NOTES ON

MATERIALS SCIENCE AND ENGINEERING

UNIT: III

Heat Treatment – Annealing and its types, Normalizing, Hardening tempering, Aus-tempering and
Mar-tempering – Microstructure observation - Surface Heat treatment processes – Carburizing,
Nitriding, cyaniding, carbonitriding, flame and induction hardening.

Compiled & Prepared by

K. Devendranath Ramkumar
Assistant Professor (Senior)

SCHOOL OF MECHANICAL AND BUILDING SCIENCES

Chapter: 1 Heat Treatment of Steels
Heat Treatment is the controlled heating and cooling of metals to alter their physical and
mechanical properties without changing the product shape. Heat treatment is sometimes done
inadvertently due to manufacturing processes that either heat or cool the metal such as welding or
forming.
Heat Treatment is often associated with increasing the strength of material, but it can also be used
to alter certain manufacturability objectives such as improve machining, improve formability,
restore ductility after a cold working operation. Thus it is a very enabling manufacturing process
that can not only help other manufacturing process, but can also improve product performance by
increasing strength or other desirable characteristics.
The operation consists of:
► Heating the steel to a certain temperature,
► "Soaking" at this temperature for a time sufficient to allow the necessary changes to occur,
► Cooling at a predetermined rate.

Full Annealing

Full
annealing is the
process of slowly raising the temperature about 50ºC (90ºF) above the Austenitic temperature line
A3 or line ACM in the case of Hypo eutectoid steels (steels
with < 0.77% Carbon) and 50ºC (90ºF) into the Austenite-
Cementite region in the case of Hypereutectoid steels
(steels with > 0.77% Carbon).
It is held at this temperature for sufficient time for all the material to transform into Austenite or
Austenite-Cementite as the case may be. It is then slowly cooled at the rate of about 20 ºC/hr (36
ºF/hr) in a furnace to about 50 ºC (90 ºF) into the Ferrite-Cementite range. At this point, it can be
cooled in room temperature air with natural convection. The grain structure has coarse Pearlite
with ferrite or Cementite (depending on whether hypo or hyper eutectoid). The steel becomes soft
and ductile.

The purpose of annealing may involve one or more of the following aims:
1. To soften the steel and to improve machinability.
2. To relieve internal stresses induced by some previous treatment (rolling, forging, uneven
cooling).
3. To remove coarseness of grain. The treatment is applied to forgings, cold-worked sheets and
wire, and castings.
Normalizing

Normalizing is the process of raising the temperature to over 60 º C (108 ºF), above line A3
or line ACM fully into the Austenite range. It is held at this temperature to fully convert the
structure into Austenite, and then removed form the furnace and cooled at room temperature under
natural convection. This results in a grain structure of fine Pearlite with excess of Ferrite or
Cementite. The resulting material is soft; the degree of softness depends on the actual ambient
conditions of cooling. This process is considerably cheaper than full annealing since there is not
the added cost of controlled furnace cooling. The main difference between full annealing and
normalizing is that fully annealed parts are uniform in softness (and machinability) throughout
the entire part; since the entire part is exposed to the controlled furnace cooling. In the case of
the normalized part, depending on the part geometry, the cooling is non-uniform resulting in non-
uniform material properties across the part. This may not be desirable if further machining is
desired, since it makes the machining job somewhat unpredictable. In such a case it is better to do
full annealing.

