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Heat Treatment

R. Manna
Assistant Professor
Centre of Advanced Study
Department of Metallurgical Engineering
Institute of Technology
Banaras Hindu University
Varanasi-221 005, India
rmanna.met@itbhu.ac.in
Tata Steel-TRAERF Faculty Fellowship Visiting Scholar
Department of Materials Science and Metallurgy
University of Cambridge
Pembroke Street, Cambridge, CB2 3QZ
rm659@cam.ac.uk
HEAT TREATMENT
Fundamentals
Fe-C equilibrium diagram. Isothermal and continuous
cooling transformation diagrams for plain carbon and
alloy steels. Microstructure and mechanical properties of
pearlite, bainite and martensite. Austenitic grain size.
Hardenability, its measurement and control.
Processes
Annealing, normalising and hardening of steels,
quenching media, tempering. Homogenisation.
Dimensional and compositional changes during heat
treatment. Residual stresses and decarburisation.
2
Surface Hardening
Case carburising, nitriding, carbonitriding, induction and flame
hardening processes.
Special Grade Steels
Stainless steels, high speed tool steels, maraging steels, high strength
low alloy steels.
Cast irons
White, gray and spheroidal graphitic cast irons
Nonferrous Metals
Annealing of cold worked metals. Recovery, recrystallisation and grain
growth. Heat treatment of aluminum, copper, magnesium, titanium and
nickel alloys. Temper designations for aluminum and magnesium alloys.
Controlled Atmospheres
Oxidizing, reducing and neutral atmospheres.
3
Suggested Reading
R. E. Reed-Hill and R. Abbaschian: Physical Metallurgy
Principles, PWS , Publishing Company, Boston, Third Edition.
Vijendra Singh: Heat treatment of Metals, Standard Publishers
Distributors, Delhi.
Anil Kumar Sinha: Physical Metallurgy Handbook, McGraw-
Hill Publication.
H. K. D. H. Bhadeshia and R. W. K. Honeycombe: Steels-
Microstructure and Properties, Butterworth-Heinemann, Third
Edition, 2006
R. C. Sharma: Principles of Heat Treatment of Steels, New Age
International (P) Ltd. Publisher.
Charlie R. Brooks: Heat Treatment: Structure and Properties of
Nonferrous Alloys, A. S. M. Publication.
4
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 period of time and cooling at some specified rate. The
aim is to obtain a desired microstructure to achieve certain
predetermined properties (physical, mechanical, magnetic or
electrical).
5
Objectives of heat treatment (heat treatment processes)
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)
6
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)
7
Fe-cementite metastable phase diagram (Fig.1) consists of
phases liquid iron(L), -ferrite, or austenite, -ferrite and
Fe
3
C or cementite and phase mixture of pearlite
(interpenetrating bi-crystals of ferrite and cementite)(P) and
ledeburite (mixture of austenite and cementite)(LB).
Solid phases/phase mixtures are described here.
8
Weight percent carbon
T
e
m
p
e
r
a
t
u
r
e
,

C
Fig.1: Fe-Cementite metastable phase diagram (microstructural)
L
L+Cm
I
L+
I
L
e
d
e
b
u
r
i
t
e
=
L
B
(

e
u
+
C
e
u
)

I
(
II
+Cm
II
)+LB (
eu
(
II
+Cm
II
)+Cm
eu
)
LB (
eu
(
II
+Cm
II
)+Cm
eu
)
+Cm
I
LB (P(
ed
+Cm
ed
)
+Cm
II
)+Cm
eu
)+Cm
I
LB
((P(
ed
(
ed
+Cm
III
)+Cm
ed
)
+Cm
II
)+ Cm
eu
)+Cm
I
(P(
ed
+Cm
ed
)+Cm
II
)+ LB (P(
ed
+Cm
ed
)
+Cm
II
+Cm
eu
)
(P(
ed
(
ed
+Cm
III
)+Cm
ed
) +Cm
II
)+
LB ((P(
ed
(
ed
+Cm
III
)+Cm
ed
)
+Cm
II
)+Cm
eu
)

