the chemical shift
range 0.5 to 5.0 ppm are considered aliphatic hydrogen,
while those in the 5.0-10.0 ppm range are considered aromatic. A t5^ical NMR spectrum of this kind is shown in Fig.
3. For " C NMR, peaks in the 10 to 70 ppm range are considered aliphatic, while those in the 100-170 ppm range are
considered aromatic carbons [9].
The biggest drawback with NMR is the expense of purchasing and running an NMR instrument. However, in circumstances where the determination of the relative proportions of various constituents of a bulk sample in different
chemical environments at high precision are required, NMR
offers a quick simple means of obtaining quick, accurate
data. For this reason, the use of NMR as a tool for hydrocarbon analysis will continue to grow.
ASTM Petroleum Products and Lubricants NMR
Test Standards Under Subcommittee D 02.04
Aromatics in Hydrocarbon Oils by High Resolution
Nuclear Magnetic Resonance
(HR-NMR)
(ASTM D 5292)
This method is applicable to a wide range of hydrocarbon oils
that are completely soluble in chloroform and Cctrbon tetrachloride at ambient temperature. The data obtained by this
method can be used to evaluate changes in aromatic contents
of hydrocarbon oils due to process changes. Hydrogen ('H)
NMR spectra are obtained on sample solutions in chloroform-d using a continuous wave or pulsed FT high resolution
NMR spectrometer. Carbon ('^C) NMR spectra are obtained

652

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

1HFTNMR

PPM
FIG. 3^H NMR spectrum of gas oil showing thie aliphatic
(-0.5 to 5.0 ppm) and aromatic (5.0 to 10.0 ppm) hydrogen
peaks. Reprinted from ASTM D 5292-93.

on the sample solution in chloroforni-<i using a pulsed FT


high resolution NMR.

GAS CHROMATOGRAPHY (GC)


Introduction
GC is one of the most widely used analytical tools in the evaluation of petroleum products, as witnessed by the n u m b e r of
relevant standcirds summarized at the end of this section that
use GC. Its principal value lies in the fact that the technique
can b e used t o separate complex mixtures of different
molecules or groups of molecules based on their physical
properties, which is precisely w h y it is such a valuable
method for fuel a n d lubricant analysis.
Because GC involves first getting the sample into the gas
phase, it is used in the analysis of the more volatile components of fuels and lubricants. Less volatile fractions are typically analyzed using the related technique of Liquid Chromatography, which will be discussed in the following section.
GC is also used to simplify several spectrometric techniques
such as Mass Spectrometry (MS) a n d Fourier Transform Infrared Spectroscopy (FTIR) by first separating the sample
into different molecular component types. The use of GC in
GC-MS and GC-FTIR is covered under the relevant spectroscopic technique. The direct application of Gas Chromatography (GC) to the evaluation and analysis of hydrocarbons
will be discussed in this section.

Gas Chromatography
Gas Chromatography can be subdivided into two categories,
gas-liquid chromatography a n d gas-solid chromatography
[10]. In each case, the technique involves the separation of
components of a gaseous sample using a stationary phase, either a liquid in the case of gas-liquid chromatography, or a
solid in the case of gas-solid chromatography. Because the
overwhelming majority of test standards used for hydrocar-

bon analysis rely on gas-liquid chromatography, we will focus exclusively on this method, although the same basic principals apply to both methods.
In gas-liquid chromatography, it is the interaction between
the gaseous sample being carried t h r o u g h the column by
means of an inert gas (the mobile phase) and a standard liquid (the stationary phase), which causes the separation of different molecular constituents. The stationary phase is either
a polar or nonpolar liquid, which either coats the inside of
the column, in the case of a capillary column, or is impregnated onto an inert solid, which is then packed into the GC
column [ 11 ]. A schematic layout of a GC instrument is shown
in Fig. 4. The basic components are a n inert carrier gas, most
commonly helium, nitrogen or hydrogen, a GC column,
which will be described below, held inside an oven that allows for precise temperature control, and some type of detector capable of detecting the sample as it elutes from the
column.
Gas-liquid GC works because the molecules in the samples
are carried along the column in the carrier gas and partition
between the gas phase a n d the liquid phase. Because this partitioning is critically dependent on the solubility of the sample in the liquid phase, different molecular species travel
along the column a n d exit or elute at different times. Those
molecules that have a greater solubility in the liquid phase
take a longer time to elute and thus are measured at a longer
time interval. Because solubility is dependent on the physical
and chemical properties of the solute, separation between
different components of the sample occurs based on molecular properties such as relative polarity (for example, oxygenated molecules, aromatics and nonaromatics) and boiling
point. A tjTDical gas chromatogram is shown in Fig. 5.
In order to create this separation, a n u m b e r of different
liquid phase materials are used that can be broadly classified
as either polar or nonpolar. For hydrocarbon analysis the two
most commonly used liquid phase materials are TCEP (1,2,3tris(2-cyanoyethoxy)propane) for polar columns, and methyl
silicone for nonpolar columns, although a multitude of different polar and nonpolar columns suitable for hydrocarbon
analysis are commercially available. I n general, polar
columns are used to separate aromatics from nonaromatics,
while nonpolar columns are used to sepeirate hydrocarbon
components by their boiling point.
There are two basic ways in which GCs are used for hydrocarbon analysis, either to separate different components of
the sample based on their differing chemical characteristics
(for example, aromatics versus nonaromatics), or to separate
different chemically similar fractions based on their boiling
point. To separate molecules based on their chemical properties, a GC is run in the method described above, with a polar column used to provide longer retention times for compounds such as aromatics relative to paraffins and olefins.
For accuracy, it is vital that the oven temperature in which
the GC column is housed is precisely controlled. This method
is called isothermal GC analysis [10].
GCs can also be used in another mode called temperature
programming. In temperature programming, the oven temperature is slowly swept from an initially low temperature
( s e e ) to a much higher temperature (typically 350-400C) at
a CcirefuUy controlled rate [12]. The effect is to cause an increased separation of chemically similar species based on

CHAPTER

24: HYDROCARBON

ANALYSIS

653

VENT

OVEN

CARRIER
GAS

^ RECORDER

INJECTION
PORT

COLUMN
R s REFERENCE
S s SENSING

FIG. 4GC Instrument with a thermal detector.

their boiling point; those low boiling fractions eluting at a


faster rate than fractions with higher boiling points. Temperature programming is used in hydrocarbon GC ancJysis to
determine boiling point ranges for various crude and refined
petroleum fractions.
Whether isothermal or temperature programmed GC analysis is used, a detector capable of measuring molecules as
they elute is required. For hydrocarbon analysis, the two
most c o m m o n types of detectors are flame ionization and
thermal conductivity [13]. In flame ionization type detectors,
the column effluent is mixed with hydrogen and air and ignited. This flame b u m s any organic material (such as hydrocarbons) when they elute from the column producing, among
other things, ions and electrons. This increase in charged
particle concentration causes an increase in current between
the tip of the burner, which is held at a high electrical potential, and a collector electrode above the flame. It is this increased current that is used to measure the elution of sample
molecules from the column. An illustration of a flame ionization type detector is shown in Fig. 6.
Thermal conductivity detectors contain a tungsten filament that is heated using a constant current [10]. The elution
of pure carrier gas (helium) has a cooling effect on the filament, which controls the temperature and hence the resistance of the filament to the applied constant current. As hydrocarbon molecules elute, they have less of a cooling effect
than the carrier gas, resulting in an increased temperature.
Sample molecule elution is determined based on a change in
resistant of the filament, c o m m o n l y m e a s u r e d using a
Wheatstone bridge electrical circuit [10].
For specialized applications where element specific detection is required (for example, the determination of sulfur
content in hght petroleum liquids by GC (ASTM D 5623)),
other detection systems are used such as atomic emission
(AED) and chemi-luminescence. These will not be covered in
detail in this chapter.
T h e U s e o f GC i n H y d r o c a r b o n Analysis
The use of GC in the analysis of petroleum products falls into
three genereJ categories: the eveJuation of the relative concentrations of different types of molecules (for example, aromatics, olefins, naphthenes etc.), the determination of boiling point ranges and carbon numbers in fuel and lubricants

u_
TIME. MINUTES

FIG. 5Gas chromatogram of C^ to C^ species in gasoline.


Reprinted from ASTM D 2427.

1 | ^

e ^ 1

-Collector electrode

Flame ignition
coil

+300V
Polarising voltage

Hydrogen
Column
FIG. 6Flame ionization detector.

using temperature programming, and the detection of certain contaminants such as diesel fuel or ethylene glycol in engine oil or oxygenated additives such as MTBE.
The determination of the aromatic content of hydrocarbon
fuels is a n important application of GC because benzene,
toluene, and other aromatics pose a serious heedth threat and

654

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

is carefully regulated in gasolines and other petroleum products. There are a n u m b e r of test methods that use GC for this
purpose, all of which follow the same basic principle (see
ASTM D 3606, D 4420, and D 5580). In each case, a sample
containing an internal calibration standard is injected into a
GC instrument equipped with two columns, one containing a
nonpolar liquid phase such as methyl silicone, the second using a polar liquid phase such as TCEP. The polar liquid phase
separates aromatics and nonaromatics because aromatics
take longer to elute from a polar column, while the nonpolar
column separates the aromatic components by their boiling
point, allowing the concentrations of benzene, toluene, and
heavier aromatics to be determined. In each case, the measurements are carried out isothermally (that is at a fixed colu m n temperature). A tjrpical gas chromatogram of the aromatic components of gasoline using this method is shown in
Fig. 7.
Another i m p o r t a n t application of GC to h y d r o c a r b o n
analysis is the simulated distillation of crude petroleum [13].
Determining the boiling point range of petroleum fractions
has a variety of uses, from determining the composition of
feed stocks to evaluating the presence of volatile components,
which may have implications on the performance or safety
cheiracteristics of finished hydrocarbon fuels and lubricants.
Historically, the boiling point range of petroleum fractions
has been determined by trial distillations in the laboratory.
While this method still has some validity, and in some circumstances may be advantageous, the use of gas chromatography offers a quick, simple alternative for controlling refining processes and product evaluations.
Boiling point range determination of petroleum products
using GC involves injecting a sample into a nonpolar column,
which is housed in a temperature programmable oven. The
GC is first calibrated using a calibration solution containing
known concentrations of normal paraffins. The temperature
of the column is increased at a known rate and the retention
time of the n-paraffins is plotted against their known boiling
points, as shown in Fig. 8. The crude sample is then analyzed
in the same way, and the retention times of the eluting sam-

Toluene

0}

c
m
N

<-8
aromatics

Switch to forward flow


(Time T2)

Non-aromatics

aromatics

t^r^

10
15
Time, minutes

25

FIG. 7Typical gas chromatogram of the aromatic


fractions of gasoline. Reprinted from ASTM D 4420.

1100

600

10

15
20
25
30
Retention Time, Minutes

35

40

FIG. 8^Typical boiling point ranges of n-paraffins as a function of column retention time. Reprinted from ASTM D 5307.

pie fractions converted to boiling points using the calibration


curve shown in Fig. 8. An example of the simulated distillation of a crude oil s a m p l e using gas c h r o m a t o g r a p h y is
shown in Fig. 9.
The third area where GC has an increasingly important role
to play is in the determination of certain contaminants in used
oil samples, such as ethylene glycol, used as a coolant in many
combustions engine, and fuel dilution in diesel engine samples. While used oil analysis is a subject unto itself, it is instructive to review how GC is applied in this area.
The determination of fuel dilution in engine oil samples is
of prime importance because it can impair the performance
of the lubricating oil [14]. Because diesel fuel is chemically
very similar to the oil itself, it is almost impossible to quantify fuel dilution by conventional wet chemistry tests. While
other physical tests such as changes in viscosity, FTIR, and
flash point offer means of determining the presence of fuel in
a lubricating oil, GC is generally a more precise and reliable
means of determining fuel dilution based o n the temperature
programmed elution of fuel relative to the larger (higher boiling point) fractions of the lubricating oil.
The same can be said for ethylene glycol coolant detection.
Ethylene glycol is an insidious c o n t a m i n a n t in engine oil
samples that can result in catastrophic engine failure if left
unchecked [15]. Again a n u m b e r of wet chemistry tests
(ASTM D 2982) and physical tests (FTIR) are available, but,
again, GC offers superior detection limits. Because ethylene
glycol is a polar molecule, GC analysis is performed by first
extracting the glycol from the used oil sample with water.
The water extract is then run directly on a n isothermal GC
column against calibration standards containing known concentrations of ethylene glycol in water. The sensitivity of GC

CHAPTER 24: HYDROCARBON

ANALYSIS

655

AIS = AREA OF CRUDE PLUS


INTERNAL STANDARD

23500-

21500
19500
17500V)
Z 15500
O
0.
tU 13500
OC

538C (1000F)

11500
BASELINE

9500
7500

JIMMAAAAMA^
AIS

5500
3500

TIME

00

CO

CM

P4

A. CRUDE + INTERNALSTANDARD
B = TOTAL ELUTED AREA
UPTO538*C(1000F)
B' = AREA CORRESPONDING TO
NON-ELUTED SAMPLE
BIS " AREA OF SEGMENT WHERE
INTERNAL STANDARD ELUTES IN
FIGURE 9A

19500

538''C(1000''F)

BASELINE

yUwiiUAAAz/AAx^
I BIS

TIME

B. CRUDE ONLY

FIG. 9Gas chromatogram of calibration mixture and crude oil sample used to determine boiling point range. Reprinted with permission from ASTM D 5307.

to detecting contaminants in used oil samples makes it an


ideal test where high precision test data is required.
Whether it is used for evaluating different molecular components of gasoline, determining boiling point ranges for
crude oil fractions, or detecting contaminants, one of the major drawbacks with GC is that while its is excellent at quantifying the relative concentrations of various eluted fractions,
it cannot determine empirically what those fractions actually
are [11]. Without the application of suitable cetlibration standards, which requires at least some knowledge of the sample
constituents, this problem could severely limit the use of GC

with complex mixtures such as fuels and lubricants. However, one way of addressing this issue is to couple GC with
some other applicable method that is capable of not only detecting eluting fractions, but can also identify their chemical
composition. For this reason, the dual combination of GC
with mass spectrometry (GC-MS), infra-red spectrometry
(GC-FTIR), and atomic emission (GC-AES) will continue to
grow in importance in the quantitative analysis of hydrocarbon fuels and lubricants [16,17]. The application of GC to MS
and FTIR is covered in the appropriate spectrometric analysis sections of this review.

656

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK
time axis from a calibration curve, obtained under the same
conditions by running a known mixture of hydrocarbons covering the boiling range expected in the sample.

A S T M P e t r o l e u m P r o d u c t s a n d L u b r i c a n t s GC
Test Standards
Aromatics in Finished Gasoline by Gas
Chromatography
(ASTM D 4420)
This test method determines benzene, toluene, Cs, C9, and
heavier aromatics, and total aromatics in finished m o t o r
gasoline and gasoline blending components. A two column
chromatographic system connected to a dual filament thermal conductivity detector (or two single filament detectors)
is used.
Aromatics

in Finished

Gasoline

by GC (ASTM D

5580)

Aromatics in the following concentration reinge can be determined by this test method; benzene 0.1-5; toluene 1-15; individual Cg aromatics 0.5-10; total C9 and heavier aromatics
5-30; and total aromatics 10-80 liquid volume percent. The
aromatic hydrocarbons are separated without interference
from other hydrocarbons in the finished gasoline. A two colu m n c h r o m a t o g r a p h i c system equipped with a columnswitching valve and a flame ionization detector is used.
Benzene/Toluene
in Gasoline
(ASTM D 3606)

by Gas

Chromatography

This test method determines benzene and toluene in finished


m o t o r and aviation gasoline by gas chromatography. The
sample is doped with an internal standard, methyl ethyl ketone (MEK), and is then injected into a gas chromatograph
equipped with two columns connected in series.
Boiling Range Distribution
of Crude Petroleum
Chromatography
(ASTM D 5307)

by Gas

The method covers boiling range distribution of water-free


crude petroleum through 538C (100F). A solution of crude
oil in carbon disulfide is injected into a gas chromatographic
column that separates hydrocarbons by their boiling point
order.
Boiling Range Distribution
of Gasoline Fractions
Gas Chromatography
(ASTM D 3710)

by

This test method is designed to measure the entire boiling


range of gasoline with either high or low Raid vapor pressure.
The sample is injected into a gas chromatographic column,
which separates hydrocarbons in boiling point order.
Boiling Range Distribution
of Petroleum
Gas Chromatography
(ASTM D 6352)

Distillates

by

The gas c h r o m a t o g r a p h i c (GC) determination of boiling


point ranges is used to replace conventional distillation
methods for control of refining operations. A nonpoleir open
tubular capillary GC column is used to elute the hydrocarbon
c o m p o n e n t s of the sample in order of increasing boiling
point.
Boiling Range Distribution
of Petroleum
Gas Chromatography
(ASTM D 2887)

Fractions

by

The d e t e r m i n a t i o n of the boiling range distribution of


petroleum fractions by gas chromatography is effective as a
rapid anal5^ical tool. The sample is introduced into a gas
c h r o m a t o g r a p h i c column that separates hydrocarbons in
boiling point order. Boiling temperatures are assigned to the

Diesel Fuel Diluent in Used Diesel Engine


Chromatography
(ASTM D 3524)

Oils by Gas

This test method covers the determination of diesel fuel as a


contaminant in used lubricating oil. A mixture of n-decane
and used lubricating oil is introduced into a gas chromatographic column that separates hydrocarbons in the order of
their boiling points.
Estimation
of Engine Oil Volatility
Chromatography
(ASTM D 6417)

by Capillary

Gas

The determination of engine oil volatility at 371C is a requirement in some lubricant specifications. A sample aliquot
diluted with a viscosity reducing solvent is introduced into
the gas chromatographic system, which uses a nonpolar open
tubular capillary gas chromatographic column for eluting the
hydrocarbon components of the sample in the order of increasing boiling point.
Ethanol Content In Denatured
(ASTM D 5501)

Fuel Ethanol

by GC

This test method covers the determination of ethanol content


of d e n a t u r e d fuel ethanol by gas chromatography. A fuel
ethanol sample is injected into a gas c h r o m a t o g r a p h
equipped with a methyl silicone bonded phase fused silica
capillary column.
Ethylene

Glycol in Used Engine

Oil (ASTM D

4291)

This test m e t h o d provides for early detection to prevent


coolant from accumulating and seriously damaging the engine. The sample of oil is extracted with water and the analysis is performed on the water extract, which is injected into a
gas chromatograph using on-column injection. The eluting
compounds are detected by a flame ionization detector.
Engine

Oil Volatility

by GC ASTM

(D

5480)

This test method provides the determination of the amount


of engine oil volatilized at 700F (371C). The sample is
mixed with an internal standard and a dilute tetracosane solution, and injected into a gas chromatograph.
Gasoline Diluent
Chromatography

in Used Engine Oils Gas


Method (ASTM D 3525)

This test method uses gas chromatograph equipped with a


flame ionization detector and a programmable oven.
Hydrocarbon
Types in Gasoline by Gas
Chromatography
(ASTM D 2427)
This test method provides information on C2 through C5 ceirbon paraffins and mono-olefins in gasolines. The sample is
injected into a gas-liquid partition column. The components
are separated as they pass through the column with an inert
carrier gas and their presence in the effluent is detected and
recorded on a chromatograph.
Methyl Tert-Butyl
(ASTM D 4815)

Ether in Gasoline

by GC

This test method determines ethers and edcohols in gasoline


by gas chromatography, a n d is applicable to both quality

CHAPTER
control in the production of gasoline and the determination
of deliberate or extraneous oxygenate additions or contamination. A gasoline sample is doped with an internal standard
such as 1,2-dimethoxyethane, and is injected into a gas chromatograph equipped with two columns and a column switching valve. The eluted components are detected by a flame ionization or a thermal conductivity detector.
Olefins In Engine

Fuels by GC (ASTM D

6296)

This test method can determine olefins in the C4 to Cio range


in spark ignition engine fuels or related hydrocarbon streams
such as naphthas and cracked naphthas. A sample fuel is injected into a computer controlled gas chromatographic system, which consists of a series of columns, traps, and switching valves operating at various temperatures. The final eluted
olefins are detected by flame ionization detector.
Oxygenates in Gasoline
(ASTM D 5599)

by Gas

Chromatography

This test method provides sufficient oxygen-to-hydrocarbon


selectivity a n d sensitivity to allow d e t e r m i n a t i o n of oxygenates in gasoline samples without interference from the
bulk hydrocarbon matrix. An internal standard of a noninterfering oxygenate (for example, 1,2-dimethoxyethane) is
added in a quantitative proportion to the gasoline sample. An
aliquot of this mixture is injected into a gas chromatograph
equipped with a capillary column operated to ensure separation of the oxygenates. Oxygenates are detected with the oxygen-selective flame ionization detector.
Oxygenates O-PONA Hydrocarbons
GC (ASTM D 6293)

in Fuels by

This test method provides for the quantitative determination


of oxygenates, paraffins, olefins, naphthenes, and aromatics
in low-olefin speirk-ignition engine fuels by multidimensional
gas chromatography. A fuel sample is injected into a computer-controlled gas chromatographic system consisting of
switching valves, columns, and a n olefin hydrogenation catalyst, all operating at various temperatures. The eluted hydroccirbons are detected by flame ionization detector.
Sulfur Determination
(ASTM D 5623)

by GC-Sulfur

Detector

This test method covers the determination of volatile sulfur


compounds in light petroleum liquids. The sample is analyzed by gas chromatography with an appropriate sulfur selective detector.

24: HYDROCARBON

ANALYSIS

657

hydrocarbon petroleum products, specifically, absorption


chromatography, high performance liquid chromatography
(HPLC), fluorescent indicator absorption (FIA) and super
critical fluid chromatography (SFC).
L i q u i d C h r o m a t o g r a p h y (LC)
In classical LC, a liquid sample is introduced either neat or
diluted with a n a p p r o p r i a t e solvent into a glass column,
which has been prepacked with an appropriate solid material
such as silica, alumina, or some other solid medium. The
sample is then washed down the column using a flowing
stream of solvent, starting with a relatively low strength solvent and progressing to stronger and stronger solvents until
the sample has been washed out or eluted from the column
[18]. Depending on the nature of the interaction between the
sample (the mobile phase) and the column material (the stationary phase), mixtures can be separated by retention time
in the column; those molecular species present in the mobile
phase which have a greater affinity for the stationEiry phase
material take a longer time to elute t h a n those that have little
or n o affinity for the stationary phase. This is called absorption chromatography and the columns used for this kind of
methodology are absorption
columns.
An illustration of absorption liquid c h r o m a t o g r a p h y is
shown in Fig. 10. In this example, a mixture of two compounds, X and o, Eire added to an LC column packed with a
stationary phase that has a greater affinity for compound x
than compound o. The mixture is washed down the column
with a suitable solvent, however, because compound x has a
greater affinity for the stationary phase than compound o, it
will take a longer time to exit or elute from the column. Sepciration is thus affected between the two compounds, which
can then be monitored as a function of their elution times by
a suitable detector. This methodology is called absorption
chromatography Eind is the most commonly used method for
hydrocarbon emalysis. In certain circumstances, absorption
by the stationary phase is so effective that the absorbed components of the sample can only be removed by washing with
a solvent that has a stronger affinity for the absorbed sample
component than the stationary phase.
Two other types of LC columns exist, specifically partition
columns and exclusion columns. Pcirtition columns work in
m u c h the same way as GC columns. In peirtition chromatography, instead of being filled with a solid stationary phase,
the LC column contains a liquid, which is coated or chemically bonded onto a solid medium contained within the col-

LIQUID C H R O M A T O G R A P H Y (LC)
TIME

Introduction
The technique of liquid chromatography (LC) is closely allied
with gas chromatography (GC) and other chromatographic
methods. Just like GC, liquid chromatography separates different molecules or molecular groups based on their physical
and chemical properties. However, unlike gas chromatography, LC as the name implies the use of a liquid mobile phase
to analyze samples. The field of liquid chromatography is
very broad ranging and is used in many different areas of analj^ical chemistry. In this section, we will cover just those areas of liquid chromatography that Eire used in the analysis of

XOXOI

oxox
xoxo
oxox

X X

oxox
xoxo
oxox

o 0

X X
X X

xoxo
oxox
0 0
0 0

X X
X X
X X

oxox
0 0
|0 O
0 0

X X
XX
X X
X X
0 0
0 0
0 0
O 0

U 1/ W U \J
FIG. 10The chromatographic process.

X X
X X
X X
X X
O 0
O 0
0 0
0 0

658

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

umn. Separation is affected by the interaction between the


Hquid mobile phase and the liquid stationary phase (often
called the partitioning phase), which separates components
of the sample based on their relative solubilities in the partitioning liquid [19]. This method is often referred to as liquidliquid chromatography. It is less commonly used for hydrocarbon analysis, but can be used to separate hydrocarbons of
the same family, which differ only by their substituents [20].
Exclusion column chromatography is another form of
solid-liquid chromatography, like absorption chromatography. However, instead of separation being affected by the
rate of absorption (and desorption) by the solid stationary
phase, exclusion columns are packed with porous materials
with carefully controlled pore sizes. In this case, the rate of
elution is controlled by molecular size, and the ability of the
sample molecules to enter the pores of the stationary phase
material. In general, very small molecules, which are smaller
on average than the pore of the stationary phase material become trapped in the column and take longer to elute, while
larger molecules cannot fit inside and thus elute faster than
smaller molecules. This method is typically used to separate
large polymeric additives, such as viscosity index (VI) improvers from base oils [21,22].
Liquid chromatography can be further subdivided into two
categories: open column liquid chromatography (OCLC) and
high performance liquid chromatography (HPLC). With
OCLC, the mobile phase (sample and solvent) is forced
through the column either under gravity, or a small head
pressure of gas, typically 25 psig or less [19]. Most modem
analytical instruments now use HPLC. Originally standing
for "high-pressure liquid chromatography," HPLC or high
performance liquid chromatography uses significantly
higher pressures than OCLC to force the mobile phase
through the column, resulting in shorter analysis times. A
schematic illustration of the basic components of an HPLC
instrument is shown in Fig. 11. A detailed review of HPLC instrumentation can be found in Ref 23.
Whether an absorption column, partition column or exclusion column is used, or whether gravity (OCLC) or high pressure (HPLC) is used to push the mobile phase through, a detection system is required to measure the sample fractions as
they elute from the column. The most common methods include UV spectrometers, used to measure the characteristic

SOLVENT RESERVOIR

5=

INJECTION POINT

DETECTOR

RECORDER

COLUMN-

\J

THERMOSTAT

FIG. 11An HPLC instrument.

UV absorption of organic molecules as they elute from the


column; refractive index (RI) detectors, which record a
change in RI as sample molecules elute relative to the solvent
being used; and flame ionization (FID) detectors, which measure a change in conductivity through a hydrogen flame as
the eluting molecules are ionized in the flame.
The Use of LC in Hydrocarbon AniJysis
Like gas chromatography (GC), LC is used for the analysis of
petroleum fuels and lubricants because of its ability to separate complex mixtures based some physical or chemical
property. Although lower in sensitivity than GC, LC has several distinct advantages, which make it more widely applicable to hydrocarbon analysis. Some of these advantages include [21]:
Shorter analysis times
Higher precision for identifying and quantifying components
Analysis in series using the same column
Selectivity for certain classes of hydrocarbons
Ability to measure high molecular weight and high boiling
point compounds
The main application of chromatographic techniques to
hydrocarbon analysis is the separation of different fractions
that possess wildly different physical and chemical properties such as polar compounds, aromatics, and saturates. This
is the principle behind ASTM D 2007, which is used to define
API base stock categories and engine oil interchangeability
rules [24].
In this test method, a dual column apparatus is used containing two columns in series. The first column contains clay,
which retains any polar compounds allowing both saturates
and aromatics to pass through using n-pentane as a solvent.
The second column contains clay and silica gel, which retains
aromatics but again allows saturates to pass through. Collecting the total effluent through both columns allows the
percentage by mass of saturates to be calculated as a function
of total sample mass, because both polar compounds and
aromatics are stripped from the sample by the two columns.
The clay column is then removed and washed with a toluene
acetone mixture allowing the absorbed polar compounds to
elute. The percentage by mass of polar compounds can then
be calculated as the total polar effluent from the toluene-acetone washed column, again as a function of the total sample
mass. Finally, the silica gel/clay column is rinsed with
toluene, which eJlows the aromatics to elute, again allowing
their percentage by mass to be calculated. The precision of
determining the saturate and aromatic content using this
method (as per API 1509) is around 2% [25].
A similar method is used in ASTM D 2549, this time to separate aromatic and nonaromatic components of high boiling
oils. In this method, a single absorption column containing
activated bauxite and silica gel is used. Initially, n-pentane is
used as a solvent, allowing nonaromatics to pass through the
column. These are then collected and expressed as a percentage by mass of the initial sample, after evaporation of the npentane solvent. The column is then washed with diethyl
ether, chloroform, and ethyl alcohol which allows the elution
of the aromatics compounds, which are then weighed and expressed as a percentage by mass of the initial sample mass. A
number of related techniques have been used to achieve sim-

CHAPTER 24: HYDROCARBON

240

ANALYSIS

659

A = Start integration of IMAIHs

B = End integration of IMAHs/Start integration of DAHs

1
1

210

180

C = End integration of DAils

>
E ISO

!&

c
o

^ 1

sQ \

j!l20

c
90

o
o
^
X
o
13
E
8

_
"

60

30

> 11
"
to

>

o I

i\^i

X- 1
I

<=
-

3i-Aromatic Hydrocarbons

c1

CO

^
6 1

"

1
I
I

M
'

Time (minutes)
FIG. 12^The use of liquid chromatographic separation to differentiate mono and di-aromatics in aviation fuel. Reprinted with permission from ASTM D 6379.

ilar separations, which differ simply by the column material


and solvents used [21].
These simple absorption techniques under atmospheric
pressure have, to a large part, been superceded by high performance liquid chromatography (HPLC), principally because of the much shorter analysis times afforded with HPLC
[21]. However, just like absorption chromatography, HPLC is
used mainly as a tool for separating samples based on physical and chemical properties.
Just like absorption chromatography, separation of complex mixtures into saturates and aromatics is possible with
HPLC, as well as differentiating between similar molecules
such as mono-ciromatics (MAHs) and diaromatics (DAHs).
This method is used in ASTM D 6379 to determine MAH and
DAH content in petroleum products. In this case, an amino
bonded stationary phase is used, together with n-heptane, as
the solvent to resolve different compounds based on elution
times. An example of a chromatogram of this type is shown
in Fig. 12.
Aside from absorption chromatography and the related
technique of HPLC, there are two other LC methods used for
hydrocarbon analysis that are worth mentioning, specificedly
fluorescent indicator adsorption (FIA) and supercritical fluid
chromatography (SFC).
Fluorescent Indicator Adsorption (FIA)
Despite its rather grandiose name, FIA is a relatively simple
technique. First developed in the early 1940s, it is used to determine the relative amounts of ciromatics, olefins, and saturates in petroleum fractions [18]. The technique involves
standard OCLC using a silica gel column. However, in addition to being packed with silica gel, the column contains a
small portion of the gel towards the top that is doped with a

mixture of dyes. The dye mixture is carried along the column


with the petroleum sample, which stcirts to separate because
the saturates have less of an affinity for the silica gel than the
olefins, which in turn have less of an affinity than aromatics.
The dye mixture contains three different components, one
which has an affinity for silica gel, which is greater than that
of the saturates, but less than that of the olefins. This dye
component thus marks the interface between saturate
molecules and olefins as they move through the column because the dye's retention time will be between the saturates
and olefins. A second dye component has an affinity for silica
somewhere between that of olefins and aromatics and thus
marks the olefin-aromatic boundary, while a third dye component falls between aromatics and the isopropyl alcohol
used as the solvent, marking the final boundary. By measuring the separation of each dye, the relative proportions of saturates, olefins, and aromatics can be determined to within
1-2% depending on conditions. This test is described under
ASTMD 1319.
Super Critical Fluid Chromatography (SFC)
Although not strictly a liquid chromatography technique,
SFC shares many of the same basic principles of HPLC. The
principal difference between SFC and HPLC is that the mobile phase containing the sample is neither a liquid, as used
in HPLC, or a gas, as used in gas chromatography, but is a supercritical fluid, most commonly CO2 [23]. A supercritical
fluid is one that has been heated above its critical temperature and pressure such that it exists in a new state of matter,
with properties between that of a gas and a liquid. In particular, supercritical fluids have greater mobility (are less viscous) than liquids, but are denser than gases. This property
of supercritical fluids has great advantages as the mobile

660 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

phase Ccuxier over conventional HPLC or gas chromatography (GC).


For hydrocarbon analysis, SFC has an advantage over GC
for fuel samples because it uses much lower temperatures
than GC and is thus less likely to cause thermal decomposition. SFC also typically offers high resolution than HPLC,
making it a more accurate test for determining different
moleculcir components in hydrocarbon fuels [26].

umn and eluted using supercritical carbon dioxide mobile


phase. The detector response to hydrocarbons is recorded
throughout the analysis time corresponding to the mono-,
polynuclear, and nonaromatic components determining the
mass percent content of these groups.

ASTM Petroleum Products and Lubricants


LC Test Standards

Introduction

ULTRAVIOLET S P E C T R O S C O P Y

Ultraviolet (UV) spectroscopy, also known as UV spectrometry, was one of the first spectroscopic techniques used to
quantify chemical composition [27]. Like other spectroscopic techniques, it is used to identify characteristic moleculEir fingerprints enabling the quantitative detection of specific molecules or molecular species in complex mixtures. UV
spectroscopy is most commonly used in hydrocarbon analysis as a detection tool after high performance liquid chromatography (HPLC).

Hydrocarbon Types by Fluorescent Indicator


Adsorption (ASTM D 1319)
This test method determines hydrocarbon types in the range
of 5-99 volume percent aromatics, 0.3-55 volume percent
olefins, and 1-95 volume percent saturates in petroleum fractions that distill below 315C.
Hydrocarbon Types Aromatic Hydrocarbon Types in
Aviation Fuels and Petroleum Distillates
(ASTM D 6379)
This test method is intended for use as one of several possible
aJtemative instrumental test methods that are used for quantitative determination of hydrocarbon t5rpes in fuels. This test
method determines mono- and di-aromatic hydrocarbon contents in aviation kerosenes and petroleum distillates boiling in
the range from 50-300C, such as Jet A or Jet A-1 fuels. The
sample is diluted 1:1 with a solvent such as heptane, cind a
fixed volume of this solution is injected into a high performance liquid chromatograph fitted with a polar column.

Basic Principles of UV Spectroscopy


In order to understand UV spectroscopy, we need to first understand the electronic structure of molecules. While a detailed quantum mechanical explanation of molecular electronic structure is beyond the scope of this book, there are a
few simple concepts that will allow us to understand the basic theory behind UV spectroscopy.
The total energy of a molecule is given by the sum of the
electronic energy, vibrational energy, and rotational energy,
with the electronic energy being significantly greater than the
vibrationed energy, which in turn is significcuitly greater than
rotationed energy. While rotational energy levels are only of
significance in gas phase spectroscopy, the electronic and vibrational energy levels will be important in solution phase
spectroscopy such as FTIR and UV spectroscopy. An illustration of the electronic and vibrational energy levels of a
molecule is shown in Fig. 13.
Under normal conditions, most of the molecules in a sample will be in the ground (lowest energy) electronic state. By

Aromatics and Polynuclear Aromatics in Diesel and


Aviation Turbine Fuels By SFC (ASTM D 5186)
The aromatic hydrocarbon content of motor diesel fuels affects their cetane number and exhaust emissions. The aromatic hydrocarbon and the naphthcdene content of aviation
turbine fuels affects their combustion characteristics and
smoke forming tendencies. In the test, a small aliquot of the
fuel sample is injected onto a packed silica adsorption col-

i k

excited electronic state

^
i k

i L

i k

>

increasing
energy

electronic energy levels,


measured using UV spectroscopy

J
ground electronic state

vibrational energy levels,


measured using FTIR spectroscopy

FIG. 13^The electronic and vibrational energy levels of a molecule.

CHAPTER 24: HYDROCARBON


passing infrared light through the sample at the exact frequency corresponding to the difference in energy of the vibrational levels, transitions within the vibrational levels of
the ground state can be induced, which is the principle behind FTIR spectroscopy.
For the same reason, passing light through the sample at an
appropriate frequency corresponding to the separation of the
electronic energy levels can induce a transition between these
levels, resulting in absorption of the light. For some
molecules, the frequency of light required to induce electronic
transitions is in the visible region of the electromagnetic spectrum, however, for most hydrocarbon molecules, the energy
that is required is much higher and requires ultraviolet radiation. This is the principle behind UV spectroscopy.
For hydrocarbon analysis, the most important factor determining the energy separation of the electronic energy levels is
what is often referred to as the molecular chromophore [28].
A chromophore is simply a covalently unsaturated bond or
group of bonds that is responsible for electronic absorption.
In tjrpical hydrocarbon fuels and lubricants, the most common types of molecules to possess a chromophore will be aromatic molecules, which have characteristic absorption bands
in the 185^00 nm wavelength range [28]. This range of the
electromagnetic spectrum is typically called the near-UV.

ANALYSIS

661

lamp

entrance
slit

diffraction
grating
photo cell
detector

FIG. 14UV spectrometer.

max

Beer's Law
In order to use UV spectrometry as a quantitative tool, we
need to understand the relationship between the concentration of specific molecules and the amount of light they absorb. This fundamental property is determined by Beer's
Law:
A = d)c
where A is the absorbance, e is the molar absorptivity, b is the
cell path length containing the sample, through which the UV
light passes, and c is the concentration in mol/L [27]. Because
the molar absorptivities of most molecules of interest have
been measured, and i> is a known quantity based solely on instrument design, measuring the amount of light absorbed by
the sample (A in the above equation) allows the concentration c to be determined simply by rearranging the Beer's law
equation.
UV Spectrometers
A schematic illustration of a UV spectrometer is shown in Fig.
14. The main components are a white light source, which is focused onto the entrance slits of a spectrometer, a cuvette or cell
containing the sample to be analyzed, and a photocell detector
to measure light intensity. The spectrometer is equipped with
a diffraction grating, which acts much like a prism to split the
white light into discrete wavelengths. Because the angle of
diffraction is defined by the wavelength of light, slowly changing the angle of the grating relative to the incoming light allows
the wavelength of light that exits the spectrometer through the
exit slits to be slowly scanned, allowing an absorption spectrum to be recorded, as shown in Fig. 15. The amount of light
absorbed at the maximum excitation wavelength (Amax). will
be dependent on the concentration c, path length b, and molar
absorptivity Smax as per Beer's Law.

'max
FIG. 15Typical UV absorption spectrum.

The Use of UV Spectrometers in the


Analysis of Hydrocarbons
UV spectrometers are used both directly and in conjunction
with high performance liquid chromatography (HPLC) instruments, principally to detect aromatics because they typically have strong UV absorption bands in the near UV region
(200-400 nm). The specific maximum absorption wavelength
and absorptivity is determined by a molecule's electronic
structure, however, in general it is found that mono-aromatics (those with a single aromatic ring such as benzene and
toluene) have an absorption maximum around 197 nm, diaromatics have absorption maxima around 230 nm, while
piclyaromatics absorb around 260 nm [29].
One application of this method, employed by several oil
companies, follows the work of Burdett [29, 30]. A typical UV
absorption spectrum of mono-, di-, and tri-aromatics is
shown in Fig. 16. The method of Burdett employs UV spectrometry to record the absorption spectrum in the range
175-270 nm. The molar absorptions is then recorded at the

662 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

Molar Absorption
1

100,000

1 Mono

|Di

[ Tricycli
1

/ / N j /^(~" \
10,000
^-^

1
1
11
1
1
1 I
1
1
1

)1
1

\.

Dicyclics

^ ^
^

1
1

Monocyclics
1,,^

/
yf
1 \
/
1 \
/
1
\ ^ /
1
1
1
1
1

1 t

180

190

'

200

210 220

230 240

\ ^

1
1

11

100

10

VMono

1,000

-/^

'iTriX/

^ '
\'

|Di

1
1
1
1
1
1
1
1
1

250

'

k.

260 A(nm)

FIG. 16UV absorption spectrum for monocyclic,


dicyclic and tricyclic aromatic hydrocarbons.

three characteristic absorption maxima, 190, 230, and 260


nm corresponding to mono-, di-, and poly-aromatics and can
be converted to a percent by weight of each type of molecular species using a simple formula based on moleculcir mass,
and the average molar absorptivity of each species at the
three wavelengths. Details of this procedure can be found in
Ref. 29.
One of the most common applications of UV spectrometry
to the analysis of hydrocarbon fuel and lubricants is its use in
determining the amount of toxic impurities, particularly
PAHs (polyaromatic hydrocarbons). The term PAH covers a
multitude of different hydrocarbon molecules, with one common theme: the presence of multiple aromatic rings. A number of different PAHs, which are known to be present in hydrocarbon fuels and lubricants, have been found to be
carcinogenic. For this reason, the EPA and other regulatory
bodies have established limits for PAH concentrations in fuels, lubricants, and other media. Because UV spectrometry is
capable of detecting polyaromatic species such as PAHs in
hydrocarbons by their characteristic absorption at 260 nm, it
is only natural that it has been used in this manor for determining PAH concentrations and carcinogen content in hydrocarbon oils [31].
While UV absorption is incapable of differentiating between two different molecules that may have absorption
bands in the same region (for example, two different PAH
molecules, both of which will absorb at 260 mm), the use of
separation techniques such as liquid chromatography (LC)
or gas chromatography (GC) can be employed to differentiate between different molecular species. In this case, the UV
spectrometer is fixed at a known absorption wavelength (for
example, 197 nm for mono-aromatic species), and is used to
measure different molecular species as they elute from the
GC or LC column; this provides a more molecule specific
means of detection than flame ionization or thermal detectors tj^ically used with GC and LC instruments.
One other technique closely related to UV absorption
spectrometry that is used in hydrocarbon analysis is spec-

trofiuorometry [29]. The principle behind spectrofluorometry is illustrated in Fig. 17, which shows theoretical absorption spectra for two different polyaromatic molecules
(molecules A and B), together with the corresponding fluorescence spectra. Because both molecules are polyaromatic,
the absorption spectrum for each will show a meiximum
around 260 nm. Recording the absorption spectrum for a
mixture of molecule A and molecule B will not allow the relative concentrations of each to be determined because both
absorb simultaneously at 260 nm. However, after excitation
at 260 nm, both molecules are in an excited electronic state
etnd will emit radiation to return to a lower lying electronic
state, typically in the form of light. Because molecule A and
molecule B possess different electronic structures, the energy of the lower lying electronic states will not necessarily
be the same. Because the emitted radiation is quantized,
measuring the emission (fluorescence) spectrum as opposed
to the absorption spectrum allows the concentration of two
molecules to be determined independently of each other.
Used in conjunction with LC, spectrofluorometry is an extremely sensitive technique capable of detecting concentrations of polycyclic aromatics and other species as low as
picograms [32].
ASTM Petroleum Products and Lubricants UV
Test Standards
Naphthalene Hydrocarbons in Aviation Turbine Fuels
by Ultraviolet (UV) Spectrophotometry (ASTM D 1840)
This test method covers the determination of the total concentration of naphthalene, acenapthene, and alkylated
derivatives of these hydrocarbons in straight-run jet fuels
containing no more than 5% of such components and having
end points below 600F. The total concentration of naphthalenes in jet fuels is measured by absorbance at 285 nm of
a solution of the fuel at known concentration.

MASS SPECTROMETERY
Introduction
Mass spectrometry is used to detect the presence of different
molecules in bulk samples. The technique involves the gas
phase cinalysis of samples that are either already gases, or are
liquids or solids that can be vaporized prior to mass spectrometric analysis. In conventional mass spectrometry, the gas
phase sample is ionized to form various primary and fragmentation ions, which are then analyzed according to their
mass-to-charge ratio. The mass spectrum thus generated can
then be used as a cheiracteristic fingerprint to detect the presence of certain molecules with the relative intensity of the
mass spectra allowing an estimate of the concentration of the
molecule or molecular species within a bulk sample. The application of Mass Spectrometry (MS) to the analysis of hydrocarbon fuels emd lubricants is outlined in this section.
MS Theory
As previously mentioned, MS works on the principal of separating primary and fragmentation ions according to their

CHAPTER
mass-to-charge (m/z) ratios. Take for example the w a t e r
molecule H2O. Bombarding water vapor with a high-energy
electron source will create both primary ions and fragmentation ions as follows:
HOH

>HOH+

+ OH+

I
primary ion
m/z = 18

+ 0+

m/z = 17

H+-F3e~

.
secondary ions
m/z = 16

m/z = 1

24: HYDROCARBON

ANALYSIS

663

of hydrocarbons typicedly found in petroleum fuels and lubricants. With many thousands of different components including paraffins, branched paraffins, naphthenic molecules,
and aromatics, the m a s s spectrum of a typical petroleum
fraction is extremely complex. Nevertheless, mass spectrometry can and has been successfully applied to the analysis of
complex petroleum mixtures as will be discussed later.
MS Instrumentation

Recording the mass spectrum of a bulk sample and measuring the relative intensities of the m/z = 1, 16, 17, and 18
peaks will allow the presence of water to be determined, and
by inference its concentration, provided a suitable calibration standard has been determined.
The biggest drawback with MS is that the complexity of the
m a s s s p e c t r u m increases exponentially with increasing
molecular size (molecular mass). Take for example benzene,
a relatively simple hydrocarbon. The electron ionization
mass spectrum of benzene (Fig. 18) has 17 different peaks
corresponding to m/z values ranging from 27-79, which include primary and fragmentation ion mass peaks, as well as
peaks associated with the naturally occurring isotope '^C
[35]. Now consider applying mass spectrometry to a mixture

The basic components of a mass spectrometer are shown in


Fig. 19. The system comprises an inlet source, which is designed to introduce the sample in the vapor phase to the spectrometer, a n ionization source that serves to ionize the sample, a mass analyzer which separates the ions by their m/z
ratio, and an ion detector for detecting the ions once they
have been mass selected. The inlet system for most basic
mass spectrometers is called a batch inlet and comprises a
means of injecting a gas, or more commonly a liquid sample
under reduced pressure and elevated temperatures such that
the sample can be vaporized for presentation to the spectrometer [34]. In m o d e m instruments, the liquid is commonly injected into the vacuum chamber using a hypodermic
syringe arrangement called a probe [35].

-* energy

UV absorption (A&B)
Amaxs260nm
absorption

molecule A
emission

emission spectrum (A)

absorption

molecule B
emission

emission spectrum (B)


FiG. 17Tlieoretical fluorescence emission spectrum of two different poiyaromatic
moiecuies, A and B.

664

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

<n
1) 60-

U 40

a:
20

1111 111 111 1111111 1111111 11 M 111 111 111 11

10

15

20

25

30

35

40

45

50

"i""|i il'i""i"'lMl'h
55

60

65

70

75

80

m/z
FIG. 18Mass spectrum of benzene.

Sample
Inlet

Ionization
Source

Mass Analyzer

Ion
Detector

FIG. 19Basic components of a mass spectrometer.

Once in the gas phase, the sample is drawn into the ionization section of the instrument where it is intersected at right
angles by a high-energy electron beam created by a hot filament. This is called an electron ionization mass spectrometer. The electron beam ionizes the sample into primary and
fragmentation ions, which are accelerated into the mass analyzer section using an electrostatic field formed by a series
of electrodes, which serve to focus and accelerate the ions
into the mass analyzer.
There are many different types of commercial mass spectrometers available. They all differ slightly in their design,
but all use one of three basic methods to mass analyze the
ionized sample, namely magnetic field deflection,
quadrupole mass spectrometry, or time-of-flight [35]. A detailed explanation of these different types of mass analyzers
is beyond the scope of this chapter, but an excellent description of these different methods can be found in Ref. 35. No
matter what type of mass analyzer is used, they all separate
ions according to their m/z ratio, with the ion signal being detected, amplified, and recorded as a function of their massto-charge (m/z) ratio.
Gas Chromatography-Mass Spectrometry (GC-MS)
One adaptation, which has served to simplify the interpretation of MS data, is to use a standard Gas Chromatograph (GC)
as the sample inlet source for the mass spectrometer. As explained earlier in this chapter, a gas chromatograph is an instrument that separates complex mixtures of chemicals into
single molecular components, or groups of components with
similar physical properties. By combining MS with GC, the
analysis of complex mixtures of chemicals such as hydrocarbon fuels and lubricants has become greatly simplified.

The usual way in which GC-MS is used for the analysis of


petroleum products is to fix the mass spectrometer to detect
one specific ion peak, for example m/z = 78, corresponding
to the primary ion peak for benzene. The ion intensity at
this fixed m/z ratio is then measured for different retention
time in the GC. The retention time is simply the time taken
for a specific molecular component of a complex mixture to
emerge or elute from the GC column, which in turn is related to the physical and chemical properties of the
molecule. By separating the signal in the m/z = 78 into different elution times, the true signal due to benzene can be
differentiated from other fragmentation ions from different
molecular species that may have an m/z ratio of 78, but
have different retention times in the GC column. This
makes the difficult task of interpreting the MS data significantly less complicated.
The Application of MS t o Hydrocarbon Analysis
Mass spectrometry is an important tool in the analysis of
petroleum products because it can give information that cannot be obtained by other means. Just like other spectrometric techniques, it gives important information on the chemical composition of complex mixtures of hydrocarbons
commonly found in fuels and lubricants, particularly when
coupled with other techniques such as gas chromatography.
The most common application of mass spectrometry to hydrocarbon analysis is in determining the composition of different process stream and boiling fractions during the refining process. There are a number of ASTM test procedures that
cover the use of MS in this area, which are listed in Table 3.
In each case, chemical composition is determined by calculating mass groupings, which correspond to the summation of characteristic mass peaks for different classes of
molecules that are likely to be present.
The m/z peaks that are used to calculate the different mass
groupings in the ASTM procedures listed in Table 3 are simply based on the known primary and fragmentation ions patterns using mass spectrometry for different molecules under
controlled laboratory conditions. For example, in ASTM D

CHAPTER
TABLE 3ASTM test procedures that use mass spectrometry for
determining the composition of different fractions.
ASTM Test Procedure
D 2425
D 2786
D 2789
D 3239

Significance
Saturates and aromatics in middle distillates
Saturates in gas oil fractions
Hydrocarbon types in low olefinic gasoline
Aromatics in gas oil fractions

2786 that is based on the Hood and O'Neal method, the mass
grouping E71 is defined as the sum of peaks at m/z = 71,85,
99, and 113 and is used to determine alkane content [37,38].
The difference in masses between each peak in the summation is simply the extension of the aJkane chain by one CH2
unit, with a corresponding increase in molecular mass of 14
atomic mass units. The biggest drawback with this method,
and indeed MS in general, for the analysis of hydrocarbons is
that the n u m b e r of mass peaks that must be considered increases significantly with molecular size. To illustrate this
complexity, consider the complete list of mass groupings,
which must be considered under ASTM D 2786, and the corresponding molecular types they represent;
S71 = 71 + 85 + 99 -F 113
alkanes
1 6 9 = 69 -I- 83 + 97 + 111 -F 125 + 139 1 ring naphthenes
E109 = 109 -I- 123 + 137 -I- 151 + 165
-I- 179 -I- 193
2 ring naphthenes
X149 = 149 + 163 + 177 + 191 -I- 205
+ 219-I-233-(-249
S189 = 189 + 203 + 217 + 231 + 245
+ 259 + 273 + 287 + 301
X229 = 229 + 243 + 257 + 271 -I- 285
+ 299 + 313 + 111 + 341 + 355
1269 = 269 + 283 4- 297 -F 311 + 325
-I- 339 + 353 -1-367-1-381
-F 395 + 409
S91 = 91 -F- 105 + 117 -I- 119 + 129
+ 131 4- 133 -I- 143 + 145 -I- 147
+ 159-1- 171

3 ring naphthenes
4 ring naphthenes
5 ring naphthenes
6 ring naphthenes

Mono-aromatics

Because of this, it is not surprising given the complex nature


of different hydrocarbon fractions, each of which may contain several thousand different types of molecules, that the
precision of using MS in this mode for different samples
types is at best 10% [36].
To circumvent these difficulties, MS is often used in conjunction with other techniques such as gas chromatography
(GC) or liquid c h r o m a t o g r a p h y (LC). In this case, chrom a t o g r a p h y is used to reduce the n u m b e r of different
molecule types that enter the mass spectrometer, reducing
the n u m b e r of mass peaks observed, and hence the complexity of interpreting the data accurately. In fact, separation of
the sample into aromatic and nonsiromatic fractions using
liquid chromatography (ASTM D 2549) prior to MS analysis
is a prerequisite for ASTM D 2425 [39].
One way in which MS Ccin be combined with GC is in fact
not to record a complete mass spectrum of the sample, but
rather to fix the mass (or more strictly the m/z ratio) of the
spectrometer to a known ion peak, and monitor this mass as

24: HYDROCARBON

ANALYSIS

665

a function of elution time. This can either be done directly by


recording the signal in a fixed mass channel, or by scanning
the spectrometer across cJl mass ranges and reconstructing
the signal in a single mass channel using softweire. The latter
is the method used u n d e r ASTM D 5769. In this method, separation of molecular species according to their characteristic
p r i m a r y a n d fragmentation ions allows a more complete
analysis to be performed. This is illustrated in Fig. 20. In this
case, by combining the selectivity of GC in separating different molecular species with the mass specificity of MS, the different molecular concentrations of specific molecules such
as benzene, toluene and other aromatics can be determined.
Without this mass selectivity, the gas chromatogram would
be extremely complex, with no guarantee that the elution
peak corresponds to a specific molecule such as benzene or
toluene.
Although limited by its ability to resolve information from
complex mixtures of chemicals typically found in petroleum
products, mass spectrometer, particularly when combined
with other separation techniques such as LC and GC is an important tool in the analysis of hydrocarbons.
ASTM Petroleum Products and Lubricants M S
Test Standards Under Subcommittee D02.04
Hydrocarbon
Types in Gasoline
(ASTM D 2789)

by Mass

Spectrometry

This test method covers the determination by mass spect r o m e t r y of total paraffins, monocycloparaffins, dicycloparaffins, alkylbenzenes, indans, or tetralins or both, and
n a p h t h a l e n e s in gasoline. Samples are analyzed by m a s s
spectrometry, based o n the s u m m a t i o n of characteristic
mass fragments, to determine the concentration of the hydrocarbon types.
Aromatics
in Gasoline by Gas
Spectrometry
(GC-MS) (ASTM D

Chromatography-Mass
5769)

This test method can be used for gasolines that contain oxygenates such as alcohols and ethers as additives. They do not
interfere with the analysis of benzene and other aromatics by
this test method. The sample is injected either through the
capillary splitter port or a cool-on-column injector into a gas
c h r o m a t o g r a p h equipped with a dimethylpolysiloxane
WCOT column interfaced to a fast scanning mass spectrometer. The mass analyzer processes the signal at specific m/z
values corresponding to the principal ion masses for various
components allowing benzene, toluene, and total aromatic
content to be measured in gasolines.

INFRARED SPECTROSCOPY
Infrared spectroscopy is a widely applied, nondestructive test
method for assessing a variety of molecular physical qualities
of a lubricant or fuel sample. The spectrum analyzed by the
method is considered a distinct physical property of the sample and, as such, is unique from other physical and chemical
properties, such as viscosity, specific gravity, flash point, etc.
From the spectrum, in most cases, a positive identification of
the sample and its greater molecular constituents can be obtained [40].

666

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Most p e t r o l e u m products, a n d more specifically, lubriCcints, fuels, additives, and contaminants are mixtures, which
results in the spectrum being a composite of m a n y different
spectral components that are additive. Nevertheless, for most
fluids, the spectrum is sufficiently characteristic to enable
the identification of the unique spectred features of individual
components. Still, in certain cases, a physical or chemical
separation of the tcirget components from the rest of the sample, such as gas chromatography, m a y be desirable to improve detection limits and resolving power of the technique.
The infreired spectrum of a substance is produced when a
portion of a beam of infrared energy passing through a fixed
path length of the sample is absorbed by a specific functional
group within a specific molecule present in the sample. This
absorption has unique wavelength dependencies relating to
the sample's molecules. Most molecules are in constant
modes of rotation, stretching, and bending at unique and often multiple frequencies. In addition, these vibrational frequencies will vary as the bonded atoms, functional groups,
a n d bond strengths are changed. These differences in absorption at certain wavelengths in the mid-infrired spectrum
collectively describe the quality and quantity of molecular
makeup of the sample [41].
Infrared spectroscopy is especially well suited for the analysis of organic c o m p o u n d s comprised of characteristic
molecular structures. The various groups, called functional

groups, which make u p part of a molecule's structure, give


rise to absorption at specific infrared frequencies but more
typically spectral b a n d s comprising a broader range of wavelengths. These cire commonly referred to as group frequencies. For example, a well-defined group frequency is associated with C = 0 at around 1700 wavenumbers (cm~').
Wavelength, Wavenumber and Frequency
The frequency or energy at which unique infrared absorptions occur is usually expressed as wavelength in micrometers (fjim) or wavenumbers in reciprocal centimeters (cm~').
Studies have shown that a tjrpical organic molecule requires
an average energy of 1.6 X lO"'^" joules (J) for vibrational excitation, which corresponds to 12 fji,m of infrared radiation.
The reciprocal of the wavelength is referred to as wavenumbers and represents the n u m b e r of cycles passing a fixed
point per unit of time. The scale in Fig. 21 shows the conversion of wavelength to w a v e n u m b e r s [42]. The use of
wavenumbers (cm~^) in infrared spectroscopy is preferred to
a scale of wavelengths (jj-m) because wavenumbers Eire linear
a n d proportional to the energy a n d frequency being absorbed. Wavenumbers are sometimes incorrectly referred to
as frequencies, a n error because the w a v e n u m b e r is expressed in reciprocal centimeters (cm~^) and frequency is expressed in units of reciprocal time (s~') [42].

Abundance.,

ION 128

80000:
70000.
60000.
SCOOO.
NAPHTHALENE

40000:
30000'
2000010000
0
Time 18 00

^
18.50

Abundance
50000

19.00

19.50

20.00

20.50

21.00

21.50

22.00

ION 142

4S000

2-METHYmAPHTHALENE

40000
39000:
1-METHYL-NAPHTHALENE,

30000

""-*

2SOO0'
20000
15000100005000;
0^
Time - 18 00

,
18.50

19.00

19.50

20.00

20.50

21.00

21.50

22.00

MINUTES

FIG. 20^Typical mass selected gas chromatogram showing the ability of GC-MS to separate molecular species by their elution time and
characteristic ion mass peak. Reprinted with permission from ASTIVI D
5769-98.

CHAPTER 24: HYDROCARBON


Wavenumber

Wavelength

4000- - 2 . 5 - 1
3500-

-3

3000;

2500- ^ 4

Functional
group
region

2000- ^ 5
1800^
: L-e /Am
(micrometei)
1600 L
f-7
1400|-8
1200^9
1 0 0 0 - |-10
8 0 0 - |-12
tl5
elength goo
P-20
conversion scale
for
efor
infrared data.
1.
400 - F 3 0
2 0 0 - ^50
Frequency Wavele ngth
-1
cm

Fingerprint
region

FIG. 21Conversion scale for infrared data.

ANALYSIS

667

The reference and sample beams are then passed ahematively by a rotating half mirror to a dispersive device, which
separates the radiation into specific frequencies (wavelengths). A prism is one type of dispersive device that separates radiation in different wavelengths based on differences
in refractive indexes at different wavelengths. Since glass will
absorb infrared radiation sodium chloride, other materials
cire required. Alternatively, a grating can be used as a dispersive device using a series of closely spaced parallel grooves
etched into a flat surface. The grating simply reflects the
diffracted light from its surface and absorbs very little radiation. Many infrared spectrometers require special temperature cind/or desiccants to prevent moisture damage to the optics in the monochromator [42].
The monochromator directs the radiation reflecting
from the grating through a series of narrow slits, which luminate onto a detector, for example, a thermocouple. This
quantifies the intensity of the energy at only the desired
band of frequencies. Many dispersive-type infrared spectrometers are of the double-beam optical null type. In such
cases, the radiation passing through the reference beam is
reduced or attenuated to match the intensity of the sample
beam [42].

Beer-Lambert Law

Fourier Transform Infrared Spectroscopy

A good place to begin the discussion of using infrared spectroscopy for quantitative analysis of fuels and lubricants is
the Beer-Lambert Law. It relates the amount of infrared light
absorbed by a given sample to the concentration of the target
compound and path length. More to the point, the law states
that concentration is directly proportional to absorbance at a
given wavelength and path length at a specified temperature
and pressure.

Compared to the dispersive spectrometer, the Fourier transform spectrometer provides improved speed and range of
spectral sensitivity in making infrared measurements. The
Michelson interferometer is a basic component of the
Fourier transform instrument. Unlike the dispersive spectrometer, the interferometer has no slits or grating. Instead,
it consists of two mirrors and a beam splitter. The beam
splitter transmits half of all the incident radiation from a
source to a moving mirror and reflects half to a stationary
mirror. Each component reflected by the two mirrors returns to the beam splitter where the amplitudes of the
waves eire combined to form an inteferogram, which is
Fourier-trEinsformed into the frequency spectrum. The interferometer scans the infrared spectrum in just fractions of
a second at moderate resolution. The resolution is uniform
across the optical range. Multiple scans can be co-added to
reduce background noise [42].

A = abc = logio I/I

(1)

A = absorbance
/ = IR power-reaching detector with sample in beam
7 IR power-reaching detector with no sample in beam
a = absorption coefficient of pure component of interest at
anal54ical wavelength; the units depend on those chosen
for b and c
b = sample path length
c = concentration of sample component
This linearity permits simple calibration plots of known
samples between absorbance (A) and concentration (C) for
analyzing the concentration in unknown samples. In addition, the Law is helpful in choosing the optimum sample path
length for accurate eincJysis, as will be further discussed [43].
Dispersive-Type Infrared Spectrometers
In this design, zin infrared source of energy is usually provided by a Nemst glower, which is composed of rare earth oxides (zirconium, cerium, etc.) formed into a cylinder. On
electrically heating to approximately 1500C, this filament
material produces the needed infrared radiation. The beam
of radiation is split into a reference and sample beam by mirrors. The reference beam is passed through air or a beam attenuator and the sample beam is passed through the sample
where selective radiation absorption occurs [42].

Analysis of Midticomponent Solutions


For solutions, samples should be diluted and placed in cells
of appropriate path length (typically 0.2-1.0 mm). It is preferred to use lower concentrations in longer path length cell
rather than higher concentrations in shorter path length cell.
The desired absorbance is in the reinge of 0.3-0.8. Lower concentrations will minimize nonlinear effects due to dispersion
(that is, change of refractive index with wavenumber). Where
freedom from intermolecular effects is uncertcdn or where intermolecular effects are known to be present, calibration
must be based on measurements taken from S5rnthetic mixtures of all components. The procedure is described in ASTM
E 168 [44].
Calibration is achieved by dissolving a known weight of a
pure component in a suitable infrared solvent. Next, the absprbcmce is measured at all analj^iceJ wavenumbers and cor-

668

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

rected for baselines as further discussed. The procedure is repeated for a range of concentrations covering the expected
concentrations. From this, absorbance is plotted against concentration. Analytical curves can also be constructed for each
of the wavenumbers or bands where the target component is
represented. So too, the procedure is repeated for each of the
components to be analyzed in the solution [44].
Analysis of Gases
For gases, all calibration measurements for a given analysis
must be made at a fixed total pressure. This pressure must be
equal to the total pressure employed in the analysis. Low
molecular weight gases frequently produce very strong, sharp
absorption features. Addition of a diluent gas and use of pressure below atmospheric may be necessary. Absorbances cire
measured for each of the standard wavenumbers selected for
analysis. Where possible, integrated absorbances are preferred to offset the effect of small pressure vetriations. The absorbances Eire plotted against the partial pressures (or mole
fractions) to produce analytical curves [44].
Achieving Reproducible Baselines
Any quantitative method depends on the choice of a reproducible baseline. The correction of raw data for baseline absorbance is important in some methods. The guiding factor
in baseline selection is the reproducibility of the results.
Methods used for drawing baselines with computerized instruments are similar in most ways to those for data recorded
on chart paper [44].
A technique known as the cell-in-cell-out method is often
used in single-beam infrared work. In this method, a blank
(that is, solvent in cell, potassium bromide (KBr) pellet, or
other substrate) is measured at a fixed wavenumber and then
the analyte readings are recorded. One variation involves the
subtraction of the absorbance minimum from the absorbance
maximum at the chosen baseline point. The point of minimum absorbance is adjacent to or at least near the band under evaluation. Alternatively, two points may be needed if the
band of interest is superimposed on a sloping background. In
such case, a line is drawn from one side to the other and absorbance is calculated as the value at the peak maximum minus the baseline absorbance minimum. An inappropriate
choice of baseline in this situation may have deleterious effects on the accuracy of the final calculation [44].
The baseline correction described above should be performed only if the spectrum is plotted in absorbance units.
When the spectrum is plotted in transmittance, the two-baseline transmittances and the transmittance at the analytical
wavenumber Eire converted to absorbance. Conversion to absorbance is required because a sloping linear baseline in
transmittance becomes curved in absorbance [44].
Employing the Difference Method
Spectral subtraction using a computer is a common practice
in qualitative infrared analysis. This technique is also used to
perform quantitative infrared analyses. The advantage of
spectral subtraction (the difference method) is that small
concentration differences can be measured with greater ac-

curacy than is possible on superimposed bands. The general


procedure involves the removal of spectral contributions of
specific and known components from a spectrum containing
multiple components in order to assess the unique spectral
characteristics of the remaining target component [44].
Band Area Methods
Band shape changes can cause peak-height data to be nonlinear. Band area, however, may remain essentially unaffected by the changes in shape of the band because band area
is a function of the total number of absorbing centers in the
sample. If the shape change is caused by changes in intermolecular forces, even band area may be linear [44].
Band area is calculated by integrating across bandwidth.
Band area is advantageous when band shape undergoes
change as a function of increasing concentration. Frequently,
band area is found to be more accurate than peak-height
measurements because one is, in effect, averaging multipoint
data. When integrated area is used for quantitative analyses,
the reliability of the results frequently depends on the baseline treatment selected. The accuracy by band area is often
improved by limiting the range of absorbances. The wings
contribute very little signal while contributing substantial
uncertainties to the totEil Eirea. A useful guideline is to limit
the integration limits to absorbance values, which are no
smaller than 20-30% of the peak absorbance [44].

Hydrocarbon Analysis
Hydrocarbon analysis using infrared spectroscopy must begin at the parent backbone structure. The simple aliphatic hydrocarbon is the root of most Ediphatic compounds and consists of simple linear chains, branched chains, and cyclic
structures. Aliphatic compounds can consist of one or more
of these structures. The infrared spectrum is useful in providing specific information on the existence of most of these
structures, by inference or directly. The spectrEd contributions
are characterized by CH and CC stretching and bending
vibrations, which are generally unique for each molecule. For
aromatic compounds, ring C=C-C stretching and bending
vibrations are distinctly characteristic as are carbon-carbon
multiple bonding in alkene and alkjrne structures [45].
In terms of recognizing a compound as having an organic
structure with aliphatic constituents, the CH stretch vibrations for methyl and methylene are the most characteristic.
In Fig. 22, methylene/methyl bands can be seen at 1470 and
720 cm"^ An important methylene rocking vibration occurs
at 725-720 cm~'. As CH stretching absorptions all occur
below 3000 cm"', bands between 3150 and 3000 cm~' and
are almost always associated with unsaturation, for example,
C=CH and/or aromatic rings. Figure 23 shows examples of
either single or pair absorbancies of unsaturated hydrocarbons featuring C=C with attached hydrocarbons. The number of bands and their associated positions point to the double bond location Emd spacing around the double bond [45].
One or more aromatic rings can tj^ically be recognized by
the C=CC and C-H ring-related vibrations/bending. Typically, the CH stretching occurs about 3000 cm~\ revealing
a number of weak-moderate bands compared with the
aliphatic CH stretch. The number and locations of the CH

CHAPTER

Saturated Aliphatic (ajlcane/allcyl) Group Frequencies


Group frequency (cm')
2970-2950/2880-2860
1470-1430/1380-1370
1385-1380/1370-1365
1395-1385/1365
2935-2915/2865-2845
1485-1445
750-720
1055-1000/1005-925
2900-2880
1350-1330
1300-700
2850-2815
2820-2780

Functional group/assignment
Methyl (-CHj>
Methyl C-H asym./sym. stretch
Methyl C-H asym./sym. bend
gem-Dimethyl or "iso" - (doublet)
Trimethyl or "tert-butyl" (mlltiplet)
Methylene (>CH2)
Methylene C-H asym./gym. stretch
Methylene C-H bend
Methylene - (CH2)-rocklng
(n>3)
Cyclohexane ring vibrations
Methyne (>CH-)
Methyne C-H stretch
Methyne C-H bend
Skeletal C-C vibrations
Special methyl (-CHj) frequencies
Methoxy methyl ether O-CH3
C-H stretch
Methylamino, N-CH3, C-H stretch

FIG. 22Saturated aliphatic (alkane/alkyl) group frequencies. Courtesy Coates Consulting.

Olefinic (alkene) Group Frequencies


Origin
0=0

C-H

Group frequency
wavenumber (cm')
1680-1620
1625
1600
3095-3075
+3040-3010
3095-3075
3040-3010

0-H

1420-1410
1310-1290

C-H

995-985+915-890
895-885

C-H

970-960
700 (broad)

Assignment
Alkenyl 0 = 0 stretch
Aryl-substituted C=C
Conjugated 0 = 0
Tenninal (vinyl) C-H stretch
Pendant (vinylldene) C-H
stretch
Medial, cis- or frans-C-H
stretch
Vinyl C-H in-plane bend
Vinylidene C-H in plane
bend
Vinyl C-H out-of-plane bend
Vinylidene 0-H out-of-plane
bend
trans 0-H out-of-plane bend
cis C-H out-of-plane bend

bonds around the aromatic ring is defined by the structure of


the bands in the spectrum. Other important bcuids for aromatic ring vibrations are positioned around 1600 and 1500
c m ~ \ which are exhibited as pairs with some splitting. The
nature and structure of these two bands are largely influenced
by the position and nature of substituents on the ring [45].
On the surface, the interpretation of halogenated comp o u n d s contained in infrared spectra is functionally very
simple. While not always true, the polar nature of the group
consisting of a single atom linked to carbon produces a dis-

ANALYSIS

669

tinctive spectral contribution. T5T3ically, a unique group frequency associated with halogen-carbon stretching is assigned to the C^X bond (Fig. 24). If more than one halogen
is present, the identification of the group frequency is somewhat more complex. It is largely influenced by whether the
halogens are on the same or different CcU"bon atoms, and if
different, their relative proximity is important.
Relating to alcohols and hydroxy c o m p o u n d s , the 0H
stretch is probably one of the most pronounced and characteristic of all the infrared group frequencies. There is typiCcdly a high degree of association coming from hydrogen
bonding with other hydroxy groups. And, in cases, these may
come from hydroxy groups from within the same molecule
(intramolecular bonding). Alternatively, they may associate
with nearby molecules (intermolecular bonding). Collectively, the effects of hydrogen bonding result in the production of a well-defined but broad band cuid the lowering of
mean absorption frequency. This is exhibited in compounds
such as carboxylic acids, which produce strong hydrogen
bonding. See Fig. 25 for alcohol a n d hydroxy c o m p o u n d
group frequencies [45].
Because alcohols exist as three distinct classes, primary,
secondcury, and tertiary, they are identified by the extent of
carbon substitution on the central hydroxy-substituted carbon. The infrared characterization of these alcohols is reflected in the position of the OH stretch absorption but also
by other absorptions including the CO stretching frequency. These can be observed in the primary and secondary
alcohols shown in the spectra shown in Fig. 26. Ethers are
somewhat related to edcohol and hydroxy compounds where
the hydrogen of the hydroxy group is substituted by an aromatic (aryl) or aliphatic (alkyl) molecular fragment. Otherwise, the overall appearance of an ether spectrum is sharply
different from any associated alcohol due to the impact of the
hydrogen bonding on the hydroxy group [45].
In amines, the terms primary, secondary, and tertisiry are
used to describe the substituted nitrogen as opposed to carbon as with alcohols. As with alcohols, these structural differences are significant and distinctly influence the infrared

Aliphatic Organohalogen Compound Group Frequencies


Origin

FIG. 23Olefinic (alkene) group frequencies. Courtesy


Coates Consulting.

24: HYDROCARBON

Group frequency
wavenumber (cm"')

C-F

1150-1000

C-CI

800-700

C-Br

700-600

0-1

600-500

Assignment

Aliphatic fluoro compounds,


C-F stretch
Aliphatic chtoro compounds,
C-CI stretch
Aliphatic bromo compounds,
C-Br stretch
Aliphatic iodo compounds,
C-l stretch

Note that the ranges quoted serve as a guide only; the


actual ranges are influenced by carbon chain length, the
actual number of halogen substituents, and the molecular
conformations present.

FIG. 24Aliphatic organohalogen compound group frequencies. Courtesy Coates Consulting.

670

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Alcohol and Hydroxy Compound Group Frequencies


Group frequency
Assignment
Origin
wavenumber (cm-1)
0-H

0-H

0-H
C-0

3570-3200 (broad)
3400-3200
3550-3450
3570-3600
3645-3630
3635-3620
3620-3540
3640-3530'
1350-1260
1410-1310
720-590
-1050'
-1100
-1150'
-1200'

Hydroxy group, H-bonded OH stretcti


Normal "polymeric" OH stretch
Dimeric OH stretch
Internally bonded OH stretch
Nonbonded hydroxy group, OH stretch
Primary alcohol, OH stretch
Secondary alcohol, OH stretch
Tertiary alcohol, OH stretch
Phenols, OH stretch
Primary or secondary, OH in-plane bend
Phenol or tertiary alcohol, OH bend
Alcohol, OH out-of-piane bend
Primary alcohol, C-0 stretch
Secondary alcohol, C-0 stretch
Tertiary alcohol, C-0 stretch
Phenol, C-0 stretch

'Frequency influenced by nature and position of other ring substituents.


"Approximate center of range for tlie group frequency.
Courtesy Coates Consulting.

FIG. 25Alcohol and hydroxy compound group frequencies. Courtesy Coates Consulting.

I I I I I I I I I I I I I
o
o
o o
o o
o

Wavenumber (cm')
100

o
<o
<o

e
M
n

o
eo
CM

.
M

Wavenumber (cm'')
ATR spectra of (a) primary (1-octanol) and (b) secondary
(2-octanol) alcohols. Courtesy poates Consulting.
FIG. 26ATR spectra of (a) primary (1-octanol) and (b) secondary (2-octanol) alcohols. Courtesy Coates Consulting.

spectra. It is possible to readily describe functional group


structures, especially for the primary and secondary amino
compounds. Although somewhat weaker than hydroxy compounds, the hydrogen bonds play an important role in the selective identification of the various amino compounds. In the
case of ammonium and amino salts, strong hydrogen bonding is observed. Primary and secondary amines are largely
characterized by the NH bond group frequencies. The tertiary amines, like esters, produce vibrations associated with
the C^N bond, see Fig. 27 for group frequencies for Amino
Compounds [45].
The carbonyl group, C = 0 absorption, is often the most
characteristic and intense of the entire infrared spectrum.
Common group frequencies for carbonyl compounds can be
seen in Figure 28. With the exception of the aldehyde, all
other carbonyl compounds can be generedly considered to be
derived from the base structure of ketone. This occurs as one
or both alky (or aryl) substituents are replaced by a single hydroxy group (carboxylic acids) or two ether groups (organic
Cctrbonate). Commonly, the group frequencies for the various
classes of carbonyl compounds overlap and the carbonyl
band alone is insufficient to identify the specific functional
group. Common examples include carboxylic acids where
CO, COH, and OH vibrations are characteristic, as
are esters C^OC and amides, CN and NH. So too, a
characteristic broad feature in the range 3300-2500 cm"'
that overlaps the CH stretching region is observed for hydrogen-bonded OH in most carboxylic acids [45].
Characterization of Inorganics
Infrared spectroscopy can be used very effectively to characterize inorganic molecular species that often co-occupy space
with various hydrocarbon compounds found in fuels and lu-

CHAPTER 24: HYDROCARBON


Amine and Amino Compound Group Frequencies

Origin

N-H

Group frequency
wavenumber (cm"^)

N-H
C-N

3400-3380
+3345-3325
3510-3460
+3415-3380
1650-1590
1090-1020

>N-H

3360-3310

>N-H

-3450

>N-H

3490-3430

=N-H

3350-3320

>N-H
C-N

1650-1550
1190-1130

C-N

1210-1150

C-N

1340-1250

C-N

1350-1280

C-N

1360-1310

N-H

Assignment

Primary amino
Aliphatic primary amine,
NH stretch
Aromatic primary amine,
NH stretch
Primary amine, NH bend
Primary amine, CN stretch
Secondary amino
Aliphatic secondary amine,
NH stretch
Aromatic secondary amine,
NH stretch
Heterocyclic amine,
NH stretch
Imino compounds,
NH stretch
Secondary amino, NH bend
Secondary amine,
CN stretch
Tertiary amino
Tertiary amine, CN stretch
Aromatic amino
Aromatic primary amine,
CN stretch
Aromatic secondary amine,
CN stretch
Aromatic tertiary amine,
CN stretch

FIG. 27Amine and amino compound group frequencies.


Courtesy Coates Consulting.

Example Carbonyl Compound Group Frequencies


Group frequency (cm-1)
1610-1550/1420-1300
1680-1630
1690-1675/(1650-1600)'
1725-1700
1725-1705
1740-1725/(2800-2700)'
1750-1725
1735
1760-1740
1815-1770
1820-1775
1850-1800/1790-1740
1870-1820/1800-1775
2100-1800

Functional group
Carboxylate (carboxyllc acid salt)
Amide
Quinone or conjugated ketone
Carboxyllc add
Ketone
Aldehydle
Ester
SIx-membered ring lactone
Alkyl carbonate
Add (acyl) hallde
Aryl carbonate
Open-chain add anhydride
Five-membered ring anhydride
Transition metal carbonyls

' Lower frequency band is from the conjugated double bond.


"Higher frequency band characteristic of aldehydes.
associated with the termlhal aldehydic C-H stretch.

FIG. 28Carbonyl compound group frequencies. Courtesy


Coates Consulting.

ANALYSIS

671

bricating oils. Essentially any compound that forms covalent


bonds within a molecular ion fragment will produce a characteristic absorption spectrum with unique group frequencies. The metal complexes and chemical fragments associated with heteroxy groups such as nitrates, sulfates,
phosphates, silicates, etc. and transition metal carbonyl compounds have already been generally discussed as related to
the salts of carboxyllc acids, amino, and ammonium compounds [45].
ASTM Petroleum Products and Lubricants IR Test
Standards w i d e r Subcommittee D02.04
Aromatics in Finished Gasoline by GC-FTIR:
ASTM D 5986
This method can be used for determining aromatic content in
gasolines that contain oxygenates such as alcohols emd ethers
as additives. It can be used for both, and does not interfere
with benzene and other aromatics by this method. The sample is injected through a cool on-column injector into a gas
chromatograph equipped with a methylsilicone WCOT column interfaced to a FT-IR instrument.
Benzene/Toluene in Gasoline by Infrared (Ir)
Spectroscopy: ASTM D 4053
A gasoline sample is examined by infrared spectroscopy and
following a correction for interference is compared with calibration blends of known benzene concentration.
Benzene/Toluene in Engine Fuels using Mid-IR
Spectroscopy: ASTM D 6277
A beam of infrared light is imaged through a liquid sample
cell onto a detector, and the detector response is determined.
Wavelengths of the spectrum that correlate highly with benzene or interferences are selected for analysis using selective
bandpass filters or mathematically by selecting areas of the
whole spectrum.
Methyl Tert-Butyl Ether in Gasoline by Infrared
Spectroscopy: ASTM D 5845
This infrared method measures MTBE and other oxygenates
in the concentration ranges from about 0.1 to about 20 mass
percent. A sample of gasoline is analyzed by infrared spectroscopy.
ASTM STANDARDS
No.
Title
D 1319 Hydrocarbon Types by Fluorescent Indicator Adsorption
D 1840 Naphthalene Hydrocarbons in Aviation Turbine Fuels by Ultraviolet (UV) Spectrophotometry
D 2427 Hydrocarbon Types in Gasoline by Gas Chromatography
D 2789 Hydrocarbon Types in Gasoline by Mass Spectrometry
D 2887 Boiling Range Distribution of Petroleum Fractions
by Gas Chromatography
D 3524 Diesel Fuel Diluent in Used Diesel Engine Oils by
Gas Chromatography

672 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


D 3525

Gasoline Diluent in Used Engine Oils Gas Chromatography Method


D 3606 Benzene/Toluene in Gasoline by Gas Chromatography
D 3 710 Boiling Range Distribution of Gasoline Fractions by
Gas Chromatography
D 4053 Benzene/Toluene in Gasoline by Infrared (IR) Spectroscopy
D 4291 Ethylene Glycol in Used Engine Oil
D 4420 Aromatics in Finished Gasoline by Gas Chromatography
D 4815 Methyl Tert-Butyl Ether in Gasoline by Gas Chromatography
D 5186 Aromatics and Polynuclear Aromatics in Diesel and
Aviation Turbine Fuels by SFC
D 5480 Engine Oil Volatility by Gas Chromatography
D 5501 Ethanol Content in Denatured Fuel Ethanol by Gas
Chromatography
D 5580 Aromatics in Finished Gasoline by Gas Chromatography
D 5599 Oxygenates in Gasoline by Gas Chromatography
D 5623 Sulfrir Determination by GC-Sulfrir Detector
D 5769 Aromatics in Gasoline by Gas ChromatographyMass Spectrometry (GC-MS)
D 5845 Methyl Tert-Butyl Ether in Gasoline by Infrared
Spectroscopy
D 5986 Aromatics in Finished Gasoline by GC-FTIR
D 6277 Benzene/Toluene in Engine Fuels Using Mid-IR
Spectroscopy
D 6293 Oxygenates O-PONA Hydrocarbons in Fuels by Gas
Chromatography
D 6296 Olefins in Engine Fuels by Gas Chromatography
D 6352 Boiling Range Distribution of Petroleum Distillates
by Gas Chromatography
D 6379 Hydrocarbon Types Aromatic Hydrocarbon Types
in Aviation Fuels and Petroleum Distillates
D 6417 Estimation of Engine Oil Volatility by Capillary Gas
Chromatography
ASTM Petroleum Products and Lubricants N M R
Test Standards under Subcommittee D02.04
Aromatics in Hydrocarbon Oils by High Resolution Nuclear
Magnetic Resonance (HR-NMR)

OTHER STANDARDS
IP 156

Hydrocarbon Types in Liquid Petroleum Products


by Fluorescent Indicator Adsorption

REFERENCES
[1] Oehler, U., NMR-A Short Course, University of Guelph, Ontario,
Canada, http://www.chembio.uogueIph.ca/driguana/NMR/TOC.
HTM, Jan. 2001.
[2] Silverstein, R., Bassler, G., and Morrill, T., Spectrometric Identification of Organic Compounds, Fifth Edition, John WUey and
Sons, Inc., NY, 1991, pp. 166-201.
[3] Shugar, G. and BaUinger, J., Chemical Technicians' Ready Reference Handbook, Fourth Edition, McGraw-Hill, Inc., NY, 1996,
pp. 802-808.

[4] NMR Spectral Archive, National Institute of Advanced Industrial Science and Technology. Tsukuba, Ibaraki, Japsin. SDBSWeb: http://www.aist.go.jp/RIODB/SDBS/.
[5] Denis, J., Briant, J., and Hipeaux, J., Lubricant Properties Analysis and Testing, Editions Technlp, Paris, 2000, p. 21.
[6] Bouquet, M., "Determination of Hydrogen Content of Petroleum
Products Using Low Resolution Pulsed NMR Spectrometry,"
Fuel, Vol. 64, 1985, pp. 226-228.
[7] Gauthier, S. and Quignard, A., "Accurate Determination of Hydrogen Content in Petroleum Products by Low Resolution," '//
NMR Revue IFF. Vol. 50, No. 2, 1995, pp. 249-282.
[8] Willis, J., Lubrication Fundamentals, Marcel-Dekker, Inc., NY,
1980, pp. 1-25.
[9] ASTM D 5292-93: Aromatic Carbon Contents of Hydrocarbon
Oils by High Resolution Nuclear Magnetic Resonance Spectroscopy, Annual Book of ASTM Standards, ASTM International,
West Conshohocken, PA, 1993.
[10] Shugar, G. and BaUinger, J., Chemical Technicians' Ready Reference Handbook, Fourth Edition. McGraw-Hill, Inc., NY, 1996,
pp. 831-864.
[11] Norris, T. A., "Chromatography II," Lubrication, Vol. 65, No. 2,
1979, pp. 13-24.
[12] ASTM D 5307: Determination of Boiling Range Distribution of
Crude Petroleum by Gas Chromatography, Annual Book of
ASTM Standards, ASTM International, West Conshohocken, PA.
[13] Altgelt, K. and Gouw, T., Chromatography in Petroleum Analysis,
Marcel-Dekker, Inc., NY, 1979, pp. 41-73.
[14] Troyer, D. and Fitch, J., Oil Analysis Basics, Nona Corporation,
Tulsa, OK, 1999.
[15] Fitch, J., "Oil and Water Don't Mix," Practicing Oil Analysis Magazine, July/August 2001, p. 20.
[16] Denis, J., Briant, J., and Hipeaux, J., Lubricant Properties Analysis and Testing Editions Technip, Paris, p. 53.
[17] "Gas Chromatography with Atomic Emission Detector for Turbine Engine Lubricant Analysis," JOAP Conference Proceedings,
University of Dayton Research Institute, Dayton, OH, 1994, pp.
485^96.
[18] Norris, T. A., "Chromatography II," Lubrication, Vol. 65, No. 2,
1979, pp. 13-24.
[19] Li, Z., "Separation Techniques with Liquid Chromatography,"
The FRH Journal, 1984, pp. 69-76.
[20] Stevenson, R., "Rapid Separation of Petroleum Fuels by Hydrocarbon Type," Journal of Chromatographic Science, Vol. 9, 1971,
pp. 257-262.
[21] Denis, J., Briant, J., and Hipeaux, J., Lubricant Properties Analysis and Testing, Editions Technip, Paris, 2000, pp. 31.
[22] "La Chromatographic d'Exclusion sur Gel," Journal of Dubois
Analysis 16, Vol. 3, No. LWVI-LXXIII, 1988.
[23] Shugar, G. and BaUinger, J., Chemical Technicians' Ready Reference Handbook, Fourth Edition, McGraw-HUl, Inc., NY, 1996,
pp. 865-896.
[24] API 1509, Engine Oil Licensing and Certification System, American Petroleum Institute, Washington, DC, 1996.
[25] ASTM Test Standard D 2007: Characteristic Groups in Rubber
Extender and Processing Oils and Other Petroleum-Derived Oils
by the Clay-Gel Absorption Chromatographic Method, Annual
Book of ASTM Standards, ASTM International, West Conshohocken, PA.
[26] RR: D02-1388, ASTM International, West Conshohocken, PA,
1996.
[27] Shugar, G. and BaUinger, J., Chemical Technicians' Ready Reference Handbook, Fourth Edition, McGraw-Hill, Inc., NY, 1996,
pp. 753-759.
[28] Silverstein, R., Bassler, G., and MorriU, T., Spectrometric Identification of Organic Compounds, Fifth Edition, John Wiley and
Sons, Inc., NY, 1991, pp. 289-314.
[29] Denis, J., Briant, J., and Hipeaux, J., Lubricant Properties Analysis and Testing, Editions Technip, Paris, 2000, pp. 41-58.

CHAPTER 24: HYDROCARBON ANALYSIS


[30] Determination
of Aromatic Hydrocarbons in Lubricating Oil
Fractions by Far Ultraviolet Absorption Spectroscopy, R. A. Burdett Molecular Spectroscopy, Institute of Petroleum, George
Sell, London, 1954, pp. 30-41.
[31] Haas, J., et al., "A Simple Analytical Test and a Formula to Predict the Potential for Dermal Carcinogenicity From Petroleum
Oils," American Industrial Hygiene Association Journal, Vol. 48,
No. 11, 1987, pp. 935-940.
[32] Ogan, K., BCatz, E., and Slavin, W., "Determination of Polycyclic
Aromatic Hydroceirbons in Aqueous Samples by Reverse Phase
Liquid Chromatography," Analytical Chemistry, Vol. 51, No. 8,
1979, pp. 1315-1320.
[33] MS Spectral Archive, National Institute of Advanced Industrial
Science and Technology, Tsukuba, Ibaraki, Japan SDBSWeb:
http://www.aist.go.jp/RIODB/SDBS/.
[34] Norris, T. A., "Chromatography II," Lubrication, Vol. 68, No. 3,
1979, pp. 25-40.
[35] Silverstein, R., Bassler, G., and Morrill, T., Spectrometric Identification of Organic Compounds, Fifth Edition, John Wiley and
Sons, Inc., NY, 1991, pp. 3-39.
[36] Denis, J., Briant, J., and Hipeaux, J., Lubricant Properties Analysis and Testing, Editions Technip, Paris, 2000, pp. 24-28.
[37] ASTM D 2786-91: S t a n d a r d Test Method for H y d r o c a r b o n
Types Analysis of Gas-Oil S a t u r a t e s Fractions by High

[38]

[39]

[40]

[41]
[42]

[43]
[44]

[45]

673

Ionizing Voltage Mass Spectrometry, Annual Book of ASTM


Standards, ASTM I n t e r n a t i o n a l , West Conshohocken, PA,
1991.
Status of Application of Mass Spectrometry to Heavy Oil Analysis,
Advances in Mass Spectrometry, AMSPA, Waldron, 1986, pp.
175-191.
ASTM D 2425-93: S t a n d a r d Test Method for Hydrocarbon
Types in Middle Distillates by Mass Spectrometry, Annual Book
of ASTM Standards, ASTM International, West Conshohocken,
PA, 1993.
Coates, P. and Setti, L., Oils, Lubricants and Petroleum Products,
Characterization by Infrared Spectra, Marcel-Dekker, Inc., NY,
1985.
Archer, E. D., "Infrared Analysis I," Lubrication, Vol. 55, 1969,
pp. 13-32.
Shugar, G. and Ballinger, J., Chemical Technicians' Ready Reference Handbook, Fourth Edition, McGraw-Hill, Inc., NY, 1996,
pp. 761-775.
Anonymous, Chapter 10.9, Infrared Analyzers.
ASTM E 168: Standard Practices for General Techniques of Infrared Quantitative Analysis, Annual Book of ASTM Standards,
ASTM International, West Conshohocken, PA, 1999.
Coates, J., Infrared Spectra, A Practical Approach to the Interpretation of Coates Consulting, Marcel Dekker, NY, 1985.

MNL37-EB/Jun. 2003

Volatility
Rey G. Montemayor^

DISCUSSION

VOLATILITY, IN ITS SIMPLEST DEFINITION, IS THE TENDENCY OF A

LIQUID TO CHANGE INTO VAPOR. For fuels, lubricants, and other


petroleum products, this tendency is measured in a variety
of ways. Volatility parameters are related to the perform a n c e characteristics and/or safety of these materials.
Among the various ways of determining the volatility properties of materials are: distillation, rate of evaporation measurement, flash point test, and vapor pressure determination. Distillation determines the temperatures required to
evaporate known portions of the material, as well as the
temperatures at which distillation begins and ends. Distillation also determines the boiling range of the materials. A
volatility property particularly important in solvents and
coating materials is the rate of evaporation. The flash point
of a liquid is the lowest temperature, corrected for bcirometric pressure, at which application of an ignition source
causes the vapor above the specimen to ignite. Vapor pressure is the force per unit area exerted on the walls of a
closed container by the vaporized portion of the liquid material in the container.
The significance of the different volatility properties
varies from one material to another. For crude oil, distillation data are critical assay information. For solvents distillation, flash point and evaporation rate are important parameters. For motor and aviation gasoline, distillation and
vapor pressure data are paramount since these properties
are related to the performance characteristics of these materials. Distillation characteristics of diesel and other nonaviation fuels exert a great influence on their performance.
Flash points and fire points for distillates and residual fuels,
as well as lubricants, are significant from the perspective of
safety in handling, storage, and transportation of these materials.
This chapter will deal with the different test methods dealing with the volatility characteristics of fuels and lubricants.
A summary of the test methods, scope, significance, precision, and results will be given. Other internationcd standards
dealing with volatility properties determination and their
corresponding ASTM standards will be referenced. Distillation for materials other than crude oils is discussed under the
section on Distillation. Flash point eind fire point determinations are discussed in the Flammability section. Distillation
test methods applicable to crude oils are dealt with in the
Crude Distillation section. Vapor pressure measurements are
covered in the Vapor Pressure section.

' Imperial Oil Ltd., Products and Chemicals Division, Sarnia, Ontario Canada

Distillation
Distillation parameters are importcuit volatility characteristics of motor and other automotive spark-ignition fuels, aviation gasoline, aviation turbine fuels, diesel and other nonaviation gas turbine fuels, solvents, and other petroleum
products. Gasolines and gasoline blends are used in a variety
of engines operating u n d e r various atmospheric and mechanical conditions. In order to provide satisfactory performance, gasoline must have the optimum distillation characteristics. Gasoline that vaporizes too readily in pumps, fuel
lines, and carburetors will cause decreased fuel flow to the
engine resulting in rough engine operation or stoppage. If the
gasoline does not vaporize easily, difficulty in start-up, poor
warm-up and acceleration, as well as unequal distribution of
fuel to the combustion cylinders may result. The distillation
temperatures of various petroleum products can be determined at atmospheric pressure using ASTM D 86, Standard
Test Method for Distillation of Petroleum Products [1] or at
reduced pressure using ASTM D 1160, Standard Test Method
for Distillation of Petroleum Products at Reduced Pressure
[2]. The 10%, 50%, and 90% (recovered) distillation points
are important control points in the production of fuel blends.
In the mid-1980s the use of automatic distillation equipment gained popularity because of increased ability to control the rate of distillation, emd efficiency in operation. Figure
1 [3] shows the classical manucJ D86 distillation set-up using
a gas burner. Figure 2 [4] shows the manual D86 distillation
apparatus assembly using electric heater. The use of an electric heater improved the ability to control the rate of distillation. However, it was still difficult to m a i n t a i n the 4 - 5
mL/min distillation rate required by the method. The advent
of automatic distillation apparatus allowed the distillation
parameters specified in the method to be controlled accurately without operator intervention. The distillation flask
and the receiving cylinder in an automatic D86 distillation
unit are essentially the same as the manual unit. Although
electric heaters eire used, the use of microprocessors to control the rate of distillation provided precise temperature control and allowed conformance to the method requirements.
Platinum resistance temperature probes or thermocouples
replaced the mercuiy-in-glass thermometers to allow unattended operation. Automatic level followers using optical
sensors removed the necessity of manually observing and
measuring recovered distillation volumes. Data obtained by
automatic distillation units are very similar to those obtained
by manual instruments. However, the data are not statisti-

675
Copyright'

2003 by A S I M International

www.astm.org

676

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

Thermometer
Distilling
Flask

Bath Cover

Heat
Resistant
Boards

Air Vents
SupportFIG. 1Manual D 86 distillation unit with gas burner.

cally equivalent. Data are available for users to compare


manual and automatic D 86 results (Tables lA and IB) [5,6].
Similar improvements have occurred with D 1160.The relative bias between manual and automatic D 1160 are given in
Table 2 [7].
ASTM D 86, Standard Test Method for Distillation
of Petroleum Products at Atmospheric Pressure
This test method is under the jurisdiction of ASTM Committee D-02 on Petroleum and Lubricants, and is the direct responsibility of Subcommittee D02.08 on Volatility. This standard was originally published in 1921. The latest edition is D
86-OOa and incorporates a major rewrite of the standard,
which was started in 1996.
This test method covers the distillation at atmospheric
pressure of natureil gasolines, motor gasolines, aviation gasolines, aviation turbine fuels, special boiling point spirits,
naphthas, white spirit, kerosines, gas oils, distillate fuel oils,
and similar petroleum products, utilizing either manual or
automatic equipment.
In a D86 distillation, a 100 mL specimen is distilled under
prescribed conditions that are appropriate to its nature.
Table 3 [8] shows the distillation group characteristics of various materials tested to provide D86 distillation data. Table 4
[9] and Table 5 [10] indicate the various test parameters required for each distillation group. Systematic observation of
temperature readings and volumes of condensate are made,
and from these data, the results of the test are calculated and
reported.
The basic method of determining the boiling range of a
petroleum product by performing a simple batch distillation
has been in use as long as the petroleum industry has existed.
It is one of the oldest test methods under the jurisdiction of
ASTM Committee D 02, dating from the time when it was still
referred to as the Engler distillation. Since the test method

has been in use for such an extended period, a tremendous


amount of historical databases exist for estimating end-use
sensitivity on products and processes. The distillation characteristics of hydrocarbons often have an important effect on
their safety and performance, especially in the case of fuels
and solvents. Volatility is the major determinant of the tendency of a hydrocarbon to produce potentially explosive vapors. It is also critically important for both automotive and
aviation gasolines, affecting starting, warm-up, and tendency
to vapor lock at high operating temperature or at high altitude, or both. The presence of high boiling point components
in these and other fuels can significantly affect the degree of
solid combustion deposit formation. Distillation limits are
often included in petroleum product specifications, in commercial contract agreements, process refinery/control applications, and for compliance to regulatory requirements.
The precision of manual and automatic D86 distillation for
group 1 materials is given in Table 6 [11]; Table 7 [12] for
groups 2,3,and 4 using manual distillation; and Table 8 [13]
for groups 2,3, and 4 using automatic distillation.
Generally, the distillation temperatures corrected for barometric pressure, corresponding to IBP, 5%, 10%, 20%, 30%,
40%, 50%), 60%), 70%), 80%, 90%, 95%, and FBP are reported.
The initial boiling point (IBP) is the corrected temperature
reading that is observed at the instant the first drop of condensate falls from the lower end of the condenser tube. The
5-95% distillation temperature is the corrected temperature
reading corresponding to each 5-95% volume distilled or recovered. The final boiling point (FBP) or end point (EP) is the
maximum corrected temperature reading obtained during
the test. Sometimes, the dry point (DP) is required. DP is the
corrected temperature reading that is observed or detected at
the instant the last drop of liquid evaporates from the lowest
point in the distillation flask. The corrections to be applied to
the observed temperature readings are obtained by means of
the Sydney Young equation given in Eqs 1,2, and 3, as appropriate, or by the use of Table 9 [14]:
Cc = 0.0009 (101.3 - Pk) (273 -I- t^)

(1)

G = 0.00012 (760 - P) (273 + tc)

(2)

Cf = 0.00012 (760 - P) (460 + tf)

(3)

where:
Cc and Cf = corrections to be added algebraically to the temperature reading in Celsius or Fahrenheit
tc = observed temperature reading in Celsius
tf = observed temperature reading in Fahrenheit
Pk barometric pressure prevailing at the time of the
test in kPa
P = barometric pressure prevailing at the time of the
test in mm Hg.
After applying the corrections, the corrected temperature
readings are rounded and reported to the nearest 0.5C
(1.0F) or 0.1 C (0.2F), as appropriate to the apparatus used.
However, other calculated values can be reported from D86
distillation data, such as percent recovery and percentages
evaporated at prescribed temperature readings.
Typical D86 results for motor gasoline, reformulated gasoline, diesel, and jet fuel are given in Table 10 [15], Table 11
[16], Table 12 [17], and Table 13 [18].

CHAPTER 25: VOLATILITY

25 min.

Length of part
' bath
approx. 390

Front View

NOTE 1^Legend:
l-Condenser bath
2-Bath cover
3-Bath temperature sensor
4-Bath overflow
5-Bath drain
6-Condenser tube
7-Shield
8-Viewing window
9a-Voifage regulator
9b-Voltmeter or ammeter
9o-Power switch
9d-Power light indicator
10-Vent

11-Distillation flask
12-Temperature sensor
13-Flasl< support board
14-Flasl support platform
15-GrDund connection
16-Electric heater
17-Knob for adjusting level
of support platform
18-Power source cord
19-Reoeiver cylinder
20-Receiver cooling bath
21-Receiver cover

FIG. 2Manual D 86 distillation unit with electric heater.

677

TABLE lARelative bias between manual and automatic D86 distillation.


Sample

IBP

5%

10%

20%

30%

40%

50%

60%

70%

80%

90%

95%

FBP

Sample

1
2
3
4
5
6
7
8
9
10
11
12
13*
14*

+ 1.1
(+0.9)
+0.7
+0.3
+0.5
+ 1.2
+0.3
+0.3
+ 1.7
+ 1.5
+0.9
+ 1.0
+0.3
+0.5

+ 1.9
(0.0)
+ 1.4
+0.6
+ 1.3
+ 1.2
+0.8
+0.5
+2.0
+ 11.5
+ 1.1
(+2.4)"
+0.3
+0.4

+2.2
+0.8
+ 1.6
+0.8
+ 1.3
+ 1.6
+0.8
+0.7
+ 1.8
+ 1.2
+ 1.2
+2.3
+0.4
+0.7

+ 1.6
+0.5
+ 1.0
+0.8
+ 1.3
+ 1.2
+0.7
+0.6
+ 1.5
+0.7
+0.8
+ 1.2
+0.3
+0.5

+ 1.4
+0.4
+0.8
0.3
+ 1.2
+ 1.2
+0.8
+0.7
+ 1.5
+0.4
+0.7
+ 1.2
+0.2
+0.8

+0.7
+0.6
+0.6
0.7
+ 1.0
+ 1.1
+0.8
+ 1.2
+ 1.5
+0.6
+0.6
+ 1.2
+0.9
+ 1.1

+0.8
+0.2
+0.3
+0.6
+0.9
+0.8
+ 1.0
+ 1.2
+ 1.2
+0.9
+ 1.1
+ 1.2
+ 1.4
+ 1.7

+0.7
+0.1
+0.1
+0.8
+0.6
+ 1.1
+ 1.5
+ 1.1
+0.9
+ 1.0
+ 1.0
+0.9
+ 1.0
+ 1.7

+0.7
+0.1
+0.2
+ 1.1
+0.8
+ 1.2
+ 1.6
+ 1.3
+ 1.3
+ 1.4
+0.4
+ 1.1
+0.1
+ 1.0

+0.1
+0.4
+0.9
+ 1.2
+ 1.0
+0.2
+ 1.6
+ 1.9
+0.6
+ 1.9
+0.5
+0.2
+ 1.1
+0.5

+0.4
(+4.7)"
+0.5
+0.8
+0.4
-0.1
+ 1.5
+ 1.1
-0.4
+0.9
-0.4
-0.7
+ 1.2
+0.3

0.7
( + 1.3)"
+0.1
+0.5
+0.4
+0.2
+ 1.7
+ 1.2
+0.4
+0.1
+0.1
(-0.8)
+ 1.0
0.0

-0.4
(-1.2)
-0.8
-0.9
-0.9
-0.3
-0.7
-0.8
-1.2
-2.1
-0.8
-0.9
-1.2
-0.8

1
2
3
4
5
6
7
8
9
10
11
12
13*
14*

''Points between parentheses have not been included in the precision analysis.
'Gasoline-alcohol blends.
NOTE1. Data reported are based on averages of ASTM and IP data.
2. Fourteen samples of gasoline were analyzed in 26 laboratories.
3. The bias reported below is (average of automated results)(average of manual results).
TABLE IBRelative bias between manual and automatic d 86 distillation, various samples [6]
(currently under review in ASTM Subcommittee D02.08).
Summary of Average Relative Bias in C (automanual)
ASTM Interlaboratory Crosscheck Data from 1994 to 1998
Sample
Jet A
Diesel
Mogas
Refor

12
14
13
36

#Lab A

#Lab M

99
129
76
86

26
43
17
8

IBP
-0.7
-1.9
-1.1
-1.1

5%
1.9
2.7
0.2
0.7

10%

20%

30%

40%

50%

60%

70%

80%

90%

1.1
2.1
-0.1
0.3

0.8
1.2
-0.5
0.2

0.6
1.2
0.1
-0.1

0.7
1.1
-0.7
-0.1

0.7
1.0
-0.3
-0.2

0.8
0.7
-0.3
0.4

0.9
0.7
-0.4
0.5

0.8
0.6
-0.5
0.1

0.6
0.5
-1.9
-0.5

60%

70%

80%

1.4
1.2
-0.5
0.8

1.6
1.2
-0.7
0.9

1.5
1.1
-0.9
0.2

90%
1.0
0.8
-3.5
-0.9

95%
0.3
0.3
-3.4
-2.1

FBP
-0.6
0.4
-1.0
0.4

95%

FBP
-1.1
0.8
-1.7
-0.7

Summary of Average Relative Bias in F (automanual)


ASTM Interlaboratory Crosscheck Data from 1994 to 1998
Sample

#Lab A

#Lab M

IBP

5%

Jet A
Diesel
Mogas
Refor

12
14
13
36

99
129
76
86

26
43
17
8

-1.3
-3.4
-1.9
-2.0

3.3
4.9
0.3
1.4

10%
2.1
3.8
-0.2
0.6

20%

30%

40%

1.3
2.2
-0.9
0.3

1,1
2.1
0.1
-0.2

1.2
2.0
-1.2
-0.2

50%)
1.3
1.9
-0.5
-0.4

0.5
0.5
-5.2
-3.8

TABLE 2Relative bias between m a n u a l and automatic D 1160 [7].


1 mm Hg Pressure (All AET Values in C)
Sample 2

Sample 1
Boiling
Point
IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
FBP

Manual

Automatic
225.1
268.2
288.9
321.0
347.1
370.1
392.1
416.0
440.8
472.1
518.5
547.5

239.7
270.1
290.1
324.0
349.5
373.4
395.7
420.0
443.5
472.5
514.1
544.8

Manual

Automatic
342.6
371.3
380.7
388.7
394.4
400.9
407.2
414.0
422.6
433.1
452.6
493.9

338.4
373.5
380.7
388.4
394.3
400.0
405.9
412.8
421.7
433.1
452.0
488.1

Sample 3
Manual

Automatic
321.3
363.7
378.7
397.5
412.1
426.6
439.9
453.2
467.7
486.0
511.5
547.4

330.8
364.4
379.0
397.2
411.8
425.9
439.6
452.4
467.8
485.6
514.1
538.7

10 m m Hg Pressure (All AET Values in C)


Sample 1

Sample 2

Sample 3

Boiling
Point

Automatic

Manual

Automatic

Manual

Automatic

Manual

IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
FBP

203.2
252.3
274.7
313.5
340.6
363.1
385.6
408.4
433.0
461.3
507.5
538.5

199.6
254.5
280.7
316.5
342.2
366.4
388.9
411.5
436.5
465.5
506.9
536.3

343.0
370.2
376.9
383.3
391.0
397.0
402.9
409.1
419.4
430.3
450.5
492.8

342.7
370.3
378.1
384.8
391.1
396.9
403.3
410.2
419.0
430.9
451.2
482.7

319.0
360.7
374.6
392.7
408.0
422.4
436.4
450.7
465.3
483.3
509.1
544.0

319.0
359.9
374.2
392.5
407.4
421.2
434.1
448.1
462.9
480.3
504.8
536.3

CHAPTER 25: VOLATILITY

679

TABLE 3Group characteristics.


Group 0
Sample
characteristics
Distillate tj^pe

Group 1

Group 2

Group 3

Group 4

a65.5
>9.5

<65.5
<9.5

<65.5
<9.5

<65.5
<9.5

S250
<482

slOO
<212
>250
>482

>100
>212
>250
>482

natural
gasoline

Vapor pressure at
37.8C, kPa
100F, psi
(Test Methods
D 323, D 4953,
D 5190, D 5191,
D 5482, IP 69 or
IP 394)
Distillation, IBP "C
"F
EPC
F

250
482

TABLE 4Preparation of apparatus.


Flask, mL
ASTM distillation thermometer
IP distillation thermometer range
Flask support board
diameter of hole, m m
Temperature at start of test
Flask
C
F
Flask support and shield

Group 0

Group 1

Group 2

Group 3

Group 4

100
7C (7F)
low
A
32

125
7C (7F)
low
B
38

125
7C (7F)
low
B
38

125
7C (7F)
low
C
50

125
8C (8F)
high
C
50

0-5
32-^0
not above
ambient

13-18
55-65
not above
ambient

13-18
55-65
not above
ambient

13-18
55-65
not above
ambient

0-5
32^0

13-18
55-65

13-18
55-65

Receiving cylinder and 100 ml charge


C
F

13-18"
55-65"

not above
ambient

13-ambient"
55-ambient''

"See 10.3.1.1 for exceptions.

TABLE 5Conditions during test procedure.


Temperature of cooling bath"

cF

Temperature of bath around


receiving cylinder

C
'F

Time from first application of heat to


initial boiling point, m i n
Time from initial boiling point
to 6% recovered, s
to 10% recovered, min
Uniform average rate of condensation
from 5% recovered to 5 mL
in flask, mL/min
Time recorded from 5 mL residue to
end point, m i n

Group 0

Group 1

Group 2

Group 3

Group 4

0-1
32-34
0-4
32-40

0-1
32-34
13-18
55-65

0-5
32-40
13-18
55-65

0-5
32-40
13-18
55-65

2-5

5-10

5-10

5-10

0-60
32-140
3
5
of charge
temperature
5-15

60-100

60-100
4-5

4-5

3^
4-5

5 max

4-5

4-5

5 max

5 max

5 max

5 max

''The proper condenser bath temperature will depend upon the wax content of the sample and its distillation fractions. The test is generally performed using one
single condenser temperature. Wax formation in the condenser can be deduced from (a) the presence of wax particles in the distillate coming off the drip tip, (b)
a higher distillation loss than what would be expected base on the initial boiling point of the specimen, (c) an erratic recovery rate and (d) the presence of wax particles during the removal of residual liquid by swabbing with a lint-free cloth (see 8.3). The minimum temperature that permits satisfactory operation shall be used.
In general, a bath temperature in the 0 to 4C range is suitable for kerosine, Grade No 1 fuel oil and Grade No. 1-D diesel fuel oil. In some cases involving Grade
No. 2 fuel oil. Grade No. 2-D diesel fuel oil; gas oils and similar distillates, it may be necessary to hold the condenser bath temperature in the 38 to 60C range.

680

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

TABLE 6Repeatability and reproducibility for group.


Manual
Repeatability'^
C

Point, %
IBP
5
10
20
30-70
80
90
95
FBP

1.9
1.2
1.2
1.2
1.2
1.2
1.2

3.3
+ 0.86Sc
+ 0.86Sc
+ 0.86Sc
+ 0.86Sc
+ 0.86Sc
+ 0.86Sc
+ 0.86Sc
3.9

3.4
2.2
2.2
2.2
2.2
2.2
2.2

Manual
Reproducibility"

Automated
Repeatability"

op

5.6
3.1 + 1.74Sc
2.0 + 1.74Sc
2 . 0 + 1.74Sc
2.0 + 1.74Sc
2.0 + 1.74Sc
0.8 + 1.74Sc
1.1 + 1.74Sc
7.2

10

+
+
+
+
+
+
+

0.86SF
0.86SF
0.86SF
0.86SF
0.86SF
0.86SF
0.86SF

5.6
3.6
3.6
3.6
3.6
1.4
1.9

+
+
+
+
+
+
+

1.74SF
1.74SF
1.74SF
1.74SF
1.74SF
1.74SF
1.74SF

13

2.1
1.7
1.1
1.1
1.1
1.1
2.5

Automated
Reproducibility"
C

-F

3.9
+ 0.67Sc
+ 0.67Sc
+0.67Sc
+0.67Sc
+0.67Sc
+0.67Sc
+ 0.67Sc
4.4

7
3.8
3.0
2.0
2.0
2.0
2.0
4.5

+
+
+
+
+
+
+

0.67SF
0.67SF
0.67SF
0.67SF
0.67SF
0.67SF
0.67SF

4.4
3.3
3.3
2.6
1.7
0.7
2.6

-F

7.2
+ 2.0Sc
+ 2.0Sc
+ 2.0Sc
+ 2.0Sc
+ 2.0Sc
+ 2.0Sc
+ 2.0Sc
8.9

13
7.9
6.0
6.0
4.7
3.0
1.2
4.7

+
+
+
+
+
+
+

2.0SF
2.0SF
2.0SF
2.0SF
2.0SF
2.0SF
2.0SF

16

"Sc or SF is the average slope (or rate of change) calculated in accordance with 13.2.

TABLE 7Repeatability and reproducibility for groups 2, 3, and 4 (manual method).


Repeatability"

Reproducibility"
"F

IBP
5-95%
FBP
% volume at
temperature reading
"Calculate Sc or Sp from 13.2.

1.0 + 0.35Sc
l.O + 0.41Sc
0.7 + 0.36Sc

1.9
1.8
1.3
0.7

0.7 + 1.92/SC

2.8
1.8
3.1
1.5

+ 0.35SF
+ 0.41SF
+0.36SF
+ 1.66/SF

+ 0.93Sc
+ 1.33Sc
+0.42Sc
+ 1.78/Sc

5.0
3.3
5.7
1.53

+
+
+
+

0.93SF
1.33SF
0.42SF
3.20/SF

TABLE 8Repeatability and reproducibility for groups 2, 3 and 4 (automated).


Repeatability"
Collected, %

Reproducibility"
op

"C

IBP
2%
5%
10%
20-70%
80%
90-95%
FBP

1.1
1.2
1.2
1.2
1.1

3.5
3.5
+ 1.08Sc
+ 1.42Sc
+ 1.42Sc
+ 1.42Sc
+ 1.08Sc
3.5

"C

6.3
6.3
2.0
2.2
2.2
2.2
2.0

+
+
+
+
+

I.OSSF
1.42SF
1.42SF
1.42SF
1.08SF

2.6
2.0
3.0
2.9
3.0
2.0

6.3

8.5
+ 1.92Sc
+ 2.53Sc
+ 2.64Sc
+ 3.97Sc
+ 2.64Sc
+ 2.53Sc
10.5

15.3
4.7
3.6
5.4
5.2
5.4
3.6

+
+
+
+
+
+

1.92SF
2.53SF
2.64SF
3.97SF
2.64SF
2.53SF

18.9

"Sc or SF is the average slope (or rate of change) calculated in accordance with 13.5.
TABLE 9Approximate thermometer reading correction.
Temperature Range
C

10-30
30-50
50-70
70-90
90-110
110-130
130-150
150-170
170-190
190-210
210-230
230-250
250-270
270-290
290-310
310-330
330-350
350-370
370-390
390-410

50-86
86-122
122-158
158-194
194-230
230-266
266-302
302-338
338-374
374^10
410-446
446-482
482-518
518-554
554-590
590-626
626-662
662-698
698-734
734-770

Correction per 1.3kPa(10mmHg)


Difference in Pressure
F
C
0.35
0.38
0.40
0.42
0.45
0.47
0.50
0.52
0.54
0.57
0.59
0.62
0.64
0.66
0.69
0.71
0.74
0.76
0.78
0.81

0.63
0.68
0.72
0.78
0.81
0.85
0.89
0.94
0.98
1.02
1.07
1.11
1.15
1.20
1.24
1.28
1.33
1.37
1.41
1.46

"Values to be added when barometric pressure is below 101.3 kPa (760 mm


Hg) and to be subtracted when barometric pressure is above 101.3 kPa.

ASTM D 1160, Standard Test Method for Distillation


Petroleum Products at Reduced
Pressure

of

This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D2.08 on VolatiHty. This standeird was originally published in
1951. The latest edition is D 1160-99.
This test method covers the determination, at reduced
pressures, of the boiling range of petroleum products that
can be partially or completely vaporized at a m a x i m u m liquid
temperature of 400C. The reduced pressure inside the apparatus during the test is measured by a Mcleod vacuum gage
or a n appropriately calibrated electronic gage such as the
Baratron. Both manual and automatic methods are specified.
The schematic diagram of a vacuum distillation apparatus is
indicated in Fig. 3 [19]. Both manual and automatic D 1160
distillation units use platinum resistance temperature probes
or thermocouples.
The specimen is distilled at an accurately controlled pressure between 0.13 and 6.7 kPa (1 and 50 m m Hg) under conditions that are designed to provide approximately one theoretical plate fractionation. The distillation pressure is
controlled by a pressure regulating system consisting of a low

CHAPTER

25: VOLATILITY

681

TABLE 10ASTM D-2 interlaboratory cross check programauto D 86 distillation for motor gasoline.
Lab Code

IBP

5%

10%

20%

30%

40%

50%

60%

70%

80%

90%

95%

FBP

%REC

1
2
3
4
5
6
7
8
10

34.6
30.6
38
34.0
33.8
31.7
34.8
37.1
35.4

51.7
52.2
54
44.5
53.0
49.7
55.1
56.4
47.0

62.0
62.8
64
56.1
62.7
60.0
64.1
65.8
57.8

79.1
81.7
83
75.7
79.7
78.9
82.3
83.9
76.5

94.8
96.1
98
92.8
95.1
95.0
96.8
99.1
94.1

105.7
106.1
107
104.6
105.7
106.2
106.6
108.8
105.7

112.9
112.7
114
112.3
112.5
112.7
113.1
115.6
113.1

119.4
119.4
121
118.7
118.7
119.2
120.2
122.4
119.6

127.4
128.9
131
127.3
126.5
127.4
129.4
131.8
127.7

141.7
146.1
149
141.4
142.1
142.0
146.5
149.0
142.2

167.2
172.2
176
166.7
166.8
164.8
171.1
174.5
166.8

184.2
198.4
217
183.8
185.5
182.2
200.6
208.3
183.4

215.8
214.4
223
223.1
222.2
218.8
214.1
225.0
225.5

97.5
96.6
95.8
96.5
97.9
97.4
96.2
96.9
97.0

TABLE 11ASTM D-2 interlaboratory cross check programauto D 86 distillation for reformulated gasoline.
Lab Code

IBP

5%

10%

20%

30%

40%

50%

60%

70%

80%

90%

95%

FBP

%REC

%LOSS

E200

E300

1
2
4
5
6
7
8
10

103.1
108.8
100.2
104
105.3
94.1
107.6
109.8

132.5
124.7
130.5
134
120.1
129.2
124.5
132.5

141.6
134.7
140.2
137
133.5
138.0
135.5
142.5

153.3
147.7
151.9
150
147.6
150.0
148.1
159.1

165.6
160.8
164.1
162
160.1
161.0
160.3
170.1

180.5
175.1
178.3
177
175.2
175.3
175.1
183.8

199.2
195.0
198.0
196
195.2
193.5
193.6
202.6

222.5
218.1
220.7
220
219.5
217.4
217.7
222.4

250.2
246.5
247.8
248
247.6
245.5
244.7
244.3

279.1
276.6
276.4
278
395.3
274.7
273.7
278.2

318.1
316.9
313.5
317
319.1
311.5
311.7
319.0

351.8
347.7
346.2
349
353.5
341.4
340.3
353.3

391.1
395.6
396.9
400
395.3
393.2
394.7
394.2

97.4
97.3
97.8
96.9
96.9
99.1
97.7
98.1

1.3
0.9
1.2
3.1
1.9
0.5

50.4
52.8
50.9
51.8
53
52.9
52.9
48.7

85.7
86.8
86.4
86.1
87
87.3
87.2
85.7

0.9

TABLE 12^ASTM D-2 interlaboratory cross check program^Auto D 86 distillation for diesel fuel.
Lab Code

IBP

5%

10%

20%

30%

40%

50%

60%

70%

80%

90%

95%

FBP

%REC

1
3
4
5
8
9
10
11
13
14

177.4
182.8
176.3
177.1
183.7
179.7
178.8
179.5
182.0
169.5

203.2
205.2
201.7
202.0

228.8
230.7
226.5
228.6
228.7
227.5
227.8
232.6
231.4
229.0

243.2
244.4
240.1
243.4
243.9
241.7
242.2
247
245.9
244.0

253.8
255.2
251.3
254.9
254.9
253.4
253.3
257.4
256.6
255.0

263.3
264.6
260.6
264.1
264.7
261.9
262.8
266.9
**268.3
265.0

271.2
273.4
269.1
273.1
274.1
270.8
271.1
276.3
274.9
273.5

281.6
282.8
278.2
282.0
283.3
280.4
280.6
285.4
283.9
283.0

293.0
294.3
289.2
293.8
294.8
291.9
291.7
297.1
296.1
293.5

309.0
311.8
305.2
310.4
311.9
308.0
308.9
315.0
313.4
309.5

323.9
330.4
319.3

341.3
343.5
336.0
335.2
340.0
339.5
340.6
343.5
341.1

98.3
97.5
98.7

203.8
204.4
203.7
200.5
201.0

209.4
214.1
210.5
210.0
210.5
212.9
212.8
216.4
211.9
212.5

98.3
98.3
97.8
97.6

Lab Code

IBP

5%

10%

20%

30%

40%

50%

60%

70%

80%

90%

95%

FBP

%REC

1
2
3
4
5
6
8
9
10

158.6
159.7
163.0
160.0
161
159.9
161.4
160.1
161.8

175.0
175.2
178.6
174.1
175
172.4
175.0
176.1
175.9

180.3
179.2
183.0
180.1
179
177.3
180.2
180.4
180.1

187.0
186.1
190.7
186.6
187
184.7
187.3
186.8
186.8

194.4
192.8
197.6
193.0
193
191.3
193.9
194.1
192.5

202.0
199.5
205.1
200.3
200
198.9
200.8
201.3
199.8

210.0
207.7
213.0
207.9
208
206.1
208.0
209.1
207.6

219.3
216.3
221.8
216.6
216
214.3
210.6
217.7
216.2

230.0
226.2
232.5
227.0
227
224.1
226.9
227.9
225.9

239.4
238
244.4
239.0
238
235.4
238.8
239.8
237.3

254.7
253.3
259.6
254.1
253
249.5
253.3
255.6
251.5

261.6
266.1
269.9
265.0
264
259.8
263.8
267.3
261.8

273.3
274
290.8
275.2
277
272.6
277.3
281.2
277.3

99.0
97.5
98.9
98.1
98
99.7
98.4
98.0
98.4

329.9
323.1
325.6
332.9
333.4

TABLE 13ASTM interlaboratory cross check programauto D 86 distillation for jet fuel.

efficiency, high capacity vacuum p u m p connected to one of


two surge tanks, each having a capacity of 10-20 L and arranged in series. A solenoid vsJve or other type of regulator is
installed in the connection between the tanks so that the first
tank is maintained at p u m p pressure and the second one at the
pressure of the distillation apparatus. Data are obtained during the distillation, from which the initieJ boiling point, the final boiling point, and a distillation curve relating volume percent distilled and Atmospheric Equivalent Temperature
(AET) can be obtained. Atmospheric Equivalent Temperature
is the temperature converted from the observed temperature
during the test, to the expected distillate temperature if the
distillation was performed at atmospheric pressure and there

was n o decomposition. The equations [20] used to convert the


observed distillation temperature to AET are:
AET =

748.1 X A
- 273.1
[1/(VT,K] + (0.3861 X A) - 0.00051606

(4)

5.143222 - (0.972546 X logp)


2 5 7 9 . 3 2 9 - ( 9 5 . 7 6 X log p)

(5)

5.994295 - (0.972546 X log P)


2 6 6 3 . 1 2 9 - ( 9 5 . 7 6 X log P)

(6)

or
A =

682

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Digital Temperature Indicator


[

J_

PRT Sensor

IvjcimoiGHel Option # 2

Pressure

Reguiating System

.L
(ColdTrap

Repressi/ring
tft^Connec

Option # 1

Surge Tanks Vacuum Pump

Vacuum Source

Thermowell
Circulating

^^ ._S2?'' I
XTCooiant F i o w ^ ^ = > ~ * / U
Thermo-RegulaW Immersion Heater

Coolant Circulating System

FIG. 3D 1160 vacuum distillation apparatus.

where:
AET =
A=
VT,K =
p=

atmospheric equivalent temperature in C


value obtained from Eqs 5 and 6
observed vapor temperature, K
pressure of the system in pKa, observed when the vapor temperature was read
P = pressure of the system in m m Hg, observed when the
vapor temperature was read.

Alternatively, the AET corresponding to the observed vapor


temperature can be obtained from a set of Tables given in the
method (Tables 14-19) [21].
This test method is used for the determination of the distillation characteristics of petroleum products and fractions
that may decompose if distilled at atmospheric pressure. The
boiling range, obtained at conditions designed to obtain approximately one theoretical plate fractionation, can be used
in engineering calculations to design distillation equipment,
to prepare appropriate blends for industrial purposes, to determine compliance with regulatory rules, to determine the
suitability of the material as feed to a refining process, or for
a host of other purposes. The boiling range is directly related
to viscosity, vapor pressure, heating value, average molecular
weight, and many other chemical, physical, and mechanical
properties. Petroleum product specifications often include
distillation limits based on data by this test method. Many engineering design correlations have been developed on data by
this test method. These correlative methods are used extensively in current engineering practice.
The precision for manual D 1160 distillation is given in
Table 20 [22]. Table 21 gives the precision for automatic D
1160 as obtained from Research Report RR:D2-1206 [7].
The observed vapor temperature readings are converted to
Atmospheric Equivalent Temperature (AET) using the tables
and/or equations mentioned earlier. The AET is reported to

the nearest degree Celsius corresponding to the volumetric


percentages of liquid recovered in the receiver. The sample
identity, density, and total amount of distillate recovered in
the receiver and the cold trap are also reported.
Other International
Distillation

Standard

Test Methods

for

All the aforementioned distillation test methods are ASTM


standard test methods. Although ASTM standard test methods are used extensively t h r o u g h o u t the world, there are
other international distillation standards that are used and
are applicable to specific geographiceJ eireas. Table 22 gives a
cross reference for a n u m b e r of international distillation
standards and their corresponding ASTM designation.
Flaitimability
From a safety point of view, a critical volatility property of fuels and lubricants is flash point. The flash point of a liquid is
the lowest temperature corrected to a pressure of 101.3 kPa
(760 m m Hg) at w h i c h application of an ignition source
causes the vapors of a specimen of the sample to ignite u n d e r
specified test conditions. Flash point measures the tendency
of the specimen to form a flammable mixture with air under
controlled laboratory conditions. It is only one of a n u m b e r
of properties that must be considered in assessing the overall
flammability hazard of a material. Flash point is used in shipping and safety regulations to define flammable and combustible materials. Flash point can indicate the possible presence of highly volatile and flammable materials in a relatively
nonvolatile Eind nonflammable material.
Various regulatory organizations use flash point to define
flammable and combustible materieds as it relates to transporting, shipping, and safety regulations. Prior to 1990, the
Federal Register of the U.S. Department of Transport defined

CHAPTER 25: VOLATILITY 683


TABLE 14AET conversion table at 0.13 kPa (1 mm Hg) pressure C.
P (mm Hg)
1

T
35
40
45
50
55
60
G5
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
160
165
170
175
180
185
190
195
200
205
210
215
220
225
230
235
240
245
250
255
260
265
270
275
280
285
290
295
300
305
310
315
320
325
330
335
340
345
350

0
195.2
202.1
208.9
215.7
222.5
229.2
235.9
242.7
249.3
256.0
262.7
269.3
275.9
282.5
289.1
295.6
302.1
308.6
315.1
321.6
328.0
334.5
340.9
347.3
353.6
360.0
366.3
372.6
378.9
385.2
391.4
397.6
403.9
410.0
416.2
422.4
428.5
434.6
440.7
446.8
452.9
458.9
465.0
471.0
477.0
482.9
488.
494.8
500.7
506.6
512.5
518.4
524.3
530.1
535.9
541.7
547.5
553.3
559.0
564.7
570.5
576.1
581.8
587.5

0.5
195.9
202.7
209.6
216.4
223.1
229.9
236.6
243.3
250.0
256.7
263.3
270.0
276.6
283.2
289.7
296.3
302.8
309.3
315.8
322.2
328.7
335.1
341.5
347.9
354.3
360.6
366.9
373.2
379.5
385.8
392.0
398.3
404.5
410.7
416.8
423.0
429.1
435.2
441.3
447.4
453.5
459.5
465.6
471.6
477.6
483.5
4^.5
495.4
501.3
507.2
513.1
519.0
524.8
530.7
536.5
542.3
548.1
553.8
559.6
565.3
571.0
576.7
582.4
588.1

1
196.6
203.4
210.2
217.0
223.8
230.6
237.3
244.0
250.7
257.4
264.0
270.6
277.2
283.8
290.4
296.9
303.4
309.9
316.4
322.9
329.3
335.7
342.1
348.5
354.9
361.2
367.6
373.9
380.1
386.4
392.7
398.9
405.1
411.3
417.5
423.6
429.7
435.9
442.0
448.0
454.1
460.1
466.2
472.2
478.2
484.1
490.1
496.0
501.9
507.8
513.7
519.6^
525.4
531.3
537.1
542.9
548.6
554.4
560.2
565.9
571.6
577.3
583.0
588.6

1.5
197.3
204.1
210.9
217.7
224.5
231.2
238.0
244.7
251.4
258.0
264.7
271.3
277.9
284.5
291.0
297.6
304.1
310.6
317.1
323.5
330.0
336.4
342.8
349.2
355.5
361.9
368.2
374.5
380.8
387.0
393.3
399.5
405.7
411.9
418.1
424.2
430.4
436.5
442.6
448.6
454.7
460.7
466.8
472.8
478.7
484.7
490.7
496.6
502.5
508.4
514.3
520.2
526.0
531.8
537.6
543.4
549.2
555.0
560.7
566.5
572.2
577.9
583.5
589.2

2
198.0
204.8
211.6
218.4
225.2
231.9
238.6
245.3
252.0
258.7
265.3
271.9
278.5
285.1
291.7
298.2
304.7
311.2
317.7
324.2
330.6
337.0
343.4
349.8
356.2
3625
368.8
375.1
381.4
387.7
393.9
400.1
406.3
412.5
418.7
424.8
431.0
437.1
443.2
449.2
455.3
461.3
467.4
473.4
479.3
485.3
491.3
497.2
503.1
509.0
514.9
520.7
526.6
532.4
538.2
544.0
549.8
555.6
561.3
567.0
572.7
578.4
584.1
589.8

2.5
198.6
205.5
212.3
219.1
225.8
232.6
239.3
246.0
252.7
259.3
266.0
272.6
279.2
285.8
292.3
298.9
305.4
311.9
318.4
324.8
331.2
337.7
344.1
350.4
356.8
363.1
369.4
375.7
382.0
388.3
394.5
400.7
406.9
413.1
419.3
425.4
431.6
437.7
443.8
449.8
455.9
461.9
468.0
474.0
479.9
485.9
491.9
497.8
503.7
509.6
515.5
521.3
527.2
533.0
538.8
544.6
550.4
556.1
561.9
567.6
573.3
579.0
584.7
590.3

3
199.3
206.2
213.0
219.7
226.5
233.3
240.0
246.7
253.4
260.0
266.6
273.3
279.9
286.4
293.0
299.5
306.0
312.5
319.0
325.5
331.9
338.3
344.7
351.1
^7.4
363.8
370.1
376.4
382.7
388.9
395; 1
401.4
407.6
413.8
419.9
426.1
432.2
438.3
444.4
450.5
456.5
462.5
468.6
474.6
480.5
486.5
492.4
498.4
504.3
510.2
516.1
521.9
527.8
533.6
539.4
545.2
550.9
556.7
562.4
568.2
573.9
579.6
585.2
590.9

3.5
200.0
206.8
213.6
220.4
227.2
233.9
240.6
247.3
254.0
260.7
267.3
273.9
280.5
287.1
293.6
300.2
306.7
313.2
319.7
326.1
332.5
338.9
345.3
351.7
358.1
364.4'
370.7
377.0
383.3
389.5
395.8
402.0
408.2
414.4
420.5
426.7
432.8
438.9
445.0
451.1
457.1
463.1
469.2
475.2
481.1
487.1
493.0
AS&.Q

504.9
510.8
516.6
522.5
528.3
534.2
540.0
545.8
551.5
557.3
563.0
568.7
574.4
580.1
585.8
591.5

4
200.7
207.5
214.3
221.1
227.9
234.6
241.3
248.0
254.7
261.3
268.0
274.6
281.2
287.7
294.3
300.8
307.3
313.8
320.3
326.7
333.2
339.6
346.0
K2.3
358.7
3^.0
371.3
377.6
383.9
390.2
396.4
402.6
408.8
415.0
421.1
427.3
433.4
439.5
445.6
451.7
457.7
463.7
469.8
475.8
481.7
487.7
493.6
499.6
505.5
511.4
517.2
523.1
528.9
534.7
540.5
546.3
552.1
557.9
563.6
569.3
575.0
580.7
586.4
592.0

4.5
201.4
208.2
215.0
221.8
228.5
235.3
242.0
248.7
255.4
262.0
268.6
275.2
281.8
288.4
295.0
301.5
308.0
314.5
320.9
327.4
333.8
340.2
346.6
353.0
359.3
365.7
372.0
378.3
384.5
390.8
397.0
403.2
409.4
415.6
421.8
427.9
434.0
440.1
446.2
452.3
458.3
464.4
470.4
476.4
482.3
488.3
494.2
500.2
506.1
511.9
517.8
523.7
529.5
535.3
541.1
546.9
552.7
558.4
564.2
569.9
575.6
581.3
586.9
%2.6

684 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


TABLE 15AET conversion table at 0.27 kPa (2 mm Hg) pressure C.
(mm Hg)
2

T
36
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
1^
140
145
150
155
160
165
170
175
180
185
190
195
200
205
210
215
220
225
230
235
240
245
250
255
260
265
270
275
280
285
290
295
300
305
310
315
320
325
330
335
340
345
350

0
180.9
187.6
194.3
201.0
207.6
214.2
220.8
227.4
234.0
240.5
247.1
253.6
260.1
266.5
273.0
279.4
285.8
292.2
298.6
305.0
311.3
317.6
323.9
330.2
336.5
342.8
349.0
355.2
361.4
367.6
373.8
379.9
386.1
392.2
398.3
404.4
410.4
416.5
422.5
428.5
434.5
440.5
446.5
452.4
458.4
464.3
470.2
476.1
481.9
487.8
493.6
499.4
505.3
511.0
516.8
522.6
528.3
534.1
539.8
545.5
551.1
556.8
562.5
568.1

0.5
181.6
188.3
195.0
201.6
208.3
214.9
221.5
228.1
234.6
241.2
247.7
254.2
260.7
267.2
273.6
280.1
286.5
292.9
299.2
30S.6
311.9
318.3
324.6
330.9
337.1
343.4
349.6
355.8
362.0
368.2
374.4
380.5
386.7
392.8
398.9
405.0
411.0
417.1
423.1
429.1
435.1
441.1
447.1
453.0
459.0
464.9
470.8
476.7
482.5
488.4
494.2
500.0
505.8
511.6
517.4
523.2
528.9
534.6
540.3
546.0
551.7
557.4
563.0
568.7

1
< 182.3
189.0
195.6
202.3
208.9
215.6
222.2
228.7
235.3
241.8
248.4
254.9
261.4
267.8
274.3
280.7
287.1
293.5
299.9
306.2
312.6
318.9
325.2
331.5
337.8
344.0
350.2
356.5
362.7
368.8
375.0
381.2
387.3
393.4
399.5
405.6
411.6
417.7
423.7
429.7
435.7
441.7
447.7
453.6
459.5
465.5
471.4
477.2
483.1
489.0
494.8
500.6
506.4
512.2
518.0
5?3.7
529.5
535.2
540.9
546.6
552.3
557.9
563.6
569.2

1.5
182.9
189.6
196.3
203.0
209.6
216.2
222.8
229.4
236.0
242.5
249.0
255.5
262.0
268.5
274.9
281.3
287.8
294.1
300.5
306.9
313.2
319.5
325.8
332.1
338.4
344.6
350.9
357.1
363.3
369.5
375.6
381.8
387.9
394.0
400.1
406.2
412.2
418.3
424.3
430.3
436.3
442.3
448.3
454.2
460.1
466.0
471.9
477.8
483.7
489.5
495.4
501.2
507.0
512.8
518.5
524.3
530.0
535.8
541.5
547.2
552.8
558.5
564.2
569.8

2
183.6
190.3
197.0
203.6
210.3
216.9
223.5
230.0
236.6
243.1
249.7
256.2
262.6
269.1
275.6
282.0
288.4
294.8
301.2
307.5
313.8
320.2
326.5
332.7
339.0
345.3
351.5
357.7
363.9
370.1
376.2
382.4
388.5
394.6
400.7
406.8
412.8
418.9
424.9
430.9
436.9
442.9
448.9
454.8
460.7
466.6
472.5
478.4
484.3
490.1
496.0
501.8
507.6
513.4
519.1
524.9
530.6
536.3
542.0
547.7
553.4
559.1
564.7
570.4

2.5
184.3
191.0
197.6
204.3
210.9
217.5
224.1
230.7
237.3
243.8
250.3
256.8
263.3
269.8
276.2
282.6
289.0
295.4
301.8
308.1
314.5
320.8
327.1
333.4
339.6
345.9
352.1
358.3
364.5
370.7
376.9
383.0
389.1
395.2
401.3
407.4
413.5
419.5
425.5
431.5
437.5
443.5
449.5
455.4
461.3
467.2
473.1
479.0
484.9
490.7
496.5
502.4
508.2
513.9
519.7
525.5
531.2
536.9
542.6
548.3
554.0
559.6
565.3
570.9

3
185.0
191.6
198.3
205.0
211.6
218.2
224.8
231.4
237.9
244.5
251.0
257.5
263.9
270.4
276.8
283.3
289.7
296.1
302.4
308.8
315.1
321.4
327.7
334.0
340.3
346.5
;K2.7

358.9
3^.1
371.3
377.5
383.6
389.7
395.8
401.9
408.0
414.1
420.1
426.1
432.1
438.1
444.1
450.0
456.0
461.9
467.8
473.7
479.6
485.4
491.3
497.1
502.9
508.7
514.5
520.3
526.0
531.8
537.5
543.2
548.9
554.5
560.2
565.8
571.5

3.5
185.6
192.3
199.0
205.6
212.3
218.9
225.4
232.0
238.6
245.1
251.6
258.1
264.6
271.0
277.5
283.9
290.3
296.7
303.1
309.4
315.7
322.1
328.4
334.6
340.9
347.1
353.4
359.6
3K.8
371.9
378.1
384.2
390.3
396.4
402.5
408.6
414.7
420.7
426.7
432.7
438.7
444.7
450.6
456.6
462.5
468.4
474.3
480.2
486.0
491.9
497.7
503.5
509.3
515.1
520.9
526.6
532.3
538.1
543.8
549.4
555.1
560.8
566.4
572.0

4
186.3
193.0
199.6
206.3
212.9
219.5
226.1
232.7
239.2
245.8
252.3
258.8
2K.2
271.7
278.1
284.5
290.9
297.3
303.7
310.0
316.4
322.7
329.0
335.3
341.5
347.8
354.0
360.2
366.4
372.5
378.7
384.8
391.0
397.1
403.1
409.2
415.3
421.3
427.3
433.3
439.3
445.3
451.2
457.2
463.1
469.0
474.9
480.8
486.6
492.5
498.3
504.1
509.9
515.7
521.4
527.2
532.9
538.6
544.3
550.0
555.7
5S^.3
567.0
572.6

4.5
187.0
193.6
200.3
207.0
213.6
220.2
226.8
233.3
239.9
246.4
252.9
259.4
26S.9
272.3
278.8
285.2
291.6
298.0
304.3
310.7
317.0
323.3
329.6
335.9
342.1
348.4
354.6
360.8
367.0
373.2
379.3
385.4
391.6
397.7
403.8
409.8
415.9
421.9
427.9
433.9
439.9
445.9
451.8
457.8
463.7
469.6
475.5
481.3
487.2
493.0
498.9
504.7
510.5
516.2
522.0
527.7
533.5
539.2
544.9
550.6
556.2
561.9
567.5
573.2

CHAPTER 25: VOLATILITY 685


TABLE 16AET conversion table at 0.67 kPa (5 mm Hg) pressure C.
P (mm Hg)
5

T
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
160
165
170
175
180
185
190
195
200
205
210
215
220
225
230
235
240
245
250
255
260
265
270
275
280
285
290
295
300
305
310
315
320
325
330
335
340
345
350

0
162.0
168.5
174.9
181.4
187.9
194.3
200.7
207.1
213.5
219.9
226.2
232.6
238.9
245.2
251.5
257.8
264.0
270.3
276.5
282.7
288.9
295.1
301.3
307.5
313.6
319.7
325.8
331.9
338.0
344.1
350.1
356.2
362.2
368.2
374.2
380.1
386.1
392.1
398.0
403.9
409.8
415.7
421.6
427.5
433.3
439.1
445.0
450.8
456.6
462.3
468.1
473.9
479.6
485.3
491.0
496.7
502.4
508.1
513.7
519.4
525.0
530.6
536.2
541.8

0.5
1^.6
169.1
175.6
182.1
188.5
194.9
201.4
207.8
214.2
220.5
226.9
233.2
239.5
245.8
252.1
258.4
264.7
270.9
277.1
283.4
289.6
295.7
301.9
308.1
314.2
320.3
326.4
332.5
338.6
344.7
350.7
356.8
362.8
368.8
374.8
380.7
386.7
392.7
398.6
404.5
410.4
416.3
422.2
428.0
433.9
439.7
445.5
451.3
457.1
462.9
"468.7
474.4
480.2
485.9
491.6
497.3
503.0
508.6
514.3
519.9
525.6
531.2
536.8
542.4

1
163.3
169.8
176.2
182.7
189.2
195.6
202.0
208.4
214.8
221.2
227.5
233.8
240.2
246.5
252.8
259.0
265.3
271.5
277.8
284.0
290.2
296.4
302.5
308.7
314.8
320.9
327.0
333.1
339.2
345.3
351.3
357.4
363.4
369.4
375.4
381.3
387.3
393.2
399.2
405.1
411.0
416.9
422.8
428.6
434.5
440.3
446.1
451.9
457.7
463.5
469.3
475.0
480.7
486.5
492.2
497.9
503.5
509.2
514.9
520.5
526.1
531.8
537.4
542.9

1.5
163.9
170.4
176.9
183.3
189.8
196.2
202.6
209.0
215.4
221.8
228.1
234.5
240.8
247.1
253.4
259.7
265.9
272.2
278.4
284.6
290.8
297.0
303.1
309.3
315.4
321.6
327.7
333.7
^9.8
345.9
351.9
358.0
364.0
370.0
376.0
381.9
387.9
^3.8
399.8
405.7
411.6
417.5
423.3
429.2
435.1
440.9
446.7
452.5
458.3
464.1
469.8
475.6
481.3
487.0
492.7
498.4
504.1
509.i3
515.4
521.1
526.7
532.3
537.9
543.5

2
164.6
171.1
177.5
184.0
190.4
196.9
203.3
209.7
216.1
222.4
228.8
235.1
241.4
247.7
254.0
260.3
266.5
272.8
279.0
285.2
291.4
297.6
}3.8
309.9
3t'6.0
322.2
328.3
334.4
340.4
346.5
352.5
358.6
.364.6
370.6
376.6
382.5
388.5
394.4
400.4
406.3
412.2
418.1
423.9
429.8
435.6
441.5
447.3
453.1
458.9
464.6
470.4
476.1
481.9
487.6
493.3
499.0
504.7
510.3
516.0
521.6
527.3
532.9
538.5
544.1

2.5
165.2
171.7
178.2
184.6
191.1
197.5
203.9
210.3
216.7
223.1
229.4
235.7
242.1
248.4
254.7
160.9
267.2
273.4
279.6
285.8
292.0
298.2
304.4
310.5
316.7
322.8
328.9
335.0
341.0
347.1
353.1
359.2
365.2
371.2
377.2
383.1
389.1
395,0
401.0
406.9
412.8
418.7
424.5
430.4
436.2
442.0
447.9
453.7
459.4
465.2
471.0
476.7
482.5
488.2
493.9
499.6
505.2
510.9
516.6
522.2
527.8
533.4
539.0
544.6

3
165.9
172.3
178.8
185.3
191.7
198.2
204.6
211.0
217.3
223.7
230.0
236.4
242.7
249.0
255.3
261.5
267.8
274.0
280.3
286.5
292.7
298.8
305.0
311.1
317.3
323.4
329.5
335.6
341.6
347.7
353.7
359.8
365.8
371.8
377.8
383.7
389.7
395.6
401.5
407.5
413.4
419.2
425.1
431.0
436.8
442.6
448.4
454.2
460.0
465.8
471.6
477.3
483.0
488.7
494.4
500.1
505.8
511.5
517.1
522.8
528.4
534.0
539.6
545.2

3.5
166.5
173.0
179.5
185.9
192.4
'198.8
205.2
211.6
218.0
224.3
230.7
237.0
243.3
249.6
255.9
262.2
268.4
274.7
280.9
287.1
293.3
299.4
305.6
311.8
317.9
324.0
330.1
336.2
342.2
348.3
354.3
360.4
366.4
372.4
378.4
384.3
390.3
396.2
402.1
408.0
413.9
419.8
425.7
431.5
437.4
443.2
449.0
454.8
460.6
466.4
472.1
477.9
483.6
4%.3
495.0
500.7
506.4
512.0
517.7
523.3
528.9
534.6
540.1
545.7

4
167.2
173.6
180.1
186.6
193.0
199.4
205.8
212.2
218.6
225.0
231.3
237.6
244.0
250.3
256.5
262.8
269.0
275.3
281.5
287.7
293.9
300.1
306.2
312.4
318.5
324.6
330.7
336.8
342.9
348.9
354.9
361.0
367.0
373.0

37ao
384.9
390.9
396.8
402.7
408.6
414.5
420.4
426.3
432.1
438.0
443.8
449.6
455.4
461.2
466.9
472.7
478.4
484.2
489.9
495.6
501.3
506.9
512.6
518.3
523.9
529.5
535.1
540.7
546.3

4.5 ,
167.8
174.3
180.8
187.2
193.7
200.1
206.5
212.9
219.2
225.6
231.9
238.3
244.6
250.9
257.2
263.4
269.7
275.9
282.1
288.3
294.5
300.7
306.8
313.0
319.1
325.2
331.3
337.4
343.5
349.5
355.6
361.6
367.6
373.6
379.6
385.5
391.5
397.4
403.3
409.2
415.1
421.0
426.9
432.7
438.6
444.4
450.2
456.0
461.8
467.5
473.3
479.0
484.7
490.5
496.2
501.8
507.5
513.2
518.8
524.4
530.1
535.7
541.3
546.8

686 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 17AET conversion table at 1.33 kPa (10 mm Hg) pressure C.
P (mm Hg)
10

T
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
160
165
170
175
180
185
190
195
200
205
210
215
220
225
230
235
240
245
250
255
260
265
270
275
280
285
290
295
300
305
310
315
320
325
330
335
340
345
350

0
146.8
153.1
159.5
165.8
172.1
178.4
184.6
190.9
197.1
203.3
209.6
215.8
222.0
228.1
234.3
240.4
246.6
252.7
258.8
264.9
271.0
277.0
283.1
289.1
295.2
301.2
307.2
313.2
319.1
325.1
331.0
337.0
342.9
348.8
354.7
360.6
366.5
372.3
378:2
384.0
389.8
395.6
401.4
407.2
413.0
418.8
424.5
430.3
436.0
441.7
447.4
453.1
458.8
464.4
470.1
475.7
481.3
487.0
492.6
498.2
503.7
509.3
514.9
520.4

0.5
147.4
153.8
160.1
166.4
172.7
179.0
185.3
191.5
197.7
204.0
210.2
216.4
222.6
228.7
234.9
241.0
247.2
253.3
259.4
265.5
271.6
277.6
203.7
289.7
295.8
301.8
307.8
313.8
319.7
325.7
331.6
337.6
343.5
349.4
355.3
361.2
367.1
372.9
378.8
384.6
390.4
396.2
402.0
407.8
413.6
419.3
425.1
430.8
436.5
442.3
448.0
4S3.6
459.3
465.0
470.6
476.3
481.9
487.5
493.1
498.7
504.3
509.9
515.4
521.0

1
148.1
154.4
160.7
167.0
173.3
179.6
185.9
192.1
198.4
204.6
210.8
217.0
223.2
229.4
235.5
241.7
247.8
253.9
260.0
266.1
272.2
278.2
284.3
290.3
296.4
302.4
308.4
314.4
320.3
326.3
332.2
338.2
344.1
350.0
355.9
361.8
367.6
373.5
379.3
385.2
391.0
396.8
402.6
408.4
414.2
419.9
425.7
431.4
437.1
442.8
448.5
454.2
459.9
465.6
471.2
476.8
482.5
488.1
433.7
499.3
504.9
510.4
516.0
521.5

1.5
148.7
155.0
161.4
167.7
174.0
180.2
186.5
192.8
199.0
205.2
211.4
217.6
223.8
230.0
236.1
242.3
248.4
254.5
260.6
266.7
272.8
278.8
284.9
290.9
297.0
303.0
309.0
314.9
320.9
326.9
332.8
338.8
344.7
350.6
356.5
362.4
368.2
374.1
379.9
385.8
391.6
397.4
403.2
409.0
414.7
420.5
426.2
432.0
437.7
443.4
449.1
454.8
460.5
466.1
471.8
477.4
483.0
488.6
^4.2
499.8
505.4
511.0
516.5
522.1

2
149.3
155.7
162.0
168.3
174.6
180.9
187.1
193.4
199.6
205.8
212.0
218.2
224.4
230.6
236.7
242.9
249.0
255.1
261.2
267.3
273.4
279.5
285.5
291.5
297.6
303.6
309.6
315.5
321.5
327.5
333.4
3^.3
345.3
351.2
357.1
362.9
368.8
374.7
380.5
386.3
392.2
398.0
403.8
409.5
415.3
421.1
426.8
432.5
438.3
444.0
449.7
455.4
461.0
466.7
472.3
478.0
483.6
489.2
494.8
500.4
506.0
511.5
517.1
522.6

2.5
150.0
156.3
162.6
168.9
175.2
181.5
187.8
194.0
200.2
206.5
212.7
218.9
225.0
231.2
237.4
243.5
249.6
255.7
261.8
267.9
274.0
280.1
286.1
292.1
298.2
304.2
310.2
316.1
322.1
328.1
334.0
339.9
345.9
351.8
357.7
363.5
369.4
375.3
381.1
386.9
392.7
398.5
404.3
410.1
415.9
421.6
427.4
433.1
438.8
444.5
450.2
455.9
461.6
467.3
472.9
478.5
484.2
489.8
495.4
501.0
506.5
512.1
517.7
523.2

3
150.6
156.9
163.3
169.6
175.8
182.1
188.4
194.6
200.9
207.1
213.3
219.5
225.7
231.8
238.0
244.1
250.2
256.4
262.4
268.5
274.6
280.7
286.7
292.7
298.8
304.8
310.8
316.7
322.7
328.7
334.6
340.5
346.4
352.4
358.2
364.1
370.0
375.8
381.7
387.5
393.3
399.1
404.9
410.7
416.5
422.2
428.0
433.7
439.4
445.1
450.8
456.5
462.2
467.8
473.5
479.1
484.7
490.3
495.9
501.5
507.1
512.7
518.2
523.7

3.5
151.2
157.6
163.9
170.2
176.5
182.7
189.0
195.3
201.5
207.7
213.9
220.1
226.3
232.4
238.6
244.7
250.9
257.0
263.1
269.1
275.2
281.3
287.3
293.3
299.4
305.4
311.4
317.3
323.3
329.3
335.2
341.1
347.0
352.9
358.8
364.7
370.6
376.4
382.3
388.1
393.9
399.7
405.5
411.3
417.0
422.8
428.5
434.3
440.0
445.7
451.4
457.1
462.7
468.4
474.0
479.7
485.3
490.9
496.5
502.1
507.6
513.2
518.8
524.3

4
151.9
158.2
164.5
170.8
177.1
183.4
189.6
195.9
202.1
208.3
214.5
220.7
226.9
233.1
239.2
245.3
251.5
257.6
263.7
269.7
275.8
281.9
287.9
293.9
300.0
306.0
312.0
317.9
323.9
329.9
335.8
341.7
347.6
353.5
359.4
3^.3
371.2
377.0
382.8
388.7
394.5
400.3
406.1
411.9
417.6
423.4
429.1
434.8
440.5
446.3
451.9
457.6
463.3
468.9
474.6
480.2
485.8
491.4
497.0
502.6
508.2
513.8
519.3
524.9

4.5
152.5
158.8
165.1
171.4
177.7
184.0
190.3
196.5
202.7
208.9
215.1
221.3
227.5
233.7
239.8
246.0
252.1
258.2
264.3
270.4
276.4
282.5
288.5
294.5
300.6
306.6
312.6
318.5
324.5
330.4
336.4
342.3
348.2
354.1
360.0
365.9
371.7
377.6
3^.4
389.3
395.1
400.9
406.7
412.4
418.2
423.9
429,7
435.4
441.1
446^8
452.5
458.2
463.9
469.5
475.2
480.8
486.4
492.0
497.6
503.2
508.8
514.3
519.9
525.4

CHAPTER 25: VOLATILITY 687


TABLE 18AEl conversion table at 2.67 kPa (20 mm Hg) pressure C.
P (mm Hg)
20

T
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
160
165
170
175
180
185
190
195
200
205
210
215
220
225
230
235
240
245
250
255
260
265
270
275
280
285
290
295
300
305
310
315
320
325
330
335
340
345
350

0
131.0
137.1
143.3
149.4
155.6
161.7
167.8
173.9
180.0
186.0
192.1
198.2
204.2
210.2
216.2
222.2
228.2
234.2
240.2
246.1
252.1
258.0
263.9
269.9
275.8
281.7
287.5
293.4
299.3
305.1
310.9
316.8
322.6
328.4
334.2
340.0
345.7
351.5
357.3
363.0
368.7
374.5
380.2
385.9
391.5
397.2
402.9
408.5
414.2
419.8
425.5
431.1
436.7
442.3
447.9
453.4
459.0
464.6
470.1
475.6
481.2
486.7
492.2
497.7

0.5
131.6
137.8
143.9
150.1
156.2
162.3
168.4
174.5
180.6
186.6
192.7
198.8
204.8
210.8
216.8
222.8
228.8
234.8
240.8
246.7
252.7
258.6
264.5
270.5
276.4
282.2
288.1
294.0
299.8
305.7
311.5
317.4
323.2
329.0
334.8
340.6
346.3
352.1
357.8
363.6
369.3
375.0
380.7
386.4
392.1
397.8
403.5
409.1
414.8
420.4
426.0
431.6
437.2
442.8
448.4
454.0
459.6
465.1
470.7
476.2
481.7
487.2
492.7
498.2

1
132.2
138.4
144.5
150.7
156.8
162.9
169.0
175.1
181.2
187.3
193.3
199.4
205.4
211.4
217.4
223.4
229.4
235.4
241.4
247.3
253.3
259.2
265.1
271.0
276.9
282.8
288.7
294.6
300.4
306.3
312.1
317.9
323.8
329.6
335.3
341.1
346.9
352.7
aSb.A
364.1
369.9
375.6
381.3
387.0
392.7
398.4
404.0
409.7
415.3
421.0
426.6
432.2
437.8
443.4
449.0
454.5
460.1
AIS5.7

471.2
476.7
482.3
487.8
493.3
498.8

1.5
132.8
139.0
145.1
151.3
157.4
163.5
169.6
175.7
181.8
187.9
193.9
200.0
206.0
212.0
218.0
224.0
230.0
236.0
242.0
247.9
253.9
259.8
265.7
271.6
277.5
283.4
289.3
295.2
301.0
306.9
312.7
318.5
324.3
330.1
335.9
341.7
347.5
353.2
359.0
364.7
370.4
376.2
381.9
387.6
393.3
%8.9
404.6
410.2
415.9
421.5
427.1
432.8
438.4
444.0
449.5
455.1
460.7
466.2
471.8
477.3
482.8
488.3
493.8
499.3

2
133.4
139.6
145.8
151.9
158.0
164.1
170.2
176.3
182.4
188.5
194.5
200.6
206.6
212.6
218.6
224.6
230.6
236.6
242.6
248.5
254.5
260.4
266.3
272.2
278.1
284.0
289.9
295.8
301.6
307.4
313.3
319.1
324.9
330.7
336.5
342.3
348.1
353.8
359.6
365.3
371.0
376.7
382.4
388.1
393.8
399.5
405.2
410.8
416.5
422.1
427.7
433.3
438.9
444.5
450.1
455.7
461.2
466.8
472.3
477.8
483.4
488.9
494.4
499.9

2.5
134.1
140.2
146.4
152.5
158.6
164.7
170.8
176.9
183.0
189.1
195.1
201.2
207.2
213.2
219.2
225.2
231.2
237.2
243.2
249.1
255.1
261.0
266.9
272.8
278.7
284.6
290.5
296.3
302.2
308.0
313.9
319.7
325.5
331.3
337.1
342.9
348.6
354.4
360.1
365.9
371.6
377.3
383.0
388.7
394.4
400.1
405.7
411.4
417.0
422.6
428.3
433.9
439.5
445.1
450.6
456.2
461.8
467.3
472.9
478.4
483.9
489.4
494.9
500.4

3
134.7
140.8
147.0
153.1
159.2
165.4
171.5
177.5
183.6
189.7
195.7
201.8
207.8
213.8
219.8
225.8
231.8
237.8
243.8
249.7
255.6
261.6
267.5
273.4
279.3
285.2
291.1
296.9
302.8
308.6
314.4
320.3
326.1
331.9
337.7
343.4
349.2
355.0
360.7
366.4
372.2
377.9
383.6
389.3
395.0
400.6
406.3
411.9
417.6
423.2
428.8
434.4
440.0
445.6
451.2
456.8
462.3
467.9
473.4
479.0
484.5
490.0
495.5
501.0

3.5
135.3
141.5
147.6
153.7
159.9
166.0
172.1
178.1
184.2
190.3
196.3
202.4
208.4
214.4
220.4
226.4
232.4
238.4
244^4
250.3
256.2
262.2
268.1
274.0
279.9
285.8
291.6
297.5
303.4
309.2
315.0
320.8
326.7
332.5
338.2
344.0
349.8
355.5
361.3
367.0
372.7
378.4
384.2
389.8
395.5
401.2
406.9
412.5
418.1
423.8
429.4
435.0
440.6
446.2
451.8
457.3
462.9
468.4
474.0
479.5
485.0
490.5
496.0
501.5

4
135.9
142.1
148.2
154.3
160.5
166.6
172.7
178.8
184.8
190.9
196.9
203.0
209.0
215.0
221.0
227.0
233.0
239.0
244.9
250.9
256.8
262.8
268.7
274.6
280.5
286.4
292.2
298.1
303.9
309.8
315.6
321.4
327.2
333.0
338.8
344.6
350.4
356.1
361.9
367.6
373.3
379.0
384.7
%0.4
396.1
401.8
407.4
413.1
418.7
424.3
430.0
435.6
441.2
446.7
452.3
457.9
463.4
469.0
474.5
480.1
485.6
491.1
496.6
502.1

4.5
136.5
142.7
148.8
155.0
161.1
167.2
173.3
179.4
185.4
191.5
197.5
203.6
209.6
215.6
221.6
227.6
233.6
239.6
245.5
251.5
257.4
263.4
269.3
275.2
281.1
286.9
292.8
298.7
304.5
310.4
316.2
322.0
327.8
333.6
3^.4
345.2
350.9
356.7
362.4
368.2
373.9
379.6
385.3
391.0
396.7
402.3
Afy&.Q

413.6
419.3
424.9
430.5
436.1
441.7
447.3
452.9
458.4
464.0
469.5
475.1
480.6
486.1
491.6
497.1
502.6

688 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 19AET conversion table at 6.7 kPa (50 mm Hg) pressure C.
=> (mm Hg) T
35
50
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
IK
160
165
170
175
180
185
190
195
200
205
210
215
220
225
230
235
240
245
250
255
260
2^
270
275
280
285
290
295
300
305
310
315
320
325
330
335
340
345
350

0
109.0
114.9
120.8
126.7
132.6
138.5
144.3
150.2
156.0
161.9
167.7
173.6
179.4
185.2
191.0
196.8
202.6
208.3
214.1
219.9
225.6
231.4
237.1
242.8
248.5
254.3
260.0
2K.7
271.3
277.0
282.7
288.4
294.0
299.7
305.3
310.9
316.5
322.2
327.8
333.4
338.9
344.5
350.1
355.7
361.2
366.8
372.3
377.8
383.4
388.9
394.4
399.9
405.4
410.9
416.4
421.8
427.3
432.7
438.2
443.6
449.1
454.5
459.9
465.3

0.5
109.6
115.5
121.4
127.3
133.2
139.0
144.9
150.8
156.6
162.5
168.3
174.1
180.0
185.8
191.6
197.4
203.1
208.9
214.7
220.4
226.2
231.9
237.7
243.4
249.1
254.8
260.5
266.2
271.9
277.6
283.3
288.9
294.6
300.2
305.9
311.5
317.1
322.7
328.3
333.9
339.5
345.1
350.7
356.2
361.8
367.3
372.9
378.4
383.9
389.4
394.9
400.4
405.9
411.4
416.9
422.4
427.8
433.3
438.7
444.2
449.6
455.0
460.4
4^.8

1
110.2
116.1
122.0
127.9
133.7
139.6
145.5
151.4
157.2
163.1
168:9
174.7
180.5
186.3
192.1
197.9
203.7
209.5
215.3
221.0
226.8
232.5
238.2
244.0
249.7
255.4
261.1
266.8
272.5
278.2
283.8
289.5
295.1
300.8
306.4
312.0
317.7
323.3
328.9
334.5
340.1
345.6
351.2
356.8
362.3
367.9
373.4
378.9
384.5
390.0
395.5
401.0
406.5
412.0
417.4
422.9
428.4
433.8
439.3
444.7
450.1
5.6
461.0
466.4

1.5
110.7
116.7
122.6
128.5
134.3
140.2
146.1
151.9
157.8
163.6
169.5
175.3
181.1
186.9
192.7
198.5
204.3
210.1
215.8
221.6
227.3
233.1
238.8
244.5
250.3
256.0
261.7
267.4
273.0
278.7
284.4
290.0
295.7
301.3
307.0
312.6
318.2
323.8
329.4
335.0
340.6
346.2
351.8
357.3
362.9
368.4
374.0
379.5
385.0
390.5
396.0
401.5
407.0
412.5
418.0
423.5
428.9
434.4
439.8
445.3
450.7
A56A
461.5
466.9

2
111.3
117.2
123.1
129.0
134.9
140.8
146.7
152.5
158.4
164.2
1701
175.9
181.7
187.5
193.3
199.1
204.9
210.7
216.4
222.2
227.9
233.7
239.4
245.1
250.8
256.5
262.2
267.9
273.6
279.3
285.0
290.6
296.3
301.9^
307.5
313.2
318.8
324.4
330.0
335.6
341.2
346.8
352.3
357.9
363.4
369.0
374.5
380.0
385.6
391.1
396.6
402.1
407.6
413.1
418.5
424.0
429.5
434.9
440.4
445.8
451.2
456.7
462.1
467.5

2.5
111.9
117.8
123.7
129.6
135.5
141.4
147.3
153.1
159.0
164.8
170.6
176.5
182.3
188.1
193.9
199.7
205.5
211.2
217.0
222.7
228.5
234.2
240.0
245.7
251.4
257.1
262.8
268.5
274.2
279.9
285.5
291.2
296.8
302.5
308.1
313.7
319.3
325.0
330.6
336.1
341.7
347.3
352.9
358.4
364.0
369.5
375.1
380.6
386.1
391.6
397.1
4(^.6
408.1
413.6
419.1
424.6
430.0
435.5
440.9
446.3
451.8
457.2
482.6
468.0

3
112.5
118.4
124.3
130.2
136.1
142,0
147.8
153,7
159,5
165,4
171,2
177.0
182.9
188,7
194,5
200,3
206,0
211.8
217.6
223.3
229.1
234.8
240.5
246.3
252.0
257.7
263.4
269.1
274.8
280.4
286.1
291.7
297.4
303.0
308.7
314.3
319.9
325.5
331.1
336.7
342.3
347.9
353.4
359.0
364.5
370.1
375.6
381.2
386.7
392.2
397.7
403.2
408.7
414.2
419.6
425.1
430.6
436.0
441.5
446.9
452.3
457.7
463.1
468.6

3.5
113.1
119.0
124.9
130.8
136.7
142.6
148.4
154.3
160.1
166.0
17f.8
177.6
183.4
189.2
195.0
200.8
206.6
212.4
218.1
223.9
229.6
235.4
241.1
246,8
252.5
258.3
263.d
269.6
275.3
281.0
286.7
292.3
298.0
303.6
309.2
314.9
320.5
326.1
331.7
337.3
342,8
348,4
354,0
359,5
365.1
370.6
376.2
381.7
387.2
392.7
398.2
403.7
409.2
414.7
420.2
425.6
431.1
436.6
442.0
447.4
452.9
458.3
463.7
469.1

4
113.7
119.6
125.5
131.4
137.3
143.1
149.0
154.9
160.7
166.6
172.4
178.2
184.0
189.8
195.6
201.4
207.2
213.0
218.7
224.5
230.2
236.0
241.7
247.4
253.1
258.8
264.5
270.2
275.9
281.6
287.2
292.9
298.5
304.2
309.8
315.4
321.0
326.6
332.2
337.8
343.4
349.0
354.5
360.1
3K.7
371.2
376.7
382.3
387.8
393.3
398.8
404.3
409.8
415.3
420.7
426.2
431.6
437.1
442.5
448.0
453.4
458.8
464.2
4^.6

4.5
114.3
1202
126.1
132.0
137.9
143.7
149.6
155.5
161.3
167.1
173.0
178.8
184.6
190.4
196.2
202.0
207.8
213.5
219.3
225.0
230.8
236.5
242.3
248.0
253.7
259.4
265.1
270.8
276.5
282.1
287.8
293.4
299.1
304.7
310.4
316.0
321.6
327.2
332.8
338.4
344.0
349.5
355.1
360.7
366.2
371.8
377.3
382.8
388.3
393.8
399.3
404.8
410.3
415.8
421.3
426,7
432,2
437,6
443,1
448,5
453,9
459,4
464.8
470,2

CHAPTER 25: VOLATILITY


TABLE 20Precision of manual D 1160.
Repeatability
Pressure

689

Reproducibility

0.13kPa(l mmHg)

1.3 kPa (10 mmHg)

0.13 kPa(l mmHg)

1.3 kPa (10 mmHg)

17
3.3

15
7.1

56
31

49
27

IBP
FBP
Volume
Recovered

5-50%

60-90%

5-50%

60-90%

5-50%

60-90%.

5-50%

60-90%

C/V%
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0
10.5
11.0
11.5
12.0
12.5
13.0
13.5
14.0
14.5
15.0

2.4
2.9
3.2
3.4
3.6
3.8
3.9
4.0
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.8
4.9
5.0
5.0
5.1
5.1
5.2
5.2
5.3
5.3
5.4
5.4
5.5
5.5

2.5
3.0
3.3
3.5
3.7
3.9
4.0
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.8
4.9
5.0
5.1
5.1
5.2
5.2
5.3
5.4
5.4
5.5
5.5
5.6
5.6
5.7
5.7

1.9
2.4
2.8
3.1
3.3
3.6
3.8
3.9
4.1
4.3
4.4
4.5
4.7
4.8
4.9
5.0
5.1
5.2
5.3
5.4
5.5
5.6
5.7
5.8
5.9
6.0
6.0
6.1
6.2
6.3

2.0
2.5
2.9
3.2
3.5
3.7
3.9
4.1
4.3
4.4
4.6
4.7
4.8
5.0
5.1
5.2
5.3
5.4
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
5.3
6.3
6.4
6.5

6.5
10
13
16
16
21
23
25
27
29
30
32
34
35
37
38
40
41
43
44
46
47
48
50
51
52
54
55
56
57

3.9
6.0
7.6
9.4
11
12
13
15
16
17
18
19
20
23
22
23
24
25
25
26
27
28
29
30
30
31
32
33
33
34

7.0
9.3
11
12
14
15
16
16
17
18
19
19
20
21
21
22
22
23
23
24
24
25
25
26
26
27
27
27
28
28

5.4
7.2
8.5
9.8
11
11
12
13
13
14
15
15
16
16
16
17
17
18
18
19
19
19
20
20
20
21
21
21
22
22

TABLE 21Precision of automatic D 1160 distillation in C [7].


1 mm Hg Pressure
Boiling
Point
IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
FBP

Repeatability
15.9
8.0
5.5
3.8
3.8
5.2
4.7
6.5
4.4
7.3
6.5
9.5

10 mm Hg Pressure

Reproducibility
29.9
17.5
16
12.2
12
9.6
8.8
9.5
11.1
13.1
24.8
37.4

Repeatability

Reproducibility
35.4
11.1
8.0
10.4
7.1
8.6
10.2
12.8
11.3
14.1
25.5
19.7

16.7
6.8
3.7
4.3
3.2
2.9
3.1
3.7
3.4
3.8
5.0
6.4

TABLE 22Cross reference of international distillation standards relative to ASTM distillation test methods.
ASTM
Designation
U.S.
D86
D 1160
D2892
D5236

Distillation
Pressure
Atmospheric
Vacuum
Vacuum
Vacuum

ISO

IP

BS

AFNOR

DIN

Europe
3405
6616
8708

U.K.
123

U.K.
7392

France
M07-002

Germany
51 751
51 356
51567
51 567

FTM

JIS

791-1001

Japan
K2254
K2258

690

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

flammable liquids as those having flash points below 37.8C


and combustible liquids as those having flash points between
37.8C and 93.3C using specified ASTM flash point test
methods. In 1990, the U.S. decided to align its definition of
flammable and combustible material with the United Nation's definition, and now defines [23] flammable liquid as
having a flash point below 60.5C and a combustible liquid
with flash point between 60.5C and 93.3C. Gasoline and
aviation fuels are obviously flammable liquids. Flash point
specifications have been established for aviation turbine fuels, kerosines, diesel fuels, fuel oils, hydrocarbon solvents, lubricants, and other petroleum products.
There are a number of ASTM flash point test methods: D
56, Flash Point by Tag Closed Tester [24]; D 92, Flash and
Fire Points by Cleveland Open Cup [25]; D 93, Flash Point by
Pensky-Martens Closed Cup Tester [26]; D 1310, Flash Point
and Fire Points of Liquids by Tag Open Cup Apparatus [27];
D 3278, Flash Point by Setaflash Closed Cup Apparatus [28];
D 3828, Flash Point by Small Scale Closed Tester [29]; and D
3941, Flash Point by the Equilibrium Method With a Closed
Cup Apparatus [30]. A new flash point method, D 6450, Flash
Point by Continuously Closed Cup (CCCFP) Tester [31] that
was recently approved as an ASTM standard is included in
this work.
Table 23 gives the comparison of the different ASTM test
methods of determining the flash point of a material. These
flash point test methods all require a given specimen size, a
prescribed rate of heating, temperature measuring device, introduction of a heating source at specific stage during the
test, some mechanism of detecting the flash point, and barometric pressure correction. In manual flash point equipment,
the ignition source is a gas test flame, and the mechanism of
detecting the flash point is the visual observation of a flame
that instantaneously propagates itself over the entire surface
of the fluid. When the ignition source is a gas flame, the application of the test flame may cause a blue halo or an enlarged flame prior to the actual flash point. Such a phenomenon is not a flash and should be ignored. In the
automated equipment, the specimen size and equipment dimensions are the same as those of the manual apparatus.
However, the rate of heating, temperature measurements,
and detection of the flash point are done automatically according to the meinual procedure requirements. Resistance

temperature probes or thermocouples are used to measure


the temperature of the specimen during the test, and changes
in the ionization current, thermal conductivity, or pressure
are used to detect the occurrence of the flash point. Table 24
gives a summary of the applicable scope, temperature range,
repeatability, and reproducibility for these various flash
point methods.
All reported flash point values are corrected for the ambient barometric pressure at the time of the test. The observed
flash point is corrected for barometric pressure by using the
equations [32]:
Corrected flash point = C + 0.25 (101.3 - p)

(7)

= C + 0.033 (760 - P)

(8)

where: p = ambient barometric pressure in kPa


P - ambient barometric pressure in mm Hg.
Historically, the proper operation of flash point testers was
verified by determining the flash point of 1,4-dimethyl benzene (p-xylene). However, due to its toxicity and its relatively
low flash point (27C), eiltemative flash point verification fluids were studied. The results of an interlaboratory study conducted in 1993 by the ASTM S-15 Coordinating Committee
on Flash Point in cooperation with the NationsJ Institute of
Standards and Technology led to the establishment of consensus reference flash point values for n-decane, n-undecane,
n-tetradecane, and n-hexadecane to be used as flash point
verification fluids for the different flash point test methods.
Table 25 summarizes the method specific flash points of
these reference standards [33,34]. The study also attempted
to determine the relative bias of the different flash point test
method as shown in Table 26 [33]. However, the report of the
study stressed that the observed relative bias among the different flash point test methods are only applicable to the pure
hydrocctrbon liquids used in the study, and may not be applicable to mixtures. The observed D 56/D 93 of 0.97 for n-decane and 0.98 for n-undecane was not unexpected since the
rate of heating for D 56 is much slower than D 93 thus allowing thermal equilibrium between the bulk of the specimen
and the vapors above it. Open cup flash point methods like D
92 are expected to give higher flash points than closed cup
flash point methods. This is because sufficient volatile vapor

TABLE 23Comparison of the test parameters of different ASTMflashpoint test methods.


ASTM
Designation
D56
D92
D 93 Free. A

Cleveland
Pensky-Martens

Open
Closed

70 mL
75 mL

slice

Stirring
Rate
N/A
N/A
N/A
90-120 r p m

D 93 Proc. B

Pensky-Martens

Closed

75 mL

>110X

250 r p m

D 1310
D3278
D3828
D3941

Tag
Setaflash
Small Scale
Equilibrium
Method
Continuously
Closed Cup

Open
Closed
Closed
Closed
Closed
Closed

50 mL
2 mL
2mL
50 mL
75 m L
ImL

All
All
All
All
All
All

D6450

Apparatus
Tag

Cup
Type
Closed

Sample
Size

Expected
Flash
Point

50 mL

<60C

aeox
N/A

ranges
ranges
ranges
ranges
ranges
ranges

N/A
N/A
N/A
N/A
90-120 r p m

Heating
Rate
rC/min
3C/mln
14-17C/min
5-6C/min
l-1.5C/min
rC/min
N/A
N/A
N/A
N/A
5.5 0.5
C/min

Flash Pt.
(FP) Test
Initiation
5C below FP
5C below FF
28C below FF
23 5 ^
below FF
23 5 ^
below FF
10C below FF
Target FF
Target FF
Target FP
Target FF
18C below FF

Repeat
FP
Test
Every

Report to
Nearest

0 . 5 X rise
1.0Crise
1.0C rise
1.0C rise

0.5''C
0.5C
1.0C
0.5C

2.0C rise

0.5C

1.0C rise
N/A
N/A
N/A
N/A
l.O-Crise

0.5^
0.5C
0.5C
0.5C
0.5C
0.5-0

CHAPTER 25: VOLATILITY

691

TABLE 24Comparison of the scope and precision of the different ASTM flash point test methods.
ASTM
Designation
D56

Apparatus
Tag

Scope

D92
D 93 Proc. A

Cleveland
Pensky-Martens

D 93 Proc. B

Pensky-Martens

D1310

Tag

D3278

Setaflash

D3828

Small Scale

D3941

Equilibrium
method

Liquids with
specimen and vapor
temperature
approximately in
equilibrium

D6450

Continuously
Closed Cup

Fuel oils,
lubricating oils,
other solvents, and
liquids

Liquids, viscosity
<5.5 mm^/s at 40C
or 9.5 mm^/s at
25C.
Petroleum products
Distillate fuels
(diesel, kerosene,
heating oil, turbine
fuels, new
lubricating oils, and
other homogeneous
petroleum liquids
not covered by
Proc. B

Temperature
Range
Below 93C

79-400''C
40-360C

Repeatability
(95%
Confidence)

Expected
Flash Point

Reproducibility
(95%
Confidence)

<60C
>60-C

1.2''C
1.6C

4.3C
5.8C

All ranges

8C
0.035 X C
X = reported
result inC

18C
0.078 X C
X = reported
result in C

Residual fuel oils.


cutback residua.
used lube oils.
mixtures of
petroleum liquids
with solids, liquids
that form surface
films, viscous
liquids.
Liquids

40-360''C

Residual
fuels
Others

2C
5C

6C
10C

- 1 8 to 165C
0-110C

2C
5C
1.7C
3.3''C

4C
7C

Paints, enamels,
lacquers, varnishes.
and related
products with
viscosity, 150 St at
25C
Petroleum products

-18to93C
93 to 165C
Solvents
Resins/paints

20-70C
above TCC

O.S'C
0.022 M"-^ C
M = mean of
two results

0.03(M + 29) "C


0.083 M"^ C
M = mean of
two results

0-1 l O X

All ranges

2C

3C

10-250C

All ranges

1.9C

3.rc

Ambient to
300C

3.3X
5.0C

TABLE 25Flash point verification fluids.


Reference
Material

Test Method

Reference Value
C

Expanded
Uncertainty (C)

# of Independent
Observations

17
0.8
1.0
21
1.2
6
0.7
17
RM8518
n-Undecane
14
2.5
1.4
21
6
1.6
RM8519
2.6
13
n-Tetradecane
17
2.7
RM 8520
2.4
13
n- Hexadecane
16
2.8
Uncertainty: The uncertainty of each value in this Report is the numerical value of an expanded uncertainty V = kuc, with U determined from a
combined standard uncertainty Uc, and a coverage factor k equal to a t-factor from the ^distribution with degrees of freedom equal to the number
of independent observations minus 1. This expanded uncertainty defines a range of values for the certified value within which the true value is believed to lie, at a confidence level of 95%.
RM8517
n-Decane

D56
D93
D 3278/D 3828
D56
D92
D93
D 3278/D 3828
D92
D93
D92
D93

50.9
52.8
49.7
67.1
73.2
68.7
65.9
115.5
109.3
138.8
133.9

692

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

TABLE 26Relative bias among various flash point test methods.


Verification Fluid

D 56/ D 93

n-Decane
n-Undecane
n-Tetradecane
n-Hexadecane

0.964
0.977

1.065
1.057
1.036

Flome Size
Bead

D 3278/D 93

D 3828/D 93

0.941
0.982

the oldest D-2 standard test method in publication. The latest


edition is D 56-OOa. The term "Tag" in this standard is a contraction of Tagliabue, who invented the original small closed
tester for flash point determination in 1861 [35]. The Tag
closed tester is a modification of the Tagliabue closed tester
and was first tried in 1916. The modified closed cup tester
was the subject of full comparison series of tests conducted
by ASTM in 1917. Figure 4 shows a schematic diagram of a
manual Tag Closed Cup tester [24].

Both
ThermomeJer

y \ Thermometer

D 92/D 93

Flome Tip
Oil
Chomber

ASTM D 92, Standard Test Method


Points by Cleveland Open Cup

for Flash and Fire

This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D2.08 on Volatility. It was originally published in 1921. The
latest edition is D 92-98b.This open cup tester has been used
in the United States since 1908. In early models, testing was
conducted by passing a small test flame across the top of the
cup by hand. Later on, this was converted to the use of a
swinging arm, which controlled the movement of the test
flame at a defined height above the top of the cup. Figure 5
[25] shows the schematic diagram of a manual Cleveland
Open Cup Apparatus.
In addition to determining the flash point of a liquid material, D 92 EJSO determines the fire point. Fire point is defined
as the lowest temperature corrected to a barometric pressure
of 101.3 kPa (760 m m Hg) at which application of an ignition
source causes the vapors of the test specimen to ignite and
sustain burning for a m i n i m u m of 5 s under specified conditions of test. The fire point determination is an extension of
the flash point test. After the flash point is determined, heating of the specimen is continued at a rate of 5-6C/min. The
test flame is applied at 2C intervals until the test specimen
ignites and sustains burning for a minimum of 5 s. Just like
flash point, the fire point is also corrected for barometric
pressure using the same equation utilized for flash point.
ASTM D 93, Standard Test Method for Flash Points
Pensky-Martens
Closed Cup Tester
FIG. 4D 56 tag closed cup tester (manual).

concentration above the liquid will tcike longer in an open


test cup relative to a closed test cup. D 92 flash point results
were indeed higher than D 93. D 3278 and D 3828, which also
allow thermeJ equilibrium between specimen and vapor temperature, gave lower flash points when compared to D 93 for
n-decane a n d n-undecane.
ASTM D56, Standard
Tag Closed Tester

Test Method

for Flash Point

by

This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D2.08 on Volatility. It was originally published in 1918 and is

by

This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D2.08 on Volatility. It was originally published in 1921. The
latest edition is D 93-00. It was developed in Germany in 1870
by Meirtens, and was based on the original tester by Pensky.
Its development in 1870 was for flash points well above 100C
to test lubricating oils and other similar materieds such as bitumen products. A schematic diagram of a manual PenskyMartens Closed Cup Flash Tester is given in Fig. 6 [26].
Test Method D 93 Procedure A covers the determination of
flash points of relatively non-viscous, homogeneous materials. Test Method D 93 Procedure B, on the other hand, is
meant to measure viscous, nonhomogeneous materials like
residual oils, materials that tend to form surface film when
heated, and liquids that contain suspended solids. A 1994 in-

CHAPTER 25: VOLATILITY

693

THCRMOMETEII
A8TM NO. l i e
IP > C

TEST FLAMC
APPLICATOR

TEST CUP
HEATIN* PLATE

ORIFICE

MCTAL aCAO

TO AS SUPPLY
HEATER PLANE TVPE
OR ELECTRIC RESISTANCE TVPE
inches

millimetres
ADiameter
BRadius
CDiameter
D
E
FDiameter

min

max

min

max

3.2
152
1.6

4.8
nominal
nominal
2
7
nominal

0.126
6
0.063

0.189
nominal
nominal
0.078
0.276
nominal

6
0.8

0.236
0.031

FIG. 5D 92 Cleveland open cup apparatus (manual).

terlaboratory study [36,37] indicated that samples with kinematic viscosity greater than 13 mm^ls at 40C gave a lower
observed flash point when tested by Procedure A compcired
to the flash point determined by Procedure B. A possible explanation is a lag in the temperature detected by the temperature measuring device as the kinematic viscosity of the sample increases, especially when equilibration of the vapor and
the bulk of the sample is not established before the flash
point is detected. Therefore, viscosity effects must be taken
into account when deciding on the appropriate procedure for
D 93 flash point determination.
ASTM D 1310, Standard Test Method for Flash Point
and Fire Points of Liquids by Tag Open Cup Apparatus
This test method is under the jurisdiction of ASTM Committee D-01 on Paints and Related Coatings, Materials, and Applications, and is the direct responsibility of Subcommittee
D1.22 on Health and Safety. It was originally published in
1952. The latest edition is D 1310-01. The modem Tag open
cup tester was derived from the Tagliabue Open cup Tester
patented in 1862.
ASTM D 3278, Standard Test Method for Flash Point by
Setaflash Closed Cup Apparatus
This test method is under the jurisdiction of ASTM Committee D-1 and is the direct responsibility of Subcommittee
D1.22. It was originally published in 1973. The latest edition
is D 3278-96. The original closed cup miniflash point tester
was invented by T. Kidd in the early 1960s. It was commer-

cialized by Stanhope-Seta Ltd. during 1967 to 1969, and became known as the Setaflash flash point tester. The Setaflash
flash test method differs from the other flash point methods
because the temperature equilibrium between the specimen
and the vapor above it is allowed to be established prior to
testing for a flash point. A fresh specimen is used for each test
temperature, unlike D 56, D92, and D 93, where multiple
flash point testing is done on a given specimen at various test
temperatures. A schematic diagram of the Setaflash apparatus is shown in Fig. 7 [28].
ASTM D 3828, Standard Test Method for Flash Point by
Small Scale Closed Cup Tester
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee D
2.08. It was originally published in 1979. The latest edition is
D 3828-98. The apparatus used in this test method is the
same as that described in D 3278. Just like the Setaflash test
method, this method allows temperature equilibrium
between the specimen and the vapor above it to be established prior to testing for a flash point. This test method is
applicable to petroleum products not covered within the
scope of D 3278.
ASTM D 3941, Standard Test Method for Flash Point by
the Equilibrium Method with a Closed Cup Apparatus
This test method is under the jurisdiction of ASTM Committee D-01 and is the direct responsibility of Subcommittee D 1.22. It was originEdly published in 1980. The latest

694

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

SHUTTER

HANDLE (OPTIONAL)
(MUST NOT TIP EMPTY CUP)

STIRRER DRIVE FLEXIBLE SHAFT


(PULLEY DRIVE OPTIONAL)
FLAME EXPOSURE DEVICE

SHUTTER OPERATING KNOB

THERMOMETER

DISTANCE PIECE

D
TEST CUP

mm
n*

F MIN THICKNESS
OVER CUP AREA
lE.METAL SURROUNDING
THE CUP

A
B
C
0

e
F

max

in.
min

max

4.37
5.16 0.172 0.203
41,94 42.06 1.651 1.6S6
1.58
3.18 0.062 0.125
9.52
0.375
Sr.23 57.86 2.253 2.278
6.35
0.25

HEATER FLAME-TYPE
OR ELECTRIC RESISTANCE
TYPE (FLAME TYPE SHOWN)

NOTE 1Lid assembly can be positioned either right or left-handed.

FIG. 6D 93 Pensky-Martens closed cup apparatus (manual).

edition is D 3941-96. The apparatus used in this test method


is the same as that described in D 56 and D 93. However,
similar to the Setaflash or Small Scale test method, this
method allows temperature equilibrium between the specimen and the vapor above to be established prior to testing
for a flash point.
ASTM D 6450, New Standard Test Method for Flash
Point by the Continuously Closed Cup (CCCFP) Tester
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee D
2.08. The first pubUshed edition will be the 1999 edition. The
apparatus is continuously closed during the test but a predetermined amount of air is injected into the test chamber after
each introduction of the ignition source. This test method is
different than the other flash point methods because a preset
change in the pressure inside the test chamber is used to detect when the flash point has been reached. In addition, an
electric arc is used as the source of ignition when testing for
a flash point occurrence. This flash point method gives simi-

lar results to those obtained by D 93. However, the results are


not equivalent [38].
Other International Flash Point Test Methods
All the aforementioned flash point test methods Eire ASTM
standard test methods. Although ASTM standard test methods are used extensively throughout the world, there are
other international flash point standards that are used and
are applicable to specific geographical jireas. Table 27 gives a
cross reference for a number of international flash point
standards and their corresponding ASTM designations.
There are flash point test methods used mainly in Europe,
which do not have an equivalent ASTM standard. The Abel
flash point tester is a closed cup tester developed originally in
1876. It is currently used in parts of the United Kingdom. It
is similar to the D 56 Tag closed-cup tester but with provision
for stirring the specimen. The Abel-Pensky closed cup tester
was developed in Germany in 1879 and adopted as the German standard for testing petroleum product in 1882. It is still
used widely use in Europe.

AHinge
BUd
CPilot flame jet
DTest flame jet
EFiling orifice
FTest flane gas control screw
GShutter guide
HShutter knob
JShutter
KUdlock
LUd sealing 0-ring
MThermometer
NSample cup
P^Thermometer well
RTest flame gage

BORE OF TEST JET


12.65
12.60

30.45

7.65
7.60

30/W

m^
12.47
12.42

5.10
5.05

Li|:W

SHUTTER
(1.22 THICK NOM.)
48.42

BORE OF FILLtNO ORIFICE


1.60/1.85 DIA.

46.37
4.00

10.00

7.65
7.60

IT^iZZZ^^
16.00

10.18
IO.I3

p
7.00 OIA.
NOM.

42.00
41.00

49.70
49.40

5.10
TYP.
5.05

12.47
12.42

SPECIMEN CUP AND LID

LID

( 2 . 0 0 THICK NOM.)

NOTE 1All dimensions are in millimetres.

FIG. 7D 3278 and D 3828 small scale (Setaflash) apparatus.

TABLE 27Cross reference of international flash point methods versus ASTM flash point test methods.
ASTM

u.s
D56
D92
D93
D 1310
D3278
D3828
D3941
D6450

ISO

IP

DIN

AFNOR

Europe

U.K.
304
36
34

Germany

France

303
303

55 680
55 680

2592
2719
3679
3679
1523

170 (Abel)
304

51 376
51 758

51 755
(Abel-Pensky)

FTM

EN

SIS

791-1101
791-1103
M07-019

K2265-1996
K2265-1996
K2265-1996

456

M07-036

ns
Japan
K2265-1996
K2265-1996
K2265-1996

Europe

150 223

696

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Crude Distillation
Crude oil is a complex mixture of mostly organic molecules
with minute quantities of inorganic materials. The organic
molecules are mostly hydrocarbons, with minor sulphur, nitrogen, and oxygen components, and trace quantities of metals such as vanadium and nickel. In the assay or preliminary
characterization of crude oil, atmospheric and reduce pressure distillations are performed in order to determine the
yields of various boiling ranges.
Two test methods are used in the distillation of crude oils,
ASTM D 2892, Standard Test Method for Distillation of
Crude Petroleum (15-Theroetical Plate Column) [39], and
ASTM D 5236, Standard Test Method for Distillation of
Heavy Hydrocarbon Mixtures (Vacuum Potstill Method)
[40]. Crude oil distillation is one of a number of tests conducted on a crude oil to determine its market value. The fractions produced during crude oil distillation can be used alone
or in combination with other fractions to produce samples
for analytical studies, engineering, and product quEility evaluations. The precision values for these two methods are summarized in Table 28.
ASTM D 2892, Standard Test Method for Distillation of
Crude Petroleum (15-Theoretical Plate Column)
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee D02.08. It was originally published in 1970. The latest
edition is D 2892-99a. It describes the procedure for the distillation of stabilized crude petroleum to a final cut temperature of 400C AET (Atmospheric Equivalent Temperature).
AET is the atmospheric equivalent temperature converted
from the observed vapor temperatures and was previously
discussed in the ASTM D1160 section. Equations 4, 5, and
6, as well as Tables 14-19, are applicable for D 2892 also.
This test method employs a fractionating column having an
efficiency of 14-18 theoretical plates operated at a reflux ratio of 5:1., thus corresponding to the standard laboratory
distillation efficiency referred to as 15/5. Figure 8 [37]
shows the schematic diagram of the apparatus used for this
test method. Distillation yields by mass or volume are calculated from the data and reported to the nearest 0.1%. Vapor temperatures are reported to the neeirest 0.5C. TypiceJ
D2892 distillation results for two different crude oils are
given in Tables 29 [41] and 30 [42].

ASTM D 5236, Standard Test Method for Distillation of


Heavy Hydrocarbon Mixtures (Vacuum Potstill
Method)
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.08. It was originally published in 1992. The latest edition
is D 5236-99. It describes the procedure for the distillation of

CONOENSOR

SOI.ENOID

li

COLUMN.WIT
MANTLE

VACUUM CONNECTION
(WHEN USED)
A P SENSOR
PRODUCT
: COOLER

RECEIVER
TEMPERATURE
PROBE

stTirri--'

I-

N 2 BUBBLER

DISTILLING FLASK WITH MANTL'ES

STIRRING MOTOR

FIG. 8D 2892 test apparatus.

TABLE 28Precision values for crude distillation methods.


ASTM
Designation

iWethod

Procedure or Cuts

Repeatability

D2892

15/5 Distillation

Under determination
Under determination

D5236

Vacuum Potstill

Atmospheric Pressure
Reduced Pressure
10 vol %
20 vol %
30 vol %
40 vol %
50 vol %
60 vol %
70 vol %
80 vol %
90 vol %

6.rc
6.rc
4.9C
4.5C

5.7C

4.rc
4.8C
4.9C
4.4C

Reproducibility
1.2 mass %
1.4 mass %
16.9C
12.8C
13.5X
11.2''C
14.2C
8.4C
11.4C

5.rc

4.4''C

1.2 vol %
1.5 vol %

CHAPTER 25: VOLATILITY

697

TABLE 29D 2892 crude distillation results for a new grade oil.
Boiling Range
(AET, C)

Weight
in
Grams

Init. to 20
21-50
93
163
200
250
280
316
330
343
343 +
Recov
Loss

88
91
212
452
199
260
188
278
208
90
1266
3332
6

Charge Density == 0.8406


API = 36.7

Wt%

Volume (mL)

2.6
2.7
6.4
13.6
6.0
7.8
5.6
8.3
6.2
2.7
38.0

146.6
144.1
300.9
593.3
247.5
312.6
221.3
323.0
237.0
102.0
1358.4
3987

No Loss
Charge

LV %
Crude

Cum
LV%

Mid
LV%

API
Gravity

Density at
15C

3.7
3.6
7.5
14.9
6.2
7.8
5.5
8.1
6.0
2.6
34.1

3.7
3.6
7.5
14.9
6.2
7.8
5.5
8.1
6.0
2.6
34.1

3.7
7.3
14.8
29.7
35.9
43.8
49.3
57.4
63.4
65.9
100.0

1.8
5.5
11.1
22.3
32.8
39.8
46.5
53.4
60.4
64.7
82.0

104.3
92.5
69.3
54.2
44.4
38.5
34.9
32.8
29.8
28.8
20.2
37.7

0.6001
0.6315
0.7046
0.7618
0.8039
0.8317
0.8479
0.8608
0.8765
0.8820
0.9320
0.8357

0.2
Charge Weight = 3345
Weight of Water = 7

T A B L E 3 0 D 2 8 9 2 C r u d e d i s t i l l a t i o n r e s u l t s for l i g h t s o u r b l e n d oil
Boiling Range
(AET, C)

Weight
in
Grams

Init. to 20
21-50
100
125
150
175
205
220
235
265
295
319
343
343+
Recov
Loss

530
1709
2063
1077
1559
1289
1896
815
945
1940
1948
1870
1538
15105
34333
68

Charge Density = 0.8508


API = 34.7

Wt%

Volume (mL)

1.5
5.0
6.0
3.1
4.5
3.8
5.5
2.4
2.9
5.7
5.7
5.4
4.5
44.0

937.1
2605.2
2812.9
1443.3
2035.2
1647.7
2383.1
1009.0
1216.8
2330.6
2286.9
2157.1
1753.3
15921.8
40540.1

No Loss
Charge

LV %
Crude

Cum
LV%

Mid
LV%

API
Gravity

Density at
15C

2.3
6.4
6.9
3.6
5.0
4.1
5.9
2.5
3.0
5.7
5.6
5.3
4.3
39.3

2.3
6.4
6.9
3.6
5.0
4.1
5.9
2.5
3.0
5.7
5.6
5.3
4.3
39.3

2.3
8.7
15.7
19.2
24.3
28.3
34.2
36.7
39.7
45.4
51.1
56.4
60.7
100.0

1.2
5.5
12.2
17.5
21.7
26.3
31.3
35.4
38.2
42.6
48.3
53.7
58.6
80.4

118.7
84.2
61.4
58.1
53.1
49.3
46.3
43.6
41.6
38.4
34.5
31.6
29.7
17.6
35.4

0.5656
0.6560
0.7334
0.7462
0.7660
0.7823
0.7956
0.8077
0.8169
0.8324
0.8518
0.8669
0.8772
0.9487
0.8469

0.2

Charge Weight = 33448


Weight of Water = 47

heavy hydrocarbon mixtures having an initial boihng point


greater than 150C such as heavy crude oil, petroleum distillates, residues, and synthetic mixtures. It employs a potstill
with a low pressure drop entrainment separator operated under total takeoff conditions. The maximum achievable AET
(see discussion on D 1160 under the distillation section) of
565C is dependent on the heat tolerance of the chcirge. A
weighed volume of sample is distilled at reduced pressures
between 6.6 and 0.013 kPa. at specified distillation rates. Cuts
are taken at preselected temperatures. Records of vapor
temperature, operating pressure, and other variables are
made at intervals and each cut point. Figure 9 shows the
schematic diagram of the apparatus used for this test method
[40]. Distillation yields by mass or volume are calculated
from the data and reported to the nearest 0.1%. Vapor temperatures are reported to the nearest 0.5C. T3fpical D 5236
distillation results for two different crude oils are given in Tables 31 [43] and 32 [44].
Other International Test Methods for Crude Distillation
All the aforementioned test methods are ASTM standard test
methods for crude oil distillation. Although ASTM standard
test methods are used extensively throughout the world.

there are other international crude distillation standards that


are used and are applicable to specific geographical areas.
Table 22 gives a cross reference for a number of international
crude distillation standards and their corresponding ASTM
designation.
Vapor Pressure
In addition to distillation characteristics, vapor pressure is a
critical volatility parameter of gasoline and other petroleum
fuels. Vapor pressure is the force per unit area exerted by the
vapors of the liquid contained in a closed container. Vapor
pressure affects the performance chsiracteristics of gasoline
and other hydrocarbon fuels, especially during cold starting
and vapor-lock conditions. Vapor- liquid ratio at specified
temperatures is also an important parameter. For gasoline
and simileir fuels, the vapor pressure is dependent on the vapor to liquid ratio in the container, and the temperature. The
vapor pressure of a fuel measured at 37.8C (100F) with a 4:1
vapor to liquid ratio in a designated container, is known as
the Reid Vapor Pressure or RVP. This important fuel characteristic is measured by ASTM D 323, Vapor Pressure of
Petroleum Products (Reid Method) [45].

698

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

There are other ASTM test methods related to the measurement of vapor pressure. Among these are: ASTM D 4953, Standard Test Method for the Vapor Pressure of GasoHne and
Gasohne-Oxygenate Blends (Dry Method) [46]; ASTM D 5190,
Standard Test Method for the Vapor Pressure of Petroleum
Products (Automatic Method) [47]; ASTM D 5191, Standard
Test Method for the Vapor Pressure of Petroleum Products
(Mini Method) [48]; and ASTM D 5482, Standard Test Method
for the Vapor Pressure of Petroleum Products (Mini MethodTO VACUUM PUKPINO LIME

RE*0 TKAP
TO VACUUM GAUGE
C080EN8ER>

VAPOR THERMOCOUPLE

HEAD COHPENSATIMG MANTLE


(not ahown)

VACUUM ADAPTER

Atmospheric) [49]. Vapor-liquid ratio measurements can be


done by: ASTM D 5188, Standard Test Method for the VaporLiquid Ratio Temperature Determination of Fuels (Evacuated
Chamber Method) [50] and ASTM D 2533, Standard Test
Method for the Vapor - Liquid Ratio of Spark-Ignition Engine
Fuels [51]. Two new vapor pressure test methods have been
approved recently: ASTM D 6377, Standard Test Method for
Vapor Pressure of Crude Oil: VPCRx (Expansion Method) [52]
and ASTM D 6378, Standard Test Method for Determination
of Vapor Pressure VPx of Petroleum Products, Hydrocarbons,
and Hydrocarbon-Oxygenate Mixtures (Triple Expansion
Method) [53]. The vapor pressure of liquefied petroleum gases
is determined using ASTM D 1267, Standcird Test Method for
the Gage Vapor Pressure of Liquefied Petroleum- (LP) Gases
(LP-Gas Method) [54].
Vapor pressure is critically important for both automotive
and aviation gasolines. It affects starting, warm-up, and tendency to vapor lock at high operating temperatures or eiltitudes. M a x i m u m vapor p r e s s u r e limits for gasoline are
legeJly mandated in some etreas as a measure of air pollution
control. Vapor pressure of crude oils is important to the
crude producer and refiner for general heindling jind initial
refinery treatment. Vapor pressure is also used as an indirect
measure of the evaporation rate of volatile petroleum solvents, with higher vapor pressure being associated with a
faster rate of evaporation.
Table 33 summarizes the salient features of these various
vapor pressure and vapor/liquid ratio test methods. The precision values for the different vapor pressure and V/L test
methods are shown in Table 34.

FLASK THERMOCOUPLE

ASTM D 323, Standard Test Method for the Vapor


Pressure of Petroleum Products (Reid
Method)

PLASK MAHTLES

OISTILLATIOH FLASK

MAGHETIC STIRRER

FIG. 9D 5236 test apparatus.

This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.08. It was originally published in 1930. The latest edition
is D 323-99.
This test method covers procedures for the determination
of vapor pressure of gasoline, volatile crude oil, and other
volatile p e t r o l e u m products. Because the external atmospheric pressure is counteracted by the atmospheric pressure
initially present in the vapor chamber, the Reid vapor pressure is an absolute pressure at 37.8C. The Reid vapor pressure differs from the true vapor pressure of the sample due to
some small sample vaporization and the presence of water

TABLE 31D 5236 crude distillation results for a new grade oil bottoms.
Boiling
Range
(AET, C)

Weight
Grams

Wt%

Volume (mL)

Init. to 375
399
450
482
525
550
565
WETT
565 +
Recov
Loss

28
261
247
130
144
66
36
5
338
1255
2

2.2
20.8
19.7
10.4
11.5
5.3
2.9
0.4
26.9

31.4
292.2
273.2
141.7
155.5
70.7
38.4
5.3
337.5
1345.9

in

Charge Density = 0.9320


Weight of Water = 0

0.2
Charge Weight = 1253
API = 20.2

No Loss
Charge

LV%
Crude

Cum
LV%

Mid
LV%

API
Gravity

Density at
15C

2.3
21.7
20.3
10.5
11.6
5.3
2.9
0.4
25.1

0.8
7.4
6.9
3.6
3.9
1.8
1.0
0.1
8.6

66.7
74.1
81.0
84.6
88.6
90.3
91.3
91.4
100.0

66.3
70.4
77.6
82.8
86.6
89.4
90.8
91.4
95.7

27.0
26.9
24.9
22.6
21.2
20.0
19.3
18.9
9.7
20.1

0.8921
0.8931
0.9041
0.9175
0.9260
0.9336
0.9375
0.9402
1.0015
0.9324

CHAPTER 25: VOLATILITY

699

TABLE 32D 5236 crude distillation results for a light sour blend bottoms.
Boiling Range
(AET, C)

Weight
in
Grams

Init. to 399
427
454
482
510
538
565
WETT
565 +
Recov
Loss

363
635
363
355
305
314
245
10
1150
3740
5

Wt%

Volume (mL)

9.7
17.0
9.7
9.5
8.2
8.4
6.6
0.3
30.7

403.3
702.4
397.0
385.6
328.6
335.1
258.1
10.5
1121.8
3942.4

No Loss
Charge

LV%
Crude

Cum
LV%

Mid
LV%

API
Gravity

Density at
15C

10.2
17.8
10.1
9.8
8.3
8.5
6.5
0.3
28.5

4.1
7.1
4.0
3.9
3.3
3.4
3.6
0.1
11.4

64.2
71.3
75.3
79.2
82.5
85.9
88.5
88.6
100.0

62.1
67.7
73.3
77.3
80.9
84.2
87.2
88.6
94.3

25.6
24.9
23.2
22.1
20.9
19.4
17.5
17.0
6.4
17.5

0.9000
0.9041
0.9144
0.9207
0.9282
0.9369
0.9492
0.9521
1.0251
0.9486

0.1

Charge Density == 0.9484


API = 17.6

Charge Weight = 3745


Weight of Water = 0

TABLE 33Comparison of ASTM vapor pressure and vapor/liquid ratio test methods.
ASTM
Designation

Reid Method

D 323 Proc. B
D 323 Proc. C
D 323 Proc. D

Reid Method
Reid Method
Reid Method

D 4953 Proc. A
D 4953 Proc. B

Dry Reid
Method
Dry Reid SemiAutomatic
Automatic
Method
Mini-Method

D5190
D5191
D5482
D6377
D6378

Scope

Test Method

D 323 Proc. A

Mini-Method,
Atmospheric
Expansion
Method
Triple
Expansion
Method

Vapor
Pressure
Range

Gasoline, volatile crude oil,


and other volatile
petroleum products
rr

Test
Temperature

Vapor to
Liquid
Ratio

All at 37.8C

4:1

Vapor
Pressure

Resuh

<180kPa
<180kPa
> 8 0 kPa
@ 50 kPa

Aviation gasoline
Gasoline and gasolineoxygenate blends, other aircontaining volatile petroleum
products

35-100 kPa

37.8C

4:1

Vapor
Pressure

//

7-172 kPa

37.8C

4:1

DVPE*

"
"

7-130 kPa
7-llOkPa

37.8C
37.8^

4:1
4:1

DVPE*
DVPE*

5-80C

4:1 to 0.021:1
4:1

Crude Oils
Volatile petroleum products,
hydrocarbons, and
hydrocEirbonoxygenate mixtures

7-150 kPa

37.8C

Vapor
Pressure
Vapor
Pressure

D5188

Evacuated
Chamber
Method

Gasoline and gasoline


oxygenate blends.

101.3 kPa

36-80C

8:1 to 75:1

V/L
Temperature

D2533

Evacuated
Chamber
Method

Gasoline

101.3 kPa

36-80C

20:1

V/L and
Temperature

D 1267

LP-Gas
Method

Liquified Petroleum Products

37.8-70C

Vapor
Pressure

*DVPE = dry vapor pressure equivalent (see discussion under individual test method)

vapor ind air in the confined space. The true vapor pressure
of the sample is the pressure exerted only by the molecular
species in the sample on the walls of the container. The vapor
pressure obtained by this method includes the vapor pressure
due to water vapor and air.
Figure 10 [45] shows the schematic diagram of the vapor
pressure apparatus for Procedure A, C, and D. Figure 11 [45]
illustrates the apparatus for Procedure B. The liquid chamber
of the vapor pressure apparatus is filled with the chilled sample and connected to the vapor chamber that has been heated
to 37.8C in a bath. The assembled apparatus is immersed in
a bath maintained at 37.8C until a constant pressure is ob-

served. The pressure reading, suitably corrected for any difference between the vapor pressure gage and calibration
manometer reading, is reported to the nearest 0.25 kPa (0.05
psi) as the Reid vapor pressure.
ASTM D 4953, Standard Test Method for the Vapor
Pressure of Gasoline and Gasoline-Oxygenate Blends
(Dry Method)
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.08. It was originally published in 1989. The latest edition
is D 4953-99.

700 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


TABLE 34Precision of various vapor pressure and V/L ratio test methods.
ASTM
Designation

Reid Method

D4953

Dry Reid
Method

D5190

Procedure/Model

Metliod Name

D323

A
B
A
A
C
D
A
B
B
B

(Gasohne)
(Gasoline)

Repeatability

Range
35-100 kPa (5-15 psi)
35-100 kPa (5-15 psi)
0-35 kPa (0-5 psi)
110-180 kPa (16-26 psi)
180kPa(>26psi)
50 kPa (7 psi)

Automatic
Method
Mini-Method

D5191

psi)
psi)
psi)
psi)

2.48 kPa (0.36 psi)

3.45 kPa (0.50 psi)

0.00807(DVPE + B)
B = 124 kPa (18.0 psi)
1.31 kPa (0.19 psi)
1.79 kPa (0.26 psi)

0.0161(DVPE + B)
B = 124 kPa (18.0 psi)
2.69 kPa (0.39 psi)
4.14 kPa (0.60 psi)
To be determined

kPa
kPa
kPa
kPa
kPa
kPa

3.65
4.00
2.14
3.58

(Gage)
(Herzog)
(Precision)

Reproducibility
5.2 kPa (0.75 psi)
4.5 kPa (0.66 psi)
2.4 kPa (0.35 psi)
2.8 kPa (0.40 psi)
4.9 kPa (0.70 psi)
1.0 kPa (0.15 psi)
5.52 kPa (0.80 psi)
5.38 kPa (0.78 psi)
2.90 kPa (0.42 psi)
4.27 kPa (0.62 psi)

3.2
1.2
0.7
2.1
2.8
0.7

(0.46
(0.17
(0.10
(0.30
(0.40
(0.10

kPa
kPa
kPa
kPa

psi)
psi)
psi)
psi)
psi)
psi)

(0.53
(0.58
(0.31
(0.52

Mini-Method,
Atmospheric
VPCRx,
Expansion
Method

Herzog SC970
ABB 4100

D6378

VPx,
Expansion
Method

Petroleum
Products

0.50 kPa (0.07 psi)

1.63 kPa (0.22 psi)

D5188

Evacuated
Chamber
Evacuated
Chamber
LP-Gas
Method

V/L

0.6 C

0.9 C

1.0 C
1.4 C
12kPa(1.8psi)

1.3 C
1.6 C
18kPa(2.8psi)

D5482
D6377

D2533
D 1267

Vapor Chambar

Key
A
B, C, D
E
F, G
H
I
J

Glycerol Mercury

V/L

'Coupling
C

0.015 VPCR4
0.055 VPCRo 1
0.065 VPCRo 02

V/L = 4 and 37.8C


V/L = 0.1 and 37.8 C
V/L = 0.02 and 37.8 C

Crude

Coupling

MUU)G 6ABE VERSION

tiquid Choinbtf
(Oni Opening)

DIMENSIONS OF VAPOR PRESSURE APPARATUS


Description
mm
Vapor chamber, length
254 3
Vapor and gasoline chambers,
51 3
Liquid ID
Coupling, ID min
4.^
Coupling, OD
12.7
Coupling, ID
12.7
\felve
12.7
Valve
6.35

in.
10 Ve
2 Vs

FIG. 10D 323 - Procedure A, C, and D apparatus.

16
Vi
%
%
Vt

non
na

"CI

~or

FIG. 11D 323 - Procedure B apparatus.