Process Annealing
Process Annealing is used to treat work-hardened parts made out of low-Carbon steels (<
0.25% Carbon). This allows the parts to be soft enough to undergo further cold working without
fracturing. Process annealing is done by raising the temperature to just below the Ferrite-Austenite
region, line A1 on the diagram. This temperature is about 727 ºC (1341 ºF) so heating it to about
700 ºC (1292 ºF) should suffice. This is held long enough to allow recrystallization of the ferrite
phase, and then cooled in still air. Since the material stays in the same phase through out the
process, the only change that occurs is the size, shape and distribution of the grain structure. This
process is cheaper than either full annealing or normalizing since the material is not heated to a
very high temperature or cooled in a furnace.
Stress Relief Annealing
Stress Relief Anneal is used to reduce residual stresses in large castings, welded parts and
cold-formed parts. Such parts tend to have stresses due to thermal cycling or work hardening. Parts
are heated to temperatures of up to 600 - 650 ºC (1112 - 1202 ºF), and held for an extended time
(about 1 hour or more) and then slowly cooled in still air.
Spheroidization
Spheroidization is an annealing process used for high carbon steels
(Carbon > 0.6%) that will be machined or cold formed subsequently. This is
done by one of the following ways:

1. Heat the part to a temperature just below the Ferrite-Austenite line, line A1 or below the
Austenite-Cementite line, essentially below the 727 ºC (1340 ºF) line. Hold the temperature
for a prolonged time and follow by fairly slow cooling. Or

2. Cycle multiple times between temperatures slightly above and slightly below the 727 ºC (1340
ºF) line, say for example between 700 and 750 ºC (1292 - 1382 ºF), and slow cool. Or

3. For tool and alloy steels heat to 750 to 800 ºC (1382-1472 ºF) and hold for several hours
followed by slow cooling.

All these methods result in a structure in which all the Cementite is in the form of small globules
(spheroids) dispersed throughout the ferrite matrix. This structure allows for improved machining
in continuous cutting operations such as lathes and screw machines. Spheroidization also improves
resistance to abrasion.
Tempering
Tempering is a process done subsequent to quench hardening. Quench-hardened parts are
often too brittle. This brittleness is caused by a predominance of Martensite. This brittleness is
removed by tempering. Tempering results in a desired combination of hardness, ductility,
toughness, strength, and structural stability. Tempering is not to be confused with tempers on
rolled stock-these tempers are an indication of the degree of cold work performed.
The mechanism of tempering depends on the steel and the tempering temperature. The prevalent
Martensite is a somewhat unstable structure. When heated, the Carbon atoms diffuse from
Martensite to form a carbide precipitate and the concurrent formation of Ferrite and Cementite,
which is the stable form. Tool steels for example, lose about 2 to 4 points of hardness on the
Rockwell C scale. Even though a little strength is sacrificed, toughness (as measured by impact
strength) is increased substantially. Springs and such parts need to be much tougher — these are
tempered to a much lower hardness.

Tempering is done immediately after quench hardening. When the steel cools to about 40 ºC
(104 ºF) after quenching, it is ready to be tempered. The part is reheated to a temperature of 150
to 400 ºC (302 to 752 ºF). In this region a softer and tougher structure Troostite is formed.
Alternatively, the steel can be heated to a temperature of 400 to 700 ºC (752 to 1292 ºF) that
results in a softer structure known as Sorbite. Sorbite has less strength than Troostite but more
ductility and toughness. The heating for tempering is best done by immersing the parts in oil, for
tempering up to 350 ºC (662 ºF) and then heating the oil with the parts to the appropriate
temperature. Heating in a bath also ensures that the entire part has the same temperature and
will undergo the same tempering. For temperatures above 350 ºC (662 ºF) it is best to use a bath of
nitrate salts. The salt baths can be heated up to 625 ºC (1157 ºF). Regardless of the bath, gradual
heating is important to avoid cracking the steel. After reaching the desired temperature, the parts
are held at that temperature for about 2 hours, then removed from the bath and cooled in still air.
Chapter: 2 Surface Hardening Methods

Depth of Hardening:
There is no technical limit to the depth of hardening with carburizing techniques, but it is not
common to carburize to depths in excess of 0.050 in.
Carburizing Time:
4 to 10 hours
Carburizing Temperature:
o
1750 F (above the upper critical
temperature-Austenite area)
Quenching:
All of the carburizing processes (pack, gas,
liquid) require quenching from the
carburizing temperature or a lower
temperature or reheating and quenching. Parts are then tempered to the desired hardness.

