HEAT TREATMENT

How to Strengthen Metals:

• Key: prevent dislocatons from moving through crystal
structure!!!
• Finer grain boundries – can be done by recrystallizing (and
cold working)
• Increase dislocaton density via COLD WORKING (strain
hardening)
• Add alloying elements to give –SOLID SOLUTION HARDENING.
• Add alloying elements to give precipitates or dispersed
partcles – PRECIPITATION HARDENING (Heat Treatment)
• DISPERSION HARDENING– fine partcles (carbon) impede
dislocaton movement.
– Referred to as Quench Hardening, Austenitzing and Quench or simply
“Heat Treat”.
– Generally 3 steps: heat to austenite T, rapid quench, then temper.
Several cells form a crystal, if many crystals are growing in a melt at
the same tme, where they meet = grain boundry as shown below:

Mat’l
constants

ky
 y  o 
d

Average grain
diameter

Called Hall-Petch
equaton
 The Efect of Grain Boundries:
• Dislocatons pile up at GB and can’t go further
– this efectvely strengthens the crystal!
 Work Hardening
Work hardening, or strain hardening, results in
an increase in the strength of a material due to
plastc deformaton.

Plastc deformaton = adding dislocatons – as

dislocaton density increases, they tend to “te
up” and don’t move.

Ludwik’s Equaton:

Strain hardening index

Hot finishing = 2
benefit
Cold finishing = 1
benefits
Solid Soluton Strengthening (Alloying):

= strengthening by deliberate
additons of impurites (alloying
elements) which act as barriers to
dislocaton movement.
Example: additon of zinc to
copper making the alloy brass
(copper dissolves up to 30% zinc).
Zinc added to copper = Zinc atoms replace copper atoms
brass. Zinc atoms are to form random substtutonal
bigger and therefore solid soluton. The zinc atoms are
distort latce! bigger than copper and by
squeezing into the copper latce,
they distort it making it harder for
Cr and Ni to Fe, etc… dislocatons to move.
Dispersion and Precipitate Strengthening
(Heat Treat):

Disperse small strong

partcles (i.e. carbon) to
impede dislocatons
Dispersion and Precipitate
Strengthening (Heat Treat):

Successive positions of a dislocation as it bypasses particles that obstruct its motion.

The critical configuration is that with the tightest curvature, shown in (b).
This is dispersion and precipitate
strengthening

This is soluton hardening

(alloying)
This is dispersion and precipitate
strengthening

This is soluton hardening

(alloying)
How to strengthen
metals:
Other strengthening methods include
remelt to remove impurites, hot roll to
reduce grain size
Steel Crystal Structures:
•Ferrite – BCC iron w/
carbon in solid soluton
(sof, ductle, magnetc)
•Austenite – FCC iron
with carbon in solid
soluton (sof, moderate
strength, non-magnetc)
•Cementte – Compound
of carbon and iron FE3C
(Hard and britle)
•Pearlite – alternate
layers of ferrite and
cementte.
•Martensite – iron –
carbon w/ body
centered tetragonal –
result of heat treat and
quench

HT: ferrite then austentte then martensite

 Definition of heat treatment

Heat treatment is an operation or combination of operations

involving heating at a specific rate, soaking at a temperature
for a certain period of time and cooling at some specified rate.
The aim is to obtain a desired microstructure to achieve
predetermined set of properties (physical, mechanical,
magnetic or electrical).

15
The Heat Treat Processes
 Objectives of Heat Treatment)
The major objectives are
• to increase strength, harness and wear resistance (bulk hardening, surface
hardening)

• to increase ductility and softness (tempering, recrystallization annealing)

• to increase toughness (tempering, recrystallization annealing)

• to obtain fine grain size (recrystallization annealing, full annealing,

normalising)

• to remove internal stresses induced by differential deformation by cold

working, non-uniform cooling from high temperature during casting and
welding (stress relief annealing)

18
• to improve machineability (full annealing and normalising)

• to improve cutting properties of tool steels (hardening and

tempering)

• to improve surface properties (surface hardening, corrosion

resistance-stabilising treatment and high temperature
resistance-precipitation hardening, surface treatment)

• to improve electrical properties (recrystallization, tempering,

age hardening)

• to improve magnetic properties (hardening, phase

transformation)

19
δ ferrite:
Interstitial solid solution of carbon in iron of body centred
cubic crystal structure (Fig .2(a)) (δ iron ) of higher lattice
parameter (2.89Å) having solubility limit of 0.09 wt% at
1495°C with respect to austenite. The stability of the phase
ranges between 1394-1539°C.

Fig.2(a): Crystal structure of ferrite

This is not stable at room temperature in plain carbon steel.

However it can be present at room temperature in alloy steel
specially duplex stainless steel.