CHAPTER
This test method is a modification of D 323, providing two
procedures to determine the vapor pressure of gasoline and
gasohne-oxygenate blends. Procedure A utilizes the same apparatus and essentially the same procedure as D 323 with the
exception that the interior surfaces of the liquid and vapor
chambers are maintained completely free of water. Procedure B utilizes a semi-automatic apparatus as shown in Figure 11 [46] with the liquid and vapor chambers identical in
volume to those in Procedure A. The apparatus is suspended
in a horizontal bath and rotated while attaining equilibrium.
Either a Bourdon gage or pressure transducer can be used
with this procedure. Just like Procedure A, the interior surfaces of the liquid and vapor chambers are maintained free of
water. The vapor pressure determined by this method differs
from the true vapor pressure of the sample due to some small
sample vaporization and includes the vapor pressure of the
air in the confined space.
The liquid c h a m b e r of the vapor pressure a p p a r a t u s is
filled with a chilled sample and connected to the vapor chamber that has been heated to 37.8C in a bath. The assembled
apparatus is immersed in a bath maintained at 37.8C until
constant pressure is observed. The pressure reading, suitably
corrected for any difference between the gage or pressure
transducer and manometer reading, is reported to the nearest 0.25 kPa (0.05 psi) as the Dry Reid vapor pressure.
Data from a 1991 interlaboratory cooperative program [55]
indicated a statistically significant bias between Procedure A
and Procedure B. The relative bias between procedures can
be corrected by applying the following equation:
For Procedure B, Gage:

25: VOLATILITY

701

FLOW SYSTEM

J*-f^*-VENTED

""^
40-80 RSI

<d. @M

PRESSURE-VAC
FOR
CAUBRATION
Z1

13' RING INSAMPLE INLET CONNECTOR

FIG. 12D 5190 apparatus.


DVPE, Procedure A = 1.029 X

(9)

For Procedure B, Transducer (Herzog):


DVPE, Procedure A = 0.984 X

(10)

where X = observed total vapor pressure using Procedure B.


ASTM D 5190, Standard Test Method for the Vapor
Pressure of Petroleum Products (Automatic
Method)
This test method is u n d e r the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.08. It was originally published in 1991. The latest edition
is D 5190-99.
This test method is suitable for gasoline samples that contain oxygenate. This method is suitable for calculation of a
dry vapor pressure equivalent (DVPE), i.e., the vapor pressure corresponding to that obtained by D 4953, using a n
equation derived from a 1991 interlaboratory cooperative
study [55].
DVPE, D 5190 = (0.954 X ) - ^ A

(11)

where:
X = m e a s u r e d total vapor pressure, in units consistent
with A, ctnd
A = 1.984 kPa (0.281 psi).
The chilled sample cup of the automatic vapor pressure instrument (Fig. 12 [47]) is filled with the chilled sample and
coupled to the instrument inlet fitting. The sample is automatically forced from the sample chamber to the expansion

chamber where it is held until thermal equilibrium at 37.8C


is reached. The total vapor pressure is measure by a pressure
trcinsducer. The measured total vapor pressure is converted
by the instrument to the DVPE value using equation 11. The
DVPE is reported to the nearest 0.1 kPa (0.01 psi) without reference to the temperature.
ASTM D 5191, Standard Test Method for the Vapor
Pressure of Petroleum Products
(Mini-Method)
This test method is under the jurisdiction of ASTM Committee D-02 a n d is the direct responsibility of Subcommittee
D02.08. It was originally published in 1991. The latest edition
is D 5191-99.
This test method is suitable for gasoline and gasoline samples that contain oxygenates. This method is suitable for CEJculation of a dry vapor pressure equivalent (DVPE) using an
equation derived from a 1988 interlaboratory cooperative
study [56].
DVPE, D 5191 = (0.965 X) - A

(12)

where:
X = m e a s u r e d total vapor pressure, in units consistent
with A, and
A = 3.78 kPa (0.548 psi).
A similar correlation equation was developed by the U.S.
Environmental Protection Agency (EPA) using its own data.
The equation they use to correlate D 5191 results to D 4953,

702

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Procedure B is:
D V P E , D5191 = (0.956 X ) - A

(13)

where:
X = measured total vapor pressure, in units consistent
with A, and
A = 2.39 kPa (0.347 psi).
Another correlation equation to correlate D 5191 results to
D 323 was developed by the California Air Resources Board
(CARB). It is given by the equation:
DVPE, D 5191 = (0.972 X ) - A

(14)

where:
X = measured total vapor pressure, in units consistent
with A, and
A = 4.93 kPa (0.715 psi)
A known volume of chilled, air-saturated sample is introduced into an evacuated, thermostatically controlled test
chamber, the internal volume of which is five times that of
the total specimen introduced into the chamber. After injection into the test chamber, the test specimen is allowed to
reach thermal equilibrium at 37.8C. The resulting rise in
pressure in the chamber is measured using a pressure transducer sensor and indicator. The total pressure measured is
converted to a DVPE using Eq 12. The DVPE is reported to
the neeirest 0.1 kPa (0.01 psi) without reference to the temperature.
ASTM D 5482, Standard Test Method for the
Vapor Pressure of Petroleum Products
(Mini-Method-Atmospheric)
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.08. It was originally published in 1993. The latest edition
is D 5482-99.
This test method is a modification of D 5191. In this test
method, the test chamber is not evacuated but rather at atmospheric pressure at the start of the test. This test method
is suitable for gasoline samples that contain oxygenates. This
method is suitable for calculation of a dry vapor pressure
equivalent (DVPE) using an equation derived from a 1991 interlaboratory cooperative study [55].
DVPE, D 5482) = (0.965 X ) + A

(15)

where:
X = measured total vapor pressure, in units consistent
with A, and
A = 0.538 kPa (0.078 psi) for Herzog Model SC970
A = 1.937 kPa (0.281 psi) for ABB Model 4100
A known volume of chilled, air-saturated sample is introduced into a thermostatically controlled test chamber at atmospheric pressure, the internal volume of which is five
times that of the total specimen introduced into the chamber.
After injection into the test chamber, the test specimen is allowed to reach thermal equilibrium at 37.8 C. The resulting
rise in pressure in the chamber is measured using a pressure
transducer sensor and indicator. The total pressure mea-

sured is converted to a DVPE using Eq 15. The DVPE is reported to the nearest 0.1 kPa (0.01 psi) without reference to
the temperature.
ASTM D 6377, Standard Test Method for the Vapor
Pressure of Crude Oil, VPCRx (Expansion Method)
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.08. It was originally published in 1998. The latest edition
is D 6377-98.
This test method covers the use of automated vapor pressure instruments to determine the vapor pressure exerted by
crude oils at temperatures between 5 and 80C. Employing
a measuring chamber with a built-in piston, a sample of
known volume is drawn from a pressurized sampling system (floating piston cylinder) into the temperature controlled chamber at 20C or higher. After sealing the chamber, the volume is expanded by moving the piston until the
final volume produces the desired V/L value. The temperature of the chamber is then regulated to the measuring temperature. After temperature and pressure equilibrium, the
measured pressure is recorded as the VPCRx of the sample.
The results are reported to the nearest 0.1 kPa with the test
temperature and vapor-liquid ratio. For results related to
ASTM D 323, the final volume of the measuring chamber
shall be five times the test specimen volume and the measuring temperature shall be 37.8C. The relative bias between the Reid vapor pressure (RVP) obtained by D 323 and
the value obtained by this method can be corrected by using the correlation equation:
RVPE, D323 = A X VPCR4(37.8-(C) + B

(16)

where:
A = 0.752
B = 6.07 kPa (0.88 psi)
ASTM D 6378, Standard Test Method for the Vapor
Pressure, VPx, of Petroleum Products, Hydrocarbons,
and Hydrocarbon-Oxygenate
Mixtures
(Triple-Expansion
Method)
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.08. It was originally pubhshed in 1998. The latest edition
is D 6378-98.
This test method is similar to D 6377 with the exception
that expansion is done in three steps to a final volume of
(x -I-1) times that of the test specimen. After each expansion,
the total pressure is determined. The partial pressure of the
dissolved air and the solubility of air in the specimen are calculated from the three resulting pressures. The temperature
of the chamber is then increased to a specified value and total pressure is determined. The vapor pressure (VPx) is calculated by subtracting the partial pressure of the dissolved
air in the liquid, which has been gas-corrected for temperature, from the total pressure. In this test method, air saturation prior to the measurement is not required. Results are reported to the nearest 0.1 kPa with the test temperature and
vapor-liquid ratio. The vapor pressure determined by this
method at a vapor-liquid ratio of 4:1 of gasoline and gasolineoxygenate blends at 37.8C can be correlated to the DVPE
value determined by ASTM D 5191. The bias of the results ob-

CHAPTER 25: VOLATILITY


tained by this test method relative to D 5191 can be corrected
by using the correlation equation:
D V P E , D 5191 VP4(37.goc) A

(17)

where:
A = 1.027 kPa (0.15 psi).
ASTM D 5188, Standard Test Method for the
Vapor-Liquid Ratio Temperature
Determination
of Fuels (Evacuated Chamber Method)
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.08. It was originally published in 1991. The latest edition
is D 5188-99.
This test method covers the determination of the temperature at which the vapor formed from a selected volume of
volatile petroleum products saturated with air at 0-1 C produces a pressure of one atmosphere in an evacuated chamber
of fixed volume. This test method is suitable for gasoline
samples that contain oxygenate. A known volume of chilled,
air-saturated sample is introduced into an evacuated, thermostatically controlled test chamber of known volume. The
sample volume is ceJculated to give the desired vapor-liquid
ratio for the chamber in use. After injection, the chamber
temperature is adjusted until a stable chamber pressure of
101.3 kPa is achieved.
The tendency of a fuel to vaporize in automotive engine
fuel systems is indicated by the vapor-liquid ratio of that fuel.
Automotive fuel specifications generally include T(V/L =20)
limits to ensure products of suitable volatility performance.
For high ambient temperature, a fuel with a high value of
T(v/L =20) indicating a fuel with a low tendency to vaporize, is
generally specified. Conversely, for low ambient temperatures, a fuel with a low T(V/L =20) value is specified.
ASTM D 2533, Standard Test Method for the
Vapor-Liquid Ratio of Spark-Ignition Engine Fuels
(Evacuated Chamber Method)
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.08. It was originally published in 1966. The latest edition
is D 2533-99.
This test method covers a procedure for measuring the volume of vapor formed at atmospheric pressure from a given
volume of gasoline. The ratio of these volumes is expressed as
the vapor-liquid (V/L) ratio of the gasoline at the temperature
of the test.
A measured volume of liquid fuel at 34-40F (0-4C) is
introduced through a rubber septum into a glycerol or mercury filled burette. The charged burette is placed in a temperature-controlled water bath. The volume of the vapor in
equilibrium with liquid fuel is measured at the desired temperature or temperatures and the specified pressure (usually
760 mm Hg). The vapor-liquid (V/L) is then calculated. If it
is desired to know the temperature corresponding to a given
V/L, the vapor-liquid ratio is determined at several temperatures, and the selected pressure. The results are plotted
and the temperature read at the given V/L. The vapor-liquid
ratio is reported to the nearest 0.1 unit and the corresponding temperature reading to the nearest 0.1 C (0.2F). If
other than 760 mm Hg the pressure in millimeters of mer-

703

cury is also reported.


ASTM D 1267, Standard Test Method for Gage
Vapor Pressure of Liquefied Petroleum (LP) Gases
(LP-GAS Method)
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.H on Liquefied Petroleum Gas. It was originally published in 1953. The latest edition is D 1267-95.
The test apparatus (see Fig. 13 [54]) consisting of two interconnected chambers and equipped with a suitable pressure
gage, is purged with a portion of the sample, which is then discarded. The apparatus is then filled completely with the portion of the sample to be tested. Thirty-three and one third to
forty volume percent of the sample content of the apparatus
is immediately withdrawn to provide adequate free space for
product expansion. The apparatus is then immersed in a water bath at the standard test temperature of 37.8C or, optionally, at some higher temperature up to and including 70C.
The observed gage pressure after temperature equilibration,
corrected for gage error and barometric pressure, is reported
to the nearest 5 kPa (0.5 psi) as the LPG Vapor Pressure at the
selected test temperature. The observed gage vapor pressure
is corrected by adding any gage correction to obtain the corrected vapor pressure. The corrected vapor pressure is then
corrected to a barometric pressure of 760 mm (29.9 in) Hg by
use of the following equations:
LPGVPcorr = observed gage pressure
+ gage correction
LPGVPeorr to 760 mm Hg

LPGVPcorr, kPa
- ( 7 6 0 - P i ) 0.1333

(CAGE)

(STRAIGHT-THROUGH

VALVE)

B (LOWER
CHAMBER)

(BLEEDER
VALVE
COUPLING)
F (INLET

VALVE)

C (UPPER C H A M B E R )

FIG. 13D 1267 apparatus.

(19)
(20)

LPGVPcorr, psi - (760 - Pi) 0.0193

(18)

704

MANUAL

3 7: FUELS

AND LUBRICANTS

HANDBOOK

TABLE 35Cross reference of international vapor pressure standards relative to ASTM distillation test methods.
ASTM
Designation
U.S.
D323
D4953
D5190
D5191
D5482
D6377
D6378
D5188
D2533
D 1267

ISO

IP

BS

AFNOR

DIN

Europe
3007

U.K.
69

U.K.
2000

France
M07-007

Germany
51754

4256

161

L P G V P c o r r to 750 mm Hg = L P G V P c o r r , k P a

(21)
- (29.92 - Pz) 3.3864
= LPGVPcorr, psi - (29.92 - P2) 0.4912

(22)

where P2 = observed barometric pressure, in. Hg.


Information on the vapor pressure of hquefied petroleum
gas (LPG) products under temperature conditions of 37.8-70
C is pertinent to the selection of properly designed storage vessels, shipping containers, and customer utilization equipment
to ensure safe handling of these products. Determination of
the vapor pressure of LPG is important for safety reasons to
ensure that the maximum operating design pressures of storage, handling, and fuel systems will not be exceeded under
normal operating temperature conditions. For LPG, vapor
pressure is an indirect measure of the most extreme low temperature conditions under which initial vaporization can be
expected to occur. It can be considered a semi-quantitative
measure of the amount of the most volatile material present
in the product.
Test Methods

for Vapor

JIS

791-1201

Japan
K2258

51 616

where P] = observed barometric pressure in m m Hg.

Other International
Determination

FTM

Pressure

All the aforementioned test methods are ASTM standcird test


methods for vapor pressure determination. Although ASTM
standard test methods are used extensively throughout the
world, there are other international vapor pressure standards
that are used and are applicable to specific geographical area.
Table 35 gives a cross reference for a n u m b e r of international
vapor pressure s t a n d a r d s a n d their corresponding ASTM
designations.

por/Liquid ratios cem be determined using a variety of techniques a n d instrumentation. For safety in handling and
transporting veirious fuels cmd lubiicemts, a variety of flash
point test methods are available.
For the most part, this chapter on volatility characteristics
of fuels and lubricants has dealt mainly with ASTM standard
test methods that are used worldwide. However, there are
other international standards that correspond to the ASTM
standards described herein that are used and are applicable
in other parts of the world. The discussions on the different
ASTM test methods mentioned in this chapter are fairly brief,
by design a n d space constraints. For m o r e details, it is
strongly recommended that the readers refer to the actual
ASTM test methods themselves.

ASTM STANDARDS
No.
D 0056
D 0086
D 0092
D 0093
D 0323
D 1160
D 1310
D 2533
D 2892

CONCLUSION
D 3278
Volatility parameters of petroleum products and lubricants
are important parameters that are related to the performance
characteristics and safety in handling and transporting these
materials. Optimum distillation and vapor pressure veJues
are paramount in the proper and efficient operation of various engines fueled by different petroleum products u n d e r
different conditions. Distillation can be carried out either at
atmospheric or reduced pressures. Vapor pressure and Va-

D 3828
D 3941
D 4953

Title
Standard Test Method for Flash Point by Tag Closed
Cup Tester
Standard Test Method for Distillation of Petroleum
Products
Standard Test Method for Flash and Fire Points by
Cleveland Open Cup Tester
Standard Test Method for Flash Point by PenskyMartens Closed Cup Tester
S t a n d a r d Test Method for Vapor Pressure of
Petroleum Products (Reid Method)
Standard Test Method for Distillation of Petroleum
Products at Reduced Pressure
S t a n d a r d Test Method for Flash Point and Fire
Points by Tag Open Cup Apparatus
Standard Test Method for the Vapor-Liquid Ratio of
Spark-Ignition Engine Fuels
S t a n d a r d Test Method for Distillation of Crude
Petroleum (15-Theoretical Plate Column)
Standard Test Method for Flash Point by SetaFlash
Closed Cup Apparatus
S t a n d a r d Test M e t h o d for Flash Point by Small
Scale Closed Cup Tester
Standard Test Method for Flash Point by the Equilibrium Method with a Closed Cup Apparatus
S t a n d a r d Test Method for the Vapor Pressure of
Gasoline and Gasoline-Oxygenate Blends (Dry
Method)

CHAPTER 25: VOLATILITY


D 5188

D 5190
D 5191
D 5236
D 5482
D 6377
D 6378

D 6450

Standard Test Method for the Vapor-Liquid Ratio


Determination of Fuels (Evacuated C h a m b e r
Method)
Standard Test Method for the Vapor Pressure of
Petroleum Product (Automatic Method)
Standard Test Method for the Vapor Pressure of
Petroleum Product (Mini Method)
Standard Test Method for Distillation of Heavy Hydrocarbon Mixtures (Vacuum Potstill Method)
Standard Test Method for the Vapor Pressure of
Petroleum Product (Mini Method-Atmostpheric)
Standard Test Method for Vapor Pressure of Cude
Oil: VPCRx (Expansion Method)
Standard Test Method Determination of Vapor
Pressure VPx of Petroleum Products (Triple Expansion)
Standard Test Method for Flash Point by Continuously Closed Cup (CCCFP) Tester

OTHER STANDARDS
No.
ISO 1523
ISO 2592
ISO 2719
ISO 3007
ISO 3405
ISO 3679
ISO 4256
ISO 6616
ISO 8708
AFNOR M07-002
AFNOR M07-007
AFNOR M07-019
AFNOR M07-036
DIN 51 356
DIN 51 376
DIN 51 567
DIN 51 616
DIN 51 680
DIN 51 751
DIN 51 754
DIN 51 755
DIN 51 758
JIS K2254
JIS K2258
JIS K2265
SIS 150 223
BIS 2000
BS 7392
IP 034
IP 036
IP 123
IP 303
IP 304
IP 069
IP 161
IP 170 (Abel)
FTM 791-1001

Title
Flash Point, Equilibrium Method, Close
Cup
Flash Point, Cleveland Open Cup
Flash Point, Pensky-Martens, Closed Cup
Reid Vapor Pressure
Distillation, Atmospheric Pressure
Flash Point, SetaFlash, Closed Cup
Vapor Pressure, LPG
Distillation, Reduced Pressure
Crude Distillation, 15/5
Distillation, Atmospheric Pressure
Reid Vapor Pressure
Flash Point, Pensky-Martens, Closed Cup
Flash Point, Abel-Pensky
Distillation, Reduced Pressure
Flash Point, Cleveland Open Cup
Crude Distillation, 15/5
Vapor Pressure, LPG
Flash Point, SetaFlash, Closed Cup
Distillation, Atmospheric Pressure
Reid Vapor Pressure
Flash Point, Abel-Pensky
Flash Point, Pensky-Martens, Closed Cup
Distillation, Atmospheric Pressure
Distillation, Reduced Pressure
Flash Point, Tag, Closed Cup
Flash Point, Abel-Pensky
Reid Vapor Pressure
Distillation, Atmospheric Pressure
Flash Point, Pensky-Martens, Closed Cup
Flash Point, Cleveland Open Cup
Distillation, Atmospheric Pressure
Flash Point, SetaFlash, Closed Cup
Flash Point, Tag, Closed Cup
Reid Vapor Pressure
Vapor Pressure, LPG
Flash Point, Abel
Distillation, Atmospheric Pressure

FTM 791-1101
FTM 791-1103
FTM 791-1201

705

Flash Point, Tag, Closed Cup


Flash Point, Cleveland Open Cup
Reid Vapor Pressure

REFERENCES
[1] Annual Book of ASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, pp. 16-37
[2] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, pp. 416^33
[3] Annual Book of ASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 18
[4] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 19
[5] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 34
[6] ASTM Research Report RR: D2-xxxx "Comparison of ASTM
Crosscheck D 86 Resuhs (Automatic versus Manual) for Various
Samples," ASTM International, West Conshohocken, PA, to be
submitted.
[7] ASTM Research Report RR: D2-1362 "Interlaboratoty Study to
Determine Precision of Automatic D 1160 and Comparison with
Manual D 1160 Results," ASTM International, West Conshohocken, PA, 1995.
[8] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 20
[9] Annual Book of ASTM Standards,Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 21.
[10] Annual Book ofASTM Standards,Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 22.
[11] Annual Book of ASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 26.
[12] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 27.
[13] Annual Book ofASTM Standards,Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 28.
[14] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 24.
[15] ASTM D-2 Interlaboratory Crosscheck Program, Motor Gasoline, ASTM International, West Conshohocken, PA, June 1999,
p. 35.
[16] ASTM D-2 Interlaboratory Crosscheck Program, Reformulated
Gasoline, ASTM InternationeJ, West Conshohocken, PA, June
1999, p. 57.
[17] ASTM D-2 Interlaboratory Crosscheck Program, Diesel Fuel,
ASTM International, West Conshohocken, PA, June 1999, p. 57.
[18] ASTM D-2 Interlaboratory Crosscheck Program, Jet Fuel, ASTM
International, West Conshohocken, PA, June 1999, p. 37.
[19] Annual Book of ASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 423.
[20] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 431.
[21] Annual Book of ASTM Standards,Vol. 5.01, ASTMlntemational,
West Conshohocken, PA, 1999, p. 417^22.
[22] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 427.
[23] Section 173.120, Ch. 1, 49 CFR, (10-1-97 edition). Codes of Federal Register, Washington DC, p. 446.
[24] Annual Book of ASTM Standards, Vol. 5.01, West Conshohocken, PA, 1999, pp. 1-10.
[25] Annual Book of ASTM Standards, Vol. 5.01, West Conshohocken, PA, 1999, pp. 44-51.
[26] Annual Book of ASTM Standards, Vol. 5.01, West Conshohocken, PA, 1999, pp. 52-61.
[27] Annual Book of ASTM Standards, Vol. 6.01, West Conshohocken, PA, 1997, pp. 126-132.

706 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


[28] Annual Book of ASTM Standards, 1997, Vol. 6.01, West Conshohocken, PA, 1997, pp. 345-351.
[29] Annual Book of ASTM Standards, Vol. 5.02, West Conshohocken, PA, 1999, pp. 596-597.
[30] Annual Book of ASTM Standards, Vol. 6.01, West Conshohocken, PA, 1997, pp. 418-420.
[31] Annual Book of ASTM Standards, Vol. 5.03, West Conshohocken, PA, 2000.
[32] Annual Book of ASTM Standards, Vol. 5.01, West Conshohocken, PA, 1999, p. 5.
[33] ASTM Research Report RR: S15-1010 "Interlaboratory Study
on Flash Point Calibration Fluids," ASTM International, West
Conshohocken, PA, 1995.
[34] Montemayor, R. G., Rogerson, J. E., Colbert, J., and Schiller, S.,
Journal of Testing and Evaluation, November 1999, pp Ali-AIl.
[35] White, E. W., "Manual on Flash Point," unpublished material.
[36] ASTM Research Report RR: D2-1350, ASTM International,
West Conshohocken, PA, 1995.
[37] Montemayor, R. G., "The EiSect of Kinematic Viscosity on the
Flash Point of Liquids Determined by ASTM 93 Procedure A,
ASTM D 93 Procedure B, and ASTM D 56," Journal of Testing
and Evaluation, November 1999, pp. 388-395.
[38] ASTM Research Report RR: D2-1464, ASTM International,
West Conshohocken, PA, 1999.
[39] AnnualBook ofASTM Standards, Vol. 5.02, ASTM International,
West Conshohocken, PA, 1999, pp. 220-246.
[40] AnnualBook ofASTM Standards, Vol. 5.03, ASTM International,
West Conshohocken, PA, 1999, pp. 197-212.

[41] Hunter, A., Technologist, Imperial Oil Ltd., Ontario, Canada.


[42] Hunter, A., Technologist, Imperial Oil Ltd., Ontario, Canada.
[43] Hunter, A., Technologist, Imperial Oil Ltd., Ontario, Canada.
[44] Hunter, A., Technologist, Imperial Oil Ltd., Ontario, Canada.
[45] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, pp. 159-166.
[46] AnnualBook of ASTM Standards, Vol. 5.03, ASTM International,
West Conshohocken, PA, 1999, pp. 32-38.
[47] AnnualBook ofASTM Standards, Vol. 5.03, ASTM International,
West Conshohocken, PA, 1999, pp. 185-189.
[48] Annual Book ofASTM Standards, Vol. 5.03, ASTM International,
West Conshohocken, PA, 1999, pp. 190-94.
[49] AnnualBook of ASTM Standards, Vol. 5.03, ASTM International,
West Conshohocken, PA, 1999, pp. 444-447.
[50] Annual Book of ASTM Standards, Vol. 5.03, ASTM International,
West Conshohocken, PA, 1999, pp. 181-184.
[51] AnnualBook ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, pp. 889-896
[52] Annual book of ASTM Standards, Vol. 5.03, ASTM International,
West Conshohocken, PA, 2000, pp. xxx
[53] AnnualBook ofASTM Standards, Vol. 5.03, ASTM International,
West Conshohocken, PA, 2000, pp. yyy
[54] AnnualBook ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, pp. 457^75
[55] ASTM Research Report RR: D2-1286, ASTM International,
West Conshohocken, PA, 1991.
[56] ASTM Research Report RR: D2-1260, ASTM International,
West Conshohocken, PA, 1988.

MNL37-EB/Jun. 2003

Elemental Analysis
R. Kishore Nadkami ^

A MAJORITY OF ELEMENTS IN THE PERIODIC TABLE ARE PRESENT IN


PETROLEUM PRODUCTS Tcinging in concentration from percent
levels of CHOS to parts per billion levels of trace elements. The metals in crude oils originate from marine animals and plants. Additives and lubricating oils have metals
purposely added to them to affect their performance in internal combustion engines.
Except for carbon and hydrogen, sulfur, oxygen, and to a
lesser extent nitrogen, are the most abundant elements typically found in crude oils. Some specific crude oils may also
contain significant amounts of vanadium and nickel, such as
those from Venezuela. Generally, it is agreed that vanadium,
nickel, and iron occur as metallo-porphyrins; mercury, antimony, and arsenic as organometallic compounds; mercury
can also occur as dissolved element mercury; molybdenum
and germanium as carboxylic acid salts, and silica and salt as
colloidal minerals [1]. Extensive data on crude oil composition are available. The so-called crude assay analysis of oils
carried out by many oil companies includes elemental analysis of sulfur, nitrogen, vanadium, nickel, and iron among
other parameters. There are probably millions of such data
points in the oil companies' proprietary databases.
Significance of Metals in Petroleum Products
The reason for interest in elemental analysis of petroleum
products is two-fold. First, many metals and nonmetals present in crude oils have a deleterious effect on the refinery and
processing operations, generally acting as catalyst poisons.
The sulfur and nitrogen compounds generated during processing are also potential environmental concerns. Second,
the lube additives and oils contain deliberately added
organometallic compounds to enhance their performance.
Though m u c h of this chemistry is proprietary, certain aspects
are universally known. Generally, the presence of sulfur,
phosphorus, alkaline earth metal, zinc, copper, etc. compounds define the composition of the additives and lubricating oils. A summary of additive elements generally used and
their effects on engine performance is given in Table 1. Two
documents published by ASTM are useful in understanding
the significance of tests carried out on petroleum products
[3,4]. In this chapter, the elemental analysis of petroleum
products will be discussed. Particulcir focus will be on the
most commonly used methods, although many other methods
may also be available.

Analysis of Petroleum Products


All well-established elemental analytical techniques have
been used for the analysis of petroleum products. Several
m o n o g r a p h s are available on this subject although all of
them are at least two decades old. A more recent monograph
has been published by ASTM, which contains papers from
several authors covering a wide variety of techniques [5].
Most prominent among these techniques are atomic spectroscopy (atomic absorption spectroscopy, AAS, and inductively coupled plasma atomic emission spectroscopy, ICPAES), X-ray fluorescence (XRF), a n d micro-elemental
techniques.
Sample

Wear Metals in Used Oils


Trace metals in used lubricating oils come from the mechanical wear from oil-wetted components of an engine or as a
contaminant from air, fuel, and liquid coolant. Generally, the
metals are present as particulate materials rather than as true
solutions. The presence of specific metals in used lubricating
oils can be associated with specific metal components of an
engine. In a normally running engine, weeir metal content
of the oil slowly increases due to normal wear. However, a
sudden increase in one or more metal concentrations in oil

' Millennium Analytics, Inc., 47 Helena Street, East Brunswick, NJ


08816.
707
Copyright'

2003 by A S I M International

Preparation

Sample preparation techniques can vary from none to quite


elaborate depending on the final measurement step. Microelemental analysis and, for some matrices, atomic spectroscopy and XRF techniques need n o sample preparation at
all. For others, it can be as simple as dilution in an organic
solvent for m e a s u r e m e n t by AAS, ICP-AES, or XRF. For
some specific analyses, a sample may be ashed (D 482 and D
874) and then brought into an aqueous acidic solution before
being analyzed by a n atomic spectroscopic technique. In
such cases, dry ashing (D 482) may not be preferred due to
the potential for the loss of volatile elements. Wet ashing using various acids or their mixtures can minimize volatilization losses. The D 874 procedure uses sulfuric acid for this
work. This method is well-suited for bringing the organic
samples into inorganic solutions, however, as a stand-alone
method for estimating the total meted oxides/sulfates in the
sample, it has several drawbacks due to the formation of intermetallic compounds during oxidation and sulfation. Generally, this results in significantly underestimating the
amount of total metal oxides using the residual weight from
D 874 compared to the ICP-AES or XRF sum of oxide results.
This means that the residual mass is less than the ICP-AES or
XRF sum of oxides [6].

www.astm.org

708

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 1Presence and role of specific elements in lubricants [2].


Element

Compounds

Borax and esters

Ba

Sulfonates, phenates, Diorganodiphosphates,


phosphonates, Thiophosphonates
Sulfonates, phenates
Dithiophosphates
Salts
Organic Compounds
Sulfonates, phenates
M0S2, dibutyldithicarbamate, phosphate
Cyclopentadienyl complexes

Ca
Cd
Cr
Hg
Mg
Mo
Ni
P
Pb
Sb
Se
Si
Sn
Zn

Metaldialkyldithiophosphates
Naphthenate
Dialkyldithiocarbamates.
Dialkylphosphorodithionates
Selenides
Silicone Polymers
Organo Compounds
Dialkyldithiophosphates, dithiocarbamates,
phenolates

TABLE 2Wear metals (elements) in used lubricating oils [2].


Elements

Wear Indication

Ag

Wrist pin bearings in railroad and auto engines, silver


plotted spline lubricating pump
Piston and bearings wear, push rods, air cooler, pump
hosings, oil pumps, gear castings, box castings
Coolant leakage in system
Bearings
Ring wear, cooling system leakage, Cr-plated parts in
aircraft engines, cylinder liners, seal rings
Wear in bushings, injector shields, coolant core tubes,
thrust washers, valve guides, connecting rods,
piston rings, bearings, sleeves, bearing cages
Wear from engine block, cylinder, gears, cylinder
liners, valuve guides, wrist pins, rings, camshaft, oil
pump, crankshaft, ball and roller bearings, rust
Cylinder liner, gear box housings in aircraft engines
Wear in bearing alloys and in oil coolers; various Moalloyed components in aircraft engines, piston rings
Antifreeze leakage
Bearings, valves, gear platings
Bearings, fuel blowby, thrust bearings, bearing cages,
bearing retainers
Crankshaft and camshaft bearings
Dirt intrusion from improper air cleaner, seal
materials
Bearings and coatings of connecting rods and iron
pistons
Various Ti-alloyed components in aircraft engines
Bearings
Neoprene seals, galvanized piping

Al
B
Cd
Cr
Cu
Fe
Mg
Mo
Na
Ni
Pb
Sb
Si
Sn
Ti
W
Zn

indicates failure or excessive wear of a specific engine component. Table 2 summarizes the typical wear metals and the
t3rpe of engine wear they may indicate, since in some cases,
more than one source may exist for certain elements.
Elemental analysis of used oils is generally performed using atomic spectroscopy techniques, particularly ICP-AES in
recent years, because of its capability of simultaneous determination of multielements. The U.S. Air Force for a n u m b e r

Performance

Antiwear agents, antioxidant, deodorant cutting


oils, greases, brake fluids
Detergent inhibitors, corrosion inhibitors, detergents, rust inhibitors, ATF, greases
Detergent inhibitors, dispersants
Stream turbine oils
Grease additive
Bactericide in cutting oil emulsions
Detergent inhibitors
Greases, extreme pressure additives
Antiwear agents, carbon deposit reduction, improved lubrication and combustion
Detergents, antirusting agents
Extreme pressure additive, greases, gear oils
Antiwear, extreme pressure, antioxidant
Oxidation and bear corrosion inhibitors
Foam inhibitors
Antiscuffing additives, metal deactivators
Antioxidant, corrosion inhibitors, antiwear additives, detergents, extreme pressure additives,
crankcase oils, hypoid gear lubricants, greases,
aircraft piston engine oils, turbine oils, ATF, railroad diesel engine oils, brake lubricants

of years conducted this kind of analysis on their jet engine


oils under the acronym "SOAP" (Spectrometric Oil Analysis
Program) [7]. As a result of the success of this program, the
U.S. Air Force, Army, and Navy established a Joint Oil Analysis Program (JOAP) in 1976. Over 100 laboratories throughout the world are involved in these analyses using AAS, ICPAES, and rotating disk electrode emission spectrometry. To
expedite in-field analysis, a portable graphite furnace multielement AAS instrument has been developed that is capable
of analyzing nine wear metals in undiluted oil samples [8]. By
use of a rapid sequential analysis mode, u p to 24 elements in
a single aspiration have been determined using a multielement AAS spectrometer [9].
Rotating disk electrode emission spectrometry either by a
single spark technique or ashing rotrode technique has been
shown to rapidly provide multielement analysis of used oils.
By anailyzing two aliquots, one directly and one after acid dissolution, differentiation can be m a d e between large and
small wear particles [10]. A correlation has been shown to exist between ICP-AES and rotrode emission techniques. Results suggest that rotrode is somewhat more effective in sampling particulates than ICP-AES [11]. ICP-mass spectrometry
has been proposed as a sensitive tool for the determination of
environmentally important elements in used oils. The technique has detection limits of parts per billion and needs no
sample preparation other than solvent dilution. However, because of the matrix interference and formation of polyatomic
species, it lacks the precision and accuracy of other atomic
spectroscopy techniques [12],
Inhomogeneous sampling, due to the effect of particle size
of wear metals, continues to be a big concern in atomic spectroscopic analysis. Severely worn engines produce large particulates. It is more important to euialyze large particles t h a n
small ones in such cases. An appreciable fraction of susp e n d e d metallic particles, especially large ones, may not
reach the atomization source; r a t h e r they collect on the
chamber walls and are washed down the drain, resulting in

CHAPTER
low biased results. Also, particulates that reach the source
may not be "totally" atomized. To overcome this particle size
effect, the so-called particle size independent methods have
been developed, which consist of heating the oil in a small
amount of minerad acids and then diluting with an appropriate organic solvent [13].
At present, in the D2 committee, the only available method
for the determination of wear metals in used oils is D 5185,
which is a n ICP-AES method. Two methods based on the
rotrode technology have also been recently published: D 6595
and D 6728.
D02 Test Methods
There are about 80 test methods under the jurisdiction of
Subcommittee 3 on Elemental Analysis (see Table 3). These
m e t h o d s could be roughly classified according to their
principle chemical/physical technique that is utilized in the
analysis of samples.
Classical

Wet Chemistry

Methods

These methods are based on the gravimetric-titrimetric finish for the final determination of the species of interest. Although at one time widely used, they have been largely displaced by spectrometric techniques particularly for metals in
most m o d e m laboratories. Many times these methods are
considered as the referee methods; however, the expertise in
conducting these tests is hard to find today. These methods
include:
Analysis
Phosphorus

Vanadium
Nitrogen
Lithium/Sodium
Chlorine
Lead
Sulfur, active
Sulfur, mercaptan

Bomb

Combustion

ASTM

Technique

D1091
D3231
D4047
D 1548
D3228
D3340
D 4929A
D5384
D3341
D3348
D4952
D3227

Photometry and Gravimetry


Photometry
Titrimetry
Photometry
Kjeldahl Titration
Flame Photometry
Potentiometry
Titrimetry
Titrimetry
Colorimetry
Colorimetry
Potentiometry

Methods

These methods utilize combustion in a b o m b (a sealed metal


container pressurized with oxygen and an ignition source) or
an enclosed flame to concentrate the species of interest
generally a gaseous elementin a n aqueous solution followed by a final determination such as gravimetry or titrimetry. Similar to the classical wet chemistry methods cited
above, many of these methods are also considered as referee
methods, but have been increasingly replaced by m o d e m instrumental methods of analyses. These methods include:
Analysis

ASTM

Detection Technique

Chlorine
Hydrogen
Sulfur

D808
D 1018
D 129
D 1266
D1552
D2784

Gravimetry
Gravimetry
Gravimetry
Gravimetry or Titrimetry
Titrimetry or IR Detection
Titrimetry or Turbidimetry

26: ELEMENTAL

ANALYSIS

709

Atomic Spectroscopic Methods


The most widely used techniques for metal analysis in
petroleum products are atomic absorption (AAS) and inductively coupled p l a s m a atomic emission (ICP-AES) spectroscopy methods. Other related techniques such as flame
emission spectroscopy, graphite furnace AAS, and hydride
generation AAS, although still viable, do not appear to be popular at least in the petrochemical analysis area, perhaps because of the adequate sensitivity offered by AAS and ICP-AES.
Atomic

Absorption

Spectrometry

(AAS)

This widely used metal determination technique, not only in


petrochemicals, but in all industrial application areas, has
evolved into a "cookbook" type of analysis. Many m o d e m instruments are fully automated. The technique is applicable to
nearly 70 elements with precision and accuracy of 1-3%
achievable u n d e r optimal conditions. Once the material is in
solution, the analysis time is less than a minute per sample although time depends on n u m b e r of elements/sample. Other
than refractory oxide-forming elements, detectability by AAS
is less than p p m for most metals. Although mostly free from
atomic spectral interferences, AAS does suffer from molecular spectral, ionization, chemical, and matrix interferences.
However, most of these are well documented and are taken
care of during routine analyses.
In AAS, a sample solution is vaporized and the elements atomized at high temperatures. The element concentration is
determined by absorption of light of a characteristic wavelength emitted by a primary source. The light source is typically a hollow cathode lamp, which consists of a tungsten anode and a cylindrical hollow cathode enclosed in a gas-tight
chamber. The cathode contains the analyte metal; usually individual lamps are needed for each element, although some
multielement lamps are available. The detector is usually a
photomultiplier tube. A monochromator is used to isolate the
spectral line, and the light source is modulated to discriminate against continuum radiation from atomization source.
Usually the AAS instruments use a flame as the atomization
source. The fuel/oxidant composition and ratio determine the
temperature of the flame. An air-acetylene flame is used for
most elements. The NaO-acetylene flame is used for elements
that form stable monoxides in air-acetylene flame.
There are literally hundreds of papers published using AAS
for industrial products including petrochemicals. An exhaustive review on this subject is available, although somewhat
dated [14]. There are several standard test methods based on
this technique in the D2 committee; these include:
Analysis
Aluminum/silicon in fuel oils by ashing, fusion and AAS
Lead in gasoline by complexation and AAS
Manganese in gasoline by AAS
Trace metals in gas turbine fuels
Additive metals in oils by AAS
Trace metals in coke by ashing, fusion, and AAS
Ni, V, Fe, and Na in crude oils and residual fuels by AAS
direct or after ashing

Graphite Furnace
(GFAAS)

Atomic

Absorption

ASTM
D 5184B
D 3237
D 3831
D 3605
D 4628
D 5056
D 5863

Spectrometry

This technique uses graphite furnace rather than a flame as


an atomization source, a n d it improves the sensitivity of

710 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 3D02.SC3 Elemental analysis subcommittee test methods.
Method Designation
D 129
D482
D808
D874
D 1018
D 1091
D1266
D 1317
D 1368
D 1548
D1552
D 1839
D2622
D2784
D3116
D3120
D3227
D3228
D3229
D3230
D3231
D3237
D3340
D3341
D3348
D3431
D3605
D3701
D3831
D4045
D4046
D4047
D4294
D4628
D4629
D4808
D4927
D4929
D4951
D4952
D5056
D5059
D5184
D5185
D5291
D5384
D5453
D5600
D5622
D5708
D5761
D5762
D5863
D6334
D6443
D6445
D6470
D6481
D6595
D6667
D6728
D6732

Current Year of Publication


2000
2000
2000
2000
2000
2000
1998
1989 (WD)
1989 (WD)
1992 (WD)
2001
1991 (00)
1998
1998
1989 (WD)
1996
2000
2001
1988 (WD)
1999
1999
1997
1998
2000
1998
1987 (WD)
2000
2001
1998
1999
1991 (00)
2000
1998
1997
1996
2001
2001
1999
2000
1997
1996
1998
2000
1997
2001
1995
2000 (00)
1998
1995
2000 (00)
1996
2001
2000
1998
1999
1999
1999
1999
2000
2001
2001
2001

Subject

Sulfur in Petroleum Products (Bomb Method)


Ash from Petroleum Products
Chlorine in Petroleum Products (Bomb Method)
Sulfated Ash
Hydrogen in Petroleum Fractions
Phosphorus in Oils and Additives
Sulfur in Petroleum Products (Lamp Method)
Chlorine Na-Alcoholate Method
Lead in Reference Fuels
Vanadium in Heavy Fuel Oil
Sulfur in Petroleum Products (High Temp. Method)
Amyl Nitrate in Diesel Fuels
Sulfur by X-ray Spectroscopy
Sulfur in LPG
Trace Lead in Gasoline
Sulfur in LPG by |x coulometry
Mercaptan Sulfur by Potentiometry
Modified Kjeldahl Method for Nitrogen
Low Level Lead in Gasoline
Salts in Crude Oil
Phosphorus in Gasoline
Lead in Gasoline by AAS
Li and Na in Lubricating Greases
Lead in Gasoline (I CI method)
Field Test Method for Pb in gasoline
Nitrogen by Microcoulometiy
Metals in Gas Turbine Fuels
Hydrogen by NMR
Mn in Gasoline by AAS
Sulfur by Hydrogenolysis
Alkyl Nitrate in Diesel Fuels
Phosphorus by Wet Chemistry
Sulfur by EDXRF
Additive Metals by AAS
Nitrogen by Chemiluminescence
Hydrogen by NMR
Additive Metals by XRF
Organic Chloride in Crude Oil
Additive Metals by ICPAES
Active Sulfur Species
Metals in Petroleum Coke by AAS
Lead in Gasoline by XRS
Al and Si by ICPAES
Metals by ICPAES
Instrumental CHN
Field Test Kit for Chlorine
Sulfur by UV Fluorescence
Metals in Petroleum Coke by ICPAES
Oxygen by Reductive Pyrolysis
Ni, V, Fe in Oils by ICPAES
Practice for Emulsification
Nitrogen by Boat Chemiluminescence
Ni, V, Fe, Na in Oils and Fuels
Sulfurs in GasoUne by WDXRF
Metals in Lubes by WDXRF
Sulfur in Gasoline by EDXRF
Salt in Crude
Metals in Lubes by EDXRF
Wear Metals in Lubes by Rotrode
Sulfur in LPG by UV-Fluorescence
Contaminants in Fuels by Rotrode
Copper in Jet Fuels by GFAAS

(WD): Standard is withdrawn from publication.


flame AAS by several orders of magnitude. Even though
GFAAS covers all elements which can be determined by AAS,
the strength of GFAAS lies in the determination of elements
at sub-ppm levels, and those that are somewhat difficult to do
by AAS, e.g., V, Ni, Pb, Sb, As, and Cd. It is not an ideal technique for additive metals in lube oils since the high concen-

tration of the metals in this matrix necessitates very large dilutions. The technique uses m u c h smaller sample than that
required for flame AAS, but it takes longer time for analysis.
Matrix interferences are also m o r e significant t h a n with
flame AAS, and this translates into poorer precision (and accuracy).

CHAPTER
Most applications of GFAAS in the petroleum products
area have been in research. Recently, a method to measure
copper in jet fiiels by GFAAS has been published (D 6732).
Inductively
Coupled Plasma-Atomic
Spectrometry
(ICP-AES)

Emission

The most significant development in atomic spectroscopy in


the last two decades has been the development and wide popularity of the ICP-AES technique. It is increasingly replacing
AAS instruments in the laboratories worldwide as a reliable,
accurate, precise, and rapid technique that is sensitive to ppb
levels for multielement aneJysis of petroleum products. It is
second only to graphite furnace AAS in its low detection limits for most elements. However, its wide dynamic range
(10''-10*) makes it unique among other atomic spectroscopic
techniques. This permits the measurement of percent levels
of some elements Eind p p m levels of others in the same solution with one aspiration without multiple dilutions. Because
of the high temperature of the plasma, chemical and matrix
interferences c o m m o n in flame AAS are not seen in ICP-AES.
In ICP-AES, the liquid sample sprayed into the argon
plasma through a nebulizer is vaporized, atomized, ionized,
and electronically excited. The excited state ions and atoms,
in returning to their ground states, emit photons of wavelengths characteristic of an element. The emitted light is
measured by a polychromator in a simultaneous spectrometer or by a single photomultiplier in a scanning or sequential
spectrometer. Nebulizers are a critical pEirt of the instrument
and a n u m b e r of models have been devised to overcome the
physical interferences encountered in nebulizers of earlier
yecirs. Commonly used nebulizers are glass concentric pneumatic, cross flow or grid pneumatic, more advanced ultrasonic, and Babington high solids nebulizers. See Ref. 15 for a
good review of ICP-AES instrumentation.
A major drawback of the ICP-AES technique is the spectral
interference that makes accurate trace element determination
difficult in complex matrices. High-resolution spectrometers
are used to separate the overlapping spectral lines and correct
for background interferences. However, usually the atomic
emission lines and their associated interfering wavelengths
are well characterized, and normEdly interference-free lines
can be selected for the elements of interest. Many sensitive
lines are "ion" lines, also. Some typically used wavelengths
a n d their detection limits for oil aneJysis are given in Table 4.
The sample preparation is usually simple in ICP-AES involving 10- to 100-fold dilution in an organic solvent such as
kerosene, xylene, methyl ethyl ketone, methyl iso-butyl ketone, etc. The organometallic standards ctre used for instrument calibration.
The viscosity of oil samples plays em important role in accurate ICP-AES measurements. Usually, base oil is added to
samples and calibration standards, to approximately equate
the viscosity. In an important piece of research, Banscd and
McElroy [16] showed that viscosity modifiers can produce
severe biases in ICP-AES measurements due to the changes
in the nebulizer aerosol formation affecting the ICP-AES
torch temperatures. The biases are largest for low excitation
potential elements. This problem can be solved by using both
an internal standard (e.g., Cobalt) and adequate sample dilution (e.g. 100-fold). This work was independently confirmed
by Jansen et al [17]. In light of this work, both D 4951 and D

26: ELEMENTAL

ANALYSIS

711

TABLE 4ICPAES Analytics for oil analysis [2].


Element
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
K
Mg
Mn
Mo
Na
Ni
P
Pb
S
Sb
Si
Sn
Ti
V
Zn

Wavelength, nm
328.07
308.22;
249.77
455.40;
393.37;
214.44;
228.62
276.65;
324.75;
259.94
766.49
279.55;
257.61;
202.03;
589.00
341.47;
214.91;
220.35;
190.00;
231.15;
288.16;
283.99;
334.94;
292.40;
206.20;

309.27; 396.15
233.53; 493.41
317.93; 315.88
226.50; 228.80
283.56; 267.71
327.40

285.21; 279.08
357.60; 293.30
204.60; 281.62
231.60;
178.29;
283.31
180.73;
206.84
251.61
189.99;
337.28;
309.31;
213.86;

216.56
177.51
182.04

242.95
350.50
311.07
202.55

Detection and Upper Limits, ppm


0.005-100
0.02-100
0.05-100
0.0003-50
0.001-20
0.007-100
0.007-100
0.001-100
0.002-50
0.004-100
0.2-50
0.0004-20
0.001-50
0.014-100
0.015-100
0.02-100
0.10-200
0.05-100
0.05-100
0.05-100
0.02-100
0.05-100
0.001-100
0.005-100
0.005-20

NOTE: Other suitable interference-iree wavelengths may also be used.


5185 test methods for the determination of metals in additive, lube oils, base oils, and used oils have been modified to
include the mandatory addition of an internal standard and
increasing the dilution factor.
Numerous applications of ICP-AES in the petroleum products area have been published. Memy of these were reviewed
in Ref. 2. Some of the work published since then is reviewed
here.
Robotics can be used for sample dilutions in ICP-AES a n d
XRF. Generally, the precision of XRF was found to be slighdy
better than that of ICP-AES [18]. Use of an internal standard
and kerosene as a preferred solvent has been shown to offer
superior precision for a n u m b e r of elements in crude oils [19].
Hausler and Carlson have reviewed vEirious sample preparation techniques used for petroleum products before ICP-AES
measurements were made at the Phillips Petroleum Company
[20]. Similar work performed in Exxon has been reviewed by
Botto [21]. Applications of more advanced ultrasonic nebulizers in ICP-AES have been described by Botto [22,23].
Although at present, there are only five test methods utilizing this technique in D2 committee, it is expected that this
will increase in the future. In many laboratories, ICP-AES instruments are replacing AAS instruments because of the former's superior capabilities discussed earlier in this chapter.
Generally, these methods are used in the petrochemical laboratories for the determination of a n u m b e r of elements in a
wide concentration range in a variety of petrochemiccJ matrices. These methods include:
Analysis
Additive elements in lubricating oils
Additive and trace elements in fresh and used lubricating
oils and base oils
Aluminum and silicon in fuel oils after ashing ind fusion
Trace metals in petroleum coke after ashing and fusion
Ni, V, and Fe in crude oils and residual fuels sifter ashing
or dissolution in a solvent

ASTM
D 4951
D 5185
D 5184A
D 5600
D 5708

712

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Although not ICP-AES, two methods based on atomic


emission spectroscopy (D 6595 and D 6728) have been pubHshed using rotrode to determine contaminants and wear
metals in lube oils and fuels, respectively.

reviewed in Ref. 2. There are, however, no test methods available in Subcommittee 3 jurisdiction at present that utilize ion
chromatography for the elemental analysis.
MicroElemental Analysis Methods

Inductively Coupled Plasma-Mass


Spectrometry
(ICP-MS)
This technique combines the power of ICP for atomizing and
ionizing the samples with the sensitivity and the selectivity of
mass spectrometric detection. By combining ICP-MS with
solution separation techniques such as high-pressure liquid
chromatography (HPLC) or ion chromatography (IC), the
technique can be used for metal speciation studies. The technique can simultaneously determine nearly 70 elements in a
sample with detection limits down to parts per trillion for
most elements. However, often these low detection limits
cannot be achieved in complex matrices. The matrix effects
are common to ICP-MS just as they are in ICP-AES. Many internal standards are required to cover the entire mass range
because of mass bias. A serious concern in ICP-MS measurement is the sample preparation step. Extreme care must be
exercised in controlling the blank contamination because of
the generally ultra-low levels of trace elements being determined.
In spite of the versatility of this technique, the applications
in the petrochemicals field are limited. Al-Swaidan [24] used
dilution of samples in xylene followed by nitric acid extraction to determine low levels of several elements in Saudi Arabian crude oil and gasoline samples. Williams [12] has used
ICP-MS to analyze diluted waste oils for the determination of
several trace elements as a screening tool to decide whether
the used oils can be recycled or must be disposed of as hazardous wastes. McElroy et al. [25] have demonstrated the use
of this technique, using cobalt as the internal standard, in determining vanadium, phosphorus, nickel, and calcium in a
number of crude oils. More interestingly, they have combined HPLC with ICP-MS to identify selenium, nickel, and
vanadium species in crude oils.
The D02.SC3 subcommittee has not published any ICP-MS
test methods so far. An informal survey did not indicate that
ICP-MS was being widely used in the petrochemical laboratories, perhaps because of the high cost of the instrumentation, as well as ICP-AES offering adequate sensitivity in most
cases.
Ion Chromatrography
This technique has revolutionized the determination of anionic species from individual wet chemistry techniques to
one simultaneous multi-anion instrumental method. The
technique is a combination of ion exchange chromatography,
eluent suppression, and conductometric, amperometric, or
UV-visible detection. It needs only microliters of a sample
and can rapidly determine several anions in a large dynamic
range in a single sample. The analysis, however, is aqueous
based which means petrochemical samples must be brought
into aqueous solution generally by combustion in an oxygen
atmosphere in a closed vessel.
The technique has been used to determine halogens, sulfur,
phosphorus, and nitrogen in samples such as fuel oil, gasoline, diesel fuel, waste oil, coke, etc. The literature has been

The micro- in this category of methods usually refers to the


presence of these non-metals in minor quantities in the
petroleum products. It may also reflect on the fact that usually a very small quantity of sample is used in the analysis. In
all of these cases, the sample is combusted and the element
of interest in the gases produced is detected by a variety of
techniques. These methods are widely used in the petrochemical industry for the analyses of a variety of different
products. Essentially all these methods are based on the commercially available instruments. This list continues to grow
as more commercial instruments become available. These
methods include:
Analysis
Carbon-HydrogenNitrogen
Chlorine, Organic
Nitrogen
Oxygen
Sulfur

ASTM
D5291
D 4929B
D4629
D5762
D5622
D3120
D4045
D5453
D6667

Technique
IR or GC
Microcoulometry
Chemiluminescence
Chemiluminescence
Reductive Pyrolysis
Oxidative Microcoulometry
Hydrogenolysis and
Rateometric Colorimetry
UV Fluorescence
UV Fluorescence

Generally, these methods eire free from interference from


other constituents of the sample, are capable of rapid and
many time automated analyses, and have precisions of about
2-5% dependent on the concentration level of the analyte
(Table 5).
Neutron Activation Analysis (NAA)
A large body of data exists on the applications of this technique to crude oil and petroleum products. However, because
of the difficulty of access to a nuclear reactor and associated
radiation hazards, it has found little use in petrochemical or
oil company laboratories.
Since the petroleum products contain essentially a
CHO matrix that does not get activated during thermal
neutron irradiation, there is very little background interference. However, there could be interference from other trace
element nuclei present in the sample. Generally, these isoTABLE 5Precision of MicroElemental test methods.
Analysis

Test Method

Repeatability

Reproducibility

Carbon
Chlorine
Hydrogen
Nitrogen

D5291
D 4929B
D5291
D4629
D5291
D5762
D5622
D3120
D4045
D5453

(X + 48.48) 0.0072
0.7 (X)O-*
(X''-^) 0.1162
0.15 (X)''-^''
0.1670
0.009 (X)
0.06 - 0.81%
28%
0.16 V ^
0.1867(X)"^

(X +48.48) 0.018
1.0 (X)"-^'
(X-5) 0.2314
0.85 iXf-^'*
0.4456
0.291 (X)
0.26 - 0.81%
38%

Oxygen
Sulfur

X: Average value of two results.

0.26 VJ
0.2217(X)0-^

CHAPTER
topic interferences are well-known and suitable alternate
interference-free g a m m a rays can be used for quantitative
analysis. The literature until the late '80s has been reviewed
earlier [2].

X-Ray Fluorescence Spectrometry (XRF)


Similar to AAS and ICP-AES, XRF is a technique widely used
in the petroleum products testing laboratories mainly for the
analyses of sulfur, chlorine, and additive metals. The technique is non-destructive, has multi-element capability, and
high level of precision combined with low (ppm level) detection limits. The cost of the instrumentation, particularly a
wavelength dispersive XRF, is quite high, typically greater
than that of ICP-AES. However, many dedicated inexpensive
single element instruments are available.
In the XRF technique, a sample is bombarded with X-rays
resulting in ejection of electrons from the inner shells of the
target atoms. In the process, X-rays of discrete characteristic
energy are emitted as electrons from the outer shells replace
the ejected electrons. Every element produces a unique secondary X-ray spectrum whose intensity is proportional to the
element concentration in the sample. XRF has been typically
applied to all elements above the atomic n u m b e r 10 (neon).
The basic components of X-ray spectrometers are a source of
excitation consisting of a high p o w e r X-ray tube (usually
comprised of a tungsten, molybdenum, chromium, rhodium,
or scandium target), a wavelength or an energy dispersive
spectrometer for selecting the characteristic fluorescent signals, and integrating or counting circuits for measurements.
Due to n u m e r o u s interelement matrix effects, standards
with compositions similar to the samples need to be used and
corrections m a d e for matrix element absorption and enhancement of the analyte element. For solids, particle size
and shape can affect accuracy.
Many of these interferences and matrix effects can be compensated by corrective techniques such as standard addition,
internal standards, matrix dilution, thin film method, and
mathematical corrections, provided interference and matrix
effects are accounted for.
Speed, convenience, minimal sample preparation, and its
nondestructive nature are the main advantages of the XRF
technique. Inherently very precise, XRF rivals the accuracy of
wet chemistry techniques in the analysis of major constituents, provided interferences and matrix effects are accounted for.
The two main types of XRF instrumentation available can
be divided into wavelength (WDXRF) and energy dispersive
(EDXRF) instruments. In WDXRF, primary X-rays irradiate
the sample and generate fluorescent X-rays. These are then
diffracted by a crystal. A goniometer selects the geometry between the crystal and detector. The geometry controls the detection of X-rays from the element of interest. Different crystals can have different sensitivities a n d cover different
wavelength ranges, and are used depending on the X-ray
wavelength of the analyte element. Many commercial
WDXRF instruments have two detectors and u p to six crystals
to optimize the instrumental conditions for each element.
The EDXRF instrument generally uses a lower power X-ray
tube. The emitted X-ray radiation from the sample impinges
directly on a detector, typically a Si(Li), which generates a

26: ELEMENTAL

ANALYSIS

713

change proportional in magnitude to energy of the incident


X-ray. The series of changes are sorted and counted by a
multi-channel analyzer. Simultaneous determination of all
elements (with atomic numbers greater than Mg) is possible.
Optimization of specific elements is accomplished through
the use of secondary targets and filters. Radioisotope sources
can be used in place of X-ray tubes in instruments designed
for limited element applications.
Sensitivity in X-ray fluorescence analysis is highly dependent on the sample matrix. Detection limits are typically in
the p p m range, with the highest sensitivity observed for the
transition metals. Sensitivity declines significantly for the
lower atomic n u m b e r elements. Resolution and sensitivity of
EDXRF is typically a n order of magnitude worse t h a n for
WDXRF. However, the cost of an EDXRF spectrometer, especially the single-element models, can be ten times less than
for a WDXRF spectrometer.
XRF is a well-established technique with numerous applications in most petrochemical testing laboratories. The pre1990 literature in this area was reviewed in Ref. 2. See Ref. 26
for a review of currently available instrumentation in both
small and large WD- and ED-XRF instruments. Sieber et al.
have described the use of XRF in complementary fashion to
other spectroscopy techniques for the determination of lubricant additive elements [27]. EDXRF has been applied to
the determination of vanadium, nickel, and iron in petroleum
and petroleum residua [28], and Mg, P, CI, K, Zn, Ca, and Mo
in crude oils and lubricating oils [29]. Both qualitative and
quantitative analysis of low atomic n u m b e r elements (e.g.,
magnesium) have recently become feasible due to the use of
synthetic multilayer crystals and improvement in detector
windows and associated electronics [30].
Several ASTM m e t h o d s use a n XRF technique a n d are
complementary to other methods using AAS or ICP-AES
listed earlier. All three techniques should produce equivalent
results when properly followed. The XRF methods include:
Analysis
Lead in gasoline with Bi internal standard or direct
comparison
Metals in lubricant and additive components
Sulfur in gasoline and methanol fuels
Sulfur in petroleum products
Metals in lube oils
Metals in lube oils
Sulfer in gasoline
Sulfer in gasoline

ASTM
D 5059
D 4927
D 2622
D 4294
D 6443
D 6481
D 6334
D 6445

In general, AAS, ICP-AES, and XRF have similar precision


for the most commonly determined elements in petroleum
products. Table 6 illustrates this by comparing the repeatability and reproducibility of D 4628 AAS, D 4927 XRF, and D
4951/D 5185 ICP-AES methods for selected additive elements
in lube oils.
Miscellaneous

Methods

There are two methods available for the determination of hydrogen content of aviation turbine fuels, and of light and
middle distillates, gas oils and residua (D 3701 and D 4808,
respectively), based on nuclear magnetic resonance.
Perhaps the oldest methods used in the elemental analysis
of petroleum products are those for the determination of ash

714

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

TABLE 6Precision of alternate methods for elemental analysis of lubricating oils.


Repeatability
Element*^

D 4628 (AAS)

Barium
Calcium
Magnesium
Phosphorus
Sulfur
Zinc

0.011
0.0050
0.0037
0.0054

D 4927 (XRF)
A
B
0.0027
0.0047

0.0015
0.0034

0.0065
0.0047
0.002

0.0042
0.0042
0.0019

Reproducibility
D 4927 (XRF)

ICP-AES
D4951

D5185

D 4628 (AAS)

0.011
0.0058
0.0032
0.0026
0.016
0.0022

0.0023
0.0032
0.0061
0.0071
0.0132
0.0066

0.04
0.017
0.015
0.012

ICP-AES

D4951

D5185

0.006
0.018

0.016
0.016

0.011
0.020
0.0051

0.018
0.019
0.012

0.019
0.0083
0.012
0.010
0.061
0.0072

0.034
0.0119
0.0147
0.0136
0.021
0.0166

[ mass percent elemental concentration.

and sulfated ash (D 482 and D 874, respectively). The methods need a minimal a m o u n t of apparatus, perhaps available
in any laboratory. Because of their apparent simplicity, the
tests, however, may give an erroneous impression about the
composition of complex products. The sulfated ash method
(D 874), in particular, is fraught with drawbacks resulting in
extremely erroneous d a t a inconsistent with the chemical
composition of the additive products. This happens because
of the formation of a n u m b e r of nonstoichiometric compounds rather than only sulfates during sulfation and combustion [6]. It has been suggested that this empirical test be
replaced by m o d e m instrumented analysis, such as AAS, ICPAES, or XRF, which give m u c h more precise information on
the metal content of the petroleum additive products.

TABLE 7Standard reference materials for elemental analysis of


petroleum products available from NIST.
Sample Type
Crude oil
Diesel fuel oil
Fuel oil, Distillate
Fuel oil. Residual

Kerosene
Lube additive
Lubricating oil

Petroleum coke
Reference Fuel

NIST Designation
8505
2723; 2724a
1624c
1618
1634c
1619a; 1620b; 162Ie;
1622e; 1623c; 2717
1616a; 1617a
1848
1818a
1819a
1836
1083; 1084a; 1085a
2718; 2719
2712-2715

Certification
Vanadium
Sulfur
Sulfur
Vanadium and Nickel
Trace elements
Sulfur
Sulfur
Additive Elements
Chlorine
Sulfur
Nitrogen
Wear Metals
Trace Elements
Lead

Standard Reference Materials


Standard reference materials (SRM) play a vital role in evaluating new anal3?tical test methods, assessing the laboratory
capability for performing the tests with required precision
and accuracy, and for routine quality assurance of the data
generated in the laboratories. Often SRMs are also used as
the calibrating materieds.
National Institute of Standards and Technology (NIST) is
perhaps the leading source of extremely reliable SRMs in a
variety of matrices. NIST certifies each SRM based on replicate analysis values obtained by at least two independently
based methods. There are other national bodies in the U.K.,
Germany, etc. which also produce similar SRMs. There are
also some commercial companies that supply reference materials, although their certified values do not undergo the rigorous scrutiny that NIST undertakes.
The NIST SRMs useful for elementzJ aneJysis Eire listed in
Table 7. As can clearly be seen, it would be highly desirable
to have additioneJ SRMs available for other analyses, particularly for additive elements in adpacks and lubricating oils.
NIST is currently engaged in preparing several other materials for certification.
Another source for reference materials is from the industry
round robins such as the Inter-Laboratory Cross-Check Programs (ILCP) conducted by Committee D2. About 1800 laboratories worldwide take part in these thrice-a-year crosschecks. At present, 16 materials are used in these cross-checks:
engine oil lubricants, #2 diesel fuel, aviation turbine fuel, motor gasoline, #6 fuel oil, automatic transmission fluid, gear oil,
automotive lubricants additives, industrial gear oil, turbine oil,
reformulated gcisoline, base oil, petroleum wcix, crude oil, inservice diesel oil, and lubricating grccise. However, the use of

these aneJyzed samples as reference materials need to be considered with caution. These are consensus values and not certified values. Experience in these programs has shown that a
large degree of uncertainty is associated with the calculated
mccin vjJues. Hence, such materials are better suited EIS quality
control materials rather than as primary reference standards.
ASTM Proficiency Testing
A n u m b e r of cross-checks Eire conducted by the coordinating
Subcommittee 92 on a four-month cycle. This program has
been extremely popular worldwide providing the participating laboratories with a measure as to how well they are performing against their counterparts in the oil industry as well
as against the precision stated in the ASTM test methods. A
large n u m b e r of Subcommittee 3 test methods are utilized in
these exercises (Table 8). The reproducibilities obtained in
these programs have genercdly been poorer than those specified in the ASTM test methods. With recent changes in the
statistical calculations to delete the outliers, the precisions
have improved and are somewhat consistent with the published reproducibilities. To help the laboratories improve
their test precision, Subcommittee 3 is adding non-mandatory "helpful hints to the analyst" sections a n d mandatory
quality control sections to the test methods under its jurisdiction.
International Test M e t h o d s Harmonization
With the increasing globalization of commerce in the petrochemicals industry, many national standeirds bodies are heir-

CHAPTER 26: ELEMENTAL ANALYSIS


monizing the test methods usage in different countries. Many
companies use alternate test methods in their product specifications to ensure that the best methods quoted are viable in
the countries where the products are sold. In such instances,
it is vital that the a h e m a t e method designations quoted produce equivalent results. Table 9 lists the test methods for elemental analysis issued by six leading national standards organizations: ASTM for U.S.A., IP for U.K., DIN for Germany,
ISO, JIS for Japan, and AFNOR for France. This table is excerpted from a m u c h larger table of equivalent test methods
available in Ref. 32 by Nadkami. Clearly, m u c h more work
on test method harmonization is necessary when Tables 3
emd 9 Eire compared.

715

Future Developments
A n u m b e r of new test methods for elemental analyses are being developed in the D02 Subcommittee 3. Many are for the
determination of trace elements and some for specific analysis in a specific matrix. Some of the work underway at the industry request includes:
lead, m a n g a n e s e , p h o s p h o r u s , and silicon in n a p h t h a ,
gasoline, and light petroleum products by ICP-AES;
phosphorus in reformulated gasoline by WDXRF;
sulfur and trace metals in petroleum coke by XRF;
chlorine in gasohol;
hydrogen by pulsed NMR;

TABLE 8Subcommittee 3 test methods used in ASTM D2 Interlaboratory Cross-check programs.


Product
Engine Oil Lubricants
#2 Diesel Fuel
Aviation Turbine Jet A
Motor Gasoline
#6 Fuel Oil
ATF
Automotive Lubricant Additives
Reformulated Gasoline
Gear Oil
Base Oil
Crude Oil
In-service Diesel Engine Lubricating Oil

Analysis (Test Method)


Additive elements (D 4628; D 4927; D 4951; D 5185); Ash (D 482);
Ash, sulfated (D 874); nitrogen (D 3228, D 4629; D 5291, D 5762);
sulfur (D 129, D 1552, D 5453).
Ash (D 482); sulfiir (D 129, D 2622, D 4294, D 5453); C-H-N (D 5291)
Mercaptan sulfur (D 3227); sulfur (D 1266, D 1552, D 2622, D 4045,
D 4294, D 5453)
Lead (D 3237); phosphorus (D 3231); sulfur (D 1266, D 2622, D 3120,
D 4294, D 5453)
Al and Si (D 5184); Ash (D 482); Nitrogen (D 3228, D 4629, D 5291,
D 5762); sulfur (D 1552, D 2622, D 4294, D 5453); V, Ni, Fe, Na
(D 1548, D 5708, D 5863)
Additive Elements (D 4628, D 4927, D 4951, D 5185); Nitrogen
(D3228, D 4629, D 5291, D 5762); Sulhxr (D 1552)
Additive Elements (D 4628, D 4927, D 4951, D 5185); Ash (D 482);
Ash sulfated (D 874); Nitrogen (D 3228, D 4629, D 5291, D 5762);
sulhir(D1552)
Sulhir (D 2622, D 3120, D 4294, D 5453)
Additive Elements (D 4628, D 4951, D5185); Ash sulfated (D 874);
sulfur (D 4294).
Nitrogen (D 4629, D 5291); Sulfur (D 2622, D 4294).
Ni-V-Fe (D 5708, D 5863); Nitrogen (D 4629, D 5762); Sulfur (D2622,
D 4294)
Additive Elements (D 5185, D 6595)

TABLE 9 --International equivalent test methods for elemental analysis of petroleum products."
Analysis

ASTM (D)

IP

DIN (51-)

Ash
Lead-AAS
ICl
Volumetric
WDX
Metals-AAS
ICP
XRF
Nitrogen-Kjeldahl
Chemilum
Phosphorus in Lubes
Si/Al in Fuels
Sulfated Ash
Sulfur-Bomb
EDX
High Temp.
Lamp
Mercaptan
Microculometry
Oxidative microculometry
WDX
Wickbold
Vanadium
V, Ni by AAS

482
3237
3341
2547
2599
4628
4951
4927
3228
4629
4047
5184
874
129
4294
1552
1266
3227
3120
3246
2622
2785
1548
3605

4
428
270
248
228
308
437
407

575

6245

EN 237
2083
769T2
391

EN 237

" Excerpted from Ref. 32.

379
149
377
163
61
336

ISO

3830

JIS (K-)

AFNOR

2272

M07-045
EN 237

M07-014
2255

M07-082

2609
2609

M07-058

391

790
575

4265
10478
3987

2272

577

107
342

8754
3012
16591

2276

373
400T6

14596
4260

790T3

8691

243

M07-025
M07-031
M07-022
M07-052
T060-142

2541
413

T60-143
T60-109

M07-027

716 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK

mercury in crude oil;


silicon on gasoline-naptha by by ICP-AES;
metals in middle distillate fuels by ICP-AES;
on-line sulfur determination in gasoline and diesel by XRF.

Quality

Control

A good quality control or quality assurance program is essential in obtaining reliable data. It has, however, been seen
that many laboratories do not incorporate this step in their
analytical sequence. To help the laboratories improve their
performance, a nonmandatory section on quality control is
being added to most of the applicable Subcommittee 3 test
methods. It is hoped that this will encourage the laboratories
to institute quality control practices as an integral and pivotal
part of their testing protocols.
Concluding Remarks
Most of the test methods used for the elemental analysis of
petroleum products are based on m a t u r e analytical techniques a n d i n s t r u m e n t a t i o n . No one technique can be a
panacea for analyzing all elements in all materials. An ideal
analytical technique should have high sensitivity, broad linear dynamic range, high precision, no matrix interferences,
m i n i m u m sample preparation, and be inexpensive to acquire
and operate, useful for all elements, simple to operate, rapid,
nondestructive, etc. [31]. Few, if any, of the methods can
meet all these criteria. The analyst has to make a wise choice
as to the best available technique for a specific analysis in a
particular matrix.

REFERENCES
[1] Role of Trace Metals in Petroleum, T. F. Yen, Ed., Ann Arbor Science Publishers, Ann Arbor, MI, 1975.
[2] Nadkami, R. A., "Overview," Modem Instrumental Methods of
Elemental Analysis of Petroleum Products and Lubricants, ASTM
STP 1109, R. A. Nadkami, Ed., ASTM International, West Consiiohocken, PA, 1991, p. 1.
[3] Significance of Tests for Petroleum Products, ASTM STP 7C, K.
Boldt, and B. R. Hall, Eds. ASTM International, West Conshohocken, PA, 1977.
[4] Manual on Significance of Tests for Petroleum Products, ASTM
MNLl, G. V. Dyroff, Ed. ASTM International, West Conshohocken, PA, 1989.
[5] Modern Instrumental Methods ofElemental Analysis of Petroleum
Products and Lubricants, ASTM STP 1109, R. A. Nadkami, Ed.,
ASTM International, West Conshohocken, PA, 1991, p. 19.
[6] Nadkami, R. A., Ledesma, R. R., and Via, G. H., "Sulfated Ash
Test Method: Limitations of Reliability and Reproducibility,"
SAE Technical Paper No. 952548, Society of Automotive Engineers, Warrendale, PA, 1995.
[7] Eisentraut, K. J., Newman, R. W., Saba, C. S., Kauffman, R. E.,
and Rhine, W. E., Analytical Chemistry, Vol. 56, 1984, p. 1086A.
[8] Niu, W., Haring, R., and Newman, R., American Laboratory,
Vol. 19, No. 11, 1987, pp. 40.
[9] Carter, J. M., Batie, W., and Bemhard, A. E., Modem Instrumental Methods of Elemental Analysis of Petroleum Products and

Lubricants, ASTM STP 1109, R. A. Nadkami, Ed., ASTM International, West Conshohocken, PA, 1991, p. 70.
[10] Lukas, M., and Anderson, D. P., Modem Instrumental Methods of
Elemental Analysis of Petroleum. Products and Lubricants, ASTM
STP 1109, R. A. Nadkarni, Ed., ASTM Intemational, West Conshohocken, PA, 1991, p. 83.
[11] Nygaard, D., Bulman, P., and Alavosus, T., Modem Instrumental
Methods of Elemental Analysis of Petroleum Products and Lubricants, ASTM STP 1109, R. A. Nadkarni, Ed., ASTM International, West Conshohocken, PA, 1991, p. 77.
[12] Williams, M. C, Modem Instrumental Methods of Elemental
Analysis of Petroleum Products and Lubricants, ASTM STP 1109,
R. A. Nadkami, Ed., ASTM Intemational, West Conshohocken,
PA, 1991, p. 96.
[13] Kauffman, R. E., Saba, C. S., Rhine, W. E., and Eisentraut, K. J.,
Analytical Chemistry, Vol. 54, 1982, p. 975.
[14] Sychra, V., Lang, I., and Sebor, G., Progress in Analytical Atomic
Spectroscopy, Vol. 4, 1981, p. 341.
[15] Noble, D., Analytical Chemistry, Vol. 66, No. 2, 1994, p. 105A.
[16] Bansal, J. G. and McElroy, F. C, "Accurate Elemental Analysis
of Multigrade Lubricating Oils by ICP Method: Effect of Viscosity Modifiers," SAE Technical Series Paper 932694, Society for
Automotive Engineers, Warrendale, PA, 1993.
[17] Jansen, E. B. M., Knipscheer, J. H., and Nagtegaal, M., Journal
of Analytical Atomic Spectroscopy, Vol. 7, 1992, p. 127.
[18] Mackey, J. R., Watt, S. T., Cardy, C. A., Smith, S. I., and Meunier, C. A., Modem Instrumental Methods of Elemental Analysis
of Petroleum Products and Lubricants, ASTM STP 1109, R. A.
Nadkami, Ed., ASTM Intemational, West Conshohocken, PA,
1991, p. 62.
[19] Gonzales, M., and Lynch, A. W., Modem Instrumental Methods
of Elemental Analysis of Petroleum Products and Lubricants,
ASTM STP 1109, R. A. Nadkami, Ed., ASTM Intemational, West
Conshohocken, PA, 1991, pp. 62.
[20] Hausler, D. and Carlson, R., Spectrochemica Acta Reviews, Vol.
14, 1991, p. 125.
[21] Botto, R. I., Spectrochimica Acta Reviews, Vol. 14, 1991, p. 141.
[22] Botto, R. I., Journal of Analytical Atomic Spectrometry, Vol. 8,
1993, p. 51.
[23] Botto, R. I. and Zhu, J. J., Journal of Analytical Atomic Spectrometry, Vol. 11, 1996, p. 675.
[24] Al-Swaidan, H. M., Analytical Letters. Vol. 21, 1988, p. 1487.
[25] McElroy, F. C, Mennito, A., Debrah, E., and Thomas, R., Spectroscopy, Vol. 13, No. 2, 1998, p. 42.
[26] Newman, A., Analytical Chemistry, Vol. 69, 1997, p. 493A.
[27] Sieber, J. R., Salmon, S. G., and Williams, M. C, Modem Instrumental Methods of Elemental Analysis of Petroleum Products
and Lubricants, ASTM STP 1109, R. A. Nadkami, Ed., ASTM Intemational, West Conshohocken, PA, 1991, p. 118.
[28] Shay, J. Y. and Woodward, P. W., Modem Instrumental Methods
of Elemental Analysis of Petroleum Products and Lubricants,
ASTM STP 1109, R. A. Nadkami, Ed., ASTM Intemational, West
Conshohocken, PA, 1991, pp. 128.
[29] Wheeler, B. D., Modem Instrumental Methods of Elemental Analysis of Petroleum Products and Lubricants, ASTM STP 1109, R. A.
Nadkami, Ed., ASTM Intemational, West Conshohocken, PA,
1991, p. 136.
[30] Vrebos, B., Spectroscopy, Vol. 12, No. 6, 1997, p. 54.
[31] Hieftje, G. M., Journal of Analytical and Atomic Spectrometry,
Vol.4, 1989, p. 117.
[32] Nadkami, R. A., Guide to ASTM Test Methods for the Analysis of
Petroleum Products and Lubricants, Manual 44, ASTM Intemational, West Conshohocken, PA, 2000.

MNL37-EB/Jun. 2003

Diesel Fuel Combustion


Characteristics
Thomas W. Ryan III^

the current procedures are needed. An alternative to the current method for rating the ignition quality of diesel fuel is
presented and described.

HISTORICALLY, FUELS HAVE BEEN MADE TO MEET THE REQUIRE-

MENTS of specific engine tj^es. This tailoring of the fuels has


been accomplished in an iterative process, in which problems
are uncovered in the field and efforts are made to resolve the
problems through a process of specification and qualification. An example of this process is the development of the
currently used "cetane number"(CN). Cetane n u m b e r is the
measured parameter defined to provide a rating of the ignition quality of fuels for diesel engines. As refinery processes
became more complex and focused on the production of
gasoline in the 1920s, and as the diesel engine gained acceptance, the quantities of high quality, straight run diesel fuel
became limited. The fuels that were available in that time period demonstrated problems with cold starting and low temperature white smoke.
As will be described in more detail in the next section, industry groups were formed to address these and other fuel related issues. The mechanism for defining specifications for fuels has evolved through the efforts of organizations such as
the Coordinating Research Council (CRC), the American
Petroleum Institute (API), the Society of Automotive Engineers (SAE), the American Society of MechaniccJ Engineers
(ASME), and ASTM International (ASTM). In more recent
times, government environmental regulatory agencies have
taken a very active role in defining limits on the fuel properties that affect the exhaust emissions. The basic mechanism
consists of the definition of standard fuel rating test procedures and the compilation of fuel specifications, which define
the allowable limits of the variety of fuel properties controlled
by the specifications. The development of specifications has
been based on a wealth of empirical data and, as indicated
above, usually in response to specific problems.
The specifications of the fuels for the various types of heat
engines caji generally be considered in terms of those properties, which affect, or reflect, fuel stability and handling, contamination, c o m b u s t i o n characteristics, and emissions.
ASTM D 975 is an example of a standard established for diesel
fuel. This specification is summarized in Table 1 and generally reflects concerns for fuel stability, and engine durability
and performance. Those properties that impact the engine
emissions are discussed in another section of this manual.
The focus of this chapter is identification and discussion of
the issues related to the fuel properties that affect the ignition
and combustion characteristics of fuels for diesel engines. It
will become clear from the discussion that modifications of
' Institute Engineer, Southwest Research Institute, 6220 Culebra
Road, San Antonio, TX 78228.

ENGINE COMBUSTION AND EMISSIONS


Combustion in any heat engine can be divided into three primary phases: (1) Formation of the appropriate mixture of
fuel and air, (2) ignition, and (3) completion of combustion.
In a diesel engine, the fuel is injected into air that has been
compressed to high pressure and temperature. Some of the
fuel from the incoming spray jet vaporizes and mixes prior to
ignition, forming a pre-mixed fraction of the fuel that ignites
and b u m s as a premixed flame. The remaining fuel is ignited
in the jet and b u m s as a diffusion flame, ideally at the same
rate as it is injected. The three processes are described in
more detail in the following subsections.

FUEL INJECTION
Combustion in a diesel engine occurs when fuel is injected at
very high pressure (up to 200 MPa) through a small orifice or
multiple orifices in the injection nozzle into the combustion
chamber, that contains air that has been compressed to high
pressure and temperature. The high-pressure injection process results in a break-up of the fuel injection jets into small
droplets due to the shear forces induced between the high velocity jets and the relatively quiescent air in the combustion
chamber. The fuel droplets, consisting of drops in sizes ranging from approximately ten micrometers to several hundred
micrometers, traverse the combustion chamber at high velocity. The droplets go through a process of heating and evaporation due to heat transfer from the hot air, and deceleration due to aerodynamic drag. The evaporation process leads
to a preferential disappearance of the small droplets and
rapid mixing of the vaporized fuel with the air resulting in the
formation of a very fuel-rich mixture in the tip of the fuel jets.
The challenge for diesel engine designers is to match the
combustion chamber size and shape with the characteristics
of the fuel injection spray jets. The fuel jets must traverse the
combustion chamber in order to reach the air in all parts of
the combustion chamber. At the same time, the fuel must vaporize, mix with the air, and start to react. If the fuel jet penetrates too far, the fuel interacts with the wall, resulting in degraded mixing, low temperature combustion on the walls,
and high u n b u m e d hydrocarbon and smoke emissions. If the

717
Copyright'

2003 by A S I M International

www.astm.org

718 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

TABLE 1Specification properties for various fuel oils.


Property

Flash, C, min
Water, v%
T90, C m a x
K. Vis.,(min) mm^/s@40C
K.Vis.,(max) mm^/s@40C
Ash, %inass,inax
Copper Corrosion
Cetane Number, m i n
Cetane Index
Aromatics, % vol, max
Cloud Pt, C, max
Sulfur, % mass, max
Ramsbottom Carbon on 10%
residue, mass %

Method

Low S
No. 1

SNo.2

No. 1

No. 2

No. 4

D93
D1796
D86
D445
D445
D482
D130
D613
D976
D1319
D2500
D2622
D524

38
0.05
288
1.3
2.4
0.01
3
40
40
35
6
0.05
0.15

52
0.05
338
1.9
4.1
0.01
3
40
40
35
6
0.05
0.35

38
0.05
288
1.3
2.4
0.01
3
40

52
0.05
338
1.9
4.1
0.01
3
40

55
0.05

0.15

0.35

fuel vaporizes and mixes too close to the nozzle, the mixture
will be overly rich, leading to high unbumed hydrocarbons
and smoke emissions.
The fuel properties that have the greatest effect on injection include viscosity, density, and surface tension. Viscosity,
a measure of the fuel's resistance to flow shear, impacts the
fuel spray characteristics through flow resistance inside the
injection system and in the nozzle holes. Higher viscosity
generally results in reduced flow rates for equal injection
pressure and degraded atomization.
Diesel fuel injection systems are designed to precisely meter the required volume of fuel into the combustion chamber
during each appropriate part of the compression portion of
the combustion cycle of the engine operation. All diesel injection systems meter the fuel on a volume basis, so that fuel
density affects the mass of fuel injected. Increased density beyond specification results in higher than designed fuel injection rates due to the direct relationship between mass, volume, and density.
Surface tension, or the tendency of the fuel to adhere to itself at the fuel-air interface, affects the tendency of the fuel to
form drops at the jet-air interface. Increased surface tension
tends to degrade atomization rates. It should be noted, however, that the surface tension of most hydrocarbons is very
similar one to another. Based on this fact, surface tension
does not play a first order role in the jet break-up and atomization process, at least on a comparative basis.

Low

5.5
24.0
0.01
30
6

ing to ignition. In reality, these processes are occurring simultaneously.


Likewise, a very simplistic view of chemical aspects of ignition is based on achievement of the fuel's autoignition temperature. This can be measured following ASTM E 659, as described in Chapter 37. In reality, ignition is a very complex
chemical process that involves pyrolysis and oxidation reactions that are kinetically controlled, with an exponential dependence on the local temperatures and a nonlinear relationship with pressure.
Diesel fuel ignition characteristics are very important for
several reasons. First, they affect the ability of the fuel to ignite during cold-start. In the limiting case, if the fuel resists
autoignition at the highest achievable compression temperature it is impossible to start the engine. Second, the ignition
characteristics are important because they affect the quantity
of fuel injected during the ignition delay time. If the ignition
delay time is long, a large quantity of injected fuel becomes
premixed prior to the start of combustion. When combustion
does occur, however, most of the premixed fuel ignites at the
same time, leading to very high rates of combustion, high
rates of pressure rise, and "diesel knock." Third, if the ignition delay time is long, the resulting premixed burning leads
to higher combustion temperatures and increased oxides of
nitrogen (NOx) exhaust emissions. The mechanism for this
NOx formation process is described below.

COMBUSTION
IGNITION
Dec [1] theorizes that ignition occurs in the rich region at
the tip of the fuel jet, when the fuel's vapors achieve temperatures sufficient for decomposition and oxidation. In a
diesel engine, the fuel does not ignite instantaneously. The
time elapsed from injection to ignition is known as the ignition delay time. The ignition delay time occurs because a
certain amount of time is required for the fuel to vaporize
and ignite. A very simplistic view of the ignition process
separates the physical and chemical aspects of the ignition
process. The time necessary for the fuel to vaporize and mix
is known as the physical delay, while the chemical delay is
the time required for the onset of chemical reactions lead-

The combustion process in diesel engines can be monitored


by measuring the pressure in the combustion chamber during the compression and combustion processes. It is possible
to apply the First Law of Thermodynamics to the diesel engine in order to obtain an estimate of the instantaneous rates
of heat release during combustion. The First Law for a
closed, constant mass system is
dQ/dt + dW/dt = dU/dt
where.
Q = heat transfer
W = work
U = internal energy

(1)

CHAPTER

27: DIESEL

(2)

dU/dt = m Cv dT/dt

(3)

and,

where,
m = mass trapped in the cyUnder (air + fuel mass)
Cv = specific heat at constant volume of mixture
T = temperature in the combustion chamber.
Also it is assumed that,
(4)

dW/dt = P dV

CHARACTERISTICS

719

Figure 1 is a heat release rate diagram for an engine condition in which there is a fairly large premixed b u m fraction.
Also plotted in Fig. 1 is the injection pressure as it was measured simultaneously with the cylinder pressure. The inflection in the injection pressure at 178 indicates the point in
time when the injection nozzle valve opens and fuel starts to
be injected into the cylinder. This is noted as the start of injection. Also indicated are the premixed and the diffusion
b u r n phases, or fractions. The time from the start of injection
to the start of the premixed b u m phase is called the ignition
delay time. Note that during this delay period a significant
quantity of fuel is injected, vaporized, and mixed with the hot
air in the cylinder. When ignition does occur, this premixed
fuel ignites spontaneously.

If it is assumed that the combustion process can be treated as


a heat transfer into the system, then Eq 1 can be rearranged
dQ/dt = dU/dt - dW/dt

FUEL COMBUSTION

As shown in Fig. 1, the premixed b u m fraction typically


has a very high heat release rate. As indicated above, this
rapid release of energy results in an increase in the engine
noise called "diesel knock." It is this almost instantaneous release of energy that raises the temperature in the cylinder
early in the combustion process and leads to high combustion temperature throughout the rest of the combustion process. While this increase in the combustion t e m p e r a t u r e
might be assumed to increase the overall cycle efficiency due
to Camot consideration, it can also increase the heat transfer
and it almost always increases the NOx emissions.

where.
P = instantaneous pressure in the cylinder
V = instantaneous volume in the cylinder.
Assuming Ideal Gas behavior,
PV=mRT
or,
dT/dt = (1/mR) (p dV/dt + V dp/dt)
where.
R = Gas Constant.

EMISSIONS

With appropriate substitution, Eq 2 becomes,


dQ/dt = (Cv/R - 1) P dV/dt + (C^/R) V dP/dt

Combustion temperatures are important because they dominate the rate of formation of NOx emissions. NOx is important because it reacts with the unburned hydrocarbons in the
atmosphere to form smog. Most of the NOx emissions result
from a chemical kinetic process, known as the Zeldovich [3]
Thermal NOx emissions mechanism, where,

(5)

It can be seen that the apparent heat release rate during combustion, dQ/dt, can be computed using Eq 5, the measured
cylinder pressure, and using the geometric relationship between cylinder volume and crankangle. The computation is
performed using cylinder pressure data that is resolved based
on crankangle [3]. The pressure is measured using a high
speed piezoelectric pressure transducer installed in one of
the engine's cylinders. The pressure data is recorded simultaneously with a record of the crankangle position.

N2 + O = NO -h N
N + O2 = NO -h O

The rate constants for the two reactions are exponential functions of the temperatures in the combustion chamber. These

20000

0.20

Heat release rate


Injection pressure

u>

I<

tu

s
X

0.15 -

15000 .S
lU
10000

0.10

UJ

z
<
Iz
<

oc
v>

0)
3
lU

- 5000

0.05

0.

o
111

"N .

0.00

Premixed
^-Diffusion-^

Start of Injection
-0.05 1

90

n-

(6)

*T**i

105 120 135 150 165 180 195 210 225 240 255 270 285

CRANK ANGLE [degrees; TDC=180]


FIG. 1Heat release rate diagram.

-5000

720

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

temperatures depend on the thermodjrnamic processes that


occur during compression and combustion, as well as on the
adiabatic flame temperature of the fuel-air mixture.
The adiabatic flame temperature is a fundamental property of the fuel air mixture, depending on the initial pressure
and temperature, the air-fuel ratio, and the fuel properties,
including hydrogen, carbon, and oxygen content, and heat of
combustion. The highest adiabatic flame temperature occurs
in stoichiometric, or chemically balanced mixtures, using fuels with high carbon contents. The adiabatic flame temperature can be computed based on the above parameters using
a n equilibrium calculation [3].
In a diesel engine, the pressure and temperature at the start
of reaction are defined by the engine design and the operating condition. If the temperatures are high, the ignition delay
times tend to be short, leading to a smaller premixed b u m
phase and lower initial temperatures for the diffusion b u m
phase. If the ignition delay times are long, a large quantity of
fuel is injected during the delay time and the premixed b u m
phase is larger, leading to higher temperatures at the start of
the diffusion b u m phase. In a diffusion flame, the fuel actually b u m s at the location where the fuel and air mix to the
chemically correct (stoichiometric) fuel-air ratio. The fuel
b u m s at the stoichiometric adiabatic flame temperature. If
there is a large quantity of fuel in the premixed b u m phase,
the initial temperature for the diffusion b u m phase is high,
leading to higher temperatures during the diffusion b u r n
phase.
M o d e m practice in diesel engine design is to minimize the
premixed b u m fraction by controlling the initial rate of fuel
injection and thereby minimizing the a m o u n t of fuel injected
during the ignition delay time. Figure 2 is a plot of the heat
release rate and injection pressure for an engine and associated operating condition in which the initial injection rate is
controlled in order to minimize the amount of fuel injected
during the ignition delay time. This is done by designing the
injection system to provide a slow initial rate of injection, followed by a rapidly increasing rate once ignition occurs. This
is demonstrated by the increasing injection pressure in Fig. 2,

which was measured in a 1994 Caterpillar 3176 engine. Note


the very small premixed b u m phase for this engine and the
fact that the injection pressure and the heat release rates have
similar shapes. The correspondence of the injection and heat
release rates indicates that the fuel is being burned as it is injected.
In addition to NOx, the u n b u m e d hydrocarbons (HC) and
particulate emissions (PM) from diesel engines are important, not only for their role in reducing efficiency and contributing to smog formation, but also from the direct health
risk associated with these pollutants. The U.S. Environmental Protection Agency (EPA) and the California Air Resources
Board [4] have defined diesel PM as an air toxin, recognizing
the potential health risks associated with h u m a n exposure to
diesel PM.
Diesel PM is defined by regulatory bodies as anything collected on a specified filter that is maintained at 125F. The
collection procedure involves dilution of the exhaust sample
with fresh air. The method has been defined by EPA to simulate what occurs when diesel exhaust is emitted into the atmosphere. Diesel PM is a complex mixture of soot, u n b u m e d
fuel, and partially reacted fuel.
The formation of u n b u m e d HC and PM is a result of the
heterogeneous n a t u r e of the diesel c o m b u s t i o n process
where fuel injection, vaporization, mixing, ignition, and combustion are all occurring nearly simultaneously in the engine.
The HC emissions result from a combination of sources including fuel that is deposited on the combustion chamber
walls and does not react, or only partially reacts. It also includes fuel that has mixed and is either too lean or too cold
to react. It should be noted that the mass of HC emissions per
BHP/hr from diesel engines are typically an order of magnitude lower than the engine out HC emissions from spark ignition engines.
Soot is the product of diffusion burning where some of the
fuel partially reacts, forming compounds that ultimately result in the growth of high molecular weight compounds that
are very rich in carbon. Soot formation is a very complex
chemical process that is affected by the physical processes

0.30
0)
0)
a

0.25

ID

0.20

25000

Heat release rate


Injection pressure

0.10

z
<
1-

0.05

<
1(/z>

0.00

a.
3
OT
V)
10000 Ui

0.15

UJ

"5
15000

1X
If)
3

20000

a.
z
5000

_-^\-

-0.05

-5000
90

105 120 135 150 165 180 195 210 225 240 255 270 285

CRANK ANGLE [degrees; TDC=180]


FIG. 2Heat release rate diagram-small premixed burn phase.

H
U
lU
-5
Z

CHAPTER 27: DIESEL FUEL COMBUSTION


that occur during the fuel mixing and combustion processes.
A simplistic view of the diesel diffusion burning process involves a relatively thin flame front formed at the interface between the fuel and air. In this view, the fuel is on one side of
the flame and air on the other. The initial soot formation reactions include thermal break down (pyrolysis) of the fuel before it enters the flame. Under these conditions, the soot precursor reactions (leading to greater soot formation potential)
favor high temperature and long residence times. More soot
precursors are formed if the mixing rates are slow and the
temperatures are high. Higher temperatures also lead to
higher soot oxidation rates. The level of PM emissions from a
given diesel engine is the result of the difference between the
formation rate and the oxidation rate. In general, higher temperatures tend to lead to lower soot and PM emissions, due
primarily to the effect of the increased temperature on the
PM oxidation rate.
The diesel engine designer faces a conflict between PM and
NOx emissions. High temperatures are desirable for PM
emission control, but they also lead to high NOx emissions. It
is this trade-off that constitutes one of the primary concerns
of modem diesel engine design. In general, current practice
is to reduce the combustion temperatures to the highest level
possible consistent with achievement of the NOx emissions
standard. The PM emissions are controlled through engine
combustion chamber and injection system design to prevent
interactions of the fuel and combustion chamber wall. In addition, higher injection pressures are used to produce higher
mixing rates that lead to lower residence times in the pyrolysis zone and thus lower soot formation rates.
The effects of fuel properties and composition on soot formation were studied extensively by Naegeli and Moses [5].
They concluded that the primary controUing fuel property is
the hydrogen content. This is demonstrated in Fig. 3 where the
soot emissions from a diffusion flame are plotted versus the
fuel hydrogen to carbon ratio. Fuel hydrogen and carbon contents are determined in the laboratory using ASTM D 5291.
It is interesting to note that the fuel hydrogen content is the
primary fuel variable affecting both NOx and PM. High hydrogen content (as H atoms) fuels have lower adiabatic flame
temperatures and thus lower NOx formation tendencies. The
NOx relationship to fuel hydrogen to carbon ratio is presented in Fig. 4, where the adiabatic flame temperatures and
the predicted NOx emissions (Zeldovich Mechanism) are
plotted versus fuel hydrogen to carbon ratio [6]. Higher hydrogen content fuels also tend to form less soot, and thus
lower PM emissions.

1.5

1.75

1.85

Fuel H/C Ratio

FIG. 3Soot concentration versus fuel H/C


ratio.

CHARACTERISTICS

721

H/C (Atomic Ratio)

FIG. 4Adiabatic flame temperature and


NOx versus fuel hydrogen to carbon ratio.

D I E S E L F U E L I G N I T I O N QUALITY
Current Practice (Cetane Number)
Diesel fuel specifications currently include only two specified
properties that are related directly to combustion. Heat of
Combustion, and cetane number. Heat of Combustion is a
fundamental property of the fuel, based on the Heat of Formation of the individual molecules. Its determination is fairly
straightforward following ASTM D 240, which employs a
bomb calorimeter. The procedure consists of completely
burning a weighed sample of the unknown fuel in a combustion bomb that is contained in a controlled temperature bath.
The Heat of Combustion is determined by measuring the
temperature increase of the bath.
Cetane number, on the other hand, as determined following ASTM D 613, is not a fundamental property of the fuel.
Cetane number is a defined parameter designed to provide an
indication of the ignition quality of diesel engine fuels.
Higher cetane number means that the fuel has better ignition
qUcJity than fuels with lower cetane numbers. Cetane number is determined in an engine test in which the ignition quality is rated versus those of blends of two reference fuels. The
history and method of ASTM D 613 and cetane numbers are
described in the following paragraphs.
In 1932, Boerlage and Broeze [7] proposed that the ignition
quality of a fuel be based on a comparison of its ignition delay time in a diesel engine to that of a blend of two reference
fuels. They developed the "cetene scale" in which a fuel was
assigned a "cetene number." The reference fuels were two
pure hydrocarbons, cetene (C16H32) and mesitylene. Cetene
burned readily in conventional engine, while mesitylene did
not bum at all.

722 MANUAL 37: FUELS AND LUBRICANTS

nil

HANDBOOK

11 u

7//////1
1

PRE-CHAMBER

w/rr/rrz/rm

FIG. 5Cross section of the CFR engine.

In 1935, ASTM adopted this form of diesel fuel rating system using hexadecane (C16H34) and alpha-methylnaphthalene ( d iH]o) as the reference fuels. The former was assigned
a cetane number of 100, while the latter was given a cetane
number of 0 [8]. In 1962, ASTM added heptamethylnonane,
(C16H34) to the cetane scale as an intermediate, low ignition
quality fuel with a defined cetane number of 15 [9].
The standard apparatus for determining and comparing ignition delay times is a Coordinated Fuels Research (CFR)
diesel engine developed by the Waukesha Motor Company. It
is a one-cylinder, four-stroke cycle engine with a cylindrical
prechamber chamber design (see Fig. 5) and a compression
ratio capability ranging from 6:1 to 28:1.
The ASTM D 613 test procedure consists of running the test
fuel at specified conditions of speed, load, and intake temperature. The injection timing is adjusted so that the start of
injection is 13 Before Top Dead Center (BTDC). The compression ratio is adjusted until ignition occurs at TDC. The
test fuel is then replaced with blends of the reference fuels
until one is determined to have a slightly higher compression
ratio and one with a slightly lower compression ratio than the
test fuel. The cetane number of the test fuel is determined by
linear interpolation of the cetane numbers of the reference
fuels. As an example, typical U.S. diesel fuel has a cetane
number of 45. The 45 cetane number reference fuel is a blend
consisting of 64.7 vol.% hexadecane and 35.3 vol.% heptamethylnonane .
Unfortunately, a number of problems are associated with
using the CFR engine for evaluating ignition delay time and
thus cetane number. It has been criticized for a variety of significant shortcomings. The primary complaint is a failure of
cetane number to consistently provide an accurate measurement of ignition quality. The specific shortcomings of the current cetane procedure were extensively discussed during a
CRC-hosted workshop, Diesel Fuel Combustion Performance,
held in Atlanta, Georgia in 1984 [10]. It appears that the main

problem with the cetane procedure is related to the fact that


neither the engine nor the test conditions are representative
of current engine design or typical operating conditions.
The current procedure, developed over 50 years ago, involves the use of the Waukesha engine. The prechamber has
a movable end plate, which is used to change the volume of
the prechamber and, thus, the compression ratio, as shown
in Fig. 5. The specified operating conditions of the test are
equivalent to a high-speed idle test, with the speed set at 900
rpm and the fuel flow set at 13 ml/min (equivalent to an
air/fuel ratio of approximately 30:1).
One of the more frequent complaints is the fact that the
CFR engine design is not representative of current diesel engines. The engine design includes a cylindrical precombustion chamber. The fuel injector is located in one end of the
prechamber and the other end is moveable and is used to
vary the compression ratio. The motion of the prechamber
end plate not only changes the compression ratio, but also
changes the distance from the injection nozzle to the combustion chamber wall. Modern diesel engines, both lightduty and heavy-duty, utilize direct in-cylinder fuel injection.
These engines have mixture preparation, surface condition,
combustion chamber geometry, and thermodynamic condition effects that are significantly different than the prechamber CFR engine. This means the current cetane test engine
and test method expose the fuel to temperature history, airfuel ratio, and surface effects that are different than those encountered in most actual engines in the field.
Another complaint is that the test condition used in the test
method is effectively a moderate load at very low speed. The
test speed is 900 rpm and the air-fuel ratio is 30:1. This speed
is much higher than cranking speed and thus does not represent cold start conditions. The speed is also much lower than
normal operating speeds in most high-speed diesel engines,
so that it is not representative of hot running conditions, and
thus it is not a good indicator of the hot running characteristics of the fuel. The moderate load, represented by the 30:1
air/fuel ratio, does not incorporate intake pressures above
ambient (not boosted) so that compression pressure histories
are different than in modem turbocharged diesel engines.
Some of the other reported problems are related to the cost
and time required for the measurement [11]. Other problems
are associated with the repeatability and reproducibility
[11-13]. Accurate and repeatable determination of the cetane
number of alternative and ignition-improved fuels, and fuels
at the lower end of the cetane scale, are all problematic
[12-15]. Many researchers are even questioning the validity
of the cetane scale as an indicator of ignition quality
[9,12,14,16-18].
The current test method has poor repeatability and reproducibility. LeBreton [12] conducted tests on the repeatability
of the CFR engine results and found the standard deviation
for the data to be 0.8 cetane numbers. However, the sample
only contained fuels with cetane numbers between 45 and 50.
Glavinceveski et al. [13] reported repeatability results for a
set of 48 fuels as being 1.57 cetane numbers. The test resuks
for these same fuels, performed in a number of engines, was
calculated to be 4 cetane numbers. Once again, the majority
of the fuels had cetane number ratings between 40 and 50,
and none had cetane number below 37. Glavinceveski et al.
[13] showed that the scatter of the cetane number rating

CHAPTER

2 7: DIESEL

method increases dramatically as the rating drops below 40


cetane number.
The standard test method (ASTM D 613) is reported to have
a repeatability of 1 CN. Indritz [19] examined data for a
large n u m b e r of reference and test fuels, tested in a n u m b e r of
test engines. The results of his comparisons are presented in
Fig. 6, where the cetane numbers are plotted versus compression ratio. Two observations can be made regarding the results. First, it is clear that there is not a universal relationship
between the cetctne n u m b e r and the compression ratio. It is
likely that the lack of a universal relationship between cetcine
n u m b e r a n d compression ratio results from day-to-day and
engine-to-engine differences in the combustion. Injection
nozzle performance, combustion chamber deposits, variation
in compression ratio calibration, a n d variations in the injection p u m p pressure and calibration all contribute to the differences. Second, the variation in the measurements is on the
order of +/ 5 CN. An error of 5 CN Ccin mean the difference
between starting or not starting in cold weather, depending
u p o n the specifics of the engine design.
Much of the research into ignition quality has centered on
how the ignition delay time a n d cetane n u m b e r relate to the
conditions under which the tests are conducted. Yu et al. [20],
in experiments performed in a specifically designed research
engine, conducted duplicate tests in which combustion occurred every other cycle. They found that the peak of the difference in the pressure traces of the fired a n d unfired cycles
increased with decreasing ignition delay time. Tsao et cd. [21]
found that delay times increased with decreasing air temperature and engine speed. Hardenberg and Hase [22] reported
the delay times decreased with increasing compression pressure a n d air temperature. Finally, Parker et al. [23] and Walsh
and Cheng [24] showed the ignition delay time can be decreased by increasing the fuel temperature at injection.
Other studies of the ignition delay time have focused on
differentiating the physical and chemical aspects of the ignition delay time. The physical aspects include the atomization, mixing rates, a n d vaporization rates of the fuel. These
physical aspects are related to the fuel properties of viscosity,
density, and distillation characteristics. The chemical aspects
relate mostly to the chemical composition of the fuel and the
corresponding impacts on the chemical kinetics of the thermal decomposition and free radical generation mechanisms.
820

80

880

WOO

t040

1080

CAtCULATB) ISENTROPIC TEMPERATURE - K

fS

FUEL COMBUSTION

CHARACTERISTICS

723

Elliott [25] noticed the ignition delay time decreased with


lower fuel/air ratio. In a more comprehensive study of physiCcil delay time, Wakil et al. [26] drew the same conclusion and
showed that it was caused by the relative spacing of the fuel
droplets. They also found that physical delay times increased
with droplet size a n d fuel boiling point due to vaporization
characteristics. Rao a n d Lefebvre [27] also determined that
the physical delay time is always a significant pEirt of ignition
delay. In a study of chemiccd delay times, Chang et al. [28]
found that the rate of reaction of high-cetane-number fuels
increases faster after ignition t h a n t h a t of low-cetanen u m b e r fuels. Cox a n d Cole [29] studied the chemical kinetics involved in chemical delay time and demonstrated a large
increase in delay time with decreasing oxygen concentration
of the air/fuel mixture.
There have been a n u m b e r of studies concerning the effects
on cetane number caused by blending alternative fuels with
diesel fuel ASTM #2 (DF-2). Saeed a n d Henein [30] found
that the addition of 10 vol% ethanol in diesel fuel caused only
a slight decrease in cetane number. However, they noted a
drastic decrease in cetane n u m b e r as the amount of ethanol
in t h e blend increased from 20-70 vol%. Henein a n d
Fragoulis [9] studied the effects of blending a number of alternative fuels with DF-2. They found that blends containing
indolene, unleaded gasoline, and No. 6 fuel oil each produced
a drastic d r o p i n cetane n u m b e r . Blends of DF-2 with
m e d i u m n a p h t h a a n d Jet A fuel p r o d u c e d very small decreases in cetane number, while a blend with No. 4 fuel oil
caused the cetcine n u m b e r to increase slightly.
Dabovisek and Savery [31] concluded that the ignition delay a n d therefore cetane n u m b e r of a blend of two fuels is
controlled by the component with the greatest autoignition
resistance, or lowest cetane number. Needham a n d Doyle
[14] determined cetane number for synthetic and alternative
fuels. They conducted studies of the cetane number of blends
containing naphtha, sunflower oil, sunflower oil ester, shale
oil, coal synthetic liquids, and tar sands. They found that
ASTM D 613 for the vegetable oil Eind the blends of naphtha
and methanol with DF-2 did not accurately predict the ignition delay. Finally, Siebers [18] conducted constant volume
combustion b o m b tests on blends of naphtha Etnd coal derived liquids with DF-2, and on a degummed sunflower oil, a
sunflower oil monoester, and methanol to determine how the
delay times varied with temperature in the bomb. All fuels behaved similarly t o reference fuels w i t h the exception of
methanol, for which the delay time increased dramaticcdly as
the temperature decreased, presumably due to the unique
chemical structure of methanol.

P r o p o s e d Alternatives to ASTM D 6 1 3

Due to the issues discussed above, including the time Eind expense required to conduct D 613 cetane n u m b e r determinations, a n u m b e r of edtemative methods have been proposed.
The proposed methods have included numerous correlations
with other physical a n d chemical properties, constantvolume combustion b o m b based methods, and correlative
techniques based on NMR and FTIR analysis of the test fuel.
Hardenberg and Hase [22] tried to use activation energy as
an indicator of cetane number. Collins a n d Unzelman [32]
used API gravity a n d mid-point temperature. Klopfenstein

R Rvtaranca FtMl
0 " Unknown Furt

"^n^^
-1HU_^,
I
12

13

It

17

COMPRESSION RATIO

FIG. 6Scatter plot of Cetane measurements.

724

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

[33] correlated density and mid-boiling point temperature


with cetane number, while Murphy [34] included percent hydrogen. Glavincevski et al. [13] tried to use aromatics to predict cetane number, and Steere [35] developed a correlation
between cetane number, aniline point, viscosity, density, and
D 86 distillation. Cetane index (ASTM D 976) involves correlations that are modified periodically, and that incorporate a
number of different properties. While all of the correlations
provide reasonable predictions of the CN of fuels that are
similcir to those used to develop the correlations, they are not
reliable for prediction of cetane numbers of fuels that are different than the fuels used to develop the coirelations. Typically, these correlations must be modified periodically to accommodate changes in feedstock source and refinery
processing technology. In addition, the accuracy of the correlation is limited to the precision of ASTM D 613 test
method and the number of engine tests used to obtain an average cetane number for an individual fuel sample.
Nuclear magnetic resonance (NMR) has been used to predict cetane number [10,36,37]. Bailey et al. [37] used the relative quantities of methine and methylene hydrogen to predict the cetane numbers of non-aromatics. They also
developed a model for aromatic hydrocarbon fuels, based on
the relative quantity of alpha hydrogen and relative squared
sum of alkyl hydrogen along with the methine and methylene
hydrogen. It was reported that the deviations from perfect
correlation with D 613 cetane number were most likely due
to scatter in the D 613 results.
Fodor [38] reported some promising results using Fourier
Transform Infrared (FTIR) analysis of the fuel. In these techniques the fuel sample is analyzed using FTIR and the resulting spectra are used to develop correlations with the cetane
number. While the techniques are generally very fast and require very small fuel samples, the methods are based on correlations and are unstable when used outside the range of
properties/specifications of the fuels used to develop the correlation. Again, as stated above, the accuracy of the correlation is related to the accuracy and number of ASTM D 613 engine tests.
Another significant issue with the current cetane rating
scale is related to a concern over whether cetane number provides an accurate and representative indication of the ignition quality of all diesel fuels. Ignition quality in a diesel engine is important for cold start, for engine noise, and can be
related to both NOx and PM. Tavacha and Cliffe [17] noted
that cetane number is a measure of the ignition temperature,
not ignition quality. Needham and Doyle [14] found that ignition delay is not the controlling factor in determining overall performance. They recommended development of a new
rating method. Sieber's [18] results showed that cetane number does not provide an accurate measure of ignition quality
of fuels whose ignition delay dependence on temperature, or
compression ratio, or the type of ignition (single two stage)
differs from the reference fuels.
Oilman et al. [39-40] studied the effects of fuel properties
on engine emissions. The tests, performed in a 1988 Detroit
Diesel Series 60 engine calibrated to near 1991 emissions levels, indicated that both the NOx and the PM were related to
the cetane number. The Series 60 is a direct injection, turbocharged, intercooled diesel engine. The CFR engine is an
indirect injection, naturally aspirated engine. Recent results

by Ryan et al. [41], however, indicate that cetane number is


not related to emissions from modem heavy-duty diesel engines operating at standard ambient conditions. Analysis of
the heat release rates indicate that the combustion process in
these modem diesel engines is dominated by diffusion burning, with the combustion rate controlled by the rate of fuel injection. Under these circumstances, cetane number, as a
measure of the ignition delay time, is not important for typical diesel fuels because the start of combustion is controlled
by the conditions in the engine and the design of the injection
system. Injection system designs that allow for control of the
rate of fuel injection can reduce the amount of fuel injected
during the ignition delay time, and thus reduce the dependence on the ignition quality of the fuel, as discussed previously.
It is clear that the current procedure for rating the ignition
quality of diesel fuel is no longer adequate. First, it probably
does not represent the sensitivity of current and future engines as indicated by the work of Ryan et al. [41], and second,
because it is not as repeatable or reproducible as it needs to
be for use in current emd older engines. If the results of Indritz [19] are accepted, a variation of +/ 5 cetane numbers
is possible. Using the results of Ullman et al. [39,40] a 5
cetane number variation can produce as much as a 4% difference in the NOx emissions and as much as a 13% variation
in the PM emissions from older and current engines.
Ryan et al. [42-45] developed a constant volume combustion bomb based technique (CVCA) for rating the ignition
quality of fuels for diesel engines. The primary objective of
these efforts was to develop a technique that is based on measurement of the ignition delay time, a fundamental combustion property of the fuel. The goal was to eliminate the engine
sensitivity inherent in the ASTM D 613 technique. A great
deal of effort was devoted to developing a technique based on
a calibration using the defining reference fuel rather than a
correlation. Several hundred fuels were examined using this
technique. The test fuels included petroleum based diesel fuels, various refinery products, coal slurries, various oxygenated fuels, blends of various fuels and fuel components, a
wide range of cetane improver additives, and a large number
of alternative fuels. The apparatus and technique, now called
the IQT (Ignition Quality Tester), has been further refined
and developed by Allard et al. (45-47) and is currently being
examined for approval as an ASTM test method.
Based upon the above discussion, it appears that the engine-based technique for diesel-fuel ignition quality rating is
not acceptable for the numerous reasons listed. It is also clear
that the other noncombustion-based techniques (FTIR,
NMR, Property Correlation) are also not acceptable because
they involve correlations that are valid only for the type of fuels used to develop the correlations. It appears that the best
approach is one in which a fundamental combustion property, such as ignition delay measured in a well-defined experiment, is used as the basis for the rating. It appeeirs that it
is also desirable to use a technique that is based on a calibration rather than one based on a correlation.
CVCA/IQT Method
As indicated above, the IQT method is based on the use of the
CVCA technique developed by Ryan et al. [42-45]. This tech-

CHAPTER 27: DIESEL FUEL COMBUSTION


nique was originally suggested by Hum et al. [ 15] and Yu et al.
[14]. In this method, the fuel sample is injected into a constantvolume combustion chamber, which contains air at a pre-selected elevated temperature and pressure. The constant-volume combustion chamber is equipped with a pressure
transducer at one end and an inward opening pintle nozzle at
the other end. A proximeter is installed on the injection nozzle
for recording the start of injection. The injection nozzle is supplied with fuel from a pneumatically driven, single-plunger
fuel injection pump. The initial conditions in the bomb, the
quantity of fuel injected, and the fuel injection characteristics
are all precisely controlled. Figure 7 is a schematic showing the
internal geometry of the constant-volume combustion chamber. Figure 8 is a photograph of the IQT.

CHARACTERISTICS

725

The test method consists of setting the initial conditions in


the bomb, followed by injection of the fuel sample and
recording of the pressure history during injection, ignition,
and combustion. The needle lift trace, using the output of the
proximeter on the injection nozzle, is used to document the
start of injection. The needle lift data and the pressure variation in the vessel are recorded and used to determine the time
from the start of injection to the start of combustion. This
time has been defined as the ignition delay time. Figure 9 is
a pressure trace showing actual data generated during a test
in the IQT.
As can be seen in the figure, the pressure in the bomb initially drops due to evaporative cooling of the injected fuel.
The pressure then rises rapidly due to combustion. The igni-

Inlet
Tc Chamber Surface

Tc High Temperature
Policeman

Injection Nozzle
Body

Tc Nozzle Tip

Exhaust

FIG. 7Schematic of the bomb geometry used in the IQT.

10

Ignition Delay (mS)


FIG. 8Photograph of the IQT.

FIG. 9Pressure versus time in the IQT during ignition and


combustion.

726

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

tion delay time is precisely defined by the initial rise of the


needle lift trace and the point at which the pressure recovers
back to the initial pressure.
The IQT is a calibrated technique, meaning that the cetane
number-ignition delay time relationship is defined by calibration with a large n u m b e r of reference fuel blends. Initially, the calibration curves were developed using blends of
the secondctry reference fuels, but recent results [48] indicate
that the use of ASTM D 613 National Exchange Group (NEG)
checks fuels provide for a more consistent and cost effective
calibration. Figure 10 is a plot showing the calibration curve

for the IQT, where the cetane n u m b e r is plotted versus the ignition delay time.
The test method consists of charging the fuel reservoir on
the injection p u m p with the unknown fuel. This requires approximately 50 mL sample of fuel to accomplish both the system flush as well as fuel charge for testing. The system is then
set for initiation a n d the test sequence is automatically
started. The sequence consists of venting the vessel and pressurizing to the initial pressure. After a short stabilization
time the test fuel is injected and the pressure and needle lift
histories are recorded and used to define the ignition delay

N-cetane: 100 CN

E
3
O

ffi

Heptamethylnonane: 15 CN
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25

Ignition Delay (mS)


FIG. 10IQT calibration curve [48].

70
\ r

65
0)

iqtvscl-613
IQTCNvsColH

Col22vsd613

Col17vsCol16
Col 25 vs Col 24

Ji 60

E
3

^k.

Z
c

55

0)

50

w^

CO

(D 45

a
^"^^

40
35
35

40

45

50

55

60

IQT Predicted Cetane Number


FIG. 11Results of recent round robin testing of the IQT.

65

70

CHAPTER 27: DIESEL FUEL COMBUSTION CHARACTERISTICS


time. The vessel is then vented and the process repeated. This
sequence is repeated 32 times for each fuel test. The entire
test is accomplished in approximately 15 min. Upon completion of the 32 injections, the average ignition delay time is
used to automatically determine the derived cetane n u m b e r
from a software based ignition delay/derived cetane n u m b e r
model. All IQT systems used the same model for determination of the cetane number. The software averaging and the resulting statistical data provide a very good indication of the
quality of the data a n d the health of the system. Routine operation of the system also involves periodic, repeated tests using a check fuel to determine the validity of the calibration
and the long-term health of the system.
Figure 11 is a plot showing the results of a small-scale
round robin test in which three different IQT units were compared to each other and to well-documented ASTM D 613
data. The results indicate that the IQT provides a very repeatable and reliable rating of the fuels. Similar comparisons
with a wide rcuige of fuels indicate that the IQT also works
very well for additized fuels and alternative fuels.

ASTM STANDARDS
No.
D86
D93
D130

D240
D445

D482
D524
D613
D975
D976
D1319

D1796

D2500
D2622

D5291

E659

Title
Standard Test Method for Distillation of Petroleum
Products at Atmospheric Pressure
Standard Test Method for Flash-Pont by PenskyMartens Closed Cup Tester
Standard Test Method for Detection of Copper Corrosion from Petroleum Products by the Copper Strip
tarnish Test
Standard Test Method for Heat of Combustion of
Liquid Hydrocarbon Fuels by Bomb Calorimeter
Standard Test Method for Kinematic Viscosity of
Transparent and Opaque Liquids (the Calculation of
Dynamic Viscosity)
Standard Test Method for Ash from Petroleum Products
S t a n d a r d Test Method for R a m s b o t t o m Carbon
Residue of Petroleum Products
Standard Test Method for Cetane Number of Diesel
Fuel Qil
Standard Specification for Diesel Fuel Oils
Standard Test Methods for Calculated Cetane Index
of Distillate Fuels
Standard Test Method for Hydrocarbon Types in
Liquid Petroleum Products by Fluorescent Indicator
Adsorption
Standard Test Method for Water and Sediment in
Fuel Oils by the Centrifuge Method (Laboratory Procedure)
Standard Test Method for Cloud point of Petroleum
Products
Standard Test Method for Sulfur in Petroleum Products by Wavelength Dispersive X-ray Fluorescence
Spectrometry
Standard Test Methods for Instrumental Determination of Carbon, Hydrogen, and Nitrogen in
Petroleum Products and Lubricants
Standard Test Method for Autoignition Temperature of Liquid Chemicals

727

REFERENCES
[1] Dec, J. and Espey, C, "Chemlluminescence Imaging of Autoignition in a DI Diesel Engine," SAE Paper 982685, Society of
Automotive Engineers, Warrendale, PA, 1998.
[2] Bowman, C. T., "Kinetics of Pollutant Formation and Destruction in Combustion," Progress in Energy Combustion Science,
Vol. 1, 1975, pp. 3 3 ^ 5 .
[3] Heywood, J. B., Internal Combustion Engine Fundamentals, McGraw-Hill, NY, 1988.
[4] "Air Quality Criteria for Particulate Matter," U.S. EPA, EPA
600/p-99/002aB, March 2001.
[5] Naegeli, D. W. and Moses, C. A., "Effects of Fuel Properties on
soot Formation in Turbine Combustion," SAE Paper 781026,
Society of Automotive Engineers, March 1978.
[6] Ryan, T. W., Ill, "Emissions Performance of Fischer Tropsch
Diesel Fuel," presented at the Intertech Gas to Liquids Conference, 17-19 May 1999, San Antonio, TX.
[7] Boerlage, G. D. and Broeze, J. J., "Ignition Quality of Diesel Fuels as Expressed in Cetane Numbers," SAE Journal, Vol. 27,
1932, pp. 283-293.
[8] Schweitzer, P. H., "Methods of Rating Diesel Fuels," Chemical
Reviews, Vol. 22, 1938.
[9] Henein, N. A., Fragoulis, A. N., and Luo, L., "Correlations Between Physical Properties and Autoignition Parameters of Alternate Fuels," SAE Paper 850266, Society of Automotive Engineers, Warrendale, PA, 1985.
[10] Diesel Fuel Combustion Performance Workshop, CRC, Atlanta,
GA, 1984.
[11] Gulder, O. L., Glavincevski, B., and Burton, G. F., "Ignition
Quality Rating Methods for Diesel Fuels-A Critical Appraisal,"
SAE SP, Qct. 1985.
[12] LeBreton, M. D., "Repeatability Test on the CFR Cetane Engine," SAE 841340, Society of Automotive Engineers, Warrendale, PA, 1984.
[13] Glavincevski, B., Gulder, O. L., and Gardner, L., "Cetane Number Estimation of Diesel Fuels from Carbon Type Structural
Composition," SAE Paper 841341, Society of Automotive Engineers, Warrendale, PA, 1984.
[14] Needham, J. R. and Doyle, D. M., "The Combustion and Ignition
Quality of Alternative Fuels in Light Duty Diesels," SAE Paper
852102, Society of Automotive Engineers, Warrendale, PA,
1985.
[15] Hum, R. W. and Hughes, K. J., "Combustion Characteristics of
Diesel Fuels as Measured in a Constant-Volume Bomb," SAE
Transactions, Vol. 6, No. 1, p. 24.
[16] Hardenberg, H. O. and Ehnert, E. R., "Ignition Quality Determination Problems with Alternative Fuels for Compression Ignition Engines," SAE Paper 811212, Society of Automotive Engineers, Wartendale, PA, 1981.
[17] Tavacha, J. W. and Cliffe, J. O., "The Effects of Cetane Quality
on the Performance of Diesel Engines," SAE Paper 821232, Society of Automotive Engineers, Warrendale, PA, 1982.
[18] Siebers, D. L., "Ignition Delay Characteristics of Alternative
Diesel Fuels: Implications on Cetane Number," SAE Paper
852102, Society of Automotive Engineers, Wartendale, PA,
1986.
[19] Indritz, D., "What is Cetane Number," Symposium on the Chemistry of Cetane Number Improvement, ACS, Miami, FL, April,
1985.
[20] Yu, T. C, Uyehara, Q. A., Meyers, P. S., Collins, R. N., and Mahadevan, K., "Physical and Chemical Ignition Delay in an Operating Diesel Engine Using the Hot-Motored Technique," SAE
Transactions, Vol. 64, 1962, p. 690.
[21] Tsao, K. C, Myers, P. S., and Uyehara, O. A., "Gas Temperatures
During Compression in Motored and Fired Diesel Engines,"
SAE Transactions, Vol. 70, 1962, p. 136.

728 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


[22] Hardenberg, H. O. and Hase, F. W., "An Empirical Formula for
Computing the Pressure Rise Delay of a Fuel from Its Cetane
Number and from the Relevant Parameters of Direct-Injection
Diesel Engines," SAE 790493, Society of Automotive Engineers,
Warrendale, PA, 1979.
[23] Parker, T. E., Forsha, M. D., Stewart, H. E., Horn, K., Sawyer, R.
F., and Oppenheim, A., "Induction Period for Ignition of Fuel
Sprays at High T e m p e r a t u r e s and Pressures," SAE Paper
850087, Society of Automotive Engineers, Wsirrendale, PA, 1985.
[24] Walsh, G. J. and Cheng, W. K., "Effects of Highly Heated Fuel
on Diesel Combustion," SAE Paper 850088, Society of Automotive Engineers, Warrendale, PA, 1985.
[25] Elliot, M. A., "Combustion of Diesel Fuel," SAE Transactions,
Vol. 3, No. 3, p. 490.
[26] El Wakil, M. M., Myers, P. S., and Uyehara, O. A., "Fuel Vaporization and Ignition Lag in Diesel Combustion," SAE Transactions, Vol. 64, 1956, p . 712.
[27] Rao, K. V. L. and Lefebvre, A. H., "Spontaneous Ignition Delay
Times of Hydrocarbon Fuel/Air Mixtures," ASME Transactions,
Vol. 70, 1985.
[28] Chiang, C. W., Myers, P. S., and Uyehara, O. E., "Physical and
Chemical Ignition Delay in an Operating Diesel Engine Using
the Hot-Motored Technique-Part II," SAS Transactions, Vol. 68,
1960, p. 562.
[29] Cox, R. A. and Cole, J. A., "Chemical Aspects of the Autoignition
of Hydrocarbon/Air Mixtures," Combustion and Flame, Vol. 60,
1985, p. 109.
[30] Saeed, M. N. and Henein, N. A., "Ignition Delay Correlations for
Neat Ethanol DF-2 Blends in a DI Diesel Engine," SAE Paper
841343,Societyof Automotive Engineers, Warrendale, PA, 1884.
[31] Dobovisek, Z. and Savery, C. W., "Ignition Delay of Selected Alternative Fuels in IC Engines," SAE Paper 859225, Society of
Automotive Engineers, Warrendale, PA, 1985.
[32] Collins, J. M. and Unzelman, G. H., "Diesel Trends Emphasize
Cetane Economics, Quality, and Prediction," presented at the
API 47th Midyear Refining Meeting, May 1982.
[33] Kloptenstein, W. E., "Estimation of Cetane Index for Esters of
Fatty Acids," JAOCS Vol. 59, No. 12, Dec. 1982, p. 531.
[34] Murphy, M. J., "An Improved Cetane Number Predictor for Alternative Fuels," SAE Paper 831746, Society of Automotive Engineers, Warrendale, PA, 1983.
[35] Steere, D. E., "Development of the Canadian General Standards
Board (CGSB) Cetane Index," SAE Paper 841344, Society of Automotive Engineers, Warrendale, PA, 1984.

[36] Bowden, J. N. and Frame, E. A., "Effect of Orgsinic Sulfur Compounds on Cetane Number," ACS, April, 1985.
[37] Bailey, B. K., Russell, J. A., Wimer, W. W., and Buckingham, J.
P., "Cetane N u m b e r Prediction Modeling," SwRI Report No.
SwRI 9435, Southwest Research Institute, San Antonio, TX,
1986.
[38] Fodor, G. E., "Analysis of Petroleum Products by Midband Infrared Spectroscopy," SAE Paper 941019, Society of Automotive
Engineers, Warrendale, PA, 1994.
[39] UUman, T., "Investigation of the Effects of Fuel Composition o n
Heavy-Duty Diesel Engine Emissions," SAE Paper 892072, Society of Automotive Engineers, Warrendale, PA, 1989.
[40] UUman, T., Mason, R. L., and Montalvo, D. A., "Effects of Fuel
Aromatics, Cetane Number, and Cetane Improver on Emissions
from a 1991 Prototype Heavy-Duty Diesel Engine," SAE Paper
9072171, Society of Automotive Engineers, Warrendale, PA,
1990.
[41] Ryan, T. W., Olikara, C , Buckingham, J., and Dodge, L. G., "The
Effects of Fuel Properties on Emissions from a 2.5 gm NOx
Heavy-Duty Diesel Engine," SAE Paper 982491, Society of Automotive Engineers, Warrendale, PA, Oct., 1998.
[42] Ryan, T. W., "Correlation of Physical and Chemical Ignition Delay to Cetane Number," SAE Paper 852103, Society of Automotive Engineers, Warrendale, PA, 1985.
[43] Ryan, T. W. and Stapper, B., "Diesel Fuel Ignition Quality as Determined in a Constant Volume Combustion Bomb," SAE Paper
870586, Society of Automotive Engineers, Warrendale, PA,
1987.
[44] Ryan, T. W. and Callahan, T. J., "Engine and Constant Volume
B o m b Studies of Diesel Ignition and Combustion," SAE Paper
881626, Society of Automotive Engineers, Warrendale, PA,
1988.
[45] Ryan, T. W., "Development of a Portable Fuel Cetane Quality
Monitor," Belvoir Fuels and Lubricants Research Report No.
277, Southwest Research Institute, San Antonio, TX, 1992.
[46] AUard, L. N., et al., "Diesel Fuel Ignition Quality as Determined
in the Ignition Quality Tester (IQT)," SAE Paper 961182, Society of Automotive Engineers, Warrendale, PA, 1996.
[47] AUard, L. N., et al., "Diesel Fuel Ignition Quality as Determined
in the Ignition Quality Tester (IQT)-Part II," SAE Paper 971636,
Society of Automotive Engineers, Warrendale, PA, 1997.
[48] AUard, L. N., et al., "Diesel Fuel Ignition Quality as Determined
in the Ignition Quality Tester (IQT)-Part III," SAE Paper 1999010, Society of Automotive Engineers, Warrendale, PA, 1999.

MNL37-EB/Jun. 2003

Engineering Sciences of
Aerospace Fuels
Eric M. Goodger^

RFNA red fuming nitric acid


RP-1 rocket propellant narrow-cut kerosine
SAE SOCIETY OF AUTOMOTIVE ENGINEERS
SIT spontaneous ignition temperature
S entropy
Sa air specific impulse
Sf fuel specific impulse
s.f.e.e steady flow energy equation
syngas synthetic, or synthesis, gas, (CO -I- H2)
AT flame temperature rise in luminometer
J"* m a x i m u m adiabatic reaction temperature at constant pressure
TAFLE Thornton aviation fuel lubricity evaluation
TLV threshold limit value
U,u internal energy, specific internal energy
UDMH unsymmetrical dimethylhydrazine
UHC u n b u m t hydrocarbons
V,v volume, specific volume
VM molar volume
VP vapour pressure
W , w work transfer, specific work transfer
WSIM water separation index modified
P fuel density
r ratio of specific heat capacities {cp/c^

NOMENCLATURE
A/F air-fuel ratio o n volume basis
a/f air-fuel ratio on mass basis
ARP Aerospace Recommended Practice (SAE)
BOCLE ball-on-cylinder lubricity evaluator
C velocity of air
CI/LIA corrosion inhibitor/lubricity improving additive
CNG compressed natural gas
CU conductivity unit (microsiemens/meter)
D(X-Y) dissociation enthalpy between a particular XY
bond
E overall energy
E activation energy
E(X-Y) m e a n empirical dissociation enthalpy between
many X-Y bonds
FBP final boiling point
FSII fuel system icing inhibitor
H, h enthalpy, specific enthalpy
\Ha
standard enthalpy of atomization
AHf standard enthalpy of formation
AH standard enthalpy of reaction
Hi total thermochemical enthalpy at temperature T
based on standard initial temperature of 298.15 K
HFRR high frequency reciprocating wear rig
HiTTS high temperature thermally stable
lATA INTERNATIONAL AIR TRANSPORT ASSOCIATION
IBP initial boiling point
Id density impulse
Is specific impulse
JFTOT jet fuel thermal oxidation tester
K partial pressure equilibrium constant
K' concentration equilibrium constant
LNG liquefied natural gas
M molar mass, g/mol
MTBE methyl tertiary butyl ether
m mass, kg
NG natural gas
NIR near infrared spectroscopy
n.f.e.e. non-flow energy equation
p pressure
Q, q heat transfer, specific heat transfer
R gas constant
Ro universal gas constant
' Managing Editor, Landfall Press, 28E Jessopp Road, Norwich, Norfolk, NR2 3QB, UK.

IN AEROSPACE APPLICATIONS, PROPULSION SETS THE MOST STRIN-

GENT requirements in terms of the levels of energy to be provided for the purpose, subject to the constraints of mass and
volume available for carriage of the fuel within the vehicle. In
this study, the following definitions are employed, with the
maximum levels of net specific energy shown in parentheses:
Conventional fuels - aviation fuel mixtures of a hydrocarbon nature invariably derived from petroleum
(44 MJ/kg)
High-performance fuelshydrogen, and individual hydrocarbon materials of particularly high energy content
(120 MJ/kg)
Substitute high-performance fuelsmaterials based on
non-cryogenic compounds of C, H, O, N, boron, etc.
(68 MJ/kg)
The performance of a bulk fuel in practice is a function of
both the properties of the fuel in question and the conditions

729
Copyright'

2003 by A S I M International

www.astm.org

730 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


under which it is used. The former in turn are dependent on
the nature and properties of the fuel components, whereas the
latter influence the extent of intrinsic energy released and its
conversion to produce vehicular thrust. This is particularly
true with ramjet and rocket engine fuels since the chemiccJ
behavior of the combustion products within the duct between
the combustion chamber and the thrust nozzle outlet can exert an overriding influence on the level of resultant thrust.
This chapter provides a concise overview of the heat input
requirements of high performance engines together with the
heat release available from candidate fuels. It also includes
brief comment on the handling characteristics of these fuels
in order to ensure that the most attractive candidates are not
precluded from use by insurmountable problems within the
distribution, storage, and vehicular fuel systems.

ENGINE THERMODYNAMICS
The strength of the bonds between individual atoms comprising a fuel molecule represents stored chemical energy,
and this energy is required to be released and transformed in
some way to produce propulsive thrust, the customary chain
of conversions following the energy route from chemical to
heat to mechanical. These events take place in a heat engine,
and the b r a n c h of engineering science that includes such
heat-to-work conversions is known as Thermodynamics.
Although the actual processes involved throughout a practical heat engine are quite complex, a simplified overview is
adopted by providing a thermodynamic basis of gases associated with idealized conditions and processes, then incorporating the necessary effects of reality since reeil gases do not
follow exactly these idealized processes. The science of thermodynamics is built on the concept of a perfect gas that follows certain laws absolutely during changes in its major
properties of pressure (p), temperature (T), and volume (V)
[Appendix 1]. Fortuitously, the complete range of properties
of such a gas at any given state can be fixed by specifying two
(unrelated) properties only. This makes it possible to represent the complete state of the gas by means of a unique point
on a two-dimensional graph of one property plotted against
another (e.g., p against V). Furthermore, when the state of the
gas changes in etn ideal (reversible) manner, this process of
change can be represented by a unique line on the graph.
Even further, when a n u m b e r of different changes follow
each other in such a m a n n e r as to return to the original state,
they form a closed loop, which represents a cycle that could
be repeated indefinitely. Careful selection of the cyclic loop
processes can therefore provide a heat transfer into the gas
together with a work transfer outwards, thus giving the basis
of an ideal cyclic heat engine [Appendix 2]. Such a cycle, even
though idccJ, is subject to the fundamental laws of thermodjTiamics which stipulate that, although energy cannot be
created or destroyed, not all the heat input can be converted
to work because part of the heat must be rejected at a lower
temperature. Hence, the net heat input must equal the work
output, but the word net must be included or implied.
Ideal gas cycles conceived by sequencing various processes
include the following:
1. CamotMeiximum efficiency between given temperature
limits, but insufficiently practical since work output low.

2. Stirling, & EricssonCamot


efficiency; approximated by
small-scale non-flow units employing continuous external
combustion.
3. OttoEfficiency
lower t h a n C a m o t ; broadly similar to
property changes in spark-ignition reciprocating piston
engine.
4. DieselEfficiency lower than Camot; broadly similar to
property changes in compression- ignition reciprocating
piston engine.
5. Bray tonEfficiency lower than Camot; broadly similar to
property changes in continuous-flow gas turbine, ramjet
and rocket engines.
A major advantage of continuous-flow over reciprocating
engines is that power is being generated continuously rather
t h a n intermittently, hence the power-volume ratios are
higher. The particular theoretical cycle of interest as a yardstick for assessing high-performance jet propulsion is therefore the Bra5?ton Cycle (known in Europe as the Joule cycle).
This comprises em initial compression without heat rejection
through the walls (i.e., "adiabatic," and in fact "isentropic"
since it is also reversible), followed respectively by heat addition at constcint pressure (isobaric), work output by isentropic
expansion, and finally an isobciric heat rejection returning to
the initial state (Fig. 1). Thermodynamic expressions are
available for the heat and work transfers applying to the various components of this cycle and, on completing an overall
energy book-keeping exercise, the thermcil efficiency of the
Brayton cycle appears as follows:
I Ur-D/r

work output
= 1
heat input

''Brayton

where rp is the pressure ratio of the cycle, equal to p^max'/'mm;


x/Pl
and
the index y is the ratio of
/ specific heat capacity of gas at constant pressure \
I specific heat capacity of gas at constant volume j
and equals 1.4 approximately for air.

E}4}ansion

Compression

Heat rejection

Heat
addition

in
Z

rejection

3to4

4to1

FIG. 1^The Brayton cycle shown


on a non-flow basis.

CHAPTER 28: ENGINEERING SCIENCES OF AEROSPACE FUELS 731


Hence, the higher the pressure ratio, the better the efficiency of heat-work conversion. AppHcations of the Braj^on
cycle to gas turbine engines are shown schematically in Fig. 2.
The Brayton and other ideal cycles were conceived as having the heat transfers effected across the boundary wall separating the working gas (usually air, hence the expression
"air standard cycle") and the surrounding atmosphere. This
is a practical possibility and is used, in fact, in Stirling and
Ericsson type engines; however such heat transfers tend to
take time. Since the chemical energy of a fuel cem be released
readily by reaction with oxygen (as shown later under Oxidation Heat Release) combustion with atmospheric air is the
most convenient and effective approach to oxidation (although not necessarily the most efficient or desirable, but
electrochemical oxidation as in a fuel cell does not appear
likely to suit the high-performance r e q u i r e m e n t s of
aerospace propulsion). The alternative oxidants required in
the case of rocket engines operating beyond the Earth's atmosphere are included in Table 1.

Heat
addition

Turbine

Compressor

Heat
rejection
a) Closed circuit (industrial)

Heat
addition

^3

/|

1/
Propulsive gases
1
b) Open circuit (propulsion)

FIG. 2Schematic of gas turbine engines utilizing the Brayton cycle on a steady-flow basis.

Fortuitously, under most conditions the behavior of real


gases, such as air upstream of the combustor and burnt products downstream, approximates very closely to that of perfect
gases, and ideal cycles can thus be used for comparative purposes with the actual changes of events in practical engines.
In practice, also, it is customary to fit a diffuser (a duct of increasing cross sectional area) upstream of the compressor so
that the reduced air velocity promotes an initial part of the
compression. The corresponding fitment of a nozzle (a duct
of decreasing cross sectional area) downstream of the turbine
reduces the pressure with a corresponding increase in exit
gas velocity and thus in thrust. Once the exit velocity reaches
the sonic level, (= V ( g RT) = 331.45 m/s in dry air at 0C),
the exit area chokes, with n o possibility of the effects of
chEmges in conditions being transferred back to the nozzle inlet. Consequently, further acceleration of the gas requires expansion of the nozzle, as shown in Fig. 3.
Thus, the key thermodjTiamic requirement of high performance fuels is an ability to b u m readily and completely within
high-pressure air or other oxidant flowing at high speed, with
minimal radiation so that the bulk of the released heat remains within the working gas. The next step, therefore, is to

TABLE 1Relative performance of rocket fuels and oxidants.


Merit order
Formula
Fuels
Liquid hydrogen
Hydrazine
UDMH
Hydyne
RP-1
Liquid a m m o n i a
Ethanol
Liquid diborane
Oxidants
Liquid fluorine
Liquid oxygen
Nitrogen tetroxide
HTP
RFNA

Chlorine trifluoride

Id

LH2

N2H4
(CH3)2N2H4

Unsymmetrical dimethylhydrazine
60/40 mass mixture of UDMH and
diethylenetriamine (NH2CH2CH2)2NH
rocket propellant narrow-cut kerosine

LNH3
C2H50H
LB2H6
LF2
L02

N204
H202
HN03

CIF4

High test peroxide with cone. H2O2 > 80%


Red fuming nitric acid containing 7% or
more of dissolved oxides of nitrogen

732

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

identify the candidate fuels available, examining their properties with a view to their meeting this requirement.

FUEL MOLECULAR STRUCTURE


The majority of conventional fuels, and also some alternative
high performance variants, are based on compounds of hydrogen and carbon (hydrocarbons). The structure of these
molecules is determined largely by the valency (chemical
combining power) of the two basic elements. Since hydrogen
is monovalent, and carbon tetravalent, the simplest hydrocarbon s t r u c t u r e possible is clearly CH4 (Fig. 4). This is
named methane, and forms the main constituent of the many
natural gases (NG) found around the world, invariably incorporating small amounts of heavier hydrocarbons, nitrogen,
carbon dioxide, etc. depending on the location and the geological history. As the standard domestic/industrial fuel, this
is one of the exceptions of using an individual hydrocarbon
fuel commercially. As a gas, it does not lend itself easily to
t r a n s p o r t applications unless stored u n d e r compression
(CNG) or cryogenically liquefied (LNG). Many other hydroFuel
Nozzle

Diffuser

Air-

Open circuit gas turbine with


Internal heat release plus
diffuser and subsonic nozzle
Fuel

t-Exhaust jet

Air-

(1)

Note that "mole" is the n a m e of the physical quantity,


whereas "mol" is the symbol. As a n example, the molar mass
of methane, CH4, is derived as follows:
-Exhaust jet

Oxidant

Since the atom of hydrogen is the lightest of all the elements,


its mass was taken as unity, cind the masses of all other atoms
assessed relative to it. With the subsequent adoption of the
C''^ isotope as the mass basis with a value of 12 exactly, adjustment to other elemental values gives a value just exceeding unity for naturally-occurring hydrogen, but approximate
rounded integers generally give sufficient accuracy in practice. Hence, the molar mass (M) of a hydrocarbon CaHb for
example would be given by:
M = 12 a + b g/mol (not kg/mol)

Fuel
Ramjet with supersonic nozzle
Fuel
Oxidant

t-

Fuel
b)

The saturated hydrocarbons contain their maximum content


of hydrogen and are, therefore, stable since they do not need
to react to seek further hydrogen. On the other hand, the unsaturated hydrocarbons incorporate multi-bonding between
adjacent carbon atoms, which imparts instability as these
bonds open relatively easily to admit additional hydrogen or
to permit inter-bonding of like molecules (polymerization),
leading to self-contamination by the formation of gums and
other deposits. Nevertheless, these unsaturated hydrocarbons do exist because although they are energetically unstable to elemental decomposition, they are reasonably stable
kinetically in that the rates of reaction are very slow below
SOO^C at low pressure in the absence of catalystscomparable to a stone remaining stationary resting on a hillside rather
than sliding down the slope.
B u o y a n c y i n Air

Fuel

b)

Storage Stability

> Exhaust jet

a)

carbon structures are feasible, most of them categorized into


a n u m b e r of "series" depending on their general formulae, as
shown in Table 2.
The main properties of the first members of these hydrocarbon series are shown in Table 3. ICnowledge of the molecular structure of a hydrocarbon in terms of size, shape, and
carbon-carbon bonding together permit prediction of a number of physical a n d chemical characteristics that transfer
across to fuel in bulk, as shown in the following analysis:

Rocl<et

FIG. 3Schematic of continuous flow jet engines.

CH4

Condensed
molecular

H-c-H

Plane
structural

(XTJD:)

12.01115 + 4 (1.00797) = 16.04303 g/mol exactly, or


12 + 4 ( 1 ) = 1 6 g/mol approximately.
Comparison of the molar mass levels with the value of 28.96
g/mol for atmospheric air shows that any leaks of methane or
ethene (plus, of course, hydrogen) would disperse upwards
into the atmosphere rather than sink and accumulate as potentially explosive mixtures with air.

S^-

Electron bond Spatial structural Ball and stick Stuart


plane structural (Tetrahedral)
model
model

FIG. 4Representations of the structure of methane [1].

CHAPTER 28: ENGINEERING

SCIENCES

OF AEROSPACE FUELS

733

TABLE 2General features of the major hydrocarbon series.


Series name
Petroleum Organic
technology chemistry

Series
molecular
formula

Description

Cg example
Condensed
formula

General properties

Plane structural
formula
HHHHHH

Paraffins

Alkanes

I I I I II

CjjH2n+2 Open-chain saturated

C5H14 H-C-C-C-C-C-C-H Stable


I I I I I I
Hydrogen-rich
HHHHHH
(high specific
energy)
Spontaneously
ignitable (imless
isomerized)
Hexane
HHHHHH

Olefins

Alkenes

CjjH2u

Open-chain unsaturated CgH22

I I I I II

C=C-C-C-C-C-H Unstable

I I II

HHHH
Hex-1-ene

Naphthenes Cyclanes

Aromatics

(CH2)jj

Aromatics CjjH2ii.6
etc.

Closed-chain saturated

C5HJ2

Closed-chain resonance
stabilized

CgHg

H2

H2

Benzene

Physical State
The variations in boiling and freezing points show that increase in molecular size incurs a progressive change from gas
to liquid to solid. Although hydrocarbon molecules are generally not polar, in that they do not tend to have their centers
of negative and positive charges so displaced as to give a permanent electrostatic field around them, they do exhibit weak
forces of inter-molecular attraction because of the orbital
movements of the myriad of electrons surrounding the host
of atomic nuclei. With small molecules (e.g., the paraffins
CH4 to CaHg) these attractions are so small that the molecules
are free to move independently, and the bulk material exists
as a gas at normal temperature and pressure. With larger
molecules (e.g., C4H10 to C16H34), the attractions are sufficient to hold the molecules together to give bulk liquids. The
even larger molecules (C17H36 plus) are so strongly attracted
as to be firmly locked together as solids. Similar arguments

Stable

Stable but attacks


elastomers
Carbon-rich
(smoke, deposits,
radiant flame)

apply to the molecules of the other hydrocarbon series. Liquid density also increases progressively with molecular size.
Spontaneous Ignitability
Molecules will commence oxidation only when sufficient energy is supplied to rupture one of the internal bonds, permitting a combination with an oxygen atom (see the section on
Oxidation Heat Release and its Appendix). This preliminary
product is liable to be unstable, so initiate a chain of reactions until eventually full combustion occurs with the formation of CO2 and H2O. This initial energy may be supplied as
heat, leading to thermal agitation of the molecules and consequent bond rupture. The minimum temperature at which
this chain process leads to ignition is known as the spontaneous ignition temperature, SIT (sometimes described as autoignition temperature, AIT). The larger molecules, being
more unwieldy, are less able to withstand thermal agitation

734 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


TABLE 3Properties of first members of the major hydrocarbon series.
Series
name

Member
name

Formula

H/C
molar

Molar
mass
g/raol

Liquid
density

Paraffins

methane

CH4

16.04

0.415''

-161.5 -184.0

bp
C

SIT Stoic a/f


C
mass kj/mol

fp

20C
540

17.19

Net calorific values


Energy
kJ/mol Specific
energy
density
MJ/kg
MJ/L

-74.90

-0.80

Maximum
combution
temperature
C

50.05

20.77

1974

ethane

C2H6

30.07

0.561''

-88.3

-172.0

515

16.05

-84.72

-1.43

47.52

26.66

2009

propane

C3H8

2.67

44.10

0.585''

-44.5

-190.0

450

15.63

-102.92

-2.05

46.39

27.14

2016

butane

C4H10

2.5

58.12

O.6OO''

-0.6

-135.0

405

15.42

-124.82

-2.66

45.77

27.46

2020

pentane

C5H12

2.4

72.15

0.626

36.2

-131.5

260

15.29

-146.54

-3.27

45.38

28.41

2022

hexane

^6^14

2.3

86.18

0.660

69.0

-94.3

255

15.14

-167.30

-3.89

45.13

29.79

2023

ethene

C2H4

2.0

28.05

0.384''

-103.8 -169.4

490

14.75

52.32

-1.32

47.19

18.20

2147

Olefins

propene

C3H6

2.0

42.08

0.610''

-47.0

-185.2

460

14.75

20.43

-1.93

45.81

27.94

2089

but-1-ene

C4H8

2.0

56.11

0.631''

-6.3

-185.4

385

14.75

1.17

-2.54

45.35

28.62

2075

pent-1-ene

275

14.75

-20.93

-3.16

45.03

28.86

2066

14.75

-77.29

-3.10

44.23

23.22

2037

C5H10

2.0

70.14

0.641

34.0

-139.0

Naphthenes cyclopentane

C5H10

2.0

70.14

0.751

49.5

-93.9

cyclohexane

C6H12

2.0

84.16

0.778

80.7

6.6

280

14.75

-123.22

-3.69

43.86

34.12

2032

benzene

C6H6

1.0

78.11.

0.878

80.1

5.5

577

13.24

82.98

-3.17

40.61

35.66

2093

toluene

C7H8

1.14

92.14

0.866

110.5

-95.0

592

13.47

50.03

-3.77

40.97

35.48

2075

xylenes (avg) C9H10

1.25

106.17

0.868

140.2

-31.3

563

13.64

18.06

-4.38

41.25

35.82

2069

-259

574

8.42

2171

72.4S

2036

Aromatics

Parent

hydrogen

H2

00

2.02

0.070''

carbon

C(gr)

12.01

2.2IS

elements

-252:7

3667 sublimes

34.19

-0.24

120.24

11.48

-0.3

32.76

b = at boiling point
s = solid

without rupture, and thus exhibit lower levels of SIT. Furthermore, molecules that are m a d e more compact by isomerization (rearrangement geometrically with n o loss or
gain of any atoms) show higher levels. These two p h e n o m e n a
are illustrated by the following examples:
Methane
CH4

Normal Octane
n-CgHig
H

H H H H
1 1
1 1 1 11
HCCCCC-CCH
1
1
H H H H H H H H

540

230

H
HCH

SIT

H H H

Isooctane
i-CgHig
(2,2,4-trimethylpentcine)
H
HCH
HC

CaHb + ms (O2 + 3.76 N2) = nj CO2 + n2 H2O + n^ N2

where nis = stoichiometric moles of O2 per mole of fuel.


Molar balances of the four elements individually give the
vEilues of the unknown molar quantities, and permit expansion of E q 2 to the following:

stoichiometric air-fuel molar ratio = (A/F)s

CH

= 4.76 m J l = 4.76 a + 1.19 b

(4)

and.

HCH

stoichiometric air-fuel mass ratio = (ci/f)s

H
467

(2)

Hence,

HCH
H

The stoichiometric mixture is chemically correct in that the


proportions of fuel and oxidant leave no excess or deficiency
of either material on reaction. With atmospheric air adopted
as the standard oxidant, it is noted that nitrogen and oxygen
exist in ratios of 3.76 by volume, aind 3.31 by mass. Consequently m moles of oxygen are contained in 4.76 m moles of
air, representing 32 m grams of oxygen and (4.31 X 32 m) or
137.9 m grams of air. The stoichiometric equation with air
for a hydrocarbon fuel of known formula, CaHb, becomes:

CaHb + (a + 0.25 b) (O2 + 3.76 N2)


(3)
a CO2 + 0.5b H2O + (3.76 a + 0.94 b) N2

Stoichiometry

"C

(A/F)s

28.96 _ 137.85 a + 34.46 b


12a+ b
12a+ b

(5)

CHAPTER

28: ENGINEERING

Since hydrogen, in comparison with carbon, needs more


air for combustion, the stoichiometric air-fuel ratios are
higher with the hydrogen-rich fuels, as in Table 3.
Oxidation Heat Release
Since the events of interest here relate to flowing, rather than
non-flowing, mixtures, changes of energy are expressed in
terms of enthalpy rather than internal energy. Thermodynamically, the standard enthalpy of formation (AHf) of a compound is the net enthalpy change occurring when the component elements are first raised to a gaseous atomic state and
then permitted to release the 'dissociation enthalpy' in forming
the compound in question. The resulting vEilue is commonly
negative, indicating an enthalpy loss of the system material due
to a net outwards flow, and showing the resultant compound
to be more stable than its parent elements. Similarly, when
both the compound and its stoichiometric proportion of O2 are
energised to gaseous atoms by provision of the dissociation enthalpy, and then permitted to react, the net enthalpy output is
known as the standard enthalpy of reaction (Af/) and, again,
is negative when flowing outwards. (In petroleum technology
terms, on the other hand, heat released by combustion is
shown as positive since this is the desired objective.) These
standard enthalpies involve equal initial and final temperatures, the standard value being 25C (298.15 K) and denoted by
the superscript o [Appendix 3]. The molar enthalpies of reaction in Table 3 are seen to increase with molecular size.
Maximum Combustion Temperature
The maximum temperature realized by combustion occurs
when no heat is lost through the combustor walls (adiabatic).
Since the conditions of interest in this study relate to mixtures flowing at constant pressure (isobaric), the relevant
m a x i m u m temperature is described here as the isobaric adiabatic reaction temperature, and denoted by T*. The method
of computation is based on the concept of equating the enthalpy released by the reactants, in generating the dissociated
products at the initial temperature, with that which would
have been required to heat these products from the initial
temperature to the final temperature T*. Hence,
AHr = physical enthalpy absorbed by products
heated from 25C (298.15 K) to T*
The first step in computation, therefore, is to derive the stoichiometric combustion equation, taking into account that at
a level of about 1800C the products of reaction become so
agitated thermally as to start dissociating back to their reactant form. The extent of this dissociation is dependent on the
level of temperature, and expressed in terms of an equilibrium constant, which is the ratio of the partial pressures of
the products and reactants. Since carbon burns in a twostage process through CO to CO2, the combustion reactions
at high temperature are written reversibly as follows:
H2 + 0.5 O2 ^ H2O, and CO + 0.5 O2

CO2

The stoichiometric equation at high temperature therefore


appears in the following form:
CaHb + m, (O2 + 3.76 N2)
ni CO2 + n2 H2O + ns CO -F n4 H2 + nj O2 + n^ N2

(6)

SCIENCES

OF AEROSPACE

FUELS

735

[Appendix 4]. By trial and error, a value of T* is found where


the total thermochemical enthalpy absorbed by the products
arising at that temperature is equal to the value of AH" [Appendix 5].
The combustion temperatures shown in Table 3 do not indicate any marked variation. This follows because any higher
hydrogen content, despite giving a higher specific energy,
would also generate larger quantities of H2O product. The
particularly high heat capacity of this product absorbs the
additional heat release and so permits little change in the resulting temperature.
As a general rule, hydrogen is preferable to carbon in view
of its high specific energy, its clean burning capability with
minimsJ emissions, its wide range of flammability, and its
relatively high flame velocity. Consequently, the hydrogenrich paraffins tend to be preferable to the carbon-rich aromatics. However, other requirements sometimes pertain.

COMMERCIAL FUELS PROPERTIES


AND TESTS
To date, the most common source of liquid fuels for high performance engines is crude oil, which evolves from decayed
marine matter and collects within the strata of porous rocks
(hence rock oil, or "petr"-"oleum"). Crude oil consists mainly
of hydrocarbons with traces of other materials depending on
the nature of the source and reservoir rocks. Individual fractions are derived by continuous distillation (fractionation)
followed by various methods of treatment to ensure the specified quality. Commercial fuels invariably comprise mixtures
of many different compounds with properties that either represent a m e a n of the c o m p o n e n t values (e.g., density) or
range over a m i n i m u m to a m a x i m u m (e.g., distillation temperatures). Exceptions occur in some cases where perform a n c e is overriding the making of individual materials,
rather than mixtures, essential (e.g., hydrogen).
The quality of aviation fuels is maintained by detailed specifications devised under the auspices of national authoritative bodies such as ASTM International in the U.S.A., the
Ministry of Defence in the U.K., and other organizations elsewhere. As well as the properties, the test methods by which
they are assessed are also specified, as with ASTM (civil) and
Department of Defense (military) in the U.S.A., the Institute
of Petroleum in the U.K. and other national bodies elsewhere.
Typical properties of representative fuels are shown in Table
4. ASTM and IP now adopt an increasing number of tests
jointiy.
A convenient technique for presenting an overview of the
major properties of petroleum-derived fuels is to select density as a basis for comparison, and to plot all other major
properties against it, as shown for petroleum fuels in Fig. 5.
The following discussion deals with the properties in an order comparable to that presented in Table 4, including values
for substitute high performance fuels and the composite plot
against density.
Density
The standard ASTM method of measuring the density (p) of a
liquid fuel is by means of a hydrometer floating in the fuel

736

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

TABLE 4Typical properties of conventional and substitute high-performance fuels.

Density Boiling range fp Kinematic Flash SIT


kg/L@
C
C viscosity point C
15C
cSt@
C
15C

Fuel

Stoic a/f Flamm. Net calorific values


Maximum
Energy combustion
limits Specific
mass
density temperature
a/f mass energy
MJ/kg
MJ/L
C

Aviation
gasoline

0.72

46 - 145

-70

0.5

-40 470

14.9

26-4

44.2

31.8

Wide cut
ftiel

0.78

73 - 235

-62

1.5

-10 270

14.5

24-4

43.6

34.0

Aviation
kerosine

0.80

152 - 256 -52

1.8

43

254

14.8

22-4

43.4

34.7

High flash
fuel

0.82

185-244 -51

2.3

63

250

14.7

22-4

43.2

35.4

Gas oil

0.84

180-360 -30

6.0

70

247

14.6

21-3

42.9

36.0

2027

Methanol
CH3OH

0.79

64.8

-95.5

0.8

11

385

6.5

12.6- 1.6 19.9

16.0

1969

MTBE
CH3OC4H9 0.75

55.0

-109

435

11.7 20.2 - 3.6 35.1

26.0

2002

Nitfomethane
1.14
CH3NO2

101

-17

0.6

35

419

1.7

10.9

12.5

2412

1.01

113.5

1.0

52

270

4.3

18.3 - 0

16.7

16.9

2219

Pentaborane
B5H9
0.63

58.4

-46.6

0.6

13.1

45-?

67.8

42.7

2527

95

-134

0.5

14.8

47.1

32.0

2025

2022

Hydrazine
N9H4

Triethyl
borane
(^2^5)36

0.68

NOTE: Lamina flame speeds:


most hydrocarbon fuels = 0.5 m/s approximately,
hydrocarbon = 35 m/s
boranes = 45 m/s

sample, correcting the results to the standard temperature of


15C by meajis of international standard tables. Details are
given in ASTM D 1298, Density, Relative Density (Specific
Gravity) or API Gravity of Crude Petroleum and Liquid
Petroleum Products by Hydrometer Method. The data in
Table 4 show that the densities of the hydrocarbon oxygenates (methanol and MTBE) differ little from those of
petroleum fuels, whereas nitrogen compounds are heavier.
Liquid hydrogen, of course, has been seen to be very much
lighter, although a 50% liquid/solid slush mode increases
density by about 18%. The droplet size resulting in fuel
sprays bears a direct relationship to density, typically showing an increase of about 20% with a doubling of density.
Volatility
The volatility characteristics of a commercial fuel mixture
can be assessed by standard methods of measuring distilla-

tion temperature/recoveries, vapor pressure, and flash point.


These data can be supported by experimental examination of
equilibrium air distillation (usually confined to piston-engine
gasolines), vapor-liquid ratio, and the direct laboratory measurement of the evaporation rates of individual droplets.
In the standard test ASTM D 86, Distillation of Petroleum
Products at Atmospheric Pressure, the apparatus comprises
a controlled heat source, a flask equipped with a thermometer, and a side arm leading into a cooled condenser tube, plus
a measuring cylinder. The 100 mL test sample is progressively vaporized in the flask, and the condensed droplets collected in the cylinder. The corresponding readings of temperature and (percentage) volume recovery are plotted as a
distillation curve. The initieJ boiling point (IBP) is taken as
the temperature at the fall of the first condensed droplet, and
the final boiling point (FBP) as the highest vapor temperature reached during the test, both temperatures being corrected for barometric pressure. The data in Table 4 show that

CHAPTER

28: ENGINEERING

the boiling points of the substitute fuels generally lie within


the range of gasoline and light kerosine.
Volatility can also be assessed by measurement of vapor
pressure, but this test applies mainly to wide-cut and the
more volatile fuels. Similarly, the vapor-liquid ratios at given
temperatures indicate volatility. For gasoline, the standard
test ASTM D 2533, Vapor-Liquid Ratio of Spark-Ignition Engine Fuels is undertciken under static conditions, whereas the
SAE ARP492, Aircraft Engine Fuel P u m p Cavitation E n durance Test relating to pumping applications with wide-cut
fuels is undertaken dynamically. In the latter test, the "vapor"
volume measured incorporates the air released during the
pumping process, and is dependent on the air solubility of
the fuel.
Another s t a n d a r d test concerns flash point. For the
petroleum fuel range, this is an assessment of volatility rather
than flammability since the m i n i m u m fuel concentration to
sustain combustion (the weak mixture limit), which exhibits
a value of about 1% by volume in the mixture with air, is
c o m m o n over the whole range of petroleum fuels from gasolines to residual fuel oils. ASTM D 93, Flash Point By PenskyMartens Closed Cup Tester is based on heating the fuel sample progressively, and repeatedly inserting a standard-sized
flame into the vapor-air mixture above the liquid free surface
until a temperature is reached where the flame promotes momentary combustion. The flash point (the weak temperature
limit), in contrast to the weak mixture limit, varies directly
with density, reflecting the change in volatility. The substitute fuels in Table 4 show slightly lower values of flash point
than the conventionals. (Note that the fire point relates to the
slightly higher temperature where combustion is continuous
rather than momentary.)
Viscosity
Viscosity arises in a bulk fuel from the weak electrostatic
forces acting between the molecules. These permit many hydrocarbon fuels to exist in the liquid phase under ambient
conditions but, at the same time, promote resistance to the
internal displacement involved in flow. This resistance is
termed dynamic viscosity, and is defined as the tangential
force on unit Eirea of either of two peirallel planes within the
fuel sample located at unit distance apart when one plane
moves with unit velocity in its own plane relative to the other
plane. Thus, dynamic viscosity is the ratio of the applied
shear stress and the rate of shear, such that:
force
Dynamic viscosity = 17 =
^

area

length .
.
.^ .
X ^r in units of Poise
velocity

The smaller unit, centipoise (cP), is more convenient, where


1 cP = 0.01 P = 1 mN s/m^
Division with density provides the kinematic viscosity, as
follows
Kinematic viscosity = v = ri/p in units of Stokes
Here again, it is more convenient to use the smaller unit, centistokes (cSt), where
1 cSt = 0.01 St = 1 mm^/s
Dynamic viscosity can be determined by measuring the terminal velocity of a small sphere falling under gravity in the

SCIENCES

OF AEROSPACE

FUELS

737

sample, based on the inverse relationship between viscosity


and sphere terminal velocity. Kinematic viscosity is generally
determined from the time taken for a given volume of sample
to flow under gravity through a U-shaped capillary-tube viscometer, usually vertically disposed, at a specified temperature, as in ASTM D445, Kinematic Viscosity of Transparent
and Opaque Liquids (The Calculation of Dynamic Viscosity).
In this test, the hydraulic head of the sample, which is density dependent, promotes the flow by gravity, whereas the dynamic viscosity resists the flow, hence the result is dependent
on the quotient of these two effects. The test involves a low
rate of shear, the kinematic viscosity of the sample being determined by multiplying the measured flow time with the calibration constant for the instrument used.
An increase in fuel density is associated with increases in
molecular size and inter-molecular forces, and also in kinematic viscosity. Raising the temperature of a fuel promotes
expansion, and the increase in molecular spacing weakens
the molecular attraction. Typical of action-at-a-distance
forces, this attraction follows an inverse power law, and plots
as a hyperbolic curve against temperature. For convenience,
these curved relationships have been converted to straight
lines by plotting on the following empirical logarithmic basis:
log log (u + a) = n log r -I- b
where a, n, and b are constants. On such axes printed on specially designed charts (e.g. ASTM D341, Standard ViscosityTemperature Charts for Liquid Petroleum Products), two
points only need be determined by experiment, the remainder being found graphically on the straight line passing
through them, limited at the high-temperature end by vaporization and/or ignition, and at the low temperature end by
freezing.
In fuel technology, dynamic viscosity is of interest in relation to the setding rate of contaminants during storage, but
the m o r e generally-used kinematic viscosity provides an
indication of the power required for p u m p i n g , filtration,
and spraying, bearing a direct relationship to spray droplet
size. Such data available in Table 4 show that the viscosities
of the substitute fuels lie between those of gasoline and wide
cut fuel.

Solidification
Comparable with the range of boiling points resulting from
progressive heating of a commercial fuel mixture as the several components distill in turn, a range of solidification temperatures can be expected from progressive cooling as each
component crystallizes as wax. Eventually a temperature is
reached where the viscosity approaches infinity as the fuel solidifies completely. The relevant solidification temperatures
can be determined and expressed in several ways. Generally,
the sample is cooled until the first appearance of wax crystals
then, in order to avoid spurious results from supercooling, it
is allowed to warm until the wax just disappears. (Thermodynamically, the temperatures of appearance and disappearance of wax must be different.) In ASTM D 2386, Freezing
Point of Aviation Fuels, the sample is stirred and the result
designated as the freezing point. D3rnamic methods are also
available, as in ASTM D 4305, Filter Flow of Aviation Fuels at
Low Temperatures, in which the sample is cooled under pre-

738

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

scribed conditions and repeatedly subjected to a low pressure


pulse directing it through a fine wire mesh filter until a temperature is reached at which the filter plugs. Other suggested
methods for assessing fiiel fi-eezing include a system for optically sensing the presence of wax crystals in the sample, and
a chemical analysis method based on the relationship of freezing to the concentrations of aromatics and saturates as determined by near-infrared (NIR) spectroscopy. An alternative
"Phase Technology" method incorporates freezing, cloud, and
pour points based on a light scattering technique [10].
The freezing points of most of the substitute fuels shown
are relatively low, with the exception of hydrazine.
Surface Tension
This property helps to determine the size of fuel droplets in a
spray. It can be assessed in a laboratory by measuring the
force required to free some flat object (e.g., a glass slide or
wire ring) vertically upwards from the surface of the fuel, and
then dividing this force by the length of periphery of the object. Values for both conventional and substitute fuels reduce
with increasing temperature but vary little from a range of
20-40 mN/m, the exception being hydrazine with values
ranging from 60-80 mN/m. ASTM D 3825 can be used, but
for liquid gases only.
Flammability
The flammable nature of a fuel can be assessed in various
ways. In the case of the petroleum fuels, the weak mixture
limit was seen to be approximately c o m m o n (at about 1% vapor in the mixture with air), consequently the weak temperature limit at which this mixture pertains, that is, the flash
point, depends on the volatility of the fuel. With different
types of fuel, however, the weak mixture limits differ, hence
flash point then gives a direct indication of fire safety. The
flash points for the substitute fuels in Table 5 are seen to be
slightly lower than those of the conventionals.
Mixture limits of flammability can be determined in a laboratory tube apparatus by seeking the particular air-fuel ratios at which the flame fails to propagate following ignition.
A similar rig can be employed to determine the rate of flame
propagation during the uniform movement over the first few
centimeters after ignition. When the flame progresses further
cdong the tube, it becomes subjected to the pressure waves

reflected from the ends of the tube, and in extreme cases may
even experience detonation involving a combination of shock
wave a n d flame. These tests are not standardized, b u t
adopted in combustion laboratories and on chamber rigs by
engine manufacturers.
The data in Table 4 show certain differences in flammable
mixture limits, with those for hydrogen and pentaborane being particularly wide. Also, the maximum flame velocity for
hydrogen is relatively high.
S p o n t a n e o u s Ignitability
In the standard ASTM E 659, Autoignition Temperature of
Liquid Chemicals, a small charge of liquid fuel is delivered as
a droplet by means of a syringe into a heated open flask, and
the delay noted before the onset of ignition. The method comprises repeated tests at progressively lower temperatures until the m i n i m u m level is found to promote ignition (the spontaneous ignition temperature, or SIT). The associated delay
period is a maximum, and usually comprises several seconds
under the test condition of atmospheric pressure. The levels
of SIT for the conventional hydrocarbons vary inversely with
density but tend to be higher for the substitute fuels.
Stoichiometry
As an extension of the treatment of hydrocarbons in the section on Stoichiometry, the stoichiometric combustion equation for the substitute fuels provides the following general expression:
CaHbOcNd + ms (O2 + 3.76 N2) = nj CO2 + Uz H2O + Us N2
From molar balances of the four elements,
m . = a + 0.25 b - 0.5 c
Hence, stoichiometric air-fuel molar ratio
= (A/F), = 4.76 a

1.19 b - 2 . 3 8 c

and, stoichiometric air-fuel mass ratio


137.85 a -I- 34.46 b 68.92 c
(a/f)s =
12 a-H b + 16 c + 14 d
The values in Table 4 show, in comparison with the hydrocarbons, the reductions in stoichiometric air-fuel ratios expected in view of the presence of oxygen and/or nitrogen in the
fuel. Hydrogen, of course, is the exception on a mass basis.

TABLE 5Relative stoichiometric calorific and specific impulse values of elements, non-carbon hydrides and organometsdlics [5].

Sp. En.

En. Dens.

Rel. Fuel
Density
Impulse (Sfd)

100
(43.4 MJ/kg)
276
153
133
57
72
43
38
168
156
98
125

100
(34.7 MJ/L)
24
353
400
124
241
33
48
90
123
103
86

100
(l.OSkNs/L)
19
119
193
48
96
63
67
58
73
69
60

Rel. Fuel
Material

Symbol

Av. kero.
Hydrogen
Beryllium
Boron
Magnesium
Aluminum
Ammonia
Hydrazine
Dlborane
Pentaborane
TEA
Aluminum borohydrlde

H2

Be
B
Mg
Al
NH3
N2H4
B2H6
B5H9
A1(C2H5)3
A1(BH4)3

Rel. Fuel
Specific
Impulse (Sf)

Rel. Air
Specific
Impulse (So)

100
(25.5 kN s/kg)
254
54
65
25
29
83
53
108
92
66
89

100
(1.76 kN s/kg)
105
116
105
122
122
88
93
107
106
108
107

CHAPTER 28: ENGINEERING SCIENCES OF AEROSPACE FUELS 739


When boron is present in the fuel, the resuking product of
combustion is B2O3, and the same principles of molar balance apply to derive the stoichiometric air-fuel ratios.

Calorific Values
Whereas the oxidation heat release was treated thermochemically in the Oxidation Heat Release section leading to the
derivation of AHr, the thermodynamic approach permits an
application to practical test methods in the laboratory. The
thermodynamic laws of gases (Appendix 6) give rise to the
following energy equation:
Q W = At/
Q - W = AH

in non flow case, and


in steady flow case with negligible
changes in potential and kinetic
energies.

where
Q = heat transfer
W = work transfer
At/ = change in internal energy
AH = change in enthalpy, where H = U +pV, andp V = flow
energy.
Since it is far easier to measure heat transfer than work
transfer, conditions are selected where work transfer is zero
so that these expressions simplify to
Q = AC/ in non flow case at constant volume, and
Q = AH in steady flow case at constant pressure.
With gaseous fuels, the enthalpy released on combustion is
determined as the energy density (MJ/L) by burning at constant pressure through a steady flow calorimeter. The heat so
released is measured from the rise in temperature of the flowing cooling water. The test result is corrected for the standardized volume of fuel gas burnt, together with the expansion of both the cooling water and the flue gases.
With liquid fuels, specific energy is determined by burning
a known mass of fuel in a stainless steel b o m b located in a
water-filled calorimeter u n d e r non-flow constant volume
conditions, as in ASTM D 4809, Heat of Combustion of Liquid H y d r o c a r b o n Fuels by B o m b Calorimeter (Precision
Method). The b o m b is pressurized to 3.0 MPa (30 atm) with
water-saturated oxygen gas to ensure complete combustion.
The combustion heat so produced raises the temperature of
the caJorimeter water by about 3K, as measured by a platinum resistance or thermistor instrument. The mathematical
product of this temperature rise and the thermal capacity of
the calorimeterdetermined previously using benzoic acid
of known specific energyprovides a value of the quantity
of heat absorbed. Division by the initial mass of the sample
thus gives the specific energy of the sample fuel at constant
volume.
Because the final temperature of this test is only marginally
above ambient, the water produced by combustion of the hydrogen content of the fuel condenses to the liquid phase,
adding its latent enthalpy of vaporization to the combustion
energy. Consequently, the resulting specific energy is described as the "gross" value. In contrast, the combustion products leaving the working section of any heat engine must, of

necessity, still be hot, following the second law of thermodynamics that permits partial conversion only of heat to work.
Hence the combustion water leaves in the vapor phase, and
the "net" value of specific energy is more meaningful in engine
practice. This is routinely derived by subtracting the latent enthalpy of the combustion water using the following expression, which also converts the non-flow constant-volume result
to steady-flow constant-pressure:
Net specific energy @ 25C and constant pressure, in units
of MJ/kg = gross specific energy @ 25C & constant volume
0.2122 (mass % hydrogen in sample)
These experimental results, of course, will not tally exactly
with values of AHr because initial and final temperatures differ in the former case, and are c o m m o n in the latter (Table 3).
In order to improve accuracy, n u m e r o u s corrections are
made to allow for the enthalpies of formation of nitric and
sulfuric acids produced on combustion, and for the heat input from the burnt firing wire. Further refinements to correct
for heat transfers into and out of the CcJorimeter during the
test are represented by the adiabatic method and the isoperibol method, both of which incorporate an outer water bath.
In the former method, the temperature of the outer bath automatically matches that of the calorimeter water, so minimizing any heat interchange. In the latter method, the outer
bath is maintained at some selected constant temperature so
that heat interchange may be c o m p u t e d accurately, the
whole instrument being heavily insulated. In this latter case,
the local environment (the outer bath) is isothermal but the
external environment (the laboratory) is not, hence the use of
the term isoperibol rather than isothermal.
Because of the requirements of test time and practiced expertise in the above methods, attention has turned towards
methods of estimating specific energy based on statistical
correlation between accurate values of related properties.
ASTM D 3338, Estimation of Net Heat of Combustion of Aviation Fuels, involves correlation between aromatic content,
density, and averages of distillation temperatures at stated
recoveries, whereas alternative methods are based on density, aniline point, and/or sulfur content. Such methods are
dependent on the combined accuracies of the test results involved, and are therefore less precise than those obtained by
direct calorimetric determination.
The results presented in Table 4 for the petroleum fuels reflect the density effect of reducing specific energy and increasing energy density shown for the individual hydrocarbons in Table 3. The former effect, again, is understandable
from the reducing level of hydrogen content, whereas the latter is underscored by the fact that energy density is the direct
arithmetical product of specific energy and density, and
whereas the former falls by a mere 20% over the density range,
the latter rises by about 50% and is therefore the dominant
term in the product, as seen in Fig. 5. A special requirement
arises in the case of ramjet powered aircraft. These are essentially high-speed vehicles, hence fuel storage volume is at a
p r e m i u m to minimize drag, and energy density becomes the
criterion. The customary rise with increasing density is shown
in Fig. 6 for some specially selected high-performance fuels
indicating the expected need for high density.
Substitute fuels of higher energy density can be achieved
by replacing the c a r b o n in the h y d r o c a r b o n with some

740 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Hydrogen 15
content 14 %Mass IS 1=
- 45 Specific
- 44 energy
43 MJ/kgnet
Energy 35
density
density
MJ/Lnet ^^ =

=-^

- 4
.
0

Viscosity
est @ 40C

Temperature C

Density, Icg/L @ 15C


FiG. 5Basic properties of jet fueis [1]. Properties in braclcets represent limits to
distiiiation ranges.

>i

^ 40-

H-cot d

Shelldyne M
Adamantines
_
Pertiydrofluoranthene
l-Methyipertiyfluorene
icalin 4 ^ '*
Cyciododecarres

Energy-dense cyclics

Normal and monocyclic


hydrocarbons C^

An interesting conclusion concerns the level of specific energy available from unit masses of stoichiometric fuel-air
mixtures. Although hydrogen enrichment of a fuel tends to a
higher specific energy on a fuel mass basis, the stoichiometric air-fuel mass ratio also rises, consequently more air is
available to share the energy output. Hence, the stoichiometric mixture values of specific energy vary little from about 2.9
MJ/kg (net). This means that, in general, whereas the fuel carrying capacity of a vehicle is largely affected by specific energy of the fuel, the performance of the engine is not.

7^

XT

Conventional petroleum fuels

Maximum Comibustion Temperature


HaW

0.4

0.8
Density kg/L at 15C

1.2

"7
1.6

FiG. 6Energy densities of candidate high-performance fuels [1,2].

element contributing more calorific value to the resultant liquid hydride. Examples of such fuels include hydrides of
boron, beryllium, lithium, magnesium, aluminium, and titanium, plus compounds of hydrogen, carbon, and boron as included in Table 4.

The isobaric adiabatic reaction temperature for a commercial fuel mixture cannot be calculated without knowledge of
the individual chemical constituents and their proportions.
However, a broad assessment can be made on the assumption of an average molecular formula in each case.
The combustion temperature values included in Table 4
have been computed on the following basis:
Fuel

Assumed Average Formula

Aviation gasoline
Aviation kerosine
Gas oil

Cl2.5H24.4
C15H27.3

C7.3H15.3

The calculated vEilues for the petroleum fuels are seen to


vary little from 2025C. On the other hand, methanol is lower

CHAPTER 28: ENGINEERING SCIENCES OF AEROSPACE FUELS 741


at 1969C, while nitromethane and pentaborane are higher at
2412 and 2527C, respectively.

FUEL COMBUSTION PERFORMANCE IN


CONTINUOUS FLOW

Smoke Tendency

Fuel Preparation and Mixing

Within fuel-rich regions of a flame, hot fuel molecules can


become so agitated thermally that they crack into portions,
involving the release of free atoms of carbon in the form of
smoke. This is undesirable in a heat engine because:
Combustion efficiency is reduced through the loss of the
calorific value of the free carbon.
Glowing particles of carbon radiate heat at a relatively high
rate and thus overheat the combustor liner so reducing
its life.
Tendencies to soot deposition within the combustor are increased, with the possibilities of mechanical damage due to
t e m p e r a t u r e gradients a n d differential expansion in the
combustor liner.
Tendencies to exhaust smoke emissions to the environment are increased.
For jet fuels, ASTM D 1322, Smoke Point of Kerosine and
Aviation Turbine Fuel, is based on determination of the maxi m u m height to which a diffusion flame, wick-fed from the
sample, can be adjusted without smoking (Fig. 7). Being
based on an early design of an illuminating oil lamp bearing
no resemblance physically to an aero gas-turbine combustor,
this method may appear primitive. Nevertheless, it does test
the fuel u n d e r diffusion conditions where smoke is m o r e
likely to be generated in the actual combustor operating at
high pressure. In ASTM D 1740, Luminometer Numbers of
Aviation Turbine Fuels, the luminometer n u m b e r is determined with a smoke-point type lamp operating at a fixed level
of flame radiation by comparing the flame temperature rise
above the inlet air level for the sample with those for two reference fuels, tetralin (an aromatic) and zsooctane (a paraffin), as follows:

Fuels b u m only in the vapor/gas phase, consequently the


first stage in satisfactory combustion is to vaporize the fuel
and mix it thoroughly with the oxidant. In an aero gas turbine engine, the low volatility of kerosine is such that carburation at ambient air temperatures would be too slow for
a satisfactory rate of vapor generation. Vaporization at
flame temperature is practicable, however, and the "walking
stick" (or T-shaped double walking stick) type of vaporizer
tube fed with air under relatively low pressure receives narrow streams of liquid fuel that are vaporized to an extent
depending upon the fuel flow rate, and introduced directly
into the flame [1].

f AT sample - \T tetralin \
Luminometer Number = 100 U j f-octane - AT tetralin I
Correspondence has been found between smoke point cUid
luminometer n u m b e r over a wide range of kerosines.

Inclined mirror for


~ viewing smoke in
flame centre

^ Photocell

In most o t h e r applications to gas-turbine engines, the


volatility of the fuel is increased substantially to an effective
level roughly equivalent to that of a gasoline by subdividing
into a large n u m b e r of very small droplets. This process of
spraying, loosely termed "atomization," gives a massive increase in surface area per unit volume of fuel, and so augments the vaporization rate by several orders of magnitude.
The fuel is also distributed in space so that mixing with air is
effected rapidly.
Immediately after a fuel droplet is injected into the flame
zone, vapor will form and b u m as a premixed flame. As the
velocity of the droplet falls, it will become surrounded by a
diffusion flame. The proportion of premixed burning may be
raised by increasing the relative velocity between the fuel and
air, consequently combustion in the gas turbine chamber is
dictated by the characteristics of the fuel injector as well as
the geometry of the combustor liner itself. This subdivision of
a film of fuel into filaments and droplets is achieved by the
shearing action arising from the velocity differences between
the spray elements and the air. A number of different pressure-jet injection designs are available.
These practices are not standardized but are adopted in engine manufacturer's development laboratories. An alternative approach is to achieve the required shear from velocity
difference by accelerating the air rather than the fuel. This
gives rise to the air-assist a n d air-blast injectors where a
stream of high-velocity air meets a stream of low-velocity
fuel. Droplet sizes tend to be small and, being controlled by
airflow, spatial distribution of fuel is largely unaffected by
fuel flow rate [1].

/
Chimney

Ignition

"niemiocouple
Reflecting scale

Luminometer Configuration
^''*''"

Flame-height
adjuster

Sample teo-ootane

J ^standard
1
1
1
U
1

/\
rs'A

Flame temperature rise, iT


Smoke Lamp

Luminometer No = 100

/Ars-AT|.\
^ATU-ATL;

FIG. 7Smoke point and luminometer number. Schematics


of apparatus [1].

Ignition is initiated by some form of high-energy spark or


torch igniter, and the flame then sustains continuous ignition
of the entering mixture, whereas in rocketry, certain fueloxidant pairs aire selected because they are hjrpergolic, i.e.,
ignitable on contact, which eliminates the need for separate
ignition equipment. In this case, however, it is essential for
spontaneous ignition to tak;e place on start-up with the minim u m of delay, otherwise a "heird start" will ensue, comparable to the mechanism of diesel knock but with much more
damaging consequences. As there is no standard laboratory
method, this refers to the method adopted in continuousflow energy practice to effect ignition.

742

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Flame Stabilization
In the aero gas turbine combustor, the flame is required to be
stabiHzed in a defined location against the entry stream of air
over a wide range of conditions, consequently a balcince must
be maintcuned at all times between the velocities of the flame
and the approaching mixture. The flame velocities of most fuels in laminar flow eire in the order of 0.5 m/s only and, although increased markedly by temperature and turbulence,
the velocity of the incoming mixture, emd thus the eiir, must be
reduced by some form of betffle in order to achieve velocity balance. In the gas turbine chamber, the velocity of the entering
air is reduced initially by diffusion. The air then goes through
a process of flow reversal by being fed around the outside of the
flame tube before entering through side apertures and encountering a low-pressure region in the core of an air swirl.
The result is a stabilized toroidal vortex of swirling air, the inner surface of which flows upstream. Introduction of the fuel
into this surface promotes a region of flame-air velocity balcince. In advanced aero gas turbine engines, a technique of premixing and prevaporization is used in order to control emissions more effectively. In rocketry, sprays of the liquid fuel Eind
oxidant may be ctrranged to impinge for thorough mixing.

Air D i l u t i o n
In contrast to piston engines where the working surfaces (piston crowns) are subjected to combustion temperatures for
only short periods of time, the blades on a gas-turbine disk operate continuously in a high-temperature environment, and
are also subjected to centrifugeJ stresses. Consequentiy, the
products from the flame must be cooled sufficiently to suit the
metallurgy of the turbine blades. Customarily, some 28% of
the chamber air is used for combustion in the primary zone,
which gives a flame temperature of about 2050C. The remaining air is introduced progressively downstream, first as
secondary Eiir to reduce the temperature of the combustion
products to about 1450C in order to offset the effects of dissociation, and then as dilution air to bring the turbine entry
temperature (TET) down further to the m a x i m u m level of
about 1000C. Higher TET values of 1350C and above are acceptable by intemeJ cooling of the nozzle guide vjines and turbine blades with air bled from the compressor. Despite fuel
residence times within the chamber of a few milliseconds only,
combustion efficiencies under design conditions are high, typically 99.5% or above. Even exhaust smoke that is just visible
represents a combustion inefficiency of no more than 0.01%.

Turbine Entry Temperatiu-e Distribution


The distribution of entry temperature over the turbine disk
should be reasonably uniform in order to avoid localized

peak temperatures that would limit blade life and engine


performance. The temperature traverse qucJity at the outlet
of the chamber is known as the pattern factor, defined as
follows:
^ mean.exit
' mean.inlet

Pattern factor =

The m e a n exit temperature values are generally obtained by


taking measurements at test points located at the centroids of
a n u m b e r of equal sub-cireas comprising the total exit area.
Customarily, velocities are also measured at these test points,
and each temperature weighted on a mass flow basis.
Specific Impulse
In ramjet engines, a higher flame temperature is permitted in
the absence of turbine blades located within the hot propelling gas stream, whereas in rocket engines, even higher
temperatures pertain in the absence of atmospheric diluents.
In both cases, therefore, the extent of dissociation of the combustion products, and of any subsequent part recombination
within the propelling nozzle, are usucJly sufficient to influence substantially the thrust level based on energy density
alone.
The performance of high speed jet engines is therefore
rated in terms of the stream thrust exerted at the nozzle
throat exit plcine where the velocity is sonic, using a parameter termed specific impulse since it is the impulse (thrust)
based on unit flow rate of the propelling products. For ramjets, this parameter may be based on the mass flow rate of the
air alone, or on either the mass of volume flow rates of the
fuel alone. Thus
,.
.r. .
,

Air specific impulse = bn =


f
t
" F
ma
_ ,
.p.
1
o
Fuel specific impulse = Sf=
f
f
T
rrif

Stream thrust
~ra
:~
Air mass flow rate
N s/kg (relates to engine thrust)
Steam thrust
-=5
5
;
Yuei mass flow rate

N s/kg (relates to mass limitation)

, J
.^ .
,
cSteam thrust
Fuel density impulse = Sf^ = Fuel volume flow rate
p
= -y- ~ Sfpf
N s /L (relates to volume limitation)
where py = fuel density, kg/L.
Relative vsJues of the specific impulse parameters are included in Table 5 for selected elements, non-carbon hydrides,
and organometallies. These show a broad interrelationship
with Ccdorific values, but eJso some significant differences.
Data for representative monoreactants are shown in Table 6.

TABLE 6Properties and performance of representative monoreactants [6-8].


Density
Monoreactant
UDMH
Hydrazine
Nitromethane
HTP
Tetranitromethane

' Expanding from 68 to 1 atm.

Formula

(kg/L)

Id*
(N s/L)

(CH3)2N2H2
N2H4
CH3NO2
H2O2
C(N02)4

0.78
1.008
1.12
1.44
1.638

1530
1958
3126
2330
2907

(N s/kg)

Reaction
Temp.
*(K)

1961
1942
2491
1618
1775

1154
905
264
1278
2170

CHAPTER 28: ENGINEERING SCIENCES OF AEROSPACE FUELS 743


For the rocket engine, the performcince is simiWly based
on variants of the specific impulse, as follows:
p
Specific impulse = Is =
N s/kg, and
Density impulse = /<; = 4 PR N s/L
where

rup = mass flow rate of propellants


= m a s s flow rate of reactant mixture in the
chemiCcJ rocket
PR = density of reactant mixture at storage conditions

Since the expression for specific impulse [1] contains the


term V'(Tc/M), where
Tc = combustion temperature, and
M = m e a n molar m a s s of combustion products
comprising propulsive fluid,
it follows that hydrogen offers the double benefits of high
Tc burning to H2O of low molar mass (18) in comparison
with a carbon-bearing fuel burning to CO2 of high molar
mass (44).
Since combustion characteristics, and resulting thrust levels, vary markedly with fuel-oxidant mixture ratio, the "peak"
values of specific impulse and density impulse are used for
comparative purposes. Figure 8 shows the variations of peak
impulse values with densities of the corresponding liquid reactant mixtures. The familiar inverse and direct relationships
are seen, reflecting earlier variations of specific energy and
energy density with fuel density. Hence, heavy reactants are
favored for atmospheric operation, and light reactants for
space flight. The values plotted are for "shifting" equilibrium,
which allows for changes in product composition along the
length of the propelling duct, a n d are approximately 5%
above corresponding values for "frozen" equilibrium where
n o further chemical changes are assumed downstream of the
combustor.

Combustion Emissions
Aero gas turbine emissions are of concern for their direct effects on airport environments, and their cumulative effects at
altitude. The m a i n emissions are CO and UHC at idle/taxiing
conditions, NOx (= NO + NO2) and smoke at high power during take-off and climb, and CO2 a n d H2O throughout.
Some ccirbon monoxide forms in the primary zone of the
gas turbine c h a m b e r but then tends to be oxidized by the secondary air. However, u n b u m t hydrocarbons may comprise
u n b u m t fuel and also partially reacted fuel in the form of
methane and related light hydrocarbons. They normally arise
through over-large spray droplet sizes and/or the chilling effects of mixing with air at low power output.
Nitric oxide occurs in atmospheric air flame-heated to
above 1800 K, a n d also following the three different sources
of thermal NO at high temperatures, prompt NO at fuel-rich
low temperatures, and fuel NO from fuel-bound nitrogen
at fuel-lean high temperature. Some of the NO oxidizes to
NO2 at full load, and more at low-temperature idle. The effects of NOx from subsonic aircraft operating in the troposphere (approximately 6-14 km altitude) are to increase the
level of ozone, which acts as a powerful greenhouse gas.
With supersonic aircraft operating in the tropopause/stratosphere (approximately 18-23 k m altitude), o n the other
hand, the ozone shield from harmful ultraviolet solar radiation is destroyed by the regeneration reactions of NO2 back
to NO.
Smoke comprises finely divided peirticles of carbon-rich
soot, and forms within fuel-rich regions of the flame such as
the core of the fuel spray, but is largely consumed downstream. ASTM D 1322 and D 1740 are used to measure combustion emissions.
The fuel parameters likely to improve emissions summarize as follows:
PhysiccJ: Low viscosity to generate small droplets in fuel
sprays. High volatility to assist rapid vaporization.
Chemical: Low carbon content a n d low aromatics to reduce smoke. Addition of organobarium or mcinganese to
reduce smoke.
The most effective hardware methods of reducing emissions appear to center on improvements in fuel prepeiration
a n d aeration in the combustor, plus the use of fuel staging,
variable chamber geometry, and lean premix vaporization.

FUEL HANDLING CHARACTERISTICS


E

-2

0.2

0.6

1
1.0

1.4

1.8

Density of peak reactant mixture kg/L

FIG. 8Values of peak specific impulse and


density impulse for liquid rocket fuels and oxidants, with comparative values for mono and
solid reactants [3,4].

For purposes of delivering fuel through the supply chain,


loading into aircraft tanks, and then transferring fuel to the
engine, the liquid phase is the most convenient. Fuels that are
normally gaseous at ambient temperature and pressure can
be liquefied, but this entails either the weight of high-pressure containers or the bulk of a cryogenic system. As indicated earlier, the density of a cryogenic liquid can be increased moderately by adopting the slush mode in which a
significant proportion is frozen. Similarly, particles of solid
fuel may be dispersed throughout a liquid fuel carrier to promote a high-density slurry. Solid fuels tend to apply to "oneshot" rocket engines only.
In aerospace, the major requirement of calorific value applies on a mass basis, i.e., specific energy, in cases of both

744

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

subsonic and extra-atmospheric operation. Supersonic and


hypersonic (Mach No. > 5 ) flight within the atmosphere,
however, is subject to such high levels of drag as to be volume-limited, thus requiring optimal energy density. The next
key requirements for handling properties relate to the following modes of operation although, of course, some requirements apply to more than one mode:
1. Preflight fuelingstatic charge explosion resistance
2. During flight^volatility, viscosity, lubricity, thermal stability
3. After flightfreedom from deposition
4. Between flightsabsence of solidification (ice and wax)
5. Throughoutfreedom from corrosion, insensitivity to
fuel-borne water
Since all these requirements are unlikely to be met at once,
it becomes necessary to employ additives.
The characteristics and methods of test for volatility and
viscosity, both of which influence the droplet formation in
sprays and subsequent vaporization in the combustor, have
been dealt with above, plus the appearance of wax. The following properties relate to the overall system of fuel production, distribution, and storage right u p to entry to the engine
bay in the aircraft.
F u e l i n g Fire Safety
During the flow of fuel through pipelines, the presence of
trace polar contaminants leads to charge separation through
the interchange of electrons, giving rise to ionization.
Charges of one sign will tend to drift towetrds and accumulate
on the walls of the container, whereas those of the opposite
sign will remain in the fuel itself, and thus fuel flow will also
constitute a streaming electrical current. This effect is augmented by the presence of droplets of water or particles of
dirt, and very m u c h so by the extensive contact area of a filter medium. Owing to the high state of cleanness of transport
fuels, the electrical conductivity is very low (e.g., 1-3 CU^ for
aviation kerosine cf. 10 X 10* CU for demineralized water).
Consequently, high electrostatic potentials are generated,
which cannot be dissipated easily through such an inert fuel
medium. Within the filter-separator or receiver tank, therefore, an electrostatic gradient develops between fuel and wall
surfaces that can r e a c h a level of breakdown leading to
sparks, and to subsequent explosions, if the vapor-air mixture lies within the flammable range.
This dissipation process is known as charge relaxation, and
the time taken for the charge to fall by one half from a given
value (the half-value time, ti/2) is a n importcint factor indicating whether static charges generated in the fuel are hazardous or not. In practical units.
12

tl/2 = Conductivity seconds

Typical values of ti/2 are 12 s for aviation turbine fuel of 1 CU,


and 1.2 /as for demineralized water of 10 X 10* CU. Charges
can accumulate to an appreciable extent only if ti/2 is high.
The generation of static electrical charges in the handling
of aviation kerosine has long been recognized as a potential
hazard during aircraft fueling. A n u m b e r of rules covering
^ 1 CU = 1 Conductivity Unit = IpS/m (picosiemen/meter)

pumping rates, line velocities, bottom loading (no splash filling), and settling times have been generally adopted by the
major fuel suppliers as standard practice for the safe handling of such products.
The electrical conductivity of a fuel is determined by applying a voltage across two electrodes immersed in the sample, and recording the resulting current, as in ASTM D 4308,
Electrical Conductivity of Liquid Hydrocarbons by Precision
Meter. An alternative method, ASTM D 2624, Electrical Conductivity of Aviation a n d Distillate Fuels, applies to fuels
containing a static dissipator additive. Civil and military requirements differ because of the different additives used. For
example, experience shows a m i n i m u m conductivity of 50
units to be safe for civil jet fuels, whereas military fuels require higher conductivity, and this offsets the slight synergism possible between the additives FSII and CI/LIA. A
m a x i m u m limit is also set for jet kerosines (450 CU), all limits applying at the point, time, and temperature of delivery to
the user.
The conductivity of a fuel in a storage tank may be measured directly by portable meters manufactured commercially. The Maihak instrument has a conductivity cell on the
end of a cable wound onto a drum. The cell is lowered into
the tank through the sampling hatch, and the direct-reading
meter attached to the drum. With the pocket-sized Emcee instrument, the conductivity cell may be detached from the cable and fitted directly to the meter to give a laboratory model
for use with a fuel sample in a beaker. Alternatively, the cell
may be attached to the end of a probe and inserted into the
tank for measurements at a series of levels (e.g., top, middle,
and bottom) to check for homogeneity of the contents.
An additional measure of safety is the use of static dissipator additives (e.g., Stadis 450 for jet fuels). Complex polymeric materials containing nitrogen and sulphur are used to
render the bulk fuel sufficiently conducting to provide rapid
dissipation of the charge to an appropriate earthing surface
[1]. Incorporating this additive into an aviation kerosine
would raise the conductivity from 1 to about 150 CU, lowering the half-value time from 12-0.08 s.
Lubricity
Lubricity, sometimes described as film strength, can be defined as the ability to lubricate with a low tendency to generate friction, wear and/or scuffing. Lubrication takes the three
basic forms:
hydrodynamic (with n o surface contact, as controlled by
viscosity)
mixed (with limited surface contact)
boundary (with predominantly surface contact).
In the latter instance, lubricity applies particularly to fuel
pumping equipment operating at high pressure, where potential surface contact predominates. Although not included in
current specifications for jet fuels, the ability to maintain
boundary lubrication in the close cleEirances between reciprocating elements or highly-loaded gears in fuel pumps is imperative to avoid adhesive wear (surface scuffing or welding) and
oxidative wear (corrosion and abrasion). This was manifested
indirectly in aviation under the following circumstances:
sticking and hang-up of fuel control systems using widecut fuel

CHAPTER

28: ENGINEERING

use of corrosion inhibitors (e.g., dilinoleic acid derivatives)


to keep pipelines clean indicated surfactant action which
prevented water from coagulating and made removal difficult. Discontinuation of the inhibitor resulted in problems
of fuel p u m p seizure, which were solved on replacement of
the inhibitor, indicating its action as a lubricity enhancer
chemical treatment to convert objectionable mercaptans
RSH to innocuous disulphides RSSR' does not appear to
affect lubricity, but severe hydrogenation to reduce mercaptans to paraffins and hydrogen sulphide removes the
polar boundary lubricants and promotes p u m p seizure.
Boundary lubrication is, in fact, dependent more on the
trace concentrations of polar compounds than on the nature
of the m a i n h y d r o c a r b o n c o m p o n e n t s of the bulk fuel.
These polar compounds most probably comprise high molar
mass polycyclic aromatics containing sulfur, oxygen, and/or
nitrogen.
Lubricity is customarily assessed in practice using a moving specimen rubbing on a stationary specimen under an applied load in the presence of the test fuel as, for example, in
the lightly-loaded ASTM D 5001, Measurement of Lubricity
of Aviation Turbine Fuels by Ball-On-Cylinder Evaluator,
BOCLE. This rig is used to measure lubricated mild wear rate
of the ball but the results m a y be influenced adversely by corrosive wear. Wear rates that are high are usually caused by
scuffing, and a new development is the BOCLE scuffing test.
The correlation between mild wear and scuffing depends on
the composition of the fuel, consequently comparing the
scuffing performance of fuels from their mild wear behavior
is valid only for fuels of similar composition. The BOCLE is
therefore satisfactory for
p u m p development using a low-lubricity fuel
monitoring supplies of low-sulfur additive-free fuel
monitoring changes in additive concentration.
The Dwell test measures friction whereas the more complex Thornton Aviation Fuel Lubricity Evaluation (TAFLE)
rig measures seizure load, friction, and wesir as well as scuffing. In the High Frequency Reciprocating Wear Rig (HFRR),
a hardened steel ball oscillates under load across a hardened
steel plate in the presence of the fuel sample. As before, lubricity rating is based on comparing the wear scar diameter
with that of a reference fuel, in this case at two test temperatures. A fuel with high lubricity is described as SOFT, and
with a low lubricity as HARD. At this time, these are experimental tests derived through industrial research. (For Lubricity Improving Additives, see the Water
Contamination
section.)
Stability
Chemical stability in storage is characterized by hydrocarbons that are hydrogen-saturated, whereas instability is endemic in the presence of double carbon-carbon bonding as in
the olefins (and even more so in the treble carbon-carbon
bonding in the acetylenes, which renders them unusable for
aviation). Reactions of the unsaturated hydrocarbons occur
as polymerization of like-to-like molecules, and/or oxidation
to H.C.O compounds, the products of both types of reaction
taking the form of gums, acids, fuel-borne solid particulates,
and/or surface deposits. Olefins do not occur in crude oils or
their straight-run fractions, of course, because of the exten-

SCIENCES

OF AEROSPACE

FUELS

745

sive time available to achieve stability during formation, but


cracking or other refinery processes can be severe enough to
promote multi-bonding. With jet fuels, for example, a maxim u m limit of 5% volume of olefins was set in order to prevent
the incorporation of non-hydrotreated cracked stocks into
the finished product.
The combined effects o n a fuel of heat, dissolved oxygen
and nitrogen, trace sulfur content (particularly disulfides and
thiols), and some initiator such as a catalj^ic metal result in
the formation of small quantities of insoluble products.
These comprise two forms depending on the conditions of
flow and temperature, as follows:
Intermediate temperature (<200C) particulate deposits
from bulk heating accumulating on filter screens causing
blockages.
High temperature (350C) films of lacquer (varnish) from
localized hot surfaces accumulating in fuel-fed oil coolers,
hydromechanical devices, injector feed arms and the fuel
injectors themselves. These promote loss of heat-transfer
efficiency, sluggishness and hysteresis with moving parts
involving fine tolerances leading to sticking and eventual
seizure o n attempts at engine starting. Furthermore, the
higher temperatures within the injector feed arms can lead
to thermal cracking, the resulting carbonaceous material
either depositing and reducing the fuel flow, or breaking
away and blocking the injectors, distorting the spray patterns with consequent thermal damage to combustor liners
and turbine blades.
During flight, the key issues for fuel stability under the action of heat are the peak temperature experienced, and the
overall thermal history u p to the point of combustion. For
subsonic civil aircraft, for example, the bulk tanks have little
effect, b u t in some supersonic aircraft, bulk tanks may make
some contribution through kinetic heating. In the latter case,
the main source of the problem is the use of fuel as a heat
sink for cooling engine lubricating oil and various items of
avionic equipment. The overall result is that fuel approaches
the injection manifold with a much higher content of sensible heat t h a n previously. This situation is exacerbated by further heating in the injector feed arms because of their location within the air stream, which is compression-heated to
t e m p e r a t u r e s approaching 600C. A m a x i m u m operating
temperature of 163C is set for the fuel reaching the inlet of
the injectors, but the objective of a currently active research
program is to raise this limit by 100F (56C) to 219C, hence
increasing the heat capacity of the fuel by 50%. Even if the injector fuel should eventually reach 254C, the SIT level for
aviation kerosine, spontaneous ignition cannot occur in the
absence of adequate oxygen. Nevertheless, hydrocarbon fuels
invariably contain u p to 14% by volume of dissolved atmospheric gases. Furthermore, the concentration of oxygen in
these dissolved gases is raised from the standard atmospheric
level of 2 1 % to about 40%. As a result, the application of heat
to such fuels can give rise to slow processes of autoxidation.
In ASTM D 381, Gum Content in Fuels by Jet Evaporation
for Aviation Fuels, the fuel sample is evaporated under controlled conditions of temperature and flow of steam (now air),
and the resulting residue weighed. In Western countries, stability at higher soak temperatures is assessed by ASTM D
3241, Thermal Oxidation Stability of Aviation Turbine Fuels
(JFTOT Procedure), comprising an aluminium tube resis-

746

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

tance-heated to 260C that experiences a skewed normal temperature distribution along its length, and downstream a
heated stainless-steel cloth precision filter of 17/Am nominal
porosity fitted with a differential gauge. The fuel sample flows
at 3 mL/min for 2.5 h along the outer surface of the tube: in
aircraft practice, the fuel flows within the tubing but external
flow is used in the test so that any deposits can be examined
visually. Any pressure drop across the filter indicates the presence of solid particulates, b u t examination of the upstream
heater tube was found to be necessary since tube deposits
were sometimes evident in the absence of filter blockage. The
sample is reported as either a pass or fail, determined jointly
by the intensity of tube deposition against set color standards
(ranging over a ten-step basis from 0, < 1 , 1, < 2 , 2, < 3 , 3, < 4 ,
4, >4) and/or level of pressure drop across the filter u p to a
maximum of 25 m m Hg. Among abnormal surface colors is
blue/gray, usually associated with copper contamination.
The JFTOT has also been used at t e m p e r a t u r e s above
260C in order to find the breakpoint, that is, the temperature
at which the fuel fails both the specified tube rating and mEixi m u m pressure drop (25 m m Hg) criteria. The currently determined brccikpoint for a typical UK aviation turbine fuel
ranges from about 280-310C, and hydrotreated fuels have
been found more stable t h a n sweetened fuels in which trace
contaminants are converted rather than removed. Generally,
breakpoint has also been found to correlate directly with hydrogen content a n d smoke point. In order to provide a
database, the US DOD is collecting information on thermal
stability results at a test temperature raised from 260-275C.
In the near future, USAF is expected to develop a "JP-8 +
100" fuel, being a JP-8 fuel with a 100F (56 K) improvement
in break point by means of a package of anti-oxidant, metcJ
deactivator, detergent, and dispersant additives. These especially stable products are now described as High Temperature Thermally Stable (HiTTS) fuels.
Thermal stability is degraded in the presence of olefins,
copper, and other metcJs, and of sulfur. Copper is a particularly potent oxidation catalyst and, even at the parts per billion level of concentration, has given rise to a n u m b e r of
problems through carryover when jet fuels were subjected to
copper sweetening. However, with the adoption of alternative methods of treatment, a limit on copper content is no
longer specified, reliance being placed on the results of the
JFTOT. Should a jet fuel contain copper, it can be chelated
(neutralized by axi isolating coating) by means of a metal deactivating additive such as a propanediamine. However, excessive use of MDA can passivate the tube surface of the
JFTOT and give rise to misleading results.

Water Contamination
Even with the strictest housekeeping discipline, traces of water invariably collect in liquid fuels during storage smd transfer. Apart from accidental ingress through carry-over from
water-washing in the refinery, or defective tank vents or
seams (pEirticularly in sea-going vessels), the main source is
the humidity of the atmosphere above the fuel surface. Water
dissolves in hydrocarbons to a n extent dependent upon temperature, any additional water existing freely as dispersed
droplets. The agitation of fuels by pumping through valves
and pipeline systems tends to disintegrate the water droplets.

hindering their coagulation and settlement. Certain soap-like


surface-active agents (surfactants) may occur naturally in
fuel, or be introduced either by contamination or in the form
of otherwise acceptable additives. These inhibit small
droplets of free water from coalescing with each other and
settling rapidly. The settlement rates of water droplets can be
determined from Stokes' law.
terminEj velocity of spherical peirticle =
where

18ij

d = diameter of particle (cm),


a = density of particle (g/cm^),
p = density of fuel (g/cm^), and
17 = dynamic viscosity of fuel (g/cm s).

Thus, settling rates are proportional to the square of the diameter of the contaminating particle, emd the density difference between the peirticle and the fuel.
As well as increasing the concentration of free water, cooling a distillate fuel from 0C to about 30C gives rise to the
progressive formation of ice crystals that tend to remain in
suspension. Supercooling may occur, but impact or contamination promotes instant freezing of both water and some hydrocarbon hydrates. A loose network of ice particles builds
u p on filter surfaces, resulting in an increased pressure differential and, eventually, complete blockage. In general, the
icing problem in civil aviation is met by the use of fuel-filter
heating, whereas military practice is to additize the fuel with
a fuel system icing inhibitor, FSII (diethylene glycolmonomethylether) u p to 0.15% by volume.
Since water, carbon, and nitrogen are essential ingredients
to life, microbiological activity is possible at the water-hydrocarbon interface. The most c o m m o n aerobic micro-organism to flourish under these conditions is Cladosporium
resinae (Lindau) de Vries. This is a fungus comprising long
threads that produce spores too small (approximately 3 ^^m)
to be filtered out. The threads branch heavily to form a visible tangled greenish-black mat or "mycelium," the mechanical strength of which is sufficient to cause filter blockage cind
malfunction of fuel-contents gauges. The fungus is able to extract the carbon from a hydrocarbon fuel such as kerosine,
and to generate products which, in association with water,
corrode through the WEJIS of aluminium fuel systems, promoting leakage. These tanks are now designed to give free access of all internal water to a drain plug, Eind/or with probes
into the low points to pick up collected water so that it CEin be
injected into the m a i n fuel delivery system to the engine.
Biostats are materials that inhibit the growth of bacteria
and fungi, whereas biocides are materials that kill them. In
military aviation practice, the fuel system icing inhibitor to
prevent water freezing problems is also relied upon as a biostat. In civil aviation, on the other hand, where filter heating
is used instead, biocidal shock treatment is given every few
months when the aircraft is out of service, by the addition of
u p to 270 p p m of a boron compound, which is left to act for
three days.
In addition to the corrosive action of the products of microorganisms discussed above, direct contact of metaJ with water and dissolved air leads to the formation of rust. Materials
employed as corrosion inhibitors are polcir in nature with hydrophilic heads and oleophilic/hydrophobic tails that accu-

CHAPTER

28: ENGINEERING

m u l a t e as an oil m o n o m o l e c u l a r layer preventing watermetal contact. As indicated in the earlier section on lubricity,
experience showed these corrosion inhibitors to serve a second purpose in improving lubricity by the same molecular
action, consequently such materials have become known as
corrosion inhibitor/lubricity improving additives, CI/LIA.
Other problems associated with water during the pumping of
fuels include the augmentation of static charging, as discussed ecirlier, and also foaming in the presence of heat.
With aviation kerosines, free water concentrations existing
as dispersed droplets become visible as a cloud (the specification calling for the fuel to be "clear") at concentrations
varying from 30-50 p p m mass depending inversely on
droplet size. The former figure is recognized by lATA as the
m a x i m u m permissible at the time a n d temperature of delivery, whereas a maximum of 15 p p m is assured by the use of
filter/separators and monitors in the supply system.
The concern with jet fuels is the potential for certain surfactants to disarm water separation equipment resulting in
the unexpected delivery of water to aircraft. A test was needed
initially to guard against the carry-over of powerful surfactants from the refinery, particularly when sulfonation techniques were much in use. ASTM D 2550, Water Separation
Characteristics of Aviation Turbine Fuels, employs a separometer to determine the efficiency by which a fuel-water
emulsion can be separated by a coalescer, assessment being
based on passing a prepared water-fuel emulsion through a
standard glass-fiber coalescer and measuring the turbidity of
the effluent by light transmission. An arbitrary scale described
as WSIM (i.e. Water Separation Index Modified) indicates 100
for clear fuel, and less for any remaining water droplets. A
small-scale version of this apparatus, D 3948, "Determining
Water-Separation Characteristics of Aviation Turbine Fuels
by Portable Separometer," comprises a portable micro-separometer with a high-speed mechanical stirrer, giving a numericaJ rating designated MSEP. However, the situation is
complicated by the fact that certain mandatory fuel additives,
either singly or in combination, depress WSIM number without, in reality, interfering with the water separator.
Tanks for kerosine usually have fixed roofs, coned to shed
rainwater and snow, with free-vents to assist drying. A coned o w n b o t t o m of m i n i m u m slope 1 in 30 leads t o a water
s u m p a n d drain valve, and a floating suction line ensures
freedom from water entrainment during offtake. After filling,
a period of 1 h is usually considered sufficient for water
droplet settlement, irrespective of tank depth.
Health Issues in Handling
The major physiological reactions on exposure to the highperformance transport fuels may have localized and/or systemic (remote) effects, a n d are tabulated under the following
headings:
Ingestionswallowing of liquid into the digestive tract
Inhalationin-breathing of vapor into the lungs
Aspirationintroduction of liquid into the lungs either
through inhalation or by vomiting
Externalcontact with skin and, particularly, eyes.
Furthermore, some materials are slow t o eliminate (for example, methanol), whereas others are cumulative (for example, decaborane).