Figure 1. Case depth versus Carburizing

time.

PACK CARBURIZING
In this process, the part that is to be
carburized is packed in a steel container so
that it is completely surrounded by
granules of charcoal. The charcoal is
treated with an activating chemical such as
Barium Carbonate (BaCO3) that promotes
the formation of Carbon Dioxide (CO2).
PACK CARBURIZING PROCESS This gas in turn reacts with the excess
carbon in the charcoal to produce carbon monoxide, CO. Carbon Monoxide reacts with the low-
carbon steel surface to form atomic carbon which diffuses into the steel. Carbon Monoxide
supplies the carbon gradient that is necessary for diffusion. The carburizing process does not
harden the steel. It only increases the carbon content to some predetermined depth below the
surface to a sufficient level to allow subsequent quench hardening.
Carbon Monoxide reaction:
CO2 + C ---> 2 CO
Reaction of Cementite to Carbon Monoxide:
2 CO + 3 Fe --->Fe3C + CO2
Quenching Process:
It is difficult to quench the part immediately, as the sealed pack has to be opened and the part must
be removed from the pack. One technique that is used often is to slow cool the entire pack and
subsequently harden and temper the part after it is removed from the sealed pack.
Depth of Hardening:
There is no technical limit to the depth of hardening with carburizing techniques, but it is not
common to carburize to depths in excess of 0.050 in.
Carburizing Time:
4 to 10 hours
GAS CARBURIZING
Can be done with any carbonaceous gas, such as methane, ethane, propane, or natural gas. Most
carburizing gases are flammable and controls are needed to keep carburizing gas at 1700 oF from
contacting air (oxygen). The advantage of this process over pack carburizing is an improved ability
to quench from the carburizing temperature. Conveyor hearth furnaces make quenching in a
controlled atmosphere possible.
LIQUID CARBURIZING
Can be performed in internally or externally heated molten salt pots. Carburizing salt contains
cyanide compounds such as sodium cyanide (NaCN). Cycle times for liquid cyaniding are much
shorter (1 to 4 hours) than gas and pack carburizing processes. Disadvantage is the disposal of salt.
(Environmental problems) and cost (safe disposal is very expensive).
NITRIDING
In this process, nitrogen is diffused into the
surface of the steel being treated. The
reaction of nitrogen with the steel causes the
formation of very hard iron and alloy
nitrogen compounds. The resulting nitride
case is harder than tool steels or carburized
steels. The advantage of this process is that
hardness is achieved without the oil, water
Figure 3 Nitriding
or air quench. As an added advantage,
hardening is accomplished in a nitrogen atmosphere that prevents scaling and discoloration.
Nitriding temperature is below the lower critical temperature of the steel and it is set between 925
o
F and 1050oF. The nitrogen source is usually Ammonia (NH3). At the nitriding temperature the
ammonia dissociates into Nitrogen and Hydrogen.

Figure 4.

Nitriding time for various types of alloy

steels
2NH3 ---> 2N + 3H2
The nitrogen diffuses into the steel and hydrogen is exhausted. A typical nitriding setup is
illustrated in Figure 3.
The white layer shown in Figure 4 has a detrimental effect on the fatigue life of nitrided parts, and
it is normally removed from parts subjected to severe service. Two stage gas-nitriding processes
can be used to prevent the formation of white layer. White layer thickness may vary between
0.0003 and 0.002 in which depends on nitriding time. The most commonly nitrided steels are
chromium-molybdenum alloy steels and Nitralloys. Surface hardness of 55 HRC to 70 HRC can be
achieved with case depths varying from 0.005 in to 0.020 in. Nitrided steels are very hard and
grinding operations should not be performed after nitriding. White layer is removed by lapping.
Carbonitriding
This process involves with the
diffusion of both carbon and nitrogen
into the steel surface. The process is
performed in a gas atmosphere furnace
using a carburizing gas such as
propane or methane mixed with several
percent (by volume) of ammonia.
Methane or propane serve as the source
of carbon, the ammonia serves as the
source of nitrogen. Quenching is done
in a gas which is not as severe as water
quench. As a result of les severe quench, there is less distortion on the material to be treated. A
typical carbonitriding system is shown in the following slide. Case hardnesses of HRC 60 to 65 are
achieved at the surface.( Not as high as nitrided surfaces.) Case depths of 0.003 to 0.030 in can be
accomplished by carbonitriding. One of the advantages of this process is that it can be applied to
plain carbon steels, which give significant case depths. Carbonitriding gives less distortion than
carburizing. Carbonitriding is performed at temperatures above the transformation temperature of
the steels (1400˚F to 1600˚F)