21
γ phase or austenite:
Interstitial solid solution of carbon in iron of face centred cubic
crystal structure (Fig.3(a)) having solubility limit of 2.11 wt% at
1147°C with respect to cementite. The stability of the phase ranges
between 727-1495°C and solubility ranges 0-0.77 wt%C with respect
to alpha ferrite and 0.77-2.11 wt% C with respect to cementite, at 0 wt
%C the stability ranges from 910-1394°C.

Fig.3(a ): Crystal structure of austenite is shown at right

side. 22
23
α-ferrite:
Interstitial solid solution of carbon in iron of body centred
cubic crystal structure (α iron )(same as Fig. 2(a)) having
solubility limit of 0.0218 wt % C at 727°C with respect to
austenite.
The stability of the phase ranges between low temperatures to
910°C, and solubility ranges 0.00005 wt % C at room
temperature to 0.0218 wt%C at 727°C with respect to
cementite.
There are two morphologies can be observed under
equilibrium transformaton or in low under undercooling
conditon in low carbon plain carbon steels. These are
intergranular allotriomorphs (α)(Fig. 4-7) or intragranular
idiomorphs(αI) (Fig. 4, Fig. 8)

24
An overview of important heat treatments
 A broad classification of heat treatments possible are given below. Many more specialized
treatments or combinations of these are possible.

HEAT TREATMENT

BULK SURFACE

ANNEALING NORMALIZING HARDENING

THERMAL THERMO-
& CHEMICAL
TEMPERING
Full Annealing Carburizing
MARTEMPERING Flame
Recrystallization Annealing Induction Nitriding

Stress Relief Annealing AUSTEMPERING LASER Carbo-nitriding

Spheroidization Annealing Electron Beam

 Ranges of temperature where Annealing, Normalizing and Spheroidization treatment are
carried out for hypo- and hyper-eutectoid steels.
 Details are in the coming slides.

Ful
l An
nea
ling n
910 C

a tio Acm
No li z
rm aliz m a
r
A3 atio
n No

723C Full Annealing

A1

Spheroidization Stress Relief Annealing


T Recrystallization Annealing

Wt% C
0.8 %
Full Annealing
 The purpose of this heat treatment is to obtain a material with high ductility. A microstructure
with coarse pearlite (i.e. pearlite having high interlamellar spacing) is endowed with such
properties.
 The range of temperatures used is given in the figure below.
 The steel is heated above A3 (for hypo-eutectoid steels) & A1 (for hyper-eutectoid steels) → (hold) → then the
steel is furnace cooled to obtain Coarse Pearlite.
 Coarse Pearlite has low (↓) Hardness but high (↑) Ductility.
 For hyper-eutectoid steels the heating is not done above Acm to avoid a continuous network of
proeutectoid cementite along prior Austenite grain boundaries (presence of cementite along grain boundaries
provides easy path for crack propagation).
Recrystallization Annealing
 During any cold working operation (say cold rolling), the material becomes harder (due to
work hardening), but loses its ductility. This implies that to continue deformation the material
needs to be recrystallized (wherein strain free grains replace the ‘cold worked grains’).
 Hence, recrystallization annealing is used as an intermediate step in (cold) deformation
processing.
Heat
 To belowthis
achieve A1 →theSufficient
sample is time →below
heated Recrystallization
A1 and held there for sufficient time for
recrystallization to be completed.
Stress Relief Annealing
 Due to various processes like quenching (differential cooling of surface and interior),
machining, phase transformations (like martensitic transformation), welding, etc. the residual
stresses develop in the sample. Residual stress can lead to undesirable effects like warpage of
the component.
 The annealing is carried out just below A1 , wherein ‘recovery*’ processes are active
(Annihilation of dislocations, polygonization).

Residual stresses → Heat below A1 → Recovery Annihilation of dislocations,

polygonization

Differential cooling

Machining and cold working

Martensite formation

Welding

* It is to be noted that ‘recovery’ is a technical term.

Spheroidization Annealing

 This is a very specific heat treatment given to high carbon steel requiring extensive
machining prior to final hardening & tempering. The main purpose of the treatment is to
increase the ductility of the sample.
 Like stress relief annealing the treatment is done just below A 1.
 Long time heating leads cementite plates to form cementite spheroids. The driving force for
this (microstructural) transformation is the reduction in interfacial energy.
NORMALIZING
 The sample is heat above A3 | Acm to complete Austenization. The sample is then air cooled to
obtain Fine pearlite. Fine pearlite has a reasonably good hardness and ductility.
 In hypo-eutectoid steels normalizing is done 50C above the annealing temperature.
 In hyper-eutectoid steels normalizing done above Acm → due to faster cooling cementite does
not form a continuous film along GB.
 The list of uses of normalizing are listed below.