SCIENCES

OF AEROSPACE

FUELS

747

The evaluation of atmospheric quality with regard to the


presence of contaminants is commonly expressed in terms of
the threshold limit value (TLV) defined as the acceptable airborne concentration of the given c o n t a m i n a n t in occupational exposures for u p to 8 h daily without adverse effects.
However, since the volatility of the contaminant determines
its vapor concentration at ambient temperature, it is also customary to use the hazard index, defined by (VP/TLV), where
VP is the vapor pressure.
In broad terms, internal effects comprise nausea, dizziness, h e a d a c h e , and irritation of the m u c o u s m e m b r a n e ,
leading to loss of consciousness with the aromatics, a n d
blindness with methanol. External contact can cause cold
b u m s , dermatitis, eye damage, and skin cancers. Reference
to the fuel manufacturers' handbooks is recommended in all

FUTURE TRENDS
Extrapolation of past experience into the future suggests continuing use of conventional fuels for as long as is practicable,
supplemented by virtually identical fuels derived from
sources other than petroleum. Subsequently, recourse will
need to be made to substitute materials, as discussed below:
Reformulation (Short Term)
In the automotive world, the fuel approach to emission reduction is a process of reformulation. This entails tighter
controls on vapor pressure, and on the m a x i m u m permitted
concentrations of aromatics, olefins, and sulfur. With jet fuels on the other hand, component concentrations are already
very closely controlled, but the "product giveaway" (the difference between the actual property and its specified limit)
has h a d to be reduced progressively for reasons of economics. Nevertheless, recent reviews show modest improvement in aromatic content a n d smoke point despite small adverse changes in sulfur, freeze point, emd flash point. As the
sources of crude oil change because of shifting markets a n d
availabilities, the product processes will have to be continually adjusted t o achieve the necessary specification, and these
will no doubt involve some form or reformulation to a greater
or lesser extent.
Supplemental Fuels (Medium Term)
Both natural gas and coal can be converted to "syngas" (CO +
H2), which in turn can be synthesized to distillate-type liquids either through WEIX, which is then hydroconverted catalytically, or via a methanol stage. Alternatively, coal can be
de-ashed a n d its molecular components reduced in size sufficiently to give liquids directly without the additional energy
required for the more extensive reduction to gaseous dimensions. Hydrogenation of the aromatic components then gives
the saturates^paraffins a n d naphthenes.
More exotic alternative sources of hydrocarbons include
shale oil, tar, coal, peat, and biomatter generally. The first
two have not yet emerged as conventioned fuel sources with
established production rates, and therefore cannot be assigned meaningful (reserves-production) ratios, but large deposits are known to exist worldwide.

748

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK
ing either pre-vaporization within the hot flame zone or
relatively fine atomization. They are burnt with minimal
radiation at virtually constant pressure, with flame stability and temperature distribution across the combustor section controlled by engine design. Combustion efficiency is
at a premium, despite the very short residence time of the
fuel molecules within the combustor, not only for fuel
economy, but also for minimal emissions. In addition, handling properties are required to meet the wide range of
temperatures and pressures pertaining throughout the supply system a n d within the aircraft itself during service. All
these requirements combine to comprise a relatively extensive specification list of some 28 items or more, as summarized in Table 7, yet without precluding either availability or economics.

Substitute Fuels (Long Term)


The longer-term approach towards future replacements is to
use alternative fuels that may bear very little similarity to the
c o n v e n t i o n a l . This class may be described as "Substitutes,"
and includes the compounds of carbon with hydrogen, oxygen, and nitrogen.
For aviation, the most promising candidate substitutes appear to be liquid methane and liquid hydrogen, but the handling problems with cryogenic fuels are substantial.

SUMMARY AND CONCLUSIONS


Current fuels for jet engines are of the petroleum-derived
mid-distillate kerosine t3'pe with moderate volatility requir-

TABLE 7Major features of representative U.S. jet fuel specifications (certain variations apply depending on type
and concentrations of additives, etc.).

Property
Color, Saybolt, min
Total acid no. mg KOH /g,
max
Aromatics, % vol., max
Olefins, % vol., max
Sulfur, total, % mass, max
Sulfur, mercaptan, % mass.
max
Initial boiling point, C
10% vol. recovered, C
20% vol. recovered, C
50% vol. recovered, C
90% vol. recovered, C
E n d point C, max
Flash point C, min
Reid vapour pressure @
38.7C, kPa
Density 15C, kg/L
Freezing point, C, max
Viscosity @ -20C, mm^/s,
max
Specific energy, net, MJ/kg,
mm
Hydrogen content, % mass.
min
Smoke point, m m , m i n
Copper strip corrosion, max
Thermal stability (JFTOT)
Change in pres. drop, m m
Hg, max
Tube deposit code
TDR spun mcix
Existent gum;, mg/100 mL,

Wide-cut
Gasoline
MIL-DTL-5624T
JP-4
NATO F-40

Kerosine
MIL-T-813133D
ASTM D-1655
JetA-l"
NATO F-35

High-flash
Kerosine
MIL-DTL-5624
JP-5
NATO F-44

Report
0.015

Report
0.015

Report
0.015

25.0

25.0
5.0
0.30
0.002

0.40
0.002
Report
Report
m i n 100
min 125
Report
270

Report
max 205
Report
Report
Report
300
38

Thermally
stable fuel
TMIL-DTL-25524E
JPTS

Low volatility
fuel
MIL-DTL-38219D
JP-7

-1-24
0.015

-1-25

23.0-27.0

5.0-20.0

0.40
0.002

0.3
0.001

0.1
0.001

Report
max 206
Report
Report
Report
300
60

min. 157
max 193

0.751-0.802
-58

0.775-0.840
-47
8.0

0.788-0.845
-46
8.5

0.767-0.797
-53
12 @ - 4 0

min 182
min 196
m i n 206
Report
max 260
288
60
max 20.7 @ 149C
& 3 3 1 @260C
0.779-0.806
-43.3
8.0

42.8

42.8

42.6

42.8

43.5

13.5

13.4

13.3-13.5

14.0

14.40

20.0
1

25.0
1

18.0-21.0
1

25.0
lb

lb

25.0

25.0

25.0

25

25.0

<3

<3

<3
12
5.0

12
5.0

max 204
max 238
260
43

14-21

7.0

7.0

7.0

High density
synthetic
MIL-P-87107B
JP-10

54.4
0.935-0.943
-79
40@-54, 10@-18
42.1 (E.D. 39.4 MJ/L)

10
2
5.0

max
1.0
1.0
1.0
0.3/0.5
0.3/0.5
1.0
Particulate matter, mg/L,
max
10
15
15
Filtration time, minutes,
max
lb
lb
lb
lb
lb
Water reaction interface
rating, max
Microscparator rating, min
70/90
70/85
70/90
85
Report
Electrical conductivity.
150-600
50-450
pS/m,
"Known as F-34 (JP-8) when additized with FSII and CI /LIA. The Jet Fueling System Check List embodies the most stringent requirements of Jet A-1, the British
DEF STAN 91-91, and the lATA Guidance Material for Aviation Turbine Fuels.
NOTE1. Distillation tests incorporate limits of 1.5% for both residue and loss.
2. Types and concentrations of additives are also specified.

CHAPTER

28: ENGINEERING

Conventional and some special aviation kerosines are


likely to be available from petroleum sources for the next few
decades, after which they are likely to be supplemented by
virtually identical materials from other natural sources. For
the higher performance applications, attention is likely to
turn to the C.H.O.N compounds, and possibly boron. From
emission considerations, molecules with the higher proportions of hydrogen are attractive, with an eventual elimination
of carbon by the adoption of liquid hydrogen. Nevertheless,
the handling problems with cryogenic fuels are substantial,
and the presence of large quantities of water vapor in the
stratosphere may incur problems.

ASTM STANDARDS
No.
D 86
D 93
D 341
D 381
D 445
D 1298

D
D
D
D
D

1322
1740
2386
2533
2550

D 2624
D 3241
D 3338
D 3825
D 3948
D 4305
D 4308
D 4809
D 5001

E 659

Title
Distillation of Petroleum Products at Atmospheric
Pressure
Flash-Point by Pensky-Martens Closed Cup Tester
Standard Viscosity-Temperature Charts for Liquid
Petroleum Products
Gum Content in Fuels by Jet Evaporation
Kinematic Viscosity of Transparent a n d Opaque
Liquids (The Calculation of Dynamic Viscosity)
Density, Relative Density (Specific Gravity) or API
Gravity of Crude Petroleum and Liquid Petroleum
Products by Hydrometer Method
Smoke Point of Kerosine and Aviation Turbine Fuel
Luminometer Numbers of Aviation Turbine Fuels
Freezing Point of Aviation Fuels
Vapor-Liquid Ratio of Spark-Ignition Engine Fuels
Water Separation Characteristics of Aviation Turbine Fuels
Electrical Conductivity of Aviation and Distillate
Fuels Containing a Static Dissipator Additive
Thermal Oxidation Stability of Aviation Turbine
Fuels (JFTOT Procedure)
Estimation of Net Heat of Combustion of Aviation
Fuels
Dynamic Surface Tension by the Fast-Bubble Technique
Determining Water-Separating Characteristics of
Aviation Turbine Fuels by Portable Separometer
Filter Flow of Aviation Fuels at Low Temperatures
Electrical Conductivity of Liquid Hydrocarbons by
Precision Meter
Heat of Combustion of Liquid Hydrocarbon Fuels
by B o m b Calorimeter (Precision Method)
Measurement of Lubricity of Aviation Turbine Fuels by the Ball-On-Cylinder Lubricity Evaluator
(BOCLE)
Autoignition Temperature of Liquid Chemicals

SAE STANDARDS
ARP492

Aircraft Engine Fuel P u m p Cavitation Endurance


Test

REFERENCES
[1] Goodger, E. M., Transport Fuels Technology, Landfall Press, Norwich, UK, October 2000.

SCIENCES

OF AEROSPACE

FUELS

749

2] Goodger, E. M. and Vera, R. A., Aviation Fuels Technology,


Macmillan Publishers Ltd., Basingstoke, UK, 1985.
3] Anonymous, "Theoretical Performance of Rocket Propellant
Combinations," Rocketdyne, CA, January 1959.
4] Goodger, E. M., "Property Requirements of Liquid Rocket Propellants," Journal of the Institute of Petroleum, London, Vol. 46,
No. 442, October 1960, pp. 314-27.
5] Wilson, W. E. and Berl, W. G., "Fuels," Ch. 6, Ramjet Technology,
TG 610-6, The Johns Hopkins University, Baltimore, MD, July
1965.
6] Glassman, I. and Sawyer, R. F., The Performance of Chemical Propellants, AGARDOgraph 129, NATO, January 1970.
7] Samer, S. F., Propellant Chemistry, Reinhold Publishing Corporation, NY, 1966.
8] Sutton, G. P., Rocket Propulsion Elements, John Wiley, NY, 1963.
9] StuU, D. R. and Prophet, H., JANAF Thermochemical Tables, National Bureau of Standards, Washington, DC, 1971.
10] Broadbank, R., "New Technology Revolutionises Fuels Testing,"
Petroleum Review, June 1999, pp. 30-31.

BIBLIOGRAPHY
1] Schobert, H. H., The Chemistry of Hydrocarbon Fuels, Butterworths, London, UK, 1990.
2] Handbook of Chemistry and Physics, R. C. Weast, Ed., CRC Press,
Cleveland, OH, republished periodically.
3] Rogers, G. F. C. and Mayhew, Y. R., Engineering Thermodynamics Work and Heat Transfer, Longmans Group Ltd., Harlow, UK,
latest edition.
4] Rose, J. W. and Cooper, J. R., Technical Data on Fuel, The British
National Committee, World Energy Conference, London, 1977.
5] Datschefski, G., Lewis, C, and Walters, M. B., Jet Fuel Specification Requirements, Defense Evaluation and Research Agency,
London, 1997.
6] Fielding, D. and Topps, J. E. C, Thermodynamic Data for the Calculation of Gas Turbine Performance, Aeronautical Reseach
Council R & M 3099, 1959.
7] Breitwieser, B., Gordon, S., and Gammon, B., Summary Report
on Analytical Evaluation of Air and Fuel Specific-Impulse Characteristics of Several Non-hydrocarbon Jet Engine Fuels, NACA R M
E52L08, 1952.
8] Dukek, W. G., Selected Hydrocarbons as High Performance Fuels,
American Chemistry Society, Symposium on High Energy Fuels,
Philadelphia, 25 Feb. 1960.
9] Brewer, G. D., Hydrogen Aircraft Technology, CRC Press, London,
1991.
APPENDIX 1
T h e r m o d y n a m i c Properties a n d their Interrelationship in Static Gases
A collection of hot gases suited to act as a working fluid in a
heat-work conversion is known as a thermodynamic system.
At any instant, this system exists in a particular thermodynamic state as defined by its set of properties, which are consequently described as state functions. Such a property is recognizable by the fact that it exhibits no change when the
system goes through a complete cycle of events (as discussed
in Appendix 2).
In a thermodynamic system:
an extensive property is dependent on the mass of the system, e.g., volume V, internal energy U, enthalpy//, energy,
entropy S, etc.
a specific property is an extensive property expressed on a
basis of unit mass of the system, e.g., specific volume v.

750 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


specific internal energy u, specific enthalpy h, specific energy e, specific entropy s, etc.
and an intensive property is independent of the mass of the
system, e.g., pressure p, temperature T, height z, etc.
In the above list, the three properties that can be measured
physically by means of instrumentation are known as prime
properties. These comprise pressure, volume, and temperature, the last-named being expressed in absolute terms in
units of kelvin. These three properties can be related by combining the following two laws of gases:
1. Boyle's law^At constant temperature, p a 1/pv, hence v =
a function of T
2. Charles' law^At constant pressure, v a T, hence v/T = a
function of p
Consider a mass m of system material at condition 1 going
through a constant temperature process to condition 3, followed by a constant pressure process to condition 2.
Then, piVi = P2V3, and V3/T1 = V2IT2
Combination leads to the prime properties being related to
give the equation of state
Pi V/ =P2V2TilTz,

S, the entropy, is a measure of molecular disorder, and is


equal to the ratio of the heat transfer between the system
and its surroundings to the temperature, hence S = Q/T.
In engineering thermodynamics, interest generally centers
on changes in the above derived properties, hence At/, A//,
AS, etc.
APPENDIX 2
The Unique Nature of Thermodynamic
Parameters
Fortuitously, the complete set of properties of a given mass of
a system at any given state is fixed by defining two properties
only, provided that these properties are independent of each
other, and that the system itself comprises a pure substance,
that is, its chemical composition is both homogeneous and
constant. This feature is known as the two-property rule. Fortunately, also, mixtures of air and gaseous fuel prior to combustion, and of exhaust gases subsequently, can both be classified as pure substances.

hence Pi vilTi = P2 V2IT2 = p v/T = constant = R The Unique Point


One very valuable consequence of the two-property rule is that
and
it enables the state of a pure-substance system to be
pV/T = mR
represented by a unique state point on conventional graph paper, which is itself two-dimensional. As an example, the equawhere R is the gas constant for the particular material
tion of state shows that a system comprising 1.23 kg of air oc(= 0.287 kJ/kgK for air).
cupying a volume of 1 m^ at a pressure of 1 atm (101.325 kPa)
A material that follows this equation exactly is known as an
would have to exist at 288 K, all other properties being set by
ideal gas. (Note that a perfect gas is an ideal gas with values
these state conditions. The two-property rule provides a most
of specific heat capacity constant at all temperatures.) The
valuable
tool in that the complete thermodynamic state of this
molar volume, VM, of a gas is the volume occupied by one
air system can be represented by a unique point, X, on the twomole of molar mass M, and from Avogadro's law, this is comdimensional p-V graph shown in Fig. A2.1.
mon for all ideal gases at the same temperature and pressure.
Hence, since
VM = M R T/p and is common,
(M R) also is common, and is known as the Universal Gas
Constant, Ro, equal to 8.3143 J/mol K at 1 atm and 0C.
The remaining properties are discussed further below:
U, the internal energy, is the sum of all forms of energy
contained within the internal structure of the system material itself. It therefore comprises: the internal potential
energy stored within the atomic and molecular particles
from work done in moving them apart against binding
forces of mutual attraction, and the internal kinetic energy
of the particles moving randomly in translation, rotation,
vibration, and spin.
H, the enthalpy, is the sum of the internal energy and the
flow energy involved in penetrating the surface of the imaginary space of interest (the control region) where conditions and processes Eire being examined. This latter term is
derived simply from the following expression:
Flow energy = work done in penetrating surface
= Force X distance moved
= (force/area) X (distance X area)
= pV
Hence, H =U+pV
E, the overall energy of the system, incorporates H and
some other parameters (see Appendix 6).

The Unique Process Line


If the initial thermodynamic state is changed progressively
through different states, for example by external transfers of
energy, the various unique points can be connected by a

0.5

1.5

Volume, Vm3

FIG. A2.1Representative reversible


{p-V) paths for ideal gas. (Point X represents 1.23 kg air at 288 K) [1].

CHAPTER 28: ENGINEERING SCIENCES OF AEROSPACE FUELS 751


unique line on the graph representing the process of change.
Such a hne follows a relationship of the form
p y " = constant.
An infinite n u m b e r of processes is possible depending on the
value of the index n, which can vary from 0 to <. The following values of n, and the names of the related processes, are
shown in the figure, and are listed below:
n

Process Name

0
1
>1 to<-)'
y

Isobaric (constant pressure)


Isothermal (constant temperature)
Polytropic
Adiabatic" (zero heat transfer)
Isochoric* (constant volume)

"Also described as isentropic in the ideal case of a reversible


process since entropy remains constant throughout.
Sometimes described as isometric.

Cyclic

TABLE A2.2Derivation of efficiency of steady-flow


Bra5^on cycle [1].
Process
(1-2) Isentropic
compression
(2-3) Isobaric
heating
(3-4) Isentropic
expansion
(94-1) Isobaric
cooling
Tn =

The transfers of heat and work associated with the above


processes are shown in Table A2.1
The Unique

ciency of the Brayton cycle, operating on a steady-flow basis,


is shown in Table A2.2, and calculated values are shown plotted in Fig. A2.2.
It is interesting to note that, although temperature (T) is a
property of a system, whereas an external transfer of heat (Q)

i -

-Cp{T, -To)'
CpiTs --T2)

Heat Transfer

Work Transfer

-CpiTj - T2)

CpiTs - T,)

Cp(T3 - T4)

-Cp{T, - T4)

{T4 - T,)
(T3 - T2)

From isentropes 1-2 and 3 ^


T4/T3 = (P4IP3)'-^ -'^"'= U/rpP - '>'^ = (pi/pzf'' ''^'->= T1/T2
Hence-n = 1 -(;/(>)<>'"-"'^

Process

It is evident that reversible processes can be arranged sequentially in a variety of ways so that they return to the initial point and comprise complete cycles. Thus, as outlined
earlier, the properties do not change once the cycle is completed since the initial and final states coincide. Clearly this
cyclic process encompasses a fixed area (which represents
work transfer in the case of pressure-volume axes), and can
be repeated indefinitely. Each individual component process
is related to external transfers of energy (as heat and/or
work), which are all calculable from thermodynamic theory.
Consequently, suitable selection of component processes,
and of their relationship within the cycle, can result in overall transfers of heat and work. Traversing the cycle diagram
clockwise gives rise to the potential of the continuous conversion of heat input to work output (as in a heat engine),
provided the second law of thermodynamics is followed in
that such a conversion can never be complete, i.e., some of
the heat input must be rejected as heat output at a level of
temperature lower than the initial. The derivation of the effi-

Compression ratio r^
10
20
L
Typical S-l
Typical C-l
may r

maX i j .

60
OTTO

2
'o
40 ic
(U

.
"
-

maxrn
Cut-off ratio
Spark ignition piston engine
Compression ignition piston engine
Gas turtine engine

r
10

"T

20

Isothermal

r=k

Non Flow

Steady Flow

Cp (T2 - Ti)

R (T2 - Ti)

R T In (p,/p2)
= RTln(v2/v;)

RT\n{p,/p2)
= r i n (V2 /V,)

^ T ^ (Ti - T2)

n= 1
Pol3^ropic
pv = k
n = n

(7 - n) , ^
Cv j^ _ J {T,

^ ,
T2)

dD

SI

30

FIG. A2.2Variation of engine cycle thermal efficiencies.

Heat Transfer

RT\n(p,/p2)
RT\n(v2/vt)

20

Pressure ratio Xp

Work Transfer
Isobaric
p = k
n = 0

75
E
)_

Typical GT
a
S-l
C-l
GT

TABLE A2.1-- E n e r g y distribution in thermodynamic processes \_p v" = constant, a n d p V = i? r ] .


Process

30

(T, - T2)

Isentropic
p v"* = k
n = -y

Cv {Ti - T2)

Cp {T, - T2)

Isochoric
v = k

Cv {T2 - T,)

R {T, - T2)

n = 00

' Assuming no changes in potential (height) or kinetic (velocity) energies.

752 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

is not, the quotient (Q/T) - which is the entropy (S) - does


meet the definition of a property since it does not change over
the complete cycle. A fuller discussion of these thermodynamic issues is given in Ref. 1.

APPENDIX 3

TABLE A3.1Thermochemlcal bond enthalpies, kj/mol [1].


Bond

Enthalpy

Bond

Enthalpy

AHa.H2(g)
AHa.02(g)
AH,.N2(g)
AHa.C2(gr)
D (HO)
E (H0)

435.4
498.2
946.2
717.2
428.7
463.1

D(HOH)
E(CH)
E(CC)
E(C=C)
E(C=C)
E(C0)

497.5
414.5
347.5
615.5
812.2
351.7

Oxidation Heat Release


The study of heat transfers associated with chemical reactions is termed Thermochemistry. Since the events of interest
here relate to flowing, rather than non-flowing, fluids at constant pressure, changes of energy Eire expressed in terms of
enthalpy r a t h e r t h a n internal energy (see the section on
Calorific Values).
The formation of a molecule (for example, a fuel) from its
component elements can be imagined as the following twostage process:
1. Absorption of sufficient enthalpy to release the individual
atoms of the c o m p o n e n t molecule into freely gaseous
form, as for example;
C(gr) ^ C(g), and H2(g) ^ 2 H(g)

which is the mean value for a n u m b e r of such bonds in different molecules, and in different locations within them. A
simple physical analogy of the complete formation process is
given by a mass descending from a depression in a hilltop;
the overall change in potential energy is the net result of the
climb to the lip of the depression, and the subsequent descent
from it (Fig. A3.1). Representative values of AHa, D(X^Y)
and E(XY) are given in Table A3.1
Hence, in the methane example above, the net enthalpy released, which is described as the standcird enthalpy of formation, AHf, is given by:
A//f .CH4 = lAHa - l E ( X - Y ) approximately

where (gr) represents carbon in its standard condition of


graphite, and (g) represents gas.
2. Release of excess enthalpy on the combination of these
free atoms on the formation of the combined molecule, as
for example;
C(g) + 4 H(g) -> CH4(g) methane
The energy involved in the first stage of the process is designated the "enthalpy of atomization," AHa, and is invariably
directed inwards. In thermochemistry, therefore, this is
classed as positive since it adds to the total stock of energy of
the elemental material. The second stage involves an energy
release which, although considered negative on the above basis, is customarily described in the opposite sense as the
"bond dissociation enthalpy," D(XY), representing the atomization enthalpy required to dissociate the X^Y bonds of
the completed molecule back to free atoms. For convenience,
use is often made of the empirical bond enthalpy, E(XY),

= [AHa-Cigr) + 2 AHa-H2{g)] - 4 [ E ( C - H ) ]
[717.2 + 870.8] - 1658.0

70 kJ/mol

(cf. 74.90 kJ/mol by measurement)


The term "standard" (superscript "o") indicates that the initial and final temperatures are c o m m o n at 25C. The negative
value above indicates that a net release of entheJpy occurs
during formation, hence the resulting methane molecule is
more stable than its parent elements. Values of AHf for other
hydrocarbon molecules are included in Table 3.
If now the dissociation enthalpy (but see activation energy
below) is applied to a fuel molecule, together with the atomization enthalpy of its stoichiometric oxygen molecules, the
total number of free atoms may rearrange themselves as oxide products, and so fall into a m u c h deeper enthalpy trough
as they release their new quantities of bond dissociation enthalpy. Hence,
Standard enthalpy of oxidation reaction
= AH?
= 2:(A//;)p -

= E(n AHf\

I(A//;?)R

- Km

AHf\

where subscripts P cmd R refer to products and reactants respectively,


mi = moles of reactcmt i, and

XD (X-Y)p

(AHpP
AH?

Uj = moles of product j .
As an example, consider the stoichiometric oxidation of
methane to gaseous CO2 and H2O given the following vaJues;
A///-CH4(g) = - 7 4 . 9 0 kJ/mol

Product
molecules

FIG. A3.1Schematic of standard molar enthalpies of formation (A H,) and of reaction (AHr) [1].

AHf C02(g) = - 3 9 3 . 5 2 kJ/mol, and


A//-H20(g) = - 2 4 1 . 8 3 kJ/mol
Since CH4(g) + 2 02(g) = C02(g) + 2 H20(g),

CHAPTER

28: ENGINEERING

it follows that A/:/^.CH4(g)


= [1 (-393.52) + 2 (-241.83)] - [1 (-74.90) + 0]

SCIENCES

OF AEROSPACE

FUELS

753

The Arrhenius plot also gives:


Gradient = E/R^ = 73 100/8.314 3 = 8792 K

= - 3 9 3 , 5 2 - 483.66 + 74.90
APPENDIX 4

= - 8 0 2 . 2 8 kJ/mol
It is noteworthy that the enthalpy of formation of O2, N2,
C(gr) and other elemental molecules at their standard conditions is zero since AHa and D(X^Y) are equal and opposite
in sign. It is also of interest to note that the above value is a
net quemtity since the product water is in the vapor phase.
(See the section on Calorific Values.)
From the above discussion on enthalpies of formation, it
might appear that the full complement of the dissociation
bond energies would be required in order to dissociate a fuel
molecule into its component free gaseous atoms of carbon
and hydrogen. However, the chain nature of the ignition process implies that only one bond need be broken to start the
chain. Furthermore, some molecules will have more than the
average level of energy, and also both bond breaking and remaking are occurring together. All these factors result in an
"activation energy" of a considerably lower level t h a n
D(CC) or D(CH). The actual value can be determined experimentally by plotting ignition temperature (T) against delay (t) on the Arrhenius basis as follows:

Proportions of Dissociated Combustion Products


At temperatures above about 1800 K, the thermal agitation of
combustion products is such that they begin to dissociate
back towards their reactant materials, giving reversibility to
the combustion reaction, thus
A + B^

combustion.
dissociation

At a sustained high temperature, therefore, a condition of


dynamic equilibrium exists with rates of combustion and dissociation exactly equal, so t h a t the reactant a n d product
materials coexist in proportions that remain constant. These
proportions can be determined by using values of parameters
known as "partial pressure equilibrium constants" at the
given temperature, as shown below.
The rates of such reactions at selected temperatures can be
determined by experiment, and are found to be proportional
to the instantaneous concentration of each material raised to
some power, that is,
forward reaction rate = kp [A]^ [B]'', and

Reaction rate
where

q
t

e
E
Ro
T

dt " ^

quantity of heat released per unit mass


reaction time
= Naperian base = 2.7183
= activation energy under the given conditions
= universal gas constant = 8.3143 J/mol K
= absolute temperature

reverse reaction rate

kR [C]'^

where

instantaneous molar
concentration of material X,

[X]

dq
Since --T- a t -\tae'^''^:

constant e

k = rate constant for the reaction,


and a, b, and c are
experimentally-determined
powers.
Since the two rates are equal at d5Tiamic equilibrium.

[Cf

It follows that
Int

In (ti/t2) =
Hence, E

_\_

J_

Rn

Ti

T2

Ro lniti/t2)
Ti

J_

T2
For n-octcine the calculations appear as follows:
8.3143 In (20/1.2)

It follows from Avogadro's law (equal volumes of all gases


at the same t e m p e r a t u r e a n d pressure contain the same
n u m b e r of molecules) that

598/
8.3143 In 16.67
0.001992 - 0.001672

8.3143 X 2.8135
0.00032

= 73 100 J/mol = 73.1 kJ/mol


This compares with 347.5 and 414.5 kJ/mol for initially dissociating the CC and CH bonds respectively, and with
208.59 for AHf.

t, = K = partial pressure equilibrium constant for


the reversible reaction,

Furthermore,

^ = -n
r. where p = total pressure.
p
total mol
^
^
Thus in each case, p^ can be expressed in the following
manner:
Px = P, (

L\

^^502

= concentration equilibrium constant for the


reversible reaction

Y + constant + constant

which is the equation of a straight line of In t against 1/T. The


value of can then be determined by taking two points on the
straight line, as follows:

^ = K'
kR

[A]^ [Bf

1, where Uj = total moles of product present.

Since carbon oxidizes in two stages, first to CO and then to


CO2, it is the final stage at the high temperature that experiences dissociation, that is
CO + O.5O2 ^ CO2
Hence,

PCO2
pCO {pOzT

,,
_
Kco,

"CO2
nr>_/n+^0.5
"C0(p"02/"t)'

754 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


Similarly for the oxidation of hydrogen,

Solution for the six unknown values of n requires six equations, four of which are provided by molar balances of C, H,
O, and N as for the simple non-dissociated case. The remaining two equations are then derived from the published values
of Kco2 and KHJO for the temperature in question, where

H2 + 0.5 O2 ^ H2O
PH2O
PH2 ip02)'

Hence,

"H2O
= K,
'' " " ' " "H2 (p"O2/"t)0-5

(Note; These two equilibrium constants are used for solving


the dissociated general mixture case below).
Since both reactions are occurring together, the half mole
of oxygen produced by dissociation of the mole of carbon
dioxide may be considered as the oxygen required by the
mole of hydrogen. Combination of the two combustion equations then gives:
CO2 + H2 ^ CO + H2O
This is known as the water-gas shift reaction (not to be confused with the water-gas reaction, which is: CO -I- H2 ^ C +
H2O) and leads to:
Water-gas shift equilibrium constant = KWGS
K,H20

PCOPHIO

KcOj
Pco2 Pw.2
(Note: This equilibrium constant is used for solving the imaginary non-dissociated rich mixture case since, although n o
dissociation complications arise, the distribution of the limited oxygen available to the CO and H2 has to be determined).
Selected values of the partial pressure equilibrium constants are given in Table A4.1.
Although at the higher temperatures dissociation proceeds
further to promote radicals such as O, H, OH and NOx (that
is, NO + NO2), a first approximation to realistic conditions
can be made by considering dissociation restricted to CO, H2
and O2 only, giving the following combustion equation for
any general mixture strength;
CaHb + m (O2 + 3.76 N2)

where m = moles of 02/mole fuel, as determined from the


given air-fuel ratio.
Solution follows by iteration on values of ns/nt. It might be
assumed that, as the products cool, the effects of dissociation
would vanish, and the combustion equation then revert to the
complete form in Eq 2 of Stoichiometry. But in fact, the partially-burnt products endure on cooling due to freezing of the
reactions when energy is lost through contact with the walls
of the containing vessel and any inert molecules present.
TABLE A4.1Partial pressure equilibrium constants for oxidation
reaction, atm~'^ [9].
298.15

300
500
1000
1500
2000
2100
2200
2300
2400
2500
2700
3000

KcOj

1.1641 X 10"^
575.44 X lO''^
10.593 X lO^''
16.634 X 10^
207.01 X 10^
765.60
345.94
168.27
87.097
47.753
27.543
10.351
3.0549

K,H20

ni
n j {p Us/Ut)"

and

n2

n4 {p ns/nt)"

Computer programs exist for the determination of product


concentrations, but the method of solution shown below permits derivation from first principles, typical of those o n
which the computer software itself is based.
1. At given temperature, read Kco2 and KHJO from Table A4.1
1. Assume value for ns/nt, and evaluate (p ns/nt)"-^
3. Evaluate ni/ua and n2/n4 from Kco2 and KHJO expressions
respectively, using Step 2 value.
4. Evaluate Ui and ns from carbon balance, and n2 and n4
from hydrogen balance using Step 3 value.
5. Evaluate ns from oxygen balance.
6. Evaluate nj from nitrogen balance.
7. Evaluate nt = n5/(assumed ns/ut), and compare with Enj,
with j = 1 to 6.
8. Repeat from Step 2 until Ut = Xnj.
Example
Allowing for dissociation to CO, H2, and O2 only, the stoichiometric combustion equation for methane-air at its isobaric adiabatic combustion temperature of 2247K (Appendix
5) appears as follows:
CH4 + 2 (O2 + 3.76 N2) = 0.903 CO2
+ 1.961 H2O + 0.097 CO + 0.038 H2 + 0.068 O2 + 7.52 N2

= ni CO2 + n2 H2O + na CO -I- n4 H2 + Uj O2 + ug N2

Temperature, K

Kco2

KH20

KWGS

11.169 X 10^^
6.1094 X 10^'
76.913 X 10^'
11.535 X 10'
530.88 X 10^
3.4670 X 10^
1.6866 X 10'
874.98
480.84
277.43
167.49
68.077
22.029

9.5945 X 10"^
10.617 X 10"^
7.2607 X 10"'
0.6935
2.5645
4.5285
4.8754
5.1999
5.5207
5.8097
6.0810
6.5769
7.2110

Comparison of these product quantities with those for the


non-dissociated case below shows clearly the influence of
dissociation.
CH4 + 2 (O2 + 3.76 N2) = CO2 + 2 H2O + 7.52 N2

APPENDIX 5
Calculation of M a x i m u m Reaction Temperature
The method of solution is based on the concept of equating
the enthalpy released by the reactants, in generating the dissociated products at the initial temperature, with that which
would have been required to heat those products from the
initial temperature to the final temperature J*. As in most
thermochemical work, the standard initial temperature is
taken as 25C (298.15 K). Hence,
[Chemical enthalpy released (negative) with reactants at
298.15 K oxidized to products at 298.15 K, that is, the standard enthalpy of reaction] is equal to
[Physical enthalpy absorbed (positive) by products in heating
from 298.15 K t o r * ]
that is,
- MIr = (//^*jp algebraically
But
\Hr = [{^H^)p - (^H^)B.'\
Thus,
(H^* + A//;)p - (AHf )R = 0

CHAPTER

28: ENGINEERING

Values of AHf for the products are listed in the literature


[9], together with values of the physical enthalpies absorbed
when heating from 298.15 K to the different levels of T. The
author has found it helpful to sum the two values shown on
the left-hand side above and designate it as total thermochemical enthalpy at temperature T, ( H i ) , tabulating these
sums for direct use at the temperature levels of interest. The
above equation then becomes

SCIENCES

OF AEROSPACE

FUELS

755

E. Repeat from step A at new level of T (say 2300 K).


F. Find T* by interpolation (or minor extrapolation) to give
zero in equation of step D.
(All values of n at T* can be found by similar extrapolation).
Example
All gaseous reaction of stoichiometric methane-air at 1 atmosphere with dissociation pattern as shown;

(AH/)R = 0

where H[*
= total thermochemical enthalpy at temperature T* based
on initial 298.15 K

CH4(g) + 2 (O2 + 3.76 N2) = ni CO2

Expansion gives

For methane, a = 1, and b 4.


A. Select T = 2200 K
B 1 Kco2 = 168.27, KHJO = 874.98
2 Assume nj/ut = 0.00519, thus (p ns/ut)"-^ = 0.07204
3 ni/nj = 0.07204 (168.27) = 11.936
n2/n4 = 0.07204 (874.98) = 61.387
4 n3 = a/(l + ni/ns) = 0.07730
ni = 1 - nj = 0.9227
n4 = (b/2)/(l + n2/n4) = 0.03206
n2 = 2 - n4 = 1.9679

Euj (Hr*)j - Emi (A//;)i = 0,

for reactants i and products j

Since AHf-Oz = Mlf-Hz = 0 due to the self-canceling of the


atomization and bond dissociation enthalpies, (for example
02i^Ha) -^ 2 O[D(0O)] -^ 02), it follows that the previous expression can be simplified further to
Euj (fff*)j - mfuei (AH/)fuei = 0, and then to
EUj ( / / r * ) j -

+ n2 H2O -t- n3 CO + n4 H2 -I- ns O2 + 7.52 N2

(A///)fuel

= 0, since only one mole of fuel is usually considered.


Since both linear and non-linear equations require solution simultaneously here, iteration is necessary on T in the
non-dissociated case, and on both n and T in the dissociated
case.
As with product concentrations, computer programs exist
for the determination of maximum reaction temperature, but
derivation from first principles using the total thermochemical enthalpy concept is as shown below.
A. Select some appropriate level of t e m p e r a t u r e T (say,
2200 K).
B. Determine all molar product "n" values;
For the non-dissociated case, from Eq 3
For the dissociated case, from the method shown in Appendix 4
C. Weight each value of n by its appropriate H[ at the selected T, from Table A5.1
D. Sum these weighted values, subtract {8Hf)iue\, and check
for zero.

5 ns

2m - X - (ni + n2) _ 3 - 2.8906

= 0.05468

6 ng = 7.52
^ 0.05468
ns
10.536
(assumed nj/ut)
0.00519
Suj = (10.52 + ns) = 10.575

7 n,

Since slight difference between Ut and Xuj, repeat from


step B. 2 using ng/ut = 0.00518
This gives reasonable equality of 10.57, and all appropriate values of n, as follows:
ni = 0.923; uj = 1.968; ns = 0.774; n4 = 0.0321; ns =
0.0547
C. Weight each n value with its appropriate Ht^ value at
2200 K
e.g., for CO2, ni {Hf) = 0.923 (-289.95) = - 267.6
D. Summation of these weighted values, less formation enthalpy for fuel, gives:
Snj (Hj)i - (A//;)f,ei = - 1 0 2 . 4 4 - (-74.85) = [-27.59]
Since this is not zero, repeat from Step A for new temperature of 2300 K.

TABLE AS. 1Standard-based total thermochemical enthalpy levels for gases, kj/mol [9] [1],
H[= (H^ + AH})
for Compounds

Hi = H"for Elements

Temperature, K

CO2

H2O

CO

H2

O2

N2

298.15
300
500
1000
1500
2000
2100
2200
2300
2400
2500
2700
3000

-393.52
-393.46
-385.21
-360.12
-331.81
-302.07
-296.02
-289.95
-283.85
-277.73
-271.60
-259.27
-240.66

-241.83
-241.76
-234.91
-215.85
-193.73
-169.14
-164.00
-158.79
-153.53
-148.22
-142.86
-132.01
-115.47

-110.53
-110.47
-104.60
-88.843
-71.680
-53.790
-50.154
-46.509
-42.853
-39.183
-35.505
-28.121
-16.987

0
0.054
5.883
20.686
36.267
52.932
56.379
59.860
63.371
66.915
70.492
77.718
88.743

0
0.054
6.088
22.707
40.610
59.199
62.986
66.802
70.634
74.492
78.375
86.199
98.098

0
0.054
5.912
21.460
38.405
56.141
59.748
63.371
67.007
70.651
74.312
81.659
92.738

756

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Similar calculations give ns/iit = 0.00785, hence;


n , = 0.881; na = 1.953; na = 0.119; n4 = 0.047; nj = 0.083
Summation of weighted values gives [ + 3 1 . 6 3 ]
This also is not zero, but interpolation with value - 27.59
from Step D gives
r * = 2247 K
Similar interpolation gives the related vEilues of the product moles:
ni = 0.903; nz = 1.961; nj = 0.097; n4 = 0.038; ns = 0.068
Note
For stoichiometric methane-air,
T* = 2327 K, nondissociated
= 2247 K, dissociated to CO, H2, and O2 only (as shown
above)
= 2223 K, dissociated to CO, H2, O2, H, O, OH, and NO
For stoichiometric methane-oxygen,
r * = 3045 K, dissociated to CO, H2, O2, H, O, OH, and NO

In the absence of the effects of gravity or motion, this energy change is located entirely within the internal energy of
the system material, hence:
n.f. (q w) =
and

The Energy Equation


From the laws of thermodynamics, it is evident that, for a
system operating in a cycle, the initial and final states are
identical, and the net heat input is equal to the work output,
with some of the heat input being rejected to a lower temperature sink. On a specific basis, therefore:
qnet - W = ( q i n -

Qout) " W = 0

This is usucJly expressed simply as: q - w = 0


When the process is not cyclic, the initial and final states
differ, and the energy equation then becomes:
q w = Ae

(A6.1)

n.f. d q z - 1W2) = M2 - Ml

This is known as the non-flow energy equation (n.f.e.e.), any


change in internal energy leading to changes in temperature
or phase.
In the presence of effects of gravity or motion, as in a system flowing steadily through a control region, balaxices of
mass cind of energy appear as shown below:
Mass balance:
mi = m2 = p A C = Ai Cj/vi = A2 C2/V2
where p = density of fluid
A = cross-sectionzJ area of flow
C = velocity of flow relative to control region, and
V = specific volume of fluid = 1/p
Energy balance: s.f.(iq2 1W2)
= (hi -hi)

APPENDIX 6

AM

+ g (z2

^2

2^

where z is the height above the Earth's surface, or some other


datum.
This is known as the steady-flow energy equation (s.f.e.e.),
which can also be expressed in various reduced forms depending on the constancy of certain terms. One useful form
concerns negligible changes in both potential and kinetic energies, applicable to horizontal flow with approximately similcir entry and exit velocities, as shown below:
Reduced s.f.e.e. = s.f. dqz 1W2) = h2 hi

(A6. 2)

This compares directly with the non-flow case in Eq A6.1.


Since this present study concerns steady flow applications to
jet engines, most t h e r m o d y n a m i c considerations deal in
terms of enthalpy rather thein internal energy.

MNL37-EB/Jun. 2003

Properties of Fuels, Petroleum


Pitch, Petroleum Coke, and
Carbon Materials
Semih Eser^ and John M. Andresen^

their important properties, including standard methods of


measurement and the significance of individual properties in
industrial applications.

THIS CHAPTER PROVIDES AN OVERVIEW ON THE ORIGIN, PROPERTIES,

AND APPLICATIONS of fuel oils, petroleum pitch, petroleum coke,


and some related carbon materials. A c o m m o n thread among
these materials is the line of p r o d u c t i o n that connects
petroleum refining to the manufacture of carbon materials.
Bottom fractions from catalytic cracking of gas oil (FCC decant oil) or from thermal cracking of naphtha (ethylene tar)
can be used as residual fuel oil, or as feedstocks for producing
carbon black, petroleum pitch, and p r e m i u m petroleum coke
for graphite electrodes. Petroleum pitch is, in turn, used for
producing carbon fibers and carbon-carbon composite materials, and for densification of graphite electrodes used in electric-arc furnaces to recycle scrap iron and steel. The residua
from vacuum distillation in petroleum refining are subjected
to severe thermal cracking in coking processes to produce
light and medium distillates and petroleum cokes that are
used as solid fuel, or as filler for manufacturing carbon anodes
for electrochemical production of aluminum. It is important
to recognize that ferrous metals and light metals industries, as
well as manufacturing a n u m b e r of carbon materials, are
closely linked with the products of petroleum refining, including decant oils, petroleum pitch, and petroleum coke.

S p e c i f i c a t i o n s a n d A p p l i c a t i o n s o f F u e l Oils
Fuel oils are burned to generate heat for different purposes
ranging from home heating to raising steam in utility boilers
to generate electricity. Different types of burners used in
these applications under various climatic and operating conditions dictate the need for different grades of fuel oils. A
standard specification by the ASTM International has divided fuel oils into five basic grades, designated as Nos. 1, 2,
4, 5, and 6 (ASTM D 396). Based on the production methods
used in petroleum refining, fuel oils fall into two broad classifications: distillates and residuals. The distillates comprise
overhead or distilled fractions, whereas the residuals consist
of bottoms remaining from the distillation, or blends of distillates with the bottoms from distillation, visbreaking, and
catalytic cracking processes [2-4]. The six grades of oils can
consist of different t5^es according to the refining processes
used in their production, as described in the section on
Petroleum Refining [5]:

For each material, production processes, product properties, and specifications are discussed in the context of respective industrial applications. Standard methods used for
characterization of these materials are identified with a focused discussion on the interpretation of the results obtained
from the standard tests. Literature references are provided
for further information on each topic.

1.
2.
3.
4.

FUEL OILS
Petroleum refining processes generate many product streams
that can be used as fuel oil either in single streams or in
blends to adjust the desired properties for specific applications. A broad definition of fuel oils does occasionally include
diesel fuels since they are closely related to distillate and
heavy fuel oils. In this section, however, diesel fuels are not
included for discussion, since they are covered separately in
this manual [1]. Industrial use of fuel oil for generating heat
is the principal focus in this section. Specifications and
applications of fuel oils are introduced with an overview of

' Department of Energy and Geo-Environmental Engineering and


The Energy Institute, respectively. College of Earth and Mineral Sciences, Pennsylvania State University, 110 Hosier Building, University Park, PA 16802.

straight-run distillate;
straight-run residual (i.e., reduced crude);
catalytically cracked distillate;
cracked residuals from thermal or catalytic cracking, or
hydrocracking;
5. blends of any of the streams listed above.
Cracked oils have rather different composition and properties from those of the straight-run oils, as discussed later.
In the ASTM specification. Grades No.l and No.2 are distillates and Grades No. 4-6 are usually residuals. Some heavy
distillates may, however, be sold as Grade No. 4 fuel oil.
Grade Nos. 4 and 5 are subdivided into light and heavy categories. Table 1 summarizes the common uses and some significant properties of the different grades of fuel oils [6].
Grades 1 and 2 are used in domestic and small industrial
burners. Grade 1 is a particularly light distillate for use in the
vaporizing type burners and under storage conditions that require low pour points. Grades 4-6 are used in pressure atomizing-type commercial/industrial b u r n e r s that can handle
high viscosity fuels. The viscosity of these residual fuels increase with the increasing number in the grade scale such
that Grade 6 fuel, also called Bunker C, requires preheating
for handling and burning [6].
In general, all grades of fuel oil should be homogeneous hydrocarbon oils, free from inorganic acid, and free from ex-

757
Copyright'

2003 by A S I M International

www.astm.org

758

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

TABLE 1Common uses and some significant properties of different grades of fuel oils.
Grade

Classification

No. 1

Distillate

No. 2

Distillate

No. 4 (Light)

Heavy Distillate

No.4

Heavy Distillate,
Distillate/Residual
blends

No. 5 (Light)
& No. 5 (Heavy)

Residual

No. 6 or Bunker C

Residual

cessive amounts of solid or fibrous foreign matter. All grades


containing residual components should remain uniform in
normal storage and not separate by gravity into light and
heavy oil components outside viscosity limits for the grades.
Table 2 lists the required specifications for all fuel oil grades
according to the standard designation ASTM D 396. A representative sample should be taken for testing in accordance
with ASTM Practice D 4057. Modifications of limiting requirements agreed upon between the seller and the buyer
should fall within limits specified for each grade, except as
stated in supplementary footnotes for Table 2. The most important considerations in selecting a burner and a particular
grade of oil include the volume of the oil consumed, and a
match between the capabilities of the b u r n e r systems and
properties of the fuel oils. The heavier grades are less expensive, but they must be handled and burned efficiently to take
advantage of the lower fuel cost, especially in large volume
applications. Sufficient heating in the storage tank and insulated transfer pipelines are usually necessary to ensure steady
flow of heavy oil to the burner. High-viscosity oils require additional preheating at the burner for proper atomization.

I m p o r t a n t F u e l Oil P r o p e r t i e s
Fuel oils are burned to generate heat. The a m o u n t of heat captured in combustion systems is the principal concern for the
fuel user. Important properties of fuel oils must, therefore,
relate to their combustion characteristics and performance in
different types of burners and fuel handling systems. Understanding these properties helps the user to select a fuel best
suited for a specific application. It is also useful to discern the
relationships between different properties of fuel oils. All the
properties of fuel oils identified in Table 2 are discussed below, with reference to standard measurement methods, and
the significance of the measured properties.
Gravity
The density of petroleum oils is often expressed in terms of
API gravity, a scale devised by the American Petroleum
Institute and National Bureau of Standards (continued as
National Institute of Standards and Technology). The API

Application
Domestic and small
industrial burners of the
vaporizing type
Atomizing type domestic and
small industrial burners
Pressure-atomizing type
commercial/industrial
burners
Pressure-atomizing type
commercial/industrial
burners; preheating not
required for handling or
burning
Industrial burners; preheating
may be required for
handling and burning
Industrial burners;
preheating required for
handling and burning

Significant Properties
Volatility and pour point
Volatility and viscosity
Viscosity and pour point
Viscosity, flash point, and
sulfur content

Viscosity, flash point, and


sulfur content
Viscosity, flash point, and
sulfur content

gravity is inversely proportional to specific gravitythe ratio


of the density of oil at 60F to the density of water at 60F
according to the following equation:
API = (141.5/spgr60F/60F) - 131.5
The API gravity is the most commonly used property to
classify crude oil and refined petroleum products since the
early days of petroleum industry. It has also been used to predict many other characteristics of petroleum oils. Recent
variations in crude oil composition coupled with new processes in petroleum refineries have, however, diminished the
usefulness of API gravity as a descriptor for other properties
of petroleum oils. Two oils with the same API gravity, for example, can have many different characteristics because of
large differences in composition (e.g., different combinations
of paraffinic, naphthenic, and aromatic hydrocarbons). The
API gravity still remains to be an important property, since it
can be measured easily, and used in a number of empirical
correlations for approximate estimation of other properties
of petroleum fractions [7].
The API gravity of fuel oils is measured by using a standard
hydrometer according to ASTM Test Method D 287 or D
1298. Because of the significant volume expansion of oils
upon heating, the API gravity varies strongly with temperature. An API gravity of 12 at 60F, for example, would correspond to an API gravity of 18 at 180F (82C) [4]. Therefore,
the volumetric heating value of oils (Btu/gal) decreases significantly with the increasing API gravity. The reasons for
this trend are discussed in the next subsection.
Table 2 shows the gravity limits for the three grades of oil
(>35 for No. 1; > 3 0 for No. 2; < 3 0 for No. 4 light). Although
the differences in gravity between different grades may vary
depending on the composition of the oils and the refining
processes, typical API gravity ranges for fuel oils are as follows: No. 2: 26-39; No. 4: 24-32; No. 5: 16-22; No. 6:
10-15. As expected, API gravity decreases with the increasing grade number. The API gravity also changes according to
the fuel types within a given grade. For No.2 fuel, for example, the API gravity of straight-run fuel oils range between 36
and 39, while that of thermally, and catalytically cracked oils
would fall in the range 24-28, and 29-32, respectively. For

CHAPTER 29: PROPERTIES

OF FUELS, PETROLEUM PITCH. PETROLEUM

COKE, AND CARBON MATERIALS

759

TABLE 2Detailed requirements for fuel oils (ASTM D 396).


Properties

Specific Gravity, 60/60F


deg API
Flash point, C (F) min
Pour point, C (F) msix
Kinematic viscosity, mm'^/s
(cSt)''
At38C(100F)min
max
At40''C(104''F)min
max
At 50C (100F) min
max
Saybolt Viscosity
Universal at 38C (100F)
min
max
Furol at 50C (122F)
min
max
Distillation temperature, C
(F)
10% point max
90% point min
max
Sulfur content, mass, mcix
Corrosion copper strip, max
Sulfated ash, % mass, max
Carbon residue, 10%*; %m,
max
Water and sediment, % vol,
max

No. 1

0.8499
35 min
38 (100)
18''(0)
1.4
2.2
1.3
2.1

No. 2

0.8762
30 min
38 (100)
- 6 " (20)
2.0"
3.6
1.9
3.4

(32.6)
(37.9)

No. 4
(Light)

No. 4

No. 5
(Light)

No. 5

No. 6

55 (130)

55 (130)

60 (140)

0.8762"
38 (100)
-6" (20)
2.0
5.8

(32.6)
(45)

55 (130)
- 6 " (20)
5.8
26.4^"
5.5
24.0'

(45)
(125)

>26.4
65^

>24
58^

(>125)
(300)

>65
194^^
>58
168^
(42)
(81)

>92
638^^

(>300)
(900)

(>900)
(9000)

(23)
(40)

(>45)
(300)

215(420)

0.5
3

282'^
(540)
338 (640)
0.5*
3

0.15

0.35

0.05

0.05

288 (550)

0.05

0.10

0.15

0.15

(0.50)"

(0.50)'

(1.00)'

(1.00)"

(2.00)"

"It is the intent of these classifications that failure to meet any requirement of a given grade does not automatically place an oil in the next grade unless in fact
it meets all the requirements of the lower grade.
''In countries outside the United States other sulfur limits may apply.
"Lower or higher pour points may be specified whenever required by conditions of storage or use. When pour point less than - 18C (0F) is specified, the mini m u m viscosity for grade No. 2 shall be L7 cSt (31 SUS) and the m i n i m u m 90% point shall be waived.
'^Viscosity values in parentheses are for information only and not necessarily limiting.
"The amount of water by distillation plus the sediment by extraction shall not exceed the value shown in the table. For Grade No. 6 fuel oil, the amount of sediment by extraction shall not exceed 0.5 weight %, and a deduction in quantity shall be made for all water and sediment in excess of I.O weight %.
^Where low su Ifur fuel oil is required, fuel oil falling in the viscosity range of a lowered numbered grade down to and including No. 4 may be supplied by agreement between purchaser and supplier. The viscosity range of the initial shipment shall be identified and advance notice shall be required when changing from one
viscosity range to another. This notice shall be in sufficient time to permit the user to make the necessary adjustments.
*This limit guarantees a m i n i m u m heating value and also prevents misrepresentation and misapplication of this product as Grade No. 2.
''Where low sulfur fuel is. Grade 6 fuel oil will be classified as low pour -H5C (60F) max or high pour (no max). Low pour fuel should be used unless all tanks
and lines are heated.

oils from a single refinery stream, the API gravity can indicate w h e t h e r they are straight-run, or cracked oils. For
blends, e.g., No. 4 oil, the concentration of different types of
oils present, would, therefore, determine the API gravity of
the blend in the corresponding range.
In general, the API gravity of fuel oils can be qualitatively
related to other properties of the oils as shown below [7]:
The higher the API gravity, the lower the viscosity and carbon residue.
The higher the API gravity, the lower the volumetric heating value (Btu/gal), and the higher the gravimetric heating
value (Btu/lb).
The higher the API gravity, the lower the C/H ratio.
The higher the API gravity, the higher the rate of combustion, and the shorter the flame length.
Heating

Value

Heating value is broadly defined as the amount of heat released by complete combustion of a unit quantity of fuel. Experimental measurements can be reported as total (or high).

or net (or low) heating values in Btu per gallon. The total
heating value includes the latent heat of evaporation of the
water vapor produced during the combustion. For determining the net heating value, the water from combustion is considered to remain in the gaseous state, and, therefore, the
latent heat of evaporation is not recovered. Although no direct reference is made to heating value measurement in the
ASTM classification of fuel oils (there is indirect reference
through limiting API gravity. See footnote g in Table 2), heating value is a n important specification requirement. The
heating value, or the heat of combustion of fuel oils, can be
measured by the ASTM D 240. The net heating values of fuel
oil samples can also be measured by the ASTM D 4529, D
3338, or D 4809.
Depending on the specific gravity and composition of fuel
oils, total heating value ranges typically between 130 000
and 160 000 Btu per gallon (36 400-44 800 kJ/liter). The
net hea-ting value is usually 8400-8500 Btu per gallon
(2350-2380 kJ/liter) lower t h a n the total heating value, depending on the hydrogen content of the fuel. Figure 1 shows

760

MANUAL

37: FUELS AND LUBRICANTS

.5' 160000
..... ...-r-:.
5 155000 J^^^/^,':: :
.:v.;-::=:;.:.;V
" 150000
oT 145000 -^sPiRiet^/.f:^***
*^ii_
&
I 140000
^'-'iftKi^> 135000
^[^-T.':--^^^^
o) 130000
~ 125000
; ri^7^:;:\
S 120000 "\r^ ^ ^i ' ^ I r' f H I". ^ ' i.":' '1
r

"^^^^feu'

'

'

'

HANDBOOK

-Total Heating
Value
-Net Heating Value

'

0 4 8 1216202428323640
API Gravity

FIG. 1Total and net heating values of fuel oils versus API
gravity.

a plot total heating value and net heating value of selected


fuel oils as a function of API gravity from the data given in
reference [8] (1 Btu/gallon = 0.28 kJ/liter). It can be seen
that the volumetric heating value increases with the decreasing API gravity, because of the decreasing hydrogen
content of the fuels with the decreasing API gravity.
In addition to measurement by standard methods and prediction from the API gravity, there are a number of empirical
correlations used to calculate the heating value. Two of the
most commonly used correlations are given below:
Total Heating Value (Btu/lb) = 14 600C
+ 62 000(H-O/8) + 4000S
where C, H, O, and S are the weight percentages of these elements in the fuel [8].
Net Heating Value (kJ/kg) = 55 500 - 14 400d - 320S
where d is the density (kg/liter), and S is the sulfur content in
wt% [9].
It should be noted that on a weight basis (e.g., Btu/lb, or
kJ/kg), the heating value of a fuel oil decreases with the increasing density (or decreasing API gravity). However, this
trend is reversed when reporting the heating value on a volu m e basis (e.g., Btu/gal, or kJ/liter) since the decreasing heating value is more than compensated by the decreasing volume
as the density increases. For example, an oil with 14 API gravity have 290 Btu less per pound (676 kJ/kg) than a 20 API gravity oil, but one a volume basis the 14 gravity oil will have 3840
Btu more per gallon (1075 kJ/liter) than the 20 gravity oil [8].
Therefore, oils with a lower API gravity will provide more heat
on a volume basis, but other properties of the fuel oil, such as
viscosity, pour point, and carbon residue, may be limiting factors in selecting a given oil, as discussed below.

ture. The kinematic viscosity, expressed in mm^/s (formerly


called centistoke, cSt), is determined as the product of the
m e a s u r e d flow time a n d the calibration constant of the
viscometer.
Although the kinematic viscometers are the approved instruments, Saybolt viscometers (Universal and Furol) are
also widely used for measuring viscosity. In Saybolt viscometers, the time for the flow of a given volume of liquid
is measured under variable head (as opposed to the constant head in kinematic viscometers), which decreases as
the volume of the oil in the tube decreases. The measured
viscosity is expressed as Saybolt Seconds. The only difference between Universal and Furol viscometers is the larger
orifice of the Furol tube (3.15 mm) t h a n that of the Universal (1.77 mm). The Universal is used for testing low-viscosity oils, while the Furol is used for high-viscosity oils to obtain reliable m e a s u r e m e n t s by avoiding the exceedingly
long, or short, test times depending on the viscosity of oil.
Most frequently used temperatures for viscosity measurements are 38C (100F) for Saybolt Universal and Kinematic
viscometers, and 50C (122F). Conversion tables can be
used for viscosity conversions between different values [11].
Table 3 gives the Saybolt and kinematic viscosity limits for
different grades of fuel oils. The grade Nos. 5 and 6 have
very broad ranges of viscosity because of the use of many
different types of burners that can handle a range of viscosities. In applications, where viscosity needs to be closely
controlled, oils can be purchased on a viscosity basis. Some
suppliers specify their oil as, for example. No. 5-300, indicating No. 5 fuel oil with a viscosity of 300 SSU (Saybolt
Seconds Universal) at 100F (38C).
The viscosity of fuels depends strongly on temperature; the
viscosity decreases sharply with the increasing temperature
[11]. This strong temperature dependence is used to control
the viscosity of residual fuel oils by preheating. When the viscosity of heavy oils is reduced, pumping becomes easier and
better atomization is achieved for combustion. Conversely,
heavy oils become viscous and extremely difficult to handle
at low temperatures. In cold weather applications, the lowest
operating temperatures must be considered for selecting the
oil with the adequate viscosity for easy pumping and handling. In some applications, the viscosity of heavy fuel oils is
controlled by blending with stocks of lower viscosity. Mixing
of fuel oils with different chemical characteristics may, however, cause incompatibility problems leading to deposit and
sludge formation in fuel handling systems [12].
The high viscosity of fuel oil causes the following problems
[11,13]:
Difficulty in pumping from storage tank to burner; loss of
p u m p suction

Viscosity
The viscosity of oil measures its resistance to flow [10]. It is
one of the most important properties of especially the residual fuel oils that affect handling, heating, pumping, and atomization of heavy residual fuels in combustion. The most
commonly used viscosity term, kinematic viscosity, is determined by measuring the time for a fixed volume of liquid to
flow under gravity through the capillary of a calibrated viscometer (ASTM D 445 with specifications given in ASTM D
446). The measurements must be m a d e under a reproducible
driving head and at a closely controlled and known tempera-

TABLE 3Summary of ASTM methods for the characterization of


petroleum pitch properties.
Property

Softening point
Viscosity
Solvent Fractionation
Coking Value
Density
Ash
Sulfur Content

ASTM Designation

D 3461, D 2319, D 36, D 61, D 3104


D5018
D 4746, D 2764, D 2318, D 4072, D 4312
D 4715, D 2416

D 2320, D 70, D 4892, D 71, D 2962


D2415
D 1266, D 4045, D 2622

CHAPTER 29: PROPERTIES

OF FUELS, PETROLEUM PITCH, PETROLEUM COKE, AND CARBON MATERIALS

Insufficient oil flow to the burner causing problems with


starting and erratic combustion
Poor atomization causing inefficient combustion and dribbling of oil at the burner nozzle
The low viscosity of the fuel oil causes, in turn, the following problems [11,12]:
Too much oil pumped to the burner causing incomplete
combustion, resulting in smoke, carbonization of burner
nozzle, and soot formation in the combustion chamber
Low heat generation because of the low heating value of
low-viscosity, or high API gravity of the fuel oil
P u m p slippage, too much oil can slip the cup with rotary
cup burners, resulting in poor atomization.
Pour

Point

Pour point represents the temperature at which a fuel oil


stops flowing. This property, measured by ASTM D 97, indicates the lowest temperature of the utility of a fuel in flow
systems, and it is particularly relevant to waxy heavy oils and
heavy oils that require preheating for pumping. Straight-run
oils usually have higher p o u r points than cracked oils because of the higher concentrations of normal paraffins in
straight-run oils. The usefulness of the pour point test in relation to residual fuel flow properties is questionable. The
pour point test does not indicate what happens when an oil
has a considerable head of pressure behind it w h e n it is
pumped along a pipeline, or gravitated from a storage tank.
Among the tests devised to assess the low-temperature flow
characteristics of heavy residual fuel oils is ASTM D 3245.
ASTM D 3245 is, however, a time-consuming test, and not
suitable for routine control testing, along with its limitations
in application to very waxy fuels.
Flash

Point

As fuel oils are heated, they evaporate, and the vapors flash at
a certain temperature when ignited by an external flame.
This temperature is called the flash point. There are two standard ASTM tests to measure the flash point: ASTM D 92
(Cleveland), a n d ASTM D 93 (Pensky-Martens), using an
open-cup, and a closed-cup flash tester, respectively. The
closed-cup tester gives lower flash points because of the more
effective retention of very light vapors that are blown away by
the air flow in the open-cup tester. Therefore, the closed-cup
test is more sensitive in detecting the small amounts of light
vapors in the fuel oil samples. As shown in Table 3, desirable
flash points of fuel oils range from 38C (Grades N o . l , 2) to
60C (Grade No.6) measured by closed-cup testers. Flash
points lower than the desired values may cause fire hazard,
whereas high flash points can lead to difficulties with starting, especially in a cold furnace.
Distillation
ASTM D 86 is used to determine the 10% and 90% points of
the distillate fuel oils (Grade No. 1 and No. 2) as specified in
Table 3. The distillation characteristics (volatility) of these
fuels are related to their ignition and combustion properties
and the tendency to form solid combustion deposits. The
lower and upper limits to volatility are set to ensure safety
and smooth operation in the use of these fuels.
Water and Sediment (BSW)The presence of water and
sediment, also called bottom sediment and water (BSW), in

761

fuel oils can cause a n u m b e r of operational problems,


including [14],
Plugging of burner tips
Erratic and unsteady combustion
Flame instabilities
Erosion of burner tips and mechaniccJ parts.
The origin of BSW can be traced back to the original
crude oil, contamination during refinery processes, or thermal degradation a n d oxidation reactions during storage.
Usually heavy oils (No. 5 and No. 6) contain greater
amounts of BSW than light oils because of the concentration of BSW of crude oil in the residual fractions due to the
high specific gravity and high viscosity of the residual fuels.
Light oils, such as No. 2 and No. 4, are usually clean, except
for some water and small amounts of fine sediment. Table
1 shows that m a x i m u m BSW is limited to 0.05%vol for oils
No. 1 and No. 2, 0.5% vol for No. 4, 1.0% vol for No. 5, and
2% vol for No. 6.
Three s t a n d a r d m e t h o d s are used to determine water
and bottom sediment either together (ASTM 1796 -by centrifugation with added toluene), or separately (ASTM D 95,
Azeotropic distillation for water and ASTM D 473, Extraction
with toluene and weighing the residue). Specific rules apply
to reporting BSW, if water and sediment measurements are
carried out separately (see footnote in Table 3).
The occurrence of BSW in fuel oils can be reduced by careful storage, blending, and transportation practices that reduce the formation and/or dispersion of the sediments in the
fuel oils [14].
Carbon

Residue

The term carbon residue is used in several different connotations related to the use of fossil fuels, including carbonaceous
particles present in fuel, carbon formed on the burner tips
and furnace walls because of incomplete combustion, and
carbonaceous residue remaining after pjTolysis of fuels in
standard tests. Only the results from standard carbon residue
tests are used in fuel specifications. It is important to distinguish between the carbon deposition due to the high carbon
residue of the fuel oil, and coke or soot formation as a result
of poor combustion [15]. Understanding the difference between these two types of deposition helps identify the root
cause of any deposition problem: fuel composition or combustion conditions [16].
Three standard methods used to determine carbon residue
are ASTM D 189, Conradson Carbon Residue (CCR), ASTM
D 524, Ramsbottom Carbon Residue (RCR), and ASTM D
4530, Micro Method. Most specifications are based on CCR,
but correlations exist to convert between CCR and RCR test
results [ASTM D 189].
Table 3 shows that carbon residue is specified only for light
fuel oils, No. 1 and No. 2, because small vaporizing-pot and
sleeve-t3^e burners used in domestic applications have less
tolerance for carbon deposition. The carbon tests are conducted on 10% bottom residue of the fuel samples remaining
after distillation.
Ash
Ash results from the noncombustible organic and inorganic
species found in fuel oils. Most of the ash can be traced back
to the constitution of the crude oil from which the fuel oils

762

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

were derived. To a lesser extent, contamination during refining and handling may be responsible for the ash content.
Most of the ash-producing materials present in crude oil
(e.g., water soluble sodium and calcium chlorides, and oil
soluble organometallic compounds of nickel and vanadium)
tend to concentrate in the heavy products, such as residual
fuel oils. Ash contents of fuel oils can be determined by
weighing the n o n c o m b u s t i b l e residue after c o m b u s t i o n
using ASTM D 482.
Table 3 shows the permissible ash contents specified for
Grades No. 4 (0.05%, 0.10% for light and heavy, respectively),
and No.5 (0.15%). No specifications are given for No. 1 and 2
because ash is seldom found in distillate oils. Also, there is n o
ash specification for No. 6 oils (which may contain u p to
0.2% ash [17]) since the combustion equipment designed for
burning heavy residual fuels can handle relatively high ash
contents.
Problems encountered with high ash contents depend on
the application and type of combustion operation, including
contamination of products in direct firing applications (e.g.,
glass and ceramic industry), erosion of p u m p p a r t s and
burner tips, and accumulation of ash on boiler tubes. High
metal contents of heavy oils would also be responsible for
producing particulate emissions from combustion with potentially significant toxicity [18].
The removal of ash from fuel oils is not practical and very
costly because most ash-forming compounds are soluble in
the oil. Problems with high ash contents are usually addressed by blending with low ash oils and/or by reducing the
impact of ash in combustion operations with fuel additives
and combustion system treatments [17].
Sulfur

Content

Sulfur is one of the most troublesome elements found in fuel


oils. Sulfur is p r e s e n t in a variety of complex chemical
compounds in crude oils. Since the molecular chemistry of
sulfur compounds is extremely complex, sulfur specifications
depend on the measurement of the total sulfur content of
fuels. Because of the high-boiling points of sulfur-containing
compounds, sulfur tends to concentrate in heavy residual
fractions obtained from petroleum refining. The sulfur
content of fuel oils generally increases with the increasing
grade number. The sulfur range in each grade shows large
variations because of differences in sulfur contents of crude
oils, refining processes, and blending. There are several
ASTM tests that are used to determine the sulfur contents of
fuel oils, inclu-ding ASTM D 1266, Lamp Method (for No. 1
only), ASTM D 1552, High-Temperature Combustion, ASTM
D 129, Oxygen Bomb, and ASTM D 4294, Non-Dispersive
X-ray Fluorescence.
The sulfur limits in fuel oil specifications shown in Table 3
designate the m a x i m u m total sulfur contents for No. 1 and
No. 2 oils as 0.5%. No sulfur specification is listed for grades
No. 4, 5, and 6. For many applications, however, consumers
specify the maximum allowable sulfur limit to comply with
the environmental regulations (e.g., Clean Air Act a n d
Amendments in the U.S.) or to limit damage to materials in
combustion systems.
Problems associated with high sulfur contents in fuels are
related principally to combustion products, namely sulfur
dioxide (SO2) and sulfur trioxide (SO3), which further react

in the presence of oxygen and moisture to produce sulfurous,


or sulfuric acid. These acids will cause corrosion of any exposed metal surfaces, such as boiler shell and tubes. The
presence of sulfur compounds may also cause problems in
various materials applications, such as glass, ceramic, and
metals production [19].
Total emissions of sulfur oxides from combustion systems
depend almost entirely on the sulfur content of the fuel without any significant effect of the boiler size, combustor design,
or the fuel grade. Sulfur contents of fuel oils can be reduced
by hydro treatment in petroleum refining [4,5] or by blending
with oils having lower sulfur contents. Flue gas scrubbers are
used in large installations to remove sulfur from stack gases
to comply with SO2 emission limits.
A particular corrosion test, ASTM D 130, Copper Strip
Corrosion, is used to characterize the corrosive properties
of fuels related mainly to sulfur compounds, such as dissolved hydrogen sulfide, mercaptans, active elemental sulfur, along with inorganic acids and ammonia. The presence
of these compounds in fuels lead to the corrosion of copper
heating lines, cooling coils, and nonferrous metal fittings.
The copper strip corrosion test measures the extent of discoloration of copper strips that came into contact with fuel
samples under specified conditions. Reference strips used to
measure the extent of discoloration are rated from No. 1
(light-orange) to No. 4 (jet black). The No. 1 and No. 2
grades have a m a x i m u m Corrosion Strip specification of
No. 3, dark tarnish.
Instability

and

Incompatibility

The instability of residual fuel oils refers to the tendency of


a fuel to produce deposit by itself, while incompatibility is
the tendency of a fuel to produce a deposit when blended
with other fuels [20]. Two oils that are each stable as single
fuels may become incompatible when they are mixed. Major incompatibility problems occur when an oil with an asphaltene content of greater t h a n 3 - 5 % is blended with
paraffinic oils. The incompatibility results in the formation
of tar-like precipitates that cause problems in handling
and combustion systems. ASTM D 4740 can be used to predict the compatibility between a residual fuel oil and a
specific distillate fuel oils, such as a No. 1 or No. 2 oil. This
test is also used for predicting the compatibility of residual
fuels, although it may not be reliable for residual oil mixtures. The asphaltene content of residual oil is believed to
affect its stability and compatibility [3,12]. ASTM D 3279
can be used to determine the asphaltene content of residual
fuel oils.

Conclusions
A standard classification of fuel oils according to selected
specifications facilitates the selection of the right fuel oil for
wide ranging applications in different combustion systems
that show significant variations in size, combustor design,
and process needs. A large number of ASTM methods exist to
characterize many properties of fuel oils that are of interest
for a particular application. Understanding the significance
of these tests and careful interpretation of the test results will
help troubleshoot m a n y performance problems in fuel oil
handling and combustion systems.

CHAPTER 29: PROPERTIES

OF FUELS, PETROLEUM PITCH, PETROLEUM COKE, AND CARBON MATERIALS

PETROLEUM PITCH
Petroleum pitch has become an important material for a
n u m b e r of industrial applications, in particular, for manufacturing high-performance c a r b o n fibers and carboncarbon composites. This section provides an overview of
p r o d u c t i o n processes, applications, and properties of
petroleum pitch.
Production Processes and Applications
Petroleum pitch is a term used for certain petroleum residues
due to their resemblance to other pitch materials, such as
coal tar pitch, that are thick, dark colored bituminous substances obtained from destructive distillation processes.
Generally, petroleum pitch is the nonvolatile product obtained from thermal or catalytic cracking of heavy petroleum
residua [4,21]. It may also be defined as the high boiling
point fraction (420-520C) obtained by vacuum distillation
(0.5-1.0 m m Hg) of catalytic cracking bottoms [22], or as solvent deasphalted bottoms [23]. Due to its resemblance to coal
tar pitch, the ASTM methods that are summarized in Table 3
are often used to test both materials. However, petroleum
and coal tar pitches are substantially different in origin,
structure, and behavior, and, therefore, a ccireful interpretation of the test results is necessary.
CoaJ tar pitch is obtained from the distillation of volatile
by-products, or tar, from coke ovens during the manufacture
of metallurgical coke from coal. The differences in the origin
and processes that lead to the production of petroleum and
coal tar pitch are apparent in their chemical composition and
respective industrial applications [24,25]. For instance, the
carbon content of petroleum pitch is around 85-90%, which
is somewhat lower than that of coal tar pitch (94-96%). This is
linked to the higher hydrogen content of 4-6% for petroleum
pitches, versus 2 - 3 % for coal tar pitches. Hence, petroleum
pitches contain a relatively high proportion of aliphatic carbons compared to coal tar pitches. Both petroleum and coal
tar pitches are predominantly aromatic, with the majority of
alkyl groups being methyl. However, while a tj^ical coal tar
pitch has an aromaticity of 98-99%, petroleum pitches have
around 10-20% aliphatic carbon. Coal tar pitches contain relatively more condensed aromatic ring structures with a
bridgehead aromatic carbon content (i.e., aromatic carbon
only bound to other aromatic carbons) of 0.45-0.50. Therefore, the volatile compounds in coal tar pitches, as detected by
GC-MS, are mainly three to six aromatic ring compounds,
such as phenanthrene, fluoranthene, pyrene, benzo[a]pyrene,
benzo[b]fluroanthene, and a n t h a n t h r e n e , while the nonvolatile compounds have a much higher condensed structure.
In contrast, petroleum pitches have a rather open structure,
with a bridgehead aromatic carbon content around 0.35-0.40
[26]. The volatile compounds are two-to four-ring compounds
that are heavily alkylated. The non-volatile compounds are
non-defined entities of larger a r o m a t i c ring structures
substituted with long-chain alkyl groups and possibly some
saturated rings. These differences in structure and composition explain the differences in softening points and
viscosity behavior, solubility, density, and coking yields from
the coal tar and petroleum pitches, as described in Properties
of Petroleum Pitch.

763

The applications of different p e t r o l e u m pitches are


governed by their properties, d e p e n d i n g largely on their
chemical composition. ASTM D 2569 is used to determine
the distillate contents of pitches. A soft pitch, which appears
semi-viscous at ambient temperatures due to its low glass
transition temperature (see Softening Point), will produce a
relatively large amount of distillate even at low temperatures
and weak vacuum (if applied). On the other hand, hard pitch
will yield little distillates even at temperatures up to 360C.
Accordingly, industrial distillation of pitches is frequently
used to produce carbon-precursors with high softening point
and coking yields [27]. An alternative approach utilizes airblowing to alter the chemical composition of the pitches to
meet the required specifications [23].
Generally, petroleum pitch is used in the production of prem i u m petroleum coke or as an impregnation pitch in the
manufacture of carbon artifacts for the aluminum and steel
industry [28]. The high carbon content and low mineral matter content of petroleum pitch makes it an excellent precursor for the production of high performance carbon fibers and
carbon-carbon composites (see Carbon Fibers from Petroleum
Pitch). Molded in sheets, carbon fibers have higher strength
than steel (227 and 200 GPa, respectively) but only 1/5 of the
density, 1720 a n d 7830 kg m~^, respectively [29]. These
impressive properties result from the formation of a discotic
liquid crystal phase, carbonaceous mesophase that produces
high tensile strength and modulus. Carbonaceous mesophase
is formed by alignment of disk-like molecules (see Formation
of Coke Microtexture in Coking Processes for a description
of carbonaceous mesophase). The a m o u n t of mesophase in
a p e t r o l e u m pitch can be established following ASTM D
4616. Although most of the terminology of this method concerns coal tar pitches, the central concept about isotropic
(non-mesophase) and anisotropic (mesophase) is valid for
petroleum pitches. The influence of primary quinoline insolubles, described in detail in Solvent Fractionation, is minimaJ
or nonexistent in petroleum pitches. Hence, mesophase is
both readily developed and detected in petroleum pitches,
with clear identification of mesophase spheres or anisotropic
texture domains. The a m o u n t of mesophase, as found
through ASTM D 4616, is generally a function of pitch condensation, heat-treatment temperature, and time. Recently,
an in-situ ^H NMR technique has been developed to follow
the mesophase development directly during heat treatment
[30]. High performance carbon products from mesophase
pitches have a wide range of applications, including lightweight components for vehicles, boats, planes and the space
industry; high strength and wear parts in brakes and engine
pistons, and medical artifacts (e.g., in artificial heart, bone
plates and ligaments) due to their bio-compatibility with
blood, soft tissue, and bones [31,32].

Properties of Petroleum Pitch


The determination of various properties of petroleum pitch is
crucial for the establishment of pitch consistency, which can
be utilized as a strong marketing tool. Pitch buyers often dem a n d that the properties described in the Softening Point
through Ash sections meet their specifications, to assure that
the product they are buying fits their requirements and process line. Currently, there are two m a i n practices used for

764

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

pitch transportation. The most frequent practice involves


transporting pitch as a hquid around 180C, but some users
prefer to receive the pitch as a soHd (often referred to as pencil pitch from its extrusion into small rods). Due to the
various ways of handling, some localized variation in pitch
composition can occur. Hence, an important tool for establishing sample uniformity is the use of ASTM D 4296, Stand a r d Practice for Sampling Pitch. The strength of this
method lies in its compatibility with both solid and liquid
pitch. A proper sampling lays the foundation for valuable
data collection from the following standard test methods.
Softening

TABLE 4Comparison of the five standard test methods used for


determining softening point in pitches.
Method

Description

D 3461

Softening point of asphaltene and pitch (Mettler cupand-ball method)The pitch is loaded in a small
metal cup with a bottom orifice and a ball is placed
on top of the solid pitch. The assembly is placed in a
furnace and a light beam is used to detect the
temperature when the ball is penetrating the pitch
(the softening point).
Softening point of bitumen (ring-and-bsdl apparatus)
The pitch is loaded in a small metal ring and a ball
placed on top of the pitch. The assembly is placed in
a bath and the temperature when the ball is
penetrating the pitch is manually detected (the
softening point).
Softening point of pitch (cube-in-air method): Molded
cubes of pitch with center holes are placed on hooks
and suspended in an oven. The temperature of the
hooks when the pitch is flowing is manually detected
(the softening point).
Softening point of pitch (cube-in-water method):
Molded cubes of pitch with center holes are placed
on hooks and suspended in water. The temperature
of the hooks when the pitch is flowing is manually
detected (the softening point).
Softening point of pitches (Mettler softening point
method): The pitch is loaded in a small metal cup
with a bottom orifice. The assembly is placed in a
furnace and a light beam is used to detect the
temperature when the pitch is flowing through the
orifice (the softening point).

D 36

Point

Petroleum pitches are mixtures of condensed aromatic compounds. As a result, petroleum pitches are eutectic, i.e.,
soften at a lower temperature than the individual melting
points of the different compounds that make u p the pitch.
At ambient temperatures, the pitch has an isotropic structure and is generally characterized as a glassy solid (hardpitch). When the pitch is heated in an inert atmosphere, it
has no defined melting point, but will pass through a glass
transition region before it becomes an isotropic liquid.
While a pure compound, e.g., anthracene, goes from a solid
to liquid at 217.5C, a mixture of similar aromatic compounds and their alkylated derivatives will exhibit a wide
temperature interval (4Tg can range from 10' to over 10^C)
from the end of the solid phase to a fully liquid state. The
transition from a glassy solid to a viscous substance gives
rise to a physico-chemical characteristic CcJled the glass
transition temperature, Tg [33]. Although there is no ASTM
method yet developed, both the Tg and the temperature interval, ZlTg can be determined by different methods [34]
such as ' H N M R , electron-nuclear double resonance (ENDOR) or differential scanning calorimetry (DSC). The enthalpy, /IH, and activation energy, Ea, for pitches can then
be derived from the above techniques, ft has been shown
that the Ea can be considered to be proportional to the
mean molecular size in pitch, and can give an estimate of
the degree of condensation [35].
During the transition from a glass to a liquid, the viscosity
of the pitch changes drastically (see Viscosity). However, it is
relatively tedious and labor intensive to determine the viscosity behavior for every single pitch. Therefore, several standard test methods, ASTM D 3461, D 36, D 2319, D 61, and D
3104, have been developed to establish when a pitch reaches
a viscosity of about 10^ Pa s, generally referred to as the
softening point of the pitch [36]. Table 4 lists the differences
between the five standard test methods given by ASTM. D
3104, Mettler Softening Point Method or D 61, Ring and Ball
Softening Point, are the most commonly used. D 3104, Mettler Softening Point Method, provides fast and accurate determination of the softening point but requires the purchase
of an instrument. D 61, Ring and Ball Softening Point, is fast
and inexpensive, and, therefore, it is also frequently used.
The softening points can be given both in C or F, and sometimes they give rise to pitch nomenclature, where Ashland
petroleum pitches A-170 and A-240 have softening points of
170 a n d 240F, respectively. Furthermore, it has been reported that pitches having similar softening point can have
different Tg, which can be associated to differences in viscosity as described below.

D 2319

D 61

D3104

Viscosity
The determination of changes in viscosity and other rheological properties during and after the glass transition region is
crucial for applications of pitch as a binder for electrodes and
road aggregate. ASTM D 5018, Standard Test Method for
Shear Viscosity of Coal-Tar and Petroleum Pitches, is a good
tool to follow the rheological properties of pitches at temperatures of 40-100C over its softening point, since it requires a
relatively simple setup. The setup consists of a hotplate, a
temperature controller, a thermometer, and a rotational viscometer. The pitch is melted into a cup on the hotplate where
the rotor from the viscometer is inserted, and at different
temperatures the viscosity is measured. The method is limited to 230C and 15 000 cps (15 Pa s).
Viscosity, 17, is defined as the ratio of the shear stress, T, to
the rate of change of shear strain, ySR, at constant temperature and pressure, TJ = r/ySR [37]. When the viscosity of a
system is only a function of temperature and pressure, and
independent of the shear rate at constant temperature and
pressure, the fluid can be classified as Newtonian. For nonNewtonian systems, such as polymers and most liquid crystals, the viscosity is dependent on the shear rate as well [34].
Isotropic pitches before thermal decomposition are mainly
Newtonian [38]. However, non-Newtonian flow, such as
Bingham behavior, has been detected where there is no flow
until the shear stress exceeds a critical value called the yield
stress [39]. The variations in viscosity with temperature for
the petroleum pitch Ashland A-240 is compared to a coal tar
pitch and its solvent fractions (see Solvent Fractionation in
Fig. 2 [40]. With increasing temperature, there is a rapid decrease in viscosity during softening of the pitch. In the tem-

CHAPTER 29: PROPERTIES

OF FUELS, PETROLEUM PITCH, PETROLEUM COKE, AND CARBON MATERIALS

765

FIG. 2Changes in viscosity with temperature for Ashland A-240 petroleum


pitch compared with a coal tar pitch, its toluene soluble (TS) and insoluble (Tl)
fraction together with various TS:TI mixtures [40]. Reprinted with permission
from Elsevier Science.

TABLE 5Nomenclature and solvents used historically in the petroleum and coal tar pitch industries.
Petroleum Pitch

Coal Tar Pitch

Carboids
Carbenes

Insoluble in CS2
Insoluble in CCI4, but
soluble in CS2

a-resin
/3-resin

Asphaltenes

Insoluble in n-pentane,
but soluble in CCI4
or CeHft

y-resin
Resinoid
Crystalloid

perature region prior to the pitch becoming a hquid, there is


a tail off in the viscosity reading, e.g., from 150-2008C for A240 petroleum pitch. ASTM D 5018 deals with the change in
viscosity in this region. From the rheological measurements,
the suitability of a pitch for certain applications can be established, e.g., as a binder or for impregnation purposes. In
Fig. 2, the increase in the viscosity after 4508C is due to
t h e r m a l induced chemical reaction in the pitch, such as
coking (Coking Value), or the development of mesophase
(further explained in F o r m a t i o n of Coke Microtexture in
Coking Processes).
In addition, rheology studies give information about elastic
properties important for the thermo-forming process of fibers
and composite impregnation [41]. An example of the effects
of the elastic properties is the die-swell during the extrusion
process in fiber spinning, which often is undesirable [42].
Solvent

Fractionation

A drawback in pitch characterization is that the nomenclature used for solvent fractionation of petroleum pitch and
coal tar pitch has been different in the past [36]. The

Insoluble in quinoline (pyridine)


Insoluble in toluene (benzene,
dimethylformamide), but
soluble in quinoline
Soluble in toluene
Insoluble in n-hexane (petroleum
ether), but soluble in toluene
Soluble in n-hexane

petroleum industry used CS2, CCI4, CsHe, and n-pentane,


while the coal tar pitch producers used quinoline or pjridine,
benzene or toluene, and petroleum ether or n-hexane. Table
5 lists the nomenclature associated with each solvent for the
two industries.
The standard test methods developed by ASTM Eire largely
based on the nomenclature and solvent fractionation scheme
originally developed for cocJ tar pitch that has become the
common terminology in pitch fractionation [43]. The a-resin,
or QI (quinoline-insoluble) content, is determined using either ASTM D 4746 or D 2318. Table 6 compares the two
methods for determining the QI content. Generally,
petroleum pitches contain very little or n o QI unless they
have been heat-treated (see below). The 7-resin, or TS
(toluene-soluble), content can be established using ASTM D
4072, D 4312, or D 2764. Table 7 compares the three methods
for obtaining the TS content. From the two previous measurements the ;8-resin, or TI - QS (toluene-insoluble and
quinoline-soluble), can be calculated by difference. The different resin fractions above consist of c o m p o u n d s with
different molecular masses and heteroatom contents. A sim-

766

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 6Comparison of the two ASTM methods for determining


the QI content in pitches.
Method
D 4746

D 2318

Description
Determination of quinoline insolubles (QI) in tar and
pitch by pressure fihration; The pitch is dissolved in
quinoHne at 75C and fihered through a porcelain
filtration crucible with a medium-porosity bottom at
a pressure in the range of 10-30 psig using nitrogen.
The sample is washed in hot quinoline until clear
followed by acetone and dried. The portion of the
pitch remaining in the crucible is defined as the QI
fraction.
Quinoline-insoluble (QI) content of tar smd pitch; The
pitch is dissolved in quinoline at 75C and digested
for 20 min. The solution is filtered through a
porcelain filtration crucible with a fine-porosity (7
yum) bottom using a suction filter apparatus. The
sample is washed in hot quinoline until clear,
followed by toluene, then acetone and dried. The
portion of the pitch remaining in the crucible is
defined as the QI fraction.

TABLE 7Comparison of the three ASTM methods used for


determining the TS content in pitches.
Method
D 4072

D 4312

D 2764

Description
Toluene-insoluble (TI) content of tar and pitch: The
pitch is dissolved in toluene at 95C for 25 min and
filtered through an extraction thimble using a
gravimetric filtration tube. The extraction thimble is
transferred to an extraction apparatus where it is
further extracted for 18 h using a toluene reflux rate
of 1 to 2 drops/s. The extraction thimble is dried at
105C for 30 min and the portion of the pitch
remaining in the thimble is defined as the TI fraction.
Toluene-insoluble (TI) content of tar and pitch (short
method): The pitch is dissolved in toluene at 95C for
25 min and filtered through an extraction thimble
using a gravimetric filtration tube. The extraction
thimble is transferred to an extraction apparatus
where it is further extracted for 3 h using a toluene
reflux rate of 120-150 drops/min. The extraction
thimble is dried at 110C for 30 min and the portion
of the pitch remaining in the thimble is defined as the
TI fraction.
Dimethylformamide-insoluble (DMF-I) content of tar
and pitch: The pitch is dissolved in dimethylformamide at 95-100C and digested for 30 min. The
solution is filtered through a porcelain filtration
crucible with a fine-porosity (7 /xm) bottom using a
suction filter apparatus. The sample is washed in hot
dimethylformamide until clear followed by acetone
and dried at 105-110C. The portion of the pitch
remaining in the crucible is defined as the DMF-I
fraction (mainly used as a rapid TI determination).

plified comparison between the three fractions could be that


the y-resin (TS) is the lowest molecular weight fraction, the
;8-resin is an intermediate, while the a-resin (QI) is very high
molecular weight material. These differences result in the
TS having high H/C atomic ratio and low softening point,
while the QI has low H/C atomic ratio and generally does
not soften.
The a-resin (QI) is a primary specification of pitches in the
carbon industry, and Table 8 summarizes the desired content
for some applications. A further sub-division of the a-resins
can be made into primary, secondary QI, and extraneous im-

TABLE 8Pitch apphcations depending on QI content [43].


Application
Binder pitch
Impregnating pitch
Needle coke manufacture
(highly anisotropic)

'-Resin (QI) content of pitcli, %


9-18
2-5
<1

purities. The primary fraction consists of material that partially retards coalescence during carbonization of pitch. The
secondary fraction is in itself able to coalesce and is therefore
referred to as the mesophase QI. The impurities consist of
dirt and metal particles, and in the case of coal tar pitch,
c a n y over coke from the by-product furnace. Both the primary and the secondary QI consist of high molecular mass
species as reflected in low atomic H/C ratios (tjrpically 0.25
and 0.35, respectively). The effect of the QI on pitch carbonization is heavily dependent on the size and the distribution of primary and secondary QI in the a-resin.
Petroleum pitches are generally free of primary QI. On the
other hand, the j3-resin can be a substantial component of the
pitches produced from petroleum (ranging from 0-80%),
while coal tar pitches for binder purposes contain around
10-20% ;S-resin. Even though the H/C ratio of around 0.40 of
the 13-resin fraction is close to that of the secondary QI, the
first will undoubtedly have a lower molecular mass since
thermal treatment of the /3-resin could transform it partially
into secondary QI. This suggests that the structures of secondary QI and /3-resin are relatively similar and only differ by
some degree of condensation [26]. The y-resin, i.e., the
toluene-soluble fraction, has the highest H/C ratio and, due to
its high solubility, it can be readily investigated by chromatographic a n d other analytical techniques. Such techniques include high-pressure liquid chromatography (HPLC)
where different aromatic compounds can be identified by
their UV spectra following a separation by elution through a
packed column with different solvents, gel permeation
chromatography (GPC) to identify the molecular mass distributions, and nuclear magnetic resonance (NMR) for the determination of the average hydrogen and carbon skeletal
parameters [26,27].
The influence of primary QI on pitch carbonization has
been the subject of intensive research. Primary QI has sometimes been referred to as "carbon black-like" due to its smeJl
particle size. However, there are several differences between
the two forms. First of all, primary QI can reach a particle
size of about 1 /xm and secondary QI much higher, while carbon black particles have an average size of 20-30 n m [44].
Scanning electron microscopy (SEM) studies have shown
that primary QI particles are generally spherical, reaching an
average particle size of 0.1-1 fim. Figure 3 illustrates the particle size distribution of (a) typical primary QI of a coal tar
pitch and compares those to (b) the particle size of secondary
QI particle from a heat-treated petroleum pitch. The differences are clearly observed in Positions A, B, and C in Fig. 3
(a) and Position N in (b). The coal tar pitch has a range of particle sizes between 0.1-1 /xm in diameter, while the
petroleum pitch contains agglomerated secondary QI particles in the range of 2-10 /xm in diameter. Secondly, carbon
black particles have the ability to form chains, where hundreds of units are aggregated together, with some degree of

CHAPTER 29: PROPERTIES

OF FUELS, PETROLEUM PITCH, PETROLEUM COKE, AND CARBON MATERIALS

an ordered microstructure and smooth particle surfaces. In


contrast, for primary QI, high-resolution transmission elect r o n microscopy (HRTEM) studies have described the
microstructure to be generally disordered, without agglomeration of the particulates [45]. Figure 4 shows HRTEM micrographs c o m p a r i n g the m i c r o s t r u c t u r e of (a) a c a r b o n
black, and (b) primary QI particle from a coal tar pitch. The
c a r b o n black has highly ordered layer planes that form
concentric spheres (Fig. 4a), while the QI shows a generally
disordered microstructure (Fig. 4b). However, it should be
mentioned that the term QI is only useful as a guide to
particulate matter in pitch, since isotropic matter that is insoluble in quinoline can be soluble in the pitch [46]. This has
been shown through heating QI where some of the material
becomes fusible. As mentioned earlier, secondary QI is less
condensed with higher H/C ratios than the primary fraction
[47]. Secondary QI in binder pitch is unwanted due to its
fusibility, which makes the pitch more viscous than that of
pitches solely containing primary QI. For a potential binder
pitch, it is therefore important to estimate the secondary
QI content. Secondary QI particles are in general larger than

(a)

(b)

FIG. 3SEM micrographs comparing the particle size distribution of (a) typical primary QI of a coal tar pitch and (b) the
particle size of secondary QI particle from a petroleum pitch.
Position A, B and C: primary QI spheres ~ 0.1 /xm in dia., agglomerated, and ~1 fim in dia., respectively. Position N: Agglomerated secondary QI particles. Reprinted with permission
from Elsevier Science.

(a)

767

1 iMui, and an attempt has been made to quantify the secondary QI content by the difference in particle size. However,
secondary QI particles are frequently coating the infusible
particles of primary QI, which makes this technique inaccurate [45].
Coking

Value

During thermal treatment of petroleum pitch in an inert or


oxygen deficient atmosphere, volatile matter is released as a
result of distillation of smaller constituents and the thermal
decomposition of the pitch [48]. The weight loss as a function
of temperature is normally measured by thermogravimetric
analysis (TGA). In general, there is no or little loss before
200-3 00C followed by a rapid release, which goes through a
m a x i m u m weight loss rate at a fixed temperature, Tmax. This
Tmax is found by taking the derivative of the TGA slope
(DTG). The rate of weight loss decreases after Tmax, reaching
a m i n i m u m at 500-600C. The standard test methods of
ASTM do not consider the weight loss profiles of pitches, but
rather the remaining carbon content, or coke, after heating to
temperatures well over 500C, which is a general coking
temperature of pitch (Fig. 2). After the pitch has formed coke,
the weight loss is minimal. Hence, the standard test method
ASTM D 4715, or "Alcan" coking value, requires 2 h heat-treatment at 550C, while the "Modified Conradson" coking value,
ASTM D 2416, is established after only 30 min at 900C.
The thermal weight loss, as determined by TGA, for a coal
tar pitch is shown in Fig. 5 and the weight loss curve for a
petroleum pitch is similar. The loss is initiated around 200C,
with the highest loss rate between 300-400C, then levels out
at 500-550C, and decreases very slowly at higher temperatures. Hence, the "Alcan" coking value (D 4715) must be established using sufficient time for the coke to form2 h
holding time at 550C. Increasing the temperature to 900C,
as for the "Modified Conradson" (D 2416), shortens the coking time, but there is also some loss of gaseous products that
does not occur during D 4715. Therefore, the "Alcan" coking
value (D 4715) is generally 2 wt% higher than the "Modified
Conradson" coking value (D 2416). For comparison with the
whole pitch, the weight-loss profiles for its three solvent fractions, TS (y-resin), beta-resin ()3-resin), a n d QI (a-resin),
weighed on their extraction yield are also stack-plotted in

(b)

FIG. 4HRTEIVI micrographs comparing the microstructure of (a) a carbon black,


and (b) primary QI particle from a coal tar pitch. Reprinted with permission from Elsevier Science.

768

MANUAL

3 7: FUELS AND LUBRICANTS

100%-

1VI1..1

;^

^'^^

NX^

T3

^^; X

75%-

HANDBOOK

50%-

^ ^ ^

F o r Sulfur I n Petroleum P r o d u c t s (High-Temperature


Method, can be used for petroleum pitches. The petroleum
pitch is combusted either in an induction or resistance type
furnace. The sulfur is released as SO2 that is retained in a KIO3
solution and quantified by titration. ASTM D 2492, Standard
Test Method for Forms of Sulfur in Coal, is often specified for
coal tar pitches, where sulfate sulfur is extracted from the
pitch using dilute HCl and pyritic sulfur is calculated as a stoichiometric c o m b i n a t i o n with iron. However, as for
petroleum pitch, a Leco sulfur analyzer is generally used.

> TT'

1^
Ivl.i-l -1II1

' --',

a
25%-

'^
0%-

'

.r'J

}*j*j

\}*J
Temperature / C

o'ju

"Jo

I'OO

FIG. 5Comparison of TGA traces for a coal tar pitch and its
TS, beta-resin and Ql fractions.
Fig. 5. There is a good agreement between the whole pitch
and the added loss profile from its solvent fractions. From the
individual solvent fractions, it is clear that the QI loses very
little weight, which is also the case for the )3-resin. The main
weight loss occurs in the TS fraction, which indicates that the
weight loss is particularly dependent on the y-resin content.
Hence, a particular concern for the utilization of petroleum
pitch as a binder for carbon artifacts is its low content of
insolubles, in particuljir QI and to some extent also )3-resin.
Density
The density of pitch is a property closely watched by consumers, since low pitch density is generally related to low
coking value, increased costs, and reduced quality of the
resultcint carbon products. The ASTM standard methods differentiate between specific gravity (density) and relative
density, however, specific gravity is usually reported for
pitches. Due to the different appearance of pitch, three standard methods for specific gravity have been developed by
ASTM: D 2320 deals with sohd fragmented hard pitch, D 70
concerns soft pitch, and D 4892 applies to pulverized pitch.
All three methods involve the use of pycnometer. Since the
pitch density is dependent on temperature, ASTM has developed a standard test method, D 2962, for calculating a volume-temperature correction. However, this test method is
only developed for coal tar pitch and there is no equivalent
m e t h o d for p e t r o l e u m pitch. The d e p e n d e n c e of specific
gravity upon pressure is normally ignored. The standard test
method for relative density, D 71, utilizes water displacement, a n d is therefore a quick method. However, relative
density of pitch is rarely reported.
Petroleum pitches have densities spanning from 1.10-1.30
gcm^^ cind are somewhat lower than that of coal tar pitches,
which have specific gravity in the range 1.30-1.40 gcm~^.
Hence, increasing the density of petroleum pitches is a key issue in their competition with coal tcir pitches.
Sulfur

Content

The sulfur content in some oil crudes may be very high (3-5
wt%) and correspondingly can result in high sulfur levels in
the resultant petroleum pitch, where levels u p to 4 wt% have
been reported [23]. Since there is no specific ASTM method
for sulfur determination in pitch, it is typical to use a Leco sulfur analyzer. However, ASTM D 1552, Standard Test Method

Ash
Petroleum pitches have generally low ash contents below
0.1%. The standard test method for ash in pitch is described
in ASTM D 2415 and applies to both hard and soft petroleum
pitches. The m a i n elements in ash from petroleum pitch are
iron, nickel, and vanadium [23], and these heavy metals are
known to m a r the carbon products used in the aluminum and
steel industries [49].
Conclusions
The ASTM standard methods for pitch chetracterization Eire
i m p o r t a n t tools for the establishment of petroleum pitch
properties such as softening point a n d viscosity behavior, solubility, density and coking yield, and ash and sulfur levels, as
described in the above sections. The monitoring of pitch
quality through standardized methods is crucial for the future of the carbon industry, due to its dependence on high
performance pitches for purposes such as binders and for impregnation of carbon materials, and precursors for carbon
fibers and composites. Although coal tar pitch is presently
dominating the market, a decline in its availability is forecasted, especially in the U.S., due to the reduced numbers of
by-product coke ovens. Hence, petroleum pitch cam gain access to these markets through innovative manufacturing processes for tailored properties. The ASTM standard methods
will be important reference points for the development of
high performance petroleum pitches.

PETROLEUJVI COKE
Petroleum coke is a generic term used to describe a variety of
carbonaceous solid products intentionally produced by severe thermal cracking of p e t r o l e u m heavy fractions. The
composition, microstructure, and properties of petroleum
cokes depends on the nature of the feedstock and the coking
process. Specific chemical a n d physical properties a n d microtextural characteristics of petroleum cokes are critically
important for their industrial/commercial uses. Petroleum
coke production processes, the composition and properties
of coker feedstocks, and the formation of coke microtexture
in coking processes are described a n d discussed in this section along with classification, properties, and uses of
petroleum cokes.
Petroleum Coke Production Processes
Low-temperature carbonization (coking) at temperatures below 500C converts high-boiling petroleum fractions or

CHAPTER 29: PROPERTIES

OF FUELS, PETROLEUM PITCH, PETROLEUM

residua into mixtures of gases, distillate liquids (naphtha and


gas oils), and carbonaceous solids (petroleum cokes). In the
general petroleum refining scheme, coking is a severe thermal
cracking process that is used primarily for producing distillate liquids from heavy ends, such as vacuum distillation
residua (VDR). The resulting petroleum coke is considered a
by-product that may have some commercial value depending
on the nature of the coke. More specialized coking processes
also exist to produce a high-value premium petroleum coke as
the primary product from more aromatic feedstcoks, such as
Fluid Catalytic Cracking Unit Decant Oil (FCCU DO). Two
principal coking processes used in petroleum refining are Delayed Coking and Fluid Coking [50]. Figure 6 shows simple
flow diagrams of Delayed Coking and Fluid Coking Processes.
Delayed Coking is the most commonly used coking process
in petroleum refining. It is a semi-continuous process. The
coker feed is preheated in externally fired tube furnaces and
continuously charged into a large insulated d r u m where coke
formation takes place at approximately 475C as the drum is
filled [51]. The pressure in the coke d r u m varies in the range
40-50 psig (0.35-0.45 Mpa). Gases and distillate liquid products from severe thermal cracking reactions are collected
from the top of the d r u m . Once the coke d r u m is filled, the
feed is switched to another d r u m for continuous charging.
Upon completion of the coking cycle, the coke product is
mechanically removed from the d r u m using high-pressure
water jets to cut the coke. Thus, the production of coke is
intermittent, although the feed is charged continuously. The
resulting delayed coke is usually regarded as a low-value byproduct, generally used as fuel coke. Higher quality delayed
cokes with lower sulfur and metal contents, called sponge
cokes because of their porous nature (see Fig. 7), are further

COKE, AND CARBON MATERIALS

APPEARANSi

< -

769

OPTICAL
TEXTURE

NEEDLE COKE

OPTICAL MICROGRAPH
OF NEEDLE COKE

SPONGE COKE

OPTICAL MICROGRAPH
OF SPONGE COKE

SHOT COKE

OPTICAL MICROGRAPH
OF SHOT COKE

FIG. 7Appearance and optical textures of


needle, sponge, and shot cokes.
(TvTSs

/"^^"N

NAPHTHA

SEPARATOR

FIG. 6Schematic flow diagrams for Delayed


Coking and Fluid Coking.

processed to manufacture carbon anodes used mainly for


aluminum production [52]. An occasioned and usually undesired co-product from delayed coking of VDR is called shot
coke because of its morphology that resembles the clusters of
buckshot [53] (see Fig. 7). Shot coke is extremely hard to
grind; it does not have any significant commercial use except
for some small-scale niche applications, such as the production of TiOa [52]. An important property of fuel coke is its
grindability, which can be measured by ASTM D 5003, HardgroveGrindability Index (HGI) of Petroleum Coke. Fuel grade
cokes should have an HGI of greater than 80.
Slurry oils (or decant oils), highly aromatic bottoms product from Fluid Catalytic Cracking Unit (FCCU DO), are also
used as feedstocks for delayed coking. Coking takes place
u n d e r slightly different conditions, e.g., higher pressures
(60-80 psig) and lower temperatures (450C), to produce a
premium petroleum coke, needle coke. The term needle coke
derives from the splintery appearance of this coke because
of its highly anisotropic microtexture (see Fig. 7). After
calcination, needle coke is used as a filler for manufacturing
graphite electrodes for electric-arc furnaces to mEmufacture
iron and steel [54]. In addition to FCCU DO, thennal tars
from naphtha and gas oil cracking are also used as feedstocks
for needle coke production. Compared to decant oils, however, thermcJ tars usually produce lower quality needle cokes
under comparable coking conditions.

770

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Very different in design and operation from Delayed Coking, Fluid Coking is another commercial coking process commonly used in petroleum refining to convert VDR and other
heavy fractions into distillate liquids, gases, and fluid coke. In
contrast to the semi-continuous nature of Delayed Coking,
Fluid Coking is a continuous process (see Fig. 6). In Fluid Coking, the feed is sprayed onto fine size hot coke particles in the
coker where coke is deposited on these seed particles by thermal cracking of the feed at temperatures between 480-525C.
Some of the coke product is introduced into a combustor
where partial combustion of the coke particles with air takes
place. Partially combusted hot coke particles are returned to
the coker to provide the heat necessary for thermal cracking/coking to complete the cycle. The resulting coke product,
fluid coke, has a different structure and different properties
compared to those of the delayed cokes, as discussed in the
following sections. Fluid coke is used principally as fuel with
some limited use in the manufacture of carbon materials.
Flexicoking process is a variation of Fluid Coking where the
fluid coke product is partially or completely gasified with air
and steam to produce fuel gas in the refinery [50,52].
Table 9 s u m m a r i z e s the coking processes, coker feedstocks, different kinds of petroleum cokes and their principal
industrial applications. Petroleum cokes produced by delayed or fluid coking are generically called green cokes because of their relatively high volatile matter content (5-15%).
Fluid cokes have generally lower volatile matter contents
than delayed cokes (typically around 5%) because of the relatively high temperatures used in fluid coking.
Formation of Coke Microtexture in Coking
Processes
Delayed cokes produced from VDR (sponge, fuel, and shot
coke) show substantial differences in microtexture, including
variations in the degree of structural anisotropy, the size
of anisotropic domains, and porosity. Sponge cokes are more
anisotropic, i.e., with a higher degree of microstructural
order, and more porous than shot cokes. Fuel cokes have
an intermediate degree of anisotropy and porosity between
those of sponge and shot cokes. Differences in the degree of
structural anisotropy of delayed cokes (illustrated in Fig. 7)
can be traced to the development of an intermediate liquidcrystalline phase, carbonaceous mesophase, during liquidphase carbonization in the delayed coker. Carbonaceous
mesophase is a unique, ordered fluid consisting of essentially
planar molecules. The prevailing molecular order, which exhibits an intermediate state between isotropic liquids and

Process
Delayed Coking

Fluid Coking
Flexi-coking

anisotropic solid crystals, is similar to that of the nematic


(thread-like) liquid crystals [55]. The basic molecular units of
mesophase are, however, disc-shaped alkyl substituted polyaromatic hydrocarbons and range widely in size [56].
Polarized-light microscopy makes use of an incident planepolarized light that is reflected from polished specimen surfaces to reveal the extent of microstructural order present in
the sample [57]. In plane polarized-light, the waves of light
are confined to a single plane, in contrast to random orientations of waves in ordinary light. Using polarized-light microscopy, uninhibited formation a n d development of
m e s o p h a s e can be observed to occur in three sequential
stages: 1) nucleation of anisotropic spheres (0.5-10 m m in
size) from an isotropic liquid; 2) growth of anisotropic
spheres; and 3) their coalescence to form anisotropic microtextures in cokes upon solidification. The polarized-light micrographs in Fig. 8 show the three stages of mesophase
development as a function of time during carbonization of a
decant oil (CCB) and an ethylene tar residue (ETR) sample in
a laboratory batch reactor at 4758C. The extent of microtextural anisotropy in the resulting cokes is described and
classified with respect to the size and shape of the anisotropic
d o m a i n s produced by mesophase development. Under a
polarized-light light microscope with a phase-sensitive retardation plate, the anisotropic domains are seen on polished
specimen surfaces as the same color areasisochromatic regions, depending on the orientation of ordered regions.
The overall appearance of the polished sections of the cokes
under a polarized-light microscope is referred to as the optical texture. Table 10 describes a commonly used classification
scheme to describe the optical texture of green cokes, or other
carbonaceous solids [57]. When a phase retardation plate is
used in a polarized-light microscope, isotropic regions seen as
light purple areas represent the lack of any structural order in
units greater than 0.5 /am (the resolution of light microscope).
Anisotropic structures display dark purple, blue, and yellow
areas of varying shape and size. In the absence of a phase retcirdation plate, the anisotropic regions appear as different
gray levels. The term mosaics describes small structures of
anisotropic units that are 0.5-10 ;u,m in diameter. Small domains and domains refer to isometric areas with diameters of
10-60 ix.m, and >60 ^im, respectively. Elongated domains that
are greater than 60 ^(,m in length and greater than 10 /am in
width are called flow domains. Flow domains are formed by
the deformation, or shearing of anisotropic domains by the
evolution of volatiles right before the solidification of
mesophase to produce coke. The polarized-light micrographs
in Fig. 9 show flow domains and mosaics textures of cokes

TABLE 9Coking proceses, feedstocks, and commercial uses of petroleum coke.


Feedstock
Product
Commercial Uses of Coke
Vacuum Distillation Residue
Sponge coke
Carbon anodes for aluminum industry pr
Vacuum Distillation Residue
Fuel for cement kilns, industrial heat and
Fuel coke
steam raising, fuel for utility industry
Vacuum Distillation Residue
Shot coke
No significant commercial use, some niche
applications, e.g., Ti02 production,
packing material
Clarified Slurry Oil from FCCU
Needle coke
Graphite electrodes for electric-arc furnaces
for iron and steel industry
Vacuum Distillation Residue
Industrial heat and steam raising
Fluid coke
Vacuum Distillation Residue
Industrial heat and steam raising
Fluid coke, or fuel gas

CHAPTER 29: PROPERTIES

OF FUELS, PETROLEUM PITCH, PETROLEUM COKE, AND CARBON MATERIALS

CCB

CCB

771

CCB

ETR
FIG. 8Stages of mesophase formation during carbonization of a decant oil (CCB)
and ethylene tar residue (ETR) sample, nucleation, growth, and coalescence of
mesophase spheres to form anisotropic coke texture.

TABLE 10Classification and description of the optical texture of


green cokes as observed by polarized-light microscopy using a
retardation plate [57].
Classification

Isotropic
Anisotropic
Fine mosaics
Medium mosaics
Coarse mosaics
Small domains
Domains
Flow domains

Description

Uniform, light purple color


Dark purple, yellow, and blue areas of
varying shape and size
Isochromatic areas (lA), 0.5-1.5 fim in
diameter
lA, 1.5-5.0 fjLTn in diameter
lA, 5.0-10.0 ^tm in diameter
lA, 10-60 fim in diameter
lA, >60 ixin in diameter
lA, >60 (u.m in length, >10 fitn in width
FLOW DOMAINS

produced by carbonization of a decant oil and a vacuum distillation residue in a laboratory batch reactor.
Figure 7 shows the optical textures of the samples of needle,
sponge, and shot coke particles, in addition to their external
morphologies, as described before. Commonly, the optical
texture of delayed cokes is heterogeneous, comprising a mixture of structures with different levels of anisotropy from mosaics to flow domains. A preponderance of a given texture, or
a mixture of textures, characterizes the principal optical texture of delayed cokes. The optical texture of needle cokes, for
example, consists mostly of straight flow domains. Sponge
cokes, on the other hand, display a predominance of acicular,
or twisted flow domains and large domains, while shot coke
texture consists mostly of mosaics and some small domains.
In other words, on the two extremes of optical texture scale,
needle cokes result from a high degree of mesophase development, whereas shot cokes display an inhibited mesophase
development. Distinct differences in the optical texture of delayed cokes explain many differences in physical and chemical properties of needle, sponge, and shot cokes, as further discussed in the Classification of Petroleum Cokes section.
Fluid cokes have very different microtextures from those of
the delayed cokes because of the substantial differences in
the operation and conditions of the two coking processes, as

MOSAICS
FIG. 9Flow domains and mosaics textures
as viewed by polarized-light microscopy.

described in Petroleum Coke Production Processes. Characteristically, fluid cokes have layered structures resembling
onions, because coke deposition tcikes place in layers on the
seed coke particles. Figure 10 shows the optical texture of a
fluid coke sample. In contrast to liquid-phase carbonization
in delayed coking, vapor phase cracking and polymerization

772

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

FIG. 10Optical texture of fluid coke (Petrographic Atlas, Prepared by Ralph Gray and Jack
Crelling, http://mccoy.lib.slu.edu/cgi-bin/projects/crelling/pageBuilder.pl?find=P36).
reactions on coke surfaces is primarily responsible for coke
formation in fluid coking. The opticcil texture of fluid cokes
is, therefore, very different from those of the delayed cokes.
Parallel orientation of concentric layers of coke creates more
isotropic structures in contrast to large anisotropic domains
present in sponge and needle cokes.
Coker Feedstocks
Commonly used coker feedstocks are vacuum distillation
residua (VDR), FCC U decant oils (DO), and thermal tars (TT).
Table 11 summarizes coker feedstock properties, presented
either as average values, or ranges of variation for typical
properties. The important differences between VDR and DO
include typically lower API gravity and higher aromaticity of
DO. VDR contains a large fraction of sulfur and metals (particularly Ni and V) found in crude oil because of their close association with asphaltene structures. VDR can contain u p to
40% wt asphaltenes (defined here as toluene solubles and pentane insolubles), whereas the maximum asphaltene content of
DO is usually not greater than 10% wt [54]. Further, the aromatic molecules in the asphaltenes of VDR, consisting of polycyclic aromatic ring systems connected with alkyl bridges, are
much larger than those in DO. Heteroatoms (S, N, and metals) tend to concentrate in these large molecules of VDR asphaltenes. The aromatic compounds in DO consist of much
simpler structures, containing mainly two- to six-ring fused
polycyclic aromatic hydrocarbons (PAH) [54,58]
Table 11 shows that despite their high API gravity (or low
specific gravity), VDR has a m u c h higher Conradson Carbon
value than DO, mainly because of the high asphaltene contents of VDR. In general, Conradson Carbon value is directly
proportional to coke yield from the delayed coking, or fluid
coking processes [50]. Generally higher sulfur contents of
VDR compared to those of DO should also be noted. Thermal
tars are similar in overall properties to DO; although TT tends
to be more aromatic than DO, and contain much less naphthenes. These differences in feedstock properties combined
with differences in coking conditions control the structure
and important properties of petroleum cokes, such as the optical texture, heteroatom contents, strength, and reactivity.
Chemical composition of coker feedstocks strongly affects
the mesophase development through the carbonization chem-

istry and the rate of coke formation [59]. In general, feedstocks with high aromaticity produce a high degree of
mesophase development, as explained by the planarity and
lower thermal reactivitity of aromatic c o m p o u n d s . Coker
feedstocks, particularly VDR, with a high asphaltene content
produce inferior cokes with a low degree of anisotropy, and
high heteroatom a n d metals contents. It has been shown,
however, that the molecular nature of the asphaltene fractions
is as important as, if not more important than, the asphaltene
contents of the feedstocks for controlling the mesophase development [60]. Hydrogen aromaticity, rather than carbon
aromaticity of the asphaltene fractions, appears to be an important structural parameter that relates to the carbonization
behavior of the coker feedstocks, such as carbonization reactivity, and hydrogen shuttling ability of the molecular constituents during carbonization. High hydrogen aromaticity,
which indicates small aromatic ring systems and low degree
of alkyl substitution on the aromatic rings, gives rise to a high
degree of mesophase development through controlling the
rate of molecular growth and fluidity (or viscosity) during carbonization. Heavily alkyl substituted, large aromatic ring systems, as found in the asphaltene fractions of VDR, lead to
rapid growth of n o n p l a n a r intermediates, and a rapid increase in the viscosity of the carbonization medium, thus impairing the mesophase development. In extreme cases, these
conditions lead to severe inhibition of mesophase development and to the formation of shot coke in delayed coking [53].
A good understanding of the chemistry of mesophase formation from complex petroleum feedstocks still remains a
current challenge, especially in terms of predicting the quality of needle cokes produced by delayed coking. Differences
in molecular constitution of DO, in terms of the distribution
of two- to four-ring aromatic compounds, have been shown
to affect the mesophase development in laboratory reactors.
An abundance of pyrene and alkylpyrenes in the DO, for example, leads to a high degree mesophase development. In
contrast, high concentrations of biphenyl, fluorene, and alkylated phenanthrenes produce inferior optical textures in the
resulting cokes [58]. Figure 11 shows a two-dimensional
high-pressure liquid chromatography trace of a decant oil
sample obtained with a photodiode array detector from normal phase separation using n-hexane and methylene chloride
as solvents. The HPLC chromatogram (x-axis:time, y-axis:ulraviolet light wavelength, and z-axis: intensity of ultraviolet
light absorption) with some indicates the complexity of the
molecular structure of the decant oils with a few peaks labeled (pyrene, methylpyrenes, and methylbenzopyrenes) for
demonstration purposes. However, individual compounds in

TABLE 11Typical coker feedstock properties [4,50].


Feedstock Property

Vacuum
Distillation
Residue

Decant Oil

Thermal Tar

API Gravity
Sulfur, wt%
Conradson Carbon, wt%
Molecular Weight
C/H Ratio, Atomic
Aromatics, % wt
Paraffins, % wt
Naphthenes, %wt

7-15
0.5-3.0
10-20
850
0.65
35
10
55

1-8
0.5-0.8
5-10
300
0.8
62
0
38

-1-4
0.5
8-9
380
0.9
68
7
25

CHAPTER 29: PROPERTIES

OF FUELS, PETROLEUM PITCH, PETROLEUM

the decant oils can be identified, based on their UV spectra,


if a good chromatographic separation can be achieved.
Classification of Petroleum Cokes
Coke is defined as "a soHd high in content of the element carbon and structurally in the non-graphitic state" [61]. It is a
carbonaceous product from carbonization of organic material, which has passed, at least in part, through a liquid or liquid crystalline state. Petroleum coke is generally defined as a
carbonization product of high-boiling fractions obtained in
petroleum processing. The overall classification of green
petroleum cokes (sponge, fuel, shot, needle, and fluid coke)
as shown in Table 9, is based on the morphology, microstructure, elemental composition, and selected physical
and chemical properties of the cokes. As discussed in the previous sections, these important characteristics of the cokes,
which determine their commercial applications, depend on a
combination of factors including feedstock properties, the
coking process, and coking conditions. Definitions of some
technical terms relevant to petroleum coke classification are
reproduced below from lUPAC's "Recommended Terminology for the Description of Carbon as a Solid" [61].
Calcined Coke is a petroleum coke obtained by heat treatment of green coke to about 1600 K. It will normally have
a hydrogen content of less than 0.1 wt%.
Filler (also called grist) is a petroleum-coke fraction of a
green carbon mix or formulation.
Graphitic Carbon represents all varieties of substances consisting of the element carbon in the allotropic form of
graphite.
Graphitizable Carbon is a nongraphitic carbon, which upon
graphitization heat treatment, converts into graphitic
carbon.

COKE, AND CARBON MATERIALS

Graphitization Heat Treatment is a process of heat treatm e n t of nongraphitic carbon, industrially performed at
t e m p e r a t u r e s in the range between 2500-3300 K, to
achieve transformation into graphitic carbon.
Green Coke (raw coke) is the primary solid carbonization
product from high boiling hydrocarbon fractions obtained
at temperatures below 900 K. It contains a fraction of matter that can be released as volatiles during subsequent heat
treatment to approximately 1600 K. This mass fraction, the
so-called volatile matter constitutes 4 and 15wt% of green
cokes.
Needle Coke is a special t5rpe of coke with extremely high
graphitizability resulting from a strong preferred parallel
orientation of its layered structure and a particular physical shape of the grains.
Premium Coke is a n extremely well graphitizing carbon
with a high degree of optical anisotropy and is characterized by the combination of the following properties: high
real density, low reversible thermal expansion, and low ash
content combined, in most cases, with low sulfur content.
Puffing is an irreversible expansion of some carbon artifacts during graphitization heat treatment between 1650 K
and 2700 K.
Petroleum Coke Properties
Green cokes with relatively low sulfur, metal, emd ash contents are calcined-heat treated to 1600 K-to remove volatile
matter. Polarized-light m i c r o g r a p h s in Fig. 12 show the
shrinkage cracks and pores developed upon calcination of a
needle coke and a sponge coke. Calcined coke has a mass
fraction of hydrogen less than 0.1%. Calcined cokes are used
as fillers for carbon anodes, graphite electrodes, or specialty
carbons. Table 12 lists the specifications of calcinable green

0.030

0.025

0.020

'immnm^KMSm

^375.00

0.00

5.00

10.00

15.00
20.00
Hinutes

773

25.00

30.00

35.00

FIG. 11A two-dimensional HPLC chromatogram for a decant oli sample.

774

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK
sis, p r o v i d e s u s e f u l g u i d e l i n e s f o r s a m p l e p r e p a r a t i o n f o r a
v a r i e t y of l a b o r a t o r y a n a l y s e s .
Volatile

Matter

V o l a t i l e m a t t e r c o n t e n t of g r e e n c o k e s is d e t e r m i n e d b y m e a s u r i n g t h e loss i n w e i g h t r e s u l t i n g f r o m h e a t i n g u n d e r r i g i d l y
controlled c o n d i t i o n s (ASTM D 4 4 2 1 , Volatile M a t t e r in
P e t r o l e u m Coke a n d ASTM D 6374, Volatile Matter in Green
P e t r o l e u m Coke, Q u a r t z Crucible P r o c e d u r e ) . T h e volatile
m a t t e r c o n t e n t is p a r t i c u l a r l y i m p o r t a n t for t h e i g n i t i o n c h a r a c t e r i s t i c s of t h e fuel c o k e s ; t h e h i g h e r t h e v o l a t i l e m a t t e r

Calcined needle coke

TABLE 13Calcined coke properties [52].


Properties

Calcined sponge coke

FIG. 12Polarized-light micrographs of


calcined needle coke and sponge coke
samples, indicating anisotropic texture,
and porosity developed by devolatilization.
TABLE 12Typical green and calcined coke specifications [50-52].
Green Coke
Ash
Calcium
Fixed carbon
Hydrogen
Iron
Manganese
Magnesium
Moisture
Nickel
Nitrogen
Real Density
Silicon
Sulfur
Titanium
Vanadium
Volatile Matter

0.1-1.0%
25-500 p p m
87-97%
3.0^.5%
50-2000 p p m
2-100 p p m
10-250
0.5-2.0%
10-100 p p m
0.1-0.5%
1.6-1.8 g/cc
50-300 p p m
0.2-2.5%
2-60 p p m
5-500 p p m
5-15%

Calcined Coke
0.2-1.5%
25-500 p p m
97-99%
<0.1%
50-2000 p p m
2-100 p p m
10-250 p p m
Negligible
10-100 p p m
<0.1%
2.08-2.13 g/cc
50-300 p p m
0.2-2.5%
2-60 p p m
5-500 p p m
<0.5%

cokes a n d calcined cokes used in c a r b o n a n o d e a n d graphite


m a n u f a c t u r e . N o t all g r e e n c o k e s p r o d u c e d b y d e l a y e d coki n g of v a c u u m d i s t i l l a t i o n r e s i d u a a r e s u i t a b l e f o r c a l c i n a t i o n . O n l y o n e - t h i r d of a p p r o x i m a t e l y 2 5 m i l l i o n t o n s of
g r e e n c o k e p r o d u c e d i n t h e U . S . a r e Ccdcined for f u r t h e r u s e
[ 5 2 ] . S o m e i m p o r t a n t p r o p e r t i e s of t h e g r e e n c o k e s t h a t d e t e r m i n e t h e i r s u i t a b i l i t y for c a l c i n e d c o k e p r o d u c t i o n a r e d e fined a n d discussed below w i t h reference to t h e industrial
s i g n i f i c a n c e of t h e k e y p r o p e r t i e s . T a b l e 13 lists a d d i t i o n a l
p r o p e r t i e s of c a l c i n e d c o k e s t h a t a r e r o u t i n e l y m e a s u r e d , a n d
T a b l e 14 l i s t s s o m e s t a n d a r d m e t h o d s u s e d f o r m e a s u r i n g
t h e s e p r o p e r t i e s . A S T M D 3 4 6 , S t a n d a r d P r a c t i c e for Collect i o n a n d P r e p c i r a t i o n of C o k e S a m p l e s for L a b o r a t o r y Analy-

Water Content
Oil Content
Granulometry
>8 mm
8-4
4-2
2-1
1-0.5
0.5-0.25
<0.25
Vibrated Bulk Density
8-4 m m
4-2
2-1
1-0.5
0.5-0.25
Grain Stability
8 ^ mm
Reactivity in CO2 at lOOOX
Ignition Temperature
Reactivity in Air at 600C
Elements
S
V
Ni
Si
Fe
Al
Na
Ca
K
Mg
CI
Crystallite Size, Lc
Density in Xylene
Specific Electrical Resistance
Total Porosity

Typical Value
0-0.2%
0.1-0.3%
10-20%
15-25%
15-25%
10-20%
5-15%
5-15%
0
0.64-0.70 kg/dm^
0.73-0.79

0.80-0.86
0.86-0.92
0.88-0.93
75-85%
5-10%
615-630C
0.1-0.20%/min
1-3%
80-300 p p m
80-160
50-250
50-250
50-250
30-120
20-100
5-15
10-30
0.1-0.2%
26-30 A
2.05-2.09 kg/dm^
480-520 Micro O h m m
15-20%

TABLE 14Standard test methods for determining calcined


coke properties.
Measurement
Granulometry
Bulk Density
Grain Stability
Oil Content (Dedusting Agent)
Xylene Density
Ash Content
Specific Electrical Resistance
Reactivity in CO2
Reactivity in Air
Chemical Elements

Method
ISO 2325
DIN 51 916
ASTM 5003-89
ISO 8723
ASTM 5004-89, ISO 8004
ASTM D 4422-89, DIN 51 903
DIN 51 911
Thermal Gravimetric Analysis
(TGA)
TGA
Elemental Analysis, X-Ray
Methods, Atomic Absorption
Spectroscopy

CHAPTER 29: PROPERTIES

OF FUELS, PETROLEUM PITCH, PETROLEUM

content, the easier the ignition. Emission of PAH from combustion of fuel grade cokes is an important environmental
concern that requires strict monitoring and control of emissions from the combustors. Fluid cokes have lower volatile
matter contents than the cokes produced by delayed coking,
because of higher coking temperatures used in Fluid Coking.
Among the cokes produced by delayed coking, needle cokes
have lower volatile matter contents (5-8%) than sponge and
shot cokes (10-15%). Green cokes with high volatile matter
content are not suitable for calcination. High volatile matter
content result from i m p r o p e r coking conditions, such as
short residence time and low coking temperatures, or feedstock properties. Calcination reduces the volatile matter content of the green cokes to less than 0.5% in the calcined cokes
used for carbon anode, or graphite electrode manufacture.
Ash
Ash content of petroleum coke can be determined by reducing the sample to an ash by heating in a muffle furnace according to the standard method ASTM D4422, Standard Test
Method for Ash in Analysis of Petroleum Coke. For fuel
cokes, high ash contents create operational a n d disposal
problems. Green cokes with high ash contents are not suitable for calcination mainly because of the detrimental effects
of inorganic impurities on calcined coke properties, e.g., reactivity, as explained below. Ash contents of less than 0.5
wt% are required for sponge cokes used for carbon anode
manufacture [52].
Sulfur
Sulfur content of petroleum cokes can be measured using
several ASTM standard methods including D 1552, Sulfur in
Petroleum Products (High-Temperature Method), D 3177,
Total Sulfur in the Analysis Sample of Coal and Coke, and D
4239, Sulfur in the Analysis Sample of Coal and Coke Using
High-Temperature Tube Furnace Combustion Methods. Sulfur content of petroleum cokes is important for both fuel
cokes, a n d green cokes calcined for c a r b o n anode and
graphite electrode applications. For fuel coke and sponge
coke applications, concerns related to SO2 emission and
equipment corrosion are the main considerations for limiting the sulfur content. Sulfur content in fuel grade petroleum
cokes and sponge cokes vary in the range 3-6 wt%, and < 3
wt%, respectively. Needle coke has a more strict specification
on the sulfur content (<0.5wt%), because sulfur causes puffing during the graphitization heat t r e a t m e n t resulting in
lower density and lower strength of graphite electrodes.
Nickel,

Vanadium,

and Other

Metals

Nickel, vanadium, a n d other trace metals contents of


petroleum cokes can be measured using different ASTM standard methods, including D 5056, Trace Metals in Petroleum
Coke by Atomic Absorption; D 5600, Trace Metals in
Petroleum Coke by Inductively Coupled Plasma Atomic
Emission Spectrometry (ICP-AES); and D 6376, Determination of Trace Metals in Petroleum Coke by Wavelength Dispersive X-Ray Fluorescence Spectroscopy. For fuel grade
cokes, nickel and vanadium contents are specified as 300-600
ppm. For sponge cokes, in addition to limits on nickel and
vanadium contents (<500 ppm), iron content needs to be less
t h a n < 2 5 0 p p m . Principal concerns with trace metals in

COKE, AND CARBON MATERIALS

775

sponge cokes used for anodes are related to the contamination of aluminum, or other produced metals with the heavy
metal impurities. Heavy metal contamination requires further treatment for purification, or limits the use of the produced metal in certain applications.
High alkali metal contents, e.g., Ca and Na, are also not
desired in sponge cokes, since these metals act as strong oxidation catalysts a n d increase anode c o n s u m p t i o n during
electrolysis.
Density
Several ASTM standard methods can be used to measure the
apparent and real densities of petroleum cokes, including D
167, Apparent and True Specific Gravity and Porosity of
Lump Coke; D 2638, Standard Test Method for Real Density
of Calcined Petroleum Coke by Helium Pycnometer; D 5004,
Real Density of Calcined Petroleum Coke by Xylene Displacement; and D 4292, Determination of Vibrated Bulk Density of
Calcined Petroleum Coke. Both apparent and real densities of
petroleum cokes depend on their thermal history and operating variables in the production processes. For many applications of petroleum cokes, apparent, or real density of the cokes
are closely monitored, since many industrial properties of
cokes, such as strength, thermal and electrical conductivity,
and reactivity of cokes can be related to coke density. Porosity of the petroleum cokes can be calculated from the apparent and true density measurements by the following formula:
Porosity = 100 - 100(apparent density/true density)
For true density measurements, helium pycnometry is commonly used to obtain meiximum penetration of the pores by
helium gas. For petroleum cokes, helium density is usually
5% below the theoretical density. This difference is attributed
to "closed porosity" in cokes that is not accessible to helium.
Porosity of cokes is particularly important for applications
where petroleum coke is used as filler in mixed formulations
with a binder (e.g., carbon anode, and graphite electrode
manufacture), usually coal tar pitch. Desired pitch/coke
ratios and the resulting properties of the baked, and graphitized carbons, therefore, depend strongly on the porosity, or
apparent density of the cokes. Strong correlations were reported between the bulk density of the filler cokes and the
electrical resistivity, strength, and coefficient of thermal expansion of the resulting graphite electrodes [62].
The real density of petroleum cokes increases with the increasing heat treatment temperature, and depending on the
graphitizability of the cokes, approaches the real density of
graphite u p o n graphitization heat treatment. Apparent density, on the other hand, can go through a m i n i m u m with the
increasing heat treatment temperature during calcination of
green cokes, because of porosity formation by devolatilization. F u r t h e r increase in h e a t t r e a t m e n t t e m p e r a t u r e increases the apparent density because of collapsing porosity
upon increasing the microstructural order.
Optical Texture

and Crystalline

Structure

Polarized-light microscopy can be used for characterization


of cokes and assessing their graphitizability. The appearance
of a polished coke sample viewed under a polarized-light microscope is described as the optical texture, which refers to
the anisotropy/isotropy of the solid phase. The isochromatic
regions seen u n d e r a polarized-light microscope represent

776

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

sections of the coke with a particular structural orientation.


Generally, the examination of green coke texture proves to be
useful to predict the calcined or graphitized coke quality. Optical texture varies greatly depending on the microstructure
of a given coke and can be broadly defined as isotropic or
anisotropic. When viewed under a polarized-light microscope, a material is considered to be isotropic if the light reflecting from the surface does not change with the direction
of observation. Non-graphitizable, or poorly graphitizing
cokes appear to be isotropic because their range of order is
smaller than the resolution of the light microscope (<0.5
fjLin). Anisotropic cokes, on the other hand, have a much
longer range order, 0.5-500 /xm, resulting from a high degree
of mesophase development. These cokes show considerable
change in reflected light intensity with direction of observation. In general, the larger the size of anisotropic, or isochromatic regions, the higher is the graphitizability of the coke.
This is particularly important for needle cokes used for manufacturing graphite electrodes.
Nomenclatures have been developed for a more precise description of different optical textures in solid carbons [63,64].
According to the proposed nomenclatures, an optical texture
index can be determined by assigning different weight
factors to different anisotropic units. Table 15 lists assigned
texture weight factors, or optical texture index (OTI) values,
proposed by Oya et al. [57] for different anisotropic structures. The larger the size of the anisotropic unit, the higher
the optical texture index. As seen in Table 15, mosaics are assigned relatively small OTI ranging from 1 to 7, depending on
the size of the mosaics, while domains and flow domains are
assigned a large OTI, 30. The optical texture of solid carbons
is usually very heterogeneous, consisting of a variety of different anisotropic structures, such as flow domains, domains, and mosaics. Consequently, a point counting method
is widely used for characterizing the texture of solid carbons
[57,65,66]. The fraction of points counted for each component is multiplied by the corresponding optical texture index
(OTI) value to calculate a factor for each component. The
OTI of a sample is, then, calculated by summing the factors
for all the texture categories.
Using the optical texture classification scheme given by Oya
et al. [57], shown in Table 15, in conjunction with a point
counting procedure one can differentiate between anisotropic
textures of solid carbons over a broad range of texture quality. This general texture classification, however, fails to distinguish between similcir textures of coke samples that fall
into a more specific category, e.g., sponge cokes, or needle
cokes. Needle cokes, for example, consist predominantly of
domains and flow domains. Small differences in texture qual-

ity, i.e., the degree of anisotropy, cause substantial differences


in thermal expansion behavior (or in coefficient of thermal expansion (CTE)) of needle coke samples. For example, different proportions of flow domains and domains in a needle coke
sample, that are assigned the same OTI value, 30, would give
very different CTE in a given direction. Low CTE of needle
cokes along their long axis is attributed to the dominant flow
domain anisotropy parallel to the long axis. On the other
hand, large isometric domains in needle cokes would give rise
to relatively high CTE. The same optical texture index value
assigned for both domains and flow domains would, therefore, not capture this critical difference in thermal expansion
anisotropy of needle coke particles. Different optical texture
index assignments were proposed by Eser [58], as shown in
Table 15, to account for the differences in thermal expansion
anisotropy of different texture units. Based on point counting
data, the optical texture index for a coke sample can be calculated using the following formula:
OTI = 100*(FD) + 50*(D) + 5*(SD) +1*(M)
where the letters represent the fractions of the flow domains
(FD), domains (D), small domains (SD), and mosaics (M), in
the order of decreasing degree of anisotropy. The higher the
OTI, the higher the degree of anisotropy (or graphitizability),
and the lower the CTE edong the long aixis of the coke particles.
Calcined needle cokes tend to have larger anisotropic units
than green cokes. Calcination usually increases the size of optical domains, but it does not change their shape. Upon calcination, flow domain structures keep their shape to form
needle-like grains along with large isometric domains. For
calcined needle cokes used as filler for graphite electrode
manufacture, the size of optical domains becomes less important compared to their shape and orientation. This is often demonstrated when coke is over calcined and display
larger anisotropic domains, but poor thermal expansion behavior [67]. Figure 12 illustrates optical textures of calcined
sponge and needle coke samples. Using scanning electron microscopy (SEM), Pysz et al. [68] proposed a different nomenclature for classification of calcined needle cokes, shown in
Table 16, to include larger texture domains. Analogous to
green coke texture characterization, using similar OTI designations for the texture components of increasing anisotropy
as shown in the last column of Table 16, Qiao [69] showed
good correlations between OTI of calcined needle coke particles and their CTE measured on the same particles.
There is no standard method for texture characterization
of petroleum cokes. ASTM D 5061, Microscopical Determination of Volume Percent of Textural Components in Metallurgical Coke describes procedures to identify the tex-

TABLE 15Optical texture index (OTI) assignments to distinguish between different


anisotropic texture components [57,58].
Classification

Description

OTI [57]

OTI [58]

Isotropic
Anisotropic
Fine mosaics
Medium mosaics
Coarse mosaics
Small domains
Domains
Flow domains

No optical activity
Isochromatic areas (lA)
lA, 0.5-1.5;u,ni in diameter
lA, 1.5-5.O^m in diameter
lA, 5.0-lO.Ojixm in diameter
lA, 10-60/!Am in diameter
lA, > 6 0 ^ m in diameter
lA, >60/Ltm in length, >10/xm in width

1
3
7
20
30
30

1
1
1
5
50
100

CHAPTER 29: PROPERTIES

OF FUELS, PETROLEUM PITCH, PETROLEUM

TABLE 16Nomenclature for and description of microtexture in


calcined needle cokes by scanning electron microscopy [68].
Classification

Description

I
A
S
F

Isometrics
Acicular
Stringy
Fibrous

Size
<100 ij.m
100-300 ixm
300-1000 fj.m
> 1000 length,
> 6 0 /iim width

OTI [58]
1
5
50
100

t u r a l c o m p o n e n t s of coke according to their degree of


anisotropism, c a r b o n form d o m a i n sizes, b o u n d a r y size,
color of individual isochromatic domains, their morphology,
relative reflectance, and other optical properties. Representative crushed particulate coke samples are prepared using
ASTM D 3997, Preparing Coke Samples for Microscopical
Analysis by Reflected Light. Gray and Devanney [70] provided a detailed description of microscopic classification and
industrial applications of coke carbon forms.
Texture characterization by optical microscopy and SEM
provides information on the degree of mesophase development that leads to the anisotropic microtexture formation in
petroleum cokes. This information is particularly useful for
studying and controlling mesophase development in delayed
coking [54,58,66] and predicting the important industrial
properties of calcined cokes such as strength, reactivity, and
thermal expansion. The microtextural properties of cokes are
related to the prearrangement of carbon atoms into three-dimensional crystalline structures, which determine the
graphitizability of cokes. X-ray diffraction is used to determ i n e the degree of crystalline alignment in cokes. For
calcined cokes, a p p a r e n t crystallite size (Lc), a n average
stacking height of graphene layers (see Fig. 13), is a good indication of pregraphitic order, and, therefore, their graphitizability upon graphitization heat treatment. The apparent
crystallite size of calcined cokes can be determined according
to ASTM D 5187, Determination of Crystallite Size (Lc) of
Calcined Petroleum Coke by X-Ray Diffraction.
Thermal

Expansion

The coefficient of linear thermal expansion (CTE) is a critically important property for many applications of graphitic
carbons, particularly graphite electrodes used in electric-arc
furnaces. CTE is defined as the increase in length per unit
length per degree rise in t e m p e r a t u r e [71]. A low CTE is
essential for high thermal shock resistance, one of the most
important properties of graphite electrodes, defined as the
ability to resist weakening, or fracture when subjected to sudden heating, or cooling [72,73]. Compared to other materials,
graphite stands out in resistance to thermal stress and high
t e m p e r a t u r e s above 1300 K. As the m a i n c o m p o n e n t s in
graphite electrodes, the needle coke fillers exert the most important influence on thermal expeuision behavior of graphite
electrodes. Strongly anisotropic crystals, such as graphite,
have layered crystalline structure, in which the bonding is
highly directional. Graphite has a m u c h lower thermal
expansion in the layer planes (a-direction) that contain covalently bonded carbon atoms, than in the direction perpendicular to the layer planes (c-direction) that are held together by
van der Waals forces [74], as shown in Fig. 13.
The major factors that influence CTE of cokes and graphites
are texture and the orientation of crystallites. Pores and cracks

COKE, AND CARBON MATERIALS

777

in the structure of cokes and graphites can also play a role in


accommodating thermal expansion, especially in the c-direction [75-77]. Many researchers have investigated how temperature affects thermal expansion of cokes and graphites [78-80].
It is known that, for anisotropic cokes, as the heat treatment
temperature increases, CTE decreases because of increased
structural ordering. After heat treatment at 600C, cokes still
have high CTE values in both a- and c-directions. There is a significant decrease in CTE upon heat treatment between 600 and
1300C. Although there is not much decrease in CTE upon heat
treatment at temperatures above 1300C, it has been suggested
that the CTE values in the c-direction decreases with the increasing stack height of crystallites (Lc) [81].
Thermal expansion measurements can be made using a
dilatometer to measure linear expansion as a function of temperature in a given direction. A linear variable differential
transformer (LVDT) mechanism is used to measure a dimensional expansion. Thermal expansion plots (expansion vs
temperature) are seldom linear. Therefore, the mean CTE,
defined as the slope of the line joining the two defined points,
depends on the temperature range used for calculating its
value, as follows [82]:
Mean CTE = (4L/L)/ (4T)
where zlL = observed changed in sample length over the temperature range AT, in
AT = temperature range of measurement, C
L = sample length at room temperature, in
The CTE values are reported using the unit 10~* in/in C. The
CTE measurements are made on calcined, or graphitized test
bars prepared by extrusion of calcined coke particles with a
standcird binder pitch. Highly graphitizable calcined needle
cokes would give mean CTEs lower than I x 10"* in/in C.
Typical temperature ranges used for measuring the m e a n
CTEs of calcined cokes are 100-600C, or 300-700C [83,84].
The CTE values measured at low temperatures are more sensitive to structural differences in cokes t h a n those measured
at high temperatures [85].

a-direction

Stacking height:

c-direction
FIG. 13A diagram of section of microcrystals of pregrahipitic order indicating covalent bonding in basal planes
(a-direction) and planes held together by van der Walls forces
(c-direction) responsible for anisotropic structure and
anisotropic properties.

778

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

Reactivity
Reactivity of cokes in oxidizing atmospheres constitutes another important industrial property of cokes. For fuel cokes,
high reactivity is desired for ease of ignition and combustion.
Relatively high volatile m a t t e r contents are, therefore,
desirable for fuel cokes. For calcined cokes used in material
applications, either intermediate or low reactivity is desired
depending on whether carbon needs to be consumed, or not
in the particular application.
Carbon anodes used for electrochemical reduction of AI2O3
are, for example, consumed in the reaction to liberate alum i n u m metal. Four major carbon-consuming reactions are
identified during electrolysis for aluminum production [25]:
1) 2Al203(diss) +2C(anode) > 4Al + SCOa - desired reduction
reaction
2) Al203(diss) +2C(anode) ^ 2Al + 3CO - generation of primary
CO, low C efficiency
3) CO2 + 2C(anode) > 2CO - uudesired consumption of carbon
4) O2 + C(anode) ^ 2C02 ; O2 + 2C(anode) ^ 2 C 0 - uudesircd
consumption of carbon by a i r b u m
Obviously, the first reaction is the desired reaction,
whereas third and fourth reactions lead to undesired consumption of anode carbon by Boudouard and a i r b u m reactions, respectively [25]. The second reaction also produces Al
but only with half of the yield obtained from the first reaction. An intermediate reactivity of carbon anodes (sponge
coke and pitch coke) is, therefore, desirable to promote the
desired reduction reaction and to inhibit the undesired anode
consumption.
In contrast to the electrochemical production of aluminum
by the consumption of carbon anodes, the consumption of
graphite electrodes in electrical-eirc production of steel takes
place only due to the uncontrolled b u m - u p of the electrodes
in air [88]. Consequently, extremely low reactivities of
graphite electrodes (made u p of needle coke filler and coal tar
pitch binder derived carbons subjected to graphitization heat
treatment) are desired to minimize electrode consumption
by a i r b u m .
The reactivity of cokes in oxidizing atmospheres depends
primarily on the degree of microcrystalline order (i.e., optical
texture), accessible surface eirea (related to the porosity), and
catalysis by inorganic impurities, such as Ni, V, Fe, K, Na,
and Ca. Oxidation, or gasification of cokes is a surface reaction that occurs at active sites at elevated temperatures. Carbon atoms at the edges of graphene layers (or basal planes)
or at defects on graphene layers such as vacancies and dislocations, are m u c h more reactive than the carbon atoms in
basal planes. The high reactivities of edge atoms result from
the dangling bonds, or unpaired sp^ electrons, at these sites
that readily chemisorb oxygen. Highly anisotropic cokes,
such as needle cokes, with relatively large microcrystallites
found in well-developed flow domains or domain textures
have low concentrations of these active edge sites, and, therefore, exhibit low reactivities. Sponge cokes, in comparison,
have a lower degree of anisotropy, and higher porosity, and,
therefore, have higher reactivities than needle cokes. High
porosity, or high accessible surface area, increases the ease of
diffusion of oxidant molecules to the active sites. Inorganic
impurities, on the other hand, promote the dissociation of
molecular oxygen to produce more active oxygen species that
readily react with carbon atoms even in the basal planes,

producing pits by removal of carbon atoms as CO, or CO2


[86]. Increasing the heat treatment temperatures decreases
the concentration of structural defects [87] and at sufficiently
high temperatures (e.g., during graphitization heat treatment
u p to t e m p e r a t u r e s 3300K), helps remove inorganic
impurities by evaporation. The graphite electrodes have low
reactivities because of low defect, or active concentration,
low porosity, and low concentrations of inorganic impurities
[88,89].
Thermal gravimetric analysis (TGA) can be used to measure the reactivity of coke samples in different oxidizing atmospheres (e.g., air, O2, or CO2). In these experiments, the
weight of a sample placed in a microbalance is monitored
and recorded continuously as a function of increasing temperature, or as a function of time at a given temperature.
ASTM D 5341 Measuring Coke Reactivity Index (CRI) and
Coke Strength after Reaction (CSR), can be adapted to measure the reactivity of petroleum cokes.

Conclusions
Petroleum cokes have many industrial applications, ranging
from generating heat (fuel coke) to manufacturing carbon
products such as carbon anodes and graphite electrodes. Produced from various petroleum heavy residua or fractions
from petroleum refining operations, petroleum cokes are
classified into different types on the basis of feedstocks (e.g.,
vacuum distillation residua or FCC decant oil), coke production processes (e.g., delayed coking or fluid coking), or their
appearance (e.g., sponge coke, shot coke, or needle coke).
Feedstock composition, the coking process used, and coking
conditions determine the structure a n d properties of
petroleum cokes that are important in various applications.
Among the important properties of petroleum cokes are
volatile matter content, density, sulfur and metal contents,
optical texture, coefficient of thermal expansion, and reactivity. Standard methods have been developed to quantitatively
determine many of these properties for selecting, or producing the most desirable cokes for a given application. A fundamental understanding of the relationships between feedstock
constitution and the structure and composition of petroleum
cokes, and those between coke properties and coke structure
is critically important for controlling the coking processes
and subsequent thermal treatment operations to manufacture carbon materials with the desired properties.

CARBON MATERIALS FROM RESIDUAL


FUEL OIL, PETROLEUM PITCH, AND
PETROLEUM COKE
As introduced previously in this chapter, residual fuel oil
(mainly FCC decant oils), petroleum pitch, and petroleum
coke are used as precursors for manufacturing a variety of
carbon materials with very different properties and applications. In this section, four different carbon materials will be
further discussed as examples to illustrate a glimpse of the
diversity in microstructure and properties of the carbon
materials. Four carbon materials are: carbon blacks, carbon
fibers, carbon anodes, and graphite electrodes that are produced from decant oil, petroleum pitch, sponge coke, and

CHAPTER 29: PROPERTIES

OF FUELS, PETROLEUM PITCH, PETROLEUM

needle coke, respectively. Manufacturing processes, properties, and applications of these four carbon materials will be
reviewed briefly with reference to their respective precursors
as discussed before in this chapter.
Carbon Blacks
Classification,
Manufacturing
and
Applications

Processes,

Carbon black is defined as "an industrially manufactured colloidal carbon material in the form of spheres and of their
fused aggregates with sizes below 1 /u-m" [61]. They are produced by gas phase thermal decomposition of hydrocarbons
using various feedstocks and processes [90-93]. Of the five
major processes, Lampblack Process, The Cheinnel Process,
Acetylene Process, Thermal Process, and Oil Furnace Process, the last one is the most widely used process to produce
most of the carbon blacks available today [90]. These processes yield products t h a t are identified by the process
names, such as lamp black, channel black, acetylene black,
themiEj black, and furnace black. Each carbon black has a
unique structure and a set of properties that are determined
by the different manufacturing processes. Except for the
Channel (or Impingement) and Acetylene processes that convert natural gas and acetylene to carbon blacks, respectively,
a r o m a t i c oils are used as principal feedstocks for carbon
black production. Most commonly used oils are residual fuel
oils, or FCC decant oils. Carbon black oils, a distillate fraction of coal tar produced in by-product coke ovens, are also
used as feedstocks in some processes. Thermal Black and
Furnace Black processes that use aromatic oils as feedstocks
are described below, along with the major applications of
carbon blacks manufactured by these processes.
Thermal blacks are produced by thermal decomposition of
oils in the absence of air using a cyclic process that consists
of heating and production cycles that rotate in a pair of furnaces (generators) in 2.5 min intervals [90]. The furnaces are
lined with open checker brickwork that is preheated before
the introduction of oil feed. Production of carbon black takes
place in a heated furnace followed by a steam purge to remove the products (carbon black and byproducts including
hydrogen gas). The products are sprayed with water for cooling and passed through a collection filter to separate the carbon black particles. Following the steam purge, air is passed
through the furnace to bum-off the carbon black remaining
in the furnace (supplemented by burning oil, if necessary) to
produce heat for the next production cycle. Pairs of furnaces
are used for continuous operation using S3rnchronous heating and production cycles in separate furnaces.
Thermal blacks consist of larger particles (250 to 500 n m
average particle diameter) with lower degree of aggregation
compared to other types of carbon black. They are used in applications that require very high volume fractions of fillers,
including the production of r u b b e r a n d cross-linked
polyethylene, as well as some specialty pol5rmers [90].
As opposed to intermittent production in the Thermal Black
process, carbon black is produced continuously from highly
aromatic oils in a combustion gas environment at high temperatures in a Furnace Process [90]. Production of furnace
black takes place in a fraction of a second when the feed is injected into a flame that is established in the reactor with oil or

COKE, AND CARBON MATERIALS

779

natural gas and excess air. Immediately after carbon black


production, the products are cooled with a water spray and
further cooled as they pass through a heat exchanger before
carbon black particles cire collected in a bag filter. Because of
high gas flow rates, the carbon black particles reach the bag
collector in less than a second after the feedstock oil is injected
into the reactor. The size distribution of furnace black particles is controlled by the rate of cooling with water spray. For
production of particles with a very small size (for high color
applications), large quantities of water are needed for cooling,
u p to 40:1 process water to carbon black ratio [90].
For use in rubber and plastic applications, a large fraction
of furnace product is pelletized (beaded) using water to provide easy handling and less dust formation. For applications
that require dry beads, such as in inks and coatings, powdered
ceirbon black particles are beaded in a rotating drum where
agglomerated carbon black act as nuclei to grow beads [90].
For carbon black production in the oil furnace process, the
feedstock oil must be completely vaporized and pyrolyzed. If
the conversion of oil to a carbonaceous solid takes place in a
liquid phase, large particles of "coke" are produced. Coke
particles, undesired contaminants in carbon black product,
are much larger in size and very different in microstructure
compared to ceirbon black particles. The formation of coke in
Oil Furnace Process probably results from the presence of
high-molecular-weight, aJkyl substituted PAH that contain
more than five rings in polycondensed aromatic systems [58].
These compounds would tend to polymerize and go through
liquid-phase carbonization to form coke. Figure 14 shows polarized-light-micrographs of some particles from a sample of
"coke" produced in carbon black manufacturing. As opposed
to the isotropic texture of small particles of carbon black, the
"coke" particles showed anisotropic texture of pyrolytic carbon microstructures produced by gas to solid transformation
taken place during liquid-phase carbonization (bottom micrograph in Fig. 14).

FIG. 14Polarized-light micrographs of "coke" produced in carbon blacl< manufacturing.

780

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Many industrial applications of c a r b o n blacks rely on


strength reinforcement (in elastomers), color (in inks and
coatings), UV protection, and electrical conductivity (in polymers). The uses of carbon blacks in these applications derive
from a n u m b e r of properties that are related to the size, morphology, and surface chemistry of carbon blacks. The meas u r e m e n t and significance of these properties for specific
applications are described in the following section.
Properties

of Carbon

Blacks

Four fundamental properties of carbon blacks that are important for industrial applications are particle size, structure
(aggregate size and shape), porosity, and surface activity.
These fundamental properties determine, to varying extents,
a n u m b e r of functional properties, such as surface area, tint
strength, and oil absorption, which are measured by well-established ASTM m e t h o d s to characterize carbon blacks.
Table 17 lists ASTM methods used for characterization of
carbon blacks.
The particle d i a m e t e r (fineness) is the most i m p o r t a n t
property of carbon blacks that relates to the level of elastomer reinforcement and color. Both the level of elastomer
reinforcement and the degree of blackness increases with the
decreasing particle size. The measurement of carbon particle
size is very difficult and highly dependent on the measurement technique used. The most dependable method involves
direct m e a s u r e m e n t of particle sizes a n d aggregate sizes
using standard transmission electron microscopy (TEM) procedures (ASTM D 3849). Surface area measurements are also
used (ASTM D 6556, D 3765, and D 1510) as indications of average particle size. All these surface area measurements are
also affected by the pore size distribution, and in some instances, by surface properties of the particles. The results obtained by a commonly used standard method (ASTM D 1765)
adopted in 1965 for characterization of rubber grade carbons
are often inconsistent with those obtained by TEM procedures (ASTM D 3849). Because of difficulties in replicating
particle size measurements even using ASTM D 3849 in different laboratories, particle size ranges reported by ASTM D
1765 have been abandoned in the ASTM designation of carbon blacks since 1996. Average nitrogen surface areas are re-

ported in ASTM D 1756 instead of particle size ranges. Using


ASTM D 1765, carbon blacks are classified into different
grades based on the average N2 surface area using a letter (N
or S - referring to Normal, or Slow cure) and a three-digit
number (e.g., N121 through N990 for rubber grades). First
n u m b e r of the designation roughly corresponds to the particle size. The average N2 surface area, and the mean particle
size of grade N121 are 121-150 m^lg, and 19 nm, respectively.
For grade N990, the same parameters are 0-10 rr?lg, and 285
nm, respectively [90].
The term structure designates the irregular shapes of the
chain- or grape-like aggregation of carbon black particles and
is m e a s u r e d by absorption of dibutylphthalate (DBTA)
(ASTM D 2414). The packing of chain- or grape-like particles
creates internal voids t h a t absorb DBTA. Therefore, the
higher the measured DBTA absorption, the higher the total
level of structure, or more irregular shaped particles in the
sample. The structure is a very important property of carbon
blacks that affects the dispersion of carbon blacks in different mixtures.
Porosity in carbon blacks is produced by steam gasification
of carbon during cooling of particles after formation. A large
fraction of porosity is found at the interior of the carbon black
particles, because the surface layers in the concentric (onionlike) structure of carbons are more stable than the disordered
internal layers. Porosity is an important property of carbon
blacks used in conductivity and color applications. Carbon
blacks used in elastomer reinforcement have low porosity.
Surface activity is defined as the tendency of a carbon
black to interact with its surroundings. Specific interactions
depend on the physical and chemical characteristics of the
surface a n d on the properties of the surrounding matrix.
Surface composition, e.g., surface functional groups, particularly oxygen functional groups, strongly affects surface
activity. Surface activity, the most difficult fundamental
property to characterize, is very important in understanding
and controlling the elastomer reinforcing properties and the
dispersion of carbon blacks, including the rheological properties of polymer and carbon black mixtures.
Other important properties of carbon blacks include sulfur
content, extractable organics, ash, and sieve residue that axe.

TABLE 17Standard test methods used for characterization of carbon blacks.


Fundamental
Property

Particle Size

Structure

Measured Property

ASTM
Method

N2 surface area
CTAB adsorption
Iodine number
Particle and
aggregate sizes
Particle size range,
N2 surface area

D4820
D3765
D1510
D3849

Tint strength
Dibutylphthalate
(DBTA) absorption
Sulfur content
Extractable
organics
Ash

D3265
D2414

Sieve residue

D1765

D1619
D4527
D1506
D1514

Remarks

Surface area is considered as a measure of particle size, but


measurements by different techniques are also sensitive to pore
size distribution and surface chemistry.
Particle and aggregate sizes are determined directly by transmission electron microscopy (TEM)
Used for rubber grade carbons; usually not consistent with the
results from D3849 especially for larger particle sizes; reporting
of particles size ranges was abandoned in 1996.
The smaller the particle size, the higher is the degree of blackness
Higher DPTA absorption, higher the total level of structurechain-or grape-like aggregation
Mostly non-reactive sulfur in aromatic heterocyles
Thermally stable compounds produced in the flame extracted
with toluene and analyzed by UV transmission at 325 nm
Mostly Inorganics irom water, or trace metals and catalyst
particles in the feedstock (FCC decant oil)
Particulate contamination reported as 35 and 325 mesh residues

CHAPTER 29: PROPERTIES

OF FUELS, PETROLEUM PITCH, PETROLEUM COKE, AND CARBON MATERIALS

measured by the standard methods hsted in Table 17. Figure


14 shows that the sieve residue may consist of coke particles
produced by liquid-phase carbonization, and by pjrolytic deposition processes.
Carbon Fibers from Petroleum Pitch
Carbon fibers are produced from polyacrylonitrile (PAN),
and pitch by melt spinning, stabilization, carbonization processes, and from hydrocarbons by vapor phase decomposition reactions catalyzed by metal catalysts [93]. Carbon
fibers are used to fabricate CC composites, or other composite materials such as ccirbon fiber reinforced plastics
(CFRP) [94,95]. Petroleum pitch is also used to produce the
carbonaceous matrix in the CC composites. Unique properties of CC composites, such as high specific strength
and stiffness, high temperature strength, high corrosion
resistance, good friction and wear properties, and low thermal expansion make them very desirable materials. Some
important applications of CC composites include manufacturing aircraft brakes, rocket nozzles, nose cones, and
materials in the aerospace industry [95]. Currently, approximately 90% of all commercial carbon fibers are produced
from PAN [94], but pitch-based fibers offer significant improvement in some fiber properties and, in some cases, reduced cost.
Compared to PAN, petroleum pitch costs less and gives a
higher carbon yield. Both PAN and petroleum pitch can be
used to produce isotropic fibers. Inferior mechanical properties of isotropic pitch-based fibers limit their use to thermal
insulation and some friction material applications. The
principal advantage of petroleum pitch-based fibers is in the
p r o d u c t i o n of anisotropic fibers from mesophase pitch.
Mesophase pitch fibers offer m u c h more ordered structures,
and, thus, much higher modulus, but lower strength properties compared to those of PAN fibers. Table 18 lists the tensile
modulus, tensile strength, and density of selected PAN- and
pitch-based fibers.
Mesophase pitch is produced by thermal or catalytic processing of isotropic petroleum pitch. Thermal processing
involves heating petroleum pitch from room temperature to
400-500C. The solid pitch melts at temperatures between
100 and 200C and its viscosity decreases. At temperatures
greater t h a n 400C, the viscosity of pitch melt starts to

TABLE 18Properties of carbon fibers [94].


Fiber
Pitch-based
P-25
P-55
P-75
P-100
E-35
E-75
E-105
PAN-based
T-300
T-2
AS-4
T-^0
HMS

Tensile
Modulus, GPa

Tensile
Strength, GPa

Density,
g/cm^

159
379
724
724
241
517
724

1.38
1.72
2.24
2.24
2.83
3.10
3.31

1.90
2.00
2.15
2.15
2.10
2.16
2.17

231
172
231
290
345

3.24
2.24
3.64
3.25
2.21

1.79
1.80
1.78
1.83

781

increase upon pyrolysis/polymerization reactions with the attendant formation of mesophase (see Formation of Coke Microtexture in Coking Process). Strictly controlled heating is
necessary to control the kinetics of mesophase formation to
produce a mesophase pitch that is suitable for melt spinning
process. A complete conversion of isotropic pitch to
mesophase is necessary, but the resulting mesophase pitch
must have a sufficiently low melting point and low viscosity
to allow melt spinning. This becomes a challenge for treating
pitches with a complex composition containing a wide distribution of molecular constituents with different reactivities
towards mesophase formation. A pre-fractionation of such
pitches may be necessary to obtain a more homogenous mixture of molecular species with comparable propensities for
mesophase formation [96]. These pretreatment processes increase the cost of producing mesophase pitches suitable for
carbon fiber production. Mesophase pitches produced from
single compounds such as acenaphthylene, naphthalene, or
methylnaphthalene by thermal, or catalytic procesess
[97-99] are ideal, but expensive precursors to anisotropic
carbon fibers.
Continuous c a r b o n fibers are p r o d u c e d in a three-step
process: spinning, stabilization (oxidation), and carbonization. To produce anisotropic carbon fibers using a melt-spin
process, powdered mesophase is heated above its melting
point and forced through a spinneret and wound onto a rotating reel. The m i c r o d o m a i n s of mesophase are aligned
along the fiber axis as the melt passes through the spinneret.
The fibers are drawn to approximately 10-/xm diameter from
100 /Am diameter at the exit of the spinneret, producing a
fiber with a high degree of molecular orientation. The spun
fibers need to be stabilized by oxidation to prevent melting
and loss of structure during carbonization. For stabilization,
fibers are oxidized at temperatures below their melting point,
typically at 275-325C, depending on the composition and dia m e t e r of the fibers [100]. The stabilized fibers are carbonized to increase their carbon content by heating to
1000-1600C in an inert atmosphere. Carbonized fibers can
be subjected to graphitization heat t r e a t m e n t to produce
graphitic fibers.
Mesophase carbon fibers have high modulus (>520 Gpa),
high thermal and electric conductivity, and low thermal expansion coefficients. These properties cannot be achieved by
PAN-based isotropic carbon fibers. In addition to being a precursor to mesophase carbon fibers, petroleum pitch is also
used to produce a carbonaceous matrix in C-C composites
with PAN fibers and as impregnating pitch for densification
of C-C composites [100,101].

Carbon Anodes for Aluminum Production


The principal function of carbon anodes in aluminum production is to provide reactant carbon for electrochemical reduction of AI2O3 to produce aluminum metal (see Reactivity).
As introduced in Section 3, calcinable sponge cokes produced
by delayed coking are used as fillers with coal-tar pitch
binders to manufacture ceirbon anodes for aluminum production. There are two types of anodes used for industrial
aluminum production: the prebaked anode and the Soderberg anode [25]. The principal difference between the
manufacture of the two anodes is found in the carboniza-

782

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

tion/baking stage. The "green" Soderberg anode paste is carbonized/baked by the heat generated by the electrolysis cell,
whereas the prebaked anode, as the n a m e suggests, is carbonized and baked in a separate furnace to produce the finished anode.
Manufacture of prebaked anode involves three stages:
green paste production
paste compaction
anode baking
For grain paste production, grains of anode grade calcined
sponge coke (55-65%) is mixed with butts (material from
used anodes) a n d coke fines (15-30%) and coal-tar pitch
binder (14-17%). The mixing is carried out at a temperature
50-60C higher than the melting point of the binder pitch to
ensure a sufficiently low viscosity of the binder to flow into
pores and voids of the aggregates. Particle size distribution of
the aggregates plays an i m p o r t a n t role in controlling the
properties and the performance of the anode.
Paste compaction, i.e., forming of the green paste into anode blocks, is achieved either by hot pressing, or vibratory
compacting. Vibratory compacting is a preferred process for
large anode blocks heavier than 700 kg [27].
The final stage of anode production is carbonization/baking
to convert the thermoplastic binder pitch into coke by heat
treatment. In this stage both expansion and shrinkage take
place, respectively, during carbonization of the pitch binder
at temperatures between 200 and 600C, and upon subsequent
heating to temperatures of 100-1250C over several weeks.
Cores (usually 2-inch diameter) taken from commercial
anodes are tested for some or all of the following properties:
green apparent density, baked apparent density, conversion
of pitch to coke, volume change during baking, electrical resistivity, carbon dioxide/air reactivity, consumption during
electrolysis, thermal expansion, thermal conductivity, compressive and flexural strength. Young's modulus, gas permeability, porosity, microstructure, and cracking resistance.
Among these properties, baked apparent density and electrical resistivity are the primary characterization parameters
that correlate well with many of the other variables. ASTM
Section D2.5E is developing standard methods for testing
laboratory anodes and cores taken from commercial anodes.
The following methods are in development: sampling, electrical resistivity, C02/air reactivity, thermal conductivity, cind
thermal expansion.
Graphite E l e c t r o d e s for Electric-Arc F u r n a c e s
High-performance graphite electrodes are required for electric-arc steel production because of extremely high temperatures, u p to 4000C, and large temperature gradients involved
in the process [102]. The function of the graphite electrodes
in electric-arc furnaces is to provide high electrical current
density to produce an arc between two- or three-electrodes to
generate sufficient heat to melt the furnace charge of scrap
iron and steel. In contrast to the use of carbon anodes in the
aluminum industry, carbon consumption is not necessary in
the operation, but is unavoidable under the extreme conditions present in the furnace. As in carbon anode production,
graphite electrodes for the steel industry are manufactured
from a green mix of petroleum coke filler and coal-tar pitch
binder. There are, however, substantial differences in preparation of the green mix and subsequent processing steps com-

pared to those employed in the carbon anode production, as


described in Carbon Anodes for Aluminum
Production. A
highly graphitizable needle coke (see Petroleum Coke) is used
as filler for the graphite electrodes. The amount of binder
pitch used is increased from about 15 %wt for anodes to 20
%wt for graphite electrodes. Processing steps for manufacturing graphite electrodes include mixing of needle coke with
the binder pitch, extrusion, baJsing, impregnation, rebaJiing,
and graphitization.
After preparation of the green mix with the carefully sized
needle coke particles and the binder pitch, the electrode is
formed by extrusion to the desired diameter and length (up
to 70 cm in diameter and 270 cm in length). An extrusion aid,
such as an aliphatic, or fatty acid, is added to the mix to provide lubrication on the adapter walls during extrusion. The
critical effect in this step is the alignment of the needle coke
particles parallel to the adapter wall, or the working direction
of the electrode [54].
Following extrusion, the green electrode is baked by
heating slowly to 800-1000C and baked for several days depending on the electrode formulation. This step converts
binder pitch into solid coke and helps maintain the shape of
the electrode. As the temperature increases, the pitch softens,
melts, devolatilizes and goes through carbonization to form
pitch coke. Rapid baking causes problems, such as expansion, distortion, and formation of pits, which would lead to
quality faults in the final product [71].
Pitch impregnation steps are employed to increase the density of the electrodes by filling the open pores in the baked
electrode, created by devolatilization and carbonization of
the binder pitch during the baking step. Usually, petroleum
pitch (see Petroleum Pitch) is used for impregnation because
it is essentially free of solids (Ql-quinoline insolubles) that
can form a cake on the surface of the electrode, slowing
down or stopping the impregnation process. After impregnation, the electrode is rebaked to convert the impregnating
pitch into coke. Depending on the desired density of the electrodes, the impregnation and rebaking cycle may be repeated
several times.
In the final step, the rebaked electrode is graphitized by
heating to approximately 3300 K to convert the filler and
pitch cokes into synthetic graphite. For graphitization heat
treatment, an electric current is passed directly through the
electrode to generate the heat necessary to reach the graphitization temperature.
The manufactured graphite electrodes must have high mechanical strength, high electrical conductivity, low chemical
reactivity, and low thermal expansion. Methods and procedures used to measure the important properties of graphite
electrodes were described by Heinz [103]. Most standard
methods described for characterization of needle cokes can
also be used for evaluation of commercial graphite electrodes
or laboratory test beirs. It should be recognized that because
of the high structural anisotropy of graphite electrodes, these
properties show extremely large variations depending on the
direction in which the measurements are made, i.e., withgrain, parallel to the working direction, or across-grain, perpendicular to the working direction. In graphite, for example,
the thermal expansion normal to the basal planes is 30 times
higher than that parallel to the planes; the electriccJ conductivity is 10 000 times higher along the basal planes than that
across the planes.

CHAPTER 29: PROPERTIES OF FUELS, PETROLEUM PITCH, PETROLEUM COKE, AND CARBON MATERIALS 783
Conclusions
A glimpse of the fascinating diversity and versatility in structure and properties of different materials made up, essentially, of a single element, carbon, should be apparent in the
four examples discussed in this section: carbon black, carbon
fibers, carbon anodes, and graphite electrodes. Carbon
blacks, particulate aggregates of carbon produced by vapor
phase decomposition of aromatic oils, provides elastomer reinforcement and color pigments used in many industrial operations. Pitch-based carbon fibers offer very high modulus
and impressive strengths that find applications in the manufacture of Carbon-Carbon composites. Carbon Carbon
anodes are used for electrochemical reduction of cJuminum
oxide to produce metallic aluminum. Graphite electrodes,
with their excellent thermal properties along with high electrical conductivity, high strength, and low chemical reactivity, find applications in electric-arc furnaces for recycling
scrap iron and steel.
These materials are manufactured from petroleum- and
coal-based feedstocks in well-established processes under
carefully controlled conditions. Although the detailed mechanisms of how the feedstocks are converted into the final
products are not well known, critical properties of these carbon materials are effectively controlled by the right selection
of feedstocks and the operating conditions. Many established
standard methods are used for the characterization of feedstocks and the finaJ products, and several ASTM standard
methods are currently under development.

D 70
D 71
D 86
D 92
D 93
D 95
D 97
D 129
D 130
D 167
D 189
D 240
D 287
D 346

CONCLUSION
Covering a vast area of petroleum-derived products ranging
from fuel oils, highly aromatic feedstocks from catalytic and
thermal cracking, petroleum pitch, and petroleum coke to industrial carbons and graphites, within the bounds of one
chapter presents a great intellectual challenge. The coverage
in this chapter has been necessarily limited to highlighting
the interconnectivity between the end products in this wide
array of materials in reference to production processes,
property characterization using standard methods, and the
significance of measured properties in relation to specific industrial applications. It is important to recognize that despite
the great diversity in the nature and applications of the materials covered in this chapter, there are common threads
that constitute the complex web of converting petroleum
feedstocks to fuels and materials. A careful use of standard
methods for classification of materieJs and quantification of
important properties has contributed to the technology of
converting petroleum feedstocks into desired fuels, hydrocarbons, and carbon materials, as discussed in this chapter
and others.

D 396
D 445
D 446
D 473
D 482
D 524
D 1266
D 1298

D 1510
D1552
D 1756

ASTM STANDARDS

D 1765

No.
D 36

D 1796

D 61

Title
Standard Test Method for Softening Point of Bitumen (Ring-and-Ball Apparatus)
Standard Test Method for Softening Point of
Pitches (Cube-in-Water Method)

D2318

Standard Test Method for Specific Gravity and


Density of Semi-Solid Bituminous Materials (Pycnometer Method)
Standard Test Method for Relative Density of
Solid Pitch and Asphalt (Displacement Method)
Standard Test Method for Distillation of
Petroleum Products at Atmospheric Pressure
Standard Test Method for Flash and Fire Points
by Cleveland Open Cup
Standard Test Methods for Flash-Point by Pensky-Martens Closed Cup Tester
Standard Test Method for Water in Petroleum
Products and Bituminous Materials by Distillation
Standard Test Method for Penetration of Bituminous Materials
Standard Test Method for Sulfur in Petroleum
Products (General Bomb Method)
Standard Test Method for Detection of Copper
Corrosion from Petroleum Products by the Copper Strip Tarnish Test
Standard Test Method for Apparent and True
Specific Gravity and Porosity of Lump Coke
Standard Test Method for Conradson Carbon
Residue of Petroleum Products
Standard Test Method for Heat of Combustion of
Liquid Hydrocarbon Fuels by Bomb Calorimeter
Standard Test Method for API Gravity of Crude
Petroleum and Petroleum Products (Hydrometer
Method)
Standard Practice for Collection and Preparation
of Coke Samples for Laboratory Analysis
Standard Specification for Fuel Oils
Standard Test Method for Kinematic Viscosity of
Transparent and Opaque Liquids (the Calculation of Dynamic Viscosity)
Standard Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers
Standard Test Method for Sediment in Crude Oils
and Fuel Oils by the Extraction Method
Standard Test Method for Ash from Petroleum
Products
Standard Test Method for Ramsbottom Carbon
Residue of Petroleum Products
Standard Test Method for Sulfur in Petroleum
Products (Lamp Method)
Standard Practice for Density, Relative Density
(Specific Gravity), or API Gravity of Crude
Petroleum and Liquid Petroleum Products by Hydrometer Method
Standard Test Method for Carbon BlackIodine
Adsorption Number
Standard Test Method for Sulfur in Petroleum
Products (High-Temperature Method)
Standard Test Method for Rubber ChemicalsSolubility
Standard Classification System for Carbon
Blacks Used in Rubber Products
Standard Test Method for Water and Sediment in
Fuel Oils by the Centrifuge Method (Laboratory
Procedure)
Standard Test Method for Quinoline-Insoluble
(QI) Content of Tar and Pitch

784

MANUAL

D2319
D 2320
D 2414
D 2415
D 2416
D 2492
D 2569
D 2622

D 2638
D 2764
D 2962
D 3104
D 3177
D 3245
D 3279
D 3338
D 3461
D 3765
D 3849

D 3997
D 4045

D 4057
D 4072
D 4239

D 4292
D 4294

D 4296
D 4312
D4421
D 4422

37: FUELS AND LUBRICANTS

HANDBOOK

S t a n d a r d Test Method for Softening Point of


Pitch (Cube-in-Air Method)
Standard Test Method for Density (Relative Density) of Solid Pitch (Pycnometer Method)
Standard Test Method for Carbon BlackOil Absorption Number
Standard Test Method for Ash in Coal Tar and
Pitch
Standard Test Method for Coking Value of Tar
and Pitch (Modified Conradson)
S t a n d a r d Test Method for F o r m s of Sulfur in
Coal
Standard Test Method for Distillation of Pitch
Standard Test Method for Sulfur in Petroleum
Products by Wavelength Dispersive X-ray Fluorescence Spectrometry
Standard Test Method for Real Density of Calcined Petroleum Coke by Helium Pycnometer
Standard Test Method for DimethylformamideInsoluble (DMF-I) Content of Tar and Pitch
Standard Test Method for Calculating VolumeTemperature Correction For Coal-Tar Pitches
S t a n d a r d Test Method for Softening Point of
Pitches (Mettler Softening Point Method)
Standard Test Methods for Total Sulfur in the
Analysis Sample of Coal and Coke
Standard Test Method for Pumpability of Industrial Fuel Oils
Standard Test Method for n-Heptane Insolubles
Standard Test Method for Estimation of Net Heat
of Combustion of Aviation Fuels
Standard Test Method for Softening Point of Asphalt and Pitch (Mettler Cup-and-Ball Method)
Standard Test Method for Carbon BlackCTAB
(Cetyltrimethylammonium Bromide) Surface Area
S t a n d a r d Test Method for Carbon BlackPrimary Aggregate Dimensions from Electron Microscope Image Analysis
Standard Practice for Preparing Coke Samples
for Microscopical Analysis by Reflected Light
Standard Test Method for Sulfur in Petroleum
Products by Hydrogenolysis and Rateometric
Colorimetry
S t a n d a r d Practice for Manual Sampling of
Petroleum and Petroleum Products
Standard Test Method for Toluene-Insoluble (TI)
Content of Tar and Pitch
Standard Test Methods for Sulfur in the Analysis
Sample of Coal and Coke Using High Temperature Tube Furnace Combustion Methods
Standard Test Method for Determination of Vibrated Bulk Density of Calcined Petroleum Coke
Standard Test Method for Sulfur in Petroleum
Products by Energy-Dispersive X-Ray Fluorescence Spectroscopy
Standard Practice for Sampling Pitch
Standard Test Method for Toluene-Insoluble (TI)
Content of Tar and Pitch (Short Method)
S t a n d a r d Test Method for Volatile Matter in
Petroleum Coke
S t a n d a r d Test Method for Ash In Analysis of
Petroleum Coke

D 4529
D 4530
D 4616

D 4715
D 4740
D 4746

D 4809

D 4892
D 5003
D 5004
D 5061

D 5056
D 5018
D 5600

D 5341

D 5187

D 6374
D 6376

D 6556

Standard Test Method for Estimation of Net Heat


of Combustion of Aviation Fuels
Standard Test Method for Determination of Carbon Residue (Micro Method)
S t a n d a r d Test Method for Microscopical Analysis by Reflected Light a n d Determination of
Mesophase in a Pitch
Standard Test Method for Coking Value of Tar
and Pitch (Alcan)
Standard Test Method for Cleanliness and Compatibility of Residual Fuels by Spot Test
S t a n d a r d Test Method for Determination of
Quinoline Insolubles (QI) in Tar and Pitch by
Pressure Filtration
Standard Test Method for Heat of Combustion of
Liquid Hydrocarbon Fuels by Bomb Calorimeter
(Precision Method)
Standard Test Method for Density of Solid Pitch
(Helium Pycnometer Method)
Standard Test Method for The Hardgrove Grindability Index (HGI) of Petroleum Coke
Standard Test Method for Real Density of Calcined Petroleum Coke by Xylene Displacement
Standard Test Method for Microscopical Determination of Volume Percent of Textural Components in Metallurgical Coke
S t a n d a r d Test Method for Trace Metals in
Petroleum Coke by Atomic Absorption
S t a n d a r d Test Method for Shear Viscosity of
Coal-Tar and Petroleum Pitches
S t a n d a r d Test Method for Trace Metals in
Petroleum Coke by Inductively Coupled Plasma
Atomic Emission Spectrometry (ICP-AES)
Standard Test Method for Measuring Coke Reactivity Index (CRI) and Coke Strength After Reaction (CSR)
Standard Test Method for Determination of Crystallite Size (Lc) of Calcined Petroleum Coke by XRay Diffraction
S t a n d a r d Test Method for Volatile Matter in
Green Petroleum Coke Quartz Crucible Procedure
S t a n d a r d Test Method for Determination of
Trace Metals in Petroleum Coke by Wavelength
Dispersive X-Ray Fluorescence Spectroscopy
Standard Test Method for Carbon BlackTotal
and External Surface Area by Nitrogen Adsorption

REFERENCES
[1] Westbrook, S. and LeCren, R., "Automotive Diesel and NonAviation Gas Turbine Fuels," Cii. 5, Fuels and Lubricants Handbook: Technology, Properties, Performance, and Testing, G. E.
Totten, R. Shah, and S. R. Westbrook, Eds., ASTM International, West Conshohocken, PA, 2003.
[2] Gruse, W. A. and Stevens, D. R., Ch. 12, Chemical Technology of
Petroleum, McGraw-Hill, NY, 1960.
[3] For, N., Stability Properties of Petroleum Products, Israel Institute of Petroleum and Energy, Tel Aviv, Israel, 1992.
[4] Gray, M. R., Upgrading Petroleum Residues and Heavy Oils,
Marcel Dekker, Inc., NY, 1994.
[5] Rakow, M. S., "Petroleum Oil Refining," Ch. 1, Fuels and Lubricants Handbook: Technology, Properties, Performance, and

CHAPTER

29: PROPERTIES

OF FUELS,

PETROLEUM

Testing, G. E. Totten, R. Shaw, and S. R. Westbrook, Eds.,


ASTM International, West Conshohocken, PA, 2003.
[6] Schmidt, P. F., Ch. 4, Fuel Oil Manual, Fourth Edition, Industrial Press Inc., NY, 1985.
[7] Schmidt, P. F., Ch. 5, Fuel Oil Manual, Fourth Edition, Industrial Press Inc., NY, 1985.
[8] Schmidt, P. F., Ch. 6, Fuel Oil Manual, Fourth Edition, Industrial Press Inc., NY, 1985.
[9] Petroleum Refining 1- Crude Oil, Petroleum Products, Process
Flow Sheets, J.-P. Wauquier, Ed., Gulf Publishing Company,
Houston, TX, 1995, p. 237.
[10] Anonymous, "Making Sense Of Fuel Oil Viscosity," Marine
Engineers Review, Vol. 56, July-August, 1999.
[11] Schmidt, P. F., Ch. 7, Fuel Oil Manual, Fourth Edition, Industrial Press Inc., NY, 1985.
[12] Mushrush, G. W. and Speight, J. G., Ch. 11, Petroleum Products: Instability and Incompatibility, Taylor & Francis, Washington, DC, 1995.
[13] Peyton, K. B., Ch. 5, Fuel Field Manual, McGraw-Hill, NY, 1997.
[14] Schmidt, P. F., Ch. 8, Fuel Oil Manual, Fourth Edition, Industrial Press Inc., NY, 1985.
[15] Walsh, P. M. and Olen K. R, "Emission of U n b u m e d Coke
from Combustion of Residual Fuel-Oil in Wall-Fired Electric
Utility Boilers," Journal of The Institute of Energy, Vol. 66,
1993, pp. 140-146.
[16] Schmidt, P. F., Ch. 9, Fuel Oil Manual, Fourth Edition, Industrial Press Inc., NY, 1985.
[17] Schmidt, P. F., Ch. 10, Fuel Oil Manual, Fourth Edition, Industrial Press Inc., NY, 1985.
[18] Miller, C. A., Linak, W. P., King, C , and Wendt, J. O. L., Combustion Science and Technology, Vol. 134, No. 1-6, 1998, pp.
477-502.
[19] Schmidt, P. F., Ch. 13, Fuel Oil Manual, Fourth Edition, Industrial Press Inc., NY, 1985.
[20] Martin, C. V. G., Proceedings of the Third World Petroleum
Congress, Section VII, 1951, Institute of Petroleum, London,
1952, pp. 66-75.
[21] Newman, J. W., Petroleum. Derived Carbons, ACS Symposium
Series No. 21, M. L. Deviney and T. M. O'Grady, Eds., American Chemical Society, Washington, DC, 1976, pp. 52-62.
[22] Dickakian, G., Petroleum Derived Carbons, ACS Symposium Series No. 303, J. D. Bacha, J. W. Newman, and J. L. White, Eds.,
American Chemical Society, Washington, DC, 1986, p p .
118-171.
[23] Newman, J. W. and Newman, K. L., Ch. 6, Introduction to Carbon Technologies, H. Marsh, E. A. Heintz, and F. RodriguezReinoso, Eds., Universidad de Alicante, Secretariado de Publicaciones, Spain, 1997.
[24] Gray, R. J. and Krupinski, K. C , Ch. 7, Introduction to Carbon
Technologies, H. Marsh, E. A. Heintz, and F. RodriguezReinoso, Eds., Universidad de Alicante, Secretariado de Publicaciones, Spain, 1997.
[25] Zander, M., Ch. 8, Introduction to Carbon Technologies, H.
Marsh, E. A. Heintz, and F. Rodriguez-Reinoso, Eds., Universidad de Alicante, Secretariado de Publicaciones, Spain, 1997.
[26] Andresen, J. M., Martin, Y., Moinelo, S. R., Maroto-Valer, M.
M., and Snape, C. E., "Sohd State C NMR and High Temperature Determination of Bulk Structural Properties for
Mesophase-Containing Semi-Cokes Prepared from Coal Tar
Pitch," Carbon, Vol. 36, 1998, pp. 1043-1050.
[27] Gray, R. J. and Krupinski, K. C , Ch. 7, Introduction to Carbon
Technologies, H. Marsh, E. A. Heintz, a n d F. RodriguezReinoso, Eds., Universidad de Alicante, Secretariado de Publicaciones, Spain, 1997.
[28] Waller, J. H., Grimes, G. W., and Matson, J. A., Petroleum Derived Carbons, ACS Symposium Series No. 303, J. D. Bacha, J.
W. Newman, and J. L. White, Eds., American Chemical Society, Washington, DC, 1986, pp. 144-154.

PITCH, PETROLEUM

COKE, AND CARBON

MATERIALS

785

[29] Beetz, Jr., C. P., Schmueser, D. W., and Hansen, W., "Summary of Panel Discussion, Challenges to the Researchers of
Carbon-Fibers and Composites from the Automotive and
Boatbuilding Industries," Carbon, Vol. 27, 1989, pp. 767-771.
[30] Andresen, J. M., Garcia, R., Maroto-Valer, M. M., Moinelo, S.
R., and Snape, C. E., "Characterization of Mesophase Develo p m e n t in Pitch by High T e m p e r a t u r e In Situ H NMR,"
Preprints., American Chemical Society, Division of Petroleum
Chemistry, Vol. 4 1 , No. 3, 1996, pp. 621-624.
[31] Fitzer, E., "The Future of Carbon-Carbon Composites," Carbon, Vol. 25, 1987, pp. 163-190.
[32] Burchell, T. D., "Carbon Material for Advanced Energy
Applications," International Conference on Carbon, Newcastle,
UK, 1996, p p . 185-188.
[33] Ehrburger, P., "Glassy Properties of Coal Tar Pitch Materials," Energeia, Vol. 5, No. 3, 1994, pp. 1-3.
[34] Marsh, H., Introduction to Carbon Science, Butterworth, London, 1989.
[35] Lahaye, L., Ehrburger, P., Saint-Romain, J. L., and Couderc,
P., "Physicochemical Characterization of Pitches by Differential Scanning Calorimetry," Fuel, Vol. 66,1987, pp. 1467-1471.
[36] Rand, B., Ch. 8, Handbook of Composites, Vol. 1, W. Watt and
B. V. Perov, Eds., Elsevier, NY, 1989.
[37] Dealy, J. M., Rheometers for Molten Plastics, Van Nostrand
Reinhold Company, NY, 1982.
[38] Cheung, T., Turpin, M., and Rand, B., "Controlled Stress, Oscillatory Rheometry of Mesophase-Pitches," Carbon, Vol. 33,
1985, pp. 1673-1679.
[39] Bhatia, G., Aggarwal, R. K., Chari, S. S., and Jain, G. C , "Rheological Characteristics of coal Tar and Petroleum Pitches
With a n d Without Additives," Carbon, Vol. 15, 1977, pp.
219-223.
[40] Bhatia, G., Fitzer, E., and Kompalik, D., "Mesophase Formation in Defined Mixtures of Coal Tar Pitch Fractions," Carbon,
Vol. 24, 1986, pp. 4 8 9 ^ 9 4 .
[41] Nazem, F. F., "Flow of Molten Mesophase Pitch," Carbon, Vol.
20, 1982, p p . 345-354.
[42] Turpin, M., Cheung, T., and Rand, B., "Controlled Stress, Oscillatory Rheometry of a Petroleum Pitch," Carbon, Vol. 32,
1994, pp. 225-230.
[43] ICremer, H. A., "Recent Development in Electrode Pitch and
Coal Tar Technology," Chemistry and Industry, Vol. 27, 1982,
pp. 702-713.
[44] Kuo, K., Marsh, H., Eind Broughton, D., "Influence of Primary
QI and Particulate Matter on Pitch Carbonizations," Fuel, Vol.
66, 1987, pp. 1544-1551.
[45] Marsh, H., Latham, C. S., and Gray, E. M., "The Structure and
Behaviour of QI Material in Pitch," Carbon, Vol. 23, 1985, pp.
555-570.
[46] Taylor, G. H., Pennock, G. M., Fitz G. J. D., and Brunckhorst,
L. F., "Influence of QI on Mesophase Structure," Carbon, Vol.
31, 1993, p p . 341-354.
[47] Romovacek, G. R., "Estimating the Concentration of Secondary
Quinoline Insolubles," Carbon, Vol. 24, 1986, pp. 4 1 7 ^ 2 1 .
[48] Menendez, R., Granda, M, and Bermejo, J., Ch. 9, Introduction to Carbon Technologies, H. Marsh, E. A. Heintz, and F.
Rodriguez-Reinoso, Eds., Universidad de Alicante, Secretariado de Publicaciones, Spain, 1997.
[49] Grjotheim, K., Krohn, C , Malinovsky, M., Matiasovsky, K.,
and Thonstad, J., Aluminium Electrolysis: Fundamentals of the
Hall-Heroult Process, Aluminium-Verlag, Diisseldorf, 1982.
[50] Gary, J. H. and Handwerk, G. E., Petroleum Refining: Technology and Economics, Marcel Dekker, NY, 1994, pp. 71-99.
[51] Ellis, P. T. ind Hardin, E. E., "How Petroleum Delayed Coke
Performs in a Drum," Light Metals, 1993, pp. 509-513.
[52] Adams, H. A., Ch. 10, Introduction to Carbon Technologies, H.
Marsh, E. A. Heintz, and F. Rodriguez-Reinoso, Eds., Universidad de Alicante, Secretariado de Publicaciones, Spain, 1997.

786 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


[53] Eser, S., Jenkins, R. G., Malladi, M., and Derbyshire, F. J.,
"Carbonization of Coker Feedstocks and Their Fractions,"
Carbon, Vol. 24, 1986, pp. 77-82.
[54] Mochida, I., Fujimoto, K., a n d Oyama, T., Chemistry and
Physics of Carbon, Vol. 24, P. A. Thrower, Ed., Marcel Dekker,
NY, 1994, pp. 111-212.
[56] White, J. L., "Petroleum Derived Carbons," ACS Symposium
Series No. 21, M. L. Deviney, and T. M. O'Grady, Eds., American Chemical Society, Washington, DC, 1976, p. 282.
[57] Oya, A., Qian, Q. Z., and Marsh, H., Fuel, Vol. 62, 1983, p. 274.
[58] Eser, S., Supercarbon: Synthesis, Properties, and Applications,
Vol. 147, S. Yoshimura and R. P. H. Chang, Eds., SpringerVerlag, BerUn, 1998.
[59] Eser, S. and Jenkins, R. G, "Carbonization of Petroleum Feedstocks. 1. Relationships Between Chemical Constitution of
the Feedstocks and Mesophase Development," Carbon 27,
1989, pp. 877-887.
[60] Eser, S. and Jenkins, R. G, "Carbonization of Petroleum Feedstocks. 2. Chemical Constitution of Feedstocks Asphaltanes
and Mesophase Development," Carbon 27, 1989, pp. 889-897.
[61] Fitzer, E., Kochling, K.-H., and Marsh, H., "Recommended
Terminology for the Description of Carbon as a Solid-(IUPAC
Recommendations 1995), Pure and Applied Chemistry, Vol. 67,
1995, pp. 473-506.
[62] Rumsey, J. C. V. and Pitt, G. J., "Some Techniques for the Characterization of Cokes and Graphites," Fuel, Vol. 57,1978, p. 155.
[63] Patrick, J. W., Reynolds, M. J., and Shaw, F. H., "Development
of Optical Anisotropy in Vitrains during Carbonization," Fuel,
Vol. 52, 1973, p. 198.
[64] Sanada, Y., Furuta, T., Kimura, H., and Honda, H., "Formation
of Anisotropic Mesophase from Various Carbonaceous Materials in Early Stage of Carbonization," Fuel, Vol. 52, 1973, p. 143.
[65] Ragan, S. and Marsh, H., "The Influence of Oxidation upon
Strength and Structure of a Needle-Coke and a Coal Extract
Coke," Carbon, 1983, Vol. 2 1 , No. 2, p. 157.
[66] Mochida, I., Korai, Y., Nesumi, Y., and Oyama, T., 'Carbonization in a Tube Bomb. 1. Carbonization of Petroleum Residue
into a Lump of Needle Coke," Industrial & Engineering Chemistry Product Development,Yo\. 25, No. 2, 1986, p. 201.
[67] Martin, S. W., Petroleum Products Handbook, V. B. Guthrie,
Ed., McGraw-Hill, NY, 1960, pp. 14.
[68] Pysz, R. W., Hoff, S. L., and Heitz, E. A., "Terminology for the
Structural Evaluation of Coke via Scanning Electron-Microscopy," Carbon, Vol. 27, 1989, p. 935.
[69] Qiao, G., "Digital Image Analysis of Needle Cokes and Other
Solid Carbons and Their Thermal Expansion Behavior," Ph.
D. Thesis, The Pennsylvania State University, May 2000.
[70] Gray, R. J. and Devanney, K. F., "Coke Carbon FormsMicroscopic Classification and Industrial Applications," International loumal of Coal Geology, Vol. 6, 1986, pp. 277-297.
[71] Mantell, C. L., Carbon and Graphite Handbook, John Wiley &
Sons, NY, 1968, p . 520.
[72] Page, D. J., The Industrial Graphite Engineering
Handbook,
UCAR Carbon Company Inc., 1991.
[73] Reynolds, W. N., Physical Properties of Graphite, Elsevier,
London, 1968, p . 80.
[74] Kingeiy, W. D., Bowen, H. K., and Uhlmann, D. R., Introduction to Ceramics, John Wiley & Sons, NY, 1976, p. 591.
[75] Hutcheson, J. M. and Price, M. S. T., Proceedings of the 4 * Carbon Conference, 1960, p. 645.
[76] Sutton, A. L. and Howard, V. C , Journal of Nuclear Materials,
Vol. 7, 1962, p. 58.
[77] Price, R., Bokros, J. C , and Koyama, K., "Thermal Expansivities and Preferred Orientation of Pyrolytic Carbon," Carbon,
Vol.5, 1967, p . 423.
[78] Zimmer, J. E. and White J. L., 1 3 * Biennial Conference on
Carbon, Extended Abstracts, 1977, p. 318.

[79] Mochida, I., Ogawa, M., and Takeshita, K., Bulletin of the
Chemical Society of Japan, Vol. 49, No. 2, 1976, p. 514.
[80] Collins, F. M., "Dimensional Changes During Heat-Treatment
a n d T h e r m a l Expansion of Polycrystalline Carbons a n d
Graphite," Proceedings, 3''''Conference on Carbon, 1957, p. 659.
[81] Matsuo, H. and Sasaki, Y., "Relation between Anisotropy Ratio of Thermal Expansion Coefficient and Bacon Anisotropy
Factor," Carbon, Vol. 12, 1974, p . 351.
[82] Widmann, G. and Riesen, R., Thermal Analysis, Terms, Methods, Application, Heidelberg, Germany, 1987, p. 17.
[83] Hole, M., Foosnaes, T., and 0 y e , H. A., "Relationship between
Thermal Expansion and Optical Texture of Petrol Coke," Light
Metals, 1991, p. 575.
[84] Eilertsen, J. L., Rrvik, S., Foosnaes, T., and 0ye, H. A., "An Automatic Image Analysis of Coke Texture," Carbon, Vol. 34,
1996, p. 375.
[85] Heintz, E. A., "Influence of Coke Structure on the Properties
of the Carbon-Graphite Artefact," Fuel, Vol. 64, 1985, p. 1192.
[86] Blyholder, G. and Eyring, H., Journal of Physical Chemistry,
Vol. 61, 1957, p. 682.
[87] Marsh, H., Taylor, D. A., and Lander, J. R., "Kinetic Study of
Gasification by Oxygen a n d Carbon Dioxide of Pure and
Doped Graphitizable Carbons of Increasing Heat Treatment
Temperatures," Carbon, Vol. 19, 1981, p. 375.
[88] Marsh, H. and Kuo, K, Introduction
to Carbon Science, H.
Marsh, Ed., Butterworths, London, 1989, p. 108.
[89] Gregg, S. J. and Tyson, R. F. S., "The Kinetics of Oxidation of
Carbon and Graphite by Oxygen at 500-600," Carbon, Vol. 3,
1965, p. 39.
[90] Taylor, R., Ch. 4, Introduction to Carbon Technologies, H. Marsh,
E. A. Heintz, and F. Rodriguez-Reinoso, Eds., Universidad de Alicante, Secretariado de Publicaciones, Spain, 1997.
[91] Donnet, J. B., Bansal, R. C , and Wang, M.-J., Carbon Black Science and Technology, Second Edition, Marcel Dekker, NY, 1993.
[92] Schwob, Y., "Acetylene Black: Manufacture, Properties, and
Applications," Chemistry and Physics of Carbon, P. L. Walker
and P. A. Thrower, Eds., 1982, p. 109.
[93] Donnet, J. B. and Bansal, R. C , Carbon Fibers, Marcel Dekker,
NY, 1984.
[94] Murdie, N., Ch. 14, Introduction
to Carbon
Technologies,
H. Marsh, E. A. Heintz, and F. Rodriguez-Reinoso, Eds., Universidad de Alicante, Secretariado de Publicaciones, Spain,
1997.
[95] Johnson, D. J., Introduction to Carbon Science, H. Marsh, Ed.,
Butterworths, London, 1989, p. 197.
[96] Edie, D. D. and Diefendorf, R. J., Ch. 2, Carbon-Carbon Materials and Composites, NASA 1254, Park Ridge, NJ, 1992.
[97] Singer, L. S., "The Mesophase a n d High Modulus Carbon
Fibers from Pitch," Carbon, Vol. 16, 1978, pp. 409-415.
[98] Yoon, S.-H., Korai, Y., Mochida, I, and Kato, I., "The Flow
Properties of Mesophase Pitches Derived from Methylnapthalene and Napthalene in the Temperature-Range of Their Spinning," Carbon, Vol. 32, 1994, pp. 273-280.
[99] Mochida, I., Yoon, S.-H., Korai, Y., Kanno, K., Sakai, Y., and
Komatsu, M., 'Carbon-Fibers from Aromatic-Hydrocarbons,"
Chemtech, Vol. 25, No. 2, 1995, p p . 29-36.
[100] Cranmer, J. H., Plotzken, I. G., Peebles, L. H., and Uhlmann, D.
R., "Carbon Mesophase-Substrate Interactions," Carbon, Vol.
21, 1983, pp. 201-207.
[101] Meyer, R. A. and Gyetvay, S. R., Petroleum Derived Carbons,
ACS Symposium Series No. 303, J. D. Bacha, J. W. Newman,
and J. L. White, Eds., American Chemical Society, Washington, D.C., 1986, pp. 380-394.
[102] Vohler, O., von Sturm, F., and Wege, E., Vlhnann's Encyclopedia of Industrial Chemistry, A5, VCH, Heidelberg, 1986, p . 98.
[103] Heinz, E. A., "The Characterization of Petroleum Coke," Carbon, Vol. 34, 1996, p. 699.

MNL37-EB/Jun. 2003

Oxidation of Lubricants and Fuels


Gerald J. Cochrac^ and Syed Q. A. Rizvi^

OXIDATION OF LUBRICANTS AND


OXIDATION INHIBITORS

viscosity index for Group III Oils is >120. In general. Group


II, Group III, and Group IV Oils are low in aromatic structures and structures with unsaturation. Hence, they oxidize
at a slower rate than Group I Oils that are high in such structures. This is because such structures more readily form hydroperoxides and peroxy radicals that are essential to the oxidation process. Synthetic basestocks (Group V Oils) have
oxidation rates that vary because of varying structures. Alkylaromatics, for example, contain aromatic rings, and hence
oxidize faster than ester basestocks, which in turn oxidize
faster than olefin oligomers (PAOs) that belong to Group IV.
Vegetable oils oxidize at a fast rate as well because of the
presence of unsaturation. The oxidatively susceptible structures in various basestocks are shown in Fig. 1. The hydrogens in the immediate vicinity of a r o m a t i c rings, double
bonds, and oxygen atoms are most vulnerable to oxidative attack. Such hydrogens are shown in Fig. 2 and discussed in detail below.

MODERN LUBRICANTS PRIMARILY COMPRISE PERFORMANCE ADDI-

TIVES such as dispersants, detergents, oxidation inhibitors,


viscosity modifiers, a n d others, blended in a base fluid
(see chapter on Additives and Additive Chemistry). Many
properties of the lubricant such as viscosity, viscosity index,
slipperiness (reduced friction), film-strength, p o u r point,
oxidation stability, volatility, and flammability, therefore depend on the properties of both the base fluid and the additive
package. However, since the base fluid in a lubricant is present in excess of 70%, its contribution towards the listed
properties predominates that of the additive package.
Oils used to lubricate today's equipment, by virtue of being
hydrocarbon based, are susceptible to oxidation. Oxidation
results in the formation of polar compounds such as aldehydes, ketones, carboxylic acids, and oxygenated polymers.
These products of oxidation are either corrosive or lead to the
formation of resin, deposits, and sludge, all of which can impair the proper functioning of the equipment.
The resin derived from lubricant oxidation consists of oxygenated oligomeric or polymeric molecules of approximately
500-1000 molecular weight. Deposits, on the other hand,
comprise materials of a m u c h higher molecular weight.
Sludge is a mixture of these materials with water, oil, and
other contaminants.
Oxidation resistance of a base oil leirgely depends upon the
structure of the hydrocarbons present. Base oils are of mineral (petroleum) origin, synthetic chemical origin, or biological origin. "While mineral oil basestocks are obtained directly
from petroleum fractionation, synthetic basestocks are manufactured through transformations of primarily petroleum
derived organic chemicals. Base stocks of biological origin
include vegetable oils and animal fats.
API (American Petroleum Institute) has established five
base oil categories on the basis of percent sulfur and percent
saturates. Group I contains oils that have >0.03% sulfur and
< 9 0 % saturates by mass. These oils have a viscosity index
range of 80-120. Group II and III Oils, on the other hand,
have <0.03% sulfur and s 9 0 % saturates by mass. However,
they differ from each other in their viscosity index. The
viscosity index for Group II Oils ranges from 80-120 and the

Each type of basestock, mineral, biological, or synthetic,


has a stable threshold beyond which oxidation inhibitors are
needed to retard oxidation. Refined base oils once contained
sulfur and nitrogen-based "natural" inhibitors, which under
mild conditions were sufficient to protect lubricants against
oxidation. However, new refining technologies used to enhance other desirable properties of base oils either partly or
fully remove these beneficial compounds. This is particularly
true for base oils belonging to API Group II and higher
Groups, where the limit on sulfur is 0.03 percent by mass or
less. Most lubricants therefore require oxidation inhibitors to
protect them under increasingly severe high temperature service environments.

' Product Manager, The Lubrizol Corporation, 29400 Lakeland


Blvd., Wickliffe, OH 44092.
^ Research & Development Manager, Lubricant Additives Division,
King Industries, Inc., Science Road, Norwalk, CT 06852.

Most lubrication applications expose lubricants to oxygen


in some manner. Oxygen readily reacts with labile hydrogens
of the hydrocarbon structures that make u p the lubricant.
Such sites, in order of decreasing ease of reaction, are benzylic, allylic, tertiary alkyl, secondary alkyl, and primary alkyl
hydrogens. Benzylic hydrogens are hydrogens on carbons
next to an aromatic ring. Allylic hydrogens are on carbons
next to a double bond. Tertiary hydrogens are on carbons attached to three other carbon atoms. Secondary hydrogens
are on carbons attached to two other carbon atoms and primary hydrogens are on carbons attached to only one other
carbon atom. Figure 2 identifies these hydrogens in model
structures. The oxidation of these hydrogens results in the
formation of peroxy and other radicals. The mechanism of
oxidation is illustrated in Fig. 3 [1].
The process of oxidation proceeds in three stages: initiation, propagation, and termination. During the initiation

787
Copyright'

2003 by A S I M International

www.astm.org

788 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


UNSATURATES

Alkenes
AROMATICS

VEGETABLE OIL

)c-0CHj

.R

R=

HCOC

R.

X-0CH,

ESTERS
CH20C^

O
O
II
II
RO C ~ ( C H 2 ) n C O R

R=C5TOCio

CH3CH2CCH2OC ^
O
CH2OC //

R=C8 TO Ci3

Alkyl Carboxylate Ester

Polyol Ester

FIG. 1Base oil structures with high susceptibility to oxidation.

Allylic
Benzylic-

AJIylic

I I
H

C'

Aflylic

I l"x/H

/\
H

- Allylic

Y"-

Allylic

I
H

BenzylicAriylic

Secondary

Tertiary

LJ

'

/\
H H

tt

'*"

\
/
HjCCH,

Primary

H,
HjC

CH,

H2
"2 H H2
-2 HI, H2
. . 2 HI, Hj H CH3H2 A_
HsC" I CH3
H

t t
Tertiary

'

Tertiary
irtiarv

tt

Secondary
I
I

Tertiary

FIG. 2Classification of hydrogens in organic molecules.

CHAPTER 30: OXIDATION OF LUBRICANTS AND FUELS

789

INITIATION
activation
RH + O2 + RH

*-

R- + H'

(1)

R- + H2O + R'

(2)

PROPAGATION
(3)

R' + O,
-^

RO,' + RH

ROOH + R'

(4)

RO- + OHRO- + RO2- + H2O

(5)
(6)

Various Products

(7)

Nonradical Products

(8)

Decomposition of Peroxide:
ROOH
2 ROOH
RO- + ROOH
ROz'
ROOH

Induced Decomposition of Peroxide:


X
Y
Z
M

+
+
+
+

ROOH
ROOH
ROOH
ROOH

Free Radicals

(9)

ROH + YO

(10)

Inactive Prodcts + Z

(11)

Free Radicals

(12)

TERMINATION
Self Termination:
ROa' + RO2-

Inactive Products

(13)

Chain-Breaking Termination:
ROz + IH

ROOH + r

(14)

RO- + IH

ROH + |-

(15)

RH + |-

(16)

R-

+ IH

RH = Organic substrate

ROa' = Peroxy radical

ROOH = Hydroperoxide

X, Y, Z = Decomposers of Radicals RO' = Alkoxy radical R- = Alkyl radical


M = IVIetal IH = Chain-breaking inhibitor or inhibitor of free radicals 1" = Inhibitor radical

FIG. 3Mechanism of oxidation.

stage, oxygen reacts with the fuel and the lubricant to form
alkyl radicals (Eqs 1 and 2; Fig. 3). During the propagation
stage, these radicals react with oxygen and the lubricant to
form peroxy radicals and hydroperoxides (Eqs 3 and 4). As
indicated by the oxygen uptake in Fig. 4 [2], hydroperoxides
are accumulated during the induction period, after which
the autoacceleration of oxidation occurs. Hydroperoxides,
either thermally or in the presence of metal, decompose to
a variety of additional radicals and oxygen-containing
compounds (Eqs 5-12, Fig. 3). The oxygen-containing compounds include alcohols, aldehydes, ketones, and carboxylic
acids. The detailed mechanism of thermal decomposition of

hydroperoxides to form these species is shown in Fig. 5, Eqs


18 and 19 [3]. Aldehydes and ketones can form polymers
(Eq 20 in Fig. 5 and Fig. 6) in the presence of acids, such as
nitric and sulfuric acids. These acids result from the interaction of nitrogen oxides and sulfur oxides, products of
combustion, with water (Fig. 7). Carboxylic acids can attack
iron metal, and copper and lead bearings to form metal
carboxylates (Eq 21 in Fig. 5 and Fig. 8), which can further
increase the rate of oxidation. Figure 9 [2] depicts the catalj^ic effect of iron carboxylate on hydroperoxide formation. Please note that certain metal salts, when present in a
low concentration, can act as oxidation inhibitors. Oxida-

790

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

tion inhibition by copper salts is described in the latter part


of the chapter.
An increase in temperature affects the oxidation process
profoundly, with the rate of oxidation approximately doubling with every ten-degree centigrade rise in temperature.
Wear metals can also enhance the rate of oxidation [4]. If
oxidation is not controlled, lubricant decomposition will lead
to oil thickening, sludge formation, and the formation of
varnish, resin, deposits, and corrosive acids (Fig. 10) [5,6].

J ^

"1
OH

"^

=^

OH

HO

/
HO

R2

.^

Ri

O x y g e n a t e d Polymer
HO

R2

FIG. 6Oxygenated polymer formation.

-*-

N2 + O2
2NO2
Induction Period

F I G . 4 E f f e c t of h y d r o p e r o x i d e c o n c e n t r a t i o n o n t h e rate of

4 - ^

HN03 +

H,0

s + o.

Time

2 NO

--

SO2

-1^

2N02

(22)

HN02

(23)

S03

(24)
(25)

12S04

H,0

oxidation.
F I G . 7 F o r m a t i o n of a c i d s .

R0-0

RO' + HjO + ROO'

H-O-O-R

(17)

6 R C O O H + 2 Fe

2 (RCOO)3Fe + 3 H2

(26)

4 R C O O H + 2 Cu

*-

2 ( R C 0 0 ) 2 C u + 2 H2

(27)

2 ( R C 0 0 ) 2 P b + 2 H2

(28)

R,.
CHOO-

/^
4 R C O O H + 2 Pb

F I G . 8 F o r m a t i o n of metal c a r b o x y l a t e s .

