ME2200

Thermal Processing and Ratna Kumar Annabattula

MDS - 208

Heat Treatment of Steels IIT Madras

ratna@iitm.ac.in
 Looking Back at Phase Diagrams

❖ In the phase diagrams, the information about

temperature and composition was discussed
❖ But, the issue of time is not mentioned anywhere!
❖ In reality, time plays a critical role in the microstructure
of the alloy obtained!
❖ Recollect the non-equilibrium cooling of isomorphous
alloys.
 Austenite transformation
(non-equilibrium cooling)

❖ Iron-Iron Carbide equilibrium diagram may not be used

to study steels cooled under non equilibrium conditions
❖ Austenite is not stable below the lower critical
temperature
❖ Hence, it is important to know how long does it take for
austenite to transform at a given sub-critical temperature
❖ Also, it is important to know the details of the
transformation products obtainable after such
transformation
 Isothermal Transformation Diagram
❖ The austenite transformation may be understood through isothermal transformation
diagram
❖ How to come up with such diagram?
❖ Step 1: Prepare a large number of samples cut from the same bar
❖ Step 2: Place the samples in a furnace or molten salt bath at the proper austenitizing
temperature for long time for transformation to complete austenite
❖ For 1080 steel it is 14250 F
❖ Step 3: Place the samples in a molten salt bath which is held at constant subcritical
temperature (below A1), say 13000 F
❖ Step 4: After varying time intervals in the salt bath, each sample is quenched in cold
water or iced brine
❖ Step 5: After cooling, each sample’s hardness and microstructure are studied
❖ Step 6: The above steps are repeated at different subcritical temperatures until
sufficient points are determined to plot the curves on the diagram
Fe-Fe3C Diagram
Isothermal Transformation Diagram
❖ Temperature plays an important role in
the rate of the austenite-to-pearlite
transformation
❖ Temperature dependence is shown in
the figure in the form of an S-curve
plotted with percentage transformation
with respect to time (log scale) for
transformation
❖ For each curve, data were collected
after rapidly cooling a specimen
composed of 100% austenite to the
temperature indicated and holding at
that temperature throughout the
reaction
Isothermal-Transformation Diagram
❖ More convenient way of showing the
temperature dependence of this
transformation is as shown on the bottom
figure
❖ Vertical axis: Temperature
❖ Horizontal axis: logarithm of time
❖ Red solid curve: Start of transformation
❖ Green solid curve: End of Transformation
❖ Blue Dotted curve: 50% transformation
line
❖ These curves are generated from a series
of experiments at different sub critical
temperatures and then transferring data as
shown for one temperature in the figure
Isothermal-Transformation Diagram
❖ This diagram is also called Time-
Temperature-Transformation (T-T-T)
diagram
❖ Horizontal eutectoid temperature line
shows the stable austenite above that
temperature
❖ Austenite-Pearlite transformation
occurs only if the alloy is supercooled to
below the eutectoid
❖ The starting time and ending time of
transformation depends on temperature
❖ Start and finish line are almost parallel
and they approach the eutectoid line
almost asymptotically
Isothermal-Transformation Diagram
❖ To the left of the transformation
start curve only austenite (unstable)
is present
❖ To the right of transformation finish
line only pearlite is present
❖ In between, the austenite is
transforming to pearlite and hence
both the constituents will be present
❖ The above diagram is only
applicable for eutectoid plain
carbon steel
❖ The diagram will change if we
change the composition
Sample cooling of an eutectoid steel
 Sample cooling of an eutectoid steel
❖ A cooling curve ABCD is superimposed on
the I-T diagram
❖ Very rapid cooling of austenite to a
temperature is indicated by near vertical
line AB
❖ Isothermal treatment at this temperature is
indicated by BCD
❖ Transformation of austenite to pearlite
begins at C (~3.5 s) and finishes at D (~15 s)

❖ Thickness of ferrite and cementite layers in pearlite depends on the

transformation temperature
❖ At high temperature carbon can diffuse long distances and hence form thick
layers leading to coarse pearlite
❖ At low temperature, diffusion is less and hence fine pearlite results
Pearlite Microstructure