Refine grain structure prior to hardening

Purposes To harden the steel slightly

To reduce segregation in casting or forgings

HARDENING
 The sample is heated above A3 | Acm to cause Austenization. The sample is then quenched at a
cooling rate higher than the critical cooling rate (i.e. to avoid the nose of the CCT diagram).
 The quenching process produces residual strains (thermal, phase transformation).
 The transformation to Martensite is usually not complete and the sample will have some
Heat above
retained A3 | Acm → Austenization → Quench (higher than critical cooling rate)
Austenite.
 The Martensite produced is hard and brittle and tempering operation usually follows
hardening. This gives a good combination of strength and toughness.
Severity of quench values of some typical quenching
conditions
 Before we proceed further we note that we have a variety of quenching media at our
disposal, with varying degrees of cooling effect. The severity of quench is indicated by the
‘H’ factor (defined below), with an ideal quench having a H-value of .
Severity of Quench as indicated by the heat transfer equivalent H
f 1 f → heat transfer factor Note that apart from the nature of the
H [m ]
K K → Thermal conductivity quenching medium, the vigorousness of the
shake determines the severity of the quench.
When a hot solid is put into a liquid
Process Variable H medium, gas bubbles form on the surface of
Air No agitation 0.02 the solid (interface with medium). As gas
Oil quench No agitation 0.2 has a poor conductivity the quenching rate is
" Slight agitation 0.35 reduced. Providing agitation (shaking the
Increasing severity of quench
" Good agitation 0.5 solid in the liquid) helps in bringing the
" Vigorous agitation 0.7 liquid medium in direct contact with the
Water quench No agitation 1.0 solid; thus improving the heat transfer (and
" Vigorous agitation 1.5 the cooling rate). The H value/index
Brine quench compares the relative ability of various
No agitation 2.0
(saturated Salt water) media (gases and liquids) to cool a hot solid.
" Vigorous agitation 5.0 Ideal quench is a conceptual idea with a heat
Ideal quench  transfer factor of  ( H = ).
Through hardening of the sample
 The surface of is affected by the quenching medium and experiences the best possible
cooling rate. The interior of the sample is cooled by conduction through the (hot) sample and
hence experiences a lower cooling rate. This implies that different parts of the same sample
follow different cooling curves on a CCT diagram and give rise to different microstructures.
 This gives to a varying hardness from centre to circumference. Critical diameter (d c) is that
diameter, which can be through hardened (i.e. we obtain 50% Martensite and 50% pearlite at
the centre of the sample).

Schematic showing variation

in cooling rate from surface
to interior leading to
different microstructures
Typical hardness test survey made along a
diameter of a quenched cylinder
Schematic of Jominy End Quench Test

Jominy hardenability test Variation of hardness along a Jominy bar

(schematic for eutectoid steel)
Q&A How to increase
hardenability?
 Hardenability should not be confused with the ability to obtain high hardness. A material
with low hardenability may have a higher surface hardness compared to another sample
with higher hardenability.
 A material with a high hardenability can be cooled relatively slowly to produce 50%
martensite (& 50% pearlite). A material with a high hardenability has the ‘nose’ of the CCT
curve ‘far’ to the right (i.e. at higher times). Such a material can be through hardened easily.

 Hardenability of plain carbon steel can increased by

alloying with most elements (it is to be noted that this is
an added advantage as alloying is usually done to
improve other properties).
 However, alloying gives two separate ‘C-curves’ for
Pearlitic and Bainitic transformations (e.g. figure to the
right).
 This implies that the ‘nose’ of the Bainitic
transformation has to be avoided to get complete
TTT diagram of low alloy steel (0.42%
Martensite on quenching. C, 0.78% Mn, 1.79% Ni, 0.80% Cr,
0.33% Mo)
U.S.S. Carilloy Steels, United States
Steel Corporation, Pittsburgh, 1948)
Tempering  ' ( BCT )  Temper

 ( BCC ) Fe3C (OR)

Martensite Ferrite Cementite
 A sample with martensitic microstructure is hard but brittle. Hence after quenching the
sample (or component) is tempered. Maternsite being a metastable phase decomposes to
ferrite and cementite on heating (providing thermal activation).
 Tempering is carried out just below the eutectoid temperature (heat → wait→ slow cool).
 In reality the microstructural changes which take place during tempering are very complex.
 The time temperature cycle for tempering is chosen so as to optimize strength and
toughness. E.g. tool steel has a as quenched hardness of Rc65, which is tempered to get a
hardness of Rc45-55.
MARTEMPERING & AUSTEMPERING
 These processes have been developed to avoid residual stresses generated during quenching.
 In both these processes Austenized steel is quenched above Ms (say to a temperature T1) for
homogenization of temperature across the sample.
 In Martempering the steel is then quenched and the entire sample transforms simultaneously
to martensite. This is followed by tempering.
 In Austempering instead of quenching the sample, it is held at T1 for it to transform to
bainite.