C=0

,CHOH +

O2

(18)

Carbonyl
Compound

RiCH2\

c=o

Carbonyl
Compound

-fe

3
u

Hydrocarbon Containing
500 ppm Iron Octanoate

2 6
X

o
u
u s
Q.
O

X
O 3-

Rl-Cs

(19)
OH

Aldehyde

Carboxylic Acid

Polymeric Materials

(20)

/ Pure Hydroarfeop

<1

/L

RCHO

c
3 2

'

_t>
cr-

10

Time (days)
RCOOH + Metal

--

Metal Salts

F I G . 5 M e c h a n i s m of h y d r o p e r o x i d e d e c o m p o s i t i o n .

(21)

F I G . 9 C a t a l y t i c e f f e c t of Iron c a r b o x y l a t e o n t h e rate of
oxidation.

CHAPTER
Oil thickening occurs mainly due to polymerization or association of certain oxidation products. A model showing oxidative and thermal degradation of lubricants is shown in
Fig. 11 [2].
During the t e r m i n a t i o n stage, t h e radicals either selft e r m i n a t e or t e r m i n a t e by reacting with oxidation inhibitors (Eqs 13-16, Fig. 3). The m e c h a n i s m involving
self-termination leading to the formation of harmful carbonyl
compounds is shown in Eq 18 of Figs 5. Oxidation inhibitors
circumvent the radical chain mechanism of the oxidation process (Eqs 9-11 and 14-16, Fig. 3). Oxidation inhibitors can be
Sulfur

F u e L ^ H2SO4

(29)
(30)

R,C=0

-*-

Resins

Resins + Soot + Oil + H2O


Resin + Soot

(31)
*"

Sludge

Resin Coated Soot

(32)
- Deposits

FIG. 10Formation of harmful products.

(33)

30: OXIDATION

OF LUBRICANTS

AND FUELS

791

classified as hydroperoxide decomposers and radical scavengers, depending upon the mode of their controlling action.
Sulfur and phosphorus-containing inhibitors, such as sulfides, dithiocarbamates, phosphites, and dithiophosphates,
structures shown in Fig. 12, act as hydroperoxide decomposers. Nitrogen and oxygen-containing inhibitors, such as
arylamines and phenols, structures shown in Fig. 13, act as
radical scavengers. Hydroperoxide decomposers convert
chain-propagating hydroperoxides to alcohols while they
themselves become oxidized to higher oxidation levels. Sulfur compounds, represented by alkylsulfides, react with hydroperoxides and are converted into sulfoxides or sulfones.
Sulfoxides can decompose thermally to form other sulfurcontaining products, such as sulfonic and sulfuric acids,
which themselves are hydroperoxide decomposers. Nonhindered phenols also act as hydroperoxide decomposers and, in
the process, are converted to polyhydroxy compounds [1].
See Parts 1 and 2 of Fig. 14 for the mechanism.
Phosphorus compounds also act as hydroperoxide decomposers. Phosphines, rarely used as inhibitors because of their
toxicity, are not as effective as other phosphorus derivatives.
This is because they react stoichiometrically with hydroperoxides to form phosphine oxides that lack further oxidationinhibiting ability. Alkyl phosphites are better because during

FIG. 11High-temperature lubricant degradation model.

792 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Sulfides

R-S-(s)-S-R

R-S-R
Monosulfide

R = Olefin or fatty
ester derived

Polysulfide

DIthlocarbamates

R.

-N-C,

R = Alkyl

Zn

CH,

S
-12

Ashless Dithiocarbamate

Zinc Dithiocarbamate

Phosphites and DIthiophosphates

RO^ /^S

R0-.
RO

R0"%

Diall<yl Hydrogen Phosphite

R = Alkyl

Zn

Zinc DialkyI Dithlophosphate

FIG. 12Hydroperoxide decomposers.

N-Phenyl-1 -naphthylamine
(PANA)

Diall^yldiphenyiamine

2,6-DI-f-butyl-4-niethylphenol
(BHT)

Arylamines
FIG. 13Radical scavengers.

hydroperoxide decomposition they are converted into phosphates, which continue inhibiting oxidation by forming
acidic materials via thermal decomposition [3]. The hydroperoxide decomposing mechanism by phosphorus additives is shown in Part 3 of Fig. 14.
Dithiophosphoric acid derivatives are the most potent of
the phosphorus compounds, primarily because they can
inhibit oxidation both by hydroperoxide decomposition and
by radical scavenging [7]. They decompose hydroperoxides
catalytically as well as by reacting with them to form compounds that are peroxide decomposers in their own right [3].
Initially, dithiophosphoric acid derivatives are converted into
dialkyl dithiophosphoryl disulfide, which is the key intermediate in the oxidation-inhibiting process. The disulfide oxidizes to thiosulfenate, followed by the sulfur-sulfur bond
cleavage to form sulfenyl and dithiophosphoryl radicals.
These radicals react with hydroperoxides and other radiccJs

to form intermediates that result in strongly acidic species,


which are also responsible for oxidation inhibition. This sequence of events is depicted in Fig. 15. Dithiocarbamic acid
derivatives, a related class of oxidation inhibitors, also act as
both hydroperoxide decomposers and radical scavengers [8].
Radical scavengers render radicals innocuous either by
transferring a hydrogen atom to them or by an oxidationreduction mechanism [1,3]. Hydrogen transfer from the
inhibitor to the radical generates a new inhibitor-derived radical. See Eqs 14-16 of Fig. 3. However, unlike the radicals
from the oxidation process, such radicals are incapable of
propagating oxidation. This is because these new radicals are
either too sterically hindered or resonance stabilized (see Fig.
16) to take part in the oxidation process. The oxidationreduction mechanism involves electron transfer to or from the
peroxy radical, thereby converting it into an ion and removing
it from the oxidation process. The formation of dialkyl dithio-

CHAPTER 30: OXIDATION OF LUBRICANTS


phosphoiyl disulfide from zinc dialkyl dithiophosphoric acid
is an example of such a mechanism. See Fig. 15.
Hindered phenols and arylamines are two prominent
classes of inhibitors that act as radical scavengers through
hydrogen transfer [3]. The most commonly used hindered
phenol inhibitor, 2, 6 di-t-butyl-4-methylphenol (BHT), controls oxidation by transferring its phenolic hydrogen to the
alkoxy radical and converts it into alcohol. The phenoxy radical that results from this process is incapable of propagating
oxidation because of steric hindrance. However, this radical
either rearranges to form the benzylic radical, which dimerizes to form the diphenoxyethane, or reacts with an alkylperoxy radical to form the quinone methide. This is shown in
Fig. 17. The diphenoxyethane still contains the hindered phenol functionality and the benzylic hydrogens; therefore, it
can act as an oxidation inhibitor.
Oxidation inhibition by arylamines, such as dialkyldiphenylamine and N-phenyl-a-naphthylamine, also involves
radical scavenging. The transfer of hydrogen from the NH
group of the amine to peroxide radicals results in the

II

3R0H

RiSR2

II

Dialkyl Sulfide

Dialkyl Sulfone

Dialkyl Sulfoxide
O
II

RlSR2

-*~

-^

H2SO4

Dialkyl Sulfoxide
2. Phenols

ROOH

ROH

3. Phosphorus C o m p o u n d s

ROOH

(Ri)3P

ROH

Trialkylphosphlne

ROOH

(RiO)3P

(R0)2P\

{Ri)3P0
Trialkylphosphlne
Oxide

ROH

(RiOJaPO

H3PO4

TrialkyI
phosphate

TrialkyI
phosphite

RC-OOH +

793

formation of the diphenylamino radical [3]. This radical is


resonance-stabilized and, hence, cannot start new chains.
However, it does react with hydroperoxides and peroxy radicals to form the nitroxy radical, which is also a very potent inhibitor. This is because it has the ability to terminate a large
number of oxidation chains through a catalytic action. The
mechanism of oxidation inhibition by diphenylamine is depicted in Fig. 17.
Transition metals can act both as oxidation promoters
and as oxidation inhibitors, depending upon their oxidation
state. They act as promoters if they facilitate the formation
of free radicals; and they act as inhibitors if they remove
free radicals from the oxidation process. For example, heavy
metals, such as iron and lead and their salts, are well known
as oxidation promoters [4,9]. Figure 18 shows how ionic
iron promotes hydroperoxide decomposition to oxidation
causing alkoxy and peroxy radicals. Metal deactivators, another class of oxidation inhibitors, are usually used to control oxidation due to metal ions. These inhibitors, extremely
effective at low concentrations, perform by forming com-

1. Sulfur C o m p o u n d s

3 ROOM + R 1 S R 2 -

AND FUELS

Zn

ROH
Alcohol

Zinc Dithiophosphate

;c=o
^Ketone

Zinc
Dithiophosphate

FIG. 14Mechanism of hydroperoxide decomposition.

794 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


//

Zn

(RO)2P^

+ 2R00-

{R0)2P\

/P(0R)2
SS

DiakyI Dithiophosphoryl Disulfide

Zinc Dithiophosphate

(RO)2P\

I!
o

/P(0R)2

Dialcyi Dithiophosplioryl Disulfide

Thiosulfenate

\
S-

2 ROOH

//

//o

^SH

II

Thiosulfonic Acid

Thiosulfenyl Radical

/o

{ R 0 ) 2 P C ^ + SO2

"^QQ"*.

On

S03(H2S04)
Oxidation-inhibiting
Species

FIG. 15Oxidation inhibition by zinc diallcyl dithiophosphate.

RO-

ROH +
^1

Arylamine

~^

ROO- +

t^;

Diphenylamino Radical

ROOH

^
R-i

R2
Arylamine

ROOH or ROO-

?
^

f^

ROH
Nitroxy Radical

^J
Resonance Stabilized/
Delocalized Radical

OH
I
N

OR
I
N

R-

P-elimination
or liydrolysis

i^
Ri

ROH + Olefin
FIG. 16Oxidation inhibition by hindered phenols.

CHAPTER

30: OXIDATION

OH

RO-

OF LUBRICANTS

AND FUELS

795

O-

f-Bu r T ^ t-Bii
II
I

t-Bu fT " ^ t-Bii

ROH +

2,6-Di-t-butyl-4methylphenol

CHj-

CH2
Quinone Methide

Benzylic Radical

HO

t-Bu

t-Bu

t-Bu

OH
t-Bu

Cn^^n2

Diphenoxyethane
FIG. 17Oxidation inhibition by arylamine.
Fe"^** + ROOH

++
Fe +

+
H + ROO

Hydroperoxide

Fe

ROOH -

Peroxy Radical

+++
Fe + OH

+ RO'
Alkoxy Radical

FIG. 18The role of metal ions in oxidation.

plexes with the metal ions and taking t h e m out of the chain
reaction. These additives have a synergistic effect with oxidation inhibitor types discussed above. Ethylenediaminetetraacetic acid derivatives, N-ScJicyhdene-ethylamine, and N,
N-disahcyhdene-1, 2-propanediamine represent the most
popular members of this class. However, their use is limited
to fuels. Other derivatives, which are used in this application, include lecithin, derivatives of heterocycles, such as
thiadiazole, imidazole, and pyrazole, and citric and gluconic
acid derivatives [10]. Figure 19 shows the structures of
some of these materials.
Copper ions promote oxidation just like other transition
metal ions. They do this by forming radicals both directly and
by delivering molecular oxygen in a more reactive state. In addition, they catalyze hydroperoxide decomposition to free radicals. Copper ions also exhibit excellent oxidation-inhibiting
ability [11]. They remove radicals by converting them into

ions, which do not have the ability to take part in the oxidation
process. Oxidation promoting and the oxidation inhibiting reactions by copper ions are presented in Fig. 20. Their oxidation-inhibiting activity is concentration dependent. They act
as inhibitors when used at low levels, i.e. at 250 p p m or below,
above which they become oxidation promoters.
In some instances, compounds that intercept oxidation by
different m e c h a n i s m s reflect synergism w h e n present together. Synergism is an effect greater than the additive effect
of the two or more compounds [12,13]. A combination of a
sulfur compound with an arylamine or a hindered phenol is
a c o m m o n way to benefit from this phenomenon.
Oxidation inhibitors are used in almost all lubricants, with
gasoline and diesel engine oils, and with automatic transmission fluids, which account for 60% of the total use. High
operating temperature and high air exposure applications
require a high level of oxidation protection. Zinc dialkyl
dithiophosphates are the primary inhibitor type, followed by
aromatic amines, sulfurized olefins, and phenols. This order
is based on effectiveness, cost considerations, and supplemental benefits.
A n u m b e r of tests are used to assess a lubricant's oxidation
stability u n d e r conditions of accelerated oxidation. A
reasonably comprehensive list of such tests is provided at the
conclusion of the chapter. Some of the tests are described in
detail in the following section.

796 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK

^CHzCOOH
CH=N-C,H=

H3C.

^ N

CH2COOH
^CHjCOOH

OH

CH2COOH

N-Salicylidene'ethylamine
Ethylenediaminetetraacetic Acid

N,N-DrsalJcyfidene-1,2propanediamine

CH,C-OH

H2C-O-C-R

HO-C-

R=C16-18

Hc-o-c;

OH
CH,C-OH

HoC-O

COOH
I
H-C-OH
HO-C-H
H-C-OH

op

II

P\
+
1^ OCH2CH2N(CH3)3

Citric Acid

HS

Lecithin

Gluconic Acid

SH

A //
N-N
Dlmercaptotliiadiazole

H-C-OH
I
CH2OH

H
N

,N
N

N
Imidazole

Pyrazole

Benzotriazole

FIG. 19Metal deactivators

Oxidation Promoting Reactions


RH + Cu**
Cu* + O2
Cu**+ROOH
Cu* + ROOH

^ Cu* + R + H *
*- Cu**(02)- + RH
-*- Cu* + R 0 2 + H *
-*- Cu** + R O + O H -

Purpose of Testing
Cu**+RO+OH-

Oxidation Inliibiting Reactions


R02- + Cu*
ROj- + Cu**
RO- + Cu*

RO2+CU**
R*+02+Cu*
RO" + Cu**

FIG. 20Role of copper ions in oxidation.

OXIDATION TESTING OF LUBRICANTS


AND FUELS
This compilation of oxidation bench tests does not claim to
address every oxidation and thermal stability test method
used in the lubricants industry. Many companies have proprietciry methods they use in-house for evaluating and assessing the performance of their additives and lubricants and
as such are not included in this chapter.

The purpose of oxidation testing is to study and evaluate the


oxidation and thermal performance of lubricant additives,
lubricant systems and fuels under simulated operating conditions in order to predict the performance of those lubricant
and fuel systems in real world applications.
There are two essential ways to test lubricant systems,
bench testing, and field testing. Bench testing studies performance of lubricants and fuels under simulated conditions
and field testing predicts lubricant performance in actual
equipment.
Because of the high costs that are often associated with field
testing, bench testing becomes the choice to study and evaluate lubricants. Bench testing can be used as a cost-effective
way to evaluate the performance of experimental or new additives and lubricant systems. It can be used to compare the
relative performance of different commercially available lubriccints, and finally it can be used to assess the remaining,
useful oxidation life of lubricants and fuels in service.
Field testing can be used to prove the performance of lubricants that have been evaluated in bench tests and have
successfully met the bench test criteria.
Description of Oxidation B e n c h Tests
A number of oxidation and thermal stability tests have been
developed by ASTM: ASTM International; IP: The Institute of

CHAPTER
Petroleum; DIN: Deutsches Institute for N o r m u r s ; ISO:
International Standards Organization, and other organizations. These tests are designed to evaluate performance of
additives and lubricant systems including industrial lubricants, greases, gear oils, engine oils, and fuels. Outlines of
these various methods and procedures follow.
Antiwear

Hydraulic,

R&O, and Turbine

Oils

ASTM D 943: Oxidation Characteristics of Iniiibited Mineral


OilsThis method was developed for and is used to determine the oxidation life of inhibited turbine oils. It is now
widely used for predicting the oxidation life of anti-wear hydraulic oils, and R&O oils, as well as turbine oils. The test is
designed to simulate the conditions found in a typical steam
turbine system. The test oil is heated in the presence of copper and iron catEilysts, which are tjrpical of the metallurgy
found in a steam turbine. Water is added to simulate steam
condensate and finally, oxygen is introduced to accelerate the
oxidation process. The degree of oxidation is determined by
an increase in the acid n u m b e r of the lubricant oil. The test
is conducted in the following mzinner:
300 mL of test oil, along with catalyst coils of copper and
steel are placed into a large glass test tube and placed into a
heated oil bath, maintained at 95C. Sixty milliliters of distilled water is introduced into the test tube. A water-cooled
condenser is used to prevent the loss of water vapor during
the test. Oxygen is bubbled through the oil sample at a rate of
3 1/h. Periodic samples of the oil are taken and the acid number is determined per ASTM D 974. The test is usually con-

30: OXIDATION

OF LUBRICANTS

AND FUELS

797

cluded when the total acid n u m b e r (TAN) reaches 2.0 mg


KOH/g. The n u m b e r of hours needed to reach 2.0 is considered to be the "oxidation lifetime" of that oil.
This test method is widely used for specification purposes,
and is considered useful in estimating the oxidation stability
of lubricants. Uninhibited oils will usually fail within 200 h,
while high quality oils can exceed 5000 h. However, it should
be recognized that the correlation between this test and actual field performance can vary markedly. Even though the
test data indicate that one oil has a n oxidation life twice as
long as another oil, this does not m e a n that the first oil will
provide twice the service life of the second oil. It is assumed
t h a t the longer the oxidation life is in the D 943 test, the
longer the lubricant will perform in the field.
Table 1 shows t5rpical results for antiwear hydraulic oils and
R&O oils when using different base oils. The additives used
were the same for each group, that is, AWH all contained the
same additives and the R&Os used another additive package.
It should be noted that the D 943 has an upper life limit of
10 000 h. Values higher than 10 000 h are considered to be
nonstandard extensions of the method (Figs. 21 and 22).

TABLE 1Typical ASTM D 943 oxidation life of various base oil


types and same additives.
AWH
R&O

Rere fined

Group I

Group II

Group III

Synthetic

2000+"
2,000+"

2500+"
8000+ "

6000+"
12 000+"

10 000+
12 000+

10 0 0 0 + "
15 000+ "

"(Hours to NNA of 2.0 mg/KOH).

I I

tOWM^K SftMMe M l

oun&ricM ciu

M * M Cki

FIG. 21Schematic drawing of ASTM D 943, Oxidation Test.

798

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK
The test apparatus consists of a pressurized vessel axially
rotating at 100 rpm, at an angle of 30 from the horizontal, in
a bath maintained at 150C (302F). Fifty grams of test oil, 5
g of distilled water, and a freshly polished copper coil are
placed into a glass liner, and inserted into the vessel. The
vessel is initieJly pressurized to 90 psi (600 kPa) at room temperature. The 150C bath temperature causes the pressure in
the vessel to increase to approximately 200 psi (1400 k Pa). As
oxidation occurs, the pressure drops, and the usual failure
point is taken at 25 psi (175 k Pa) from the maximum pressure obtained at 150C. The results are reported as the number of minutes to 25 psi (175 k Pa) loss.

FIG. 22ASTM D 943, Oxidation Test, progression of test.

TABLE 2Typical sludge and copper requirements.


Insoluble Sludge (mg.)
Total Copper (mg.)

AWH

R&O

100 max.
200 max.

100 max.

D 4310: Determination of the Sludging and Corrosion Tendencies of Inhibited Mineral OilsThis method is a modified
alternate to the ASTM D 943 test method, and is used to
determine the tendencies of inhibited mineral oils, especially
turbine oils, to form sludge during oxidation (see Table 2),
The test conditions described under ASTM D 943 are used.
After 1000 h, the test is stopped. The oil and water layers are
separated and filtered. The weight of insoluble material is determined gravimetrically by filtration of the contents of the
oxidation test tube through a 5 micron pore size filter. The
a m o u n t of copper in the oil, water, and sludge phases is also
determined according to any suitable method, such as atomic
absorption (AA), direct current plasma (DCP), inductively
coupled plasma (ICP), or x-ray fluorescence (XRF). It should
be noted that there is n o requirement for the amount of iron
present.
This method is used primarily for specification purposes. It
is widely accepted that the presence of sludge and insoluble
material is due to oxidation. Formation of oil insolubles or
metal corrosion products during this test may indicate that
oil will form insolubles or corrode metals, or both, during
field service. However, correlation with field service has not
been established.
D 2272: Oxidation Stability of Steam Turbine Oils by Rotating
Pressure Vessel (formerly Rotary Bomb)The Rotaiy Pressure
Vessel Oxidation Test (RPVOT) is a rapid method of comparing the oxidation life of lubricants in similar formulations, in
the presence of water and a copper catalyst. This method can
be used to evaluate the oxidation characteristics of turbine
oils, hydraulic oils, and transformer oils.

The RPVOT is favored as a quality control test because it is


rapid. Results are usually available within 2-5 h, as opposed
to 1000 h or more in the ASTM D 943 test. The RPVOT is not
intended as a replacement for the commonly used ASTM D
943. The RPVOT result is useful in controlling the continuity
of this property for batch-to-batch acceptance of production
lots, having the same composition. No correlation has been
established between RPVOT and ASTM D 943 methods. The
RPVOT is also useful in determining the remaining oxidation
life of in-service systems by charting the original RPVOT
value versus subsequent samples of that system. It should be
noted that the D 2272 test method is dependent on additive
chemistry. Comparisons of oils having different formulations
are of limited value.
As with the D 943, there is no established correlation between the D 2272 method and actual field service (Figs. 23
and 24).
In Service Monitoring of a Turbine Oil
Using the ASTM D 2272
(RPVOT)
Warning Limits:
Interpretation:
Action:
Warning Limits:
Interpretation:
Action:

System

Less than 50% of original value, u p to 20


000 h.
Indicates above normal degradation.
Investigate cause; Increase frequency of
testing; Consider reinhibition.
Less thzm 25% of original value.
Together with high TAN indicates oil
nearing end of its service life.
Resample, if value is the same, consider
changing oil.

IP-280: Determination of Oxidation Stability of Inhibited Mineral Turbine OilsThis method comes u n d e r the jurisdiction
of the Institute of Petroleum (IP) and is commonly used for
E u r o p e a n specifications relating to turbine oils and other
hydraulic fluids. This method is technically identical to the
CIGRE method "Turbine Oil Oxidation Stability Test."
The test apparatus consists of a suitable size test tube containing 30 g of test oil, plus copper naphthenate and iron
n a p h t h e n a t e as soluble catalysts. The sample test tube is
placed in a heated bath, 120C for 164 h. During the test period, oxygen is bubbled through the oil sample at a rate of 1.0
1/h. Both the test temperature and the oxygen flow rate must
be carefully m a i n t a i n e d t h r o u g h o u t the test period. The
volatile acids are trapped in a tube containing distilled water
and alkali blue solution. At the conclusion of the test period
the oxidized oil sample is filtered and the sludge is determined. The water in the absorption tube is titrated with alcoholic potassium hydroxide (KOH) to determine the volatile

CHAPTER 30: OXIDATION OF LUBRICANTS


QXVOCN

AND FUELS

799

C.

-624 JOIMT

;S5-2fr5 Qg WAUI-2-W

4<-5<OgWAL(.0-7-M

-OIL SAMPLE

r-J

FIG. 23Schematic drawing of D 2272, Rotary Vessel Test


(RBOT).

WSTiaEO WATER
+ INDICATOR

m^
100-200

OXIDATION TUBE

ABSORPTION TUBE

FIG. 25IP-280, Cigre Oxidation. Oxidation and absorption


tubes.

FIG. 24ASTM D 2272, Rotary Vessel Test (RBOT), rotary


vessel oxidation charts.

acids. The oxidized oil is mixed with heptane, and this solution is titrated with alcoholic KOH to determine the soluble
acids. The volatile acids, soluble acids, and the sludge are
used to calculate the "Total Oxidation Products" (TOP).
Because of the relatively short test time, this method is
sometimes used as a replacement for the longer running
ASTM D 943. However, no correlation between this test and
the D 943 exists. Formation of acids and oxidation products
during this test may indicate that the oil will form sludges
and acids that might corrode metals during field service
(Figs. 25 and 26).
IP-306: Determination of Oxidation Stability of Straight Mineral OilsThis method is designed to give an indication of
the oxidation stability of straight, unadditized, mineral oil
based lubricants under specific conditions.
This test method employs the same apparatus and a similar procedure to those used in IP-280. IP-306 differs from the
IP-280 procedure in (a) the time test time is reduced to 48 h,
(b) two conditions, namely no catalyst and solid copper catalyst, are used and (c) the degree of oxidation is expressed as
"total oxidation products" (TOP) percent.
IP-307: Determination of Oxidation Stability of Mineral Insulating OilsThis method is designed to give an indication
of the oxidation stability of insulating oils under specific
conditions. Insulating oils are nonelectric conducting oils
used in various electrical applications, for example, electric
transformers.

FIG. 26IP-280, Cigre Oxidation. Typical metal heating bath.

This test method employs the same apparatus and a similar procedure to those used in IP-280. IP-307 differs from the
IP-280 procedure in (a) the test temperature is reduced to
100C (212F), (b) a solid copper catalyst is used, and (c) the
degree of oxidation is expressed as sludge and acidity.
D 2070: Standard Test Method for Thermal Stability of Hydraulic OilsAt elevated temperatures, the long hydrocarbon chains in mineral oils may break apart into shorter

800

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

hydro-carbon chain lengths (thermal decomposition). While


some of the chains may vaporize and escape into the atmosphere, others tend to combine with other chains (pol5rmerize) to form hard, sticky byproducts known as gums, varnish,
and other deposits.
Thermal stability is a lubricant's ability to resist breakd o w n u n d e r conditions of high t e m p e r a t u r e s . The zinc
dialkyl dithiophosphates (ZDP) anti-wear agents used in the
early 1970s lacked thermal stability and would decompose
u n d e r high t e m p e r a t u r e s (approximately 135-140C) a n d
form acids of phosphorus and sulfur. These acids would then
attack the yellow metals, copper, bronze, and brass that were
commonly used in hydraulic systems. Of particular sensitivity were the bronze piston shoes, used in piston p u m p s . The
lack of thermal stability of these ZDPs led to the premature
failure of many piston p u m p s because of corrosion problems.
Cincinnati Machine (formerly Cincinnati Milacron), a
leading manufacturer of machine tools, originally developed
this test method to assess the thermal stability of the zinc dialkyl dithiophosphates containing oils that were being used
in their equipment. The motivation behind this test was the
high cost of warranty claims this manufacturer experienced.
The test apparatus consists of a beaker, a copper and steel
test rod, and an electric convection oven capable of maintaining 135C (275F) for 168 h. The copper and steel test rods are
polished, weighed, and placed into a beeiker of test oil. The
rods are arranged in an "X" pattern with a single contact
point. The assembled apparatus is placed in the test oven. This
method does not involve the use of air or oxygen blowing, nor
is any agitation involved. At the end of the test period, the test
rods are compared to a reference chart to determine the degree of chemical attack. Ideally, the rods should show little evidence of any discoloration. The oil is evaluated to determine
any changes in viscosity, to measure ciny increase in acid n u m ber, and to determine the amount of sludging.
This method is widely used for approval purposes and is
useful in evaluating the thermal stability of lubricants. It is
used primarily for hydraulic oils, but it can also be used to
evaluate other industrial fluids. A lower temperature is used
to evaluate industrial gear oils. This ASTM method differs
from the Cincinnati Machine version as follows: Cincinnati
requires a potassium cyanide (KCN) wash of the test rods in
order to determine metal weight loss. Because of the hazards
related to the use of potassium cyanide, ASTM does not endorse this step. See Cincinnati Machine test method 'Procedure A,' 'Procedure B' (see Figs. 27 and 28).
D 4636: Standard Test Method for Corrosiveness and Oxidation
Stability of Hydraulic Oils, Aircraft Turbine Engine Lubricants,
and Other Highly Refined OilsThis method is the result of
combining Federal test methods 5307.2 and 5308.7. Currently, this method is of interest primarily to the military who
use it to determine the resistance to oxidation and corrosion
tendencies of hydraulic oils, aircraft turbine engine lubricants, and other highly refined oils used in military aircraft
and equipment. This method is no longer a mandatory requirement for any major steam turbine manufacturer.
The test method can b ^ used to evaluate mineral oils as
well as synthetic fluids. It Ccin be r u n using dry or moist air,
as well as with or without the metal test specimens.
There are two basic versions of this test method. Procedure
1 uses "washer" type metal specimens, which include

Acceptable

Unacceptable

FIG. 27ASTM D 2070, Thermal Stability Test. Results,


Cincinnati Procedure A.
- 1

Unacceptable

Acceptable

FIG. 28ASTM D 2070, Thermal Stability Test. Results,


Cincinnati Procedure A.
titanium, magnesium, steel, bronze, silver, and aluminum.
Procedure 2 uses "square-shaped" metal specimens, which
include copper, steel, aluminum, magnesium, and cadmium.
The test is conducted in the following manner:
The specified a m o u n t of test oil, 100 m L or 200 mL, is
placed into a large test t u b e along with the polished and
weighed test specimens. The assembled apparatus is weighed
and placed into the constant temperature bath. Test temperature can range from 100C (212F) to 360C (680F), for a
specified amount of time. At the end of the test period the
tube assembly is removed from the bath Euid the meted specimens are reweighed to determine weight loss, which is an indication of the oil's corrosiveness. The final viscosity and
TAN of the oil is determined. Any sludge remaining in the test
tube is determined gravimetrically.
This method simulates the environment encountered by
fully formulated lubricants in actual service, and uses an accelerated oxidation rate to permit measurable results in a
timely manner. Interpretation of results should be done by
comparison with data from oils of known field performance
(see Fig. 29).

CHAPTER 30: OXIDATION OF LUBRICANTS

(0.2Acm)

AND FUELS

801

DRILL 2 HOLES
j ^ WAMETER
(0.16cin)

MAGNESIUM
STEEL

ALUMINUM
CADMIUM
COPPER
FIG. 29ASTM D 4636, Oxidation of Hydraulic Fluids. Metal
square dimensions and arrangement.

D 5846: Universal Oxidation Test for Hydraulic Fluids and


Turbine OilsThis test method was developed to evaluate the
oxidation stability of petroleum base, rust, and oxidation inhibited hydraulic oils, antiwear hydraulic oils, and oils for
steam and gas turbine.
This test method covers a procedure for evaluating the oxidation stability of inhibited mineral oils in the presence of air,
copper and iron metals, and utilizes the Universal Oxidation
test apparatus. The test is conducted in the following manner:
One hundred grams of the test oil is weighed into the test
cell, along with freshly polished coils of copper and iron
wire. The assembled test cell is placed into a heated block
capable of maintaining the test oil at a temperature of
135C (275F). Air is bubbled through the test oil at a rate
of 3 1/h. The acid number and spot forming tendencies of
the oil are measured daily. The oil is considered to oxidize
or degrade when either the acid number has increased by
0.5 mg KOH/g over the fresh oil, or when the oils begin to
form insoluble solids so that when a drop of oil is placed
onto filter paper it shows a clearly defined dark spot surrounded by a ring of clear oil.
Degradation of hydraulic fluids and turbine oils caused by
oxidation and thermal breakdown can result in the formation
of acids or insoluble solids, and render the oil unfit for further use (see Figs. 30 and 31).
D 6514: High Temperature Universal Oxidation Test for Turbine OilsThis test method is designed to compliment test
method D 5846 and is intended for evaluation of fluids that
do not degrade significantly within a reasonable period of
time at 135C. This test uses the universal oxidation test
equipment and was developed for, and is used to evaluate the
high temperature oxidation stability and deposit forming
tendencies of oils for steam and gas turbines. A summary of
the test method is as follows:
One hundred grams of test oil is weighed into the test cell
along with freshly polished coils of copper and iron wire. The

FIG. 30D 5846, Universal Oxidation Test. Test apparatus.

FIG. 31D 5846, Universal Oxidation Test. Universal Oxidation


glassware.

assembled test cell is placed into a heated block capable of


maintaining the test oil at a temperature of 155C (310F). Air
is bubbled through the test oil at a rate of 3 1/h for 96 h. At the
end of the oxidation time, the sample is cooled and the oil is
filtered through a preweighed No. 41 Whatman filter and a
preweighed 8 micron filter membrane and reweighed. Total
weight of insoluble material, change in acid number, percent
increase in viscosity at 40C, and the veirnish adhering to the
test cell is reported.

802 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Degradation of fluid lubricants because of oxidation or


thermal breakdown can result in fluid thickening or in the
formation of acids or insoluble acids and render the fluid unfit for further use as a lubricant.
DIN 51352: Pneurop OxidationThis test method is designed
to evaluate the oxidation stability of compressor oils, and is
used to qualify compressor oils in European manufactured
equipment. The test is conducted in the following manner:
Soluble ferric (III) oxide is used as a catalyst and is measured into the glass test tube. Forty mL of test oil is then measured into the tube. The assembled apparatus is placed in an
oil bath at 200C (392F), and air is bubbled through the oil
mixture at a rate of 15 1/h. The test is conducted for 24 h. At
the end of the test period, the apparatus is allowed to cool
and reweighed to determine any evaporation loss. The oxidized oil is then submitted for determination of carbon
residue using either the Conradson Carbon Method ASTM D
189, or the Ramsbottom Carbon Method ASTM D 524.
The amount of carbon residue formed in the oxidized oil is
used to predict field performance. The carbon residue should
not exceed 2.5% for and ISO 46 oil (see Fig. 32).

CSimensions in m m

Vent lube

Insert

NS 29/32
conical ground
joint
a$ specified
in DIM 122^2
Part I

Ageing vessel

Gear Oils
D 2893: Oxidation Characteristics of Extreme Pressure Lubricating OilsThis test was developed to measure the high
temperature oxidation stability of industrial gear oils. It is
important to note that D 2893 was designed to run at 95C.
However, to meet the requirements of U.S. Steel requirement, #224, and AGMA 9005 (American Gear Manufactures
Association), the temperature is elevated to 121C (250F).
The other test conditions remain unchanged.
The test method is designed to measure resistance to oxidation by determining the change in viscosity.
In this test, the same glassware required by the D 943 T.O.
Oxidation test is used. Three hundred milliliters of the test lubricant is measured into the tube. The glass inlet tube from D
943 is used to introduce the air into the test lubricant. The entire assembly is placed in an oil bath at 95C, (121C for the
USX S-200 procedure (U.S. Steel)). Dry air is bubbled
through the sample at 10 1/h for a period of 312 h. At the end
of the test the final viscosity and precipitation number are determined. The appearance of the test tube and oil may be inspected for evidence of oxidation.
Qualifying industrial gear oils give 0-6% viscosity increase
in test. Though unspecified, cleanliness of the glassware is
very important for today's industrial gear oils. It is felt that
glassware cleanliness is an indication of the lubricant's thermal stability (see Figs. 33 and 34).
D 5763: Oxidation and Thermal Stability Characteristics of
Gear Oils Using Universal GlasswareThis test method is a
modification of D 2893. Of significant value is the determination of sludge in this method, which is not done in D 2893.
This method can be used to evaluate both extreme pressure
and nonextreme pressure gear oils.
This test method is run using universal glassware apparatus. A 100 g sample of gear oil is weighed into the test tube.
The test assembly is placed in a heated bath at 120C for 312
h. Dry air is bubbled through the sample at a rate of 3 1/h. At
the end of the test period the apparatus is cooled to room
temperature and reweighed to determine any oil loss. The

Ring mark
at 4 0 ml

*25,S--o.s

FIG. 32DIN 51352, Pneurop Oxidation. Test apparatus for determining the aging characteristics of
lubricating oils.

oxidized oil is filtered through at 2.8 micron filter. Any sludge


adhering to the glassware is rinsed down and filtered through
the filter. The total sludge is then determined. Kinematic viscosity is determined on the filtered oil and the percent
change in viscosity is reported.
This is the only test method that employs glassware to
measure the amount of sludge produced during oxidation
and thermal degradation of industrial gear oils. Sludge build
up from oxidation and thermal degradation can render the
oil unsuitable for further use as a lubricant. The correlation
between this test and actual field performance is unknown.
D 5704: Evaluation of the Thermal and Oxidative Stability of
Lubricating Oils Used for Manual Transmissions and Final
Drive AxlesThis test method is commonly referred to as the
L-60-1 test. It measures the oil-thickening, insolublesformation, and deposit formation characteristics of automotive manual transmissions and final drive axle lubricating
oils when subjected to high temperature oxidizing conditions.

CHAPTER 30: OXIDATION OF LUBRICANTS

AND FUELS

803

Thermometer

Flowmeter
Measures Air
Liters per Hour

Air Inlet

FIG. 33ASTM D 2893, Gear Oil Oxidation. Apparatus schematic.

KJ

Thermally
Stable Oil

i fi
Borderline
Thermally
Stable Oil

Non-Thermally
Stable Oil

FIG. 34ASTM D 2893, Gear Oil Oxidation. Examples of typical results.

A 120 mL sample of the lubricant to be evaluated is placed


in a heated gear case containing two spur gears, a test bearing, and a copper catalyst. The lubricant is heated to a temperature of 163C (325F) and the gears are operated at 175
rpm for 50 h at a predetermined load of 128W, which is provided by an automotive alternator. Air is bubbled through the
lubricant at a rate of 1.11/h. Upon completion of the 50-hour
test period, the oil is evaluated for change in viscosity and the
presence or amount of insoluble materials. The test gears are
evaluated and rated for their cleanliness. The copper catalyst
is weighed and any weight change of the copper is reported
(see Figs. 35 and 36).
JIS-K2514: Oxidation Stability of Automotive Gear OilsThis
test method is a part of the Japanese standard JASO M33991, and is basically identical to the Indiana Stirrer Oxidation
Test (ISOT).
Because of the trend of increasing operating temperatures
encountered during normal service, geeir oils having superior
oxidation stability are required to meet the demands of GL-3
and GL-5 performance. The test is outlined as follows:

FIG. 35ASTM D 5704 (L-60-1), Gear Oil Test. Test stand.

Mineral

Mineral

Mineral

Mineral

o
o
o
O O C#

o o o o
Minimum

Standard

Premium

Top Tier

FIG. 36ASTM D 5704 L-60, Gear Oil Test. Thermal stability


of industrial gear oils.

804 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


Polished steel and copper catalysts are placed in the bottom
of a suitable sized beaker (see Table 3). Two hundred and fifty
mL of test gear oil is measured into the beaker. A phenolic
resin cover, with holes provided to allow a glass varnish rod,
and a glass stirrer to be immersed in the test lubricant is
placed on the beaker. The assembled apparatus is placed in a
heated bath capable of maintaining the test lubricant at a temperature of 150C (302F) for 96 h. Air is drawn and mixed into
the test lubricant through the vortex generated by the stirrer.
At the end of the test period the oxidized lubricant is evaluated
for change in viscosity increase, acid n u m b e r (AN) and the
amount of pentane in solubles. The glass varnish rod is inspected for lacquer deposits.
This method is primarily used for specification purposes,
and shall be applied to gear oils designed to meet GL-3 to GL5 as specified by API service classification, which are used for
manual transmission gears and final reduction gears in passenger cars, trucks, and buses.
CEC-L-48-08: Test Method for Oxidation Stability of Lubricating Oils Used in Automotive Transmissions to Artificial Aging
(DKA Method)This
m e t h o d indicates the tendency of
transmission lubricants to deteriorate by oxidation u n d e r
specified conditions. The methods apply to fully formulated
transmission lubricants, ATF, and gear oils. The tests are
conducted in the following m a n n e r (see Table 3):
Apparatus AThree hundred mL of test fluid is measured
into a preweighed, suitably sized Erlenmyer flask. A glass
air delivery tube is placed into the test oil and is connected
to an airflow meter. The assembled apparatus is then placed
into a heated bath, maintained at 150C (302F) during the
test duration. Airflow is adjusted and maintained at 10 1/h.
After 192 h the test is ended, the flask is removed from the
heated bath, and the test fluid is measured for % change in
viscosity, heptane insolubles, and change in AN. Sludge is
determined and carbon/varnish deposits on the Erlenmyer
flask are noted. (See Table 4 for test limits.)
Apparatus BOne hundred mL of test fluid is measured
into a suitably sized glass test tube. The test tube is fitted
with a water cooled condenser, a n d a glass air delivery
tube. The assembly is placed into a heated bath and the
temperature of the test fluid is maintained at 160C for the
duration of the test. The air flow is adjusted and maintained at 5.01/h. After 192 h, the test is ended, the glass test

tube is removed from the heated b a t h and the test fluid is


measured for % change in viscosity, for change in AN, and
sludging is determined by using a blotter spot test (see
Table 4 for limits and Table 5 for oxidation stability of test
fluids) (Figs. 3 7 ^ 0 ) .
Grease
D 942: Oxidation Stability of Lubricating Greases by the Oxygen
Vessel MethodThe D 942 Vessel Oxidation Stability Test was
specifically developed to evaluate the oxidation stability of lubricating greases when stored under static conditions for extended periods of time. This test is included in most of the industrial and automotive grease specifications.
The test is performed by subjecting a sample of grease to
pure oxygen under a pressure of 110 psi (758 kPa) at 99C
(210F) for 100 h or longer. The degree of oxidation is then
related to the amount of oxygen reacted and is determined by
pressure decrease. The pressure is recorded every 24 h over
the duration of the test.
ASTM D 942 Grease Vessel
Aluminum Complex Grease + Additive
Additive
A

Psi loss
@ 100 hours

Additive
B
C

10.0

Additive

Additive
D

No
Additive

1.8

1.9

14.2

0.6

Base Grease (No Additive)


Grease
Type

Aluminum
Complex

Calcium
Complex

Lithium

Lithium
Complex

Psi loss
@ 100 h o u r s

14.2

2.6

1.4

3.6

TABLE 4Equivalence and differences between the results with


Apparatus A and Apparatus B.
Viscous Oils ( > 0 mm^/s at 100C)
Low Viscosity
Oils, ATFs
(<mm^/s at 100C)

s i SOX
160C
170C

Equivalent
A more severe
thanB
Only B is
evaluated

Current Type
E x : R L 181

High Temperature
Resistant Gear Box
OilEx:RL 184

Equivalent
B more severe
than A

Equivalent
Equivalent

TABLE 3Gear oil oxidation test comparison.


L-60-1

Test Apparatus
Duration, h
Temperature, (C)
Oil Volume (1)
Air Flow, (1/h)
Agitation
Metal Catalysts
Air/Oil Volume Ratio

Steel Case
50
163
0.12
1.1
Gears at 1725 min~*
Iron and Copper
458

Viscosity A%
A AN
Insolubles
Carbon/Varnish
Sludge
Blotter Test

100% max

CEC
L-48-08 (DKA)

Glass Tube
192
160
0.1
5.0
Air
None
9600
Evaluation Criteria
< 2 cSt.
<2.0 cSt. mg KOH/gm

2% max.
7.5 large gear
9.4
100% (no sludge)

ISOT
JIS-K2514

Glass Beaker
96
135
0.25
None
Impeller at 1300 m i n . " '
Iron and Copper

CHAPTER 30: OXIDATION OF LUBRICANTS AND FUELS 805


TABLE 5Oxidation stability of the test fluids.
CAT-1
CAT-2
PAT-1

IT-1

Fluids
DKA Oxidation
Test (192 h, 170C)
AN Increase
% Viscosity
Increase at 40C
% Viscosity
Increase at 100C
Tube Rating
Blotter Spot Rating

Industrial
Traction
Fluid

Commercial
Automotive
Traction
Fluid 1

PAT-2

PAT-3

PAT-4

Commercial
Automotive
Traction
Fluid 2

Prototype
Automotive
Traction
Fluid 1

Prototype
Automotive
Traction
Fluid 2

Prototype
Automotive
Traction
Fluid 3

Prototype
Automotive
Traction
Fluid 4

4.0
10.5

1.1
7.2

7.6
53.4

0.9
10.6

1.3
13.7

0.7
8.8

0.2
5.0

4.7

3.4

26.2

5.9

4.8

0.2

1.3

light
100

light
100

light
100

light
100

light
100

light
100

heavy
48.5

04.2.1
04.2.2
04.2.3
04.2.5
04.2.10

Special Erlenmeyer
Oil bath
Flowmeter enabling to control 101/h + 0.5 1/h
Clean and dry air supply
Silicone hosepipe

\\\\\\\\v\\\\A\\\\\\\\\^:\T
FIG. 37CEC L-48-08, Gear Oil Oxidation. Sample storage container.

806 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Afe^^'^
^ ^ . . : i ^ ^

te:iJ
Aspects

Aspect 2

Aspect 1

Several factors, including type and quantity of the oxidation inhibitor, influence the performance of a grease in this
test. Most grease specifications require no more than a 5 psi
loss after 100 h, or 10 psi after 500 h (see Figs. 41 and 42).
D 5483: Oxidation Induction Time of Lubricating Greases by
Pressure Differential Scanning Calorimetry (PDSC)This
method covers the determination of oxidation induction time
of lubricating greases subjected to oxygen at 500 psig (3.45
mPa) and temperatures between 155C (SITF) and 210C
(410F). Oxidation Induction Time (OIT) is the period of time
from the first exposure to an oxidizing atmosphere until the
extrapolated onset time.
A small quantity of grease is weighed into a sample pan and
placed in a test cell. The cell is heated to a specified temperature and then pressurized with oxygen. The cell is held at a
regulated temperature and pressure until an exothermic reaction occurs. The extrapolated onset time is measured and

FIG. 38CEC L-48-08 Gear Oil Oxidation. Apparatus


or glassware for Part A.

Dimensions in mm
Air inlet tube

DIN 1 2 2 4 2 - V 2 9 / 3 2
conical ground joint

Air outlet tube

DIIM 1 2 2 1 5 - D 1 1 adapter

DIN 1 2 2 1 5 - D T I adapter

FIG. 40CEC L-48-08 Gear Oil Oxidation. Assembled apparatus for Part B.

-DIN 1 2 2 4 2 - V 2 9 / 3 2
conical ground joint

Lead Gasket

0 = diameter

Oxygen Atmosphere
s

Supplier
0'i

W.O. Schmidt OHG


Eschenbunjstr. 7
33106 Bnaunschweig
Tel.: 0531-331572
Fax: 0531-338032

FIG. 39CEC L-48-08 Gear Oil Oxidation. Dimensions of glassware for Part B.

Grease
Sample

Oxygen Bomb
Oil Bath
210F-rF
FIG. 41ASTM D 942, Grease Vessel Oxidation. Oxygen
vessel apparatus.

CHAPTER 30: OXIDATION OF LUBRICANTS AND FUELS

FIG. 42ASTM D 942, Grease Bomb Oxidation. Test


end.

reported as the oxidation induction time for the grease under


the specified test temperature.
Oxidation induction time can be used as an indication of
the oxidation stabiHty. This method is used for research and
development, q u a h t y control, a n d specification purposes.
However, no correlation has been determined between the
results of this method and actual service performance (see
Fig. 43fl and b).
Evaluating the Oxidation Stability of Greases Using the Penn
State Micro-Oxidation Test Apparatus (PSMO)This method
is not an ASTM standard; it is under consideration within an
ASTM technical committee, but has not received all of the approvals required to become an ASTM standard.
This method is a modification of the Penn State MicroOxidation Test designed to evaluate heavy-duty diesel lubricants. The PSMO test is of interest because of the micro-sized
sample used for the test evaluation and the relatively short
time required to perform the oxidation test.
Using the PSMO apparatus, a 100 mg sample of test grease
is oxidized at the following temperatures and time periods; 6
h at 150C (302F), 3 h at 160C (320F), or 1.5 h at 170C
(338F). The grease sample is blown with air during the test
period to accelerate the oxidation. At the end of the oxidation
period the oxidized grease sample is reweighed and the weight
loss of the grease is determined. This weight loss is related to
the oxidative volatiles lost during oxidation. The oxidized
grease sample is solubilized in hexane or tetrahydrofuran
(THF) and is subjected to analysis by GPC to determine the
molecular weight distribution of the oxidation byproducts.
The formation of the polymeric byproducts is an indication of
the oxidation stability of the test grease.
This method is a useful bench test for studying the thermooxidative stability of greases. The PMSO test, when coupled
with GPC, a chromatographic test m e t h o d that separates
molecules based on molecular weight, is useful for studying
high molecular weight product formation that leads to increased viscosity during oxidation.
D 3527: Life Performance of Automotive
Wheel Bearing
GreaseThis test method covers a laboratory procedure for
evaluating the high t e m p e r a t u r e life, (oxidation stability)

807

performance of wheel bearing greases. A summary of the test


method follows:
A 5-gram sample of test grease is distributed in the bearings of a modified, automobile front wheel hub-spindlebearings assembly. While the bearings are thrust-loaded to
11 IN, the hub is rotated at 1000 rpm and the spindle temperature maintained at 160C (320F) for 20 h, 4 h off operating cycle. The test is terminated when grease deterioration
(oxidation) causes the drive motor torque to exceed a calculated motor cut off value. The grease life is expressed as accumulated on-cycle hours, or hours to failure.
This method differentiates among wheel bearing greases
having distinctly different high temperature (oxidation) characteristics. It is not equivalent of long-time service tests nor
is it intended to distinguish between the products having similar high temperature performance properties.
This test method has proven helpful in screening greases
with respect to life performance for automotive wheel bearing applications (see Fig. 44).
Engine

Oils

D 4742: Thin Film Oxygen Uptake Test


(TFOUT)This
method evaluates the oxidation stability of engine oils for

Thermal Analyzer
PDSC
Cell

rc^
0

4>*\A I 8 B

Flowmeter

mm

0000000 i
00000001

ill

ooooooo j

>-/

' r '. %^''m^

'fgJMvDSC
Oxygen
Cylinder
FIG. 43aASTM D 5483, Grease Oxidation by PDSC. Test
unit.

200

Typical PDSC Thermal

180
120
80
40

Sample: Grease A
Size: 2.00 mg
Temperature: 210C
Oxygen Flow: 100 mUminutes
Induction Time: 42.4 minutes

EXO

ENDO
42.4

-40

209.8C

-80 J
0.0 4.0 8.0 12.0 16.0 20.0 24.0 28.0 32.0 38.0 40.0 44.0
Time (min)
FIG. 43bASTM D 5483, Grease Oxidation by PDSC. Onset
temperature.

808

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

Wheel Bearing Lubricant Tester (Elevation View)

tdclfontc pick up

Inboard 8arlng

LM&704e Cone
LM&7CI0 Cup

OulboTd Baannq-

LM11949 Cone
LMII9I0 Cup

FIG. 44ASTM D 3527, Wheel Bearing Life. Test apparatus.

gasoline automotive engines. This test is run at 160C (320F)


and utilizes a high-pressure reactor pressurized with oxygen,
along with a soluble metal catalyst package, a fuel catalyst,
and water. These conditions partially simulate the environment to which an oil may be subjected in a gasoline combustion engine.
The test oil is mixed with an oxidized/nitrated fuel component; a mixture of soluble metal naphthenates (lead, copper,
iron, manganese and tin naphthenates), and distilled water.
The oil mixture is placed into an oxidation vessel charged
with oxygen to a pressure of 620 kPa (90 psig). The assembled
pressure reactor is placed in an oil bath held at 1608C, and is
rotated axially at a speed of 100 rpm. A thin film of oil is
formed within the glass container by vessel rotation, result-

ing in effective oil-oxygen contact. The test is terminated


when a rapid decrease of the reactor pressure is observed.
The time when the pressure begins to decrease rapidly is
called the Oxygen Induction Time, and is used as a measure
of the oil's oxidation stability.
This method is used to evaluate oxidation stability of
lubricating base oils with additives in the presence of
chemistries similar to those found in gasoline engine service.
This test does not constitute a substitute for engine testing,
which measures wear, oxidation stability, volatility, and deposit control characteristics of engine oil lubricants (see Figs.
45 and 46).
Thermo Oxidation Engine Oil Simulation Test (TEOST)
(MHT-4 Protocol)This method is not an ASTM standard; it

CHAPTER
is under consideration within an ASTM technical committee,
but has not received all of the approvals required to become
an ASTM standard.
Savant Laboratories originally developed this test in the
1980s. In 1989, Savant, with cooperation of the Chrysler Corporation, developed a procedure that correlated with turbocharger deposits. The e q u i p m e n t b e c a m e k n o w n as the
Chrysler/Tannas TEOST apparatus.
This test method describes the general oxidation and depositforming characteristics of engine oils at moderately high temperatures (MHT) of 285C, using the TEOST apparatus.
Using a TEOST test apparatus, a 10-gram sample of the engine oil containing an organo-metallic catalyst (lead, iron,
manganese, tin and copper naphthenates) is forced to flow
past a tarred, wire-wound depositor rod held in a glass mantled casing. The rod is resistively heated to obtain a constant

30: OXIDATION

OF LUBRICANTS

Drive Unit

FIG. 45ASTM D 4742, Thin Film Oxygen Uptake Test (TFOUT). Test apparatus.

To Pressure
Recorder
Ctosure

0.64 cm

^'-^"^ ti
Sample Container

O-Ring Seal
TFE Cover
Sample Container

Aluminum Insert

7.46 cm

6.03 cm Diameter
Aluminum Insert

809

temperature of 285C (545F) for 24 h. During this time, dry


air is forced to flow through the mantle chamber at a specific
rate of 10 mL/minute. At the end of the test, the depositor rod
and the components of the chamber are carefully rinsed of oil
residue using a volatile hydrocarbon solvent. After drying the
rod, the mass of the deposits is determined. The hydrocarbon
solvent rinse is filtered and weighed, and the mass of the accumulated filter deposits is determined. The mass of deposits
on the rod plus the mass of deposits on the filter is the total
deposit mass. The mass of deposits that have accumulated on
the inside surface of the mantle are also weighed.
The maximum deposit requirements for this method Eire:
ILSAC GF-2/Factor Fill = 60 mg; Chrysler Service Fill Only =
30 mg; API SJ = 60 mg.
Table 6 shows typical test results for six oils, plus additional GF-3 prototype, used in round robin testing.

Bomb Stem

AND FUELS

(Bomb I.D. Is 6.03 cm)

FIG. 46ASTIM D 4742, Thin Film Oxygen Uptal<e Test (TFOUT). Assembled
vessel, aluminum insert, and glass sample container.

810

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 6Relative oxidative stability of various


biodegradable fluids.
Formulation
1) Sunflower oil
(no additive)
2) Rapeseed oil
(no additive)
3) Trioleate ester
(no additive)
4) Sunflower oil +
additive
5) Rapeseed oil +
additive
6) Sunflower +
ester (70/30) +
additive
7) Rapeseed +
ester (70/30) +
additive

Orig cSt
at 40C

Final cSt
at 40"'C

% Vis increase

39.6

56.2

41.9

33.3

63.1

89.5

46.5

79.6

71.2

39.3

40.7

3.5

33.4

38.7

15.8

46.1

46.8

1.5

41.5

42.0

1.2

Average percent viscosity increase indicates that degree of


viscosity change does not correlate with level of deposits
formed.
This method is designed to predict the moderately high
temperature deposit forming tendencies of engine oils, especially in the piston ring belt area (see Fig. 47).
D 6335: Determination
of High Temperature Deposits by
Thermo-Oxidation Engine Oil Simulation Test (TEOST)This
method covers the procedure to determine the amount of deposits formed by automotive engine oils at high temperatures
(480 C) utilizing the thermo-oxidation engine oil simulation
test (TEOST).
A sample of the engine oil that contains ferric naphthenate
is heated to a temperature of 100C (212F). The mixture is in
contact with nitrous oxide and moist air, and is pumped at a
set flow rate past a tcirred depositor rod. The nitrous oxide
simulates the byproducts of combustion Eind acts as a precursor to oxidation. The rod is resistively heated through
twelve, 9.5 m i n t e m p e r a t u r e cycles t h a t go from 200C
(392F) to 480C (896F). When the twelve-cycle program is
complete, the depositor rod is rinsed with hexane to remove
the oil residue, dried, and the gross rod mass is obtained. The
oil sample is flushed from the system and filtered through a
tcirred polypropylene filter. The mass deposits on the rod,
plus the mass deposits on the filter, are reported as the total
deposit mass.
The test method is designed to predict the high temperature deposit forming tendencies of an engine oil, particularly
in the piston/bare areas. This method can be used to screen
engine oil samples or as a quality assurance tool (see Fig. 48a
and b).
Ford, Mercon V; Aluminum Beaker Oxidation Test (ABOT)
Since 1987, the Aluminum Beaker Oxidation Test (ABOT)
has replaced full transmission testing (i.e., the Mercomatic
Transmission Oxidation Test) needed for Ford Mercon
product approval.
This procedure is used to determine the oxidative stability
of automatic transmission fluids (ATFs) in a thermal, shear,
and air stressed environment typical of an automatic transmission. The ABOT evaluates the oxidative stability of a n
ATF in the presence of some of the materials currently used

in the construction of automatic tremsmissions. The test is


conducted as follows:
Air is introduced into the sample at a flow rate of 5
mL/min. The sample fluid is held at a specific temperature,
155C (310F), for a specified time of 300 h. To assure intimate mixing of the air and sample fluid, the air is introduced
directly into a rotating gear p u m p immersed in the oil. This
gear p u m p also serves to circulate the oil at approximately 5
mL/min and also subjecting the test fluid to a shearing action. A clccin, freshly etched aluminum beaker is used as the
oxidation vessel. This beaker is equipped with a cover from
which test strips of veirious metals, copper, aluminum, and
steel, for example, can be suspended into the fluid and then
withdrawn after different lengths of exposure (see Table 7).
Deterioration of the fluid during the test is determined by
analysis of aliquot samples withdrawn periodically and by
examination of the test strips a n d beaker components for
deposits.
For ATFs a copper strip is withdrawn and rated for corrosion at specified times during the test, and re-inserted for the
duration of the test. An aluminum strip is rated for varnish
deposits at the end of the test. Also at the end of the test, the
beaker is disassembled and the top surface of the p u m p housing is rated for sludge deposits.
The control of this test is dependent upon control of the
test variables, motor rpm, temperature, airflow rate, and others that have been determined to affect the precision of the
test results (see Figs. 49 and 50).
Caterpillar Micro-Oxidation Test (CMOT)This method describes an experimental procedure to measure the thermal
and oxidative stability of fully formulated diesel engine oils.
Caterpillar indicates that this test method shows good correlation to performance in Caterpillar 3600 series engines. The
results generated give an Induction Time of Percent Insoluble deposits versus time.
A small sample of the oil to be evaluated (0.02g) is
placed on a polished metal coupon and is held at a temperature of 230C (446F) for a m i n i m u m of 40 min in a special
glass test cell while being air blown at a rate of 20 mL/min.

FIG. 47Thermal Oxidation Engine Oil Simulation Test (TEOST). Chrysler/Tannas apparatus.

CHAPTER 30: OXIDATION OF LUBRICANTS AND FUELS 811

Gas
Outlet
ControIUnj
Tharmocaupla L

N,0-

Oil now Path

Vdve

ThrTnocoupls

P0I-I11.S<S

(a)
FIG. 48a) Thermal Oxidation Engine Oil Simulation Test (TEOST). Configuration of TEOST
layout for Test Protocol #33; b) Depositor rod ratings.

Eight test cells are used concurrently and the test is a representation of insoluble development in 10-minute intervals;
i.e., 40, 50, 60, 70, 80, 90, 100, and 110 min. If the induction
time is not reached in the first test series, a second series
stcirting at 80 min and continuing u p to 150 min is conducted. The air blowing is continued for a one-minute mini m u m after completion of the test period. The test coupon
is rinsed in tetrahydrofuran (THF) and the total weight gain
of coupon plus the weight of the THF insolubles is converted to a percentage of the initial sample weight versus
the test time and are plotted to determine the sample induction time.
The results of the CMOT have been correlated to piston
deposit levels measured on Caterpilleir oil evaluation tests.
Engine oils having an induction time less than 90 min have
generally produced excessive levels of piston deposits in laboratory test engines and in actual field operations.
The CMOT is only one part of the oil selection criteria. A
high.CMOT induction time does not assure adequate oil performance in the 3600 series diesel engine. Caterpillar will
only recognize CMOT results from tests performed at certified laboratories. Presently only Caterpillar offers this service^ (see Figs. 51a and b and 52a and b)
BT-10: International Harvester Oxidation
CorrosionInternational Harvester developed this m e t h o d during the early

^ To obtain this Caterpillar approval, fluids must be submitted to:


Caterpillar Inc., Anal3^ical Chemistry Laboratory, Component Development, Division 876, Technical Center, Bldg. E, Peoria, IL 616561875, Ph: 309-578-4858, Fax: 309-578-4496.

1960s. This method is used to evaluate the oxidation stability


of lubricants and their corrosive attack on metals. The test is
conducted as follows:
Polished and weighed metal strips of steel and bronze are
suspended in the sample lubricant at temperatures of 121C
(250F), for either 100 h (Version A) or 190 h (Version B).
Oxygen is bubbled through the sample lubricant at a flow
rate of 50 mL/min. After the specified test period, each metal
strip is eveJuated by determining the weight loss of the test
strip, and the weight of residue on the test strip. The test lubricant is submitted for elemental analysis by inductively
coupled plasma (ICP). The oxidation tube is edlowed to drain
for 24 h, after which time a visual inspection is made to rate
the sludge build-up remaining in the oxidation tube.
Gasolines

and

Fuels

D 381: Existent Gums in Fuels by Jet EvaporationThis test


method covers the determination of the existent gum content
of aviation fuels, the g u m content of m o t o r gasolines, or
other volatile distillates in their finished forms, and at the
time of the test.
The gums that occur in gasolines and fuels are varnish like
oxidation products formed in the gasoline/fuel during the
conditions of the test. The test is conducted in the following
manner:
50 mL of test sample is measured into a clean, weighed
glass beaker cind placed into a heated evaporation bath maintained at 162C (325F). Dry steam heated to 232-246C
(450-475F) is introduced into the sample at a rate of 1000
mL/s for 30 min. At the end of the evaporation time, the

812 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK

TEOST MHT4-GF3
NEW

'

.'

' . ' ' .

VERY GOOD

PASS

BORDERLINE PASS

FAIL

TEOST D6335-GF2
NEW

VERY GOOD

PASS

BORDERLINE PASS

lUK^l

FAIL
(b)
FIG. 16(Continued)

CHAPTER

30: OXIDATION

OF LUBRICANTS

AND FUELS

813

TABLE 7TEOST MHT-4 total deposits.


TEOST
W t/M g

33 R e f e r e n c e O i l

T E O S T 33
W t/M g

-TotalDeposits

80 -

60
40
20

CRO-l

m
CRO-2

CRO-3

CRO-4

hn
o

^ ^

^^

^^
N O IR O N
WITH

IRON

Races and
Bearing
Set Screw

Shaft
Bearing

Pump Housing
Teflon
Gasl<et

Cu and Pb
Plates

FIG. 49Aluminum Beaker Oxidation Test (ABOT). Assembly drawing.

beakers are cooled a n d reweighed to determine the unwashed gum, for aviation gasohne and aircraft turbine fuel.
For motor gasolines, the residue is washed with n-heptane.
The heptane washed residue is reported as existent g u m
content.
The gums contained in gasolines and fuels can be harmful,
causing sticking of the intake valves, and plug carburetor jets.
It may interfere with the action of moving parts and, in general, obstruct the flow of fuel through the lines and p u m p .
Existent gum is related to the quantity of gum already present in gasoline and fuel (see Fig. 53).

FIG. 50Aluminum Beal<er Oxidation Test (ABOT). Complete


test cell parts.

D 525: Oxidation Stability of Gasoline (Induction Period


Method)This test m e t h o d covers the determination of
the oxidation stability of finished gasolines under accelerated conditions. The test is conducted in the following
manner:
A 50 mL sample of gasoline is measured into a glass sample container and is placed into the pressure vessel. The as-

5/8" Dia Hole Drilied


in Insulation
1-3/8" Dia Hole in
Insulation Typical for 8

Marinite Board
Insulation
Cover Plate

Test Block

Fiber Frax
Loose Insulatiai
Case

1-5/32" Dia
Hole Typical
2" Dia Hole
Marinite Board
Insulation

(a)

(b)
FIG. 51a) Caterpillar Micro-Oxidation Test (CiVIOT). Test apparatus side view of cover plate, b) Blotter spots showing acceptable versus unacceptable sludge deposits.
Inlet Tube
Inlet/Outlet Cap
27 cm

Outlet Tube

4 mm ID
24/40 Ground Glass Joint

Glass Vessel

Metal Catalyst Specimen

(a)

(b)
FIG. 52a) CMOT glass test vessel; b) Test coupon.

814

CHAPTER

30: OXIDATION

OF LUBRICANTS

AND FUELS

815

This thermometer ond


thermometer well ore
optional
Cotton or Gloss Wool Filter
Air Supply

Removoble
Adopter

if-in, 0.0.

FIG. 53ASTM D 381, Existent Gums in Fuels. Test apparatus.

sembled pressure vessel is charged with oxygen to a pressure


of 690-705 kPa. The pressurized vessel is placed in a heated
oil bath, maintained at 98-102C (208 to 215F). The pressure
is observed and read at stated time intervals until the breakpoint is reached. The breakpoint is described as the point
when the pressure drops 14 kPa in 15 min, followed by a drop
of not less than 14 kPa in 15 min. The minutes to this break
point are reported.
The induction period may be used as an indication of the
tendencies of the motor gasoline to form gums in storage. It
should be noted that its correlation with the formation of
g u m in storage may vary under different storage conditions
and with different gasolines (see Figs. 54 and 55).
D 873: Oxidation Stability of Aviation Fuels (Potential Residue
Method)This test method covers the determination of the
tendency of aviation reciprocating, turbine, and jet engine
fuels to form gum and deposits under accelerated aging conditions. A summary of the test procedure follows:
A weighed glass sample beaker containing 100 mL of test
sample is placed into a pressure vessel. The vessel is assembled and charged with oxygen to a pressure of 690-705 kPa.
The cheirged pressure vessel is then placed into a heated bath
maintained at 100C (212F). At the end of the oxidation period, the aged sample is transferred to a graduated cylinder.
The glass sample container is washed with "gum solvent,"
which is a mixture of equal pairts of toluene and acetone. This
wash is added to the oxidized fuel, and is filtered through a
weighed sintered glass crucible. The crucible is dried and

weighed. The increase in weight will be used as a part of the


calculation to determine the gum content. The filtered oxidized fuel gum solvent mixture is divided into two equal portions and submitted to testing under ASTM D 381, Existent
Gum in Fuels by Jet Evaporation. The final "soluble gum" is
calculated in accordance with the test method.
The results of these tests can be used to indicate the storage stability of these fuels. The tendency of fuels to form gum
deposits in these tests has not been correlated with actual
field performance and varies widely under different storage
conditions.
D 3241: Thermal Oxidation Stability of Aviation Turbine Fuels
(JFTOT Procedure)This test method covers the procedure
for rating the tendencies of gas turbine fuels to deposit decomposition products within the fuel system. The test is conducted in the following manner:
This test method for measuring the high temperature stability of gas turbine fuels uses the Jet Fuel Thermal Oxidation
Tester (JFTOT). The JFTOT subjects the test fuel to conditions that can be related to those occurring in gas turbine engine fuel systems. The JFTOT can be run to a maximum tube
t e m p e r a t u r e of a b o u t 350C (662F). The t e m p e r a t u r e at
which the test should be run and criteria for judging results
are normally embodied in the fuel specification. The fuel is
pumped at a fixed volumetric flow rate through a heater after which it enters a precision stainless steel filter where fuel
degradation products may become trapped. The apparatus
uses 450 mL of test fuel ideally during a 2.5-hour test. The es-

816

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

^mn

II

Hi

NOTE 1Toterance 0.25 mm unless otherwise specified.


NOTE 2Key.
A-Bomb
B Bomb closure
C - B o m b jtem
. 0Connectioo
E - Btitstdisc assembly
F-RHerrod

FIG. 54ASTM 0 525, Potential Gums in Fuels. Test apparatus.

sential data derived are the amount of deposits on the aJuminum heater tube and the rate of plugging of a 17-micron
nominal porosity precision filter located just downstream of
the heater tube.
The test results are indicative of fuel performance during
gas turbine operation and can be used to assess the level of
deposits that form when liquid fuel contacts a heated surface.
The test is rejected if the amount of spent fluid pumped
during the test is less than 405 mL. The final result from this
test method is a tube color rating based on an arbitrary scale,
established for the method, plus two additional yes/no crite-

ria that indicate the presence of an apparent large excess of


deposit or unusual deposit, or both.
D 2274: Oxidation Stability of Distillate Fuel Oil (Accelerated
Method)This method covers the measurement of inherent
stability of middle distillate petroleum fuel under accelerated
oxidizing conditions. It is not applicable to fuels containing
residual oil, or any significant component derived from a
nonpetroleum source. A summary of the method is as
follows:
A 350 mL volume of filtered middle distillate is aged at
95C (203F) in ASTM D 943 glassware for 16 h while oxygen

CHAPTER

COVER
PORCeUMN OR OLASS

-Z BUSTS OR
DEPRESSIONS

SAMPLE

30: OXIDATION

OF LUBRICANTS

AND FUELS

817

Because the storage periods are long (4-24 weeks), the test
method is not suitable for quality control testing, b u t does
provide a tool for research on storage properties of fuels, ft
should be noted that the results obtained by this test are not
necessarily the same as those obtained during storage in a
specific storage situation (see Figs. 58 and 59).
D 6468: High Temperature Stability of Distillate FuelsThis
test method covers relative stability of middle distillate fuels

CONTAINER
OLASS
CLASS CONDENSER

FIG. 55ASTM D 525, Potential


Gums In Fuels. Glass sample container and cover (glass or porcelain).
is bubbled through the fuel sample at a rate of 3L/h. After aging, the sample is cooled to approximately room temperature
before filtering the aged fuel through a 0.8-micron filter, to
obtain the filterable insolubles quantity. Adherent insolubles
are removed from the oxidation cell and associated glassware
with tri-solvent (equal volumes of toluene, acetone, a n d
methanol). The tri-solvent is evaporated t o obtain t h e
quantity of adherent insolubles. The sum of the filterable and
inherent insolubles, expressed as milligrams per 100 mL, is
reported.
This test method provides a basis for the estimation of the
storage stability of middle distillate fuels with a n initial
boiling point above approximately 175C (347F) and a 90%
recovery point below 370C (698F) such as No. 2 fuel oil. It
is not applicable to fuels containing residual oil, or any significant component derived from a nonpetroleum source.
The test method may not provide a prediction of the quantity of insolubles that will form in field storage over any given
period of time. The amount of insolubles formed in such field
storage is subject to the specific conditions, which are too
variable for this test method t o predict accurately (see Figs.
56 and 57).
D 4625: Distillate Fuel Storage Stability at 43C (110F)This
test method covers a method for evaluating the inherent storage stability of distillate fuels having flash points above 38''C
(100F) and 90% distilled points below 340C (644F).
This method is not suitable for quality control testing, but
rather it is intended for reseairch use to shorten storage time
relative to that required at ambient storage temperatures. A
summary of the method is as follows:
Four 100-mL volumes of filtered fuels are aged by storage
in borosilicate glass containers at 43C (110F) for periods of
0, 4, 8, 12, 18, and 24 weeks. After aging for a selected time
period, a sample is removed from storage, cooled to room
temperature, and analyzed for filterable insolubles and adherent insolubles.
Fuel oxidation and other degredative reactions leading to
formation of sediment (and color) are mildly accelerated by
the test conditions, compared t o typical storage conditions.
Test results have been shown to predict storage stability more
reliably thaji other more accelerated tests.

MM O.D.

FIG. 56ASTM D 2274, Oxidation Stability of Distillate Fuel


Oil. Test apparatus.

FILTER

FUNNEL

MEMBRANE

FILTER

SUPPORT

FIG. 57ASTM D 2274, Oxidation Stability of


Distillate Fuel Oil. Filter apparatus.

818

MANUAL 37: FUELS AND LUBRICANTS


'^

HANDBOOK

GLASS S T O P P E R

tive relationship exists between the pad rating and the gravametric mass of filterable insolubles.
Lubricants

500 ML S E P A R A T C
FUNMEL

*4 PORCELAIN CRUCIBLE

OOOCH HOLDER

TO VACUUM

500 M L P V R E X
SUCTION FLASK

FIG. 58ASTM D 4625, Distillate Fuel Storage


Stability at 43C (110F). Self feeding filtering
assembly.

under high temperature aging conditions with limited air exposure. A summary of the method is as follows:
Two 50-mL volumes of filtered middle distillate fuel are
aged for 90 or 180 min at 150C in open glass tubes with air
exposure. After aging and cooling, the fuel samples are filtered through a Whatman No. 1 filter. The average amount of
filterable insolubles is estimated by measuring the light reflectance of the filter pads. The 100 and 0% extremes of the
reflectance rating range are defined by an unused filter pad
and a commercial black standard, respectively.
This test method provides an indication of thermal
oxidative stability of distillate fuels when heated to high temperatures that simulate those that may occur in some types of
recirculating engine or burner fuel delivery systems. Results
have not been substantially correlated to engine or burner
operation. The test method can be useful for investigation of
operational problems related to fuel thermal stability.
When this method is used to monitor manufacture or storage of fuels, changes in filter rating values can indicate a
relative change in inherent stability.
The test method uses a filter paper with a nominal porosity of 11 microns, which will not capture all of the sediment
formed during aging, but allows differentiation over a broad
range. Reflectance ratings eire also affected by the color of filterable insolubles, which may not correlate to the mass of the
material filtered from the aged fuel. Therefore, no quantita-

D 6186: Oxidation Induction Time of Lubricating Oik by Pressure Differential Scanning Calorimetry (PDSC)This method
covers the determination of oxidation induction time of
lubricating oils subjected to oxygen at 3.5 MPa (500 psig) and
temperatures between 130C and 210C (265^10F). Oxidation Induction Time (OIT) is the period of time from the first
exposure to an oxidizing atmosphere until the extrapolated
on-set time. A summary of the test procedure follows:
A small quantity of oil is weighted into a sample pan and
placed into a test cell. The cell is heated to a specified temperature and at a regulated temperature and pressure until
an exothermic reaction occurs. The extrapolated on-set time
is measured and reported as the oxidation induction time for
the lubricating oil at the specified test temperature.
Oxidation Induction Time (OIT) may be used as an indication of oxidation stability. This test method is faster than other
oil oxidation tests and requires a very small amount of sample. This method may be used for research and development,
as a quality control, and for specification purposes. However,
no correlation has been established between the results of this
method and actual service performance.
Panel Coker TestThe Panel Coker Test is a method for determining the relative stability of lubricants in contact with
hot metal surfaces.
The test apparatus consists of a rectangular stainless steel
reservoir, inclined 25 from horizontal. The reservoir is fitted
with a machined steel piece fitting integrally into the top of
the reservoir, and framing a 95 mm by 45 mm aluminum
panel. The test panel is held in place by a heating element,
which is fitted with thermocouple probes to control the
temperature of the aluminum test panel. A horizontal shaft,
BOROSILICATE GLASS BEND

CAP WITH PTFE INSERT

500 ml. BOROSILICATE


' GLASS BOTTLE

FIG. 59ASTM D 4625, Distillate Fuel Storage Stability at 43C (110F). Sample storage
container.

CHAPTER
fitted with a series of tines, is positioned above tlie oil and is
rotated at 1000 rpm. During rotating of tlie shaft, the tines
sweep through the test lubricant and lubricant droplets are
thrown onto the heated aluminum test panel. A summary of
the procedure follows:
The apparatus is assembled forming a closed system and
the test panel is heated to the specified test temperature, usually 260-325C. The shaft is rotated at 1000 r p m and the test
lubricant is splashed onto the heated, weighted test panel.
The splashing heating cycle is continued for normally 2-6 h,
from the time the splasher is started. Some other variables in
the p r o c e d u r e w o u l d b e the i n t r o d u c t i o n of air, a n d the
splash/bake cycle. At the end of the specified time period, the
heat is removed, the splasher is stopped, and the test panel is
allowed to cool. The test panel is reweighed and the a m o u n t
of deposit is determined.
Weight gain of the aluminum test panel and the amount of
test lubricant consumed during the test are an indication of
the lubricant's performance under high temperature conditions. Examples of accepted performance are as follows:
Gear Oils: leaded type give deposits in the range of
700-1000 mg, in contrast to sulfur/phosphorus t5T3es which
give 150-220 mg.

S/P Lub*

174 mg Wt Cain

30: OXIDATION

OF LUBRICANTS

AND FUELS

819

Quench Oils: Non-thermally stable chemistries give 20-25


m g deposits, with contrast to thermally stable chemistries
that give 1-2 mg deposits.
Diesel Lubricants are normally rated per the universal rating system where 100% is best and 0% worst. Better than
65% is considered acceptable in this test. (See Fig. 60.)
ft is important to note that the temperature, splash rate,
time cycle, and metallurgy of the test panel can vary depending on the tjrpe of lubricant being evaluated.
D 37H: Deposition Tendencies of Liquids in Thin Films and
VaporsThis test m e t h o d covers the determination of the
tendency of liquids in thin films and of vapors to form deposits on heated metal surfaces. This m e t h o d applies to
petroleum based and synthetic lubricants, engine oils, hydraulic fluids, heat-transfer fluids, and related materials. The
test is conducted in the following manner:
One hundred milliliters of test lubricant is allowed to flow
slowly (50 mL/hour) in a thin film over a steel test specimen
in a constant temperature chamber (furnace liner). A test
temperature of 533 K has been found useful for evaluating
the thin film deposit characteristics of engine oils, and similar petroleum based lubricants. Higher temperatures may be

L**d<l Lub 959 mo Wl Gain

FIG. 60Panel Coker Test. Typical samples.

820

MANUAL 3 7; FUELS AND LUBRICANTS

HANDBOOK

used for sjTithetic materials and highly refined petroleum fluids if desired. Circulation of the sample from the sump to the
heated surface and back to the pump is accomplished by
means of a peristaltic pump. After the prescribed test period,
normally 5 h, the steel test specimen is removed from the
apparatus and evaluated. The masses of deposits remaining
after washing with pentane, after washing with chloroform,
and after wiping with a tissue, are reported. An optional procedure provides a method for the determination of the tendency of sample vapors to form deposits on heated surfaces.
A second test specimen is placed in the vapor space over a
thin flowing film of the liquid in the constant temperature
chamber. After circulation of the test liquid, the deposits on
the test specimen exposed to the liquid and vapor phases, cire
measured as above.
The test method shall measure the deposit formation tendencies of liquid petroleum products on heated steel surfaces, in air, at 101.3 kPa (10 atm) pressure. Other surfaces
and other atmospheric media may be substituted for steel
and air at 1 atm, provided the substitution is noted in the test
report.
RULER (Remaining Useful Life Evaluation Rig)This
method is not an ASTM standard. It is under evaluation
within an ASTM technical committee, but it has not received
the approvals required to become an ASTM standard.
The RULER was originally designed for use by the U.S. Air
Force to determine the remaining useful life of lubricants.
The remaining useful life of a lubricant is the length of time
from the original lubricant sampling, until large changes in
the lubricant's physico-chemical properties occur. This test
can be performed with any lubricant containing at least one
antioxidant species. The test is conducted as follows:
The test vial (electrolytic cell) is prepared by mixing an oil
sample with a solvent and a solid substrate. The solvent separates the antioxidant from the oil as the vial is shaken. When

C/)
Q.

the substrate settles to the bottom of the vial, the oil and
other debris common to used oil adheres to the substrate
particles.
An electrode is inserted into the vial and a controlled voltage ramp is applied to the electrode inserted into the diluted
oil sample. As the voltage potential increases, the antioxidants become more chemically active, causing the increasing
oxidation current to reach a peak, and then decrease as voltage potential continues to increase.
Through time-series testing, the remaining useful life of a
lubricant can be tracked from test to test, enabling the user
to identify "normal" trends for a given lubricant. Variations
from this trend can be indicative of changes in operating conditions causing accelerated oxidation. Determinations can be
made to predict when rapid changes in the lubricant are
likely to occur and decisions can be made regarding oil
changes of additive reinforcement.
This method can be used to determine the remaining useful life of automotive engine oils, diesel oils, hydraulic fluids,
turbine engine lubricants, transmission fluids, and greases
(See Figs. 61 and 62).
Biodegradable

Lubricants

AOCS Official Method Cd 12-57: Fat Stability, Active Oxygen


Method (AOM)This method measures the time required for
a sample of fat or oil to attain a predetermined peroxide value
under the specific conditions of the test. The test is conducted as follows:
A 20 mL of sample is measured into a cleaned glass test
tube. An aeration tube assembly is placed into the test tube,
and the assembled apparatus is placed into a bath of boiling
water for 5 min. The assembly is removed from the boiling
water bath, wiped dry, and placed into a heated bath maintained at 97.8C (208.8F). Air is blown into the sample at a
rate of 2.33 mL per second. This is continued until the sam-

Compound "B"
Phenyl - a - naphylamine

Linear Ramp (Voltage)

E
CO

CD

o
Voltage increases with time
FIG. 61RULER test. Oxidation curve for the RULER test.

CHAPTER

30: OXIDATION

OF LUBRICANTS

AND FUELS

821

Hours: 25
Sample ID: GO 1
Sample Date: 5/06/98
Standard:
60&

/Sample

/Additive

10

11 12 13 14 15 16

17

Seconds (V lUlode)
Ruler Numbers
Standard: 552
Sample: 441
RUL: 80%

Ruler Areas
Standard: 7451
Sample: 6294
RUL: 84%

Additive RULs

#1:85%
#2: 77%

FIG. 62RULER test.

pie reaches a peroxide value of 100 milliequivalents. The peroxide value is determined by method AOCS official method
Cd 8-53.
The length of this period of time is assumed to be an index of resistance to rancidity. The exact relationship
between peroxide value and such queJities as shelf-life, actual rancidity, and oxidative stability has not been firmly
established.
AOCS Official Method Cd 126-92: Oil Stability Index (OSI)
This method measures the oxidation resistance of oils and
fats. Initially the oxidation proceeds slowly until the oxidation resistance is overcome, at which point the oxidation
rate accelerates a n d becomes very rapid. The length of
time before this rapid oxidation occurs is commonly referred to as the "induction period." The test is conducted as
follows:
A sample of oil or fat is heated at the specified test temperature, and a stream of purified air is bubbled through the
sample at a rate of 2.5 mL/s. The effluent air from the sample
is then bubbled through a test tube containing 50 mL of
deionized water. The conductivity of the water is continually
monitored. The effluent air contains volatile organic acids
that increase the conductivity of the water as the oxidation
proceeds. The conductivity of the water is monitored by computer or strip chart recorder. The Oil Stability Index (OSI) is
defined as the point of m a x i m u m change of the rate of
oxidation. The test time is normally a m i n i m u m of 4 h or a
maximum of 15 h. The OSI may be r u n at temperatures of
100, 110, 120, 130, and 140C.

This method is applicable in general to all fats and oils and


has been subjected to collaborative studies covering a wide
range of sample tj^es.
DIN 51554: Test of Susceptibility
to Ageing According to
BaaderThe Baader ageing test is an accelerated oxidation
test enabling the probable in-service behavior of various lubricants to be predicted. The Baader test was developed to
evaluate mineral oil based hydraulic fluids. However, today it
has found wide acceptance in predicting the performance of
biodegradable hydraulic fluids. Both vegetable oil (triglyceride) and synthetic ester based fluids are evaluated. The test
is conducted in the following manner.
Three hundred millimeters of freshly cleaned copper wire
is wound into a coil per the procedure. The coil is then placed
into the glass test tube containing 60 mL of test fluid. A
Liebig condenser is fitted to the glass test tube. The assembly
is then placed into the heated oil bath.
The catalyst coil is attached to a mechanical lifting device
that raises and lowers the catalyst coils into and out of the
test fluid at a rate of 25 cycles/min. A cycle is understood to
be one full upward and downward movement, during which
the catalyst coil must be alternately totally positioned for
identical periods of time in the test fluid and in the air. The
test conditions are 140 h at 110C for insulating oils and synthetic ester hydraulic fluids, and 72 h at 95C for mineral oil
hydraulic fluids and vegetable based hydraulic fluids. At the
end of the ageing period, the viscosity of the aged fluid is determined and compared to the original fluid viscosity. Percent viscosity increase at 40C is reported.

822 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


TABLE 8Oxidation stability of the test fluids.

Fluids
ABOT Test
(300 h, 155C)
(requirement*)
TAN Increase
(3.5 mix)
IR Carbonyl
Increase (30 max)
% Viscosity Increase
at 40C
(25 max)
% Pentane Insolubles
Increase
(0.35 max)

IT-1

CAT-1

CAT-2

PAT-1

PAT-2

Industrial
Traction
Fluid

Commercial
Automotive
Traction
Fluid 1

Commercial
Automotive
Traction
Fluid 2

Prototype
Automotive
Traction
Fluid 1

Prototype
Automotive
Traction
Fluid 2

0.50

0.9

20

14.4

9.2

0.20

1.4

0.6

13

7.5

13

22

16.4

13.1

0.09

4C, flaking

Copper Strip

2.4

3B

Prototype
Automotive
Traction
Fluid 4

1.2

2.4

12
8.7
0.07

3A

3B

3B

PAT-4

PAT-3
Prototype
Automotive
Traction
Fluid 3

3B

35
19.7
1.73

3B

are for biodegradable fluids and require less than a 20% increase in viscosity to be considered acceptable.
Table 8 represents the relative oxidative stability of various
biodegradable fluids as measured by their change in viscosity before and after being subjected to the Baader test (see
Fig. 63).

<P5T

TEST METHODS
Hydraulics, R & O, and Turbine Oils
D943
Olive DIN

12215-08

D4310
D2272

Ground taper
NS 45127
in accordance
witfi DIN 12242

IP-280
IP-306
IP-307
D2070
D4636
D5846
D6514

Tolerances for ground


taper corresponding to
NS 45/40 in accordance
with DIN 12 242

DIN 51352

Gear Oils
D2893

Test apparatus according to Baader


FIG. 63Baader Oxidation Test apparatus. Dimensions of
tine glassware.
Though not required by any of the current specifications,
saponification number, % insolubles (sludge), and the dissipartion factor are sometimes determined.
There are currently two European specifications requiring
the Baader test. They are the Swedish ECO standard, SS
155434, and the ISO DIS 15380. Both of these specifications

Oxidation Characteristics of Inhibited Mineral


Oils
Determination of Sludging and Corrosion
Tendencies of Inhibited Mineral Oil
Oxidation Stability of Steam Turbine Oils by
Rotating Pressure Vessel (formerly Rotary
Vessel)
Oxidation Stability of Inhibited Mineral
Turbine Oils
Oxidation Stability of Straight Mineral Oils
Oxidation Stability of Mineral Insulating Oils
Thermal Stability of Hydraulic Oils
Corrosiveness and Oxidation Stability of
Hydraulic Oils, Aircraft and Turbine Engine
Lubricants and Other Highly Refined Oils
Universal Oxidation Test for Hydraulic Fluids
and Turbine Oils
High Temperature Universal Oxidation Test For
Turbine Oils
Pneurop Oxidation Test

D5763
D5704

nS-K2514
L-48-08

Oxidation Characteristics of Extreme Pressure


Lubricating Oils
Oxidation and Thermal Stability Characteristics
of Gear Oils Using Universal Glassware
Evaluation of the Thermal and Oxidative
Stability of Lubricating Oils Used for Manual
Transmissions and Final Drive Axles L-60 and
L-60-1 Tests
Oxidation Stability of Automotive Gear Oils
(ISOT Method)
Test Method for the Oxidation Stability of
Lubricating Oils Used in Automotive
Transmissions by Artificial Aging (DKA
Method).

CHAPTER 30: OXIDATION OF LUBRICANTS AND FUELS 823


Grease
D942
D5483

D3527

Oxidation Stability of Lubricating Greases by


the Oxygen Vessel Method
Oxidation Induction Time of Lubricating
Greases by Pressure Differential Scanning
Calorimetiy (PDSC)
Penn State Micro-Oxidation Test (PSMO)
Life Performance of Automotive Wheel Bearinjg
Grease

Engine Oils
D4742
D6335

BT-10

Thin Film Oxygen Uptake Test (TFOUT)


Thermo Oxidation Engine Oil Simulation Test
(TEOST) (MHT-4 Protocol)
Determination of High Temperature Deposits
by Thermo-Oxidation Engine Oil Simulation
Test (TEOST)
Ford, Mercon V Aluminum Beaker Oxidation
Test (ABOT)
Caterpillar Micro-Oxidation Test (CMOT)
International Harvester Oxidation Corrosion
Test

Gasolines and Fuels


D381
D525
D873
D3241
D2274
D4625
D6468

Existent Gums in Fuels by Jet Evaporation


Oxidation Stability of Gasoline (Induction
Period Method)
Oxidation Stability of Aviation Fuels (Potential
Residue Method)
Thermal Oxidation Stability of Aviation Fuels
(JFTOT Procedure)
Oxidation Stability of Distillate Fuel Oil
(accelerated method)
Distillate Fuel Storage Stability at 43C (110F)
High Temperature Stability of Distillate Fuels

General Lubricants
D6186
D3711

Oxidation Induction Time of Lubricating Oils


by Pressure Differenticil Scanning Calorimetry
(PDSC) Panel Coker Test
Deposition Tendencies of Liquids in Thin Films
and Vapors
RULER (Remaining Useful Life Evaluation
Routine)

VW1302 Test
VW Diesel intercooler test
VW DI engine test
Peugeot XUDl lATE and XUDUBTE
M-B OM 364A and M-B OM 441LA
MAN 5305 tests

Engine Tests For Japanese Oils


Toyota IG-FE
Nissan VG 20E
Nissan SD22
Nissan TD25
OMC 40-HP and 70-HP for two-stroke cycle engine oils

CROSS REFERENCE OF TEST METHODS


ASTM
D381
D525
D873
D942
D943
D2070
D2272
D2274
D2893
D3241
D3527
D3711
D4310
D4625
D4636
D4742
D5483
D5704
D5763
D5846
D6186
D6335
D6468

IP
131
40
138
142
157

DIN
51780
51575
51808
51587

ISO
6246

4263

388
51586

280
306
307
51352
51554

15380

Biodegradable Lubricants
AOCS Cd 12-57
AOCS Cd 12b-92
DIN 51554

Fat Stability, Active Oxygen Method (AOM)


Oil Stability Index (OSI)
Baader Oxidation Test

The following listing of engine tests is included for reference only and outlines of these methods are not included in
this chapter.

Engine Tests For North American Engine Oils


ASTM Sequence IIIE/F
ASTM Sequence VE/G
CRC L-38
Caterpillar IK/IN/IM-PC/IP
Cummins M-11
Mack T-6/T-7/T-8/T-9

Engine Tests for European Engine Oils


Peugeot TU-3M high temperature test
M-B M i l l black sludge test

REFERENCES
[1] Ingold, K. U., "Inhibition of Autoxidation of Organic Substances
in Liquid Phase," Chemical Reviews, Vol. 61, 1961, pp. 563-589.
[2] Rasberger, M., "Oxidative Degradation and Stabilization of
Mineral Oil Based Lubricants," Ch. 4, Chemistry and Technology
of Lubricants, R. M. Mortier and S. T. Orszulik, Eds., VCH Publishers, Inc., NY, 1992, pp. 83-123.
[3] Rizvi, S. 0. A., "Lubricant Additives and Their Functions," ASM
Handbook, Friction, Lubrication and Wear Technology, Vol. 18,
1992, pp. 98-112.
[4] Abou El Naga, H. H. and Salem, A. E. M., "Effect of Worn Metals on the Oxidation of Lubricating Oils," Wear, Vol. 96, 1984,
pp. 267-283.
[5] Lachowicz, D. R. and Kreuz, K. L., "Peroxynitrates. The Unstable Products of Olefin Nitration with Dinitrogen Tetroxide in the
Presence of Oxygen. A New Route to a-Nitroketones," Journal of
Organic Chemistry, Vol. 32, 1967, pp. 3885-3888.
[6] Kreuz, K. L., "Gasoline Engine Chemistry as Applied to Lubricant Problems," Lubrication, Vol. 55,1969, pp. 53-64. (b) Kreuz,

824 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


K. L., "Diesel Engine Chemistry as Applied to Lubricant Problems," Lubrication, Vol. 56, 1970, pp. 77-88.
[7] Johnson, M. D., Korcek, S., and Zinbo, M., "Inhibition of Oxidation by ZDTP and Ashless Antioxidants in the Presence of Hydroperoxides at 160C," Lubricant and Additive Effects on Engine
Wear, SP-558, pp. 71-81, Fuels and Lubricants Meeting, San
Francisco, 31 Oct.-3 Nov. 1983.
[8] Al-Malaika, S., Marogi, A., and Scott, G., Journal of Applied Polymer Science, Vol. 33, 1987, pp. 1455-71.
[9] Vijh, A. K., "Electrochemical Mechanisms of the Dissolution of
Metals and the Contaminants Oxidation of Lubricating Oils Under High-temperature Friction Conditions," Wear, Vol. 104,
1985, pp. 151-158.
[10] Klamann, D., "Additives," Ch. 9, Lubricants and Related Products: Synthesis, Properties, Applications, and International Standards, Verlag Chemie, Weinheim, Germany, 1984.
[11] Scott, G., Developments in Polymer Stabilization, G. Scott, Ed.,
Elsevier Applied Science Publishers, NY, 1984, pp. 65-104.
[12] Scott, G., "New Developments in the Mechanistic Understanding of Antioxidant Behavior," Journal of Applied Polymer Science, Applied Polymer Symposium, Vol. 35, 1979, pp. 123-149.
[13] Hamblin, P. C , Kristen, U., and Chasan, D., "A Review: Ashless
Antioxidants, Copper Deactivators, and Corrosion Inhibitors,
Their Use in Lubricating Oils," Lubrication Science, Vol. 2, 1990,
pp. 287-318.

BIBLIOGRAPHY
[1] Aspects of Lubricant Oxidation, ASTM STP 916, Stadmiller and
Smith, Eds., ASTM International, West Conshohocken, PA,
1986.
[2] Significance of Tests for Petroleum Products, ASTM STP 7C (now
ASTM Manual 1), Boldt and Hall, Eds., ASTM International,
West Conshohocken, PA, 1934.
[3] American Society of Metals (ASM) Handbook, Volume 18,
P. J. Blau, Volume Chairman, American Society of Metals, Materials Park, OH, 1992.
[4] Lubrication Engineers Manual, Association of Iron and Steel Engineers (AISE), Pittsburgh, PA, 1996.

[5] Standard Handbook of Lubrication Engineering, J. J. O'Connor


and J. Boyd, Eds., McGraw Hill, NY, 1968.
[6] Annual Book of ASTM Standards, Section 5, Petroleum Products, Lubricants, and Fossil Fuels, Vols. 05.01, 05.02 and 05.03,
ASTM International, West Conshohocken, PA, 2000.
[7] Standard Methods for Analysis and Testing of Petroleum and Related Products Institute of Petroleum, Vols. 1 and 2, Institute of
Petroleum, London, 2002.
[8] Ingold, K. U., "Inhibition of Autoxidation of Organic Substances in Liquid Phase," Chemical Reviews, Vol. 61, 1961, pp.
563-589.
[9] Rasberger, M., "Oxidative Degradation and Stabilization of
Mineral Oil Based Lubricants," Ch. 4, Chemistry and Technology
of Lubricants, R. M. Mortier and S. T. Orszulik, Eds., VCH Publishers, Inc., NY, 1992, pp. 83-123.
[10] Rizvi, S. Q. A., "Lubricant Additives and Their Functions," ASM
Handbook, Friction, Lubrication and Wear Technology, Vol. 18,
American Society of Metals, Materials Park, OH, 1992, pp.
98-112.
[11] Rasberger, M., Stroud, P. M., Mortier, R. M., Orszulik, S. T.,
Hoyes, T. J., a n d Brown, M., "Oxidative Degradation and
Stabilization of Mineral Oil Based Lubricants," Chemistry and
Technology of Lubricants, R. M. Mortier and S. T. Orszulik, Eds.,
VCH Publishers, Inc., NY, 1992.
[12] Lansdown, A. R., Lubrication and Lubricant Selection, Mechanical Engineering Publications, Anthony Rowe, Ltd., Chippenham, Wihshire, 1996.
[13] Heinz, P. and Block, P. E., Practical Lubrication for Industrial
Facilities, Fairmont Press, Inc., Lilbum, GA, 2000.
[14] Cincinnati Machine Book of Lubricant Purchase
Specifications,
Pub. # 10-SP- 00038, Part # 9703432212A, CM Worldwide Support Services Group, Cincinnati, OH, 2000.
[15] Florkowski, D. W. and Selby, T. W., "The Development of a
Thermo-Oxidation Engine Oil Simulation Test (TEOST)," SAE
# 932-837, Society of Automotive Engineers, Warrendale, PA,
1993.
[16] Tipton, C. D., Qureshi, F., and Huston, M., "Automotive Traction Fluids: A Shift in Direction for Transmission Fluid Technology," SAE #2000-01-2906, Society of Automotive Engineers,
Warrendale, PA, 2000.

MNL37-EB/Jun. 2003

Corrosion
Maureen E. Hunter^ and Robert F. Baker^

P E R A S T M G 15, CORROSION IS "THE CHEMICAL OR ELECTRO-

CHEMICAL REACTION between a material, usually a metal, and


its environment that produces a deterioration of the material
and its properties." Corrosion is one of the causes of premature failure of a lubricated system. Fuels and lubricants will
be exposed to water, one of the necessary components for
electrochemical corrosion to occur. This chapter will outline
the nature of ferrous and non-ferrous corrosion and the comm o n additive approach to inhibiting corrosion and will summarize the c o m m o n tests employed to evaluate the effects
and prevention of corrosion.
There are fluid performance properties sometimes referred
to as "corrosion," such as fretting and fatigue failure, which
are not electrochemical. They are better characterized as a
form of wear and are not covered in this chapter. These properties and the tests for them are discussed in Chapters 35, 36,
and 37 on Lubrication and Wear.

BACKGROUND
Corrosion becomes a problem when the appearance or functionality of metal is impaired. To some extent, corrosion is inevitable and may not be prevented, only delayed or retarded.
Chemical "inhibitors" are added to fuels and lubricants to
protect metal surfaces. The metcJs requiring protection are
typically iron and its alloys (steel) and copper and its alloys
(primarily brass and bronze). Other metals, including aluminum, lead, tin, zinc and cadmium, come in contact with
fuels and lubricants and are subject to veirious forms of corrosion, but most fuel and lubricant testing focuses on the corrosion of copper and the oxidative corrosion of iron, commonly called "rust."

Electrolytea wet p a t h connecting the anode and cathode


(generally aqueous).
Conductora metal bridge that electrically connects the
anode and cathode to complete the circuit.
The rust corrosion cell is very similar to a battery-energized
electrical circuit. Figure 1 shows the flow of electrons in an external circuit between an anode ( - ) and a cathode (-I-) and the
departure of ions from the anode in a simple wet battery cell.
The mechanism of oxidative corrosion of iron is depicted in
Fig. 2 where electrons flow from the anode to the cathode and
ions (positively charged iron atoms) leave the anode surface
and enter the electrolyte as ferrous ions. This degradation of
the anode surface coupled with hydration and further oxidation of the ferrous ions is the mechanism known as rusting.
Chemistry

of

Rust

Even small differences in electrical potential can cause the


formation of reactive cinodic sites. This can be the result of
surface imperfections, grain boundaries in alloys, temperature gradients, physical stress, and electrochemical polarization [1]. The formation of these sites causes electrons to leave
the anode at the electrical contact with the cathode. The departing electrons turn the iron atoms into ferrous ions at the
anode-electrolyte interface resulting in disintegration of the
anode:
F e ^ F e + + + 2e

The ferrous ions react with water to form ferrous hydroxide:


Fe++ -H 2H2O -> Fe(0H)2 + 2H+

(3)

The combined anode equation is obtained by adding the


above equations:

Electrochemical Nature of Rust Formation


As indicated above, the rusting of iron and its alloys is an
electrochemical process. There are four essential elements
required for the electrochemical process to occur. The elimination of any one of the four prevents the formation of the
electrical cell and inhibits corrosion.
Anodea site where oxidation of a metal generates positively charged metal ions and electrons.
Cathodea site where reduction of oxygen and hydrogen
in water consumes electrons.

4Fe + 4H2O + 0 2 - ^ 2Fe203 -I- 8H+ + 8e

(4)

The electrons migrate from the anode towards the cathode


and at the cathode-electrolyte interface they react with oxygen and water forming hydroxide ions:
O2 + 2H2O + 4e ^ 4 0 H ~

(5)

The result of combining Eqs 4 and 5 is


4Fe + 8H2O + 3O2 -^ IFCiOi + 8H2O

(6)

Note that in Eq 6 water is conserved and only oxygen and


iron are consumed. It is important to recognize, therefore.

' Technical Service Manager and National Accounts Manager,


respectively. King Industries, Inc., Norwalk, CT 06852.
825
2003 by A S I M International

(2)

The ferrous hydroxide reacts with oxygen to produce ferric


oxide (the commonly recognized form of rust) and water:
4Fe(OH)2 + 0 2 ^ 2Fe203 + 4H2O

Copyright'

(1)

www.astm.org

826

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

-> electron flow

catalyst metals for signs of corrosion, deposits, discoloration,


and/or weight changes.

External Circuit

Surface
MX+
N

MX+
MX+
_ electron
flow

Cathode

Anode

FIG. 1Typical electrochemical cell.

H,0

H,o

Cathodic Site

Cathodic Site
0,

^o

^
X
0

o
OH

HjO

Fe++
electrons

Fe

Fe/

^
Fe++
Fe++
Fe

Fe Fe

Activity

Inhibitors

electrons

<

Anodic Site
Iron oxide layer is porous and non-passivating
FIG. 2Mechanism of rust formation.
that once a corrosion cell has been established, the formation
of rust is maintained without the further addition of water.
Only oxygen is required for rust to propagate.
The rusting of iron and steel is destructive to engines, machinery, equipment, and containers contacting fuels and lubricants. Additionally, in a lubricated system, ferrous ions
are recognized to have a catalytic pro-oxidant effect on the
degradation of the lubricant [2], so the rust inhibitor also assists in prolonging the life of a lubricant by the inhibition of
oxidation.
Copper

of Corrosion

There are numerous strategies that can be used to inhibit the


formation of a corrosion cell, including material selection
and design [3]. All involve eliminating at least one of the four
elements required for the electrochemical process to occur.
Tjrpically, additives are incorporated into fuels a n d lubricants to prevent water a n d oxygen from interacting with the
metal surface. These additives consist of polar compounds
commonly known as rust inhibitors (for iron and iron alloys
only) or corrosion inhibitors (for other metals and/or iron).
The chemistries that are effective rust inhibitors are genercdly hydrophobic polar compounds that function as surfaceactive agents. The structure of these polar compounds, as
represented in Figs. 3 a n d 4, consists of a "head," which h a s
a strong affinity for the metal surface a n d a hydrocarbon
"tail," which orients itself away from the surface in the bulk
of the fuel or lubricant. Figure 3 illustrates how these
molecules m a y form a tightly adsorbed monolayer t h a t
inhibits water and oxygen from reaching the metal surface.
When water (the electrolyte) and oxygen are excluded, the
corrosion cell is incomplete, a n d the formation of rust is
prevented.
Figure 4 shows the c o m m o n chemistries for the polar
"head" part of the molecules for ferrous corrosion (rust) in-

HjO
O,

O,

O,

FIG. 3Polar mechanism for rust inhibition.

Corrosion

Copper and its alloys will also experience corrosion similar to


the oxidation process of iron described above. Copper corrosion tends not to be as destructive, cJthough pitting can occur, but discoloration occurs easily. Any sulfur present in the
fuel or lubricant will also participate in the copper corrosion
chemistry, forming copper sulfate on the surface.
In addition, dissolved copper ions, especially at concentrations between 100 and 300 ppm, are known to have a catalytic pro-oxidant effect on the degradation of lubricants [2].
This can also be recognized by the review of the oxidation test
procedures where iron a n d copper are routinely added as catalysts to accelerate oxidation of a fluid. Since oxidation and
corrosion are significantly linked, the criteria for several of
the oxidation tests mentioned in the previous chapter (ASTM
D 2070, D 4310, and D 4636) include the examination of the

Carboxylic Acid

-CO2-H+

Carboxylic Acid Ester

-CO2R

Carboxylate

-CO2M+

Sulfonate

-SO3-M+

Imidazoline
Amine

,N ->__/

-NH2

FIG. 4Common rust inhibitor


chemistries.

CHAPTER 31: CORROSION


hibitors. Figure 5 shows c o m m o n chemistries for inhibiting
copper corrosion, generally different from the ferrous inhibitor chemistries. The ferrous and non-ferrous chemistries
cire frequently added together to achieve a combined effect.
Depending upon the application and performance tests required, typiccd rust and corrosion inhibitor additive levels in
liquid lubricants and functionzil fluids range from 0.05-0.5%.
Additive levels in greases typically range from 0.05-2.0%. See
Chapter 9 for further discussion of additive chemistries.

HS^S
SH
\\ //

HS^^S
SSR
\\ //
N-N

N-N
Dimercaptothiadiazole
(DMTD)

DMTD Derivative

827

CORROSION TESTS
The test methods and practices most commonly used to measure performance and/or specify the requirements for lubriCcints to resist rust emd corrosion will be covered in this section. The significemce of each test will be discussed and a brief
summary of the test procedure will be given. The rust and corrosion methods and procedures eire outlined in Tables 1 and 2.
Generally the procedures fall into four categories: fuels, automotive lubricants (including engine and gear oils), industrial (non-automotive) lubricants, and greases. Greases are
separated because they have unique tests and they do not distinguish between automotive and non-automotive applications. The ability to resist rust and corrosion is an important
lubricant characteristic; however, fuels are generally not
evaluated for anti-rust. In some fuel specifications, copper
corrosion testing is required.
Fuels and Lubricants

H,C

ASTM D 130, Standard Test Method for Detection of


Copper Corrosion from Petroleum Products by the
Copper Strip Tarnish Test

H,C
Tolyitriazoie
Tolyitriazoie
Derivative

FIG. 5Common yellow metal deactivator chemistries

The ASTM D 130 test method is used to detect the corrosivity


of petroleum products to yellow metals. This test is widely
used for R&O, turbine, hydraulic and gear oils where non-

TABLE 1Corrosion specifications and test methods for fuels and lubricants.
ASTM
D 130

Common Name
Copper Strip Corrosion

Fuels
D910

Description
Copper corrosion test widely
used for fuels and lubricants

Related Procedures"
DIN 51 759
IP 154

Standard specification for


aviation gasolines
Standard specification for
diesel fuel oils

D975
Automotive Engine OUs
D4485
D5844

Sequence IID

D6557

Ball Rust Test

Heavy Duty Diesel Engine OUs


D 5968
Cummins Bench Test

Standard specification for


performance of engine oils
Stationary engine rust test for
automotive engine oils
Bench rust test for automotive
engine oils
Corrosion test for copper,
lead, tin and bronze
components

Gear Oils
CRC L-33 Gear Oil
Corrosion Test
Industrial Fluid Lubricants

Rust test for gear oils


subjected to water

FTMS791B(M5326.1)

B 117

Salt Spray (Fog)

DIN 50 021

D665

Spindle Test

D 1748

Humidity Cabinet

D2070
D3603
D4310

Cincinnati Milacron
Thermal Stability Test
Horizontal Disk Test
1000 Hours Sludge Test

D4627

Iron Chip Test

D4636

Oxidation-Corrosion Test

ASTM practice defines


conditions, not evaluation
Standard rust test for most
industrial fluids
Rust test for temporary
coatings
ThermEil stability test of oils in
presence of copper and steel
Rust test for steam turbine oils
Sludging and corrosion test for
oils (variation of D 943
oxidation test)
Rust test for water dilutable
metalworking fluids
Corrosion test for various metals

' Test procedures may not be identical but evaluate similar characteristics.

DIN 51 585
IP 135
DIN 51 359
IP 366

DIN 51 360 IP 287


DIN 51 394 FTM 5307.2

828

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

TABLE 2Corrosion test methods for greases.


ASTM
Greases
D 1743

Bearing Rust Test

D4048

Copper Strip Corrosion

D5969

Bearing Rust Test with


Sea water
Emcor Rust Test

D6138

Description

Related Procedures"

Tapered roller bearing test with


distilled water
Copper corrosion test (D 130
for greases)
D 1743 modified to use
synthetic sea water
Double row ball bearing test
with various types of water

DIN 51 802
IP 220

Common Name

" Test procedures may not be identical but evaluate similar characteristics.
TABLE 3 --Copper strip
Classification

Appearance
Designation

Color Descripti on

Slight tamish
Moderate tamish

Dark tamish
Corrosion

ferrous bushings, gears, and bearings are employed as well


as for cutting fluids used in the machining of non-ferrous
metals.
A three-inch copper strip is prepared by cleaning and polishing all sides so that n o discoloration or blemishes are visible. The strip is then placed in the test oil and held for a specified time at a specified temperature. Three hours at 100C is
the typical starting point. At the end of the exposure period,
the strip is removed, wiped clean and matched with colored
reproduction strips characteristic of the descriptions provided in Table 3. Classification results are reported along
with the duration of the test and the test temperature.
Fuels
ASTM D 910 and D 975, Standard Specification
Aviation Gasolines and Standard Specification
Diesel Fuel Oils

for
for

These two standards define limits of acceptability for two


fuel types. They are employed primarily for purchasing specifications to allow agreement between a buyer and a seller.
The specifications do not provide for any rust inhibiting requirements, but both use ASTM D 130 to define acceptable
levels of copper corrosion.
A u t o m o t i v e E n g i n e Oils
ASTM D 4485, Standard Specification
Performance of Engine Oils

classifications.

of

ASTM D 4485 is not a procedure, but the "specification covers engine oils for light-duty and heavy-duty internal com-

a = Light orange, almost the same as the


freshly polished strip
b = Dark orange
a = Claret red
b = Lavender
c = Multicolored with lavender blue or silver,
or both, overlaid on claret red
d = Silvery
a = Brassy or gold
a = Magenta overcast on brassy strip
b = Multicolored with red and green (peacock),
but no gray
a = Transparent black, dark gray or brown with
peacock green barely showing
b = Graphite or lusterless black
c = Glossy or jet black
bustion engines used under a variety of operating conditions
in automobiles, trucks, vans, buses and off-highway farm, industrial, and construction equipment." If refers to the actual
test methods, both engine tests and bench tests, used to define the various American Petroleum Institute (API) performance categories.
Rust and corrosion requirements are written into the API
performance categories to be run according to the standard
test methods ASTM D 130, D 5844, D 5968, and D 6557.
ASTM D 5844, Standard Test Method for
Evaluation
of Automotive
Engine Oils for Inhibition
of Rusting
(Sequence
IID)
This test was designed to evaluate the rust inhibiting characteristics of engine oils, particularly under service conditions
of short trips in winter conditions. The formation of corrosion products in engines will interfere with any closetolerance parts and contribute to the overall engine wear.
This procedure has been correlated with vehicles using
leaded gasoline prior to 1978. It is, however, still employed
in the current engine oil specifications, including API Category SJ.
This test uses a 350-in^ (5.7-L displacement) Oldsmobile
V-8 engine that is mounted on a test stand and connected to
a dynamometer. After the engine is completely disassembled,
cleaned, and reassembled prior to each test, it is run under
specified operating conditions for a total of 32 h. The engine
is disassembled a n d specified p a r t s (including the valve
lifters, plungers, balls, and pushrods) are examined for evidence of rust and corrosion. Results are reported according
to the rating criteria enumerated in the test method.

CHAPTER
ASTM D 6557, Standard Test Method
of Rust Preventive Characteristics
of
Engine Oils

for
Evaluation
Automotive

This bench test was designed to replace ASTM D 5844, both


because the engine test was costly and because it was only correlated with vehicles using leaded fuel in a less-than-modem
engine. However, this test has not replaced D 5844 in the API
service categories, although it provides a less costly screening
test. ASTM D 6557 uses a Ball Rust Test (BRT) procedure that
subjects metal test specimens to an acidic solution in test
tubes. The results have been shown to correlate reasonably
well with D 5844 and therefore indicate the ability of an oil to
prevent or resist the formation of rust under short-trip conditions where the engine tends to build u p corrosive acids.
Multiple test tubes, each containing test oil and a carbon
steel ball, are placed in a mechanical shaker. Air and an acid
solution (consisting of HCl, HBr and acetic acid) are continuously fed into each test tube for 18 h. The balls are then
rinsed and analyzed by an opticcil imaging system designed
to qucmtify the amount of rusting. The anti-rust capability of
the test oil is generally compared to the results of a reference
oil r u n simultaneously.
H e a v y Duty D i e s e l E n g i n e Oils
ASTM D 5968, Standard Test Method for
of Corrosiveness
of Diesel Engine Oil

Evaluation

The ASTM D 5968 test method is used to determine the tendency of diesel engine lubricants to corrode various metals,
specifically alloys of lead and copper commonly used in cam
followers and bearings. This test method is similar to the
Cummins Bench Corrosion Test and is based on Federal Test
Method Standard 791, Method 5308.
Four clean, polished, pre-weighed metal coupons of copper, lead, tin, and phosphor bronze are tied together and
placed in a test tube containing 100 ml of test oil. The test
tube is heated in a bath to 121C and air is delivered to the
system at a rate of 5 L/h. The test is r u n for 168 h. An industrial reference oil is evaluated with each group of tests to verify test acceptability. Upon completion of the test, the following results are reported:
the raw data of the calibration and the analysis of the reference oil
concentrations of copper, lead and tin in the oil before and
after adjustment based on the internal standard
corrected change in lead concentration
the tarnish rating of the copper coupon
the change in weight of each of the coupons

31: CORROSION

motored for 4 h at 82.2C. At the end of 4 h of operation, the


whole differential unit is stored in an environmental storage
box for 162 h at 51.7C. At the end of the storage time, the
unit is disassembled and rated for corrosion, sludge, and
other deposit formation.
Industrial Fluid Lubricants
ASTM B 117, Standard Practice for
Salt Spray (Fog)
Apparatus

Operating

The ASTM B 117 Salt Spray is commonly referred to as Salt


Fog. Salt spray and salt fog are frequently thought of as different but are in fact the same, as noted in the title. It may be
easier to think of this apparatus as producing a mist. In any
case, it offers an accelerated method for evaluating the rust
prevention characteristics afforded by a coating on a metal
surface. For example, failure (rusting) can occur in a few
hours for a thin, oily coating, or in thousands of hours for a
thick, hard coating. Often used as a screening test because of
the speed at which results can be obtained, an aqueous solution of 5% sodium chloride is continuously atomized in the
cabinet engulfing the test panels, creating an environment
conducive to accelerated corrosion.
The test apparatus consists of a cabinet capable of maintaining a temperature of 35C where pressure and the introduction of the salt containing vapors can be controlled. Test
panels are set on internal racks, as shown in Fig. 6, and are
subjected to the salt a t m o s p h e r e for variable amounts of
time. Results are tjrpically reported as the number of hours to
failure (onset of rust).
ASTM D 665, Standard Test Method for
Rust-Preventing
Characteristics
of Inhibited
Mineral Oil in the Presence of Water
Originally designed to determine the rust prevention characteristics of steam-turbine oils when contaminated with water, the ASTM D 665 test method now is used to indicate the
rust preventive properties of almost all types of industrial lubricants, particularly hydraulic fluids and circulating oils
where water contamination can be expected. Rusting of steel
is, of course, destructive to the hydraulic or circulating system itself. Also, rust particles in the fluid can cause plugging
of close-clearance passages and/or filters and, being abrasive

Gear Oils
CRC L-33, Gear Oil Corrosion

Test

This test method evaluates the rust and corrosion inhibiting


properties of gear oils subjected to water contamination and
elevated temperature. It duplicates service conditions where
water condenses on metal parts. (This test method is based
on Federal Test Method 5326.1.)
This test utilizes a Dana Model 30 hypoid differential unit.
This unit is cleaned (including shotblasting), assembled, and
then filled with 1200 ml of oil and 30 ml of water. The unit is

829

FIG. 6ASTM B 117, Salt


Spray (Fog) Panel.

830

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

in nature, can contribute to wear, particularly of p u m p s . Additionally, particles of rust in the oil can act as catalysts to increase the rate of oil oxidation.
A polished steel rod (spindle) is suspended in a 400 ml
beaker containing 300 ml of the test oil, which is stirred at
60C. After 30 min, 30 ml of water are added to the oil. It is
customary to run the test for 24 h; however, other times may
be specified. The 10% water addition to the oil can be either
distilled water (Procedure A) or a defined synthetic sea water
(Procedure B). The test is normally r u n in duplicate and any
visible rust on both rods indicates failure. Results are reported as a pass or fail. Because of the greater severity, the
synthetic sea water (Procedure B) is frequently used as a
screening test [salt makes water a better electrolyte and accelerates the corrosion process]. Results should always specify which procedure (A or B) was used a n d the amount of
time the test was run. Figure 7 shows a passing (rust-free)
spindle on the left and a failing spindle on the right.
ASTM D 1748, Standard Test Method
Rust Protection by Metal Preservatives
Humidity
Cabinet

for
in the

The ASTM D 1748 test method is used to evaluate the relative


abilities of metal preservatives to prevent the rusting of steel
panels under conditions of 100% relative humidity at 50C.
This test is not as severe as the Salt Fog Test (ASTM B 117).
It is not u n c o m m o n for test panels to r u n well over 1000
hours before the onset of rust.
Steel panels are prepared to a prescribed surface finish,
dipped in the test fluid, allowed to drain and then suspended
in the humidity cabinet, as shown in Fig. 8. A continuous
supply of air is delivered to the cabinet, which is held at 50C.
Water is m a i n t a i n e d in the b o t t o m of the cabinet as the
source of humidity. Panels are periodically checked for signs
of rust. A failure occurs at the point in time when either a rust
spot Icirger than 1 m m in diameter appears or four rust spots
of any size are observed. Results are reported as hours to failure as described above.
ASTM D 2070, Standard Test Method
Thermal Stability of Hydraulic
Oils

for

The ASTM D 2070 test m e t h o d is widely known as the


"Cincinnati Milacron" test. This test method is designed to

FIG. 8ASTM D 1748, Humidity Cabinet Interior.

evaluate the thermal stability of h y d r o c a r b o n based hydraulic oils in the presence of copper a n d steel at 135C.
However, oxidation of the oil may also occur during the test.
Clean, polished, pre-weighed copper a n d steel rods are
placed in a 250 ml beaker, which contains 200 ml of the test
oil. The bcciker is placed in an aluminum block in an oven
for 168 h at a test temperature of 135C. At the completion of
the test, the copper and steel rods are rated visually for discoloration and the oil is analyzed for the quantity of sludge
formation.
ASTM D 3603, Standard Test Method for
Rust-Preventing
Characteristics
of Steam Turbine Oil
in the Presence of Water (Horizontal Disk
Method)
The ASTM D 3603 test method is used to eveJuate the ability
of steam-turbine oils (under full flow and quasi-static conditions) to prevent the rusting of horizontjil and vertical ferrous
surfaces w h e n water becomes mixed with oil. Horizontal
metal surfaces, on which water droplets tend to be retained,
are more prone to corrosion than vertical or sloping surfaces.
This test m e t h o d is therefore more discriminating t h a n
method ASTM D 665 Procedure A, since it gives a separate
evaluation of the oil on a horizontal emd a vertical surface.
A horizontal steel disk and vertical steel cylinder assembly
is placed in a bath of 275 ml of oil, which is stirted at 60C.
After 30 min, 25 ml of distilled water are added to the oil. The
test is r u n for 6 h. The test is r u n in duplicate and any visible
rust on b o t h assemblies indicates failure. Results are reported as a pass or fail.
ASTM D 4310, Standard Test Method for
of the Sludging and Corrosion Tendencies
Inhibited Mineral Oils

FIG. 7ASTM D 665,


Passing and Failing
Spindles.

Determination
of

The ASTM D 4310 test procedure is a modification of the test


method D 943. It is used to determine the tendencies of inhibited mineral oil based steam turbine lubricants and mineral oil based anti-wear hydraulic oils to corrode copper catalyst metcil and to form sludge during oxidation. The test is
conducted in the presence of oxygen, water, and copper and
iron metals at an elevated temperature. This test method is
also used for testing circulating oils having a specific gravity
less t h a n that of water and containing rust and oxidation
inhibitors.

CHAPTER
This test utilizes a special piece of glassware known as a n
oxidation cell. A 300 ml sample of the test oil, 60 ml of water,
and a catalyst (a 225 m m braided low carbon steel-copper
coil) are placed in the oxidation cell, which is heated in a bath
to 95C. Oxygen is delivered to the system at a rate of 3 L/h.
The test is run for 1000 h. Upon completion of the test, the
weight of the insoluble material (sludge) that is formed and
the total a m o u n t of copper in the oil, water, a n d sludge
phases is reported.
ASTM D 4627, Standard Test Method for Iron Chip
Corrosion for Water-Dilutable
Metalworking
Fluids
Also known as the Cast Iron Chip Test, the ASTM D 4627 test
method evaluates the ferrous corrosion control characteristics of water-dilutable metalworking fluids. The results obtained by this test are useful in determining the ability of water-diluted metalworking fluids to prevent or minimize rust
under specific conditions. This procedure is typically used
for screening and comparative purposes.
Cast iron chips are placed in a petri dish containing a filter
paper and a water-diluted metalworking fluid. The dish is
covered and allowed to stand for 20-24 h. At the end of the
test period, the filter paper is rinsed with water and the percent of the filter paper area that was stained by the rusting
chips is estimated. The amount of rust stain on the filter paper is an indication of the corrosion control provided by the
fluid. The "breakpoint" is defined as the weakest concentration tested that left no stain on the filter paper.
ASTM D 4636, Standard Test Method for
Corrosiveness
and Oxidation Stability of Hydraulic
Oils, Aircraft Turbine Engine Lubricants,
and Other
Highly Refined Oils
The ASTM D 4636 test method is used to test hydraulic oils,
aircraft turbine engine lubricants, and other highly refined
oils to determine their resistance to oxidation and corrosion
degradation and their tendency to corrode various metaJs.
Petroleum and synthetic fluids may be evaluated using moist
or dry air with or without metal test specimens. (This test
method is basically Federal Test Method 5307.2 expanded to
include Federal Test Method 5308.7.)
This test method consists of a standard test procedure and
two alternative procedures. In the test procedure, a large
glass tube containing the test oil and pre-weighed metal specimens is placed in a constant temperature bath and heated
for a specified n u m b e r of hours while air is passed through
the oil. The different test procedures allow for various oil
sample sizes (200 ml, 165 ml and 100 ml), various bath temperatures (typically 100C to 360C) and different shaped
(washer-shaped and square) specimens of various metals (titanium, magnesium, steel, bronze, silver, aluminum, copper,
cadmium and others).
At desired test times, oil samples are withdrawn from the
test oil and checked for changes in viscosity cind acid number. At the end of the test, the amount of sludge present in the
oil remaining in the tube and the quantity of oil lost (evaporated) during the test are determined. The corrosiveness of
the oil is determined by loss of mass of the metal specimens
and microscopic examination of the metal surfaces. Also, the
presence of liquid or solid material o n the inside of the
condenser and the appearance of deposit on the sample tube
are reported.

31: CORROSION

831

Greases
ASTM D 1743, Standard Test Method for
Determining
Corrosion Preventive Properties of Lubricating
Greases
Since the early 1960s, the most popular grease rust test in the
United States has been ASTM D 1743. This method determines the rust preventive properties of greases using tapered
roller bearings stored under static conditions in the presence
of distilled water.
Tapered roller bearings, as shown in Fig. 9, are packed with
grease and r u n under a light load to distribute the grease
evenly. The bearings are exposed to distilled water and then
stored at 52C and 100% relative humidity for 48 h. After
cleaning, the bearing races are examined for rust. Since 1987,
the ASTM D 1743 procedure has specified a pass or fail rating on the basis of a single corrosion spot of 1.0 m m or larger
in the longest dimension on two of three bearings tested simultaneously.
ASTM D 4048, Standard Test Method for Detection
Copper Corrosion from Lubricating
Grease

of

The ASTM D 4048 test method is similar to the ASTM D 130


test used for industrial oils but is designed to evaluate the
copper corrosion prevention properties of greases.
A polished and cleaned 3-in. copper strip as prescribed in
ASTM D 130 is placed in a jar in which the copper strip is totally i m m e r s e d in the test grease. The jar is capped and
heated to a specified temperature for a defined period of
time. Commonly used conditions are 100C for 24 h. At the
end of the exposure period, the strip is removed, wiped clean
and matched with colored reproduction strips characteristic
of the descriptions provided in Table 3.
ASTM D 5969, Standard Test Method for
CorrosionPreventive Properties of Lubricating
Greases in Presence
of Dilute Synthetic Sea Water
Environments
The ASTM D 5969 test method is the synthetic seawater version of ASTM D 1743, which specifies the use of only distilled
water. The test methods are identical except for the following
changes, which are incorporated into the ASTM D 5969
method:
The tapered roller bearings are exposed to desired concentrations of synthetic seawater (prepared as specified in test

FIG. 9ASTM D 1743 and


ASTM D 5969, Tapered
Rolling Bearing.

832

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

method ASTM D 665, Procedure B) diluted with distilled


water.
The test time is reduced from 48 h to 24 h.
Tapered roller bearings are packed with grease and r u n under a light load to distribute the grease evenly. The bearings
are exposed to desired concentrations of synthetic seawater,
then stored at 52C and 100% relative humidity for 24 h. After cleaning, the bearing races are examined for corrosion.
This procedure specifies a pass or fail rating on the basis of a
single corrosion spot of 1.0 m m or larger in the longest dimension on two of three bearings tested simultaneously.
ASTM D 6138, Standard Test Method for
CorrosionPreventive Properties of Lubricating
Greases Under
Wet Conditions
(Emcor
Test)

FIG. 11ASTM D 6138, Emcor


Bearing Race (showing rust spots).

The ASTM D 6138 test method is commonly referred to as the


"Emcor Test" and is an adopted version of the IP 220 European procedure. This test is a dynamic procedure used to determine the corrosion protection of a grease in the presence
of water approximating typical service conditions.
Double r o w self-aligning ball bearings are packed with
grease and r u n to distribute the grease evenly. The bearings
are exposed to distilled water, synthetic seawater, or sodium
TABLE 4Emcor corrosion classifications.
Ranking

Description
No evidence of corrosion
No more than three spots of a size just sufficient to
be visible
Up to 1% surface corrosion
Between 1% and 5% surface corrosion
Between 5% and 10% surface corrosion
More than 10% surface corrosion

FIG. 12ASTM D 6138, Emcor


Apparatus.
chloride solution, and the test rig is operated under alternating r u n n i n g a n d standing conditions for one week. After
cleaning, the bearing races are examined for corrosion and
rated "0" to "5" as detailed in Table 4. Figure 10 shows a rustfiree Emcor bearing race. Figure 11 shows an Emcor bearing
race with rust. The test rig, as shown in Fig. 12, will simultaneously run eight bearings. Duplicate determinations are required, so the rig is normally used to evaluate four different
formulations at a time.

REFERENCES

FIG. 10ASTM D 6138, Emcor


Bearing Race (rust-free).

[1] Basic Corrosion Technology for Scientists and Engineers, The


Institute of Materials, London, 1996, pp. 37-61.
[2] Clark, D. B., Klaus, E. E. and Hsu, S. M., "The Role of Iron and
Copper in the Oxidation Degradation of Lubricating Oils," Lubrication Engineering, May, 1985, pp. 280-286.
[3] Basic Corrosion Technology for Scientists and Engineers, The
Institute of Materials, London, 1996, pp. 95-130.

MNL37-EB/Jun. 2003

Flow Properties and


Shear Stability
Robert E. Manning^ and M. Richard Hoover^

T H E IMPORTANCE OF FLOW PROPERTIES IN THE MANUFACTURE AND

USE OF MATERIALS Cannot be over emphasized. The flow properties of materials ranging from gasses, such as oxygen, to
hquids, such as water, paints and lubricants, to semi-solid
and solid materials such as asphalt cements, glass, and steel
aire important in both the manufacture and use of these materials. In the manufacturing of materials, flow properties
can affect the manner in which materials are handled and
packaged. For example, p u m p s , mixing equipment, and
packaging equipment must be correctly selected and sized to
handle the material being processed. Likewise, flow properties are important in the use of materials. Paints must be
designed to flow when brushed, but remain on the painted
surface, even when the surface is vertical. Lubricants must
have flow properties allowing them to be distributed to the
required location and then remain to provide appropriate
lubrication. As can be seen from these few examples,
m e a s u r e m e n t and characterization of flow properties are
essential.
There is a long history of the measurement of flow properties of materials. Isaac Newton laid the groundwork for the
m a t h e m a t i c a l t r e a t m e n t of the flow of materials in his
Philosophiae Naturalis Principia Mathematica, 1687, Book 2,
Section IX,
HYPOTHESIS: The resistance arising from the want of
lubricity in the parts of a fluid is, other things being
equal, proportional to the velocity with which the parts
of the fluid are separated from o n e another.
In 1823 Navier stated the general equations for fluids in
motion [1]. Hagen [2] and Poiseuille [3] both studied the viscosity of water flowing in capillaries in the mid 1840s, and
they determined the relationship between the quantity of
flow and the pressure drop, diameter, and length of the capillary tube. In 1890 Couette developed the rotating concentric
cylinder apparatus [4]. In the early 1900s A. Pochettino noted
a n u m b e r of types of apparatus for the measurement of viscosity of semi-solid materials such as asphalts and tars [5].
Bingham and Jackson [6] reviewed viscosity data attributed
to water, and selected a value (1.005 mPa-s at 20C) for the
primary viscosity standard, a value that was unchanged for
nearly 40 years. Ubbelohde [7] and Cannon and Fenske [8]
developed glass capillary viscometers in the mid-1930s,
which were responsible for the adoption and wide use of
kinematic viscosity measurements in the petroleum industry.

' Consultant, 225 Harris Drive, State College, PA 1680L


^ President, Cannon Instrument Company, State College, PA 168040016.

Research by Appeldoorn [9], Klaus [10], Wright [11], and


many others in the 1950-1960s and later led to many of the
instruments and specifications for m o d e m - d a y lubricants.
Very active interest in viscosity and flow properties continues today within the scientific and engineering communities.
International organizations such as ISO (International Standards Organization) and OIML (International Organization
of Legal Metrology) along with national organizations
such as the Institute of Petroleum (United Kingdom), DIN
(Germany), JIS (Japan), and ASTM International (International), actively develop and maintain test methods and specifications for viscosity and fluid flow properties. Although
there are differences between each of the several test methods, all of the test methods relating to similar properties are
interrelated and, in some cases, derived from a corresponding ASTM test method. In cases where more than one test
method is available for a given measurement, the selection of
the method to use is based on factors such as the specifications to be met, the sample size, equipment already available
in the laboratory, budget, etc.
Within ASTM International, various committees have responsibility for viscosity-related test methods to support the
development and specification of materials falling under the
jurisdiction of the individual committees. Some of these
committees include Petroleum Products a n d Lubricants
(D02), Road and Paving Materials (D04), Paints and Related
Coatings (DOl), Plastics (D20), Rubber ( D l l ) , and Adhesives
(D14). This chapter focuses primarily on the ASTM methods
for the measurement and characterization of flow properties
of petroleum products, although reference to other types of
material is m a d e as appropriate. Various characterization
techniques are discussed along with their historical perspectives. Specific references to ASTM test methods are included
to provide the reader with a better understanding of both the
m e a s u r e m e n t technique and the application of the test
method. Note that all referenced ASTM methods are included
in a table at the conclusion of the chapter.

NOMENCLATURE AND RHEOLOGY


CONSIDERATIONS
The science of the deformation and flow of matter including
both the flow and elasticity of material is defined as rheology.
The material may be a solid such as tar or bitumen, or a
liquid such as molasses or water, or a gas such as air. In addition, there are many materials that do not deform when a
small stress is applied to the material, but flow readily at a

833
Copyright'

2003 by A S I M International

www.astm.org

834

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

higher stress. Rheology is central to the measurement of flow


properties of materials. All measurements of viscosity involve
imparting motion to a fluid and observing the resulting deformation of that fluid. Often a material shows both flow and
elastic c o m p o n e n t s , such as the example of Silly Putty*,
which can be formed into a ball that bounces when dropped,
but flows as a viscous liquid u p o n standing. Materials that
have the ability to absorb some of the applied stress (and
when the stress is relieved, giving back the energy) are said to
be viscoelastic, because they exhibit both viscous and elastic
properties. Some materials exhibit a decreased viscosity as
the applied stress is increased (shear thinning), while other
materials exhibit an increased viscosity with an increase in
the applied stress (dilatant material).

Dynamic ViscosityTJ, the ratio of the shear stress, T, to the


shear rate, y. Another term for viscosity, dynamic viscosity
is used, especially in Europe. It should be noted that the
term dynamic viscosity is also used for the determination of
viscosity when the stress is applied in an oscillatory mode.
Hopefully this dual use of dynamic viscosity will not be
confusing. In this chapter, unless otherwise stated, the
term viscosity is equivalent to dynamic viscosity and does
not imply stress applied in an oscillatory mode.
Kinematic Viscositythe ratio of viscosity, TJ, to the density
of the fluid, p, both at the same temperature. It is a measure
of the resistance to flow of a liquid under gravity.

To assist the r e a d e r in u n d e r s t a n d i n g the details of


viscosity measurement, terminology related to viscosity is
presented in Table 1.
Throughout this chapter, the System International (SI)
units are primarily used; these units are based on the meterkilometer-second (mks) system of units, and should not be
confused with the centimeter-gram-second (cgs) system of
units.
Because the current usage of terms includes both the SI
and the cgs systems of units, the conversions in Table 2 may
be helpful.
Some definitions of c o m m o n terms (mostly adapted from
ASTM methods) that will be used in this chapter are:

Viscoelastic Materialsmaterials
that exhibit both elastic
and viscous properties. Under an oscillatory mode of applying the stress to Newtonian liquids, stress a n d the
resulting strain are in p h a s e with each other. For viscoelastic liquids, the stress and strain are out of phase. The
phase angle between stress and strain is a measure of the
elasticity of the liquid. Certain automotive engine oils
contain polymers that cause the oil to be viscoelastic.
Shear Stressthe motivating force per unit area for fluid
flow.
Shear Ratethe velocity gradient in fluid flow.
Newtonian Liquida fluid that exhibits a constant viscosity at all shear rates. If the viscosity is not constant, the
liquid is non-Newtonian.
Simple liquids such as water,
hexane, and refined oils without polymeric additives are
Newtonian.
Fluiditythe reciprocal of viscosity.
Consistencythe resistance of a non-Newtonian material
to deformation or flow. Consistency is not a fundamental
property but is m a d e u p of viscosity, plasticity, and other
rheological phenomena. These are not normally found in
petroleum jargon.
Shear Thinning (pseudoplastic)the
property of a nonNewtonian material exhibiting r e d u c e d viscosity at increasing shear rates. Lubricating Oils with high molecular
weight polymeric additives are t3^ically shear thinning.
Shear Thickening
(dilatancy)the
property of a nonNewtonian material exhibiting increased viscosity at increasing shear rates. Suspended particles emd slurries can
be examples of dilatant materiEils.
Yield Stressthe stress required to initiate flow. For all
Newtonian fluids and some non-Newtonian fluids, yield
stress is zero. Automotive oils when cooled slowly to low
temperature can form a partial, interconnecting wax structure; this structure can cause a yield stress sufficient to
prevent pumping of the oil.
Plastic (Bingham) Bodya liquid having a yield stress, TQ,
to be overcome before flow results, and thereafter the flow
is Newtonian.

Rheologythe science of t h e deformation a n d flow of


materials
Viscositythe resistance experienced by one portion of a
material moving over another portion of the material. It is
the ratio of the shear stress existing between laminae of
moving fluid and the rate of shear between these laminae.
Viscosity is often called the coefficient of viscosity. Viscosity, rj, is defined as the ratio of the shear stress, T, to the
shear rate, y.
Tj =

riy

(1)

TABLE 1Terminology & units.


Quantity

Symbol

SI Units

cgs Units

Shear stress
Shear rate
Viscosity
JCinematic viscosity
Viscosity of Solution
Relative viscosity, % = {riJ^i)
Specific viscosity, (% 1)
Intrinsic viscosity,
[rj] = lim(rjsp/c ), c ^ 0
First normal stress.
Weissenberg effect

T or <T
y
f]
V
rjs

Pa (Pascal)
s~'
Pa-s
m'^/s
Pas

dyn/cm^
s->
P (Poise)
St (Stokes)
P

7)r
%p

[ij]

m^/kg

mL/g

Ni(y)

V = (T-

TABLE 2 --Conversion factors.


Viscosity:

Kinematic Viscosity:

1 Pa-s
1 mPa-s
1 Pas
1 m^/s
1 mm^/s
1 m^/s

=
=
=
=
=
=

V = Tj/p = r / p y

10 P
IcP
1000 m P a s
lO^'St
IcSt
IC* mm^/s

To)ly

(2)

(3)

Thixotropythat
p r o p e r t y of a material to thin u p o n
isothermal agitation, and to thicken upon subsequent rest.
Some paints are m a d e to be thixotropic, such that the energy needed to b r u s h the paint at high shear is reduced, but
when the brushing is stopped the structure reforms and the
paint stays in place.

CHAPTER 32: FLOW PROPERTIES


Apparent ViscosityThe viscosity determined for a nonNewtonian material using a test method for which Newtonian standards are used for cahbration, for example, the
viscosity determined according to test method D 5293,
Apparent Viscosity of Engine Oils Between 5 and 30C
Using the Cold-Cranking Simulator. The apparent viscosity
so determined is thus also a function of the test apparatus.
Softening Pointthe temperature at which a material becomes soft enough to flow, as determined by an arbitrary,
narrowly defined method.
Power Law Modela mathematical model used to describe
the behavior of shear-thinning liquids. Experimental results for many shear thinning liquids fit closely the power
law model over a limited shear rate range - often up to
three decades of shear rates
r] = Ky'( n - l )

(4)

when n = 1
Newtonian liquid
n< 1
Shear thinning liquid
First Normal Stress, Weissenberg EffectThe vector normal
to the direction of the applied shear stress. The first normal
stress is a measure of the elastic component of viscoelastic
materials. This elastic component can cause viscoelastic
materials to "climb" a rotating shaft or push the cone away
from the plate in a cone-plate instrument. Automotive engine oils with some polymeric additive packages can exhibit the Weissenberg Effect. See the Annex to ASTM D 5293
for a discussion of the Weissenberg Effect as related to the
Cold-Cranking Simulator. Note that all referenced ASTM
methods are included in a table at the conclusion of the
chapter.
Shear StrainThe quotient of shear deflection divided by
the thickness of the test piece.
ModulusThe ratio of stress to strain; that property of a
material which, together with the geometry of a specimen,
determines the stiffness of the specimen; may be static or
dynamic, and if dynamic, is mathematically a vector quantity, the phase of which is determined by the phase of the
complex force relative to that of deflection (ASTM D 5992).
Elasticas a modifier of dynamic force, descriptive of that
component of complex force in phase with dynamic deflection, that does not convert mechanical energy to heat,
and that can return energy to an oscillating mass-spring
system; denoted by the single prime (') as a superscript
symbol, as F' (ASTM D 5992).

AND SHEAR STABILITY

For two planes of a unit area A separated by a unit distance


Y, the viscosity TJ of the material between the planes can be
defined [12] as
V = (F/A)/(V/Y)

(5)

Many of the general measurements of viscosity incorporate


a rotational geometry. For example, the fluid may be between
a flat plate and a cone (see e.g., ASTM D 4287, D 3205) (Fig.
2) or between two flat plates (Fig. 3).
Two additional rotating viscometers include the concentric
cylinder incorporating the annular space between a cylindrical rotor inside a cylinder (Couette geometry), Fig. 4, (e.g., D
4864, D 5133), and a paddle in a cup (e.g., D 562), Fig. 5.
In these rotational geometry viscometers, either the inner
or outer member may rotate while the other member is held
static. The rotational speed may be constant while the torque
or stress is measured, or the torque or stress may be held constant while the speed is measured. The speed may increase
from zero to a maximum and back to zero, or it may follow a
sinusoidal speed variation.

drive

mechanism

torque

spring

cone
''.:.",] t e s t sample
plate
FIG. 2Cone-and-plate viscometer.

drive

mechanism

Viscometer Geometries and General Techniques


There are a number of geometries and techniques commonly
used to determine viscosity. To visualize viscosity, we first
refer to Fig. 1.
torque

spring

MOVING PLANE, AREA

THICKNESS OF
FLUID FILM = h

STATIONARY PLANE AREA = A

FIG. 1Visualization of viscosity.

835

"7~|^ upper plate


test sample
] lower plate
FIG. 3Plate-to-plate geometry.

836

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Another c o m m o n geometry involves the flow of a fluid


through a capillary tube (Fig. 6).
If the motion of the fluid through the capillary is driven by
its hydrostatic head under the influence of gravity, kinematic
viscosity will be the measured property. If the fluid is forced
t h r o u g h the capillary by a n applied pressure (or d r a w n
through the capillary by a vacuum), viscosity is measured. As
noted above for the various rotational geometries, there are
also many special geometries used for the measurement of
kinematic viscosity.
Other less c o m m o n techniques for the measurement of viscosity exist. An object such as a ball (e.g., D 1343) or a needle
(e.g. D 5478) can be moved through a liquid under the influence of gravity at a rate influenced by the difference in
density between the ball and fluid in a vessel. Alternatively,
the ball m a y merely roll down hill through a cylinder, or a

drive

flow through
capillary

Newtonian Liquid

driving head

piow Patte

Bingham Liquid

FIG. 6Flow through capillary tube profiles.

mechanism

torque

spring
Falling Ball viscometer

Rolling Ball visconneter

FIG. 7Falling and rolling ball viscometers.

rotor
cup

FIG. 4Concentric cylinder viscometer.

drive

mecinanism

torque spring

paddle
cup
FIG. 5Paddle type rotational viscometer.

bubble of air can rise in a cylinder containing the test sample


(e.g., see D 1545) (Fig. 7).
Other variations include needle and crystal viscometers. A
needle can be caused to descend through a fluid, wherein its
velocity is proportional to the ratio of its velocity to the density difference between the liquid and the needle. A crystal or
a tuning fork can be caused to oscillate in a liquid. The restrictive force of the fluid along the surface of the crystal is a
measure of the viscosity, the elasticity, or both. A vibrating
crystal can cause a wave to be generated through the fluid.
The reflection of the wave back to the crystal allows the measurement of the viscosity of the fluid by the attenuation of the
wave, and a measure of the elasticity of the fluid by the phase
change of the wave.
There are numerous ASTM methods used to determine the
viscosity of petroleum products. As shown in Table 3 the type
of viscometer used in each method differs.

FLOW PROPERTIES OF PETROLEUM


MATERIALS
Measurement and control of flow properties are extremely
important to the petroleum a n d lubricants industries. The
ASTM subcommittee on Flow Properties (D02.07) is prominent in the development of test procedures for petroleum

CHAPTER 32: FLOW PROPERTIES AND SHEAR STABILITY

837

TABLE 3Table of petroleum related viscometer methods.


Title of Method
Saybolt Viscosity
Kinematic Viscosity of Transparent and Opaque Liquids (and the Calculation
of Dynamic Viscosity)
Measuring Apparent Viscosity of Lubricating Greases
Basic Calibration of Master Viscometers and Viscosity
Viscosity and Viscosity Change After Standing at Low Temperature of Aircraft
Turbine Lubricants
Apparent Viscosity of Petroleum Waxes Compounded with Additives (Hot
Mehs)
Low-Temperature Viscosity of Automotive Fluid Lubricants Measured by
Brookfield Viscometer
Apparent Viscosity of Hot Melts Adhesives and Coating Materials
Pumpability of Industrial Fuel Oils
Predicting the Borderline Pumping Temperature of Engine Oil
Kinematic Viscosity of Volatile and Reactive Liquids
Measuring Apparent Viscosity by Capillary Viscometer At High-Temperature
and High-Shear Rates
Measuring Viscosity at High Shear Rate and High Temperature by Tapered
Bearing Simulator
Determination of Yield Stress and Apparent Viscosity of Engine Oils at Low
Temperature
Measuring Viscosity at High Temperature and High Shear Rate by TaperedPlug Viscometer
Shear Viscosity of Coal-Tar and Petroleum Pitches
Low Temperature, Low Shear Rate, Viscosity/Temperature Dependence of
Lubricating Oils Using a Temperature- Scanning Technique
Apparent Viscosity of Engine Oils Between - 5 and -30C Using the ColdCranking Simulator
Measuring Apparent Viscosity at High-Temperature and High-Shear Rate by
Multicell Capillary Viscometer
Evaluation of Diesel Engine Oils in the T8 Diesel Engine
Defining the Viscosity Characteristics of Hydraulic Fluids

Method No.
D88
D445
D 1092
D2162
D2532
D2669
D2983
D3236
D3245
D3829
D4486
D4624
D4683
D4684
D4741
D5018
D5133
D5293
D5481
D5967
D6080

Type of Viscometer/Geometry
short capillary
capillary low shear
capillary high shear
capillary low shear
capillary low shear
rotational coaxial cylinder
rotational coaxial cylinder
rotational coaxial cylinder
rotational coaxial cylinder
rotational coaxial cylinder
capillary low shear
capillary high shear
rotational tapered cylinder
rotational coaxial cylinder
rotational tapered cylinder
rotational coaxial cylinder
rotational tapered cylinder
rotational coaxial cylinder
high shear capillary
capillary low shesir
capillary low shear

products from high temperature (<150C) and high shear


rates (>10* s~') to low temperatures (< SOX) and to low
shear rates approaching zero s~'. Their flow-related test procedures are widely used in product specifications, within
both the ASTM and the Society for Automotive Engineers
(SAE).

The factor, p-H, is the hydrostatic pressure that forces the


liquid through the capillary. By combining the density, p,
with the viscosity, TJ, neither density nor viscosity have to be
separately measured to determine kinematic viscosity (ASTM
D 445, ASTM D 446).

Kinematic Viscosity

Most generally the equation for the glass capillary kinematic


viscometers combines into a constant, C, all of the factors
that are not normally individually measured except the flow
time, t, resulting in the equation:

Kinematic viscosity, v, is the ratio of viscosity, rj, to density,


p. It is very widely used in petroleum specifications and in
specifications for many other materials.
V = Tj/p

(6)

While the measurement of viscosity and density allows the


calculation of kinematic viscosity, the direct measurement of
kinematic viscosity is most frequently done with simple, lowcost glass capillary viscometers. For glass capillary viscometers,
viscosity, -rj, is defined by:
Tj = ( i 7 g D 4 H p t ) / ( 1 2 8 V L )
where

g
D
L
H

=
=
=
=

(7)

acceleration due to gravity


diameter of the capillary
length of the capillary
average distance between the upper and lower
menisci
V = the timed volume of liquid passing through the
capillary
t = flow time

V = Tj/p = (TTg D" H t) / (128 V L)

V = Tj/p = C t
where

(8)

(9)

C = viscometer constant
t = measured flow time between two timing meirks

The constant, C, is determined by using a certified reference


viscosity standard, paying careful attention to the filling of
the viscometer, mounting the viscometer in the same orientation to ensure a constant driving head, temperature measurement and control, etc., as is required in the measurement
of kinematic viscosity.
For short flow times (less than 200 s) and for liquids having
a kinematic viscosity of less than 10 mui^/s, a "kinetic energy"
correction should be applied. The equation then becomes
V = C t - E/t^

(10)

The kinetic energy correction, E, is represented by the equation


E = 52.5 V^'^/L (C D)"2

(n)

838 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


where

L
V
C
D
E

=
=
=
=
=

working capillary length


timed volume
viscometer constant
working capillary diameter
kinetic energy correction factor

The equation for the calculation of E allows the estimation of


the kinetic energy correction. If possible, it is preferable to
determine the value of E using several viscosity standards
[13]. The three general types of glass capillary, kinematic
viscometers that are most frequently used include the:
modified Ostwald tj^es for transparent liquids,
suspended level types for transparent liquids, and
reverse-flow types for transparent and opaque liquids.
The m i n i m u m and maximum kinematic viscosity ranges for
each instrument type are found in Tables 46. The viscometers
are shown in Figs. 8-10.
While there are precise instructions for running each of the
above kinematic viscometers, generally all procedures follow
the same set of basic steps. The test sample is inserted into
the viscometer and allowed to reach bath temperature. The
b a t h temperature is normally controlled to 0.01C. After
reaching test temperature the test sample is allowed to flow
under gravity past the two timing marks, and the flow time is
measured to the nearest 0.1 s or more recently, 0.01 s. Kinematic viscosity is calculated as the product of the flow time
and the calibration constant, C. All of the modified Ostwald

TABLE 4Modified Ostwald types for transparent liquids.


Kinematic Viscosity
Range, mm^/s
Type
Comments
Cannon-Fenske routine
0.5 to 20 000
widely used
Zeitfuchs
0.6 to 3000
rarely used
BS/U-tube
0.9 to 10 000
used in Europe
BS/U/M miniature
0.2 to 100
<2 mL sample
SIL
0.6 to 10 000
rarely used
Cannon-Manning semi-micro
0.4 to 20,000
< l m L sample
Pinkevitch
0.6 to 17 000
rarely used

TABLE 5Suspended-level Types for Transparent Liquids


Kinematic Viscosity
Range, mm^/s
Type
Comments
used in Europe
BS/IP/SL
3.5 to 100 000
rarely used
BS/IP/SL(S)
1.05 to 10 000
<2 mL sample
BS/IP/MSL
0.6 to 3000
widely used
Ubbelohde
0.3 to 100 000
rarely used
0.6 to 1200
FitzSimons
rarely used
0.75 to 5000
Atlantic
widely used
0.5 to 100 000
Cannon-Ubbelohde
dilute solution
0.5 to 100 000
Cannon-Ubbelohde
dilution
0.4 to 20 000
<2 mL sample
Cannon-Ubbelohde
semi-micro

TABLE 6Reverse-flow types for transparent and opaque liquids.


Kinematic Viscosity
TypeRange, mm^'sComments
0.4 to 20 000
widely used
Cannon-Fenske opaque
0.6 to 100 000
asphalt solutions
Zeitfuchs cross-arm
0.6 to 300 000
widely used
BS/IP/RF U-tube reverse flow
60 to 100 000
rarely used
Lantz-Zeitfuchs reverse-flow

Euid suspended-level viscometers are used for liquids that are


transparentthat is, the meniscus can be observed through
the sample at the timing marks. Choosing which of these
several viscometers is to be used is generally a m a n n e r of
choice of the operator, since the precision of the measurement is nearly the same.
While all of the listed glass-capillary, kinematic viscometers can be used for accurate kinematic viscosity measurements, some of t h e m have special advantages or regional
uses.
Reverse-flow

Viscometers

The severed reverse-flow viscometers can be used for liquids


so dark (opaque) that the timing of the test liquid cannot be
observed after the test sample has previously wet the glass
capillary as is required in the modified Ostwald a n d suspended-level types. Tj^jically, the precision of the reverseflow viscometers is slightly poorer than the precision of the
modified Ostwald and suspended level viscometers; however,
the dark liquids, such as marine fuels, liquid asphalts, etc. are
often somewhat non-Newtonian. In North America, the Zeitfuchs Cross-arm viscometers are generally used for asphalts
(ASTM D 2170) while the Cannon-Fenske Opaque viscometers are typically used for lubricants that are so dark that the
meniscus cannot be seen through the test sample. In Europe,
the BS/IP/RF U-tube reverse flow viscometers are m o r e
popular.
British

Standard

(BS)

Types

The British Standard (BS) types are only infrequently used in


North America, while a n u m b e r of the other tj^es of viscometers commonly used in North America are less often
found in Europe.
Small

Volume

Types

For requirements where only a small amount of test sample


is available, the Cannon-Manning semi-micro, Zeitfuchs
cross-arm, and miniature suspended-level (BS/IP/MSL) are
preferred.
All of the suspended-level viscometers are distinguished by
having the bottom of the working capillary open to the atmosphere; thus, the driving head (the distance between the upper and the lower menisci) is independent of the precise volu m e of sample in the viscometer, and the calibration
constant is independent of temperature.
Modified

Ostwald

Viscometers

Certain modified Ostwald viscometer designs have the precise volume of charge at test temperature adjusted so as to
have the calibration constant independent of the test temperature. Several of the Modified Ostwald designs have a precise
volume of chcirge (generally at ambient temperature) initially
introduced, with a small temperature correction required if
the test temperature is not the same as that of the initial
charge temperature (Figs. 8-10).
Some liquids are either very reactive to the surrounding atmosphere (they could explode in the presence of oxygen) or
too volatile (at the temperature of test, the pressure is near or
above that of the atmosphere) to be measured in the normeil
kinematic viscometers. Such liquids may be able to be run in
specially designed "tilting" viscometers, in which the test

CHAPTER 32: FLOW PROPERTIES AND SHEAR STABILITY


o
o

o
CZ3

i
o
O

i
2
I

CO

B
in

C5
UJ

U.

nil
'I
I

I r

_Ll

I^1

o
u

o
U

839

840 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

^T7^

u
!Z!
U

, .

'

I
o

ti

E
o
O
(B

E
0)

00

>
a
0)

o
c

a
(0
3

(A

w
00

i^-Ni
1

^r

;5-^j^^^i_

-I

; ^
y

'

>

- *

*-%

00

Be

CHAPTER 32: FLOW PROPERTIES

Caimon-Fenske Opaque

Zeitftichs Cross-Arm

AND SHEAR STABILITY

BS/IP/RF U-tube Reverse-flow

841

Lantz-Zeitfiichs Reverse-Flow

FIG. 10Reverse-flow kinematic viscometers.

sample is sealed in the viscometer. See Fig. 11. By tilting the


viscometer, the test sample is allowed to fill the upper timing
bulb. Then the viscometer is restored to the normal upright
position, and run in the manner of other kinematic viscometers
(ASTM D 4486).
To measure kinematic viscosity, the typical practice is to assume that the net hydrostatic pressure used to force the test
sample through the capillary is p-H, where p is the density of
the test sample. However, the test sample is always buoyed up
by the density of the gas on the other side of the viscometer.
Thus, the true hydraulic force is H-(pi pg), where pi and pg
are the density of the test liquid on the one side of the viscometer and the gas on the other side (ASTM D 2162). Normally the density of the gas is insignificant in comparison to
that of the liquid; operation of kinematic viscometers at high
static pressures requires correction of the density of the gas.
Other special short capillary viscometers (such as the Saybolt, Redwood, Engler, Ford cup, ISO cup, Zahn cup, Shell
cup, and bubble rise tubes ) are widely used to determine a
measure of kinematic viscosity, although the results are often
expressed as "instrument seconds", (e.g., Saybolt Universal
Seconds, SUS) instead of kinematic viscosity units. See Figs.
12 and 13.
Kinematic Viscosity History
The kinematic viscosity of a liquid has long been recognized
as a very important property. In 1840, Poiseuille, a professor
of physics in the Paris medical schools, studied the viscosity

CONNECTOR

KOVAfl TO
GLASS SEAL

I8ml VOL.

o
o

CAPILLARY
TUBING

e
(O

E
lOmm 0.0.
ARM ROTATED
9 0 * TO REAR

HEAVY WALL
CONSTRUCTION
THROUGHOUT

12mm O.D.
8
4SmfflO.O.

FIG. 11Tilting viscometer for vulnerable liquids.

842

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK
of water flowing in glass capillaries of 0.013-0.65 m m in diameter and u p to 1 m in length so as to better understand the
flow of blood through h u m a n capillaries [14,15]. The following equation was developed:
Q = k P D^'/L

(12)

where:
Q
L
D
P
k

ZAHN

GARDCO EZ

GARDCO Fisher

=
=
=
=
=

rate of flow through the capillary


length of the capillary
diameter of the capillary
applied pressure drop across the capillary
constant for water at a given temperature

Thus, the foundation of the flow properties of materials


was laid. Fortunately, the study of water flowing through
capillaries instead of blood was pursued. Blood is a non-Newtonian liquid, whose apparent viscosity varies with the shear
rate, and it does not obey the above equation.
Books by Barr [15] and Bingham [16] give an excellent history of early measurements of viscosity, the equations used,
cind the equipment. The term kinematic viscosity appears to
have been used only sparingly in the early 1920s, as Barr (loc.
cit., p. 4) implies in 1931:
The quotient of viscosity by density (TJ/P) assumes much
importance in hydraulics and aerodynamics, and has received the name "kinematic viscosity," usually abbreviated
as Greek letter nu (v). It has been suggested that the concept of kinematic viscosity should be regarded as the more

GARDCO FORD

FIG. 12Dip-cup viscometers. Viscosity cup drawings provided by the Paul N. Gardner Company, Inc.

32.5 0.5

LEVEL OF LIQUID
IN BATH-

OVERFLOW
RIM

1.7650.015
(0.0695t 0.0006)

12.25tO.10
(0.48210.004)

IOl

^ 3.0 + 0.2
(0.12t 0.01)
UNIVERSAL TIP
12511.0
(4.92t0.04)

3 MIN
3 MIN. _,;.
. 3 . 1 5 0 0.020

'^.i24otaoooe
I 12.25*0.1 0
r(0.482t0jl
0X)04)

BOTTOM OF BATH

CORK
STOPPER

;^ 4.3+0.2
1(0.17 10,01)
FUROL TIP

FIG. 13Saybolt viscometer tube and receiver.

I.D. AT GRADUATION
MARK

CHAPTER 32: FLOW PROPERTIES


fundamental, that of the ordinary or dynamical viscosity
being derived from it, instead of vice versa.
The importance of technical viscometers even into the later
part of the 20th century perhaps is best illustrated by Bingh a m [16] in 1922, for these viscometers continued to play a
prominent position in the history of the petroleum industry,
as described by Bingham:
Instruments very different from, those employed in scientific work are much in vogue both in this country (United
States) and abroad for industrial purposes, particularly in
the oil industry. Thus we have the Engler Viskosimeter in
Germany, the Redwood Viscometer in Great Britain, the
Saybolt Viscosimeter in the United States, the Barbey
Ixometre in France, and a host of others. Most of them
seem to have been devised with the idea in mind that the
time of flow of a given quantity of various liquids through
an opening is approximately proportional to the viscosity,
without much regard to the character of the opening. There
is usually a container that is filled to a certain level and a
short efflux tube opening into the air. The number of seconds required for a given quantity of liquid to flow out under gravity is taken as an indication of the viscosity.
As it was gradually realized that these times of flow were
not even proportional to the true viscosities, efforts have not
been wanting to reduce the times of flow to true viscosities.
Since the pressure is due to an average head of liquid h, the
pressure is hgp and the viscosity formula may be written
7]/p=At-B/t

(13)

Having obtained the values of the constants A and B by calibrating the viscometer with liquids of known viscosity it appears possible to calculate the kinematic viscosity -q/p, but if
absolute viscosities are desired it is necessary to make a supplementary determination of the density p. Thus, elaborate
tables and charts have been devised for converting Engler
"Degrees" (cf. Ubbelohde (1907)), and Redwood (cf. Higgins
(1913), Herschel (1918) o r Saybolt "Seconds") into true
viscosities.
ASTM D 88 - 21 T, Standard Test Method for SayboU Viscosity was originally published in 1921, and it is still cited in
a few specifications, although none for petroleum products.
Glass capillary viscometers appear to have been used little
if at all in ASTM specifications until the late 1930s, when
ASTM D 445 made its appearance in 1937. This delay is probably due to the overwhelming use of the viscometers (in particular the Saybolt viscometer), as described by Bingham.
However, the Saybolt, Engler, and Redwood viscometers all
have a problem in the measurement of kinematic viscosities
less than about 2.0 mm^/s. This problem may not have been
realized in the petroleum industry until the late 1930s. The
problem is illustrated by the Saybolt Universal kinematic viscosity scale at very low kinematic viscosities, where the efflux
time becomes essentially constant regardless of the kinematic viscosity of the liquid. Thus, the Saybolt Universal
scale is limited to a m i n i m u m kinematic viscosity of 32.0 SUS
(about 1.8 mm^/s).

The lubrication of bearings and cylinders in severe service in


automotive engines is influenced by the high-temperature.

843

high-shear (HTHS) properties of the lubricant. Lubricant


temperatures in the bearings of engines can reach 150C and
higher and shear rates can exceed 10* s" ^ under such extreme
conditions. A lubricant of low viscosity may not provide sufficient protection to ensure boundary lubrication at critical
bearing surfaces, resulting in unacceptable bearing wear. Additionally, an engine lubricant having a high viscosity can result in excessive energy requirements and poor fuel efficiency.
A comprehensive review of literature is available [17,18].
For lubricants such as engine oils, which have a base stock
and a high-molecular-weight polymer-containing additive
package, the log of viscosity as a function of the log of shear
rate can exhibit a complex curve as shown in Fig. 14. Such
liquids can be Newtonian at the lower shear rates, since there
is not sufficient energy t o change the alignment of the
molecules of the high molecular weights of the polymer (A).
At somewhat higher shear rates, the polymeric additive becomes partially aligned with the axis of flow, showing decreasing viscosity with increasing shear rate (shear thinning
behavior) and the relationship between viscosity and shear
rate can approximate a power-law segment of the curve (B).
At the highest shear rates, the polymer can become fully
aligned with the axis of flow, and the liquid can again approach Newtonian behavior, the second Newtonian region
(C). In the second Newtonian region, the lubricant viscosity
can approach that of the base stock.
Severe operating conditions in an automotive engine can
subject the lubricant to extremely high shear rates, causing
the oil to approach the second Newtonian region. The resulting reduction in viscosity can have an advantage in the reduction in absorption of energy within the engine, but it has
a disadvantage in that the lower viscosity Ccin reduce the ability of the lubricant to provide adequate boundary lubrication
[19].
The types of viscometers used to study the high-temperature, high-shear rheology of lubricants include both rotational (ASTM D 4683, ASTM D 4741) and capillary (ASTM
D 4624, ASTM D 5481) geometries, and test results using
these viscometers are in SAE specifications J300. The viscosity of gasoline engine lubricants is generally about 2- to
7-mPa-s at 150C and a shear rate of 1 X 10* s^'. At these
low viscosities and high shear rates, the state of the art of
measurement instrumentation is pushed to its limits. Precise calculations of the shear rates for both types of instruments are complicated by difficulties in measuring the tight

high

- shear

Newtonian

A
\ ^ B
F
(n
o
u

Base Stock
3
10

High-Temperature High-Shear

AND SHEAR STABILITY

4
10

5
10
1

6
10
1

7
10
1

Rote of shear y

FIG. 14Log viscosity versus log shear rate.

844

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

gap between the rotor and stator in the rotational instruments and in measuring the precise diameter of the capillary in the capillary instrument.
Because of the very close tolerances required to achieve the
very high shear rates in the rotational viscometers, the designs have used a slight, matching taper to allow precise adjustment of the gap between the stator and rotor (Figs. 15 and
16). This adjustment ensures that the proper shear rate will
be maintained during the running of the test.
As described in the test method,
A motor drives a tapered rotor that is closely fitted inside a
matched stator. The rotor exhibits a reactive torque re-

FILTER
SCREEN

w
(

>

^-

PLUG
VALVE
PRESS./EXH,
" CDNNECTDR

ALUMINUM
SHELL

HEATED
-ALUMINUM
CYLINDER

^CAPILLARY
FIXTURE

FiSei- HoWi

FIG. 15Tapered bearing simulator viscometer tapered bearing simulator viscometer.

FIG. 16Rotor, stator and stator housing of the tapered bearing simulator viscometer.

Viscometer Cell
FIG.
17Capillary
high-temperature highshear viscometer.

sponse when it encounters a viscous resistance from an oil


that fills the gap between the rotor and stator. Two oils, a
calibration oil and a non-Newtonian reference oil, are
used to determine the gap distance between the rotor and
stator so that a shear rate of 1 X 10'' s^^ is maintained.
Additional calibration oils are used to establish the viscosity/torque relationship, which is required for the determination of the apparent viscosity of test oils at 150C (ASTM
D 4683).
The HTHS multicell capillary viscometer (see Fig. 17) uses
capillaries of very short lengths (about 15 mm) and very
small capillary diameters (about 0.15 mm). Unlike the rotational designs, the rate of shear in the capillary design varies
from zero at the center of the capillary to a maximum at the
capillary wall. Because of the variation in the shear rate
across the diameter of the capillary, the equivalent shear rate
to that of the rotational design apparatus is 1.4 X 10* s~' at
the wall of the capillary (ASTM D 5481). Like the rotational
viscometer, the capillary viscometer design also requires
calibration with Newtonian oils for each of the five test cells.
The group of test cells is held at 150C with a controUedtemperature aluminum block. A 10-mL test sample is

CHAPTER
inserted into the test cell and allowed time to reach test temperature. The excess sample is withdrawn, and a controlled
pressure applied to the sample, forcing it through the working capillary. With automatic timing (approximately 10-30
s), the viscosity and shear rate are ceJculated. If necessary, a
second measurement is made with a revised applied pressure
to ensure a shear rate at the wall of the working capillary of
1.4 X 10* s " ^ This apparatus can also be used from 35-175C
[20,21] (see Fig. 17).
For automotive gasoline engines, the m i n i m u m HTHS SAE
specifications at 150C are 2.6 mPa-s (SAE 20 grade), 2.9
mPa-s (SAE 30, OW-40, 5W-40 and lOW-40 grades), and 3.7
mPa-s (SAE 15W-40, 20W-40, 25W-40, 40, 50 and 60 grades)
as of December 1999 [22]. However, as the SAE Fuels and Lubricants Committee continues their studies of the best specifications, the HTHS specifications can be expected to be
continuously u p d a t e d in the future. There is significant
interest for measurements at other temperatures (100-200C)
and shear rates u p to at least 1 X 10^ s~'.
Much research in automotive lubricants also is related to
rheological studies, even though there may not be a n ASTM
test or SAE specification. One example of this research relates to the study of dynamically loaded journal bearings, the
m i n i m u m oil film thickness (MOFT) and the load bearing
capacity of engine oil lubricants. Many engine lubricants are
polymeric solutions, and as such many are also viscoelastic.
The research requires a n u m b e r of rheological studies, such
as the slit die rheometer (Lodge Stressmeter [23]) to study
the first normal stress difference [24], studies of the MOFT
[25,26], and cavitation [27].

LOW TEMPERATURE REQUIREIVIENTS OF


ENGINE LUBRICANTS
In the 1950s and 1960s the nature of the light-duty engine oil
lubricants changed with the addition of polymers to blended
oils. The changes in both the lubricants and the automotive
engines caused three major cooperative, industry-wide research programs to be undertaken in order to improve the engine lubricants, and these programs have had a profound
influence in the improvement of engine lubricants.
Prior to the changes in the engine oils, the kinematic viscosity at low temperature had been calculated using the measured kinematic viscosities at 100F (37.8C) and 210F
(98.9C). The kinematic viscosity at 0F (-17.8C) was calculated by extrapolation using the ASTM viscosity-temperature
charts (ASTM D 341), or calculated tables using the MacCouU
equation, or calculations using the MacCoull (Walther)
equation:
logio (logio (v -f 0.7)) = A - B logio (t + 460)
where:

(14)

v = kinematic viscosity, mm'^/s (or cSt)


t = temperature, F
A and B = constants

The low-temperature lubricant specification was based on


the extrapolated kinematic viscosity at 0F. However, it was
found that with the wax components of the base stock and
the polymeric additives, the correlation between the extrapolated kinematic viscosity of the lubricant at low temperature
a n d the ability to start the automotive engine no longer

32: FLOW PROPERTIES

AND SHEAR

STABILITY

845

existed. In June 1954, C. W. Georgi [28] reported.


It appears motor oils become non-Newtonian
fluids at
subzero temperatures and may have actual
viscosities
ranging up to ten times higher than indicated by the
customary ASTM Viscosity-Temperature
extrapolations.
Some caution seems necessary in interpreting
ASTM
charts in the low temperature region, as well as in
formulating motor oils for low temperature service.
In the 1960s a very large research program was undertaken with the cooperation of the Society of Automotive
Engineers (SAE), the Coordination Research Council (CRC)
and the petroleum division of ASTM Subcommittee D02.07
on Flow Properties [29,30,31,32]. Two groups of special oils
were prepared to study the effect on cranking current engines at low temperature. Oils in the first group were essentially Newtonian viscosity calibration standards at 0F
over the viscosity range of 1390-8400 mPa-s. They were
used to calibrate full-size, motored engines as if the engines
were large viscometers. The second series of oils were
multigrade engine lubricants blended from paraffinic base
stocks with polyisobutylene, vinyl copolymer, and polymethacrylate viscosity index improver-polymer types.
These were intended to be non-Newtonian oils at low temperature and typical of commercial engine oils. The viscosity for the second series of oils was determined in the calibrated, motored engines. These data were also used to
develop bench scale viscometers. This program was further
extended to include additional reference oils to develop
data at - 2 0 F . The results of this program are discussed in
the Low-Temperature High-Shear Tests of Engine Lubricants in a later section.
In 1973-4, ASTM and SAE sponsored a second, similar
large program that used motored engines at low temperatures to determine the lowest temperature that each special
oil could be p u m p e d to the bearing surfaces in the engines
without loss of pressure [33]. These data were used to
develop b e n c h scale i n s t r u m e n t s to correlate with the
pumpability data. The results of this program are discussed
in the Low-Temperature Pumpability of Engine Lubricants
in a later section.
Since the 1970s, the design of the automotive engines has
undergone many improvements both in cold starting and in
pumping ability of lubricants. There has been concern as to
whether the design data of the 1970s r e m a i n s adequate.
ASTM and SAE sponsored a third large low-temperature
study in May 1992, using the then current engine designs.
The ASTM Low Temperature Engine Performance (LTEP)
program within ASTM subcommittee D02.07.C issued a summary research report in November 1998 [34]:
Cold starting and pumpability studies have been carried
out in the 1993/1994 model year light duty gasoline engines under controlled climatic conditions and correlated
to rheological properties of test oils. It was found that,
within the engines, oils and cooling profiles tested in these
protocols:
1. Modem design engines start, on average, at lower temperatures than earlier engine designs
(approximately
5V).
2. An operational safety margin of 5-9 tT exists
starting and pumping of these test oils.

between

846

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

3. The cranking and pumping characteristics of single


grade (non VI improved) engine oils can be predicted
from their low temperature rheological properties.
4. These modern engine designs have limiting average
pumpability viscosities of approxim.ately 93 Pa -s as
measured by the MRV [Mini-Rotary Viscometer] test,
which is outside the measurement range of the current
Scanning Brookfield technique. Air-binding was observed when significant structure was detected in the
oils (>40 gelation index or MRV Yield Stress 70 Pa)
TABLE 7Viscosity data for analyses of low-temperature
high-shear studies at 0F.
Average Viscosity, mPa-s, at 0F
CRC* 8-engine Average
210/100FExtrap.

Oils
REO-174-63
REO-151-61
REO-152-61
REO-153-61
REO-154-61
REO-155-63
REO-156-63
REO-157-63
REO-15 8-61
REO-159-61
REO-160-61
REO-161-63
REO-162-63
REO-171-63
REO-172-63
REO-173-63
REO-175-63

(730)
(1390)
(2340)
(3500)
(8400)
1470
1830
2700
1800
2590
3110
1000
2760
1700
600
890
5040

670
1320
2320
3410
8050
1970
1710
1900
1910
1990
1900
1080
3190
1710
790
730
5850

NOTE: Items in parentheses are Newtonian calibration oils.


TABLE 8Viscosity data for analyses of low-temperature
high-shear studies at - 2 0 F .
Average Viscosity, mPa-ii, at -20F
Oils

aiO/lOO-FExtrap.

CRC* 10-engine Average

REO-174-65
REO-151-65
REO-152-65
REO-153-65
REO-155-63
REO-156-63
REO-158-63
REO-159-63
REO-172-65
REO-173-65
REO-183-65
REO-184-65

(3000)
(6320)
(11500)
(19800)
6920
11400
6480
14360
2260
4040
3600
9440

2700
5760
10600
18900
6590
5280
5630
5880
2180
1800
2570
6750

NOTE: Items in parentheses are Newtonian calibration oils.

Low-Temperature High-Shear Tests


of Engine Lubricants
With the changes to engine lubricant formulations in the
1970s, it was anticipated that a problem might develop in low
temperature starting. It had been known that some engines,
when cranked by the starting motor, could start at cranking
speeds as low as 6 rpm. Other lubricants were so high in viscosity that even though the engine could be cranked, the initial firing of the engine would not allow acceleration and
starting of the engine.
Prior to the 1970s, the normal way of estimating the kinematic viscosity at 0F (-17.8C) was by extrapolation, using
the MacCoull-Wright equation from kinematic viscosity data
at 100 and 210F. Problems with this method became obvious. The new formulations sometimes were semi-solid at 0F,
even though the prediction by equation indicated the lubricant to be sufficiently fluid to allow flow at low temperatures,
thus allowing the automotive engine to readily stcirt at low
temperatures.
Because there was a general lack of accepted information
on both automotive engines and their lubricants at starting
conditions, a large program [29,35,36,37] was undertaken
with the cooperation of the Society for Automotive Engineers
(SAE) Fuels and Lubricants committee, the ASTM Committee on Petroleum Products and Lubricants (Subcommittee 7
on flow properties), and the Coordinating Research Council
(CRC). A group of five "Newtonian" Reference Engine Oils
(REO) was prepared to cover the viscosity range of 730-8400
mPa-s at 0F ( 17.8C). These were used to calibrate full-size,
motored engines in cold rooms at 0F as if the engines were
super-large viscometers. In addition, a group of twelve,
multigrade REOs was prepared. This group of oils was typical of the variety of non-Newtonian, commercial engine oils.
The viscosity of this second group of special oils was
determined in the calibrated, full-scale engines also at 0F. As
part of this program, the same set of oils with the addition of
several additional oils was also studied at 20F (28.9C).
The results, at 0F and -20F, respectively, are found in Tables 7 and 8.
With this information, various bench-scale test instruments were tested to determine which would correlate with
the engine-viscosity data. See Table 9. Data analysis was done
on the 0F data using linear regression [38].
Those viscometers in the above table generally did not undergo a full round robin program, but this is an excellent
analysis of their various capabilities. On the initial analysis of
the correlation data, the Brookfield rotational viscometer.

TABLE 9Results of linear regression analysis.


Intercept (mPa-s)
Std Error of Est. (R)

Instrument

Slope

Extrap Kin Vis x density


Ferranti-Shiriey (CAP)
GMR Forced Ball
GMR Forced Ball
Brookfield
Haake Rotovisco (CAP)
PRL (16 cm capillary)
PRL (8 cm capillary)
SOD
Mason Torsion Crystal
High Shear-rate Rotational
Cannon-Manning Pressure

0.817
0.908
0.999
0.979
0.572
0.962
0.881
1.08
0.824
0.923
1.65
0.985

447
-105
-54
-284
442
-86
79
-284
-23
139
-1340
-300

534
138
147
355
1400
153
257
358
381
193
390
582

Corr Coef
0.908
0.994
0.997 (gel-corrected)
0.984 (Uncorrected)
0.705
0.992
0.991
0.983
0.981
0.989
0.984
0.958

CHAPTER

32: FLOW PROPERTIES

AND SHEAR

STABILITY

847

the SOD viscometer, and the Cannon-Manning Pressure viscometers were ehminated iirom additional consideration, as
the shear rate was too low. The Mason Torsion Crystal and
Texaco High Rate of Shear viscometers were both very complex and of a limited availability. However, all of the data
from laboratory instruments indicated that a higher shear
would correlate better with the engine cranking data.
About the time the above data became available, there was
a progress report on the development of low temperature viscometric techniques by ASTM Section B on Flow Properties
of Non-Newtonian Fluids. The GMR Forced Ball viscometer
consisted of a thermostatted, closed-end cylinder filled with
the test sample. A ball with a heavy weight was forced
through the test sample, and the time of fall automatically
measured (Fig. 18).
Manning reported that the GRM Forced Ball viscometer,
even with the Gel correction, would give inadequate correlation with the engine data [39].
At this same symposium two specially designed instruments showed promise. The reciprocating action of a single
cylinder model airplane engine [40] (later made m u c h more
sophisticated) by Stewart and Spohn gave much promise. At
the same time, a single Couette rotational viscometric cell

FIG. 19Cannon cold-cranking simulator. Reprinted with


permission from the Cannon Instrument Company, State College, PA.

AIR BEARINGS
PUTFORM
REUASE CABLE

WEIGHTS

COUNTERWEIGHT

CONTACT SWITCHES
AIR BEARING

BALL & SHAFT

OIL CYLINDER

FIG. 1 8 G M R f o r c e d ball viscometer. Reprinted with permission f r o m t h e C a n n o n Instrument C o m p a n y , State College, PA.

turned by an AC/DC series-wound motor was suggested by


Kim [41]. The AC voltage to the motor was plotted against the
acquired speed of the rotor on an x-y chart recorder. Both
sets of special oils were run at a range of voltages. The optim u m voltage was determined for best fit to the data from the
motored-engine average. While b o t h instruments showed
good correlation with the 7-engine data from motored engines, the Couette geometry seemed to be a more straightforward principle to develop into an instrument.
Using the concept of Kim, Lloyd and Manning designed an
improved bench-top Cold-Cranking Simulator (CCS), that
has become the basis of engine oil viscosity measurements at
high shear (10"* to 10^ s e c ^ ^ at low temperatures (Fig. 19).
The CCS consists of a direct current electric motor that
drives a rotor inside a copper stator; a tachometer to measure rotor speed; a controlled direct current to drive the motor; a stator temperature control system; and a coolant circulator compatible with the temperature control system.
When the test oil is in the annular space between the rotor
and stator and at test temperature, current is applied to the
motor. The speed that the motor attains is a measure of the
viscosity at high shear rate. The shear rate is in the range of
lO^-lO^ s " ^ The use of this instrument and its later improvements serve as the partial basis for engine oil viscosity
specifications [22].
Initially, the SAE use of the ASTM D 2602 test procedure
required all test oils to be measured at 0F ( - 17.8C). The test

848 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 10CCS requirements
SAE
Low-Temperature
Viscosity Grade
Cranking Viscosity (mPa-s)

ow
5W

low

15W
20W
25W

6200 at - 3 5 C
6600at-30C
7000 at - 2 5 C
7000 at - 2 0 C
9500at-15C
13000 a t - 1 0 C

NOTE: Reprinted with permission from SAE J300_19912


1999 SAE International.

and specification temperature was later lowered to 18C.


The current test temperatures and specifications for each low
temperature grade in SAE J300-99, and in ASTM D 5293 are
found in Table 10.

LOW TEMPERATURE PUMPABILITY OF


ENGINE LUBRICANTS
Lubricant pumpability is critically i m p o r t a n t to engines.
Catastrophic failure can occur if there is a lack of a full-flow
of lubricant to the bearings (bearing starvation) of m o d e m
engines and, thus, the rheology of oils at low temperatures is
of highest importance. Thus, the term pumpability has been
widely used in the lubricant industry to indicate the ability of
a lubricant to be pumped and/or to flow to the surfaces being
lubricated, especially at low temperature.
Several papers appeared in the 1940s concerning the pour
point stability of lubricating oils [42,43,44, 45]. In the early
1960s a study by Moyer [46] indicated that there may be a
problem with the pumpability of engine lubricants at low
temperatures. He observed that on pumping in a test apparatus, as the temperature is lowered in the oil pan, a hole can
be drawn in the oil in the reservoir, causing the p u m p assembly to be air bound. Selby [47] measured rheological
characteristics of reblends of oils previously studied by
Moyer, showing that cavitation occurred at sheeir rates less
than 50 s^^ and above a critical viscosity of 24,000 mPa-s.
McMillan and Murphy noted that:
An analysis of oil pumpability
reveals that engine oil
pumping failures may occur because either the oil cannot
flow under its own head to the oil screen inlet, or the oil is
too viscous to flow through the screen and inlet tube fast
enough to satisfy pump demands [48].
They constructed a laboratory apparatus (Fig. 20), "to identify the rheological factors involved in low-temperature
engine oil pumpability problems" over the temperature range
of - 1 7 . 8 to - 4 0 C . Their work included Brookfield-type,
cone-and-plate and concentric cylinder rotational viscometers. Soak-time, low-temperature studies for the oils were
also included. Cavitation due to oil starvation and oil soak
time contributing to pumping failures were important conclusions. A model relating to pumping failures was proposed,
which suggests an oil with a Brookfield viscosity near 10 000
mPa-s will fail to p u m p due to oil starvation at the screen inlet if either it exhibits a yield stress or it is found to have a
low-shear (0.2 s " ' ) to high shear (6.5 s~') viscosity ratio
greater t h a n 2. If a hole from the surface of the oil to the inlet of the p u m p is formed and the surrounding oil cannot col-

lapse fast enough into the hole, the p u m p will become "airbound" and not continue to p u m p oil to the bearings of the
engine (Fig. 6).
Moyer [49] reported that ASTM pour points, channel tests
and the 17.8C extrapolated kinematic viscosities were poor
predictors of oil pumpability. Stewart and Smith [50]
and Stewart and Spohn [51] reported that high shear ColdCranking Simulator viscosities, Brookfield viscosities, GM
pour times, and ASTM pour points all failed to predict the oil
gallery pump-up time in their test engine. "One test oil, which
had a pour point of 15F and appeared to be solid at 20F,
p u m p e d satisfactorily in a test engine at 20F." It was quite
evident t h a t a cooperative study of the factors regarding
pumpability of engine oils at low temperatures must be performed, a n d a reliable bench test m u s t be developed for
predicting this low-temperature pumpability. Many benchtest procedures were proposed, including (a) pour point (see
ASTM D 97), vacuum viscometer (along the lines of ASTM D
2171), (c) Brookfield viscometer (see ASTM D 2983), (d) GM
Pour Time, (e) pressure glass capillary viscometer, (f) cylinder with a hole in the bottom, (g) and several specially modified low-temperature, high-shear instruments including the
Cold-Cranking Simulator (see ASTM D 2602), and Haake
Rotovisco viscometers. Engine gallery pump-up times gave
a temperature at which the oil failed to p u m p . The ability of
each of the several bench tests to predict the temperature at
which full scale engines noted pumpability failure served as
the criteria for a successful bench test. As a result of these
works and those of many other investigators, the SAE Fuels
and Lubricants Subcommittee 2 and the ASTM Subcommittee D02.07 on Flow Properties defined pumpability characteristics of reference oils in engines and developed a bench
test method to predict satisfactory pumpability for use in
lubricant specifications.
In 1973, a large cooperative p r o g r a m was initiated by
ASTM subcommittee D02/07, as described by Shaub, Smith
and Murphy [55] by the following:
A joint ASTM/SAE symposium, the first of several, was
held in 1973 to better define the mechanisms of oil pumpability failures. A number of studies [48,50,52,53] were beneficial in this respect and provided a basis for formulating
an ASTM program. The ASTM program established an
engine test procedure and determined the pumpability performance of thirteen Pumpability Reference Oils (PROs) in
seven full-scale engines. This program was begun in 1973,

PUMP OUTtET

'PUMP

AVAILABtE HEAD

J
Olt INLET SCREEN

PUMP INLET TUBE

FIG. 20McMillan/Murphy pumpability apparatus. Reprinted


with permission from SAE Paper #730478 1973.

CHAPTER
completed in 1974, and summarized in an ASTM report
and an SAE Paper in 1975 [33,54]. The engine pumpability program included a degree of complexity that earlier
engine cranking programs did not: in the engine pumpability program, oils were run at successively lower temperatures until the oil actually failed to pump. The data and
mechanisms from the ASTM Engine Oil Pumpability Program have served as a basis to develop bench tests and to
assess their ability to predict engine pumpability.
There were 13 fully formulated engine oils r u n in 7 engines,
according to the prescribed procedures, at successively lower
cold room temperatures until pumping failure occurred. The
temperature at which failure occurred was defined as the
Borderline Pumping Temperature (BPT) and the mechanism
of p u m p i n g failure recordedair binding (AB) or flow
limited (FL). See Table 11 [55].
Note that the several engines show as m u c h as 17C differences in the FL BPT temperatures. Thus the design of the
pumping assembly in the engine as well as the lubricant is
very important.
With the results of the ASTM Pumpability Program as a
guide, a n u m b e r of instruments were evaluated to assess
their ability to predict pumpability. These i n s t r u m e n t s
included the Philippoff Rotary Viscometer (Fig. 21), a vacu u m capillary viscometer, the Haake rotary viscometer, the
Texaco orifice viscometer, the Brookfield rotciry viscometer,
and others.
In order to narrow down the selection relative to possible
round-robin studies, the Pumpability Data Analysis Panel
(acting on a motion passed at the December 1975 ASTM
meeting) visited the sites of the various pumpability test
methods. Based upon the (1) degree of correlation with
pumpability engine data, (2) cost, (3) ease of operation,
and (4) number of samples which could be run at one
time, the Data Analysis Panel recommended (at the June,
1976 ASTM meeting) that two teststhe mini-rotary viscometer (a miniaturized version of the (Phillippoffj rotary
viscometer) and the vacuum pipettebe considered for
round-robin studies. The panel also suggested that other
tests be considered if their sponsors could provide a set of
data showing correlation with the engine data [55].
The bench test resulting from this work was based on a simplified Couette-type rotary viscometer (mini-rotary viscometer or MRV) (Fig. 22).

32: FLOW PROPERTIES

AND SHEAR STABILITY

The test procedure included a two-hour soak period at 80C


to allow solution of any material not in solution at ambient
temperatures. This was followed by a slow, carefully controlled cool down cycle similar to that experienced in engines
over a 10-hour period and a final 6-hour soak at test temperature. The "Yield-Stress," if any, is first measured with static
weights to cause rotation. Any yield stress detected is cause
for suspicion that the lubricant may not be satisfactory for
use at low temperature. Then using a higher stress (325 Pa),
the viscosity of the lubricant is measured. This test procedure
was formalized as ASTM D 3829.
The MRV viscometer showed good correlation with the engine pumpability data [54], and ASTM D 3829 was adopted.
Later work showed that the original 16-hour cooling cycle
should be revised, and thus the current 48-hour slow cooling
cycle (TP-1) has been adopted in ASTM D 4684 [54,56,57,58].
Through this study, much has been learned about the lowtemperature pumpability of engine lubricants and the gel-

'/////////////

AIR BEARING

OIL
WEIGHT

STATOR

FIG. 21Philippoff rotary viscometer.


Reprinted with permission from SAE Paper
#730481 1973.

TABLE 1 lEngine BPT ("C).


Individual Engine Averages
Number of Engines
PRO No

Total

AB

FL

01
03
05
06
07
08
09
10
11
12
13
15
16

7
4
7
7
4
4
4
7
7
7
7
7
7

3
0
5
0
0
0
3
5
0
0
2
0
0

4
4
2
7
4
4
1
2
7
7
5
7
7

849

Flow Limited
Avg (Min/Max)

Avg (Min/Max)

- 3 5 (-38.5/-30)
- 2 9 (-33.5/-24.5)
-25(-32.5/-17)
-23.5(-33/-15.5)
-28(-31/-24)
-28.5 (-31.5/-24.5)

- 3 7 (-39.5/-35.5)

-24

-28.5 (-30/-27)
- 3 3 (-33.5/-32.5)

- 3 1 (-31.5/-30.5)
-30.5 (-34.5/-25)
-28.5 (-34.5/-23.5)
- 3 1 (-33.5/-29.5)
-33 (-38.5/-24.5)
-23 (-29.8/-15)

-14.5(-22/-12)

-34.5

850 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


made about the behavior of fully formulated engine oils at
low temperature with regard to pumpability problems:
Two modes of pumpability failure have been identified.
The first and generally the more important is "air binding,"
wherein the oil does not slump adequately on pumping
when the engine is started at a low temperature. As the oil
immediately above the p u m p inlet is moved through the
pump, air is drawn through a hole in the oil in the oil pan
and into the oil p u m p . Thus further oil is not pumped to
the bearings and overhead cam. The second failure mode is
identified as "flow limited." In this failure mode, the oil is
too highly viscous to flow adequately to the engine bearings. An oil exhibiting flow limited failure will most likely
also show too high a viscosity for starting the engine as
tested by the Cold-Cranking Simulator (CCS).

FIG. 22Mini-Rotary Viscometer


(l\1RV).
TABLE 12SAE J300 maximum low-temperature
viscosity specification.
SAE Viscosity Grade
OW
5W

low

Low-Temperature Viscosity, Maximum"


60
60
60
60
60
60

000 m P a s at - 4 0 C
000 mPa-s at - 3 5 C
000 mPa-s at - S C C
000 mPa-s at - 2 5 C
000 m P a s at - 2 0 C
000mPa-sat-15C

15W
20W
25W
" Tlie presence of any yield stress detectable by this method constitutes a
failure regardless of viscosity.
NOTE: Reprinted with permission from SAE J300_19912 1999 SAE International.

structure that can form when engine lubricants are cooled


slowly.
The Engine Oil Classification Specification J300 [59]
sets limits for both yield stress and viscosity as indicated in
Table 12.
In the meantime, other cool-down cycles and rotational
instrumentation have been proposed and considered by the
appropriate ASTM subcommittee. In particular, a slowly rotating, continuously recording viscometer cdso can show a
sudden increase in viscosity whenever a gel-structure occurs
at a narrow reinge of temperatures during a slow-cool cycle.
One such instrument is the Scanning Brookfield design. (See
Fig. 23) After preheating at 90C, the test cell is immersed in a
liquid cold bath and cooled at lC/h over the temperature
range of 5 to 40C. Gelation Index, Gelation Index
t e m p e r a t u r e a n d Critical Pumpability (in the range of
30 000-40 000 mPa-s) are processed in the computer from the
viscometric data. This test has been given the general name
"Temperature-Scanning Technique" ASTM D 5133 [60,61].
With a great a m o u n t of work by many investigators, in
particular Henderson [62] and many others on ASTM subcommittee D02.07.C, a n u m b e r of generalizations have been

As formulated oils cool to low temperatures, the wax can


crystallize out of solution. If the wax crystallizes into small,
unconnected particles within the continuous phase of
liquid, it is unlikely that any structure will form that would
prevent the oil slumping to the inlet of the oil p u m p . Conversely, if it crystallizes onto a relatively small number of
wax crystals, long, interconnected chains of wax fibers can
occur throughout the liquid oil solution. This forms a "gelstructure" which can have a yield-stress sufficient to cause
an air-binding t j ^ e failure of the oil at low temperature.
Some formulated oils are designed to have base stock and
additive packages containing such a small amount of wax
that no significant gel-structure will form at low temperature.
A pour-point depressant is often a part of the formulation
of engine oil. This depressant can form crystal sites at a
predetermined low temperature, thus providing many sites
onto which wax will crystallize on cooling to lower
temperatures. The temperature at which these sites form
must be higher than the temperature at which the wax will
crystallize by itself. Otherwise, significant wax can crystal-

Operating
" fluid level
leve

Glass Stator
(Inner dianrefer 22.07 mm)

Rotor
(Length: 65.5 mm;
Diameter 18.42 mm)

Fill line

(marked on Sfator)

FIG. 23Scanning Brookfield cell


diagram.

CHAPTER 32: FLOW PROPERTIES AND SHEAR STABILITY


lize before crystal sites are formed by the pour-point depressant crystal, and the conditions may be right for forming a gel-structure, thus causing air-binding pumpability
failure.
The rate of cool-down through a temperature range can be
very important. A very rapid cool-down through a temperature range m a y not allow sufficient time for the formulation of a gel-structure. As the viscosity of the engine oil
increases at lower temperatures, the mobility of the wax
molecules in the solution is greatly diminished and this
reduced mobility can prevent formation of a gel-structure.
It has been difficult to formulate a test oil that demonstrates only marginal pumpability problems in engines.
Fortunately, there have been only a few commercial oils
that have shown failures in the field, although these oils
have actively been sought for testing.
The design of the engine pumpability hardware is very important. It has been demonstrated that the temperature for
pumping failure can vary by more than 10C between engines
due to the differences in the p u m p and inlet designs.
By the early 1990s, the design of the engines had changed
such that the earlier studies of pumpability might no longer
be valid for m o d e m engines. Thus, the Society of Automotive Engineers's Fuels and Lubricants Division requested a
new study on pumpability of engine oils, with the following
goals:
to determine if there exists a "safety margin" between
limiting cranking and p u m p i n g viscosities in m o d e r n
engines,
to determine the cranking and p u m p i n g limitations of
single-grade (non Vl-improved) engine oils, and
to assess the benefits or limitations of current methods for
identifying oils which could result in pumpability failures
in engines [63].
This Low Temperature Engine Performance (LTEP ) study
included preparation of test oils for study in both modern
engines and test apparatus, and has served as a basis for revision of the SAE low temperature specifications for engine
oils (SAE J300) [22].

a still lower temperature and through a critical temperature


range rapidly, will flow in a normal manner.
As the temperature of a petroleum product is lowered, wax
contained in the product can crystallize into long crystals,
thus forming a gel structure. Frequently, chemicals such as
"pour-point depressants" are added to fluids to lower the
t e m p e r a t u r e at w h i c h gels can form. S u c h pour-point
depressants serve to lower the pour-point of the fluid by
forming many, m a n y crystals at a temperature somewhat
higher t h a n the t e m p e r a t u r e at which wax crystals form.
With cooling to still lower temperatures, wax will crystallize
onto the unconnected crystal sites of the pour-point depressant instead of forming a gel structure. Without the yield
stress provided by an interlocking gel-structure, the material
will show a much lower pour point.
Chapter 33, entitled Cold Flow Properties, discusses in detail p o u r point tests, aviation fuels freezing tests, and the
cloud point and wax appearance point tests.

SHEAR STABILITY OF
POLYMER-CONTAINING OILS
With the advent of polymer-containing lubricating oils in the
1960s, there was concern that the polymeric additives may
degrade under the influence of the high-shear and high-temp e r a t u r e environment found in a n operating engine. A
n u m b e r of devices, including mechanical shear devices, a
sonic oscillator and nuclear irradiation, were examined as
possible bench-test apparatus. This research resulted in the
development of a sonic oscillator device (Fig. 24) specified in

OTHER LOW TEMPERATURE TESTS


The viscosity of a liquid consisting of only one type of
molecule will increase when the liquid is cooled. If the liquid
is cooled sufficiently, the viscosity will increase until the liquid solidifies (freezes). However, most petroleum products
are composed of mixtures of m a n y different types of
molecules, each of which has its own freezing point. When
these liquids are cooled to low temperatures, unanticipated
results can occur. The diesel fuel for cars and trucks can form
crystals that will plug the fuel filter while the vehicle is being
driven, causing the vehicle to stop. Heating oil can be loaded
into a delivery vehicle, but at very low temperatures the oil
may not flow through the delivery hose to the business or
h o m e receiving the oil. Automotive engine p r o d u c t s in
conventional quart, liter, or gallon containers may, when left
outside the filling station in the winter, solidify so they will
not p o u r out of the container. Some petroleum products will
form a "gel" structure at a certain low temperature. However,
the same material when cooled from a warm temperature to

851

FIG. 24Sonic shear stability cell.

852

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

V) Motor
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(TO)
(11)
(12)
(73)
(14)

Pump
Filter
Nozzle holder
Nozzle
Upper reservoir
Solenoid drain valve
Lower reservoir
Solenoid drain valve
Sample-collection bottle
Pump control rack
Rack adjustment screw
Rack spring
Filling funnel

FIG. 25Fuel Injector Shear Stability Test (FISST).


A S T M D 2 6 0 3 m 1967:
This test method permits the evaluation of shear stability
with minimum interference from thermal and oxidative
factors that may be present in some applications.
Within
the limitations expressed in the scope of this test method,
it has been successfully
applied to hydraulic
fluids,
transmission fluids, tractor fluids and other fluids of similar applications. It has been found applicable to fluids
containing both readily sheared and shear-resistant polymers. Correlation with performance in the case of automotive engine applications
has, to date, not been
established (ASTM D 2603) (Fig. 24).
Correlation of the shear stability found in mechanical devices
with the shear stability found in bench tests is limited to
within a given family of polymers. Such correlation has not
been found to be very successful when comparisons are made
between polymer families. Nevertheless, correlation between
members of the same polymer family has been established. A
30-mL sample of a poljoner-containing oil is irradiated in a
sonic oscillator for a preset time, and the changes in kinematic
viscosity are determined according to ASTM D 445.
This device has been established to evaluate the shear stability of a hydraulic fluid in terms of the final viscosity that
results from irradiating a sample of the hydraulic fluid in a
sonic oscillator (ASTM D 5621).
Considerable development work on alternate shear stability devices has been undertaken both in Europe and in North
America. The use of a diesel injector nozzle to study the
degradation of polymer-containing blends has resulted in
the use of the European diesel injector test equipment and
the Fuel Injector Shear Stability (FISST) equipment (ASTM

D 3945, ASTM D 5275, ASTM D 5621) [64]. See Fig. 25. Both
procedures:
. . . evaluate the percent viscosity loss for polymer-containing fluids resulting from polymer degradation in the high
shear nozzle device. Minimum interference from thermal
or oxidative effects are anticipated. . . . This test method is
not intended to predict viscosity loss in field service for different polymer classes or for different field
equipment.
Some correlation for a specific polymer type in specific
field equipment can be possible.
The a p p a r a t u s consists of two fluid reservoirs, a singleplunger diesel fuel injection p u m p with a n electric motor
drive, a pintle-tjqDe fuel injection nozzle and control instrumentation. The shearing severity of the apparatus is verified
by a standard reference oil and measurements of the kinematic viscosity at 100C. Test specifications in Europe also
refer to the Coordination European Council (CEC) standards
(ASTM D 6278) [65-67].
According to test method D 3945:
[T]he polymer-containing fluid is passed through a diesel
injector nozzle at a shear rate that causes the less shear stable molecules to degrade. The resultant
degradation
reduces the kinematic viscosity of the fluid under test.
This loss of kinematic viscosity is a measure of the shear
stability of the fluid. It is important in the use of these
polymer-containing lubricating oils that the viscosity of the
oils remain stable and not decrease as a result of degradation of the polymer, especially in the high shear and high
t e m p e r a t u r e conditions of m o d e r n gasoline and diesel
engines.

CHAPTER
The permanent shear stabUity index (PSSI, see ASTM D
6022) is a m e a s u r e of the change due to shearing in an
additive's contribution to the lubricant's viscosity.
PSSI= 100X(Vo-Vs)/(Vo-Vb)
where:

PSSI
Vo
Vs
Vb

=
=
=
=

(15)

Permanent Shear Stabihty Index,


viscosity of the unsheared oil,
viscosity of the sheared oil, and
viscosity of the base fluid.

From the notes to ASTM D 6022,


Some methods, especially engine tests and field service,
may include conditions where other effects (e.g., evaporative loss, oxidation, fuel dilution, soot accumulation, etc.)
contribute to viscosity changes. The PSSI calculated from
these types of services may not be representative of pure
shearing.... PSSI may depend more strongly on base fluid,
additive concentration, additive chemistry, and the presence of other additives for base fluids of unusual composition (e.g., esters) or if additives outside the common range
of chem^istries and concentrations
are used. Caution
should be exercised when interpreting results from,
different sources.

USE OF ASTM FLOW PROPERTY


PROCEDURES
While there are many rheological test instruments, the ASTM
flow-related methods of test are developed to satisfy a need
for a specific test related to the performance of the material
in the use to which the material is to be put. The particular
rheological device(s) in each test is selected because it is satisfactory for the test or in some cases, it may have been
developed specifically for the needs of the test. The wide
n u m b e r of rheologicsd devices available is of little consideration in the writing and use of the flow-related test methods,
except that those chosen represent the specific needs for testing the material. In general they will allow the test method to
be used in a specification for the material.
There are a great many specifications for petroleum materials, most of which refer to one or more of the flow-related
methods. An outstanding example of such specifications is
for the performance of engine oils, as described in the
introduction to ASTM D 4485.
This document covers all the currently active American
Petroleum Institute (API) engine oil performance
categories that have been defined in accordance with the ASTM

32: FLOW PROPERTIES

AND SHEAR STABILITY

consensus process
In the ASTM system, a specific API
designation is assigned to each category. The system is
open-ended, that is, new designations are assigned for use
with new categories as each new set of oil performance
characteristics are defined.... Other service categories not
shown in this document have historically been used to
describe engine oil performance (SA, SB, SC, SD, SE, SF,
SG, CA, CB, CC, CD, CD-II, CE).
The Society for Automotive Engineers, Inc. (SAE) has specified engine oil performance categories and classifications for
many years. The SAE defines engine oil performance categories for gasoline and diesel engines. SAE J183, Engine Oil
Performance and Engine Service Classifications [68],
outlines the engine oil performance categories and classifications developed t h r o u g h the efforts of the American
Petroleum Institute (API), ASTM International (ASTM), the
American Automobile Manufacturers Association (AAMA),
the Engine Manufacturers Association (EMA), the International Lubricant Standardization and Approval Committee
(ILSAC), and SAE.
These specifications for engine oils incorporate a great
many ASTM methods such as sequence tests, volatility, chemicals, flash point, foaming tendency, etc. in addition to those
for flow-properties. Included in this specification is a discussion as to the background for each category, the dates the category was in use and the reasons why the category became
technically obsolete. The several categories are included in
Table 13. The reader is encouraged to refer to SAE J183.
Current flow-property specifications for gasoline engines
are included in SAE J300 [22], making reference to II ASTM
flow-property methods. This specification states that "the
limits specified are intended for use by engine manufacturers
in determining the engine oil viscosity grades to be used in
their engines, and by oil marketers in formulating,
manufacturing, and labeling their products."
The OW, 5W, lOW, 15W, 20W a n d 25W SAE viscosity
grades for engine oils specifications at low-temperatures
from 35 to 10C refer to the high shear Cold-Cranking
Simulator (CCS ASTM D 5293) tests. Pumpability specifications include temperatures from 40 to 15C and reference the Cannon Mini-Rotary Viscometer (MRV ASTM D
4684). Each of the "W" grade oils has a m i n i m u m kinematic
viscosity limit at 100C. From SAE J300,
. . . because engine pumping, cranking, and starting are all
important at low temperatures, the selection of an oil for
winter operation should consider both the viscosity required for successful oil flow, as well as that for cranking
and starting, at the lowest ambient temperature expected.

TABLE 13Lubricant category chronology.


API Category
API Category SA (1900-1930)
API Category SB (1931-1963)
API Category SC (1964-1967)
API Category SD (1968-1971)
API Category SE (1972-1979)
API Category SF (1980-1988)
API Category SG (1989-1992)
API Category SH (1993-1996)
API Category SJ (1996-)

853

Description
No additives. Not suitable for use in gasoline automotive engines built after 1930.
Minimum level of performance additives. Oil considered non-detergent.
Additives improved to meet multicylinder engines sequence tests.
Enhanced additive treatment to meet performance requirements for current engines.
Emission control, high speed driving. CAFE advances required improved oils.
Reduced oil consumption, oxygenated fuels, longer drain intervals requuired new oils
Sequence HIE and VE to evaluate oxidation and sludge, CAFE and fuel injection.
Phosphorus and volatility control tests added. Reduced oil consumption.
Continuous improvements in motor oils as required for modem engines.

NOTE: reprinted with permission from the Society of Automotive Engineers, Warrendale, PA. The reader is encouraged to refer to SAE J183.

854

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

Each of the five SAE grades 20, 30, 40, 50, cind 60 reference
the low-shear-rate kinematic viscosity test range (ASTM D
445). The same grades also reference high shear (10* s"')>
150C tests (ASTM D 4683, or D 4741, or D 5481) to ensure a
m i n i m u m high-shear viscosity for each of the five SAE
grades.
KINEMATIC VISCOSITY/TEMPERATURE
RELATIONSHIP
In 1921, Neil MacCoulI created a viscosity - t e m p e r a t u r e
chart (Fig. 26) for sale by The Texas Company [69]. The ordinate of the chart was the double logio of the kinematic viscosity plus a constant and the abscissa was the logio of the absolute temperature. This chart was used to graphically show
the relationship between viscosity a n d t e m p e r a t u r e for
mineral oils. It was stated that
A close study of the various values of viscosity at different
temperatures reveals the fact that temperature-viscosity relations can be so expressed by a simple formula that when
plotted to the proper coordinates a straight line relationship is shown ... It has been found that there is no curvature to the line for any mineral oil so far tested, until the
temperature has been reduced to the point where paraffine
begins to precipitate . . . [69].
The equation used in the graph was
logio (logio {v + constant)) = A - B logio T
where,

pears that Walther may not have been aware of the prior
work by MacCouU until 1929 when advised by Herschel [73].
The constant in the above equation is required for the hightemperature, low-kinematic-viscosity part of the chart. The
constant was the subject of study in the 1930s, and various
values from 0.6 to 0.8 have been used. However, as reported
by W. Andrew Wright [74],
. . . a constant of 0.6 was used down to viscosities of 1.5
cSt. Below this viscosity, the constant was changed to 0.65
for the range from 1.5 to l.OcSt, 0.70for l.Oto 0.7 cSt, and
0.75 for 0.7 to 0.4 cSt.
This problem was the subject of an intensive study by Wright
resulting in the development of an improved chart at very low
kinematic viscosities and high temperatures. The equation
for the new charts is listed in the appendix to ASTM D 341 93. In 1974, Manning suggested a modification of the equations by Wright. These equations, shown below, are also
listed in the appendix to ASTM D 341 - 93, and have been
widely used, especially in the computational fitting of kinematic viscosity-temperature data by computers [75]. This
relationship is expressed as follows:
logio logio Z = A - B logio T

(17)

Z = V -I- 0.7 + exp(-1.47 - 1.84v - 0.51 v^)

(18)

V = [Z - 0.7] - exp(-0.7487 - 3.295 [Z - 0.7]


+ 0.6119 [Z - O.lf - 0.3193 [Z - 0.7]^)

^^^^

(16)

v = kinematic viscosity, mm'^/s or cSt


T = absolute t e m p e r a t u r e , degrees Rankine or
Kelvin
A, B = coefficients determined for the liquid.

In addition to charts prepared with kinematic viscosity in


units of centistokes versus temperature in degrees Fahrenheit
and degrees Centigrade (Celsius), charts were also prepared
with the ordinate in Saybolt Universal seconds (SUS) and Saybolt Furol seconds (SFS). The abscissa of these charts is the
logarithm of the absolute temperature and could be in degrees
Fahrenheit or in degrees Celsius. The "constant" in the above
equation is necessary if the kinematic viscosity is less than 1.
Otherwise, the term logio (logio W)) cannot be evaluated because it would require the taking of a logarithm of a negative
number. According to an article in Lubrication [70], the early
charts had a constant varying from 0.4 to 1.0, and 0.7 was
"considered to give the best overall results." The chart (see Fig.
26) was later published in the 1927 International Critical Tables [71], along with the following paragraph:
Variation of Viscosity with TemperatureIf the viscosity
of an oil is known at two temperatures, its viscosity at a
third temperature may be obtained graphically with the aid
of [Fig. 26]. When the viscosity temperature values for any
oil are graphed on this chart, a straight line will be obtained for all portions of the temperature range within
which the oil remains a homogeneous liquid of constant
composition [69]. Copies of this chart may be obtained by
addressing The Texas Company, New York City.
In the meantime, C. Walther published other viscosity-temperature charts in the late 1920s. After experimenting with
several different equations, Walther adapted the equations of
MacCouU, using a constant of 0.8 instead of 0.7 [72]. It ap-

V = kinematic viscosity, xnm^ls (or cSt)


T = temperature, K (or R)
A and B = constants
A review of the MacCoull viscosity-temperature charts is
given in the May and June 1950 issues oi Lubrication. Various alternative charts have been proposed by others
[76,77,78,79]. Andrew Wright was chairman of the ASTM
D02 Subcommittee 7 on Flow Properties for a n u m b e r of
years, and his paper [74] contains information on the development of the ASTM Viscosity-Temperature charts and their
use within ASTM.
The MacCoull chart has been published by ASTM since
1932, starting with the standard D 341 - 32T.
Some liquids show a good relationship with the equation
given in the Andrade [80] paper of 1930 (and also those of
S. E. Sheppard, Ejring and others). This is of the form:
77 = A e^'T

(20)

The MacCoull equation is essentially of a similar form:


77 + 0.7 = A e'^'T'^

(21)

The SUS/F charts were abandoned many years ago with the
worldwide emphasis on the use of the System Internationale
(SI) units in the specifications for petroleum products.
For many years a segment of these viscosity-temperature
charts has been used for blending two-component stocks.
The constant-temperature method of blending requires the
kinematic viscosity of each component at a given temperature. Using the chart from 0-100F as if these temperatures
represented 0 and 100% of the two components respectively,
the kinematic viscosity is plotted on the charts, drawing a
straight line between 0 and 100% of the components. Thus,
the approximate kinematic viscosity of blends could be estimated from the straight line connecting the two components

CHAPTER 32: FLOW PROPERTIES AND SHEAR STABILITY

855

LI 3UIDFUE LS
TE M P ERj
20
1

0
1

>o.oao
!
'

0.000

. 1

as
1

GD

r
1

( !
'

. _ 41.

IGD
1

1
t

1
=4-b i
+-^

200 210 220


1
"
1

1 ;
1 '
1 '
1 i

20
1

2SD
1

3O0
1

i
1

30

..1 .
1
1

1r
1
'

-TT

}
1 1
j
-'"''i

s.ooo
E-t.ooo

"-'

3.000

_4_
1

2.00O

^508'

j*
1J

300

'^

w
oO

200
-

I '

: J
'rH
...

20

;. 1 : J

^=

1
t

1.'

;t -

;
I

1 .

^-i

) :!
I

""!
I

. ,

,y.n
100

:^o

1.-

-i

5^

^~i

7.0

> s
= 5

o5.0

'

CO

1
1
. 1
1

iO

o
10

r '

"

> J
1 ;

o '

1
1

,
1

1
1

IS

'

i '
;

i
11

:
/

.1

I
1

0.70

-0 ca

11 -'*
.

^ =

C.SO

Z_,5

1 ..

11

j
1

t \
( '

1!

1 =

.1.'.

.1
L_
(1.50

.-. ^ c o o

. :
20

30

IB

j
1
t

'

11

I.OO

0.90

'r

;
t -

1
1

m
CC

F=:=

1 ; 1

1-20

_
<^

60

-fi.eo

.
I
.
!
!
j

!
1
I

1
11

^2.00

11

a.