II
+Cm
II

I
+
P(
ed
+Cm
ed
)
+Cm
II
P(
ed
(
ed
+Cm
III
)+Cm
ed
)
+Cm
II

I
+ (P(
ed
+Cm
ed
)

I
(+Cm
III
)+
(P(
ed
(
ed
+C
m
III
)+Cm
ed
)

+Cm
III

+
+L
Cm
A
o
=210C
A
1
=727C
A
4
=1147C
A
5
=1495C
A
2
=668/
770C
A
3
0.0218
0.77
2.11
4.30
0.09
0.17
0.53
0.00005
910C
1539C
1394C
1227C
6.67
L=liquid, Cm=cementite, LB=ledeburite, =delta ferrite, =
alpha ferrite, = alpha ferrite(0.00005 wt%C) =austenite,
P=pearlite, eu=eutectic, ed=eutectoid, I=primary,
II=secondary, III=tertiary
P
e
a
r
l
i
t
e

I
+LB LB+Cm
I
A
D E F
B
C
9
ferrite:
Interstitial solid solution of carbon in iron of body centred
cubic crystal structure (Fig .2(a)) ( iron ) of higher lattice
parameter (2.89) 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.
10
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.
11
Fig. 3(b): Polished sample held at austenitisation temperature.
Grooves develop at the prior austenite grain boundaries due to the
balancing of surface tensions at grain junctions with the free
surface. Micrograph courtesy of Saurabh Chatterjee.
12
-ferrite:
Interstitial solid solution of carbon in iron of body centred
cubic crystal structure ( 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 transformation or in low under undercooling
condition in low carbon plain carbon steels. These are
intergranular allotriomorphs ()(Fig. 4-7) or intragranular
idiomorphs(
I
) (Fig. 4, Fig. 8)
13
Fig. 4: Schematic diagram of grain boundary allotriomoph
ferrite, and intragranular idiomorph ferrite.
14
Fig.5: An allotriomorph of ferrite in a sample which is partially
transformed into and then quenched so that the remaining
undergoes martensitic transformation. The allotriomorph grows
rapidly along the austenite grain boundary (which is an easy
diffusion path) but thickens more slowly.
15
Fig.6: Allotriomorphic ferrite in a Fe-0.4C steel which is slowly
cooled; the remaining dark-etching microstructure is fine
pearlite. Note that although some -particles might be identified
as idiomorphs, they could represent sections of allotriomorphs.
Micrograph courtesy of the DOITPOMS project.
16
Fig.7: The allotriomorphs have in this slowly cooled low-
carbon steel have consumed most of the austenite before the
remainder transforms into a small amount of pearlite.
Micrograph courtesy of the DoITPOMS project. The shape of
the ferrite is now determined by the impingement of particles
which grow from different nucleation sites.
17
Fig. 8: An idiomorph of ferrite in a sample which is partially
transformed into and then quenched so that the remaining
undergoes martensitic transformation. The idiomorph is
crystallographically facetted.
18
There are three more allotropes for pure iron that form under
different conditions
-iron:
The iron having hexagonal close packed structure. This forms
at extreme pressure,110 kbars and 490C. It exists at the centre
of the Earth in solid state at around 6000C and 3 million
atmosphere pressure.
FCT iron:
This is face centred tetragonal iron. This is coherently
deposited iron grown as thin film on a {100} plane of copper
substrate
Trigonal iron:
Growing iron on misfiting {111} surface of a face centred
cubic copper substrate.
19
Fe
3
C or cementite:
Interstitial intermetallic compound of C & Fe with a carbon content
of 6.67 wt% and orthorhombic structure consisting of 12 iron atoms
and 4 carbon atoms in the unit cell.