800
Eutectoid temperature
723 Austenite
Pearlite
600
 + Fe3C
500 Pearlite + Bainite

T →
400 Bainite

300 T1
Ms
200 Austempering
Mf
100
Martempering Martensite

0.1 1 10 102 103 104 105

t (s) →
 Heat Treatment of Steels for Strength:
• Steel = 0.06% to 1.0% carbon
• Must have a carbon content of at least .6% (ideally) to heat
treat.
• Must heat to austenitc temperature range.
• Must rapid quench to prevent formaton of equilibrium
products.
• Basically crystal structure changes from BCC to FCC at high
Temp.
• The FCC can hold more carbon in soluton and on rapid cooling
the crystal structure wants to return to its BCC structure. It
cannot due to trapped carbon atoms. The net result is a
distorted crystal structure called body centered tetragonal
called martensite.
• Almost always followed by tempering.
 10.4 Direct Hardening – Austenitzing and
quench:
• Austenitzing – again taking a steel with .6%
carbon or greater and heatng to the austenite
region.
• Rapid quench to trap the carbon in the crystal
structure – called martensite (BCT)
• Quench requirements determined from
isothermal transformaton diagram (IT
diagram).
• Get “Through” Hardness!!!
 Austenitzing:

Heat to austenite range.

Want to be close to
transformaton
temperature to get fine
grain structure.
For this partcular steel want to cool from about 1400 F to <400 F in about 1 second!
 Quenching:
• Depending on how fast steel must be quenched
(from IT diagram), the heat treater will determine
type of quenching required:
– Water (most severe)
– Oil
– Molten Salt
– Gas/ Air (least severe)
– Many phases in between!!! Ex: add water/polymer to
water reduces quench tme! Adding 10% sodium
hydroxide or salt will have twice the cooling rate!
 13.4 Direct Hardening - Selectve
Hardening :
• Same requirements as austenitzing:
– Must have sufcient carbon levels (>0.4%)
– Heat to austenite region and quench
• Why do?
– When only desire a select region to be hardened: Knives,
gears, etc.
– Object to big to heat in furnace! Large castng w/ wear
surface
• Types:
– Flame hardening, inducton hardening, laser beam
hardening
Flame Hardening:
Inducton Hardening
Difusion Hardening (aka Case Hardening):

• Why do?
– Carbon content to low to through harden with previous
processes.
– Desire hardness only in select area
– More controlled versus fame hardening and inducton
hardening.
– Can get VERY hard local areas (i.e. HRC of 60 or greater)
– Intersttal difusion when tny solute atoms difuce into
spaces of host atoms
– Substtutonal difusion when difusion atoms to big to
occupy intersttal sites – then must occupy vacancies
 Difusion Hardening:
• Requirements:
– High temp (> 900 F)
– Host metal must have low concentraton of the
difusing species
– Must be atomic suitability between difusing
species and host metal
 Difusion Hardening:
• Most Common Types:
– Carburizing
– Nitriding
– Carbonitriding
– Cyaniding
 Difusion Hardening - Carburizing:
• Pack carburizing most common:
– Part surrounded by charcoal treated with
actvatng chemical – then heated to austenite
temperature.
– Charcoal forms CO2 gas which reacts with excess
carbon in charcoal to form CO.
– CO reacts with low-carbon steel surface to form
atomic carbon
– The atomic carbon difuses into the surface
– Must then be quenched to get hardness!
 Difusion Hardening - Nitriding:
• Nitrogen difused into surface being treated.
Nitrogen reacts with steel to form very hard
iron and alloy nitrogen compounds.
• Process does not require quenching – big
advantage.
• The case can include a white layer which can
be britle – disadvantage
• More expensive than carburizing
Source of nitrogen

Reducton process: 2NH3 2N + 3H2

 13.6 Sofening and Conditoning -
• Recrystallizaton
• Annealing
– Process anneal
– Stress relief anneal
– Normalizing
• Tempering
 13.6 Sofening and Conditoning -
Recrystallizaton
• Done ofen with cold working processes
• Limit to how much steel can be cold worked
before it becomes too britle.
• This process heats steel up so grains return
to their original size prior to subsequent cold
working processes.
• Also done to refine coarse grains
13.6 Sofening and Conditoning - Annealing

• Annealing – primary purpose is to sofen the

steel and prepare it for additonal processing
such as cold forming or machining.
• If already cold worked - allows
recrystallizaton.
13.6 Sofening and Conditoning - Annealing

• What does it do?

1. Reduce hardness
2. Remove residual stress (stress relief)
3. Improve toughness
4. Restore ductlity
5. Refine grain size
13.6 Sofening and Conditoning - Annealing

• Process Steps:
1. Heat material into the asutenite region (i.e.
above 1600F) – rule of thumb: hold steel for one
hour for each one inch of thickness
2. Slowly furnace cool the steel – DO NOT QUENCH
3. Key slow cooling allows the C to precipitate out
so resultng structure is coarse pearlite with
excess ferrite
4. Afer annealing steel is quite sof and ductle
 Annealing versus Austenitzing:
• End result: One sofens and the other hardens!
• Both involve heatng steel to austenite region.
• Only diference is cooling tme:
– If fast (quenched) C is looked into the structure =
martensite (BCT) = HARD
– If slow C precipates out leading to coarse pearlite (with
excess cementte of ferrite) = SOFT
 13.6 Sofening and Conditoning – Other
forms of Annealing
• Normalizing – use when max sofness not
required and cost savings desired (faster
than anneal). Air cooled vs. furnace cooled.
• Process Anneal – not heated as high as full
anneal.
• Stress Relief Anneal – lower temp (1,000F),
slow cooled. Large castngs, weldments
13.6 Sofening and Conditoning - Temper

