The Cr-Mo Steels

A Cornerstone of the Modern Power and

Petrochemical Industries
J. F. Henry

IIW-AWS
Technical Lectures
The Cr-Mo Steels
January/February 2006

Topics of Discussion

History of the Cr-Mo Steels Lesson 1

Basic Metallurgy of the Cr-Mo Steels Lesson 2
Welding Issues Lesson 2
Temper Embrittlement Lesson 3
Weld-Related Failures Lesson 4
The New Generation of Creep Strength-Enhanced
Ferritic Steels Lesson 5
Issues of Concern Regarding Control of the Advanced
Alloys Lesson 6
Lesson 1
IIW-AWS
January/February 2006

History: 80 Years of Critical Industrial

Service

Tosco, Martinez oil refinery

Oil is King!
Texas Newspaper - 1922

Lesson 1
IIW-AWS
January/February 2006

History of Development

Serious development of alloy steels began

in early 1920s
Development driven by changes in refinery
practice

Lesson 1
IIW-AWS
January/February 2006

Changes in Refining Requirements

Increasing demand for gasoline, spurred by mass

production of automobiles
Higher temperatures required for cracking process used to
produce gasoline
Refining temperatures began to exceed the capabilities of
carbon steels in terms of both mechanical strength (i.e.,
creep strength) and corrosion resistance

Lesson 1
IIW-AWS
January/February 2006

Corrosion Resistance

Increasing use of West Texas Sour crudes

Excessive corrosion of carbon steels
Initial use of 12Cr & 18Cr/8Ni stainless steels to combat
more aggressive feed stocks
Desire for cheaper materials led to development of 5%Cr
steel in 1928

Lesson 1
IIW-AWS
January/February 2006

Elevated Temperature Strength

At higher processing temperatures required for new cracking

operations, carbon steel inadequate
Discovery that additions of molybdenum (Mo) or tungsten (W)
substantially improved elevated temperature performance
Addition of Mo and/or W to 5Cr steel offered better elevated
temperature strength (compared to CS) in an alloy that was
more resistant to sulfur-based corrosion than CS
Mo became the alloy addition of choice lower cost and
improved resistance to temper embrittlement

Lesson 1
IIW-AWS
January/February 2006

Milestones In Alloy Development

Lesson 1
IIW-AWS
January/February 2006

Developing New Alloys

Variations in the composition of refinery feed stock,

particularly sulfur content of crude, led to demand for
alloy tailoring
For sweet crudes (lower S), lower Cr content needed for
corrosion resistance, and improved creep strength obtained
through additions of Mo and, in some cases, vanadium (V).
This led to development of leaner alloys:
a) 1-3%Cr with Mo or W
b) 2Cr-1/2Mo for resistance to graphitization
Lesson 1
IIW-AWS
January/February 2006

By the mid
1930s the
basic group of
Cr-Mo steels
had been
approved by
ASTM/ASME

Lesson 1
IIW-AWS
January/February 2006

Evolution of Alloy Development

Piercing Mill Making A Seamless Tube Of

7%Cr Steel
(Timken Roller Bearing Co.)
Lesson 1
IIW-AWS
January/February 2006

Evolution of Alloy Development

Refining of increasing amounts of sour crude led to

experimentation with Cr contents >5%, but <12% needed
for stainless steels
7-9% Cr-Mo steels developed
For refining applications improvement in corrosion
resistance was significant:
5Cr steels 4-10X more corrosion resistant than CS
7Cr steels 2X more corrosion resistant than 5Cr steels
9Cr steels 4X more corrosion resistant than 5Cr steels
Lesson 1
IIW-AWS
January/February 2006

Evolution of Alloy Development

For critical bolting applications at lower temperatures,

high tensile strength desired
Materials such as 4140 CrMo alloy with 0.40% C were
developed to facilitate through hardening

Lesson 1
IIW-AWS
January/February 2006

Cr-Mo Steels - Carbon Content

For many of the most widely-used Cr-Mo alloys, the

carbon content is maintained < 0.15% (weight)
Higher C adversely affects weldability
Higher C does not substantially improve creep strength
Higher C can reduce corrosion resistance through excess
carbide formation

Lesson 1
IIW-AWS
January/February 2006

Cr-Mo Steels in the Power Industry

In the Power Industry, the introduction of welding
for major pressure parts spurred rapid increase in
steam temperatures and pressures

Lesson 1
IIW-AWS
January/February 2006

Cr-Mo Steels in the Power Industry

At steam outlet
temperatures >400C
(750F) there was a need
for alloys with higher
creep strength and
improved oxidation
resistance
The Cr-Mo steels
developed for the
petrochemical industry
proved to be a good fit

Lesson 1
IIW-AWS
January/February 2006

Development of Advanced Ferritic Steels

Work in the 1930s and 1940s had demonstrated the potent

strengthening effect of small additions of V, Ti, Cb, and
other carbide forming alloy additions
The successful introduction of X20CrMoV, a higher
carbon vanadium fortified 12Cr alloy, in Europe in the
early 1960s was an early result of these efforts
Further advances were made in support of the nuclear
industrys fast breeder reactor programs beginning in the
early 1970s
These efforts culminated in the development of the
modified 9Cr-1Mo alloy, now known as Grade 91
Lesson 1
IIW-AWS
January/February 2006

Creep Rupture Strength

Lesson 1
IIW-AWS
January/February 2006

Creep Strength Enhanced Alloys

Following cancellation of the fast breeder programs in the

late 1970s, application of Grade 91 and later variants (i.e.,
Grades 92, 911, 122, 23, etc.) shifted to the fossil power
industry
Favored by designers for improved performance in cyclic
service (conventional boilers and HRSGs)
An essential component of the materials strategy for ultrasupercritical boilers

Lesson 1
IIW-AWS
January/February 2006

Design Interest In CSEF Steels

Design Codes do not penalize for increased thickness.

Thermal stress varies with square of thickness.
Fatigue life varies with cube of stress.
25

High creep-strength
materials (e.g.,P91)
reduce wall thickness in
high temperature areas,
which improves cycling
capability.

P91 gives 40% thickness

reduction for same creep
life and 12 times the
fatigue life.

Allowable Stress (ksi)

20

P91
15

10

P22

0
800

850

900

950

1000

Temperature (F)

1050

1100

1150

Lesson 1
IIW-AWS
January/February 2006