Coarse Pearlite Fine Pearlite

T-T-T Diagram of eutectoid steel

A- Austenite
P - Pearlite
B- Bainite
 T-T-T Diagram of eutectoid steel
❖ Austenite transforms to another
product called Bainite (feathery
structure) at low temperatures while at
high temperatures pearlite forms
❖ Austenite transforms to another phase
called martensite (needle like
structure) at much lower temperatures
❖ Austenite-to-Martensite
transformation is diffusionless unlike
A-P and A-B transformations
❖ Martensite is a non-equilibrium phase
and hence does not appear in Iron-Iron
Carbide equilibrium diagram
Formation of Pearlite and Bainite
 Little more about Bainite
❖ Bainite forms as needles or plates (depends on temperature)
❖ Bainite is composed of ferrite matrix and elongated particles of
Fe3C
❖ Pearlite forms above the nose and bainite forms below the nose
❖ Pearlitic and Bainitic transformations are competitive
❖ If some portion of an alloy transforms to pearlite/bainite,
transformation to other microstructure is not possible unless it
is re-austenetized.
 Spheroidite
❖ Spheroidite forms when a pearlitic/bainitic steel is heated
and held at temperature below eutectoid for sufficiently
long time
❖ e.g., at 700c for 18-24 hours
❖ Fe3C phase appears as sphere-like particles embedded in
continuous ferrite matrix
❖ This transformation happens by additional carbon
diffusion with no change in compositions or relative
amounts of ferrite and cementite phases.
 Martensite
❖ Another transformation product like
pearlite or bainite
❖ Forms when austenetized iron-carbon
alloy is rapidly cooled
❖ Martensite is a nonequilibrium single
phase structure
❖ Formed by diffusion-less transformation
❖ FCC austenite changes to BCT martensite
Martensite Microstructure

Photomicrograph showing
the martensitic
microstructure. The needle
shaped grains are the
martensite phase, and the
white regions are austenite
that failed to transform
during the rapid quench.

Source: Callister’s book

 Martensite Transformation
❖ The transformation is diffusion-less and there is no change
in chemical composition
❖ Small volumes of austenite suddenly changes its crystal
structure
❖ The transformation proceeds only during cooling and
ceases if cooling is interrupted
❖ Hence, the transformation depends only on the decrease in
temperature and is independent of time
❖ The transformation of above type is called athermal in
contrast to one that will occur at constant temperature
 Martensite Transformation
❖ The amount of martensite formed with reduction in temperature is
not linear
❖ Number of martensite needles produced at first is small; then the
number increases, and finally, near the end, it decreases again
❖ The temperature of the start of martensite transformation is known
as Ms temperature and that of the end of martensite formation is Mf
temperature
❖ If the steel is held at any temperature below Ms, the transformation
to martensite will stop and will not proceed again unless the
temperature is dropped
❖ Martensite transformation of a given alloy can not be suppressed,
nor can the Ms temperature be changed by changing the cooling rate
 Martensite Transformation
❖ The temperature range of the formation of
martensite is characteristic of a given alloy and
can not be lowered by increasing cooling rate
❖ Ms temperature is a function of chemical
composition only
❖ Theoretically, austenite to martensite
transformation is never complete and small
amounts of retained austenite will remain even at
low temperatures
❖ The transformation of last traces of austenite
becomes very difficult as the amount of austenite
decreases
❖ Hence, Mf temperature is clearly not defined as
there is always some retained austenite
 Martensite Characteristics
1. Hardest and most brittle microstructure obtainable in a given steel
2. Martensite hardness of the steel is a function of carbon content in
that steel
3. Martensite results from cooling from austenite temperature
rapidly by quenching before pearlite can form
4. Quenched martensite structures are too brittle to be used and
hence they should be tempered
5. Reheating the as quenched martensite to a temperature just below
the A1 results in the best combination of strength and toughness
 Martensite Transformation
❖ Martensite is never in a condition of real
equilibrium although it persists indefinitely
at room temperature
❖ The structure may be considered as a
transition between the unstable austenite
phase and the stable mixture of ferrite and
Rockwell C Hardness vs
cementite %C for Martensite
❖ Martensite is potentially very hard material
❖ Although martensite is harder than http://pmpaspeakingofprecision.com/2011/03/15/martensite-five-facts/

austenite, extreme hardness is possible only

with sufficient carbon content
❖ High hardness of martensite is believed to
be due to severe lattice distortion
 Martensite transformation