• Almost always done following heat treat as

part of the austenitzing process!
• Because of lack of adequate toughness and
ductlity afer heat treat, high carbon
martensite is not a useful material despite its
great strength (too britle).
• Tempering imparts a desired amount of
toughness and ductlity (at the expense of
strength)
13.3 Sofening and Conditoning - Temper

• Typical HT steps (Summarized Again):

– Austenize: Heat into stable single phase region and
HOLD for uniform chemistry single phase austenite.
– Quench: Rapid cool – crystal changes from Austenite FCC
to Martensite BCT which is hard but britle.
– Temper: A controlled reheat (BELOW AUSTENITE
REGION). The material moves toward the formaton of a
stable two phase structure – tougher but weaker.
– Quench: The propertes are then frozen in by dropping
temperature to stop further difusion
 TTT diagrams

TTT diagram stands for “time-temperature-transformation” diagram. It is

also called isothermal transformation diagram

Definition: TTT diagrams give the kinetics of isothermal

transformations.

70
 Determination of TTT diagram for eutectoid steel

Davenport and Bain were the first to develop the TTT diagram
of eutectoid steel. They determined pearlite and bainite
portions whereas Cohen later modified and included M S and
MF temperatures for martensite. There are number of methods
used to determine TTT diagrams. These are salt bath (Figs. 1-
2) techniques combined with metallography and hardness
measurement, dilatometry (Fig. 3), electrical resistivity
method, magnetic permeability, in situ diffraction techniques
(X-ray, neutron), acoustic emission, thermal measurement
techniques, density measurement techniques and
thermodynamic predictions. Salt bath technique combined
with metallography and hardness measurements is the most
popular and accurate method to determine TTT diagram.

71
Fig. 1 : Salt bath I -austenitisation Fig. 2 : Bath II low-temperature
heat treatment. salt-bath for isothermal treatment.

72
In molten salt bath technique two salt baths and one water
bath are used. Salt bath I (Fig. 1) is maintained at
austenetising temperature (780˚C for eutectoid steel). Salt bath
II (Fig. 2) is maintained at specified temperature at which
transformation is to be determined (below Ae1), typically 700-
250°C for eutectoid steel. Bath III which is a cold water bath
is maintained at room temperature.
In bath I number of samples are austenitised at AC1+20-40°C
for eutectoid and hypereutectoid steel, AC3+20-40°C for
hypoeutectoid steels for about an hour. Then samples are
removed from bath I and put in bath II and each one is kept for
different specified period of time say t1, t2, t3, t4, tn etc. After
specified times, the samples are removed and quenched in
water. The microstructure of each sample is studied using
metallographic techniques. The type, as well as quantity of
phases, is determined on each sample. 73
The time taken to 1% transformation to, say pearlite or bainite is
considered as transformation start time and for 99%
transformation represents transformation finish. On quenching in
water austenite transforms to martensite.

But below 230°C it appears that transformation is time

independent, only function of temperature. Therefore after
keeping in bath II for a few seconds it is heated to above 230°C
a few degrees so that initially transformed martensite gets
tempered and gives some dark appearance in an optical
microscope when etched with nital to distinguish from freshly
formed martensite (white appearance in optical microscope).
Followed by heating above 230°C samples are water quenched.
So initially transformed martensite becomes dark in
microstructure and remaining austenite transform to fresh
martensite (white). 74
Quantity of both dark and bright etching martensites are
determined. Here again the temperature of bath II at which 1%
dark martensite is formed upon heating a few degrees above
that temperature (230°C for plain carbon eutectoid steel) is
considered as the martensite start temperature (designated M S).
The temperature of bath II at which 99 % martensite is formed
is called martensite finish temperature ( MF).

Transformation of austenite is plotted against temperature vs

time on a logarithm scale to obtain the TTT diagram. The
shape of diagram looks like either S or like C.

Fig. 4 shows the schematic TTT diagram for eutectoid plain

carbon steel

75
 Fig.4: Time temperature transformation (schematic) diagram for plain carbon eutectoid steel
% of Phase
100
T1 T2 At T1, incubation
50%
period for pearlite=t2,
0 Pearlite finish time
=t4
Ae1
T2 s t a rt te n i te + pearlite
e Aus Coarse Pearlite Minimum incubation
Pearlit a tion
sfor
m n is h
r a n Pe a rlite fi Pearlite period t0 at the nose
T
T1 50% of the TTT diagram,
t1 t2 t3 t4 t Fine pearlite
t0 Au 5