Cyaniding
It is similar to carbonitriding, and involves the diffusion of both carbon and nitrogen into the
surface of the steel. The source of the diffusing element in this method is a molten cyanide salt
such as sodium cyanide. It is a supercritical treatment involving temperatures in the range of
1400oF to 1600oF. Case depths are between 0.010 in. and 0.030 in. Diffusion times are less than
one hour. Water or oil quench is required. This type of cases presents a significant distortion.
Advantage of this method is the short time it requires to complete the diffusion; otherwise it should
be avoided because of high distortion.
INDUCTION HARDENING
In this process an electric current flow is induced in the work piece to produce a heating action.
Every electrical conductor carrying a current has a magnetic field surrounding the conductor. Since
the core wire is a dead-end circuit, the
induced current cannot flow anyplace, so
the net effect is heating of the wire. The
induced current in the core conductor
alternates at frequencies from 60 cycles
per second (60 Hz) to millions of Hertz.
The resistance to current flow causes
very rapid heating of the core material.
Heating occurs from the outside inward.
Induction hardening process includes
water quench after the heating process.
The big advantage of this system is its
Figure 7. Induction hardening speed and ability to confine heating on
small parts. The major disadvantage is the cost.
Flame Hardening
Flame hardening is the process of selective hardening with a combustible gas flame as the source
of heat for austenitizing. (The material should have at least 0.40 % Carbon content to allow
hardening.) Water quenching is applied as soon as the transformation temperature is reached. The
heating media can be oxygen acetylene, propane, or any other combination of fuel gases that will
allow reasonable heating rates. This procedure is applied to the gear teeth; shear blades, cams,
ways on the lathes, etc. Flame hardening temperatures are around 1500oF. Up to HRC 65 hardness
can be achieved. For best results the hardness depth is 3/16 inch. There are three methods:
(1) SPOT Flame Hardening: Flame is directed to the spot that needs to be heated and hardened.
(2) SPIN Flame Hardening: The work piece is rotated while in contact with the flame
(3) PROGRESSIVE Flame Hardening: The torch and the quenching medium move across the
surface of the work piece.
Laser and Electron Beam Hardening
These methods can be used to perform selective hardening of hardenable steels. They perform the
same function as the flame in flame hardening or the induction coil in induction hardening. It is
only applicable to steels that have sufficient carbon and alloy content to allow quench hardening.
The laser or electron bam is used to raise the surface temperature of the part. Electron Beam
Hardening requires vacuum. Laser beam do not require vacuum and quenching can be done by
using a gas. Electron beam spot sizes are about 0.010 to 0.015 in2. Lasers can be larger but usually
no larger than about 0.150 in2. Both methods present two disadvantages:
(1) Equipment cost
(2) High alloys may not respond. These methods are limited to plain carbon steels and low alloy
steels and irons.

How to Select the Right Surface Hardening Method

(1) Carburizing is the best method for low carbon steels.
(2) Nitriding is a lower distortion process than carburizing but it can be used for certain type of
steels such as chromium-molybdenum alloy steels or Nitralloy-type steels.
(3) Flame hardening is preferred for heavy cases or selective hardening of large machine
components.
(4) Induction hardening works best on parts small enough and suitable in shape to be compatible
with the induction coil.
(5) Electron beam and laser hardening are limited to the low alloy steels and plain carbon steels
only.