~i

j ^ _

j
1

=;
-
o
^-<
s

1
11
1

tn

70

.0

ii-

3|

1,1

260
1

i;

1
1
- [

50

[-*- = f =
1 <
j '__
\ *
j ;

7nn

100

, 1

,..j.

in

=
-=
-=
:>.

X 0

121
1

;^

J R E - F A R EiSTHE I T

100

inml
i.OCDt

I.DOD

..

40

SO

60

70

80

90

100

110

128

130

MU

TEMPERATURE CENTIGRADE

VISCOSITY-TEMPERATURE CHART
FIG. 26Neil MacCoull 1927 chart. Reprinted with permission from Texaco, Inc., White Plains, NY.

t.

ISO

<
"

856 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


Using the equations of the viscosity-temperature charts (see
Figs. 27, 14, a n d 15), this m e t h o d can be calculated by
computer. It can be adapted to multi-component blends.
Table 14 shows the seven charts available from ASTM [82]
as described in ASTM D 341 (see Figs. 28 and 29).

at blends from 0-100% of the one component. This constanttemperature blending method is not very accurate, and mention of this process (as well as a special chart) was withdrawn
from ASTM D 341 many years ago. The constant-viscosity
method reported by W. A. Wright [81] is more accurate and
is described in the appendix to ASTM D 341-93 as follows:
Plot the known data for each component on an ASTM Viscosity-Temperature Chart and carefully draw straight lines
through the points. The lines should extend beyond the
blend kinematic viscosity required. Locate, or draw, the desired blend kinematic viscosity horizontal line on the chart
through both of the component oil lines. Lay a centimeter
scale along this line and carefully measure the distance between the lines for the two oils where they cross the line of
the desired blend kinematic viscosity. Without moving the
scale, on the same horizontal kinematic viscosity line read
the distance from the low viscosity oil line to the temperature desired. Dividing the latter by the first measurement
between the two oils gives the volume fraction needed for
the high viscosity oil.

VISCOSITY INDEX
As described in the Significance and Use section of ASTM D
2270 (originally published by ASTM as D 567 - 40T, and
revised and renumbered in 1964),
The viscosity index is a widely used and accepted measure
of the variation in kinematic viscosity due to changes in
the temperature of a petroleum product between 40 and
100C. A higher viscosity index indicates a smaller decrease
in kinematic viscosity with increasing temperature of the
lubricant. The viscosity index is used in practice as a single
number indicating temperature dependence of kinematic
viscosity.

ui
O

o
z

hi
O
I;;
U>

in
O

<
w
z

40

50

eo

ro

80

90

100

120

TEMPERATURE. DEGREES. CELSIUS


F I G . 2 7 O i l b l e n d i n g calculations,

TABLE 14ASTM viscosity-temperature chart descriptions.


Kinematic Viscosity
Chart #

Description

Range (cSt)

Temperature

I
II
III
IV
V
VI
VII

High Range
Low Range
High Range
Low Range
High Range
Low Range
Middle Range

0.3 to 20 000 000


0.18 to 6.5
0.3 to 20 000 000
0.18 to 6.5
0.3 to 20 000 000
0.18 to 3.0
3 to 200 000

-70to+370C
-70to+370C
- 7 0 to -l-370C
-70to+370''C
-100to-l-700F
-100to+700C
-40to+150C

NOTE: Additional information is given in ASTM D 341-93.

Size (mm)
680 by
680 by
217 by
217 by
680 by
520 by
217 by

820
820
280
280
820
820
280

Facsimile
Reference
Fig. 28
Fig. 29
not included
not included
not included
not included
not included

CHAPTER

32: FLOW PROPERTIES

AND SHEAR

STABILITY

857

i U . tHOHH. MLStuS

ittttrMnjt. onma. ceiaiua

FIG. 28Facsimile of Kinematic Viscosity-Temperature Chart 1 High Range (temperature in degrees Celsius).

Viscosity index (VI) numbers have been used for many years
in the marketing of petroleum products. It was well known
t h a t lubrication fractions of oils from various sources of
crude oils showed large differences in their variation of viscosity with a change in temperature, and a way to characterize this change was needed. As described on page 69 of the
June, 1950 edition oi Lubrication [83],
The original viscosity index system was set up by an arbitrary selection of two series of oils derived from opposite
extreme types of crude oil: The "H" series having the less
change in viscosity with temperature, and the "L" series the
greater change. Seven blends were made up in each series,
with viscosities varying from about 200 to 1200 seconds
Saybolt at WOT. Each oil in the "H"series was arbitrarily
assigned a V.I. value of 100, whereas each oil in the "L" series was assigned a V.I. value of 0. In practice, a reference
oil is selected from each series with the same viscosity at
210 as the oil to be evaluated. The numerical difference in
viscosities of these two oils at WOT will always, by defini-

tion, represent 100 V. I. divisions. Thus the V. I. of an oil


may he computed by the equation below:
VI = ((L - U)/(L - H)) X 100
Where

(22)

L = kinematic viscosity at 100F of an oil of 0 viscosity index having the same kinematic viscosity, Y, at 210F as the oil whose viscosity index
is to be calculated, mm^/s (cSt)
H = kinematic viscosity at 100F of an oil of 100 viscosity index having the same kinematic viscosity, Y, at 210F as the oil whose viscosity index
is to be calculated, mm^/s (cSt),
U = kinematic viscosity at 100F of the oil whose
viscosity index is to be calculated, mm^/s (cSt).
The original scale was proposed by Dean and Davis in 1929
[84] and revised by Davis, Lapeyrouse, and Dean in 1932 [85]
and in ASTM D 567. The original scale was based on data for
L and H in the range of 7.29 to 75 cSt at 210F. Later, light
oils were used to extend the table between 2.0 and 3.99 cSt.

858

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

FIG. 29Facsimile of Kinematic Viscosity-Temperature Chart 11 Low Range (temperature in degrees Celsius).
Values for L and H were obtained for the range of 4.00 to 7.29
mm^/s (cSt)

developed in the use of Method D 567 - 53. W. A. Wright,


September 1965.

. . . by a special method of calculation which was equivalent to graphic interpolation on a greatly magnified scale.
In this range of viscosity the constants are not defined by
equations [86].

With the world using the System International (SI) metric


units, it was agreed at a London conference [92] in November
1972 that the traditional measurements of kinematic viscosity
at 100 and 210F would be replaced by measurements at 40
and 100C. The Viscosity Index tables were redone using the
MacCouU equation of kinematic viscosity versus temperature
for recalculation of the new tables of L and H. The change in
these tables results in only minimal changes in the VI of oils as
previously based on the kinematic viscosities at 100 and 210F
[93]. With the adoption of the 40 and 100C temperatures for
kinematic viscosity measurements, a book of viscosity index
tables [91] has replaced the former degree Fahrenheit tables.

It had been assumed that all oils would have Vis between 0
and 100. However, many m o d e m oils, especially those with
the additive packages, have a VI above 100. Extrapolation of
Vis u p to 120 seemed to fit the viscosity index scale without
a problem. However, there was a serious problem above 130.
Accordingly, in the late 1950s W. Andrew Wright [87,88] devised a special calculation to extend the VI calculation above
100. This was adopted into ASTM D 2270 in 1964, and for
several years the viscosity index so calculated used the
symbol Vlg to differentiate VI between the new extended VI
equation and that by extrapolation from the equation for use
u p to a VI of 100.
ASTM had published a book of viscosity index tables based
on 100 and 210F temperatures as a Special Technical Publication [89,90]. This book was replaced by another book [91]
based on D 2270 - 64, but for temperatures in degrees Celsius.
The forward states in part
The studies leading to the change in calculating the viscosity index are the result of recommendations by the Third
and Fourth World Petroleum Congress that a method be selected which would avoid the problems which ultimately

Calculation of Viscosity Index


The equations for the calculation of viscosity index are given
in ASTM D 2270, along with the tables of L and H, and equations for the values of L and H above 70 mm^/s. For values of
viscosity index from less t h a n 0 u p to and including 100, the
equation (Procedure A)
VI = ((L - U)/(L - H)) X 100

(23)

is used. Viscosity index of 100 and above use (Procedure B)


VI = [((antilogio N) - 1)/0.00715] X 100

(24)

CHAPTER
where
N = (logio H - logio U)/logio Y

(25)

The values for L and H are shown in Table 15.


Table X2.2 from ASTM D 2270 (Table 16) provides the values for determination of L and H at different viscosities. For
kinematic viscosities above 70 mm'^/s at 100C, the following
values are used:

L = 0.8353 Y^ + 14.67 Y - 216

(26)

H = 0.1684 Y 2 + 11.85 Y - 9 7

(27)

and

The following example demonstrates the calculation of viscosity index both for values of VI below 100 and above 100
(see Table 17).
Calculation example A: Measured kinematic viscosity, U,
a t 4 0 C = 171.8
Measured kinematic viscosity, Y,
at 100C = 15.69 by interpolation,
L = 320.74 and H = 159.95
VI = 100*(320.74 171.8)/(320.74 - 159.95) = 92.63
and rounding to the nearest
whole number, VI = 93
Calculation example B: Measured kinematic viscosity, U,
a t 4 0 C = 120.1
Measured kinematic viscosity at,
Y, 100C = 15.78 by interpolation, H = 158.28
N = [(log 158.28 - log 120.1)/log
15.78] = 0.100060
VI = [((antilog 0.100060) - 1)/
0.00715] + 100 = 136.24
and rounding to the nearest
whole number, VI = 136
There are some highly waxy base stocks that can be determined at 100C but not at 40C due to wax formation. The
kinematic viscosity of such materials can often be determ i n e d at a higher t e m p e r a t u r e , e.g., SOX. Using the
MacCouU equation the kinematic viscosity at 40C can be estimated. This allows the VI to be estimated, but this value is
not to be considered the true VI of the material.
The precision attributed to the viscosity index is based
entirely on the precision of the kinematic viscosity measurement. For base and formulated oils, information in Table 18
is calculated from the repeatability and reproducibility of
ASTM D 445. Tak:e note that the precision of the kinematic
viscosity measurement is different for each of the types of
materials, and thus the precision attributed to viscosity index
is a function of the product. Table 18 indicates the precision
to be attributed to viscosity index for base and formulated
oils [94]. Because of the importance of VI in the metrketing of
petroleum products, it is important to keep in mind that the
reproducibility attributed to base and formulated oils may
vary from 2-9 VI units. Thus, the rounding of the VI to the
nearest whole n u m b e r is required.
Other proposals have been made for characterization of
the vatriation of kinematic viscosity with temperature [95,96],
especially by E. E. Klaus et al. from the Petroleum Refining

32: FLOW PROPERTIES

AND SHEAR STABILITY

859

Laboratory of The Pennsylvania State University. While the


use of the calculated VI serves as a measure of the rate of
change of kinematic viscosity with temperature, the slope of
the kinematic viscosity data plotted on the ASTM Viscosity
Charts also serves this purpose. This slope, when plotted on
the ASTM Viscosity Charts, is known as the "ASTM Slope."
From the introduction of a report [97],
"ASTM Slope" has become a well-known term and has
attained rather wide usage as a measure of the viscositytemperature characteristics of oik. Plots of the viscosity
temperature data for petroleum oils on the ASTM Charts
for Liquid Petroleum Products (D 341-39) result in straight
lines. . . ASTM Slope of an oil may be defined as the negative "measured" slope, or the measured linear distance on
the ordinate of ASTM Charts C and D (D 341-39) between
viscosity values at 100and 210F divided by the measured
linear distance between 100and 210F on the abscissa.
For base stocks of mineral oils without polymeric additives, the VI may also serve as an indication of the chemical
nature of the liquid. For example, a material with a VI = 10
likely has a high naphthalenic component, while a paraffinic
base stock may have a VI = 95. A lubricant with a VI = 150 is
likely a blend of mineral oil and a polymeric additive, or a
synthetic fluid (Fig. 30).
The use of the ASTM Slope has diminished over the years,
probably due to the wider use of Viscosity Index in lubricant
specifications.
Pressure Considerations
It is well known that the viscosity of lubricants increases with
an increase in isotropic pressure at a constant temperature.
Indeed, the increase in viscosity can be several orders of magnitude, as illustrated in Fig. 31 [98,99].
An empirical model for the effects of both temperature and
pressure is
7 = K e'^'T e"P
where

TJ =
T =
P =
a =
K, b =

(28)

viscosity,
the absolute temperature,
the pressure
pressure-viscosity coefficient, Euid
constants for the material.

Typically, this equation is valid over a 50 Kelvin temperature


range and 1 Kbar pressure range for polymers [100,101].
Measurements of the viscosities of liquids at high pressures
have been made by a n u m b e r of investigators. The works of
So and Klaus [102] and Wu, Klaus, and Duda [103] show
correlations of the pressure-viscosity coefficient developed
for various types of liquids, including hydrogenated, naphthenic, ciromatic, and paraffinic mineral stocks, a number of
pure hydrocarbons, etc. The correlations of the pressureviscosity coefficient of Wu are of the form
a = mo(0.1657 + 0.2332 logvo)
where

(29)

mo: Viscosity-temperature property from the ASTMMacCoull equation and equal to (ASTM
slope)/0.2
VQ: Atmospheric kinematic viscosity at the temperature of interest, mm^ls

860 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


'=:j-od'-H'^r^O'^oO'.-HiooNf^^doiooNroo6rii>r^'r^'^
t~^t^^^l>^^t~~l>000000000000000^0^a^0^0^0^0^OOOOOOO'-H.iii^H

incO'-HrfcO'-Ht^rotf*^0\orn'iooor^i>r^r^r~^ooc>0(^\oorosoO'OfN
0^0^00'-HrH*-H^^^^^^r*^<:J-^lnln^o<?t~^t^ooooc>0^00'-H^irS(Nl<^<^':t

ti .tt 5^ vi

5 oo cc

i n o i r i o i r i o i n o t o o i o o u ^ O u - i O i n p i o p u - i o i n o i n o i o o i o o u - ) 0

II'

oo^o^OOa^c^oot^t~^ln^^ro^i-lO<?^^'^^'0^ocoO'0'-Hr^^u^l^l^o^~^'^
OOO^^(NfS^^^^0r^T^rt':tmm^0^0'^^^t^0000000^0^OOO^^(N^0

)<Navc~~-iofN(Nrnr-;'^^ooo

'iop<)rn'^oosDO(Nrt|'<t

coo^O'-H^^^ro^u^\ot^o^O'ifNro'ri-ir)'<>oo(^o^^<N(^io^r^cooN'ifNin
\o^t^c~^^~^^~-^~^^^t^t~^c^oococococoooooooooo^c^a^o^o^o^a^c7^o^ooo

i O (N

'

pr^'^_Nqooprsj'^_\qcor^'^^oooor^"^_^oqor^_-^sqoqo

1 > s "
^vJr^^^0^lr:lrH^-;^00^^q(N00Tto^0r00^^q^0pt^^^t~-'^^<
O ^ r ^ - ^ vO 0 0 ON ^ (N ^' MD l > ON ^ f S ' ^ ' l O t^' cK >--< <N '^* NO* ^ ^
OOOOOOOOOOOOCOONONCTvOvONONOOOOOO'-fT-HT-HT-HT-H,i(N<N<N(N(N<N(^

^m'lOONONf^r-^

ONrot^'-H'^cdr4N6o'^cdr4^0'^aNf^t^''-iinoN'^'odrsir^
\oi~^t-^ooooooaNONOOO'^'^rsi(Nr^ror*^-^'^'=^u^ir)^o\or~^r~--t^ooooa\o

S 'S b,^C^

E o o g cfl
c .2! 4^ E "-^

t^t~^c->^i>t^t^'i>r^'r~-^c~^'cdcdododododo6odo6o6

1I rj-' r-' o <^* 'O CJv (N in CO

^ir^o6r-^-rffr^(^<^{:^cir^-<>0-\r^\6<>r*i'Sosr^^C>

000'<-H'.-HT-H^rvirNir^i(^r^f^-<^Tj--<:tioioio\o^ci\0\or^r^t^oooooooNaNO

lilt
a-5

^--1-HC^ooooooc^o^lno^o^lnoO(Noo'^o^^or^(Nr^^<-)^oor^<)r^r^oo
odON0^04rou-i^dt~--'odO\0'^*ro-rfiovor^'o6oN'^'r^^

Ou-)ONrooir)-Tro<^(N
OrslrntONOcopr^'^_t~-;0<^^oaNr^ioaNr^ioONror^O'^oor*^t^^Ht^rs)r^(N-)
corsi'=t\dcd'^<^iot^OfS'^'^av'^(^'^o6oroiricx3
t~^0000000000aNaNaN0NOOOOO'^'^'^^(N(N(N(Nf0r*-ir*-)rn-^'=1-'^'!rii-)
u
E o o

g cfl

o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
0'-Hrsif*^^iri'^t^oqONO'-HrN|fO'^i/^^r^oooNO^H<NirO's1-iONOt^ooONO'-H

3>
^ ^ o '<i- ^ r^ r^
aNON'-HTtoN^'^iot^ou^rst^'^<^^cir^ONr^i>^or-^i-Hirir^-rHT-<frii^roONso
\0\dc^i>cdo\(JNC)0'-Hr4r^rn'^'^uS<JKr^odaNO'-HrNi

^ O ON
0N'!l-OO^iO'^OOr*^0N\0'O00<NO\000Nrn0vfN)Ou-ir--00O(Nf00NOrn0N
ON\Or*^pt->;'rfrNjOoo-0'^fOrNj'-Hi-HOOP'^'-Hr^iOi>0^
t^cdo^OO'-^^^'^*^^n^'l/i^dt--^o6o^O'--H^^irn^lri

iJHIi

o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
lOi ^^ r^ rn rt IT) <:>t^oo o^<o ^^ C'^ rr) -^ in <> t^ CO 0\C> ^
rvi r s r^i <N fS r4 <N CM (N H r*^ rn r*^ rn ro r^ r<i fO rn

CHAPTER 32: FLOW PROPERTIES AND SHEAR STABILITY


vnO'OfNOO-^O'OrriON'OfNO'OfNOS^O'^'-tQO'Or'^'.-^OO

ON0'^l>r<iaNl0O\0(N00^O^0(NOin'-f00'^Ot^f0O

ioiONCi'>cii>t~~-oooNONOO'^r\ifNro(^'=l-inio>or~--i>ooav

i n o i o o i n o i o o m o i o o i n o i n o i o o i o o i o o i o o

^^^O0^0^O---^^0'^_lnO^q^^0f^^.-^O^rSC0(N-0r-<0^
^ir)'or~-ooaNO(Nro'^u-)or^ONO'-H(Nf^msoi>ooo

O'-H'(>(rN(N(Nrnr*-)rn'^'^iniOiO\0^0Or^l>000000

Ou-)Oii*)Oinoinoioomoioomomomoioo

(N(N<N(N(N(NfNr^(N<N(N(Nr^rstfs|(N<N(N
ooaNOO^ir)r^'^\OrNOr*^(N't^O'^ooror-OO^cdod^-^^D^dlOlOlO<:}-^Trr*^fn^orOr<^

T t s o 00 O

<N **. ^ _ 0 0 O

fN -^^ NO 0 0 p

(N -sf sO 0 0

OOO'''-H'--H'-H'-Hrsirjr^'fNrsir*Srnrof^rn
fN(N<N<N<NfNrs|rs|rs|<N(N(N(NfNfNfs<N(N

sq'-Hsqosq^^D'^\q'^i><Ni>rnoq'^osq
r^''^'int~-^odO'-Hr^Tt\dr^'oNO(Nrninr^'o6
ioioiomm^>sosOsOsci\os>r-r~--r~-r-r^r^

r*S s d O

r n t ^ T-H Tf od ^" l O ON fN s d O

^' oo' ' ^

lO

(N(^Ttio\Dr-;OoaNO'^(Nrn^iosoi>oqoN
i/SidioiouSi/iioirisd^Jsdsdsdsdsdsdsosd

O'^tNirjONOLOfSOiO'^t^
f^irit^aN'--;'^^ONT-H-^i>av(NiooO'I'^it--;
ui^dt'-^ooo^fNr'Stosdr^odo'(fS'rrinvd
OOOOOOOOOvCfNOONONONONONOOOOOO
0^^p\qfN00lO(N0^sq"^'--^O^s0'!:1-^n<Np
^^iuSo6o^OlOo6'-Hrn^do^<N^'t~-^Or^sdo^

irimin<3sosooi>i>i>t^ooooooa\a\0\a\

r^l rO '*_ i n s o t-~. Oo 0 \ O

'-H C^l f<^ -rr u ^ s o l > 0 0 Ov

mor^^(Ncr\sor*^a\f^in(^'<^oO'^fO'!:l-'-H
dT-Hrsro'^ioso'i-^'o6oNd'-H(Nr*^'=^'irisdt^

sOr*-)'^ONl>'^(NOt^'=^(N(NOO(NsOONOO(N
r~^u^rOpOOsO'!:rr^a\C^inr^'-HT-H,ifS'=rC~--_

^^^^'Ou'iioioiomsosOsO'sOsor^t^t^

o o o o o o o o o o o o o o o o o o
(Nf^'^insqi^oooNO'^tNrn-^insoooqov
iniriuSi/SininuSiovD<J<J^sbsosdsdsdsd

861

862 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 16Coefficients of quadratic equations. ASTM D 2270.


Ymin

Ymax

2.0
3.8
4.4
5.0
6.4
7.0
7.7
9.0
12
15
18
22
28
40
55
70

3.8
4.4
5.0
6.4
7.0
7.7
9.0
12
15
18
22
28
40
55
70
Up

1.14673
3.38095
2.5000
0.10100
3.35714
0.01191
0.41858
0.88779
0.76720
0.97305
0.97256
0.91413
0.87031
0.84703
0.85921
0.83531

1.7576
-15.4952
-7.2143
16.6350
-23.5643
21.4750
16.1558
7.5527
10.7972
5.3135
5.2500
7.4759
9.7157
12.6752
11.1009
14.6731

-0.109
33.196
13.812
-45.469
78.466
-72.870
-56.040
-16.600
-38.180
-2.200
-0.980
-21.820
-50.770
-133.310
-83.19
-216.246

0.84155
0.78571
0.82143
0.04985
0.22619
0.79762
0.05794
0.26665
0.20073
0.28889
0.24504
0.20323
0.18411
0.17029
0.17130
0.16841

1.5521
1.7929
1.5679
9.1613
7.7369
-0.7321
10.5156
6.7015
8.4658
5.9741
7.4160
9.1267
10.1015
11.4866
11.3680
11.8493

-0.077
-0.183
0.119
-18.557
-16.656
14.610
-28.240
-10.810
-22.490
-4.930
-16.730
-34.230
-46.750
-80.620
-76.940
-96.947

L = aY' +bY+ c
H = dY' + cY+f

TABLE 17Segment of table from ASTM D 2270.


Kinematic Viscosity
at 100C, mm^/s
15.5
15.6
15.7
15.8
15.9

313.9
317.5
321.1
324.6
328.3

157.0
158.6
160.1
161.6
163.1

TABLE 18Precision attributable to VI calculations.


Procedure A
VI == 100

VI = 0
Kinematic
Viscosity
at100C
(mm^/s)
4
6
8
15
30
50

Reproducibility, R

Repeatability, r

Repeatability, r

Reproducibility, R

Base Oil

Formulated

Base Oil

Formulated

Base Oil

Formulated

Base Oil

Formulated

0.98
0.71
0.57
0.45
0.39
0.36

2.31
1.68
1.35
1.06
0.92
0.85

5.77
4.20
3.38
2.56
2.29
2.11

6.75
4.91
3.95
3.11
2.68
2.47

0.73
0.40
0.30
0.20
0.14
0.11

1.73
0.94
0.70
0.48
0.33
0.26

4.32
2.35
1.75
1.19
0.82
0.65

5.05
2.75
2.05
1.39
0.96
0.76

Procedure B
VI == 200

Vl= 100
Kinematic
Viscosity
at 100C
(mm^/s)
4
6
8
15
30
50

Repeatability, r

Reproducibility, R

Repeatability, r

Reproducibility, R

Base Oil

Formulated

Base Oil

Formulated

Base Oil

Formulated

Base Oil

Formulated

0.50
0.37
0.31
0.23
0.19
0.17

1.18
0.87
0.74
0.55
0.44
0.40

2.94
2.18
1.84
1.37
1.11
0.99

3.44
2.55
2.15
1.61
1.30
1.16

0.77
0.57
0.48
0.36
0.29
0.26

1.82
1.34
1.13
0.84
0.68
0.61

4.54
3.35
2.82
2.11
1.71
1.52

5.31
3.92
3.30
2.46
2.00
1.78

Wu, Bflaus and Duda [103] note the following:


A simple and accurate method is presented for the prediction of the pressure-viscosity coefficients of various kinds
of lubricating oils. For a given oil, the correlation only
required the viscosity-temperature relationship and the viscosity at the temperature of interest of the oil. When it is
applied to a polymer blend, the viscosity-temperature relationship of the base oil is also needed. The failure of this
method to predict the pressure behavior of some synthetic
hydrocarbons and nonhydrocarbons appears to be related
to the unusual high, or low, bulk moduli of these fluids....
The proposed method has the simplest equation form of all

the methods published to date and is the only one related


to free-volume theory.
It is of importance to ensure that the lubricant will have the
ability to function under pressure to lubricate bearings and
gears. There are a number of tests related to the ability of the
lubricant to resist adhesive wear, or scuffing under pressure.
This is illustrated (ASTM D 5182) as follows:
The transmission of pcnver in many automotive and industrial applications is accomplished through the use of
geared systems. At higher operating speeds it is well known
that the lubricant/additive system can be a significant factor in preventing scuffing (adhesive wear) damage to gears.

CHAPTER 32: FLOW PROPERTIES AND SHEAR STABILITY


This test method (ASTM D 5182) is used to screen the
scuffing load capacity of oils used to lubricate spur and
helical (parallel axis) gear units.
There are several extreme-pressure tests for lubricating fluids
to differentiate the ability of the lubricant/additive systems to
prevent scuffing damage:
ASTM D 5182 Test Method for Evaluating the Scuffing
(Scoring) Load Capacity of Oils
ASTM D 2782 Test Method for Measurement of ExtremePressure Properties of Lubricating Fluids (Timken
Method)
ASTM D 2783 Test Method for Measurement of ExtremePressure Properties of Lubricating Fluids (Four-Ball
Method)
ASTM D 5183 Test Method for Determination of the Coefficient of Friction of Lubricants Using the Four-Ball Wear
Test Machine

ABSOLUTE VISCOSITY OF WATER


The primary viscosity standard is distilled water at 20C. The
measurement of the absolute viscosity of the primary viscosity standard from the absolute dimensions of the apparatus
has sdways been a challenge. The establishment of the primary viscosity standard is made by measurements carried
out in special instruments of known physical dimensions.
The severEil geometries of these instruments include capillary
tubes [104,105], the damping of oscillations of a water-filled
glass sphere [106], and the damping of an oscillating disk or
cylinder [107,108]. The measurement of physical dimensions
of the several apparatus and the calculations of the viscosities
of water by the several methods is very complex, and it is difficult to ensure that all uncertainties have been properly evaluated. The data from these several sources have been
reviewed by Marvin [109] and Bauer [110]. Of especial note

A.S.T.M. STANDARD VISCOSITY-TEMPERATURE CHARTS


FOR LIQUID PETROLEUM PRODUCTS (D 341-43)

soo
400

CHART C: KINEMATIC VISCOSITY, HIGH RANGE

300

200

ISO
S

I/)

100

\,
>>=s^

i> s

S,

^' S

II

v ^ V-

so

t^
TT
V
^.*
\ /o s;

40

s,

-^
-^

II

1/3

HJ T^
^
i> ^^ \C
S 1

30

"^

u
^^
H

S, s^ s .
\
X s
\,
X ^

N k.
v^

20

s^

V S
v

'>

IS

SOs .

N*^

^^
^ ^

10
9.0
8.0
7.0
6.0

90

100

110

120

130

140

863

150

160

170

180

190

200

TEMPERATURE, DEGREES FAHRENHEIT


FIG. 30Illustration of VI for VI = 10, 95, and 150.

210

220

230

240

864 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


VISCOSITY STANDARDS

10,000

1000
o

a.

E
>-"

100 -^

h;
00

O
O

00

>

1000

2000

3000

PRESSURE, ATMOSPHERES
FIG. 31Viscosity as a function of pressure.

For almost all of the tests and procedures for the measurement of kinematic viscosity and viscosity, viscosity standards
are necessary to calibrate the equipment and to ensure that
the test is being carried out correctly.
The kinematic viscosity range of standards commercially
available is from about 0.6- to 100 000-mm^/s, over a temperature range from about 40 to 150C. These standards cover
the full range of the instruments used for the measurement of
kinematic viscosity. The viscosity range of standards commercially available is from about 0.6- to 5 000 000-mPa-s
(5000 Pa-s) over a t e m p e r a t u r e range from about 40 to
150C.
From the late 1930s to about 1959, ASTM Subcommittee
D02.07 Section A on Newtonian Viscometry made available
three API viscosity standards. These standards were sponsored by the American Petroleum Institute, and certification
was done by m e m b e r s of ASTM D02.07.A. The standards
were
API Standard

Alpha
Beta
Gamma

T A B L E 1 9 V i s c o s i t y of w a t e r .
Temperature
(C)

Viscosity
(mPa-s)

Density
(kg/m')

Kinematic
Viscosity (mm^/s)

15
20
23
25
30
40

1.1378
1.0016
0.9321
0.8899
0.7971
0.6524

999.10
998.20
997.54
997.04
995.65
992.21

1.1388
1.0034
0.9344
0.8925
0.7995
0.6575

is t h a t the several m e a s u r e m e n t s , while close, vary from


1.00035-1.00334 mPa-s, a variation of nearly 0.3%.
For many years the viscosity value of 1.005 mPa-s (cP) at
20C was accepted throughout the world. This value was derived from the evaluation by Bingham and Jackson [111],
and based on their evaluation of all the available measurements [112]. New measurements of the value assigned to
the viscosity of water began in the late 1930s and were completed in the early 1950s by Swindells, Coe, and Godfrey
[113]. In 1953 these data resulted in a recommended revision to 1.002 mPa-s at 20C based on the international temperature scale of 1948. It must be noted that there have
been a number of temperature scales (e.g., in 1927, 1948,
1968, and 1990), each of which have small differences in the
precise definition of t e m p e r a t u r e at 20C. The data by
Swindells et al. has been updated by Bauer [110] to the International Temperature Scale of 1990 (ITS90). The currently accepted values for the viscosity of water at atmospheric pressure are found in Table 19.
This is published in ISO 3666 [114], which contains additional information on the variation of the viscosity of water
at other pressures. The overeJl uncertainty of the viscosity
and kinematic viscosity of water at 20C is estimated to be
0.17%.

Kinematic Viscosity and Temperature

60 mm^/s at 100?, and 8 mm^/s at 210F


400 mm^/s at 100F, 190 mm^/s at 120F
and 27 mm^/s at 210F
3 mm^/s at 100F, 86 mm^/s at -40''F and
350 mm^/s at -65F

By the late 1950s, these limited kinematic viscosity ranges


did not adequately meet the needs of the petroleum industry.
Accordingly, a new set of seven viscosity standards (later
expanded to nine standards and including density measurements) covering t h e range of 3- to 27 OOO-mm'^/s w a s
sponsored by ASTM, and made available from Cannon Instrument Company (P. O. Box 16 State College, Pennsylvania
16804-0016). The standards from ASTM D 445 are found in
Table 20.
At the same time, the National Bureau of Standards had a
separate series of viscosity standards widely used in the
chemical industry, while the ASTM series was widely used by
the petroleum industry. This series was available from the
late 1930s, covering the range of 2- to 45 000-mPa-s [115]. After the expanded ASTM series became available, these two
series duplicated each other for the most part, and the two series were merged [116] into the series now listed in ASTM D
445 (Table 20).
Viscosity standards are generally available throughout the
world, both from semi-official laboratories such as Cannon
Instrument Company, and the various official laboratories in
Germany, France, Russia, Japan, China, Australia, and South
America, as well as many commercial laboratories. A n u m b e r
of viscosity standards have been developed for specific
instruments and applications such as the special low temperature requirements of gear oils, the cold cranking simulator,
the mini-rotary viscometer, the high-temperature high-shear
viscometers, etc.
S a y b o l t , S h o r t C a p i l l a r y a n d Orifice V i s c o m e t e r s
Early in the development of the measurement of flow as one
of the important properties of petroleum lubricants, a number of "technical viscometers" were developed and widely

CHAPTER

32: FLOW PROPERTIES

AND SHEAR STABILITY

865

TABLE 20Table A1.2 from ASTM D 445, Viscosity Oil Standards.


Designation"
20C

...40C

S3
S6
S20
S60

4.6
11
44
170
640

80

S200
S600
S2 000
S8 000
S30 000

Approximate Kinematic Viscosity, mm /s


40C''
25C

2 400
8 700
37 000

50C

2.9
5.7
18
54
180
520

4.0
8.9
34
120
450
1 600
5 600
23 000
81000

100C'
1.2
1.8
3.9
7.2
17
32
75

280

1 700
6 700
23 000

11 000
" The actual values for these standards are established and annually reaffirmed by cooperative tests. In 1991, tests were made using 15 different types of viscometers in 28 laboratories located in 14 countries.
* Kinematic viscosities may also be supplied at 100F.
^ Kinematic viscosities may also be supplied at 210F.

used. Bingham [16] in 1922 describes t h e m in Appendix C as


follows:
Instruments very different from those employed in scientific work are much in vogue in this country [England]
and abroad for industrial purposes, particularly in the oil
industry. Thus, we have the Engler Viskosimeter
in
Germany, the Redwood Viscometer in Great Britain, the
Sayholt Viscosimeter in the United States, the Barbey
Ixometre in France and a host of others. Most of them
seem to have been devised with the idea in mind that the
time of flow of a given quantity of various liquids through
an opening is approximately proportional to the viscosity,
without much regard to the character of the opening. There
is usually a container which is filled to a certain level and
a short efflux tube opening into the air. The number of seconds required for a given quantity of liquid to flow out
under gravity is taken as an indication of the viscosity.
Kinematic viscosity calculations for these viscometers
follow the equation
V = rj/p = A t - B/t
where

2000

1000-

SAYBOLT UNIVERSAL, SECONDS


as 0 function of
KINEMATIC VISCOSITY

600

200-

30
6

10

20

30

60

100

200 300

600

KINEMATIC VISCOSITY mm V s

FIG. 32Saybolt viscosity vs. kinematic viscosity.

(30)

v = kinematic viscosity
77 = viscosity
p = density
A, B empirical constants

Tables a n d charts have been constructed for converting


Engler Degrees (cf. Ubbelohde 1907), Redwood seconds (cf.
Higgins 1913), Saybolt Universal seconds (SUS), and Saybolt
Furol seconds (SFS) into kinematic viscosity units. An
example is found in Fig. 32.
The Saybolt Universal seconds (SUS) units are defined by
the following equation.
Ut = [1.0 +0.00006 l(t

100)]
[1.0 +0.03264 v)]
4.6324 v +
(3930.2 + 262.7 v + 23.97 v^ + 1.646 v^) X 10"

Where:
V = kinematic viscosity, mm^s (cSt) at fF
Ut = Saybolt Universal Viscosity at ?F
Until recently, charts with SUS units as a function of temperature in degrees Fahrenheit were published by ASTM.
These charts have been replaced by kinematic viscosity in
mm^/s as a function of temperature in degrees Celsius (ASTM
D 341 - 32 T, ASTM D 341-93), as it is the custom to use the
International Systems of Units (SI).

Over the years, there has been relatively little change in


these instruments. Until quite recently, the units SUS, Redwood and Engler degrees were extensively used, and there is
still widespread use of SUS units in technical publications,
advertisements etc. in the United States. Related expressions
such as "100 Neutral" are widely used in the petroleum industry, where it is understood the "100" refers to the Saybolt
Universal Seconds kinematic viscosity at 100F.
While the use of the short capillary viscometers has largely
faded from the petroleum industry, short capillary or orifice
viscometers are widely used in the paint and coatings industry. Examples of these instruments are the Zahn and the Shell
dip cups (ASTM D 4212), the Ford Cup (ASTM D 1200), the
ISO Cup (ASTM D 5125), and a host of other cup viscometers
used in the United States and throughout the world. The following equation is generally used to represent the correlation
of the sample efflux time with the kinematic viscosity of the
sample:
V = 7j/p = A t - B/t

where

v=
t] =
p =
A, B =

kinematic viscosity
viscosity
density.
empirical constants

(31)

866

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

However, often there is no attempt to convert the efflux time


for a particular device with kinematic viscosity. Instead, the
cups are more often used for control purposes, and kinematic
viscosity is reported as "seconds" for whatever cups and size
are used.
This equation limits the low-kinematic-viscosity (and also
short efflux-time) use of each of these viscometers. Under
these conditions, the kinematic viscosity becomes almost
independent of the efflux time.
Temperature Measurement Considerations
The importance of accurate temperature measurement cannot be overemphasized. Because of the extreme sensitivity of
viscosities of various materials to changes in temperature,
calibration of thermometers to a national standard is
required. To a large extent, both toluene- (or other non-mercury-liquids) and mercury-filled thermometers are used
throughout flow-related ASTM methods. The continued use
of mercury-in-glass thermometers in the future may be in
question. Environmental regulations in some countries may
prohibit the use of mercury in any device. There is considerable help to ensure understanding of thermometry in the
writings of ASTM Committee E20. However, other thermometric sensors such as resistance elements, thermocouples,
thermistors, diodes etc. are also widely used.
The practical temperature scale [117] is based on two fixed
temperatures. Absolute zero and the triple point of water are
assigned, respectively, 0 K and 273.16 K in the Kelvin Thermodynamic Temperature Scale (KTTS). The KTTS references are assigned the symbol T (ASTM E 1594), without a
degree symbol. The unit of temperature in the KTTS is the
Kelvin, symbol K (without the degree sign). The unit of Celsius (centigrade) temperature is the degree Celsius (C). By
definition one degree Celsius is equal to a temperature incre-

O
00
CD

0.02
O
(D
O
C
CD

^._
CD

CD
s^

D
CD
CL

E
CD

100

100

200

t, X
FIG. 33Temperature correction between
IPTS-68 and ITS90 temperature scales.

TABLE 21Standard platinum reference


thermometer calibrations.
Temperature
Material

Equilibrium State

T90 (K)

tso {C)

02
Ar
Hg
H2O
Ga
In
Sn
Zn

Triple point
Triple point
Triple point
Triple point
Melting point
Freezing point
Freezing point
Freezing point

54.3584
83.8058
234.3156
273.16
302.9146
429.7485
505.078
692.677

-218.7916
-189.3442
-38.8344
0.01
29.7646
156.5985
231.928
419.527

ment of one Kelvin, and t = 0C is the same as the thermodynamic temperature T = 273.15 K [118]. The practical
temperature scale now in use is the International Temperature Scale of 1990 (ITS-90). Formerly used temperature
scales include the International Practical Temperature Scale
of 1968 (IPTS-68), the International Practical Temperature
Scale of 1948 (IPTS-48), and the International Temperature
Scale of 1927. There are small differences in temperatures
between the several temperature scales, and for accurate
experimental work, the temperature scale used should be
specified. See Fig. 33 (ASTM E 1594), which describes the
differences between the ITS-90, adopted on January 1, 1990,
and the IPTS-68 temperature scale.
Liquid-in-glass thermometers are fundamental to accurate
viscosity measurements. ASTM methods El and E77 give
considerable guidance in the construction and use of thermometers. These thermometers must be calibrated against Standard Platinum Resistance Thermometers (SPRT) for the
most highly accurate temperature measurements. Once
calibrated, liquid-in-glass thermometers need only be recalibrated at one of the temperatures in the futuremost often
the ice point temperature, as follows: [119]
High quality liquid-in-glass thermometers require only one
complete calibration in their lifetime and it is possible to
avoid the usual requirement for complete recalibration of
the instrument by the recalibration of a single previously
calibrated temperature. The need for recalibration of properly manufactured liquid-in-glass thermometers is due to
the gradual relaxation of residual mechanical strains in the
glass that have a significant effect on the volume of the
bulb. The recalibration of a single point provides a reliable
indication of the effect of this change in volum^e and provides a means for the accurate adjustment of the remainder of the scale. Those calibrated, mercury-in-glass
thermometers which have an ice-point scale allow verification of the complete calibration by measurement of the
ice point. A change in the ice point reading, if any, from the
original calibration at the ice point will apply to all temperatures in addition to any corrections given in the original
calibration.
The certificate of calibration for the thermometer must state
whether the thermometer is to be used at total immersion, at
partial immersion, or at complete immersion. Total immersion thermometers require immersing those parts of the thermometer's liquid at test temperature, while keeping the
emergent stem exposed to ambient temperatures. Complete
immersion thermometers are to be completely immersed

CHAPTER 32: FLOW PROPERTIES AND SHEAR STABILITY


including the emergent stem, and they are rarely so used or
calibrated.
Replacement thermometric devices include highly accurate resistance thermometer devices (RTDs, ASTM E 644)
a n d industrial p l a t i n u m resistance t h e r m o m e t e r s (PRTs,
ASTM E 1137). For S t a n d a r d Platinum Resistance Thermometers (SPRT), which are used to define the temperature
scale, the resistance at the triple point of water (ASTM E
1750) is a very important reference temperature. The SPRT
t h e r m o m e t e r s are calibrated at the triple point of water
and one or more of several "fixed point" temperatures. See
Table 2 1 .
Various thermistor thermometers are often used (ASTM E
879). A thermistor is a thermally sensitive resistor, the primary function of which is to exhibit a large change in electrical resistance w i t h a change in sensor t e m p e r a t u r e . The
equation relating temperature and resistance is
t = [ao -t- ai (InR) -I- a2 (InR)^
-I- as (lnR)3]-i - 273.15.

(32)

Elsewhere, the equations for thermistors sometimes omit the


second degree, aa, term. A t h e r m i s t o r can be calibrated
against a SPRT at a n u m b e r of temperatures using a good five
or six place digital ohmmeter allowing the measurement of
temperature to a precision close to 0.01C.
Another temperature measuring devices is a thermocouple. Thermocouples are used over the temperature range of
- 1 8 0 to 1700C. The eight types of thermocouples (Types B,
E, J, K, N, R, S, and T) are most commonly used (ASTM D
230). Depending on the temperature remge and the type of
thermocouple, the uncertainty in the interpolated temperature using thermocouples is 0.1 to 5C (ASTM E 220).

867

the rheological tests are used in c o m m o n to the various materials, but the preparation of each material for testing is
often specific to the particular material.
Paints and Coatings Flow-Related Instruments
The paint and coatings industry has many rheological measurements made on its products. Adaptations of a n u m b e r
of these measurements are of use to petroleum products.
The viscosities of printing inks, solvents (vehicles), and similar materieils are measured by the Leiray or Duke fallingrod viscometers (ASTM D 4040). These apparatuses are
based on measurements of the time required for a weighted
rod to fall through a n aperture containing the specimen at
25C having a viscosity in the range of 1 to 30 Pa-s at a
shccir rate of 2500 s ^ ^ Calibration of the apparatus is by
the use of multiple viscosity standards at 25C, and includes
the determination of the fall time equivalent to a shear rate
of 2500 s ^ Using the power-law relationships between
shear stress and shear rate, the apparent viscosity at a shear
rate of 2500 s " ' , the degree of non-Newtonian behavior
(shear-thinning or shear-thickening) and reference temperature are determined, although the complete rheological
properties are not defined. Low shear rate properties are
not measured. Such information is useful in the practical
control and use of ink.
The viscosities of paints, varnishes, lacquers, coil coatings,
and related liquid materials are measured by dip-type and
short capillary cups such as Zahn dip cup. Shell, Ford, and
ISO cups (ASTM D 4212, ASTM D 1200, ASTM D 5125). See
Fig. 34.
Dip Cups

OTHER NON-PETROLEUM MATERIALS


USING ASTM FLOW PROPERTIES
While we think of petroleum-related products especially in
connection with lubricants and fuels, the chemistry of derived petroleum products includes such materials as paints,
coatings, adhesives, rubber, bitumen, plastics, etc. The flow
properties of these materials are of the highest importance in
their manufacture and use. In addition, non-petroleum materieds such as tar, medical products, glass, ceramics, metals,
etc. have flow properties that are important in their manufacture and use. There is a wealth of rheologiccJ information
about these materials in various ASTM documents. Many of

Zahn Cup

ISO Cup

Dip cups are tjrpically used for kinematic viscosities in the


range of 5-1800 mm^/s at 25C and flow times of 20-100 s.
There are a n u m b e r of such cups, such as the Zahn, Ford,
Fisher, etc. dip cups. Flow time measurement begins with the
start of flow as the cup breaks the surface of the liquid into
which it had been lowered and ends with the first definite
break in the stream at the base of the cup. The relation between kinematic viscosity and flow times is generally given
by the equation
Kinematic Viscosity = K t B/t
where

K, B = constants
t = flow time

Ford Cup

FIG. 34Dip and paint cup instruments.

Shell Cup

(33)

868

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

K and B are cup constants determined through the use of


kinematic viscosity standards. Other equations are somet i m e s used to approximate the relationship. The Unear
equation
Kinematic Viscosity = K (t - c)
where

(34)

K, c = cup constants
t = flow time

is sometimes used over a part of the total range of the dip-cup


(ASTM D 4212). It is very important to observe the m i n i m u m
flow-time restrictions for these short-capillary instruments,
since the kinematic viscosity relationships cannot be extrapolated to lower flow-times. In a similar manner, the maxim u m flow time specification m u s t also be observed, as a
m u c h longer flow-time results in a premature break of the
efflux stream and a shortened measurement of the flow time
without a fully emptied cup.
Bubble Tubes
A measure of the kinematic viscosity at 25C of polymers and
resins is approximated by the rise time of an air bubble inside
a clear glass tube (10.65 m m in diameter by 108 m m long)
filled with the liquid (ASTM D 1545). The result of the comparative measurement is reported as the Gardner-Holt letter
(A5-A1, A-Z, and Zl-ZlO) grade of the bubble tube standard
having a rise time closest to that of the test sample. Over a
limited range, the bubble rise time approximates the
kinematic viscosity in stokes (1 stokes = 100 mm^/s). But
generally these tubes are used to compare the bubble rise
times to one or more calibrated tubes, such that, for example,
a material has a bubble rise time between R and S tubes. The
result may also be reported as the rise time in "bubbleseconds."
Falling Needle
The viscosity of Newtonian and non-Newtonian varnishes
and paints can be measured by allowing various thin needles
to fall through the liquid, measuring the velocity of the nee-

dle (ASTM D 5478). By varying the density of the needle,


shear rates can be adjusted.
The Brush Drag of Latex Paints is said to generally give
good rank order between the brush test (ASTM D 4958) and
the high-shear test (ASTM D 4287). In the brush test a 50-mm
polyester brush is used to apply the test paint on a lOO-cm'^
(1.076-ft^) area at a spreading rate of 400 ft^/gal and is to be
completed in 30-35 s. From the Note 1 to the ASTM D 4958
reference.
The brush drag of paints is directly related to their highshear viscosity. There is generally good rank order agreement between results obtained by this method and Test
Method D 4287. The sensitivity of this brushout method
has been found sufficient to distinguish betv^een brushabilities corresponding to high-shear viscosity differences
not lower than 0.3 poise (0.03 Pa-s).
Cellulose derivatives are measured by a variety of viscometers. Commonly used glass viscometers include the CannonFenske Routine, the Ubbelohde, the Wagner, and other
modified capillary instruments (ASTM D 871, ASTM D 914,
ASTM D 1347, ASTM D 1439, ASTM D 1795, ASTM D 2363).
The ball-drop method (ASTM D 871) and the low shear rotational viscometers (ASTM D 1439, ASTM D 5400) are also
used.
The viscosities of rosin and tall oils (ASTM D 803, ASTM D
1131, ASTM D 1725) m a y be m e a s u r e d by bubble tubes
(ASTM D 4958), the Saybolt viscometer (ASTM D 88), and
rotational viscometers (ASTM D 2196).
The low shear Stormer viscometer (ASTM D 562) (Fig. 35)
has been in use since at least the year 1909 [120], and still is
widely used.
A m o d e r n electronic version of the Stormer/Krebs viscometer is also available. Other low and moderate shear rate
viscometers (ASTM D 2196) along with high shear-rate viscometers (ASTM D 4287) are also widely used. Rotational
viscometers play a large part in the measurements of the
viscosities of paints and coatings (Fig. 36).
The viscosity of molten powder coatings at baking temperatures is determined using a cone and plate Weissenberg
rheogoniometer (cone-plate geometry, ASTM D 3451).

^ g ( N o . 22 US. Ooge}
All Oimwsions Subject to o
,. . , ... . , ^olewnce of 0.004"
Material: Sloinless Steel

FIG. 35Stormer paddle-type rotor with stroboscope timer.

CHAPTER

32: FLOW PROPERTIES

AND SHEAR

STABILITY

869

lUPAC is the International Union of Pure and Applied


Chemistry.
Intrinsic viscosity: [TJ] = lim (7] tjoVv c
(36)
c > o
Intrinsic viscosity can be used to calculate the molecular
weight
[TJ]

There is a series of mechanical tests for determining and


reporting the viscoelastic properties of thermoplastic, thermosetting resin, a n d composite systems. These polymeric
materials may be in solution, or melts, or solids. A compilation of definitions and descriptions of technical terms used in
all of these dynamic mechanical properties is given in ASTM
D 4092. From the "significance and use" of these methods:
Dynamic mechanical testing provides a sensitive method
for determining thermomechanical characteristics by measuring the elastic and loss moduli as a function of
frequency, temperature, or time. Plots of moduli and tan
delta of material versus temperature provide graphical
representations indicative of functional properties, effectiveness of cure (thermosetting-resin systems), and damping behavior under specified conditions (ASTM D 5023,

rotational

Plastics
Flow-related tests are fundamental in the making of plastic
products. There are many "dilute solution" methods of tests
for plastics (ASTM D 789, ASTM D 1243, ASTM D 1601,
ASTM D 2857, ASTM D 3591, ASTM D 4603, ASTM D 4878,
ASTM D 5225, ASTM D 1823); typically there is a specific
procedure for each polymer. These methods allow the meas u r e m e n t of the viscosity ratio, which is the ratio of the
viscosity of a very dilute polymeric solution to that of the
pure solvent. Generally, a glass kinematic viscometer is used
to measure both the kinematic viscosity of the solution and
of the solvent. Because the density of the dilute solution is
nearly the same as the density of the solvent, the relative viscosity is merely the ratio of the flow time, t, of the solution to
that of the solvent, to (assuming there is no significant kinetic
energy correction to be applied to the flow time).
Viscosity Ratio: Tjr = TJ/TJO = t/to

(37)

M''

M = molecular weight
a, b = constants determined for each type of polymer.

where

FIG. 36Electronic
paint tester.

= a

Inherent Vticoilty
_(I-ogrtthn.lc Vl.coalty Number)

Incrinilc Vlscotlty
(Limiting Vlicoaity Number)

(35)

where

T]^ = viscosity ratio


17 = viscosity of the solution
Tjo = viscosity of the solution
t = flow time of the solution
to = flow time of the solvent
With the known concentration of the solution, the reduced
viscosity and limiting viscosity n u m b e r (intrinsic viscosity)
are calculated. A sample plot to determine intrinsic viscosity
is found on Fig. 37.
From the viscosity n u m b e r the intrinsic viscosity is determined (often extrapolated to zero concentration). It is used to
determine the molecular weight of polymer molecules. The
reader of these methods is alerted that there is a double set of
nomenclature, as indicated in Table 22.
Many tests are done at 30C, with some tests performed at
135X.

Polymer Concentration, g / c m '

FIG. 37Example of plot to determine intrinsic


viscosity (limiting viscosity number).
TABLE 22Polymer viscosity measurement nomenclature.
Conventional Term

lUPAC Alternative Term

Relative Viscosity
Reduced Viscosity
Inherent Viscosity

Viscosity Ratio
Viscosity Number
Logarithmic Viscosity
Number
Limiting Viscosity Number

Intrinsic Viscosity
"where

Definition"

Vr = V'no
%ed = (Vr - 1)/C
ijinh = In r)r /c
[TJ]

rf = viscosity of the dilute polymeric solution


r)o = viscosity of the solvent
c = concentration of the solution in units of g/mL

870

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

ASTM D 5024, ASTM D 5026, ASTM D 5279, ASTM D


5418, ASTM D 5422).
Each of these tests is characterized by the different designs of
the apparatus and the required special test procedures.
Pol3aneric powders are appHed to surfaces by electrostatic
spray or fluidized bed procedures. The Weissenberg Rheogoniometer (cone and plate geometry, ASTM D 3451) is used to
study the use of such powders at baking temperatures. A separate test consists of making a small pellet of the powder and
measuring the flow at 150C on ein inclined plane.
Bituminous Materials
The use of rheological properties is highly important for the
specifications and uses of asphalt cements, liquid asphalts,
emulsified bitumens, and tar materials.
Since the early 1900s, b i t u m i n o u s materials have been
graded according to the results of a "rheological test" using
the penetration of a needle (Fig. 38) into a specially prepared
asphalt test sample. The needle is allowed to vertically
descend into semi-solid and solid materials u n d e r known
conditions of loading (typically 100 g), time (5 s) and temperature (25C), although other conditions may be specified
(ASTM D 5). The results are expressed in tenths of a millimeter, and specifications for paving grade asphalts include
penetration ranges, e.g., 40-50, 85-100, 200-300, etc. (ASTM
D 946).
In the early 1960s, several new rheologicEilly-based specifications and related tests for bituminous materials [121] at
three defined temperature zones were created:
135C, a temperature approximating the temperature in
the hot-mix towers for the mixing of aggregate with the bituminous material, glass capillary kinematic viscometers
(ASTM D 2170),
60C, approximating the temperature of a road surface in
the hot s u m m e r sun, glass capillary vacuum viscometers
(ASTM D 2171, ASTM D 4957) [122], and
4C, approximating the temperature of a pavement at a
temperature just above the freezing point of water, test
methods and specifications never implemented.
Where the viscosity of the material is higher than can be
tested with kinematic viscometers, force is applied by means
of a regulated vacuum to glass capillary viscometers, thus extending the viscosity range u p to 580 000 Pa-s (ASTM D
2171). Some examples of vacuum viscometers may be found
in Fig. 39.
Other tests include the Saybolt viscometer (ASTM E 102,
ASTM D 88, ASTM D 244) and the Engler viscometer (ASTM
D 1665) especially for specifications of roofing, waterproofing, and bituminous materials for liquid and emulsified asphalts and tars. Rotational viscosity tests are also utilized for

0.14 k) 0.16 mm
./.GO h 1.02mm 840'io 940'^
I

>

ZIL
I

as required

_=j opprox.
^6.35 mm

FIG. 38Needle for penetration test.

these products both at high temperatures (ASTM D 2994)


and very high viscosities (ASTM D 3205) using special coneplate and Rheogoniometer viscometers.
In the early 1990s the Federal Highway Administration
(FHWS) sponsored a large program for the improvement of
the bituminous materials comprising much of our highwaypaving program. The Strategic Highway Research Program
(SHRP) resulted in a n u m b e r of rheological recommendations for the specifications for bituminous materials.
The Bending-Beam Rheometer (BBR, Fig. 40) performs
low-temperature flexural creep stiffness measurements on
asphalt binders as specified in ASTM D 6648, American Association of State Highway a n d Transportation Officials
(AASHTO), and SHRP methodology over the temperature
range of 36 to 0C and creep stiffness range from 20 MPa to
1 GPa and creep compliance values in the range of 50 n P a ~ '
to 1 n P a " ' [123]. (Note that 1 MPa = 10* Pa, and 1 GPa = 10^
Pa). A "beam" (6.35 m m by 12.7 m m by 127mm) of asphalt is
cast using a mold. At the specified low temperature (such as
18C), the beam is supported at each end. Under computer
control, a very low load is applied, 100 g, to the center of the
beam and rate of deflection is determined. From the collected
data, the stiffness modulus is calculated and reported.
The Dynamic Shear Rheometer (DSR) [124] with parallel
plate geometry is used to measure the complex shear modulus (G*) and phase angle (5) of asphalt binders over the temperature range of 5-85C and a dynamic shear modulus between 100 Pa to 10 MPa. Test specimens 1-mm thick by
25-mm in diameter are tested at a n oscillatory loading
frequency of 10 rad/s in a temperature controlled environm e n t a l c h a m b e r (some have liquid baths). The complex
shear modulus and the phase angle are calculated automatically. The test t e m p e r a t u r e for this test is related to the
t e m p e r a t u r e experienced by the p a v e m e n t in the geographical area for which the asphalt binder is intended. The
complex shccir modulus is a n indicator of the stiffness or
resistance of the binder to deformation under load. The complex shear modulus and the phase angle define the resistance
to shear deformation of the asphalt binder in the linear
viscoelastic region.
For certain tests, the asphalt binder must be processed using several aging methods. These practices simulate the effects of a long-term environment with oxidation and high
temperature and pressures, which include a rolling thin-film
oven and a pressure-aging vessel (AASHTO PPl). Binder so
tested is a part of the SHRP program.
Adhesives
Adhesives present special p r o b l e m s to the rheologist,
although the m e t h o d s used for the analysis of adhesives
are very similar to those used for other materials. For freeflowing adhesives, the Saybolt, Zahn dip cup. Ford cup, bubble t i m e tubes, S t o r m e r low shear rotational, and other
rotational viscometers are a m o n g the viscometer methods cited (ASTM D 1084). The apparent viscosity of shearrate-dependent adhesives is measured
. . . based upon a reversible isothermal change in apparent
viscosity with change in rate of shear. Measurement is performed with a spindle, disk, T-bar, or coaxial cylinder
rotational viscometer under standardized conditions with

CHAPTER 32: FLOW PROPERTIES AND SHEAR STABILITY

k-S-|-8*|*8'*|44
I

F;

mw 9

lililll?

o ..I-- o J-i o .,1, o J u

t t t t t tt
7 XI
o JC
X XI
o oJ t m uS CD 5 CD 5
o>
o*
o>
<=

t-

iT

f
!
w

(3
u.

871

872

MANUAL

3 7: FUELS

AND LUBRICANTS

HANDBOOK

FIG. 40Cannon bending beam rheometer.


rigid control of the time intervals of measurement. Readings are obtained on the viscometer dial scale at the end of
a minute for each rotational speed. Changes from the lowest speed to the highest speed, and return to the lowest
speed, are made without stopping the instrument (ASTM D
2556).
The apparent viscosity of hot m e h adhesives and coating materials at temperatures u p to 175C and apparent viscosities
u p to 200 Pa-s are m e a s u r e d using low-shear rotational
viscometers (ASTM D 3236, ASTM D 4499).

Rubber
Rheology is the science of deformation and flow of materials.
Deformation can be divided into reversible deformation
(elasticity) and irreversible deformation (flow). Many materials exhibit b o t h reversible a n d irreversible deformation,
exhibiting what is called viscoelasticity. This property is of
critical importance in the manufacture of rubber products,
although it is exhibited in many other products including
lubricants, paints, and coatings, etc.
The variety of terms used relating to the rheology of rubber
illustrate the complexity of this subject: viscosity, real
dynamic viscosity, relaxation, shear, strain, stress, modulus,
loss modulus, storage modulus, complex shear modulus, dynamic complex viscosity, elastic recovery, elastic fatigue, and
many others. Types of instruments used to measure the rheological behavior of unvulcanized raw rubbers and rubber
compounds include:

rotating disk within a cylindrical cavity (ASTM D 1646)


capillary rheometry-piston type (ASTM D 5099)
capillary rheometry-screw extrusion type (ASTM D 5099)
dynamic testing using servohydraulic, mechanical a n d
electrodynamic exciters (ASTM D 5992)
compression between parallel plates (ASTM D 6049)
rotorless shear rheometers (ASTM D 6204)
The widely used Mooney viscosity is defined at the shearing
torque resisting rotation of a cylindrical metal disk embed-

ded in r u b b e r within a cylindrical cavity. The Mooney


viscometer is:
. . . an instrument consisting of a motor-driven rotating
disk within a cylindrical die cavity formed by two dies
maintained at specified conditions of temperature and die
closure force. The Mooney viscometer measures the effect
of temperature and time on the viscosity of rubbers. If the
stress relaxation test is to be performed, the instrument
must be capable of stopping the rotation of the disk and
monitoring the relaxation of stress versus time (ASTM D
1646, ASTM D 3346).
Piston, or screw extrusion-type capillary rheometers (ASTM
D 5099, ASTM D 3835) are widely used for characterizing
plastics and rubber products. There is an excellent, detailed
description of rheological terms in the terminology of ASTM
D 5099 including terms such as the Rabinowitsch shear rate
correction for capillary geometry, the Bagley "end-effect" correction, and power law fluids, as well as the significance and
use of this these apparatus as related to rubber products. Additionally, there is an extended technical description of the
stress relaxation testing of raw rubber, unvulcanized rubber
compounds and thermoplastic elastomers (ASTM D 6049,
ASTM D 6048). Unvulcanized rheological properties using rotorless shear rheometers measure viscoelastic properties of
raw r u b b e r as well as unvulcanized r u b b e r c o m p o u n d s
(ASTM D 6204).
In a m a n n e r similar to the plastics industry, dilute solutions of synthetic rubber in a suitable solvent (e.g., methyl
ethyl ketone or toluene) are m e a s u r e d using kinematic
viscometers (ASTM D 445). In low-gel or gel-free rubbers,
the dilute solution viscosity correlates directly with the
molecular weight (ASTM D 3616).

ASTM STANDARDS

No.
ASTM D 5
ASTM D 88
ASTM D 88-21 T
ASTM D 97
ASTM D 244
ASTM D 341
ASTM D 341-32 T
ASTM D 341-93
ASTM D 445

ASTM D 446

ASTM D 562

Title
Test Method for Penetration of Bituminous Materials
Test Method for Saybolt Viscosity.
Standard Test Method for Saybolt
Viscosity, 1921
Test Method for Pour Point of
Petroleum Products
Test Method for Emulsified Asphalts
Viscosity-Temperature Charts for Liquid Petroleum Products, Appendix XI
Viscometer-Temperature Charts for Liquid Petroleum Products
Viscometer-Temperature Charts for Liquid Petroleum Products
Standard Test Method for Kinematic
Viscosity of T r a n s p a r e n t a n d Opaque
Liquids (the Calculation of Dynamic
Viscosity)
Standard Specifications and Operating
Instruction for Glass Capillary Kinematic Viscometers
Test Method for Consistency of Paints
using the Stormer Viscometer

CHAPTER
Test Methods for Determination of Relative Viscosity, Melting Point and Moisture Content of Polyamide (PA)
Test Methods for Tall Oil
ASTM D 803
Test Methods of Testing Cellulose
ASTM D 871
Acetate
Test Methods of Ethylcellulose
ASTM D 914
Specification for Penetration-Graded
ASTM D 946
Asphalt Cement for Use in Pavement
Construction
ASTM D 1084
Test Methods for Viscosity of Adhesives
Methods of Testing Rosin Oils
ASTMD 1131
Test Method for Viscosity by Ford VisASTM D 1200
cosity Cup
Test Method for Dilute Solution ViscosASTM D 1243
ity of Vinyl Chloride Polymers
Test Methods for Methylcellulose
ASTM D 1347
Test Methods for Sodium CarboxymethylASTM D 1439
cellulose
Test Method for Viscosity of TransparASTMD 1545
ent Liquids by Bubble Time Method
ASTMD 1601
Test Method for Dilute Solution Viscosity of Ethylene Polymers
Test Methods for RubberViscosity,
ASTM D 1646
Stress Relaxation, and Pre-Vulcanization
Characteristics (Mooney Viscometer)
Test Method for Engler Specific ViscosASTM D 1665
ity of Tar Products
Test Method for Viscosity of Resin
ASTMD 1725
Solutions
Test Method for Intrinsic Viscosity of
ASTMD 1795
Cellulose
ASTM D 1823
Test Method for Apparent Viscosity of
Plastisols and Organosols at High Shear
Rates by Extrusion Viscometer
ASTM D 2162
Standard Test Method for Basic Calibration of Master Viscometers and Viscosity Oil Standards
Test Methods for Kinematic Viscosity of
ASTMD 2170
Asphalts
Test Methods for Viscosity of Asphalts
ASTMD 2171
by Vacuum Capillary Viscometer
Test Methods for Rheological Properties
ASTMD 2196
of Non-Newtonian Materials by Rotational (Brookfield) Viscometer
ASTM D 2270 - 93 Standard Practice for Calculating Viscosity Index From Kinematic Viscosity
at 40 and 100C. (Originally pubUshed
by ASTM as D 567 - 40T, and revised and
renumbered in 1964.)
Test Methods for
Hydroxypropyl
ASTM D 2363
Methylcellulose
ASTM D 2556
Test Method for Apparent Viscosity of
Adhesives Having Shear-Rate-Dependent Flow Properties
Test Method for Apparent Viscosity of
ASTM D 2602
Engine Oils at Low Temperature Using
the Cold-Cranking Simulator, Note: Replaced by D 5293
Sonic Shear Stability of PolymerASTM D 2603
Containing Oils
ASTM D 789

32: FLOW PROPERTIES


ASTM D 2857
ASTM D 2983

ASTM D 2994
ASTM D 3205
ASTM D 3236
ASTM D 3346

ASTM D 3451
ASTM D 3591

ASTM D 3616

ASTM D 3829

ASTM D 3835

ASTM D 3945
ASTM D 4040

ASTM D 4092

ASTM D 4212
ASTM D 4287
ASTM D 4485
ASTM D 4486
ASTM D 4499
ASTM D 4603

ASTM D 4624

ASTM D 4683

ASTM D 4741

ASTM D 4878

AND SHEAR

STABILITY

873

Test Method for Dilute Solution Viscosity of Polymers


Test Method for Low-Temperature Viscosity of Automotive Fluid Lubricants
Measured by Brookfield Viscometer
Test Methods for Rubberized Tar
Test Method for Viscosity of Asphalt
with Cone and Plate Viscometer
Test Method for Apparent Viscosity of Hot
Melt Adhesives and Coating Materials
Test Methods for Rubber PropertyProcessability of SBR (Styrene-Butadiene Rubber) with the Mooney Viscometer
Practice for Testing Polymeric Powders
and Powder Coatings
Practice for Determining Logarithmic
Viscosity N u m b e r of Poly (Vinyl Chloride) (PVC) in Formulated Compounds
Test Method for Rubber, RawDetermination of Gel, Swelling Index, and Dilute Solution Viscosity
Test Method for Predicting the Borderline Pumping Temperature of Engine
Oil
Test Method for Determination of Properties of Polymeric Materials by Means
of a Capillary Rheometer
Shear Stability of Polymer-Containing
Fluids Using a Diesel Injector Nozzle
Test Method for Viscosity of Printing
Inks and Vehicles by the Falling Rod
Viscometer)
Standard Terminology Relating to Dyn a m i c Mechanical Measurements on
Plastics
Test Method for Viscosity by Dip-Type
Viscosity Cups
Test Method for High-Shear Viscosity
Using the ICI Cone/Plate Viscometer
Specification for Performance of Engine
Oils
Standard Test Method for Kinematic Viscosity of Volatile and Reactive Liquids
Test Method for Heat Stability of HotMelt Adhesives
Test Method for Determining Inherent
Viscosity of Poly (Ethylene Terephthalate) (PET)
Test Method for Measuring Apparent
Viscosity by Capillary Viscometer at
High-Temperature a n d High Shear
Rates
Test Method for Measuring Viscosity at
High Shear Rate and High Temperature
by Tapered Bearing Simulator
Test Method for Measuring Viscosity at
High Temperature and High Sheeir Rate
by Tapered-Plug Viscometer
Test Methods for Polyurethane Raw
Materials: Determination of Viscosity of
Polyols

874

MANUAL

ASTM D 4957

ASTM D 4958
ASTM D 5023

ASTM D 5024

ASTM D 5026

ASTM D 5099

ASTM D 5125
ASTM D 5133

ASTM D 5182
ASTM D 5225

ASTM D 5275
ASTM D 5279

ASTM D 5293

ASTM D 5400
ASTM D 5418

ASTM D 5422

ASTM D 5478
ASTMD 5481

ASTM D 5621
ASTM D 5992

ASTM D 6022
ASTM D 6048

37: FUELS AND LUBRICANTS

HANDBOOK

Test Method for Apparent Viscosity of


Asphalt E m u l s i o n Residues and NonNewtonian Bitumens by Vacuum Capillary Viscometer
Test Method for Comparison of the
Brush Drag of Latex Paints
Test Method for Measuring the Dynamic
Mechanical Properties of Plastics Using
Three Point Bending
Test Method for Measuring the Dynamic
Mechanical Properties of Plastics in
Compression
Test Method for Measuring the Dynamic
Mechanical Properties of Plastics in
Tension
Test Methods for RubberMeasurem e n t of Processing Properties Using
Capillary Rheometry
Test Method for Viscosity of Paints and
Related Materials by ISO Flow Cups
Test Method for Low Temperature, Low
Shear Rate, Viscosity/Temperature Dependence of Lubricating Oils Using a
Temperature-Scanning Technique
Test Method for Evaluating the Scuffing
(Scoring) Load Capacity of Oils
Test Method for Measuring Solution
Viscosity of Polymers with a Differential
Viscometer
Fuel Injector Shear Stability Test
(FISST) for Polymer Containing Fluids
Test Method for Measuring the Dynamic
Mechanical Properties of Plastics in
Torsion
Apparent Viscosity of Engine Oils Between - 5 a n d - 3 0 C Using the ColdCranking Simulator
Test Methods for Hydroxypropylcellulose
Test Method for Measuring the Dynamic
Mechanical Properties of Plastics Using
a Dual Cantilever Beam
Test Method for M e a s u r e m e n t of
Properties of Thermoplastic Materials
by Screw-Extrusion Capillary Rheometer
Test Method for Viscosity of Materials
by a Falling Needle Viscometer
Test Method for Measuring Apparent
Viscosity at High-Temperature a n d
High-Shear Rate by Multicell Capillary
Viscometer
Sonic Shear Stability of Hydraulic Fluid
Guide for Dynamic Testing of Vulcanized Rubber and Rubber-Like Materials
Using Vibratory Methods
Calculation of Permanent Shear Stability Index
Practice for Stress Relaxation Testing of
Raw Rubber, Unvulcanized R u b b e r
Compounds, a n d Thermoplastic Elastomers

ASTM D 6049

ASTM D 6204

ASTM D 6278

ASTM D 6648

ASTM E 1
ASTM E 77
ASTM E 102

ASTM E 220
ASTM E 230

ASTM E 644
ASTM E 879

ASTM E 1137
ASTM E 1594
ASTM E 1750

Test Methods for Rubber PropertyMea s u r e m e n t of the Viscous and Elastic


Behavior of Unvulcanized Raw Rubbers
and Rubber
Test Method for RubberMeasurement
of Unvulcanized Rheological Properties
Using Rotorless Shear Rheometers
Shear Stability of Polymer Containing
Fluids Using a European Diesel Injector
Apparatus
Test Method for Determining the Flexural Creep Stiffness of Asphalt Binder Using the Bending B e a m Rheometer
(BBR)
Specification for ASTM Thermometers
Test Method for the Inspection and Verification of Thermometers.
Test Method for Saybolt Furol Viscosity
of Bituminous Materials at High Temperatures
Test Method for Calibration of Thermocouples by Comparison Techniques
Specification and Temperature-Electromotive Force (EMF) Tables for Standcirdized Thermocouples.
Test Methods for Testing Industrial Resistance Thermometers
Specification of Thermistor Sensors for
Clinical Laboratory Temperature Measurement
Specification for Industrial Platinum
Resistance Thermometers
Guide for Expression of Temperature
Guide for Use of Water Triple Point Cells

OTHER STANDARDS
Saybolt

Viscosity

AASHTO T 72
Pour Point of Petroleum

Products

AFNOR T60-105: Determination of Pour Point


JIS K 2269: Pour Point and Cloud Point of Crude Oils and
Petroleum Products
IP 15: Pour Point of Petroleum Products
ISO 3016: Determination of Pour Point
Viscosity

Measurement

and

Calculation

AFNOR T60-100: Measurement of Viscosity


DIN 51562: ViscometryMeasurement of Kinematic Viscosity by Mecins of the Ubbelohde Viscometer - Part 1: Viscometer
Specification and Measurement Procedure
IP 71, Section 1: Kinematics Viscosity of Transparent and
Opaque Liquids
IP 71, Section 2: Specifications and Operating Instruction for
Glass Capillary Kinematic Viscometers
ISO 3104: Viscosity of Petroleum Products
ISO 3105: Viscometers, Glass Specs and Operating Instructions
JIS K 2283: Kinematic Viscosity at 40C
T60-100: Viscosity Measurement.

CHAPTER 32: FLOW PROPERTIES AND SHEAR STABILITY


Kinematic Viscosity
A F N O R T 4 2 - 0 1 1 : Latex
A F N O R T60-136: K i n e m a t i c Viscosity
D I N 5 1 3 7 7 : T e s t i n g of L u b r i c a n t s - D e t e r m i n a t i o n of t h e A p p a r e n t V i s c o s i t y of M o t o r Oils a t L o w T e m p e r a t u r e F r o m 5
C t o - 3 5 C - U s i n g t h e C o l d - C r a n k i n g S i m u l a t o r
I P 2 2 2 : V i s c o s i t y of Asphalts b y V a c u u m C a p i l l a r y V i s c o m e t e r
IP 226: Calculating Viscosity Index from K i n e m a t i c Viscosity
at40andl00C
I P 2 6 7 : D e t e r m i n a t i o n of L o w T e m p e r a t u r e V i s c o s i t y of
Automotive Fluids-Brookfield Viscometer M e t h o d
I P 3 1 9 : K i n e m a t i c V i s c o s i t y of A s p h a l t s
ISO 2909: Viscosity Index
Fuel Injector

Shear

Stability

Test

D I N 5 1 3 8 2 : T e s t i n g of L u b r i c a n t s - D e t e r m i n a t i o n of S h e a r
S t a b i l i t y of L u b r i c a t i n g Oils C o n t a i n i n g P o l y m e r s - M e t h o d
W i t h Diesel Injection Nozzle, Relative Viscosity Loss D u e to
Shear
I P 2 9 4 : D e t e r m i n a t i o n o f S h e a r Stability of P o l y m e r - c o n t a i n i n g
Oils-Diesel I n j e c t o r R i g M e t h o d

REFERENCES
[1] Navier, C. L. M. H., Memoire Sur les Lois du Mouvement des
Fluides., Memoires de TAcademie Royal des Sciences de I'lnstitute
de France, Vol. 6, 1823, p . 389.
[2] Hagen, G., Annalen der Physik, Vol. 46, 1839, p. 423.
[3] Poiseuille, J. L. M., Memoires Savants Etrangers, Vol. 9, 1846,
p. 433.
[4] Couette, M. M., Annates de Chimie et de Physique, Vol. 21, 1890,
p. 433.
[5] Pochettino, A., "Viscosity a n d Elasticity of Highly Viscous
Materials," Nuovo Cimento, Vol. 8, 1914, p. 77.
[6] Bingham, E. C. and Jackson, R. F., Standard Substances for the
Calibration of Viscometers, Vol. 14, Scientific Paper 298, National Bureau of Standards, Washington DC, 1918-1919, p. 59.
[7] Ubbelohde, L., "Das Einfachste und Genaueste Viskosimeter
u n d Andere Appciratemit Hangendem Niveau," Journal of the
Institute of Petroleum, Vol. 19, 1933, pp. 376-^20, and Vol. 22,
1936, p. 37.
[8] Cannon, M. R. and Fenske, M. R., Industrial and Engineering
Chemistry, Analytical Edition, Vol. 10, 1938, p. 297.
[9] Appeldoorn, J. K., "The Present State of Lubrication and Its Relation to Rheology," ASME Paper #68.1.Kll-5, ASME-ASLEASTM Symposium
on Lubrication and Lubricant
Rheology,
1968.
[10] Klaus, E. E., "Energy Conservation in Road Transportation
Through Lubricant Technology," Lubrication Engineering, Vol.
34, No. 11, 1978, pp. 611-617.
[11] Wright, W. A., "An Improved Viscosity-Temperature Chart for
Hydrocarbons," Journal of Materials, JMLSA, Vol. 4, No. 1,
March 1969, pp. 19-27. See also "Changes in ISO Industrial Oil
Viscosity Classification," ASTM Standardization
News, April
1973, pp. 36-38.
[12] Yeaple, F., Ch. 1, Fluid Power Design Handbook,
Marcel
Dekker, Inc., NY, 1990, pp. 6-7.
[13] Cannon, M. R., Manning, R. E., and Bell, J. D., "Viscosity Measurement, The Kinetic Energy Correction and a New Viscometer," Analytical Chemistry, Vol. 32, March 1960, p. 355-358.
[14] Poiseuille, J. L. M., Comptes Rendus, Vol. 11, 1840, p p . 961,
1041.
[15] Barr, G., A Monograph of Viscometry, Oxford University Press,
London, 1931.

875

[16] Bingham, E. C , Fluidity and Plasticity, McGraw-Hill, NY, 1922.


[17] The Relationship Between High-Temperature Oil Rheology and
Engine Operation, ASTM Data Series 62. Also parts II, III, IV
and V, ASTM International, West Conshohocken, PA, 1985.
[18] Rheotribology of Automotive Lubricants and Fluids, Society of
Automotive Engineers, Warrendale, PA, 1994.
[19] Sorab, J., Holdeman, H. A., and Chui, G. K., "Viscosity Prediction for Multigrade Oils," SAE #932833, Tribological Insights &
Performance Characteristics of Modem Engine Lubricants, SAE
Sp-996, Society of Automotive Engineers, Warrendale, PA, 1993.
[20] Bala, V., Klaus, E. E., Duda, J. L., and Palekar, V., "Extension
of the Temperature and Shear Rate Range for Polymer Containing Lubricants Using the C a n n o n H T H S Capillary Viscometer," SAE #932695, Tribological Insights & Performance
Characteristics of Modem Engine Lubricants, (SP-996), 1993,
pp. 69-85.
[21] Bala, V., Klaus, E. E., and Duda, J. L., "Improving the Precision
of High T e m p e r a t u r e High S h e a r Rate Viscosity Measurements," SAE #932688, Tribological Insights & Performance
Characteristics of Modem Engine Lubricants, (SP-996), 1993,
pp. 1-8.
[22] SAE J300: Engine Oil Viscosity Classification, Society of
Automotive Engineers, Warrendale, PA, 1999.
[23] Lodge, A. S., A New Method of Measuring Multigrade Oil Shear
Elasticity and Viscosity at High Shear Rates, SAE #872043,
Society of Automotive Engineers, Warrendale, PA, 1987.
[24] Williamson, B. P. and Milton, A., "Characterisation of the Viscoelasticity of Engine Lubricants at Elevated Temperatures
and S h e a r Rates," SAE #951032, Society of Automotive
Engineers, Warrendale, PA, 1995.
[25] Bates, T. W., Williamson, B . P., Spearot, J. A., and Murphy, C.
K., "A Correlation Between Engine Oil Rheology and Oil Film
Thickness in Engine Journal Bearings," SAE #860376, Society
of Automotive Engineers, Warrendale, PA, 1986.
[26] Bates, T. W., Roberts, G. W., Oliver, D. R., and Milton, A. L., "A
Journal Bearing Simulator Bench Test for Ranking Lubricant
Load-Bearing Capacity; A Theoretical Analysis," SAE #922352,
Society of Automotive Engineers, Warrendale, PA, 1992.
[27] Li, X. K., Scales, L. E., Phillips, T. N., Davies, A. R., Gwynilyw,
D. Rh., and Williamson, B. P., "The Effect of Lubricant Rheology on the Performance of Dynamically Loaded Journal Bearings," SAE #973002, Society of Automotive Engineers,
Warrendale, PA, 1997.
[28] Georgi, G. W., A Few Technical Problems Introduced by the New
Trend in Motor Oils, The Role of Engine-Oil Viscosity in LowTemperature Cranking and Starting, SAE, Pergamon Press, NY,
1966.
[29] "Development of Research Technique for Determining the LowTemperature Cranking Characteristics of Engine Oils," CRC
Report No. 374, Coordinating Research Council, Inc., NY, 1964.
[30] "Determination of Low-Temperature Cranking Characteristics
of Engine Oils at 20F Using CRC L-49 Research Technique,"
CRC Report No. 405, Coordinating Research Council, Inc., NY,
1967.
[31] "Prediction of Low-Temperature Cranking Characteristics of
Engine Oils by Use of Laboratory Viscometers," CRC Report
No. 381, Coordinating Research Council, NY, 1965.
[32] "Evaluation of Laboratory Viscometers for Predicting Cranking Characteristics of Engine Oils at 0F and 20F," CRC Report No. 409, Coordinating Research Council, Inc., NY, 1968.
[33] "Low-Temperature Pumpability Characteristics of Engine Oils
in Full-Scale Engines," ASTM Report DS-57, ASTM International,
West Conshohocken, PA, 1975.
[34] "Cold Starting and Pumpability Studies in M o d e m Engines,"
ASTM Research Report RR-D02-1442, ASTM International,
West Conshohocken, PA, November 1998.
[35] "Extrapolated Oil Viscosities," SAE Handbook, SAE J305a, Society of Automotive Engineers, Warrendale, PA, 1966, p. 299.

876 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


[36] Lowther, H. V., Meyer, W. A. P., Selby, T. W., and Vick, G. K.,
"Development of Research Technique for Determining t h e
Low-Temperature Cranking Characteristics of Engine Oils,"
Presented at t h e SAE Automotive Engineering Congress,
Detroit, January 1964.
[37] "Prediction of Low-Temperature Cranking Characteristics of
Engine Oils by Use of Laboratory Viscometers," CRC Report
No. 381, Coordinating Research Council, NY, March 1965.
[38] Vick, G. K., Meyer, W. A. P., and Selby, T. W., "Prediction of the
Low-Temperature Cranking Characteristics of Engine Oils by
Use of Laboratory Viscometers, The Role of Engine-Oil Viscosity in Low-Temperature Cranking and Starting," Progress in
Technology, Volume 10, Society of Automotive Engineers,
Warrendale, PA, 1966.
[39] Selby, T. W. and StafHn, G. D., "The Development of ASTM
Low Temperature Viscometric Techniques, The Role of Engine-Oil Viscosity in Low-Temperature Cranking and Starting," Progress in Technology, Volume 10, Society of Automotive
Engineers, Warrendale, PA, 1966.
[40] Stewart, R. M., Lion, W. D., and Meyer, W. A. P., "A Reciprocating Viscometer for Predicting the Low Temperature Cranking Characteristics of Engine Oils, The Role of Engine-Oil Viscosity in Low-Temperature Cranking and Starting," Progress in
Technology, Volume 10, Society of Automotive Engineers,
Warrendale, PA, 1966.
[41] Kim, D. S., commentary on Stewart, R. M., Lion, W. R., Meyer,
W. A. P., "A Reciprocating Viscometer for Predicting the Low
Temperature Cranking Characteristics of Engine Oils," SAE
Paper #650443, SAE Progres in Technology, Vol. 10, 1965,
pp. 205-225.
[42] Henderson, L. M. and Annable, W. G., "Pour Point Stability of
Lubricating Oils," Oil and Gas Journal, 9 Sept. 1943, p p . 54-9.
[43] Hodges, C. E. a n d Boehm, A. B., "Pour Point Stability of
Treated Oils Under Winter Storage Conditions," Oil and Gas
Journal, 24 June 1943, pp. 103-6.
[44] Hodges, C. E. and Rogers, D. T., "Some New Aspects of PourDepressant Treated Oils," Oil and Gas Journal, 4 Oct. 1947, pp.
89-93, 99.
[45] McNab, J. G., Rogers, D. T., Michaels, A. E., and Hodges, C. E.,
"The Pour-Point-Stability Characteristics of W i n t e r - G r a d e
Motor Oils," SAE Quarterly Transactions, Vol. 2, No. 1, Jan.
1948, pp. 34-44.
[46] Moyer, R. G., "Low Temperature Pumpability of Oils," Journal
of the American Society of Lubrication Engineers, April 1962,
pp. 165-8.
[47] Selby, T. W., "Viscosity and the Cranking Resistance of Engines at Low Temperature", Sixth World Petroleum Congress
Proceedings, Section VI, Frankfort, June 1963, pp. 241-258.
[48] McMillan, M. L. and Murphy, C. K., "The Relationship of LowTemperature Rheology to Engine Oil Pumpability," SAE National Automobile Engineering Meeting, Detroit, 14-18 May
1973, Paper #730478, Society of Automotive Engineers,
Warrendale, PA.
[49] Moyer, R. G., "Low Temperature Pumpability of Oils," Journal
of the American Society of Lubrication Engineers, April 1962,
p p . 165-8.
[50] Stewart, R. M. and Smith, M. F., Jr., "Proposed Laboratory
Methods for Predicting the Low-Temperature Pumpability
Properties of Crankcase Oils," SAE National Automobile Engineering Meeting, Detroit, 14-18 May 1973, Paper #730479,
Society of Automotive Engineers, Warrendale, PA.
[51] Stewart, R. M. and Spohn, C. R., "Some Factors Affecting the
Cold Pumpability of Crankcase Oils," SAE Transactions, Vol.
81, 1972, Paper #720150.
[52] Nolf, A. R., "Engine Oil Pumpability and Related Properties,"
SAE SP-382, Viscometry and Its Application to Automotive Lubricants, Paper #730480, Society of Automotive Engineers,
Warrendale, PA, 1973.

[53] Tao, F. F. and Waddey, W. E., "Low-Shear Viscometry and


Cold Flow Mechanism-Engine Oils," SAE SP-382, Viscometry
and Its Application to Automotive Lubricants, Paper #74038,
Society of Automotive Engineers,Warrendale, PA, 1973.
[54] McMillan, M. L., Stewart, R. M., and Smith, M. F., Jr., "LowTemperature Pumpability Characteristics of Engine Oils in
FuU-Scale Engines," Paper #750691, 3-5 June 1975, Society of
Automotive Engineers, Warrendale, PA.
[55] Shaub, H., Smith, M. F., and Murphy, C. K., "Predicting Low
Temperature Engine Oil Pumpability with the Mini-Rotary
Viscometer," SAE Congress and Exposition, Detroit, 25-29
Feb. 1980, Paper #790732, Society of Automotive Engineers,
Warrendale, PA.
[56] Stambaugh, R. L. a n d O'Mara, J. H., "Low Temperature Flow
Properties of Engine Oils," SAE Paper #821247 or 820509,
Society of Automotive Engineers, Warrendale, PA.
[57] Stewart, R. M., Shaub, H., Smith, M. F., Jr., and Selby, T. W.,
Summary of ASTM Activities on Low Temperature Engine Oil
Pumpability,
SAE Paper #821206, Society of Automotive
Engineers, Warrendale, PA.
[58] Smith, M. F., Jr., "Better Prediction of Engine Oil Pumpability Through a More Effective MRV Cooling Cycle," SAE Paper #831714, Society of Automotive Engineers, Warrendale,
PA.
[59] SAE J300: Engine Oil Viscosity Classification, Society of
Automotive Engineers, Warrendale, PA, December 1999.
[60] Selby, T. W., "The Scanning Brookfield Technique of LowTemperature, Low-Shear RheologyIts Inception, Development, Eind Applications," Low-Temperature Lubricant Rheology
Measurement and Relevance to Engine Operation, ASTM STP
1143,R.K Rhodes, Ed., ASTM International, West Conshohocken,
PA, 1992, pp. 33-64.
[61] Selby, T. W., "The Use of the Scanning Brookfield Technique to
Study the Critical Degree of Gelation of Lubricants at Low
Temperatures," Paper #910746, Society of Automotive Engineers,
Warrendale, PA, 1991.
[62] "Cold Starting and Pumpability Studies in Modem Engines,"
ASTM Research Report D02-1442, ASTM International, West
Conshohocken, PA, November 1998 and March 1999.
[63] Henderson, K. O., Manning, R. E., May, C. J., and Rhodes, R.
B., "New Mini-Rotary Viscometer Temperature Profiles That
Predict Engine Oil Pumpability," Paper #850443, Society of
Automotive Engineers, Wartendale, PA.
[64] CEC L-14-A-93: Evaluation of the Mechanical Shear Stability
of Lubricating Oils Containing Polymers, Coordinating European Council Secretariat, B-1210 Brussels, Belgium, 1993.
[65] CEC L 37 T 85: Shear Stability of Polymer-Containing Oils
(FZG), Coordinating European Council, Leicester, UK, 1985.
[66] CEC L 45 T 93: Viscosity Shear Stability of Transmission Lubricants (KRL), Coordinating E u r o p e a n Council, Leicester,
UK, 1993.
[67] CEC L-14-A-93: Evaluation of the Mechanical Shear Stability
of Lubricating Oils Containing Polymers, Coordinating European Council Secretariat, Brussels, Belgium, 1993.
[68] SAE J183: Engine Oil Performance and Engine Service Classification, Society of Automotive Engineers, Warrendale, PA,
1999.
[69] "A New Chart for Viscosity Temperature Relations," Lubrication, May 1921, pp. 5-8.
[70] "VISCOSITY, Part IVEffects of Temperature and Pressure,"
Lubrication, June 1950, pp. 63-64.
[71] "International Critical Tables of Numerical Data," Physics,
Chemistry, and Technology, McGraw-Hill, NY, 1927, p p .
146-147.
[72] Walther, C , "The Variation of Viscosity with TemperatureI,
II, III," Erdol und Teer, Vol. 4, 1928, pp. 510, 526, 614.
[73] Walther, C , "The Variation of Viscosity with Temperature
IV," Erdol und Teer, Vol. 5, 1929, p p . 34, 619.

CHAPTER 32: FLOW PROPERTIES AND SHEAR STABILITY


[74] Wright, W. A., "An Improved Viscosity-Temperature Chart for
Ky diocsLrhons," Journal of Materials, Vol. 4, No. 1, March 1969,
pp. 19-27.
[75] Manning, R. E., "Computational Aids for Kinematic Viscosity
Conversions from 100 and 210F to 40 and 100C," Journal of
Testing and Evaluation, Vol. 2, No. 6, 1974, pp. 522-8.
[76] Ubbelohde, L., Zur Viskosimetrie, 5th ed., S. Hirzel Verlay,
Leipzig, Germany, 1941.
[77] Umstatter, H., "Einfuhrung in die Vikosimetrie und Rheometrie," Viskogramm nach Dr.-Ing. H. Umstatter, Springer-Verlag
O. H. G., Berlin/Gottingen Heidelberg Germany, 1952,
pp. 138-139.
[78] Roelands, C. J. A., Bloc, H., and Vlugter, V. C , "A New Viscosity -Temperature Criterion for Lubricating Oils," ASME-ASLE
International Lubrication Conference, Washington, DC, Oct.
1964.
[79] Roelands, C. J. A., "Correlational Aspects of the Viscosity-Temperature-Pressure Relationship of Lubricating Oils," Druk.
V.R.B., Kleine der A 3 - 4 Groningen, 1966.
[80] Andrade, E. N. da C , Viscosity and Plasticity, Chemical
Publishing, NY, 1951.
[81] Wright, W. A., Prediction of Oil Viscosity Blending, American
Chemical Society, Atlantic City Meeting, 8-12 April 1946.
[82] "Standard Viscosity-Temperature Charts for Liquid Petroleum
Products," ADJD 034101-ADJD 034107, ASTM International,
West Conshohocken, PA, 1974.
[83] "part V-Viscosity Index," Lubrication, Vol. 36, 1950, p. 69.
[84] Dean, E. W. and Davis, G. H. B., "Viscosity Variations of Oils
with Temperature," Chemical and Metallurgical
Engineering,
V o l 36, 1929, p. 618.
[85] Davis, E. W., Lapeyrouse, M., and Dean, G. H. B., "Applying
Viscosity Index to Solution of Lubricating Problems," Oil and
Gas Journal, Vol. 30, March 1932, p. 92.
[86] Dean, E. W., Bauer, A. D., and Berglund, J. H., "Viscosity Index
of Lubricating Oils," Industrial and Engineering Chemistry, Vol.
32, 1941, pp. 102-107.
[87] D 2270: S t a n d a r d Practice for Calculating Viscosity Index
From Kinematic Viscosity at 40 and 100C, RR: D02-1009,
ASTM International, West Conshohocken, PA, 1998.
[88] Wright, W. A., "A Proposed Modification of the ASTM Viscosity Index," Proceedings of the American Petroleum Institute,
Vol. 44, Sec. 3, Refining, 1964, pp. 535-541.
[89] ASTM Viscosity Index, Calculated from Kinematic
Viscosity,
ASTM DS 39a, ASTM International, West Conshohocken, PA,
1965.
[90] Watt, J. J., et al., ASTM Viscosity Index, Calculated from Kinematic Viscosity, ASTM STP 168, ASTM International, West
Conshohocken, PA, 1965.
[91] Wright, W. A., Talbot, A. F and Manning, R. E., Viscosity Index Tables for Celsius Temperatures, ASTM DS 39b, ASTM
International, West Conshohocken, PA, 1975.
[92] "Changes in ISO Industrial Oil Viscosity Classification," ASTM
Standardization News, April 1973, pp. 36-7.
[93] D 2270: Metrification of Viscosity Index System Method, RR:
D02-1009, ASTM International, West Conshohocken, PA,
1998.
[94] ISO 2909: Petroleum ProductsCalculation of Viscosity Index
from Kinematic Viscosity, International Organization for
Standardization, Geneva, 2002.
[95] Klaus, E. E. and Fenske, M. R., "The Use of ASTM Slope for
Predicting Viscosities," ASTM Bulletin, July 1956.
[96] Geniesse, J. C , "A Comparison of Viscosity-Index Proposals,"
ASTM Bulletin, July 1956.
[97] Eby, L. T., Tables for Determination of ASTM Slope and Prediction of Viscosities,
Chemical Division, S t a n d a r d Oil
Development Co, 21 July 1946.
[98] Schiessler, R. W. and Sutherland, H., "The Synthesis and
Properties of High Molecular-Weight Hydrocarbons," API Re-

[99]

[100]
[101]
[102]
[103]

[104]

[105]

[106]

[107]

[108]

[109]

[110]

[Ill]

[112]

[113]

[114]

[115]

[116]

[117]
[118]
[119]

877

search Project 42, Proceedings of the American


Petroleum
Institute, Section III, Vol. 32, 1952.
Lowitz, D. A., Spencer, J. W., Webb, W., and Schiessler, R. W.,
"Temperature-Pressure-Structure Effects on the Viscosity of
Several Higher Hydrocarbons," Journal of Chemical Physics,
Vol. 30, 1959, pp. 73-82.
Tanner, R. I., Engineering Rheology, Oxford University Press,
London, 1985.
Macosko, C. W., Rheology Principles, Measurements,
and
Applications, VCH PubUshers, NY, 1994.
So, B. Y. C. and Klaus, E. E., "Viscosity-Pressure Correlation of
Liquids," ASZ,: Transactions, Vol. 23, No. 4, 1980. pp. 4 0 9 ^ 2 1 .
Wu, C. S., Klaus. E. E., and Duda, J. L., "Development of a
Method for the Prediction of Pressure-Viscosity Coefficients of
Lubricating Oils Based on Free-Volume Theory," Journal of
Tribology, Vol. I l l , 1989, pp. 121-128.
Swindells, E. C , Coe, J. R., Jr., and Godfrey, T. B., "Absolute
Viscosity of Water at 20C," Journal of Research of the National
Bureau of Standards, Vol. 48, 1962, pp. 1-31.
Mailiarov, G. A., "Determination of the Viscosity of Water at 20
C," Proceedings of the AU-Union Science Research Institute of
Metrology, Vol. 97, No. 37, 1959, pp. 125-140 (in Russian).
Roscoe, R. and Bainbridge, W., "Viscosity Determination by
the Oscillating Vessel Method. II. The Viscosity of Water at 20
C," Proceedings of the Physical Society, Vol. 72, 1958,
pp. 585-595.
Kestin, J. and Shankland, J. R., "The Free Disk as an Absolute
Viscometer and the Viscosity of Water in the Range 25 C-150
C," Journal of Non-Equilibrium Thermodynamics, Vol. 6, 1981,
p p . 241-256.
Berstad, D. A., Knapstad, B., Lamvik, M., Skjorklep, K., and
Oye, H. A., "Accurate Measurements of the Viscosity of Water
in the Temperature Range 19.5 C - 25.5 C," Physica A, Vol.
151, 1988, pp. 246-280.
Marvin, R. S., "The Accuracy of Measurements of Viscosity of
Liquids," Journal of Research of the National Bureau of
Standards, Vol. 75A, Nov-Dec 1971, pp. 535-540.
Bauer, H., Binas, E., Broeke, H., and Volkel, L., 'New Recommended Viscosity Value for Water as the MetrologicEil Basis of
Viscometry," PTB-Mitteilungen,
Vol. 105, Feb. 1995, p p .
99-105.
Bingham, E. C. and Jackson, R. F., "Standard Substances for
the Calibration of Viscometers," National Bureau Standards
(U.S.) Bulletin, Vol. 14, 1919, pp. 59-86.
Marvin, R. S., "The Accuracy of Measurements of Viscosity of
Liquids," Journal of Research of the National Bureau of
Standards, Vol. 75A, Nov-Dec 1971, pp. 535-540.
Swindells, E. C , Coe, J. R., Jr., and Godfrey, T. B., "Absolute
Viscosity of Water at 20 "C," Journal of Research of the National
Bureau of Standards, Vol. 48, 1962, pp. 1-31.
ISO/TR 3666: Viscosity of Water, International Organization
for Standardization, Case postale 56, CH-1211, Geneva,
Switzerland, 1998.
Hardy, R. C , "NBS Viscometer Calibrating Liquids and Capillary Tube Viscometers," National Bureau of Standards Monograph 55, U.S. Department of Commerce, Washington DC, 26
Dec. 1962.
"Viscometer Calibrating Liquids, Notice of Discontinuance,"
Federal Register, Doc. 67-1245, U.S. Department of Commerce,
Washington DC, Filed Feb. 2, 1967.
"The International Temperature Scale of 1990 (ITS-90),"
Metrologia, Vol. 27, 1990, pp. 3-10.
"The International Temperature Scale of 1990 (ITS-90),"
Metrologia, Vol. 27, 1990, pp. 3-10.
Wise, J. A., "A Procedure for the Effective Recalibration of Liquid-in-Glass Thermometer," NIST Special Publication
819,
National Institute of Standards and Technology, Gaithersburg,
MD, 1991.

878 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


[120] Stormer, E., Transactions of the American Ceramic Society, Vol.
11, 1909, p. 597.
[121] Griffith, J. M. and Puzinauskas, V. P., "Relation of Empirical
Tests to Fundamental Viscosity of Asphalt Cement," Symposium on Fundamental Viscosity of Bituminous Materials, ASTM
STP 328, ASTM International, West Conshohocken, PA, 1962,
pp. 20-47.
[122] Pochettino, A., Nuovo Cimento, Serie 6, Vol. 8, No. 2, 1914, pp.
77-108.

[123] AASHTO TPl-98: Method for Determining the Flexural


Creep Stiffness of Asphalt Binder Using the Bending
Beam Rheometer (BBR), American Association of State
Highway and Transportation Officials, Washington DC,
1998.
[124] AASHTO TP5-98: Method for Determining the Rheological
Properties of Asphalt Binder Using a Dynamic Shear Rheometer (DSR), American Association of State Highway and
Transportation Officials, Washington DC.

MNL37-EB/Jun. 2003

Cold Flow Properties


Robert E. Manning^ and M. Richard Hoover^

POUR POINT

T H E VISCOSITY OF A LIQUID CONSISTING OF ONLY ONE TYPE OF

MOLECULE will increase when the liquid is cooled. If the liquid is cooled sufficiently, the viscosity will increase until the
liquid solidifies (freezes). However, most petroleum products are composed of mixtures of many different types of
molecules, each of which has its own freezing point. When
these liquids are cooled to low temperatures, unanticipated
results can occur. The diesel fuel for cars and trucks can
form crystals that will plug the fuel filter while the vehicle
is being driven, causing the vehicle to stop. Heating oil can
be loaded into a delivery vehicle, but at very low temperatures the oil may not flow through the delivery hose to the
business or home receiving the oil. Automotive engine products in conventional quart, liter, or gallon containers may,
when left outside the filling station in the winter, solidify so
they will not pour out of the container. Some petroleum
products will form a "gel" structure at a certain low temperature. However, the same material, when cooled rapidly
from a w a r m temperature to a still lower temperature and
through a critical temperature range, will flow in a normal
manner.
As the temperature of a petroleum product is lowered, wax
contained in the product can crystallize into long crystals
thus forming a gel structure. Frequently, chemicals such as
"pour-point depressants" (wax-crystal modifiers) are added
to fluids to lower the temperature at which gels can form.
Such pour point depressants serve to lower the pour point of
the fluid by forming many smaller crystcJs at a temperature
somewhat higher t h a n the temperature at which wax crystals
form. With cooling to still lower temperatures, wax will crystallize onto the unconnected crystal sites of the pour-point
depressant instead of forming a gel structure. Without the
yield stress provided by a n interlocking gel-structure, the material will show a much lower pour point.

In the 1910s, it was realized that some petroleum products


failed to flow when subjected to low temperatures. Thus, a
simple test apparatus (Fig. 1) was devised to characterize the
fluidity of many petroleum products and to establish a temperature below which the material does not readily flow^the
"pour point" temperature. Such materials include:

Lubricating oils
Distillate and residual fuels
Black oils used in heavy-duty equipment
Cylinder stock
Heat transfer fluids
Crude oils
Originally published as ASTM D 4 7 i n l 9 1 7 and revised and
renumbered D 97 in 1927, the Pour Point of Petroleum Products is among the oldest of petroleum test methods still in
use.
A test sample is placed in a jar and heated without stirring
to 9C above its expected pour point (but to a minimum of
45C) by placing the jar in a bath at a m i n i m u m of 48C. The
jar is cooled in a non-uniform manner by cooling in sequence
inside a group of successively lower temperature baths from
0 to -69C. These sequences include:

Specimen is at 45C (or above), place in a bath at 24C


Specimen is at -l-27C, move to 0C bath
Specimen is at -l-9C, move to - 1 8 C bath
Specimen is at 6C, move to 33C b a t h
Specimen is at -24C, move to - S T C bath
Specimen is at 42C, move to 69C bath
At temperature intervals of 3C, the test sample jar is removed and tilted:
. . .just enough to ascertain whether there is a movement of
the specimen in the test jar. The complete operation of removal, wiping, and replacement shall require not more
than 3 s . . . . Continue in this manner until a point is
reached at which the specimen shows no movement when
the test jar is held in a horizontal position for 5 s. Record
the observed reading of the test thermometer (ASTM D 97).
A similar method of test is written specifically for crude
oils (ASTM D 5853). With the desire to use automatic or automated pour point apparatus, several methods have been
developed and accepted that cire less labor intensive (ASTM
D 5949, ASTM D 5950, ASTM D 5985, ASTM D 6749) than the
manual procedure of ASTM D 97. Each of these methods
uses its own geometry and special techniques, but essentially
the same cool-down sequence. Although the specific tech-

This chapter discusses p o u r point tests, aviation fuels


freezing tests, and the cloud point and wax appearance point
tests used for a variety of petroleum products. The behavior
and performance of engine oil products at low temperature is
of very high importance and is incorporated into the general
Society of Automotive Engineers (SAE) flow properties specifications. Engine oil lubricants at low temperatures are discussed in detail in Chapter 32, Flow Properties and Shear
Stability. Note that all referenced ASTM methods are included at the conclusion of the chapter.

' Consultant, 225 Harris Drive, State College, PA 16801.


^ President, Cannon Instrument, State College, PA 16804.

879
Copyright'

2003 by A S I M International

www.astm.org

880 MANVAL 37: FUELS AND LUBRICANTS HANDBOOK


THERMOMETER
' t l . 2 - -15.8 ID.
3 0 - 32.4 ID.
33.2 - 3 4 . 8 OD.

CORK

25 MAX.
- L

COOLANT LEVEL

DISK
NOTE 1Dimensions are in miUimelres (not to scale).

FIG. 1Pour point cell (ASTM D 97).

niques of sensing pour point differ from one instrument to


another, the determined p o u r points from each method have
shown correlation to the resuUs from ASTM D 97 [1]. These
automatic test instruments allow the determination of pour
point at temperature intervals of 1, 2, or 2.5C in addition to
the 3 X interval specified in ASTM D 97.
Novel changes introduced a m o n g t h e several devices
include:
heating a n d cooling accomplished by a Peltier device
(ASTM D 5949),
a pressurized pulse of nitrogen gas imparted onto the surface of the specimen, a n d multiple optical detectors observing the response of the surface (ASTM D 5949),
automatic tilting of the cell and observation by optical detector of the tilt of the surface of the specimen (ASTM D
5950),
rotation of the test specimen cup at approximately 0.1 r p m
against a stationary, counter balanced, spherical b o b
(ASTM D 5985), a n d
a slightly positive air pressure gently applied to the surface
of the specimen causes upward movement of the specimen
in a communication tube (ASTM D 6749).
While each of these methods has been extensively tested and
all have been compared against ASTM D 97, various test
specimens can be expected to show smeJl differences in each
of the several pour point instruments. Although the use of the
automated/automatic instruments improves the precision of
the determination of pour point temperature, ASTM D 97 remains as the referee method.
It should also be noted that a free-flowing (i.e., without gel
structure) liquid can become so highly viscous at low temperature so as to also have a pour point, a so called viscous
pour point.

AVIATION FUELS FREEZING POINT


The freezing point of aviation fuels is defined in ASTM D
2386 as
. . .the fuel temperature at which solid hydrocarbon crystals, formed on cooling, disappear when the temperature of
the fuel is allowed to rise
The freezing point of an aviation fuel is the lowest temperature at which the fuel remains free of solid hydrocarbon crystals that can restrict
the flow of fuel through filters, if present, in the fuel system
of the aircraft. The temperature of the fuel in the aircraft
tank normally falls during flight depending on aircraft
speed, altitude, and flight duration. The freezing point of
the fuel must always be lower than the minimum operational tank temperature (ASTM t) 2386).
To measure the freezing point of an aviation fuel, a 25-mL
specimen is transferred into a clean, dry, jacketed sample
tube. The tube with stirrer, thermometer, and moisture-proof
collar is placed in a vacuum flask, and allowed to cool. The
cooling medium may be solid carbon dioxide in acetone or
methyl, ethyl o r isopropyl alcohol, or liquid nitrogen, or mechanical refrigeration maintained at 70 to 80C. The fuel
is stirred continuously while moving the stirrer u p and down
at a rate of 1-1.5 cycles/s. The temperature at which crystals
of hydrocarbon appear is recorded (ignoring a water haze
which may form at 10C). Upon the formation of hydrocarbon crystals, the jacketed sample tube is removed from the
coolant a n d allowed to warm, with continued stirring. The
temperature at which the crystals completely disappear is reported to the nearest 0.5C as the freezing point.
The manual method of test has been automated (ASTM D
5901, ASTM D 5972) using apparatus similEir to the traditional a p p a r a t u s with mechanical refrigeration o r Peltier

CHAPTER 33: COLD FLOW PROPERTIES


CLOUD POINT AND WAX
APPEARANCE POINT

Stirring Rod

Moistureproof
Collar

881

Thermometer
Cork Stopper

Refrigerant
Carbon Dioxide
Vacuum Flask
NOTE 1^AIl dimensions are in mm and 0.1 mm glass wall thickness
isl mm.

FIG. 2Freezing point apparatus (ASTiVI D 2386).

cooling and optical detection of the appearance a n d disappearance of the hydrocarbon crystals. The automated apparatus allows reporting the freezing point to the nearest 0.1 C,
and somewhat improved repeatability and reproducibility as
compared to ASTM D 2386 (Fig. 2).
The lowest temperature at which aviation fuels remain free
of solid hydrocarbon crystals is a key safety parameter in the
specification and use of fuels, because the hydrocjirbon crystals can restrict the flow of fuel through filters in an aircraft
fuel system. A cooling and warming cycle of the fuel through
a specified filter can also be used to determine the temperature, called the flow point, at which the filter becomes unblocked on weirming (ASTM D 4305). There is a small bias between the flow point t e m p e r a t u r e a n d the freezing point
temperature. This procedure can also be used to investigate
the formation of wax crystals or cold flow properties of other
products.
As low temperatures can materially affect the aircraft fuels, low temperatures can also affect the aircraft turbine lubricants (ASTM D 2532). On prolonged standing at low temperature, a structure can form in the lubricant, causing an
increase in the kinematic viscosity of the lubricant. This viscosity increase can cause lubrication problems in aircraft
engines. Thus, kinematic viscosity is measured typically
at - 6 5 F (-53.9C) by allowing the test sample to soak in
the viscometer at test temperature for periods of 35 min, 3
h, a n d 72 h. The percent increase in kinematic viscosity over
the initial m e a s u r e d value at 3 h or/and 72 h is also
reported.

The presence of wax crystals in burner fuels, diesel fuels, and


turbine engine fuels is an indication of the lowest temperature of the material's utility for certain applications. In sufficient quantity, such crystals can plug filters in fuel systems.
This property may cause limitations on the use of the fuel at
low temperatures, or it can require reblending of the fuel.
The cloud point of a petroleum product is the temperature
at which a cloud of wax crystals first appears in a liquid when
it is cooled under the specific conditions prescribed in the
test method. The wax appearance point is the temperature at
which wax first begins to separate from the fluid when it is
cooled under the conditions prescribed in the test method.
An apparatus used to measure cloud point is illustrated in
Fig. 3. The sample is placed in a clear, cylindrical glass jar,
which is cooled in a series of b a t h s as shown in Table 1
(ASTM D 2500).
This cooling sequence allows a slow, controlled cooling of
the test vessel. As the sample temperature drops, the test jar
is removed quickly b u t without disturbing the oil, inspected
for the presence of cloudiness or a cloud formation at the bottom of the test cell, a n d replaced, all within 3 s. The cooling
bath materials used include water and ice (at 0C), crushed
ice and sodium chloride crystals (at 18C), crushed ice and
calcium chloride crystals (at 33C), acetone, or methyl or
ethyl alcohol, or petroleum naphtha and solid carbon dioxide
(at - 5 1 and -69C).
A note from ASTM D 2500 states the following:
A wax cloud or haze is always noted first at the bottom of
the test jar where the temperature is lowest. A slight haze
throughout the entire sample, which slowly becomes more
apparent as the temperature is lowered, is usually due to
traces of water in the oil. Generally this water haze will not
interfere with the determination of the wax cloud point. In
most cases of interference, filtration through dry lintless filter papers is sufficient.
The cloud point is reported to the nearest 1 C
Automated Cloud Point apparatus and specific test methods have been developed. These include cooling in steppedcooling temperature baths (ASTM D 5771), linear cooling
rate (ASTM D 5772), a n d constant cooling rate (ASTM D
5773) of the test sample, with optical detection of the cloud
point. When the specification requires Test Method D 2500,
an automated cloud point method may not be substituted.
The test method to determine the Wax Appearance Point of
Distillate Fuels (ASTM D3117) is similar to the cloud point
test, b u t the test sample is stirred while being cooled. The
"wax appearance point" is that temperature at which wax
p h a s e first begins to separate from the liquid when it is
cooled under the prescribed conditions.

Bath
1
2
3
4
5

TABLE 1Bath and sample temperature ranges.


Bath Temperature Setting, C
Sample Temperature Range, C
- 1 to2
-18to-15
-35 to-32
- 5 2 to - 4 9
- 6 9 to - 6 6

Start to 10
10 t o - 7
-7 to-24
- 2 4 to - 4 1
- 4 1 to - 5 8

882 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

3ta- a4LB.

NOTE All dimensions in millimeters


FIG. 3Apparatus for cloud point test (ASTM D 2500).

LOW-TEMPERATURE HIGH-SHEAR TESTS


OF ENGINE LUBRICANTS

LOW TEMPERATURE PUMPABILITY OF


ENGINE LUBRICANTS

With the changes to engine lubricant formulations in the


1970s, it was anticipated that a problem might develop in low
temperature stcirting. It had been known that some engines,
when cranked by the starting motor, could start at cranking
speeds as low as six rpm. Other lubricants were so high in viscosity that even though the engine could be cranked, the initial firing of the engine would not allow acceleration and
starting of the engine.
Prior to the 1970s, the normal way of estimating the kinematic viscosity at O^F (17.8C) was by extrapolation using
the MacCouU-Wright equation from kinematic viscosity data
at 100 and 210F. Problems with this method became obvious. The new formulations sometimes were semi-solid at 0F,
even though the prediction by equation indicated the lubricant to be sufficiently fluid to allow flow at low temperatures,
thus allowing the automotive engine to readily start at low
temperatures.
Because there was a general lack of accepted information
on both automotive engines and their lubricants at starting
conditions, a large program [2,3,4,5] was undertaken with
the cooperation of the Society for Automotive Engineers
(SAE) Fuels and Lubricants committee, the ASTM Committee on Petroleum Products and Lubricants (Subcommittee 7
on flow properties), and the Coordinating Research Council
(CRC). A group of five "Newtonian" Reference Engine Oils
(REO) was prepared to cover the viscosity range of 730-8400
mPa-satOF(-17.8C).
The low-temperature high-shear tests of engine lubricants
are discussed in Chapter 32, Flow Properties and Shear Stability.

Lubricant pumpability is critically important to engines.


Catastrophic failure can occur if there is a lack of a full
flow of lubricant to the bearings (bearing starvation) of
modern engines. Consequently, the rheology of oils at low
t e m p e r a t u r e s is of highest importance. Thus, the t e r m
pumpability has been widely used in the lubricant industry
to indicate the ability of a lubricant to be p u m p e d and/or
to flow to the surfaces being lubricated, especially at low
temperature.
Several papers appeared in the 1940s concerned with the
pour point stability of lubricating oils [6,7, 8, 9]. In the early
1960s a study by Moyer [10] indicated that there might be a
problem with the pumpability of engine lubricants at low
temperatures. He observed that on pumping in a test apparatus, as the temperature is lowered in the oil pan a hole can be
drawn in the oil reservoir, causing the p u m p assembly to be
air bound. Selby [11] measured rheological characteristics of
reblends of oils previously studied by Moyer showing that
cavitation occurred at shear rates less than 50 s ' ' and above
a critical viscosity of 24 000 mPa-s.
McMillan and Murphy noted that:
An analysis of oil pumpability
reveals that engine oil
pumping failures may occur because either the oil cannot
flow under its own head to the oil screen inlet, or the oil is
too viscous to flow through the screen and inlet tube fast
enough to satisfy pump demands [12].
The low-temperature pumpability of engine lubricants is discussed in Chapter 32, entitled Flow Properties and Shear Stability.

CHAPTER 33: COLD FLOW PROPERTIES


ASTM METHODS

IP 444/99

No.
D 97
D 2386
D 2500
D 2532

IP 445/99

D 3117
D 4305
D 5771
D 5772
D 5773
D 5853
D 5901
D 5949
D 5950
D 5972
D 5985
D 6749

Title
Test Method for Pour Point of Petroleum Products
Test Method for Freezing Point of Aviation Fuels
Test Method for Cloud Point of Petroleum Products
Test Method for Viscosity and Viscosity Change After Standing at Low Temperature of Aircraft Turbine Lubricants
Test Method of Wax Appearance Point of Distillate
Fuels
Test Method for Filter Flow of Aviation Fuels at
Low Temperature
Test Method for Cloud Point of Petroleum Products
(Optical Detection Stepped Cooling Method)
Test Method for Cloud Point of Petroleum Products
(Linear Cooling Rate Method)
Test Method for Cloud Point of Petroleum Products
(Constant Cooling Rate Method)
Test Method for Pour Point of Crude Oils
Test Method for Freezing Point of Aviation Fuels
(Automated Optical Method).
Test Method for Pour Point of Petroleum Products
(Automatic Pressure Pulsing Method)
Test Method for Pour Point of Petroleum Products
(Automatic Tilt Method)
Test Method for Freezing Point of Aviation Fuels
(Automatic Phase Transition Method
Test Method for Pour Point of Petroleum Products
(Rotational Method)
Test Method for Pour Point of Petroleum (Automatic Air Pressure Method)

OTHER STANDARDS
No.
AFNOR M07-048

AFNORT60-105
DIN 51421

IP
IP
IP
IP

15/95
16
219/94
441/99

Title
Petroleum Products:
Determination
Point of the Dissipation Point of Aviation
Motor Fuel CrystcJs
Petroleum Products:
Determination
Point of Discharge
Testing of Mineral Oils; Determination of
Freezing Point of Aviation Fuels, Gasolines and Motor Benzols
Pour Point of Petroleum Products.
Freezing Point of Aviation Fuels.
Cloud Point of Petroleum Products
Pour Point of Crude Oils.

IP 446/99
ISO 3013
ISO 3015
ISO 3016
JIS K 2269
JIS K 2276

883

Cloud Point of Petroleum Products (Optical Detection Stepped Cooling Method)


Cloud Point of Petroleum Products (Linear Cooling Rate Method).
Cloud Point of Petroleum Products (Constant Cooling Rate Method)
Determination of Freezing Point of Aviation Fuels
Determination of Cloud Point
Determination of Pour Point
Pour Point and Cloud Point of Crude Oils
a n d Petroleum Products
Testing Method for Aviation Fuels

REFERENCES
[1] ASTM Research Report D02-1312, ASTM International, West
Conshoshocken, PA, 1993.
[2] SAE J305a: Extrapolated Oil Viscosities, SAE Handbook, Society of Automotive Engineers, Warrendale, PA, 1966, p. 299.
[3] "Development of Research Technique for Determining the LowTemperature Cranking Characteristics of Engine Oils," CRC Report No. 374, January 1964.
[4] Lowther, H. V., Meyer, W. A. P., Selby, T. W., and Vick, G. K., "Development of Research Technique for Determining the Low-Temperature Cranking Characteristics of Engine Oils," presented at
SAE Automotive Engineering Congress, Detroit, January 1964.
[5] "Prediction of Low-Temperature Cranking Characteristics of
Engine Oils by Use of Laboratory Viscometers," CRC Report No.
381, March 1965.
[6] Henderson, L. M. and Annable, W. G., "Pour Point Stability of
Lubricating Oils," Oil and Gas Journal, 9 Sept. 1943, pp. 54-59.
[7] Hodges, C. E. and Boehm, A. B., "Pour Point Stability of Treated
Oils Under Winter Storage Conditions," Oil and Gas Journal, 24
June 1943, pp. 103-6.
[8] Hodges, C. E. and Rogers, D. T., "Some New Aspects of Pour-Depressant Treated Oils," Oil and Gas Journal, 4 Oct. 1947, pp.
89-93, 99.
[9] McNab, J. G., Rogers, D. T., Michaels, A. E., and Hodges, C. E.,
The Pour-Point-Stability Characteristics of Winter-Grade Motor
Oils, SAE Quarterly Transactions, Vol. 2 No. 1, Jan. 1948, pp.
34-44.
[10] Moyer, R. G., "Low Temperature Pumpability of Oils," Journal
of the American Society of Lubrication Engineers, April 1962, pp.
165-168.
[11] Selby, T. W., "Viscosity and the Cranking Resistance of Engines
at Low Temperature," Sixth World Petroleum Congress Proceedings, Section VI, Frankfort, June 1963, pp. 241-258.
[12] McMillan, M. L. and Murphy, C. K., "The Relationship of LowTemperature Rheology to Engine Oil Pumpability," SAE National Automobile Engineering Meeting, Paper #730478, Detroit,
ML 14-18 May 1973.

MNL37-EB/Jun. 2003

Environmental Characteristics
of Fuels and Lubricants
Mark L. Hinman^

sure concentration is continuously changing due to:


Diffusion away form the point of release
Movement to other media (i.e., transport between soil, water, sediment, and air)
Degradation (biological and abiotic) of the material
The spatial and temporal variability present in the natural
populations results in an increased range of responses to the
exposure. Other materieJs and chemicals in the background
could contribute to any effects observed. Further, the need
for data on the fate and effects of materials for regulatory
purposes exceeds the data available from both intentional
and unintentional releases.
A more reliable approach to evaluate the inherent hazard
of a material to the environment is by testing the individual
chemical properties in the environmental components of
concern in separate, carefully controlled laboratory test systems:

FUELS AND LUBRICANTS RANGE FROM MODERATELY SIMPLE MIX-

TURES OF SIMILAR MOLECULES to very complex mixtures of very


different molecules. As the performance of the product becomes more demanding, the composition of the product generally becomes more complex. There are few products that
do not have additives to modify the inherent performance
characteristics of the base material (or materials) and enhance its application for a specific use.
Fuels are generally a blend of specific hydrocarbon distillation fractions with additives to facilitate performance.
The fuel use defines the type and range of hydrocarbon fractions and any additives, whereas lubricants reduce friction,
heat, and wear when applied to the surface of moving parts.
Frequently, the lubricity or other key characteristic of the
base material is enhanced by additive treatment to meet a
specific need. The base material may be of various origins
(petroleum, synthetic, or vegetable oil). For this discussion,
various specialized industrial fluids that do not fall into the
fuels category are included in with the lubricants. These
would include a range of products, such as hydraulic fluids,
metal cutting fluids, turbine oils, greases, etc.

The media exchange rates of a material may be deduced


from measurements of key physical properties
The degradation rates under specific conditions may be determined in controlled tests of biodegradability, hydrolysis
rate, photolysis rate, etc.
The toxicity to organisms may be determined in single
species tests using organisms of k n o w n n u m b e r , age,
health and u n d e r carefully controlled, constant environmental conditions.
Controlled laboratory tests of physical properties, degradation rates, and toxicity may be used to indicate the potential
fate and effects of the material in the environment under various conditions and exposure possibilities. Conventional wisdom suggests that transport properties and degradation rates
may be combined in mathematical models to calculate the
exposure concentrations and the exposure-response relationship is used to estimate the environmental effects. Controlled
laboratory test results could be extrapolated to the environment when the exposure regimes are similar. This is possible
because the standardization of tests has permitted the development of data for the necessary predictive models. Most of
these methods have been developed for simple, water-soluble, non-volatile substances and have been shown to be useful for these materials.

Fuels are seldom released into the environment intentionally. More often, the release is the result of spillage at transfer, during storage, disposal, or some unexpected event (e.g.,
transport collision, pipeline break, etc.). Some lubricating
fluids are intentionally introduced into the environment as a
function of their use (rail-flange grease, chainsaw oils, 2stroke oil passthrough residuals, etc.). For the remaining lubricants, between 13% (EU Countries) and 32% (USA) of
t h e m cire released to the environment after use. This results
in an annual worldwide loss to the environment of approximately 12 million tons [1].
Rationale for Standardized Testing
The potential for materials to cause harmful effects in the environment needs to be evaluated. The most straightforward
way to accomplish this might seem to be to evaluate organism populations in areas where the material has been released or spilled into the environment of interest. Although
field studies are the most realistic way of evaluating all possible chemical effects, they are usually impossible to quantitatively evaluate in terms of the level of the h a r m associated
with the magnitude of the release. This is because the expo-

In contrast, most fuels and lubricant products are mixtures


(simple and complex) of organic molecules, often relatively
insoluble in water, and/or volatile. Further, additives can introduce metals and other inorganic compounds into the mixture. If the testing and interpretation account for the solubility and volatility properties of the test material, the media

' Environmental Scientist, ExxonMobil Biomedical Sciences, Inc.,


1545 Route 22 East, Annandale, NJ, 08801-0971.

885
Copyright'

2003 by A S I M International

www.astm.org

886

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

exchange and degradation rates may be combined in mathematical models to calculate the exposure concentrations and
the exposure-response relationship is used to estimate the environmental effects. Controlled laboratory test results can be
extrapolated to the environment because of the development
of predictive models ([2,3,4], E 978-92, Standard Practice for
Evaluating Mathematical Models for the Environmental Fate
of Chemicals).
Another benefit of standardized testing is that different
materials m a y be c o m p a r e d on a c o m m o n basis. For instance, testing toxicity with the same species of fish in water
of the same quality allows one to compare the relative toxicity of the substances. Such comparisons have led to the development of scientific relationships between the chemical
structures and their physico-chemical and biological properties. For example, when a homologous series of chemicals is
tested, such as alcohols of increasing carbon chain length,
there is a fairly continuous change in the physical properties
and toxicity. The predictable change may be used to extend
the result (through interpolation) to untested members of the
series. This process is often called "read-across."
Correlations developed between chemical structure, physical properties, and biological activity have led to validated relationships referred to as Quantitative Structure Activity Relationships (QSAR). The most widely accepted QSARs are the
relationship between the lipophilicity of a material and the
water solubility, soil sorption, bioconcentration, and toxicity.
The precision of the QSAR estimates for some classes of
chemicals has led to the acceptance of QSAR generated data
for some regulatory activities and substitution for missing
data [4].

PHYSICO-CHEMICAL PROPERTIES
A number of physical properties are especially relevant to the
environmental behavior of substances. Some of these characteristics (e.g., water solubility, vapor pressure, etc.) are measured on a routine basis for products. However, complex mixtures often require more detailed information about the range
of the property than pure substances (i.e., for a product that is
a mixture of components with greatly differing boiling points).
T5rpically, the boiling range is reported as a n average. When
the boiling range is broad, there is also a broad range in vapor
pressures of the components. This leads to differences in the
environmental compartmentcilization of the components. The
more volatile components will partition into the air phase to a
greater extent and so will be present to a lesser extent in the soil
and aquatic environments than the less volatile components.
Consequently, for substances with multiple components, specific test methods need to be applied eind reported which measure the range rather than the average of a property.
Chemical Structure
The properties of chemicals depend u p o n their chemical
structures. For fuels, this may involve a n u m b e r of hydrocarb o n structures having a range of molecular weights and
chemical types, as well as a variety of organic and inorganic
compounds included in additive treatments. Knowledge of
the relative hydrocarbon and specific additive composition is
important (see Table 1).
For lubricants, the structure types range widely. Mineral
hydroccirbon basestocks, synthetic basestocks, or plant oil

TABLE 1Physical properties that are of environmental importance (Adapted from Ref. 7).
Definition

Physical Property

Environmental Importance

Molecular weight (range)


Formula
Functional groups
branching
Equilibrium concentration
ratio between octanol and
water

Determines other physical and


chemical properties

Vapor Pressure" (VP)

Partial pressure of vapor

Water Solubility"

Aqueous concentration at
saturation

Characterizes tendency to leave liquid


state cind become a gas which can
enter the air
Allows estimation of evaporation and
volatilization rates and extent
Characterizes extent to which it will
dissolve in water
Allow estimation of water
concentration and volatility

Soil (Organic Carbon)


Partition Coefficient (Ka or Koc)

Equilibrium concentration
between soil and water

Dissociation Constant (Ka)

Ionization of acids or bases

Melting" and Boiling Point"


(MP, BP)

Critical temperature for phase


changes:
solidliquidgas

Chemical Structure

OctanolAVater
Partition Coefficient" (Kow)

"A range of values is appropriate for complex mixtures.

Characterizes partitioning to lipids in


organisms or the organic carbon of
sludges and soils
QSAR estimates of toxicity,
partitioning, and water solubility

Chciracterizes the tendency to sorb to


particles in the soil
Allows estimation of mobility through
soil and sediment
Ionization extent at environmental pH
ranges influences other properties
Characterizes physical form in the
environment
Related to vapor pressure and
solubility

CHAPTER

34: ENVIRONMENTAL

CHARACTERISTICS

basestocks may be involved as well as a variety of additives.


The m a i n classes of additives are succinimide ashless dispersants, calcium sulphonates, calcium phenates, zinc dialkyldithiophosphates, oxidation inhibitors, and antiwear
inhibitors [5]. In addition to providing one or more specific
characteristics to the final product, additives increase the
complexity of the mixture and difficulty of predicting the
environmental impact of the material on the environment.
O c t a n o l / W a t e r P a r t i t i o n C o e f f i c i e n t (Kow)
The octanol / water partition coefficient (Kow or Pow) is the
ratio of a chemical's solubility in n-octanol and water at
steady state. The Kow is a characteristic of significant importance in environmental studies. It is a c o m m o n surrogate for
bioconcentratition for classification determinations and is a
key parameter in QSAR calculations. There are three basic
approaches to the determination of Kow:
The original a n d reference m e t h o d is the "shake flask
method." An aqueous solution of the material is equilibrated with n-octanol. After equilibrium is reached, the
water and the n-octanol phases are separated and analyzed
for the material. The ratio of the material concentration in
n-octanol to water is the Kow[6].
The HPLC (high-pressure liquid chromatography) method
m e a s u r e s the retention t i m e of the material on a hyd r o p h o b i c column a n d compares it with the retention
times of a n u m b e r of standards with known Kow values (E
1147-92 (1997), Standard Test Method for Partition Coefficient (N-OctanolA/Vater) Estimation by Liquid Chromatography). The method is based on the correlation of the retention time with the Kow.
The QSAR estimation method involves the calculation of
Kow based upon the known, empirical contribution of the
various structural fragments of the molecule to the Kow
value. This gives excellent results for many hydrocarbons
[4].
Due to the wide range of measured values, Kow is usually
expressed as the logarithm (Log Kow or Log Pow). The ranges
are a direct outcome of both the carbon n u m b e r range and

in
ifl

OF FUELS AND LUBRICANTS

the chemical types present in the mixture. I n general within


a chemicEil class, as carbon numbers increase, so does the
Kow. However, for the same carbon number, aromatic compounds have a lower Kow than the aliphatic counterpart. The
Kow values for classes of aliphatic structures do not differ
very much, while the linear ("normal") paraffins have slightly
higher values than the corresponding branched ("iso") paraffins or cyclic paraffins ("Naphthenes"). A m e a n Kow value for
a mixture is less meaningful than the range of values for all
components in the mixture [7].

Water Solubility
The persistence, biodegradation, and toxicity of a material in
the aquatic environment are very dependent upon its water
solubility. Generally, the solubility of hydrocarbons decreases as the carbon n u m b e r increases [8]. However, this
parameter is cdso affected by the structure. Water solubility
will be different for linear, branched, and cyclic paraffins
with t h e s a m e c a r b o n n u m b e r . The m e a s u r e m e n t of this
characteristic Ccin be very straightforwEird:
Increasing additions of the pure material are made to water and the water analyzed until saturation is reached. The
analysis must be specific to the material.
An QSAR method is available for hydrocarbons that provide good water solubility estimates.
For complex mixtures, the individual components in the mixture have different water solubility limits. Once the least soluble component saturates the water, an undissolved phase
begins to form (typically at the water's surface). The remaining c o m p o n e n t s will partition between the water and the
undissolved phase and therefore never reach their individual
water solubility limit. The composition of the water extract
will be different than the composition of the complete mixture as it also depends on the ratio of material volume to the
water volume (Fig. 1). This solubility behavior is very complex. It should be remembered that the definition of solubility as it relates to pure substances does not readily apply to
complex mixtures [7].

100

SS
o

>
C

o
re
u
o
a

>>
X
Pure Gasoline

0.01

887

100

Loading (Gasoline: Water, mg/L)


FIG. 1Water solubility of gasoline components at different gasoline:water ratios (personal communication [83]).

888

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Vapor Pressure
The vapor pressure of a substance is a measure of its tendency to enter the gas phase. This is important for determining both the rate of evaporation and the relative amount of
the substance that will be in the air phase. Vapor pressure
tends to decrease with increasing molecular weight, thus the
materials that are the most water soluble tend to have high
vapor pressures and move from the water to the air fairly
quickly [7,8]
For pure materials, direct pressure measurements may be
used. For materials with very low vapor pressure values or for
a mixture, a vapor saturation method is used. The stationeiry
medium in a generator column is coated with the material
and air is cycled over the medium until it is saturated [7].
Henry's Law Constant
Henry's Law Constant (HLC or H) is essentially the partition
coefficient of a material between air and water. It is important in estimating the degree and rate of volatilization of a
material from water into air. It may be measured directly by
analytical means within a test system or taken as the ratio of
the vapor pressure to the molar water solubility. Henry's Law
Constant is generally expressed as Pa-m^ / mole.
For complex mixtures, each component has a different water solubility and vapor pressure, so the HLC may cover a
wide range. The low water solubility and relatively high vapor
pressure of hydrocarbons result in high HLC values. Generally, an HLC value of 10 Pa-m^/mole or higher indicates that
volatilization is a significant fate process for the material.
Hydrocarbons are particularly likely to volatilize from water.
This is more likely for paraffins than for aromatics, which
have somewhat greater water solubilities. The solubility of
most substances decreases faster then the vapor pressure
with increasing molecular weight, so that the HLC values
increase with increasing molecular weight. For large
molecules, the vapor pressure becomes too low for volatilization to be an important fate process [7].
Adsorption / Desorption
Adsorption is the taking u p of a gas, vapor, or dissolved material on the surface of a solid. Desorption is the release of a
gas, vapor, or dissolved material from a solid under the same
conditions. The adsorption of organic chemicals from water
into organisms, sediment, or soil plays an important role in
the fate of materials. This process is also important in accumulation of materials by aquatic, sediment dwelling, and soil
organisms. The soil/water equilibrium also has a determining influence on the rate at which chemicals will leach into
ground water. For simple un-ionized organic chemicals, the
adsorption/desorption behavior is strongly affected by the organic matter contained in the soil or sediment.
This concentrating behavior is not always a simple linear
relationship and is usually described as an "isotherm." However, for most materials, the assumption of a constant distribution coefficient between soil and water (Ka) is adequate.
For organic substances, the important determinant of adsorption is the organic matter contents of the soil or sediment. As a result, the values for various soils/sediments are
"normalized" by calculating the partitioning coefficient be-

tween water and soil organic matter (KQC) ( E 1195-87 (1993),


Standard Test Method for Determining a Sorption Constant
(Koc) for an Organic Chemical in Soil and Sediments). The
Koc is often calculated directly from the Kow [7].
Dissociation Constant
Some components of both fuels and lubricants dissociate
into ionic form in the aquatic environment. Dissociation constants (pKa) are only moderately affected by changes in temperature a n d ionic strength. In general, dissociation decreases with increasing temperature, while increasing the
environmental ionic strength tends to favor the ionic form.
Dissociation greatly influences all other environmental processes and properties such as sorption, bioconcentration,
and toxicity [2]. Ions cannot partition into the air or nonpolar environments. Additionally, the ionic species may have
very different aquatic toxicity from the unionized form [7] as
a result of different mechanisms to transport the molecule
across cell membranes.

FATE IN THE ENVIRONMENT


Upon entering the environment, a material may be transported within and between environmental media (also called
compartments or phases) and respond to ambient factors in
the environment (Fig. 2). The primary factors that affect the
fate of materials are as follows:
Physical transport (advection, dispersion, partitioning)
Transformation (biotic and abiotic)
Accumulation (bioaccumulation, bioconcentration)
The final equilibrium distribution of a material between the
air, water, sediment, soil, and biota significantly influences
the potential impact of the material within each media.
The characteristics of the material and the environmental
media determine which of a variety of transformations that
the material may undergo. Abiotic transformations include
hydrolysis, photolysis, and oxidation. Biodegradation is not a
physical property of a material, such as water solubility. Microbial organisms may modify a material in a variety of ways,
all of which could be considered biodegradation. The different types of biodegradation have been classified according to
the extent of the modification. These are simple structural
changes to complete degradation to CO2.
Transport Processes
Environmental transport can be divided into movement
within and between media. For example, a material released
into a river will be transported by the river flow. If this material is highly volatile, it will move from the aquatic comp a r t m e n t to the air c o m p a r t m e n t . Both types of transfer
processes involve advective and diffusive mechanisms. Advection causes the material to move in the same directions
the media (e.g., air or w a t e r currents). Diffusion causes
movement in response to concentration gradients. Table 2
lists some of the important transport processes.
Environmental media are comprised of different phases.
For example, surface water consists not only of an aqueous
component, but also contains suspended solids. Similarly,

CHAPTER

34: ENVIRONMENTAL

CHARACTERISTICS

UV/Visible Light

OF FUELS AND LUBRICANTS

889

Volatilization

Hydrolysis
\
Biotransformation - ^

- - Adsorption
Biological \ \
*
Uptake
\ \ Dissolved Organic
\ \ Materials

Biodegradation

/
Food Web Transfer

Suspended Particles

Sediment
FIG. 2Possible degradation pathways for a substance in the aquatic environment.
TABLE 2Examples of important environmental transport
processes (adapted from [7]).
Movement within Media

Movement Between Media

Air advection (winds)


Air diffusion
Surface water advection
(currents)
Surface water diffusion
Ground water advection
(currents)
Ground water diffusion

Wet and dry atmospheric deposition


Volatilization
Gas absorption
Soil leaching/run-off
Sediment burial
Sedimentwater exchange

the atmosphere is composed of air and particulates. An important driving force for diffusive transport is the tendency of
a material to reach equilibrium between these phases. Partition coefficients quantify the equilibrium distribution of a
material between these different phases. The use of equilibrium partitioning theory is an important element of current
environmental fate assessments, since the form and compartmentalization of the material influences subsequent
transformations and accumulation processes in the environment [7].

tions convert the chemical into degradation products, but


usually do not totally convert it to the inorganic forms (e.g.,
CO2, H2O). Transformation of a material may result in a
change in toxicity and physical characteristics. Toxicity of
the product(s) may change, but do not necessarily result in a
reduction. Thus, it is useful to understand the degradation
products, if possible, to be able to evaluate their impact on
the environment.
Biodegradation is m u c h more complicated than abiotic
degradation. Only certain microorganisms can accomplish it
and not all microorganisms can degrade all materials in all
environments. In some cases, a microorganism may be able
to degrade only the products of a previous biodegradation
process. The multitude of organisms and the highly variable
genetic make-up of the microbial communities usually result
in at least some microorganisms that can degrade an organic
material to some extent. The outcome of this degradation
may range from a simple chemical modification to a complete utilization by the organism for growth of new cells or
for energy. The type and number of organisms are as important to the outcome as the structure of the material.
Abiotic Degradation

Transformation Processes

Hydrolysis

Standardized tests have been developed to allow some prediction of the degradability of materials in the environment.
These are generally divided into chemical (abiotic) degradation and biodegradation tests. Standardized tests for determining the degradation rates are available from many Standards Developing Organizations (e.g., ASTM, ISO, etc.).
International Consortia (e.g., OECD, CONCAWE, etc.), and
Regulatory Bodies (e.g., U.S. EPA, Environment Canada, European Union, etc).
Abiotic degradation of fuels and lubricants is primarily due
to photolysis, hydrolysis, and photooxidation. These reac-

Hydrolysis is a chemical transformation process in which an


organic molecule, R-X, reacts with water to form a new carbon-oxygen bond and cleaving a carbon-X bond in the original molecule. It is a well-understood chemical process and
the types of chemicals that hydrolyze and the catalysis of the
process has been studied extensively [2]. The standard test
for hydrolysis involves preparing aqueous solutions of the
material at pH 4, 7, and 9, incubating at 50C in the dark, and
analyzing the remaining concentration at various time intervals (E 895-89 (1995) Standard Practice for Determination of
Hydrolysis Rate Constants of Organic Chemicals in Aqueous

890

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

Solutions). Stability for more than a week indicates n o significant hydrolysis has occurred.
The bonds in most hydrocarbons do not tend to hydrolyze.
In general, only those materials with ester bonds are expected
to be affected by this process. Hydrolysis half-lives can range
from days to years for these materials, with the rate of hydrolysis of organic compounds increasing with temperature
in an exponential relationship [2]. Hydrolysis in not expected
to be a major fate pathway for hydrocarbon-based fuels and
lubricants, while synthetic and vegetable oil based lubricants
may be more susceptible.
Photolysis
Photolysis is a light-initiated transformation reaction that is
a function of the incident light energy (typically at wavelengths between 290 and 400 nm) and the structure of the
material. Different classes of molecules absorb sunlight
at different wavelengths a n d with different efficiencies.
Molecules need to have a strong adsorption band in this region to undergo significant photolysis in the environment, so
the UVA'isible spectrum of chemicals is used to screen for the
likehhood of photolysis (E 896-92 (1997) S t a n d a r d Test
Method for Conducting Aqueous Direct Photolysis Tests). It
is not necessary that the material directly absorb the light to
undergo photolysis. With indirect (or sensitized) photolysis,
an intermediary chemical becomes energized and then energizes the material of interest. Generally, phenols, furans, aromatic amines, sulfides, and nitro-aromatics are susceptible
to indirect photolysis [2],
Some polynuclear aromatic hydrocarbons (PAHs) can undergo a light-mediated increase in toxicity. Some intermediate weight PAHs, such as anthracene, fluoranthene, a n d
pyrene, have demonstrated photo-induced toxicity (greatly
enhance toxicity when compared to the inherent toxicity of
the material). When the PAH is present in the tissues of a n organism, phototoxicity can occur when UV radiation is absorbed by the molecule. The current theory is that oxygen
free radicals are produced that are highly oxidizing and can
destroy the molecules in the tissue [9].
Photooxidation
Atmospheric photooxidation is the degradation of chemicals
in air due to reaction with ozone or hydroxyl radicals and is
dependent upon the structure of the chemical, its concentration, and the ozone/hydroxyl radical concentration. Hydroxyl
radical attack is the predominant degradation mechanism
for alkanes, olefins, alcohols, and simple aromatics, which
are rapidly oxidized in air [2]. Hydroxyl radicals are produced through the interaction of sunlight with oxygen and
other substances in the atmosphere. The volatility of hydrocarbons and the rapid oxidation in air promotes photooxidation as a significant fate process for most hydrocarbons.
There is a significant amount of test data on the rate of hydroxyl radical reaction for chemicals that has allowed for the
development of effective QSAR models that ceJculate atmospheric half-lives.
Biodegradation
As indicated by the name, biodegradation is the biologically
mediated transformation of a material. The microorganisms

that accomplish the biodegradation are very important to the


n a t u r e of the result. Generally, the interest in studying
biodegradation is to use the results to predict the environmental fate of a chemical. Thus, the microorganisms used in
laboratory tests are mixtures of species collected from particular environments. For a variety of reasons, sewage sludge
has become the standard source of mixed inoculum for introduction into laboratory biodegradation test systems.
In the aquatic environment, bacterial numbers are lower
than in sewage. They are also exposed to low concentrations
of a variety of chemicals and nutrients. I n the standardized
tests, the organisms are constrained within a small volume
and presented with a high concentration of the test material
as the sole source of carbon. Those organisms capable of degrading the chemical will use it for a source of carbon for new
cells and energy. Pre-exposure to petroleum products cam result in an increase of petroleum-degrading microorganisms
from 1-10% of the total population [10]. The rate of this
biodegradation reflects the growth rate of those particular organisms u n d e r the conditions of the test. Although the kinetics are completely defined by the test and are not easily related to a rate in the environment, the test results are used to
classify the persistence of the material and estimate its halflife in the environment.
Certain environmental conditions (e.g., availability of oxygen) greatly influence the types of o r g a n i s m s and their
metabolic pathways. Standardized tests exist for aerobic and
anaerobic conditions in the major environmental compartments (freshwater, marine water, sediments, and soils). In
some cases, simulation tests are intended to replicate the natural conditions of the organisms, their environment, a n d
their exposure to the chemical [11].
Certain standardized tests have been developed for regulatory p u r p o s e s to evaluate b o t h the rate a n d extent of
biodegradation (Table 3). The primary terms used to describe
biodegradation (primciry and ultimate) distinguish between
two extents of biodegradation. Primary refers to the initial
transformation from the parent material and ultimate refers
to mineralization of the material. Rate is described by the
t e r m s inherent a n d Ready. To b e classified as inherently
biodegradable, there m u s t be unequivocal evidence of
biodegradation by any test method. The OECD method regulates degradation of the material for this classification. Ready
Biodegradability is a regulatory classification originating in
the European Union that has very specific criteria. The tests
are characterized by low initial biomass ( < 3 0 mg/L) of
sewage organisms, which have not been previously exposed
(adapted) to the material. The substance must meet the criterion of 60% degradation to CO2 or O2 (or 70% removal of
DOC) within 28 days. Further, the pass criteria must be met
within 10 days after the biodegradation exceeds 10% of the
mass loaded [12,13]. The Ready biodegradation tests are considered so stringent that if a substance passes the test, it will
also rapidly degrade under most environmental conditions. If
a material does not pass a ready test, it does not meeui that it
will not degrade in the environment
A n u m b e r of ready biodegradability tests are available and
differ mainly in the method of analysis. The different assays
give different results. The analytical methods dictate details
of the procedures and result in different applicabilities for
each test. Generally, the disappearance of dissolved organic

CHAPTER 34: ENVIRONMENTAL CHARACTERISTICS OF FUELS AND LUBRICANTS

891

TABLE 3Types and characteristics of biodegradation tests (adapted from [7]).


Attribute
xtent of
Biodegradation

Categories
Ultimate

Ease of
Biodegradation

Measurement

Properties
Measures total conversion to inorganic forms (e.g.,
CO2, etc.)
Mineralization
Based on analysis of specific chemical or chemical or
chemical class
abiotic losses controlled

O2
CO2
CH3

Primary

Specific Analysis

Removal

Specific Analysis

Ready

O2
CO2

Primary biodegradation
Both abiotic and biodegradation
Regulatory definition of "rapid" biodegradation
Uses <30 mg/L non-adapted inoculum
reaches minimum 60% degradation to O2 or CO2 or
70% removal of DOC in 28 days
must go from 10% to the pass level (60 or 70%) in 10
days

DOC

Inherent

O2
CO2
CH3

Enhanced conditions to show possibility of eventually


biodegrading
Generally a high biomass adapted inoculum

DOC
Specific Ansilysis
Specific Analysis

Simulation

Reflects actual environmental behavior


Difficult to simulate most actual exposure situations

9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

Day of Test
FIG. 3Typical biodegradation curves for the same material when analyzed for different endpoints (adapted from [7]).
carbon (DOC) is more rapid than the utilization of O2 or the
production of CO2 (Fig. 3). Table 4 provides a list of commonly used standardized tests, the general characteristics of
the test, Emd general applicability.
Comparing the results from different test methods for the
same or similar materials can be problematic. The "percent
biodegradation" is very dependent u p o n what type of
biodegradability was tested. A result of 100% p r i m a r y
degradation in an inherent test cannot be compared to the
results of a Ready test, where 100% mineralization is not
possible emd where conditions are much more stringent.
Even within similar test methods, the inoculum makes a

great deal of difference in the outcome of the test. The number of competent organisms greatly affects the duration of
the lag phases. If the n u m b e r of these organisms in sewage
sludge is low, different tests could show either good
biodegradation or none at all. The microorganisms in the
inoculum may vary significantly over time. The tests for
biodegradation, even using a "standard" inoculum, will give
much more variable results than the tests for physical properties or toxicity. As a result of this and various complications resulting from use of inappropriate tests for the physical characteristics of the material, the comparison of
biodegradability between materials is only quantitative if

892 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


O tS

"3^

>

C/3 O

a1
fe
PH

m
OT U

&8

CIJ

"N M

a
.o
2

!i
3
3
O

.^
c a
1)

t/l

5H

ap

u ^
^^ "3o
(/J
(1)

fl
3

(1>

t/i

o
1

n wo
u y T-H

< M PH ^

as

C<5

Pi

II

I S
P PL,

<

I
as

(N

<N

^
ro <; (VI

^,

QSo

^ 00 00
'H (N i n

Q
W
O

PQ O
* 5
U OT
BJ <

o m
(N ro

o ^ o o
fO pH ro <;
Q rt- Q &<

is

W O M c/3

f^ O o

<;

Q * nC P^
(J U ^ rt
<Z)

u ^H o

O W(/)
fflp

PLi O

om
o

fl d
o (/)
ta T3

ni
OJ Ti T3

O
fi
<u -d jd
O o

O
U

s1

l-l

o
fl

J3
M

ri J3
a) -r)
O 01
(T
O
U

ai

cn

-a

T3

<^ IS
,2
(i< pp

.n
<\>
T3 u

CJ

u M "O -a 13

O CO

jy ^- l-l - ' 1 - 1

Pi

CHAPTER 34: ENVIRONMENTAL CHARACTERISTICS OF FUELS AND LUBRICANTS


0

C/D

o
O

c
o

u '4-
13
o 0 3
w
Z

t B

>

o
2

g
u B
c
o

n
o
0)

B^
^

fi 3

ID

op 71 .

'T3 '

ft o

o rl t^
c 3 o

1^2

a ^

C3

< PH I

-^ .2

3 u^

;3 8 S

o
5 B.

O -5 T3

00 o

-a ts td

_ 2
^

c/D

Si

ft

1:3

'00

60
"O

:3 <L

0<N

K _

<5

ft--

w o 3

3
(U

=1.1

a
c
o
o
I
pq

"s

<u

0) t

II

EB
K

K C <U
Vf^Oi

'P

3
_0

ta 3

1 6

11

p fc

e
o
'+-
13

B
M

3
B
c

0-

"

"43 S
^

3 ^

<

d
Z

O lO
ON

fN O
r<^
ffl 0 0 iri < fS O lO in
r1
00 CO
O 00 00
r<^ PM 00
m 00
I')

00

ON

<! 2 ^ i n Pi f
^ ON J2

O rr)

O 2 P^

m
o^E2

3
O

O rri

o -'
3 'O
3 W

So

w
oS2S J2

C/3 C/}

"I

3 ^

o-a
3

(U

.S ft
i> S 3
3 CJii

II

00

I/^

ON

^ m
^00

f-N ^

ID

'"^
m

n i C/D

t/5

81 CQ P

t^

S<:
1^ o

a J"
0

>

t3 <;

o I
m

0
0

(U

5 OH

< p

<

'+-* Cfl

3T3
<u CJ
0 "ta

- a

t^ f^^

ON
ON

rO (N <;

<

O
a ^ c/5

5:

^ ft
f^ (Mi

00-9

.S -2

III?

(U ,>H

C/3

893

894

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

they are tested in the same test systems using the same ino c u l u m p r e p a r e d at the same time. The major use of
biodegradation tests is to provide an estimate of the potential of a material to degrade in the environment.
In general, hydrocarbons are biodegradable to varying degrees [14,15]. Fuels and lubricants are mixtures with some
components having low water solubility. This low water solubility often limits the concentration in solution and thus
their availability to the microorganisms. The aromatics tend
to be slightly more water-soluble and give "better" results in
standardized tests than the paraffins. Among the paraffins,
the linear hydrocarbons are considered more biodegradable
t h a n the branched hydrocarbons. This results from microbial
oxidation of one end of the linear molecule to a carboxylic
acid. The metabolic processes in nearly all organisms can
easily degrade the resulting fatty acid. The presence of
branching hinders degradation to some extent.
Much of the older data for volatile hydrocarbons used the
Closed Bottle test (OECD 301D)[12]. This is an un-stirred test
system with a low inoculum. Using this method resulted in most
of these hydrocarbons being considered as non-Readily
biodegradable. Recent testing of the same materials using the
Manometric Respirometry Test system (OECD 30IF)[12] has
identified many of them to be readily biodegradable (Fig. 4)[ 16].

1022-94 Standard Guide for Conducting Bioconcentration


Tests with Fishes and Saltwater Bivalve MoUusks; E 1688-00
Standard Guide for Determination of the Bioaccumulation of
Sediment-Associated Contaminants by Benthic Invertebrates; E 1676-97 Standard Guide for Conducting Laboratory
Soil Toxicity or Bioaccumulation Tests With the Lumbricid
Earthworm Eisenia fetida).
Past research has generally focused on accumulation in
the aquatic environment. Terms commonly used to quantify
accumulation potential by aquatic organisms are the bioconcentration factor (BCF) [17], the bioaccumulation factor
(BAF) [18], and biota-sediment accumulation factor (BSAF)
100
Manometric Respirometry Metliod

S 8 0 n
2
g" 60
o
.2
"
40
c

20
Closed Bottle IVIethod
'

Accumulation Processes
Accumulation processes result in the transfer of a substance
from a primary environmental m e d i u m (e.g., air, water, soil,
and sediment) to a plant or animal. Materials that pose the
greatest concern for accumulation potential enter the environment from diffuse sources, are poorly degraded in the primary medium, exhibit a high affinity for lipids, and are resistant to the metabolic breakdown by plants and animals (E

T
3

T
7

'
13

20

24

Day Of Test

^^J^
Termination

FIG. 4Comparison of hexadecene biodegradation curves


for data from tfie Closed Bottle test method and the Manometric Respirometry Method (personal communication [16]).

TABLE 5Comparison of acute and ciironic environmental toxicology tests (adapted from [7]).
Test

Onset of effect
Concentration of test material
Exposure frequency

Test duration

Effects typically measured

Chronic

Acute

Determine test material


concentration that causes
effect on organism during
siiort term exposure
Evaluates relative toxicity of
different materials to same
organism
Evaluates relative sensitivity
of different species to same
material

Objective

28

Designed to determine the


lowest observable effect and
the no observable effect
concentrations of a material

Sudden or delayed

Delayed

Relatively high

Relatively low

Static
Static renewal
Continuous (Flow-through)
Pulsed

Static renewal
Continuous (Flow-through)
Pulsed

Typically < 4 days


Exposure period small when
compared to total life-cycle

Weeks to months to years


May include sensitive part of
life-cycle, entire life-cycle,
multiple life-cycles

Mortality
Immobilization
Changes in growth rates (algae)

Organism development and


growth
Reproductive success
Based on most sensitive
endpoint

CHAPTER

34: ENVIRONMENTAL

[19]. The BCF is a laboratory derived measurement that


simply defines the partition coefficient of the substances between aquatic organism tissue (primarily the lipid component) a n d the surrounding water. The BAF is generally a
field-derived m e a s u r e m e n t determined from monitoring
data. The BAF is calculated by dividing the observed field
tissue concentration of the material by the corresponding
(dissolved) concentration of the material in the water (soil,
sediment, or food), although the value can also be determined from microcosm and mesocosm experiments. The
BAF differs from the BCF in that the BAF represents the accumulation via all possible exposure routes that may occur
in the field (i.e., water, sediment, soil surface, and diet),
whereas the BCF only reflects the accumulation due to
aqueous exposure. The BSAF expresses the steady-state difference between the concentration of a bioaccumulating
nonpolar organic chemical normalized to the organic carbon content of a sediment and the concentration measured
in the total extractable lipids of an organism for which that
sediment represents the source of the contamination in its
habitat.
Although the BAF and BSAF values provide a more realistic appraisal of the accumulation potential of a material,
there is a high degree of uncertainty associated with field
data due to variability in the exposure values from various
environmental sources a n d associated contaminates. Further, field derived data are not available for most materials.
Consequently, BCF provides a valuable surrogate parameter
for assessing the relative bioaccumulation potential of materials under controlled laboratory conditions.
The BCF test methods generally include both uptake and
depuration (loss) of the material in different segments of the
test. During the uptake segment, the organism is exposed
to a constant aqueous concentration of the substance. At periodic intervals, organisms are sampled and analyzed to determine the tissue concentrations. Once steady-state tissue
concentrations are approached, the test organisms are transferred to clean water to determine how rapidly the material
is depurated. Based on the results of both segments, a simple
model is used to estimate the BCF and the half-life for the test
material. BCF measurements are applicable to test materials
that are well-defined single components, b u t not to complex
mixtures.
Based o n the results of numerous BCF experiments for different substances, QSARs have been developed that relate the
BCF value to the KQW. In the absence of BCF data, the Log
Kow values are used to predict the bioaccumulation potential
for materials. These predictions are often used for hazard
classification and risk assessment. However, this approach
may be overly conservative for two reasons:
1. QSARs are generally based on measured BCF values for
substances t h a t are poorly metabolized. Many hydrocarbons and industrial chemicals can undergo significant
enzymatic degradation once absorbed into an organism.
This process is referred to as biotransformation (or
metabolism) and serves to lower the BCF value when compared to the QSAR prediction.
2. QSARs are limited to materials with Log KQW values generally lower than 6.0. For materials with higher KQW values,
research indicates that the BCF declines as the Log Kow increases even for substances that are poorly metabolized.

CHARACTERISTICS

OF FUELS

AND LUBRICANTS

895

EFFECTS IN THE ENVIRONMENT


Standardized Tests
Standardization of toxicity testing is important. Within a
population of organisms, there may be a wide variation in
age, size, vitality, and health among individuals. These variations lead t o different sensitivities within t h e population.
Further, there can be significant variation in sensitivity between different species. Reducing sources of variability improves the reproducibility of the test results. In standardized
tests, biological variability is reduced by using organisms of
selected species that are the same age range, similar in size,
and in good health with no observable abnormalities.
When the goal of the test is to measure toxicity parameters
such as mortality or effects on reproduction, a single species
test is used. Concerns about different species sensitivities are
addressed in environmental toxicology by testing representative or indicator species from various levels in the food chain
(tropic levels). Considerable research and test method development has gone into the selection of test species that are
representative of the more sensitive species (within the same
grouping of organisms) in the environment (Fig. 5). One advantage of u s i n g such representative species is that substances tested at different times and in different laboratories
can be compared for relative toxicity (Table 6).
The good predictability of QSARs that have been developed
for specific species and classes of organisms has demonstrated the utility of this standardization approach. These
QSARs allow prediction of toxicity t o a q u a t i c organisms
based on structural or physical properties of the substance (E
1242-97 Standard Practice for Using Octanol-Water Partition
Coefficient to Estimate Median Lethal Concentrations for
Fish Due to Narcosis). As with the biodegradation test methods, each specific test provides data that is representative of
a specific aspect of the natural environment. The dominating
factor relating the toxicity test to the environment is the
mode of exposure.
Exposures
As with the variability associated with the test organisms,
each test material has unique characteristics that must be
considered when conducting a standardized toxicity test. The
volatility, water solubility, and complexity/variability of composition of the material can significantly affect the exposure
of the test organism to the material and must be considered
in the design of the test. Appropriate test design considerations allow for reproducibility of results within the same laboratory and comparison between laboratories for the same
test material.
In order t o relate effects t o exposure, one needs to have a
defined, quantified exposure test material concentration for
a specific period of time. Since the effect is related to the internal dose received by the organisms (a value not generally
known), exposure duration must be adequately long to insure
maximum uptake of the material by the test organism. For
low solubility materials, such uptake may be quite slow. As a
result of these considerations, the exposure duration of
aquatic toxicity tests has been standardized. For acute toxicity tests, these periods range from two days for Daphnia tests
to four days for most fish tests.

896 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

100
90
a

Caddisfly
r Acroneuria
.
...
g Argia
Anguilla
^
Campeloma ^^^ Procambarus
Lepomis ^
Orconectes

80

<-

Funduius MAmnjcoia

u
0>

(A

60

50
Q.
(A
O 40
V
O)
re SO
4->

sc

Least Sensitive

Moron
j^Tilapi
Lumbriculus
^Notropis
Cyprinus
Gambusi
Gonlobasis
Carasslus
Etheostoma
Pectinatella
Acrochellus
Corbicula
Salvetinus
Poecilis
Pimephales
Nais
Rhinichthys
Semotilus
Compostoma
Chironomus
Oncorhynchus
Ictalurus
Gammarus
Gyraulus
Limnodrilus
Salmo
Lophopodella, Plumatella
Physa

3= 70
<

20

1.

D. i n

Most Sensitive

Ptychocheilus J" Ceriodaphnia


Daphnia

0.1

10

100

1,000

10,000

100,000

Copper Concentration, |ig / L


FIG. 5Species Sensitivity to Copper Sulfate (adapted from [84]).

For stable, water soluble, pure materials, maintaining a


constant exposure concentration is not difficult. T5rpically, an
arithmetic or geometric series of exposure concentrations
Eire tested. The test method and preliminary testing usually
determines the specific range and number of concentrations.
This facilitates having a range in which the extremes provide
no mortality and complete mortality. Test guidelines usually
require that the actual concentration be analytically confirmed over the course of the exposure period. The resulting
data allow the use of statistical techniques to develop a concentration-response curve and to find the midpoint or LC50
(E 1847-96 Standard Practice for Statistical Analysis of Toxicity Tests Conducted under ASTM Guidelines; E 1023-84
(1996) Standard Guide for Assessing the Hazard of a Material
to Aquatic Organisms and Their Uses; E 729-96 Standard
Guide for Conducting Acute Toxicity Tests on Test Materials
with Fishes, Macroinvertebrates, and Amphibians). The
same approach is used to establish other effect endpoints
such as impact on growth or reproduction for chronic testing. For endpoints not involving lethality, EC is often used to
indicate the "effect concentration" rather than the "lethal
concentration." Discussing the concentration-response can
be confusing. The smaller the concentration of the material
that causes an effect, the greater the toxicity of the material.
Typically, lubricant and fuel products are considered "difficult materials" for aquatic toxicity testing. Difficult materials may have low water solubility, be volatile, or be complex

mixtures. Much of the historical information on the toxicity


of these materials can be misleading or confusing. Often, the
toxicity values are not reasonable (e.g., reported LC50 exceeds
the water solubility of the material) and the value does not accurately represent the toxicity of the material. All that can be
said is that the LC50 is greater than the water solubility. Generally, the material must be retested to develop scientifically
defensible values. Designing, conducting, and interpreting
aquatic toxicity studies on such materials involves special
consideration [20].
Volatility
For volatile or unstable materials, it is difficult to maintain a
consistent concentration for the exposure period. The traditional approach is to replace the exposure matrix concentrations with frequent renewals of the exposure medium from
freshly prepared test solution (static renewal test), or even
with a continuous flow of test solution through the exposure
chambers (flow-through tests). An approach that has been
successfully used for volatile substances is to prevent loss by
testing in tightly closed containers with no headspace. Precautions that organisms get sufficient oxygen must be taken.
It should be re-emphasized that the purpose of these tests is
to produce a quantitative concentrationresponse relationship, not to simulate the fate and effects of the substance in
the environment. So the expected (nominal) concentration
must be confirmed with periodic analyses and, if necessary.

CHAPTER 34: ENVIRONMENTAL CHARACTERISTICS OF FUELS AND LUBRICANTS


^ l O

o
o\

^CN
^

(0

(/3

o
00

(U
T3

00
r-

(U

o "N"

'3
o

r-4 l o

<o
rt ol O

Q "
on
C/D

rt o

O W 3

00

r^

O
00
rt

ON

ON
1 ,
, ^00
" " 5
NO
2:
^ .iT) Cfl

II

"J- l o

T^ U-l

'^ S

ON

2;
^ ^_ ^<^ N
( N^ il O^ PH 1 1 yf
O uiUi ON (NW IG w
S O > S 2
2 ON 2 OO -"I
H '"!, H o O o

^ P H O O

- ^ W <;

^5M

H
(Z)

M O W
< PJ P

ID

o lo o
00

ON

NO

O Csl r^ NO
<N <N CNl ON

00

o ^ . "* '^ - i

3S

H H
c (Z)

O
(N

< < < W


W W p< PL, PM 5

PH PH

00
^ < ;
rM PH

IZ) (Z) (Z) c/3

0 0 <-H

ON

o<-'w
Wow

W WW g

CO

\0 ( N O
o o ^O
in -^

in

^
lO ON i n i n O O d
00 00 i n i n i n 00
00 00 00 ^H

, ^ 2-

^^

O W t3

^ W

PH

S z WwS
W

^ 00

tN o <:
O f=i, W

Wfsw

J2w

S ^

s5
S

i/i

UJ

wi

-o

O
J3

<u

6
03
z
u
ss
^ s s
'S
^<U fii o^
C/3

P
"

1""

CO
>o

1s
1-^

S
n.
0

Cfl
CD

s^

B
S

B
;^

&0 o)

5-
B

to

fH

to

52

B 5!

.2 8

K a, s?

S -S -S
e s s

&0 s:

II

S K

-s -s: ^
a, n. D,

S4l

to

a . ts
. C

CO c/3

OH

-sB

Q Q Q

a 'c

a-
iij4

a
<u

73

B
a

^
'>
a

a
m
i~>
O

ft.;

Oi

c/l U
ID (D

lU

^y

3
o
t ^

O
(/}

1
L-

> !

el

T3

S
'S
^T3

CI
ta

cfl
W

T3

y) w t j

B
w

S ^w

S
0)

rl
o
'+-
ft
'D
o
c

(U
T3

3 0)
o >
'C
'S
bo ca
<Z

.s s

M
o
-o
rl
a
0)

-d
tu

gPQ

cO

"3
iZ <a
3 ft
-*-> t/j

tS

J3
en

LH

Ca

01 . ^
> . c/j

JH

ID

ta

- V)
d

<D
U

o
w

<-;O
W

(A

O o

U hJ

3.
B
01

ofirl-M

m m

ob 3 S)0 O <-> KJ

MpqatLlZHjpLlpLl

Ocj

O o

(-lo

ggww s s g w s g w

gggw

O j O o O h - l O o O h - l O o O j O o
WWZh-lWWZhJWWZJWWZi-1

Ou

ojgoow
W W Z h-1 h-I hJ

JiJI

\.ri
"O

crt

t^

fi

"S
1)

OS

bo 4^

S op
tu rl

01
N

Pi

G rl
3 "^

"S
>
fi
t
CJ
3

W W

-H + j 11

?
G
u
O

o +e
O O
J3 O
WPJ

j s c
00 +H

3
^3
O
u
ft

e *H H-l - a

14

Ot/OPi! O

-d

T3

lU

^ O -M G
o o o C
h

J:^

5^
bo+3
C SP

G 00-3
cu cl ta

1)

tu C
J 3 - 1 OJ
e *j >-i
J O -JH

o o o

2 2
GO

"3

>

-a> 13>
g

'E3

c
0

OS
u

s
Q

NO

-a

lU
+-

:
1/3

tu

<u
H

t.
0)

00

01

0) 5.
3

3
00

897

898 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

IS
O
S; ON "*
g; ov t^
^~' \o o
t/o (^ lo
PL, - H

PJ
Z
5f
B

<
P^
W
P

B-l
S
r^
<

^1
s S

^-^
00

i~~i

r1

lo

in

i n 2H

lO r o
O ON
ON r^ \ o ON ^ -

00 i n rt
00 ON O ON

O O o (N O
t ^ IT) <%J ^H IT)
rt 00 r^ , H 00

W < W W <
5 fc 5 5 OH
7 3 C/3 c/0 1/5 t/0

< D<<; 3

vT \ 0 O

-^

(N u^ m rr
(-,. rt 00 rt
rt rt < pLi
cil
H H *T H
CO W O) cfl

< <P <

to
V)

o o
o o
rt vO
vO "n
11

11

(/5

C/J

< <

00

^o

y^,
fN
QH
o ON
<N lO M
Q r5 Z
O O
<
PJ U
u
O W M

vO
vO

O
CO

ts

t J 1 1

c
etoa >*^>
u ^
-s ^^

P-

s2

Ki

a -fe-

S Sio 's I H a.

^^
o o
00
(^ m
m
a\ , _ , o
<N " - 1 " ; ; ' ^ n;
ON ON , O O
^ <N t o l o i n
--I -H O 0
rt rt f- <; <
"S 5 2 0-1 fi
H H o
i/y<V); ><
<
K D(nP</i
ON
r^

s i,

tS

to

0 0 NO
NO NO

s
S

^g

<N
NO
IT)

t/3 <Z)
OH B H

^-t

mN
Z2
< <

O (J
P-l W

<3 -2
s

t ? ^

ta

,,^
^f^

2 -2 2 ^
s s ,.
^ ^ . is

-*

sta

CQ

^r;-

)Q
o^

I I

tu

s s l 3 I *^ 3 s
?^?.
~ o

;s
p^
^
s
"
t/D

11

lO

II

c -5 -S -o

lis

NO

^o
^

<

a
s
'c

S.s

o t^ t3

Qi

O -^t; -ti;

^^

0
to

s S
2 S

ta
to to

^ ^
-a
-t~i -g
s a
c a
I i
^
:?;:?:

^
tu

o
a

IB

<

ID
C c

t3

3^

1tu 3g

h-l

h-l

tD

c V)
H,

Sd

0
t/j

>
"Zi
>

S-i

MS

(U

fc

<

tu

s =atu
C

W ^J^l
B
B,

13

>

13

t3 tu>

3
C/D

13

>

c/) Q

^1
00
*

>

J5
NO

VI

a
tti

si
11 in

S tu

^1

IS

a
<u

13

i>

&

PQ

q
rt

0
ft

-C
tt
<N

"O
0

iiiM

ON

1
00
tj-

-^1
<D

ffj

&i

tu - r tu
S ^ B
OS - ^

O j O o O h j O o O j O O
pqpaZJP-lPLiZHJWW2h-i

3 j S
C/3 Pii H.

T3 -O
Tf -H
^H CNJ

M VI

.a t
2|
o

S HJ [/)

2
^ o
o -a

]
J=
NO

13^
C

9. o
T3

CHAPTER 34: ENVIRONMENTAL CHARACTERISTICS OF FUELS AND LUBRICANTS


t N 11

^i^ t ^
m
i__t
rt ON
0\ O

o\

00 00

[^

S
OO

CO I/)

C/3

t ; M--^

rt

1 . *

o
^
00 d

ON"

^ w w

2S

O C^ OH CU \ 0 ^ ^O ON O
r^ W M ^ ' I - * 0 0 < ; (N
>- ro m
R Z Z Z t ^ r^
^
O O OO
cr.M
W O O

ir
1
^

o
S

- s ^;^

t ^ <3N ,,

S - i <~^
PLH

^ H fv.

ow<

OP

H n

11

;^
K

'O

cj ^ 2
S & o

00

fcf^pqc/jsioOO

SH

?j

JS -a

A
rt
^M H,

7v

^^

5^

t5^

-s-g

<U

cfl C

P 3

fc S

o
ou o
IT) m g W S g
O hJ O o o J
pq w Z h j H-i HJ

s;

-s
a.
5r

OJ

o^

1 J^

to

^a

c ?
a 0
c
-a fl

a B

a> 'U >-(

s^

o
-^o
s
'C

.<o

2_ |^'Qih,
^

S
8

" T t/3 ( L J - ^
. . ; B-i o

C/)

a^

&

_rH d

W
2

z2

O ^
s. ^o s
^ &

<

CO
PL,

tfl <N o ^

(N <
Q Pi W W (N

< o ww

J ^1
!

o'
o S 00

ss

:^^^

ON t ^ ^

(N

r<1 00
m (N

O o

<-> O

O h j O o O j O o
pq tf 2 HJ rt w Z 1-1

w M 2 h4

C3

^o
o

o
ft
^

oi

1>

.S ^

J3

-y

'

3
C/3

C/5 h-1 >

CO

T3

o
T3

VI

NO

ft J3
^ u
oi "S

O H - I O O

T3

899

900

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

the LCso calculation may be based upon the measured concentrations [20].
Low

Solubility

There are a n u m b e r of issues related to low solubility materials. The acute LC50 values for a homologous series of chemicals may sometimes seem confusing. In general, the members of the series with lower water solubility will have greater
toxicity. However, as the n u m b e r of carbon atoms in the series increases, the water solubility decreases. The decrease in
solubility is usucJly greater than the increase in toxicity. So a
point will be reached when no acute mortality is evident. This
is sometimes referred as the "solubility cut-off." Larger members of the series are too insoluble to cause acute mortality
(Fig. 6). Although it is possible that the small amount of the
larger members in solution may cause chronic toxicity and
may contribute to the acute toxicity caused by other dissolved substances, they contribute little or no acute toxicity
unto themselves. Further additions of a single material above
its solubility limit will not increase the dissolved portion that
is absorbable by the test organisms, a n d therefore is not
bioavailable. The conclusion of these tests should be "no
acute toxicity at the m a x i m u m water solubility of the substance."
Sometimes tests are conducted as limit tests. These are tests
in which the substance is added in an a m o u n t greater than its
solubility to meet arbitrary toxicity limits (usually regulatory), such as 100 mg/L. In this example, if less than 50% mortality is observed, the LC50 is reported as >100 mg/L and is
considered to have minimal toxicity. There are two potential
sources of error inherent in this approach:
The presence of minor components that are water-soluble
may affect the results. At additions above the water solubility of the main substance, the contaminants may continue to dissolve and may constitute a higher percentage of
the water solution than the substance itself. In these cases,
the toxicity observed is generally erroneously ascribed to
the main substance.

Solubility is greater than LC50


<ind toxiciry is lilceiy
ro -J

a. S

-1 Cut-off Point

1= o
i i *^

2 S
oO
w -I

feg"

S-J

5 SI

''inXParaffins jo fish'r'',

v..-js!if-.:A'.v-;'r'.':"''-'L!--'' ,
^ >.(iV;7.':><'f;',jiS';r,;:,i.,.Xi .1
'f>viTSr'!ift'Vr'fsdl'iibility is less than.Lc;
<-i -'^'''il'Jo' w ' - . ' . - i
-5 rt''t>.'.,,i,'.T.-^ ', and (toxicity
toxicity is not expect
-6 -r4

-.X-

10

12

14

Carbon Number
Igggi Log Water Solubility of n-Paratfin (mM / L)

FIG. 6Relationship of water solubility and aquatic toxicity


of linear paraffins (adapted from [7]).

The occurrence of physical effects caused by the undissolved test material. Such effects may become confused
with the chemiccJ toxicity of the bioavailable portion. Examples of such problems cire the fouling of fish gills by oil
droplets, which causes suffocation, or surface entrapment
of Daphnia in a surface film of a chemical, causing immobility (an endpoint in the Daphnia acute toxicity test).
In some cases, emulsifiers or solvents are used to attain solution of poorly soluble substances. Generally, these aids only
speed dissolution to equilibrium and do not significantly influence solubility. If there is n o associated toxicity with these
dissolution aids, there is n o problem with this procedure. If
large amounts of such materials are used and the water properties are significantly affected, material a m o u n t s may be put
into solution above its water solubility. In this case, there are
concerns with this approach. It may distort the environmental conditions prevailing in the test system a n d may significantly alter the test results, which further complicates its interpretation [20].
Complex

Mixture

Toxicity

Fuels and lubricants do not consist of a single chemiccJ compound. Some products consist of isomers with a similar number of carbons that differ primarily in branching pattern. As
a result, the toxicity of these materieds is similar between individual components, since isomeric differences tj^sically
have little effect on aquatic toxicity. In contrast, other materials are composed of components that vary significantly in
carbon n u m b e r and chemical characteristics. Consequently,
evaluating the toxicity of these materials is more complicated
and involves both the amount and toxicity of individual components. Most hydrocarbons are believed to be toxic by the
same mode of action and so are considered to have additive
toxicity. Thus, the toxic unit (TU) approach can be used to
predict the acute toxicity of such products [21]. This approach involves the following steps:
1. A TU for each component in the product is determined. A
TU is defined as the aqueous concentration of the component divided by the component's corresponding LC50.
2. The TUs for each component in the mixture are summed.
3. If the s u m of TUs > 1 , toxicity is expected; whereas, if the
sum of TUs is < 1, toxicity is not expected.
For complex mixtures of poorly water-soluble substances,
another challenge becomes apparent in testing and evaluating the results. For complex mixtures there is n o exact definition of water solubility. Each component may have a different water solubility so that with increasing additions of the
substance to water, some components reach their solubility
limit, become insoluble and float on the surface, while other
components continue to dissolve. In fact, a complex equilibrium is established between the insoluble chemical component phase (usually at the surface) and the water, never quite
reaching true saturation for any but the least soluble component (Fig. 1).
Additions of a complex material to water at levels beyond
the water solubility of the components results in a solution
and a toxicity measurement which does not accurately reflect
the composition or toxicity of the complete material. Some
scientific and regulatory organizations have suggested using
the "Lethal Loading" approach to overcome these difficulties

CHAPTER 34: ENVIRONMENTAL CHARACTERISTICS OF FUELS AND LUBRICANTS


[20]. This test methodology is specifically for poorly watersoluble complex mixtures and bases the toxicity measurement on the a m o u n t of substance added to water (not the
concentration of the dissolved components that the organism
is exposed to). The "amount of substance added" has been
dubbed the "loading" as a simpler term. The toxicity value derived from this testing approach is described as LL50 (ELso)
for "lethal loading, 50%" ("effect loading 50%") to distinguish
the results from tests on soluble, simple substances (LC50 or
EC50). For fuels a n d lubricants, the "Lethal Loading" approach is preferred for developing information on the quantity of released material that might be required to initiate significant ecologiccd risk and classification/labeling schemes.
The lethal loading approach is not a reliable surrogate for
quantified exposure data. An uninformed reader may confuse the loading values for the exposure values (which are
usueJly much smaller than the loading values) and underestimate the inherent toxicity of a material. Nor is this approach
the same as the nominal concentration since:
entire substance is generally not all dissolved
dissolved fraction is different in composition from the substance
composition of the dissolved fraction changes with the
loading and often different components predominate at
different loadings
The information derived from the different exposure approaches is of great value if applied to appropriate environmental situations.
An additional reason for the use of a separate (LL50) terminology is that when conducting lethal loading tests, it is generally unknown whether the water phase is a true solution.
The test substcince is brought to equilibrium with water at
each concentration (loading) to be tested. The portion of substance which separates after equilibration is generally removed and the aqueous phase referred to as the "water accommodated fraction" (WAF). The WAF may be a solution or
a n emulsion. Unlike previous methodologies, dilutions of the
WAF are not tested but rather WAFs are prepared at each
loading tested. This allows the toxicity result to be related to
the entire substance, giving a result that is relevant to realistic environmental situations. For example, if a product spill
occurs, it will not be of a concentrated water extract of the
substance but of the whole substance (generally) at rather
low substance to water ratios. LL50 data allows an immediate
quantitative assessment of how m u c h substance in a given
volume of water is likely to result in toxicity [20,22].
Beyond the problems of low water solubility, some materials also pose the additional problem of being quite volatile
from water (high Henry's Law Constant). The same discussion given above for volatile substances applies here, since
such substances need to have the water concentrations held
constant. The difficulty is more operationcil than conceptual,
since the composition of the WAF is usucdly unknown and
varies with the loading. It is necessary to test in closed systems with very close attention to minimizing any air spaces
or losses to air of volatile components either in performing
the test or in preparing the WAF. Generally, water concentrations of one or more volatile components are evaluated analytically, not to measure exposure concentration, but rather
to confirm that equilibrium is achieved in WAF preparation,
and that losses to air are minimized during exposures.

901

Standardized Toxicity Test ProceduresAcute


The general approach to all toxicity tests is to expose the organisms to a series of concentrations of the test substance.
The concentrations are chosen, often based on some preliminary tests, so that the biological effect (e.g., mortality) occurs over the range of concentrations. At the lowest concentration, little to n o effect is observed, while at the highest
concentration the effect is maximal. See Table 6 for a listing
and description of standardized environmental toxicology
test methods.
Aquatic

Toxicity

Tests

Tests to determine the aquatic toxicity of substances have


been in place longer than tests in other media. The intention
is to provide testing at different levels within the aquatic food
web. Algae, invertebrates (which graze on the algae), and fish
(which feed on the invertebrates), are included in the usual
aquatic testing scheme. A variety of species have been identified which are used as standard test organisms in these studies (Fig. 5). The intent is to have representative or indicator
species that have the following characteristics:
life histories are well understood and can be cultured in the
laboratory
survive well in the laboratory
are relatively sensitive to a broad range of toxins
are well studied so that their responses may be readily interpreted
These species are intended to be a conservative representation
of the entire aquatic environment because of the preference
for selecting sensitive species and usually sensitive life stages
for testing. The species frequently selected for freshwater toxicity tests are the fishrainbow trout {Oncorhynchus
mykiss)
or fathead minnow (Pitnephales promelas), invertebrate^waterflea (Daphnia magna and Ceriodaphnia dubia), and green
algae {Selenastrum capricomutuni).
(The scientific n a m e of
this green alga has recently been changed to Pseudokirchneriella subcapitata (Korshikov) Hindak [23]. In that this n a m e is
not yet in common use, the name Selenastrum
capricomutum
will be used in this document.) Data resulting from toxicity
tests are generally used to calculate the concentration of material that will adversely affect 50% of the test orgcinisms (i.e.,
LC50, LL50, a n d EC50).

Tests With

Algae

Cultures of algae in their exponential growth phase are exposed to various concentrations of a substEince over several
generations under defined conditions. Cell density is determined by microscopic counting of cells or by a spectrophotometric m e a s u r e m e n t of chlorophyll. The inhibition of
growth in relation to a control (non-exposed) culture over a
fixed period of time is determined. The algal cell density in
each flask is determined at 24, 48, and 72 h (and 96 h for
some test methods) after the start of the test. The mean cell
density for each concentration is plotted against time to
produce growth curves. The growth endpoint is determined
by comparing the area under the growth curves for each
concentration against the control. The average specific
growth rate (the increase in cell density over time) is also
evaluated (D 3978-80 (1998) Standard Practice for Algal
Growth Potential Testing with Selenastrum capricomutum;

902

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

E 1218-97a Standard Guide for Conducting Static 96-h Toxicity Tests with Microalgae). Examples of growth curves and
exposure-response curves (for both endpoints) for the effects of Light Naphtha on Selenastrum capricomutum are
depicted in Fig. 7. Because several generations of algal cells
are exposed in this test system, it is sometimes referred to
as a chronic test.
Tests With Invertebrates
Acute toxicity tests with invertebrates generally expose organisms to a potentially toxic substance for 2-4 days. This period of exposure encompasses at least one sensitive period of
growth during the juvenile life-stage. In the acute immobilization test with Daphnia, effects on the swimming capability are investigated. The number of immobile organisms for
each concentration is compared to the control to calculate
the ECso value. An example of the exposure-response curve

for the effect of Light Naphtha on Daphnia magna is depicted


in Fig. 7.
Tests With Fish
A variety of fish are routinely used for acute toxicity tests.
One of the most widely utilized species is the rainbow trout,
Oncorhynchus mykiss (formerly Salmo gairdneri). Fish are
exposed to the test substance for a 96-h period. Mortality observations are performed daily and the concentration that
kills 50% of the fish (LC50) is calculated for each observation
period. An example of the exposure-response curve for the effect of Light Naphtha on Rainbow Trout is depicted in Fig. 7.
The test may be performed under flow-through, semi-static
(solution is renewed at regular intervals), or static (no replacement of solution) conditions as long as constant environmental conditions and test material concentrations are
maintained.

100

ii 3 x
0 (0
."- o>
t - *-

80
60

*0

4U

20

S!

DC

Light Naphtha Loading (mg / L)

FIG. 7Exposure-Response curves for acute toxicity tests with algae, Daphnia,
and Rainbow Trout for exposure to light naphtha (adapted from [7]).

CHAPTER

34: ENVIRONMENTAL

Standardized Toxicity Test ProceduresChronic


and Subchronic
There are a variety of chronic toxicity test exposures:
Short term chronic, where orgainisms are exposed for a relatively short duration (often seven days) during a critical
life-stage
Prolonged toxicity tests (usually two or more weeks)
Full-life cycle test (usually two to three generations).
The chronic tests all have in c o m m o n the measurement of
sub-lethal effects, e.g., growth (weight or length), development, r e p r o d u c t i o n (fecundity, n u m b e r of offspring produced), or survival of offspring (Table 6). These endpoints are
important to the survival of the population and are thus considered m o r e sensitive endpoints t h a n those of the acute
tests. Endpoints for chronic toxicity tests are usually expressed as a calculated concentration with a low level of toxicity (e.g., ECio) or as a concentration that is not statistically
different than the control. The no observable effect concentration (NOEC) is the effect value corresponding to greatest
concentration of the test substance that is not statistically different when compared to the control. The lowest observable
effect concentration (LOEC) is the effect value corresponding
to the lowest concentration of the test substance that is statistically different when compared to the control. See Table 6
for a listing and description of standardized environmental
toxicity test methods.
Tests With

Invertebrates

A c o m m o n chronic toxicity test with invertebrates is the


Daphnia Reproduction Test in which less t h a n 24-hr old
daphnia are exposed to a range of test substance concentrations for at least 14 days. Within this time period, each
healthy daphnid can produce three or more broods of young.
The n u m b e r of broods and the n u m b e r of young per brood
are recorded. This test may be extended to three or four
weeks, in which six to nine broods of young should be produced. This test is performed u n d e r semi-static or flowthrough conditions. Both survival of the peirent generation
and the n u m b e r of young produced are evaluated. See Table
6 for other test methods using invertebrates.
Tests With

CHARACTERISTICS

OF FUELS AND LUBRICANTS

903

Length and weight data


Any abnormalities observed.
The exposure period for the ejirly life-stage test varies for
each species; for example, tests with the warm, marine water
fish (Sheepshead m i n n o w ) t e r m i n a t e after 28-days posthatch, whereas tests with the cold, freshwater fish (Rainbow
trout) terminate after 60-days post-hatch.
Non-Aquatic Toxicity Tests
Sediment

Toxicity

Tests

Sediment tests are primarily performed on invertebrates,


which will either burrow into or ingest the sediment, using
standard test protocols developed for freshwater amphipods
{Hyalella azteca), midges (Chironomus tentans, C. riparius),
mayflies (Hexagenia sp.), worms (Tubifex tubifex), saltwater
amphipods (Rhepoxynius abronius, Eohaustorius sp.), and
polychaetes {Neanthes arenacoedentata, N. virens). A control
sediment can be spiked with a test chemical or a contaminated natural sediment can be tested. Exposure ranges from
10-30 days, with renewal of the overlying water during extended periods. Endpoints evaluated during short-term acute
tests can consist of survival (LC50), growth and development
(EC50), and reproduction (egg production and n u m b e r of
young produced).
Terrestrial

Toxicity

Tests

As with aquatic toxicity tests, a variety of species have been


identified which are used as standard test organisms in terrestrial studies. These studies are focused on plants and animals that live in soil. For some applications, birds are tested
[24]. See Table 6 for c o m m o n invertebrate and plant test
methods. The plant toxicity studies allow the use of a very
long list of species, most of which are grains or vegetables of
commercial or native value. The acute studies relate the concentration of the chemical or diet to the mortality of the test
organism or to germination (in the case of plants). For many
tests with soil, the test material is dissolved, or emulsified in
de-ionized water and then thoroughly mixed with artificial or
reference soil. Diluting a contaminated soil with an artificial
or reference soil, then exposing the organisms, can allow testing of a field sample.

Fish

There eire two c o m m o n chronic toxicity tests for fish. The


first is a 14-day prolonged test, which is performed under
similar conditions as the acute toxicity test, previously discussed. A representative weight and length measurement is
taken for the fish, at the start of the test. The test is performed
using either semi-static or flow-through exposure conditions
for 14 days. At termination, all surviving fish Eire weighed and
measured. The NOEC a n d LOEC values are determined
based on survival, weight or length, or other abnormal effects
observed throughout the test. The second is an early life-stage
test that begins exposure on newly fertilized eggs. This test
encompasses the embryo, larval, and juvenile stages of various fish species (Table 6). A flow-through test design is preferred to semi-static. This test design allows for evaluation of
the following endpoints:
Mortality during the embryonic stage, larval stage, and juvenile stage
Days to hatch, zmd n u m b e r hatched

Tests With

Plants

GenerEilly, a m i n i m u m of three species is exposed to the test


chemical. One of the three species is usually a monocotyledon, and the others dicotyledons (a legume and a root crop).
The test is t e r m i n a t e d 14 days after 50% of the control
seedlings have emerged. Several endpoints are usually evaluated. The n u m b e r of plants that emerge (LC50) and the meem
dry weight at termination (ECso) as compared to the controls
are c o m m o n endpoints. Shoot and/or root length or mass
may also be evaluated for this test.
Tests With

Worms

There are m a n y m e t h o d s for testing material toxicity to


earthworms, including spot application and immersion tests.
Often, a simple paper contact toxicity test cem be used as an
initial screen test to identify those substances that should be
tested in artificial soil. For this test, artificial soil is spiked
with the test chemical, diluted into a concentration series.

904

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

and added to the exposure chambers. Earthworms are rinsed


and placed on top of the soil in each chamber. Since worms
are negatively phototropic (they do not like light), the test is
performed u n d e r continuous lighting to encourage the
worms to borrow and maximize exposure to the soil. Mortality observations are performed after 7 and 14-day exposures
for subsequent LC50 determinations.

HAZARD AND RISK


Ecotoxicity assessments are used to define environmental
h a z a r d s a n d concentration-response relationships which,
w h e n used together with m e a s u r e d or predicted environmental exposure concentrations, enable environmental risk
to be quantified. The distinction between the terms hazard
and risk is important. Hazard refers to the inherent capacity
of a substance to cause an adverse effect. By contrast, risk is
the likelihood that the hazard will occur in the real world,
based on likely exposures. Thus, a product can pose an environmental hazard by causing the death of fish under exposure conditions achieved in laboratory toxicity tests but not
constitute a significant environmental risk if such exposures
have a very low probability of occurring in the aquatic environment.

SUMMARY
Over the past decade or more, n u m e r o u s standard testing
methods and computer-based predictive models have been
developed to help assess the environmental persistence,
biodegradation, and toxicity of materials. Most of these
m e t h o d s have been developed for simple, soluble, nonvolatile substances. In contrast, most fuels and lubricant
products are not defined as such, but rather are mixtures
(simple and complex) of organic molecules, often relatively
insoluble in water, and/or volatile. Further, additives can introduce metals and other inorganic compounds into the mixture. Nevertheless, the same standard methods were and are
used to test these products. This often produces misleading
results and interpretations.
In a mixture, each c o m p o n e n t has properties that are
unique to its structure and composition. As such, a range of
values for a specific characteristic is often more meaningful
than the average value when describing mixtures. Care must
be taken when choosing the test method for producing these
values. Characteristics such as water solubility, vapor pressure, dissociation constant, and sorption can render a specific test method inappropriate for many of these materials.
In many cases, the results of different test methods for the
same basic characteristic (e.g., biodegradation) cannot be directly compared.
Toxicity testing of these materials requires that specicJ
care and consideration be given to the characteristics of the
material. The key to any toxicity test is ensuring that the
test organism is properly exposed to the material being
tested, thus the preparation and maintenance (or appropriate quantification) of the exposure matrix is critical to the
success of the test. For fuels and lubricants, the "Lethal
Loading" approach is preferred when developing informa-

tion on the quantity of released material that might be required to initiate significant ecological risk or for labeling.
This approach is not a reliable surrogate for quantified exposure data. An uninformed reader may confuse the loading
values for the exposure values (which are usually much
smaller than the loading values) and underestimate the inherent toxicity of a material. Various standards, practices,
and guidelines have recently been published that address
the different approaches that are successful and those that
aren't for difficult to test materials.
Terminology
Acute

Aerobic
Anaerobic
BAF
BCF
Bioaccumulation

Bioaccumulation
Factor

Bioconcentration
Factor

Biodegradation

Biota-Sediment
Accumulation
Factor

A brief exposure to a stressor or the effects associated with such an exposure.


It can refer to an instantaneous exposure
or continuous exposure of minutes to a
few days [25].
Taking place in the presence of oxygen
(D 6006-97a).
Taking place in the absence of oxygen (D
6006-97a).
See Bioaccumulation Factor.
See Bioconcentration Factor.
The net accumulation of a substance by
an organism as a result of uptake from
all environmental sources (E 943-97b).
A value that is the ratio of tissue
chemical residue to chemical concentration in an external environmental phase
(i.e., sediment or food). BAF is measured
at steady state in situations where organisms are exposed from multiple
sources (i.e., water, sediment, food), unless noted otherwise [26].
A term describing the degree to which a
chemical can be concentrated in the tissues of an organism in the aquatic environment as a result of exposure to waterborne chemical. At steady state during
the uptake phase of a bioconcentration
test, the BCF is a value that is equal to
the concentration of a chemical in one or
more tissues of the exposed aquatic organisms divided by the average exposure
water concentration of the chemical in
the test [26].
The transformation of a material resulting from the complex enzymatic action
of microorganisms (e.g., bacteria, fungi).
It usually leads to the disappearance of
the parent structure and to the formation of smaller chemical species, some of
which are used for cell metabolism. Although tjTDically used with reference to
microbial activity, it may also refer to
general metabolic breakdown of a substance by any living organism [26].
The steady-state difference between the
concentration of a bioaccumulating
non-polar organic chemical normalized

CHAPTER

BSAF
Chronic

Dissolved
Orgcinic
Carbon

DOC
EC50 or EC50
Effect

Henry's Law
Constant

HLC
Incipient LC50

Indicator
Species

Inherent
BiodegradabiHty

Inhibition
Concentration xx

34: ENVIRONMENTAL

to the organic carbon content of a sediment and the concentration measured in


the total extractable lipids of an organism for which that sediment represents
the source of the contamination in its
habitat [19].
See Biota-Sediment
Accumulation
Factor.
An extended exposure to a stressor (conventionally taken to include at least a
tenth of the life span of a species) or the
effects resulting from such an exposure.
[25].
The fraction of the organic carbon pool
that is dissolved in water and that passes
through a 0.45 /xm glass fiber filter. DOC
quantifies the chemically reactive organic fraction a n d is an accurate measure of the simple and complex organic
molecules maJsing u p the dissolved organic load. The majority of the DOC is
humic substances [26].
See Dissolved Organic Carbon.
See Median Effective Concentration.
A change in the state or dynamics of an
organism or ecological system resulting
from exposure to a chemical or other
stressor (equivalent to response but used
with the emphasis on the chemical) [25].
A partition coefficient defined as the ratio of a chemical concentration in air to
its concentration in water at steady state.
The constant can be dimensionless or
with units [26].
See Henry's Law Constant.
See Inhibition Concentration xx.
The concentration of a chemical that is
lethal to 50% of the test organisms as a
result of exposure for periods sufficiently long (time independent) t h a t
acute lethal action has essentially
ceased. The asymptote (part of the toxicity curve parallel to the time axis) of the
toxicity curve indicates that value of the
incipient LC50, approximately [26].
A species that is surveyed or sampled for
analysis because it is believed to represent the biotic community, some functional or taxonomic group, or some population that cannot be readily sampled
or surveyed [25].
Classification of chemicals for which
there is unequivocal evidence of
biodegradation (primary or ultimate) in
any test of biodegradability [13].
A point estimate of the chemical concentration that would cause a given percent
reduction (e.g., IC25) in a (typically) nonlethal biological measurement of the test
organisms, such as reproduction or
growth [26].

CHARACTERISTICS
Inoculum

LC50 or LC50
Lethal Load xx

Loading Rate

LOEC
Lowest Observed
Effect
Concentration

Median Effective
Concentration

Median Lethal
Concentration

OF FUELS

AND LUBRICANTS

905

Living spores, bacteria single celled organisms, or other live materials that are
introduced into a test medium (D 638499a).
See Octanol-water Partition Coefficient.
See Median Lethal Concentration.
A statistically or graphically estimated
loading rate of test material that is expected to be lethal to xx% of a subpopulation of organisms under specified conditions.
DiscussionThis terminology should be
used for lubricants instead of the standard LCxx to designate that the material
is not completely soluble at the test treatment rates (D 6384-99a).
The ratio of test material to water (in
mg/L) used in the preparation of a WAF
[20].
See Lowest Observed Effect Concentration.
The lowest concentration of a material
used in a toxicity test that has a statisti
cally significant adverse effect on the exposed population of test organisms compared with the controls. Also called the
lowest observed adverse effect level
(LOAEL) [26].
The concentration of a material in water
to which test organisms are exposed
that is estimated to be effective in producing some sublethal response in 50%
of the test organisms. The EC50 is usually expressed as a time-dependent
value (e.g., 24 h or 96 hr EC50). The sublethal response elicited form the test organisms as a result of exposure to the
test material must be clearly defined.
For example, test organisms may be immobilized, lose equilibrium, or undergo
physiological or behavioral changes
[26].
The concentration of material in water
to which test organisms are exposed that
is estimated to be lethal to 50% of the
test organisms. The LC50 is often expressed as a time-dependent value (e.g.,
24 h or 96 h LC50; the concentration estimated to be lethal to 50% of the test organisms after 24 or 96 h of exposure).
The LC50 may be derived by observation
(i.e., 50% of the test organisms may be
observed to be dead in one test material),
by interpolation (i.e., mortality of more
than 50% of the test organisms occurred
at one test concentration and mortality
of fewer than 50% of the test organisms
died at a lower test concentration, and
the LC50 is estimated by interpolation
between the two data points), or by calculation (i.e., the LC50 is statically de-

906 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

NOEC
No Observed
Effect
Concentration

Octanol-Water
Partition
Coefficient

Primary
Biodegration
QSAR
Quantitative
Structure
Activity
Relationship
Readily
Biodegradable

SAR
Sorption

Structure-Activity
Relationship

Toxic Unit

rived by analysis of mortality data from


all test concentrations) [26].
See No Observed Effect Concentration.
The highest concentration of a material
in a toxicity test that has no statistically
significant adverse effect on the exposed
population of test organisms compared
with the controls. Also called the n o observed adverse effect level (NOAEL) or
the no observed effect level (NOEL) [26].
The ratio of a chemical's solubility in
n-octanol and water at steady state; also
expressed as P. The logarithm of P or
Kow (i-C-, log P or log Kovv) is used as an
indication of a chemical's propensity for
bioconcentration by aquatic organisms
[26].
Degradation of the test substance resulting in a change in its physical or chemical properties, or both (D 6006-97a).
See Structure-Activity Relationship.
See Structure-Activity Relationship.

An arbitrary classification of chemicals


that have passed certain specified
screening tests for ultimate biodegradability; these tests are so stringent that it
is a s s u m e d t h a t such c o m p o u n d s will
rapidly a n d completely biodegrade in
aquatic environments u n d e r aerobic
conditions [13].
See Structure-Activity Relationship.
The process by which molecules of a
chemical dissolve into or are retained on
the surface of a material. Inclusive of absorption and adsorption processes [27].
Studies relating the structure (and related properties) of chemicals to their
activities in biological systems. SARs are
used to assist in explaining (and predicting) the occurrence and mechanisms of
biological responses to chemicals and to
aid in prediction of incidence and magnitude. Although lethal and sublethal
toxicity test results are often employed,
other biological activities, such as bioaccumulation, biodegradation, a n d biotransformation, may also be used. SARs
can also be used to explain or predict
physiochemical characteristics of chemicals. Also called quantitative structureactivity relationships (QSARs) [26].
The strength of a chemical (measured in
some unit) expressed as a fraction or
proportion of its threshold acute effect
concentration (measured in the same
unit). The strength may be calculated as
follows: toxic unit = actual concentration of chemical in solution/threshold ef-

Toxicity

TU
Ultimate
Biodegradation

WAF
Water
Accommodated
Fraction

Water Soluble
Fraction

WSF

feet concentration. For the case where


1.0 toxic unit equal the incipient LC50, a
TU greater t h a n 1.0 should cause the
death, during long exposures, of m o r e
t h a n half of a group of aquatic organisms. If the TU is less than 1.0, less than
half of the organisms should be killed
[26].
The inherent potential or capacity of an
agent or material to cause adverse effects in a living organism when the organism is exposed to it [26].
See Toxic Unit.
Degradation achieved when a substance
is totally utilized by microorganisms resulting in the production of carbon dioxide (and possibly methane in the case of
anaerobic biodegradation), water, inorganic c o m p o u n d s , a n d new microbial
cellular constituents (biomass or secretions, or both) (D 6006-97a).
See Water Accommodated Fraction.
The predominately aqueous portion of a
mixture of water a n d a poorly watersoluble material that sepEirates in a specified period of time after the mixture has
undergone a specified degree of mixing
a n d includes water, dissolved components, a n d dispersed droplets of the
poorly water soluble material.
DiscussionThe composition of t h e
WAF depends on the ratio of poorly soluble material to w a t e r in the original
mixture as well as on the details of the
mixing procedure (D 6384-99a).
The filtrate or centrifugate of the water
accommodated fraction that includes all
parts of the WAF except the dispersed
droplets of the poorly soluble material
(D 6384-99a).
See Water Soluble Fraction.

REFERENCES
[1] Bartz, W. J., "Lubricants and the Environment," Tribology International, Vol. 31, Nos. 1-2, 1998, pp. 3 5 ^ 7 .
[2] Lyman, W. J., "Transport and Transformation Processes, in
Fundamentals of Aquatic Toxicology: Effects," Environmental
Fate and Risk Assessment, G. M. Rand, Ed., Taylor & Francis,
Washington, DC, 1995, pp. 449-492.
[3] Mackay, D., Bums, L. A., sind Rand, G. M., "Fate Modeling, in
Fundamentals of Aquatic Toxicology: Effects," Environmental
Fate and Risk Assessment, G. M. Rand, Ed., Taylor & Francis,
Washington, DC, 1995, pp. 563-588.
[4] Lipnick, R. L., "Structure-Activity Relationships, in Fundamentals of Aquatic Toxicology: Effects," Environmental Fate and
Risk Assessment, G. M. Rand, Ed., Taylor & Francis, Washington, DC, 1995, pp. 609-656.
[5] Cisson, C. M., Rausina, G. A., and Stonebraker, P. M. "Human
Health and Environmental Hazard Characterization of Lubricating Oil Additives," Lubrication Science, Vol. 8, No. 2, 1996,
pp. 145-177.

CHAPTER 34: ENVIRONMENTAL CHARACTERISTICS OF FUELS AND LUBRICANTS


[6] Lyman, W. J., "Octanol/Water Partition Coefficient," Handbook
of Chemical Property Estimation Methods: Environmental
Behavior of Organic Compounds, W. J. Ljraan, W. F. Reehl, and D. H.
Rosenblatt, Eds., McGraw-Hill, NY, 1982, pp. 1-54.
[7] A Practical Guide to Protecting Man and the
Environment,
Machelen, Exxon Chemical Europe, Inc., Machelen, Belgium,
1999.
[8] A Critical Review of Toxicity Values and an Evaluation of the Persistence of Petroleum Products for Use in Natural Resource Damage Assessments, American Petroleum Institute, Washington,
DC, 1995, p. 196.
[9] Pelletier, M. C , Burges, R. M., Ho, K. T., Huhn, A., McKinney,
R. A., and Ryba, S. A., "Phototoxicity of Individual Polycyclic
Aromatic Hydrocarbons and Petroleum to Marine Invertebrate
Larvae and Juveniles," Environmental Toxicology and Chemistry,
Vol. 16, No. 10, 1997, pp. 2190-2199.
[10] Wrabel, M. L. and Peckol, P., "Effects of Bioremediation on Toxicity and Chemical Composition of No. 2 Fuel Oil: Growth Responses of the Brown Alga Fucus Vesiculosus," Marine Pollution
Bulletin, Vol. 40, No. 2, 2000, pp. 135-139.
[11] OECD Guideline for Testing of Chemicals: 303ASimulation
TestAerobic Sewage Treatment: Coupled Units Test, Organization for E c o n o m i c Cooperation a n d Development, Paris,
1981, p . 14.
[12] OECD Guideline for Testing of Chemicals: 301Ready
Biodegradability, Organization for Economic Cooperation and
Development, Paris, 1992, p. 62.
[13] Harmonized Test Guidelines: 835Fate, Transport and Transformation Test GuidelinesOPPTS 835.3110 Ready Biodegradability, U.S. Environmental Protection Agency, Office of Prevention, Pesticides, and Toxic Substances, Washington, DC,
1998, p. 45.
[14] Petroleum Microbiology, R. M. Atlas, Ed., Macmillan Publishing
Company, NY, 1984, p. 692.
[15] Microbial Degradation of Organic Compounds, Isted., D. T. Gibson, Ed., Microbiology Series, Vol. 13, A. I. Laskin and R. I.
Mateles. Eds., Marcel Dekker, NY, 1984, p. 535.
[16] Parkerton, T. F., Hexadecene Biodegradation Data for Closed Bottle Test and Manometric Respirometry Test Methods, ExxonMobil
Biomedical Sciences, Inc., 2001.
[17] Bysshe, S. E., "Bioconcentration Factor in Aquatic Organisms,"
Handbook of Chemical Property Estimation Methods: Environmental Behavior of Organic Compounds, W. J. Lyman, W. F.
Reehl, and D. H. Rosenblatt, Eds., McGraw-Hill, NY, 1982,
p. 30.
[18] Spacie, A., McCarty, L. S., and Rand, G. M., "Bioaccumulation
and Bioavailability in Multiphase Systems," Fundamentals of
Aquatic Toxicology: Effects, Environmental Fate, and Risk Assessment, G. M. Rand, Ed., Taylor & Francis, Washington, DC,
1995, pp. 493-521.
[19] McFarland, V. A., Evaluation of Field-Generated
Accumulation
Factors for Predicting the Bioaccumulation Potential of SedimentAssociated PAH Compounds, U.S. Army Corps of Engineers,
Washington, DC, 1995, p. 158.
[20] Guidance Document on Aquatic Toxicity Testing of Difficult Substances and Mixtures, OECD, Paris, 2000, p. 53.
[21] Guidance Document on Application and Interpretation of Singlespecies Tests in Environmental
Toxicology,
Environment
Canada, E n v i r o n m e n t Technology Centre, Ottawa, Ontario,
Canada, 1999, p. 203.
[22] Singer, M. M., Aurand, D., Bragin, G. E., Clark, J. R., Coelho, G.
M., Sowby, M. L., and Tjeerdema, R. S., "Standardization of the
Preparation and Quantitation of Water-Accommodated Fractions of Petroleum for Toxicity Testing," Marine Pollution Bulletin, Vol. 40, No. 11, 2000, pp. 1007-1016.
[23] Nomenclature for "Selenastrum capricomutum,"
International
Organization for Standardization, Geneva, 1999, p. 4.

907

[24] OECD Guideline for Testing of Chemicals: 205Avian Dietary


Toxicity Tests, Organization for Economic Cooperation and Development, Paris, 1984, p. 9.
[25] Ecological Risk Assessment, G. W. Suter, Ed., Lewis Publishers,
Boca Raton, FL, 1993, p. 538.
[26] Fundamentals
of Aquatic Toxicology: Effects,
Environmental
Fate, and Risk Assessment, 2nd ed. G. M. Rand, Ed., Taylor &
Francis, Washington, DC, 1995, p. 1125.
[27] Bioaccumulation: How Chemicals Move from the Water into Fish
and Other Aquatic Organisms, American Petroleum Institute,
Washington, DC, 1997, p. 54.
[28] "C-4 Biodegradation: Determination of the "Ready" Biodegradability," Official Journal of the European Communities, L383A,
29 Dec. 1992, pp. 187-226.
[29] ISO 7827: Water Quality, Evaluation in an Aqueous Medium of
the "Ultimate" Aerobic Biodegradability of Organic Comp o u n d s M e t h o d by Analysis of Dissolved Organic Carbon
(DOC), ISO, Geneva, 1994, p. 7.
[30] ISO 9439: W a t e r Quality, Evaluation of Ultimate Aerobic
Biodegradability of Organic Compounds in Aqueous Medium
Carbon Dioxide Evolution Test, ISO, Geneva, 1999, p. 17.
[31] Harmonized Test Guidelines: 835Fate, Transport and Transformation Test Guidelines, U.S. EPA, Washington, DC, 1996.
[32] OECD Guideline for Testing of Chemicals: 302CInherent
Biodegradability: Modified MITI Test (II), Organization
for Economic Cooperation a n d Development, Paris, 1981,
p. 21.
[33] ISO 10707: Water QualityEvaluation in an Aqueous Medium
of the "Ultimate" Aerobic Biodegradability of Organic CompoundsMethod by Analysis of Biochemical Oxygen Demand
(Closed Bottle Test), ISO, Geneva, 1994, p. 9.
[34] ISO 10708: Water QualityEvaluation in an Aqueous Medium
of the Ultimate Aerobic Biodegradability of Organic CompoundsDetermination of Biochemical Oxygen Demand in a
Two-Phase Closed Bottle Test, ISO, Geneva, 1997, p. 17.
[35] ISO 9408: Water QualityEvaluation of Ultimate Aerobic
Biodegradability of Organic Compounds in Aqueous Medium
by Determination of Oxygen Demand in a Closed Respirometer,
ISO, Geneva, 1999, p. 17.
[36] OECD Guideline for Testing of Chemicals: 306Biodegradability in Seawater, Organization for Economic Cooperation and
Development, Paris, 1992, p. 27.
[37] OECD Guideline for Testing of Chemicals: 302BZahnWellens/EMPA Test, Organization for Economic Cooperation
and Development, Paris, 1992, p. 8.
[38] ISO 9888: Water QualityEvaluation of Ultimate Aerobic
Biodegradability of Organic Compounds in Aqueous Medium
Static Test (Zahn-Wellens Method), ISO, Geneva, 1999, p. 11.
[39] OECD Guideline for Testing of Chemicals: 302AInherent
Biodegradability: Modified SCAS Test, Organization for Economic Cooperation and Development, Paris, 1981, p. 7.
[40] ISO 9887: Water QualityEvaluation of the Aerobic Biodegradability of Organic Compounds in an Aqueous MediumSemicontinuous Activated Sludge Method (SCAS), ISO, Geneva,
1992, p. 9.
[41] ISO 11733: Water QualityEvaluation of the Elimination and
Biodegradability of Organic C o m p o u n d s in an Aqueous
MediumActivated Sludge Simulation Test, ISO, Geneva,
1995, p. 15.
[42] OECD Guideline for Testing of Chemicals: 304aInherent
Biodegradability in Soil, Organization for Economic Cooperation and Development, Paris, 1981, p. 11.
[43] ISO 14239: Soil QualityLaboratory Incubation Systems for
Measuring the Mineralization of Organic Chemicals in Soil Under Aerobic Conditions, ISO, Geneva, 1997, p. 17.
[44] ECETOC, "Evaluation of Anaerobic Biodegradation," Technical
Report No. 28, ECETOC: Brussels, 1988.