Hardness
s ten 50% very fine pearlite + 50% upper bainite MS=Martensite
ite
+ start temperature
Me

up
pe M50=temperature
Temperature

tast

rb Upper bainite
ai n
for 50%
abl

Ba ite
i ni Au
ea

Bai e ni t
te
fi n
st martensite
ust

n ite e+ ish formation

st a l ow
e ni

rt er MF= martensite
te

ba
i ni
te Lower bainite finish temperature
MS, Martensite start temperature
M50,50% Martensite
Metastable austenite +martensite
MF, Martensite finish temperature

Martensite
76
Log time
At close to Ae1 temperature, coarse pearlite forms at close to
Ae1 temperature due to low driving force or nucleation rate.
At higher under coolings or lower temperature finer pearlite
forms.
At the nose of TTT diagram very fine pearlite forms

Close to the eutectoid temperature, the undercooling is low so

that the driving force for the transformation is small. However,
as the undercooling increases transformation accelerates until
the maximum rate is obtained at the “nose” of the curve.
Below this temperature the driving force for transformation
continues to increase but the reaction is now impeded by slow
diffusion. This is why TTT curve takes on a “C” shape with
most rapid overall transformation at some intermediate
temperature.
77
Pearlitic transformation is reconstructive. At a given temperature (say
T1) the transformation starts after an incubation period (t 2, at T1).
Locus of t2 for different for different temperature is called
transformation start line. After 50% transformation locus of that time
(t3 at T1)for different temperatures is called 50% transformation line.
While transformation completes that time (t 4 at T1) is called
transformation finish, locus of that is called transformation finish line.
Therefore TTT diagram consists of different isopercentage lines of
which 1%, 50% and 99% transformation lines are shown in the
diagram. At high temperature while underlooling is low form coarse
pearlite. At the nose temperature fine pearlite and upper bainite form
simultaneously though the mechanisms of their formation are entirely
different. The nose is the result of superimposition of two
transformation noses that can be shown schematically as below one
for pearlitic reaction other for bainitic reaction (Fig. 6).
Upper bainite forms at high temperature close to the nose of TTT
diagram while the lower bainite forms at lower temperature but above 78
M temperature.
Fig. 5(a) : The appearance of a (coarse) pearlitic
microstructure under optical microscope.

79
Fig. 5(c): Optical micrograph showing colonies
of pearlite . Courtesy of S. S. Babu.

80
Fig. 5(d): Transmission electron micrograph
of extremely fine pearlite.

81
Fig. 5(e): Optical micrograph of extremely
fine pearlite from the same sample as used to
create Fig. 5(d). The individual lamellae
cannot now be resolved.

82
 Fig. 6: Time Temperature Transformation (schematic) diagram for plain carbon eutectoid steel

γ=austenite
α=ferrite
γ CP=coarse pearlite
Ae1 P=pearlite
FP=fine pearlite
UB=upper bainite
Metastable γ γ+P CP LB=lower bainite
M=martensite
P MS=Martensite start

Hardness
temperature
FP M50=temperature for
Temperature

50% martensite
50% very FP + 50% UB formation
MF= martensite finish

γ UB temperature

M +
eta UB
sta γ
bl +L
eγ B LB
MS
Metastable γ + M
M50
MF
M
Log time 83
On cooling of metastable austenite 1% martensite forms at
about 230°C. The transformation is athermal in nature. i.e.
amount of transformation is time independent (characteristic
amount of transformation completes in a very short time) but
function of temperature alone. This temperature is called the
martensite start temperature or MS.
Below Ms while metastable austenite is quenched at different
temperature amount of martensite increases with decreasing
temperature and does not change with time.
The temperature at which 99% martensite forms is called
martensite finish temperature or MF. Hardness values are
plotted on right Y-axis. Therefore a rough idea about
mechanical properties can be guessed about the phase mix.

84
 TTT diagram gives

Nature of transformation-isothermal or athermal (time

independent) or mixed
Type of transformation-reconstructive, or displacive
Rate of transformation
Stability of phases under isothermal transformation conditions
Temperature or time required to start or finish transformation
Qualitative information about size scale of product
Hardness of transformed products

85
 Factors affecting TTT diagram
Composition of steel-
(a) carbon wt%,
(b) alloying element wt%

Grain size of austenite

Heterogeneity of austenite

Carbon wt%-
As the carbon percentage increases A3 decreases, similar is the case for Ar3, i.e.
austenite stabilises. So the incubation period for the austenite to pearlite
increases i.e. the C curve moves to right. However after 0.77 wt%C any increase
in C, Acm line goes up, i.e. austenite become less stable with respect to cementite
precipitation. So transformation to pearlite becomes faster. Therefore C curve
moves towards left after 0.77%C. The critical cooling rate required to prevent
diffusional transformation increases with increasing or decreasing carbon
percentage from 0.77%C and e for eutectoid steel is minimum. Similar is the
behaviour for transformation finish time. 86
Pearlite formation is preceeded by ferrite in case of
hypoeutectoid steel and by cementite in hypereutectoid steel.
Schematic TTT diagrams for eutectoid, hypoeutectoid and
hyper eutectoid steel are shown in Fig.4, Figs. 7(a)-(b) and all
of them together along with schematic Fe-Fe 3C metastable
equilibrium are shown in Fig. 8.