❖ Martensite transformation was believed to be unique to

steel for many years
❖ Martensite type of transformation is observed in many
other alloy systems (iron-nickel, copper-zinc and copper
- aluminium)
❖ Shape-Memory alloys involve the martensitic phase
transformation
Shape-Memory Effect

http://www.youtube.com/watch?v=QYp9rIJRM8s
Shape-Memory Effect

http://www.youtube.com/watch?v=QYp9rIJRM8s
T-T-T Diagram for 1.13 wt %C Steel
❖ For iron-carbon alloys of other
compositions (hyper or
hypoeutectoid steels), a
proeutectoid phase exists
❖ Hence, there should be
another curve describing that
reaction
❖ Figure shows I-T diagram for
a hypereutectoid steel (1.13
wt% C) which forms a
proeutectoid cementite phase
 Effect of different cooling rates
❖ Cooling curve 1
❖ Transformation begins at x1 and
finishes at x1’
❖ Similar to annealing
❖ Forms Coarse pearlite
❖ There is a slight change in size of
pearlite that forms at beginning to
the end due to slight change in
temperature
❖ Transformed product is relatively
soft (R/C 15)
❖ After x1’, the sample may be cooled
down to room temperature rapidly
as there will be no further
transformation (useful info for
companies)
 Effect of different cooling rates
❖ Cooling curve 2
❖ Transformation begins
at x2 and finishes at x2’
❖ Describes isothermal
annealing
❖ Uniform coarse pearlite
microstrure and
hardness
❖ The transformation
finishes at much shorter
time scale than case 1
 Effect of different cooling rates
❖ Cooling curve 3
❖ Much faster cooling rate than
annealing
❖ Typical of normalizing
❖ Transformation starts at x3, indicating
formation of coarse pearlite in much
shorter time than annealing
❖ Finishes at x3’ forming medium
pearlite
❖ Larger temperature difference
between x3 and x3’
❖ Structure shows greater variation in
fineness of pearlite
❖ Smaller portion of coarse pearlite
than annealed sample
 Effect of different cooling rates
❖ Cooling curve 4
❖ Much faster cooling
rate than normalising
(slow oil quench)
❖ Microstructure will be
a mixture of medium
and fine pearlite
❖ Transformation starts
at x4 and finishes at
x4’
 Effect of different cooling rates
❖ Cooling curve 5
❖ Typical of intermediate cooling rate
❖ Starts transforming to fine pearlite at x5
in relatively short time
❖ Transformation to fine pearlite continues
until curve becomes tangent to some
percentage transformed, (here 25%) at x5’
❖ Below this curve the cooling curve is
going in the direction of decreasing
percent transformed
❖ Transformation stops with further
cooling until it hits Ms line at x5’’
❖ The remaining austenite would
transform to martensite
❖ Microstructure: 25% fine pearlite and 75%
martensite
 Effect of different cooling rates
❖ Cooling curve 6 & 7
❖ Typical of drastic quench
missing nose region
❖ It remains austenitic until
Ms and then transforms to
Martensite
❖ 100% Martensite of high
hardness
❖ Cooling curve 7 is the
critical cooling rate below
which there will be either
pearlite or bainite
transformation
 Effect of different cooling rates
❖ Cooling curve 8
❖ Cooling rate similar to 6
❖ But at 8 holding at
constant temperature
❖ Starts to transform to
bainite
❖ Inorder to form complete
bainite cool at faster rate
to miss the nose and then
hold it at constant
temperature for
sufficiently longer time
Transformation on Continuous Cooling
Transformation on Continuous Cooling
❖ I-T Diagram can’t be used when the
cooling is done continuously
❖ The diagram must be modified for
transformations that occur as the
temperature is constantly changing
❖ For continuous cooling, the time required
for a reaction to begin and end is delayed
❖ This diagram is called Continuous
Cooling Transformation (CCT) diagram
❖ Ms and Mf line occurs at the same
temperature for I-T and CCT diagrams
Transformation on Continuous Cooling
❖ Two cooling rates (slow and fast)
shown on the CCT diagram
❖ In Continuous cooling , bainite is
not formed as the transformation
to pearlite would have finished
before it reaches the bainite
temperature
❖ Hence, the diagram doesn’t have
lower nose region
❖ The transformation terminates
along AB curve
Microstructure and Cooling rates
 C-C-T diagram of an alloy steels
❖ Carbon and other
alloying elements shift
the pearlite and bainite
noses to longer times,
thus decreasing the
critical cooling rate
❖ Bainite formation is
possible for non-eutectoid
plain carbon steels
❖ The CCT diagram shown
is for 4340 steel
 Reading Assignment