908 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


[45] ISO 11734: Water QualityEvaluation of the "Ultimate" Anaerobic Biodegradability of Organic C o m p o u n d s in Digested
SludgeMethod by Measurement of the Biogas Production,
ISO, Geneva, 1995, p. 16.
[46] CEC L-33-A-93 Test Method, Coordinating European Council,
Brussels, 1995, p. 18.
[47] ISO 14593: Water QualityEvaluation of Ultimate Aerobic
Biodegradability of Organic Compounds in Aqueous Medium
Method by Analysis of Inorganic Carbon in Sealed Vessels (C02
Headspace Test), ISO, Geneva, 1999, p. 16.
[48] A Test Method to Assess the 'Inherent' Biodegradability of Oil
Products, CONCAWE, Brussels, 1999, p. 33.
[49] Battersby, N. S., "The ISO Headspace C 0 2 Biodegradation
Test," Chemosphere, Vol. 34, No. 8, 1997, pp. 1813-1822.
[50] Biological Test Method: Toxicity Test Using Luminescent Bacteria
(Photobacterium phosphoreum),
Environment Canada, Environment Technology Centre, Ottawa, Ontario, Canada. 1992,
p. 61.
[51] OECD Guideline for Testing of Chemicals: 201Alga, Growth
Inhibition Test, Organization for Economic Cooperation and
Development, Paris, 1984, p. 14.
[52] "C-3 Algal Inhibition Test," Official Journal of the European
Communities, 1992, pp. 179-187.
[53] H a r m o n i z e d Test Guidelines: 850Ecological Effects Test
Guidelines, U.S. EPA, Washington, DC, 1997.
[54] ISO 8692: Water QualityFresh Water Algal Growth Inhibition
Test with Scenedesmus subspicatus and Selenastrum capricornutum, ISO, Geneva, 1989, p. 6.
[55] ISO 10253: Water QualityMarine Algal Growth Inhibition
Test with Skeletonema costatum and Phaeodactylum tricornutum, ISO, Geneva, 1995, p. 9.
[56] Biological Test Method: Growth Inhibition Test Using the
Freshwater Alga Selenastrum c a p r i c o r n u t u m . Environment
Canada, E n v i r o n m e n t Technology Centre, Ottawa, Ontario,
Canada. 1992, p. 41.
[57] Biological Test Method: Test for Measuring the Inhibition of
Growth Using the Freshwater Macrophyte, Lemna minor. Environment Ccinada, Environment Technology Centre, Ottawa, Ontario, Canada. 1999, p. 98.
[58] OECD Guideline for Testing of Chemicals: 202Daphnia sp..
Acute Immobilisation Test and Reproduction Test, Organization for Economic Cooperation and Development, Paris, 1984,
p. 16.
[59] "C-2 Acute Toxicity to Daphnia," Official Journal of the European
Communities, 1992, pp. 172-179.
[60] ISO 6341: Water QualityEvaluation of the Inhibition of the
Mobility of Daphnia m a g n a Straus (Cladocera, Crustacea)
Acute Toxicity Test, ISO, Geneva, 1998, p. 9.
[61] Biological Test Method: Acute Lethality Test Using Daphnia
spp.. Environment Canada, Environment Technology Centre,
Ottawa, Ontario, Canada, 1990, p. 78.
[62] OECD Guideline for Testing of Chemicals: 207Earthworm,
Acute Toxicity Tests, Organization for Economic Cooperation
and Development, Paris, 1984, p. 9.
[63] ISO 11268-1: Soil QualityEffects of Pollutants on Earthworms
(Eisenia fetida)Part 1: Determination of Acute Toxicity Using
Artificial Soil Substrate, ISO, Geneva, 1993, p. 6.
[64] Biological Test Method: Acute Test for Sediment Toxicity Using
Marine o r Estuarine Amphipods, Environment Canada, Envir o n m e n t Technology Centre, Ottawa, Ontario, Canada. 1992,
p. 83.
[65] ISO 14669: Water QualityDetermination of Acute Lethal Toxicity to Marine Copepods (Copepoda, Crustacea), ISO, Geneva,
1999, p. 16.
[66] Biological Test Method: Test of Reproduction a n d Survival

[67]

[68]

[69]

[70]

[71]

[72]

[73]

[74]

[75]

[76]

[77]

[78]

[79]

[80]

[81]

[82]

[83]

[84]

Using the Cladoceran Ceriodaphnia dubia. Environment


Canada, E n v i r o n m e n t Technology Centre, Ottawa, Ontario,
Canada, 1992, p. 72.
ISO 10706: Water QualityDetermination of Long Term Toxicity of Substances to Daphnia m a g n a Straus (Cladocera, Crustacea), ISO, Geneva, 2000, p. 17.
Biological Test Method: Fertilization Assay Using Echinoids
(Sea Urchins and Sand Dollars), Environment Canada, Environment Technology Centre, Ottawa, Ontario, Canada, 1992,
p. 97.
ISO 11268-2: Soil QualityEffects of Pollutants on Earthworms
(Eisenia fetida)Part 2: Determination of Effects on Reproduction, ISO, Geneva, 1998, p. 16.
ISO 11268-3: Soil QualityEffects of Pollutants on EarthwormsPart 3: Guidance on the Determination of Effects in
Field Situations, ISO, Geneva, 1999, p. 8.
OECD Guideline for Testing of Chemicals: 203Fish, Acute
Toxicity Test, Organization for Economic Cooperation and Development, Paris, 1992, p. 9.
Biological Test Method: Reference Method for Determining
Acute Lethality of Effluents to Rainbow Trout, Environment
Canada, E n v i r o n m e n t Technology Centre, Ottawa, Ontario,
Canada, 1990, p. 18.
Biological Test Method: Acute Lethality Test Using Rainbow
Trout, Environment Canada, Environment Technology Centre,
Ottawa, Ontario, Canada, 1990, p. 51.
Biological Test Method: Test of Larval Growth and Survival Using Fathead Minnows, E n v i r o n m e n t Canada, Environment
Technology Centre, Ottawa, Ontario, Canada, 1992, p. 70.
ISO 7346-1: Water QualityDetermination of the Acute Lethal
Toxicity of Substances to a Freshwater Fish (Brachydanio rerio
H a m i l t o n - B u c h a n a n (Teleostei, Cyprinidae))Part 1: Static
Method, ISO, Geneva, 1996, p. 11.
ISO 7346-2: Water QualityDetermination of the Acute Lethal
Toxicity of Substances to a Freshwater Fish (Brachydanio rerio
Hamilton-Buchanan (Teleostei, Cyprinidae ))Part 2: SemiStatic Method, ISO, Geneva, 1996, p. 11.
ISO 7346-3: Water QualityDetermination of the Acute Lethal
Toxicity of Substances to a Freshwater Fish (Brachydanio rerio
Hamilton-Buchanan (Teleostei, Cyprinidae ))Part 3: FlowThrough Method, ISO, Geneva, 1996, p. 11.
ISO 12890: Water QualityDetermination of Toxicity to Embryos and Larvae of Freshwater Fish - Semi-Static Method, ISO,
Geneva, 1999, p. 14.
OECD Guideline for Testing of Chemicals: 204Fish, Prolonged Toxicity Test: 14-Day Study,. Organization for Economic
Cooperation and Development, Paris, 1984, p. 9.
OECD Guideline for Testing of Chemicals: 210Fish, EarlyLife Stage Toxicity Test, Organization for Economic Cooperation and Development, Paris, 1992, p. 18.
Biological Test Method: Toxicity Tests Using Early Life Stages
of Salmonid Fish (Rainbow Trout, Coho Salmon, or Atlantic
Salmon), Environment Canada, Environment Technology Centre, Ottawa, Ontario, Canada, 1992, p. 81.
ISO 10229: Water QualityDetermination of the Prolonged
Toxicity of Substances to Freshwater FishMethod for Evsduating the Effects of Substances on the Growth Rate of
Rainbow Trout (Onchorhynchus mykiss Walbaum (Teleostei,
Salmonidae)), ISO, Geneva, 1994, p. 12.
Parkerton, T. F., Gasoline WAF Composition Data, personal
communication, ExxonMobil Biomedical Sciences, Inc., Clinton, NJ, 2001.
1995 Updates: Water Quality Criteria Documents for the Protection of Aquatic Life in Ambient Water, U.S. EPA, Washington, DC, 1996, p. 114.

MNL37-EB/Jun. 2003

Lubrication and Tribology


Fundamentals
Hong Liang, ^ George E. Totten,^ and Glenn M. Webster-^

LUBRICANTS PLAY A VITAL ROLE IN EVERY INDUSTRY INCLUDING:

ELECTRONIC, automotive, aerospace, forestry, naval, and numerous others. Lubrication failure m a y result in thousands
of dollars of p r o d u c t i o n losses including downtime a n d
equipment failure. Therefore, the general area of lubrication
is one of the most important in industrialized societies.
A lubricant may be a gas, a liquid or a solid and operates by
preventing direct interfaciaJ contact of surfaces in relative
motion to each other and/or minimizing damage when interfacial contact does occur. In this chapter, the fundamental
concept of lubrication a n d w e a r will be discussed. Wear
surfaces, contact geometry and stress, wear mechanisms,
materials properties, and lubrication mechanisms will be addressed. Wear mechanisms will include corrosive, abrasive,
adhesive, fretting, ploughing, and rolling contact fatigue failure. Identification a n d troubleshooting of these w e a r
regimes, particuleirly with respect to bearing and gear wear
under varying lubrication regimes, will be included.
This is the first in a series of three chapters; Chapter 35 (Lubrication Fundamentals), Chapter 36 (Bench Test Modeling),
and Chapter 37 (Lubrication Friction and Wear Testing). In
this chapter, the fundamental principles involved in lubrication and wear processes and how these basic principles are applied to lubrication testing will be discussed. In Chapter 36,
the most commonly encountered bench tests will be discussed
in detail. In addition to describing all of the pertinent engineering details of the standardized tests such as wear contact
conformity, loading, speed, reciprocating or linear motion,
and testing principle being measured, this chapter will provide guidelines for actual testing such as test selection, cleaning, material pair chemistry, and other factors related to currently existing bench tests and those in development. In
Chapter 37, the elements and application tribological design
as it relates to new test development will be outlined in detail.
ASTM G 40 defines tribology as "the science and technology concerned with interacting surfaces in relative motion,
including friction, lubrication, wear and erosion." Since this
chapter addresses basic design principles of tribological
processes involved in lubrication and weeir testing, various
equations are utilized. The applicability of these relationships to tribological testing is an important consideration.
The structure of this chapter is to first address basic principles involved in friction and wear. After friction and wear,
principles of fluid lubrication will be discussed. The last sec-

tion of this chapter will provide a brief overview of additive


chemistry involved in the formulation of lubricants and related testing protocols.

DISCUSSION
Friction
The ASTM D 996 definition of friction is "resistance to relative motion of two bodies in contact." The force (Fp) that
must be applied to an object to initiate and maintain relative
motion is proportional to the applied load (L). The proportionality constant is the coefficient of friction (/A).
F = liL
There are two values reported for the coefficient of friction.
The static co-efficient of friction is used in reference to the initial movement of the object from the rest position and is defined by ASTM D 996 as "the ratio of force required to move
one surface over another, to the total force applied normal to
those surfaces, at the instant motion starts." The kinetic coefficient of friction is used for two surfaces in relative motion
and is defined by ASTM D 996 as "the ratio of force required
to move one body over another, to the total force applied normal to those surfaces, once that motion is in progress." Representative of diy static and kinetic coefficients of friction for
various material pairs are provided in Table 1[1]. It has been
suggested that the best material pair candidates for non-lubricated contacts should exhibit ;u, < 2 [2].
Factors that affect dry sliding friction include [3]:
1. True area of contact between the sliding surface
2. Bond strength between the two bodies at the contact interface
3. Mechzinism of material shear and rupture processes in the
contacting region
The coefficient of friction is often used as a measure of the
transition between boundary lubrication and elastohydrodynamic (EHD) lubrication. The transition between these two
regimes is designated as either "mixed" lubrication or "mixed
EHD." Variation of the coefficient of friction with increasing
film thickness between two metal surfaces is shown schematically in Fig. 1 [4].
Area of True

' Department of Mechanical Engineering, University of Alaska Fairbanks, P.O. Box 755905, Fairbanks, AK 99775-5905.
^ G. E. Totten & Associates, LLC, P.O. Box 30108, 514 N. 86* St.,
Seattle, WA 98103.

Surfaces are are covered with asperities, meaning they are


not perfectly smooth. An asperity is defined by ASTM G 40 as
a "protuberance in the small-scale topographical irregulari-

909
Copyright'

2003 by A S I M International

Contact

www.astm.org

910 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


ties of a solid surface." When two surfaces are in contact, the
"area of true contact" or "real contact area" (Ar) is dependent
on the total area of asperity contact (asperity contact area) as
illustrated in Fig. 2. The area of friction is assumed to be dependent on Ar and shear strength (Ss) [1,3]:

TABLE 1Coefficients of dry static and kinetic sliding friction.


Material Pair

/x (Static)

/A (Kinetic)

Hard steel on Hard Steel


Mild Steel on Mild Steel
Hard Steel on Graphite
Hard Steel on Babbitt(ASTM 1)
Hard Steel on Babbitt (ASTM 8)
Mild Steel on Phosphor Bronze
Mild Steel on Lead
Aluminum on Mild Steel
Magnesium on Magnesium
Teflon on Teflon
Teflon on Steel
Cadmium on Mild Steel
Copper on Mild Steel
Nickel on Nickel
Brass on Mild Steel
Brass on Cast Iron
Zinc on Cast Iron
Copper on Cast Iron
Tin on Cast Iron
Lead on Cast Iron
Aluminum on Aluminum
Cast Iron on Cast Iron
Bronze on Cast Iron

0.78
0.74
0.21
0.70
0.42

0.42
0.57

0.95
0.61
0.6
0.04
0.04
0.53
1.10
0.51
0.85
1.05
1.05
1.10

0.33
0.35
0.34
0.95
0.47

0.46
0.53
0.53
0.44
0.30
0.21
0.29
0.32
0.43
1.40
0.15
0.22

Area of real contact


FIG. 2Illustration of two surfaces in contact,
"area of true contact" or "real contact area" (Ar)
is dependent on the total area of asperity contact. Ui = velocity of surface 1, U2 = velocity of
surface 2,di= asperity hieight of surface 1, 2 =
asperity fieight of surface 2, and h = fluid film
thicicness.

O
-I-'

LL

d
^
O

0.020.01

o
O
Adsorption! Multiple Multiple Multiple
iLayer
: Reaction Reaction 1 Reaction
i Layers
Layers
! Layers
+
+
Liquid
Liquid
Film
Layers
FIG. 1Dependence of coefficient of friction (/u) on the layer thickness between two
metal sliding contact pairs.

CHAPTER 35: LUBRICATION


If the load (L) is carried by asperity contact area (Ar) creating the contact pressure P^ then [1]:
M =

Although conceptually illustrative, in practice the calculation of the coefficient of friction is much more complex requiring the integration of other interfacial bonding and failure modes including [5]:
1. area of true contact
2. friction due to adhesion
3. friction due to ploughing
4. friction due to deformation
Adhesion, ploughing, and deformation are wear processes
that will be described in detail subsequently.
Another wear mode is scuffing, which ASTM G 40 defines
as "a form of weeir occurring in inadequately lubricated tribosystems that is characterized by macroscopically observable changes in surface texture, with features related to the
direction of relative force." Alternatively, ASTM D 4175 defines scuffing as "surface damage resulting from localized
welding at the interface of rubbing surfaces with subsequent
fracture in the proximity of the weld area." An acceptable
scuffing criterion for metals may be estimated from the plasticity index (i/*), which is dependent on the area of true contact [5]:
^=
where : E is the elastic modulus,
Py is the yield pressure,
cr is the root mean square average asperity height
and
P is the radius of contact.
It ^< 0.6, the contact is classified as elastic and if ^ > 1,
the plastic deformation will occur within the contact. From
this relationship, the area of true contact (Ar) is estimated [5]:
For elastic contact:
Ar-

wY

where: Vi < n < 1, W is the normal load and, E is the elastic


modulus.
For plastic contact;
^'-

^ Py

where: C is the proportionality constant and H is the hardness.


Park and Ludema have shown that this approach should be
used with considerable caution. [6].
Friction Due to Adhesion
Adhesive wear is defined by ASTM G 40 as "wear due to localized bonding between contacting solid surfaces leading to
material transfer between two surfaces or loss from either
surface." In some cases, these moving surfaces, such as each
of the four balls in a 4-ball wear testing machine, can actually
weld together and the complete ball assembly may undergo
seizure. Fracture during the adhesive wear process is caused
by the rupture of interfacial adhesive bonds, which are the

AND TRIBOLOGY FUNDAMENTALS

911

summation of all of the component bond strengths within the


contact including, van der Waals, metallic, ionic, and metallic bonds. The adhesive component of the coefficient of friction ifia) has traditionally been determined from:

where: Fa is the interfacial shear strength and L is the load.


Friction Due to Ploughing
An object may undergo a change in its dimensions after applied stress is removed. This is referred to as "plastic deformation." Plasticity is the susceptibility at a certain temperature and loading condition to permanent deformation after
application of sufficient stress to exceed the yield point of the
material.
Ploughing is defined by ASTM G 40 as "the formation of
grooves by plastic deformation of the softer of the two surfaces in relative motion." The formation of a groove in the
material surface may be caused by either wear debris or by
asperities within the wear contact. The contribution due to
ploughing may dominate the friction force. Currently, there
is no reliable model to estimate the contribution to friction
force by ploughing [5]. Figure 3 illustrates typical damage
due to abrasion, scuffing, and ploughing [7].
Friction Due to Deformation
Deformation is a stress-induced change of form or shape. A
material may undergo deformation either plastically, as
defined above, or mechanically. Mechanical deformation is
the dimensional change of a material that occurs from its initial dimensions due to continued cyclic loading over a specific time.
Friction is the most fundamental factor in tribologicaJ processes and therefore, experimental determination of friction
is an important lubrication and wear parameter. ASTM D
4999 describes the evaluation of friction effects on oil cooled
brakes with bronze friction material in combination with
steel disks. Often, surface deformation failure occurs with
ploughing or adhesion when the braking materials are insufficiently lubricated.
Wear Surfaces
Surface Roughness
Real surfaces are covered with asperities, as shown in Fig. 4.
Characterization of surface roughness is fundamentally important. One way to represent surface roughness effects on
lubrication, particularly fatigue life failure, is to use the
Lambda {A) factor (specific film thickness) correlation,
which is defined as [8]:
A = ho/cr
where: ho is the lubricating film thickness and cr is the average surface roughness for the two surfaces coming into asperity contact and is defined as:
If the film parameter A is equal to 1, boundary lubrication
and asperity contact occurs, mixed lubrication occurs when
A = 1-3, and EHD lubrication occurs when A = 3-10 [8].

912 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

FIG. 3Examples of: a) three-body abrasion


occurring using one 10 mm dia. round SUJ 2
steel disc standing (axially) on another 25 mm
dia. round SUJ S45C steel disc lying down flat
(radially). The abrasive is SiC #400 suspended in
paraffin oil. The load on the wear contact is SON,
sliding amplitude is 10 mm, sliding speed is 10
mm/s and the sliding distance is 36 m (source:
Prof. T. Kawazoe, Nagasake University, Nagasaki City, Japan); b) ploughing using the
same SUJ 2 round disk on a 60 mm round tin
(Sn) disc. The contact load is 2.479 N, sliding
speed is 0.3 mm/s, and sliding distance is 50
mm. (source: Prof. T. Kawazoe, Nagasake University, Nagasaki City, Japan); c) ploughing for
a medium carbon steel pair block-on-shaft, load
= 110-184 N, 156-220 rpm and the picture has
250X magnification (source: Dr. Sergey
Tarasov, Institute of Strength Physics and IVIaterials Sciences, Tomsk, Russia); and d) scuffing
as illustrated by the cross-section of an AISI
1045 disk at 2000X showing the highly deformed
zone after scuffing (source: Prof. Liu Jiajun, Tsinghua University, Beijing, PRC).

Table 2 provides a correlation of A factors with fatigue cracking of roller bearings [8]. T3^ically, A factors of 1.2-1.5 are
used for bearing life calculations [9]. Representative surface
roughness values for different types of bearing applications
are summarized in Table 3 [3,8].
The Lambda ratio provides Ein indication of the lubricant
film thickness relative to the surface roughness (asperity
height <T) and clearly ought to be greater than 1 if asperity
contact is to be minimized. Table 2 illustrates reported levels
of damage and fatigue cracking for roller bearings as a function of Lambda value [8].
Increasing Lambda values provide greater fatigue life. In
addition to the general observations indicated in Table 2,
Zaretsky a n d Moyer [10] described this relationship for
rolling element bearings. Townsend a n d Shimski showed
that increasing Lambda values increase surface fatigue life of
gears, as shown in Fig. 5 [11]. The Lambda factor relationship also means that as the surface asperity size increases (increasing surface roughness), the thickness of the lubricating
film m u s t also increase to maintain the magnitude of the

TABLE 2Correlation of lambda (A) and fatigue cracking


of roller bearings.
A Value

Wear Observation

< 1.0
1-1.5
1.5-3.0
a3.0

Surface smearing or deformation


Surface distress accompanied by surface pitting
Surface glazing accompanied by subsurface failure
Minimal wear, long life, eventual subsurface fatigue
failure

TABLE 3Representative values of composite surface finish for


different bearing applications.
Composite Surface Finish
Bearing Application

/im (rms)

Large Industrial
Industrial Off-the-Shelf
Aerospace

0.25
0.12
0.65

Height (^m)
Depth (|i,m)

Width (|im)
FIG. 4Illustration of surface roughness. The peaks covering this sample area
are called "asperities."

(U.in (rms)

10
5
25

CHAPTER 35: LUBRICATION


Lambda factor. Therefore, achieving a fundamental understanding of surface roughness is crucial for tribological
design, testing, and failure analysis.
Although A factors provide a useful approximation of the
interdependence of fluid film thickness and combined surface roughness of bearings, it is an over simplification of the
lubrication problem. For example, thick films may result in
high power losses (efficiency loss) due to oil churning, or excessive operational temperatures may prohibit the required
fluid viscosity, preventing the desired film thickness. In addition, non-newtonian behavior of the oil, often due to the
addition of various additives such as viscosifiers, etc., may
lead to oil film collapse. Therefore, the use of A factors for
characterizations for thin film lubrication should be used
with caution, particularly for a film thickness that is less than
the combined surface roughness parameter [9].

AND TRIBOLOGY FUNDAMENTALS

913

(a) M-system

(b) Ten-point average

Analysis of Surface Roughness Data


Experimental surface roughness data, typiccdly obtained by
profilometry, is numerically analyzed [12] to obtain an average roughness value such as those provided in Table 4. Dur-

5
I

(c) Least squares


FIG. 6illustration of numerical methods used to calculate
surface roughness values.

I
&

Specific Film Thicicness Ratio


FIG. 5Increasing Lambda values
(Specific Film Ratio) provide greater fatigue life.
TABLE 4Surface roughness nits
and interconverslons.
Roughness Values (Ra)
/Am

/lin

Grade

50
25
12,5
8.3
3.2
1.6
0.8
0.4
0.2
0.1
0.05
0.025

2000
1000
500
250
125
63
32
16
8
4
2
1

N12
Nil
NIO
N9
N8
N7
N6
N5
N4
N3
N2
Nl

ing numerical analyses of experimental data it is necessary to


establish a roughness line through the topographical peaks
and valleys. Computerized data analyses are usually performed by one of the three methods, as illustrated in Fig. 6
[13].
1. M-System^A line is selected that passes through the topographical profile such that the areas above and below the
line are equal, as shown in Fig. 6a.
2. Ten Point Average^A line is drawn through the center of
the five highest peaks and the five lowest valleys as shown
in Fig. 6b.
3. Least Squares Reference^A least squares average through
the topographical peaks and the valleys is determined as
shown in Fig. 6c.
The texture of a surface is complicated and there are many
parameters used to quantify the various surface characteristics. Three methods often used to numerically represent are
surface roughness, centerline average (Re), root mean square
(Rq), and maximum peak-to-valley height (Rt). These parameters are defined as:
1. Centerline average (CLA)^This is the most common designation of surface roughness and is cilso denoted as arithmetic average (Ra). Here Ra is calculated from:
Ra^

1 '^

\Zi\

where: A^ is the total number of measurements, Z is the


absolute peak to valley height with respect to a reference
line.

914 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


2. Root-Mean-Square (RMS)The RMS representation of a
specific height (Rq) is:
" 1

Ra = N

"ll/2

^ ^ '

3. Maximum Peak-to-ValleyThe m a x i m u m peeik-to-valley


asperity height (Rt) is:
R, R

Kn

Typically, the m a g n i t u d e of these peak asperity height


measurement methods follow the relative order:
Ra^Rg^

Rt

Surface roughness may also be represented by a surface


roughness grade based on the Ra value [14]. Surface roughness is also referred to as Ra ("average roughness") or it may
be referred to as "roughness grade." Typical values for tribological surface roughness are provided in Table 4 (ISO 1302).
There are various ASME and ISO standards for instrument
calibration, data processing, and data analysis, which are
listed at the end of this chapter. Surface roughness values
typically encountered for various components are provided
in Table 5 [13].
Surface

Conformity

To understand the wear process, it is necessary to determine


the load acting on the contacting surfaces, the type of
motion, e.g., rolling vs. sliding or linear vs. oscillating, and
the geoemetry of the wear contact. The geometry of the
contacting surfaces may be classified as conformal or nonconformal (or counter-formal), as shown in Fig. 7. Conformal surfaces, such as a journal - sleeve bearing and hydrodyn a m i c t h r u s t bearings, fit together geometrically. The
loading of conformal surfaces is typically carried over a wide
area of peak asperities and the load-bearing surface area remains nearly constant with increasing loads. The lubrication
contact area is relatively large.
Non-conformal surfaces, such as two mating gear teeth,
vane-on-ring, and rolling elements in their raceways, do not
fit together geometrically and the load is concentrated on a
relatively small contact area that increases significantly with
increasing load. Classification of the non-conformal contact
depends on the scale. A seemingly non-conformal pair of surfaces might be conformal at an atomic level. It could also be
true that a pair of worn non-conformal surfaces could become conformed as a result of the wear process.
The contacting area is called the Hertzian Contact Area, as
illustrated in Fig. 8 and is defined by ASTM G 40 as "the app a r e n t area of contact between two nonconforming solid
bodies pressed against each other, as calculated from Hertz's

TABLE 5Typical component surface roughness values.


Component

Arithmetic
Average (Ra) /iM

ju.m.

Gears
Plain Bearing-Journal
Plain Bearing-Bearing
Rolling Elements
Rolling Bearing
Tracks - Roller Bearing

0.25-10
0.12-0.5
0.25-1.2
0.025
0.12
0.1-0.3

10-400
5-20
10-50
1-5
5
4-12

FIG. 7The geometry of the contacting surfaces are classified as conformal or non-conformal (or counter-formal).

Pressure-,
(a)

Inlet Region ^Hertzian Region

I Outlet Region

(b)
FIG. 8a) Hertzian contact region, b)
Hertzian contact area.

equations of elastic deformation." The pressure at this contact is called the Hertzian Contact Pressure and is defined by
ASTM G 40 as: "the magnitude of the pressure at any specified location in a Hertzian contact area, as calculated from
Heitz's equations of elastic deformation."
The geometry of a tribocontact is usually defined as a point
contact (ball or pin-on-disk), line contact (vane-on-ring,
roUer-on-disk), emd area contact (flat surface-on-disk). Tribo-

CHAPTER

35: LUBRICATION

contact classifications are illustrated in Fig. 9. However, contact geometry may veiry. Contact geometry affects the load
actually applied, surface area, and conformation. Contact geometry, taken together with other variables such as sliding
speed, material chemistry, and the physical and chemical
properties of the lubricant presents a specific tribological
problem. This is important because a bench test is selected to
evaluate certain lubricating properties of a fluid/additive system with a specific material pair of interest or to model real
wear systems of interest in industrial equipment. Therefore,
the specific contact geometry selected for wear testing is dependent on the tribological system being modeled (or generated) by the test. Figure lOa-h illustrates eight different wear
contact variations that may be used with a single test machine, including the well-known 4-ball test [15]. (Other test
geometries are also possible.) Bench tests, such as the 4-ball
test, are often used to examine lubricant additive reactivity
[15]. However, ranking of lubrication properties depends on
the test conditions and performance criteria.

Line

Area

Point

FIG. 9Examples contact geometries


of various common bench test configurations.

H
FIG. 10Illustration of various tribocontact geometries that were used by
Matveesky with a 4-ball machine: a) four
ball, 8 mm dia. balls made from chromium
steel Re = 61-62; b) four roller, 5 mm dia.
rollers and 45(contact; c) ball-ring, ball
from chromium steel of Re = 61-62, dia.
12.7 mm, ring from different materials
with geometry-20 x 18 x 4 mm; d) diskball; ball from chromium steel, Re =
61-62, d = 8 mm, disk from different materials with geometry 60 x 18 x 4 mm;
e) ball-three-roller; ball from chromium
steel. Re = 61-62, d = 12.7 mm, 5 mm dia.
rollers made from different materials;
f) ball-three plates, ball and materials the
same as: "e"; g) conical-ring, cone (110),
geometry of ring 20 x 8 x 4 mm; h) ballplate, plate from different materials with
geometry 40 x 40 x 5 mm, ball from
chromium steel Re = 61-62 and d = 8
mm.

AND TRIBOLOGY

FUNDAMENTALS

915

One test machine was developed to evaluate the kinetics of


the tribochemiccd reaction of additives to a metal substrate
during lubrication [16]. From a kinetic correlation, tribochemical mechanisms could be esterblended. This test machine has been constructed where varying loads are applied
to a rotating disk that is brought into contact with a stationary disk [16]. Both disks were constructed from S45 plain
carbon steel (without heat treatment). The test machine may
be configured to provide line, whole-plane, Eind partial plane
contact [16].
This test apparatus is used to determine the value (ki),
which is the rate constant of the reaction between the additive, in this case radioactive dibenzyl disulfide, DBDS, eind
the metcJ (Fe) friction surface in ni^ mol'^s"'. The value 1 is
the effective concentration of the DBDS in mol. m"'^ in the oil
film adsorbed on the friction surface. The value k2 is the rate
constant of chemical wear of iron sulfide in s"'.
Okabe et al. also used the reaction rate constant ki in analyzing the corresponding wear data. In this case, kj increases
with sliding velocity, which will also increase the contact
temperature, thus increasing reaction rates. The value 1 will
increase with the hydrodynamic effect of the lubricating oil.
The data could not be explained by considering ki eJone since
it cannot decrease with increasing sliding speed. However,
excellent correlations were obtained with the product kil
[16]. This experimental approach illustrated how tribochemical and tribophysical prospects can be extracted from experimental wear data.
Figure 1 l a shows the significant effect of contact pressure
on tribochemical reactions, which is partially determined by
the conformity of the wear contact [16]. This is illustrated in
the typically poor correlation between the 4-ball test and the
Timken test in which both exhibit different surface contact
conformity, as well as test conditions [17]. Figure lib shows
the effect of sliding velocity [16].
These data show:
The tribochemical reaction is affected by base oil viscosity that affects not only hydrodynamic lubrication but
also additive diffusion from the bulk oil to the metal-oil
interface.
Wear is not totally controlled by tribochemical reactions
but also mechanical processes, since totcil wear depends
on the sliding distancenot reaction time. This is because friction processes may remove (detach) the additive
from the surface, which then must be reformed (readsorption).
For line contact, both kil and ka are independent of contact
pressure. However, for whole -plane contact kjl and ka vary
with contact pressure since the value 1 is reduced with increasing pressure.
For line contact, increasing sliding velocity produces a convex curve for kjl Emd ka is independent of sliding velocity.
However, ka increases with sliding velocity for whole-plane
contact.
Taken together, it is very important to note that additive
behavior is not only controlled by base-oil interactions, but
edso by contact pressure, sliding speed, and contact geometry. For example, increasing contact pressure increases
wear, as illustrated by a palm oil lubricated contact in Fig.
I2a-c.

916

MANUAL 37: FUELS AND LUBRICANTS

xlO
5

T^

o'

HANDBOOK

whole plane contact

A
'

2" 2
1

T^

0
0.1

(a)

10

too

Contact pressure ,

woo

integral component of the overall wear contact and must be


treated as such. Figure 14 illustrates physically adsorbed
films, and tribochemical reaction films, which are discussed
in more detail in the Surface Films section.
The micro-EHL thin film is the first hne of protecting sliding failure. Its thickness depends on the fluid viscosity and
therefore is enhanced by increasing pressure on the lubricating contact. Fluid viscosity, however, is significantly increased by increasing pressure, particularly at the pressures
encountered both on the inlet region to the Hertzian contact
and within the Hertzian contact itself. The exponentially

M Pa

xlO,

xlO

XlO
3

3
'in

1
0
XlO

,X

T^"

partial plane
7 contact
6
S
4
3 ("whole
,
plane contact

0.01

(b)

0.1
S l i d i n g velocity ,

1
m-s'

FIG. 11The quality ranking of lubricants


strongly depends on test conditions and performance criteria, a) The effect of contact geometry and pressure on tribochemical reactions and wear; b) the effect of contact
geometry and sliding speed on tribochemical
reactions and wear.

Wear Contact Material Structure


Four structural elements involved in wear mechanisms are
shown in Fig. 13 [18]. These are: surface films, which are typically present at < 1 ^nm; near-surface structures, which are
typically present within 1-150 ^im from the surface; subsurface structures, which are observed from 50-1000 fjum from
the surface; and bulk material properties. One type of surface
film is an oxide film that is formed by surface oxidation with
oxygen that may be present in the atmosphere [18], dissolved
in the lubricant, or both.
Pressure-Viscosity
Coefficient
Surface asperities and lubricating thin films determine tribological behavior and types of lubrication modes, as illustrated
in Fig. 14 [19]. It is important to note that the lubricant is an

FIG. 12Effect of load on wear of AISI 52100


steel ball on cast iron plate where contact lubricated with a 5% palm oil methyl ester. Test conditions: sliding speed 0.34 m/s, 1 hour test time,
ambient temperature at the start of the test, a =
SOON, b = 700N and c = 1100N. As expected, increasing the load increases the wear. (Source:
Prof. M. Maleque, Oept. of Mechanical Eng., University of Malasia, Kuala Lumpur, Maylasia.)

CHAPTER

35: LUBRICATION

AND TRIBOLOGY

FUNDAMENTALS

917

EHD/Mlcro-EHD Films
(<1nm)

Surface Films
(<1nm)

Lubricant

Near Surface
(< 50 urn)
Residual
Stress
(Bulk)

Hardness
(case)

Principal
Shearing
Stress ( X )
Subsurface
(<50-1000^m)

Core

FIG. 13Structural elements of a wear contact.

Surface Films

lubrication analysis. The value of aoT is defined as [21]:


_dlnri\
n
. ^
1 diq
T,P = I atm
aor =
= ; \T,P = 1 atm =
dt, \
n dP
However aox, which is obtained by graphical differentiation, is dependent on relatively few low-pressure data points,
which contribute substantially to overall error. A more favorable alternative solution, w h i c h provides a m o r e reliable
viscosity-pressure response, is to solve for a* as shown in
Fig. 15b by graphically integrating the following equation for
a* [22]:

Adsorbed,

Film

li

Oxide

Metal

Metal

FIG. 14Surface asperities and lubricating thin films determine tribological behavior and types of lubrication modes.

increasing viscosity with increasing pressure relationship has


been classically modeled by the Barus Equation [20].
The classic Barus equation describes the effects of pressure
on viscosity [20]:
VP

where:

= Voe

TTP is the centipoise viscosity at pressure (P),


T/o is the viscosity at atmospheric pressure,
a is the pressure-viscosity coefficient.

Jones et. al. have shown by plotting log rj as a function of


pressure (P) that a linear graphical solution to the Barus
equation is not obtained except at low pressures (Fig. 15a)
[21]. The slope of the tangent to log 17 as a function of pressure (P) isotherm (aox) at atmospheric pressure is often used
for the calculation of the pressure-viscosity coefficient used
in the Reynolds equation for elastohydrodynamic (EHD)

T? (r, P = 1 atm)
dP
V iP, T)
The advantage of a* is that all of the variations of viscosity
with pressure over the entire pressure range are included in
the calculation as illustrated in Fig. \5b [21],
In many cases, the value of a is not available. One early attempt to predict a for petroleum oils at pressures u p to 10 000
psi was reported by Fresco et al. [23]. Fresco's a- prediction
chart is shown in Fig. 16 and is based on the viscosity-temperature properties of a fluid, which are represented by the
so-called "ASTM Slope" [24]. The ASTM slope is the slope of
the viscosity temperature line of the McCouU-Walther equation that is plotted as described in ASTM D 341. In addition
to a graphical solution, it can also be calculated from:
ASTM Slope =

log log {V1IV2)


l o g (Tz/Ti)

where: v is the kinematic viscosity and T is the absolute temperature. The ASTM slope is the slope of the viscosity-temperature line of the Walther equation that is described in
ASTM D 341. Note: The ASTM slope is n o t equivalent to the
value B in the Walther equation [25]:
log log {v + 0.7) = A - 5 log r

918

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

"OSIOK*"'

10
(a)

(b)

3x10'

Pressure (N/nf )
i
I
30 X 10'
20

Pressure (PSI)

Pressure
FIG. 15a) Viscosity-pressure beliavior witli aor and uos (Barus Equation); b) Illustration of a viscosity-pressure isotherm and the calculation of a*.

CHAPTER

35: LUBRICATION

AND TRIBOLOGY

FUNDAMENTALS

919

The pressure-viscosity relationship for a paraffinic and a


n a p h t h e n i c mineral oil at different temperatures is illustrated by Fig. 17 [28], Table 7 tabulates pressure-viscosity coefficients for different temperatures of different oils [25].

0.90

Surface

Films

There are numerous t5rpes of surface films that are used to reduce wear. Physical or chemical adsorption also provides a
protecting film for lubrication. A thin surface film is formed
by adsorption of polar lubricant molecules onto the surface,
providing an effective barrier against metal-to-metal contact.
Physical adsorption (vein der Waals adsorption or physisorption), as defined by ASTM D 2652, refers to "the binding of an
adsorbate to the surface of a solid by forces whose energy
levels approximate those of condensation." Chemical adsorption (chemisorption) is defined by ASTM D 2652 as: "the
binding of an adsorbate to a surface of a solid by forces
whose energy levels approximate those of a chemical bond
without the formation of a new chemical bond." Chemisorption may be irreversible.

2 3 45

10

20 30 50

100 200

500

1000

Atmospheric Viscosity (cSt)


FIG. 16Fresco's nomogram for predicting viscosity-pressure coefficients of a mineral oil hydraulic fluid.

Both A and B are fluid dependent constants. Since fluid viscosity usually decreases with increasing temperature, the
slope of B will be negative.
The viscosity-temperature coefficient is obtained from the
first derivative of the McCouU-Walther equation and is equal
to [25]:
Slope B =

dr

Other methods that have been used to predict the value of


a are summarized in Table 6 [26].
The Appledoom equation has been proposed for the calculation of the effects of both temperature and pressure on viscosity simultaneously [27]:
log (V/VA) = a log (F/Fo) + aP

Where: v is the viscosity at temperature F, expressed in F,


and pressure P, VA is a reference viscosity at atmospheric
pressure and temperature FQ, a is the viscositytemperature
(Appledoom) co-efficient and a is the pressure^viscosity coefficient.
Both temperature amd pressure exhibit potentially large effects on viscosity and the simultaneous inclusion of both in
viscosity calculations is desirable. However, there are n o
broadly accepted methods for conducting these calculations
at the present time.

The effectiveness of the adsorbed film is dependent on temperature. A thicker film provides better surface protection.
Two types of protective films, adsorbed films and reaction
films, are illustrated in Fig. 14, respectively [18]. Examples of
the use of adsorbed films that will reduce interfacial friction
include the ionically adsorbed (chemisorption) fatty acids on
steel (and other metal) surface layers as shown in Fig. 18 [ 18],
or the physical adsorption of hydrocarbons as illustrated in
Fig. 19 [18].
Metal surfaces may also be modified by the formation of
reaction films. Some reaction films are formed during heat
treating processes such as carburizing, carbonitriding and
nitriding. Others are formed in situ by surface chemical reactions between a n additive such as ZDDP (zinc dialkydithophosphates) as shown in Fig. 20 [18]. The formation of
a chemical film produced by a paraffinic base oil containing
ZDDP as an additive is illustrated in Fig. 20b. An illustration
of the ability of a n oil additive to reduce wear is provided by
comparing Fig. 3c and Fig. 21. Some surface films are formed
by tribochemical processes such as tribopolymerization
[37-40] during the lubrication process.
Surface topographical structure is shown in Fig. 22 [18].
Lubrication failure in this region will produce plastic flow
and failure mecheinisms such as ploughing caused by a hard
asperity sliding in the softer plastically deformed metal.
Various illustrations of ploughing wear are provided in
Fig. 3c.
Near Surface

Structure

As indicated in Fig. 23, near-surface structure occurs u p to


approximately 50 /i and is affected by surface hardening or
reactions film formation in this region [18]. Near-surface
structure, as indicated in Fig. 23, is particularly susceptible to
severe deformation a n d is i m p o r t a n t since the residual
stresses in this region will affect crack propagation during lubrication failure.
Sub-Surface

Structure

Sub-surface structure, shown in Fig. 23, predominates at


depths of 50-1000 yam [18]. This region is susceptible to gross
deformation a n d is affected by the bulk properties of the

920 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 6Various methods used in the comparisons of the effectiveness in predicting the pressure effects on viscosity
Developer

Correlation

Kouzel

log ^

Roelands, Vlugter

for non-polymer fluids

and Wateman

=( P V
i g ^ = i5ooo; [ ( 0 . 0 0 2 C A

Reference

= 3 ^ ( 0 . 0 2 3 9 + 0.01638^;

[29]
[30]

3L

+ 0.003Cw

0.055) log r,o + 0.228]

l o g {y - 0 . 8 9 0 ) = 0 . 0 0 9 5 5 (CA + l.SCjv) - 1.930for polymer fluids

log (log r,p + 1.200) = ZBI log f l + 2 8 ^ ) + ^^ ^^^ '^'> + ^-^OO)


Zfii = O.eZgr + OAZBI
Fresco

log = Pa'" (lO-'') a = ^

[31]

a' = A + B log (Va) + C(log V)^

A, B, and C are function of ASTM slope


Kim

[32]

log = Pia' + /3)(10-'')


a' is calculated from Fresco's Method
p = A'logVr + B'(logK)^
A' and B ' are function of temperature
graphical method is also available

So and Klaus

log

Voj

[33]

a(98.1 XP)

a = 2 ^ ^ [1.216 + 4.143 [log (Vjf '>'


s = 2.848 X 10-" m^'^o^ [log (VJl'-^'^'
t = 3 . 9 9 9 [ l o g (yJ]3.0975p0.0Tl62

Chu and cameron

log ( ^ ) = 16 log 1 +

0.062 (10+") PIO^o.o

[34]

+ a = [0.183 + 0.2951 log ( r j j ]

for naphthenics
log (^]

Worster

= aKlO"'*) + a = [0.183 + 0.2951 log(T)o)] for naphthenics

Johnston

PEr
a, ICRT^

Shibada

a = 0 . 6 2 0 4 4 ^d"^'^

[35]
[36]

^2.04746 ^0.29292

[26]

TABLE 7Selected pressure-viscosity coefficients.


aoxCNm^)"'
Dynamic Viscosity (mPa.s) at:

^ 100,000
O, 10,000
"^
(0

o
o
(A

1000

Fluid

38C

99C

149C

2-Ethylhexyl Sebacate
Paraffinic Oil
Naphthenic Oil A
Naphthenic Oil A + VI
Improver'
Naphthenic Oil B
Polybutene (Mn = 409)
a. VI Improver = 4% PMA
(Mv = 560,000)

11
29
22
60

1.39
2.18
2.15
1.83

1.19
1.78
1.44
1.24

68
90

3.07
3.18

1.81
2.22

100
10
1
0.1
0

Paraffinic OH
Napthenic Oil

20 40 60 80 100 120 140

Pressure (xlO^ psi)


FIG. 17Pressure-viscosity relationship for a paraffinic and a napfithenic mineral oil at different temperatures.

m a t e r i a l . S p a l l i n g failure t y p i c a l l y o c c u r s i n t h i s r e g i o n . Figu r e 2 4 p r o v i d e s v a r i o u s i l l u s t r a t i o n s of s p a l l i n g . W e a r p r o c e s s e s s u c h a s s p a l l i n g l e a d t o f a t i g u e failure, o n e of t h e m o s t


c o m m o n g e a r f a i l u r e m e c h a n i s m s . V a r i o u s i l l u s t r a t i o n s of
g e a r f a i l u r e m o d e s a r e s h o w n i n F i g . 15a-i. T h e s e s u b - s u r f a c e
w e a r m o d e s i n c l u d e : p i t t i n g (Fig. 25a,b,d); m i c r o p i t t i n g (Fig.
2 5 c ) ; scuffing (Fig. 25f,h,j); " t e a r i n g " (Fig. 2 5 i ) ; r i p p l i n g (Fig.
25e); a n d s e v e r e w e a r (Fig. 25g). S p a l l i n g a n d f a t i g u e failure
p r o c e s s e s will b e d e s c r i b e d i n m o r e d e t a i l s u b s e q u e n t l y .

CHAPTER 35: LUBRICATION


Cohesion

FIG. 18Adsorbed films which will reduce interfaclal friction include the ionic adsorbed fatty acids to
the steel (and other metal) surface layer.

AND TRIBOLOGY

FUNDAMENTALS

921

Bulk Material Properties


Some of the most common bulk material properties that influence wear are: melting point, Young's modulus, yield
strength, hardness, and surface energy. Table 8 provides a
summary of these values for selected pure metals [41].
Young's modulus (elastic modulus) is the ratio of change of
stress to change in strain within the elastic region of a material. This is limited to materials exhibiting a linear stressstrain relationship over the range of loading being tested.
ASTM E 6 defines yield strength as the "engineering stress
at which, by convention, it is considered that plastic elongation of the material has commenced. This stress may be specified in terms of (a) a specified deviation from a linear stress
relationship, (b) a specified total extension attained, or (c)
maximum or minimum engineering stresses measured during discontinuous yielding." Yield stress as defined by ASTM
D 653 is "the stress beyond which the induced deformation is
not fully annulled after complete distressing." Hardness is
defined by ASTM E 6 as "resistance of a material to deformation, particularly permanent deformation, indentation, or
scratching." The magnitude of hardness is often simply considered to be the softer of two materials with respect to the
material pair of the wear contact. However, hardness is a
much more complex variable. Rigney [42] has shown that
hardness can vary with position and time and is dependent
on temperature, sliding speed, and the chemical environment. The sign of the hardness gradient adjacent to the sliding surface affects sliding behavior. Furthermore, hardness
variations may affect the transition from friction to wear.
Therefore, potential variations in hardness in friction and
wear testing must also be considered.

n-Hexadecane (Cetane)
(C16H34)

FIG. 19Physical adsorption of hydrocarbons. Note the weaker van der Waals interactions and related orientational effects between the hydrocarbon and the metallic substrate relative to those illustrated for chemisorbed additives illustrated in
Fig. 18.

922

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

FIG. 21Illustration of the ability of an additive to


reduce wear on a copper substrate. IVIedium carbon
steel pair block-on-shaft lubricated with a mineral oil
with a copper nanometal additive, load = 110-184 N,
156-220 rpm and the picture has 750X magnification.
(Source: Dr. Sergey Tarasov, Institute of Strength
Physics and Materials Sciences, Tomsk, Russia).
Compare to Fig. 3c.

FIG. 20Surface additive reactions are tribochemical processes which are driven by the conditions within the wear
contact. This is illustrated by the following examples: a) The
in situ reaction film is formed by surface chemical reactions
between an additive such as ZDDP (zinc dialkydithophosphates). b) Illustration of cracking of a chemical reaction film
produced on a gray cast iron surface lubricated with a paraffininc base oil containing ZDDP as an additive under a contact pressure of 16.7 MPa and at 135C for 17 h. The sliding
velocity was 1.4 m/s and the base oil viscosity was 0.053 Pa
at 38C. (Source: Prof. Hon So, Dept. of Mechanical Engineering, iviational Taiwan University, Taipei, Taiwan.)

Surface energy is the energy (work) required to expand the


surface area of a hquid and is quantified as energy per surface area. Surface energy is related to the surface tension of
a Hquid, which is defined by ASTM B 374 as "the property
due to molecular forces, that exists in the surface film of aJl
liquids and tends to prevent the liquid from spreading." Surface energy defines the ability of a fluid to "wet out" a solid
surface. Surface "wet out" refers to how well a liquid or viscoelastic solid flows and intimately covers a surface. The
greater the wet out, the better the surface coverage and the
greater the attractive forces between the fluid and the solid
surfaces. Surfaces with high surface energy bond more readily because they are easier to wet than low-energy surfaces.
Surface free energy is time consuming to measure. It
would be helpful if structure could be correlated with surface
free energy to enable prediction of the surface energy. This
correlation is done using a Zisman plot, developed at the
Naval Research Laboratory. The plot is made by plotting the

cosine of the contact angle versus the surface free energy of


various wetting liquids on a given solid. The resulting plot is
a straight line. Thus, there exists some unique value for each
solid where the cosine of the contact angle is unity. This value
is termed the critical surface free energy. A liquid with surface free energy below the critical value will wet and spread
over the solid surface, whereas a liquid with surface energy
above the critical value might wet but will not spread.
To provide optimal antiwear properties, the material
should:
1. Possess high strength to resist plastic flow.
2. Have high ductility to withstand repeated plastic strain
without cracking. Ductility is the ability of a material to deform plastically before fracturing.
3. Be homogeneous and free from discontinuities such as impurities and soft transformation products. Smooth Eind homogeneous material generally has better anti-wear properties since failure takes place at higher energy areas such
as boundaries and rough area sites.
Two general classes of steels are typically used as materials
for wear contacts. Based on the phase diagram shown in Fig.
26 [18], a eutectoid steel contains 0.8% carbon (see dashed
line). Hyper-eutectoid steel contains greater than 0.8% carbon
and hypo-eutectoid steel contains less than 0.8% carbon. Hyper-eutectoid steel is a deep-hardening steel typically containing 0.8-1.15% carbon. Hypo-eutectoid steel is used for
various surface-hardening processes such as carburizing, carbonitriding and nitriding. These steels typically contain
0.1-0.25% carbon. A summary of the effect of various steel microstructures on wear is provided in Fig. 27 [18]. Table 9
shows the effect of metallurgical microstructure on wear [43].

CHAPTER

35: LUBRICATION

AND TRIBOLOGY

FUNDAMENTALS

923

FIG. 22Lubrication performance depends on surface topographical structure.


Lubrication failure in this region will produce plastic flow and failure mechanisms
such as ploughing caused by a hard asperity siding in the softer plastically deformed metal. See Fig. 3b for an illustration of ploughing.

Severe Deformation
Gross Deformation
Bulk

FIG. 23Sub-surface structure predominates at depths of


50-1000 fim. This region is susceptible to gross deformation
and is affected by the bulk properties of the material.

Wear Mechanisms
The primetiy wear mechaxiisras that occur in non-lubricated
contacts are: adhesive wear, abrasive wear, tribochemical
wear, and fatigue wear.
Adhesive

Wear

Adhesive wear occurs when surface asperities come into sUding contact under a load. If sufficient heat is generated, microwelding of the two contacting asperities with subsequent
shearing and material transfer will be observed, as illustrated
schematically in Fig. 28a. When two interacting surfaces are
not sufficiently lubricated, adhesive transfer or removal of
near-surface material may be observed. Surface adhesion is
dependent on the nature of the contacting surface. Wear material transfer in this region h a s been called "solid-phase
welding" (also known as the micro and macro-welding pro-

cess), which occurs at asperity contacts [7,44]. Adhesive wear


can be reduced by the proper selection of material pairs and
sufficient lubrication to provide a protective surface a n d
EHD/micro-EHD film. (EHD films will be described subsequently.) Examples of adhesive wear are shown in Fig. 28.
One form of adhesive wear is "smearing." If the contact
temperature is sufficiently high, metal flow and smearing
will be observed. If the material is constructed from steel,
tempering colors may be observed, and if the temperature is
high enough, plastic deformation and fracture may result. An
example of smearing wear is illustrated in Fig. 29a.
Polishing wear is a special case of smearing. One method
by which polishing wear may occur is during a break-in process when surface asperities undergo an adhesive wear process until a very fine, polished surface results. This is caused
by insufficient EHD lubrication to prevent such asperity contact. An example of polishing weeir is provided in Fig. 29b.
(Polishing weeir may also be caused by EP additives that may
be too aggressive, leaving a bright, mirror-like surface. This
is an undesirable process since this process typically leaves
the metal surface less resistant to wear.)
This series of events is partially observed with Fig. 30. (Provided by D. Drees, Falex Tribology NV, Belgium.) In this case,
a series of pin-on-v-block tests was conducted in a lubricant
containing extreme pressure additives. In Fig. 30a, the machine was sufficiently loaded to cause a change of color (bluing) due to the high frictional temperature of the material
pair. When the lubricant failed, welding of the metal test
specimens occurred, resulting in adhesive wear as shown in
Fig. 30b.
Another term relating to adhesive failure is "galling," which
is defined by ASTM G 40 as "a form of surface damage arising between sliding solids, distinguished by macroscopic,
usually localized, roughening and creation of protrusions
above the originEd surface; it often includes plastic flow and
material transfer, or both." An example of galling wear is
illustrated in Fig. 31, which shows the results of surface wear

924 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

FIG. 24Illustrations of wear by spalling. a) Spalling wear of a AISI52100 steel ball


on a nitrlded AISI 1045 steel disk under lubricated conditions loaded at 150N and
sliding speed of 2.0 m/s; b) spalling wear is also illustrated by this example of nitrided AISI 52100 after testing with a No. 20 engine oil at 1500 N and 650 rpm. The
spalling occurred in the nitrlded layer; c) Close up of the spalling pit shown in b.
(Source: Prof. Liu Jiajun, Tsinghua University, Beijing, PRC.)

(a,b)
FIG. 25Gears may wear by several modes and the FZG test may be used to evaluate wear resistance by Identifying
failure modes. Illustration of various potential gear wear modes observed in the FZG gear test are shown here: a) pitting/spalling on a case carburized test gear; b) pitting/spalling from a micropitted area on a case carburized test gear; c)
severe micropitting on a case carburized test gear; d) pitting on a through-hardened gear in practice; e) rippling on a
case-carburized test gear; f) scuffing on a case-carburized test gear; g) severe wear on a case carburized test gear; h)
scuffing on a case carburized test gear (compare to Fig. 24 e on the same gear geometry); i. "tears" on a nitrlded test
gear; j) severe scuffing on a case carburized test gear. (Source: Dr. K. Michaelis, Lehrstuhl fur Maschine Elemente, Technical University of Munich, Munich, Germany.)

CHAPTER 35: LUBRICATION AND TRIBOLOGY FUNDAMENTALS 925

(g,h)

(i)
FIG. 25(continued)
T A B L E 8 P r o p e r t i e s of m e t a l l i c e l e m e n t s .

Metals

Melting
Temp.
(C)

Young's
Modulus (E)
Dyne/cm2

Aluminum
Cadmium
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Tin
Zinc

660
270
1083
1534
325
650
1245
2.08
232
420

0.63
0.32
1.20
2.04
0.16
0.44

Yield
Strength (<7y)
109 Dyne/cm2

Hardness
(P) K=/mm^
erg/cm2

1.0

27
7
80
82
4
46
300
210
5.3
38

3.2
2.5
0.09
1.5
2.5
3.2
0.15
1.3

0.44
0.91

900

y+Fe,C

I
'

600 ^

Cementite ( FesC )
+ Pearlite

Ferrite + Pearlite
Pearlite
-1
0.0

11I1I
0.2
0.4
0.6

1
1.0

'

1
1.2

Weight percentage carbon


FIG. 26^The phase diagram of hyper-eutectoid and hypoeutectoid steel.

Surface
Energy

900
390
1100
1500
450
560
1700
570
790

926 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

Sliding Velocity V(m/s)


STEEL
Wear-Mechanism Map
Pin-On-Disk Configuration

2
tn
0)
T3
(U
_N
ID

. Ultra' Mild
Wear

Normalized Velocity V
FIG. 27Effect of steel martensitic structural transition on wear as
shown by a wear mechanism map for a non-lubricated sliding steel pinon-desk pair. Contours of wear rates (which are normalized) are superimposed on regions with different wear mechanisms. Wear rates in
parentheses represent mild wear. The transition between mild and
severe wear are indicated by the shaded area.

TABLE 9Effect of metallurgical microstructure on wear [24].


Microstructure

Ferrite

Comment

Poor wear, low hardness and high toughness


Good firecrack resistance
Lamellar
Good strength Emd firecrack resistance
Pearlite
Fine pearlite structure improves strength and wear
but reduces ductility and firecrack resistance
Spheroidized High toughness and good wear resistance,
Pearlite
Soft steel with good firecrack resistance
Bainite
High strength a n d hardness with good wear resistance a n d good firecrack resistance
Martensite
Very high hardness, very good wear resistance poor
toughness and firecrack resistance carbide
Carbide
Extremely good wear resistance, high content carbridge causes embrittlement
Graphite
Improves firecrack a n d spall resistance, reduces
strength

CHAPTER 35: LUBRICATION AND TRIBOLOGY FUNDAMENTALS

a) Surfaces
being pressed
together

(b)

(a)

(d)
FIG. 28Mechanism and illustration of adhesive wear, a) A schematic illustration
of the mechanism of adhesive wear, b) Illustration of adhesive wear with an Fe/IVIg
wear contact under the following conditions: 5 N/cm^, 1 m/s, > 10 l<m, 2x10"^ Torr
and n = 0.29. (Source: E. Santner, BAM, Berlin Germany.) c) Adhesive wear from an
AISI52100 steel ball on an AIS11045 steel disk under lubricated conditions loaded at
150N and sliding speed of 1.5 m/s (Source: Prof. Liu Jiajun, Tsinghua University, Beijing, PRC.) d) Adhesive wear from a lubricated AISI 52100 steel ball and an AIS11045
steel disk loaded at 300 N and a sliding speed of 2.0 m/s. (Source: Prof. Liu Jiajun,
Tsinghua University, Beijing, PRC.) e) Adhesive wear obtained with a medium carbon steel pair block-on-shaft, load = 110-184 N, 156-220 rpm and the picture has
750X magnification. (Source: Dr. Sergey Tarasov, Institute of Strength Physics and
Materials Sciences, Tomsk, Russia.) f) 2 steel ball on an SUS 304 3/8 inch brass
(YbsC2) ball on an 18 mm nickel disk with a test load of 14.7N, sliding speed of 1 m/s
over a 15 m distance and a vacuum of 10~^ Pa (Source: Prof. T. Kawazoe, Nagasake
University, Nagasaki City, Japan.) g) Severe adhesive wear with a 3/8 in SUJ stainless steel disk with a load of 49 N, sliding speed of 1 m/min, over a total distance of
15 m and a vacuum of 10~^ Pa. (Source: Prof. T. Kawazoe, Nagasake University, Nagasaki City, Japan.)

927

928 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK

BS
(3/8" brass ball)

((|)18x*30Nidisk)

Ni - BS (1.5 kgf)

(f)

200^
I

x50

SUS 304
(({)18 X* 30 stainless steel disk)
(g)

SUJ2
(3/8" stainless steel ball)

SUS - SUJ2 (5.0 kgf)


FIG. 28(continued)

CHAPTER 35: LUBRICATION AND TRIBOLOGY FUNDAMENTALS

(b)
FIG. 29a) Cam ring smearing damage and discoloration. (Courtesy of Caterpillar
Inc, Peoria, IL.) b. Hydraulic pump piston with polishing wear by a smearing mechanism. (Courtesy of Caterpillar Inc., Peoria, IL)

(a)

(b)
FIG.
30P!n-on-V-block
test results of an lubricant
showing: a) when the machine was sufficiently loaded,
a change of color (blueing)
was observed due to the high
frictional temperature of the
material pair; b) when the lubricant failed, welding of the
metal test specimens occurred resulting in adhesive
wear. (Courtesy of D. Drees,
Falex Triboiogy NV, Heverlee,
Belgium.)

FIG. 31Surface wear obtained with


two copper cylinders tested in a crossedcyllnder geometric configuration under
dry sliding conditions. This figure is an
SEM photograph, which shows typical
signs of galling or seizure, with grooves, a
heavily deformed surface layer and material transfer. (Source: S. Hodgmark, Uppsala University, Sweden.)

929

930

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

obtained with two copper cylinders tested in a crossedcylinder geometric configuration u n d e r dry sliding conditions. This figure is an SEM photograph, which shows typical signs of galling or seizure, with grooves, a heavily
deformed surface layer, and material transfer.
The classic expression to quantitatively describe the volu m e (V) of adhesive wear debris removed for a given load (L),
on a material over the sliding distance (x) for a dry wear contact is known as Archard's equation.
V

k Lx
H

where: k is the Archard's wear constant and H is the hardness


of the softer material of the material pair. Typical values of
Archard's wear constant (for non-lubricated wear) are provided in Table 10 [45]. F o r non-lubricated wear contacts
(solid friction and wear), it has been recommended that the
wear constant should be < 10"* mm^ N"^ m ~ ' [2].
Archard's wear constant "k" is also defined in ASTM G 40
as the "wear co-efficient," "wear factor," or "specific wear
rate." However, to avoid confusion, it is recommended that
these terms be fully defined within the context that they are
used.
Figure 32 provides a schematic illustration of the Rabinowitz abrasive wear model [45].
dV _L
dl ~

tan e
TTH

where dV/dl is the change in volume (dV) due to the wear that
is removed after sliding a distance dl, L is the load being applied, 0 is the angle of the hypothetical cone indenting the
horizontal surface, and H is the hardness of the softer surface.
Archard's equation shows that material hardness is an important variable in the wear process. However, hardness is a
complex value that is dependent on: position and time, temperature, sliding speed, and environment. Localized hardness

TABLE 10Wear constant (k) for various sliding


combinations [25].
Material Pair

Zinc on Zinc
Low Carbon Steel on Low Carbon Steel
Copper on Copper
Stainless Steel on Stainless Steel
Copper on Low Carbon Steel
Carbon Steel on Copper

Wear
Constant
(k 3 103)

160
45
32
21
L5
0.5

variation can affect the transition between friction and wear


[46]. Meng and Ludema have reviewed various wear models
that have been reported to date and have found that there is
no single set of general equations that adequately describe a
wide range of practical wear prediction problems [47].
Abrasive

Wear

Abrasive wear refers to the cutting of a metal by a hard particle or a rough surface by a ploughing or microcutting
(scratching) mechanism [10,48]. ASTM G 40 defines spalling
as: "the separation of macroscopic particles from a surface in
the form of flakes, or chips, usually associated with rolling element bearings and gear teeth, but also resulting from impact events."
Abrasive wear is dependent on particle size distribution,
shape, toughness (capacity of a material to absorb energy),
and hardness. Giltrow has demonstrated that an excellent, although non-linear, correlation exists between abrasive wear
and cohesive energy for both thermoplastic polymers and
metals [49]. Cohesive energy is that energy, composed of
physical and chemical forces, that holds the constituents of a
mass of material together. It is desirable to use a value such
as cohesive energy since it can be calculated based on chemical composition of the material and thus provides the opportunity to interrelate wear with chemical composition.
Giltrow reported that abrasive wear of many metals was inversely proportional to the cube of the cohesive energy and
inversely proportional to the square root of the cohesive energy of thermoplastic polymers [49]. Note: cohesive energy of
metals may be related to the latent heat of sublimation (at
25C) minus the work (RT) required to expand atoms beyond
their sphere of influence. Latent heats of metals are readily
available from thermodynamic tables [49].
The abrasive wear mechanism involves the penetration of
a surface by a hard particle that is subsequently embedded
into one of the wear surfaces. Abrasive wear occurs when one
of the contacting surfaces is harder than the other. The observed wear behavior involves plastic deformation and material displacement during ploughing or smearing. Ploughing
was described in the Friction Due to Ploughing section. This
results in surface-initiated fatigue spalling. EHD and microEHD films reduce or eliminate local surface plastic flow.
Abrasive wear m a y also be measured by determining the
wear volume, as discussed previously.
When abrasive wear is caused by a hard particle between
two surfaces, it is called three-body wear, as illustrated in Fig.
33a [50]. Hard particles causing three-body wear may be introduced into a system from the manufacturing process, gen-

V Bearing
surface

FIG. 32Rabinowitz simplified abrasive wear model with material removal by a


cone tip.

CHAPTER

35: LUBRICATION

AND TRIBOLOGY

FUNDAMENTALS

931

"Hard" Surface

toothed, tapered cutting tool across a workpiece surface or


through a pilot hole [51].

"Soft" Surface

Cavitation Wear
Cavitation refers to the formation and rapid collapse, by implosion, of cavities or bubbles that contain vapor or gas or
both (ASTM G 15). The collection of a large n u m b e r of cavitation bubbles is called a cavitation cloud. The bubbles in a
cloud are small, typically less than 1 m m in cross section. A
surface that is being eroded by cavitation is typically obscured by a cavitation cloud (ASTM G 40). Different studies
have shown that every bubble in the cloud does not cause
damage upon implosion and that the damage frequency is reported to vary from 1 in 16 000 to 1 in 30 000. A cavitation
bubble m a y undergo multiple collapse a n d reformation
processes. A single bubble may undergo as many as seven collapse and reformation processes. A wide range of bubblecollapse pressures, u p to > 7 0 Mpa, have been reported [52].
Cavitation damage is exemplified by pitting and the formation of holes and craters on the wear surface, as illustrated in
Fig. 34.

(a)

'Soft" Surface
Hard" Surface
(b)

(d)

(c)
FIG. 33Mechanisms and examples of abrasive wear, a) Schematic illustration of a threebody abrasive wear model; b) schematic illustration of a two-body abrasive wear process;
c) illustration of abrasive wear: Fe/AI material
pair, 2.3 N/cm^, 1 m/s, ? 10 km, 5 x 10~ Torr,
and fji varies from 0.61-1.3 (Source: E. Santner,
BAM, Berlin Germany); d) abrasive wear obtained with AISI52100 steel ball on an AtSI Type
304 stainless steel disk, load = 150 N, sliding
speed = 1.5 m/s. (Source: Prof. Liu Jiajun, Tsinghua University, Beijing, PRC.)

Erosion

Wear

Erosion wear is the "progressive loss of original material


from a solid surface due to mechanical interaction between
that surface and a fluid, a multicomponent fluid, or impinging liquid or solid particles" (ASTM G 40). Such wear may result in scratching, surface indentation, chipping, and gouging as shown in Fig. 35. Erosion wear occurs where there is a
change in fluid-flow direction such as in orifices, line restrictions turns in fluid passageways, and the leading edge of rotating parts.
Corrosion

erated internally as wear debris, introduced as a contaminant


with the lubricant being tested, or possibly by all three introduction mechanisms.
Two-body wear is caused by a harder surface with asperity
dimensions sufficiently large enough to penetrate the lubricating oil film, causing a ploughing or microcutting (scratching) action on the softer metal surface of the wear contact,
which is in relative motion [50]. The mechanism of two-body
wear is shown in Fig. 33b.
Examples of abrasive wear, which may involve cutting,
ploughing, lapping, gouging, grinding or broaching, are provided in Fig. 33. Lapping is defined by ASTM B 374 as "rubbing two surfaces together, with or without abrasives, for the
purpose of obtaining extreme dimensional accuracy or superior surface finish." "Gouging" refers to the formation of a
groove in an object by mechanically or manually removing
material, possibly using the sharp edges of a hard particulate
abrasive material.
ASTM E 7 defines grinding as "the removal of material
from a surface of a specimen by abrasion through the use of
randomly oriented hard-abrasive particles bonded to a suitable substrate," such as paper or cloth, where the abrasive
particle size is generally in the range of 60-600 grit (approximately 15-150 jam), but may be finer.
Broaching refers to cutting a finished hole or contour in a
solid material by axially pulling or pushing a bar-shaped.

Wear

Corrosion wear is surface damage related to chemical electrochemical attack of a metal surface, resulting in significant
surface damage as illustrated in Figs. 36 and 37. Common
causes of corrosive wear include:
1. Water from humid air ingression and subsequent condensation, liquid water from spray or splash contamination,
water ingression from defective enclosure, cooling coil
leakage and water-contaminated lubricant.

FIG. 34Surface damage by pitting and cratering due to cavitation. (Reprinted with permission of IFAS, Aachen, Germany.)

932

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK
plate in seawater. In this case, electrons wiU flow from steel
to copper, resulting in a deposit of iron oxide on copper. This
is gcilvanic corrosion.
Combinations

FIG. 35Illustration of erosion surface wear.


(Reprinted with permission of IFAS, Aachen,
Germany.)

of Cavitation/Erosion/Corrosion

(a)

FIG. 36Illustration of the porous nature of


corroded surfaces. (Reprinted with permission
of IFAS, Aachen, Germany.)

2. Corrosive chemical vapors in the atmosphere.


3. Corrosive processing fluids such as coolants and cleaning
fluids.
4. Lubricant chemistry: poor lubricant formulations using
aggressive extreme pressure (EP) additives, presence of
acids from decomposition or exposure to active metals.
One example is provided in Fig. 37 where increasing additions of palm oil as an additive in a petroleum oil resulted in
increased corrosion of the wear surface.
Shi et al. have shown that there is a synergistic effect between corrosion and wear a n d that wear rates of steels under
corrosive conditions were m u c h higher than in the dry wear
condition [53]. (Ion implantation could reduce but not eliminate this effect.)
Galvanic CorrosionGcilvanic corrosion is recognizable by
the appearance of increased corrosion near the junction of
dissimilar metals, caused by electrochemical transfer of one
metal to another. The propensity for galvanic corrosion is dependent on the position of two metals in the galvanic series.
Any metal will have a greater tendency to corrode when it is
in contact with another metal in a lower position in the series
and when it is in the presence of an electrolyte. The further
apart the two metals in the series, the greater the potential for
galvanic attack. For example, consider steel rivets in a copper

Wear

There are various combinations of cavitation/erosion/corrosion wear. These will be briefly summarized as defined by
ASTM specifications.
Cavitation CorrosionThis is a form of localized, accelerated
corrosion characterized by deep pitting and caused by high
mechanical forces resulting from coolant vapor bubble collapse at the surface of a metal. (ASTM D 4725)
Cavitation ErosionDefined as the loss of material from a
solid surface from exposure to cavitation. This may include

(b)

(c)
FIG. 37Corrosive wear obtained with
an AISI 52100 steel ball on cast iron with
0%, 5%, and 10% palm oil methyl ester
(POME) used added to an oil lubricant.
The test was conducted at 80C, 0.34 m/s
for 50 h. (Source: Dr. M. Maleque, Univ. of
Malasia, Kuala Lumpur, Maylasia.)

CHAPTER 35: LUBRICATION


loss of material, surface deformation, or changes in properties or appearance. (ASTM G 40)
Cavitation Erosion CorrosionThe mechanical removal of
protective films on metal by the formation and collapse of vapor bubbles in a liquid and the abrasive action of a liquid,
which may contain suspended solids moving at high velocity.
(ASTM D 4725)
Erosion CorrosionThis is a synergistic process involving
both erosion and corrosion, in which each of these processes
is affected by the simultaneous action of the other and in
many cases is thereby accelerated (ASTM G 40). Meyer et al.
has briefly reviewed various testing procedures to evaluate
erosion corrosion processes [54a].
Oxidational Wear
Archard and Hirst originally classified the sliding wear of metals in the presence of air as "severe" during the initial stages
of the sliding wear process and "mild" in later stages [54b].
Therefore, the term "mild wear" is often used to indicate "oxidation wear" or "oxidative wear." Quinn's model of oxidation
wear involves oxidation of the metal asperities while in contact during the sliding process [55a]. The extent of oxidation
depends on the surface temperatures developed at the asperity contacts during the wear process. The oxidation wear process involves removal of oxide films after a critical thickness
is obtained. The formation of porous oxide films as a result of
the tribooxidation process are provided in Fig. 38.
Tribochemical Wear
Different from chemical reactions, tribological reactions are
initiated by friction causing processes resulting in wear. Tribochemical wear may be viewed as one type of corrosive
wear. When corrosion is activated by mechanical interactions between the contacting surfaces, it produces an activated surface site and localized high temperatures sufficient
for chemical reaction. Tribochemical wear involves surface
charging of electrons, surface passivation, and surface film
removal processes. The mechanisms of tribochemical wear

AND TRIBOLOGY FUNDAMENTALS

are complicated and they Eire still under investigation. Tribochemical wear can be controlled by the use of appropriate inhibiting additives.
Fatigue Wear
ASTM G 40 defines fatigue wear as "wear of a solid surface
caused by fracture arising from material fatigue." Material
fatigue, as defined by ASTM E 1823, refers to "the process of
progressive locedized permanent structural change occurring
in a material subjected to conditions that produce fluctuating
stresses and strains at some point or points that may culminate in cracks or complete fracture after a sufficient number
of fluctuations."
Fatigue wear prior to cracking is indicated microscopically
by surface pitting and spalling, which are caused by induced
subsurface shear stresses that exceed the critical shear stress
of the material. Pitting is defined by ASTM G 40 as "a form of
wear characterized by the presence of surface cavities the formation of which is attributed to processes such as fatigue, localized adhesion, or cavitation."
Spalling is defined as "the separation of macroscopic particles from a surface in the form of flakes or chips, usually associated with rolling element bearings and gear teeth but also
resulting from impact events." Various examples of pitting
and spalling due to fatigue wear processes are illustrated in
Figs. 39-41. Severe types of wear often involve scuffing, as
shown in Fig. 42.
Fatigue life is influenced by EHD lubricant film/surface
roughness ratio [10,11]. High localized stresses at surface defect sites, asperities, dents, and material inhomogeneity, will
reduce fatigue life [55b]. Figure 39 is an example of the fatigue wear in a diesel engine lifter. The effect of surface
roughness and lubricant film thickness on fatigue wear was
provided previously.
Bench tests may be used for fatigue evaluation. Figures 40
and 41 provide examples of fatigue wear evaluation using
bench test equipment. It should be noted that the fatigue lives
of nominally identical rolling contact bearings tested under
identical conditions could be widely different. This results in
the generation of a fatigue pit (see Fig. 41), which typifies incipient fatigue failure as dependent upon the action of cyclic
stresses and the motion of the rolling elements that randomly
contacted at asperities. The fatigue strength at N cycles, SN
(FL ^) of a material may be determined by ASTM D 1823.

(a)
FIG. 38Illustrations of oxidative wear, a) Oxidative wear obtained witli a medium carbon steel block-on-shaft lubricated
with a mineral oil in the presence of a copper nanometal additive, load = 110-184 N, 156-220 rpm and the picture has 750X
magnification. (Source: Dr. Sergey Tarasov, Institute of
Strength Physics and IVIaterials Sciences, Tomsit, Russia);
b) tribooxidation (oxidative wear) occurring om a Fe pin run on
a Co disk run under the following conditions: 14 N/cm^, 1 m/s,
> 10 km, 760 Torr and ft, = 0.25-0.28 (Source: E. Santner, BAM,
Berlin, Germany).

933

FIG. 39Fatigue wear in a diesel engine lifter.


Shows subsurface cracks at 500X magnification. (Source: J. Zackarian, Chevron Research
Company, Richmond, CA.)

934

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

.->"- ..i.=^=,.--.

^pn

(a)
(b)
FIG. 40Examples of fatigue wear: a) Co pin/Fe disk material pair at 14 N/ cm^, 1 m/s, 710 km, 1 Torr, and
fi = 0.33-0.34. (Source: E. Santner, BAM, Berlin Germany.), b) An AISI52100 pin on an AIS11015 steel disk,
load = 15 kg, sliding speed = 500 rpm and lubricated with a liquid paraffin. (Source: Prof. Liu Jiajun, Tsinghua University, Beijing, PRC.)

Direction of Rotation

^
FIG. 41Pitting fatigue wear obtained with twin 60 mm rotating S25C carbon steel disks The /u value for the driver is 1.0 and
the ft value for the follower is 0.40. The load is 1.6 x 10^
''Hertz = 950 MPa, and the rotating pair was lubricated with a
paraffin oil at 2 L/min. (Source: Prof. T. Kawazoe, Nagasake
University, Nagasaki City, Japan.)

The SN value is a value of stress at exactly N cycles as determined by an S-N diagram. The value of SN, thus determined,
is subject to the same conditions as those that apply for the
S-N diagram [50].
Fretting WearFretting is small amplitude oscillatory motion, usucdly tangential, between two surfaces in contact and
fretting wecir is wear that results from fretting motion (ASTM
G 40). Fretting is a form of adhesive wear that may occur
when the tips of the asperities of adjacent moving surfaces
come into contact and microwelding occurs. Continued
surface movement causes the tip of microwelded asperities to

FIG. 42Scuffing of a surface of a 7075-T6


aluminum disk sliding on a gearing steel ball of
6.36 mm dia. at a sliding velocity of 0.33 m/s with
a normal load of 4 kg. The sliding pair was lubricated with a paraff inic oil with a viscosity of 0.11
Pa s at 40C containing a colloidal PFTE
(Source: Dr. Sergey Tarasov, Institute of
Strength Physics and Materials Sciences,
Tomsk, Russia.)

pull off, producing a pitting effect. The heat of the microwelding process enhances oxidation of the fresh metal surfaces. If water is present, corrosion will result (fretting
corrosion). Waterhouse has reported that the fretting process
of steel is dependent on amplitude of slip; frequency and
normal force of the oscillatory process; condition of the steel,
particularly hardness; and temperature and humidity of the
environment [56,57].
Fretting wear will occur in locations where there are oscillatory deflections of clamped joints, spline and gear couplings, and connecting rod joints in internal combustion engines. Fretting wear is often accompanied by the production
of finely powdered and oxidized wear debris [58].
The four regimes of wear that are dependent on the displacement amplitude have been observed by Baker and Olver

CHAPTER

35: LUBRICATION

[59]. These four regimes, which are shown in Fig. 43, are designated as:
Regime 1"Stick" occurs at very small amplitudes producing very little damage,
Regime 2"Stick-slip" occurs with increasing displacement and wear rates increase slowly,
Regime 3Gross slip produces severe damage by oxidation
assisted wear which is the "fretting wear" regime
Regime 4In this region, reciprocating sliding wear occurs
eind if the amplitude is sufficient, the wear rate becomes
approximately constant which is characteristic of unidirectional sliding wecir.
i 1 1 = Slip

2 = Stick-Slip
3 = Gross Stick-Slip (Fretting)
4 = Oscillating Wear

c
0)
o
!^

^__4____
/

(D
O
3 /

o(D
<4mJ

CO

,1

on
L_

CD
<D

^ -t ^

1 y"^

Amplitude of Displacement (urn)


FIG. 43The four wear regimes including fretting
and reciprocating wear.

AND TRIBOLOGY

^^

935

The transition from Regime 3 to Regime 4 is the transition


from fretting wear to reciprocating sliding wear. This transition is controlled by the instantaneous quantity of wear debris remaining within the contact [59].
Although fretting and cracking are not related, cracking of
the metal at the wear contact may occur as shown by Zhou
and Vincent for fretting weeir of various aerospace aluminum
alloys such as that shown in Fig. 44 for 2091 and 7075 alum i n u m alloys [60]. In this case, a fretting fatigue crack was
nucleated due to the contact traction stress in the fretting
wear regime and then propagated. The cracking direction
was perpendicular to the fretting direction. No cracking was
observed until after 5 X 10^ for 2019 and 10* cycles for 7075,
at which time cracking occurred to a depth of 200 /j,m and
3500 /xm for 2019 and 7075 respectively, in this experiment.
Kalin et al. have examined fretting wear and the role of tribochemical reactions in the wear process under lubricated
conditions in detail [61-63]. It is shown that the very high
flash t e m p e r a t u r e s within the wear contact affect microstructural changes a n d phase transformations of steel.
However, one of the most important factors under lubricated
conditions was the effect of flash temperature on the tribochemical processes that may occur, even u n d e r relatively
low-speed, low-temperature conditions [61,62]. These studies showed that oil is a n important and chemically active
component of the wear contact. For example, carbon and
other elements that may be present may undergo thermally
induced surface reactions. One such reaction that was

eOOtim

lOOtom
(a)

FUNDAMENTALS

.e?^

Z-> '- ^^-~^^-:^

(c)

(b)
FIG. 44Fretting wear test results obtained with aluminum alloys: a) Al-Li (2091) alloy, N = 5 x 10^ cycles,
Fn = 500 N, f = 1 Hz, cracl( depth is 200 fjitn; b) Al-Zn (7075) alloy, N = 10^ cycles, Fn = 1000 N, f = 5 Hz, crack
depth is 3500 /tm (Source: Z.R. Zhou, Southwest Jiaotong University, Chengdu, China.)

936

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

observed was the introduction of carbon into the surface


structure of steel (carburizing) if the flash temperature at the
wear contact is sufficiently high. This is important because
increasing carbon content typically increases hardness, thus
affecting wear [61,62].
Recently, Kalin et al. examined these processes (along with
fretting wear of different material combinations) using a
commercially available ball on plate high-frequency fretting
machine [63]. The ball was composed of silicon nitride and
the plate was manufactured from AISI 52100 bearing steel.
The load was 88 N and the oscillation frequency was 210 Hz.
The lubricant was a petroleum oil. The wear surfaces were
examined microscopically, wear scars were measured and
examined by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS).
Selected wear test results are shown in Fig. 45. Figure 45a
shows cracks perpendicular to the sliding direction on the
steel plate after 360 min, and at a 5 /am amplitude [63]. The
size of the cracks increased with time. Figure 45b illustrates
that a tribochemical layer was formed on the steel plate after
10 min of testing at a frequency of 25 /im [63]. This layer was
brittle and it is evident that spalling has occurred, which was
consistent with the high wear loss that was observed over this
time. SEM and EDS analysis of the brittle layer shown in Fig.
45b suggested that a tribochemical reaction between the silicon nitride and the steel had occurred. Figure 45c shows the
results of SEM analysis of the wear scar on the steel plate after 360 min and a 50 /xm amplitude [63]. EDS analysis of this
tribolayer indicated a high amount of silicon from the silicon
nitride ball. The cracks occurred during cooling.

Scuffing
Scuffing is defined as "a form of wear occurring in inadequately lubricated tribosystems that is characterized by
macroscopically-observable changes in surface texture, with
features related to the direction of relative motion" (ASTM G
40). Surface texture is a term relating to surface finish, which
is described by the roughness (peak) height in microinches
and the n u m b e r of peaks per inch or it may be described as a
surface pattern relative to a smooth finish. In lubrication,
ASTM D 4175 defines scuffing as "surface damage resulting
from localized welding at the interface of rubbing surfaces
with subsequent fracture in the proximity of the weld area."
An example of scuffing wear is provided in Fig. 42.
The "Borsoff effect," which was originally published in
1959 [64], assumes that surfaces will scuff when adsorbed
(polar) molecules, which are used to provide extreme pressure (EP) activity, become critically depleted or disoriented.
A four-ball machine test was conducted to determine the
scuffing loads for hexadecane containing various concentrations of hexadecanoic acid. (The EN31 steel balls contained
1% chromium.) The rotational speed of the moving ball was
200 rpm. A plot of the scuffing load as a function of hexadecanoic acid is shown in Fig. 46 [65]. It was assumed that the
rotational speeds were sufficiently slow to permit molecular
response to the adsorption/desorption equilibrium process
and that scuffing occurred at the rear of the contact where
the contact temperature is maximum and surface coverage is
reduced to a constant, although unknown, value.
To explain this wear process. Spikes a n d Cameron assumed that scuffing failure will occur by an additive desorption process. At the point where this occurs, there is n o EP

FIG. 45Illustration of fretting wear under


petroleum oil lubricated conditions. The wear contact is a SiN4 ball on an AISI 52100 disk, a) SEM micrograph of the wear scar of the steel plate after 360
min. at 5 fivn amplitude; b) SEM micrograph of the
steel plate after 10 min at a 25 /jivn amplitude; and c)
SEM micrograph of the lubricating layer on the steel
plate after 360 min. at 50 fivn aplitude. (The cracks
occurred during cooling) (Source: M. Kalin, Center
of Triboiogy and Technical Diagnostics, University
of Ljubljana, Ljubljana, Slovenia.)

activity that would be analogous to a base oil with no EP additives. This effect may be shown thermodynamically using
the Langmuir adsorption equation for adsorbed (physisorption) polar molecules [66,67].
1 - 0

kC exp

-AH
RT

CHAPTER

35: LUBRICATION

AND TRIBOLOGY

FUNDAMENTALS

dislocations, and that the low speed sliding wear of metals is


caused by the subsurface crack nucleation and propagation
nearly parallel to the surface" [69,70].
Figure Ala shows subsurface deformation and strain gradients of AISI 52100 steel [70]. Figure 47fe shows crack formation due to delamination wear in cold-worked 1020 steel
[58]. Lim and Ashby proposed a mechanism for delamination
wear, which is illustrated in Fig. 48 [71]. In this model, it is
proposed that under conditions of plastic strain, voids nucleate around inclusions in the metal at a critical depth. Continual shearing action and compression cause the shape of the

600

0.002

0.004

Concentration (molar)
FIG. 46Scuffing load as a function of hexadecanolc acid in hexadecane obtained using a four-ball
machine at 200 rpm.

where: 6 is the proportion of surface covered by adsorbed polar molecules, k is a temperature-independent adsorption
constant, AH is the enthalpy of adsorption, T is absolute temperature, R is the gas constant, and C is a proportionality
constant. AH for reversible adsorption of additives is a constant and a value of 40 cal/mol has been reported by Spikes
and Cameron [67] and a value of 46 cal/mol was reported
by Grew and Cameron [68] for a dodecanoic acid/dodecane
system.
This work provides a reasonable explanation of the generally accepted view that a thick oil film is "safer" than a thin
film, even w h e n there is continual intermittent contact.
When there is a thick film, the tips of the asperities alone will
touch and touch only momentarily. This means that the time
when there is metal-to-metal contact is very short. Due to the
short time duration of the contact, a considerably higher
temperature is needed to desorb the polar materials than the
equilibrium value. As the film gets thinner, the areas in contact increase so each asperity is in contact longer and the
molecules have a longer time to respond to the asperity tip
temperature. For constant friction load, the load that can be
carried safely is also lowered. This means that a large film
thickness requires a higher surface temperature for scuffing
than does a thin film, therefore, thick films may carry greater
loads. Recent studies show that the scuffing is based on the
residence time of molecules physically or chemically adsorbed [66]. Scuffing wear is illustrated in Figs. 25a,b,c and
Fig. 42.
Delamination

937

(a)

Wear

Steel, and other metals, may undergo more traditional heat


treating processes such as carburizing, nitriding, and carbonitriting, in addition to newer methods such as PVD, CVD,
ion implantation, etc. to achieve more wear resistant surfaces, which are partially due to increased hardness and also
to increases in compressive stresses. When these materials
are subjected to a wear process they may produce "delamination," which is defined by ASTM A 902 as "the separation
of a coating (either full or partial thickness) from underlying
layers: the separation can occur in smaJl localized areas or in
large areas of a surface." This process is called "delamination
wear." The mechanism of the delamination wear process is
described by Suh et al. as "a non-work-hardening soft layer
surface which deforms continuously due to the instability of

(b)
FIG. 47a) Subsurface deformation of AISI
1020 steel; load = 2.25 kh after sliding 54 m in
argon atmosphere; b) three segments of a subsurface crack in cold-worked AIS11020 steel, a
and c show the ends of the crack and b shows
the mid-section of the crack. (Source: S. Janhanmir, NIST, Gaithersburg, MD.)

938

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

Surfaca^.

voids to change, leading to crack formation as shown in Fig.


48 [71].
Wear

In actual practice, there is typicEilly more than one mechanism


in a wear process. Wear volume, for example, depends on the
contact geometry, test conditions, lubricating additives, and
materiEds. Wear volume or weight loss can be measured continuously during the test or at the conclusion of a test. T3'pes
of wear, however, must be analyzed through surface characterization. Micrographs of different types of wear have been
shown in previous sections. Examples of wear as a function of
some of these variables are shown in Fig. 49 [72]. These figures illustrate the experimental evidence of load, sliding
distance, speed, and thermal conductivity. The combination
of basic wear processes is summarized in Fig. 50 [72].
In summary, it is difficult to simulate a specific wear pattern by using a particular test machine with standardized test
conditions from a standard test. Instead, it is necessary to

FIG. 48Photomicrographs of void formation around inclusions and crack propagation from these voids near the surface
in annealed Fe-1.3% Mo alloy. (Source: S.C. LIm, National University of Singapore, Singapore.)

O)

CO

Testing

10"

5r

10-'
o

10"

"TO
(0
0)

>
10

J_

10"
10

J-

10^

10

10^

800

c 55

<D

600

CO

0)

/c
a

/
/

c
1

(b)

SAE 1095 Steel


Mineral Oil Lubricant

25

~20

CO o

400
o ^

<D

<s>
a.
CO

30

^
// o)

0)

- O (/)

.ii

E
-a

o S

Sliding Distance (cm X 10" )


Load 0

- c
c

^ri-2kg
,

223 BHN Hardness


X 430 BHN Hardness

5^1
iilO

200

(c)

Load (g)

(a)

0.2

3 kg
1

0.4

Thermal Conductivity
(caL/cm-sec^C)

<u
E
o

>
SO

-r'9-7
0.1

0.2

0.3

J
0.4

i_j.
0.5

Normal Pressure / Hardness

FIG. 49Wear is dependent on several factors, a) load and material; b) sliding distance and material;
c) thermal conductivity, load and speed on the conditions to produce a photographic hot spot; d) wear
dependence on load and hardness.

(d)

CHAPTER 35: LUBRICATION

Metallic Bearing
Surfaces

Transferred

Metallic
Wear
Debris

Corroded
Surfaces

Corrosion
Product
Debris

1 Plowing or Fatiguo
SAdhosion
3 Corrotioii

FIG. 50Summary of basic wear mechanisms.

C
FIG. 51Pin-on-V-block tests
conducted by progressively increasing the load on the rotating pin
to evaluate the lubricating properties of a petroleum oil loaded with
EP additives. The test results indicated that the steel pin would
undergo extrusion without wear indicating excellent lubricating properties. (Source: D. Drees, Falex Tribology NV, Heverlee, Belgium.)

systematically consider materials, contact geometry, lubricants, applied pressure, and surface speeds in order to appropriately model the expected wear in a particular lubrication process. It is also necessary to develop test conditions
that simulate actual use conditions and failure modes that
are typically encountered during the use of the lubricant
through a tribological wear test design process.
There are numerous bench testing machines and standardized testing protocol. Current testing machines and procedures will be discussed in the next chapter and will not be discussed further here. However, two illustrations of the value
of lubricant testing will be provided here from the standpoint
of wear analysis.
In one test, the lubricant properties of a petroleum oil containing extreme pressure (EP) additives was evaluated using
a pin-on-V-block machine. In this case, the rotating pin was

AND TRIBOLOGY

FUNDAMENTALS

939

loaded at very high loads, which caused extrusion of the steel


pin, instead of wear, as shown in Fig. 51. These results indicated excellent lubricating properties. More extensive, but
similar, tests were conducted using a block-on-ring test configuration to classify the antiwear properties of a lubricant
and are shown in Fig. 52.
While wear test machines (tribometers) are commonly
used to determine relative lubrication and wear performance
of a lubricant and additive system, these results do not directly indicate how the test lubricant will perform in any particular application. Instead, opposite results may be obtained
in industrial equipment, rendering such bench test results as
misleading. Therefore, before such an assessment can be
made, some correlation of test results obtained under certain
conditions using a tribometer with actual performance in industrial equipment must first be performed.
Wear Debris AnalysisFerrography, which is an optical (visual) anal3rtical procedure, is one of the principle methods of
wear debris analysis. Ferrography is conducted using a ferrograph where a sample is prepared by depositing wear particles on a glass slide placed over a strong magnetic field. This
analysis procedure provides a measure of the concentration
and distribution of wear particles. Generally "benign" wear
occurs when the particles are less than 15 fim. Wear particles
producing catastrophic failure are typically > 200 jtim. Ferrography can be used to detect and characterize particles in
this range [73].
Examination of wear debris may be a useful indicator of
wear life of industrial machinery, which can be obtained
without shutting the equipment down and incurring often
immense production cost losses. Wear debris analysis may
also be considered to be a validation of wear tests if the debris analysis indicates the same wear is obtained in the industrial machine and in the bench test [74].
Cho has suggested a phenomenological approach to wear
debris analysis, which reportedly provides a concurrent correlation of material surface, wear mechanism, wear debris
analysis, and subsurface deformation [74]. Considerably
more complex wear maps have been developed for lubricated
contacts like those developed for steel as shown in Fig. 53
[75,76]. The map developed by Beerbower is based on a large
body of literature data for the correlation of Specific Wear
Rate, which was defined in the Adhesive Wear section, and
Specific Film Thickness (A), which is calculated from the oil
film thickness (ho) divided by the composite surface roughness ((aj + aiy^) as follows:
A='

ho

The importance of such an approach is illustrated by the


work reported by Leng and Davies who used wear debris
analysis to identify characteristic types of wear resulting in
scuffing, which were obtained using the four-ball test machine [77]. The conclusions of this study showed:
1. Scuffing generates large particles of wear debris showing
evidence of shear fracture on one surface. However, such
debris can be generated by a single overload.
2. Both carburized steel and AISI 52100 bearing steel, two
common steels used in tribological applications, exhibit a
featureless white layer during scuffing. It was proposed
that this white layer resulted from a friction weld.

940

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

(a,b)

(c)

FIG. 52Illustration of lubricant evaluation using the block-on ring tests by wear mode identification. The
tests conducted include: a) an example of adhesive wear on the test block caused by a bad lubricant; b) micrograph of the test block indicating mostly uniform wear, but in some parts of the wear track there is adhesive wear. This behavior is often called "scoring" but it signifies the limiting load that a lubricant can carry,
c) General adhesive wear, also called seizure, indicated by excessive scoring of the test block; d) some parts
of the ring (of the block-on-ring pair) show that adhesive failure occurred; e) in this case, there is uniform
wear on the test block which, in this case, indicates that the lubricant prevented adhesive wear. The extent
of the wear scar (width) can be used to characterize "antiwear" properties. (Courtesy of D. Drees, Falex Tribology NV, Heverlee, Belgium.)

10'-

/Pseudo - Scuffing
^
scumng
Corrosive IVIod^

Severe
Scuffing
^

y'^

<,#^/Mixed
^"S^- /Mixed

\<^

^'X^

_cp' C!^

/ ^
/

\,

Corrosive I

\
.

Corrosive

and Transfer I
1 Modes
L.

IVIodes

Violently Corrosive

\
\
\

10-*

)
| /
"S '
/ ^/
ro I Transfer / v. /
%>^ Mode
f/
r|.5l
11
^ a j
1 ^
w:

Vv

Sliding
(Contact)
Fatigue

Mixed
Corrosive
Fatigue

X.

\
\

Ideal System ^

I "Molecular Wear"

I
I I

0.5

1.0

1.5

2.0

Specific Film Thickness

2.5

3.0

Mode
_L
3.5

4.0

1/2

A=ho/ (oi+ai)'

FIG. 53Wear map for lubricated steel wear variation with changes in specific oil film
thickness.

CHAPTER 35: LUBRICATION AND TRIBOLOGY FUNDAMENTALS


3. Adhesion wear debris on the contact surfaces is very rare
in this system.
4. This wear debris cannot be used to characterize scuffing
wear generated using a four-ball machine.
This work shows that like all well-performed laboratory
work, proper correlations must be performed to assure the
applicability of the test data to the problem being analyzed.

941

where: U is the sliding speed in ft/min, and Tm is the flash


temperature in F.
In performing lubrication studies, there are occasions
when it is necessary to estimate the contact temperature,
such as when performing lubricant scuffing studies with a 4ball lubricant testing machine. To calculate the TCR, it is necessary to estimate the flash temperature (AT). The ATmax temp e r a t u r e for a "standard" 4-ball wear contact m a y be
calculated from a Blok-type equation [79]:

Flash Temperature
Flash

^Tn

Temperatures

As the wear surfaces come into contact, there is cin increase


in temperature due to a n increase in the heat of friction. The
contact temperature at the wear interface is dependent on the
applied load at the wear contact, time within the contact
zone, and sliding speed [78]. Work by Okabe et al. [16] and
Matveevsky [15] have shown that the effectiveness of additive
chemistry is also dependent on the geometry of the wear contact. The contact temperature is therefore a critically important controlling factor in controlling the effectiveness of lubricant additive chemistry and is a n important psirameter to
be measured [16,79].
Within a wear contact, there is localized instantaneous rise
in surface temperature due to friction. In most cases the temperature of the two frictionally heated surfaces is assumed to
be approximately equal and is defined as [80]:
Tc = Ts + AT
where: Tc is the m a x i m u m instantaneous surface temperature of the wear contact, Ts is the quasi-steady-state surface
temperature which is, although incorrectly, assumed to be
the equivalent to the oil bulk temperature of the lubricating
oil, and AT is the maximum rise of the instantaneous surface
temperature above the quasi-steady-state oil temperature.
The value of AT is also called the "flash temperature" [80].
When the value of Tc is sufficient to cause scuffing, this is
called the "critical contact temperature for scuffing" (TCR)
and is equal to:
TCR = TS +

AT

This is k n o w n as Blok's Critical Contact t e m p e r a t u r e


model. The value of TCR is a constant for a given oil-metcd
surface and (oil-metal surface-atmosphere) c o m b i n a t i o n
[80]. Interestingly, the value of TCR is independent of the oil
viscosity. However, variation of the metal and/or surface
treatment will significantly affect the value of TCR. The interrelationship between steel chemistry and antiwear protection
offered by various additives containing sulfur or phosphorous was described in detail by Huang et al. [81].
Rabinowicz has used the following general rule to estimate
the flash temperature of pure dry sliding motion [45]:

1.61nW^'V
k[l + 0.627(W/a)]0

where: /M is the coefficient of friction, W is the top ball load


(kg), n is the rotational speed in revolutions/second of the top
ball, k is the thermal conductivity (2.604 kg/s C), a is the
thermal diffusivity of steel (6.045 mm^/s), and r is the Hertz
contact in mm.
Experimentally, the flash temperature (AT) has been estimated directly from wear data using a 4-ball wear tester using the equation [82,83]:
AT = ^ W
1.4
where: W is the applied load in newtons (N), and d is the
m e a n wear sccir diameter (mm).
NOTE: The test balls used for the 4-ball wear tester Eire
constructed from 0.5 in diameter AISI 52100 Steel. The nominal composition of these balls is listed in Table 11 [82] and
the physical properties of AISI 52100 steel are summarized in
Table 12 [82]:
Sethuramiah reported that the relationship between load
and Hertzian (elastic) contact radius of the tetrahedreJ test
bcdl geometry was:
Load
(kg) = W (applied load) X 0.408
Ball
Radius of elastic contact (a) = 5.9 X lO""* W-^
Other equations for the calculation of flash temperature
have been reported by Cowan a n d Winer [84] a n d
Kuhlmann-Wilsdorf and will not be discussed in detail here
[85,86].
The effect of sliding versus rolling motion on flash temperature at the wear contact is illustrated in Fig. 54 [87]. Sliding
m o t i o n generates significantly higher flash temperatures

Tm - y ( factor of 3)

TABLE 12Physical properties of MSI 52100 steel.


Property
Hardness
Thermal Conductivity
Specific Heat
Density
Thermal Diffusivity

Value
760 kg/mm^
0.109 cal/cm C-s
0.11caygC
7.78 g/cm^
0.127 cm^/s

TABLE 11Composition of AISI 52100 used for test balls for 4-ball machine.
Composition
C

Mn

Si

Cr

0.95-1.10

0.25-0.45

0.025 max

0.025 max

0.20-0.35

1.30-1.60

942

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

90C
Pure Sliding

Pure Rolling

FIG. 54Illustration of the effect of rolling versus


sliding motion on flash temperature. As the relative
amount of sliding motion increases, there is a corresponding increase in flash temperature.

than rolling motion within the wear contact. This suggests


that wear in a rolling contact is mostly dependent on the rheology of the lubricant, whereas lubrication of sliding contacts
is m u c h more dependent on the additive chemistry since the
tribochemistry of some additives is "activated" by the temperature within the wear contact.
Wear

Maps

There has always been great interest in being able to predict


not only failure but also the failure mode. For example, Lim
and Ashby have reported a wear mechanism m a p for a nonlubricated sliding steel pin-on-disk pair, which is shown in
Fig. 27 [87]. In this particular study, four major wear mechanisms were identified including: seizures, melt-dominated
wear, oxidation-dominated wear, and plasticity-dominated
wear. (It should be noted that the term seizure in lubrication
has been defined in ASTM D 4176 as "welding between surfaces in relative motion that results in immobilization of the
parts,") Lim and Ashby defined the following wear mechanisms, which are indicated on the m a p in Fig. 27 [87]:
1. The seizure process involves large localized pressures,
which can form metallic junctions if the load is sufficient
to cause plastic flow. During sliding, these welded junctions are sheared and welded areas grow. If the loading is
sufficient, the real contact area will grow until it reaches
the nominal area at which point seizure occurs.
2. Melt wear occurs when the friction-induced localized temperatures are sufficient to melt the metal.
3. At sliding speeds below 1 m/s, the wear debris is mostly
metallic. However, at sliding speeds of 1 m/s, the flash temperatures (approx. 700C) are sufficient to cause mild oxidation wear. This is a localized oxidation but the oxide that
is formed is hard and brittle. However, at higher sliding
speeds, e.g., 10^ m/s, a thicker oxide film is formed, which
is hotter and more plastic and an even lower wear rate is
obtained. This is called sever-oxidation wear. The terms
"mild" and "severe" refer to the extent of oxidation, not
wear rate.
4. Plasticity-dominated wear is adhesive and delamination
wear. These processes were detailed in the Adhesive Wear
section above.

5. Ultra-mild wear occurs in a regime where the loads and


sliding velocities are sufficiently low so that very little wear
occurs.
Frictionally-induced temperature increases occur within
the wear contact, and the associated thermal stresses are induced, which should be accommodated in the analysis of
sliding wear. This was performed by Cowan and Winer using
a t h e r m o m e c h a n i c a l wear model to generate micro-and
macro-contact wear maps for designer use (Fig. 55) [84]. This
was performed by superimposing isothermal stresses induced from the surface traction on the thermal stresses from
frictional heating. These results were integrated with material yield criteria required for plastic surface deformation to
occur in the form of wear.
The wear m a p in Fig. 55 was generated for AISI 52100
bearing steel. The dimensionless Hertzian contact pressure is
(Po/<Tyo), which is the peak Hertzian pressure on the wear
contact divided by the failure strength of the material. Gt is a
measure of the relative importance of the thermal stress contribution and is defined as:
G, =

yfVa

Eac
kCl-r

where: E is elastic modulus of the material, at is the thermal


expansion coefficient, k is thermal conductivity, y is the heatpartition factor, V is Poisson's ratio, f is the coefficient of friction, and V is the relative sliding velocity of two bodies. Winer
uses the value of Gt as a thermomechanical wear control parameter.
With respect to Fig. 55, a micro-contact possesses a contact
radius of 0.1 ^tm-1 m m . A macro-contact exhibits a contact
radius of 1-10 mm. There are also four curves in Fig. 55 representing a thermal steady state (FQ), 0, 0.1, 1, and 10. The
scuffing wear region is above the FQ line. The n o wear region
is below the FQ line for the material of interest. For AISI

10'

a.
3
(A
(0

Wear Region
10
Conditional Wear Region

10 y

9>
c

10

CQ

(D

10'

CO
M

c
o
'm
c
(D

E
b

No Wear Region

lO"!
10
10^

\ 1 lUiK^I 1 luiiH\ 1 mill\ \ UiiitI 'siuii|

10 '

10'
10
1_
micro-contact
(G,<1.7X10'')

10'
TI

10'
G,

10'
J

macro-contact
(10 < G t < 1.7x10^)

FIG. 55The Cowan and Winer thermomechanical wear map


for AISI 52100 steel.

CHAPTER

35: LUBRICATION

0.5
0.4-

0
0.2
0.4
0.6
0.8
1.0
Shear Strength at the Contact Surface (f)
FIG. 56Wear mapping procedures have also
been developed to elucidate the classification
of specific types of wear such as the model for
abrasive wear.

52100 steel, the Fo line is approximately 10. The conditional


wear region is located between the FQ = 0 and Fo = 10.
No wear will occur in the "no wear" region because the applied stress (represented by the dimensionless Hertzian pressure) is less than that required to cause failure. Wear will occur in the wear region because the dimensionless Hertzian
pressure exceeds the strength of the material. In the conditional wear region, the possibility of wear depends on the Fo
value, which is a dimensionless measure of the contact time.
Wear mapping has also been performed to elucidate the
mechanism of abrasive wear [88,89]. The wear m a p shown in
Fig. 56 [88] provides a correlation of the degree of penetration (Dp) and the shear strength of the material. The depth of
penetration is calculated from:
D

= ^

^ -

AND TRIBOLOGY

Dp = R

UH,
2W

UH
rR^
2W

The lubrication mechanism for the transition from Region


I to Region II is that as the load increases, the asperities
within the contact are separated (/JL = 0.2) until the load is
sufficient to bring the asperities close enough to begin to
make contact. The higher asperities undergo deformation
and oxidation and tribochemical reaction films are formed if
suitable additives are present. At this point, the coefficient of
friction decreases (/a < 0.1). With further increases in the
load, there is an exponential increase in the n u m b e r of asperity contacts. However, until F ^ = FNm, the deformation,
oxidation and additive tribochemical surface modification
process is sufficient to maintain a low coefficient of friction.
At loads greater than F^^, the n u m b e r of asperities within

III
"Scuffing Regime"

\ 1

Where: a is the contact radius, h is the depth of the groove,


Hv is the Vickers hardness of the flat specimen, R is the radius of the cutting pin tip, and W is the load.
The shear strength (f) at the contact surface is calculated
from:

II
"Boundary"

f= 0.3-0.5

\
\

E
o
"5.

Where: r is the contact shear stress and k is bulk shear stress.


The abrasion mechanism, ploughing, wedge formation or cutting, was identified by determining the wear volume/groove
volume by SEM analysis [75]. On the basis of this work, the
following conclusions were drawn:
There are three mechanisms of abrasive wear;
The degree of penetration provided a wear severity index
that was dependent on normal load, cutting pin radius, and
material hardness.

943

This figure illustrates the complexity of steel lubrication.


Clearly, given the information here, it is inappropriate to take
a single value indicating fluid lubricating properties and attempt to apply t h e m in any application where the fluid may
be used.
De Gee et al. developed a load-velocity failure m a p representing "lubricated wear," shown in Fig. 57 to classify the
mode of lubrication as a function of applied force (L) and
speed (V) for AISI 52100 steel ball on a cylinder using paraffin oil as the lubricant [90]. In this approach, three wear regions were observed: Region I, which is partial elastohydrodynamic (EHD) lubrication; Region II where b o u n d a r y
lubrication occurs; and Region III which is representative of
wear for an unlubricated contacteven though the contact
was fully submerged in the paraffin oil lubricant. The lower
curve, Ai-S represents the transition from Region I to Region
2 and S- A3 is the transition from Region I to Region III. The
curve A2-S is the transition from Region II to Region III. Because the position of curve Ai-S-As is viscosity dependent, it
is assumed that it represents the transition from EHD lubrication. The point FNIH is the maximum load carrying capacity, which occurs at the velocity of V^. The increase of load
carrying capacity at V > Vm was assumed to be due to a loss
of lubricating film viscosity because of frictional heating.

1/2

D =

FUNDAMENTALS

Q.

<

f= 0.2-0.4

^I

Al

Region I Negligible Wear


Region II Mild Wear
Region III . Severe Wear and Scuffing

I
^ \ .
"(Partial) EHD"
f= 0.04-0.1,

"^
1
1
1
1

- _ ^

A3

v
Velocity (V) FIG. 57de Gee, Begelinger and Solomon wear map (transition diagram) for n AISI 52100 ball-cylinder wear contact in a
super refined paraffin oil at 30C and a viscosity of 1.4 x 10~^
Pa.s in dry air.

944

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Microattrition
# Micro-abrasion
-Mechanical fatigue
* Thermal fatigue
+ Chipping

.500

H.275

T3.200

60

cutting speed m/min.


J
I
L
120
180
240

360

Wear Mechanism Map, C5 Milling Inserts, 4140 Preheated Steel

FIG. 58Wear map illustrating the wear mechanisms involved in cutting of preheat treated AISI4140 steel using an uncoated C5 carbide insert.

the contact exceed the oxidation and tribochemical modification rate and incipient scuffing (Region II) or full-scale
scuffing (Region III) begins (Vs).
De Gee and coworkers have shown that the contact temperatures in this system may be as high as 500C at the A2-S
transition, which would be sufficient to lead to metallurgiccJ
transformations [90]. It is therefore proposed that the onset
of scuffing may be "triggered" by a metallurgical transformation. The general subject of metallurgical transformations
that may occur on the wear surface will not be discussed further here, however, the reader is referred to Refs. 91-97 for a
more detailed discussion of these processes.
As a result of this work de Gee cited that the often widely
varying wear rates reported in the literature may be more due
to differences in the wear regime during testing than differences in additive performance. Furthermore, meaningful additive evaluation could only b e achieved with identical conditions of boundary lubrication.
De Gee et al. have studied the wear mechanisms involved
in the cutting of preheat treated AISI 4140 steel [98]. The
mechanisms of flank wear of a n uncoated C5 carbide insert
(as well as various nitride coated inserts) were determined
and mapped as a function of cutting speed and feed rate. The
predominant wear mechanisms were determined to be adhesion wear (also referred to as attrition wear) abrasion wear,
mechanical fatigue, cind thermal fracture. The wear map for
the use of a C5 carbide insert to cut preheat treated AISI 4140
steel is provided in Fig. 58 [98]. Figure 59 is SEM photographs of flank face wear, which illustrates the trend of mi-

0.275
mm/rev.

0.200
mm/rev.

3"
(D
Q.

3J
0.125
mm/rev.

59.9 m/min

119.7 m/min

179.6 m/min

239.4 m/min

359.1 m/min

7m/s

2m/s

3m/s

4m/s

6m/s

Speed
FIG. 59Wear of the flank face using a scanning electron microscope (SEIU) at 1000X magnification to illustrate the trend of microattrition wear, microabrasion wear and thermal pitting for cutting of preheat treated
AISI 4140 steel using a C5 carbide insert under "wet cutting" conditions. Increasing cutting speed is shown
going from left to right and increasing feed rate is shown going from bottom to top of the photo array.
(Source: S. Tung, GM Research and Development Center, USA.)

CHAPTER

35: LUBRICATION

croattrition wear, microabrasion wear, and thermal pitting


for cutting of preheat treated AISI 4140 steel using a C5 carbide insert under "wet cutting" conditions.
A single load capacity n u m b e r does not adequately define
the multi-dimensional character of a lubricant and provides
little help to the designer. A multi-dimensional characterization of an oil must also include such attributes as "antiwear,"
EHD film-forming ability, and traction coefficient. Wedeven
has demonstrated a more comprehensive approach to evaluate the lubricating characteristics of an oil by mapping the
performance of a contact system over a range of rolling amd
sliding velocities. This is illustrated in Fig. 60 for the oil HercoA [18]. These diagrams are called "Performance Maps."
Performance maps Eire developed in terms of rolling (entraining) velocity versus sliding velocity. The generation of a n
EHD film is primarily a function of the entraining velocity in
the inlet region of the contact upstreemi of the Hertzian contact region. In this region, the lubricating film generation is
primarily a function of the physical properties of the lubricant (viscosity and pressure-viscosity coefficient).
The sliding speed determines the shear strain in the
Hertzian contact region. This region is important with respect to heat generation, surface film formation, and wear
and scuffing within the tribo-contact. The magnitude of the
sliding velocity component within the Hertzian contact region, along with the degree of surface interactions, invoke the
chemical properties of the fluid, e.g., adsorbed films, chemical reaction films, tribochemical reactions, and thermal/oxidative stability.
A "performEmce m a p " is used to characterize the scuffing
boundaries for a lubricant. These scuffing boundaries are

AND TRIBOLOGY

FUNDAMENTALS

identified by plotting the onset of scuffing after testing the lubricant on a precision ball-on-disk machine at various rotational and sliding speeds at a given load as shown in Fig. 60
[18].
These examples show that development of a wear m a p permits a more global illustration of various lubrication and wear
mechanisms that may potentially be involved in a wear process and provide a much greater and more useful overview of
lubricant performance than a single bench test [99].
Lubrication Mechanisms
Lubricants are delivered to two surfaces undergoing relative
motion to reduce friction. Although lubricants may be in liquid, gaseous, and solid states, this chapter will focus on liquid lubricants, primarily those derived from petroleum oil. It
is genercdly accepted that liquids exhibit three lubrication
regimes: boundsiry lubrication, elastohydrodynamic lubrication, and hydrodynamic lubrication.
The Stribeck curve is a plot of the friction coefficient (/i) as
a function of the product of absolute viscosity (17) and the rotation speed in revolutions per unit second (N) divided by the
load per unit projected bearing area (P), as illustrated in Fig.
61 [100]. Because the Stribeck curve exhibits a characteristic
minimum, this suggested to McKee and McKee as early as
1929 that more than one lubrication mechanism is involved
[101]:
M
At least four lubrication regimes [18] are indicated in Fig.
62, which is a plot of the coefficient of friction versus the

Performance Map
Herco-A, 300 KSI Stress
"HG" M50 Ball (Ra=10), M50 Disc (Ra=3)
6S0

600 -

NA276-NA306

sso 1^

500

1,30
IS

400

o
>
(SO

MO

g
j3

250

200 -

XTl

ISO 100 -

945

Scufr

50

^
so

250

R. Entraining Velocity (in/s)


FIG. 60Wedeven performance map correlating sliding and rolling velocity at a
constant load to identify the scuffing region for a lubricant. (A precision ball-on-disk
test.)

946

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK
substantially greater t h a n surface asperity heights. EHD lubrication is characterized by thin film lubrication with film
thickness of approximately 0.025-2.5 fim. Although these are
thin films, they are greater than the asperity contact heights.
Boundary lubrication is characterized by film thickness of ^
0.025 /u,m, which is less than the height of the asperity contacts. Mixed film, or EHD/boundary lubrication, occurs at
the transition from boundary to EHD lubrication. For comparison, the relative sizes of various components of a wear
contact are provided in Table 13 [102].
Hertzian

Contact

If one body is pressed against another with sufficient pressure, an elastic deformation will result, as shown in Fig. 8
[103]. The pressure generated in this contact is the Hertzian
200

Z = centipoise
N" = rev/min

400

600

stress (CTH):

ZN'
P

(TH

load/length x dia p.s.i.


= clearance ratio thou/inch

1.5 LE^
TT^r^dv'Y

where: L is the contact loading, v is Poisson's ratio, for most


materials it is 0.3, r is the contact radius, and E is the modulus of elasticity. Table 14 provides typical values for the
elastic modulus for various materials including: aluminum,
copper, and stainless steel [104].
Hertz's equation for plastic deformation permits the calculation of the "true area of contact" (A^) in the Hertzian Contact region is [45]:

FIG. 61The Stribeck curve.

rBoundary
rMixed

rElastohydrodynamic

Ar = 2.9 [L rf^

c
o

assuming that Poisson's ratio (j') for both surfaces is 0.3.


Lubricated Hertzian ContactIt was shown previously that a
ball will elastically deform in the Hertzian contact region,
which is much smaller than the radius of curvature [105].
The "Hertzian pressure" that produces the elastic deforma-

Hydrodynamic

c
o

TABLE 13Size ranges of various components of a


wear contact.

(D
O

o
0

10

Specific Film Parameter

20
A=.

JL^

(af+ai)

0.5

FIG. 62Characterization of lubrication regimes as a function of the coefficient of friction and the dimensionless film
parameter.

"Typical" Component

Approximate Size
Range (lira)

Monomolecular Layer
Sliding Wear Debris
Boundary Film
EHD Film
Asperity Height
Rolling Wear Debris
Asperity Contact
Hydrodynamic Film
Asperity Tip Radius
Concentrated Contact Width
Engineered Counterformal Radius
Engineered Conformal Radius

0.2-2 X 10^^
0.002-0.1
0.002-3
0.01-5
0.01-5
0.7-10
0.7-10
2-100
10-1000
30-500
1-100 X 10^
12-2500 X 0*

TABLE 14Elastic modulus of selected materials

lambda VcJue described earlier and which is also known as


the dimensionless film p a r a m e t e r . The four lubrication
regimes are: hydrod3mamic, elastohydrodynamic (EHD or
EHL), mixed EHD (or EHL) and boundary lubrication, and
dry-film boundary lubrication.
Hydrodynamic lubrication is characterized by relatively
large film thickness, tj^jically greater than 0.25 /tm, which is

Materials

Elastic Modulus (Gpa)

Aluminum
Copper
Stainless steal
Alumina
Silicon nitride
Polyethylene-high density
PTFE (25% glass fiber)

70.6
12.98
180-220
300-400
280-310
0.5-1.2
1.7

CHAPTER 35: LUBRICATION


tion exhibits a parabolic distribution, as shown in Fig. 8a and
Fig. 13, which is high in the center and low at the edges of
contact. Typical Hertzian pressures found in bearing and
gear contacts are very high, approximately 1.4 X 10' N/m^
(200 000 psi).
The Hertzian contact is a dominating feature of elastohydrodynamic (EHD) lubrication. It establishes the overall
shape of the contacting surfaces. The fluid will first enter an
"inlet region" and then pass through the converging surfaces
and finally exit through a diverging region. The hydrodynamic pressure in this region must be sufficient to separate
the surfaces that are forced together by the approximately 1.4
X 10' N/m^ pressure within the Hertzian contact.
Inlet RegionThe surfaces shown in Fig. 63 are in pure
rolling motion, each moving with the same velocity (U). Each
surface carries with it a certain quantity of fluid that joins to-

AND TRIBOLOGY FUNDAMENTALS

gether at the same location to fill the gap between the surfaces. Due to surface convergence, fluid in the interior must
slow down, as shown in Fig. 63, or even flow in the reverse direction. The reduction in velocity causes an increase in hydrodjmamic pressure of the fluid. Because of the viscositypressure relationship of the fluid, as illustrated in Fig. 64,
fluid viscosity increases as the pressure increases within the
inlet region [18]. (See the Pressure-Viscosity Coefficient section for more discussion on the viscosity-pressure relationship of fluids.)
EHD Film Thickness Measurements by InterferometryEHD
film thickness measurements may be experimentally determined using the optical fringe color in the center of the contact as a function of rolling velocity. Optical film thickness is
measured at the "center" of each fringe and at the transition
between each fringe. The optical film thickness data is con-

Rlm

FIG. 63Illustration of fluid flow contours with the Inlet region. Pure
rolling motion at relative velocities Ui and U2 is assumed for this illustration.

O Fluorinated Polyether

Linear Polyperfluoroalkylether
A Super-Refined Naphthenic Mineral Oil
V Synthetic Hydrocarbon (traction fluid)
V- Advanced Ester

50

947

100

Temperature C

FIG. 64Fluid viscosity increases with increasing pressure as the fluid enters the inlet region and Hertzian contact region. Typical viscosity pressure relationships of different base fluids is provided.

948 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 15Conversion of optical fringe colors
to film thickness.
Optical
Fringe Color

Optical Film Thickness


(M X 10"')

First yellow
Red
Blue
Green
Second Yellow
Red
Blue
Green
Third Yellow
Red
Blue
Green

2.0
2.7
3.4
4.3
4.7
5.6
6.1
6.7
7.6
8.6
9.0
9.6

verted to actual film thickness by making corrections for the


refractive index of the test fluid, including the effect of pressure on density under the Hertzian contact. Fringe colors and
their relation to film thickness are shown in Table 15. The
Lorenz equation [106] is used to correct the refractive index
for density emd the Hartung's empirical formula for hydrocarbons is used to correct the density for the Hertzian pressure used in the test.
Reynolds EquationThe practiced importance of the EHD lubrication mechanism lies in the thickness of the oil film between the surfaces, which is controlled by operating conditions such as surface velocity, load, cind fluid viscosity. The
influence of various operating parameters on film thickness
(hm) is illustrated by the following Reynolds equation for a
line contact formed by a cylinder on a plane [107]:

h
Where:

0.7 ,0.54
DO.43
2.65 (rjo f/r^
a'
R"

hm = film thickness at the rear constriction of the


Hertzian contact
rjo = viscosity at atmospheric pressure
a = pressure - viscosity co-efficient
U = velocity defined as 1/2 (Ui + U2) where Ui and
U2 are the individual velocities of the moving
surfaces
R = radius of equivalent cylinder
L = load per unit width
E = elastic m o d u l u s of equivalent cylinder (flat
surface assumed completely rigid)

An important feature of EHD lubrication is that the influence of load on film thickness is relatively small since increasing the contact load would result in an increase in the
maximum Hertzian pressure, which increases the Hertzian
contact region. Therefore, there is little effect on the inlet region where hydrodynamic pressure is generated.
Although the effect of pressure on lubricant viscosity is an
i m p o r t a n t p a r a m e t e r in lubricant fluid-film analysis, the
pressure-viscosity coefficient is often unavailable. However,
this data can be obtained by calculation using the Reynolds
equation if film thickness can be measured in the contact region [108]. This is obtained from a plot of the dimensionless
film thickness parameter (ho/R) where:
ho = film thickness in the center of the contact,
R = combined radius of curvature of the Hertzian contact

and the speed parameter which is defined as:


E^R
where:

Ue =
E' =
R =
T/o =

entraining velocity = 'A (Ui + U2)


combined elastic modulus
combined radius of curvature
viscosity at atmospheric pressure and at the
test temperature.

The only EHD lubricant characteristic missing from the


two dimensionless parameters is the pressure viscosity coefficient (a) and load (w). The "effective" pressure-viscosity coefficient is calculated from the slope of the line for the fluid
being eveduated as shown in Fig. 65 [108]. For the work illustrated, the film thickness measurements were conducted under the same load. If the a-value for each fluid was the same,
the film thickness data would fall on the same line. Higher
values of ho/R for the same (rjoUe/E'R) reflect higher pressure-viscosity coefficient.
Non-Newtonian EHD and Micro-EHD LubricationFluid viscosity within the inlet region of the Hertzian contact is not
only dependent on temperature and pressure but also on the
non-Newtonian rheological properties of the fluid [109].
Hirst and Moore demonstrated that the critical factor is not
shear rate but shear stress within this region [110]. The critical stress is dependent on the pressure and molecular size.
When the critical stress is exceeded in EHD lubrication, traction coefficients, heat generation, and film thickness will be
affected.
The impact of non-Newtonian viscosity behavior on effective film thickness has been successfully modeled with an
equation developed by Bair and KhansEiri, which incorporates the "second Newtonian" obtained from the Carreau viscosity equation [109]:

"l+A(f^^*"""^
Dimensionless Film Thickness vs Speed Parameter

Nominal Test Temperature 23 C

E'R
FIG. 65Dimensionless film thickness versus speed for different fluids at 23C.

CHAPTER

35: LUBRICATION

where A is a time constant, n is the well-known power law


coefficient, ryo is the viscosity at zero shesir rate, TJOO is the
viscosity at very high shear rates, 17 is the non-Newtonian
viscosity, and dV/dz is the change of viscosity with cheinge of
shccir rate.
The Carreau model provides a continuous transition between the first and second Newtonian regions of the power
law viscosity curve (Log viscosity versus Log shear rate).
Chang a n d Zhao have c o m p a r e d Newtonian a n d nonNewtonian analysis of micro-EHD contacts. Based on numerical analysis, it was concluded that the shear thinning
effects of the lubricant would produce significant errors if the
non-Newtonian behavior is not properly accounted for [111].
Effective pressure-viscosity coefficients have been reported
to be dependent on the non-Newtonian behavior of lubriczints within the inlet region of the Hertzian contact [112].
Mixed EHD Film LubricationMixed-EHD
film lubrication
is encountered during the transition from fuU-EHD film to
boundary lubrication. In this region, surface roughness (texture) effects are particularly critical. A c o m m o n method of
accounting for surface roughness effect is through the use of
the specific film parameter (A):
h

RMS

+Ritr'

(^q,a

where: Rms is the RMS composite asperity amplitude [R^,a +


R^b]"'^ for surfaces a and b of the wear contact. Figure 57 illustrates the effect of the magnitude of the film pairaxneter on
the lubrication mechanism [3].
The effect of both oil viscosity and surface roughness has
been studied [113,114]. The influence of surface roughness is
m u c h greater than the effect of fluid viscosity. The loading
capacity before scoring, galling, scuffing or seizure was
highly dependent on surface smoothness. The presence of a
single scratch may cause total failure by seizure.
Hydrodynamic

Lubrication

Hydrodynamic lubrication is characterized by conforming


surface so that the load is carried over a large area. Since relatively thick films characterize this region, lubrication is primarily dependent on bulk fluid viscosity at the operating
temperature of the system as predicted by the Stribeck curve
parameters (ZN/P).
Petroff's LawPetroff, in his classic aneJyses of lubrication,
assumed that the lubricant sticks to the surfaces of the journal bearing, the shaft was concentric, and that the velocity
gradient was equal to U/c where U is the surface speed of the
shaft jind c is the film thickness. The frictional torque (T) is:
^
vRU
T =
c

,
A

Where : rj is viscosity, R is the radius of the bearing and A


is the "wetted" area [115].
The coefficient of friction (/LA) is:
jLt =

vn

1000

where: n is the rotational speed in 1000 revolutions per


second, P is the load per unit area, and 8 is the radial cleareince ratio 1000 c/R in thouscindths of inch per inch of shaft
diameter.

AND TRIBOLOGY

FUNDAMENTALS

949

This may be rewritten in the more familiar form of the


Stribeck curve shown in Fig. 6 1 .
Zn
Where: Z is Zahigkeit, the German term for viscosity, n is the
surface speed, P is the applied pressure, and ho is the average
film thickness.
It is important to note that although the most c o m m o n
form of this equation, the so-called Stribeck curve, only provides a plot of the coefficient of friction (^tt) versus Zn/P. However, this is not rigorously correct. The actual value of ho is
not 1.0, although it rarely exceeds 1.5 [115]. The nearly linear
right hand portion of the Stribeck curve representing hydrodynamic lubrication is called the "Petroff Line."
In Fig. 61, both the experimental relationship for the coefficient of friction and ZN/P cind the Petroff line are shown. The
experimental data differs from Petroff s line at low values of
ZN/Pho because Petroff did not account for the temperature
dependence of viscosity, especially at higher temperatures or
the effects of surface asperity vziriation at low cleareinces.
Boundary

Lubrication

Tribochemistry of the Lubricated Wear Contact


Wear Material SurfacesAs the Stribeck curve in Fig. 61
shows, if a fluid film with sufficient thickness and viscosity
separates two surfaces, lubrication is hydrodynamic with no
asperity contact. However, as the load is increased or speed
decreases, the two surfaces will converge, and if they are sufficiently close, asperity contact will just begin to occur. Of
course, thicker fluid films are required as the surface roughness increases as indicated by the Lambda {A) factor (see previous discussion).
This region is designated as "Mixed-film" lubrication as
shown in Fig. 62. As the two surfaces come even closer in
proximity to each other there will be sufficient asperity contact to enter the "boundciry lubrication" regime. Under conditions of asperity contact, increased friction, asperity welding, and adhesive weeir will result [116]. To prevent excessive
w e a r and m a c h i n e c o m p o n e n t failure u n d e r these conditions, the use of boundary additives is necessary.
Although nascent metal surfaces may be formed during the
wear process and may be involved in some lubrication mechanisms, the surfaces that are most commonly encountered
are typically in an oxide form. The surface chemistry and the
lubricant films that are subsequently formed through additive interactions are dependent on the presence of oxygen
and water [117,118].
In addition to the identification of the failure mode, it is often desirable to examine the mechanism of the surface chemical reactions that have occurred. This may be accomplished
by conducting the additive reaction during the lubrication
process using bench testing laboratory equipment. After the
test, the surface chemistry is studied by various surface
chemical characterization methods. It is beyond the scope of
this chapter to review the characterization methods such as
those summarized in Table 16 [119a].
Friction

Modifiers

Friction modifiers are polar compounds, usually derived


from animal or vegetable oils, and they operate by adsorbing

950 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 16Summary of various methods of surface analysis.
Acronym

Name

Probe

Detection Signal

Information

Space Resolution

Applications to Tribology

Elemental
analysis of the
surface

= 50 nm.
depth
1.5 m m

Illumination
spectrum,
composition
Electronic
status of very
small portion

= 5 fan

Depth direction
profile of each
element at friction
surface (+ ion gun)
Lattice defects and
compression analysis
{+ EPMA)
Elemental
analysis, electron
state analysis
(4-TEM)
Stress due to slip.
film thickness
changes, etc.
50 n m
Analysis of slip
products

AED

Auger electron
spectroscopy

Electron

CL

Cathode
luminescence

Electron

Photon

EELS

Electron
energy loss
spectroscopy

Electron

Electron
(Scattered)

ELL

EUipsometry

Light (laser)

Light
(polarized)

Optical
constant, film
thickness

EPMA

Electron probe
microanalysis

Electron

Characteristic xray

EDX, WDX
quantitative
analysis

ESR

Electron spin
resonance

Magnetic
field

Electromagnetic
wave

Unpaired
electron
(radicals, etc.)

XAFS

X-ray
absorption fine
structure

X-ray

X-ray
absorption

0.2 n m

FIM

Field ion
microscopy

Neutal
molecule +
electric
field

Cation

EXAFS
(distcince to
surrounding
atoms,
number):
XANES
(atmic value
configuration)
Atomic
configuration

NMR

Nuclear
magnetic
resonance

Magnetic
field

Electromagnetic
wave

Molecular
bonding
condition

> 10 fim

IR

Infrared
absorption
spectroscopy

Light
(infrared)

Light
(infrared)

Vibration
condition

Thin film
acceptable

LEED

Low energy
electron
diffraction

Electron

Electron
(diffraction)

Molecular
bonding
condition

RBS

Rutherford
backscattering
spectroscopy
Optical
profilometry

Ion beam

Scattered ion

Vibration
condition

Several
atom layers
below the
surface
> 100 fjLm

Light (laser)

Light
(interference)

Surface atomic
structure

RS

Raman
scattering

Light (laser)

Light (Ramsin
scattering)

SEM

Scanning
electron
microscope

Electron

Electron
(secondary
scattering)

Trace
elements,
atomic
configuration
Surface
topography

OPM

Auger electron

= 10 n m
Depth
direction
50 fjon
Several 10
/Lim, depth
direction
= 0.5 /xm.
depth
direction
0.3 to
several ^ m
10' spins

Sub - /jan.
depth
direction
0.5several n m
1 fj,m

= 1 nm.
depth
direction
0,3several /nm

Lubricant
deterioration and
dangling bond
analysis
Composition of
adsorbed
substances

Three dimension
structure at atomic
level resolution,
(+ electric field
evaporation)
Adsorption
condition of
lubricant,
molecular
mobility, surface
functioned radicals
Analysis of
adsorption
performance of
gases and
lubricants (FT-IP,
RAS, ATR,
polarization)
Gas adsorption at
surface (+AES,
RHEED)
Alalysis of slip
products, thin film
density)
Imaging to slip
surface

Electronic
properties of thin
films, etc
Damage forms
(In-situ as well.
+ EPMA)

(continues)

CHAPTER 35: LUBRICATION AND TRIBOLOGY FUNDAMENTALS

951

TABLE 16(continued).
Acronym

Name

SIMS

Secondary ion
mass
spectroscopy

SPA

Surface
potential
analysis
Scanning
probe
microscopy

SPM

STEM

TA

TEM

TOFSIMS

TDS

TXRF

Probe
Ion beam

Detection Signal

Information

Secondary ion

Combination
condition

Electric field

Topography

Space Resolution

Applications to Tribology

Several
fan, depth
direction
0.5several n m
Several 10s

Exrtremely small
quantity elements
detection including
hydrogen
Slip charge

fjm

Electric
field

Tunnel current

Sixrface and
subsurface
formation

Scanning
transmission
microscopy
Thermal
analysis

Electron

Electron
(transmission)

Polarization

Thermal
energy

Heat dissipation

Transmission
electron
microscopy
Time of flight
SIMS

Electron

Ion beam

Electron
(transmission.
diffraction)
Secondary ion

Thermal
desorption
spectroscopy
Total-relection
x-ray
flourescence
spectroscopy

Thermal
energy

Desorbed atoms,
molecules

Microscopic
surface
structure
Shape,
structure
elements
Heat of
adsorption,
heat of
transition
Imaging

X-ray

Fluorescent
x-ray

Composition
distribution

0.1 nm.
depth
direction =
0.1 n m
< 1 n m

10 n m
0.1 n m
100 fjim.
depth
direction 1
nm

10^

atoms/cm^
depth
direction
several n m
1 fim

UPS

Ultraviolet
photoelectron
spectroscopy

Light
(tdtraviolet)

Photoelectron

Adsorption,
material
decomposition

XRD

X-ray
diffraction

X-ray

X-ray diffraction

Trace element
cmalysis

Several
100s fjan,
depth
direction

XPS

X-ray
Photoelectron
spectroscopy

X-ray

Photoelectron

Chemical
composition

100 /xm.
depth
direction
several n m

on to the wear surface by a physisorption or chemisorption


process from the fluid lubricant. Other terms used to refer to
this class of additives include: oiliness additives, lubricity improvers a n d film strength enhancers [119b]. Although the
thickness of these adsorbed boundary lubricating molecular
films is typically 2 X 1 0 ^ to 3 X 10~^m, they reduce friction
and wear under sliding conditions that are too severe for the
base lubricating oil [120]. Friction modifiers are typically
used under low to medium load conditions. Under more severe conditions where the load ind contact temperature increases at the wear contact, the protective adsorption film
ruptures, resulting in increased wear.
Although investigation of additive reactions are commonly
studied by tribological experiments, it is also important to
consider the effect of not only contaminated surfaces but also
solvent cleaning procedures since either may exhibit enor-

Various
applications
including STM
and AFM
Crystallization in
very fine regions
(+ EDX, + EELS)
Adsorption energy.
lubricant
deterioration, etc.
Transition cell
structure, reaction
products, etc.
Lubrication
distribution,
deterioration
Identification of
adsorbed and
stored materials
Surface
contaminants

Surface oriented
tribological
anedysisbonding
state
Thin film
structure, internal
pressure defects,
etc. (including
neutron
diffraction)
Surface oriented
tribological
analysis, bonding
state, lubricant
film thickness
(+ ion gun)

m o u s and often a n o m a l o u s affects on fluid lubrication


[121,122]. Therefore, it is essential that the various surface
cleaning procedures as well as lubrication conditions be reported.
Additive Classification
As indicated above, as the wear contact surfaces approach
each other with decreasing film thickness, surface asperities
come into contact. To prevent reduced friction and wear,
boundary lubrication additives are used. Table 17 provides a
summary of the c o m m o n classes of boundary lubricant additives used in lubricant formulation along with their purpose,
function, and chemical type [123].
The selection of appropriate friction modifiers, and antiwear and extreme-pressure additives is dependent on a number of factors including: activation temperatures, load effects
and reaction mechanisms between the additive and the sub-

952 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 17Common additive types and function in lubricating oil formulations.
Additive
Friction Modifier
(FM) or Oiliness
Additive

Purpose
Reduce friction under
near-boundary
conditions

Antiwear Additive

Reduce wear

Extreme Pressure (EP)


Additive

Prevent, galling,
scoring and seizure

666666666666

Typical Compounds
High molecular weight
compounds such as fatty oils,
oxides, waxes, fatty acids,
fatty alcohols
Organic phosphates, phosphites,
zinc dithiophosphates
Sulfur, phosphorous, chlorinecontaining materials

It

Van Der Waal


Forces

EsSSJ^
(a)

Function
Adherence of polar
materials to metal surfaces
Forms a film on metallic
contacting surfaces
Formation of low-shear
films on metal surfaces at
the wear contact

C-ssO
1 ;
0 .'

IV

H
t

OCu 0 Cu 0

OCuO CuO

FIG. 67A hydrogen exchange interaction for fatty acids on a copper substrate.

iJjggJjgffivjSJi
(b)
FIG. 66Adsorption models for: a) physisorptlon; b) chemisorption.

strata. These effects will be discussed in detail in the subsequent discussion.


Friction ModifiersFriction modifiers are adsorbed from the
lubricant on to the wear surface, either physically (physisorptionsee Fig. 66a) or chemically (chemisorptionsee
Fig. 66b). Physisorption is a thermodynamically reversible,
relatively weak adsorption processes (no chemical bond formation) based on dipole or van der Waal's forces [124].
Chemisorption is thermodynamically irreversible and is
based on considerably stronger ionic bond formation with
the metallic oxide wear surface. The adsorption forces between a carboxylic acid and a metal substrate due to hydrogen bonding and debye orientation forces have been reported
in the range of 13-15 kcal/mol [125]. Figure 66 illustrates the
difference between the two bonding mechanisms [126]. A hydrogen exchange interaction for fatty acids on a metal substrate such as copper has been postulated, as shown in Fig.
67 [127].
Additive adsorption on to the metal substrate of interest is
an important method of characterization of friction modifiers. The role of surface adsorption of various carboxylic
acids on boundary lubrication was studied as early as 1922
by Hardy and Doubleday [128]. More recent work by Studt
has illustrated that increasing fluid temperature decreases
the efficiency of adsorption of stearic acid from cetane, as
shown in Fig. 68 [129,130,150].
Steric hindercince on the adsorption efficiency of the adsorbing group with respect to the remainder of the molecule
signiflcantly affects adsorption of 1-, 2- and 3-octadecanol in

-or

8 x 1 0

Mole Fraction of Stearic Acid in Cetane


FIG. 68Increasing fluid temperature has decreased adsorption of stearic acid from cetane.

heptane, as shown in Fig. 69 [102,130]. In general, adsorption efficiency decreases as the polar group is moved from
the end (1-octadecanol) to the middle (5-acdecanol), which is
due to increasing stearic hinderance of the adsorbing group.
Hironaka illustrated the dramatic differences in the heat of
adsorption of stearic acid as a function of the surface condition of the metal substrate, as shown by the heat of adsorption of stearic acid on FeS, Fe304 and Fe203 in Fig. 70 [120].
Experimental determination of adsorption isotherms, such
as those shown in Figs. 68 and 69, m a y b e performed through
procedures described earlier by Forbes and Reid and others
[130] where a tumbling a p p a r a t u s described by Clunie is
used [131]. For these experiments, 5 mL borosilicate glass adsorption tubes are used into which 1.0 g of the iron powder

CHAPTER 35: LUBRICATION

AND TRIBOLOGY FUNDAMENTALS

953

Glass Tube

1-Octadecanol
Solution

FIG. 71The horizontally clamped tube


allows the Iron powder and solution to
equilibrate separately.

2-Octaclecanol
5-Octadecanol

J_
O.S

1.0

1.S

2.0

2.S

3 . 0 x 1 0- 1

Mole Fraction of Octadecanols in Heptane


FIG. 69The position of the adsorbing group significantiy
affects adsorption.

and a mL of the solution containing the additive of interest is


placed. The tube is sealed and rotated in an oil bath until the
iron powder and the additive solution is thoroughly mixed. At
the end of the experiment, the iron powder is separated at the
test temperature from the solution with a strong magnet. The
tube is then clamped horizontally, as shown in Fig. 71, to allow the iron powder and solution to equilibrate separately.
The iron powder is separated as before, the tube was cooled
in liquid nitrogen and the end containing the iron powder is
sealed off. The solution concentration of the additive is determined by gas chromatography and the heat of adsorption
is determined by the microcalorimetric procedure described
previously [131-133]
Fowkes [134] adapted the Yamins and Zisman method
[135] to determine the adsorption isotherm of various carboxylic acids and amines from a naphthenic white oil. In this
method, a vibrating gold reference electrode (100-500 c.p.s.)
was mounted approximately 1 mm from a parallel test electrode. The signal was detected with an oscilloscope after amplification. The potential between the two electrodes was
compensated with a potentiometer until a null point was observed. The change of the null potential (AV) of the potentiometer for a given metal due to the adsorption of the additive was measured by determination of the potential of the
metal plate with a thin layer of the oil (0.1 mm) and then
measuring the potential of a similar layer of the oil containing the additive. Similar procedures have been described by
Sewig and Zisman [136], Frumkin [137] and Jahanmir [133].
Using this procedure, adsorption isotherms for different additives on different metals can be determined in addition to
adsorption time and the "strength of adsorption."
Adsorption isotherms can also be derived from coefficient
of friction data using standard bench testing machines such
as a four-baJl machine [133,138] and a ball-on-cylinder machine [139]. Jahanmir determined the adsorption isotherms
from [133]:
f = fb(i - e) + f^e
where: 0 = the fractional additive surface coverage, f = friction coefficient for boundary lubrication, fa = friction coefficient for the additive at S = 1.0, fb = friction coefficient of the
base fluid at S = 0. The fractional additive surface coverage
(ff) is calculated from:
e=(fb-f)/(fb-fa)

0
0.5
10.0
Heat of Adsorption, (mJ/m^) Adsorbent
FIG. 70The dramatic differences in the heat of adsorption of stearic acid as a function of the surface
condition of the metal substrate.

The values of fa and fb are determined from two bench tests;


one without any additive and one with a high concentration
of the additive. The value of 0 is determined by measuring the
coefficient of friction at various intermediate additive concentrations.
Jahanmir, et. al. found that the data was fit better using a
Temkin adsorption isotherm which states that the exother-

954

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

m i c a d s o r p t i o n free e n e r g y d e c r e a s e s l i n e a r l y w i t h s u r f a c e
coverage [140]:
AGads = AGo + aO
w h e r e AGQ = t h e p r i m a r y a d s o r p t i o n free e n e r g y a t fl = 0 a n d
a = p o s i t i v e c o n s t a n t t h a t is d e p e n d e n t o n t h e i n t e r a c t i o n of
t h e additive with t h e surface.
At l o w a d s o r b a t e c o n c e n t r a t i o n s w h e r e 0 a fl a 0.2, t h e n :
e ( R T / a ) (C/Ko)
w h e r e : C i s t h e a d d i t i v e c o n c e n t r a t i o n i n m o l e fraction
Ko is t h e p r i m a r y a d s o r p t i o n c o n s t a n t d e f i n e d a s :

and

Ko = e x p ( d G o / R T )
At i n t e r m e d i a t e a d d i t i v e s u r f a c e c o v e r a g e w h e r e : 0.2 < 6 s
0.8, t h e f o l l o w i n g i s o t h e r m m a y b e u s e d [ 1 3 3 ] :
e = ( R T / a ) In (C/Ko)
At h i g h levels of c o v e r a g e , 0.8 ^ fl s 1.0, t h e T e m k i n i s o t h e r m
becomes:
9 1 - ( R T / a ) [ e x p ( a / R T ) - 1] (Ko/C)
Using this a p p r o a c h , J a h a n m i r d e t e r m i n e d the friction coefficients a n d free e n e r g y of a d s o r p t i o n for a s e r i e s of c a r boxylic acids in a solvent-refined, dewaxed, hydrorefined
n e u t r a l l u b r i c a n t b a s e s t o c k w i t h a v i s c o s i t y of 32 c S a t 40C.
T h e d a t a o b t a i n e d is s u m m a r i z e d i n T a b l e 18. T h i s d a t a
s h o w s t h a t t h e f r i c t i o n coefficient d e c r e a s e s w i t h i n c r e a s i n g
h y d r o c a r b o n c h a i n l e n g t h ind w i t h i n c r e a s i n g free e n e r g y of
adsorption [133,141,142].

T h e a n t i w e a r a c t i v i t y i s d u e t o t h e f o r m a t i o n of a m o n o l a y e r of s t e a r a t e a s t h e l u b r i c a t i n g film. As s h o w n b y J a h a n m i r , I n c r e a s i n g c h a i n l e n g t h s of c a r b o x y l i c a c i d s g e n e r a l l y
d e c r e a s e coefficient of f r i c t i o n [ 1 2 7 , 1 2 8 , 1 3 3 ] . H o w e v e r , it h a s
b e e n p r o p o s e d t h a t a l t h o u g h at lower sliding speeds the coefficient of friction is c o n t r o l l e d b y m o n o l a y e r f o r m a t i o n , a t
higher sliding speeds, o r d e r e d multilayers control friction
[125,127].
G r o s z e k , d e s c r i b e d t h e u s e of a p u l s e flow m i c r o c a l o r i m e t e r t o s t u d y t h e a d s o r b a n c e of m o l e c u l e s of v a r y i n g polctrity
o n t o different s u b s t r a t e s including: graphite, cast iron, i r o n
a n d steel p o w d e r s , i r o n oxides, nickel oxide a n d lithium
s t e a r a t e [ 1 4 3 a ] . Also, v a r i o u s s o l v e n t m e d i a w e r e e v a l u a t e d .
This w o r k showed t h a t certain metal oxides a n d graphite
preferentially adsorb molecules with long hydrocarbon
c h a i n s from l o w m o l e c u l a r w e i g h t s o l v e n t s . H o w e v e r , i r o n ,
steel a n d F e 2 0 3 d o n o t e x h i b i t a n y t e n d e n c y t o p r e f e r e n t i a l l y
a d s o r b l o n g c h a i n h y d r o c a r b o n s . I n a d d i t i o n , it w a s s h o w n
that detergent additives are strongly adsorbed o n a l u m i n a
a n d engine deposits.
H i r o n a k a a n d o t h e r s h a v e a l s o s h o w n t h a t t h e effectiveness
of v a r i o u s friction m o d i f i e r s o n f r i c t i o n a n d w e a r r e d u c t i o n
is r e l a t e d t o t h e h e a t of a d s o r p t i o n . T h i s is i l l u s t r a t e d b y t h e
d a t a s h o w n i n T a b l e 19 [ 1 2 4 ] a n d T a b l e 2 0 [ 1 2 0 ] . F r o m t h e s e
r e s u l t s a n d o t h e r s , t h e f o l l o w i n g r u l e of t h u m b is u s e d : " t h e
g r e a t e r t h e h e a t of a d s o r p t i o n , t h e b e t t e r t h e l u b r i c i t y " [ 1 2 0 ] .
Antiwear a n d E P additives are classified by t h e t e m p e r a t u r e s r e q u i r e d t o activate t h e m . Antiwear additives typically
act by a d s o r p t i o n a n d E P additives r e q u i r e a t h e r m a l activat i o n as illustrated schematically in Fig. 72 a n d Fig. 7 3 .

TABLE 18Effects of hydrocarbon chain length on friction coefficient and free energy of adsorption.
Carboxylic Acid

Acid Structure

Friction Coefficient

AGo (kcal/mole)

Capiic Acid
Laurie Acid
Myiistic Acid
Palmitic Acid
Stearic Acid
Oleic Acid

CH3(CH2)sCOOH
CH3(CH2)ioCOOH
CH3(CH2)i2COOH
CH3(CH2)i4C00H
CH3(CH2)i6COOH
CH3(CH2)7 CHBCH (CHj)? COOH

0.111
0.104
0.099
0.086
0.077
0.099

-5.5
-5.4
-4.9
-5.2
-5.0
-4.8

TABLE 19Friction and wear metal transfer for cadmium surfaces at r o o m temperature.
Lubricant
None
Cetane-C 15H31CH3
Cetyl Alcohol-Ci5H3iCH20H
Palmitic Acid-C,5H3iCOOH

Coefficient of Friction
0.8
0.6
0.4
0.07

Metal Pick-Up
X lO^g/cmof Track
50 000
500
100
1

TABLE 20Relationship between heat of adsorption and wear reduction.


Wear Volume
Heat of Adsorption
( X lO""* cm^)^
(cal/g)'
Mineral Oil
3.5
8.5
Aromatic Distillate
4.5
3.5
Castor Oil
3.9
4.3
8.0
2.4
Cetyl Alcohol
0.8
Stearic Acid
36.0
0.4
38.5
Cetyl Amine
1.7
Oleic Acid
9.6
1.9
BUcinoleic Acid
12.3
Adsorption from benzene solution on to iron.
Pin-on-disk friction testing machine, contact pressure 16,800 kgl^cm^
Lubricant

Initial Galling Load


(kgf)
40
40
70
40
40
60
40
40

CHAPTER

35: LUBRICATION

Paraffin Oil
c
o

0)

o
O

l_ EP and Polar
Film Formers

Temperature
FIG. 72Increasing temperatures will lead to failure of lubricating films formed by friction modifiers.

j 1

-t>
1> s
S

1> S

II

S +2R-

II

Alkane,
Olefin, etc.

Fe Surface
I
11 Surface Extrusion
[Adsorption
Bond Formationll Into Steel Surface
AW Region
EP Region
I > > >^)

11 >'i I > I > 11 > } \ > > I > 11 >} > > > ) \ > I > >\ > > I > >

Temperature
FIG. 73Illustration of the difference of surface reactions for
antiwear and EP additives.
Increasing temperatures will lead to failure of lubricating
films formed by friction modifiers t h a t are related to:
[32,124]
Adsorption films undergo two-dimensional melting at temperatures close to the bulk melting point, disorienting temperature, of the additive. This disorientation temperature
distinguishes physisorbed additives from chemiadsorbed
additives. In some cases, it has been reported that if the
temperatures are sufficiently high, the adsorbed films will
"bum" forming carbonaceous residues [143b]
While physisorbed films become detached from their surface at the melting point of the additive, chemisorbed additives are effective above their bulk melting point although they do ultimately fail with further increases in
temperature [32].
Therefore, the relatively limited film strength and thermal
instability of the friction reducing films formed by friction
modifiers necessitates the use of additives that Eire more effective in this region.
Antiwear AdditivesAntiwear
additives often contain phosphorous such as those compounds illustrated in Fig. 74 [144].
Generally, eintiwear additives are most effective under mixed
lubrication conditions where low-medium loads or high temperature conditions Eire encountered. In this region, there is
intermittent asperity contact. The antiwear additive reacts
with the metal asperities at the wear contact temperatures to

AND TRIBOLOGY

FUNDAMENTALS

955

form films which are not intended to prevent scoring or


seizure but to reduce wear that may occur during times of insufficient full-film lubrication. Under high loads, the lubricating film breEiks down due to shear and/or friction heat and
galling results [120].
There is not a clear trEinsition from friction modifiers to antiwear additives and friction modifiers. In fact, there are conditions where friction modifiers may exhibit both friction reduction a n d a n t i w e a r properties [120]. It is proposed,
however, that the m e c h a n i s m of the phosphorous derivatives, such as ZDDP (zinc dialkyldithiophosphate) or tiicresyl
p h o s p h a t e passes t h r o u g h all three stages: adsorption,
chemisorption, and chemical reaction [145]. These multiple
reaction pathways, which occur tribochemicEdly within the
wear contact, Eire evident when considering the complexity of
a recently determined structure of zinc dithiophosphate reaction film which is illustrated in Fig. 75 [146].
Extreme-Pressure (EP) Additives^As the load on a wear contact is increased still further, the contact temperature increases still further until the fluid film collapses a n d the
metal asperities come into contact. This will be accompanied
by a still further sudden rise in temperature and adhesive failure with subsequent welding of the surfaces [120,143] However, when extreme pressure additives are present, such as
organic halides, organic phosphates and organosulfur compounds, the wear surface will react u n d e r conditions of high
load and temperature forming iron halides, iron phosphorous or iron sulfides (see Fig. 76 ) respectively which exhibit
greater film strength t h a n those formed with friction modifiers or antiwear additives [147]. The lubricity exhibited by
EP additives is dependent on the contact temperatures and
the reactivity of the EP additive with the metal surface under
these conditions Eind shear strength of the reaction films that
are formed [120]. Generally, the load carrying capacity of the
reaction films increase with chemical reactivity. The following generalizations can be made:
Iron chloride films exhibit relatively low melting points
(approx. 350C) a n d therefore relatively low wear resistEince.
Organophosphorous-based EP additives react at somewhat
lower temperatures than organic halides thus exhibiting an
improvement in wear resistance.
HO,
i--3M

Metal dialkyl
dithiophosphate

RO

\ )

Tricresyl phosphate
(R = cresyl)
I.e.

Dialkyl phosphite

XM

(S

CH,

Phosphate

FIG. 74Antiwear additives often contain


phosphorous such as those compounds.

956

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK
representative
thickness (nm) - 9 0 0

alkylphosphate
precipitates

(poly)idiospbate
sulphide/oxide
ferrous
substrate
FIG. 75Multiple reaction pathways, which occur tribochemically within the wear contact, are evident
when considering the complexity of a recently determined structure of zinc dithiophosphate reaction film.

4-

1 Sutfur-type
/ EP agents

#3.5.

1
(0

o
c

O)

1
1
/
/
/

S o

2-

1 1.5- J/ / r
7
1 //

DC

//
1 .

/
1
1
j

f2.5.

0
.2

/
/

^,,,^

fi--<7.

Phosphorus-type
EP agents
/
/

^A--

^^-"^'^
Chlorine-type
EP agents

~ ,, . -

1.1
1.2
1.3
1.4
Relative chemical reactivity

1.5

FIG. 76Correlation of relative reactivity and load carrying capacity of EP additives with respect to the functionality
class.

The iron sulfide surfaces formed from organosulfur based


EP additives exhibit excellent heat resistance (750C) and
superior wear resistance.
For dithiophosphate derivatives, although the antiwear activity increases with decreasing thermal stability, the EP
activity decreases [143]
All EP additives are corrosive to the surface for which they
are used to protect. Since the reacted surface has lower

shear strength, friction is reduced, as is the tendency for severe adhesive failure. [144]
There is often no clear division between the mechanism of
activity between antiwear and EP additives. In some cases, a
given additive may exhibit activity by either mechanism, depending on the use conditions. This is illustrated in Fig. 73
where the disulfide additive is adsorbed on wear surface with
subsequent disulfide bond cleavage to form an iron sulfide
[148]. As the load increases and the lubrication regime undergoes a transition from mixed film to boundary lubrication, the contact temperatures increase causing a cleavage of
the carbon sulfur bond resulting in an iron sulfide layer similar to that shown in Fig. 73. Thus a given additive may exhibit both antiwear and EP activity.
It has been shown that EP activity is dependent on the reaction or wear contact temperature. Therefore, it is important to determine the reaction temperature of an additive if
an assessment of its ability to continuously form, or regenerate, boundary lubrication films in the wear contact [79]. Figure 77 provides a summary of the additive EP requirements
as a function of the contact temperature [103] which provides a useful guideline for additive classification.
One of the problems in applying Fein's EP additive selection criteria is that additive activation temperatures are often
unknown. One method that may be used for studying the influence of contact temperature on the generation of EP films
is to use the "hot-wire method", originally developed by Barcroft and Rossett et al. [148,149] This method permits the
fast generation of surface temperatures of several hundred C
with significantly increasing the bulk fluid temperatures.
Surface analysis is then used to characterize the reaction
products formed under these conditions.

CHAPTER 35: LUBRICATION

5 350

Strong
EP

s
a
E 300
0)
H

I 200
o
150"-

NonEP

FIG. 77EP Requirements with respect to


contact temperatures for additized hydrocarbon oils with a steel material pair.

CONCLUSIONS
An overview of fundamental principles involved in lubrication
has been provided. This included fundamental material and
surface properties along with an overview of friction. Also
provided was an extensive overview of weeir mechanisms and
their identification. This discussion was followed by a review
of fluid film lubrication and the role and criteria of additive
chemistry in friction reduction. The fluid was treated as a
component of the tribocontact and methodologies of examining and classifying -wear mechanisms was provided. Finally,
the role of additives in lubrication was discussed. This information can be applied to the test procedures and experimental designs proposed in the following chapters to provide a
greater depth of understanding of the data obtained. This information, in combination with the discussion provided in
Chapters 25 and 26, will provide the reader with a reasonably
in-depth overview of the basic principles of lubrication and
wear: its measurement and test methodologies and design.

ASTM STANDARDS

D 996
D 2652
D4175
D 4725
E 6
E 7
E 1823
G 15
G 40

ASME
ASME Y14.36M: Surface Texture Symbols.
ASME B46.1: Surface Texture (Surface Roughness, Waviness, and Lay).
ISO

B 374
D 653

957

Mild
EP

.2 250

No.
A 902

FUNDAMENTALS

OTHER STANDARDS

O 400

u
c

AND TRIBOLOGY

Title
Standard Terminology Relating to Metallic Coated
Steel Products
Standard Terminology Relating to Electroplating
Standard Terminology Relating to Soil, Rock, and
Contained Fluids
Standard Terminology of Packaging a n d Distribution Environments
Standard Terminology Relating to Activated Carbon
S t a n d a r d Terminology Relating to Petroleum,
Petroleum Products, and Lubricants
Standard Terminology for Engine Coolants
Standard Terminology Relating to Methods of Mechanical Testing
Standard Terminology Relating to Metallography
Standard Terminology Relating to Fatigue and Fracture Testing
Standard Terminology Relating to Corrosion and
Corrosion Testing
Standard Terminology Relating to Wear and Erosion

ISO 1302: Technical DrawingsMethod of indicating surface texture.


ISO 4288: Geometrical product specifications (GPS)Surface texture: Profile method - Rules and procedures for the
assessment of surface texture.
ISO 12085: Geometrical Product Specifications (GPS)Surface texture: Profile method - Motif parameters
ISO 3274: Geometrical Product Specifications (GPS)Surface texture: Profile method - Nominal characteristics of
contact stylus instruments.
ISO 11562: Geometrical Product Specifications (GPS)
Surface texture: Profile method - Metrologiccd characteristics of phase correct filters.
ISO 13565-1: Geometrical Product Specifications (GPS)
Surface texture: Profile method; Surfaces having stratified
functional properties - Part 1: Filtering and general measurement conditions
ISO 13565-2: Geometrical Product Specifications (GPS)
Surface texture: Profile method; Surfaces having stratified
functional properties - Part 2: Height Characterization using the linear material ratio curve.
ISO 4287: Geometrical Product Specifications (GPS)Surface texture: Profile method - Terms, definitions and surface texture psirameters.
ISO 5436: Calibration specimensStylus instruments
Types, calibration and use of specimens.
ISO 1302: Technical Drawings - Method of indicating surface
texture.
ISO/TR 14638: Geometrical product specification (GPS)
Masterplan (This is an ISO Technical Report (TR), not an
ISO Standard.)

REFERENCES
[1] Ludema, K. C, "Friction," in Handbook of Lubrication Theory
and Practive of Tribology: Vol 2, E. R. Booser, Ed., CRC Press,
Inc., Boca Raton, FL 1988, pp. 31-48.
[2] Czichos, H., Klaffke, D., Santher, E., and Woydt, M., "Advances
in Tribology: The Materials Point of View," Wear, 1995, Vol.
190, pp. 155-161
[3] Tabor, D., "Friction-The Present State of Our Understanding,"
Transactions of the ASME Journal of Lubrication Technology,
1981, Vol. 103, pp. 169-179.
[4] Dunken, H., "The Importance of Tribochemical Reactions Between Additives and Metals in Friction and Weair Processes,"
Journal of Chemistry, 1971, Vol. 11, No. 6, pp. 213-219.
[5] Stolarski, T. A., "Basic Principles in Tribology," Tribology in
Machine Design, Industrial Press Inc., Oxford, England, 1990,
pp. 13-63.
[6] Park, K. B. and Ludema, K. C, "Evaluation of the Plasticity Index as a Scuffing Criterion," Wear, 1994, Vol. 175, pp. 123-131.

958 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


[7] Kato, K., "Wear Mechanisms," New Directions in Tribology, I.
Hutchings, Ed., World Tribology Congress, London, Mechanical Engineering Publications Ltd., London, 1997, pp. 39-56.
[8] Zaretsky, E. V., STLE Life Factors for Roller Bearings, Society of
Tribologists and Lubrication Engineers, Park Ridge, IL, 1992,
pp. 199-201.
[9] Gann, P., loannides, E., Jacobson, B., and Lubrecht, A. A., "The
Lambda Ratio^A Critical RE-examination," Wear, Vol. 175,
1994, pp. 177-188.
[10] Moyer, C. A., "CompEulng Surface Failure Modes in Bearings
and Gears: Appearances versus Mechanisms," Technical Paper
91 FTM 6, Automotive Gear Manufacturers Association,
Alexandria, VA, 1991.
[11] Townsend, D. P. and Shimsky, J., "EHL Film Thickness, Additives and Gear Surface Fatigue," Gear Technology, May/June,
1995, pp. 26-31.
[12] Poon, C. Y. and Bhushan, B., "Comparison of Surface Roughness Measurements by a Stulus Profiler, AFM, and a Non-Contact Optical Profiler," Wear, Vol. 190, 1995, p p . 76-88.
[13] Hamrock, B. J., "Fundamentals of Lubrication," Presentation
at Union Carbide Corporation, Tarrytown, NY, July 17, 1990.
[14] Williamson, J. B. P., "The Shape of Surfaces," Handbook of Lubrication Theory and Practice of Tribology, Volume III, E. R.
Booser, Ed., CRC Press Inc., Boca Raton, FL, 1988, p. 7.
[15] Matveevsky, R. M., "Chemical Modification of Friction Surfaces in Boundary Lubrication," ASLE Transactions, Vol. 25,
No. 4, 1981, pp. 4 8 3 ^ 8 8 .
[16] Okabe, H., Masuko, M., and Oshino, H., "Effects of Viscosity
a n d Contact Geometry o n Tribochemical Surface Reaction,"
ASLE Transactions, Vol. 25, No. 1, pp. 39-43.
[17] De Gee, A. W. J., Lossie, C. M., and Mens, J. W. M., "Characterization of Five High-Performance Lubricants in Terms of
IRG Transition Diagram Data," ImeChE, CI54/87, 1987, pp.
427-436.
[18] Wedeven, L. D., "What is EHD?," Lubrication Engineering, Vol.
31, No. 6, 1975, p p . 291-296.
[19] Chueng, H. S., "Lubrication Regimes," ASM Handbook, S. D.
Henry, Ed., Vol. 18, 1988, pp. 89-97.
[20] Barus, C , "Note on the Dependence of Viscosity on Pressure
and Temperature," Proceedings of the National Academy of Sciences of the United States of America, Vol. 19, 1893, p . 13.
[21] Jones, W. R., Johnson, R. L., Winers, W. O., and Sanborn, D.
M., "Pressure Viscosity Measurements for Several Lubricants
to 5.5 X 10'* Newton Per Square Meter ( 8 x 1 0 " PSI) and 149C
(300F)" ASL Transactions, Vol. 18, No. 4, 1974, pp. 249-262.
[22] Roelands, C. J. A., "Correlation Aspects of the Viscosity-Temperature-Pressure Relationship of Lubricating Oils," University of Groningen, Groningen, Netherlands, University Microfilm, University of Michigan, Ann Arbor, MI, 1966.
[23] Fresco, G. P., Klaus, E. E., and Tewksbury, E. J., "Measurement and Prediction of Viscosity-Pressure Characteristics of
Liquids," Journal of Lubrication Technology, July, 1969, p p .
451^58.
[24] Klaus, E. and Fenske, M. R., "The Use of ASTM Slope for Predicting Viscosities," ASTM Bulletin, No. 215, July 1956, pp. TP
143 - TP150.
[25] Kinker, B. G., "Fluid Viscosity and Viscosity Classiflcation,"
Chapter 5, Handbook of Hydraulic Fluid Technology, G. E. Totten, Ed., Marcel Dekker, Inc., NY, 2000, pp. 305-338.
[26] Shibada, J. and Rebyu, N., "Basic Characteristics of Lubricant
OilsHigh Pressure Viscosity of Lubricants," Vol. 39, No. 2,
1997, p p . 46-56.
[27] Appledom, J. K., "A Simplified Viscosity-Pressure-Temperature Equation," SAE Technical Paper #709A, International
S u m m e r Meeting, Montreal, Canada, June 10-14, 1963.
[28] Anon., "Viscosity-II," Lubrication, Vol. 47, 1961, pp. 13-27.
[29] Kouzel, B., "How Pressure Affects Viscosity," Hydrocarbon Processing and Petroleum Refiner, Vol. 44, No. 3, 1965, p. 120.

[30] Roelands, C. J. A. and Druk, V. R. B., Kleine der A3-4 Groningen, Holland, 1966.
[31] Fresco, G. P., "Measurement and Predicting of Viscosity-Pressure Characteristics of Liquids," M. S. Thesis, The Pennsylvania State University, University Park, PA, 1962.
[32] Kim, H. W., "The Viscosity-Pressure Studies of Polymer Solutions," Ph. D. Thesis, The Permsylvcinia State University, Uiiiversity Park, PA, 1970.
[33] So, B. Y. and Klaus, E. E., "Viscosity-Pressure Correlation of
Liquids," ASLE Transactions, Vol. 23, No. 4, 1980, pp. 4 0 9 421.
[34] Chu, P. S. Y. and Cameron, A., "Pressure Viscosity Characteristics of Lubricating Oils," Journal of the Institute of Petroleum,
Vol. 48, 461m, 1962, p p . 147-155.
[35] Worcester, R. C , Discussion of paper presented by A. E. Bingham, "Some Problems of Fluids For Hydraulic Power Transmission," Proceedings of the Institution of Mechanical Engineers, Vol. 165, Institution of Mechanical Engineers, London,
1951, p p . 254-261, 269-270.
[36] Johnson, W. G., "A Method to Calculate The Pressure-Viscosity
Coefficient From Bulk Properties of Lubricants," ASLE Transactions, Vol. 24, No. 2, 1981, p p . 232-238.
[37] Lauer, J. L. and Dwyer, S. R., "Tribochemical Lubrication of
Ceramics by Carbonaceous Vapors," STLE Preprints, Preprint
No. 90-TC-6A, STLE, Park Ridge, IL, 1991.
[38] Kempinski, R., Kedzierska, E., Kardaze, K., Wilkanowicz L.,
and Konopku, M., "Tribopolymerization - Type Additives for
Lubricants, Part I: C12- Cis Alkyl Methacrylates," Trihologia,
Vol. 26, No. 3, 1995, p p . 277-298.
[39] Novotny, V. J., Pan, X., and Bhatia, C. S., "Tribochemistry at
Lubricated Interfaces," / . Vac. Sci. Technical., 1994, Vol. 12,
No. 5, p p . 2879-2886.
[40] Kajdas, C , Lafleche, P. M., Furey, M. J., Hellgeth, J. W., and
Ward, T. C , "A Study of Tribopolymerization Under Fretting
Contact Conditions," Lubrication Science, Vol. 6, No. 1, 1993,
pp. 51-89.
[41] Selected data from Appendix Table A.1, "Physical Properties of
Metallic Element," Friction and Wear of Materials, E. Rabinowicz, John Wiley & Sons, NY, 1964, p. 235.
[42] Rigney, D. A., "The Roles of Hardness in the Sliding Behavior
of Materials," Wear, Vol. 175, 1994, p. 63-69.
[43] Barwell, F. T., "Metallic Wear," Handbook of Lubrication Theory and Practice of Tribology-Vol. 2, Theory and Design, E. R.
Boose, Ed., CRC Press, Boca Raton, FL,1988, p . l 7 9 .
[44] Dorinson, A. and Ludema, K. C , Mechanics and Chemistry in
Lubrication, Elsevier, NY, 1985.
[45] Rabinowicz, E., Friction and Wear of Materials, John Wiley &
Sons, NY, 1964, p. 35.
[46] Rigney, D. A., "The Rules of Hardness in the Sliding Behavior
of Materials," Wear, Vol. 175, 1994, pp. 63-69.
[47] Meng, H. C. and Ludema, K. C , "Wear Models and Predictive
Equation: Their Form and Content," Wear, Vol. 181-183, 1995,
pp. 4 4 3 ^ 5 7 .
[48] Godfrey, D., "Gear Wear Caused by Contaminated OUs," Gear
Technology, September-October, 1996, pp. 45-49.
[49] Giltrow, J. P., "A Relationship Between Abrasive Wear and the
Cohesive Energy of Materials," Wear, Vol. 15, 1970, pp. 71-78.
[50] Fitch, E. C , Hong, I. T., and Xuan, J. L., "Abrasion Wear,"
BFPR Journal, Vol. 2 1 , 1988, pp. 9-29.
[51] Tomsic, J., Dictionary of Materials and Testing, 2"^ Edition, Society of Automotive Engineers, Wartendale, PA, 2000.
[52] Totten, G. E., Webster, G. M., and Yeaple, F. D., "Physical
Properties and Their Determination" Chapter 4, Handbook of
Hydraulic Fluid Technology, G. E. Totten, Ed., Marcel Dekker,
Inc., NY, 2000, pp. 195-304.
[53] Shi, J., Gao, M. Z., Wang, T. M., Wen, X. Y., and Shi, W. D.,
"Corrosion Wear Behavior of loji Implanted Steel," Wear, Vol.
175, 1994, p p . 145-149.

CHAPTER 35: LUBRICATION AND TRIBOLOGY FUNDAMENTALS


[54] Meyer, U., Brosnan, C. C , Bremhorst, K., Tomlins, R., and
Atrens, A., "A New Impinging Jet Test Rig Used to Identify the
Important Parameters in Service Erosion Corrosion in Bayer
Liquor and to Study t h e Damage Morphology," Wear, Vol. 176,
1994, pp. 163-171.b. Archard, J . F . a n d H i r s t , W., "TheWearof
Metals u n d e r Unlubricated Conditions," Proceedings of the
Royal Society of London., Series A., Vol. 236,1959, pp. 397-410.
[55] Quinn, T. F. J., "Oxidational Wear ModellingPart II. The
General Theory of Oxidational Wear," Wear, Vol. 175,1994, pp.
199-208. b. Sachs, N. W., "Metal Fatigue," Lubrication Engineering, Vol. 47, No. 12, 1991, pp. 977-981.
[56] Waterhouse, R. B., McCoU, I. R., Harris, S. J., and Tsujikawa,
M., "Fretting Wear of a High-Strength Heavily Work Hardened
Eutectoid Steel," Wear, 1994, Vol. 175, pp. 51-57.
[57] Waterhouse, R. B., Metals Handbook, Vol. 18, Lubrication and
Wear Technology, 1992, ASM International, Materials Park,
OH, p p . 242-256.
[58] Neale, M. J. and Gee, M., Guide to Wear Problems and Testing
for Industry, William Andrew Inc., Norwich, NY, 2001, p p .
4-16.
[59] Baker R. F. and Olver, A. V., "Direct Observations of Fretting
Wear of Steel," Wear, Vol. 203-2-4, pp. 4 2 5 ^ 3 3 .
[60] Zhou, Z. R. and Vincent, L., "Cracking Induced by Fretting of
Aluminum Alloys," Transactions of the ASME, Vol. 119, No. 1,
1997, pp. 36-42.
[61] Kalin, M. and Vizintin, J., "A Tentative Explanation for the Tribochemical Effects in Fretting Wear," Wear, Vol. 250, 2001,
pp. 681-689.
[62] Kalin, M. and Vizintin, J., "High Temperature Phase Transform a t i o n s u n d e r Fretting Conditions," Wear, Vol. 249, 2001,
pp. 172-181.
[63] Kalin, M., Vizintin, J., Novzik, S., and Drazic, G., "Wear Mechanisms in Oil-Lubricated and Dry Fretting of Silicon Nitride
against Bear Steel Contacts," Wear, Vol. 210, pp. 27-38.
[64] Borsoff, V. N., "On t h e Mechanism of Gear Lubrication,"
ASME Transactions, Journal of Basic Engineering, 1959, SOD,
p. 79.
[65] Enthoven, J. and Spikes, H. A., "Infrared and Visual Study of
the Mechanisms of Scuffing, ASLE Transactions, Vol. 39, No. 2,
1996, p p . 441-448.
[66] Cameron, A., "The Role of Surface Chemistry in Lubrication
and Scuffing," ASLE Transactions, Vol. 23, No. 4, pp. 388-392.
[67] Spikes, H. A. and Cameron, A., "Scuffing as a Desorption Process^An Explanation of the Borsoff Effect," ASLE Transactions, 1974, Vol. 17, No. 2, p p . 92-96.
[68] Grew, W. J. S. and Cameron, A., "Thermodynamics of Boundary Lubrication and Scuffing," Proceedings of the Royal Society
of London, Vol. A 327, 1972, p. 47.
[69] Suh, N. P., Jahanmir, S., Abrahamson, E. P., and Turner, A. P.
L., "Further Investigation of the Delamination Theory of
Wear," Journal of Lubrication
Technology, October 1974,
pp. 631-637.
[70] Jahanmir, S., Suh, N. P., and Abrahamson, E. P., "The Deleimination Theory of Wear and the Wear of a Composite Surface,"
Wear, Vol. 32, 1975, p p . 33-49.
[71] Lim, S. C. and Ashby, M. F., "Overview No. 55^Wear Mechanism Maps," Acta Metallurgica, Vol. 35, No. 1, 1987, pp. 1-24.
[72] Anon., Lubrication,
Vol. XLII, No. 12, December 1956,
pp. 149-160.
[73] Anon. "A Report on Ferrography and its Application for Determining Wear Particle Equilibrium," Technical Report, Engineered Lubricants, Maryland Heights, MO, 1998.
[74] Cho, U., "Phenomenological Approach to Wear Debris Analysis," Journal of Friction and Wear, Vol. 2 1 , No. 3, 2000,
pp. 27-31.
[75] Hsu, S. M., Lim, D. S., Wang, Y. S., and Munro, R. G., "Ceramic
Wear Maps: Concept and Method Development," Lubrication
Engineering, Vol. 47, No. 1, 1991, pp. 49-54.

959

[76] Beerbower, A., "Boundary Lubrication," Contract No. DAHC


19-69-0033, U.S. Army Officer of the Chief of Research and
Development, Alexandria, VA, June 1972.
[77] Leng, J. A. and Davies, J. E., "Examination of Wear Debris Produced Using a Four-Ball Machine," Tribology
International,
Vol. 22, No. 2., 1989, pp. 137-142.
[78] Bartz, W. J., "Tribology, Lubricants and Lubrication EngineeringA Review," Wear, Vol. 49, 1978, pp. 1-18.
[79] Sethuramiah, A., Okabe, H., and Sakurai, T., "Critical Temperatures in EP Lubrication," Wear, Vol. 26, 1973, pp. 187-206.
[80] Ku, P. M., Staph, H. E., and Carper, H. J., "On the Critical Contact Temperature of Lubricated Sliding-RoUing Disks," ASLE
Transactions, Vol. 2 1 , No. 2, 1978, pp. 161-180.
[81] Huang, Y. W., Cheng, G. X., and Dong, J. X., "Studies on the Interrelationships Between the Character of Metals and Antiwear
Additives," Lubrication Science, Vol. 2, No. 3, p p . 253-266.
[82] Singh, T. a n d Verma, V. K., "EP Activity Evaluation of tris(Narylthiosemicarbazido)-tnolybdenum (III) on Steel Balls in a
Four-Ball Test," Wear, Vol. 146, 1991, pp. 313-323.
[83] Bhattacharya, A., Singh, T., Verma, V. K., a n d Prasod, N.,
"1,3,4-Thiadazoles as Potential EP AdditivesA Tribological
Evaluation Using a Four-Ball Test," Tribology
International,
Vol. 28, No. 3, 1995, pp. 189-194.
[84] Cowan, R. S. and Winer, W. O., "Thermomechanical Wear
Modeling," Tribotest Journal, December 1994, p p . 111-123.
[85] Kuhlmann-Wilsdorf, D., "Demystifying Flash Temperatures I.
Analytical Expressions Based on a Simple Model," Materials
Science and Engineering, Vol. 93, 1987, pp. 107-117.
[86] Kuhlmann-Wilsdorf, D., "Demystifying Flash Temperatures 11.
First-Order Approximation for Plastic Contact Spots," Materials Science and Engineering, Vol. 93, 1987, pp. 119-133.
[87] Lim, S. C. and Ashby, M. F., "The Temperature of Sliding Surfaces. A Literature Review a n d Theoretical Development,"
PB86-177029, Cambridge University, Cambridge, England,
Nov. 1985.
[88] Hokkirigawa, A. K., "Recent Research on Wear Maps," Japanese
Journal of Tribology, Vol. 37, No. 10, 1992; b. Hokkirigawa, A. K.
and Kato, K., "An Experimental and Theoretical Investigation of
Ploughing Cutting and Wedge Formation During Abrasive
Wear," Tribology International, Vol. 21, No. 1, 1988, pp. 51-57.
[89] Norose, S., "Developments in Wear Theory," Journal of Tribology, Vol. 39, No. 3, 1994, p p . 281-289.
[90] de Geer, A. W. J., Begellinger, A., and Salomon, G., "Lubricated
Wear of Steel Point Contacts^Application of the Transition
Diagram," Proceedings of the 11th Leeds-Lyon Symposium on
Tribology, Paper V(i), University of Leeds, Leeds, UK, 1984, pp.
105-116.
[91] Hirth, J. P. and Rigney, D. A., "Microstructm-jil Models for Friction a n d Wear," Proceedings of the International
Conference
on Strength of Metals and Alloys V, Vol. 3, Aachen, Germany,
Aug. 26-Sept. 1, 1979, P e r g a m o n Press, Oxford, 1980, p p .
1483-1502.
[92] Rigney, D. A., "Transfer, Mixing and Associated Mechanical
Processes During the Sliding of Ductile Metals," Wear, 2000,
Vol. 245, p p . 1-9.
[93] Lepper, K. and Rigney, D. A., "Application of EDS Peak Enhancement Ratios for Compositional Analysis of Microstructures Evolved During Sliding Wear," Wear, Vol. 221, 1998, pp.
134-137.
[94] Rigney, D. A., "Implications of Structural and Chemical
Changes During Sliding," Position Paper for Workshop on the
Mechanics and Materials Science of Contact Issues and Opportunities, Vanderbuilt University, July 18-20, 1994.
[95] Torrence, A. A. and Cameron, A., "Steel Transformation in
Scuffing," Wear, Vol. 28, 1974, p p . 299-311.
[96] Archard, J. J. and Rowntree, R. A., "Metjdlurgical Phase Transformations in the Rubbing of Steels," Proceedings of the Royal
Society of London, Ser. A., Vol. A418, 1988, p p . 405-424.

960 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


[97] Rigney, D. A. and Glasser, W. A., "Significance of Near Surface
Microstructure in the Wear Process," Wear, Vol. 46, 1978, pp.
241-250.
[98] Gu, J., Barber, G., Tung, S., and Gu, R.-J., "Tool Life and Wear
Mechanism of Uncoated and Coated Milling Inserts," Wear,
Vol. 225-229, 1999, pp. 273-284.
[99] Lim, S. C , "Recent Development in Wear-mechanism Maps,"
Tribology International, Vol. 31, Nos. 1-3, 1998, pp. 87-97.
[100] Stribeck, R., "Characteristics of Plain and Roller Bearings,"
Zeitung des Vereins Deutscher Ingenieure, Vol. 46, 1902, pp.
1341-1348.
[101] McKee, S. A. and McKee, T. R., "Friction of Journal Bearings
as Influenced by Clearance and Length," Transactions of the
American Society of Mechanical Engineers, Vol. 51, 1929, pp.
161-171.
[102] Fein, R. S., "Boundary Lubrication," Handbook of Lubrication
Theory and Practice of Tribology - Vol. II Theory and Design,
CRC Press, Inc., Boca Raton, FL, 1988, pp. 49-68.
[103] MoUer, U. L. and Boor, U., Lubricants in Operation, VDI Verlag, Diisseldorf, Germany, 1996, pp. 1-28.
[104] Goodfellow CataJog, http://www.goodfellow.com,
Goodfellow
Corporation, viewed Oct. 2001.
[105] Hertz, H. R., "Uber die Beruhrung fester elastische Korper und
uber die Harte (On the Contact of Rigid Elastic Solids and on
Hardness,)" Verhandlungen des Vereins zur Beforderung des
Gewerbefleisses, Leipzig, 1881, Vol. 92, pp. 156-171.
[106] Glasstone, S., Textbook of Physical Chemistry, Macmillan and
Co., Ltd., London, 1948.
[107] Dowson, D., "Elastohydrodynamics," Proceedings of the Institute of Mechanical Engineers, Vol. 182, Part 3A, 1967-68, pp.
151-167.
[108] Wedeven, L. D., Totten, G. E., and Bishop, R. J., "Performance
Map and Film Thickness Characterization of Hydraulic Fluids," SAE Technical Paper #952091, Society of Automotive Engineers, Warrendale, PA, 1995.
[109] Bair, S. and Khonsari, M., "An Inlet Zone Analysis Incorporating the Second Newtonian," Journal of Tribology, Vol. 118, No.
2, 1996, pp. 341-343.
[110] Hirst, W. and Moore, A. J., "Non-Newtonian Behavior in Elastohydrodynamic Lubrication," Proceedings of the Royal Society of London, A., Vol. 337, 1974, pp.101-121.
[ H I ] Chang, L. and Zhao, W., "Fundamental Differences Between
Newtonian and non-Newtonian Micro-EHL Results," Journal
of Tribology, Vol. 117, January 1995, pp. 29-35.
[112] Aderin, M., Johnson, G. J., Spikes, H. A., and Capuriccio, G.,
"The Elastohydrodynamic Properties of Son\e Advanced NonHydrocarbon- Based Lubricants," Lubrication Engineering,
August 1992, pp. 633-638.
[113] Patir, N. and Cheng, H. S., "Effect of Surface Roughness Orientation o n the Central Film Thickness in EHD Contacts,"
Proceedings of the Leeds Lyon Symposium on Tribology, 1978,
pp. 15-21.
[114] Anderson, S. and Salas-Russo, E., "The Influence of Surface
Roughness and Oil Viscosity o n the Transition in Mixed
Lubricated Sliding Steel Contacts," Wear, Vol. 174, 1994,
pp. 71-79.
[115] Cameron, A., Principles of Lubrication, Longmans Green & Co.,
Ltd., London, 1966.
[116] Kajdas, C , "Chapter 3.1Engine Oil Additives: A General Review," Engine Oils and Automotive Lubrication, W. J. Bartz,
Ed., Expert Verlag GmbH, Ehningen, Germany, pp. 149-176.
[117] JQaus, E. E., Tewksbury, E. J., and Bose, A. C , "Some Chemical Reactions in Boundary Lubrication," Proceedings of the
JSLE-ASLE International Lubrication Conference, June 9-11,
1975, p p . 39-48.
[118] Nakayama, K., "Tribophysical Phenomena and Chemical Reactions," Toraiborozsuto, Vol. 42, No. 9, 1997, pp. 712-717.

[119] a. Yanagisawa, M., "Molecular S t r u c t u r e of Thin Organic


Films," Japanese Journal of Tribology, 1994, Vol. 36, No. 5, pp.
549-559. b. Schilhng, G. J. and Bright, G. S., "Fuel and Lubricant Additives," Lubrication, Vol. 63, No. 2, 1977, pp. 13-24.
[120] Hironaka, S., "Working Mechanisms of Additives in Lubricating Oils," Sosei to Kako, Vol. 36, No. 413, 1995-1996, pp.
579-585.
[121] Bemett, M. K., Kinzig, B. J., Murday, J. S., and Ravner, H.,
"Surface Analysis of Bearing Steels After Solvent Treatment,"
ASLE Transactions, Vol. 26, No. 1, 1981, pp. 98-106.
[122] Bemett, M. K. a n d Raven, H., "Surface Analysis of Bearing
Steels After Solvent Treatment II: Lubricant-Coated Bearing
Surfaces," ASLE Transactions, Vol. 25, No. 1, 1982, pp. 55-63.
[123] Chu, J. and Tessmann, R. K., "Additive Packages for Hydraulic
Fluids," The BFPR Journal, Vol. 12, No. 2, 1979, pp. 111-117.
[124] Anon., "Fundamentals of Wear," Lubrication, Vol. XLII, No.
12, 1956, pp. 149-160.
[125] Crawford, J. and Psaila, P., "Miscellaneous Additives," Chemistry and Technology of Lubricants, R. M. Mortier and S. T.
Orszulik, Ed., Blackie, VCH, Glasgow, New York, 1992, pp.
160-173.
[126] Makowska, M., Gradowski, M., and Molenda, J., "Interfacisil
Interactions in Tribological Contact," Tribologia, Vol. 3, 1998,
pp. 254-264.
[127] Hu, Z.-S., Hsu, S. M., and Wang, P. S., "Tribochemical and
Thermochemical Reactions of Stearic Acid on Copper Surfaces
Studied by Infrared Microspectroscopy," Tribology Transactions, Vol. 35, No. 1, 1992, pp. 189-193.
[128] Hardy, W. B. and Doubleday, I., "Boundary Lubrication-The
Paraffin Series," Proceedings of the Royal Society of London,
Vol. AlOO, 1921, pp. 550-574.
[129] Studt, P., "Boundary Lubrication: Adsorption of Oil Additives
on Steel and Ceramic Surfaces smd its Influence on Friction
a n d Wear," Tribology International,
Vol. 22, No. 2, 1989,
pp. 111-119.
[130] Forbes, S. and Reid, A. J. D., "Liquid Phase Adsorption/Reaction Studies of Organo-Sulfur Compounds and Their LoadCarrying Mechanism," ASLE Transactions,
Vol. 16, 1973,
pp. 50-60.
[131] Clunie, A. and Giles, C. H,, "TumbUng Apparatus for Liquid
Phase Adsorption Experiments," Chemical Industry, April
1957, pp. 481-482.
[132] Allum, K. G. and Forbes, E. S., "The Load-Carrying Properties
of Organo-Sulfur Compounds. The Influence of Chemical
Structure on Anti-Wear Properties of Organic Disulfides,"
Journal of the Institute of Petroleum, Vol. 53, 1967, p. 174.
[133] Jahanmir, S. and Beltzer, M., "Effect of Additive Molecular
Structure on Friction Coefficient and Adsorption," Journal of
Tribology, Vol. 108, 1986, pp. 109-116.
[134] Fowkes, F. W., "Orientation Potentials of Monolayers Adsorbed at the Metal-Oil Interface," Journal of Physical Chemistry, Vol. 64, 1960, pp. 726-728.
[135] Yamins, H. G. and Zisman, W. G., "A New Method for Studying the ElectriccJ Properties of Monomolecular Films on Liquids," Journal of Chemical Physics, Vol, 1, No. 9, 1933, p.
656-661.
[136] Sewig, K. W. and Zisman, W. A., "Low Energy Reference
Electrodes for Investigating Adsorption by Contact Potential
Measurement," Advances in Chemistry Series, Vol. 33, 1961,
pp. 100-113.
[137] Frumkin, A., "Influence of Electric Field on the Adsorption
of Neutral Molecules," Journal of Physics, Vol. 35, 1926,
pp. 792-802.
[138] Askwith, T. C , Cameron, A., and Crouch, R. F., "Chain Length
of Additives in Relation to Lubricants in Thin Films and
Boundary Lubrication," Proceedings Royal Society of London,
Vol. 291A, 1966, p p . 500-519.

CHAPTER 35: LUBRICATION AND TRIBOLOGY FUNDAMENTALS 961


[139] Jahanmir.S., "Chain Length Effects in Boundary Lubrication,"
Wear, Vol. 102, 1985, pp. 331-349.
[140] Temkin, M. L, "Adsorption Equilibrium and Kinetics of Processes on Nonhomogeneous Surfaces and in the Interaction
Between Adsorbed Molecules," Journal of Physical Chemistry,
Vol. 15, 1941, pp. 296-332.
[141] Jahanmir, S. and Beltzer, M., "An Adsorption Model for Friction in Boundary Lubrication," ASLE Transactions, Vol. 29,
No. 3, 1985, pp. 423^30.
[142] Beltzer, M. and Jahanmir, S., "Effect of Additive Structure on
Friction," Lubrication Science, Vol. 1, No. 1, p. 326.
[143] Groszek, A. J., "Heat of Adsorptiom Measurements in Lubricating Oil Research," Chemistry and Industry, Meirch 20, 1965,
pp. 482-489. b. Sellei, H., "Sulfurized Extreme-Pressure Lubricants and Cutting Oils-Part 1, literature Survey," Petroleum
Processing, September 1949, pp. 1003-1009.
[144] Forbes, E. S., "Antiwear and Extreme Pressure Additives for
Lubricants," Tribology, Vol. 3, 1970, pp. 145-152.
[145] Lansdown, A. R., "Chapter 12-Extreme-Pressure and Antiwear
Additives," Chemistry and Technology of Lubricants, R. M.

Mortier and S. T. Orszulik, Eds., Blackie, VCH, Glasgow, New


York, 1992.
[146] Bee, S., Tonck, A., Georges, J. M., Coy, R. C, Bell, J. C. and
Roper, G. W., "Relationship Between Mechanical Properties
and Structures of Zinc Dithiophasphate Anti-Wear Films,"
Proceedings of the Royal Society of London, Vol. 455, 1999,
pp. 4181^203.
[147] McFadden, C, Soto, C, ind Spencer, N. D., "Adsorption and
Surface Chemistry in Tribology," Tribology International, Vol.
30, No. 12, 1997, pp. 881-888.
[148] Barcroft, F. T., "A Technique for Investigating Reactions Between E.P. Additives and Metal at High Temperatures," Wear,
Vol.3, 1960, pp. 440-453.
[149] Rosset, E., Matthieu, H. J., and Landolt, D., "A New Experimental Technique for the Study of Surface Reactions of Extreme Pressure Additives at Elevated Temperatures," Wear,
Vol. 94, 1984, pp. 125-133.
[150] Studt, P., "Adsorption of Lubricating Oil Additives. The adsorption of Lubricating Oil Additives on Steel Surfaces and its
Tribological Significance," Tribologie + Schmierungstechnik,
Vol. 34, No. 1, 1987, pp. 2-9.

MNL37-EB/Jun. 2003

Bench Test Modeling


Lavem D. Wedeven^

THIS IS ONE IN A SERIES OF THREE CHAPTERS DEALING WITH Lu-

brication a n d Wear (Chapter 35), Bench Test Modeling


(Chapter 36), and Wear and Lubricant Testing (Chapter 37).
In this chapter, the lubrication a n d wear mechanisms discussed in Chapter 35 are used to extend the selection and application of the tribology tests discussed in Chapter 37.
The challenge in tribology testing is to make bench testing
meaningful. Meaningful bench testing is critical for performance prediction in service. In addition, meaningful bench
testing is an essential part of design and the development of
materials and lubricants. Without the development of more
meaningful tests, major advances in complex mechanical
systems will continue to be h a m p e r e d by developmental
risks. The root cause of the problem lies in the ability to capture lubrication m e c h a n i s m s in design a n d to assure the
working of these mechanisms in service. It is essential that
tribology mechanisms be assured prior to the execution of
fabrication and performance testing of the final system.
As part of the design process, tribology issues must be addressed and validated u p front. Compared to other engineering and design disciplines, the level of capability for tribology
design a n d testing is primitive. There is' a general lack of
appreciation for the multitude of lubrication a n d failure
mechanisms that control durability at the contact interface
of major mechaniccil systems. In the aerospace bearing industry, material enhancements for surface fatigue are frequently accompanied by a n offset in abrasive or adhesive
wear. High thermal stability oils frequently come at the expense of wear and scuffing performance. Unknowingly, when
one tribology attribute is sacrificed for a gain in another, the
net result can be disastrous.
It is recognized at the outset that when chemical and material interactions are in the equation for life and durability,
engineering design for bearings, gCctrs, and other mechanical
components is not a rigorous or high precision process. It is
further recognized that, while tribology mechanisms operate
on a micro-scale, we m u s t cope with the r e q u i r e m e n t of
translating micro-scale processes into engineering scale parameters. The path to success is through mechanistic testing
that captures an empirical link to design and performance
testing. This process is called "Systematic Tribology." Systematic Tribology treats the tribo-contact as a system of technologies, which can be systematically developed to capture
tribology mechanisms that are assured to provide durability
in the application system.. The goal of Systematic Tribology is
to leave no attribute behind.

In this chapter, the Systematic Tribology theme is illustrated by highly stressed Hertzian contacts commonly represented by rolling element bearings, gears, and other contacts
with non-conformal geometry. The sections from Dynamic
Mechanisms of the Tribo-System through Generalized Performance Map identify the key tribology parameters that control
lubrication and failure mechanisms and allow linkage to service performance. The sections from Simulation of Gear Lubrication with Systematic Tribology Testing through Load Capacity Database for Qualified Aviation Gas Turbine Oils
illustrate the bench test modeling process with the simulation of lubrication and failure mechanisms in a gear mesh.

THE DYNAMIC MECHANISMS OF


THE TRIBO-SYSTEM
The performance of a tribo-system contact is derived from
the integrity of four general regions shown in Fig. 1. Each region is required to perform specific functions with respect to
lubrication and failure mechanisms. The output of the tribosystem depends upon h o w well lubrication mechanisms handle the normal stress a n d the accommodation of tangential
shear within these regions. The general features of the structured elements of a contact are given below.
Hydrodynamic

Surface

Film

Region

The surface film region contains the thin outer layers of the
surface. They may consist of surface oxides, adsorbed films,
ctnd chemical reaction films derived from the lubricant and

963
2003 by A S I M International

Region

The formation of an oil film between bodies in contact is a


structural element that is dynamically generated. Its creation
is a function of motion, which generates a pressure within a
viscous fluid. Hydrodynamic films generated within conformal contacts may be tens of microns (/Am) thick. Hydrodynamic or elastohydrodynamic (EHD) films generated in nonconforming contacts m a y be on the order of 1 fim thick. On
a global scale, the EHD film is derived from the hydrodynamic pressure generated in the inlet region of the contact.
On a local or asperity scale, hydrodynamic pressure is derived from the micro-EHD lubrication action associated with
the local topographic features of the surfaces. These microEHD films are typically m u c h less than 1 /am thick. Since the
performance benefit of EHD film generation is enormous,
the philosophy of the tribo-system design is to assure operation of hydrodynamic a n d EHD mechanisms.

' Wedeven Associates, Inc., 5072 West Chester Pike, Edgmont, PA


19028-0646.

Copyright'

Film

www.astm.org

964 MANUAL 3 7; FUELS AND LUBRICANTS HANDBOOK


Dynamic Interactions of a Tribo-system

TritwttYStem
Hydrodi/nainio fflm

QnBiatl^lBMjutahlea
Contact sifeki
Kiiwniatlca
Teoiperatultt

gtturtwral.QlwTiBnte

Siirhinm

otatnhifiaMtem
Hydrodynamic fihn
Suffece film
Near-surface
Sub-surface

Hoar surftca

Input
I I
^^^^L

Tribo-system
/ interations^

Trtbo-agtein
m^chpnisma
atemm^chpnisma
Viscous film generation
SurfacA filiti formation
Hsapurbce accommodation
AdheslDii', chemical reaction
PMSlie fldvi^
Fatigue

Output

fc\

^ ^ t

^p
I
'

Tribology Induced
changes In
structural
elements

Triht^-watem neifbrmanca
'Wear, fatigue Me
Souffins 'luatiility

FIG. 1Structural elements and dynamic interactions of a tribo-system.

its additives. These surface films Eire Ejmost always less than
1 /u-m thick. While the surface film region is extremely thin,
its formation by mechanisms of surface forces and chemical
reactions has a profound effect on surface lubrication. In
highly stressed long-life mechanical systems, surface films
maintciin the integrity of the surface topography to promote
hydrodjTiamic jtnd EHD mechanisms.
Near-Surface

Region

The near-surface region contains the inner layers of the surface. During operation this region may include a finely structured and highly worked or mechanicEilly mixed layer. It may
also include compacted wear debris or transferred material
from a mating surface. The deformed layers, which are of a
different microstructure than the matericJ below them, may
arise from surface preparation techniques such as grinding
and honing. They may EJSO be induced during operation; for
example, during run-in. Hardness and residual stress may
vary significantly in this region. They may also be substantially different from the bulk material below. The nearsurface region may be on the order of 50 ^im below the surface. For life and durability, the mechanistic processes in this
region are designed to provide near-surface accommodation
of tangenticJ stress without loss of surface integrity.
Subsurface

Region

The subsurface region is particuleirly important for highly


stressed concentrated contacts. The subsurface region can be
on the order of 50-1000 /tm below the surface. This region is
not significantly affected by mechanical processes that produce the surface or by the asperity-induced changes that occur during operation. Material microstructure and hardness
may still be different from the bulk material below it, and sig-

nificant residual stresses may still be present. These stresses


and microstructures, however, are the result of macro processes such as heat treatment, surface hardening, and forging. For typical Hertzian contact pressures a n d neglecting
asperity pressures, the m a x i m u m shear stress is located
within the subsurface region (see Fig. 1). In other words, the
detrimental global contact stresses are c o m m u n i c a t e d to
t h e subsurface region w h e r e subsurface-initiated fatigue
commences.
The above structured regions define the operating environment for lubrication and failure mechanisms. They EJSO form
the ingredients by which surface life and durability is determined. Since some of the structural regions are self-generated within the contact, it is clear that the structural regions
constitute a dynamic system, as shown in Fig. 1. When one
considers the practical construction of this dynamic system,
we find the wide-ranging businesses of mechanical and
chemical technology intimately linked. The lubricated contact is a "tribo-system" where everything is joined together
and operated in a dynamic fashion. The tribo-system is a
melting pot for many commercial contributions involving
materials, surface treatments, lubricating fluids, additives,
equipment designs, and manufacturing. What is created in
the tribo-system during operation can be m u c h different
from the technologies assembled in the structural regions at
the outset.
The dynamics of this interdisciplinary tribo-system are
generally not adequately known. This state of affairs makes it
difficult to design for enhanced performance a n d to assure
success in service. Tribo-system development is t5^ically a
disjointed effort in developing mechanical system technology. This is a c o m m o n problem among non-integrated businesses and disciplines, which supply matericds and lubricants

CHAPTER 36: BENCH TEST MODELING


into the interdisciplinary field of tribology. Clearly the assembly of new tribology technology has not teiken advantage
of the potential synergism that can be obtained by constructing load-carrying materials, fluids, and designs as a system,
which operates on amazingly powerful mechEinisms. In view
of the complexity of these mechanisms, particularly the interactions between surface films and the near-surface region,
the Systematic Tribology process relies on simulation testing
of the mechanisms that control performance in service.

TRIBO-SYSTEM SIMULATION
Tribo-system tests generally have two practical purposes: (1)
they provide fundamental material property data as well as
mechanistic understanding and (2) they are used to predict
performance in service. For any test to have practical value,
there must be a clear link between testing and hardware performance. The challenge associated with this task is due to
the complexity of p e r f o r m a n c e m e c h a n i s m s in a tribosystem. An effective linkage between testing and hardware
performance can only be obtained with suitable simulation
of the mechanistic processes that control performance. In
most cases, it is more important to simulate lubrication and
failure mechanisms than it is to simulate the mechanical parameters of loads and speeds of component hardware. An important ingredient in test simulation is the pathway to failure. Performance limits of bearings, gears, a n d other
component hardware are defined as much by the lubrication
and deterioration mechanisms on the way to failure as by the
final failure mode itself.

Key Parameters Controlling Lubrication and


Failure M e c h a n i s m s
The key to unlocking the mysteries behind lubrication and
failure mechanisms is the identification of the functional regions of a lubricated contact, as shown in Fig. 2. The EHD
contact can be divided into three regions. The inlet region is
the convergent inlet section upstream of the high pressure
Hertzian contact region. The inlet region is the functioned region for EHD pressure generation, which has rigorous math-

ematical foundations for predicting film thickness within the


Hertzian region. The dynamic motions within the inlet region p u m p s the film up. The Hertzian region rides the film,
and the exit region discharges the film. The decoupling of
these functional regions is the key feature behind simulation
testing machines and testing methods [1].
Oil, with its viscosity and pressure-viscosity properties
within the convergent inlet region, controls EHD film thickness in a reliable cind predictable fashion. The shear and traction of the pressurized film within the Hertzian contact region gives rise to heat generation, which is dissipated within
the contacting bodies. For surface life and durability, the
preservation of the EHD or micro-EHD mechanism is essential. The primary purpose of oil chemical attributes is to preserve the EHD m e c h a n i s m s as m u c h as possible. Loss of
"surface integrity" to accommodate the EHD mechanism is
the first step toward wear and scuffing failure mechanisms.
While EHD mechanisms are essential for life and durability,
chemical attributes for boundary lubrication mechanisms
are equeJly essential. Chemical attributes play a critical role
in preserving surface integrity. The processes of physiceil adsorption and chemical reaction heal and protect the surfaces
against local adhesion and disruption of the surface topography. Tribo-contact systems, which have oil properties for
EHD film-forming capability and chemical attributes for surface film-forming ability working together, cein achieve remarkable levels of durability.
The decoupling of the inlet region EHD lubrication functions from the Hertzian region boundary and micro-EHD
mechEinisms provides a means to identify the key parameters
associated with lubrication mechanisms with failure mechanisms. Failure mechanisms of wear, scuffing, and surface initiated fatigue, are the result of micro-scale events associated
with roughness features, as illustrated in Fig. 3. The level of
EHD film thickness relative to surface roughness height determines the normal stress at asperity sites. If roughness features do not "run-in" or accommodate local stress by plastic
flow, high normal stresses with repeated contact cycles can
result in surface-initiated fatigue or "frosting." Since EHD
film thickness is a function of viscous properties in the inlet
region and the entraining velocity (Ug), the entraining velocity becomes a key test parameter.

^PRESSURE

0.71 ,0.57 i-)0.40

(^oUe)""a"^^R'
hm= 3.07

ijfh-

(NIJET ->+*HERTZ REGION^ >|<- EXIT

E H D pressure and film

965

,0.03 ^ 0 . 1 1

hm = min. film thickness


Ho = viscosity at atm press
Ue = entraining velocity, /4(ui + U2)
a = pressure-viscosity coefficient
R = combined radius of curvature
E' = combined elastic modulus
w = applied load

FIG. 2Functional regions of an EHD contact.

966 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

EHD pressure

Entraining

Lubr mechanisms
Surface film
EHD
Micro-EHD
Failure mechanisms
Wear
Scuffing
Fatigue

Sliding
FIG. 3Entraining veiocity affects asperity normal stress; sliding velocity affects tangential shear.

The sliding velocity within the Hertzian region determines


the tangential strain at asperity sites. The tangential stress at
these sites is directly connected to the frictional conditions
created at asperity sites. The chemical or physical processes
that occur at the local interface between roughness features
determine the frictional conditions. These processes can be
highly sensitive to local temperatures. Since sliding velocity
controls the strain at asperity sites, as well as frictional heating, sliding velocity becomes a key parameter.
The material response to normal and tangential stress and
its reaction with oil chemistry will determine the outcome on
asperity encounters. High normal stresses at asperity sites
can lead to a distressed or frosted surface deterioration. Tangential stress and strain at asperity sites can lead to polishing
wear, "corrosive" wear, or adhesive wear. Tangential stress
and strain under high-speed conditions, and without sufficient chemical response at the interface, can lead to scuffing
failure. In some contact situations, wear, scuffing, and fatigue may occur simultaneously. The dominant failure mode
will depend upon the key parameters.
With respect to lubrication and failure mechanisms for a
given tribo-contact system, the key performance parameters
are the entraining velocity, Ue, the sliding velocity. Us, and
temperature. Temperature can be viewed as the bulk temperature (Tb) of the contacting bodies and contact temperature
(Tc) within the contact itself. The bulk temperature controls
the viscous properties of the fluid in the inlet region for EHD
film thickness. The contact temperature controls the bulk
fluid traction coefficient in the Hertzian region. The contact
temperature is also a major contributor to oil and material
chemical reactivity within the Hertzian region.

It is recognized that contact load or stress is an important engineering parameter. Contact stress is certainly important with respect to subsurface initiated fatigue, where
material crack initiation is directly related to shear stresses
below the surface. From a tribological perspective of processes at the surface interface, particularly under highspeed lubricated conditions, load is translated into contact
size, heat generation, and to some degree, asperity stress
and strain. While engineers like to work in terms of load
and stress, the critical phenomena within the contact is really seen to a greater degree as temperature or tangential
stress and strain.
Theories have gone a long way in prediction of EHD film
thickness including micro-EHD mechanisms associated with
interaction of roughness features. These modeling activities
support theories of rolling contact fatigue, where stresses and
strains within the material or at the surfaces are used to predict fatigue initiation. What is missing from these theories is
the chemical and physical boundary lubricating mechanisms
that control surface topography, friction phenomena and the
strength properties of the surface and near-surface material.
While surface analytical tools can probe the chemical elements of the surface, little is known about the shear strength
of the interfacial material under stress. The only way forward
is to conduct tests for surface durability under service-like
simulated conditions. These tests are essential for oil and material development as well as for oil qualification. To make
tests relevant to service performance, the key parameters and
their domain of operation must be understood. The lubrication and failure mechanisms that these key parameters invoke must then be properly simulated.

CHAPTER 36: BENCH TEST MODELING


WAM Test Machine Technology
Wedeven Associates, Inc. machine (WAM) technology provides a highly flexible tribology testing environment. Machines like that shown in Fig. 4 are used to conduct tribology
research in Europe and the U.S. by major bearing companies
and other research organizations. These machines are capable of controlling the entraining velocity, sliding velocity, and
bulk temperature of the specimens independently. Ball and
disk test specimens are used to create a simulated contact
system. Custom designed crowned rollers are used in place of
ball specimens when special materials or surface finishes are
required.
The relative position of the specimens can be arranged to
change the orientation of the surface velocity vectors of the
two specimens at the contact point. This feature provides in-

dependent control of the entraining velocity and sliding velocity. The spindles are said to be aligned when the velocity
vector of the ball is coUinear with the velocity vector of the
disk at the point of contact. To obtain pure rolling across the
contact interface, the axis of the ball is tilted.
The test machine allows the direction of the velocity vectors to be changed by moving away from the aligned position.
The angle Z between the ball and disk velocity vectors can be
continuously varied between 0 and 180. The entraining velocity is defined as one-hsdf the sum of the ball and disk velocity vectors. The sliding velocity is defined as the vector difference between the ball and disk velocity vectors. The ability
to vary surface velocities in direction and magnitude
provides a large range of entraining velocities and sliding velocities. The independent control of entraining velocity and
sliding velocity allows the formation of EHD film separation

PLATE

VERTICa.L--'
LOAD CELL

967

Ball and disc velocity

A:R BEARING
LOAD CELL
BALL SPINDLE
SALi.
DISC

Ball angle

0m ,
1

I i f ^ i^'^\K\f"'

>

(c)
Disc velocity

Entraining velocity

_X

Sliding velocity

FIG. 4Performance mapping of lubrication attributes and life-limiting surface modes.

968

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

between the surfaces to be m a d e independent of the tangential strain within the contact. The decoupUng of film thickness from teingential strain provides the opportunity to control EHD and boundary lubrication mechanisms along with
their failure pathways.
The EHD mechanism is a remarkably powerful lubrication feature that is fundamentally linked to oil properties. As
long as a minute quantity of fluid is captured in the inlet region of a moving contact, EHD pressure and film thickness
is generated. With proper oil supply, EHD film generation is
a highly stable process. The separating film has enormous
"stiffness." The thickness of the film is precisely determined
from the entraining motion of the surfaces, geometry of the
contacting bodies, Eind temperature of the fluid in the confined space upstream of the contact. Other t h a n temperature, most of the controlling parameters are readily available. These features make EHD film thickness an obvious
tool to control surface separation a n d the failure processes
associated with the degree of asperity penetration between
surfaces. The following sections describe the use of EHD
film thickness with lubricating oils for controlling wear and
scuffing modes of failure.
M u l t i - d i m e n s i o n a l Oil C h a r a c t e r i z a t i o n
(Performance Mapping)
The performance of oils and materials can be mapped out by
conducting tests over a range of entraining velocities, Ue, (i.e.,
EHD film thicknesses) and sliding velocities Us. In addition, the
mapping of performcince with these parameters can be directly
connected to gear and bearing hardware. This linkage is made
possible by specific relationships between Ue and Us that exist
in bearing emd gear contacts. With this linkage, the characterization of oils and materials can potentially be translated into
design and performance prediction. In addition, oil and material characterization tests can b e linked to service hardweire.
Performance mapping is illustrated below with two DODL-85734 aviation oils. These oils, which have "load-carrying"
or "EP" additives, are used in helicopter transmissions and
supersonic aircraft (Concorde) [2]. The tests were carried out
u n d e r the following conditions:

The performance m a p s for the DOD-L-85734 oils are


shown in Figs. 5 and 6. Each data point marks the Ue and Us
operating conditions for a ten-minute test. A solid circle indicates a test that encountered a scuffing event. The two solid
circles shown in the performance m a p for oil PE-5-L1705 at
R = 100 in./s indicate the scuffing point for two test series. A
second test series was r u n because of an incorrect operating
position during the first test series, which would be expected
to cause an early scuff. The second test series gave a slightly
higher scuff point.
Each performemce m a p can be divided into three regions:
in EHD region, where the oil separates the surfaces with an
EHD film; a mixed-film lubrication region where the interaction of surface features between the surfaces takes place in
conjunction with a partial EHD film; and finally, a scuffing
or severe wear region, where neither EHD films nor boundary films are sufficient to preserve the integrity of the
surfaces. The transition between the EHD region and the
mixed-film region in this case was judged by visual evidence
of polishing wear of the surface features when observed in a
microscope at lOOx magnification. Actually, the unaided eye
is more sensitive to local surface polishing because only
slight modifications in surface topography are easily detected
by the reflection of light from the surface. Since both DODL-85734 oils have essentially the same viscosity, the transition boundary for each oil should b e the SEime. The performance maps show that the transition from the EHD region is
not exactly the same for the two oils. This may be due to the
chemistry of oil PE-5-L1761, which tends to preserve the topographical features from polishing wear better t h a n oil
PE-5-L1705.
The most striking feature of the performance maps is the
shape and location of the scuffing boundary, which is quite
different for each oil. At Ue = 100 in./s, the scuff performance
of oil PE-5-L1761 is significantly greater than oil PE-5-L1705.
Yet, the latter oil does as well, or better than, the former oil
at Ue = 170 in./s. This behavior is investigated below in the
sections that focus on traction, wear, and specimen temperature within the performance maps.