87
 Fig. 7(a) :Schematic TTT diagram for plain carbon hypoeutectoid steel

γ=austenite
Ae3 α=ferrite
CP=coarse pearlite
P=pearlite
Ae1 γ+α FP=fine pearlite
UB=upper Bainite
α+CP LB=lower Bainite
α+P M=martensite

γ +P FP MS=Martensite start
t0

Hardness
temperature
M50=temperature for
FP + UB
Temperature

50% martensite
UB formation
MF= martensite finish
temperature
Metastable γ

MS LB
M50 Metastable γ + M
MF
M
Log time 88
 Fig. 7(b): Schematic TTT diagram for plain carbon hypereutectoid steel
Aecm
γ=austenite
CP=coarse pearlite
γ+Fe3C P=pearlite
FP=fine pearlite
Ae1 UB=upper Bainite
LB=lower Bainite
Fe3C+CP M=martensite
MS=Martensite start
Fe3C+P temperature
γ +P Fe3C+FP M50=temperature for

Hardness
t0 very FP +UB 50% martensite
Temperature

formation
γ+ UB
UB

γ+
Metastable γ LB
LB
MS
M50 Metastable γ + M
Log time 89
 Fig. 8: Schematic Fe-Fe3C metastable equilibrium diagram and TTT
diagrams for plain carbon hypoeutectoid, eutectoid and hypereutectoid
steels
γ=austenite M=martensite
P=pearlite
α=ferrite FP=fine pearlite MS=Martensite start temperature
CP=coarse UB=upper bainite M50=temperature for 50% martensite
pearlite LB=lower bainite formation
MF= martensite finish temperature

(a) Fe-Fe3C (b) TTT diagram for (c ) TTT diagram (d) TTT diagram for
metastable phase hypoeutectoid steel for eutectoid steel hypereutectoid steel
diagram

MS
90
Under isothermal conditions for various compositions
proeutectoid tranformation has been summarised below
(Fig. 9). In hypoeutectoid steel the observable ferrite
morphologies are grain boundary allotriomorph (α)(Fig.11(a)-
(d)), Widmanstätten plate (αW)(Figs. 12-16), and massive (αM)
ferrite (Fig.11(f)).

Grain boundary allotriomorphs form at close to Ae3

temperature or extension of Aecm line at low undercooling.
Widmanstätten plates form at higher undercooling but mainly
bellow Ae1. There are overlap regions where both
allotriomorphs and Widmanstätten plates are observed.
Equiaxed ferrite forms at lower carbon composition less than
0.29 wt%C.
91
 There are overlapping regions where both equiaxed ferrite
and Widmanstätten plates were observed. However at very
low carbon percentage massive ferrite forms. The
reconstructive and displacive mechanisms of various phase
formation is shown in Fig. 10.

In hypereutectoid steel both grain boundary allotriomorph and

Widmanstatten plates were observed. Massive morphology
was not observed in hypereutectoid steel. Grain boundary
allotriomorphs were observed mainly close to Aecm or close to
extension of Ae3 line but Widmanstätten plates were observed
at wider temperature range than that of hypoeutectoid steel. In
hypereutectoid steel there are overlapping regions of grain
boundary allotrioorph and Widmanstätten cementite.

92
 Fig. 24 : Schematic illustration of
various other morphologies: (a)
Nodular bainite, (b) columnar bainite
a along a prior austenite boundary, (c)
grain boundary allotriomorphic
bainite, (d) inverse bainite

d
93
Within the bainitic transformation temperature range, austenite of
large grain size with high inclusion density promotes acicular
ferrite formation under isothermal transformation condition. The
morphology is shown schematically (Figs. 25-27 )

Fig. 25 : shows the morphology and nucleation site of

acicular ferrite.
94
Fig . 26: Acicular ferrite

95
Fig. 27: Replica transmission electron micrograph of
acicular ferrire plates in steel weld. Courtesy of Barritte.
96
For eutectoid steel martensite forms at around 230°C. From
230°C to room temperature martensite and retained austenite are
seen. At room temperature about 6% retained austenite can be
there along with martensite in eutectoid steel. At lower carbon
percentage MS temperature goes up and at higher percentage M S
temperature goes down (Fig. 4, Figs. 7-8, Fig. 28). Below 0.4
%C there is no retained austenite at room but retained austenite
can go up to more than 30% if carbon percentage is more than
1.2%. Morphology of martensite also changes from lathe at low
percentage of carbon to plate at higher percentage of carbon.
Plate formation start at around 0.6 % C. Therefore below 0.6 %
carbon only lathe martensite can be seen, mixed morphologies
are observed between 0.6%C to 1%C and above 1% it is 100%
plate martensite (Figs. 29-39).