❖ Tempered Martensite
❖ Effects of various alloying elements in alloy steels
 Heat Treatment

❖ A combination of heating and cooling operations,

timed and applied to a metal or alloy in the solid state
in a way that will produce desired properties
Source: Materials Handbook
 Heat Treatment
❖ Basic heat treatment of steel involves transformation or
decomposition of austenite
❖ Final properties (physical and mechanical) of heat treated steel
depend on the nature and form of transformation products
❖ First step: Heat the steel above a critical temperature to form austenite
❖ Rate of heating to the desired temperature is not important in
many cases
❖ However, highly stressed material due to cold working should be
heated slowly compared to stress-free steels to avoid distortion
❖ Practical Rule: Heating to be done as slow as possible to avoid ill
effects
 Annealing
❖ Annealing: Material is exposed to elevated temperature for a
long time and then cooled slowly
❖ Annealing is carried out to
❖ relieve stresses
❖ increase softness, ductility and toughness
❖ produce a specific microstructure
❖ Variety of annealing heat treatments are possible characterised
by the changes induced in the microstructure and mechanical
properties
 Steps in Annealing

❖ Step 1: Heating to desired temperature

❖ Step 2: Holding or Soaking at that temperature
❖ Step 3: Cooling down to room temperature
❖ Time is an important parameter in these processes due
to thermal gradients that exist in the interior and
exterior of the material
Fe-Fe3C diagram in the heat treatment temperature range
 Annealing Processes

❖ Full annealing
❖ Spheroidizing
❖ Stress-relief annealing
❖ Process annealing
❖ Normalizing
Full Annealing (Hypoeutectoid steels)
❖ Heat the steel to proper temperature
and then cool slowly through the
transformation range in the furnace.
❖ Purpose: refine the grain, induce
softness, improve electrical/
magnetic properties and improve
machinability
❖ Very slow cooling process and hence
close to iron-carbide equilibrium
diagram
❖ Heat treat a coarse-grained 0.2%
carbon steel to refine the grain size
Full Annealing (Hypoeutectoid steels)
❖ No change in microstructure occurs during
heating until A1 (lower critical temperature)
❖ At A1, pearlite areas will transform to small
grains of austenite through eutectoid
reaction
❖ The original large ferrite grains remain the
same
❖ If we cool from this temperature, grain
refinement doesn’t happen
❖ Continued heating between A1 and A3
allows the large ferrite grains to transform
to small austenite grains
❖ Above A3 entire microstructure will be
small grains of austenite
Full Annealing (Hypoeutectoid steels)

❖ Subsequent furnace cooling

results in small grains of
proeutectoid ferrite and
small areas of coarse
lamellar pearlite
❖ The proper annealing
temperature for
hypoeutectoid steels is 500F
above A3 line
Full Annealing (Hypereutectoid steels)
❖ Refinement of grain size for hypereutectoid steels occur at 500F above the
lower-critical-temperature (A1)
❖ Heating above this temperature will coarsen the austenitic grains, which on
cooling will transform to large pearlitic areas
❖ The microstructure of annealed hypereutectoid steel will consist of coarse
lamellar pearlite areas surrounded by a network of proeutectoid cementite
network
❖ The excessive cementite network is brittle and tends to be a plane of
weakness
❖ Hence, annealing should not be final heat treatment process for
hypereutectoid steels
❖ Presence of thick, hard grain boundary will also result in poor machinability
 Full Annealing
❖ Approximate tensile strength of annealed hypoeutectoid
steels may be determined by the proportion of ferrite and
pearlite present
40,000(percent ferrite)+120,000(percent pearlite)
Approximate tensile strength =
100

❖ An annealed 0.2% carbon steel contains approximately

25% pearlite and 75% ferrite whose approximate tensile
strength is 40000(0.75)+120000(0.25) = 60000 psi
❖ The same formula can’t be applied to hypereutectoid
steels since their strength is determined by continuous
cementite network
 Spheroidizing
❖ Annealed hypereutectoid steels have poor
machinability due to the microstructure
(pearlite+cementite network)
❖ Since cementite is hard, the cutting tool
can’t cut through these plates.
❖ Spheroidizing produces a spheroidal or
globular form of carbide in ferritic matrix ❖ One of the methods for Spheroidizing
(see figure)
❖ Prolonged holding at a temperature just
below A1
❖ Prolonged time at elevated temperature
will completely break up the pearlitic ❖ Heating and cooling alternately between
temperatures that are just above and
structure and cementite network below A1