Wear and Traction Within Performance Maps


Ball specimen
Disk specimen

AISI 9310, 13/16 in. dia, Ra = 10 ^lin


AISI 9310, 4 in. dia X 0.5 in. thick, Ra = 6
/xin
Contact stress
300 Ksi (2.07 GPa), 93 lb load
Rolling velocity 30, 100, a n d l 7 0 i n . / s
Sliding velocity Increasing from 14 in./s, until scuff
Test time
10 min for each set of conditions
Oil flow rate
Drip feed, 2.7 ml/min
Temperature
Ball and disk temperatures allowed to increase with frictional heating; specimen
temperatures measured with trailing thermocouples
Two types of test series: (1) constant U^, deProcedure
creasing Ue and (2) constant Ue, increasing
Us until scuff for three values of Ue. New
specimens are used for each test series.
DOD-L-85734 oils PE-5-L1705 and PE-5Test Oils
L1761

The performance maps outline the operating conditions that


define the boundaries of vsirious lubrication and failure regions. The scuffing boundaries of the two DOD-L-85734 oils
are found to b e quite different. If an oil is to be judged by its
scuffing performance, we see that its performance cannot be
adequately defined by a single test. In addition, the relative
performance or load capacity ranking of the two oils varies
considerably depending on the selected operating conditions.
The ranking of these oils is relative to how they are tested.
Likewise, their performance in service will depend on the key
operating parameters encountered in service.
AdditionaJ insight into the performeince of these oils can be
obtained by investigating the wear and traction behavior as
the contact transitions into and through the various lubrication and wear regions. The initial traction coefficient of the
two oils as they transition from the EHD region into the
mixed-film region is on the order of 0.08. This is higher than
the maximum traction coefficient of 0.057 found for full-film
EHD conditions with smooth surfaces. The higher traction is

300 KSI Stress


"HG" 9310 Ball (Ra=10Min), 9310 Disc (Ra=6Min)
600 -

Scuff
DOD-L-85734 Oil PE-5-L1761

Severe wear
and scuffing
region

o 400 c

' Measured ball


temperature

200
Scuff

EHD_regioD - soi50

100

200

150

Ue, Entraining Velocity (in/sec)


FIG. 5Performance Map for DOD-L-85734 oil PE-5-L1761.
700
650
600
O
O
-W

500

450

JO

250 C

550

400

350

300

250

D)

Contact stress: 300 Ksi (2.07 GPa)


9310 ball (Ra=10 ^lin), 9310 disc (Ra=6 fxin) scuff

Bulk temp,
of test ball

DOD-L-85734 Oil PE-5-L1705

Severe wear
and scuffing

Testing
direction

=> 200
150
100

50
0

EHD region
75

100

125

150

Ue, Entraining velocity, in/sec


FIG. 6Performance Map for DOD-L-85734 oil PE-5-L1705

175

200

225

970

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

due to surface finish, which seems to influence traction even


when there is no noticeable wear of the surface features. As
the entraining velocity and EHD film decreases, the traction
coefficient for oil PE-5-L1761 increases at a more rapid rate
than oil PE-5-L1705. The greater increase in traction is due
to better preservation of the surface features from wear by
the former oila behavior found repeatedly, at least when
the surface temperatures are not very high.
The traction behavior of the DOD-L-85734 oils from the
performance map tests decreases with sliding velocity. The
traction coefficient decreases due to the increased frictional
heating with sliding velocity. The initial traction coefficient
at the lowest sliding velocity of 14 in./s is on the order of 0.08,
and it is approximately the same for each oil. As discussed
above, the maximum traction coefficient for a full EHD film
at the same stress, but with smooth surfaces, is 0.057. The
boost in traction is due to the contribution from the surface
features. The initial traction coefficient is noticeably less for
high entraining velocities, which generate thicker EHD
films. The initial traction coefficients for each oil are listed
below:
Initial Traction Coefficient (Ug = 1 4 in./s)
Entraining Vel
(in./s)

Traction Coefficient
PE-5-L1705

PE-5-L1761

30
100
170

0.0845
0.0747
0.0739

0.0857
0.0776
0.0744

These results show that the traction coefficient decreases


with entraining velocity because of its direct connection with
EHD film thickness. Yet, the traction coefficient at Ue = 170
in./s, which is on the order of 0.074, is still greater than that
measured for smooth surfaces, which is on the order of
0.057. It is quite remarkable that surface features can have a
significant impact on traction coefficient, even when there is
no visible evidence of wear on the surface features. The boost
in traction is assumed to be due to micro-EHD pressure generation at loccJ asperity sites when there is relative motion
between the surfaces due to the sliding component. It is also
evident that the traction coefficients for oil PE-5-L1761 are
greater than for oil PE-5-L1705. This is due to more polishing wear of the surface features with the latter oil. These results show that traction is sensitive to the tribological interaction of surface features at various locations within a
performance map. Traction is a sensitive measure of the interfacial conditions within the lubricated contact. From a
testing perspective, traction coefficient is the "heartbeat" of
the contact.
As the sliding velocity increases, the traction coefficient decreases due to frictional heating of the oil film, which lowers
the limiting shear strength of the pseudo-solid oil in the contact. The impact of this thermal phenomenon on traction
does not seem to be offset by the increase in traction that one
would anticipate as more asperity interaction occurs with
decreased surface separation. The onset of a scuffing event
frequently occurs when the traction coefficient is no longer
reduced by the sliding velocity. This may indicate that a
smaller portion of the contact is being sheared by an oil film,
and a greater portion is being sheared by surface films or the
plastic flow of near-surface material. In all tests, the traction

coefficient for oil PE-5-L1705 is less than oil PE-5-L1761. The


two oils show consistently different traction behavior,
although their differences may be diminished if the topographical run-in of the surfaces proceeds to a similar level for
each oil. One could argue that with sufficiently long running
time, the two oils may eventually reach identical traction coefficients. The difference in traction behavior and heat generation between these oils in field hardware may only have
significance during the initial operating life or during an
event where the surfaces have not completed the run-in process. This may explain why difficulties during green-run of
new propulsion hardware, particularly gearboxes, are sensitive to the particular oil selected.
In any case, the data suggest a strong association between
traction coefficient and surface finish. This association can
be illustrated with the help of Figs. 7-9, which are plots of the
visible wear track width on the test ball following each 10min test at a selected sliding velocity. Wear is a qualitative
measure, judged by the width (measured in mm) of the visible polishing wear of the surface topographical features on
the ball. In all cases, oil PE-5-L-1705 shows more polishing
wear on the ball than oil PE-5-L1761. If the wear data is compared with the traction data, the greatest traction differences
between the oils tend to occur when they have the greatest
difference in polishing wear.
Lubrication Regions and Thermal Considerations
The above results with Performance Mapping show that precision control of the EHD film separation between surfaces
with the entraining velocity Ue can be used to map scuffing
performance over a range of conditions. A Performance Map
goes beyond the identification of a scuffing boundary. Performance Maps identify regions of safe EHD lubrication,
mixed-film lubrication region and a region of severe wear or
scuffing. These regions are characterized by traction coefficient, a key parameter for monitoring the health and welfare
of the contact. While the entraining velocity creates the EHD
separation between the surfaces, the response to this separation when asperity interactions occur is decided by oil chemistry. Oil chemistry can significantly affect wear and scuffing
within the domain of a Performance Map, as demonstrated
by the two DOD-L-85734 oils PE-5-L1705 and PE-5-L1761.
These differences are reflected in traction coefficient, which
is a function of the shear strength of the bulk oil within the
contact, the degree of asperity interaction and the shear
strength of surface films. Since traction coefficient is directly
connected to heat generation, the temperature within the
contact and surrounding surfaces is linked to the tribological
phenomena created within the contact.
Temperature isotherms are shown in the Performance
Maps in Figs. 5 and 6. Oil PE-5-L1761 generally runs hotter
than PE-5-L1705. Since temperature affects chemiccJ reaction rates, the preservation or wear of surface features and
how they affect traction are intimately linked to how the oil
performs. This dynamic action among surface asperity interaction, wear, traction coefficient and temperature leads one
to conclude that single point testing to characterize oil for
service is not likely to be sufficient in order to assure performance. Performance Mapping, covering the domain of operating conditions in service, is a more reliable approach.

CHAPTER 36: BENCH TEST MODELING

Rolling Velocity = 30 in/sec


Ball: 9310, Ra = 10 (j-inch
Disc: 9310, Ra = 6 jj-inch
Stress = 300 KSI

0.5
0.4
0.3
50

100

150

200

250

300

350

400

450

500

550

600

650

700

Sliding Velocity, in/sec


FIG. 7Wear track width versus sliding velocity for two DOD-L-85734 oils (Ue = 30 inVs).

-i

1.3
1.2

Scuff

Ball: 9310, Ra = 10 M-inch


Disc: 9310, Ra = 6 M-inch
Stress = 300 KSI

Rolling Velocity = 100 In/sec

1.1

0.5
0.4
0.3
0

50

100

150

200

250

300

350

400

450

500

550

600

650

700

Sliding Velocity, in/sec


FIG. 8Wear track width versus sliding velocity for two DOD-L-85734 oils (Ue = 100 ln./s).

971

972 MANUAL 37: FUELS AND LUBRICANTS


1.3

HANDBOOK

Rolling Velocity = 170 in/sec

1.2

Ball: 9310, Ra = 10 M-inch


Disc: 9310, Ra = 6 M-inch
Stress = 300 KSI

1.1

0.5
0.4
0.3
0

50

100

150

200

250

300

350

400

450

500

550

600

650

700

Sliding Velocity, in/sec


FIG. 9Track width versus sliding velocity for two DOD-L-85734 oils (Ue = 170 inJs).

Linkage B e t w e e n Bearing and Gear Contacts


and Performance Maps
The importance of the entraining velocity with respect to its
control over EHD oil film thickness and the degree of asperity interaction has been shown. Once some asperity interaction is initiated, the above sections show the importance of
the relative sliding velocity, U^, across the interface. Low sliding velocities result in wear of roughness features according
to how the chemistry of the oil responds to the severity of the
interaction. High sliding velocities are required to invoke
scuffing failures. The parameters Ue and Us, along with temperature, control the lubrication and failure mechanisms
within a testing environment. Also, Ue and Us control lubrication and failure mechanisms in service hardware.
With proper replication of thermal and surface conditions,
a linkage can be made between performance testing and lubricated contacts in service. Every contact in service can be
characterized with respect to the distribution of entraining
velocities and sliding velocities within the contact. The range
and magnitude of sliding velocities within a gear contact can
be high. By contrast, rolling element bearings operate under
micro-slip conditions. In either case, the kinematic conditions of service hardware can be linked to Performance Maps
as illustrated in Figs. 10 and 11. High sliding velocities near
the root or tip of gear teeth are vulnerable to scuffing failure,
as illustrated in the Performance Map in Fig. 10. The low slip
operation in rolling element bearings is more vulnerable to
wear and surface initiated fatigue failures. The initiation of
surface-initiated fatigue under low slip conditions is discussed in the next section.

Impact of Oil Attributes on Surface Fatigue


Following initial engine or gearbox operation, the long-term
durability of rolling element bearings and gears is genercJly a
surface distress mode of failure. Surface distress is used as a
generic term. It can include several surface deterioration
modes of failure. The surface features produced by surface
distress are usually characterized with descriptive terms such
as: peeling, frosting, micro-cracking, micro-pitting, pitting,
gray staining and wear. The gear and bearing communities
will frequently use different descriptive terms to characterize
the same surface phenomena. The surface distress features
formed are precursors to major life limiting failures, such as
spalling or excessive wear. Failure modes by surface initiated
fatigue can be interactive and competitive with failure modes
of wear and scuffing.
One of the characteristic features of surface distress for
bearings and gears is that it is primarily controlled by a surface fatigue process. As such, the normal stress and tangential (friction) stress cycles that a surface must encounter are
important. At least part of the tangential stress that initiates
surface distress is due to the interaction of surface features
under low film thickness (h) operation, where the average
surface roughness height (a) is of the same order of magnitude as h. Low hJcr operation also causes wear, especially under non pure-rolling contact conditions.
The process of initiating micro-cracks at a surface is frequently in competition, or at least interactive, with wear processes. If the surfaces wear at a faster rate than micro-cracks
can initiate and propagate, no micro-pitting will occur. For
this reason, it is wise to consider the fatigue processes asso-

CHAPTER 36: BENCH TEST MODELING


12

OU: 4 cSt, Herco-A


10

Ball specimen: M50, Ri


Disc specimen: M50, Ri

Sliding
Velocity, e
Us (m/sec)

cS.

, ^

: #

Entraining velocity, Ue (m/sec)


FIG. 10Linkage between Performance Map and gear contacts.

600
500
400

Oil: 4 cSt, Herco-A


Stress: 300 ksi (2.07 GPa)
Ball: M50, Ra = 10 pin (0.25 fun)
Disc: M50, Ra = 3 jUn (0.075 mn)

Sliding
Velocity, ^^
Us (in/sec)
100

-100

-200

Entraining velocity, Ue (in/sec)


FIG. 11Linkage between Performance Map and roliing element bearing contact.

973

974

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

ciated with surface distress under low h/cr operation along


with wear processes.
Because surface interaction under low h/cr operation can
produce nascent surfaces and high local temperatures, it is
not unexpected to find oil chemistry playing an important
role in surface distress as well as bearing and gear life. There
is sound evidence that good oil chemistry for scuffing can
sometimes be detrimental to surface distress modes of failure. The user of an oil product would feel most comfortable
if he could be assured of its performance with respect to three
failure modes: (1) scuffing, (2) wear, and (3) surface distress
(fatigue). A meaningful screening test for all three is an important goal.
Exploratory tests have been conducted to show how the
utilization of entraining velocity and sliding velocity can be
used to introduce surface-initiated fatigue damage [3]. The
test m e t h o d includes surface deterioration for b o t h mild
wear and micro-pitting. The results give support to a testing
approach that can screen oils for surface distress performance in a relatively short period of test time.

must exist a sufficient local surface stress to initiate cyclic fatigue. The formation of micro-cracks may be a low cycle or
high cycle fatigue process, depending on the severity of the
local stresses produced. The severity of loccJ stresses is controlled by the ratio of h/cr. However, the h/cr ratio is not a sufficient parameter to control the details of the local stresses
within a lubricated contact. The average roughness height (a)
does not reflect the shape of surface features that control asperity pressure. Peak asperity pressures depend on the slope
of asperities near their summits. One also has to consider asperity size relative to the Hertzian contact width and the size
of the inlet region, which generates the EHD film thickness.
A stylus trace of the surface finish generated for surface
distress tests is shown in Fig. 12. The disk surface has a
roughness of 24 ^lin, Ra as measured by a stylus instrument.
Figure 12 also includes a calculation of the EHD film thickness (h) relative to the combined surface roughness height
(cr). A 5 cSt oil operating at 180C under the prescribed test
conditions gives a calculated h/cr of 0.10. The relatively rough
surfaces of the specimens are designed to accelerate the surface distress process so that micro-pitting can be achieved
within a relatively short testing period.

Testing for Surface Distress Under


Incipient Sliding
WAM tests for surface distress were run with a re-circulating
oil flow within a heated test chamber. To engage a surface
distress failure mode, the contact is operated in a low h/cr
regime. Operating conditions were selected to invoke oil
chemistry during the process of generating surface distress
features. The tests include the following features:
1. M50 steel test specimens to focus oil evaluation toward
bearing surface-initiated failure
2. Simulation of turbine engine bearing temperatures at approximately 180C
3. Operation n e a r pure-rolling to simulate rolling element
bearing contacts and pitch line conditions for gears
4. Operation at high rolling velocities to introduce as many
cycles as possible
5. Introduction of surface distress by high "asperity" contact
pressures instead of high Hertzian contact stress
6. Initiation of each surface distress test with a run-in period
to promote repeatability
Tests are run under low h/cr conditions with a disk surface
texture that causes high local stresses at grinding ridges to induce micro-cracking and micro-pitting. A run-in test stage is
used with a new M50 ball. When the run-in is completed, the
micro-pitting test is initiated with the following conditions:
Mat'ls:
Load:
Temp:
Spd:
Time:
Analysis:

M50 ball with "hard grind" finish vs M50 disk


(Ra = 24 fiin)
120 lbs. (apply load slowly, from 60 lbs to 120 lbs;
10 lbs every min)
Initiate test at 100C and work u p to 180C
300 in./s (selected to give an h/cr < 0.3), 2% slip
120 min.
Traction and temperature plots, measure wear,
p h o t o m i c r o g r a p h s of surfaces and count of
micro-pits

To create surface distress in the form of micro-cracking


and micro-pitting within a reasonable period of time, there

Features of Surface Distress Testing


With the above test protocol, typical surface distress in the
form of micro-pitting after approximately 4 h of testing is
shown in Fig. 13. Longer running times increase the n u m b e r
of micro-pits as well as their size. The micro-pits are on the
order of 30-60 /xm in diameter.
The ball surface in Fig. 13a is from a test conducted with a
4 cSt polyol ester oil, Herco-A, with n o additives. The surface
contains gray areas in addition to micro-pits. The gray appearance of the surface may be the result of oxide formation.
We have noticed that areas with gray staining seem to have
less wear, but more micro-cracking and micro-pitting. This
may be due to the frictional behavior of the oxide film or its
susceptibility to micro-cracks.
The ball surface in Fig. I3b is from a test conducted with a
9 cSt gearbox oil (PE-9-G0041) with a load-carrying additive
package. The gearbox oil results in less wear but approximately the same amount of micro-pitting as Herco-A. A phen o m e n o n of "gray staining" is a surface distress feature
sometimes observed in field hardweire.
The test results can be examined in terms of wear and micro-pitting. Wear and micro-pitting results cire plotted in Fig.
14 for three oils. They include the 4 cSt oil, Herco-A, the 9 cSt
gearbox oil PE-9-0041 and a 5 cSt corrosion inhibited oil PE5-L1785. Wear is a qualitative m e a s u r e m e n t obtained by
measuring the polished track width on the ball and dividing
the track width by the Hertzian contact width. Micro-pitting
is measured by estimating the n u m b e r of pits on the running
track of the ball. Some of the data points in Fig. 14 are from
tests conducted for 2 h (Condition 3.2), and some of the tests
have been run for 4 h.
The data in Fig. 14 show that it is possible to have a 9 cSt
gearbox oil with a load-carrying additive result in more micro-pitting than a 5 cSt corrosion inhibited oil. On the other
hand, the gearbox oil shows less wear. The non-formulated 4
cSt oil, Herco-A, shows higher wear and micro-pitting compared to the formulated oils.

CHAPTER 36: BENCH TEST MODELING

975

M50 ball, Ra = 0.25nm (10 nin)


}4-100.0 itin
+50.0 |iin

^ ^ j ^ ^

^J^ V H I * ^ ' * . * ^

r-

0.0 Itin
-50.0 iiin

I-

I
Hertzian contact width

M50 disc, Ra = 0.60nm (24 ^iln)

/^VM^Ww'
Contact stress:
Entraining velocity:
Contact slip:
Temperature:
h/a (5 cSt oil):

2.25 GPa (327 ksl)


7.62 m/sec (300 in/sec)
2%
180C(356F)
0.10

FIG. 12Surface roughness for surface initiated fatigue tests.

Testing for Surface Distress Under Gross Sliding

FIG. 13Wear and micro-pitting with


surface initiated fatigue protocol, a) 2hour fatigue initiation test with 4.5 cSt
non-formulated oil, Herco-A; b) 2-hour fatigue initiation test with 9 cSt gearbox oil,
PE-9-G0041.

The micro-pitting tests discussed above were conducted under conditions with 2% micro-sUp. Surface distress, particularly for gear contacts, encounter a range of sliding that goes
well beyond incipient sliding found in rolling element besirings. An increase in the sliding component of velocity promotes wear and generates more frictional heat.
An accelerated test protocol for surface distress with gross
sliding is shown in Fig. 15a and 15b. The test protocol continuously decreases the entraining velocity and increases the
applied load. The entraining velocity provides a continued reduction in EHD film thickness. As the surface features lose
their geometric sharpness due to wear, the load is increased
to continue the application of local stress at each roughness
feature. With independent control of the entraining and sliding velocities, the test can be run with a near-constant or decreasing sliding velocity so that the frictional heat generation
within the contact can be maintained at a desired level.
The test protocol can be completed in approximately one
hour. With properly selected test conditions, this approach
causes the surfaces to wear without initiation of scuffing. The
degree of contact severity can be continually increased by
running multiple tests at progressively increasing temperatures. The final operating temperature can be selected to correspond to the operating temperature of the component
hardware of interest.
The traction data for three tests run at ambient temperature, 50C and 90C, are shown in Fig. I5b. The traction coefficient progressively increases at each incremental change

976

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Surface Distress Tests


Wear and Micropitting: Conditions
5000
Each ball was run for a total 4 hrs
under severe surface distress test
conditions. Open symbols are results
after 2 hrs..

PE-9-G0041
(Load additive)
Condition 3.2 + 2 hrs
EX482

4500
4000

1
o
6

3500
3000

2500

1500

Heroo-A
(Basestocit) y^
Condition 3.2 \ /
EX429

PE-9-G0041
(Load additive)
Condition 3.2 + 2 hrs
EX480

2000

1000

500

Condition 3.2
EX470
^

PE-5-L1785
(Anti-wear additive)
Condition 3.2 + 2 lirs
EX483
PE-6-L1785
(Anti-wear additive)
Condition 3.2 + 2 tire
EX479

Condition 3.2
EX472

1.0

1.1

1.2

1.3

1.4

1.5

1.6

Wear (Tracic widtii/Hertz width)


FIG. 14Relationship between micro-pitting and wear for three types of oils

of entraining velocity and load. Repeating the test protocol at


a higher temperature increases the surface traction further.
If the operating conditions are properly selected, the final set
of conditions can introduce micro-pitting within a few hours
of testing. The photomicrograph in Fig. 15a shows transverse
micro-cracks and micro-pits on the ball specimen following 1
h of testing.
The test protocol above allows at least one surface to lose
its original surface features by a mild wear process before the
onset of micro-pitting. This is a common scenario found in
the areas of high sliding velocity on gear teeth. The high sliding eu"eas are vulnerable to wear and scuffing. This is a more
difficult simulation than the initiation of micro-pitting under
incipient sliding, where surface roughness features are much
less affected by wear. The latter situation is more often found
near the pitch line of spur gears, where the sliding velocities
are low. Because of the close interaction between wear and
micro-pitting, simulation testing must consider wear and micro-pitting together. Since the rates of wear and micropitting processes frequently vary, both of these pjirameters
should be monitored over time.
Other Types of Surface-Initiated Distress
The above tests demonstrate surface fatigue-initiated distress
due to two types of contact conditions: (1) high local asperity
stresses under incipient sliding conditions and (2) high as-

perity stress accompanied by tangential stress under gross


sliding conditions. While the latter promotes wear mechanisms, they both invoke a material fatigue process. Tribology
mechanisms, which alter asperity stress, wear and nearsurface properties, certainly enter the equation of fatigue life.
At least two other surface-initiated fatigue mechanisms
can also be operative. Surface-initiated distress can be influenced by corrosive reactions under high stress contact conditions. In addition, micro-pitting can be initiated at local sites
that have accumulated micro-scuffing damage. This is frequently found in gears following initial operation with relatively rough surfaces.
Figure 16 illustrates at least four mechanisms that can
cause surface distress involving fatigue. One is due to high
normal stresses at asperity sites caused by low h/cr operation
under incipient sliding conditions. Oil performance with respect to EHD film thickness and wear resistance is expected
to be a significant factor. A second mechanism is due to high
local traction under low h/cr conditions. Oil attributes associated with surface film protection with low friction are expected to be significant. A third mechanism is associated
with chemical attack. Chemical attack can create corrosion
pits. It also influences wear and crack initiation or propagation. Finally, a fourth possible mechanism is associated with
breik-in damage, where superficial micro-cracks or microscuffs during initial running create initiation sites for subsequent fatigue propagation.

CHAPTER 36: BENCH TEST MODELING

primary parameter for load capacity tests, sometimes plays a


secondary role for tests to invoke surface-initiated distress.
Intrinsic in the test parameters that control surface separation are the oil properties that control EHD film generation.
These are viscosity and pressure-viscosity coefficient. These
fundamental properties of the oil are controlled within the inlet region by the bulk temperature of the contacting surfaces.
Depending upon the particular operating parameters within
the contact, the above tests show that a number of surface
distress features can be initiated. Inherently, the nature of

Discussion of Micro-pitting Results


Surface distress, which covers a variety of surface damage
including fatigue processes, has been demonstrated by controUing the normal stresses and tangential strain within the
contact. These stresses and strains tend to be concentrated
locally on the upper-most surface features of the surfaces.
For asperity interaction, surface separation is precisely
controlled with the entraining velocity. Tangential strain is
controlled with the sliding velocity. Contact load, which is a

lOOx

(a)
Traction During WAM3 Wear/Micro-pitting Tests

500

1000

1S0O

977

2000

2S00

3000

3SO0

4000

Run Time (seconds)

(b)
FIG. 15Test protocol for micro-pitting and micro-cracking, a) Transverse cracks and micro-pitting; b)
Traction results from wear and micro-pitting test protocol.

978 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

CHAPTER
surface distress and the stochastic processes of fatigue mzike
surface-initiated failure processes complex.
A flexible test machine can be programmed to provide a
controlled decrease in h/crin order to cause micro-pitting and
wear within a few hours of testing. The degree of test acceleration, as well as the sequence of wecir and micro-pitting
events along the p a t h w a y t o w a r d failure, can be easily
changed. In most cases, due to the mystery behind what actucdly tremspires in real hardware, the practical relevEuice of
simulation testing for micro-pitting may be questionable. To
obtain a short-term screening test with meaningful connection to specific hardware, a good understanding of the wear
and surface fatigue process in service hardware is needed.
Until controlled data from the field is obtained, there is no assurance that these test methods for surface distress are giving
meaningful information for oil formulation, material construction, design or operating condition.

Oil a n d M a t e r i a l T e s t i n g f o r A d h e s i v e W e a r
The above sections focused on testing for oil or material attributes with respect to wear, scuffing and surface-initiated
fatigue. Traditional testing of oil attributes for weeir, scuffing,
and fatigue resistance is less than adequate to fully characterize an oil and to predict performance in service. The same
can be said about bearing and gear materials. Traditional
bearing material test methods, which generally focus on subsurface-initiated fatigue, do not assure success in component
hardware. The whole notion of oil and material testing and
development is rccilly intimately linked in the real world. One
cannot address oil eveiluation without immediately crossing
the boundary into material evaluation.
Load, speed, temperature and corrosion protection are driving bearing and gesir materials toward greater rolling contact
fatigue life, wear/scuffing resistance, and corrosion resistance.
The introduction of hybrid ceramic/metal materials presents
new surface chemistry that may be incompatible with conventional lubricating oils. Corrosion resistant bearing materials
with different surface chemistry, as the result of chrome oxides
instead of iron oxides on the surface, can significantly affect
the reaction rates between material and oil chemistry to form
surface films. Surface distress tests with some corrosion resistant materials, conducted with low EHD film thickness relative to surface roughness, show that surface fatigue mechanisms ccin be preempted by local adhesion events.
The term "adhesive wear" is commonly used when failed
surfaces appear to have undergone plastic flow due to local
"adhesion" at the interface. Surface failure by adhesive wear
can be initiated at microscopic sites of insufficient surface
film lubrication or at sites of debris encounters. With limited
chemical reactivity between lubricating oil and some corrosion resistant materials, locEil adhesion events, which are not
able to recover, propagate into broad patches of adhesive
wear damage. In addition, material microstructure and properties, like hardness, that affect plastic flow seem to influence
the onset of adhesive wear. With sufficient sliding velocity
and contact stress, adhesive wear can transition into a major
scuffing event. A scuffing event is characterized by a rapid
rise in friction and temperature. These tribological features,
as measured with Ein adhesive wear test method, correlate
with experience in full-scale bearing tests.

36: BENCH

TEST MODELING

979

At the heart of surface durability is material compatibility with lubricating oil chemistry to form surface films,
which prevents local adhesion. The adhesive wear test
method described below progressively increases the degree
of asperity encounter at the interface u n d e r rolling/sliding
conditions. The test method invokes tribological interactions, which are measured in terms of friction (traction),
gentle polishing wear of surface features, adhesive wear
events, and scuffing.
Adhesive

Wear Test

Method

Adhesive wear tests, run with the WAM test machines, use
ball and disk specimens representing bearing rolling element
and raceway surfaces. Ball specimens are supplied by beeiring vendors. The disk specimens are heat treated and finished
to simulate bearing ring specifications. Surface preparation
of the disks consists of fine grinding, followed by abrasive
lapping to a surface finish of 2 /A-inch, Ra. The lapping operation is done with specimen rotation about its centerline to
create a circumferentieJ lay in the direction of rolling motion.
The finishing method consists of several lapping stages to obtain a consistent surface texture. Care is taken to avoid microscopic bends and folds ("leafing") in the surface texture.
The final finish is similar to a finely honed bearing raceway
of aircraft quality.
Ball sizes may range from 0.5 in. (12.7 m m ) to 1.125-in.
(28.58 m m ) diameter. The selection of ball size and quality is
determined by availability. The test ball specimens, which
are production quality, have m u c h better surface finish than
the disk specimen. Highlights of the test conditions are given
below.
Maximum
Hertzian
contact stress:
Entraining
(rolling)
velocity, Ug:
Contact slip:

1.95 GPa (282 ksi)

1 0 . 1 6 - 1.27m/sec
(400 - 50 in/s)
Ue reduced in four stages of 180 s each
15%, subsequent tests 30% and 50% until
failure
If adhesive wear occurs at 15% slip, 8%
slip is run
% slip = (Ub - Ud)/ l/2(Ub + Ud) X 100
where Ub = surface velocity of ball
Ud = surface velocity of disk
MIL-PRF-23699 (Mobil Jet II), reference
Test oil;
oil
Test temperature: 200C (392F)
An adhesive wear test series for a materieJ generally consists of three tests: one each at 15% slip, 30% slip, and 50%
slip. If an adhesive wccir event occurs at 15% slip, the test is
repeated at 8% slip. Generally, two test series are run for each
material pair. At the end of each test, the running tracks on
the ball and disk specimens are photographed at lOOX. Traction coefficient is plotted over time for each test. The surfaces
of ball and disk specimens are documented with photomicrographs, which are stored as digital images.
At 200C the disk surface can become lightly discolored
with oxide or surface films from the oil. To avoid the influence of accumulated surface chemistry on the disk, the test
track on the disk specimen is refinished after each test.

980

MANUAL

Traction

Test

37: FUELS AND LUBRICANTS

HANDBOOK

Plots

Tj^ical traction test plots are shown in Fig. 17. Initial operation at an entraining velocity of 10.16 m/s gives an EHD film
thickness to surface roughness ratio (h/cr) close to 1.0 and a
traction coefficient on the order of 0.02. Incremental reductions in entraining velocity increase the traction coefficient
due to thinner EHD films and greater surface interaction. A
gradual decrease in traction coefficient is attributed to polishing wear of surface features.
An adhesive wear event is identified by a rapid excursion in
traction coefficient. While the traction may recover after a few
seconds, the local surface damage that occurs during the adhesive wear event is permanent. The local adhesive wear damage becomes a vulnerable site for surface-initiated fatigue.
Ranking

Adhesive

Wear

Resistance

A system of ranking adhesive wear performance has been developed to characterize the overall lubricating performance
of various material pairs and lubricants. Performance is
based on measured behavior reflecting the ability of the material pair to accommodate low h/cr and high slip operation
without adhesive wear and with traction behavior reflecting
good lubrication at the interface. A point system is used to
give weighting factors for tribology attributes that we feel are
important for high-speed rolling element bearings. The criteria and weighting factors for performance ranking are shown
in Table 1.

Perfoimance is judged relative to a baseline material pair


and lubricant of M50/M50 and Mobil Jet II. Mobil Jet II is
classified as a Standard (STD) MIL-PRF-23699 oil. The lubricating ability of Mobil Jet II ranks high among typical jet
engine oils. The material pair of M50/M50 gives excellent
performance for adhesive wear resistance. These baseline
materials, which survive the test protocol with no significant surface damage, achieve a score of 50 with the performance criteria discussed above. Other materials and lubricants can be ranked relative to the baseline materials, as
shown in Fig. 18.

TABLE 1Criteria for tribology attributes.


Weighting Factor
Measured Tribology Attribute
No adhesive wear events at 15% slip.
10
No large step increases in traction @ low A
6
(15% slip).
No rapid decline in traction coefficient
reflecting advanced polishing wear.
Survives 8% slip without adhesive wear.
Survives 8% slip without major increase
in traction.
Survives high slip (>15%) without adhesive
wear events:
30% slip = 8; 50 % slip = 17
"Steady" traction behavior (no fluctuations
due to a struggling contact).
Survives without a catastrophic scuff.

100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400
Run Time (seconds)
FIG. 17Adhesive wear test protocol and traction results.

CHAPTER

36: BENCH

TEST MODELING

981

M50/M50
M50/M50
MSO/Stainless M50/Stainless M50/Stainless M50/Stainless M50/Stainless
High qual. STD Low qual. STD High qual. STD Run-in with
Low qual.
High qual. HTS NTS brand of
IMIL-PRF-23699IHIL-PRF-23699 MIL-PRF-23699 DOD-L-85734 MIL-PRF-23699 MIL-PRF-23699 IMIL-PRF-23699
Operation with
High qual. STD

Mafis tested in
bearing

MIL-PRF-23699
rig

g^u ^lafi/Disc mat'l

Ball diameter: 12.7 mm (G.5 inch)

FIG. 18Summai^ bar chart of adhesive wear attributes.

Discussion

of Adhesive

Wear

Testing

Some material pairs and lubricants m a y experience adhesive


wear problems with this test protocol under low h/a conditions, particularly in the presence of high slide-to-roll ratios.
A deficiency in adhesive wesir compared to the baseline materials does not preclude the successful utilization of certain
materials and lubricants. The vulnerability of a tribo-system
to adhesive wear can be at least partially offset by careful runin, where the presence of chemically active additives and improvement in surface topography condition the surface for
durability. However, sudden "events" like skidding or debris
rollover, may again make the surfaces vulnerable to adhesive
wear. If start/stop cycles are not severe with respect to microslip and contact stress, and if near full-film EHD conditions
are prevalent during operation, a material pair deficient in adhesive wecir may operate satisfactorily. On the other hand, a
good performance ranking in this test does not assure perform a n c e in service. Successful performance u n d e r the selected
test conditions of the test protocol does not guEirantee success
u n d e r other conditions. Assessment of the trlbological parameters for the peirticular application, along with simulation
testing, is recommended for applications with challenging operating conditions. As a minimum, the test protocol provides
a good screening test for materials and lubricants.

Oil Evaluation

with Adhesive

Wear

Testing

Adhesive wear testing can be used to evaluate jet engine oils


as well as bearing materials. Bearing materials were evaluated with a reference oil, MIL-PRF-23699 (Mobil Jet II). The
data in Fig. 18 shows that improved durability against adhesive wear can be achieved with an initial run-in with a high
load-Ccirrying DOD-L-85734 oil. The more reactive chemistry
in the DOD-L-85734 oil conditions the surface with protective surface films to avoid adhesion. If follow-on operation after run-in is conducted with MIL-PRF-23699 oil, the run-in
surface films may be a temporary benefit.
Perhaps the most interesting finding with oil evaluation
with the adhesive wear test protocol is that high performing
oils in load capacity tests are not always reflected in adhesive wear tests, psirticulzirly when corrosion resisteint materiEils are used. In load capacity tests, standard (STD) oils
generally have higher scuff resistance than high thermal stability (HTS) oils. Figure 18 shows that this is not the case
for adhesive wear tests. In addition. Fig. 18 shows that the
"Low Quality" MIL-PRF-23699 oil, according to scuffing
load capacity tests, does better than a "High Quality" MILPRF-23699 oil. This appears to be the case when at least one
surface is chkracterized with chromium oxide for corrosion
resistance.

982 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

More recent adhesive wear testing confirms the finding


that some low performing oils for scuffing resistance can do
quite well in adhesive wear tests. This seems to lead to two
conclusions: (1) the effectiveness oil chemistry is dependent
upon material surface chemistry and (2) oil attributes for
scuffing resistance are not necessarily translated into adhesive wear resistance. The reason for this may be associated
contact conditions that affect chemical reactivity. Contact
temperature can have a significant effect.
Oil-off Testing
The adhesive wear testing described above increases the contact severity by reducing the entraining velocity to decrease
EHD film thickness. A concern in service hardware is momentary oil interruption or starvation. A "starved" contact is
actually a reduction of fluid within the inlet region of the contact to the degree that it affects EHD pressure generation. A
starved contact operates with a reduced EHD film thickness
according to the degree of starvation.
Oil-off testing is a method to evaluate oil attributes for
their ability to make surfaces survive or recover with
marginal quantities of lubricant. Starvation prevents the entrainment of fresh chemistry into the contact. The sections
below describe an oil-off test protocol and test results with
the three aviation oils.
Oil-off Test Procedure
An oil-off test protocol evaluates bearing materials and lubricants for durability and operational life under marginal lubrication conditions sometimes experienced in service. The
commonly used aircraft bearing steel M50 is used as a baseline for evaluation purposes. Oil-off tests generally support
other tribology tests for material and lubricant performance.
Oil-off test conditions are derived from adhesive wear tests
discussed above. The test specimens consist of a .5 in. ball
specimen (or alternate ball sizes), which rides against a flat
disk specimen. The disk specimen represents bearing ring
materials. Surface preparation of the disk specimen is the
same as adhesive wear tests discussed in the Adhesive Wear
Test Method section.
An oil-off test protocol for bearing operation was developed with the following test conditions:
Ball
Disk
Contact stress
Entraining velocity
Contact slip
Temperature (disk)
Lube supply

M50, .5 in. dia., Grade 5 (or alternate


size or Grade)
M50, finished to 2 /tin Ra (baseline
material and finish)
2.49 GPa (360 ksi)
10.16 m/s (400 in./s)
5%
200 C (392F)
drip feed until oil-off at 600 s

The test is initiated after the disk specimen temperature


stabilizes at 200C. The first 60 s of the test is operated at or
near pure rolling. The remainder of the test is run at 5% slip.
A computer-controlled peristaltic pump is shut off after
600 s. To avoid release of residual oil on the bcJl and disk surfaces, tests are conducted with the ball thermocouple, oil
shielding material and parts of the heating equipment re-

moved from the test area immediately following oil shut off.
Oil-off tests can be conducted with various criteria for test
termination. These include: (1) oil-off operation until a rapid
rise in traction coefficient to an arbitrary value; (2) oil-off operation until a rise in traction coefficient to 0.15; and (3) oiloff operation for 220 s, which is beyond the time typically required to reach a maximum traction coefficient (0.4) and
the onset of a high wear rate.
Except where noted, the test oil is Mobil Jet II. From testing with qualified jet engine oil products, Mobil Jet II has excellent lubricating ability compjired to most oil brands on the
qualified products list for MIL-PRF-23699.
Typical Oil-off Test Results
To establish the role of oil lubricating characteristics during
oil-off conditions, two tests were run with a 4 cSt MIL-PRF7808 oil (TEL-0004), which has known difficulties in certain
applications. Oil-off tests were also conducted with high
load-carrying DOD-L-85734 oil, which is used in aircraft
gearboxes and demanding engine applications.
Typical oil-off traction behavior for M50/M50 materials
and the three oil types are shown in Fig. 19. With continuous
oil supply and a test temperature of 200C, the traction coefficient for a full EHD oil film is on the order of 0.025. A t3rpical traction coefficient for jet engine oil at ambient temperature (~23C) is on the order of 0.07.
The rise in traction coefficient after oil-off is associated with
local adhesion and transfer of matericJ from the ridges of the
finishing marks on the disk specimen. The local material transfer, smearing, and oxidation creates material pileup and a loss
of surface integrity. At this stage the surfaces encounter high
local friction events due to material pileup and high friction oxides. The amount of wear is not significant. While the surface
disturbance appears to be minor at the time of test termination,
the situation is in a run-away condition heading for gross surface failure and a traction coefficient on the order of 0.4.
The maximum traction coefficient of 0.4 is attributed to
massive adhesion and material transfer between the surfaces.
The rise in traction coefficient is associated with the spread
of adhesive events across the operating track on the specimens. A momentary departure from an increase in traction is
believed to be the result of lower tangenticil shear caused by
the onset of wear.
These tests show that oil starvation leads to local adhesion
and pileup of material on the surfaces with a corresponding
rise in traction coefficient. Once this process starts (and without subsequent oil replenishment) adhesion and oxidation of
transferred material become a run-away process. The runaway process seems to be well on its way by the time the traction coefficient has increased from 0.025-0.15a six-fold increase in traction coefficient.
Effect of Material or Oil Lubricating

Quality

The above results show that the initiation of run-away traction is due to adhesion and oxide growth at local sites. Resistcmce against adhesion depends upon the material pair, along
with protection against removal of surface films that prevent
atomic bonding between the surfaces. If this is the case, the
important attributes of the material for oil-off performance
cire associated with the material's response to chemistry or
"tribo-chemistry" of the oil.

CHAPTER 36: BENCH TEST MODELING 983


300

0.40

Ball: M50 (0.5 In. dia)


Disc: M50
Entraining Velocity: 400 In/sec.
Slip: 5%
Temperature: 200C
Stress: 360 ksl

0.35 -

- 250

0.30 1 of 2 heat
sources removed

Disc Temperature

200

8 0.25 ^
S 0.20
c
.g

150 I

MIL-PRF-7808K
(TEL-0004)
Gra.de 4

Q.

DOD-L-85734

MIL-PRF-23699

S 0.15

e
100 "

PWM53

0.10

PWM55

Lube supply
removed @ 600 sec

0.05

50

Traction Coefficient

0.00 1

500

j _

550

600

650

700

Run Time (seconds)


FIG. 19Oil-off test protocol and effect of oil quality on oil-off performance.

The oil-off test results with the three test oils in Fig. 19 are
summarized below with respect to the average time to a traction coefficient of 0.15.
Test Oil

Average time to traction


coefficient of 0.15

TEL-0004 (4 cSt) MIL-PRF-7808


Mobil Jet II (5 cSt) MIL-PRF-23699
DOD-L-85734

10.5 s (2 tests)
42.0 s (3 tests)
81.0 s ( l test)

Oil additive chemistry and other factors affecting the lubricating ability of the oil are significant contributors to oiloff capability. An eight-fold difference between the time-tofailure is evident between a low queility oil for lubrication
compared to a high quality oil. The traction data in Fig. 19
show that the onset of failure for oil TEL-0004 is a sudden
event. The additive chemistry in the DOD-L-85734 oil results
in a gradual rise in traction coefficient. The gradual rise in
traction coefficient is associated with a controlled tribological process, which results in less severe local damage to the
surfaces. There are noticeably fewer areas of material transfer or islands of oxidized material on the surfaces with the
DOD-L-85734 oil.
Discussion

of Oil-off Test

Results

These results strongly suggest that a high quality oil for


lubrication can provide greater tolerance against surface damage during oil-off operation with better probability
for recovery after a high traction event due to momentary oil

interruption conditions. The significant feature that these


tests bring out is that testing for bearing or material performance for oil-off capability can be significantly affected by
oil type.
The oil-off test protocol can also be used to evaluate bearing materials, surface finishing processes (roughness a n d
texture) and effects of surface defects. The test protocol can
be expanded to include material a n d oil attributes a n d their
potential for recovery following a high traction and material
transfer event. The recovery is accomplished by repair of the
surfaces through a wear process. However, incomplete surface repair and accumulated damage below the surface are
likely to reduce fatigue life. In any case, recovery, even with a
sacrificial wear process, has the potential to achieve survivability in the near term.

EHD FILM-FORMING CAPABILITY OF OIL


The above simulation tests have been developed using key
performance parameters including entraining velocity, sliding velocity, contact temperature, a n d surface topography.
These parameters should be viewed with respect to fundamental properties of the oil, or at least characteristic oil "attributes." The simulation approach is to link test (or service)
parameters with fundamental oil properties as much as possible. This can be done with physical properties like viscosity,
pressure-viscosity coefficient, and even traction coefficient.

984

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

The direct and sensitive connection between entraining velocity and EHD film thickness holds the key to linking practical engineering peirameters to tribology phenomena within
a lubricated contact. This linkage makes the task of deeding
with chemical attributes of oils and materieds m u c h easier.
EHD theory provides the only useful design guide among all
the complex mechanisms in tribology. EHD film generation
mechanisms give a n opportunity to establish a c o m m o n denominator between testing and service performance. The importance of entraining velocity is its association with the entrainment of oil into the contact to generate a hydrodynamic
or EHD film. Since the ratio (h/cr) representing EHD film
thickness (h) and surface roughness (cr) is important with respect to the degree of asperity penetration within the confines of the contact, fundamental fluid properties of viscosity
and pressure-viscosity coefficient are essenticJ for oil characterization. Viscosity and pressure-viscosity coefficient give
rise to an inherent capability of oil to generate Ein EHD film
for surface separation. The sections below describe a test
method for determining EHD film-forming capability and
the determination of pressure-viscosity coefficient.
If EHD film thickness can be measured, it can be used to
calculate pressure-viscosity coefficient. If the EHD filmforming capability of cin oil can be determined directly from
oil film thickness m e a s u r e m e n t s , the characterization of
a n oil can go beyond the standard viscosity properties used
in oil specifications. These viscosity features include nonNewtonian effects and enhanced viscosity due to molecular
forces at the surface. The sections below s u m m a r i z e the
method used to measure EHD film thickness. Discussions include the role of pressure-viscosity coefficient on EHD filmforming capability and its impact on oil specification.
WAM Configuration for Optical E H D Film
Thickness Measurement
The oil film thickness of test oils can be m e a s u r e d between ball and disk test specimens under dynamic EHD con-

tact conditions with the WAM test machine configured for


optical measurements. The configuration for opticcJ interference is shown in Fig. 20. The contact load, surface speed and
temperature of the test specimens are computer-controlled.
Typical film thickness tests are conducted with the test specimens and contact conditions identified below.
Ball

13/16 in. dia. M50 steel (grade 5), Ra <


1 /tin.
Disk
4 in. dia X 0.5 inch, Pyrex 7740 with
optical coatings
MEIX. Hertz Stress
0.59 GPa (86 000 psi)
Entraining Velocity Variable, defined as 1/2 sum of surface
velocities
Sliding velocity
0, pure rolling
Nominal Temp
Ambient to 130C
The control and measurement of temperature is a critical
factor, especially for the precision required to obtain the
pressure-viscosity coefficients from film thickness measurements. Tests are conducted within a heated chamber with a
recirculating oil supply, which uses approximately 100 ml of
test oil. A computer-controlled oil heater, resistance heater
and heat lamp EJIOW for a disk temperature that varies between 1 and 2C during the course of a test. As the test progresses, temperature fluctuations for optical film thickness
measurements are due to veirying amounts of windage created by the rotating test specimens. Surface speeds may
rcinge from 0.1-10 m/sec.
For optical measurements, a Pyrex disk is used as a mating
specimen. The bcdl is mounted below, rather than above the
disk, as shown in Fig. 20. The Young's Modulus of the Pjrex
disk is 9.1 X 106 psi and the Poisson's ratio is 0.20. The
t r a n s p a r e n t disk is coated with a partially reflecting
chromium coating to allow interference fringes to form between the ball and disk at the contact point.
The contact is illuminated with white light filtered with a
special d u o c h r o m a t i c filter that transmits red a n d green

FIG. 20WAM machine with optical configuration to measure EHD film thickness with
interferometry.

CHAPTER

TEST MODELING

985

EHD Film Thickness at 2 m/s


Hertz Stress: 0.59 GPa
Bali Diameter: 2.06 cm.

CO

c
o
i

36: BENCH

CO
Q.

(0

PE-9-G0041

PE-5-L1876

O)
c

H/IIL-L7808
Herco-A

0.1

O
I

LU

20

30

40

50

60

70

80

90 100

Temperature (C)
FIG. 21EHD film-forming capability versus temperature at 2 m/s.

wavelength bcinds. This optical system forms a sequence of


colored fringes in and around the contact (see Fig. 20). Each
colored fringe corresponds to a particular optical thickness
between the surfaces. These optical fringes allow the wavelength of light to be used as a unit of measure to determine
the thickness of a n EHD generated oil film. The colored
fringes are calibrated to determine the optical film thickness
corresponding to each color. The average oil film thickness
between each colored fringe is 0.076 /xm (3 X 10"* in.). If one
includes the thickness determinations corresponding to the
transitions between each colored fringe, the average thickness between each fringe is 0.038 /xm (1.5 X 10 * in.). The
resolution of oil film thickness is on the order of 0.025 /xm
(l.OX 10"* in). An ultra-thin film technique for oil film thicknesses significantly improves resolution. It also allows oil
film thicknesses to be measured down to 3 nanometers. The
entraining velocity (rolling velocity) is used to control the
thickness of the EHD film. A film thickness test is run from
low speed to high speed for a given test temperature.
Film thickness measurements Eire obtained by determining
the entraining velocity (rolling velocity) corresponding to
each fringe color. Since the wavelength of light varies with
the optical properties of the media of transmission, the optical film thickness data are converted to actual film thickness
by making corrections for the refractive index of the test oil.
The corrections include the effect of pressure on density.
E H D Film-forming Capability of Test Oils
The EHD film-forming capability of an oil can be defined as
the ability of the oil to generate a n EHD oil film. The oil is
judged by the thickness of the oil film, which is a function of
the viscosity and pressure-viscosity properties of the oil. The
EHD film-forming capability of an oil is a function of several
rheological factors that go beyond the simple viscosity used
in oil specifications.
The raw oil film thickness data are plotted on log-log plots.
The data on the log-log plots show that the relationship be-

tween film thickness and speed is exponential. From EHD


theory, the film thickness varies with entraining velocity, Ue,
to the power of 0.67 as seen below.
1.9

(^oUe)"

3RO

(1)

where
film thickness, center of contact
combined radius of curvature 1/R = 1/Ri -II/R2
vis at atm. press and test t e m p
^o
a
pressure-viscosity coefficient
Ue
entraining vel., Ue = l/2(Ui + U2)
E'
combined elastic modulus, 1/E' = 1/2[(1
o^/Ei) + (1 - o^/Ez)]
Film thickness decreases with temperature due to the sensitivity of viscosity with temperature. The pressure-viscosity
coefficient (a) can also decrease with temperature. Because
the thickness of the EHD film is sensitive to temperature and
to the difficulty in controlling each test at exactly the required temperature, the test results are plotted in terms of
film-forming capability versus temperature. To do this we
have selected a reference entraining velocity of 2 m/s.
Using a reference entraining velocity of 2 m/s, the film
thickness for test oils is determined from the test plots of film
thickness versus speed for each test temperature. These EHD
film thickness values are then plotted as a function of temperature. The EHD film-forming capability for a number of
polyolester t5^e aviation oils supplied by the U.S. Navy is
shown in Fig. 2 1 . These aviation oils cover a range of viscosities from 3-9 cSt. The property data provided for these oils
are given in Table 2.
ho

Pressure-Viscosity Coefficients
The film thickness results of the test oils can b e plotted in dimensionless form where a film thickness parameter (ho/R) is
plotted against a dimensionless speed parameter (T7oUe/E'R).

986

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 2Properties

of test oils.

Code

Oil Type

Viscosity @100C

Viscosity @ 40C

SpecGr@15C

SpecGr@40C

SpecGr@70C

Refractive Index

PE-5-L1557
PE-5-L1818
PE-5-L1876
PE-5-G0041
MIL-L-7808J
PE-5-L1274
Krytox 143AB
16350, lot 12

5 cSt basestock
5 cSt basestock
5 cSt basestock
9 cSt formulated
3 cSt formulated
4.5 cSt Herco-A
lOcStPFPE
80 cSt PFPE

4.84 cSt
4.93 cSt
5.06 cSt
8.79 cSt
3.15 cSt
4.5 cSt
9.8 cSt
80cSt

23.47 cSt
22.98 cSt
24.61 cSt
50.99 cSt
12.22 cSt
20.0 cSt
75cSt
900 cSt

0.9954
0.9683
0.9961
0.9858
0.955
1.003
1.902
1.925

0.9829
0.9574
0.9836
0.9739
0.938
0.9900
1.861
1.882

0.9743
0.9491
0.9736
0.9663
0.910
0.9808
1.808
1.830

1.4513
1.4526
1.4511
1.4610
1.56
1.56
1.36
1.3

r-

Values calculated from reference fluid Krytox 143AB

<u
o

Krytox 16350

it

0)

o ;r2?

s.

Referance fluid
(Kiytox 143AB)

8 -5
=?
fl)
3
CO

10

<a
3

^
ro

(1) r
n
LL <

2-

a)

>

o
(1)
11=

20

110

30
Temperature (C)

FIG. 22Pressure-viscosity coefficients determined from EHD film thickness measurements.

The only EHD lubricating parameter missing from these two


dimensionless parameters is the pressure-viscosity coefficient (a). Since all the tests were run under the same load, the
applied load (w), which is also missing from these dimensionless parameters, is neglected.
If the a-value for each oil were the same, the data on a plot
of these dimensionless parameters would fall on a single line.
The test results, which depart from a single line, reflect a different pressure-viscosity coefficient. A "relative" pressureviscosity coefficient for a test oil can be obtained from test
data for a reference fluid with known pressure-viscosity versus temperature behavior. A reference fluid, Krytox 143AB, is
selected for this purpose. The pressure-viscosity coefficient
for this fluid was determined by a high-pressure capillary viscometer. The pressure-viscosity coefficient used for the reference fluid is defined as the reciprocal asymptotic isoviscous pressure (a*). Pressure-viscosity data seldom follow a
simple mathematiccJ relation. The definition of a* takes into
account variations of viscosity with pressure over a pressure
range.
Using a reference fluid, it is possible to calculate "relative"
a-values for each test oil at a given temperature, with the following equation derived from EHD theory:
ho/R'
01= a?efoil

(ho/R)refoil

According to EHD theory, the above equation assumes that


ho is proportional to o:"'^^. The relative pressure-viscosity coefficients for the test oils are determined at a selected speed
parameter of 1 X 10"^". This value is selected because it has
corresponding film thickness data for essentially all the tests.
The value of ho/R for the test oil at each temperature is determined from log-log plots of (ho/R) vs (rjoUe/ E'R), where
(TJOUE/ E'R) = 1 X 10~^. These values are used in the above
equation to calculate an a-value, which is determined relative
to the reference fluid data.
With the above procedures, the pressure-viscosity coefficients of all the oils are determined for each test temperature.
The calculated values, which were used to determine the
pressure-viscosity coefficient, are plotted in Fig. 22.
The plot in Fig. 22 includes the reference oil, Krytox
143AB, as well as the high molecular weight PFPE oil
16350. Over the temperature range in Fig. 22 the aviation
oils have a-values that range between 0.5 and 2.0 X 10~*
Pa~'. Pressure-viscosity coefficients tend to decrease with
temperature.
Discussion of Pressure-Viscosity Data
The most important feature of the data in Fig. 22 is that the
pressure-viscosity coefficients of the polyolester gas turbine
and gearbox oils are noticeably different. The average pres-

CHAPTER 36: BENCH TEST MODELING


sure-viscosity coefficient between 30C and 70C for each oil
is given in Table 3.
From the data in Table 3, which includes oil viscosity at
100C, it can be seen that the pressure-viscosity coefficients
increase with base oil viscosity. The EHD film-forming quality of an oil is associated with the pressure-viscosity coefficient as well as its viscosity. Higher viscosity oils benefit from
an increase in pressure-viscosity coefficient as well as its viscosity. Oils with similar molecular structures and molecular
weights seem to have similar pressure-viscosity coefficients.
The measurement of EHD film thickness and the determination of the pressure-viscosity coefficients are essential for
c o m p o n e n t design, performance prediction, a n d testing
simulations.

GENERALIZED PERFORMANCE MAP


The availability of viscosity and pressure-viscosity coefficients allows calculations to be made for lubrication regimes
of operation in component hardware and test simulations.
For first order calculations, EHD film thickness (h) can be
calculated and related to the combined surface roughness (a)
of the contacting surfaces. Calculated values of hJa greater
than three are generally considered fuU-EHD film lubrication
where surface roughness has no influence on friction or surface deterioration. When h/cr is less than 3, and particularly
less than 1, the lubrication regime is considered "mixed film,"
where lubrication is a mixture of EHD film and surface film
(or boundary) lubrication.
The use of the ratio h/cr normalizes tests r u n over a range
of entraining velocities and surface roughness. The ratio h/cr
also reflects the degree of asperity interaction with the con-

TABLE 3Measured pressure-viscosity coefficients.


Viscosity, cSt Avg. Press-Vis Coef
for 30, 40 &70 "C
at100C
Oil Code
Description
High mw PFPE
80.0
5.11. X 10' Pa
PFPE, 16350
10.5
3.99
Krytox 143AB PFPE ref. oil
9 cSt formulated
8.79
1.87
PE-9-G0041
5 cSt basestock
5.06
1.75
PE-5-L1876
5 cSt basestock
4.84
1.68
PE-5-L1557
5 cSt basestock
4.93
1.65
PE-5-L1818
4.5 cSt ref. oil
4.50
1.31
Herco-A
3 cSt formulated
3.15
1.26
MIL-L-7808J

tact region. In a similar fashion, tests cem be normalized with


the slide-to-roll ratio, which is the ratio of the sliding velocity
(Us) to the rolling (or entraining) velocity (Ue). The slide-toroll ratio is sometimes expressed as S/R. The S/R ratio reflects the tangential strain of asperity interaction within the
contact region. These two dimensionless p a r a m e t e r s describe a simple first order connection between micro-scale
tribology p h e n o m e n a in a lubricated contact and macro engineering parameters of bearing or gear hardware.
The dimensionless parameters, h/cr and S/R can be used in
place of the entraining and sliding velocity parameters (Us
a n d Ue) used in the Performance Maps discussed in the
Multi-dimensional
Oil Characterization (Performance Mapping) section. This substitution creates a more generalized
Performance Map reflecting life-limiting failure modes, as
shown in Fig. 23. The mapping of the surface failure modes
was determined from thousands of tribo-system simulation
tests with typical bearing and gear materials.
When h/cr is larger than three, we can expect minimal surface interaction and long life. Small values of h/cr, along with
low sliding velocities compared to rolling velocities, will result in mild polishing wear or perhaps micro-pitting. High
sliding-to-roll values can introduce severe wear and scuffing
failures, particularly for high-speed operation. These scuffing
failure modes can be sudden events. Low speed applications
can operate at extremely low h/cr without scuffing. Here the
life-limiting failure mode is accumulation of wear over a period of time. While this two-dimensional m a p does not illustrate the role of temperature, the methodology provides an
approach to link lubrication and failure mechanisms to engineering parameters.
Flexible tribo-system testing provides an opportunity to
connect micro-scale tribological mechanisms with macroscale engineering parameters. Micro-scale tribology mechanisms leading to selected surface deterioration modes of
wear, scuffing, or fatigue are invoked by precision control of
normal stress and tangential shear at topographiccd features.
The degree of normal stress and tangential shear at topographical features can be crudely linked to engineering parameters of slide-to-roll ratio S/R (or Us/Ue) and the ratio h/cr,
which gives the relative thickness (h) of the oil film compared
to the surface roughness dimension (cr).
Because Ug/Ue and h/cr can be related to bearing and gear
tribo-contact systems, performance testing can be directly
connected to specific service hardware. Performance tests

(Low speed)

(High speed)

Slide to

Roll Ratio
(S/R)
L ong I rt- - I EHD nim-tomiinB capablll^

987

^ --^^"^

Lub film thickness / surface roughness ratio {hh}


FIG. 23Schematic Performance Map of lubrication attributes and life-limiting
surface failure modes (boundaries are postulated).

988 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


can EJSO be mapped over a range of conditions to locate performance limits and the effectiveness of the tribo-system attributes. From thousands of tribo-system simulation tests,
life-limiting surface failure modes can be mapped as illustrated in Fig. 23. While this two-dimensional map does not illustrate the role of temperature, the methodology provides an
approach to link lubrication and failure mechanisms to engineering parameters.

SIMULATION OF GEAR LUBRICATION


WITH SYSTEMATIC TRIBOLOGY TESTING
The above sections develop the key tribology parameters required to test a lubricated contact as a system with connection to bearing or gear contacts in service. The ability to independently control key parameters, such as entraining
velocity, sliding velocity, and temperature, gives the opportunity to simulate a multitude of lubrication and failure mechanisms. Meaningful bench test modeling for specific performance limits like scuffing, various types of wear, and surface
initiated fatigue can then be accomplished.
This section demonstrates the application of Systematic
Tribology. The application selected is the development of a
simulation test for an historic gear test method used for jet
engine oil qualification. Similar simulation steps can be used
for the simulation of rolling element bearings and other
highly loaded lubricated contacts.
Overview of Gear Testing for Aviation Gas
Turbine Oil Qualification
Since the early days of jet engines, gear tests have been used
to develop and qualify aviation gas turbine engine oils. The
most widely accepted tests for lubricating performance of engine oils are the Ryder Gear Test and lAE Gear Test. Highspeed gear tests eveiluate the ability of candidate oils to prevent gear tooth scuffing. Gear tests have served the industry
for five decades, since the early formulations of synthetic aviation oils. Virtually every jet engine oil in use today has been
subjected to Ryder Gear testing.
The Ryder Gear Test Method, which was developed by
Earle Ryder [4], was derived from a gear test rig when the
need for an oil test was required for gas turbine engines. Because of operating cost, test gear availability and test reliability, gear tests are in limited use. Today, there is only one
operational Ryder Gear Test, which is operated by the U.S.
Navy, Patuxent River, Maryland.
Alternative bench tests have been developed over the last
decade [5]. The development of alternative test methods, particularly the test efforts supported by the U.S. Navy [6-8],
have provided a better understanding of the complexities and
mechanisms associated with oil lubricating attributes. Alternative test methods show that scuffing performance is a function of test paramieters. Test parameters are artificvEilly selected in order to rank oils according to Ryder Gear test data.
Activation of oil chemistry is so closely linked to conditions
of local contact temperature and micro-scale tribological
stress that simple qualification tests have difficulty characterizing oil performance in a meaningful way.
Since the Ryder Gear Test has amassed a large database,
alternate test methods have focused on replicating Ryder

Gear testing with scuffing criteria. While the huge Ryder


Gear database should not be ignored, replication of gear test
results do not provide the critical link to bearing and gear
hardware needs in service. Yet the tribological phenomena
that occur in a gear test have value with respect to potential lubrication and failure mechanisms that may operate in
service.
It is now recognized that if industry is to be properly
served, performance tests for oils must be integrated with
performance tests for materials. Advanced testing, which is
needed for oil qualification, not only requires inclusion of
material considerations, but requires a paradigm shift in the
whole process of technology development of lubricants, materials, and components. While this paradigm shift has not
yet occurred in many industries, some companies are now
endorsing new strategies toward a systems approach [9] for
development and testing. In the meantime, improvements in
test methods are being made using concepts of Systematic
Tribology. Some of these concepts are illustrated in the sections below.

Ryder Gear Test Conditions


The Ryder Gear Test Method defines the maximum load at
which a test gear pair experiences gross surface distress, as
evidenced by excessive gear "scuff." The Ryder gear test head,
which is shown in Fig. 24, hydraulically loads a pair of spur
gears. The test geeir, which has a narrow face, drives a wide
gear with equal number of teeth. Ryder gears have the following specifications:
Pitch diameter:
88.9 mm (3.5 in.)
Pressure angle:
22.5 degrees
Material: AISI 9310

Number of teeth: 28
Surface finish: 0.45-0.63 ;u,m (18-25
fiin.), Ra

Hardness: 63 HRC minimum

The test method uses an oil jet feed which is stabilized at a


bulk oil temperature of 74C (165F). The test gears are operated at 10 000 rpm in a series of 10-min intervals with increasing load prior to each interval.
The test gear is visually inspected after each load interval
to assess the percent scuff. Failure is defined when the 28
teeth on the test gear have an average scuffing area of 22.5%
across the tooth face. In the following sections, Ryder test
gear surfaces are examined to identify the tribological features and the progression of events that occur as the operator
counts the "scuffed" area that eventually reaches the arbitrary criteria of 22.5% of the gear teeth surfaces scuffed. The
detailed tribological features of the Ryder test gears are documented to understand the lubrication and failure mechanisms required for simulation tests and to show how they
may or may not be representative of service hardware. Of
particular interest are: the initiation of scuffing, the propagation of the scuffing front along the tooth face, the thermal response of the gear tooth surface, the stress profile across the
tooth face, and the rolling/sliding velocity profile across the
tooth face.
The U.S. Navy conducted the Ryder gear tests described below. Because of limited availability of "good" Ryder gears,
these tests were run with Allison gears, which have a gener-

CHAPTER 36: BENCH TEST MODELING 989


Maj^eticPidcUp
Coiqiling
to Drive
TUitine
(10,000 rpm)

Load Chamber

Slave Oear (Spur)

Ryder Gear Test (Top View)

FIG. 24Cross section of Ryder Gear machine test head and gear mesh.

990

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

ous tip relief. Tip relief reduces the stress at the tip of the
tooth where the sliding velocity is high. This results in higher
than average load capacity with these geeirs. Because of this,
tests r u n with high load carrying DOD-L-85734 oils, suspended prior to the 22.5% scuffing point. Nevertheless, the
tests are very useful for establishing the onset of scuffing and
the progression of the scuffing phenomena.
Scuff Initiation Features o n Ryder Gears
Figure 25 shows side 'A' of the Ryder tests gears (Allison
T630603R) used to evaluate a DOD-L-85734 oil with Navy
reference n u m b e r PE-5-L1761. This test was suspended at an
80 psi load pressure (8th load stage) which gives a tooth load
of 3696 ppi (pounds per inch). The Allison geeirs with generous tip relief resulted in only 4.21% scuffed area. The n u m b e r
1 tooth of the narrow test gear is shown in the upper photo of
Fig. 25 and its mating tooth on the wide gear is shown in the
lower photo. The Ryder operator counted 5% scuff on the
n u m b e r 1 tooth of the test gear surface. The lighting used on
the tooth face for the photograph in Fig. 25 is similar to what
is used in the Ryder test to illuminate the test gear surface for
inspection with a TV camera. The small dark patches on the
dedendum of the test gear are areas where the grinding fea-

FIG. 26No. 1 tooth pair from Ryder gears in FIG.


2.2 used for microscopic examination. Light scuff
(5%) on dedendum of narrow test gear (a). Polishing
wear footprint on wide gear (b) shows axial movement
with load stage.

(b)

FIG. 25Allison gear set (T630603R) with generous


tip relief; oil PE-5 1761. Run to 80 psi load, avg. scuff
4.21%. No. 1 tooth has 5% scuff. Dark areas on test
gear (a) and wide gear (b) caused by polishing wear.

tures have been polished. The polished areas appear dark because the oblique lighting reflects the light away from the
camera, which is mounted normal to the face of the gear
tooth. These dark areas of polishing wear are also seen by the
Ryder operator on the TV monitor, but they are ignored by
the Ryder operator with regard to its contribution to the
scuffed area.
The wide gear in Fig. 25 shows similar polishing areas, but
they appear at the addendum rather than the dedendum. The
narrow test gear drives the wide gear. As the gear teeth mesh,
the initial contact occurs at the dedendum of the test gear
and the a d d e n d u m of the wide gear. There is much less polishing wear on the opposite ends to the tooth face where the
teeth go out of mesh, at least for this gear set. The polishing
wear footprint on the wide gear clearly shows the axial movement of the wide gear that occurs as the torque is increased
for each load stage. The amount of axial movement seems to
decrease with loading stage. The axial movement of the wide
gear causes the right hand edge of the test gear to run against
fresh material on the wide gear for each load stage. This explains why there is frequently more scuffing on the right side
of the test gear.

CHAPTER 36: BENCH TEST MODELING

(a)
100 nm

991

damage in these areas seem to contribute very little to the total traction across the contact. In the Ryder test, polishing
wear seems to precede scuff initiation. The first few % scuff
that is counted may be nothing more than polishing wear of
the grinding ridges with abrasive scratches in the direction of
the sliding velocity. It seems that the scuff criteria for the Ryder operator is a disruption of the cixial grinding features by
perpendicular smearing of material, even to the relatively minor level of abrasive scratches.
Further evidence of scuff initiation is shown in Figs. 28 and
29, which aire taken from Ryder gears supplied by the U.S.
Navy from tests conducted with the reference fluid Herco-A
and a MIL-PRF-23699 oil (PE-5-L1790), respectively. These
tests were conducted with Pratt & Whitney gears. The two
teeth represent only a minor degree of scuffing compared to
the other teeth on the test gears. In both cases, scuff initiation
occurs at the dedendum of the test gear, where the meshing
teeth initiate contact and where the sliding velocity is maximum. The scuffed Eirea grows in the direction of the pitch
line. The scuffing damage is more advanced on the right side
of the tooth, which, as discussed above, is due to the presence
of fresh material on the wide gear introduced into the contact

100 nm

FIG. 27Photomicrographs of 5% "scuffed" area


on dedendum shows that abrasive scratches are
counted as part of the % area scuffed. Location of
photomicrographs (a) and (b) identified in FIG. 26

Microscopic Examination of Tribological Features


To conduct a microscopic examination of the gear teeth surfaces, the gear teeth were cut off as shown in Fig. 26. These
photographs were taken with shghtly different obhque Hghting, which causes some of the pohshed areas to appear highly
reflective and other polished areas to appear dark as before.
Examination of the test gear reveals that the 5% scuffed area
is located on the bottom right hand side of the tooth face.
Photomicrographs of this area are shown in Fig. 27. The
dominant tribological features are extensive polishing wear,
abrasive scratches, ajid small areas of micro or superficial
scuffing. The length of the abrasive scratches are an indicator that the observed area is at the dedendum, where the sliding velocity is high. The surfaces also show brown and blue
surface films in the most disturbed eireas. In some areas the
blue film appears to have been removed.
From simulation test experience, surfaces that have encountered polishing wear with abrasive scratches, and even
superficial scuffing, do not produce any significant change in
traction. The surface damage is very local and relatively minor. The local frictional perturbations that accompany the

'M'*%|i*i4# fi-P't '. ;>! I *!:'

(b)

100 Jim

FIG. 28Tooth from Pratt & Whitney test gear (a)


having 7% scuff with oil PE-5-L1274. Photomicrograph of scuffed area (b) showing polishing wear and
superficial scuffing confined to the grinding features
only.

992 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK
Herco-A. From the severity of the scuffed area, one would
judge that a notable increase in traction would result as the
tooth contact traverses this area of the tooth face. The increase in traction will accelerate the frictional heating of the
tooth surface.
Propagation of the Scuffing Front
In the above sections we determined that scuff initiation,
where the scuffed area is less than 10%, consists of superficial scuffing associated with the grinding features only. The
Ryder operator will even include narrow abrasive scratches
as part of the scuffed area. Polishing wear, even when quite
extensive, is not included. Scuff initiation, at least in this
case, occurs at the dedendum of the test gear where the sliding velocity is maximum. But the final judgment of load capacity is not made until, on average, 22.5% of the tooth face
surfaces are scuffed. The percent area scuffed counted for
each load stage as the scuffing progresses to, or just beyond,
22.5% is used to extrapolate, or interpolate, the load at which
22.5% is reached. This is accomplished by plotting the log of
the percent scuff versus the load pressure. The progression of
scuffing is frequently, but not always, an extension of the
scuffed area that has initiated at the dedendum, or possibly
the addendum. The scuffed area grows in the direction of the
pitch line, even though the sliding velocity decreases in that
direction. The "scuffing front" is able to move in that direction with increasing load.

(a)

100 ^m

FIG. 29Tooth from Pratt & Whitney test gear (a)


having 10% scuff with oil PE-5-L1790. Photomicrograph of scuffed area (b) which is likely to cause an increase in traction coefficient.

by the axial movement of the wide gear as the load is increased. The photomicrographs in Figs. 28 and 29 show that
polishing wear precedes scuff initiation. In Fig. 28, where 7%
scuff has accumulated with Herco-A, the scuffed area is composed of smeared surface material. Some original grinding
furrows are still present indicating that the smeared materiEd
is quite shallow, involving primarily the grinding features of
the surface. Some of the protruding material in the scuffed
area shows polishing wear, indicating that the scuffing event
is followed by some degree of recovery with continued running. The degree of surface disturbance in the scuffed area
appears to be similar to what we call a "micro-scuff," which
is surface damage confined to the roughness features. From
this, we would judge that the 7% scuff damage on this tooth
has occurred with a less than significant perturbation in
traction.
The Ryder tooth in Fig. 29 has accumulated 10% scuff with
oil PE-5-L1790. The scuffed area appears more severe than
the 7% scuff in Fig. 28. This oil, which includes an anti-wear
additive (TCP), shows more brown and blue surface films in
the unscuffed area than the test run with Herco-A, which has
no anti-wear additive. The scuffed area shows much wider
paths of smeared material than the 7% scuffed material with

The progression of a scuffing front past the 22.5% criteria


is shown in Fig. 30. This gear tooth pair has accumulated
32% scuff with oil DOD-L-85734 (PE-5-L1761). These gear
teeth are the side 'B' of the gear teeth shown in Fig. 25. The
test was terminated at a load pressure of 90 psi with em average scuff of 18.71%. The axial movement of the wide geeir can
easily be seen from the polishing wear footprint. The polishing wear path also shows that contact is not made at the root
and tip of the gear face until about the seventh load stage.
This is consistent with the generous tip relief and relatively
high load capacity with these particular Allison gears.
The tribological features at the scuffing front are shown in
Fig. 31. Colored surface films have formed in both the unscuffed and scuffed areas as shown in Fig. 31. Surface films
are not as apparent in the lower photomicrograph in Fig. 31,
where the scuffing is more advanced. The formation of these
protective surface films is expected to inhibit the propagation
of the scuffing front. We find that the presence of a reaction
film to a thickness that causes a blue interference film gives
very good wear protection. The reaction film forms on the
grinding ridges that encounter the most severe surface interaction and localized temperature. The reaction film seems to
protect the surfaces from polishing wear as well as scuff initiationa feature consistent with simulation testing with this
DOD-L-85734 oil. Colored surface films can also be seen in
the scuffed area, as shown in the upper photomicrograph of
Fig. 31. This implies that the load additive may be functioning in the scuffed region by helping the surface to recover topographically and chemically after a scuff has occurred.
Effect of OU Chemistry on Ryder Scuffing Criteria
The benefit of the load additive in oil PE-5-L1761 can be seen
in the Ryder test data plotted in Fig. 32. Following scuff ini-

CHAPTER 36: BENCH TEST MODELING

'tew

993

face films. Surface films become visible on the unscuffed areas as well as the scuffed areas. It can be postulated that if the
test conditions are not appropriate to invoke the load additive, the ranking of the oils could be quite different. Also, it is
clear that oil ranking may vary if the selected scuff criteria
were different from the arbitrary selection of 22.5%.
Tribological Processes During Scuff Progression
For oils with the same viscosity, the tribological processes
that control the progression of the scuffing front will determine the scuffing load capacity and the relative ranking of
test oils. An understanding of the tribological progression of
events is important with respect to how the oil functions as
well as how a Ryder load capacity test should be simulated.
While scuffing on the narrow test gear is used to determine
load capacity, it is the wide gear that provides more useful information on the progression of events that lead to the scuff
criteria. Figure 33 shows the #15 gear tooth pair that has encountered 33% scuff with DOD-L-85734 oil FE-5-L1705. The
axial movement of the wide gear with load preserves a history
of the surfaces for each load stage. The upper photomicro-

s. 4 # i \ i^,.^^':^,'

"ff'tfit

'ff-i

FIG. 30Tooth pair #1, side 'B' (bacic side of gear


teeth in FIG. 2.2) having 32% scuff, oil PE-5-L1761.
Scuff propagates from dedendum toward pitch line on
test gear (a), and from addendum to pitch line on wide
gear (b).

tiation, which may only be minor abrasive scratches, the progression of the scuff for this oil with the Sier Bath gears is
much less than the reference oil PE-5-L1274 (Herco-A) as
well as the MIL-L-23699 oil, PE-5-L1664. The results are not
plotted in semi-log fashion, as is customary for Ryder data,
so that the real progression of scuffing versus load can be
illustrated.
It is interesting that in the early days of the Ryder test,
Earle Ryder acknowledged that the slope of the data on a
semi-log plot vsiried from test to test. He attributed this to "a
random effect that can never be tamed" [4]. Actually, the
slope has a tribological explanation. The slope is a measure
of the rate of propagation of the scuffing front on the tooth
face from the dedendum or addendum toward the pitch line.
The slope is lower for oils with a load additive because once
a scuff is initiated the additive inhibits its propagation. From
the data in Fig. 32, it seems that the presence of a load additive does not influence the first evidence of a scuff. This could
be due to insufficient surface temperature or asperity interaction to cause the additive to react. Once the scuff progresses beyond 5 or 10%, the tooth temperature increases,
and the additive chemistry is activated to form protective sur-

(a)

I-

100 (un

FIG. 31Photomicrographs of the scuffing front


shown in FIG. 2.7. Colored surface films inhibit propagation of scuffing front (a). Area of more advanced
scuffing (b).

994 MANUAL 3 7: FUELS AND LUBRICANTS

50
45
40

HANDBOOK

Each plot is the average of


two tests - side 'A' and
side 'B' of the same gear
set

DOD-L-85734
PE-5-L1304(A)
PE-5-L1761 (B)
Sler Bath #6
gears

Herco-A
PE-5-L1274
SierBath#3
gears

CQ

u.
u.

3
CO

i
DOD-L-85734
PE-5-L1705
side 'A' only
30

40

50

60

70

100

LOAD OIL PRESSURE, psi


FIG. 32Effect of load stage on Ryder Gear scuffing.

graph in Fig. 34 shows the left edge of the load path during
the first load stage where polishing wear of the grinding
ridges is clearly evident. Calculation of the ratio of elastohydrodynamic (EHD) film thickness to surface roughness (h/cr)
for a surface temperature equal to the inlet oil temperature of
74C (165F) is less than one. If this is correct, some sort of
polishing wear or surface damage is expected. In fact, with
such a small h/a, more surface interaction would be expected
than shown in Fig. 34. This leads one to question the assumption that the tooth surface temperature for the first load
stage is as high as the inlet oil temperature of 74C (165F).
Prior to the start of test, the gear mesh exit, which is located
at the bottom of the gear pair, is heated with the oil supply at
a flow rate of 270 ml/min for a period of 1/2 h. The gears are
not rotated during this heat-up period. The oil supply is the
only source to control gear temperature. The actual gear
tooth temperature will depend on the rate of heat dissipation
through the gear and shaft support system. The inlet oil temperature cam be viewed as an upper bound for the tooth surface temperature. The actual temperature, at least when the
test is initiated, will be less than the inlet oil temperature.
The lower photomicrograph in Figure 34 shows the left
edge of the scuffed area as well as the surface areas adjacent
to the scuff, which have only seen contact at previous load
stages. As one views the photomicrograph from left to right,
the tribological history of the surfaces is revealed. When the
load (and surface temperature) increases, the surfaces en-

counter: (1) polishing wear of the tips of the grinding ridges,


(2) more extensive polishing wear with abrasive scratches, (3)
superficial scuffing, or smearing of the grinding features and
(4) macro-scuffing where the topographical features are completely removed. From simulation testing experience, only the
latter event will cause a significant increase in traction coefficient. In this particular case, the test was terminated because
of excessive smoke 9 min. into an 81 psi load stage. The average scuffed cirea at the end of the test is 53.6%.
These surfaces show very little evidence of colored reaction
films like that with oil PE-5-L1761 in Fig. 31. This is consistent with simulation tests where DOD-L85734 oil PE-5-L1761
more readily forms surface films than DOD-L85734 oil PE-5L1705. Simulation tests show that the latter oil tends to show
more polishing wear which, incidentally, is ignored by the
Ryder operator as a contribution to scuffing.
The scuffed area in Figs. 33 and 34 show all the features of
what we would call a macro-scuff, where there is a complete
loss of surface integrity and a sudden rise in traction coefficient. A surface that has suffered a macro-scuff event is not
likely to recover. Continued running results in severe wear,
high traction coefficient, and high surface temperature.
These features are evident in the #1 tooth pair of the same
gear set, as shown in Fig. 35. This tooth pair has accumulated
98% scuff. Both dedendum and addendum areas of the teeth
are scuffed. The macro-scuff has caused several teeth in the
vicinity of the #1 tooth to become thermally discolored, as

CHAPTER 36: BENCH TEST MODELING

995

From the scuffing data in Fig. 32, it seems that the selected Ryder operating conditions cause typical MIL-L23699 oils and DOD-L-85734 oils to transition into a macroscuff failure mode about the time that the 22.5% scuff
criteria is reached. This is a tentative statement because
most of the gear teeth examined were from Allison gears
with generous tip relief that fail at relatively high loads
where a macro-scuff event is more likely (see scuff data for
Allison gears in Fig. 32).
Since the oils tested have the same base oil viscosity, the
scuffing differentiation between the oils is a result of the way
oil chemistry handles the roughness features on the gear
tooth face. To activate oil chemistry, gear tooth temperature
must be an important factor. Another important factor is the
"tribologiccd" interaction at asperity (or grinding ridge) sites.
Tribologicai interaction involves normal load and tangential
strain at asperity sites. Asperity pressure and tangential
strain (sliding velocity) control the local temperature that activates oil chemistry. Oil chemistry is also influenced by activated iron surfaces, where the rubbing process removes surface films to expose material at a high energy state. What
makes the Ryder Geetr Test work then are two important fea-

FIG. 33No. 15 tooth pair, side 'B' of Allison gears


having 33% scuff with oil PE-5-L1705. Wide gear (b)
used to identify progression of tribologicai events.

shown in Fig. 35. The only unscuffed area is a small band at


the pitch line, where the sliding velocity component is small
and reverses direction. The tooth surface has turned gray, indicating a highly thermally distressed material that may have
undergone significant changes in metallurgical structure.
The high temperature generated at these gear teeth must
have produced the excessive smoke that caused the termination of the test before the end of the 10-minute load stage.
Discussion of Ryder Gear Scuffing Criteria
The above description of the tribologicai progression of
events that lead to the selected scuff criteria of 22.5% scuff
shows that the scuffing phenomenon is very broad in scope.
The scuffed area that is counted ranges from minor abrasive
scratches and superficial scuffing, which are accompanied by
only small perturbations in traction coefficient, to macroscuffing events, which are accompanied by a very rapid rise
in traction coefficient with little chance of surface recovery
with continued running. A single point on the gear surface
near the dedendum may encounter a progression of events
including polishing wear, abrasive scratches, superficial
scuffing (or smearing of the grinding ridges only) and finally
a macro-scuff event.

100fun

FIG. 34Photomicrographs of wide gear from FIG.


2.10. Polishing wear during first load stage (a) progression of polishing wear, abrasive scratches, superficial scuffing and macro scuff (b).

996 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

FIG. 35No. 1 tooth pair, side 'B' of Allison gears


having 98% scuff with oil PE-5-L1705. Scuffing on
both addendum and dedendum for narrow test gear
(a) and wide gear (b).

tures: (1) bulk and asperity temperatures of the contacting


bodies and (2) the degree of asperity interaction.

CONDITIONS FOR RYDER GEAR


TEST SIMULATION
A basic premise for the value of simulation of field hardware
in a test machine is to capture the same lubrication and failure mechanisms that the field hardware experiences. The
gear pair in the Ryder test can be viewed as an example of
field hardware that is worthy of tribological simulation. The
focus of the simulation is to address the important tribological features that control the performance of an oil in a gear
pair.
It is clccir that an oil does not have an inherent "load capacity" property. Its performance can only be judged by the
tribological system in which it must operate. The sections below examine some of the parameters that are relevant to the
simulation of a gear pair, specifically the Ryder test gears.
Estimated Ryder Tooth Temperatures
The shapes (or slopes) of the Ryder scuffing curves in Fig. 32
are influenced by oil chemistry. This is due to the formation

of surface films that can control the initiation and progression of the scuffing front toward the pitch line. Temperature
is a key parameter that controls surface film formation. Surface temperature is also an important parameter for controlling the EHD film thickness. Two temperatures seem to be
important: (1) the tooth surface temperature, which controls
the inlet oil viscosity and possibly the out-of-contact surface
film formation, and (2) the total temperature within the contact (flash temperature plus out-of-contact surface temperature). The total temperature is frequently used as a scuff prediction criteria (flash temperature theory). The flash
temperature is the thermal response to frictional heating
within the contact. It is directly related to the traction coefficient, applied load, and sliding velocity. Flash temperature is
a calculated quantity with quite limited precision because of
heat partitioning and dissipation assumptions that have to be
made. Flash temperature in the Ryder test is difficult to estimate because the traction coefficient is not measured. It is
now possible to improve the calculated flash temperature in
the Ryder test by using the traction coefficients measured in
simulation tests for load capacity. The flash temperature that
is calculated is the global flash temperature associated with a
single heat source represented by the Hertzian contact. Since
we found much of the tribological action to occur at the
grinding ridges, it is likely that local asperity flash temperatures may be a more relevant quantity in the control of surface film formation. In this case, the precision of temperature
prediction depends on surface topography and local traction
coefficients at asperity sitesboth of which are not steady
state phenomenon. With regard to Ryder Gear simulation
tests, it is possible, and desirable, to be able to refine the calculation of the relevant temperatures due to frictional heating. Several temperatures are relevant. They range from the
bulk specimen temperatures to the asperity temperatures
within the contact. For now, we confine our thinking to the
two temperatures identified above.
From a practical viewpoint, with regard to Ryder test simulation, it is more important to focus on the out-of-contact
surface temperature. If the surface temperature is correct,
then the flash temperatures will take care of themselves provided the other contact parameters are appropriately simulated, such as: contact stress, sliding velocity, surface finish,
h/cr, and contact dimensions.
There does not seem to have been a detailed study of the
Ryder tooth surface temperatures. At the start of the first
load stage one can assume that the tooth surface temperature
is similar to the inlet oil temperature of 74''C (165F). Actually, from the above discussion on polishing wear and h/oduring the first load stage, the initial tooth temperature is
likely to be less than the oil supply temperature.
A second data point on the temperature profile for Ryder
Gear simulation can be derived from the "smoke point." The
smoke point is the temperature at which the surface immediately outside the contact area becomes hot enough to vaporize the oil to produce "smoke." In our Ryder Gear simulation tests we found ball temperatures in a few cases to be
sufficiently high to produce smoke. The measured ball temperatures that produce smoke are on the order of 200C
(392F) for typical MIL-L-23699 and DOD-L-85734 oils. The
Ryder tests frequently produce smoke, especially when the
percent scuff goes beyond 22.5%. It is assumed that the tooth

CHAPTER 36: BENCH TEST MODELING


surface temperature increases rapidly when a high friction
macro-scuff occurs. In the absence of a macro-scuff, where
the traction coefficient is not significantly perturbed by polishing wear or even superficial scuffing, the tooth surface
temperature must increase with load, despite the constant oil
supply temperature. The Ryder tests with the Allison gears
having generous tip relief and high load capacity show that
the smoke point can be reached without any significant scuffing. The Ryder test for DOD-L-85734 oil PE-5-L1705 shown
in Fig. 32 reached a load oil pressure of 80 psi with only
0.61% scuff. Ryder "smoke" was observed 8.5 min into the
load stage. This means that somewhere on the tooth surface,
outside the contact, the surface temperature is on the order
of 200C (392F).
From WAM ball and disk temperature measurements in
simulation tests, the relation between temperature and load
is not linear. The temperature may vary with load to a power
less than one. We have selected, as a starting point, a relationship where the temperature varies with load to the power
1/3. This is based on the assumption that the rate of heat input is proportional to the nominal contact pressure. For a
line contact, the pressure varies with the load to the power
1/3. It is assumed that the Ryder tooth temperature will have
a similar relationship. A simulated Ryder tooth surface temperature profile might look something like that in Fig. 36. In
simulation tests for load capacity, the measured bcdl temperature increases more rapidly than the disk temperature because of the different thermal mass of the specimens. This

must also be the case for the narrow and wide gears used in
the Ryder test. A visual comparison of the simulation test
specimens and Ryder specimens is shown in Fig. 37.
The Wedeven Associates, Inc. WAM load capacity tests to
date have not addressed a precise simulation of the Ryder
tooth surface temperatures, which are still unknown quantities. If our assessment of the Ryder tooth temperatures is correct, simulation tests may have ball temperatures higher than
the narrow test gear temperatures and disk temperatures
lower than the wide gear of the Ryder.
Rolling and Sliding Velocities Across
the Tooth Face
The rolling and sliding velocities across the tooth face are directly linked to oil performance because they are key parameters that control lubrication and failure mechanisms. The
rolling (R) and sliding (S) velocities are defined as
R = 1/2 (Ui + U2)
S = (Ui - U2)
where Ui and U2 are the velocities of surfaces 1 and 2.
Note: Rolling velocity, R, is sometimes referred to as the
entraining velocity Ue, and sliding velocity, S, is sometimes
designated as Us.
The rolling, or entraining, velocity generates an EHD pressure in the inlet region that separates the surfaces in the
Hertzian region with an EHD film. The sliding velocity con-

SIMUUTED RYDER TEMPERATURE PROFILE

zao

1'r

180

.0-0-0"

,-o-<^<^^'

.-o-o-O'

0 LtI

10

20

30

40

50

997

-I

60

lU

70

-1

80

90

i_

100

110

120

130

Loadt (lbs)
FIG. 36Simulated surface temperature profile for WAM3 tests based on estimated Ryder tootli surface
temperatures.

998

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK
trols the rate of shear and heat generation within the
Hertzian region. A necessary condition for scuffing is that the
EHD film is sufficiently thin to cause the surfaces to interact
and that the shear and heat generation within the contact region is sufficiently great to cause the breakdown of microEHD and boundary film lubrication mechanisms.
The rolling and sliding velocities across the Ryder tooth
surface can be calculated from the geeir geometry and rotating speed. The calculated rolling and sliding velocities,
shown in Fig. 38, are plotted as a function of roll angle. For
reference, specific points are identified along the tooth face
using the following notations:
LPC
LPSTC
PD
HPSTC
OD

low point of contact


low point single tooth contact
pitch diameter
high point single tooth contact
outside diameter

At the Ryder gear speed of 10 000 rpm, the rolling velocity


across the tooth face is nearly constant at about 17.8 m/s (700
in./s). The sliding velocity is zero at the pitch line. It increases
to a maximum of 13.1 m/s (517 in./s) at the low point of contact (LPC) and the tip of the tooth (OD). A typical Ryder scuff
initiation occurs near the root or tip of the tooth where the
sliding velocity is maximum; but the final judgment of load
capacity is not made until scuffing has propagated to 22.5%
of the tooth face. If the scuff is initiated at the lower point of
contact (LPC) and propagates toward the pitch line, the location at which the scuff reaches 22.5% is almost up to the low
point single tooth contact (LPSTC). This is illustrated on the
FIG. 37WAM and Ryder test specimens.
LPC

24

LPSTC

PD

HPSTC

OD

22 h
20
18
o

16 I14

o
^

8
6
4
2
0
12

14

16

18

20

22

24

26

28

30

32

34

36

Roll Angle, Degrees


FIG. 38Rolling and sliding velocities across the Ryder tooth face expressed in terms of roll
angle.

CHAPTER 36: BENCH TEST MODELING


24

LPC

18

u 16
(0
in

14

12

1
1
1
1 Entraining
1
Valoclty

1
1
1
1

1
1
1
1
1
1
1
1
1
1
1
1

1
1
1
1
1
1
1
1
1
1
1
1
1

o 10

<

8
6
4
2

1
1
1
1
1

>

OD

HPSTC

22
20

PD

LPSTC

999

12

14

\
\.
\
\
\

1
1
1
1
1

1
1
1
1
1
1
1
1
1
1
1
1

1 \^
1
\
1
\
1

18

20

22

24

,^Sliding
/ Valoclty

/ \

1,

16

26

1
1
1
1
1.

28

30

32

34

36

Roll Angle, Degrees

HPSTC

I.PS1fC

Anticipated pragzeBsioa
t o 22,5% scuff.

yvc
FIG. 39Geometric positions across Ryder tooth face Including anticipated progression to 22.5% scuff.

silhouette of a Ryder tooth in Fig. 39. The sliding velocity at


22.5% scuff is about 7.3 m/sec (290 in./s)see Fig. 38.
It is interesting to note that if the scuffing front progresses
past the 22.5% criteria, it transitions into the area on the
tooth face where the load rises very rapidly because there is
now only a single tooth pair that is carrying the load. This
may be one reason why the scuff propagation rate increases
so rapidly beyond the 22.5% criteria, as shown in Fig. 32.
In simulation tests for load capacity, a sliding velocity of
8.78 m/s (346 in./s) is used. This sliding velocity is midway between the maximum sliding velocity at the lower point of
contact and the sliding velocity where hypothetically 22.5%

scuff occurs. One could argue that a more appropriate sliding


velocity would be 7.3 m/s (290 in./s) so that the shear strain
and heat generation within the contact would more precisely
simulate the conditions at the position where the 22.5% scuff
criteria is typically reached.
For Ryder simulation tests a rolling velocity of 5.72 m/s
(225 in/s) is used. This rolling velocity is less than 1/3 of the
Ryder gear mesh rolling velocity. This rolling velocity was selected to generate an EHD film thicknesses (h) on the order
of the combined surface roughness (cr). The selected rolling
velocity allows only minor polishing wear at the first load
stage, but causes a macro-scuff at loads within typical limits

1000

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

of the Ryder contact stresses. A trade-off in rolling velocity is


m a d e to a c c o m m o d a t e differences in surface finish. The
combined surface roughness (a) of the ball and disk specimens used in simulation tests is 0.29 /Am (11.7 /tin). The Ryder gear surfaces have a combined roughness on the order of
0.8 /im (32 /tin).
It is believed that the difference in the absolute values of
surface finish is a sacrifice that should not be made for good
simulation. This is based on the fact that m u c h of the tribological interaction is associated with surface features. If there
is a significant difference in the absolute value of surface
roughness, a duplication of hJa alone is not likely to provide
the appropriate simulation. The size and shape of surface features are important for micro-EHD mechanisms, local asperity temperatures and local deformation or plastic flow associated with run-in and scuff initiation. However, practical
simulation tests require some c o m p r o m i s e . In this case,
rougher surfaces, as found in the Ryder gears, would require
higher surface speeds or larger test specimens to achieve an
EHD film thickness in keeping with the heights surface
roughness features. Satisf3ring these requirements requires a
test machine of impractical size. A compromise on surface
roughness not only brings the test machine size down to reality, but cJso makes the simulation closer to roughness features found on rolling element bearings.

Contact Stress Simulation


During the mid portion of the Ryder gear mesh cycle, the load
is carried by a single tooth. The load is sheired between two
teeth when the geeirs are coming into mesh and when they are
going out of mesh. The high eind low points of the single tooth
contact are identified in Figs. 38 and 39. As noted above, the
typical progression of a scuffing front to the criteria of 22.5%
arrives very close to the low point single tooth contact (LP-

1000

2000

3000

STC). For the most part, one would expect the load on the area
being scuffed to be a portion of the total load that is shared between two pairs of teeth. Only under ideal conditions would we
find equal load sharing between two pairs of meshing teeth.
Because of practical geometric tolerances and dynamic loads,
the contact stresses that actually exist on the tooth face can be
m u c h higher thein that predicted under ideal conditions. For
this reason, the contact stress profile at the low point single
tooth contact (LPSTC) is used as a reference for simulation.
The contact stress profile on the tooth face at the LPSTC is
plotted in Fig. 40 as a function of tooth load in pounds per
inch (ppi). The relationship between the Ryder load oil pressure (psi) and the tooth load (ppi) is approximately ppi = 46
X (psi). The contact stress from the first to the ninth load
stage for the Ryder remges from 0.79 GPa (115 ksi) to 2.07
GPa (300 ksi). The load and stress profiles used in simulation
load capacity tests are similar. Thirty load stages are used
from 17.9 N (4 lbs) to 623 N (140 lbs) in order to provide a
contact stress from 0.73 GPa (106 ksi) to 2.4 GPa (348 ksi).
With a proper selection of sliding velocity, contact stress
protocol and degree of asperity interaction, as represented by
hJcr, the tribological mechanisms experienced in the Ryder
Gear Test Method (or any other gear operation), can be simulated. All that is needed is a test machine to cover these conditions and test specimens that replicate the material qualities of Ryder gears. Simulation tests with these conditions cire
described in the next section to illustrate how a tribology test
machine can simulate a high-speed gear machine.

GEAR TEST SIMULATION FOR


OIL EVALUATION
The above sections described the Ryder Gear Test Method
and identified the key operating peirameters for simulation.

4000

5000

6000

7000

8000

Tooth Load - PPI


FIG. 40Hertzian contact stress (KSI) at low point single tooth contact (LPSTC)
versus Ryder tooth load pounds per inch (PPI).

CHAPTER
The purpose of this section is to show h o w the Ryder Gear
Test Method can be simulated with respect to the lubrication
and failure mechanisms that control scuffing performance.
Simulation tests are different from correlation tests. The aim
of correlation tests is to rank oils like the Ryder Gear Test
Method. Simulation tests invoke lubrication a n d failure
mechanisms with test parameters that can be linked to the
gear test method. The development of a simulation test is
given in detail to illustrate the process of linking tribology
testing with a full-scale component, like a gear pair. This process is foundational to linking oil testing to field service
performance.
B a c k g r o u n d of Load Capacity Simulation Testing
The U.S. Navy has supported efforts [3,7,10] to provide
Ryder-like load capacity data of gas turbine and gearbox oils.
These efforts EJSO expand the scope of oil characterization beyond the perspective of a pass/fail or ranking of oils, with
scuffing performance being the only criteria. To provide continuity between Ryder Gear load capacity data and future oil
characterization methods, a "WAM Economical Load Capacity Screening Test" was developed to rank a wide range of engine and geEirbox oils similar to the Ryder Gear Test Method
[5]. This test method ranks oils with respect to a scuffing failure event. It also characterizes oils with respect to traction
(friction) behavior.
The introduction of high thermal stability (HTS) oils, and
particularly corrosion inhibited (CI) oils, has highlighted the
need for greater testing sensitivity for oils exhibiting lower
than average lubricating performance. Low lubricating performance, as evidenced in the Ryder test, reveals itself in the
form of a superficial form of scuffing ("micro-scuffing").
The test conditions selected highlight the load capacity performance features of oils that are submitted for qualification
under the MIL-PRF-23699 specification. Load capacity tests
are conducted with ball and disk specimens, which are operated u n d e r tribological contact conditions similar to the U.S.
Navy Ryder Gear Test Method. The WAM High Speed Load
Capacity Test Method has been approved by SAE E-34C for
incorporation into AIR4978 "Temporary Method for Assessing the Load Carrying Capacity of Aircraft Propulsion System
Lubricating Oils."
Failure Criteria in T e r m s o f Scuffing
a n d Micro-scuffing
The purpose of this test method is to evaluate oils according
to the Ryder Gear Test Method, with enhanced sensitivity for
lower than average lubricating performance. It is importcint
to recognize that the Ryder Gear performance criteria are
based upon the visucJ observations of "scuffing" damage on
Ryder geeir teeth. Since some scuffing features found on Ryder geEir teeth are superficial, a Ryder-like test method must
also invoke the same t5^e of surface deterioration mechanism. Micro-scuffing is a superficial form of scuffing, which
is confined to the surface topographical features of the gear
teeth. Micro-scuffing is generally associated with surface
damage at low load stages where contact stresses are too low
to cause "macro" scuffing. Scuffing, or "macro-scuffing," is
associated with the complete loss of surface integrity. Scuff-

36: BENCH

TEST MODELING

1001

ing involves gross failure of near-surface material, in addition to surface roughness features. When traction (friction) is
measured, micro-scuffing is generally detected by a rapid decline in traction coefficient. The decline in traction coefficient is associated with the removal of surface roughness features. While this action actually restores some of the EHD
fluid film separation between the surfaces, the rapid removal
of surface features by plastic flow and rapid polishing wear
reflects a failure of the oil to provide adequate surface films
for boundary lubrication. In contrast, macro-scuffing is associated with a sudden increase in traction coefficient resulting from massive adhesion and plastic flow of near surface
material. A sudden and massive scuffing failure requires high
contact stresses in the presence of high sliding velocities.
The observation of traction coefficient during a load capacity test is quite informative. High precision measurements of traction coefficient clearly identify "events" like
scuffing and micro-scuffing, as discussed above. Traction behavior also reflects the continual interactive process between
oil chemistry and the mating material pair within the contact. Subtle chatnges in topographical features due to wesir
are reflected in traction behavior.
Simulation Approach
The load capacity test protocol is conducted with a WAM test
facility shown in Fig. 4 1 . The test machine controls specimen
position, contact load, and motions of a single contact in
space. A computerized r u n file controls load and contact
kinematics between the specimens. Specimen temperatures
are recorded with trailing thermocouples. The high-speed
test protocol uses AISI 9310 bedl and disk specimens with
tight specifications for surface finish and hardness. To capture Ryder-like oil performance features, the following test
specimen specifications ctnd test conditions have evolved.
BaU

Disk

Ball vel.
Disk vel.
Orientation
Entraining vel.
Sliding vel.
Load
Test duration
Failure criteria

Performance

2.0638 cm (13/16 in.) dia., AISI 9310, "hard


grind" surface roughness, Ra = 0.25 /am
(10 fjuin), hardness HRC 62.5-63.5.
10.16 cm (4 in.) dia., AISI 9310, surface finish Ra = 0.15 /xm (6 /tin), hardness, HRC
62-64.
Ub = 7.21 m/s (284 in./s)
Ud = 7.21 m/s (284 in./s)
Non-coUinear velocity vectors (angle between velocity vectors = 75)
5.72 m/s (225 in./s)
8.78 m/s (346 in./s)
Exponential increase from 1.8 kg (4 lbs) to
63.6 kg (140 lbs) in 30 stages
Until scuff, or suspension (30 stages = 30
min)
Scuff defined by loss of surface integrity
and s u d d e n increase in traction. Microscuff defined by rapid decline in traction
coefficient.
Oil performance is judged by load stages
causing micro/macro scuffing event(s) and
traction behavior, which reflects wear of
surface topography.

1002

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

TOP PLATE
A m BEAKING
BALL SPINDLE
BALL
DISC
SmE MOTION

TC INPUT
AC OUTPUT

FIG. 41WAM4 Test Facility.


Temperature

Oil supply

Specimen temperatures controlled by frictional heating. Surface t e m p e r a t u r e s increase with load stage from a m b i e n t to
- 2 0 0 C.
Computer controlled peristaltic p u m p , approximately 1 drop/s. Oil flow rate is selected for adequate lubrication without significant cooling.

The entraining velocity (Ue) and sliding velocity (Us) are defined below:
Ue = l/2(Ub + Ud)
Us = (Ub - Ud)
where

Ub = surface velocity vector of the ball at the contact


point
Ud = surface velocity vector of the disk at the contact point

The entraining velocity (Ue) and sliding velocity (Us) are


key parameters that control the degree of surface separation
and the rate of surface tangential shear that the oil must accommodate. With the parameters selected, the initiation of a
load capacity test is similar to the Ryder Gear Test in that
there is generally little or no evidence of surface damage during the first load stage.

The test parameters recorded include the following:


Ball and disk temperatures
Traction coefficient
Ball and disk surface velocities
Contact load
Time
Option: video recording of running track on disk specimen
The test method utilizes the following features:
1. Slow application of load to avoid surface damage during
test startup
2. Exponential rather than linear increase in load so that a final scuffing event is reached, rather than a transition into
a wear mode without scuffing.
3. Prominent surface finishing features to highlight surface
film formation and wear protection through the use of
traction coefficient behavior.
4. Use of frictional heating to control specimen temperature
and to cover a wide range of temperatures.
5. Continuous specimen contact rather than cyclic contact to
avoid load/unload damage.
6. Small incremental load stages to increase resolution.
7. Non-coUinear velocity vectors to capture Ryder-like sliding
velocities and film thickness-to-surface roughness ratio.
The test protocol parameters focus on creating tribological
conditions that activate the same type of chemical response

CHAPTER 36: BENCH TEST MODELING


as the Ryder gear test. The key parameters controUing these
conditions are: (1) entraining velocity to control EHD film
thickness, (2) sliding velocity, (3) surface topography, and (4)
specimen temperatures (including effects of frictional heating). If the ranking of oils by a scuffing event falls in line with
the Ryder Gear Test, it is assumed that the key tribological
conditions invoked must be similar to the Ryder. The progression of surface features (like abrasive scratches, polishing of grinding ridges, and surface film formation) formed
prior to a scuffing event eJso follows the same sequence generated in the Ryder test.
Test Procedure
Prior to each test series, the ball and disk specimens are
cleaned in an ultrasonic bath with petroleum ether, followed
by acetone. The AISI 9310 "hard grind" ball specimens are
processed through the hard grind stage of a ball manufacturing process. The "hard grind" ball specimens tend to have a
consistent surface finish of Ra = 0.25 - 0.33 (Ra = 1 0 - 13
^in) for good repeatability. The test balls are obtained from a
single manufacturing batch consisting of approximately
8000 balls. The disk specimens are carburized to a hardness
of HRC 62.5-64.5
Following machine calibration, checkout tests are conducted with reference oil, Herco-A. Load capacity tests conducted with Herco-A encounter micro-scuff events. Continued testing beyond a micro-scuff event eventually results in a
scuffing event. A scuffing event is not always clccirly defined
for Herco-A when it is preceded by multiple micro-scuffing
events. Exploratory testing, conducted under Navy PO No.
N00421-98-M-6001, shows that specimen hardness influences both micro-scuff and scuffing events. Disk specimens
are heat treated in large batches to maintain consistency.
The test protocol gives an exponential rise in load with load
stage. The exponential rise is to partially offset a cube root relationship between load and contact stress. The exponential
rise in load also balances an increase in chemical activity
with temperature so a scuffing event can be reached before
the end of the test protocol with typiccd jet engine oils. A minimum of four test determinations is made for each test oil.
Test Description
Figure 42 shows a typical load capacity test plot. A test plot
includes the contact load, ball and disk temperatures, and
traction coefficient. Typical traction coefficients during the
first few load stages are on the order of 0.03. The test conditions during the first few load stages provide nearly full-film
EHD lubrication. Ball and disk temperature increase with
load stage due to frictional heating. As load and temperature
increase, the ratio of EHD film thickness to surface roughness decreases. An increasing traction coefficient reflects a
greater degree of asperity interaction within the contact. The
rate of rise in traction coefficient reflects the ability of the oil
to form surface films at asperity sites for wear resistance. A
decreasing traction coefficient reflects polishing wear. A sudden drop in traction is associated with a rapid loss of surface
topographical features. This is generally preceded by a micro-scuffing event caused by adhesion and plastic flow of surface features. The surface features following a micro-scuffing

1003

event are shown in Fig. 43. Micro-scuffing events, represented by momentary reductions in traction coefficient, reflect marginal oil chemistry to sustain surface films for protection against local adhesion and wear of surface features.
Some oils show multiple micro-scuffing events. Multiple micro-scuffs are characteristic of the non-formulated 4 cSt oil,
Herco-A. A macro-scuffing event is easily detected by a sudden increase in traction coefficient.

Data Processing and Traction Behavior


The way oil chemistry reacts with the surface to control wear
of topographical features is reflected in traction coefficient.
Oil chemistry is activated by contact temperature and exposure of "clean" metal surfaces caused by shear at asperity
sites. For the selected test conditions, oils show characteristic traction behavior. The characteristic traction behavior of
two formulated oils is shown in Figs. 44 and 45.
Since traction behavior reflects oil chemistry for wear resistance, the traction data for each test is processed to obtain
an average traction coefficient for each load stage. The average traction coefficient versus load stage is then plotted to
compare the traction behavior of the test oil with other oils,
as shown in Fig. 46. The vertical arrows on the test plots identify the average load stage at which micro-scuffing or scuffing events occur.
Figure 46 includes the traction behavior for Herco-A,
which is the reference oil used for Ryder Gear testing. The
test oils show different traction and scuffing behavior compared to Herco-A. During the first few load stages, the high
traction of Herco-A may be associated with two factors: (1)
lower base oil viscosity (4.5 cSt at 100C) and EHD films thinner than the 5 cSt test oils, and (2) the formation of wear protective, and perhaps high friction, oxides. Once the oxides
and organo-metallic films are removed from the surface by
wear with Herco-A, there is little boundary lubricating chemistry available to allow continued running without local adhesion and plastic flow of asperities. Load capacity tests with
Herco-A show multiple micro-scuff and scuffing events
between load stages 8 and 14. The traction and scuffing behavior of Herco-A is used as a reference for low lubricating
ability.
Figure 46 also includes the traction behavior of a test conducted with polished surfaces. To quantify the effect of surface finish on the measured traction during a load capacity
test, experiments were conducted with smooth surfaces to establish a baseline traction behavior where the effect of surface topographical features are minimized. This was accomplished with a standard MIL-PRF-23699 oil and the use of
smooth M50 balls cind a polished M50 disk. The results show
that with smooth surfaces the traction coefficient is very low
(0.02). The traction coefficient under ambient conditions
with low sliding velocity was found to be about 0.057. The
low traction coefficient of 0.02 under the conditions for a
load capacity test is due to the frictioncil heating of the oil
film caused by the high sliding velocity used to simulate the
Ryder Gear Test Method.
The data in Fig. 46 show that with smooth surfaces the
traction is nearly constant for the entire loading profile. Actually, under typical EHD conditions the traction coefficient
increases with load and decreases with temperature. These

1004 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

(Oo) sjn^BjedLuai '(sqi) peoi


o

C D ' s l - C N J O C O C D ' ^ C N O O O O O
C M C s l C g C M T - T - T - T - T - O O C O - ^ C S I

0
00

"^
0

in

CO

"^

'is

0
0

10

T
*i

i
?s

ID

1^

djX
3

Q
CD.

CO

""

CJ

<a
m

II

5.^i,

(0
g

0
0
CM
0
10
0

^ /

/*^^
(0
a

B
<D

0
0

(0

C5>

(D

10
1^

1-

c
3
Q:

ix'

3.

CO II

OH
o"

3 : <-

tl

^13

c
CO
CO
Cvl

li.

a:

JO

ir> 00

( 0 o .. <

o a.
Q

CM

<X5
O

CO
O
O

O
CD

juapiyaoQ uogoBJi

CM

CD

CD

CM
O
CD
I

5
!

.K%

a:1

h- J CD Q

d>

0
0
CO

CD CO

0
0
CO

in
-^

1
r^

'

CHAPTER 36: BENCH TEST MODELING


220
Test: NA1292
Lube: PE-5-L-1836
Ball: HG1455-9a, 9310, Ra=10 (Jin.
Disc: 9-14a, 9310, Ra=6 (Jin.
Entraining Velocity: 225 in/sec.
Sliding Velocity: 346 in/sec.
Ambient Temperature
Velocity Vector Angle (Z): 75

0.14

0.12

0.10
c
0)
o

200
180

\- 160
Ball

100x

Disc

lOOx

140

0.08

120

0.06

100

c
o

fs

o
S^

Traction Coefficient

0.04

80

Ball Temperature

: W^l^^^^M**w*H^^^

60

0.02

Vertical Load

0.02
400
500
600
Run T i m e (seconds)

E
h(0
D

CD
O

h 20
0

I
300

CD
3
0
Q.

40

Disc Temperature
0.00

O
O

900

800

700

FIG. 43Test terminated after tenth load stage to show micro-scuffing features.

220
Test: NA1333,NA1334,NA1335,NA1336
Lube: PE-5-L2053
Ball: 9310, Ra=10 |jin
Disc: 9-49b, 9310, Ra=6 pin.
Entraining Velocity: 225 in/sec.
Sliding Velocity: 346 in/sec.
Temperature: Ambient
Velocity Vector Angle (Z): 75

0.14

0.12

0.10

: 200
7 180
- 160

c
o

c
o
o

140

120

a>
a.

0.08
Ball Temperature

<D
O

NA1336
J

0.06
Traction Coefficient

h 100
80

0.04

60
0.02 Disc Temperature

40

0.00 -

20

Vertical Load
-0.02

'

I '

150

'

I '

300

'

I '

450

'

I '

600

'

I '

750

'

I '

900

'

I '

'

I '

'

I '

'

I '

'

I '

1050 1200 1350 1500 1650

Run Time (seconds)


FIG. 44Traction characteristics of formulated oil (four test determinations).

0
1800

in
o
CO
o

1005

O
o

a.

JD

I
-11

1 1 1 1 1 1 1 1 1 I

1 1 I 1 1 1 1 1 1 I 1 1 1 1 I 1 1 1 1 I I

r-

150 300 450 600 750 900 1050 1200 1350 1500 1650
1800

Run Time (secxjnds)


FIG. 45Traction characteristics of formulated oil.

0.10

Run File: naa.run


Ball: 9310, Ra = .25 ^m (10 ^in)
Disc: 9310, Ra = .15 urn (6 pin)
Entraining Velocity: 5.72 m/s (225 in/sec)
Sliding Velocity: 8.78 m/s (346 in/sec)
Velocity Vector Angle (Z): 75
HTS oil with

0.09

c
'o

0.08

high wear and


scuff resistance
(4 tests)

i t 0.07
0
o 0.06
O
c
_o 0.05
"o
CO
CD
O)
CD
CD

>
<

-Scuff or micro-scuff
failure criteria
(avg. for all tests)

0.04
STD oil
high scuff
resistance
(3 of 4 tests
suspended)

0.03
0.02
^Cl oil with unacceptable wear
resistance and scuff resistance
(2 tests)

0.01
0.00

-11r~'''I

'

''I''f1''1'1'

'

I''I''I

Lower bound reference,


polished surfaces, STD oil

Ir1'IIIII!'Ir1I'['IIIrr-

10 12 14 16 18 20 22 24 26 28 30 32

Load Stage
FIG. 46Scuffing and traction behavior of MIL-PRF-23699 type oils.

CHAPTER 36: BENCH TEST MODELING


two effects seem to offset each other to result in an almost
constant traction coefficient with load.
During the loading sequence, the EHD film thickness decreases due to the rise in specimen temperature with frictional heating. The EHD film thickness also decreases with
stress. If one assumes a combined surface roughness of 0.012
(tm (0.5 fJLin), the calculated h/o-at the first load stage is 15. At
the last load stage of 569 N (128 lbs) h/cr is 1.4. Examination
of the specimens after the test, shown in Fig. 47, reveals only
a few minor surface scratches and the initiation of a light
brown and blue surface film.
An additional load capacity test with smooth surfaces was
conducted with a DOD-L-85734 oil. The results for a DOD-L85734 oil are essentially the same as a MIL-PRF-23699 oil.
The traction characteristics under full film EHD conditions
are very similsir among oils so long as their basestocks do not
differ in molecular structure. Since a DOD-L-85734 oil has
a load-carrying additive package, it appears that the loadcarrying additive in the DOD-L85734 oil does not make any
significant difference in the traction behavior under full film
EHD conditions.
There is also evidence that the formation of a surface film
does not significantly affect the measured traction. As shown
in Fig. 47, a visible brown and blue reaction film has formed
on the ball. The blue surface film that has formed on the ball
is thicker than the slightly brown film on the disk. The thicker
film on the ball may be due to the higher temperature (200C)

(b) disk track

100 |m

FIG. 47Smooth M50 specimens from test


NA912: a) ball track with brown and blue surface
films; b) minor scratches and light brown film
on disc surface.

1007

that the ball has reached compared to the disk (130C). The
reaction films are likely to have formed near the end of the
load capacity test where the specimen temperatures are high
and h/cr is small. Even with the presence of a significcint reaction film on the ball, there seems to be no perturbation in
traction coefficient.
The above tests show that the variation in traction behavior during a load capacity test does not seem to be affected by
bulk oil shear of an EHD film or perhaps even the presence
of boundary films. The traction behavior appears to be a
function of how oil chemistry affects the topographical features on the surfaces by way of polishing wear and scuffing.
The traction data with smooth surfaces and a standard
(STD) MIL-PRF-23699 oil provide a lower bound traction,
which is essentially unaffected by surface roughness features
and boundary lubrication. The lower bound traction is attributed to the shear behavior (traction) of the bulk oil. Interactions between surface topographical features do not
occur until late in the test protocol, when the contact temperatures are high and the EHD film is thin.
Performance Criteria
From all the load capacity traction data collected over time,
there seems to be a strong connection between traction coefficient and wear of surface finishing features. While fluid
temperature within the contact zilso affects traction, the rise
and fall of traction coefficient still reflects the process associated with how the physical and chemical properties of the
oil handle the intimate collisions of surface features within
the contact during a load capacity test. Since the WAM High
Speed Load Capacity Test protocol covers a large temperature range, we assume that the lubricating ability of the oil,
as reflected in traction, is also being tested over a large temperature range. If this is the case, the lubricating ability of the
test oils can be differentiated with respect to preservation of
surface topographical features, at least over a limited range
of temperature or contact severity. Additional investigations
are required to determine if subtle differences in traction
truly reflect variations in chemical activity for wear resistance in service hardware.
It can be postulated that the desired lubricating attributes
of oils are good wear resistance and scuffing resistance (and
surface fatigue resistance) "across-the-board" of temperature
and stress. The WAM High Speed Load Capacity Test protocol may be covering at least some of the desired performance
features and test conditions. For gear or other surfaces with
prominent roughness features one could argue that some
mild polishing wear is desired to topographically condition
the surfaces for low asperity stress to prevent early micro-pitting. If this were the case, good performance would be
associated with relatively low traction coefficient and high
scuffing load stages. Further tribology studies of service
hardware are needed to clarify the desired oil attributes and
testing conditions. Until this is done, we have to live with a
tenuous link between qualification testing and field performance. For now, the traction behavior and scuffing resistance of an oil, as determined with the present set of Ryderlike test conditions, can serve as an initial step toward full
characterization and clarification of performance criteria. In
the meantime, the collection of a database for test oils, along

1008

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

with field experience, should provide greater confidence in


the test method and a near-term tool for evaluation of oil formulations.

attributes include various types of wear (adhesive, abrasive,


chemical) and various types of surface initiated fatigue.
While a comprehensive picture of oil performance attributes is unfinished business, there is a way to utilize the
current database with field experience in order to establish a
preliminary connection between load capacity testing and
field service performance. Thanks to the unfortunate experience in military hardware with two oils, there is now a link
between WAM High Speed Load Capacity testing and known
deficiencies in the field. The average traction data for these
two test oils are plotted in Fig. 48. Oil DLA 522 resulted in
high iron content in engine oil systems with specific engine
hardware (T53). Oil TEL-0004 caused wear problems in the
Canadian Air Force.
Both oils in Fig. 48 show a rapid rise in traction coefficient reflecting resistance to polishing wear of surface finish
protrusions. At early load stages, these oils consistently transition into micro-scuffing and a rapid wear mode. Micro-scufHng
is a superficial form of scuffing where loss of surface film lubrication causes local adhesion and wear of surface features.
The plastic flow and rapid wear of surface roughness features
is amply revealed by a sudden reduction in traction coefficient.
The test data from these two oils are presented in Fig. 49,
along with other U.S. Navy oils that are qualified products.
The other oils are currently used in the field with no appar-

Preliminary Link to Service Performance


The WAM High Speed Load Capacity Test Method provides
traction and scuffing evaluation of jet engine oils with no specific connection to service performance. The test method is
designed to simulate Ryder Gear ranking of selected reference
oils supplied by the U.S. Navy. Qualification of MIL-PRF23699 oils with the Ryder Gesir Test Method requires oils to
pass a gear scuffing load a few percentage points above the
reference oil, Herco-A. The WAM High Speed Load Capacity
Test Method provides greater differentiation between formulated oils and Herco-A than the Ryder Gear. Although there is
greater differentiation, the alternative test method(s) for the
Ryder Gear are no more useful with respect to judging the
level of performance required for reliable performance in service. While the gear mesh contact conditions of the Ryder
Gear do come close to engineering parameters of some aeropropulsion systems, extrapolation of results to other thermal,
kinematic and material systems is not reliable. It is further
recognized that scuffing performance is only one of several
other tribological attributes that control performance. Other

0.10
0.09
C
0

0.08

Run File: naa.run


Ball: 9310, Ra = .25 jam (10 pin)
Disc: 9310, Ra = .15 ^m (6 |jin)
Entraining Velocity: 5.72 m/s (225 in/sec)
Sliding Velocity: 8.78 m/s (346 in/sec)
Velocity Vector Angle (Z): 75

Failure criteria
(avg. of all tests)

iE 0.07
0

o
O 0.06
c
o 0.05
o

\ ,
\ I

CO

0.04

MIL-L-7808 Grade 4
TEL-0004
(4 tests)
(NA1368-NA1371)

0
CO

MIL-PRF-23699 CI
DLA 522
(4 tests)

0.03
0.02 -\

- Q-'

O'

e~^-o

Lower bound reference,


polished surfaces, S I D oil

0.01
0.00

-T1111IIIr-'I11111r

-ii11r-i1111I1r-

10 12 14 16 18 20 22 24 26 28 30 32

Load stage
FIG. 48Traction and scuffing failure characteristics of oils with known performance difficulties is specific military aircraft
hardware.

CHAPTER 36: BENCH TEST MODELING

0.10

0.09

Run File: naa.run


Ball: 9310, Ra = .25 ^m (10 |jin)
Disc: 9310, Ra = .15 urn (6 |Jin)
Entraining Velocity: 5.72 m/s (225 in/sec)
Sliding Velocity: 8.78 m/s (346 in/sec)
Velocity Vector Angle (Z): 75

I Lower bound
{
I failure stage
|
I based on militaryi
hardware
I
experience
I
IProposed OEM
(scuffing limit

1009

I \ Scuffing or micro-scuffing
failure criteria
(avg, of all tests)
Oils DLA 522 and TEL-0004
have known deficiencies in
field service.
Oils DLA 562 and PE-5-L1859
failed the Ryder Gear test.

PE-5-L1874
4 tests)

DOD
DLA 511
(4 tests)
4 of 4 tests
suspended
DOD
PE-5-L2040
5> (4 tests)

3 of 4 tests
suspended

10 12 14 16 18 20 22 24 26 28 30 32

Load stage
FIG. 49^Traction and scuffing characteristics of qualified oils and oils with known performance deficiencies.

ent difficulty. The family of oils in Fig. 49 includes STD, HTS,


CI and DOD oils. The oils with known deficiencies are a CI oil
(DLA 522) and a MIL-PRF-7808 Grade 4 oil (TEL0004). The
traction data show that both of these oils encounter microscuffing at low load stages between 11 and 14. Early microscuffing and a rapid wear mode are consistent with high iron
content detected in service with the engine oil DLA 522.
Figure 49 also shows two CI oils (DLA 562 and PE-5L1859) that have failed the Ryder Gear test. These oils are
plotted in bold. While these oils are not directly connected
with field experience, the low Ryder performance is sufficient
to raise questions about their qualification. The scuffing load
stages for these oils are relatively low (15 and 18). A unique
feature of these oils is that the traction behavior is substantially different from the previous two oils with known deficiencies in the field. The traction coefficient rises rapidly
with load stage indicating a resistance to polishing action of
roughness features. Apparently, the surface film chemistry
that provides early resistance to polishing wear is not sufficient to prevent early scuffing. The connection between high
traction and low scuffing performance is not understood.
Anti-wear performance (high traction) does not translate into
good scuffing performance, at least for these oils. Oil PE-5L1874, which also has high traction, shows good scuffing
performance. The traction behavior of this oil implies good
anti-wear and anti-scuffing attributes.

The oils plotted in gray in Fig. 49 are qualified products


currently being used in service by the U.S. Navy. Many of the
oils, except for the CI oils, are also used in commercial service. The family of oils in Fig. 49 shows significantly different
traction behavior due to varying degrees of polishing wear. It
is not known how variations in polishing wear translate into
service performance. On the other hand, the scuffing performance criteria do have connection with service experience.
The two oils with low scuffing (i.e., micro-scuffing) performance have known deficiencies from service experience. The
two DOD oils, which are suspended at load stage 30 without
a scuffing event, are known to be high performing oils for
power transmissions. Based on somewhat limited field experience, one can establish a lower bound for load capacity
scuffing performance. If military hardware has experienced
difficulty with oils showing scuffing failures at load stages
around 12 and 14, then a lower bound (without margin)
could be established at a load stage 15.
OEM Proposed Criteria
The scuffing and traction performance data in Fig. 49 identifies the lower bound performance based on military hardwEire experience. A qualification limit of load stage 19 has
also been proposed. The proposed scuffing limit is also identified in Fig. 49. With a proposed load stage limit of 19, some

1010 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

of the oils in Fig. 49 would be just short of passing. It is


tempting to say that the difference between the lower bound
at load stage 15 cind the OEM proposed limit at load stage 19
is a performance meirgin. Since performance margin is engine and application specific, any naargin above the lower
bound is generic at best.
The data in Fig. 49 reflect the scuffing or micro-scuffing
performance of engine oils under specific test conditions. Extrapolation of this data to other operating conditions is not
reliable. Since wear and fatigue attributes are not included in
load capacity testing, the oil evaluation results should be considered incomplete. Some additional value to the scuffing results can be obtained by considering the traction behavior
throughout the test. While the linkage between traction behavior and service performance is not clear, traction data and
its connection with polishing wear can at least identify which
oils are in-family or out-of-family.
From preliminary examination of surface conditions of
engine hardware at overhaul shops, we believe that the tribological surface conditions generated during the early
load stages of the test protocol represent many of the features found on bearing and gear hardware under normal
operation. If this is true, the wide variation in traction coefficient during the early load stages indicates that the performance of these oils may be noticeably different in service. Detailed tracking of test engine hardware and field
service hardware with specific oils is a highly recom-

0.10
0.09
0.08

mended activity to sort out the significance of oil performance characteristics. This action is also an essential step
for the development of testing methods, which are truly
linked to service performance.
Applicability of WAM High Speed Load Capacity
Test Method
The WAM High Speed Load Capacity Test Method is a simulation of Ryder Gear Test ranking. The test conditions are
carefully selected to mtike the results correlate with the Ryder Gear Test. While the Ryder Gear Test operating conditions, in terms of rolling/sliding speeds, temperatures and
contact kinematics, are representative of helicopter gearbox
hardware, slight operational changes are likely to cause different rjinking. This is based on WAM load capacity tests conducted over a range of test conditions, which affect EHD film
generation and contact temperature. Load capacity tests over
a range of conditions are recommended. The conditions selected here are specific to Ryder ranking using a set of five
reference oils supplied by the U.S. Navy. In addition, there is
no confirmation that scuffing load capacity performance is in
any way connected with other prominent life-limiting performance criteria, expressed as surface distress (wear and micro-pitting). Additional tests for surface distress, or a complete simulation of specific hardware, are recommended to
supplement scuffing load capacity results.

260

Run File: naa.run


Ball: 9310, Ra=.25|jm(10)Jin)
Disc: 9310, Ra= .15 |jm (6 iim)
Entraining Velocity: 5.72 m/s (225 in/sec)
Sliding Velocity: 8.78 m/s (346 in/sec)
Velocity Vector Angle (Z): 75

Failure criteria
(avg. of all tests)

r 240
7 220
- 200

0.07

180

c
0)

160

PE-5-L2000
(4 tests)

;o 0.06

140

O 0.05
c
o
g 0.04

PE-5-L1823
(3 of 4 tests suspended)

OilB
(4 tests)

0)
CO
<D

100
80
60

0.03
..Q^.-eee--^*~^49-

40

Lower bound reference,


polished surfaces, STD oil

20

0.01
0.00

a.
120 E

0)

0.02

0
6

10

12

14 16 18 20 22
Load Stage
Qualified STD MIL-PRF-23699 Oils

24

26

28

30

FIG. 50Average traction and scuffing stages for qualified Standard (STD) IVIIL-PRF-23699 oils.

32

CHAPTER 36: BENCH TEST MODELING


LOAD CAPACITY D A T A B A S E F O R
Q U A L I F I E D AVIATION G A S T U R B I N E O I L S
Since the initiation of the WAM High Speed Load Capacity
Test Method a large database of jet engine oils has been established. A summary of the qualified oils in this database reflects the general performance of gas turbine oils available today, at least with respect to the current test method. Most of
the commonly used qualified oil products under the specifications MIL-PRF-23699 and DOD-L-85734 are included in
the database. The oil brands, which are coded, are presented
according to oil type, such as standard (STD), high thermal
stability (HTS) and corrosion inhibited (CI).
Standard MIL-PRF-23699 Oils
Five STD qualified oils are presented in Fig. 50. Oil PE-5L1823, which has been evaluated many times during test
method development, consistently shows high scuffing load
capacity. Three of four tests represented in the traction curve
in Fig. 50 were suspended without a scuffing failure.
Oil B, and particularly oil A, show relatively low scuffing
load capacity compared to the other STD oils. The traction
behavior for oil A reflects somewhat different chemical response than the other oils.

0.10
0.09
0.08

1011

High Thermal Stability MIL-PRF-23699 Oils


Figure 51 shows four HTS oils with widely varying traction
behavior. The steep rise in traction coefficient, along with the
high scuffing failure stage, for oil B reflects highly responsive
chemiccd film forming capability that protects surface features from wear and scuffing. The relative low traction coefficient for oil A reflects more polishing or chemical wear. Except for oil B, the scuffing failure stage for HTS oils is
clustered around load stage 20.
Corrosion Inhibited MIL-PRF-23699 Oils
Except for one oil, the CI oils in Fig. 52 fail by a micro-scuffing event. The relatively low scuffing performance of CI oils
is attributed to the competition between anti-wear additive
(TCP) and the corrosion inhibitor. Advanced formulations,
such as oil NAVAIR.00072, have been able to overcome this
problem.
High Load-Carrying DOD-L-85734 Oils
The two DOD-L-85734 oils in Fig. 53 operate through the
test protocol without a scuffing event. The good scuffing
load capacity of these oils is attributed to a load-carrying

260

Run File: naa.run


Ball: 9310, Ra=.25|jm(10Min)
Disc: 9310, Ra= .15 jm (6 pin)
Entraining Velocity: 5.72 m/s (225 in/sec)
Sliding Velocity: 8.78 m/s (346 in/sec)
Velocity Vector Angle (Z): 75

Failure criteria
(avg. of all tests)

I- 240

220
200 O
h 180

0.07 -_
c
PE-5-L1990
(4 tests)

0.06 -_
<u
o
O

c
o

SI

o
CD

0.05 -_

160
OilB
(4 tests)

Oil A
(4 tests)
(PWL14-PWL17)

0.04 ^

140

Q.

120

.0)

100

I
I

80

0.03 z

h 60

0.02 ^

-e&o-

~*G"^"'

40

Lower bound reference,


polished surteces, STD oil

0.01 -

20

0.00

10

12

14 16 18
Load Stage

20

22

24

26

28

30

32

Qualified HTS l\/IIL-PRF-23699 Oils


FIG. 51Average traction and scuffing stages for qualified High Thermal Stability (HTS) MIL-PRF-23699 oils.

1012 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

0.10
Run File: naa.run
Ball: 9310, Ra = .25 urn (10 |jin)
Disc: 9310, Ra = .15 ^im (6 iJin)
Entraining Velocity: 5.72 m/s (225 in/sec)
Sliding Velocity: 8.78 m/s (346 in/sec)
Velocity Vector Angle (Z): 75

0.09

0.08

it 0.07
o

PE-5-L1997
(4 tests)
NAVAIR.00072
(4 tests)

0.06

c
o 0.05
o
03

NI

0.04

PE-5-L2001
tests)

O)

0.03

PE-5-L2002
(4 tests)

0.02
Lower bound reference,
polished surfaces, STD oil

0.01
0.00

10 12 14 16 18 20 22 24 26 28 30 32

Load Stage
Qualified CI MIL-PRF-23699 Oils
FIG. 52Average traction and scuffing stages for qualified Corrosion Inhibited (CI) MIL-PRF-23699 oils.

additive package. While both oils have good scuffing performance, their traction behavior reflects quite different
wear performance. Extensive testing with these oils reveals
significantly more chemical polishing wear with oil A compared to oil DLA 511. The lower traction coefficient with oil
A is consistent with lower oil out temperature, as measured
in Ryder Gear tests. While both oils have extensive field service, the noticeable difference in wear behavior, as reflected
in these tests, has not been investigated in field service
hardware.

Basestocks

S e l e c t e d U . S . Air F o r c e O i l s M I L - P R F - 7 8 0 8
Grade 3 and Grade 4

Master Chart S h o w i n g Lubricating P e r f o r m a n c e


of Qualified Oils

The U.S. Air Forces oils in Fig. 54 show the effect of oil viscosity during the initial load stages where temperatures are
relatively low. The markedly different traction behavior of
the two Grade 4 (4 cSt at 100C) oils indicates the strong role
oil chemistry has on wear and scuffing capacity. The Grade 3
MIL-PRF-7808 has higher load capacity t h a n the Grade 4
oils. Since viscosity differences at elevated temperatures are
insignificant, oil chemistry becomes the dominating factor in
scuffing and wear performance.

Figure 56 shows a master chart of lubricating ability for the


various classes of oils. This chart was created by averaging
the traction and failure load stages of all the oils in a particular class. The Grade 4 MIL-PRF-7808 oils and the CI MILPRF-23699 oils show quite different traction and scuffing
performance than the other oil categories.
It is significant to note t h a t the more recent and "advanced" oils, such as HTS, CI and the U.S. Air Force Grade 4
have lower scuffing capacity t h a n the vintage STD oils. En-

The load Ccurying performemce of six basestocks is shown in


Fig. 55. The higher traction and lower scuffing failure stages
for oils PE-5-L2039 and PE-5-L1836 reflect m u c h different
lubricating ability t h a n the other basestocks. At least for
some oils, basestock performance affects the wear and scuffing capacity of the formulated oil [11]. In other cases, it appears that the additive chemistry can overwhelm the influencing chemistry of the basestock.

0.10
0.09
0.08

260

Run File: naa.mn


Ball: 9310, Ra=.25|jm(10Min)
Disc: 9310, Ra=.15Mm(6|jin)
Entraining Velocity: 5.72 m/s (225 in/sec)
Sliding Velocity: 8.78 m/s (346 in/sec)
Velocity Vector Angle (Z): 75

*^ 0.07
c

Failure criteria
(avg. of all tests)

b 240

220
200

180
160 I

DLA511
(4 tests)
(Na1251-Na1254)

<u

1 0.06
a>
O 0.05
c
g 0.04

0)

140 Q120 ^

100

CD
I-

80
0.03

CD
O

60

0.02

40

Lower bound reference,


polished surfeces, STO oil

20

0.01
0.00

T"

"T

T"

"T

"T

10 12 14 16 18 20 22 24 26 28 30 32
Load Stage
Qualified DOD Oils, DOD-L-85734

FIG. 53Average traction and scuffing stages for qualified DOD-L-85734 oils.

0.10
0.09
0.08
c
0)
0.07
o

Scuffing or
micro-scuffing
failure criteria
(avg. of all tests)

Run File: naa.run


Ball: 9310, Ra = .25 urn (lOnin)
Disc: 9310, Ra = .15 urn (6 jjin)
Entraining Velocity: 5.72 m/s (225 in/sec)
Sliding Velocity: 8.78 m/s (346 in/sec)
Velocity Vector Angle (Z): 75
Grade 4
MIL-PRF-7808
TEL-0001 A
(4 tests)

O 0.06 :
c
o
0.05 o

Grade 3
MiL-PRF-7808L
(4 tests)
. Original
/^ 27502
Prototype
(4 tests)

CO

0.04
O)
CO
1-

0.03

0.02

Grade 4
H/IIL-PRF-7808
TEL-0004
(4 tests)

CD

6.5 cSt

e& o

Lower bound reference,


polished surfaces, STD
MiL-PRF-23699 oil

0.01
0.00

10 12 14 16 18 20 22 24 26 28 30 32

Load Stage
U.S. Air Force Oils
FIG. 54Average traction and scuffing stages for U.S. Air Force oils.

1013

0.10
0.09

0.08

Run File: naa.run


Ball: 9310, Ra = .25 urn (10 |jin)
Disc: 9310, Ra = .15 urn (6 pin)
Entraining Velocity: 5.72 m/s (225 in/sec)
Sliding Velocity: 8.78 m/s (346 in/sec)
Velocity Vector Angle (Z): 75

Failure criteria
(avg. of all tests)

PE-5-L1876
(4 tests)
(NA1306-NA1309)

0.07

PE-5-L1887
(4 tests)
(NA1300-NA1303)

(D
O

O 0.06
c
o
0.05
o

PE-5-L2039
(4 tests)
(NA1293-NA1296)

PE-5-L2056
(6 tests)
(NA1360-NA1385)

CO

0.04
(D
CD

0.03

PE-5-L2057
(4 tests)
(NA1364-NA1367)

PE-5-L1836
(4 tests)
(NA1287-NA1296)

0.02
Lower bound reference,
polished surfaces, STD oil

0.01
0.00 J
0

10 12 14 16 18 20 22 24 26 28 30 32

Load stage
Basestocks
FIG. 55Average traction and scuffing stages for basestocic oils.

0.10
0.09
0.08
c
o
o 0.07
JE
CD
O

Run File: naa.run


Ball: 9310, Ra = .25 urn (10 |jin)
Disc: 9310, Ra = .15 urn (6 jjin)
Entraining Velocity: 5.72 m/s (225 in/sec)
Sliding Velocity: 8.78 m/s (346 in/sec)
Velocity Vector Angle (Z): 75

If' Failure criteria


(avg. of all tests)

CI Oils
MIL-PRF-23699

(4 oils)

Grade 4
MIL-PRF-7808
(2 oils)

HTS Oils
MIL-PRF-23699
(4 oils)

0.06 ]
STD Oils
MIL-PRF-23699
(5 oils)

c
o 0.05
o
CO

0.04 ]

D)
CO

0.03

DOD Oils
DOD-L-85734
(2 oils)
all tests suspended

0.02

Lower bound reference,


polished surfaces, STD oil

0.01 0.00
)

10

12

14

16

18

20

22

24

26

28

Load Stage
Qualified product types and basestocks
FIG. 56IVIaster chart with average traction and scuffing stages for various oii types.

1014

30

32

CHAPTER 36: BENCH TEST MODELING


gine temperature demands for HTS properties and component corrosion problems requiring CI properties are being
satisfied at the expense of lubricating performance. Advanced formulations have been able to avoid this problem
with the aid of simulation test methods.
The above experience d e m o n s t r a t e s h o w a quick turnaround performance test can be used by the oil formulator.
While the qualified CI oils appear to be functioning in service, their development for b o t h corrosion inhibition
attributes and lubricating performance has been difficult.
Surface chemistry for corrosion protection easily interferes
with the activation of surface films for boundary lubrication. Much can be accomplished with the availability of a reliable test.

SUMMARY AND CONCLUSIONS


To reduce the risk in development of major mechanical systems, it is possible to make tribology simulation tests meaningful to service hardware. The secret to linking bench testing with performance prediction is the identification and
quantification of key tribology parameters. These parameters
include entraining velocity, sliding velocity, contact temperature, and degree of asperity contact. Effective simulation of
the controlling lubrication and failure mechanisms requires
highly flexible testing equipment. The independent control of
entraining velocity and sliding velocity provides a means to
development tribology Performance Maps. Performance
Maps, which identify regimes of lubrication and failure
modes, can be linked to lubricated contacts in service. If the
operating parameters of service h a r d w a r e are sufficiently
known, specific tests for scuffing, wear and fatigue can be
conducted.
The process of bench test modeling for material and lubricant development (Systematic Tribology) was illustrated
with the simulation of a gear test (Ryder) used for jet engine
oil qualification. Traction behavior and the documentation
of surfaces reveals the controlling EHD and surface film lubrication mechanisms, as well as competitive failure mechanisms of wear and scuffing. To reduce the risks involved in
the development of major mechanical systems, bench test
modeling, involving multiple tribology attributes, aire needed
to assure success.

1015

Acknowledgments
The author gratefully acknowledges support from the U.S.
Navy, U.S. Air Force, QinetiQ, and Pratt and Whitney, along
with several lubricant suppliers and bearing companies.

REFERENCES
[1] Wedeven, L. D., "Method and Apparatus for Comprehensive
Evaluation of Tribologlcal Materials," United States Patent
Number 5,679,883, Washington DC, 1997.
[2] Wedeven, L. D., Goodell, A. J., Black, W. F., Stimler, M. J., and
Ajayi, O. O., "Assessment of the Friction Characteristics and
Scuffing Performance of DOD-L-85734 Oils," University of Dayton Subcontract No. RI-21494X, U.S. Air Force Contract No.
F33615-92-C-2218, Feb. 11, 1994.
[3] "WAM3 Economical Load Capacity Test," U.S. Naval Research
Laboratory PO No. N00173-95-P-9981, September 11, 1995;
U.S. Navy PO No. N00421-95-M-0037, September 28, 1995.
[4] Ryder, E. A., "The Gear Rig as an Oil Tester," presented at the
ASLE Gear Symposium, Chicago, IL, 26-27 Jan. 1959.
[5] SAB AIR4978: Temporary Methods for Assessing the Load Carrying Capacity of Aircraft Propulsion System Lubricating Oils,
Society of Automotive Engineers, Warrendale, PA, 1997.
[6] Wedeven, L. D. and Hille, E., "Tribology Testing for Load Carrying Capacity of Aircraft Propulsion System Lubricating Oils,"
Bench Testing of Industrial Fluid Lubrication and Wear Properites
Used in Machinery Applications, ASTM STP1404, G. E. Totten, J.
R. Dickey, L. D. Wedeven, and M. Anderson, Eds., ASTM International, West Conshohocken, PA, 2001, pp. 318-332.
[7] Wedeven, L. D., "Tribologlcal Performance Measurement Research," U.S. Navy Contract No. N00140-92-C-BD32, August 2000.
[8] Wedeven, L. D. and D'Orazio A. J., "Technical Approach to Oil
Testing and Field Service Performance," Presented at the SAEE34 Propulsion Lubricants Technical Symposium, 22-23 Sept.
1999, Cardiff, Wales.
[9] Brown, S. C, Chin, H. A., Haluck, D. A., and Wedeven, L. D.,
"Linking Lubricants, Materials, Design and Tribology," Lubrication and Fluid Power, Vol. 2, No. 4, November 2001, pp. 7-21.
[10] "R&D Technique to Determine Scoring Load Capacity of Lubricants," U.S. Navy Contract No. N00140-88-C-1717, August 1988.
[11] Wedeven, L. D. and Hille, E., "Tribology Testing for Load Carrying Capacity of Aircraft Propulsion System Lubricating Oils,"
Bench Testing of Industrial Fluid Lubrication and Wear Properties Used in Machinery Applications, ASTM STP 1404, G. E. Totten, L. D. Wedeven, J. R. Dickey, md M. Anderson, Eds., ASTM
International, West Conshohocken, PA, 2001, pp. 118-332.

MNL37-EB/Jun. 2003

Lubricant Friction and


Wear Testing
Michael Anderson^ and Frederick E. Schmidt^

THIS CHAPTER PROVIDES VARIOUS METHODS TO EVALUATE THE FRIC-

TION AND WEAR PROPERTIES of lubricants and materials. If friction and wear can be controlled then the engineer can select
materials and lubricants with a high degree of confidence.
Many laboratory tests are used to evaluate the interaction of
materials under a broad range of test conditions and controlled environments.
In this chapter, the following topics will be discussed:
History of tribology testing
Basic types of tribology test systems and reasons for their
use
Fundamentals in designing tribology tests
How to select a test device to simulate a field condition
Contact geometry used in bench tests
Standard and commonly used test devices
Designing special application bench tests
Common terminology relating to friction and wear testing

HISTORY OF TRIBOLOGY [1]


From the beginning of time, m a n has tried to overcome friction and wear. The earliest application of friction is its use for
building fires. To early man, fire offered many advantages including safety, light, warmth, and cooked food. Man also
needed weapons to kill animals for food. Primitive techniques were used to sharpen sticks and stones. As simple as
these would appear, this use of friction greatly enhanced
man's quality of life during this primitive period.
Later, as m a n began to cultivate the land to provide food to
supplement his diet of animal meat and fish, agricultural
tools became a necessity. Not only must they be durable, but
they also had to be shaped. Simple manufacturing techniques were employed such as grinding. More durable materials were more difficult to make. As time went on, m a n used
new techniques to help in this manufacturing stage. Simple
engineering methods were employed such as pottery wheels.
At the time the great pyramids and monuments in ancient
Egypt were being built, m a n was beginning to use not only
engineering techniques, such as rolling elements (logs) to reduce friction, but he was also introducing liquid media between the surfaces. Sometimes, these liquids were simply hydrated earth (clays, soaps, or other materials). Nevertheless,
lubrication was becoming a part of life.
' Vice President, Falex Corporation, 1020 Airpark Drive, Sugar
Grove, IL 60554.
^ Manager Services for Industry, Engineering Systems Inc., 3851 Exchange Avenue, Aurora, IL 60504.

Even though m a n was employing simple engineering principles and lubrication for manufacturing, it wasn't until the
late 15th century, when Leonardo DiVinci first deduced laws
governing the motion of a block over a flat surface, that the
science of friction and lubrication was developed. During this
time, primitive testing devices were developed to measure the
force of one object moving against another. Scientist during
this time also realized that measured forces were less when a
material such as pig fat was introduced between sliding or
moving surfaces; hence, the study of lubrication had begun.
During the years that followed, friction, wear, and lubrication studies increased. As the industrial revolution brought
more advanced machines for transportation and power generation, engineering became part of the curriculum at universities. These studies included the fundamentals of friction,
lubrication, and wear. With new extraction techniques for
obtaining crude oil and the ability to refine this oil, lubricants
became m o r e commonplace. As lubricants became more
widely used, technology was needed to eveduate the differences in properties and in various applications. In 1927, the
first commercial tribomoter was introduced to blenders and
manufacturers of finished lubricants. This tester "Pin and
Vee Block test machine" provided suppliers with a method of
measuring anti-wear and extreme pressure properties of the
lubricants they were selling. Subsequently, tribometers such
as the Timken^ tester. Four Ball Wear and Four Ball EP,
Block-on-Ring, and others were introduced to evaluate lubricants and materials under a variety of test conditions. These
machines are described in this chapter.
Further developments in transportation, medicine, and
space exploration have provided impetus for the development of new lubricants and materials. With these technologies has come the development of test machine designs and
test methods to meet the challenges of these new applications. Today, over 225 commercial and independent testing
devices [2] have been developed.

BASIC TYPES OF TRIBOLOGY


TEST SYSTEMS
Laboratory testing of lubricants used in a tribology system
involves different levels of sophistication. A tribological system consists of all relevant test parameters, materials in contact including the lubricant, if present, and any external, environmental conditions [3]. Each level of test sophistication
^ Timken Corporation, Canton, OH.

1017
Copyright'

2003 by A S I M International

www.astm.org

1018 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


has benefits and drawbacks. The three levels of test sophistication Eire as follows [4]:
Laboratory bench test devices (simple geometric contacts)
Component bench test devices (use of actual parts and assemblies in a laboratory test rig)
Field tests (materials and lubricants tested in actual
systems)
The most representative test program is one that uses the
proposed material combination in the actual field situation
[4,5]. Generally, this approach is not practical for several reasons. Costs can be prohibitive; the time to develop a meaningful program may be too long; and the environmental or
ambient conditions are difficult if not impossible to control.
These limitations leave many uncontrollable variables and
possibly, a wide scatter of test data. Even component testing,
which is a laboratory test rig that uses the particular section
of the machine (or field application) that is of interest and in
which the parts are made of the materials under evaluation,
is more cost effective but rarely used as a first approach [3,6].
These instrumented laboratory test devices possess the same
limitations as field tests, except that the ambient conditions
are more controllable. However, laboratory bench tests are
designed to move test pieces with simplified geometry under
a variety of test loads, speeds, and environmental conditions.
Although these simplified devices cannot produce exact operating conditions, they have the potential to produce results
that provide meaningful data for a range of similar applications [5]. The wide use of these test devices, such as the Four
Ball and Timken machines, for determination of extreme
pressure properties reflects the low cost and ease of such
measurements and the belief that test results correlate to
some extent with performance [7]. The use of simple bench
testing reduces the test evaluation to a single, specific tribological condition simulating, as close as possible, the operating conditions for the material and lubricants. Data generated from these tests are compared and those materials and
lubricants are selected that jaeld the best wear life or performance for further testing under more specific test designs.
Repeatability of the obtained test results can be better when
the test is kept as simple as possible. Figure 1 gives a relative
economic comparison versus repeatability for bench tests,
component tests, and field tests.

The ability to use a bench test offers many benefits including:


Simplicity of operation
Lowest testing cost
Accelerated test results
Real time presentation of data to facilitate recognition of
changing conditions.

BENCH TESTS
Test
tvDe

Relative
cost

Repeatabiltv

bench

component

$$$

***

field
FIG. 1Economic comparison of test types.

Accurate and precise indication of wear rates and performance properties given the test parameters under which
the test is conducted
Inexpensive and uniform consumable test pieces
Test pieces from a wide range of materials and conditions
Small volumes of test fluid
Controlled test environments and ambient conditions
Convenience of operation.
Commercial test devices offer significant benefits over
test equipment made in-house. Because commercial test
machines are made in quantity to the same manufacturing
specifications, they can offer better test result comparisons
between the laboratories using them. Commercial testers
are often used when developing standardized test methods
because of the availability of users willing to cooperate in
the development of precision statements. In most cases, the
test parameters are listed in standardized test methods.
However, they may not provide the user all the necessciry information for evaluating his materials. Therefore, standardized test methods can be suitable starting points, but the
user may need to modify the test parameters to achieve
meaningful test results [3,8]. Usually more data can be obtained throughout the test rather than just the final specified endpoint or reported test result. Many data occur during the course of a test, including but not limited to,
changes in lubricating mechanisms, changes in surface areas giving different contact pressures, development of lubricating films and surfaces, and so on. Therefore, the operator must identify these changes and develop test methods
that facilitate obtaining as much pertinent information as is
possible or required.
Commercial test devices provide the following benefits:
Established and known precision
Simplicity of test operation
Many meet ASTM, SAE, ISO and other standard test
methods
Flexible test procedures
Ability to compare results worldwide
Correlation with previously published field results
Support and assistance in operation and method development by the manufacturer

FUNDAMENTALS IN DESIGNING THE


TRIBOLOGY TEST
One of the most important concepts in understanding tribological testing is that it is a system. As a system, each test parameter affects the test result. Changing any test parameter
can effect differences in wear rates and/or frictionaJ properties. One must identify the components and possible conditions that exist during the test as part of the test program and
try to match these as closely as possible with those that are
occurring in the field. The objective of testing is to produce,
on the test rig, similar surface damage to that which occurs
after failure in service [5,6].
The first step is to obtain a complete understanding of the
field condition. The second step is the selection of the most
representative bench test available and the development of
the test procedure to be used. The third step is to conduct
the test. And the fourth and final step is the review of the
test data and development of conclusions [3]. Formulation

CHAPTER
of conclusions at the end of the test requires the user to analyze the data obtained with respect to actual field conditions. The user then draws the appropriate conclusions and
then may develop models for predicting wear of future applications involving similar materials and operating conditions [9].
When designing a laboratory test program, the basic steps
for successful testing are as follows:
Field Problem
1. Identify the location of the wear problem in the test system
2. Determine the failure mechanism
3. Identify the tribological conditions
Motion
Sliding, unidirectional
Sliding, bidirectional or reversing
Rolling
Fretting
Speed
Linear velocity
Rotational velocity
Contact Geometry
Point
Line
Area
Pressure/Load
Normal loads
Surface area of contact
Temperature
Bulk lubricant
Contact temperature
Type of Lubricant
Fluid
Solid
Semi-solid (grease)
Dry film
None
Lubricant Performance Properties
Anti-wear
Extreme pressure
Chemistry
Lubricating Mechanism
Enclosed chamber (flooded sump)
Constant circulation
Spray
Coated
Contacting Materials
External Operating Conditions
Ambient temperature
Atmosphere
Humidity
Vibration
Contaminants
B e n c h Test Selection
1.
2.
3.
4.

Experience
Standardized test methods
Available test equipment
Analytical methods such as Tribological Aspect Number
(TAN) [3]

37: LUBRICANT

FRICTION

AND WEAR

TESTING

1019

Test Parameter Selection


1. Motion
Sliding
Rolling
Combination roll/slide
Unidirectional
Reciprocating
2. Speed
Constant
Ramping
Changing
3. Load
Constant
Ramping (to failure)
Cycling
4. Contact Pressure (Normal Load Over Area of Contact)
Hertzian (constant)
Hertzian (changing)
Area (constant)
5. Materials
Composition
Hardness
Surface finish
Micro-structure
Coatings
Surface treatments
6. Duration
Fixed (compare amount of wear)
Time
Number of cycles
Total linear distance
Time to failure (compare life of test)
Excessive friction/torque
Excessive temperature
Excessive wear rate
Excessive total wear
Test Results
1. Wear
Volume of material lost
Weight loss
Dimension of wear scar
Dimension change of material
2. Friction Force or Torque
3. Coefficient of Friction
Static Coefficient of Friction
Dynamic Coefficient of Friction
Maximum
Minimum
Average
4. Correlation with Field Results
Type of wear mechanism
Type of failure mechanism
Relative a m o u n t of wear
Comparative ranking of different material's performance with field results
Meets specification
5. Lubricant Analysis
Additive depletion
Wear particle count
Viscosity change

1020

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

All controlled laboratory testing yields test data that reflect what is happening in the test device under the selected
test conditions. If the test results do not correlate with the
field results, then either the test device is not representative
of the field application or an incorrect test procedure was
chosen. Therefore, it is of the utmost importance that the
user develops a meaningful test procedure and utilizes the
type of test equipment that best represents the field condition. There Eire many approaches that are used to select the
best test machine and the test parameters. This chapter will
reference and discuss a practical, analytical approach to selecting the best bench test for simulating a particular field
condition.

SELECTING AND DESIGNING THE TEST


The first and most challenging step in conducting a successful laboratory test program is the selection of a test that will
accurately simulate the field condition being investigated. As
mentioned previously, there are three basic types of tests:
bench, component, and field.
Field tests are time consuming, and generally very expensive. They tend to have poor repeatability as they are subject
to many complications in the control of their test parameters
and ambient conditions. For these reasons this chapter is
limiting the discussion to laboratory tests. Materials selected
using laboratory tests must be qualified in a field test before
actually being p u t into service. This is ultimately where the
tested materials must work, but considerable testing can be
done in the laboratory far more economically.
Two types of tests that will be discussed in detail are bench
tests and component tests. A good rule is to attempt the simplest test possible that accurately simulates what occurs in
service. To that end, test devices have been developed that are
used to simulate service conditions in the laboratory [2]. Selection of a laboratory test rig should be based on the ability
to simulate as closely as possible the conditions of the field
application. There are many ways to select a bench test, including experience, standardized test m e t h o d s , a n d p u b lished analjrtical approaches. One such approach is a paper
written by R. Voitik, "Realizing Bench Test Solutions to Field
Tribology Problems by Utilizing Tribological Aspect Numbers," incorporates an analytical approach to selecting the
best bench test [3].
Laboratory tests are used in two basic functions: specification testing (or quality assurance) and research testing. Specification testing uses standardized laboratory bench tests,
such as those based on the Pin and Vee Block, Timken, FourBall Wear, and Four-Ball EP test machines. Considerable
testing has been performed on these test machines in the
evaluation of materials for specific applications. Industrial
laboratories have a sufficiently high degree of confidence
that test results obtained on these test machines under prescribed conditions will correlate with performance in the
field. These tests work well for screening formulations during
lubricant development, for monitoring the quality of lubricant production and for lubricant specification [7]. Other
uses for specification testing include evsiluation of a new formulation to meet an existing application, competitive performance properties evaluation, and approving new batches of

materials. Laboratory tests for specifications are generally


accepted for verifying material performance.
A widely used test procedure is generally submitted to a
standardization organization to develop a test method for determining certain properties. A standardized test method is
selected for use in specifications because the user determined
that standardized test results correlate with field experience.
Qualifying materials to a specification allows further development and improvement of materials for field use, and provides a means for assuring performance quedity. A critical
part of the standardization process is the development of the
precision of the test method. Precision is developed through
the efforts of many testing laboratories participating in a cooperative testing program. In such a program, participants
test selected materials according to a prescribed sequence.
The laboratories obtain back-to-back duplicate test results.
These test results form the basis for determining both repeatability and reproducibility of the test procedure. Precision gives the user of the test method the confidence to determine whether the test results obtained are significant, in
other words, whether the results obtained are merely within
the repeatability of the test method and are not actually different. Additionally, uncertainty could be reduced by a duplicate test or comparison with reference oil [7].
When there is no established or agreed upon test procedure, test method development can be more involved and create significant delays. The test method developer must select
the test device, design the test method, run the tests and then
determine the validity of the test results [3,6]. This process of
developing a laboratory test method to predict field conditions can be difficult due to lack of information about the
field conditions, availability of the certain test equipment and
desired acceleration of the test. The volume of field performance data available for various test materials will determine the level of difficulty in developing base case information for test validation.
Sometimes the designer chooses a component test as being
the preferred approach for materials evaluation. Frequently,
the customer requires data to be produced on the actual components. Or quite possibly, preliminary test data was generated on a simple bench test and subsequent developmental
testing must be performed at the component level. Nevertheless, the fundamental criteria for selecting test conditions
and parameters Eire similar whether one selects a component
test or a bench test.

B e n c h Test
Bench Test, as used in this chapter, is the term used to describe laboratory test devices that are simple in design, yet
complex enough to rank a materiEil's performance for a specific property or to simulate an actual field condition. Unlike
component test stands, bench tests are designed to isolate
specific contacts, motions, loads, and geometric contacts.
These physical characteristics combined with the selected
test parameters give the researcher a means of easily evaluating materials for their effects in field applications or further
component testing. In a properly designed test, operating under a lubrication regime similar to the field condition, the asperities at the point of contact will react the same as they
would in the field condition that the bench test is represent-

CHAPTER
ing. Correlation has been shown by Faville [8] when using the
Pin and Vee Block for evaluating transmission and other
lubricants.
Component Test Design
Component testing, which includes, but is not limited to,
p u m p tests and engine test beds, uses actual parts or components from manufactured equipment. The test stand designer
must carefully select these parts to be within well-defined
manufacturing tolerances for dimensions, surface finish, and
hardness. The component fixturing is typically designed to
hold the components and test them in a manner that represents, as close as possible, the actual field conditions and environment while maintaining the desired test parameters.
The test device design should be sufficiently flexible to permit
a wide range of operating conditions.
To achieve reasonable repeatability and reproducibility
with the test results obtained from the test stand, close control of the test parameters must be maintained. In the actual
field condition it is virtually impossible to control all of the
a m b i e n t conditions, due to the wide fluctuations in surrounding conditions. These test parameters for a component
test stand should be selected to represent conditions that
might occur in actual applications. The selected parameters
must be closely controlled, and the test stand must be designed to provide provisions for monitoring the selected test
parameters. Monitoring the test parameters will provide the
operator with a recorded history indicating whether these parameters were maintained during the test. Often times controlled atmospheres, large sumps for test fluids, special air
and fluid filtration, temperature control, load control, and
other more specific systems must be designed into the test
stand to maintain test parameters or for better simulation of
field conditions. These test devices are designed to simulate a
particular aspect of actual operation and are valuable for the
development of additives and lubricant formulations [10]. In
engine test stands, for example, proper simulation of actual
driving conditions includes cycling of load, speed, and temperatures according to a designed test program. It is essential
to integrate the cyclic characteristics to simulate the actual
driving conditions on the laboratory test rig. The use of a
computer to control test parameters provides more consistent test operation and facilitates data acquisition
Monitoring test variables during the test sequence is critical. The computer, with its capability of acquiring and storing the test data, has offered considerable benefit to the test
operator by recording data throughout the test. This data will
advise the operator that the test has run within the selected
controlled parameters and that the test is operating as desired. It will also alert the operator to a change or failure in
any of the measured properties. Because ambient conditions
can also influence test results, it is important that these conditions such as t e m p e r a t u r e and relative humidity be
recorded. The computer may provide more rapid data collection when one or more of the variables exceed an alarm condition. This rapid data collection will give more detailed information of the test results when unusual conditions are
present. The computer can also activate the control function
of the test stand, eliminating the need for the operator to
make the control adjustments after the test has initiated. The

3 7: LUBRICANT

FRICTION

AND WEAR

TESTING

1021

computer can also cause the test to terminate if a predetermined set-point is exceeded or if a dangerous condition exists. And finally the computer can organize, calculate, and
present the data in tabulated or graphic format for ease of interpretation. This valuable tool is used in most component
test formats and for an increasing number of standard bench
tests stands.
With component tests, the parts chosen for the test fixturing must have some sensitivity to the materials under evaluation [11]. For example, p u m p s that are used to evaluate
wear of hydraulic fluids should be sensitive to formulated fluids that have sufficient anti-wear properties and those that do
not [12]. There should always be some check that the test device and selected test parameters and sequences are robust
enough to discriminate between materials with known poor
field performance and those with acceptable field performance. The user should prove that the component test has a n
acceptable degree of precision, both in repeatability and in
reproducibility. Repeatability is the closeness of the agreement of test data on back-to-back testing on the same test
stand, in the same laboratory, with the same operator, on the
same test materials or fluids, within a short time span. Reproducibility is the agreement of test results using the same
test materials or fluids but on different test stands, with different operators, in different laboratories, and run at different times.
When designing any laboratory test rig, the design should
provide for wide latitude of test parameters. This will assist
in discriminating between materials or components tested
with materials of varying performance properties. When a series of test parameters has been chosen that demonstrates
differences in materials of known field performances, the test
stand should successfully rank materials with unknown field
performance. Extreme care should be exercised when selecting existing manufactured parts for use as testing components, as these parts must have some guarantee of consistency of manufacture and known tolerances for dimensions
and materials. Nevertheless, successful testing has been developed and has given the test engineer considerable information on the performance of materials predicted from the
results of component testing under actual or near field conditions. Properly designed test stands should mimic the field
conditions as closely as possible so that the contacting materials will exhibit properties exactly as if they were in the actual field condition.

TEST PARAMETER SELECTION


The basic test parameters to be considered when developing
any type of test method are discussed in this section.
Temperature
Temperature control can be effected by the use of heating
systems if elevated temperatures are required and/or cooling systems if lower than ambient test temperature is required. The test fixturing can be designed to contain heaters
or cooling tubes to maintain the bulk temperature of the lubricant or the test pieces. It is virtually impossible to measure the temperature at the point of asperity contact, but by

1022

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

locating the temperature sensor in close proximity to the


contact surface, one can get an idea of the contact temperature versus the bulk lubricant temperature. In some test
designs, the atmosphere surrounding the test area must
have a controlled temperature. This is usually achieved
through some type of air circulation if lower than ambient
temperature is required, or through the use of heaters external to the test component but within the enclosed testing
chamber. Large fluid reservoirs can help in maintaining the
stability of test temperature by providing a large volume for
heat absorption. A large reservoir also permits the use of the
fluid in extended duration testing with a minimal amount of
additive depletion.

Load
Load control must be considered when selecting a test. Test
load can be applied by a static or dead weight system, a pneumatic system, hydraulic system, or by fluid pressure. Consideration should be given to including an initial "break-in" or
"wear-in" at a lighter load representing partial EHD [13]. Inclusion of a break-in can form a more uniform surface rather
t h a n testing under machined conditions. This more uniform
surface can add to the consistency of test results.
It can be difficult to select test loads that will be representative of the loads encountered in the field, yet of a magnitude
large enough to challenge the test system without introducing any complex or other type wear mechanisms. Selecting
loads that are excessive could produce results that are not
representative of what is occurring in the actual field condition. If the operator chooses a test load that is low, he may encounter very long test duration before failures occur. Another
way to determine an appropriate test load is to conduct a step
load test and look for an erratic change in the torque or friction force as load is increased [8]. This variability of the
torque indicates a breakdown of the lubricant film, allowing
for metal to metal contact. The load immediately prior to the
load that corresponds to the erratic torque or friction force
can be looked at in terms of the threshold limit of the test system load. The operator can choose a test load at or below the
threshold load that should give a controlled amount of wear
in a reasonable time. Note that too light a test load may not
give enough weeir to discriminate between samples and too
heavy a load may yield too m u c h wear to discriminate. At this
point, it is basically an educated guess as to the best test load.
Several loads in this area may have to be tried in order to select the test load that gives the best discrimination with regards to the other test variable. Ideally, if materials with
known field data are being used to set u p the test procedure,
discrimination should be the focus. If discrimination is obtained, then this test load should be used as the starting point
for the tests, that is to say that at some point in the testing
with other materials, these test parameters may have to be
reevaluated.
Often times the load must be controlled to allow for cycling of test loads to simulate in-field conditions. Cycling
versus static load can better simulate the stresses encountered in the test system and is used to better maintain the
temperature of the test system in long-term endurance or
life tests.

Speed
If possible, select the linear test speed to be the same as the
field condition. This is done in rotational tests by taking
the speed of the field condition and dividing by diameter of
the point of contact or wear track, and by pi, msiking the appropriate conversions for distance units results in the corresponding rpm. Certain applications require very slow or very
fast test speeds. Test speeds have a profound effect on lubrication regime in the test system. The operator should consult
the Stribeck curve for general effects of the change in load or
speed on the coefficient of firiction and lubricating regime.
The Stribeck curve (Fig. 2) shows the relation of coefficient
of friction to the ratio of viscosity, speed, and the inverse of
load, known as the Sommerfeld N u m b e r [14] with respect to
coefficient of friction.
Sommerfeld Number = speed X viscosity/load
This fundamental curve gives an illustration of the effect of
changing viscosity, speed or load on the coefficient of friction
in the various lubrication regimes of boundary, elastohydrodynamic, mixed and hydrodynamic [15].
1. Hydrodynamic lubrication: the surfaces are separated by
the lubricant film resulting in low friction.
2. Mixed lubrication: the load is carried by the lubricant and
the interacting asperities
3. Boundary lubrication: the load is solely carried by the interacting asperities, resulting in high friction.
Although it may be impractical to construct the entire classic Stribeck curve, specific portions of the curve for vEirious
test systems can be determined as illustrated in the curves
listed. It should also be noted that different materials, geometries, and test systems can yield curves that are different
in shape than the classic Stribeck Curve. For example, certain
systems may not have a boundary lubrication region and may
rise directly to a very high friction value indicating severe
metal-to-metal contact.
The curve in Fig. 3 depicts Stribeck curves in the mixed lubrication region as a function of lubricant thickness [15]. By
changing speed and/or load in the Sommerfeld number, the
resulting change in coefficient of friction is determined and
plotted for each lubricant thickness. In the self-lubricated

speed X viscosity/ioad
FIG. 2Theoretical Stribeck Curve. Reprinted with
permission of STLE.

CHAPTER 37: LUBRICANT FRICTION AND WEAR TESTING

tion and the wear of each material combination is compared.


Test duration in this case is either by time or by number of
cycles. If the materials are being severely challenged, tests
can be run to a predetermined failure point such as a friction,
wear, or temperature limit. In this type of test, the result is
the time to failure or in the case of increasing load or speed,
the load or speed at which failure occurred.
When selecting test parameters to represent a field condition, it may not be practical in the laboratory to have failure
occur in the same time frame or duration as it would in the
field, or it may be desired to accumulate data in a relatively
short period of time. This is referred to as an "accelerated
test." Therefore, the test parameters must be selected to enhance the desired wear condition or to produce a desired
wear condition in a shorter period of time. Careful consideration of accelerating test results must be given since it is important not to introduce any wear mechcinisms into the test
system that are not occurring in the field. Verification must
be made at the end of test to insure that the wecir mechcuiism
or failure is the same as that which occurs in the field. Otherwise, it is possible to obtain test results that do not correlate with field results.

. . ... 1.00E-04
1.00E-05
1.00E-06
5.00E-07
3.00E-07

0.14
0.12

2.00E-07

^ ^ v
"~~-
\ ^ ^S-.-.--''>^

1.00E-07
8.00E-08
4.50E-08

*- 0.08

4.20E-08

%\.

-4.00E-08
3.90E-08

0.04

-3.80E-08
370E-08

0.02 -

3.65E-08
3.64E-08

1.E -06 1.E-05 1.E-04 1.E-03 1.E -02

3.63E-08

1023

3.60E-08

FIG. 3Stribeck curves for starved lubricated line


contacts as a function of the applied lubricant layer
thickness in )j.m [15]. Reprinted with permission of
Prof. D. J. Schipper, University of Twente, The Netherlands.

Materials
0.20

Standardized test methods generally specify the materials


cuid conditions of the test pieces consumed in the test. Simulation tests should utilize consumable test pieces from the
same materials and conditions that are present in the system
being modeled. The use of different materials than present on
the system being modeled, can result in poor correlation of
the test with the system [11].

U 0.15
U-

p:

0.10-

o
O

0.05

c
<p
"o

N=0.2 N/cm2

Special Atmospheres

N=0.4 N/cm
N=1.0N/cm

N=0.8 N/cm
I

10"

IQ-

10 -6

10"

10"

10"

Sommerfeld Number
FIG. 4Coefficient of friction as a function of Sommerfeld
number for a plastic on a PMMA disk lubricated by a saline solution [14]. Reprinted with permission from the Society of Plastics Engineers.

condition, as illustrated in Fig. 4, changes in speed with constant loads are plotted against coefficient of friction determined by testing. Similarly, tests could be conducted by varying the load maintaining constant viscosity and speed.
Although it is possible to vary more than one variable in determining Sommerfeld numbers and their relation to coefficient of friction, it is more typically studied by varying just
one of the variable's affect on the coefficient of friction, as
illustrated in the above examples.
Duration
Test duration is also important. Often tests are conducted on
many different samples at the same predetermined test dura-

If special atmospheres are present in the field condition, the


test designer should consider these when designing the laboratory test procedure. Special atmospheres would include
humidity, pressurization, and inert or reactive gases. Gases
can be introduced into any closed test chamber. Inert gases
can be introduced in an attempt to exclude the formation of
oxide layers at the surface. Specialty gases, for example
Freon, can be introduced into the lubricant, often under pressure, to understcuid the effect of these gases when solublized
in the test lubricants. This approach is used for eveduating lubricants for use in compressors or refrigeration systems [16].
Test Fluids
Test design of lubricated systems will always include the
presence of test fluids and their influence on the prevention
of wear or on load carr5dng ability. The method of lubricant
introduction into the contact zone will affect test results. The
most commonly used system is the test fluid bath. This lubricated system uses a contained quantity of test fluid, into
which the moving test pieces are placed and remain as the
test is performed. The contact may be submerged in the test
fluid or a portion of the test piece enters the test fluid and carries the lubricant into the contact zone. Another lubricated
system involves the use of an external reservoir, which intro-

1024

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

duces the test fluid into the contact zone either by continuously changing the fluid in a flooded test chamber or by injecting or depositing a controlled volume of test fluid directly
into the contact zone.
Special Testing
Special testing is the addition of a test variable that is unique
to a situation to better understand certain phenomena. These
would include the introduction of abrasives or solid particles,
the testing of used oils or test fluids with known history, or
the addition of contaminants such as water or some other
solid or liquid. Special testing is generally used in the laboratory test program when the field condition typically contains
these special materials. Anything that can be done to better
simulate field results will improve the simulated laboratory
test results.

TEST SELECTION AND USE OF THE


TRIBOLOGICAL ASPECT NUMBERS
Selecting the best bench test is the first part of a test development program. Prudently selecting the bench test will provide for a more efficient development of test data. There are
many ways used to select the best bench test to evaluate materieJs for a specific application. A common and important
method is to draw on experience. Although experience is critical in developing any test method, it is also a limitation when
evaluating materials and processes for new applications.
Trial and error is another method that can be successful, but
can also be very tedious and frustrating. Others have expanded geometry, speed, load, etc. and studied their effect on
friction and wear [8,11,12]. In 1993, a paper was presented at
the ASTM symposium on Wear Test Selection for Design and
Application, entitled, "Realizing Bench Test Solutions to
Field Tribology Problems by Utilizing Tribological Aspect
Numbers" [3]. This paper and a subsequent review paper by
Anderson [17] describe an analytical approach to selecting
the best bench test for simulating a particular field application. This procedure identifies the tribological condition and
characterizes it in a four-digit number based on motion, geometry, load (pressure), and entry angle of the test fluid. This
approach can be used to select laboratory bench tests for simulating field conditions.
Field applications can involve many different tribological
conditions in the same system. It is the premise of using the
Tribological Aspect Number (TAN) approach to isolate the
tribological condition under consideration and then select
the bench test that has the same TAN.
The TAN is a four digit number that characterizes a tribological condition. The first digit identifies the velocity or
motion characteristic. The second digit identifies the contact
area. The third digit identifies the load or pressure. And
finally, the fourth digit identifies the entry angle of the
lubricant.
The first step in the process of using the TAN system is to
identify the TAN of the field condition. Second, the user selects the bench test that has the same TAN number. Note that
a testing device may have been designed to provide for more
than one TAN and there may be more than one tester that can

yield the same TAN. After identifying the bench tester to be


used, the researcher must select the test parameters under
which the test will be performed. These conditions should be
selected to mimic or reflect the actual field conditions. These
parameters are discussed earlier in this chapter. With the
exact match of the TAN for the field and the tester, and selecting the same test parameters, the proposed test program
is identified as a simulation. A simulation is a set of conditions that exactly represents the field condition. It is under
this condition that the contact asperities should behave in
an identical manner as those contact asperities in the field
condition.
First DigitSpeed
The contact velocity or motion characteristic is subdivided
into four types. Unidirectional, identified as 1, is a motion
that does not change directions. It is unidirectional and is the
sliding motion encountered in most typical wear testers.
Cyclic motion, identified as 2, is motion that changes direction. It is also known as reciprocating motion and is more
specific to select applications involving this type of motion.
Roll/Slip, identified as 3, is motion that includes partial or
complete rolling. Complete rolling occurs in ball or roller
bearings; partial rolling, or those conditions that only have a
percentage of rolling, is typical of gear simulations. Finally,
fretting, identified as 4, is given its own, unique condition.
Second DigitContact Area
The contact area describes the geometry of the areas in which
the moving pieces contact each other. The descriptions simply and accurately describe the type of geometric contacts
that are present in the system. The open nature of the TAN 7
and 8 is unique in that one of the contact surfaces is being
contacted in a previously untouched area. The fixed refers to
non-changing contact geometry; the variable refers to changing contact geometry.
Third DigitContact Pressure or
Loading Characteristic
Unidirectional, third digit of 1, identifies a condition of constant load or increasing load. High frequency, third digit of 2,
is a quickly changing test load. Cyclic Loading, third digit of
3, refers to a condition of cycling the test load.
Fourth DigitEntry Angle
The entry angle identifies the geometric angle of the leading
edge of the tribological contact. It indicates the facility at
which the lubricant can enter the contact zone. An angle of
0-0, fourth digit of 1, describes a contiguous contact. That
is to say, there is no provision for the lubricant to enter the
contact zone. This TAN is typical of thrust washer or seal applications. Because no lubricant can enter into the contact
zone, these applications would do well using solid bonded lubricants, self-lubricating plastics, or high wear resistant ceramics. An angle of 90 to 75, TAN of 2, is a very steep angle
and would typically allow very little lubricant into the contact
zone acting like a plow. As one moves from a fourth digit of

CHAPTER 3 7: LUBRICANT FRICTION AND WEAR TESTING


2 through Tan of 7, the angle of entry gets increasingly
smaller. This smaller entry angle permits entry of the lubricant with ever increasing ease. An entry angle of < 10 - >2,
TAN of 8, has a very small angle of entry. This small angle of
entry allows for the lubricant to come into the contact zone
and reveals the effectiveness of the ability of a journal bearing, with its small entry angle, to easily carry the lubricant
into the contact zone. And finally, >2->0, fourth digit of 9,
illustrates the very, very small entry angle as is t5T3ical of
rolling elements.
Once the TAN for a field condition has been identified,
matching the bench test's TAN to the field condition's TAN
can easily affect selecting the bench test. However, this is not
always possible. Many times there is no exact match available
to the researcher. This occurs because of the complexity on
one or more of the TAN digits or in the fact that the best test
device just is not available to the researcher. In such cases,
the researcher should select a bench test with a TAN as close
as possible to the field condition. He may then have to make
some test procedural compromises to permit as close a representation of the selected laboratory tester with the field application. This condition represents a ranking rather than a
simulation. A ranking test basically will provide performance
test data for a particular property based on the value obtained from running the test.
Additional considerations when testing in the laboratory
are to select the material for the consumable test pieces to be
representative of the field condition material. This includes
selecting not only the type of material, but the condition of
the material such as hardness, case depth, surface finish,
coatings, surface treatments, and microstructure. In the laboratory environment, if one were to simulate the test parameter conditions exactly as in the field, the test would take
about the same time to fail in the laboratory as in the field.
This just is not feasible; therefore, it is always desirable to acquire the data under accelerated conditions. Care should be
taken not to introduce any complex or catastrophic wear
mechanisms that are not present in the field and may adversely affect representative test results.
This chapter has discussed some of the techniques available for selecting bench tests, choosing test parameters, acquiring test data and evaluating the results with respect to the
test procedure. The following sections will contain some of
the more common test devices available and their respective
standardized test methods.

The basic design of the Pin and Vee Block consists of two
opposing Vee blocks loaded against a rotating journal pin
(Fig. 6). It conducts tests in four-line contact, unless optional
C-Blocks are used. C-Blocks give a conformal area contact.
The test is run with the pins and blocks submerged in the test
lubricant (D 2670, D 3233) (Fig. 7), with the test pieces coated
with a bonded film lubricant (D 2625), or with the lubricant
coating the test pieces (D 5620). Load is applied via a ratchet
wheel and eccentric pawl. Each turn of the motor will advance the ratchet wheel one tooth when the pawl is engaged.
Tests can be run at constant load (D 2670, D 2625 procedure
A) or at increasing load until failure (D 3233, D 2625 procedure B). In the increasing load test, failure is indicated by a
break in either the shear pin or test pin or in the inability of

FIG. 5Pin and Vee Block Tester (Falex Lubricant


Tester).

FIG. 6Pin and


Vee Block test
pieces.

COMMON TYPES OF B E N C H
TEST DEVICES
Pin and Vee Block
This Pin and Vee Block (Fig. 5) is the most widely used commercialized wear tester for evaluating lubricants [18] Also
known as the Falex'* Lubricant Tester, the Pin and Vee Block
test machine has been successfully used for evaluating lubricating and wear preventing properties of lubricants, both
fluid and solid, for over 75 yccirs. This tester is used for evaluating metalworking fluids, automotive and industrial lubricants, and bonded solid film lubricants [8].
'' Falex Corporation, Sugar Grove, IL

1025

FIG. 7Pin and Vee Block test piece configuration.

1026

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

FIG. 8Falex Test Pieces [8]. A: Unused (new); B: After ASTM D 2670 wear test;
C: After ASTM D 3233 EP test, torque failure; D: After ASTM D 3233 EP test, weld
failure.
the test system to maintain test load. Careful monitoring of
the torque with respect to the test load can yield valuable information as to the lubricating properties of the test fluid as
it interacts with the selected test piece materials [8,19]
Changes in the slope of the torque curve can reveal changes
in the lubricating regime of the test system. Careful examination of the torque, load, and wear values gives information
on the anti-wear and extreme pressure properties of the tribology system.
Tests can be r u n at constant load for evaluating anti-wear
properties and also u n d e r increasing load conditions to evaluate lubricating effects at different load conditions. Although
the ASTM test m e t h o d s for evaluating extreme pressure
properties of lubricants directs the user to increase load u p to
the point where either the test or shear pin breaks, the information obtained during the entire test can provide important
data as to the performance of the lubricating properties. An
important p h e n o m e n o n described by Faville [8] and later
elaborated by Helmetag [19] is the occurrence of a sudden increase in the torque, also referred to as the torque "pop-up."
Anti-weld evaluations can be made only in the load range immediately following this initial seizure. Products lacking
anti-weld properties tear out metal, resulting in weld type
seizure (Fig. 8D), while some products develop high torque,
which result in twisting off the shear pin without any occurrence of scoring (Fig. 8C). The latter failures cire referred to
as torque seizures [20].
The ASTM test methods that relate to the Pin and Vee
Block test machine and their typical test results (Fig. 8) Eire:
ASTM D 2625, Endurance (Wear) Life and Load-Carrying
Capacity of Solid Film Lubricants (Falex Pin and Vee
Method)
ASTM D 2670, Measuring Wear Properties of Fluid Lubricants (Falex Pin and Vee Block Method)
ASTM D 3233, Measurement of Extreme Pressure Properties of Fluid Lubricants (Falex Pin a n d Vee Block
Methods)
ASTM D 5620, Evaluating Thin Film Fluid Lubricants in a
Drain and Dry Mode Using a Pin and V-Block Test Machine
Pin on Disk
Pin-on-Disk test is the simplest and most c o m m o n wear test
device [21]. It consists of a rotating disk upon which is loaded
a pin or ball (Figs. 9 and 10) In the simplest versions, the ball
rotates on the Scune wear scar. Other mechanisms can be incorporated such that the pin or ball comes in contact with a n
untouched portion of the rotating disk. This results in a spiral type of wear track. Pin-on-disk testing is used most widely

FIG. 9Pin-on-Disk.

FIG. 10Pin on disk test configuration.

for determining wear rates and endurance life of coatings


and bonded film lubricants, but can be used with liquid lubricants for determining wear rates and coefficients of friction (G 99). As wear progresses, material can be removed
from the pin or ball or from the disk or transferred from one
piece to the other. Therefore, as with any wear test, both
pieces should be examined for wear or material transfer. The
pin or ball can be eveJuated by measuring the diameter of the
wear scar and observing any material transfer. The wear scar
on the disk can best be characterized by a profilometric trace
across the surface to determine depth juid width of the wear
scar or by another surface characterization method (Chapter
35). Pin on Disk tests will give relative wear rates only, as few
actual field components match a pin-on-disk configuration.
The test methods that relate to the Pin on Disk test machine are:
ASTM G 99, Wear Testing with a Pin-on-Disk Apparatus
ASTM G 132, Pin Abrasion Testing
Four Ball
Four Ball tests include the Four Ball Wear Test, the Four Ball
Extreme Pressure (EP), Rolling Four Ball, and Ball on Three
Disks. Both the Four Ball Wear and the Four Ball EP test machine have three lower balls that are either held stationary
(Fig. 11) or allowed to roll in a race. The upper ball is held in

CHAPTER 3 7: LUBRICANT FRICTION AND WEAR TESTING


a chuck and rotated. The tests in which the three balls are
held stationary are the most common of the Four Ball tests.
It provides for pure sliding wear in initial three-point contact.
After initial motion begins, the point contact develops into a
load bearing, area contact. At the end of the test run, the
width of the wear scar on each ball is measured using a microscope designed for this purpose (Fig. 12). Measurements
are taken, once with the striations of wear and again at 90
(Figs. 13 and 14). The six scar diameter measurements are averaged for the reported wear scar diameter. The main advantage of testing with balls is that they are very consistent in
shape and properties and that if they Eire available, they are
very cost effective. The main disadvantage is that if they are
not available, they can be very expensive to manufacture and
perhaps impossible to manufacture depending on the shape
of the bulk material. For instance, if the materiEd is available
only in sheet stock, a ball cannot be made. In this case an
adapter called the Ball-Three-Disks can be used to effect sim-

1027

FIG. 14Ball scar measurement.

FIG. 11Four Ball.

FIG. 15Four Ball Wear test machine.

ilar geometrical contact. It allows geometry similar to the


Standard Four-Ball configuration while permitting the testing of additional materials. This test has found application
for testing for Einti-wear properties of diesel fuels containing
lubricity additives [22,23,24].
FIG. 12Typical scar measurement system (microscope).

FIG. 13Typical wear scars.

Four Ball Wear


In the Four Ball Wear tests (D 2266, D 4172), the upper ball
is allowed to rotate under load for an extended, predetermined period of time, tj^pically 60 min. The wesir scar average is reported Eind compared against a specification or other
wear scars obtained by testing comparative fluids under the
same conditions. The Four Ball Wecir test machine (Fig. 15)
has a very precise loading system Eind because of this, has a
limited range of test loads. Coefficient of friction is often a
desired result of the test. ASTM D 5183, using the Four Ball

1028 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Wear test machine, was standardized because the friction


trace in standard wear tests (D 2266, D 4172) can be erratic
under normal operating conditions, making it difficult to determine a reportable value. This alternate test provides for a
break-in run using a mineral oil to intentionally create a consistent load bearing area contact prior to the introduction of
the test lubricant. The minereJ oil is drained from the ball
cup; the balls aire cleaned without their removal from the ball
cup; and the test is run in a series of 10 kg increment loads
for 10 min each to determine the coefficient of friction at
each load tested. Incipient seizure, which is the localized fusion of metal between the rubbing surfaces of the test pieces,
can also be observed. Incipient seizure indicates that the film
is breaking down and allowing metal-to-metal contact. One
can report the coefficient of friction at any desired test load.
This test will generally give a steady, coefficient of friction
value that will be easy to determine.
The standardized test methods that use the Four-Ball "Wear
test machine are as follows:
ASTM D 2266: Wear Preventive Characteristics of Lubricating Greases (Four Ball Method)
ASTM D 4172: Wear Preventive Characteristics of Lubricating Fluids (Four Ball Method)
ASTM D 5183: Determination of Coefficient of Friction of
Lubricants Using the Four-Ball Wear Test Machine

APPLIED LOAD, kgf


ABEcompensation line.
BPoint or last nonseizure load.
ECRegion of incipient seizure.
CDRegion or immediate neizure.
DWeld point.

FIG. 16Schematic plot of scar diameter


versus applied load.

Four Ball EP
In the Four Ball EP test (D 2596, D 2783), the upper ball is allowed to rotate under load for 10 s, after which the resultant
wear scars are measured and averaged. In this test, a series of
test runs is performed at logarithmically increasing loads up
to the weld point. The weld point is the load at which the lubricant film breaks down and the temperature at the point of
contact is so high that it melts the metal, causing the test balls
to weld together, indicating that the extreme pressure level of
the lubricant has been exceeded. When the lubricant is performing as designed, the wear scars will be very smzdl, only
slightly larger than the corresponding theoretical Hertzian
scar diameters for the given materials, load, and radii of the
test balls. The Hertzian scar diameter is the average diameter
of an indentation caused by the deformation of the balls under static load (prior to test). The line that parallels the
Hertzian line is referred to as the compensation line. When
the lubricating film breaks down, metal-to-metal contact occurs and mild to severe incipient seizure occurs. This seizure
is evidenced by the disproportionate increase in the average
scar diameter. When incipient seizure is present, the test ball
scar diameter is no longer on the compensation line. The
highest test load that yields a scar diameter within 5% of the
compensation line value for the corresponding load is the last
non-seizure load. The ASTM D 2596 and D 2783 test methods
provide an index of the relative wear performance with respect to load for the lubricant under evaluation., which is
shown in a graph of the wear scar versus test load (Fig. 16).
This term is called the Load Wear Index (LWI).
Because of the wide range of test loads (8-1000 Kg) 2ind the
severe conditions that occur when a weld point is reached,
the Four Ball EP test machine (Fig. 17) is designed to be very
robust in construction. ASTM D 2266, D 4172, and D 5183
warn against using the Four Ball EP test machine for running

FIG. 17Four Ball EP test machine.

wear tests, as it lacks the necessary precision. When running


wear tests, the Four Ball Wear Test Machine should be used.
The Four Ball EP test machine is also used for testing
rolling elements (Fig. 18). This is because of the high test
loads that are available. These tests are referred to as contact
fatigue tests and are used to predict the life of a lubricant
when used in ball or roller bearings. A vibration detection device is required to identify the onset of surface fatigue. Another test of interest is a lubricant shear test. Also known as
the KRL test (CEC L-45-T-93), this test uses a tapered roller
bearing under high test load to shear polymer containing lubricants. The viscosity is measured before and after shearing
to determine viscosity loss. Results of this test have correlated well with the shear losses experienced with multiviscosity gear oils used in manual transmissions.

CHAPTER

37: LUBRICANT

FRICTION

AND WEAR

TESTING

1029

The standardized test methods that use the Four Ball EP


test machine are as follows:
ASTM D 2596, Measurement of Extreme Pressure Properties of Lubricating Greases (Four Ball Method)
ASTM D 2783, Measurement of Extreme Pressure Properties of Lubricating Fluids (Four Ball Method)

Block on Ring
The Block-on-Ring test machine (Fig. 19) is more of a research tool. It is primarily used to determine wear rates of
materials and to rank materials in pure sliding motion. The
tester is designed to accommodate different test fixtures to
effect point, line, ellipsoid, and area contact. The standard
block-on-ring test uses a rectangular block on a rotating ring
and starts as Hertzian line contact. As motion begins, a load
carrying bearing surface forms, allowing the formation of
anti-wear and/or EP films to form on the surface. The wear
scar width is measured and reported at the end of the test
(Fig. 20). The preferred method of reporting is volume loss;
however, if the same metals are being used, simply reporting
the wear scar diameter for comparative wear is acceptable. A
table in ASTM G 77 gives block scar volumes for measured
wccir scar widths. Oscillating drive mechanisms can be installed to effect reciprocating (back and forth) motion. This
motion is used in test methods for evaluating greases and
bonded film lubricants. Testing with a ball on ring combination results in initial high Hertzian point contact. After motion begins, the Hertzian point contact area develops into a
load carrying bearing surface. With increasing loads, moni-

FIG. 20Block on ring test piece


configuration. TImken size (left);
Falex size (right).

RING a. BLDCK

BOTATIDN

ROTATION

FIG. 21High pressure (rectangular) block (left); Low pressure (conformal) block (right).

FIG. 18Rolling four ball.

FIG. 19Block-on-ring test chamber.

toring the friction force of lubricants containing EP additives


has shown good correlation with predicting load limits obtained from more sophisticated component tests [11]. Area
tests that simulate journal bearing applications are effected
on this test machine using the conforming or curved test
block (Fig. 21). This configuration is most effective when
testing polymeric or plastic materials. When testing under
area contact, it is advisable to perform an initial break-in to
achieve complete contact between the mating surfaces. If
complete contact is not achieved, limited contact will give
higher t h a n desired pressures on the contacting aireas, resulting in premature failure. Recently, a new adapter has shown
promise in predicting anti-wear properties and coefficient of
friction values of thin film lubricants s u c h as automatic
transmission fluids. The canted cylinder adapter holds a
cylinder against the test ring with initial Hertzicin point contact. An additional benefit is the ease of alignment during
setup. As wear develops, an elliptical wear scar develops. The
resultant wear scar provides for easy measurement eind determination of wear and friction properties.
The standardized test methods that use the Block-on-Ring
test machine sire as follows:
ASTM D 2714, Calibration and Operation of the Falex
Block-on-Ring Friction a n d Wear Testing Machine
ASTM D 2781, Wear Life of Solid Film Lubricants in Oscillating Motion

1030 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

ASTM D 3704, Wear Preventive Properties of Lubrication


Greases Using the (Falex) Block on Ring Test Machine in
Oscillating Motion
ASTM G 77, Ranking Resistance of Materials to Sliding
Wear Using the Block-on-Ring Wear Test
ASTM G 137, Ranking Resistance of Plastic Materials to
Sliding Wear Using a Block-on-Ring Configuration
Timken
The Timken Extreme Pressure Test Machine (Fig. 22) was developed in 1932 to measure load carrying capacity of EP lubricants for use in steel production. It too, is a block-on-ring
type test (Fig. 20, Fig. 23) and is CcJled out in many specifications for oils and greases requiring extreme pressure

properties or high levels of load carrying ability. This tester


is designed to evaluate lubricants for low, medium, and
high levels of extreme pressure for lubricating greases (D
2509) and fluids (D 2782). The test is carried out by running
a series of 10 min duration test runs at increasing test loads
to the point where scoring or seizure is indicated on the wear
scar. This scoring is evident as lines that extend past the edge
of the wear scar or as a scar in which scuffing is evidenced
by jagged irregularities (Fig. 24) The tester is also designed
to provide friction data, but is seldom used for this function [25].
The standardized test methods that use the Timken Extreme Pressure test machine are as follows:
ASTM D 2509, Measurement of Load Carrying Capacity of
Lubricating Grease
ASTM D 2682, Measurement of Extreme Pressure Properties of Lubricating Fluids
Tapping Torque

FIG. 22Timken test machine.

The Tapping Torque test machine (Fig. 25) is designed to perform actual metalworking applications in a laboratory environment. Originally designed to perform thread cutting and
thread forming, the Tapping Torque test machine can perform additional metalworking functions. There are two basic
metalworking applications: metal removal and metal deformation. Metal removal techniques remove material to
achieve the desired final shape, while metal deformation
techniques reshape or form the existing material into the desired shape. Under metal removal, there are thread cutting
(tapping), drilling, and reaming. Under metal deformation,
there are thread forming (tapping), roll forming, drawing,
and rolling mill simulation.
The tool rotates and descends at a rate determined by the
rotational speed and pitch of the lead screw of the tapping
head. The test machine measures the torque as the tool descends and enters the material to be machined (Fig. 26). The
piece to be machined will have various forms depending on
the test selected. It is most important to observe the tight tolerances required for the consumable test pieces. Even slight
variances can have an affect on the precision of the test results.
The ASTM standardized test method that uses the Tapping
Torque test machine is as follows:
ASTM D 5619, Comparing Metal Removal Fluids Using the
Tapping Torque Test Machine
Multi-Specimen/Multi-Purpose
(Thrust Washer Tester)

FIG. 23Timl<en
ring and block configuration.

The Multi-Specimen test machine (Fig. 27) is designed to be


a versatile tribology test apparatus. It consists of two opposed, vertical test shafts. One rotates; the other is stationary.
It is called Multi-Specimen because of the use of different
adapters that can be placed between the opposing vertical
shafts. These adapters affect many different tribological configurations. The Multi-Specimen can measure friction and
wear under point, line, and area contacts, in pure sliding,
pure rolling or combination roll/slide motion in unidirectioneJ or oscillation. Because a lubricant is another parameter for the tribological system, virtually any of the adapters

CHAPTER 3 7: LUBRICANT FRICTION AND WEAR TESTING

T>pic4l OK
No Storing

1031

Improper Sclup

Scoring (failure)
FIG. 24Typical Timken test wear scars.

Pin-on-Disk (G 99), (Figs. 9,10)


Oscillating Roll Slide for evaluating greases used in constant velocity joints of front wheel drive automobiles (Fig.
29) [26]
Stick/Slip for determining static coefficients of friction of
way lubricants
Gear Cam Contact and Hypoid Gear with combination
rolling and sliding motion for evaluating wear and friction
of lubricants used in gear applications (Fig. 30) [27]
Ball Bearing tests for evaluating a lubricant's effect on
wear in a ball bearing assembly
Sliding Bottle test for evaluating lubricants used on conveyors in beverage bottle filling machines
Sheet Metal Forming for evaluating the friction obtained
during the forming of a flat piece of sheet stock into a
grooved surface
Linear Reciprocation
PILOT PLUG
SEALS WITI
O'RINC

FIG. 25Tapping Torque - exploded view of test area.

can accept a lubricant to determine its effect on friction and


wear of the selected tribological system.
Some of the adapters that are most specific to the evaluation of lubricants are as follows:
Vane on Disk test for evaluating friction and wear of hydraulic fluids under cycling stressed pressures (Fig. 28)
Thrust Washer test for area contact wear of plastic and ceramic materials (D 3702)

Linear reciprocation test machines are popular because they


add the element of reciprocation or back and forth motion.
This type of motion has proven effective in studying the friction, wear, and lubricating films occurring in applications
such as a piston ring on a cylinder wall [28-30]. High-speed
linear reciprocation has also shown good correlation in testing greases used in constant velocity joints of front wheel
drive automobiles.
Linear reciprocation can be achieved in point, line, or area
contacts. Load is applied vertically. The speed is controlled
by the rate of reciprocation, stroke length and test machine
design and is not constant, but rather a sinusoidal wave
shape, due to the start/stop reversal of the reciprocation function. The rate of reciprocation is measured in Hertz, or cycles
per second. Therefore, the user must specify the rate of re-

1032 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

T I M E (RCJTATION)

FIG. 2BTapping Torque trace of tap entering test piece (insets show position of tap in specimen
blank).

FIG. 29Oscillating roll/slide.


GEAR/CAM CONTACT

R0TAT1C3N

FIG. 27Multi-Specimen type tester.

TORQUE

FIG. 28Vaneon-disk.

LOAD

FIG. 30Gear cam contact.

CHAPTER 37: LUBRICANT FRICTION AND WEAR TESTING


ciprocation (Hertz), stroke length, load, and temperature.
The wear scar on the ball and disk can be evaluated as a measurement for wear. In EP tests, the load at which incipient
seizure occurs is typically identified as the load carrying capacity of the lubricant with this test apparatus. The ball on
flat reciprocating test is used for evaluating the lubricity of
diesel fuels (D 6079) [31-33].
Depending on the design of the test machine, longer stroke
lengths may compromise the rate of reciprocation. The user
should verify desired requirements with the capabilities of
the test equipment. The commercially available linear reciprocating test machines are the Flint and Partners TE77, High
Frequency Friction Machine [34] (Figs. 31 and 32) and the
SRV5 [35] (Figs. 33 and 34). The TE77 test machine also
provides for contact resistance measurements for evaluating
lubricating surface films in elastohydrodynamic and boundary lubrication conditions.
The ASTM standardized test methods that use linear reciprocating test machines are as follows:
ASTM D 5706, Determining Extreme Pressure Properties
of Lubricating Greases Using a High-Frequency, LinearOscillation (SRV) Test Machine
ASTM D 5707, Measuring Friction and Wear Properties
of Lubricating Grease Using a High-Frequency, LinearOscillation (SRV) Test Machine
ASTM D 6425, Measuring Friction and Wear Properties of
Extreme Pressure (EP) Lubricating Oils Using SRV Test
Machine
ASTM G 133, Linearly Reciprocating Ball-on-Flat Sliding
Wear
' Optimol Insturments, Munich, Germany.

1033

COMMON TYPES OF WIDELY U S E D


COMPONENT TEST DEVICES
FZG Gear
The FZG Gear Test Rig [36], (Fig. 35) is a standard laboratory test machine, designed to test wear and load carrying
capacity of fluid lubricants. The tester uses a matched set of
spur gear (Fig. 36), referred to as Type A test gears, as the
consumable test pieces. These are used for evaluating fluids
for wear (scuffing) [37] and load carrying properties. Alternatively, a gear set of slightly different geometry having
greater surface area is available, referred to as Type C gears.

FIG. 33SRV test machine. Reprinted with permission of Optimol Instruments Priiftechnik GmbH.

tanOtrii t p a c R w m

m<\

Rntrr hMr*i(5 gurtx w r v p n anlfvtf |Wf n nr i n .

t-^^i^ -^Bjfijl^j
point
FIG. 31High speed linear reciprocating test
rig (TE77). Reprinted with permission from
Phoenix Tribology.

twm

am

FIG. 34Schematic of SRV test pieces. Reprinted with permission of Optimol Instruments Pruftechnilc GmbH.

FIG. 32Schematic of the test area geometries


for TE77. Reprinted with permission from Phoenix
Tribology.

1034

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Type C gears are used for evaluating pitting and micro-pitting tendencies of industrial gear oils [38]. As with most
component tests, this gear tester uses actual parts, in this
case, gear sets.
A constant load test is used for evaluating anti-wear properties of tractor hydraulic oils (D 4998). The test gears are
weighed before and after the test. A load stage test of increasing test loads is used for evaluating industrial gear oils
for their ability to carry a load. After each test load, the gear
teeth are evaluated for signs of scoring (D 5182) (Figs. 37 and

PlBion

LodUng Pin

GMrWiietl

Uver Ann with WelgM Kk

Oriva QitMm

TOKpi* Mtaswing Ciuteh

UMd Clutch

38). Lubrication can be either dip lubrication in which the


test gears are submerged in a known quantity of test oil, or in
jet spray lubrication. Jet spray lubrication uses a nozzle to deliver the test lubricant directly onto the test gears.
The ASTM standardized test methods using the FZG Gear
Test Rig are as follows:
ASTM D 4998, Evaluating Wear Characteristics of Tractor
Hydraulic Fluids
ASTM D 5182, Evaluating the Scuffing Load Capacity of
Oils (FZG Visual Method)

TtmptnMm Stnser

FIG. 36FZG test gears on test rig.


Reprinted with permission from StramaIV1PS IVIaschinenbau GmblH & Co. KG.

FIG. 35Diagram of FZG test rig.

Polishing

Scoring

Scoring and Scuffing


FIG. 37Examples of FZG gear distress.

Scuffing

CHAPTER

37: LUBRICANT

FRICTION

AND WEAR

TESTING

1035

CONCLUSION

3 |

Distress;

Pass

Scoring (15mm)

Scorinq (Smm)

Rating :

See 10.4.2

Scratches & Scoring

Rating

See 10.4.2

In this chapter, a systematic method to evaluate how to select


appropriate bench or laboratory tests has been described using the TAN approach. Test equipment, methods, and their
advantages have been detailed. Using the tools available in
the market today, researchers can develop meaningful tests,
acquire test data easily and rapidly, and then draw appropriate conclusions for improving the life and performance of industrial equipment.
In summary, extensive progress has been made to formalize the procedures, practices, and test methods required to
obtain predictive information on the performance of materials and lubricants. Additional information on the use of test
e q u i p m e n t and the significance of test results can be obtained from the meuiufacturer and can be found in the Significance of Test section in the respective ASTM test methods.

eBj

5 m

ASTM STANDARDS
Friction and Wear Properties
Distress:

Scoring (20mm)
Fail

7 M

Scratches & Scuffing (2mm)


R8tlns

See 10.4.2

No.
D1367

8 |M
D2266

Oistmss:
Rating :

Scoring & Scuffing (Smm)


See 10.4.2

[)istress:

Scuffing (20mm)

Rating :

Fail

FIG. 38Examples of FZG gear distress.