97
 Fig. 44: Martempering heatreatment superimposed on TTT diagram for plain carbon
hypoeutectoid steel

Ae3

Ae1 Austenite+ferrite
Centre

γ=austenite
α+CP
α=ferrite
Surface

a rl ite α+P CP=coarse pearlite

e +Pe
t0 teni t FP P=pearlite
Aus FP=fine pearlite
t0=minimum incubation
50% FP + 50% UB
Temperature

period
UB UB=upper bainite
LB=lower bainite
M=martensite
Metastable γ Tempering MS=Martensite start
temperature
MS LB M50=temperature at which
50% martensite is obtained
M50 Metastable γ + martensite MF= martensite finish
temperature
MF

Martensite Tempered martensite

Log time 98
 Austempering

Austempering heat treatment is given to steel to produce lower

bainite in high carbon steel without any distortion or cracking to
the sample. The heat treatment is cooling of austenite rapidly in a
bath maintained at lower bainitic temperature (above M s)
temperature (avoiding the nose of the TTT diagram) and holding
it here to equalise surface and centre temperature (Fig. 45) and .
till bainitic finish time. At the end of bainitic reaction sample is
air cooled. The microstructure contains fully lower bainite. This
heat treatment is given to 0.5-1.2 wt%C steel and low alloy steel.
The product hardness and strength are comparable to hardened
and tempered martensite with improved ductility and toughness
and uniform mechanical properties. Products donot required to
be tempered.

99
 Fig. 45: Austempering heatreatment superimposed on TTT diagram for plain carbon
hypoeutectoid steel

Ae3

Ae1 Austenite+ferrite
Centre

γ=austenite
α+CP
α=ferrite
Surface

a rl ite α+P CP=coarse pearlite

e +Pe
t0 teni t FP P=pearlite
Aus FP=fine pearlite
t0=minimum incubation
50% FP + 50% UB
Temperature

period
UB UB=upper bainite
LB=lower bainite
M=martensite
Metastable γ Tempering MS=Martensite start
temperature
MS LB M50=temperature at which
50% martensite is obtained
MF= martensite finish
M50 temperature
Metastable γ + martensite
MF
Martensite
Lower bainite

Log time 100

 Isothermal annealing

• Isothermal annealing is given to plain carbon and alloy steels

to produce uniform ferritic and pearlitic structures. The
product after austenising taken directly to the annealing
furnace maintained below lower critical temperature and hold
isothermally till the pearlitic reaction completes (Fig. 46). The
initial cooling of the products such that the temperature at the
centre and surface of the material reach the annealing
temperature before incubation period of ferrite. As the
products are hold at constant temperature i.e. constant
undercooling) the grain size of ferrite and interlamellar
spacing of pearlite are uniform. Control on cooling after the
end of pearlite reaction is not essential. The overall cycle time
is lower than that required by full annealing.

101
 Fig. 46: Isothermal annealing heat treatment superimposed on TTT diagram of plain carbon
hypoeutectoid steel

Ae3

Ae1 Austenite+ferrite
Surface

γ=austenite
Centre

α+CP
α=ferrite
a rl ite α+P CP=coarse pearlite
e +Pe
t0 teni t FP P=pearlite
Aus FP=fine pearlite
t0=minimum incubation
50% FP + 50% UB
Temperature

period
UB UB=upper bainite
LB=lower bainite
M=martensite
Metastable γ MS=Martensite start
temperature
MS LB M50=temperature at which
50% martensite is obtained
MF= martensite finish
M50 temperature
Metastable γ + martensite
MF
Martensite
Ferrite and pearlite

Log time 102

 Patenting

Patenting heat treatment is the isothermal annealing at the

nose temperature of TTT diagram (Fig. 47). Followed by this
the products are air cooled. This treatment is to produce fine
pearlitic and upper bainitic structure for strong rope, spring
products containing carbon percentage 0.45 %C to 1.0%C.
The coiled ropes move through an austenitising furnace and
enters the salt bath maintained at 550°C(nose temperature) at
end of salt bath it get recoiled again. The speed of wire and
length of furnace and salt bath such that the austenitisation get
over when the wire reaches to the end of the furnace and the
residency period in the bath is the time span at the nose of the
TTT diagram. At the end of salt bath wire is cleaned by water
jet and coiled.

103
 Fig. 47: Patenting heat treatment superimposed on TTT diagram of plain carbon hypoeutectoid
steel

Ae3

Ae1 Austenite+ferrite
γ=austenite
α+CP
α=ferrite
a rl ite α+P CP=coarse pearlite
i te +Pe P=pearlite
t0 ten FP
Aus FP=fine pearlite
t0=minimum incubation
50% FP + 50% UB
Temperature

period
UB UB=upper bainite
LB=lower bainite
M=martensite
Metastable γ MS=Martensite start
temperature
MS LB M50=temperature at which
50% martensite is obtained
MF= martensite finish
M50 temperature
Metastable γ + martensite
MF
Martensite
fine pearlite and upper bainite

Log time 104