❖ Cementite becomes spherical which is the ❖ Heating to a temperature above A1 and

then cooling very slowly in the furnace or
equilibrium geometric shape holding at a temperature just below A1
 Spheroidizing
❖ Spheroidized structure is desirable when minimum
hardness, maximum ductility or maximum machinability is
important
❖ Low carbon steels are seldom spheroidized for machining
as in the spheroidized condition, they are excessively soft;
the cutting tool tends to push the material rather than
cutting it.
❖ Too long exposure to spheroidize-annealing temperature
leads to coalescence of cementite particles to form elongated
structures which in turn leads to reduced machinability
 Normalizing
❖ Normalizing is carried out by heating steel to 1000F above A3 (upper
critical temperature) followed by cooling in still air to room
temperature
❖ Purpose: To produce harder and stronger steel than full annealing
❖ For hypereutectoid steels, it is necessary to heat above Acm line in
order to dissolve the cementite network
❖ Normalizing may also be used to improve machinability, modify and
refine cast dendritic structures, refine the grain and to homogenise
the grain structure
❖ The increase in cooling rate due to air cooling as compared to furnace
cooling affects the transformation of austenite and resultant
microstructure
 Normalizing
❖ Iron-Iron carbide equilibrium can’t be used to predict the
proportions of proeutectoid ferrite and pearlite or proeutectoid
cementite and pearlite as the cooling is not done under
equilibrium conditions
❖ There is less time for formation of proeutectoid constituent
❖ Hence there will be less proeutectoid ferrite in normalised
hypoeutectoid steels and less proeutectoid cementite in
hypereutectoid steels
❖ In hypereutectoid steels, some times the cementite network may
be absent altogether
❖ Hence, normalising increases the strength of hypereutectoid steels
 Normalizing

❖ Normalizing also affects the temperature of austenite transformation and the fineness of
pearlite
❖ Faster cooling rate leads to lower temperature of austenite transformation and finer pearlite
❖ The difference in spacing between cementite plates in pearlite is shown for annealing and
normalising
❖ Cementite plates closer together in the case of normalised medium pearlite; they tend to
stiffen ferrite so it will not yield easily, thus increasing hardness
❖ Normalizing produces finer and more abundant pearlite structure than that of annealing
which results in harder and stronger steel
 Hardening
❖ Under slow or moderate cooling rates, the carbon atoms are able to
diffuse out of the austenite structure.
❖ The iron atoms then move slightly to become b.c.c
❖ The gamma to alpha transformation takes place by a process of
nucleation and growth and is time-dependent
❖ With increase in cooling rate, there is less time for carbon to diffuse
out of solution
❖ Although some movement of iron atoms takes place, the structure
can not become b.c.c while the carbon is trapped in the solution
❖ The resultant structure called martensite, is a supersaturated solid
solution of carbon trapped in a body-centered tetragonal structure
 Hardening
❖ The two dimensions of the unit cell are equal and the third dimension is
elongated because of trapped carbon
❖ The axial ratio c/a increases with increase in carbon content to a maximum
of 1.08
❖ This highly distorted lattice structure is the prime reason for the high
hardness of martensite
❖ Atoms of martensite are less densely packed than austenite and hence an
expansion occurs during transformation
❖ This expansion produces high localised stresses which result in plastic
deformation of the matrix.
❖ After drastic cooling, martensite appears microscopically as a white
needle like acicular structure some times described as pile of straw
 References
❖ Sidney H Avener, Introduction to Physical Metallurgy, Tata
McGrawHill, Second Edition, (2010)
❖ William D Callister Jr. and David G. Rethwisch Materials
Science and Engineering: An Introduction, John Wiley, 8th
Edition, (2009)
❖ Reza Abbaschian, Lara Abbaschian and Robert E. Reed-
Hilll, Physical Metallurgy Principles, CENGAGE Learning,
4th edition, (2009)
❖ http://practicalmaintenance.net/?p=1329