D2271

D2625

Vickers P u m p Stand
The Vickers P u m p Stand is a controversial yet widely used
component bench test. Although u n d e r current scrutiny for
i m p r o v e m e n t of its precision, this test stand evaluates
hydraulic fluids for wear using an actual p u m p . The p u m p
parts are inspected metrologically a n d corrected, cleaned,
weighed, and assembled prior to beginning each test. The test
load is the fluid pressure, which can be either 1000 psi or
2000 psi depending on the test method. In some tests the
loaded pressure exceeds that pressure recommended for normal operation. This pressure is chosen to challenge the test
system in order to screen lubricants. At the end of the test, the
p u m p cartridge pieces are again inspected for damage,
cleaned, and weighed.
This test is undergoing considerable modifications. It is
recommended to review the latest draft prior to beginning
ciny test program using this tester.
The ASTM standardized test methods using the Vickers
P u m p Stand are as follows:
ASTM D 2271, Preliminary Examination of Hydraulic Fluids (Wear Test)
ASTM D 2882, Indicating the W e a r Characteristics of
Petroleum and Non-Petroleum Hydraulic Fluids in a Constant Volume Vane P u m p

D2670

D2714

D2882

D2981

D3336

D3704

Title
Standard Test Method for Lubricating Qualities of
Graphites (general laboratory test)
Standard Test Method for Wear Preventive Characteristics of Lubricating Grease (Four Ball
Method) (general laboratory test for wear of
greases in sliding contact)
Standard Test Method for Preliminziry Examination of Hydraulic Fluids (Wear Test) (general laboratory test for wear of hydraulic fluids under low
pressures in p u m p test)
Standard Test Method for Endurance (Wear) Life
and Load Carrying Capacity of Solid Film
Lubricants (Falex Pin and Vee Method) (genercil
laboratory tests for load carrying and wear
properties of solid lubricants)
Standard Test Method for Measuring Wear Properties of Fluid Lubricants (Fcdex Pin and Vee Block
Method) (general laboratory test for sliding wear)
Standard Test Method for Calibration and Operation of the Falex Block- on-Biing Friction and Wear
Testing Machine (generzJ laboratory test in sliding
motion)
S t a n d a r d Test Method for Indicating the Wear
ChEiracteristics of Petroleum a n d Non-Petroleum
Hydraulic Fluids in a Constant Volume Vane
Pump (general laboratory test, known as the Vickers p u m p stand test)
Standard Test Method for Wear Life of Solid Film
Lubricants in Oscillating Motion
(general laboratory test)
Standard Test Method for Life of Lubricating
Grease in Ball Bearings at Elevated Temperatures
(general laboratory test)
Standard Test Method for Wear Preventive Properties of Lubricating Greases Using the (Falex)
Block-on-Ring Test Machine in Oscillating Motion
(general laboratory test)

1036 MANUAL 3 7: FUELS AND LUBRICANTS


D 4172
D 4173
D 4998
D 5001

D 5183

D 5619
D 5620

D 5707

D 6078

D 6079
D 6425
G 77
G 83
G 99
G 115
G 118
G 133

HANDBOOK

Standard Test Method for Wear Preventive Characteristics of Lubricating Fluid (Four Ball
Method) (general laboratory test)
Standard Practice for Sheet Metal Forming Lubricant Evaluation (general methodology for testing)
Standard Test Method for Evaluating Wear Characteristics of Tractor Hydraulic Fluids (general
laboratory test)
Standard Test Method for Measurement of Lubricity of Aviation Turbine Fuels by the Ball-onCylinder Lubricity Evaluator (BOCLE) (general
laboratory test)
Standard Test Method for Determination of the
Coefficient of Friction of Lubricants Using the
Four-Ball Wear Test Machine (general laboratory
test)
Standard Test Method for Comparing Metal Removal Fluids Using the Tapping Torque Test Machine (general laboratory test)
Standard Test Method for Evaluating Thin Film
Fluid Lubricants in a Drain and Dry Mode Using a
Pin and V-Block Test Machine (general laboratory
test)
Standard Test Method for Measuring Fiction and
Wear Properties of Lubricating Grease Using a
High-Frequency, Linear-Oscillation (SRV) Test
Machine (general laboratory test)
Standard Test Method for Evaluating Lubricity of
Diesel Fuels by the Scuffing Load Ball-on-Cylinder
Lubricity Evaluator (SLBOCLE) (general laboratory test)
Standard Test Method for Evaluating Lubricity of
Diesel Fuels by the High-Frequency Reciprocating
Rig (HFRR) (general laboratory test)
Standard Test Method for Measuring Friction and
Wear Properties of EP Lubricating Oils Using the
SRV Test Machine (general laboratory test)
Standard Test Method for Ranking Resistance of
Materials to Sliding Wear Using Block-on-Ring
Wear Test (general laboratory test)
Standard Test Method for Wear Testing with
a Crossed Cylinder Apparatus (general laboratory test)
Standard Test Method for Wear Testing With a
Pin-on-Disk Apparatus (general laboratory test)
Standard Guide for Measuring and Reporting
Friction Coefficients (guide for methodology)
Standard Guide for Recommended Data Format
for Sliding Wear Test (guide for methodology)
Standard Test Method for Linearly Reciprocating
Ball-on-Flat Sliding Wear (general laboratory test)

Extreme Pressure Properties


D 1947

D 2509

Standard Test Method for Load-Carrying Capacity


of Petroleum Oil and Synthetic Fluid Gear Lubricants (general laboratory test for testing load carrying capacity of oils in sliding and rolling contact)
Standard Test Method for Measurement of Load
Carrying Capacity of Lubricating Grease (Timken
Method) (general laboratory test for extreme pres-

D 2596

D 2782
D 2783
D 3233

D 5182
D 5706

sure using block-on-ring type tester for seizure,


galling and scuffing)
Standard Test Method for Measurement of Extreme-Pressure Properties of Lubricating Grease
(Four Ball Method) (general laboratory test for extreme pressure properties in sliding motion)
Standard Test Method for Measurement of Extreme Pressure Properties of Lubricating Fluids
(Timken Method) (general laboratory test)
Standard Test Method for Measurement of Extreme Pressure Properties of Lubricating Fluids
(Four-Ball Method) (general laboratory test)
Standard Test Method for Measurement of Extreme Pressure Properties of Fluid Lubricants
(Falex Pin and Vee Block Method) (general laboratory test)
Standard Test Method for Evaluating the Scuffing
Load Capacity of Oils (FZG Visual Method) (general laboratory test)
Standard Test Method for Determining Extreme
Pressure Properties of Lubricating Greases Using
a High-Frequency, Linear Oscillation (SRV) Test
Machine (general laboratory test)

OTHER STANDARDS
Friction and Wear Properties
DIN-Deutsches
No.
50280

Institut fur

Normung

Title
Running Test on Radial Plain Bearings; General
Plain Bearings; Testing of the Tribological Behavior of Plain Bearings with Hydrostatic and Mixed
Lubrication in Bearing Testing (General Laboratory Test for Sliding Wear of Bearings)
50281
Friction in Bearings; Definitions; Tjrpes; Conditions; Physical Quantities (definitions)
50320
Wear; Terms; System Analysis of Wear Processes;
Classification of Wear Phenomena
(definitions of wear terms and classifications)
5032l.G Wear Quantities (definitions of various wear
types)
50322
Wear; Wear Testing Categories (definitions of
scales of testing of all tjrpes of wear)
50323
Tribology; Terms (4 parts) (terms and definitions
of wear t5fpes)
50324
Tribology; Testing of Friction and Wear Model
Test for Sliding of Solids (Ball on Disc System)
51350
Testing in the Shell Four-Ball Tester (lubricant
characterization)
Determination of the Wearing Characteristics of
Liquids (Part 3);
Determination of the Wearing Characteristics
for Consistent Lubricants (Part 5);
Determination of Shear Stability of Lubricating
Oils Containing Polymers (Part 6)
51354
Mechanical Testing of Lubricants in the FZG Gear
Rig Test (gear lubricant classification in
sliding/rolling contact)

CHAPTER 37: LUBRICANT FRICTION AND WEAR TESTING

51389

51509

51834

General Working Principles, (Part 1);


Method 1/8.3/90 for Lubricating Oils, (Part 2)
Shear Stability of Polymer Containing Oils
(Parts)
Mechanical Testing of Hydraulic Fluids in the
Vane-Cell P u m p (lubricant characterization of
hydraulic fluids)
General Working Principles (Part 1)
Method A for Anhydrous Hydraulic Fluids
(Part 2)
Method B for Aqueous Not Easily Inflammable
Fluids (Part 3)
Selection of Lubricants for Gears (recommended
use of hydraulic fluids in sliding/rolling contact)
Gear Lubricating Oils (Part 1)
Semi-Fluid Lubricants (Part 2)
Testing of LubricantsTribological Test in Translatory Oscillation Apparatus
General Working Principles (Part 1)
Determination of Friction and Wear Data for
Lubricating Oils (Part 2)
Determination of Tribological Behavior of Materials (Part 3)

ISO-International
7148/1

TR6281

Standards

Organization

Testing of the Friction and Wear Behavior of Bearing Material / Mating Material / Oil Combinations
under Conditions of Boundary Lubrication (bearings, friction and wear tests)
Testing Under Conditions of Hydrodynamic and
Mixed Lubrication in Test Rigs-Guidelines (guidelines for bearings in sliding wear)

JIS - Japanese Agency of International


Technology Standards
Department
K2519

334

166
239

240

326

and

Testing Methods for Load-Carrying Capacity of


Lubricating Oil (note: Japanese Timken Test)
(lubricant testing in sliding or rolling contact)

IP - Institute
281

Science

of

Petroleum-UK

Determination of the Anti-Wear Properties of Hydraulic FluidsVane P u m p Method (lubricant


characterization of hydraulic fluids in a vane pump)
Determination of Load Carrying Capacity of Lubricants-FZG Gear Machine Method (lubricant
characterization of gear oils in sliding and rolling
contact)
Load Carrying Capacity for Oils-IE A Gear Machine (testing of geeir oils in gear test rig)
Extreme Pressure Properties: Friction and Wear
Tests for Lubricants: Four Ball Machine (seizure
and welding characteristics using Four Ball EP)
Standard Method for Measurement of Extreme
Pressure Properties of Lubricating Fluids (Timken
Method) (general laboratory test for extreme pressure properties of oils)
S t a n d a r d Method for Measurement of Extreme
Pressure Properties of Lubricating Grease
(Timken Method) (general laboratory test for extreme pressure properties of greases)

1037

ASTM RELATED STANDARDS


D4175
G40

S t a n d a r d Terminology Relating to Petroleum,


Petroleum Products, and Lubricants (terminology
compilation)
Standard Terminology Relating to Wear and Erosion (terminology compilation)

REFERENCES
[1] Dowson, D., History ofTribology, Professional Engineering Publishing Limited, London, UK, 1998.
[2] Benzing, R., Goldblatt, I., Hopkins, V., Jamison, W., Mecklenburg, K., and Peterson, M., Friction and Wear Devices, STLE,
Park Ridge, IL, 1976.
[3] Voitik, R. M., "Realizing Bench Test Solutions to Field Tribology
Problems," Tribology: Wear Test Selection for Design and Application, ASTM STP 1199, A. W. Ruff, and Raymond G. Bayer,
Eds., ASTM International, West Conshohocken, PA, 1993.
[4] Sture, H. and Staffan, J., "Hints and Guidelines for Tribotesting
and Evaluation," Lubrication Engineering, Vol. 48, No. 5, 1991,
pp. 401-409.
[5] Neale, M. J. and Gee, M., Guide to Wear Problems and Testing for
Industry, y^ ed., Williams Andrew Publishing, Norwich, NY,
2001.
[6] Calabrese, S. J. and Muray, S. F., "Methods of Evaluating Materials for Icebreaker Hull Coatings," Selection and Use of Wear
Tests for Coatings, ASTM STP 769, R. G. Bayer, Ed., ASTM International, West Conshohocken, PA, 1982, pp. 157-173.
[7] Banniak E. A. and Fein R. S., "Precision of Four Ball and
Timken Tests and Their Relation to Service Performance," NLGI
Spokesman, January 1973.
[8] Faville, F. and Faville, W., "Falex Procedures for Evaluating Lubricants," Journal of the American Society of Lubrication Engineers, STLE, Park Ridge, IL, August 1968.
[9] Bayer R. G., Shalkey A. T., and Wayson A. R., "Designing for
Zero," Machine Design, IBM Corporation, Endicott, NY, 1969.
[10] Wei D.-P., "Future Directions of Fundamental Research in Additive Tribochemistry," Lubrication Sciences, Vol. 7, April 1995.
[11] Mizuhara K. and Tsuya Y., "Investigation of a Method for Evaluating Fire-Resistant Hydraulic Fluids by Means of an Oil-Testing Machine," JSLE International Tribology Conference, Tokyo,
Japan, 8-10 July 1985.
[12] Feldman, D. G. and Kessler, M., "Development of a New Application-RelatedTest Procedure for Mechanical Testing of Hydraulic Fluids," Hydraulic Failure Analysis: Fluids, Components
and System Effects, STP 1339, G. E. Totten, D. K. Wills, and D.
G. Feldman, Eds., ASTM International, West Conshohocken,
PA, 2001, pp. 75-89.
[13] De Gee, A. W. J., "Characterization of Five High-Performance
Lubricants in Terms of IRG Transition Diagram Data," Proceedings of the IMechE, International Conference on Tribology-Friction. Lubrication, and Wear, Fifty Years On, London, Mechsinical
Engineering Publications Lmtd., Bury St. Edmunds, 1987, Vol.
1, pp. 427-436.
[14] Vaim, J. A. and Jising, T.-B, "Measurement of the Friction and
Lubricity Properties of Contact Lenses," Proceedings of the ANTEC1995, Boston, MA, May 7-11, 1995.
[15] Schipper, D. J. and Faraon, I. C, "Stribeck Curves for Starved
Line Contacts," University of Twente, The Netherlands, Report
number TROl-2227, 2001.
[16] Sanvordenker, K. S., "Lubrication by Oil-RefrigerEint Mixtures:
Behavior in the Falex Tester," ASHRAE Transactions, KC-84-14,
No. 3, pp. 799-805.
[17] Anderson, M., "The Use of Tribological Aspect Numbers in
Bench Test Selection-A Review Update," Bench Testing of In-

1038 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


dustrial Fluid Lubrication and Wear Properties Used in Machinery Applications, ASTM STP 1404, G. E. Totten, L. D. Wedeven,
J. R. Dickey, and M. Anderson, Eds., ASTM International, West
Conshohocken, PA, 2001.
[18] Condensed Catalog ofFalex Test Equipment and Custom Services,
QG-18, Falex Corporation, Sugar Grove, IL, 1999.
[19] Helmetag, K., "A New Look at an Old Idea: The Torque Curve
Revisited," Bench Testing of Industrial Fluid Lubrication and
Wear Properties Used in Machinery Applications, ASTM STP
1404, G. E. Totten, L. D. Wedeven, J. R. Dickey, and M. Anderson, Eds., ASTM International, West Conshohocken, PA, 2001.
[20] "Extreme Pressure Lubricant Test Machines," Mobil Technical
Bulletin, Mobil Oil, Roswell, GA, 1970.
[21] "A Compilation of International Standards for Friction and
Wear Testing of Materials," VAMAS Technical Working Area 1,
Peter J. Blau, Ed., Report No. 14, NIST, Gaithersburg, MD,
1993.
[22] Voitik, R., and Ren, N., "Diesel Fuel Lubricity by Standard Four
Ball Apparatus Utilizing Ball on Three Disks, BOTD," SAE Paper #950247, Society of Automotive Engineers, Warrendale, PA,
1995.
[23] Voitik, R., "Diesel Fuel Lubricity BOTD Status-1995," Presented
at the Fuels & Lubricants Meeting & Exposition, Toronto, Ontario, 16-19 Oct. 1995, SAE Paper #952371, Society of Automotive Engineers, Warrendale, PA, 1995.
[24] Nikeinjam, M., " Diesel Fuel Lubricity: On the Path to Specifications," presented at the International Spring Fuels & Lubricants
Meeting & Exposition, Dearborn, MI, 3-6 May 1999, SAE Paper
#1999-01-1479, Society of Automotive Engineers, Warrendale,
PA, 1999.
[25] The Timken Company Model 1750 Lubricant and Wear Tester,
The Timken Company, Canton, OH, 1977.
[26] Anderson, M., "Oscillating Roll/Slide Test Machine for Screening Properties of Greases Used in Constant Velocity Joints,"
Journal of the National Lubricating Grease Institute: NLGI
Spokesman, Vol. 54, No. 3, June 1990.
[27] Voitik, R. M., and Heerdt, L. R., "Wear and Friction Evaluation
of Gear Lubricants by Bench Test," Journal of the American Society of Lubrication Engineers: Lubrication Engineering, Vol. 40,
No. 12, pp. 719-724.
[28] Bell, J. C. and Delargy, K. M., "Lubrication Influences on the
Wear of Piston-Ring Coatings," Proceedings of the 16''' Lees-Lyon
Symposium, Mechanics of Coatings, 1989, pp. 371-377.
[29] Patterson, D. J., Hill, S. H., and Tung, S. C, "Bench Wear Testing of Engine Power Cylinder Components," Lubrication Engineering, Vol. 49, No. 2, 1993, pp. 89-95
[30] Hartfield-Wunsch, S. E., Tung, S. C, and Rivard, C. J., "Development of a Bench Wear Test for the Evaluation of Engine
Cylinder Components and the Correlation with Engine Test Results," Tribological Insights and Performance Characteristics of
Modem Engine Lubricants, SAE SP-996, SAE Paper #932693,
1993.
[31] Lacey, P. I. and Lestz, S. J., "Fuel Lubricity Requirements for
Diesel Injection Systems," SWRI Report No. BFLRF 270, Southwest Research Institute, San Antonio, TX, 1991.
[32] Spikes, H. A., Meyer, K., Bovington, C, Caprotti, R., and
Krieger, K., "Development of a Laboratory Test to Predict Lubricity Properties of Diesel Fuels and its Application to the Development of Highly Refined Diesel Fuels," presented at the 9*^
International Colloquium, Ecological and Economical Aspects of
Tribology, Paper 3.22, Technische Akademie Esslingen, Germany, 1994, pp. 1-16.
[33] Hadley, J. W., Owen, G. C, and Mills, B., "Evaluation of a High
Frequency Reciprocating Wear Test for Measuring Diesel Fuel
Lubricity," SAE Paper #932692, Society of Automotive Engineers, Warrendale, PA, 1993.
[34] Plint and Partners Catalog of Tribology Test Equipment, Flint and
Psutners, Newbury, Bershire, England, 2001.

[35] SRV Test System for Evaluating the Tribological Properties of


Lubricants and Materials, Optimol Instruments Priiftechnik
GmbH, Miinchen, Germany, 1996.
[36] D-94303: FZG Zahnrad-Verspannungs-Prufstand FZG Gear
Test Rig, Strama GmbH & Co. KG, Straubing, Germany, 1995.
[37] "Method to Assess the Scuffing Load Capacity of Lubricants
with High EP Performance Using an FZG Gear Test Rig," FVA
Information Sheet, Research Project No. 243, Forschungsvereinigung Antriebstechnick E.V., 60528 Frankfurt/Main, 1995.
[38] "Test Procedure for the Investigation of the Micro-Pitting Capacity of Gear Lubricants," FVA Information Sheet, Research
Project No. 54/1 - IV, Forschungsvereinigung Antriebstechnick
E.V., 60528 Frankfurt/Main, 1993.

APPENDIX
Terminology Related to Fuels
and Lubricants Testing
abrasive wear, nwear due to hard peirticles or hard protuberances forced against and moving cdong a solid surface.
additive, na material added to another, usueJly in small
amounts, to impart or enhance desirable properties or to suppress undesirable properties.
adhesive wear, nwear due to localized bonding between
contacting solid surfaces leading to material transfer between the two surfaces or loss from either surface.
apparent area of contact, nin tribology, the area of contact
between two solid surfaces defined by the boundaries of their
macroscopic interface. (Contrast with real a r e a of contact.)
asperity, nin tribology, a protuberance in the small-scale
topographical irregularities of a solid surface.
break-in, nin tribology, an initicJ transition process occurring in newly established weEuing contacts, often accompanied by transients in coefficient of friction or wear rate, or
both, which are uncharacteristic of the given tribological system's long-term behavior.
catastrophic vwear, nrapidly occurring or accelerating
surface damage, deterioration, or change of shape caused by
wear to such a degree that the service life of a part is appreciably shortened or its function is destroyed.
coefficient of friction, fi or f, nin tribology, the dimensionless ratio of the friction force (F) between two bodies to
the normal force {N) pressing these two bodies together.
/x or f = (F/N)
Discussiona distinction is often made between static coefficient of friction and kinetic coefficient of friction.
corrosive wear, n^wear in which chemical or electrochemical reaction with the environment is significEuit.
debris, nin tribology, pjirticles that have become detached
in a wear or erosion process.
dry solid film lubricants, ndry coatings consisting of lubricating powders in a solid matrix bonded to one or both
surfaces to be lubricated.
extreme pressure (EP) additive, nin a lubricant, a substcince that minimizes damage to metcil surfaces in contact
under high stress rubbing conditions (D 4175).
fatigue wear, n^wear of a solid surface caused by fracture
arising from material fatigue.
fretting wear, na form of attiitive wear caused by vibratory or oscillatory motion of limited amplitude characterized

CHAPTER 37: LUBRICANT FRICTION AND WEAR TESTING


by the removal of finely-divided particles from the rubbing
surfaces. Discussion^Air can cause immediate local oxidation of the wear particles produced by fretting wear. In addition, environmental moisture or humidity can hydrate the
oxidation product. In the case of ferrous metals, the oxidized
wear debris is abrasive iron oxide (FeaOs) having the appearance of rust, which gives rise to the nearly synonymous terms
fretting corrosion and friction oxidation. A related, but somew h a t different, p h e n o m e n o n often accompanies fretting
wccir. Fedse brinelling is localized fretting weeir that occurs
when the rolling elements of a bearing vibrate or oscillate
with small amplitude while pressed against the bearing race.
The mechanism proceeds in stages: (1) asperities weld, are
torn apart, and form wear debris that is subsequently oxidized; (2) due to the small-amplitude motion, the oxidized
detritus cannot readily escape, and being abrasive, the oxidized wear debris accelerates the wear. As a result, wear depressions are formed in the bearing race. These depressions
appear similar to the Brinell depressions obtained with static
overloading. Although false brinelling can occur in this test,
it is not chcu-acterized as such, and instead, it is included in
the determination of fretting wear.
fretting corrosion, na form of fretting wear in which corrosion plays a significEuit role.
fretting wear, nwear arising as a result of fretting (see
fretting).
friction, nthe resistance to sliding exhibited by two surfaces in contact with each other. Basically, there are two frictional properties exhibited by any surface: static friction EUid
kinetic friction.
friction force, n^the resisting force tangential to the interface between two bodies when, under the action of an external force, one body moves or tends to move relative to the
other. (See also coefficient of friction.)
Hertzian c o n t a c t area, nthe a p p a r e n t area of contact
between two nonconforming solid bodies pressed against
each other, as calculated from Hertz's equations of elastic
deformation.
Hertzian c o n t a c t pressure, nthe m a g n i t u d e of the
pressure at any specified location in a Hertzian contact Eirea,
as calculated from Hertz's equations of elastic deformation.
kinetic coefficient of friction, nthe coefficient of friction
u n d e r conditions of macroscopic relative motion between
two bodies.
kinetic friction, nthe force that resists motion when a surface is moving with a uniform velocity; it is, therefore, equal
and opposite to the force required to maintain sliding of the
surface with uniform velocity.
lubricant, nany substance interposed between two surfaces for the purpose of reducing the friction or wear between them.
lubricating grease, na semi-fluid to solid product of a dispersion of a thickener in a liquid lubricant.
Discussionthe qualifying term, lubricating, should always be used. The term, grease, used without the qualifier
refers to a different product, namely certain natural or processed animal fats, such as tallow, lard, cind so forth (D 128).
Discussionthe dispersion of the thickener forms a twophase system a n d immobilizes the liquid lubricant by surface
tension eind other physical forces. Other ingredients cire commonly included to impart specied properties (D 217).

1039

lubricating oil, na liquid lubricant, usually comprising


several ingredients, including a major portion of base oil and
minor portions of various additives (D 5966).
lubricity, na qualitative term describing the ability of a lubricant to minimize friction between and damage to surfaces
in relative motion u n d e r load (D 4857, D 4863).
precision, nthe degree of agreement between two or more
results on the same property of identical test material. In this
practice, precision statements are framed in terms of the repeatability and reproducibility of the test method (D 3244).
pitting, nin tribology, a form of wear characterized by the
presence of surface cavities, the formation of which is attributed to processes such as fatigue, local adhesion, or cavitation.
repeatability, nthe quantitative expression of the random
error associated with a single operator in a given laboratory
obtaining repetitive results with the same apparatus under
constant operating conditions on identiced test material. It is
defined as the difference between two such results at the 95%
confidence level.
Discussioninterpret as the value equal to or below which
the absolute difference between two single test results obtained in the above conditions may expect to lie with a probabihty of 95%.
Discussionthe difference is related to repeatability standard deviation but is not the standard deviation or its estimate.
reproducibility R, nquEintitative expression of the r a n d o m
error associated with operators working in different laboratories, each obtaining single results on identical test material
when applying the same method.
result, nthe value obtained by following the complete set of
instructions of a test method.
rolling contact fatigue, na damage process in a triboelement subjected to repeated rolling contact loads, involving
the initiation and propagation of fatigue cracks in or under
the contact surface, eventually culminating in surface pits
or spalls.
rolling wear, nwear due to the relative motion between
two nonconforming solid bodies whose surface velocities in
the n o m i n a l contact location are identical in magnitude,
direction, and sense. DiscussionRolling wear is not a
synonym for rolling contact fatigue, although the latter can
be considered one form of rolling wear.
run-in, nin tribology, an initial transition process occurring
in newly established wearing contacts, often accompanied by
transients in coefficient of friction, or wear rate, or both,
which ju-e uncharacteristic of the given tribological system's
long term behavior. {Synonym: break-in, wear-in.)
run-in, vin tribology, to apply a specified set of initial operating conditions to a tribological system to improve its long
term frictional or wecir behavior, or both. {Synonym: break
in, V. and wear in, v. See also run-in, n.)
scoring, nin tribology, a severe form of wear characterized
by the formation of extensive grooves and scratches in the direction of sliding.
scratching, n^the formation of fine lines in the direction of
sliding that may be due to asperities on the harder slider or
to h a r d particles between the surfaces or embedded in one of
them. DiscussionScratching is considered less damaging
than scoring or scuffing.

1040 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

scuff, scuffing, nin lubrication, damage caused by instantaneous localized welding between surfaces in relative motion, which does not result in immobilization of the parts.
scuffingn, a form of wear occurring in inadequately lubricated tribosystems that is characterized by macroscopiccJlyobservable changes in surface texture, with features related
to the direction of relative motion.
Discussionfeatures characteristic of scuffing include
scratches, plastic deformation, and transferred material. (Related terms: galling, scoring.)
seizure, nin lubrication, welding between surfaces in relative motion that results in immobilization of the parts. Localized fusion of metal between the rubbing surfaces of the
test pieces (D 5707). DiscussionSeizure is usually indicated
by an increase in coefficient of friction, wear, or unusual
noise and vibration. In this test method, increase in coefficient of friction is displayed on the chart recorder as rise in
the coefficient of friction from a steady state value.
sliding wear, nwear due to the relative motion in the tangential plane of contact between two solid bodies.
speilling, nin tribology, the separation of macroscopic particles from a surface in the form of flakes or chips, usually associated with rolling element bearings and gear teeth, but
also resulting from impact events.
standard test, na test on a calibrated test stand, using the
prescribed equipment according to the requirements in the
test method, and conducted according to the specified operating conditions. Discussionthe specified operating conditions in some test methods include requirements for determining a test's operational validity. These requirements are
applied after a test is completed, and can include (1) midlimit ranges for the average values of primary and secondary
parameters that are narrower than the specified control
ranges for the individual values, (2) allowable deviations for
individual primary and secondary parameters from the specified control ranges, (3) downtime limitations, and (4) special
parameter limitations.
static coefficient of friction, nthe coefficient of friction
corresponding to the maximum friction force that must
be overcome to initiate macroscopic motion between two
bodies.
stick-slip, nin tribology, a cyclic fluctuation in the magnitudes of friction force and relative velocity between two
elements in sliding contact, usually associated with a relaxation oscillation dependent on elasticity in the tribosystem
and on a decrease of the coefficient of friction with onset of
sliding or with increase of sliding velocity.
DiscussionClassical or true stick-slip, in which each cycle
consists of a stage of actual stick followed by a stage of overshoot "slip," requires that the kinetic coefficient of friction is
lower than the static coefficient. A modified form of relaxation oscillation, with near-harmonic fluctuation in motion,
can occur when the kinetic coefficient of friction decreases
gradually with increasing velocity within a certain velocity
range. A third t5^e of stick-slip can be due to spatial periodicity of the friction coefficient along the path of contact. Random variations in friction force measurement do not constitute stick-slip.
test oil, nany oil subjected to evaluation in an established
procedure.

test sample, na portion of the product taken at the place


where the product is exchanged, that is, where the responsibility for the product quality passes from the supplier to the
receiver. Actually, this is rarely possible and a suitable sampling location should be mutually agreed on.
triboelement, none of two or more solid bodies that comprise a sliding, rolling, or abrasive contact, or a body subjected to impingement or cavitation. (Each triboelement contains one or more tribosurfaces.)
DiscussionContacting triboelements may be in direct
contact or may be separated by an intervening lubricant, oxide, or other film that affects tribological interactions between them.
tribology, nthe science and technology concerned with interacting surfaces in relative motion, including friction, lubrication, wear, and erosion.
tribosurface, nany surface (of a solid body) that is in moving contact with another surface or is subjected to impingement or cavitation.
tribosystem, nany system that contains one or more triboelements, including all mechanical, chemical, and environmental factors relevant to tribological behavior, (See also
triboelement.)
thin film Quid lubricant, nfluid lubricants consisting of a
primary liquid with or without additives or lubricating powders and without binders or adhesives, which form a film on
one or both surfaces to be lubricated and perform their function after application and after excess material has drained
from the application area, and without additional material being supplied by either a continuous or intermittent method.
wear, ndamage to a solid surface, generally involving progressive loss of material, due to relative motion between that
surface and a contacting substance or substances.
wear, nthe removal of metal from the test pieces by a mechanical or chemical action, or by a combination of mechanical and chemical actions.
wear rate, nthe rate of material removal or dimensional
change due to wear per unit of exposure parameter; for example, quantity of material removed (mass, volume, thickness) in unit distance of sliding or unit time.
wear coefficient, nin tribology, a wear parameter that relates sliding wear measurements to tribosystem parameters.
Most commonly, but not invariably, it is defined as the dimensionless coefficient k in the equation
wear volume = k (load X sliding
distance/hardness of the softer material)
(1) The equation given above is frequently referred to in the
literature as "Archard's equation" or "Archard's law."
(2) Sometimes the term wear coefficient has been used as a
sjrnonym for wear factor. While this usage is discouraged, the
term should always be fully defined in context to prevent confusion.
wear rate, nthe rate of material removal or dimensional
change due to wear per unit of exposure parameter, for example, quantity of material removed (mass, volume, thickness) in unit distance of sliding or unit time.
DiscussionBecause of the possibility of confusion, the
manner of computing wear rate should always be carefully
specified.

CHAPTER 3 7: LUBRICANT FRICTION AND WEAR TESTING


welding, nin tribology, the bonding between metallic surfaces in direct contact, at any temperature.
Terminology Specific to Standards
load-canying capacity, nas determined by D 2782, the
maximum load or pressure that can be sustained by the lubricant (when used in the given system under specific conditions) without failure of the sliding contact surfaces as evidenced by scoring or seizure or asperity welding (D 2509, D
2782).
OK value, nas determined by D 2782, the maximum mass
(weight) added to the load lever weight pan at which no scoring or seizure occurs (D 2509, D 2782).
score value, nas determined by D 2782, the minimum
mass (weight) added to the load lever weight pan, at which
scoring or seizure occurs (D 2509, D 2782).
DiscussionWhen the lubricant film is substantially maintained, a smooth scar is obtained on the test block, but when
there is a breakdown of the lubricant film, scoring or surface
failure of the test block takes place, see Fig. 24. In its simplest
and most recognized form, scoring is characterized by the
furrowed appearance of a wide scar on the test block and excessive pick-up of metal on the surface of the test cup. The
form of surface failure more usually encountered, however,
consists of a comparatively smooth scar, which shows local
damage that usually extends beyond the width of the scar.
Scratches or striations that occur in an otherwise smooth
scar and that do not extend beyond the width of the scar are
not considered as evidence of scoring.
seizure or asperity welding, nlocalized fusion of metal between the rubbing surfaces of the test pieces. Seizure is usually indicated by streaks appeciring on the surface of the test
cup, an increase in friction and wear, or unusual noise and vibration. Throughout D 2782, the term seizure is understood
to mean seizure or asperity welding (D 2509, D 2782).
load-wear index, n(or the load-carrying property of a lubricant)an index of the ability of a lubricant to minimize
wear at applied loads. Under the conditions of this test, specific loadings in kilograms-force (or Newtons) having intervals of approximately 0.1 logcirithmic units, are applied to the
three stationary balls for ten runs prior to welding. The loadwear index is the average of the sum of the corrected loads
determined for the ten applied loads immediately preceding
the weld pair (D 2596, D2783).
weld point, nunder the conditions of this test, the lowest
applied load in kilograms at which the rotating ball welds to
the three stationary balls, indicating the extreme-pressure
level of the lubricants-force (or Newtons) has been exceeded.
DiscussionSome lubricants do not allow true welding,
and extreme scoring of the three stationary balls results. In
such cases, the applied load that produces a maximum scar diameter of 4 mm is reported as the weld point (D 2596, D 2783).

1041

corrected load, nthe load in kilograms-force (or Newtons)


for each run obtained by multiplying the applied load by the
ratio of the Hertz scar diameter to the measured scar diameter at that load (D 2596, D 2783).
Hertz scar diameter, nthe average diameter, in millimeters, of an indentation caused by the deformation of the balls
under static load (prior to test). It may be calculated from the
equation
Dh = 8.73 X \Q-^ (P)''3
Where:
Dh = Hertz diameter of the contact area, and
P = the static applied load.
(D 2596, D 2783)
compensation scar diameter, nthe average diameter, in
millimeters, of the wear scar on the stationary balls caused by
the rotating ball under an applied load in the presence of a lubricant, but without causing either seizure or welding (D
2596, D 2783).
DiscussionThe wear scar obtained shall be within 5% of
the values noted in Table 1, Column 3 of ASTM D 2596/D
2783.
Hertz line, na line of plot on logarithmic paper, as shown
in Fig. 16, where the coordinates are scar diameter in millimeters and applied load in kilograms-force (or Newtons),
obtained under static conditions.
compensation line, na line of plot on logarithmic paper,
as shown in Fig. 1, where the coordinates are scar diameter
in millimeters and applied load in kilograms-force (or
Newtons), obtained under dynamic conditions. (D 2596,
D 2783)
DiscussionCoordinates for the compensation line are
found in Table 1, Columns 1 and 3 of ASTM D 2596/D 2783.
DiscussionSome lubricants give coordinates which are
above the compensation line. Known examples of such fluids
are methyl phenyl silicone, chlorinated methyl phenyl silicone, silphenylene, phenyl ether, and some mixtures of
petroleum oil and chlorinated paraffins.
last nonseizure load, nthe last load at which the measured scar diameter is not more than 5% above the compensation line at the load (D 2596, D 2783).
incipient seizure or initial seizure region, nthat region
at which, with an applied load, there is a momentary breakdown of the lubricating film. This breakdown is noted by a
sudden increase in the measured scar diameter and a momentary deflection of the indicating pen of the optional friction-measuring device (D2596, D2783).
immediate seizure region, nthat region of the scar-load
curve characterized by seizure or welding at the startup or by
large wear scars. Initial deflection of indicating pen on the
optional friction-measuring device is larger than with nonseizure loads (D 2596, D 2783).

MNL37-EB/Jun. 2003

Statistical Quality Assurance


of Measurement Processes
for Petroleum and
Petroleum Products
Alex T. C. Lau^

I N A QUALITY CONSCIOUS AND COST COMPETITIVE ENVIRONMENT,

proficiency and statistical control of measurement processes


used for product certification are expected between suppliers
and customers. Statistical control occurs when the measurement process is operated with stable and quantifiable accuracy and precision. Likewise, proficiency occurs when the
measurement process accuracy and precision performance
metrics are reasonable when compared to similar processes
that are operated with an industry-agreed upon standard protocol. ASTM test methods are examples of such standardized
protocols.
This chapter reviews the measurement process used in the
petroleum industry, and measurement process performance
metrics that are adopted and promoted by ASTM Committee
D02. The main body deals with the application of statistical
quality assurance techniques to design and implement measurement process quality assurance (QA) programs to assess
measurement process performance. The chapter then summarizes discussion on various importcint aspects of QA program implementation.
Discussion of theory for the referenced statisticcd tools and
control charts are beyond the scope of this chapter. Interested readers should see textbooks on statistics and statistical
quality assurance, such as An Introduction to Statistical Quality Assurance by D.C. Montgomery.
Portions of the ASTM D 6299 Annex on the computational
mechanics with worked examples are reproduced, with min o r modifications, at the end of this chapter. They are
included to assist practitioners in the proper use of the described tools.

USE OF MEASUREMENT PROCESS IN THE


PETROLEUM INDUSTRY
The m e a s u r e m e n t process is a sub-process integral to all
manufacturing processes. Like any process, it has input(s)
and output(s). Input(s) to the measurement process are usually sample(s) taken at various stages of the manufacturing
process; the output(s) are usually numerical values. In the
petroleum refining industry, two types of measurement processes are commonly encountered. One is the traditional laboratory-based process where a small sample is extracted
from the main process streams and analyzed off-line using

standard test methods, most of which are those developed


a n d m a i n t a i n e d b y ASTM D02. The other, c o m m o n l y
referred to as a continuous process analyzer system, is a
field-deployed, fully automated instrumentation system designed to provide analytical information on representative
samples continuously extracted from the m a i n process
streams, or on the actueil process stream using in-line probes.
The use of measurement process outputs (numerical values), can be categorized into three c o m m o n applications:
1. manufacturing process control: to support decisions on appropriate manipulations (known as control actions) to key
manufacturing process variables in order to meet required
process performance criteria
2. product property conformance
to specification: to test
the hypothesis t h a t the batch of product from which
the test sample is taken meets required quality criteria
(specifications)
3. measurement process self-monitoring: to test the hypothesis
that the results generated by the measurement process are
fit-for-use.
Manufacturing P r o c e s s Control
In this application, the measurement process is used to provide a window to the refining (raw materiEd manufacturing)
and blending (product manufacturing) processes. The outputs from the measurement process tre compEired to target
values, and appropriate manipulations (known as control action) are made to key operating variables (pressure, temperature, flow, level) in these processes based on evaluation of the
current and past deviations of actual versus target values.
Both laboratory-based and continuous process analyzer systems are used for this application. Due to the high cost of installation and maintenance of continuous process analyzer
systems, the latter are usually deployed only on critical manufacturing process streams suitable for feedback control.
Control action frequency and magnitude are tailored to the
processes' gain and dynamics, and calculated using process
models and cJgorithms derived from classical process control
theories. These process models, in general, are quite different
than the steady-state Gaussian model commonly employed in
the discrete components manufacturing open-loop processes.

Product Property Conformance to Specification


' Blending Performance Optimization Specialist, Exxon Mobil Research and Engineering, Fairfax, VA 22037.

This is the most c o m m o n application for ASTM D02 test


methods. The measurement process is used to inspect small

1043
Copyright'

2003 by A S I M International

www.astm.org

1044 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

quantities of material that are representative of the finished


product. The results, or outputs, from the measurement
process are used to ascertain the specification conformance
status of the product. Depending on governing stcindards and
regulations, either laboratory-based processes or continuous
process analyzer systems, or both, can be used.
Measurement Process Self-Monitoring
This application is the focus of this chapter. In order to be
able to use results generated from a measurement process
with confidence, the fitness-for-use of these results must be
demonstrated continuously. This can be achieved by reguleir
application of the measurement process to samples of special
status, known as quality control samples, as well as engaging
the measurement process in regular interlaboratory collaborative testing programs (round robins). Through application
of statistical control chart techniques to the quality control
samples and round robin results, the performance of the
measurement process over time can be monitored and assessed against required standards. The set of activities used
to achieve this objective is known as a measurement process
quality assurance program.
MEASUREMENT PROCESS
PERFORMANCE METRICS
Precision
Some inherent sources of the measurement process cause
random variation. A generic term commonly used to describe
this type of random variation is common-cause variation.
The specific term for common-cause variation is precision.
Outlined below are the ASTM E 456 [1] definitions of precision, and conditions under which precision is measured.
These definitions are internationally accepted, hence similar
definitions can be found in ISO 4529, and ISO 5725:
precision, nthe closeness of agreement between test results obtained under prescribed conditions (E 456).
repeatability conditions, nconditions where mutually independent test results are obtained with the same test
method in the same laboratory by the same operator with
the same equipment within short intervals of time using
test specimens taken at random from a single sample of
material (E 456/E 177).
reproducibility conditions, nconditions where test results
are obtained in different laboratories with the same test
method using test specimens taken at random from the
same sample of material (E 456/E 177).
ASTM Form and Style (Blue Book) requires that all test
methods have published estimates of precision under both
repeatability and reproducibility conditions. Furthermore,
these estimates must be calculated from data collected in accordance with interlaboratory study protocol meeting the
technical requirements as prescribed in ASTM E 691 [2] or
other equivalent standards. For ASTM D02 test methods, the
equivalent protocol that had been in use for decades predates
E 691. It is described in the Manual on Determining Precision
Data for ASTM Test Methods on Petroleum Products and Lubricants (RR: D02-1007), published in December, 1972. In
1998, an updated version of this protocol was published as

ASTM D 6300 [3], under the jurisdiction of ASTM D02.CS94


Coordinating Subcommittee on Quality Assurance and
Statistics.
For ASTM D02 test methods, the repeatability and reproducibility figures published are obtained in accordance with
their definitions in D 6300:
repeatability, nthe quantitative expression of the random
error associated with a single operator in a given laboratory obtaining repetitive results with the same apparatus
under constant operating conditions on identical test material. It is defined as the difference (see 3.1.10.1) between
two such results at the 95% confidence level. (RR
D02:1007)
reproducibility, nis a quantitative expression of the random error associated with different operators using different apparatus, etc., each obtaining a single result on an
identical test sample when applying the same method. It is
defined as the 95% confidence limit for the difference between two such single and independent results (RR: D021007).
These figures are interpreted as the maximum value expected for the absolute difference between two single test
results obtained in the prescribed conditions for about
95% of the time. They are obtained by multiplying the variation estimates for the prescribed conditions by a factor based
on an assumed statistical distribution for these absolute
differences.
In addition to the above, ASTM D 6299 [4] defines an additional set of conditions under which precision can be estimated as follows:
site precision conditions, nconditions under which test
results are obtained by one or more operators in a single
site location practicing the same test method on a single
measurement system using test specimens taken at random from the same sample of material over an extended
period of time spanning at least a 15 day interved.
Repeatability and reproducibility conditions as described
above are intended to provide precision estimates under the
"most controlled" to "least controlled" scenarios, while site
precision condition prescribes a scenario common to most
individual laboratories. In general, the magnitude of common cause variation measured under site precision conditions lies somewhere between that for repeatability and reproducibility conditions, due to the difference in controlled
factors as illustrated in Fig. 1.
Site precision conditions should include all sources of variation that are typically encountered during normal, longterm operation of the measurement system. Thus, all operators involved in the routine use of the measurement system
should contribute results. Since the objective is to estimate
long-term common cause variation, multiple results obtained
within a 24 h period are discouraged.
Bias
The following are definitions for bias and two key related
terms quoted from ASTM E 456 and D 3244[5]:
bias, na systematic error that contributes to the difference between a population mean of the measurements or
test results in an accepted reference or true value (E456).

CHAPTER 38: STATISTICAL

QUALITY ASSURANCE

B l not allowed to vaiy by design

measurement process
environment

operator

equipment

not altowed to vary by design

measurement process
antftfonment

[" operator 1

OF MEASUREMENT

PROCESSES

FOR

PETROLEUM

based on collaborative expeiimental work under the auspices of a scientific or engineering group (E456).
true value, nfor practical purposes, the value towards
which the average of single results obtained by N laboratories tends, when N becomes veiy large. Consequently, such
a true value is associated with the particular test method
employed (D 3244).
The term true value as defined above, is also referred to as
a consensus value as described by item (3) under the definition of accepted reference value (ARV).
Hence, if an average was calculated from N results obtained for the same material, from a single measurement process, under site precision conditions, AND, if the material has
an accepted reference value, then, for large values of N
(greater than 30), any statistically significant difference between this average and the ARV of the material is referred to
as bias. Bias provides a quantitative measure of how well the
actual process outcome agrees with an expected value.
accuracy, nthe closeness of agreement between a test result and an accepted reference value.
Note: The term accuracy, when applied to a set of test
results, involves a combination of a random component and of a common systematic error or bias component (E 456).
Hence, precision and bias are quantitative measures of different attributes of the measurement process. The combined
effect of both attributes affects the accuracy of the results.
M E A S U R E M E N T P R O C E S S QUALITY
A S S U R A N C E (QA) P R O G R A M

pj^^^i^.
B
not allowed to vary by design

measurement process
May or may not vary

environment

operator

material

FIG. 1a) ASTM reproducibility conditions; b) ASTM repeatability conditions; c) site precision conditions.

accepted reference value, na value that serves as an


agreed-upon reference for comparison, and which is derived as: (1) a theoretical or established value, based on scientific principles, (2) an assigned value, based on experimental work of some national or international
organization such as the U.S. National Institute of Standards and Technology (NIST), or (3) a consensus value,

The primary objectives of a measurement process quality assurance program are:


1. to obtain quantitative estimate of precision and bias
achievable by the measurement process under site precision conditions;
2. to continue monitor capability to sustain the above values;
3. to ensure compliance of precision and bias performance
measures with values mutually agreed upon between supplier and customer.
These objectives can be achieved through the following activities:
monitoring stability and precision through quality control
sample testing;
monitoring bias through testing of materials with ARV;
periodically evaluating system performance in terms of
precision and/or bias
periodically and independently validating the system
regularly participating in interlaboratory exchange programs
Monitoring Stability and Precision Through
Quality Control Sample Testing
Summary of Activity: For the purpose of establishing the instatistical-control status of the measurement process since
the last valid calibration, quality control samples are regularly analyzed as if they are production samples. Results are
immediately plotted on control charts, followed by chart

1046

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Einalysis in accordcince with industry-accepted rules to ascertain the statistical control status of the measurement process.
Any out-of-control data should trigger a n investigation for
root causes in a timely manner. Pending on outcome of this
investigation, remedial action may be required.

ance is due to c o m m o n cause variation associated with the


combination of time/operator/reagents/instrument calibration factors, which will not b e observable u n d e r repeatability
conditions.
Data

Quality Control Material


and Storage

Selection,

Preparation,

Selected materials should be a stable, finished material with


quality values and composition similar to those regulcirly
tested by the measurement process. For off-line (lab-based)
processes, a batch of smaller aliquot portions can be prepared from a large volume of sample, usually, but not necessarily, extracted from the manufacturing process. The large
volume of sample should be mixed thoroughly prior to
aliquot preparation to ensure between-aliquot homogeneity.
These smaller portions are then stored in a controlled environment to preserve sample integrity over time.
For c o n t i n u o u s process analyzer systems, customdesigned sub-systems and procedures are usually employed
to carry out the batch extraction, mixing, storage, cind delivery functions.
Sufficient volume should be extracted per batch at one
time to support as mjiny quality control sample tests as practical (depending on the planned testing frequency, the number of samples could range from 30 to 100). This would EJIOW
performance statistics to be calculated with reasonable n u m ber of data points, using each batch as a subgroup.
Quality

Control Material

Testing

The testing should b e CEurried out under site precision conditions, with participation of as many operators as practical,
and test time during the day should be randomized to avoid
any unknown systematic effects. Test frequency should be
designed in accordance with the business needs, taking into
considerations the following factors:
frequency of use of measurement process
criticality of the parameter being measured
measurement process stability and precision performance
based on historical data
business economics
regulatory, contractual, or test method requirements.
The sample treatment and testing of quality control materials should emulate the processing of day-to-day samples.
Application of special treatment to the quality control sample
in order to get a better result is discouraged, as this would undermine the integrity of the data in providing a valid estimate
of the long-term measurement process precision under normal production conditions. TypicEilly, for automated large
batch analyses commonly practiced in testing using autosamplers, it is good practice to include a quality control sample in the beginning, middle, emd end of batch run. Periodic
re-submission of quality control samples, disguised as normal samples, provides data to test the authenticity of precision established using known quality control samples as truly
representative of the test m e t h o d precision u n d e r n o r m a l
testing conditions.
Testing multiple aliquots of quality control samples as a
batch, under repeatability conditions, is not appropriate for
estimating the m e a s u r e m e n t process long t e r m precision.
The bulk of the total long term measurement process vari-

Treatment

The most practical and technically applicable tool for recording and assessing quality control sjimple data is the control
chart. Quality control test results should be plotted on control charts as soon as they cire generated and the chart should
be interpreted immediately to assess the acceptability of process performance. For measurement processes where there is
n o issue with quality control sample homogeneity among
aliquots prepeired from one batch of materieJ, the Individual
(I) cind Moving Range of 2 (MR2) are the appropriate charts.
These charts have been the basic workhorses in the statistical
process control (SPC) discipline for over half a century, primarily deployed in the discrete component manufacturing
sector. They are also known as "Shewart" charts, a tribute to
Dr. Walter Shewhart, one of the early quality pioneers w h o
preached the use of these charts for manufacturing process
monitoring and control.
Designed with simplicity in mind, the I chart is not as effective in detecting small process shifts as it is for large shifts.
To address this shortcoming, its use is often augmented with
a set of r u n rules, often referred to as the "Western Electric"
r u n rules, a tribute to the company that pioneered their use.
More advanced statistical techniques such as the Exponentially Weighted Moving Average (EWMA), or Cumulative
Sum (CUSUM) can be deployed in lieu of the r u n rules with
equivalent effectiveness. The EWMA is recommended due to
ease of deployment, a n d its close emulation to detection
power of the r u n rules [6]. An abridged summeiry description
of these cheirts and the r u n rules can be found in the Annex
under the section on Control Charts.
Hence, a combination of the I chart with the run rules, or
augmented with EWMA, should be used for the detection of
both large and small shifts of the location value simultcineously. The MR2 chart tracks the total process variation (precision) over multiple operators cind time.
In order to deploy control chcirts for regular use, control
limits and center values need to be CEilculated. These values
can be obtained initially after a veJid test equipment calibration from a m i n i m u m of 15 valid quality control test results
(for the same batch of qucJity control samples), then periodically updated as new data arrive. Prior to calculating the initial values, the following screening steps should be CEirried
out:
1. Screen for suspicious resultsResults should first be visually screened for unusual values, such as those that could
have been caused by transcription errors. Results flagged
as suspicious should be investigated. Discard of any data
at this stage must be supported by evidence that the discarding is due to special causes that Eire not part of the normal testing process.
2. Screen for unusual patterns^The next step is t o plot the results in chronological order. In SPC terminology, this is
known as a r u n chart. The chart should be examined for
non-random patterns such as continuous trending in either
direction, unusual clustering, eind cycles. Several of the
non-random patterns described in control chart literature

CHAPTER 38: STATISTICAL

QUALITY ASSURANCE

can be used as guides at this step [8]. Detection of any nonrandom pattern should trigger investigation for causes.
3. Test distribution assumptionsIf, after removal of appropriate results, there is a minimum of 15 observations remaining, the normal distribution assumption for the control chart needs to be validated, as this assumption is used
to predict the behavior of the measurement process under
statistical control. For a small number of observations
(15-25), the tool of choice is the normal probability, or
quantile-quantile plot, since it tends to provide better information regarding the "goodness-of-fit" of the data to the
assumed model than the more commonly known histogram, which generally requires 40 or more data points to
be effective. A plot indicating a departure from the assumed model may reveal abnormal conditions not discovered by previous screening steps.
4. Assess process stabilityIf no obvious non-random patterns are detected from the run charts, and the normal
probability plot reveals no unusual pattern, proceed with
detail calculations of control limits. Use the control chart
rules (or EWMA), in conjunction with the control limits, to
determine if the measurement process is under the influence of common causes variation only (in statistical control). Out-of-control points should be investigated in detail. For those associated with special causes, their
exclusion from further data analysis is warranted only if
the special causes are deemed not part of the normal process. These control limits should be viewed as starting values only, with appropriate reassessment and/or updating
as more data become available.
The initial control chart limit established above should be
re-assessed based on a minimum number (15) of new data
points. Update calculations should be preceded by an appropriate statistical test to assess if the precision of the new data
is essentially the same as previous data. If the test is not significant, a new estimate of the total process precision should
be re-estimated using data from both periods. A significant
test outcome should trigger an investigation for root causes.
When the total number of data points used to estimate process precision exceeds 100, a re-estimate of the site precision
when additional data becomes available reaches the point of
diminishing return. The value based on 100 data points is a
fairly accurate representation of the long term site precision.
Batch Change of Quality Control Material
Due to inherent variation of the manufacturing process and
different operation targets, differences may exist between
batches of materials extracted at different times for quality
control use. Since control limit calculations for the I chart require a center value usually established by the process itself,
a special procedure is required to ensure that the center line
for a new batch of QC material is established with a process
that is in statistical control. This procedure can be designed
as follows:
Collect and prepare a new batch of QC material as the current supply is close to depletion.
Start a new set of I, MR2 charts for the new material. Commence collection of data for the new material each time a
current quality control sample is tested. The new data is
deemed valid if the process in-control status is established
by the current QC material.

OF MEASUREMENT

PROCESSES

FOR

PETROLEUM

Use the control limits for the current MR2 chart or a previous MR2 chart where the matericil is at nominally similar
property level, for the new MR2 chart.
After a minimum of 5 in-control data points are collected
on the new material, calculate a temporary center line for
the new I chart.
Calculate the control limits for the new I chart using the
new center and MR-BAR value from previous MR2 chart.
Assess subsequent data points for new material against the
new control limits. Temporatrily suspend the run rules.
After 15 data points have been accrued, re-calculate the
new I-chart center line. Assess the precision of the new
dataset against the previously established precision for
equivalency. Combine and re-estimate the precision if
necessary.
Deploy the new control chart and activate all run rules.
The reason for the temporary center line is to minimize the
commissioning period for the new QC material. The suspension of run rules is to avoid false alarms due to a less precise
estimate of the center line using five data points. With an effective QC material inventory management program, the calculation and transfer of control chart limits between batches
of quality control materials should be seamless.
When the System is in statistical-control, i.e. no assignable
cause is present, the expected outcome when switching QC
material are:
fluctuation between I-chart center line values for different
QC batches; it represents material difference only;
no statisticcdly significant difference is expected for the MR
chart control limits for different batches of QC material at
similar nominal levels.
For detailed instructions on how to execute the aforementioned calculations and techniques, refer to the Appendix at
the end of this chapter.

Monitoring Bias Through Testing of Quality


Control Materials with Accepted Reference
Values (ARV)
Summary of activities: For the purpose of ascertaining
whether the measurement process is biased, the testing
activities described above for quality control material are
periodically carried out on material(s) with ARV(s). ASTM
D 6299 refers to this type of material as "check standards."
Deviations between the test result and the check steindard
ARV are immediately plotted on control charts and analyzed similarly to those for quality control materials. Acceptable deviations from ARV (or, control limits for this
chart) should be based on the site precision estimates obtained from quality control samples at similar levels described above. The factors considered for determining the
frequency of check standard testing are similar to those described above for quality control material testing. T5^ically,
due to the higher costs and/or availability of check standards, bias monitoring with check standards are conducted
less frequently, and testing of locally produced quality control material is used to demonstrate the in statisticctl control
status of the measurement process between check standard
testing.

1048

MANUAL

3 7: FUELS AND LUBRICANTS

Check Standard Composition


assignment
Process

and

HANDBOOK

ARV

In an ideal world, a check standard should have a specified


composition that is representative of routinely produced materieJ, and have an ARV determined with zero error. Unfortunately, in the real world, ARV with zero error is virtually
unattainable. However, ARV with error that is small relative
to the test method precision can be achieved by averaging the
results from multiple testing organizations. As well, for
ASTM test methods that are designed to measure performance properties, it is not u n c o m m o n to find products with
similar performance properties but significantly different
compositions (e.g., octane rating, cloud, flash). For these
types of test methods, only the equipment, equipment set-up
and operating procedures are standardized, with very limited
testing and compositional requirements on check standards.
Even for those test methods that do have limited check standard testing requirements, the check standards specified are
typically pure compounds, or a blend of pure compounds,
which are typically not compositionally representative of the
products tested. Therefore, unknown, or unknowable composition effects preclude the extrapolation of the performance statistics obtained on these specified check standards
to that for routine products testing.
For these test methods, check standards are usually compositionally specific to the site that produced the material.
Typically, a manufacturing site extracts a large quantity of a
check standard candidate material from the production facilities (e.g., gasoline or diesel fuel blender). Aliquots prepared from this material are then round robin tested. After
statistical examination and outlier treatment has been applied, the average of test results is assigned as the ARV for
this material. (Refer to ASTM D 6300[3] and E-178[7] for
protocol in statistical and outlier treatment of round robin
data.) Hence, acquisition of check standard materials with
composition representative of the current production for an
individual producer can be a time-consuming and expensive
undertaking.
Materials circulated as part of an interlaboratory exchange
program can offer a cost-effective alternative to site-specific
check standards. This is provided the measurement process is
not adversely affected by the composition difference between
the exchange sample and the composition of material that the
measurement process is normally set u p for, and the timeliness of receiving exchange results is not an issue. In order for
an exchange sample to be usable as a check standard, the stand a r d deviation of the interlaboratory exchange p r o g r a m
should not be statistically greater than the reproducibility
standard deviation for the test method, even though the uncertainty in the ARV can be acceptable as the latter is inversely
proportional to the square root of the n u m b e r of values used
to calculate the average. In general, it is recommended that a
m i n i m u m of 16 non-outlier results be used in cedculating the
ARV to reduce the uncertainty of the ARV by a factor of 4 relative to the measurement system single value precision.
Examples of exchanges that may be used to generate ARVs
are: ASTM-D02.CS92 Inter-laboratory Crosscheck Program
(I.L.C.P); ASTM-D02.01 National Exchange Group(N.E.G.);
ASTM D02.01.A Regional Exchange Programs; Alberta Research Council -International Cooperative Exchange Testing
Programs

Test results from ARV testing can be treated in a similar


fashion as those from QC material testing. Typically, the results are pre-treated by subtracting the ARV in order to highlight the sign and magnitude of any bias. For test methods
with precision that changes with level, the bias can also be expressed in units of the steindard deviation to facilitate performance comparison over check standards with different values. Readers are referred to the Appendic for examples of
Check Standard results treatment.
Test Equipment

Calibration

It is a well-known fact (Deming Funnel Experiment) that frequent and unnecessary adjustment to any process will result
in the inflation of the c o m m o n cause variation of the process.
Therefore, equipment calibration should only be done when
there is evidence, supported by quality control testing data,
suggesting that the process requires adjustment as the calibration process itself is subject to c o m m o n cause variation. A
c o m m o n and frequently overlooked source of calibrationinduced variation is the calibration s t a n d a r d preparation
process, a n d / o r c o m m o n cause composition variation of
commercial standards themselves.

Estimate Process Precision and Bias


Periodically, results from control charts, excluding those
with assignable causes, should be analyzed to achieve the following:
1. Test for BiasIf the quality control material has an ARV
for the measured property, a one-sample t-test should be
used to determine if a statistically significant bias exists for
the measurement process versus the ARV. If the test outcome is significant, and, if the magnitude is of practical
concern in the application of the test method, all efforts
should be made to establish the root causes for bias. The
reason for assessing the bias magnitude for practical concern is that as the n u m b e r of data increases, the power of
detecting bias also increases. Hence, there may be situations where the statistical test is significant, but the magnitude of bias detected is fairly small relative to the business application need. In these instances, the bias is
deemed of statistical but not practical significance. The decision on practical significance is a purely subjective call
based on the business application and domain knowledge.
The best estimate of the bias is the difference between the
average of all the results obtained on the quality control
material and its ARV.
2. Precision estimateEither the average of MR chart, or the
more traditional root-mean-square calculation technique
using the results from the I-chart can be used to estimate
the process variability u n d e r site-precision conditions.
This should be statistically assessed against that published
for ASTM-reproducibility condition to see if it is larger. If
so, follow up investigation should b e conducted since comm o n cause veiriation under site-precision conditions is not
expected to be larger than that for ASTM-reproducibility
conditions.
Readers can refer to the Appendix for detailed instructions
on h o w to perform the aforementioned statistical assessments of system precision and bias.

CHAPTER 38: STATISTICAL

QUALITY ASSURANCE

Periodic and Independent System Validation


If practicable, quality control samples should be periodically
introduced blindly without revealing their identity, among
regular production samples. This is to verify that the precision calculated using quality control sample results is representative of what's achieved during routine operation when
there is no priori knowledge of sample identity and expected
value. D 6299 refers to materials used for this purpose as Validation Audit (VA) samples.
For measurement systems susceptible to human influence,
the precision and bias estimates calculated from data where
the analyst is aware of the sample status (QC or check standard) and/or expected values, may underestimate the precision and bias achievable under routine operation. At the discretion of the users, and, depending on the criticality of these
measurement systems, the QA program may include blind
testing of VA samples where the information regarding the
sample VA status and expected value are withheld from the
analyst. Precision and bias estimates calculated using VA
samples test data can be used as an independent VEilidation of
the routine QA program performance statistics
The specific design and approach to the VA testing program will depend on features specific to the measurement
system and its associated quality management process, and is
beyond the intended scope of this chapter. Two possible approaches are noted below:
QC samples and/or check standards may be submitted as
unknown samples at a specific frequency. Such submissions should not be so regular as to compromise their blind
status.
Retains of previously analyzed samples may be re-submitted as unknown samples under site-precision conditions.
Generally, data from this approach can only yield precision
estimates as retain samples do not have ARVs.
Regular Pari:icipation in Interiaboratory
(Roundrobin) Exchange Testing
Participation in regularly conducted interiaboratory exchanges where tjrpical production samples are tested by multiple production test facilities, using a specified (ASTM) test
protocol, is a cost-effective supplement to in-house check
standard testing, provided the timeliness of receiving the results is not critical. Participants can control chart their
signed deviations from the consensus values established by
the exchange averages to ascertain if their measurement processes Eire in statistical control and non-biased.
Use of interiaboratory exchange statistics (consensus value
and precision) requires scrutiny of how these statistics are
generated. The latter should be generated with tools that provide adequate safeguard against outliers. Bamett and Lewis
defined outliers as a subset of observations that appears to be
inconsistent with the remainder of that set of data. These outliers usually have non-random assignable cause(s) associated
with them, such as transcription error, incorrectly executed
procedure, out-of-calibration instrumentation, or sample
contamination/degradation. Without the proper safeguards,
these outliers can incorrectly skew the consensus value and
inflate the sample standard deviation value to beyond that
deemed reasonable by experienced practitioners. The exchanges quoted above (ASTM-D02.CS92 Inter-laboratory

OF MEASUREMENT

PROCESSES

FOR

PETROLEUM

Crosscheck Program (I.L.C.P); ASTM-D02.01 National Exchange Group(N.E.G.); ASTM D02.01.A Regional Exchange
Programs; Alberta Research Council -International Cooperative Exchange Testing Programs) all use outliers treatment to
generate exchange statistics.
With regular and meaningful participation in these exchanges, an industry benefit is the availability of an on-going
estimate of the achievable precision in executing the standard test methods. The test method custodian (e.g., ASTM
subcommittee member) can regularly compare this information to the published precision to identify the need for
method improvement, and/or revisions to published precision figures. For example, the cetane method (ASTM D 613)
precision was revised based on historical exchange data, primary from the NEG (National Exchange Group), with data
from exchanges such as IP in the UK also considered.

IMPORTANT ASPECTS OF QA PROGRAM


IMPLEMENTATION
Successful implementation of measurement process QA programs requires the recognition that the efforts are at least
80% organizational and 20% technical:
Organizational
Workers have to pEirticipate in the complete control charting
process from data generation to chart intrepretation. They
must be proficient with and own the QA tools if they're expected to maintain their processes in statistical control. The
person generating the QA data must have the capability and
the authority to interpret the control chart and make sound
technical decisions as to the "fitness-for-use" status of the
measurement process. Then and only then would the workers feel a sense of ownership of their control charts.
Management must "walk the talk" by:
providing clear priority to workers that control charting
is PART of the toteJ work process, not done in their spare
time,
accounting for the control charting efforts in resource
planning.
Management must address incapable processes by providing the necesscity training, equipment and/or procedure
upgrade as identified by the control chart data.
Management must foster an environment of trust and open
communication

Technical
Resist the temptation of being seduced by computer automation technology: Computers can't think. People do.
Make the paper system work first before making any attempt at automation. When designing for automation, do
not settle for partial charts or text entries without the pictorial information and the capability to directly annotate
on the chart. Insist on the fuU features and functionalities
to include as a minimum:
instant access to a pictorial representation of at least 16
previous points
direct emnotation features on cheirt

1050

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

CONCLUSION
In summary, proficiency in executing standardized measurement protocol for product quality testing is a key mutual expectation between suppliers and customers. Proficiency assurance requires data to demonstrate:
m e a n a n d precision of measurement process in statistical
control, i.e., the process is stable, (hence predictable), and,
the total magnitude of c o m m o n cause variation is
quantifiable
precision metrics obtained on samples compositionally
representative of product routinely tested cire acceptable
relative to standards
measurement process is non-biased when testing materials
that have ARVs (check standards) assigned by the standard
measurement protocol.
An effective quality management system that ensures the
timely and proper collection of the required data, documentation, and review of performance statistics will provide the
assurance of measurement proficiency, as well as continued
improvement of the measurement processes.

ASTM STANDARDS
No.
D 3244
D 6299

D 6300

E 456
E 69

E 178

Title
Standard Practice for Utilization of Test Data
to Determine Conformance with Specifications
Standard Practice for Applying Statistical
Quality Assurance Techniques to Evaluate Analytical Measurement System Performance
Standard Practice for Determination of Precision and Bias Data for Use in Test Methods for
Petroleum Products a n d Lubricants
Standard Terminology for Relating to Quality
and Statistics
Standard Practice for Conducting an Interlaboratory Study to Determine the Precision of a
Test Method
Standard Practice for Dealing with Outlying
Observations

[3] ASTM D 6300: Standard Practice for Determination of Precision


and Bias Data for Use in Test Methods for Petroleum Products
and Lubricants, Annual Book of ASTM Standards, ASTM International, West Conshohocken, PA, 2002.
[4] ASTM D 6299: Standard Practice for Applying Statistical Quality
AssurEince Techniques to Evaluate Analytical Measurement System Performance, Annual Book of ASTM Standards, ASTM International, West Conshohocken, PA, 2002.
[5] ASTM D 3244: Standard Practice for Utilization of Test Data to Determine Conformance with Specifications, Annual Book of ASTM
Standards, ASTM International, West Conshohocken, PA, 1998.
[6] Hunter, J. S., "A One-Point Equivalent to the Shewhart Chart
with Western Electric Rules," Quality Engineering, Vol. 2, No. 1,
1989-90, pp. 13-19.
[7] ASTM E 178: Standard Practice for Dealing with Outlying Observations, Annual Book of ASTM Standards, ASTM International, West Conshohocken, PA, 2002.

APPENDIX
Statistical Quality Control Tools
Purpose

of this

Appendix

This appendix provides guidance to practitioners, including


worked examples, for the proper execution of the procedures
described in this chapter.
Pretreatment

of Test

ISO 5725

Title
Determination a n d Application of Precision
Data in Relation to Methods of Test
Accuracy (Trueness and Precision) of Measurement Methods and Results

REFERENCES
[1] ASTM E 456: Standard Terminology for Relating to Quality and
Statistics, Annual Book of ASTM Standards, ASTM International,
West Conshohocken, PA, 1997.
[2] ASTM E 69: Standard Practice for Conducting an Interlaboratory
Study to Determine the Precision of a Test Method, Annual Book
of ASTM Standards, ASTM International, West Conshohocken,
PA, 2000.

[Al]

/; = Yu

with no pretreatment being required.


An example of a sequence of results, Y/, from a single QC
sample is given in Column 2 of Table A l .
If [Yi'J = 1. . .M] is a sequence of results from a single check
standard, from multiple check standards having nominally
the same ARV, or from multiple check standards having different ARVs where the precision of the measurement system
does not vary with level, and if [X,:7 = 1. . .n) is the sequence
of corresponding ARVs, then

OTHER STANDARDS
No.
ISO 4259

Results

Throughout this appendix, [Yi:! = 1 . . .n] denotes a sequence


of measured test results. [/;:/= 1. . .n] will signify a sequence
of test results after pretreatment, if necessary.
If [Y,:/ = 1 . . .M] is a sequence of results from a single QC
sample, then

/,- = Yi-

[A2]

Xi

TABLE Al
Sequence
Number
I

QC/Check
Standard Result

1
2
3
4
5
6
7
8
9
10
11
12
13

55.3
55.8
56.3
56.1
55.8
55.5
55.3
55.4
56.6
56.1
55.0
55.5
55.5

Yi = Ii

Sequence
Number
I

QC/Check
Standard Result

14
15
16
17
18
19
20
21
22
23
24
25

55.2
56.5
55.7
55.6
55.2
55.7
56.1
56.3
55.2
55.4
55.4
55.6

Yi = Ii

CHAPTER 38: STATISTICAL

QUALITY ASSURANCE

TABLE A2
Sequence
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25

Difference
Result - ARV

(Yi)

Accepted Reference
Value
(ARV = Xi)

55.3
55.8
56.3
56.1
55.8
55.5
55.3
55.4
56.6
56.1
55.0
55.5
55.5
55.2
56.5
55.7
55.6
55.2
55.7
56.1
56.3
55.2
55.4
55.4
55.6

55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88

-0.58
-0.08
0.42
0.22
-0.08
-0.38
-0.58
-0.48
0.72
0.22
-0.88
-0.38
-0.38
-0.68

Check Standard
Result

li

0.62
-0.18
-0.28
-0.68
-0.18
0.22
0.42
-0.68
-0.48
-0.48
-0.28

The reproducibility standard deviation of the measurement


process must be essentially the same for EIII values [Xi].
An example of a sequence of results from a single check
standard is given in Table A2. The preprocessed result, /,-, is
given in Column 4 of Table A2.
If [Yi ] is a sequence of results from different check standards, and if the reproducibility varies with the level of the
accepted reference values, [Xi], then
li = (Yi - XiVOi

[A3]

where D, are estimates of the reproducibility standard deviation of the measurement process at levels [Xi].
Table A3 shows an example of results for multiple check
standards where the precision of the measurement system is
level dependent.

OF MEASUREMENT

PROCESSES

FOR

PETROLEUM

rection to accommodate the expected minimum and maximum of the data.


Example of a run chart for QC resultsThe first 15 results
from Column 2 of Table Al are plotted in sequence as they
are collected, as shown in Fig. Al. The data would be examined for unusual patterns.
Example of a run chart for multiple results from a single
check standardThe first 15 preprocessed results (differences) from Column 4 of Table A2 are plotted in sequence as
they are collected as shown in Fig. A2. The data would be examined for unusual patterns.
Example of a run chart for results from multiple check standardsThe first 15 preprocessed results (differences scaled
by <Ji) from Table A3 are plotted in sequence as they are collected, as shown in Fig. A3. The data would be examined for
unusual patterns.

TABLE A3
Result
Sequence
Number, i

Raw
Result
Yi

XI

Raw
Difference

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24

71.0
65.8
70.3
66.2
93.8
102.9
102.2
103.2

71.4
64.9
70.2
67.7
93.4
104.0
101.8
103.9
99.8
71.5
76.4
61.8
43.9
69.7
59.19
98.87
95.21
103.94
96.7
100.65
84.15
83.75
65.93
68.0

-0.40
0.90
0.10
-1.50
0.40
-1.10
0.40
-0.70
0.20
0.10
0.30
-0.60
0.20
0.01
0.31
0.76
-1.51
-0.17
-0.52
-0.95
0,17
-0.46
-0.77
0.19

100
71.6
76.7
61.2
44.1
69.71
59.5
99.63
93.7
103.77
96.18
99.7
84.32
83.29
65.16
68.19

ARV

Preprocessed
Result
li

1.14
1.10
1.13
1.11
1.26
1.33
1.31
1.32
1.30
1.14
1.16
1.08
0.98
1.13
1.06
1.30
1.27
1.32
1.28
1.31
1.21
1.21
1.10
1.12

-0.35
0.82
0.09
-1.35
0.32
-0.83
0.30
-0.53
0.15
0.09
0.26
-0.56
0.20
0.01
0.29
0.59
-1.19
-0.13
-0.41
-0.73
0.14
-0.38
-0.70
0.17

The Run Chart


A run chart is a plot of results in chronological order, which
can be used to screen data for unusual patterns. Preferably,
pretreated results are plotted. Use a run chart to screen data
for unusual patterns such as continuous trending in either
direction, unusual clustering, and cycles. Several nonrandom patterns are described in control chart literature
[3,4]. When control parameters have been added to a run
chart, it becomes a control chart of individual values
(/-chart).
Plot results on the chart. Plot the first result at the left, and
plot each subsequent point one increment to the right of its
predecessor. The points may be connected in sequence to facilitate interpretation of the run-chart.
Allow sufficient space in the x-axis direction to accommodate as many results as you expect to obtain from a consistent batch of material. Allow enough space in the y-axis di-

10

15

20

Result Sequence Number


FIG. A1Example of a run chart for QC results.

30

1052 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


Normality Checks

10

A normal probability plot (a special case of a q-q plot) is used


to test the assumption that the observations are normally distributed. Since the control chart and limits prescribed in this
practice are based on the assumption that the data behavior
is adequately modeled by the Normal distribution, it is recommended that a test of this Normality assumption be
conducted.
To construct a normal probability plot:
1. Create a column of the observations sorted in ascending
order.
2. Select the appropriate column from Table Al based on the
number of observations (n).
3. Plot each observation in the sorted column (y-value)
against its corresponding value from Table A4 (z-value).
Visually inspect the plot for an approximately linear relationship. If the results are normally distributed, the plot
should be approximately linear. Major deviations from linecirity are an indication of non-normal distributions of the
differences.
Note Al: The assessment methodology of the Normal
probability plot advocated in this practice is strictly visual, due to its simplicity. For statistically more rigorous assessment techniques, users are advised to consult a statistician.

15

Result Sequence Number


FIG. A2Run chart for multiple results from a single check
standard.

10

Anderson-Darling
Statistic
The Anderson-Darling Statistic is used to test for normality.
The test involves the following steps:
Order the non-outlying results such that Xi X2 ^ . . . . Xn
Obtain standardized variate from the Xj's as follows:

15

Result Sequence Number

FIG. A3Run chart for results from multiple check standards.

Wi = {xi -

[A4]

x)/s

TABLE A4z-values.
n

Order

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32

-1.83
-1.28
-0.97
-0.73
-0.52
-0.34
-0.17
0.00
0.17
0.34
0.52
0.73
0.97
1.28
1.83

-1.86
-1.32
-1.01
-0.78
-0.58
-0.40
-0.24
-0.08
0.08
0.24
0.40
0.58
0.78
1.01
1.32
1.86

-1.89
-1.35
-1.05
-0.82
-0.63
-0.46
-0.30
-0.15
0.00
0.15
0.30
0.46
0.63
0.82
1.05
1.35
1.89

-1.91
-1.38
-1.09
-0.86
-0.67
-0.51
-0.36
-0.21
-0.07
0.07
0.21
0.36
0.51
0.67
0.86
1.09
1.38
1.91

-1.94
-1.41
-1.12
-0.90
-0.72
-0.55
-0.41
-0.27
-0.13
0.00
0.13
0.27
0.41
0.55
0.72
0.90
1.12
1.41
1.94

-1.96
-1.44
-1.15
-0.93
-0.76
-0.60
-0.45
-0.32
-0.19
-0.06
0.06
0.19
0.32
0.45
0.60
0.76
0.93
1.15
1.44
1.96

-1.98
-1.47
-1.18
-0.97
-0.79
-0.64
-0.50
-0.37
-0.24
-0.12
0.00
0.12
0.24
0.37
0.50
0.64
0.79
0.97
1.18
1.47
1.98

-2.00
-1.49
-1.21
-1.00
-0.83
-0.67
-0.54
-0.41
-0.29
-0.17
-0.06
0.06
0.17
0.29
0.41
0.54
0.67
0.83
1.00
1.21
1.49
2.00

-2.02
-1.51
-1.23
-1.03
-0.86
-0.71
-0.58
-0.45
-0.33
-0.22
-0.11
0.00
0.11
0.22
0.33
0.45
0.58
0.71
0.86
1.03
1.23
1.51
2.02

-2.04
-1.53
-1.26
-1.05
-0.89
-0.74
-0.61
-0.49
-0.37
-0.26
-0.16
-0.05
0.05
0.16
0.26
0.37
0.49
0.61
0.74
0.89
1.05
1.26
1.53
2.04

-2.05
-1.55
-1.28
-1.08
-0.92
-0.77
-0.64
-0.52
-0.41
-0.31
-0,20
-0.10
0.00
0.10
0.20
0.31
0.41
0.52
0.64
0.77
0.92
1.08
1.28
1.55
2.05

-2.07
-1.57
-1.30
-1.10
-0.94
-0.80
-0.67
-0.56
-0.45
-0.34
-0.24
-0.15
-0.05
0.05
0.15
0.24
0.34
0.45
0.56
0.67
0.80
0.94
1.10
1.30
1.57
2.07

-2.09
-1.59
-1.32
-1.13
-0.97
-0.83
-0.70
-0.59
-0.48
-0.38
-0.28
-0.19
-0.09
0.00
0.09
0.19
0.28
0.38
0.48
0.59
0.70
0.83
0.97
1.13
1.32
1.59
2.09

-2.10
-1.61
-1.35
-1.15
-0.99
-0.85
-0.73
-0.62
-0.51
-0.41
-0.32
-0.23
-0.13
-0.04
0.04
0.13
0.23
0.32
0.41
0.51
0.62
0.73
0.85
0.99
1.15
1.35
1.61
2.10

-2.11
-1.63
-1.36
-1.17
-1.01
-0.88
-0.76
-0.65
-0.54
-0.45
-0.35
-0.26
-0.17
-0.09
0.00
0.09
0.17
0.26
0.35
0.45
0.54
0.65
0.76
0.88
1.01
1.17
1.36
1.63
2.11

-2.13
-1.64
-1.38
-1.19
-1.04
-0.90
-0.78
-0.67
-0.57
-0.48
-0.39
-0.30
-0.21
-0.13
-0.04
0.04
0.13
0.21
0.30
0.39
0.48
0.57
0.67
0.78
0.90
1.04
1.19
1.38
1.64
2.13

-2.14
-1.66
-1.40
-1.21
-1.06
-0.93
-0.81
-0.70
-0.60
-0.51
-0.42
-0.33
-0.25
-0.16
-0.08
0.00
0.08
0.16
0.25
0.33
0.42
0.51
0.60
0.70
0.81
0.93
1.06
1.21
1.40
1.66
2.14

-2.15
-1.68
-1.42
-1.23
-1.08
-0.95
-0.83
-0.72
-0.63
-0.53
-0.45
-0.36
-0.28
-0.20
-0.12
-0.04
0.04
0.12
0.20
0.28
0.36
0.45
0.53
0.63
0.72
0.83
0.95
1.08
1.23
1.42
1.68
2.15

CHAPTER 38: STATISTICAL

QUALITY ASSURANCE

OF MEASUREMENT

PROCESSES

FOR

PETROLEUM

Table A4 (cont.)
n

Order

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50

-2.17
-1.69
-1.43
-1.25
-1.10
-0.97
-0.85
-0.75
-0.65
-0.56
-0.47
-0.39
-0.31
-0.23
-0.15
-0.08
0.00
0.08
0.15
0.23
0.31
0.39
0.47
0.56
0.65
0.75
0.85
0.97
1.10
1.25
1.43
1.69
2.17

-2.18
-1.70
-1.45
-1.26
-1.12
-0.99
-0.87
-0.77
-0.67
-0.58
-0.50
-0.42
-0.34
-0.26
-0.19
-0.11
-0.04
0.04
0.11
0.19
0.26
0.34
0.42
0.50
0.58
0.67
0.77
0.87
0.99
1.12
1.26
1.45
1.70
2.18

-2.19
-1.72
-1.47
-1.28
-1.13
-1.01
-0.89
-0.79
-0.70
-0.61
-0.52
-0.44
-0.37
-0.29
-0.22
-0.14
-0.07
0.00
0.07
0.14
0.22
0.29
0.37
0.44
0.52
0.61
0.70
0.79
0.89
1.01
1.13
1.28
1.47
1.72
2.19

-2.20
-1.73
-1.48
-1.30
-1.15
-1.02
-0.91
-0.81
-0.72
-0.63
-0.55
-0.47
-0.39
-0.32
-0.25
-0.17
-0.10
-0.03
0.03
0.10
0.17
0.25
0.32
0.39
0.47
0.55
0.63
0.72
0.81
0.91
1.02
1.15
1.30
1.48
1.73
2.20

-2.21
-1.74
-1.49
-1.31
-1.17
-1.04
-0.93
-0.83
-0.74
-0.65
-0.57
-0.49
-0.42
-0.35
-0.27
-0.20
-0.14
-0.07
0.00
0.07
0.14
0.20
0.27
0.35
0.42
0.49
0.57
0.65
0.74
0.83
0.93
1.04
1.17
1.31
1.49
1.74
2.21

-2.22
-1.76
-1.51
-1.33
-1.18
-1.06
-0.95
-0.85
-0.76
-0.67
-0.59
-0.52
-0.44
-0.37
-0.30
-0.23
-0.17
-0.10
-0.03
0.03
0.10
0.17
0.23
0.30
0.37
0.44
0.52
0.59
0.67
0.76
0.85
0.95
1.06
1.18
1.33
1.51
1.76
2.22

-2.23
-1.77
-1.52
-1.34
-1.20
-1.08
-0.97
-0.87
-0.78
-0.69
-0.62
-0.54
-0.47
-0.40
-0.33
-0.26
-0.19
-0.13
-0.06
0.00
0.06
0.13
0.19
0.26
0.33
0.40
0.47
0.54
0.62
0.69
0.78
0.87
0.97
1.08
1.20
1.34
1.52
1.77
2.23

-2.24
-1.78
-1.53
-1.36
-1.21
-1.09
-0.98
-0.89
-0.80
-0.71
-0.64
-0.56
-0.49
-0.42
-0.35
-0.29
-0.22
-0.16
-0.09
-0.03
0.03
0.09
0.16
0.22
0.29
0.35
0.42
0.49
0.56
0.64
0.71
0.80
0.89
0.98
1,09
1.21
1.36
1.53
1.78
2.24

-2.25
-1.79
-1.55
-1.37
-1.23
-1.11
-1.00
-0.90
-0.82
-0.73
-0.66
-0.58
-0.51
-0.44
-0.38
-0.31
-0.25
-0.18
-0.12
-0.06
0.00
0.06
0.12
0.18
0.25
0.31
0.38
0.44
0.51
0.58
0.66
0.73
0.82
0.90
1.00
1.11
1.23
1.37
1.55
1.79
2.25

-2.26
-1.80
-1.56
-1.38
-1.24
-1.12
-1.02
-0.92
-0.83
-0.75
-0.67
-0.60
-0.53
-0.46
-0.40
-0.33
-0.27
-0.21
-0.15
-0.09
-0.03
0.03
0.09
0.15
0.21
0.27
0.33
0.40
0.46
0.53
0.60
0.67
0.75
0.83
0.92
1.02
1.12
1.24
1.38
1.56
1.80
2.26

-2.27
-1.81
-1.57
-1.40
-1.26
-1.14
-1.03
-0.94
-0.85
-0.77
-0.69
-0.62
-0.55
-0.48
-0.42
-0.36
-0.30
-0.24
-0.18
-0.12
-0.06
0.00
0.06
0.12
0.18
0.24
0.30
0.36
0.42
0.48
0.55
0.62
0.69
0.77
0.85
0.94
1.03
1.14
1.26
1.40
1.57
1.81
2.27

-2.28
-1.82
-1.58
-1.41
-1.27
-1.15
-1.05
-0.95
-0.87
-0.79
-0.71
-0.64
-0.57
-0.50
-0.44
-0.38
-0.32
-0.26
-0.20
-0.14
-0.09
-0.03
0.03
0.09
0.14
0.20
0.26
0.32
0.38
0.44
0.50
0.57
0.64
0.71
0.79
0.87
0.95
1.05
1.15
1.27
1.41
1.58
1.82
2.28

-2.29
-1.83
-1.59
-1.42
-1.28
-1.16
-1.06
-0.97
-0.88
-0.80
-0.73
-0.66
-0.59
-0.52
-0.46
-0.40
-0.34
-0.28
-0.22
-0.17
-0.11
-0.06
0.00
0.06
0.11
0.17
0.22
0.28
0.34
0.40
0.46
0.52
0.59
0.66
0.73
0.80
0.88
0.97
1.06
1.16
1.28
1.42
1.59
1.83
2.29

-2.29
-1.84
-1.60
-1.43
-1.29
-1.18
-1.07
-0.98
-0.90
-0.82
-0.74
-0.67
-0.61
-0.54
-0.48
-0.42
-0.36
-0.30
-0.25
-0.19
-0.14
-0.08
-0.03
0.03
0.08
0.14
0.19
0.25
0.30
0.36
0.42
0.48
0.54
0.61
0.67
0.74
0.82
0.90
0.98
1.07
1.18
1.29
1.43
1.60
1.84
2.29

-2.30
-1.85
-1.61
-1.44
-1.31
-1.19
-1.09
-1.00
-0.91
-0.83
-0.76
-0.69
-0.63
-0.56
-0.50
-0.44
-0.38
-0.33
-0.27
-0.21
-0.16
-0.11
-0.05
0.00
0.05
0.11
0.16
0.21
0.27
0.33
0.38
0.44
0.50
0.56
0.63
0.69
0.76
0.83
0.91
1.00
1.09
1.19
1.31
1.44
1.61
1.85
2.30

-2.31
-1.86
-1.62
-1.45
-1.32
-1.20
-1.10
-1.01
-0.93
-0.85
-0.78
-0.71
-0.64
-0.58
-0.52
-0.46
-0.40
-0.35
-0.29
-0.24
-0.18
-0.13
-0.08
-0.03
0.03
0.08
0.13
0.18
0.24
0.29
0.35
0.40
0.46
0.52
0.58
0.64
0.71
0.78
0.85
0.93
1.01
1.10
1.20
1.32
1.45
1.62
1.86
2.31

-2.32
-1.87
-1.64
-1.47
-1.33
-1.21
-1.11
-1.02
-0.94
-0.86
-0.79
-0.72
-0.66
-0.60
-0.54
-0.48
-0.42
-0.37
-0.31
-0.26
-0.21
-0.15
-0.10
-0.05
0.00
0.05
0.10
0.15
0.21
0.26
0.31
0.37
0,42
0.48
0.54
0.60
0.66
0.72
0.79
0.86
0.94
1.02
1.11
1.21
1.33
1.47
1.64
1.87
2.32

-2.33
-1.88
-1.64
-1.48
-1.34
-1.23
-1.13
-1.04
-0.95
-0.88
-0.81
-0.74
-0.67
-0.61
-0.55
-0.50
-0.44
-0.39
-0.33
-0.28
-0.23
-0.18
-0.13
-0.08
-0.03
0.03
0.08
0.13
0.18
0.23
0.28
0.33
0.39
0.44
0.50
0.55
0.61
0.67
0.74
0.81
0.88
0.95
1.04
1.13
1.23
1.34
1.48
1.64
1.88
2.33

for (I = 1 . . . n), where s is sample standard deviation of the


results, and x is the average of the results.
Convert the Wi's to standard normal cumulative probabilities Pi's using the cumulative probability table for the standardized normal variate z (Table A5):
Pi = Probability (z < Wj)

[A5]

Compute A as
( 2 i - l)[ln(p;) + ln(l - p + i - 0
12 _ i s l _

- n

[A6]

Compute A^* as
A^ I +

0.75 I 2.25
n
n^

[A7]

If the computed value of A^* exceeds 0.752, then the hypothesis of normality is rejected for a 5% level test.
Example of Normal Probability Plot for QC ResultsOnce
15 results have been obtained (Table Al), they are sorted in

ascending order and paired with the corresponding z-values


from Table A4. The paired results (Table A6) are plotted as
(x,y) points (Figs. A3 and A4). A line can be added to the plot
to facilitate examination of the data for deviations from linearity.
For the above example, the w^ emd Pi values used in the calculation of the Anderson-Darling statistic are shown in Table
A6, as is the individual terms in the summation for A^. The
value for A^ is 0.415, and the value for A^* is 0.440. Since this
value is less than 0.752, the hypothesis of normality is accepted at the 95% confidence level.
Example of Normal Probability Plot for Multiple Results
From a Single Check StandardThe first 15 preprocessed results (Table A2, Column 4) are sorted in ascending order and
paired with the corresponding z-values from Table A4. The
paired results (Table A7) are plotted as x,y points (Fig. A5). A
line can be added to the plot to facilitate examination of the
data for deviations from lineeuity.
For this example, the Wi, and pi values used in the calculation of the Anderson-Darling statistic are shown in Table A7,

TABLE A5Pi values. Probability ( z < wj) where w, is the sum of the number in the left column and top row.
-0.09

-0.08

-0.07

-0.06

-0.05

-0.04

-0.03

-0.02

-0.01

0.00

0.0

0.0002
0.0002
0.0003
0.0005
0.0007
0.0010
0.0014
0.0019
0.0026
0.0036
0.0048
0.0064
0.0084
0.0110
0.0143
0.0183
0.0233
0.0294
0.0367
0.0455
0.0559
0.0681
0.0823
0.0985
0.1170
0.1379
0.1611
0.1867
0.2148
0.2451
0.2776
0.3121
0.3483
0.3859
0.4247
0.4641

0.0002
0.0003
0.0004
0.0005
0.0007
0.0010
0.0014
0.0020
0.0027
0.0037
0.0049
0.0066
0.0087
0.0113
0.0146
0.0188
0.0239
0.0301
0.0375
0.0465
0.0571
0.0694
0.0838
0.1003
0.1190
0.1401
0.1635
0.1894
0.2177
0.2483
0.2810
0.3156
0.3520
0.3897
0.4286
0.4681

0.0002
0.0003
0.0004
0.0005
0.0008
0.0011
0.0015
0.0021
0.0028
0.0038
0.0051
0.0068
0.0089
0.0116
0.0150
0.0192
0.0244
0.0307
0.0384
0.0475
0.0582
0.0708
0.0853
0.1020
0.1210
0.1423
0.1660
0.1922
0.2206
0.2514
0.2843
0.3192
0.3557
0.3936
0.4325
0.4721

0.0002
0.0003
0.0004
0.0006
0.0008
0.0011
0.0015
0.0021
0.0029
0.0039
0.0052
0.0069
0.0091
0.0119
0.0154
0.0197
0.0250
0.0314
0.0392
0.0485
0.0594
0.0721
0.0869
0.1038
0.1230
0.1446
0.1685
0.1949
0.2236
0.2546
0.2877
0.3228
0.3594
0.3974
0.4364
0.4761

0.0002
0.0003
0.0004
0.0006
0.0008
0.0011
0.0016
0.0022
0.0030
0.0040
0.0054
0.0071
0.0094
0.0122
0.0158
0.0202
0.0256
0.0322
0.0401
0.0495
0.0606
0.0735
0.0885
0.1056
0.1251
0.1469
0.1711
0.1977
0.2266
0.2578
0.2912
0.3264
0.3632
0.4013
0.4404
0.4801

0.0002
0.0003
0.0004
0.0006
0.0008
0.0012
0.0016
0.0023
0.0031
0.0041
0.0055
0.0073
0.0096
0.0125
0.0162
0.0207
0.0262
0.0329
0.0409
0.0505
0.0618
0.0749
0.0901
0.1075
0.1271
0.1492
0.1736
0.2005
0.2296
0.2611
0.2946
0.3300
0.3669
0.4052
0.4443
0.4840

0.0002
0.0003
0.0004
0.0006
0.0009
0.0012
0.0017
0.0023
0.0032
0.0043
0.0057
0.0075
0.0099
0.0129
0.0166
0.0212
0.0268
0.0336
0.0418
0.0516
0.0630
0.0764
0.0918
0.1093
0.1292
0.1515
0.1762
0.2033
0.2327
0.2643
0.2981
0.3336
0.3707
0.4090
0.4483
0.4880

0.0002
0.0003
0.0005
0.0006
0.0009
0.0013
0.0018
0.0024
0.0033
0.0044
0.0059
0.0078
0.0102
0.0132
0.0170
0.0217
0.0274
0.0344
0.0427
0.0526
0.0643
0.0778
0.0934
0.1112
0.1314
0.1539
0.1788
0.2061
0.2358
0.2676
0.3015
0.3372
0.3745
0.4129
0.4522
0.4920

0.0002
0.0003
0.0005
0.0007
0.0009
0.0013
0.0018
0.0025
0.0034
0.0045
0.0060
0.0080
0.0104
0.0136
0.0174
0.0222
0.0281
0.0351
0.0436
0.0537
0.0655
0.0793
0.0951
0.1131
0.1335
0.1562
0.1814
0.2090
0.2389
0.2709
0.3050
0.3409
0.3783
0.4168
0.4562
0.4960

0.0002
0.0003
0.0005
0.0007
0.0010
0.0013
0.0019
0.0026
0.0035
0.0047
0.0062
0.0082
0.0107
0.0139
0.0179
0.0228
0.0287
0.0359
0.0446
0.0548
0.0668
0.0808
0.0968
0.1151
0.1357
0.1587
0.1841
0.2119
0.2420
0.2743
0.3085
0.3446
0.3821
0.4207
0.4602
0.5000

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
3.0
3.1
3.2
3.3
3.4
3.5

0.5000
0.5398
0.5793
0.6179
0.6554
0.6915
0.7257
0.7580
0.7881
0.8159
0.8413
0.8643
0.8849
0.9032
0.9192
0.9332
0.9452
0.9554
0.9641
0.9713
0.9772
0.9821
0.9861
0.9893
0.9918
0.9938
0.9953
0.9965
0.9974
0.9981
0.9987
0.9990
0.9993
0.9995
0.9997
0.9998

0.5040
0.5438
0.5832
0.6217
0.6591
0.6950
0.7291
0.7611
0.7910
0.8186
0.8438
0.8665
0.8869
0.9049
0.9207
0.9345
0.9463
0.9564
0.9649
0.9719
0.9778
0.9826
0.9864
0.9896
0.9920
0.9940
0.9955
0.9966
0.9975
0.9982
0.9987
0.9991
0.9993
0.9995
0.9997
0.9998

0.5080
0.5478
0.5871
0.6255
0.6628
0.6985
0.7324
0.7642
0.7939
0.8212
0.8461
0.8686
0.8888
0.9066
0.9222
0.9357
0.9474
0.9573
0.9656
0.9726
0.9783
0.9830
0.9868
0.9898
0.9922
0.9941
0.9956
0.9967
0.9976
0.9982
0.9987
0.9991
0.9994
0.9995
0.9997
0.9998

0.5120
0.5517
0.5910
0.6293
0.6664
0.7019
0.7357
0.7673
0.7967
0.8238
0.8485
0.8708
0.8907
0.9082
0.9236
0.9370
0.9484
0.9582
0.9664
0.9732
0.9788
0.9834
0.9871
0.9901
0.9925
0.9943
0.9957
0.9968
0.9977
0.9983
0.9988
0.9991
0.9994
0.9996
0.9997
0.9998

0.5160
0.5557
0.5948
0.6331
0.6700
0.7054
0.7389
0.7704
0.7995
0.8264
0.8508
0.8729
0.8925
0.9099
0.9251
0.9382
0.9495
0.9591
0.9671
0.9738
0.9793
0.9838
0.9875
0.9904
0.9927
0.9945
0.9959
0.9969
0.9977
0.9984
0.9988
0.9992
0.9994
0.9996
0.9997
0.9998

0.5199
0.5596
0.5987
0.6368
0.6736
0.7088
0.7422
0.7734
0.8023
0.8289
0.8531
0.8749
0.8944
0.9115
0.9265
0.9394
0.9505
0.9599
0.9678
0.9744
0.9798
0.9842
0.9878
0.9906
0.9929
0.9946
0.9960
0.9970
0.9978
0.9984
0.9989
0.9992
0.9994
0.9996
0.9997
0.9998

0.5239
0.5636
0.6026
0.6406
0.6772
0.7123
0.7454
0.7764
0.8051
0.8315
0.8554
0.8770
0.8962
0.9131
0.9279
0.9406
0.9515
0.9608
0.9686
0.9750
0.9803
0.9846
0.9881
0.9909
0.9931
0.9948
0.9961
0.9971
0.9979
0.9985
0.9989
0.9992
0.9994
0.9996
0.9997
0.9998

0.5279
0.5675
0.6064
0.6443
0.6808
0.7157
0.7486
0.7794
0.8078
0.8340
0.8577
0.8790
0.8980
0.9147
0.9292
0.9418
0.9525
0.9616
0.9693
0.9756
0.9808
0.9850
0.9884
0.9911
0.9932
0.9949
0.9962
0.9972
0.9979
0.9985
0.9989
0.9992
0.9995
0.9996
0.9997
0.9998

0.5319
0.5714
0.6103
0.6480
0.6844
0.7190
0.7517
0.7823
0.8106
0.8365
0.8599
0.8810
0.8997
0.9162
0.9306
0.9429
0.9535
0.9625
0.9699
0.9761
0.9812
0.9854
0.9887
0.9913
0.9934
0.9951
0.9963
0.9973
0.9980
0.9986
0.9990
0.9993
0.9995
0.9996
0.9997
0.9998

0.5359
0.5753
0.6141
0.6517
0.6879
0.7224
0.7549
0.7852
0.8133
0.8389
0.8621
0.8830
0.9015
0.9177
0.9319
0.9441
0.9545
0.9633
0.9706
0.9767
0.9817
0.9857
0.9890
0.9916
0.9936
0.9952
0.9964
0.9974
0.9981
0.9986
0.9990
0.9993
0.9995
0.9997
0.9998
0.9998

-3.5
-3.4
-3.3
-3.2
-3.1
-3.0
-2.9
-2.8
-2.7
-2.6
-2.5
-2.4
-2.3
-2.2
-2.1
-2.0
-1.9
-1.8
-1.7
-1.6
-1.5
-1.4
-1.3
-1.2
-1.1

-1
-0.9
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1

CHAPTER 38: STATISTICAL QUALITY ASSURANCE OF MEASUREMENT PROCESSES FOR PETROLEUM


as is the individual terms in the summation for A^. The value
for A^ is 0.415, and the value for A^* is 0.440. Since this value
is less than 0.752, the hypothesis of normality is accepted at
the 9 5 % confidence level.
Example of Normal Probability Plot for Results from^ Multiple Check StandardsThe first 15 preprocessed results (Table
A3, Column 6) are sorted in ascending order and paired with
the corresponding z-values from Table A4. The paired results
(Table A8) are plotted as x,y points (Fig. A6). A line can be
added to the plot to facilitate examination of the data for deviations from linearity.

Original
Sequence #, I
11
14
1
7
8
6
12
13
2
5
10
4
3
15
9

zvalue
1.83
-1.28
-0.97
-0.73
-0.52
-0.34
-0.17
0.00
0.17
0.34
0.52
0.73
0.97
1.28
1.83

TABLE A6
Sorted
Result
55.0
55.2
55.3
55.3
55.4
55.5
55.5
55.5
55.8
55.8
56.1
56.1
56.3
56.5
56.6

-1.47
-1.07
-0.86
-0.86
-0.66
-0.46
-0.46
-0.46
0.15
0.15
0.76
0.76
1.16
1.57
1.77

0.07
0.14
0.19
0.19
0.25
0.32
0.32
0.32
0.56
0.56
0.78
0.78
0.88
0.94
0.96

i^Term
in [A6]
-5.91
-14.35
-18.70
-21.94
-25.77
-21.44
-25.34
-22.80
-16.52
-18.46
-11.50
-10.80
-8.65
-5.79
-3.25

FIG. A5Example of a normal probability plot for multiple results from a single check standard.

Sort*
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15

Original
Sequence #
11
14
1
7
8
6
12
13
2
5
10
4
3
15
9

TABLE A8
Sorted
Result
z-value
1.83
1.28
0.97
0.73
0.52
0.34
0.17
0
0.17
0.34
0.52
0.73
0.97
1.28
1.83

-1.35
-0.83
-0.56
-0.53
-0.35
0.01
0.09
0.09
0.15
0.2
0.26
0.29
0.3
0.32
0.82

i* Temi
in [A6]
-3.12
-1.94
-1.32
-1.25
-0.84
-0.02
0.16
0.16
0.30
0.41
0.55
0.62
0.64
0.69
1.83

0.00
0.03
0.09
0.11
0.20
0.49
0.56
0.56
0.62
0.66
0.71
0.73
0.74
0.75
0.97

-10.41
-15.11
-18.58
-24.98
-25.59
-19.68
-19.93
-21.05
-22.33
-20.75
-11.91
-9.73
-9.99
-8.34
-1.02

z-values

FIG. A4Example of a normal probability plot for QC results.


TABLE A7
Sort#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15

Original
Sequence *
11
14
1
7
8
6
12
13
2
5
10
4
3
15
9

Sorted
Result
-0.88
-0.68
-0.58
-0.58
-0.48
-0.38
-0.38
-0.38
-0.08
-0.08
0.22
0.22
0.42
0.62
0.72

zvalue
-1.83
-1.28
-0.97
-0.73
-0.52
-0.34
-0.17
0
0.17
0.34
0.52
0.73
0.97
1.28
1.83

Pi

-1.47
-1.07
-0.86
-0.86
-0.66
-0.46
-0.46
-0.46
0.15
0.15
0.76
0.76
1.16
1.57
1.77

0.07
0.14
0.19
0.19
0.25
0.32
0.32
0.32
0.56
0.56
0.78
0.78
0.88
0.94
0.96

i* Tenn
in [A6]
-5.91
-14.35
-18.70
-21.94
-25.77
-21.44
-25.34
-22.80
-16.52
-18.46
-11.50
-10.80
-8.65
-5.79
-3.25

FIG. A6Example of a normal probability plot for results


from multiple check standards.

The Control Chart


I-Chart
The Control Chart of Individual Values (/-Chart) is a run
chart to which control limits and center line have been
added. In order to establish placement positions of the control limits for the I chart, an estimate of the process variability will need to be obtained from the data. While there are

1056

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

several statistical techniques that can be used for this purpose, this practice advocates use of an MR (Moving Range of
Two) chart for its simplicity axid robustness to outliers.
Produce an /-Chart only after a m i n i m u m of 15 preprocessed results have been obtained from the measurement system, and the data have been screened (8.3.1 and 8.3.2) and
tested for normality (A3).
A horizontal center line is added at the level of the mean of
eJl the results, / :

lli
(A8)
Upper and lower control limits are added, also, computed
from the average moving range of two:

equation:
EWMAi = h
EWMAi = (1

A)WMA;-i + \Ii

(A15)

where X is the exponential weighting factor. For application


of this practice, a A value of 0.4 is recommended.
Note A2: For the EWMA trend, a A value of 0.4 emulates
closely t h e run rule effects of conventional control
charts, w h i l e a value of 0.2 h a s o p t i m a l prediction
properties for the next e x p e c t e d value. In addition,
these A values also conveniently place t h e control limits (3-sigma) for the EWMA trend at the 1 (for A = 0.2)
to 1.5-sigma (for A = 0.4) values for I chart.
The control limits for the EWMA chart are calculated using
a weight (A) as follows:

S|/.-..
MR =

(A14)

UCLx = 1 + 2.66MR

(A16)

LCLx = / -

(A17)

UCLi = 1 + 2.66 MR,

(AlO)

LCL, = 7 - 2.66 MR.

(All)

Individual values that are outside the upper or lower control


limits are indications of a n unstable system, a n d efforts
should be made to determine the cause. Optionally, any one
of the following occurrences should be considered as potential signals of instability:
1. Two out of three consecutive results on the /-Chart that are
more than 1.77 MR distant from the center line in the same
direction;
2. Five consecutive results on the /-Chart that are more than
0.89 MR distant from the center line in the same direction;
3. Eight or more consecutive points in the /-Chart that fall on
the same side of the center line.

2.66MR

E x a m p l e s o f C o n t r o l C h a r t s f o r QC
and Check Standard Results
Example of an MR Chart for QC ResultsMRi values for the
data from Table Al are calculated and plotted in sequence.
After 15 results are obtained, the MR = 0.500 value is calculated and added to the plot. Computations are shown in Table
A9. A UCLMR=
1.64 is a d d e d to produce the MR Chart
(Fig. A7).
Example of I Chart and EWMA Overlay for QC ResultsThe
average of the first 15 QC results (Table A9, Column 2) is calculated and plotted on the r u n chart as 7 = 55.73. The upper

TABLE A9

MR-Chart

Sequence Number,
I

A Moving Range of Two {MR) Chart is obtained by plotting


the sequential range of two values given by:
MRi = \Ii - /;-,!

(A12)

and connecting each point.


The upper control limit for the MR chart is given by
UCLMR

= 3.27

AIR.

There is no lower control limit for an

(A13)

MR-chait.

EWMA-Overlay
A EWMA overlay is a trend line constructed from Exponentially Weighted Moving Average {EWMA) values calculated
using the I-values. The EWMA trend line is typically overlaid
on the /-chart to enhance its sensitivity in detecting m e a n
shifts that are small relative to the measurement system precision. Each EWMA value is a weighted average of the current result and previous results, with the weights decreasing
exponentially with the age of the reading.
A sequence of values, EWMA,, are calculated, and overlaid
on the /-chart and connected. Use the following recursion

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Average
16
17
18
19
20
21
22
23
24
25

QC Result
(Y, = li)
55.3
55.8
56.3
56.1
55.8
55.5
55.3
55.4
56.6
56.1
55
55.5
55.5
55.2
56.5

Moving Range
MRi
0.5
0.5
0.2
0.3
0.3
0.2
0.1
1.2
0.5
1.1
0.5
0.0
0.3
1.3

55.73

0.500

55.7
55.6
55.2
55.7
56.1
56.3
55.2
55.4
55.4
55.6

0.8
0.1
0.4
0.5
0.4
0.2
1.1
0.2
0.0
0.2

EWMAi
55.3
55.50
55.82
55.93
55.88
55.73
55.56
55.49
55.94
56.00
55.60
55.56
55.54
55.40
55.84
55.78
55.71
55.51
55.58
55.79
55.99
55.68
55.57
55.50
55.54

CHAPTER 38: STATISTICAL QUALITY ASSURANCE OF MEASUREMENT PROCESSES FOR PETROLEUM

10

15

10

20

Result Sequence Number


FIG. A7Example of an MR chart for QC results.

57.5

20

FIG. A9Example of a MR chart for multiple results from a


single check standard.
o EWMA Value

o Result Value

EWMA Value

acL,

57
56.5
^

15

Result Sequence Number

UCL,
VCL,

acLEtna

56
LCL,

(0 55.5

LCL'EtmA

55
54.5

LCL-,
10

LCL,

15

20

30

Result Sequence Number


54

10

15

20

25

30

Result Sequence Number

FIG. AlOExample of an l-Chart with EWMA overlay for multiple results from a single check standard.

FIG. A8Example of an i-Chart with EWMA overlay for QC


results.

TABLE AlO
Sequence Number

and lower control limits are calculated from Eqs A6 and A7


as 54.40 and 57.06 and added to the r u n chart to produce the
/ chart (Fig. A8). EWMA values (Table A9, Column 4) and
EWMA control limits, 55.06 and 56.39, are overlaid on the /
chart. Additional results and calculated EWMA values are
added as they are determined.
Example of an MR Chart for Multiple Results From a Single
Check StandardMRi values are calculated and plotted in sequence. After 15 results are obtained (Table A2), the MR
value is calculated and added to the plot. A UCLMR is added
to produce the MR Chart (Fig. A9).
Example of I Chart and EWMA Overlay for Multiple Results
From a Single Check StandardThe average of the first 15 QC
results (Table^A2, Column 4) is calculated and plotted on the
r u n chart as / . The upper and lower control limits cU"e calculated from Eqs A6 and A7 and added to the r u n chart to produce the I chart. EWMA values and EWMA control limits
may be overlaid on the I chart (Fig. AlO). Additional results
and calculated EWMA values are added as they are determined. The MR values for this example are shown in Table
AlO, Column 3.)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Average
16
17
18
19
20
21
22
23
24
25

Check Standard
Result (li)

Moving Range
MRi

-0.58
-0.08
0.42
0.22
-0.08
-0.38
-0.58
-0.48
0.72
0.22
-0.88
-0.38
-0.38
-0.68
0.62

0.5
0.5
0.2
0.3
0.3
0.2
0.1
1.2
0.5
1.1
0.5
0.0
0.3
1.3

-0.153

0.500

-0.18
-0.28
-0.68
-0.18
0.22
0.42
-0.68
-0.48
-0.48
-0.28

0.8
0.1
0.4
0.5
0.4
0.2
1.1
0.2
0.0
0.2

EWMAi
-0.58
-0.38
-0.06
0.05
-0.00
-0.15
-0.32
-0.39
0.06
0.12
-0.28
-0.32
-0.34
-0.48
-0.04
-0.10
-0.17
-0.37
-0.30
-0.09
0.11
-0.20
-0.31
-0.38
-0.34

1058

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Example of an MR Chart for Results From Multiple Check


StandardsMRi
values are calculated a n d plotted in sequence. After 15 results are obtained (Table A3, Column 6,
displayed again in Table A l l ) , the MR value is calculated a n d
added to the plot. A UCLMR is added to produce the MR Chart
(Fig. A l l ) .
Example of I Chart and EWMA Overlay for Results From Multiple Check StandardsThe average of the first 15 QC results
(Table A3, column 6) is calculated and plotted on the r u n chart
as I. The upper and lower control limits are Ccdculated from
equations A6 a n d A7 and added to the r u n chzirt to produce
the I chart. EWMA values emd EWMA control limits may be
overlaid on the I chart (Fig. A12). AdditioncJ results and calculated EWMA values are added as they are determined.

Result Value

. EWMA Value

DCL,

CC 1

PCi,

*(D

-LCL,

10

15

20

25

30

Result Sequence Number

FIG. A12Example of an l-Chart with EWMA overlay for results from multiple check standards.

TABLEAU
Result Sequence
Number, i

Preprocessed Result

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15

T-Test
Moving Range
MRi

EWMAi

-0.35
0.82
0.09
-1.35
0.32
-0.83
0.30
-0.53
0.15
0.09
0.26
-0.56
0.20
0.01
0.29

1.17
0.73
1.44
1.67
1.15
1.13
0.83
0.68
0.06
0.17
0.82
0.76
0.19
0.28

-0.35
0.12
0.11
-0.48
-0.16
-0.43
-0.14
-0.29
-0.12
-0.03
0.08
-0.17
-0.02
-0.01
0.11

erage

-0.073

0.791

16
17
18
19
20
21
22
23
24

0.59
-1.19
-0.13
-0.41
-0.73
0.14
-0.38
-0.7
0.17

0.3

li

1.78
1.06
0.28
0.32
0.87
0.52
0.32
0.87

0.30
-0.29
-0.23
-0.30
-0.47
-0.23
-0.29
-0.45
-0.20

A two sided t-test is used to check if a sample of veilues comes


from a population with a mean different from ein hypothesized value, Ho. In this practice, a t-test may be performed on
pretreated check standard test results to check for bias relative to the ARVs. Since during pretreatment, accepted reference value(s) have been subtracted from the raw results, the
hypothesized mean value is zero.
For the purpose of perfoiming the t-test, two methods for
calculating the t-value are presented:
1. By the Root-Mean Square Method, the standcU"d deviation
of the pretreated results is calculated as

[A18]
2. The t vEilue is calculated as:
t = V ^ | 7 , - iJLoVs,,

[A19]

where /AQ is the hypothesized mean which is zero (A6.1).


3. Alternatively, by the MR approach, compute the alternate
t value as:
tMR = V ^ | / , -

M'(MR/l.n8),

[A20]

30

where /no is the hypothesized mean which is zero (A6.1).


Compare the computed t value from [A19] with the critical
t vEilues in Table Al2 for (nl) degrees of freedom. If IMR from
[A20] is used, the appropriate degrees of freedom is (n 1)/2.
If the absolute veJue of the calculated t (or IMR) value is less
than or equcil to the criticcd t vzJue, then (IQ is statisticcJly indistinguishable from the mecin of the distribution. For the
case of check standard testing, this would indicate that there
is n o statistically identifiable bias.
If the absolute value of t is greater t h a n the critical t value,
then /Ao is statisticcJly distinguishable from the mean of the
distribution, with 9 5 % confidence. For the case of check
standard testing, this would indicate a statistically identifiable bias in the measurement system.

FIG. A11Example of an MR chart for results from a multiple


check standards.

Example of t test applied to multiple results from a single


check standard - F o r t h e first 15 preprocessed results in colu m n 4 of Table A2, / i s 0.153. Since the results being ana-

10

15

20

Result Sequence Number

CHAPTER 38: STATISTICAL

QUALITY ASSURANCE

OF MEASUREMENT

PROCESSES

FOR

PETROLEUM

TABLE A1295th percentile of student's \t\ distribution.

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

Degrees
of Freedom

Degrees
of Freedom

Degrees
of Freedom

21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40

12.7062
4.3027
3.1824
2.7764
2.5706
2.4469
2.3646
2.3060
2.2622
2.2281
2.2010
2.1788
2.1604
2.1448
2.1314
2.1199
2.1098
2.1009
2.0930
2.0860

2.0796
2.0739
2.0687
2.0639
2.0595
2.0555
2.0518
2.0484
2.0452
2.0423
2.0395
2.0369
2.0345
2.0322
2.0301
2.0281
2.0262
2.0244
2.0227
2.0211

lyzed are the difference relative to the ARV, (IQ is 0. The standard deviation of the first 15 preprocessed resuUs is 0.493, and
the t vaJue is 1.2034. The t value is less than the critical value
for 14 degrees of freedom (t^ = 2.1448), so the average difference between the check standard results and the accepted
reference value is statistically indistinguishable from zero.
Example oft test applied to results from multiple check standards - For the first 15 preprocessed results in column 6 of
Table A3, 7 is 0.0719. Since the results being analyzed are
the difference relative to the ARV, ^o is 0. The standard deviation of the first 15 preprocessed results is 0.550, and the t
value is 0.506. The t value is less than the critical value for 14
degrees of freedom (fis = 2.1448), so the average difference
between the check standard results and the accepted reference value is statistically indistinguishable from zero.
Approximate Chi-Square Test
The chi-square (x^) test is used to compare the estimated site
reproducibility to a published reproducibility value, as instructed in section 9.1.2.
Compute the Chi-Square

Statistic

.2_{n-\)R'
X-

n2

2R^

[A21]

where R' is the estimated site reproducibility (MR) and R is


the published reproducibility of the method.
Compare the computed x^ value to the critical x^ value in
Table A13, with (n-l)/2 degrees of freedom. If n is even, interpolate.
If the computed x^ value exceeds the tabled value, then the
site reproducibility exceeds the published reproducibility of
the method, with 95% confidence.
If the computed x^ value is less than or equal to the tabled
value, then the site reproducibility is either less than or statistically indistinguishable from the published reproducibility of the method.
Example:The site reproducibility calculated from R' = 2.46
AIR for the first 15 QC results in Table Al is 1.23. The pub-

Degrees
of Freedom

41
42
43
44
45
46
47
48
49
50
55
60
65
70
75
80
85
90
95
100

105
110
115
120
125
130
135
140
145
150
155
160
165
170
175
180
185
190
195
200

2.0195
2.0181
2.0167
2.0154
2.0141
2.0129
2.0117
2.0106
2.0096
2.0086
2.0040
2.0003
1.9971
1.9944
1.9921
1.99006
1.98827
1.98667
1.98525
1.98397

1.98282
1.98177
1.98081
1.97993
1.97912
1.97838
1.97769
1.97705
1.97646
1.97591
1.97539
1.97490
1.97445
1.97402
1.97361
1.97323
1.97287
1.97253
1.97220
1.97190

TABLE A1395th percentiles of the chi square distribution.


Degrees
Freedom

Degrees
Freedom

Degrees
Freedom

7
8
9
10
11
12
13
14
15
16

14.1
15.5
16.9
18.3
19.7
21.0
22.4
23.7
25.0
26.3

17
18
19
20
21
22
23
24
25
26

27.6
28.9
30.1
31.4
32.7
33.9
35.2
36.4
37.7
38.9

27
28
30
35
40
45
50
60
70
80

40.1
41.3
43.8
49.8
55.8
61.7
67.5
79.1
90.5
101.9

lished reproducibility for the measurement method at the


58.88 level is 1.05. x^ is therefore 14 1.23^/2 1.232/2 1.05^
= 11.57. This value is less than the critical x^ value of 14.1 for
7 degrees of freedom, so the site reproducibility is not statistically greater than the published reproducibility of the
method.
Approximate F-Test
In this practice, an approximate F-test is used to compare the
variation exhibited by a measurement system over two different time periods. It can also be used to compare the site reproducibility estimated from a series of result from one QC
sample with that estimated using a different QC sample (section 8.6.1).
Compute the F value as
F = MRllMRl,

[A22]

where MRi is the larger of the two average moving ranges,


and Mi?2 is the smsdler.
Compare the computed F value to the critical F value read
from Table A14, with (ni l)/2 degrees of freedom for the
numerator and (M2 ~ l)/2 degrees of freedom for the denominator.
If the computed F value exceeds the tabled value, then the
two precisions are statistically distinguishable. We can be
95% confident that the process that gave rise to the moving

1060

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

TABLE A1497.5 Percentiles of the F Statistic.


Numerator Degrees of Freedom

Denom

d.f.

7
8
9
10
11
12
13
14
15
16
17
18
19
20
25
30
35
40
45
50
60
70
80
90
100

10

12

14

16

18

20

25

30

40

50

100

4.99
4.53
4.20
3.95
3.76
3.61
3.48
3.38
3.29
3.22
3.16
3.10
3.05
3.01
2.85
2.75
2.68
2.62
2.58
2.55
2.51
2.47
2.45
2.43
2.42

4.90
4.43
4.10
3.85
3.66
3.51
3.39
3.29
3.20
3.12
3.06
3.01
2.96
2.91
2.75
2.65
2.58
2.53
2.49
2.46
2.41
2.38
2.35
2.34
2.32

4.82
4.36
4.03
3.78
3.59
3.44
3.31
3.21
3.12
3.05
2.98
2.93
2.88
2.84
2.68
2.57
2.50
2.45
2.41
2.38
2.33
2.30
2.28
2.26
2.24

4.76
4.30
3.96
3.72
3.53
3.37
3.25
3.15
3.06
2.99
2.92
2.87
2.82
2.77
2.61
2.51
2.44
2.39
2.35
2.32
2.27
2.24
2.21
2.19
2.18

4.67
4.20
3.87
3.62
3.43
3.28
3.15
3.05
2.96
2.89
2.82
2.77
2.72
2.68
2.51
2.41
2.34
2.29
2.25
2.22
2.17
2.14
2.11
2.09
2.08

4.60
4.13
3.80
3.55
3.36
3.21
3.08
2.98
2.89
2.82
2.75
2.70
2.65
2.60
2.44
2.34
2.27
2.21
2.17
2.14
2.09
2.06
2.03
2.02
2.00

4.54
4.08
3.74
3.50
3.30
3.15
3.03
2.92
2.84
2.76
2.70
2.64
2.59
2.55
2.38
2.28
2.21
2.15
2.11
2.08
2.03
2.00
1.97
1.95
1.94

4.50
4.03
3.70
3.45
3.26
3.11
2.98
2.88
2.79
2.72
2.65
2.60
2.55
2.50
2.34
2.23
2.16
2.11
2.07
2.03
1.98
1.95
1.92
1.91
1.89

4.47
4.00
3.67
3.42
3.23
3.07
2.95
2.84
2.76
2.68
2.62
2.56
2.51
2.46
2.30
2.20
2.12
2.07
2.03
1.99
1.94
1.91
1.88
1.86
1.85

4.40
3.94
3.60
3.35
3.16
3.01
2.88
2.78
2.69
2.61
2.55
2.49
2.44
2.40
2.23
2.12
2.05
1.99
1.95
1.92
1.87
1.83
1.81
1.79
1.77

4.36
3.89
3.56
3.31
3.12
2.96
2.84
2.73
2.64
2.57
2.50
2.44
2.39
2.35
2.18
2.07
2.00
1.94
1.90
1.87
1.82
1.78
1.75
1.73
1.71

4.31
3.84
3.51
3.26
3.06
2.91
2.78
2.67
2.59
2.51
2.44
2.38
2.33
2.29
2.12
2.01
1.93
1.88
1.83
1.80
1.74
1.71
1.68
1.66
1.64

4.28
3.81
3.47
3.22
3.03
2.87
2.74
2.64
2.55
2.47
2.41
2.35
2.30
2.25
2.08
1.97
1.89
1.83
1.79
1.75
1.70
1.66
1.63
1.61
1.59

4.21
3.74
3.40
3.15
2.96
2.80
2.67
2.56
2.47
2.40
2.33
2.27
2.22
2.17
2.00
1.88
1.80
1.74
1.69
1.66
1.60
1.56
1.53
1.50
1.48

range MRy is less precise (has larger site-reproducibility)


than the process that produced MR2.
Note : Although the approximate F-test is conducted at
the 95% probability level, the critical F values against
w h i c h the calculated F is compared c o m e from the 97.5
percentiles of the F-statistic. If the ratio MR|/MRb is
calculated without requiring that the larger variance is
in the numerator, the ratio would have to be compared
against both the lower 2.5 percentile point and the upper 97.5 percentile point of the F-distribution to determ i n e if the t w o variances w e r e statistically distinguishable. Because of the nature of the F-distribution,
comparing MRa/MRb to the 2.5 percentile point w h e n
M R | < MRg is equivalent to comparing MRb/MR| to the
97.5 percentile point. Requiring that larger varieuice is
always in the numerator allows the "two-tailed" test to
be accomplished in one step. If the variance of the two
populations were equal, t h e n there w o u l d b e only a
2.5% chance that MR? > MRi by more than the tabulated amount, and a 2.5% chance that MRi > MRf by
more than the tabulated amount with degrees of freed o m reversed.
If the computed F value is smaller than the tabled value,
then the precisions of the two samplings of the measurement
process are statistically indistinguishable.
If two precision estimates are statistically indistinguishable, they may be pooled into a single estimate. For example,
if MRi was obtained from measurements on a single lot of QC
sample material, while MR2 was obtained from measurements on a different lot of material, and, if they are not statistically distinguishable, they may be pooled. The appropriate pooled precision estimate is
MR,pooled

(fij - 1) MRi +

(M2

- 1) MR2

Ml + W2 2

[A23]

TABLE A15
Sequence Number

QC Result

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23

54,2
56.1
55.2
54.1
53.7

54
54.3
54.8
53.9
53.2
52.5
52.8
54.3
52.7
53.4
53.1

54
53.2
52.8
53.2
53.1
53.3
52.8

MR

1.9
0.9
1.1
0.4
0.3
0.3
0.5
0.9
0.7
0.7
0.3
1.5
1.6
0.7
0.3
0.9
0.8
0.4
0.4
0.1
0.2
0.5

55.15
55.17
54.90
54.66
54.55
54.51
54.55
54.48
54.35
54.18
54.07
54.08
53.99
53.95
53.89
53.90
53.86
53.81
53.78
53.74
53.72
53.68

LCL

UCL

54.21
54.08
53.75
53.47
53.34
53.28
53.31
53.22
53.09
52.91
52.79
52.81
52.70
52.66
52.61
52.61
52.57
52.51
52.48
52.44
52.42
52.38

56.09
56.25
56.05
55.85
55.76
55.75
55.79
55.73
55.61
55.45
55.34
55.36
55.27
55.23
55.18
55.19
55.15
55.10
55.07
55.04
55.02
54.98

Example: Table A15 contains QC results for a second QC


sample measured by the same measurement system as was
used to generate the results in Table Al. The MR value for the
25 results from the original QC sample (Table Al) was 0.454.
The MR value for the 23 results for the new QC sample is
0.700. The F value is 2.38 which is less than the critical value
of 3.33 for 11 and 12 degrees of freedom in the numerator
and denominator, respectively. The precision of the measurements for the two QC batches is statistically indistinguishable.

MNL37-EB/Jun. 2003

Index
olefin-based polymers, 224-226
performance package, 200-201
performance testing, 235-242
engine oils, 237-239
finished formulations, 235-236
gear oils, 239-240
greases, 242
hydraulic fluids, 240-241
individual additives, 235
machine tests, 236
metalworking fluids, 241
miscellaneous industrial oils, 241-242
physical tests, 236
ttansmission fluids, 239
viscosity tests, 237
polymeric, 223-233
pour point depressants, 230-232, 373
primary fimctions, 200
refrigeration lubricants, 418-420
rust and corrosion inhibitors, 218, 220-223, 318-320
stabilizers/deposit control agents, 201-211
standard, 243-246
for turbines, 312-323
antifoams, 321-323
antioxidants, 312-318
antiwear and extreme-pressure, 319-321
rust and corrosion inhibitors, 318-320
viscosity modifiers, 223-224
see also Antifoam additives; Antiwear additives;
Antioxidants; Corrosion inhibitors
Adhesion, friction due to, 911
Adhesives, viscosity, 870-872
Adhesive wear, 435, 923, 927-930, 979-982
resistance ranking, 980-981
testing, oil evaluation, 981-982
test method, 979
traction test plots, 980
Adiabatic flame temperature, gasoline, 84
Adiabatic operation, 384
Adipic acids, synthesis, 276, 279
Adsorption, environmental characteristics, 888
Adsorption efficiency, steric hinderance, 952-953
Adsorption isotherms, 953-954
Aeration, hydraulic fluids, 366-367
Aero-derivative gas turbines, 301-302
Aerospace, engine thermodynamics, 730-732
Aerospace fuels, 729-756
air dilution, 742
bouyancy in air, 732
calorific values, 739-740
combustion emissions, 743
density, 735-736
flame stabilization, 742

Abiotic degradation, environmental characteristics, 889-890


Abrasive wear, 435, 930-931
Accepted Reference Values, 1047-1048
Accumulation processes, environmental characteristics,
894-895
Acid catchers, refrigeration lubricants, 419
Acidity, automotive lubricants, 474-475
Acid neutralizing agents, 221
Acid number
compressor lubricants, 400
gear lubricants, 456
mineral oil heat transfer fluids, 582
quench oils, 609-610
turbine lubricating oils and hydraulic fluids, 329, 331
Acids
formation, 790
for lubricants, 272
Acoustical measurements, steel quenching, 600-602
Active oxygen method, 820-821
Additives, 199-246
antiseize, 218
aviation fuels, 104-105
classification, 951-957
demulsifiers, 232-233, 366
detergents, 208-211
dispersants, 203-208
dispersant viscosity modifiers, 228-229, 231
dyes, 234
emulsifiers, 232-233
environmental impact, 234
ester polymers, 225-228
film-forming agents, 211-223
filterability, 368
friction modifiers, 211-213, 441, 949, 951-952
gear lubricants, 439-443, 447
hydraulic fluids, 363
introduction of new, 234
metalworking and machining fluids, 511-519
alkalinity agents, 516
antimicrobial agents, 517-518
anti-misting agents, 516
corrosion inhibitors, 516-517
coupling agents, 513
dispersants, 516
dyes, 519
emulsion promoters, 512-513
film-forming agents, 513-515
foam inhibitor, 518
inorganic/organic solids, 519
odor control agents, 519
oxidation inhibitors, 518-519
multifunctional nature, 234
1061
Copyright'

2003 by A S I M International

www.astm.org

1062

MANUAL 3 7: FUELS AND L UBRICANTS

flammability, 738
fueling fire safety, 744
future trends, 747-748
handling characteristics, 743-747
health issues in handling, 747
ignition, 741
lubricity, 744-745
maximum combustion temperature, 735, 740-741
molecular structure, 732-734
oxidation heat release, 735
performance of rocket fuels and oxidants, 731
physical state, 733
preparation and mixing, 741
properties, 735-736
reformation, 747
smoke tendency, 741
solidification, 737-738
specifications, 748
specific impulse, 742-743
spontaneous ignitability, 733-734, 738
standards, 749
stoichiometry, 734-735, 738-739
storage stability, 732, 745
substitute fuels, 748
supplemental fuels, 747
surface tension, 738
thermal stability, 745-746
turbine entry temperature distribution, 742
viscosity, 737
volatility, 736-737
water content, 746-747
Aging, Baader aging test, 821-822
Air conditioning lubricants, 484
Aircraft, sumpingprocedure. 111
Aircraft range, aviation fuels, 100-101
Air-fuel ratio, octane number requirement, 76
Airport
fuel systems, 106
quality control, 110-111
Air release
compressor lubricants, 398
gear lubricants, 460
turbine lubricating oils and hydraulic fluids, 332-334
Alcohol bonds, environmentally friendly oils, 271-272
Alcohols
hydrogen bond, 270
for lubricants, 271-273
Algae, acute toxicity tests, 901-902
Alkalinity agents
automotive lubricants, 474-475
metalworking and machining fluids, 516
Alkanes
lattice transition, 534
physical properties, 532
Alkenylsuccinates, synthesis, 206
Alkylated cyclopentanes, 260
Alkylation, 15-17

HANDBOOK
Alkylbenzene
compressor lubricants, 395
refrigeration lubricants, 415
Alkyl lead
history, 62
phasedown, 63
Alkyl lead content, 68
ASTMD4814, 82
Alkylphenols, 209
Alkyl phosphates, synthesis, 216, 218
Alkyl phosphites, synthesis, 216-217
Alternative fuels, diesel engines, 138-139
Aluminum, production, carbon anodes, 781-782
Aluminum beaker oxidation test, 810, 813
Aluminum complex soap greases, 559
Aluminum soap greases, 558
Ammonia, in LPG, 50
Amonton's Law, 383
Aniline point, hydrocarbon base oil, 181
"Anti-dumping" provisions, 65
Antifoam additives, 233-234
gear lubricants, 441
hydraulic fluids, 367
metalworking and machining fluids, 518
refrigeration lubricants, 419-420
for turbines, 321-323
Anti Knock Index, 73-74
ASTMD4814, 78
Antimicrobial agents, metalworking and machining fluids,
517-518
Anti-misting agents, metalworking and machining fluids,
516
Antioxidants, 201-202, 793-796
arylamine, 795
gasoline, 69, 82-83
gear lubricants, 441,445
hindered phenols, 794
hydraulic fluids, 356-358
metalworking and machining fluids, 518-519
refrigeration lubricants, 419
structures, 314
synergistic combination, 315
turbine lubricating oils and hydraulic fluids, 312-318
zinc dialkyl dithiophosphate, 794
Antiseize additives, 218
Antiwear additives, 69, 213-216, 955-956
gear lubricants, 440,444
hydraulic fluids, 363
refrigeration lubricants, 419
surface reactions, 954-955
turbines, 319-321
Antiwear performance testing, hydraulic fluids, 361-364
Antiwear properties, compressor lubricants, 402-406
API CF oils, 473
API CG-4 oils, 473-474
API CH-4 oils, 474
API gravity

INDEX

diesel fuel, 117-118


fuel oils, 758-759
gear lubricants, 456
API service designation, gear lubricants, 448-453
Appledoom equation, 919
Approximate F-test, 1059-1060
Aquatic toxicity tests, acute, 901
Aqueous polymer quenchants, 605-606
Archard's equation, 930
Aromatic esters, 249-250
Aromatics, 28
determination, 195
diesel fuel, 131-132
saturation, 17-20
Arrhenius equation, 127-128
Arylamine, oxidation inhibition, 795
Aryl phosphates, synthesis, 216, 218
Aryl phosphites, synthesis, 216-217
Ash content
diesel fuel, 135
fuel oils, 761-762
marine petroleum fuels, 150
petroleum coke, 775
petroleum pitch, 768
quench oils, 614
Ash modifiers, marine petroleum fiiels, 154
Asphaltene content, marine fuels, 151
Association of Natural Gasoline
Manufacturers, 36
ASTMD 4814, 77-83
alkyl lead content, 82
anti-knock index, 78
copper corrosion test, 82
driveability index, 78-79
gasoline and gasohol blending, 80, 82
oxidation stability, 82-83
phosphorus content, 82
soluble gum, 83
sulfur content, 82
vapor pressure specifications, 78- 81
volatility, 78-80
class specifications, 82
water tolerance, 83
ASTM proficiency testing, elemental
analysis, 714
Atmospheric gas oil, 3
Atomic absorption spectrometry, elemental analysis, 709
Austenite, 587
Autoignition
compressor lubricants, 399
mineral oil heat transfer fluids, 581
temperature, gasoline, 83-84
Automatic tank gauging, 645
Automatic transmission fluids
aluminum beaker oxidation test, 810, 813
hydraulic fluids, 374
performance testing, 239

1063

Automotive wheel bearing grease, 807


Automotive engine oils, 467-470
ASTM standard test methods, 469-470
corrosion tests, 828-829
issues in test method development, 469
performance standards, 467-468
performance tests, 468-469
Automotive gear lubricants, 442, 446, 448
oxidation stability, 803-804
performance testing, 239-240
Automotive lubricants, 465-494
additional fluids, 484
air conditioning lubricants, 484
axle lubricants, 483
brake fluids, 483
composition, 466-467
extent of oxidation, 476-477
functions, 465-466
greases, 478-481
ILSAC GF-2 and API SJ standard
tests, 470-476
acidity and alkalinity, 474-475
ball rust test, 472-473
city service engine sludge and valve train wear, 470-471
corrosiveness, 475
diesel engine oil, 473-474
energy conserving characteristics, 471
entry of water, 475
foaming tendency, 471
high temperature copper-lead bearing water, 470
phosphorus content, 471
short-trip-service engine rusting, 471
standard tests, 472
viscosity, 475-476
volatility, 471
solid lubricants, 483-484
standards, 485-494
test methods, 466-467
Automotive transmission fluids, 477-478
oxidation stability, 804
Auto-Oil Air Quality Improvement Research Program, 65
Auto propane, 51-52
Auto-refrigeration, 46
Autoxidation, ester based fluids, 277, 279
Aviation fuels, 89-113
additives, 104-105
aircraft range, 100-101
combustion, 97-98
corrosion tests, 828
corrosivity, 101-102
freezing point, 880-881
gasoline, 89-92
high temperature, 95-97
history, 89
jetfuel, 89, 91-93
low temperature
fuel related, 93-95

1064

MANUAL 3 7: FUELS AND LUBRICANTS

water related, 95
lubricity, 102-103
manufacturing, 103-104
metering, 99-100
oxidation
stability, 813
standards, 823
quality control, 106-111
aviation gasoline, 107
contaminants, 106
contamination detection equipment, 109-110
contamination removal equipment, 107-109
jet fuel, 107
procedures, 110-111
standards, 112-113
static electricity, 103
storage stability, 102
transportation, 105-106
volatility and flammability, 98-99
Aviation gas turbine oils
basestocks, 1012, 1014
corrosion inhibited MIL-PRF-23699 oils, 1011
gear testing, 988
high load-carrying DOD-L-85734 oils, 1011- 1012
high thermal stability MIL-PRF-23699 oils, 1011
load capacity database, 1011-1015
master chart, 1012, 1014
selected MIL-PRF-7808 grade 3 and grade 4 oils, 10121013
standard MIL-PRF-23699 oils, 1011
Aviation turbine fuels, thermal oxidation stability, 815-816
Avogadro's Law, 383
Axle lubricants, 483
B
Baader aging test, 821-822
Backpressure control, 164-165
Bainite, 587
Ball bearings, greases, at elevated temperatures, 565-566
Ball on Cylinder Lubrication Evaluator, 102
Ball rust test, 472-473
Band area methods, infrared spectroscopy, 668
Barus equation, 917-918
Base number, gear lubricants, 458
Base oil, see Hydrocarbon base oil
Bearing contacts, performance maps and, 972-973
Beer-Lambert law, 667
Beer's law, 661
Beeswax, 525-526
Bench test, 1020-1021
Block-on-Ring test, 1029-1030
four ball extreme pressure test, 1028-1029
four ball tests, 1026-1027
four ball wear test, 1027-1028
linear reciprocation, 1031 -1033
multi-specimen test machine, 1030-1031
pin and vee block tester, 1025-1026

HANDBOOK
Pin-on-Disk test, 1026
selection, 1019
tapping torque test, 1030
Timken extreme pressure test machine, 1030-1031
Bench test modeling, see Ryder gear; Systematic tribology
Bending-beam rheometer, 870, 872
Benzene, 28
Benzene Emission Number, 66
Bessemer Gas Engine Company, 37
Bias
measurement process, 1044-1045
monitoring, 1047-1048
Bioaccumulation factor, 894-895
Biocides, marine petroleum fuels, 154
Bioconcentration factor, 894-895
Biodegradability
diesters, 252
environmental characteristics, 890-894
hydrocarbon base oil, 182
polyolesters, 252
synthetic lubricants, 263
Biodegradable lubricants, oxidation
standards, 823
testing, 820-822
Biodiesel, 138-139
Biological properties, hydrocarbon base oil, 181-182
Biological stability, polymer quenchants, 620-623
Biota-sediment accumulation factor, 894-895
Bituminous materials, viscosity, 870-872
Black deposits, LPG, 49-50
Black penetration, lubricating greases, 561
"Blaugas", 35-36
Blending
marine fuel oils, 147-148
petroleum oil, 28
Blocking point, petroleum waxes, 552-553
Block-on-Ring test, 1029-1030
Boeing 747-400 fuel tankage, 93
Boiling point, 28
Boiling range, synthetic hydrocarbons, 195
Bomb combustion methods, elemental analysis, 709
Bomb oxidation test, lubricating greases, 565
Bonded fuel, aviation fuels, 106
Boost systems, diesel fuel system, 164
Borsoff effect, 936
Boundary lubrication, 214, 498, 949
Bouyancy, aerospace fuels, 732
Brake fluids, 483
standards, 493
Brayton cycle, 730-731
Broomwade 2050H Compressor Rig Test, 403
Brush drag of latex paints, 868
Btx recovery, 14-15
Bubble tubes, 868
Bulk material properties, flow properties, 921-922, 925-926
Bunsen Coefficient, 406
Bureau of Mines Correlation Index, 186

INDEX

Butadiene
analysis, 193
production, 190-192
purity, 193
Butane, 46
Butane-butene mixtures, chlorides in, 194
Butylene
analysis, 193
production, 190-192

Cadmium corrosivity, aviation fuels, 102


Calcium complex soap greases, 559
Calcium soap greases, 558-559
Calorific values, aerospace fuels, 739-740
Canadian Environmental Protection Act, 66
Candelilla wax, 525-526
Carbon acids, hydrogen bond, 270
Carbon anodes, for aluminum production, 781-782
Carbon blacks, 779-781
Carbon fibers, petroleum pitch, 781
Carbonizable substances, petroleum waxes, 549
Carbon residue
compressor lubricants, 399
dieselfuel, 135-136
fuel oils, 761
marine petroleum fuels, 151-152
mineral oil heat transfer fluids, 580
quench oils, 611-613
standards, 783-784
Carbonyls, in C4 hydrocarbons, 194
Carbonyl sulfide, in propylene, 193
Carboxylic acids
environmentally friendly oils, 272-273
isomers, 270
Camauba, 525-526
Carreau viscosity equation, 948-949
Casinghead gasoline, 36-37
Catalytic reforming, 12-15
yield/octane relationship, 14
Caterpillar micro-oxidation test, 810-811, 813-814
Cat fines, marine petroleum fuels, 150
"Cat" gasoline, 11
Cavitation corrosion, 932
Cavitation erosion, 932-933
Cavitation erosion corrosion, 933
Cavitation wear, 931-941
corrosion, 931-932
delamination, 937-938
erosion, 931-932
fatigue, 933-936
oxidational, 933
scuffing, 936-937
tribochemical, 933
CCT diagrams, 589
Cementite, 587
Centrifugal compressor, 389-390

1065

Centrifuges, diesel fuel system, 161, 163


Centrifuge tests, 365
lubricating greases, 564-565
Cetane index, 119-120
Cetane number, 119
diesel fuel oils, 721-723
Channel point FTM, gear lubricants, 459
Chemical analysis, lubricating greases, 569
Chemical corrosion, 220
Chi-square test, 1059
Chlorine content
butane-butene mixtures, 194
gear lubricants, 457
turbine lubricating oils and hydraulic fluids, 334
City service engine sludge and valve train wear, 470-471
Clay treatment vessels, 108-109
Clean Air Act of 1963,63
Clean Air Act of 1970, 64
Clean Air Act Amendments of 1977, 64
Clean Air Act Amendments of 1990, 65-66, 135
Cleanliness
dieselfuel, 124-125
turbine lubricating oils and hydraulic fluids, 341-343
Cleveland Open Cup, 692
Cloud point, 881-882
dieselfuel, 121-122
petroleum waxes, 545-546
polymer quenchants, 619
'^C NMR spectrometry, hydrocarbon analysis, 650-651
CNS effects, LPG, 54-55
Coalescer Blocking Tendency Test, compressor lubricants,
404-406
Coatings, flow-related instruments, 867
CoBr test, 47-48
Coefficient of kinetic friction, petroleum waxes, 552, 554
Cogeneration, 28
Coking, delayed, 21-23
Coking value, petroleum pitch, 767-768
Cold crank simulator, 850
gear lubricants, 458
Cold Filter Plugging Point, diesel fuel, 123-124
Cold flow properties, 879-883
aviation ftiels freezing point, 880-881
cloud point, 881-882
high-shear tests of lubricants, 882
pour point, 879-880
pumpability of lubricants, 882
standards, 883
wax appearance point, 881-882
Color, petroleum waxes, 549-551
Combustion, diesel fiiel, 118-119
Combustion products, dissociated, 753-754
Combustion temperature, aerospace fuels, 735, 740-741
Compatibility
gear lubricants, 460
marine pefroleum fiiels, 152
turbine lubricating oils and hydraulic fluids, 343-346

1066

MANUAL 37: FUELS AND LUBRICANTS

see also Seal compatibility


Compressibility factor, 384
Compression, power requirement, 385-386
Compression ignition engines, 115-116
Compression ratio, octane number requirement, 76
Compressor lubricants, 383-411
acid number, 400
air release, 398
antiwear properties, 402-406
autoignition, 399
basestocks, 392-395
carbon residue, 399
classification, 391
copper corrosion, 398
corrosion, 398-399
demulsibility, 397-398
elastomeric seals compatibility, 409
evaporation, 399
Filter Bowl Compatibility Test, 410
fire point, 398-399
flash point, 398-399
fluid oxidation, 400-401
foaming tendency, 398
gas solubility, 395-396, 406-409
heat transfer efficiency, 408-409
hydrolytic stability, 398
infra-red spectroscopy, 400-401
iron corrosion, 398
kinematic viscosity, 396-397
Liquid Heptane Washing Test, 401-402
oxidation stability, 802
Paint Compatibility Test, 409-410
performance demands, 389-392
pour point, 397
precipitation number, 399-400
solubility in the gas, 396, 398
specific gravity, 397
specific heat, 408-409
standards, 410-411
thermal conductivity, 408-409
viscosity of gas/liquid mixtures under pressure, 408
water content, 397
Compressor tests, 403
Concentric cylinder viscometer, 835-836
Conductance, polymer quenchants, 618-619
Conductivity, gasoline, 85
Cone-and-plate viscometer, 835
Cone penetration, lubricating greases, 561
Congealing point, petroleum waxes, 545
Conradson carbon residue, compressor lubricants, 399
Consistency, lubricating greases, 560-561
Consistency stability, lubricating greases, 561-562
Construction materials, gas turbine fiael system, 166-167
Contact stress, 966
simulation, Ryder gear, 997-1000
Contamination
aviation fuels, 106

HANDBOOK
detection equipment, aviation fuels, 109-110
gasoline, 69
lubricating greases, 568-569
quench oils, 610-614
removal equipment, aviation fuels, 107-109
Continuous cooling transformation diagrams, 589
Control chart, 1055-1056
Conventional Oxidation Catalyst, 63-64
Coolants, secondary, 574
Coolant separability, hydraulic fluids, 370-371
Cooling curve analysis, polymer quenchants, 621-623
Copper corrosion, 826
aviation fuels, 101-102
compressor lubricants, 398
lubricating greases, 567-568
Copper corrosion inhibitors, 69
Copper corrosion test, ASTM D 4814, 82
Copper deactivation, 221
Copper passivators, 221-222
Copper strip corrosion, diesel fuel, 134-135
Copper strip tarnish test, 827-828
gear lubricants, 454, 456
Corrosion, 825-832
compressor lubricants, 398-399
in LPG, 49
specifications, 827
Corrosion behavior, turbine lubricating oils and hydraulic
fluids, 340-341
Corrosion inhibitors, 218, 220-223
gear lubricants, 441
hydraulic fluids, 369-370
metalworking and machining fluids, 516-517
polymer quenchants, 619-620
surface activity, 826-827
for turbines, 318-320
Corrosion protection, hydraulic fluids, 368-370
Corrosion tests, 827-832
automotive engine oils, 828-829
aviation gasolines, 828
diesel fiiel oils, 828
gear oils, 829
greases, 831-832
lubricants, 827-828, 829-831
Corrosion wear, 931-932
Corrosivity
aviation fuels, 101-102
diesel engine oil, 475
Coupling agents, metalworking and machining fluids, 513
Cracking, crude oil, 146-148
Critical pressure, 384
Critical temperature, 384
Crude oil gases, 3
disposition, 5
Crude oils, 6-7, 145-148
classification, 526-527, 575-576
cracking, 146-148
distillation, 146-147

INDEX

distillation, 696-698
preparation and separation, 9-10
refinery blending and storage, 147-148
refining, 528-529
vapor pressure, 702
waxy, 527-528
Crystalline structure, petroleum coke, 775-776
Crystallization, esters, 289-291
Cyclic durability test, gear lubricants, 458
Cyclohexane derivatives, 260
D
Dalton's Law, 383
Defoamers, see Antifoam additives
Deformation, friction due to, 911
Degree of overbasing, 208
De-icers, 68
Delamination wear, 937-938
Delayed coking, 21-23
Demulsibility
compressor lubricants, 397-398
gear lubricants, 457-458
hydraulic fluids, 366
Demulsifiers, 232-233
gear lubricants, 441
marine petroleum fuels, 154
Density
aerospace fuels, 735-736
crude oil, 6
dieselfuel, 117-118
marine petroleum fuels, 149
petroleum coke, 775
petroleum pitch, 768
refrigeration lubricants, 421
turbine lubricating oils and hydraulic fluids, 332
Deposit control additives, 69-70
Desorption, environmental characteristics, 888
Detergents, 208-211
gear lubricants, 440, 444
hydraulic fluids, 358
micellar structure, 210-211
synthesis, 210
Dewaxing, hydrocarbon base oil, 171-172
Dewaxing process variables, 530-531
Dew Point test, 47-48
Dialkyl dithiophosphoric acid derivatives, synthesis, 215
Dibasic acid esters, refrigeration lubricants, 416
Diesel engines
alternative fuels, 138-139
history, 115-116
Diesel fuel oils, 9
API gravity, 117-118
aromatics, 131-132
ash, 135
carbon residue, 135-136
cetane index, 119-120
cetane number, 119

cleanliness, 124-125
Cloud Point, 121-122
Cold Filter Plugging Point, 123-124
composition/performance correlations, 178-179
copper strip corrosion, 134-135
corrosion tests, 829
corrosiveness, 475
density, 117-118
distillation, 120-121
dyed, 135-137
Flashpoint, 128-129
formation of insolubles, 125
grades, 116-117
heat content, 132-134
heat of combustion, 132-134
ignition and combustion characteristics, 118-119
low-sulfur, 135-137
Low-Temperature Flow Test, 123
lubricity, 129-131
oxidation stability, 126-127
performance categories, 473-474
Pour Point, 122-123
premium, 137-138
requirements, 118
specifications, 116-117
stability, 125-126
storage stability, 127-128
thermal stability, 126
total sulfur, 134
viscosity, 121
volatility, 120-121
World Wide Fuel Charter, 137
Diesel fuel combustion, 717-727
combustion process, 718-719
emissions, 719-721
fuel injection, 717-718
ignition, 718
Diesel fuel oils
cetane number, 721-723
corrosion tests, 828
CVCA/IQT method, 724-727
ignition quality, 721-727
proposed alternatives to ASTM D 613, 723-724
specifications, 718
standards, 727
Diesel fuel system, 161, 163-165
back pressure control, 164-165
boost systems and deaeration, 164
centrifuges, 161, 163
emulsifiers, 165
filters and strainers, 163-164
fuel final filter, 164
fuel service heaters, 164
fuel supply flowmeter, 164
homogenizer, 165
viscosity control, 164
waste heat economizers, 165

1067

1068

MANUAL 3 7: FUELS AND L UBRICANTS

Diesel index, 118


Diesel-injector nozzle, shear resistance, turbine lubricating
oils and hydraulic fluids, 340
Diesel plant fuel system, 161-162
Diesters, 249-252
application and performance characteristics, 252
biodegradability, 252
chemical characteristics, 251
chemistry and manufacturing, 249-251
manufacturing technology, 250-251
physical properties, 251
Difference method, infrared spectroscopy, 668
Differential scanning calorimetry
petroleum waxes, 539-542
transition temperatures, 548
Dip cups, 867-868
Dispersants, 203-208
bridged structure, 206-207
gear lubricants, 440-441,445
hydraulic fluids, 358
in marine petroleum fuels, 153
metalworking and machining fluids, 516
performance, 204-205
structural features, 205-206
uses, 206, 208
Dispersant viscosity modifiers, 206, 228-229, 231
Dispersive-type infrared spectrometers, 667
Disposition tendencies, liquids in thin films and vapors,
819-820
Dissociation constant, environmental characteristics, 888
Distillate fuels
high temperature stability, 817-818
oxidation stability, 816-817
storage stability, 817-818
Distillation, 675-682
atmospheric pressure, 676-680
crude oils, 146-147, 696-698
dieselfiiel, 120-121
fiiel oils, 761
hydrauhc fluids, 365
hydrocarbon base oil, 171
international standards, 689
mineral oil heat transfer fluids, 582
reduced pressure, 680-690
Distillation fractions, 3-4
2,6-Ditertiarybutyl-4-methylphenol, 314-315
DOD-L-85734 oils, 1011-1012
Driveability index, 78-79
Dropping point, lubricating greases, 563-564
Dyes, 234, 519
Dynamic seals test, gear lubricants, 460
Dynamic shear rheometer, 870
E
Ecological tests, environmentally friendly oils, 289, 291292
Elastohydrodynamic contact, functional regions, 965

HANDBOOK
Elastohydrodynamic film-forming capability, engine oil,
983-987
optical thickness measurement, 984-985
pressure-viscosity coefficients, 985-987
Elastohydrodynamic lubrication, 413, 968
film thickness, 1007
measurements by interferometry, 947-948
mixed film lubrication, 949
non-Newtonian, 948-949
Reynolds equation, 948
Elastomeric seals, see Seal compatibility
Elastomers, turbine lubricating oils and hydraulic fluids
compatibility, 344
Electric-arc furnaces, graphic electrodes, 782
Electrochemical corrosion, 218, 220
Electrostatic stabilization, 204-205
Elemental analysis, 707-716
ASTM proficiency testing, 714
atomic absorption specttometry, 709
bomb combustion methods, 709
classical wet chemistry methods, 709
D02 test methods, 709-710
future developments, 715-716
graphite furnace atomic absorption spectrometry, 709-711
inductively coupled plasma-atomic emission spectrometry,
711-712
inductively coupled plasma-mass spectrometry, 712
international test methods harmonization, 714-715
ion chromatography, 712
microelemental analysis methods, 712
neutron activation analysis, 712-713
sample preparation, 707
standard reference materials, 714
wear metals in used oils, 707-709
X-ray fluorescence spectrometry, 713
Elemental content, gear lubricants, 458
Emissions
aerospace fuels, 743
diesel fuel combustion, 719-721
Emulsifiers, 232-233
diesel fuel system, 165
gear lubricants, 441-442
Emulsion promoters, metalworking and machining fluids,
512-513
Energy conserving characteristics, 471
Energy content, gasoline, 72
Energy equation, 756
Engine deposits, effect on octane number requirement, 77
Engine management systems, 71
Engine oils
adhesive wear testing, 981-982
elastohydrodynamic film-forming capability, 983-987
hydraulic fluids, 374
oxidation
standards, 823
testing, 807-811
performance tests, 237-239

INDEX

standards, 485-488
thermo oxidation engine oil simulation test, 808-812
traction and scuffing failure characteristics, 1008-1009
traction characteristics, 1003, 1005
WAM high speed load capacity test method, 1010
Engine spark timing, octane number requirement, 76-77
Engine tests, engine oils, 823
Entraining velocity, 966-967
Environmental acceptability, synthetic lubricants, 262-263
Environmental characteristics, 885-906
abiotic degradation, 889-890
accumulation processes, 894-895
acute toxicity tests, 894, 901-902
adsorption, 888
biodegradation, 890-894
chemical structure and, 886-887
chronic and subchronic tests, 894, 903-904
complex mixture toxicity, 900-901
desorption, 888
dissociation constant, 888
exposures, 895-896, 900-901
hazard and risk, 904
Henry's Law Constant, 888
low solubility materials, 900
noo-aquatic toxicity tests, 903-904
octanol/water partition coefficient, 887
rationale for standardized testing, 885-886
standardized tests, 895-899
terminology, 904-906
transformation processes, 889
transport processes, 888-889
vapor pressure, 888
volatility, 896, 900
water solubility, 887
Environmental considerations, marine petroleum fuels, 156
Environmental impact, 234
Environmentally acceptable hydraulic fluids, 377-378
Environmentally friendly oils, 267-294
alcohol bonds, 271-272
carboxylic acids, 272-273
chemical properties, 273-276
crystallizing, 289-291
ecologically toxic properties, 289, 291-292
esterification, 270-271
functional groups and elementary compound, 269-270
functions and requirements, 267-268
future developments, 291-293
hydrolysis, 274
low temperature properties, 289-291
native esters, 275, 277-278
oxidation stability, 274-275
standards, 293-294
synthetic esters, 276, 278-279
viscosity, 273, 289-290
see also Pressure media
Equation-of-state approach, 423, 535-539
Equipment line sizing, refrigeration lubricants, 426

1069

Erosion corrosion, 933


Erosion wear, 931-932
Ester fluids, viscosity vs. temperature, 289-290
Esterification, 249-250
catalysis, 251
mechanism, 270-271
Ester polymers, 225-228
Esters
compressor lubricants, 394
native, environmentally friendly oils, 275, 277-278
native and synthetic
chemical bases, 269-273
chemical properties, 273-276
pour points, 273
synthetic
environmentally friendly oils, 276, 278-279
turbines, 309-311
Ethanol, in propane, 47
Ethylene
characterization, 192
producdon, 186-190
commercial production, 188-190
feedstock, 186-188
thermal cracking reaction, 188
Ethyl mercaptan, as odourant, 52, 55
Evaporation, compressor lubricants, 399
Evaporation loss, lubricating greases, 564
EWMA overlay, 1056
Exhaust emissions, marine petroleum fuels impact, 154
Exponentially Weighted Moving Average values, 1056
Exposures, environmental characteristics, 895-896, 900-901
Exfreme pressure additives, 213-214, 216-219, 955-957
gear lubricants, 440,444
hydraulic fluids, 363
metalworking and machining fluids, 513-515
standards, 1036
surface reactions, 954-955
turbines, 319-321, 457, 1030-1031
Extreme pressure Timken method, lubricating greases, 566

Failure, parameters controlling, 965-966


Falling needle, 868-869
Falling viscometer, 836
Fatigue wear, 933-936
Fat solubility, 820-821
Ferrite, 587
Ferrous corrosion inhibitors, 69
Film boiling, shock, steel, 599-602
Film-forming agents, 211-223
metalworking and machining fluids, 513-515
Filterability, hydraulic fluids, 367-368
Filter Bowl Compatibility Test, compressor lubricants, 410
Filters, diesel fuel system, 163-164
Filter-separators, 107-108
Fire point
Cleveland Open Cup, 692

1070

MANUAL 3 7: FUELS AND L UBRICANTS

compressor lubricants, 398-399


gear lubricants, 454
quench oils, 609
Tag Open cup, 693
Fire-resistance tests, turbine lubricating oils and hydraulic
fluids, 334-337
Fire resistant fluids, hydraulic fluids, 375-377
Fischer-Tropsch diesel fuels, 138
Fischer-Tropsch process, 525-526
Fish, toxicity tests, 902-903
Fixed bed hydrocracking, 24
Flame ionization detector, 653
Flammability, 682, 690-696
aerospace fuels, 738
aviation fuels, 98-101
gasoline, 84
LPG, 52
see also Fire point; Flash point
Flash point
bias among test methods, 692
Cleveland Open Cup, 692
compressor lubricants, 398-399
continuously closed cup, 694
diesel fuel, 128-129
equilibrium method with closed cup, 693-694
fuel oils, 761
gear lubricants, 454
international test methods, 694-695
marine petroleum fuels, 150
Pensky-Martens Closed Cup Tester, 692-694
quench oils, 609
Setaflash Closed Cup, 693
small scale closed cup, 693
Tag Open cup, 693
test methods, 690-691
verification fluids, 691
Flash temperatures, 941-942
Fluorescent indicator adsorption, hydrocarbon analysis, 659
Fluorinated basestocks, compressor lubricants, 395
Flow properties, 833-875
ASTM procedures, 853-854
bulk material properties, 921-922, 925-926
flash temperatures, 941-942
high-temperature high-shear, 843- 845
kinematic viscosity, 837-841
history, 841-843
temperature relationship, 854-856
low temperature tests, 851
lubricating greases, at high temperatures, 562
near surface structure, 919, 923
nomenclature, 833-835
non-petroleum materials, 867-872
pressure-viscosity coefficient, 916-920
standards, 072-875
sub-surface structure, 919-920, 924
surface conformity, 914-916
surface films, 919, 921-923

HANDBOOK
viscometer geometries, 835-836
wear maps, 942-945
wear surfaces, 911-913
see also Cold flow properties; Viscosity
Fluid biodeterioration, polymer quenchants, 620-621
Fluid catalytic cracking, 9-12
yields, 11
Fluid coking, 770
Fluidized bed hydrocracking, 24-25
Fluid oxidation, compressor lubricants, 400-401
Foaming
automotive lubricants, 471
compressor lubricants, 398
gear lubricants, 456-457
hydraulic fluids, 366-367
turbine lubricating oils and hydraulic fluids, 332-334
Foam inhibitors, see Antifoam additives
Foam testing, polymer quenchants, 620
Four ball extreme pressure test, 457, 1028-1029
compressor lubricants, 402
lubricating greases, 566-567
Four ball tests, 1026-1027
Four ball wear test, 457, 1027-1028
Fourier transform infrared spectroscopy, 667
Free water, 639-640, 646
in aviation fuels, 109-110
Fretting wear, 567, 934-936
Friction, 909-911
area of true contact, 909-911
due to adhesion, 911
due to deformation, 911
due to ploughing, 911-912
standards, 1035-1037
types of, 497
Friction coefficient, 945
effect of hydrocarbon chain length, 954
Friction modifiers, 211-213, 949, 951-952
gear lubricants, 441
F-test, 1059-1060
Fuel additives, marine petroleum fuels, 153-154
Fuel-injection system, 115-116
Fuel injector shear stability test, 852
standards, 875
Fuel oils, 8, 757-762
API gravity, 758-759
ash, 761-762
carbon residue, 761
compatibility of blended, 762
distillation, 761
flashpoint, 761
heating value, 759-760
instability, 762
pour point, 761
specifications and applications, 757-759
sulfiir content, 762
viscosity, 760-761
Fuels, oxidation testing, 811, 813, 815-818

INDEX

Fuel service heaters, diesel fuel system, 164


Fuel treatment, gas turbine fuel system, 165-166
Fuses, aviation fuels, 108
FZG Gear Test Machine, 320, 322, 1033-1035
compressor lubricants, 402-403
FZG Pits C 180 TS, gear lubricants, 459
FZG scuffing test, gear lubricants, 458
FZG test, 362

Galling wear, 923, 929-930


Galvanic corrosion, 932
Gas chromatography
hydrocarbon analysis, 652-657
liquified petroleum gas, 40
petroleum waxes composition, 549
principles, 652-653
Gas chromatography-mass spectrometry,
hydrocarbon analysis, 664
Gas compression cycle, 384-386
Gas compressors, 386-389
Gas hydrates, 44-46
Gas laws, 383-384
Gas line anti-freeze, 68
Gasohol, blending with gasoline, 80, 82
Gasoline, 7-8, 61-86
additives, 68-70
adiabatic flame temperature, 84
autoignition temperature, 83-84
aviation, 89, 91-92
additives, 105
combustion, 97
history, 89-90
knock resistance, 97
low temperature, 94-95
manufacturing, 103
quality control, 107
volatility and flammability, 98
combustion, 70-77
air-fuel ratio and stoichiometry, 71-72
engine management systems, 71
gasoline energy content, 72-73
spark ignition engines, 70-71
composition, 66-68
conductivity, 85
flammability, 84
heat capacity, thermal conductivity, and heat of
vaporization, 84
heat of combustion, 84
history, 61-66
2004+ vehicle and fuel regulation, 66
alkyl lead, 62
Clean Air Act Of 1963, 63
Clean Air Act of 1970 and 1977 amendment, 64
Clean Air Act Amendments of 1990, 65-66
leaded gasoline, 61-62
nonleaded gasoline, 63-64

octane ratings, 62-63


vapor controls, 64-65
nonleaded, 63-64
octane performance properties, 73-77
anti-knock ratings, 73-74
combustion and knock, 73
motor octane number, 73-74
octane distribution through fuel boiling range, 75
octane number requirement, 75-78
on-line analyzer octane rating, 74-75
research octane rating, 74
oxidation
stability, 813, 815-817
standards, 823
testing, 811,813, 815-818
oxygenates in, 68
performance additives, 69-70
reformulated, 65-66
specifications, see ASTM D 4814
standards, 85-86
static electricity, 85
trace constituents and contaminants, 69
vapor pressure, 699, 701
viscosity and lubricity, 84-85
Gasoline-oxygenate blends, vapor pressure, 699, 701
Gas solubility
compressor lubricants, 395-396, 406-408
petroleum oils, 406-407
Gas turbine engines, 115, 298-299
development, 302-303
lubrication system, 301-302
Gas turbine fuels, 139-142
requirements, 140-141
standards, 142-143
trace metal limits, 141-142
see also Ryder gear
Gas turbine fuel system, 165-166
construction materials, 166-167
Gearbox oils, see Ryder gear
Gear contacts, performance maps and, 972-973
Gear corrosion test, gear lubricants, 460
Gear lubricants, 431-462, 481-483
acid number, 456
additives, 439-443, 447
air release, 460
antiwear agents, 440, 444
API gravity, 456
API service designation, 448-453
base number, 458
channel point FTM, 459
chlorine level, 457
cold crank simulator, 458
compatibility, 460
compounded, 439
Copper Strip Tarnish Test, 454, 456
corrosion inhibitors, 441
cyclic durability test, 458

1071

1072

MANUAL 3 7: FUELS AND L UBRICANTS

demulsibility, 457-458
demulsifiers, 441
detergents, 440, 444
dispersants, 440-441, 445
dynamic seals test, 460
early, 431-432
elemental content, 458
emulsifiers, 441-442
extreme pressure, 439
oxidation, 458
extreme pressure agents, 440, 444
fire point, 454
flash point, 454
foam characteristics, 456-457
foam inhibitors, 441
four ball EP, 457
four ball wear, 457
friction modifiers, 441
function, 431
future trends, 460-461
FZG Pits C 180 TS, 459
FZG scuffing test, 458
gear corrosion test, 460
gear scoring test, 459-460
GFC oxidation, 459
greases, 439
high temperature foam inhibition, 459
insolubles in used oils, 457
kinematic viscosity, 456
low speed high torque hypoid test, 459
low temperature Brookfield viscosity, 458
MIL-PRF-2105E, 451-452
nitrogen level, 458
OEM specifications, 451, 453
open gear compounds, 439
oxidation inhibitors, 441, 445
phosphorus level, 457
polymeric thickeners, 441-442
pour point, 454
pour point depressants, 441
precipitation number, 453
rust and oxidation inhibited, 439
rust inhibition, 456
Ryder gear test conditions, 988-990
SAE 3306 viscosity classification, 449-451
scuffing
front, propagation, 992-993
initiation, 990-992
seal compatibility, 459
shear stability, 459
standards, 461-462, 493
standard tests, 482-483
storage solubility, 460
sulfur level, 457
synchronizer SSP 180 test, 459
systematic tribology, 988-996
thermal and oxidation test, 458

HANDBOOK
Timken EP Tester, 457
fribological features, microscopic examination, 991-992
fribological processes, 993-996
types, 437,439
viscosity index, 457
water content, 457
Gear oils
corrosion tests, 829
oxidation, standards, 822
oxidation testing, 802-804
performance testing, 239-240
Gears
failure modes, 434-436
lubrication, 434, 436-438
types, 432-434
Gear scoring test, gear lubricants, 459-460
Gear testing, aviation gas turbine oil, 988
GFC oxidation, gear lubricants, 459
Glass capillary vacuum viscometers, 870-871
Gloss retention, petroleum waxes, 549
GM quenchometer cooling times, 604-606
Graphic electrodes, for elecfric-arc furnaces, 782
Graphite furnace atomic absorption spectrometry, elemental
analysis, 709-711
Greases, see Lubricating greases
Grossmann hardenability, 592-593
Gum content, gasolines and fuels, 811, 813, 815
H
Halocarbons, in LPG, 50
Hardenability, steel, 589-591
measurement, 591-593
Hardness, petroleum waxes, 547-548
Hazard, environmental characteristics, 904
Health effects, LPG exposure, 54-55
Health issues, aerospace fuels handling, 747
Heat capacity, gasoline, 84
Heat content, diesel fuel, 132-134
Heating value
fiiel oils, 759-760
marine petroleum fuels, 149-150
Heat of adsorption, wear reduction and, 954
Heat of combustion, 72
diesel fuel, 132-134
gasoline, 84
Heat of vaporization, gasoline, 84
Heat resistance, lubricating greases, 563-565
Heat transfer
efficiency, compressor lubricants, 408-409
hydraulic fluids, 353-354
Heat fransfer coefficient, 573-575
Heat transfer fluids, see Mineral oil heat transfer fluids
Heat transfer fluid system, design and construction, 583-584
HEES fluids, 377
Henry's Law Constant,;
HEPG fluids, 378
HEPR type fluids, 378

INDEX

Hertzian contact, 914, 946-949, 965-966


Heteroatom, removal, 17-20
HETG fluids, 377
HFA fluids, 375-376
HFB fluids, 376
HFC fluids, 376
HFD fluids, 376-377
High frequency reciprocating rig, 129, 131
High Pressure Difl^erential Scanning Calorimetry, 258
High-shear
high-temperature, 843-845
low-temperature, lubricants, 846-848
High temperature copper-lead bearing wear, 470
High temperature foam inhibition, gear lubricants, 459
High temperature stability, distillate fuels, 817-818
Hindered phenols, oxidation inhibition, 794
' H N M R spectroscopy, hydrocarbon analysis, 651
Homogenizer, diesel fuel system, 165
Hot surface tests, turbine lubricating oils and hydraulic
fluids, 335
Hot tack, petroleum waxes, 552
HSR, 3
HVAC cycle, refrigeration lubricants, 424-426
Hydraulic fluids, 353-379
aeration and foam, 366-367
antifoam additives, 367
antioxidants, 356-358
antiwear and extreme pressure additives, 363
antiwear performance testing, 361-364
automatic transmission fluids, 374
boundary conditions, 360-361
coolant separability, 370-371
corrosion inhibitors, 369-370
corrosion protection, 368-370
demulsibility, 366
detergents, 358
dispersants, 358
engine oils, 374
environmentally acceptable, 377-378
fiherability, 367-368
fire-resistant, 301-302, 375-377
frictional properties, 212-213
heat transfer, 353-354
hydrolytic stability testing, 365-366
low temperature pumpability, 372-373
lubrication, 353
machine builder specifications, 364
metal passivators, 369-370
mineral oils, 374-375
oxidation
stability, 355-359, 801
standards, 822
tests, 356-357
performance testing, 240-241
petroleum base stocks, 355
pour point depressants, 373
power transfer, 353-354

1073

rust inhibitors, 369-370


seal compatibility, 370
shear stability, 371-372
standards, 378-379
thermal stability, 355-359
tractor fluids, 374
trends, 353-355
types, 268-269
viscosity, 359-360
viscosity index improvers, 371-372
water content, 363, 365
wear protection, 359-364
see also Pressure media
Hydraulic oils
oxidation characteristics, 797-798
thermal stability, 799-800, 830
Hydrocarbon analysis, 649-672
"C NMR spectrometry, 650-651
fluorescent indicator adsorption, 659
gas chromatography, 652-657
gas chromatography-mass spectrometry, 664
infrared spectroscopy, 668-670
liquid chromatography, 657-660
mass spectrometry, 664-665
NMR spectroscopy, 649-652
standards, 671-672
super critical fluid chromatography, 659-660
ultraviolet spectroscopy, 661-662
Hydrocarbon base oil, 169-183
biodegradability, 182
biological properties, 181-182
composition/performance correlations, 178-179
effects in industrial lubricants, 179-180
hydrocarbon type analysis, 172-173
impact of sulfur compounds on chemistry, 176-177
market, 169-170
molecular structures, 174-175
naphthenic vs. paraffmic, 172
nitrogen compound reactivity, 177-178
NMR spectroscopy, 174-175
olefins, 178
oxidation, 175-176
refining and processing technology, 170-172
refining capacity. United States, 169-170
rheology and composition, 178
rubber compatibility, 181
solvency effects, 181
spectrometric identification components, 173-174
standards, 182-183
structures with high susceptibility to oxidation, 788
viscosity-pressure coefficient composition effect, 180-181
Hydrocarbon oils, turbines, 305-306
Hydrocarbon-oxygenate mixtures, vapor pressure, 702-703
Hydrocarbons
crude oil composition, 6
in gasoline, 66-67
physical adsorption, 921

1074

MANUAL 37: FUELS AND LUBRLCANTS

HANDBOOK

terminology, 5-6
see also Synthetic hydrocarbons
Hydrocracked basestocks, turbines, 307-308
Hydrocracking
fixed bed, 24
fluidized bed, 24-25
hydrocarbon base oil, 171
Hydrodynamic film region, 963
Hydrodynamic lubrication, 214, 413,498, 949
Hydrofinishing hydrocarbon base oil, 172
Hydrogen
in petroleum fractions, 195
classification in organic molecules, 788
Hydrogen production, 25-26
Hydrogen refining, hydrocarbon base oil, 171
Hydrolysis
environmental characteristics, 889-890
environmentally friendly oils, 274
pressure media, 279-281
Hydrolytic stability
compressor lubricants, 398
diesters, 251-252
polyolesters, 251-252
pressure media
laboratory aging, 285-287
test stand aging, 287-289
turbine lubricating oils and hydraulic fluids, 339-340
Hydrolytic stability testing, hydraulic fluids, 365-366
Hydroperoxide
decomposers, 791-792
decomposition, 790, 793
oxidation rate and, 790
Hydroprocessing
options, 19
terminology, 18
Hydrostatic tank gauges, 645
Hydrotteated basestocks, turbines, 307-308
Hyfinishing, hydrocarbon base oil, 172
I
/-Chart, 1055-1056
Icing, in LPG systems, 45
Ideal Gas Law, 383
Ignition quality, marine petroleum ftiels, 149-150
Indiana Stirring Oxidation Test, compressor lubricants, 401
Induction Period Method, 813, 815-817
Inductively coupled plasma-atomic emission spectrometry,
elemental analysis, 711-712
Inductively coupled plasma-mass spectrometry, elemental
analysis, 712
Industrial gear lubricants, 453-456
perfr)rmance testing, 240
Indusfrial hydraulic fluids, performance testing, 241
Industrial lubricants, base oil effects, 179-180
Infrared specfroscopy, 665-671
achieving reproducible baselines, 668
analysis of multicomponent solutions, 667-668

band area methods, 668


Beer-Lambert law, 667
compressor lubricants, 400-401
difference method, 668
dispersive-type infrared specttometers, 667
Fourier fransform, 667
gas analysis, 668
hydrocarbon analysis, 668-670
inorganic characterization, 670-671
quench oils, 610
standards, 671
wavelength, wavenumber and frequency, 666-667
Inhibitor content, determination, 194
Inorganic/organic solids, metalworking and machining
fluids, 519
Insolubles, in used oils, 457
Instability, fiiel oils, 762
Insulation fires, mineral oil heat fransfer fluids, 583
International Harvester oxidation corrosion, 811
Invertebrates
acute toxicity tests, 902
chronic and subchronic toxicity tests, 903
Ion chromatography, elemental analysis, 712
Iron based organo-metallics, in gasoline, 69
Iron carboxylate, oxidation rate and, 790
Iron chip corrosion, metalworking fluids, 831
Iron corrosion, compressor lubricants, 398
Isomerization, 14, 16
Iso-propanol, in propane, 47
Isothermal operation, 384
Isothermal transformation diagrams, 589

Jet fiiel, 8, 92-93


additives, 104-105
combustion, 97-98
history, 89, 91
low temperature, 93-94
manufacturing, 103-104
product color, 109
quality control, 107
Smoke Point, 98
visual appearance, 109
volatility and flammability, 98-101
Jet Fuel Thermal Oxidation Tester, 96, 815-816
Jominy bar end-quench test, 591-592
Joule-Thomson cooling, 46
K
Karl Fisher Titration Test, 365
Kerosine, 3
Kinematic viscosity, 837-841
compressor lubricants, 396-397
gear lubricants, 456
history, 841-843
quench oils, 608-609
standards, 875

INDEX

temperature relationship, 854-856


Kinetic coefficient of Iriction, 909

Laboratory aging
hydrolysis stability, 285-287
oxidation stability, 281-283
Lambda values, 912-913
Lattice transition, alkanes, 534
Lead corrosion, 221
Leakage, lubricating greases, from wheel bearings, 565
Leidenfrost temperature, 593
"Liedenfrost effect", 53
Light hydrocarbons
high temperature vapor pressure, 32
low-temperature vapor pressures, 33
Linear reciprocation, 1031-1033
Liquid chromatography
fluorescent indicator adsorption, 659
hydrocarbon analysis, 657-660
principles, 657-658
standards, 660
super critical fluid chromatography, 659-660
Liquid Heptane Washing Test, compressor lubricants, 401402
Liquified petroleum gas, 31-56
auto propane, 51-52
exposure, 54-55
flammability, 52
gas hydrates, 44-46
handling, 52-54
history, 31-32, 35-38
industry, 32, 35
use, 35-37
odorization, 55
properties and thermodynamics, history, 37-38
sample cylinder approvals, 54
specifications, 38-50
composition, 40
contaminants, 49-50
density, 40
dryness of propane, 42-49
history of ASTM standards, 38-39
naturally occurring radioactive materials, 50
octane, 40
olefins, 40-41
residual matter, 49
sampling, 39-40
sulfiir content, 49
vapor pressure, 40-42
volatility residue, 42
uses, 56
vapor, 53
vapor pressure, 703-704
volume correction factors, 50-51
water in, 47-49
LISCIC/NANMAC quench probe, 623-625

1075

Lithium soap greases, 559


Low speed high torque hypoid test, gear lubricants, 459
Low temperature Brookfield viscosity, gear lubricants, 458
Low-temperature flow test, diesel fuel, 123
Low-temperature high-shear tests, lubricants, 882
Low temperature properties
diesters and polyolesters, 251
environmentally friendly oils, 289-291
Low temperature pumpability
hydraulic fluids, 372-373
lubricants, 882
Low temperature storage stability, turbine lubricating oils
and hydraulic fluids, 329
Low-temperature torque, lubricating greases, 563
LPG injector systems, 52
LSR, 3
Lube oil base stock production, 25
Lubricant base oil, market, 169-170
Lubricants
basestocks, 199-200
category chronology, 853
composition, 199
corrosion tests, 827-831
function, 413
high-temperature degradation model, 791
low-temperature high-shear tests, 846-848, 882
low temperature pumpability, 848-851, 882
low temperature requirements, 845-848
oxidation
standards, 823
testing, 818-821
quality ranking, 915-916
Lubricating greases, 439, 478-481, 557-572
accelerated corrosion tests, 568
aluminum soap, 558
apparent viscosity, 562-563
in ball bearings at elevated temperatures, 565-566
black penefration, 561
bomb oxidation test, 565
calcium soap, 558-559
chemical analysis, 569
chemical properties, 478-479
classification, 560
compatibility of blends, 569
complex soap, 559
composition, 557-558
cone penefration, 561
consistency, 560-561
consistency stability, 561-562
contamination, 568-569
copper corrosion, 567-568
corrosion tests, 831-832
dropping point, 563-564
elastomer compatibility, 569
evaporation loss, 564
extreme pressure four-ball test, 566-567
extreme pressure Timken method, 566

1076

MANUAL 3 7: FUELS AND L UBRLCANTS

flow properties, at high temperatures, 562


fretting wear, 567
heat resistance, 563-565
leakage from steel bearings, 565
lithium soap, 559
low-temperature torque, 563
NLGI consistency numbers, 561
oil separation, 564-565
organo-clay, 560
oscillating motion, 567
oscillating wear test, 567
oxidation
induction time, 806-807
stability, 565-566
standards, 823
testing, 804-807
PDSC oxidation test, 565
performance, 480-481
performance testing, 242
polyurea, 559-560
roll stability, 562
rust prevention, 568
selection, 558
in small bearings, 566
sodium soap, 559
specifications, 560
standards, 570-572
discontinued, 570
under development, 570
static bleed test, 569
viscosity, 479-480
water spray-off, 568
water washout, 568
wear preventive characteristics, 567
wheel bearing grease life, 566
Lubricating oil
additives, 952
extreme pressure, oxidation testing, 802
oxidation induction time, 818
Lubrication, 497-500, 909-957
boimdary, 949
elastohydrodynamic, 947-949
friction, 909-911
friction modifiers, 949, 951-952
Hertzian contact, 946-949
hydraulic fluids, 353
hydrodynamic, 949
parameters controlling, 965-966
performance, turbine lubricating oils and hydraulic fluids,
341-342
Petroff s law, 949
regions, thermal considerations, 970
standards, 957
synthetic lubricants, 261-262
types, 214
Lubricity
aerospace fuels, 744-745

HANDBOOK
aviation fuels, 102-103
dieselfiiel, 129-131
gasoline, 85
Lubricity additives, 69
Luminometer, 98
M
MacCoull equation, 854
MacCoull-Walther equation, 919
Macroemulsions, metalworking and machining fluids, 503
Magnetic quenchometer method, quench oils, 614-615
Magnetic residues, LPG, 49-50
Manifold, air temperature and pressure, octane number
requirement and, 76
Mannich products, synthesis, 206-207
Marine petroleum fuels, 145-167
ash, 150
ash modifiers, 154
biocides, 154
carbon residue, 151-152
cat fines, 150
compatibility, 152
demulsiflers, 154
density, 149
diesel plant fuel system, 161-162
environmental considerations, 156
flashpoint, 150
fuel additives, 153-154
heating value, 149-150
ignition quality, 149-150
impact on exhaust emissions, 154
on board testing, 157
oxidation, 152
pour point, 150
sampling, 156
sediment, 152-153
shore side analysis, 156
sodium in, 152-153
specifications, 154-156
stabilizers and dispersants, 153
standards, 167
steam plant fuel service system, 157, 161
storage systems, 157-160
sulfiir, 151
toxicity, 154
transfer systems, 157
vanadium and nickel in, 152
viscosity, 148-149
water in, 151
Marine transport, aviation fuels, 105-106
Mass spectrometry, 662-665
hydrocarbon analysis, 664-665
instrumentation, 663-664
standards, 665
theory, 662-663
Master chart, aviation gas turbine oils, 1012, 1014
McMillan/Murphy pumpability apparatus, 848

INDEX

Measurement process
bias, 1044-1045
manufacturing process control, 1043
precision, 1044-1045
product property conformance to specification, 10431044
self-monitoring, 1044
see also Quality assurance
Melting point, petroleum waxes, 542-545
Mercaptan odorants, 55
Metal content, mineral oil heat transfer fluids, 580-581
Metal deactivators, 795-796
Metal forming fluids, 509, 520
Metal passivators, 319-320, 369-370
Metal preservatives, 830
Metal protecting fluids, 510
Metal ratio, 208
Metal removal fluids, 505-509, 519
Metals
crude oil, 6
oxidation potentials, 220
significance in petroleum products, 707-708
Metal treating fluids, 510
Metalworking and machining fluids, 234, 497-524
additives, 511-519
alkalinity agents, 516
antimicrobial agents, 517-518
anti-misting agents, 516
corrosion inhibitors, 516-517
coupling agents, 513
dispersants, 516
dyes, 519
emulsion promoters, 512-513
film-forming agents, 513-515
foam inhibitors, 518-519
inorganic/organic solids, 519
odor control agents, 519
base fluid, 510-511
classification based on end-use, 505-510
formulations, 519-521
metal forming fluids, 509
metal protecting fluids, 510
metal treating fluids, 510
oil-based, 501
performance testing, 241
semisynthetic fluids, 504-505
slideway lubricants, 510
solid dispersions, 505
soluble oils, 503
synthetic fluids, 503-504
tests, 521-523
used, recycling, 521-522, 524
water-based, 501-503
classification, 503-505
Metering, aviation fiiels, 99-100
Methane, structure, 732
Methanol

Kill

in propane, phase behavior, 46-47


in propylene, 193
Methylcyclopentadienyl manganese tricarbonyl, in gasoline,
68-69
Micellar solutions, metalworking and machining fluids,
501-502
Micro-elastohydrodynamic lubrication, 948-949
Microelemental analysis methods, 712
Microemulsions, metalworking and machining fluids, 504505
Microfihers, 109
"Micro Method" for carbon residue, compressor lubricants,
399
Micronic filters prefilters, 109
Microorganisms, in aviation fuels, 110
Micropitting, 434-435, 977, 979
Micro-scuffing
engine oil performance, 1009-1010
failure criteria, 1001
Military fuel specifications, marine petroleum fuels, 155156
M1L-PRF-2105E, gear lubricants, 451-452
MIL-PRF-7808 oils, 1012-1013
MIL-PRF-23699 oils, 1011
Mineral gas turbine oils, 317-318
Mineral oil heat transfer fluids, 573-585
acid number, 582
autoignition, 581
carbon residue, 580
classification, 575
composition, 575-578
distillation, 582
elastomeric seal compatibility, 581
fluid maintenance, 581
metal content, 580-581
oxidative stability, 580
physical properties, 578-581
pumpability, 579
safety, 583
sampling, 581-583
specific gravity, 580
specific heat, 581
standards, 584-585
thermal conductivity, 581
thermal stability, 579-580
viscosity, 579, 582-583
water content, 583
Mineral oils
aero-engine lubricants, 301
compressor lubricants, 392
hydraulic fluids, 374-375
inhibited
oxidation characteristics, 797-798
oxidation stability, 798-799
rust-preventing characteristics, 829-830
sludging and corrosion tendencies, 798, 830-831
metalworking and machining fluids, 501

1078

MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

organic structures, 576


refrigeration lubricants, 414-415
Mini-rotary viscometer, 849-850
Mixed-film lubrication, 214
Modified Ostwald viscometers, 838-841
Monitors, aviation ftiels, 108
Motor gasoline, see Gasoline
Motor octane number, 73-74
MR-Chart, 1056
MTBE, 16-17, 66
Multi-specimen test machine, 1030-1031
N
Naphthenic base oils, 172
Naphthenic hydrocarbon fractions, 527
Naphthene, determination, 195
Natural gas liquids volume correlation factors, 50-51
Natural Gasoline Association of America, 37
Naturally occurring radioactive materials, in LPG, 50
Near-surface region, 964
Neutron activation analysis, elemental analysis, 712-713
Nickel content, 152,775
Nitrogen, crude oil, 6
Nitrogen compound reactivity, hydrocarbon base oil, 177178
Nitrogen level, gear lubricants, 458
NLGI consistency numbers, 561
Nonleaded gasoline, 63-64
Non-lubricating process fluids, 587-632
aqueous polymer quenchants, 605-606
standards, 630-632
temperature gradient quenchant analysis, 623-629
see also Quench oils
Non-petroleum materials using ASTM flow properties, 867872
Normality checks, 1052-1055
NOK,Clean Air Act, 64
Nuclear magnetic resonance spectroscopy
hydrocarbon analysis, 649-652
hydrocarbon base oil, 174-175
principles, 649-650
standards, 651-652
O
Occupational exposure limits, LPG, 54
Octane
distribution throughout fuel boiling range, 75
liquified petroleum gas, 40
Octane number requirement, 75-78
air-fuel ratio, 76
compression ratio, 76
effect of engine deposits, 77
engine design parameters, 76
engine spark timing, 76-77
manifold air temperature and pressure, 76
Octane rating, history, 62-63
Octane rating analyzers, on-line, 74-75

Octanol/water partition coefficient, 887


Odor, petroleum waxes, 549, 551
Odor control agents, metalworking and machining fluids,
519
Odorization, LPG, 55
OEM specifications, gear lubricants, 451, 453
Oil blending calculations, 856
Oil content, petroleum waxes, 546
Oil film wash-oil resistance, compressor lubricants, 401-402
Oil-off testing, 982-983
Oil separation, lubricating greases, 564-565
Oil-soluble dye, in gasoline, 69
Oil stability index, 821
Oil stain, LPG, 49
Olefin
saturation, 17-20
sulfurization, 216
Olefin-based polymers, 224-226
Olefin content, 28
hydrocarbon base oil, 178
liquified petroleum gas, 40-41
Optical texture, petroleum coke, 775-776
Organo-clay greases, 560
Organo-metallics, iron based, in gasoline, 69
Orifice viscometers, 864-865
Oscillating motion, lubricating greases, 567
Oscillating wear test, lubricating greases, 567
Oxidation, 787-823
automotive lubricants, 476-477
aviation fuels, standards, 823
biodegradable lubricants, standards, 823
engine oils, standards, 823
extreme pressure oils, 458
gasolines, standards, 823
gear oils, standards, 822
grease, standards, 823
hydraulic fluids, standards, 822
hydrocarbon base oil, 175-176
hydroperoxide decomposers, 791-792
lubricants, 787-796
standards, 823
marine petroleum fuels, 152
mechanism, 789
pressure media, 277, 279
radical scavengers, 791-792
role of metal ions, 793-794
turbine oils, standards, 822
Oxidational wear, 933
Oxidation heat release, 752-753
aerospace fuels, 735
Oxidation induction time, lubricating oils, 818
Oxidation inhibitors, see Antioxidants
Oxidation potentials, metals, 220
Oxidation stability
ASTM D 4814, 82-83
automotive gear oils, 803-804
automotive transmission fluids, 804

INDEX

aviation fuels, 813


diesel&el, 126-127
distillate fuel oil, 816-817
environmentally friendly oils, 274-275
gasoline, 813, 815-817
lubricating greases, 565-566
mineral oil heat transfer fluids, 580
pressure media, 281-284
laboratory aging, 281-283
test stand aging, 282-284
synthetic lubricants, 258. 260-261
turbine lubricating oils and hydraulic fluids, 338-339
Oxidation Stability test, aviation fuels, 102
Oxidation testing, 315, 317, 796-822
antiwear, 797-798
biodegradable lubricants, 820-822
engine oils, 807-811
fuels, 811,813, 815-818
gasolines, 811,813, 815-818
gear oils, 802-804
grease, 804-807
hydraulic fluids, 356-357
lubricants, 818-821
purpose of testing, 796
using universal glassware, 802-803
Oxygen, crude oil, 6-7
Oxygenated polymer, formation, 790
Oxygenates, 7, 29
addition to gasoline, 65-66
in gasoline, 68

Paddle type rotational viscometer, 835-836


Paint Compatibility Test, compressor lubricants, 409-410
Paints, flow-related instruments, 867
Panel Coker Test, 818-819
Paraffin, determination, 195
Paraffinic base oils, 172
Paraffinic hydrocarbon fractions, 527
Partial least squares modeling, 179
Partial oxidation, 26
Particulate emissions, diesel engines, 720
Particulates, in LPG, 49-50
PDSC oxidation test, lubricating greases, 565
Pearlite, 587
Peng-Robinson Equation of State, 81
Penn State micro-oxidation test apparatus, 807
Pensky-Martens Closed Cup Tester, 692-694
Perfluoroalkyl ethers, 259
Performance additives, gasoline, 69-70
Performance maps, 945, 968-969
bearing and gear contacts and, 972-973
generalized, 987-988
lubrication atfributes, 967
wear and fraction within, 968, 970
Performance package, 235
Performance testing, see Additives

1079

Permanent shear stability index, 853


Peroxide number, pefroleum waxes, 549
Peroxides, in butadiene, 193-194
Petroff s law, 949
Pefroleum coke, 768-778
ash, 775
classification, 773
crystalline structure, 775-776
density, 775
feedstocks, 772
microtexture formation, 770-772
optical texture, 775-776
production processes, 768-770
properties, 773-774
reactivity, 778
standards, 783-784
sulfijr content, 775
thermal expansion, 777
frace metals contents, 775
volatile matter, 774-775
Petroleum fractions, hydrogen in, 195
Petroleum gas, sulfur content, 194-195
Pefroleum industry, history, 145
Petroleum oil, 3-29
classification, 576
alkylation, 15-17
capacity as percent of crude, 5
catalytic reforming, 12-15
cogeneration, 28
crude oil, 6-7
preparation and separation, 9-10
fluid catalytic cracking, 9-12
fufrire, 28-29
gas solubility in, 406-407
heteroatom removal and aromatic/olefin saturation, 17-20
hydrogen production, 25-26
isomerization, 14, 16
lube oil base stock production, 25
MTBE, 16-17
pollution control, 27-28
product blending, 28
products, 7-9
refinery flow plan, 3-5
resid conversion and upgrading, 20-25
sulfur recovery, 26-27
Petroleum pitch, 763-768
ash, 768
carbon fibers, 781
coking value, 767-768
density, 768
production processes and applications, 763
properties, 763-764
softening point, 764
solvent fractionation, 765-767
standards, 783-784
sulfur content, 768
viscosity, 764-765

1080

MANUAL 37: FUELS AND LUBRICANTS

Petroleum waxes, 525-555


additive effect, 542
blocking point, 552-553
carbonizable substances, 549
cloud point, 545-546
coefficient of kinetic friction, 552, 554
color, 549-551
composition, gas chromatography, 549
compositional and molecular characteristics, 531-533
congealing point, 545
crystal structure, 533-535
dewaxing process variables, 530-531
differential scanning calorimetry, 539-542
equations of state, 535-539
gloss retention, 549
hardness, 547-548
hot tack, 552
melting point, 542-545
odor, 549, 551
oil content, 546
peroxide number, 549
physical properties, 533
pour point, 545
solvent dewaxing process, 529-530
solvent solubility, 546
specular gloss, 549, 552
standards, 554-555
surface wax, 549, 551
total wax content, 552
transition temperatures, differential scanning calorimetry,
548
types of, 531
viscosity, 546-547
wax finishing process, 531
weight of wax applied during coating, 552
pH determination, polymer quenchants, 617-618
Philippoff rotary viscometer, 849
Phosphate esters, compressor lubricants, 395
Phosphonic acid dispersants, synthesis, 206-207
Phosphorus content
ASTMD4814, 82
automotive lubricants, 471
gear lubricants, 457
Photolysis, environmental characteristics, 890
Photooxidation, environmental characteristics, 890
Pin and Vee Block tester, 1025-1026
Pin-on-Disk test, 1026
Pitting, 434
Pipelines, aviation fuels, 105
Plants, toxicity tests, 903
Plastics, viscosity, 869-870
Plate-to-plate geometry, 835
Ploughing, friction due to, 911-912
Polar additives, adsorption on metal surface, 211-212
Polishing wear, 923, 929
Pollution control, petroleum oil refining, 27-28
Polyalkylene glycols, 252-256

HANDBOOK
application and performance characteristics, 255-256
chemical characteristics, 254-255
chemistry, 253
compressor lubricants, 392-393
physical properties, 254
refrigeration lubricants, 417-418
synthesis, 253-254
Polyalphaolefins, 257-258
compressor lubricants, 393-394
refrigeration lubricants, 415-416
for turbines, 308-309
Poly(ethylene) waxes, 525
Polymer, viscosity, 869
loss due to degradation, 228-230
Polymer-containing oils, shear stability, 851-853
Polymeric additives, 223-233
Polymeric thickeners, gear lubricants, 441-442
Polymer molecular weight analysis, polymer quenchants,
620
Polymer quenchants
appearance, 616
biological stability, 620-623
cloud point, 619
conductance, 618-619
cooling curve analysis, 621-623
corrosion inhibitor, 619-620
fluid biodeterioration, 620-621
foam testing, 620
pH determination, 617-618
polymer molecular weight analysis, 620
refractive index, 616-617
viscosity, 617-618
water content, 617
Polyolesters, 249-252
application and performance characteristics, 252
biodegradability, 252
chemical characteristics, 251
chemistry and manufacturing, 249-251
manufacturing technology, 250-251
physical properties, 251
refrigeration lubricants, 416-417
Polyphenyl ethers, 259-260
Polyurea greases, 559-560
Polyvinylethers, refrigeration lubricants, 418
Potential Residue Method, 815
Pour point, 879-880
compressor lubricants, 397
diesel fuel, 122-123
effect of double bonds, 273
esters, 273
fuel oils, 761
gear lubricants, 454
marine pefroleum fuels, 150
petroleum waxes, 545
standards, 874
turbine lubricating oils and hydraulic fluids, 329
Pour point depressants, 205, 230-232

INDEX

gear lubricants, 441


hydraulic fluids, 373
Power transfer, hydraulic fluids, 353-354
Power transmission fluids, performance testing, 239
Precipitation number
compressor lubricants, 399-400
gear lubricants, 453
quench oils, 613-614
Precision
measurement process, 1044-1045
monitoring, 1045-1047
Pressure differential scanning calorimetry, 806, 818
Pressure drop, 574-576
Pressure media, 267
hydrolysis, 279-281
hydrolysis stability, aging, 285-289
oxidation, 277, 279
oxidation stability, aging, 281-284
type, 268-269
see also Hydraulic fluids
Pressure-viscosity coefficient, 916- 920, 985-987
Propane
auto, 51-52
depressurized, 46
dryness, 42-49
auto-refrigeration, 46
dissolved water, phase of behavior, 43-44
gas hydrates, 44-46
methanol, phase behavior, 46-47
water measurement, 47-49
water sources, 47
liquid, 53
phase behavior of dissolved water in, 43-44
Propane deasphalting, hydrocarbon base oil, 171
Propane hydrates, 45
Propane P-H diagram, 34
Propylene
characterization, 192-193
production, 190
Pumpability
low temperature, lubricants, 848- 851
mineral oil heat transfer fluids, 579
PV curves, 384

Quality assurance, 1043-1060


approximate F-test, 1059-1060
ARV assignment, 1048
batch change of material, 1047
check standard composition, 1048
chi-square test, 1059
control chart, 1055-1056
data treatment, 1046-1047
estimate process precision and bias, 1048
EWMA overlay, 1056
implementation aspects, 1049
interlaboratory exchange testing, 1049

1081

material selection, preparation and storage, 1046


material testing, 1046
monitoring bias, 1047-1048
monitoring stability and precision, 1045-1047
MR-Chart, 1056
normality checks, 1052-1055
run chart, 1051-1052
standards, 1050
statistical tools, 1050-1051
system validation, 1049
Mest, 1058-1059
Quality control
aviation fuels, see Aviation fuels
airport, 110-111
elemental analysis, 716
Quench oils, 602-605
acid number, 609-610
ash content, 614
carbon residue, 611-613
contamination, 610-614
fire and flash points, 609
infra-red spectroscopy, 610
kinematic viscosity, 608-609
magnetic quenchometer method, 614-615
precipitation number, 613-614
properties, 604
saponification number, 610
specific gravity, 609
water content, 610-611
R
Rabinowitz abrasive wear model, 930
Radical scavengers, 791-792
Rail transport, aviation fuels, 106
Ramsbottom carbon residue, compressor lubricants, 399
RBOT test, 315-316
compressor lubricants, 401
Reaction temperature, maximum, 754-756
Reactivity, petroleum coke, 778
Reavell VHP 15 Compressor Rig Test, 403
Reciprocating compressors, 386-388
Recycling, used lubricants, 521-522, 524
Redlich-Kwong equation, 536
Reference gauge point, 636
Reformulated gasoline, 65-66
Refractive index, polymer quenchants, 616-617
Refrigeration lubricants, 413-429
acid catchers, 419
additives, 418-420
alkylbenzene, 415
antifoaming agents, 419-420
antioxidants, 419
antiwear additives, 419
chemical structure, 414-418
choice, 413-414
circulation, 424-428
density, 421

1082

MANUAL 3 7: FUELS AND LUBRLCANTS

dibasic acid esters, 416


equipment line sizing, 426
HVAC cycle, 424-426
mineral oils, 414-415
performance effects, 428
polyalkylene glycols, 417-418
polyalphaolefms, 415-416
polyolesters, 416-417
polyvinylethers, 418
properties, 415, 420
selection, 426-427
solubility, 422-424
standards, 428-429
system operational envelope, 427
viscosity, 420-422
Reid method, 698-700
Reid vapor pressure, 99
Remaining useful life evaluation rig, 820-821
Repressed oil, refining process, 278
Re-refining, hydrocarbon base oil, 172
Research Octane Rating, 62, 74
Resid, 20-25
delayed coking, 21-23
fixed bed hydrocracking, 24
fluid coking/flexicoking, 24
fluidized bed hydrocracking, 24-25
solvent deasphalting, 21-22
visbreaking, 20-21
Residual matter, LPG, 49
Reverse-flow viscometers, 838
Reynolds equation, 948
Rheology, 833-835
hydrocarbon base oil, 178
Risk, environmental characteristics, 904
Road transport, aviation fuels, 106
Rolling ball viscometer, 836
Rolling velocity, Ryder gear, 997-1000
Roll stability, lubricating greases, 562
R & O oils, performance testing, 241-242
Rotary compressors, 388-389
Rotary lobe compressor, 389
Rotary Pressure Vessel Test, 281, 798
Rotary screw compressor, 388-390
Rubber, base oil compatibility, 181
RULER, 820-821
Run chart, 1051-1052
Rust, chemistry, 825-826
Rust formation, electrochemical nature, 825-827
Rusting behavior, turbine lubricating oils and hydraulic
fluids, 340-341
Rust inhibitors, 218, 220-223
gear lubricants, 456
hydraulic fluids, 369-370
lubricating greases, 568
for turbines, 318-320
Ryder gear

HANDBOOK
applicability of WAM high speed load capacity test
method, 1010
backgroimd of load capacity testing, 1001
contact stress simulation, 997-1000
data processing and traction behavior, 1003, 1004-1007
failure criteria in terms of scuffing and micro-scuffing,
1001
link to service performance, 1008-1009
OEM proposed criteria, 1009-1010
oil evaluation, 1000-1010
performance criteria, 1007-1008
procedure, 1003
rolling and sliding velocities across tooth face, 997-1000
simulation approach, 1001-1003
surface film formation, 1007
test description, 1003-1005
tooth temperatures, 996-997
Ryder gear scuffing
criteria, 995-996
effect of oil chemistry, 992-994
effect of load stage, 993-994
initiation, 990-992
Ryder Gear Test, 320-321
simulation conditions, 996-1000
test conditions, 988-990

SAE 3306 viscosity classification, gear lubricants, 449-451


Safety
aerospace fuels fueling, 744
mineral oil heat transfer fluids, 583
Salt spray, 829
Sampling, LPG, 39-40, 48
Saponification, esters, 280
Saponification number, quench oils, 610
Sasol distillate fuels, 138
Saybolt patent, 37
Saybolt viscometer, 842, 865, 870
Saybolt viscosity, standards, 874
Scuffing, 435, 458, 936-937
boundary, 968-969
engine oil performance, 1009-1010
failure criteria, 1001
front, propagation, 992-993
initiation features on Ryder gears, 990-992
oil chemistry effect, 992-994
progression, tribological processes, 993-996
Scuffing load ball-on-cylinder lubricity evaluator, 129-130
Seal compatibility
compressor lubricants, 409
gear lubricants, 459
hydrauhc fluids, 370
lubricating greases, 569
Seals, functions, 233-234
Seal swell agents, hydraulic fluids, 370
Sediment, marine petroleum fuels, 152-153
Sediment toxicity tests, 903

INDEX

Semisynthetic fluids, metalworking and machining fluids,


504-505
Servo-operated automated tank gauge, 645
Setaflash Closed Cup, 693
Shear stability
gear lubricants, 459
hydraulic fluids, 371-372
polymer-containing oils, 851-853
requirements, 228-229
turbine lubricating oils and hydraulic fluids, 340
Short capillary viscometers, 865
Short-trip-service engine rusting, 471
Silicones, 258-259
compressor lubricants, 394-395
Slideway lubricants, 510
Sliding
gross, surface distress testing, 975-977
incipient, surface distress testing, 974-975
velocity, 966, 997-1000
Sludge, formation by zinc dialkyldithiophosphate, 356-357
Small scale closed cup, 693
Smearing wear, 923, 929
Smoke Point, 98
Smoke tendency, aerospace fuels, 741
Snelling, Walter, 36
Soap content, detergents, 208
Soave-Redlich-Kwong equation, 536
Sodium, in marine petroleum fuels, 152
Sodium soap greases, 559
Softening point, petroleum pitch, 764
Solid dispersions, metalworking and machining fluids, 505
Solidification, aerospace fuels, 737-738
Solid lubricants, 483-484
Solid particles, in aviation fiaels, 109
Solubility, refrigeration lubricants, 422-424
Soluble gum, ASTM D 4814, 83
Soluble oils, metalworking and machining fluids, 503
Solvent
deasphalting, 21-22
dewaxing process, 529-530
fractionation, pefroleum pitch, 765-767
refining
hydrocarbon base oil, 171
process, 306-307
solubility, pefroleum waxes, 546
Sommerfeld number, 1022-1023
Sonic shear, turbine lubricating oils and hydrauHc fluids,
340
Soot, 203-2-4, 720-721
"Space velocity", 18
Spark-ignition engine fiiels
specifications, see ASTM D 4814
vapor-liquid ratio, 703
Spark ignition engines, 70-71
Specific gravity
compressor lubricants, 397
mineral oil heat transfer fluids, 580

1083

quench oils, 609


Specific heat
compressor lubricants, 408-409
mineral oil heat fransfer fluids, 581
Specific impulse, aerospace fuels, 742-743
Specfromettic identification, base oil components, 172-174
Specular gloss, pefroleum waxes, 549, 552
Sponge coke, removal, 23
Spontaneous ignitability, aerospace fiiels, 733-734, 738
Spray ignition tests, turbine lubricating oils and hydraulic
fluids, 334-336
Squeeze films, 499
Stability, diesel fiiel, 125-126
Stabilization patent, 37
Stabilizers, in marine petroleum fuels, 153
Stabilizers/deposit control agents, 201-211
Standard platinum resistance thermometers, 866-867
Standard reference materials, elemental analysis, 714
Surfactants, in aviation fiiels, 110
Static bleed test, lubricating greases, 564, 569
Static elecfricity, 85, 103
Static gases, thermodynamic properties, 749-750
Static petroleum measurement, 635-648
automatic tank gauging, 645
bottom sample, 641-642
examples, 644-645
free water, 639-640
gauging diagram, 636
gross observed volume, 646-647
innage gauge, 643-644
official sample, 641, 643
on-board quantity/remaining on board, 645
other standards, 648
pipeline samples, 642
representative sample, 641
spot samples, 641-642
standards, 656-657
tapes and bobs, 636-638
temperature in tank, 638, 643
weighted bottle sampler, 640-641
Statistical quality conttol tools, 1050-1051
Steam cracking, ethylene, 188-190
Steam plant fuel service system, 157, 161
Steam reforming, 25-26
Steam turbine, 297-298
conttol fluid system, 301
shaft driven lubrication system, 300
Steam turbine oil
oxidation stability, 798
rust-preventing characteristics, 830
Steel
cooling behavior, wetting process impact, 594-595, 597
cooling curve analysis, standards, 606-607
cooling curve data acquisition and analysis, 595-598
cooling time and rate parameters, 597, 599
corrosivity, aviation fuels, 102
film boiling, factors influencing, 594, 596

1084

MANUAL 37: FUELS AND LUBRICANTS

hardenability, 589-591
measurement, 591-593
hardening capability, 599
shock film boiling, 599-602
transformation, 587-589
wetting kinetics, 593-596
Steel quenching
acoustical measurements, 600-602
bath maintenance, 607-608
process analysis example, 626-629
Steric stabilization, 204-205
Stoichiometry, aerospace fuels, 734-735, 738-739
Storage stability
aerospace fuels, 732
aviation fuels, 102
diesel fuel, 127-128
distillate fuel, 817-818
gear lubricants, 460
low temperature, 329
Stormer viscometer, 868
Strainers, diesel fuel system, 163-164
Stribeck curve, 945-946, 949, 1022-1023
Styrene-diene polymers, 225
Subsurface region, 964-965
Sulfur content, 19, 28-29
ASTMD4814, 82
diesel fuel, 134
crude oil, 6
fuel oils, 762
gear lubricants, 457
impact on base oil chemistry, 176-177
LPG, 49
marine petroleum fuels, 151
petroleum coke, 775
petroleum gas, 194-195
petroleum pitch, 768
Sulfur recovery, 26-27
Super critical fluid chromatography, hydrocarbon analysis,
659-660
Surface analysis, methods, 950-951
Surface conformity, 914-916
Surface distress testing
other types, 976-978
imder incipient sliding, 974-975
Surface energy, 922
Surface fatigue, impact of oil attributes, 972, 974
Surface film region, 963-964
Surface films, 919, 921-923
Surface roughness, 911-913
data analysis, 913-916
Surface tension, aerospace fuels, 738
Surfacewax, 549, 551
Synchronizer SSP 180 test, gear lubricants, 459
Synthetic basestocks, compressor lubricants, 392
Synthetic ester fluids, for turbines, 309-311
Synthetic fluids, metalworking and machining fluids, 503504

HANDBOOK
Synthetic hydrocarbons, 185-196
analytical test methods, 192
basestocks, 185-186
boiling range, 195
butylene and butadiene production, 190-192
C-4 product, characterization, 193-194
ethylene, 186-190, 192
propylene, 190, 192-193
standards, 195-196
Synthetic lubricants, 249-264
alkylated cyclopentanes, 260
biodegradability, 263
classes, 249
cyclohexane derivatives, 260
environmental acceptability, 262-263
FDA incidental food contact approval, 263
lubrication, 261-262
perfluoroalkyl ethers, 259
polyalkylene glycols, 252-256
polyalphaolefins, 257-258
polyphenyl ethers, 259-260
raw materials, 249-250
relative cost, 263
silicones, 258-259
standards, 263-264
Synthetic waxes, 525
System operational envelope, refrigeration lubricants, 427

Tag Open cup, 693


TAME, 17
Tankage, gas turbine fuel system, 165
Tapping torque test, 1030
Temkin isotherm, 953-954
Temperature, kinematic viscosity relationship, 854-856
Temperature gradient method, 623, 625
Temperature gradient quenchant analysis, 623-629
Terminology, 1038-1041
Terrestrial toxicity tests, 903
Test stand aging
hydrolysis stability, 287-289
oxidation stability, 282-284
Thermal and oxidation test, gear lubricants, 458
Thermal conductivity
compressor lubricants, 408-409
gasoline, 84
mineral oil heat transfer fluids, 581
Thermal cracking reaction mechanism, ethylene, 188
Thermal expansion, petroleum coke, 777
Thermal oxidation stability, aviation turbine fuels, 815-816
Thermal stability
aerospace fuels, 745-746
diesel fuel, 126
diesters, 251
hydraulic oils, 799-800, 830
mineral oil heat transfer fluids, 579-580
polyolesters, 251

INDEX

turbine lubricating oils and hydraulic fluids, 339


Thermodynamic properties, 750
static gases, 749-750
Thermo oxidation engine oil simulation test, 808-812
Thickening efficiency, 225-226
Thin film oxygen uptake test, 807-809
Three-terminal resistivity cell, 343
Thrust washer tester, 1030-1031
Timken extreme pressure test machine, 1030-1031
lubricating greases, 457, 566
Tool wear, metal removal fluids, 507-509
TOST test, 315
Total base number, detergents, 208-209
Total wax content, petroleum waxes, 552
Toxicity
acute tests, 894,901-902
chronic tests, 894
complex mixture, environmental characteristics, 900-901
marine petroleum fuels, 154
Trace metal contents
limits, gas turbine fuels, 141-142
petroleum coke, 775
turbine lubricating oils and hydraulic fluids, 343
Traction, within performance maps, 968, 970
Traction coefficient, 970-972
Traction test plots, 980
Tractor fiuids, 374
Tractor hydraulic fluids, performance testing, 240-241
Transformation processes, environmental characteristics,
889
Transition metals, as both oxidation promoters and
inhibitors, 793, 795
Transmission fluids, 477-478
irictional properties, 212-213
performance tests, 239
standards, 489-490
Transport processes, environmental characteristics, 888-889
Triaryl phosphates, for turbines, 310, 312
Tribochemical wear, 933
Tribochemistry, lubricated wear contact, 949
Tribological aspect number, 1024-1025
Tribological features, microscopic examination, 991-992
Tribological processes, scuff progression, 993-996
Tribology
definition, 909
history, 1017
systematic
dynamic mechanisms, 963-965
gear lubrication, 988-996
hydrodynamic film region, 963
impact of oil attributes on surface fatigue, 972, 974
lubrication regions, thermal considerations, 970
micro-pitting results, 977, 979
multi-dimensional oil characterization, 968-969
near-surface region, 964
oil-off testing, 982-983

1085

parameters controlling lubrication and failure


mechanisms, 965-966
performance maps, generalized, 987-988
subsurface region, 964-965
surface distress testing, 974-976
under gross sliding, 975-977
under incipient sliding, 974-975
surface film region, 963-964
testing for adhesive wear, 979-982
traction coefficient, 970-972
WAM test machine technology, 967-968
Tribology test systems, 1017-1018
component test design, 1021
designing, 1018-1020
duration, 1023
economic comparison, 1018
load, 1022
materials, 1023
parameter selection, 1021-1024
selecting, 1020-1021, 1024-1025
special atmospheres, 1023
special testing, 1024
speed, 1022-1023
temperature, 1021-1022
test fluids, 1023-1024
Tribo-system, see Tribology, systematic ?-test, 1058-1059
TTT diagrams, 589
Turbine lubricating oils and hydraulic fluids, 297-349
acid number, 329, 331
additives, 312-323
antifoams, 321-323
antioxidants, 312-318
antiwear and extreme-pressure, 319-321
rust and corrosion inhibitors, 318-320
air release, 332-334
basestocks, 305-312
hydrocarbon oils, 305-306
hydrocracked/hydrotreated, 307- 308
polyalphaolefins, 308-309
solvent-refined types, 306-307
synthetic ester fluids, 309-311
triaryl phosphates, 310, 312
chlorine content, 334
classification, 323-324
cleanliness, 341-343
compatibility with system materials, 343-346
density, 332
duty cycle, 304
effect of maintenance, 304
fire-resistance tests, 334-337
fire-resistant, 301, 311
foaming, 332-334
function, 300
future trends, 349
hot surface tests, 335
hydrolytic stability, 339-340
importance of system cleanliness, 346-347

1086

MANUAL 3 7: FUELS AND L UBRICANTS

low temperature storage stability, 329


lubrication performance, 341-342
maintenance, 347-348
oil types, 305
operating environment, 300-305
oxidation
characteristics, 797-798
stability, 801
standards, 822
oxidative stability, 338-339
performance requirements, 326-328
performance testing, 241-242
pour point, 329
resistance to shear in a diesel-injector nozzle, 340
rusting and corrosion behavior, 340-341
shear stability, 340
sonic shear, 340
spray ignition tests, 334-336
stability testing, 317, 400-401
standards, 323-326
thermal/oxidative stress, 303
thermal stability, 339
top-up rates, 304
trace metals, 343
viscosity, 326-330
volatility, 346
volume resistivity, 343-345
water content, 331-332
water separability, 335-336, 338
wick tests, 335, 337
Turbine oil system, in service monitoring, 798-802
Turbines
gas, 298-299
steam, 297-298
system cleanliness, 346-347
water, 298-299
wind, 299
Turbofan combustion system, 97
U
Ultraviolet spectroscopy
Beer's law, 661
hydrocarbon analysis, 661-662
principles, 660-661
standards, 662
Unique process line, 750-752
Used oils, wear metals, 707-709

Vacuum gas oils, 4


Vacuum potstill method, 696-697
Vacuum resid, 4
Vanadium content, 152-153, 775
Vane pump wear test, 362-363
Vapor control systems, 64-65
Vapor-liquid ratio, 78, 703
Vapor lock temperature, 79

HANDBOOK
Vapor pressure, 697-704
automatic method, 701
crude oils, 702
environmental characteristics, 888
evacuated chamber method, 703
gasoline, 699, 701
gasoline-oxygenate blends, 699, 701
liquified petroleum gas, 40-42, 703-704
mini-method, 701-702
mini-method-atmospheric, 702
Reid method, 698-700
triple-expansion method, 702-703
vapor-liquid ratio
Vegetable waxes, 525
Vehicle emission standards, history, 63
Vickers pump stand, 1035
Visbreaking, 20-21
Viscometer geometries, 835-836
Viscosity, 500-501
absolute, water, 863-864
adhesives, 870-872
aerospace fuels, 737
apparent, lubricating greases, 562-563
automotive lubricants, 475-476
bituminous materials, 870-872
bubble tubes, 868
coatings, 867
diesel fuel, 121
diesters, 251
dip cups, 867-868
environmentally friendly oils, 273, 289-290
falling needle, 868-869
fuel oils, 760-761
gas/liquid mixtures under pressure, 408
gasoline, 84-85
greases, 479-480
hydraulic fluids, 359-360
jet fuel, 94
loss
due to polymer degradation, 228-230
shear-related, 225, 227-228
marine petroleum fuels, 148-149
mineral oil heat transfer fluids, 579, 582-583
paints, 867
petroleum pitch, 764-765
petroleum waxes, 546-547
plastics, 869-870
polymer quenchants, 617-618
polyolesters, 251
refrigeration lubricants, 420-422
rubber, 872
standards, 864-867, 872-875
temperature measurement considerations, 866-867
tests, 237
turbine lubricating oils and hydraulic fluids, 326-330
visualization, 835
see also Kinematic viscosity

INDEX

Viscosity control, diesel fuel system, 164


Viscosity index, 856-863
calculation, 858-863
gear lubricants, 457
pressure considerations, 859, 862- 863
Viscosity index improvers, hydraulic fluids, 371-372
Viscosity modifiers, 223-224, 235
Viscosity-pressure coefficient, effect of base oil
composition, 180-181
Volatile matter, petroleum coke, 774-775
Volatility, 675-705
aerospace fiiels, 736-737
automotive lubricants, 471
aviation fuels, 98-101
class specifications, ASTM D 4814, 82
crude oil distillation, 696-698
diesel fuel, 120-121
diesters, 251
distillation, 675-682
environmental characteristics, 896, 900
flammability, 682, 690-696
gasoline, 78-80
polyolesters, 251
standards, 704-705
turbine lubricating oils and hydraulic fluids, 346
vapor pressure, 697-704
Volatility residue, LPG, 42
Volume correction factors, liquefied petroleum gas, 50-51
Volume resistivity, turbine lubricating oils and hydraulic
fluids, 343-345
W
Walther equation, 917
WAM configuration, optical EHD film thickness
measurement, 984-985
WAM high speed load capacity test method, engine oils,
1010
WAM test machine technology, 967-968
Waste heat economizers, diesel fuel system, 165
Water, absolute viscosity, 863-864
Water-absorbing cartridges, 108
Water-based, metalworking and machining fluids, 501-503
Water content
aerospace fuels, 746-747
compressor lubricants, 397
dissolved in propane, phase behavior, 43-44
gear lubricants, 457
hydraulic fluids, 363, 365
LPG, 42-49
marine petroleum fuels, 151

1087

mineral oil heat transfer fluids, 583


polymer quenchants, 617
quench oils, 610-611
turbine lubricating oils and hydraulic fluids, 331-332
Water separability, turbine lubricating oils and hydraulic
fluids, 335-336, 338
Water solubility, environmental characteristics, 887
Water spray-off, lubricating greases, 568
Water tolerance, ASTM D 4814, 83
Water turbines, 298-299
Water washout, lubricating greases, 568
Wax appearance point, 881-882
Waxy crude oil, 527-528
Wear
combinations of cavitation/erosion/corrosion wear, 932933
debris analysis, 939-941
mechanisms, 923, 927-931
standards, 1035-1037
testing, 938-941
within performance maps, 968, 970
Wear contact, material structure, 916-925
Wear maps, 942-945
Wear material, surfaces, 949
Wear metals, used oils, 707-709
Wear preventive characteristics, lubricating greases, 567
Wear protection, hydraulic fluids, 359-364
Wear reduction, heat of adsorption, 954
Wear surfaces, 911-913
Weathering, liquified petroleum gas, 42
Weighted bottle sampler, 640-641
Wheel bearing grease life, 566
Wheel bearings, grease leakage, 565
Wick tests, turbine lubricating oils and hydrauhc fluids,
335, 337
Wind turbines, 299
Wolf Strip Oxidation Test, compressor lubricants, 401
World Wide Fuel Charter, 137
Worms, toxicity tests, 903-904
X
X-ray fluorescence spectrometry, elemental analysis, 713

Yellow metal corrosion, 221

Zinc dialkyldithiophosphate, 314


oxidation inhibition, 794
sludge formation, 356-357

You might also like