Stability of the phase ranges from low temperatures to 1227 C
Fig.9(a): Orthorhombic crystal structure of cementite. The purple
atoms represent carbon. Each carbon atom is surronded by eight iron
atoms. Each iron atom is connected to three carbon atoms.
20
Fig.9(b): The pearlite is resolved in some regions where the
sectioning plane makes a glancing angle to the lamellae. The
lediburite eutectic is highlighted by the arrows. At high temperatures
this is a mixture of austenite and cementite formed from liquid. The
austenite subsequently decomposes to pearlite.
Courtesy of Ben Dennis-Smither, Frank Clarke and Mohamed Sherif
21
Critical temperatures:
A=arret means arrest
A
0
= a subcritical temperature (<A
1
) = Curie temperature of
cementite=210 C
A
1
=Lower critical temperature=eutectoid temperature=727 C
A
2
=Curie temperature of ferrite=768/770 C
A
3
=upper critical temperature=+ / phase field boundary
=composition dependent=910-727 C
A
4
=Eutectic temperature=1147 C
A
5
=Peritectic temperature=1495 C
22
A
cm
=/+cementite phase field boundary=composition dependent =727-
1147 C
In addition the subscripts c or r are used to indicate that the temperature is
measured during heating or cooling respectively.
c=chaffauge means heating, A
c
r=refroidissement means cooling, A
r
Types/morphologies of phases in Fe-Fe
3
C system
Cementite=primary (Cm
I
), eutectic (Cm
eu
), secondary (Cm
II
)(grain
boundary allotriomophs, idiomorphs), eutectoid (Cm
ed
) and tertiary(Cm
III
).
Austenite= austenite()(equiaxed), primary (
I
), eutectic (
eu
), secondary
(
II
) (proeutectoid),
-ferrite=ferrite () (equiaxed), proeutectoid or primary (grain boundary
allotriomorphs and idiomorphs)(
I
), eutectoid(
eu
) and ferrite (lean in
carbon) ().
Phase mixtures
Pearlite (P) and ledeburite(LB)
23
Fig.10: -ferrite in dendrite form in as-cast Fe-0.4C-
2Mn-0.5Si-2 Al0.5Cu, Coutesy of S. Chaterjee et al.
M. Muruganath, H. K. D. H. Bhadeshia
Important Reactions
Peritectic reaction
Liquid+Solid
1
Solid
2
L(0.53wt%C)+(0.09wt%C)(0.17wt%C) at 1495 C
Liquid-18.18wt% +-ferrite 81.82 wt%100 wt%
24
Fig.11: Microstructure of white cast iron containing
massive cementite (white) and pearlite etched with 4%
nital, 100x. After Mrs. Janina Radzikowska, Foundry
Research lnstitute in Krakw, Poland
Eutectic reaction
LiquidSolid
1
+Solid
2
Liquid (4.3wt%C) (2.11wt%C) + Fe
3
C (6.67wt%C) at 1147C
Liquid-100 wt% 51.97wt% +Fe
3
C (48.11wt%)
The phase mixture of austenite and cementite formed at eutectic
temperature is called ledeburite.
25
Fig. 12: High magnification view (400x) of the white cast iron
specimen shown in Fig. 11, etched with 4% nital. After Mrs.
Janina Radzikowska, Foundry Research lnstitute in Krakw,
Poland
26
Fig. 13: High magnification view (400x) of the white cast
iron specimen shown in Fig. 11, etched with alkaline sodium
picrate. After Mrs. Janina Radzikowska, Foundry Research
lnstitute in Krakw, Poland
27
Eutectoid reaction
Solid
1
Solid
2
+Solid
3
(0.77wt%C) (0.0218wt%C) + Fe
3
C(6.67wt%C) at 727 C
(100 wt%) (89 wt% ) +Fe
3
C(11wt%)
Typical density
ferrite=7.87 gcm
-3
Fe
3
C=7.7 gcm
-3
volume ratio of - ferrite:Fe
3
C=7.9:1
28
Fig. 14: The process by which a colony of pearlite
evolves in a hypoeutectoid steel.
29
Fig. 15 : The appearance of a pearlitic
microstructure under optical microscope.
30
Fig. 16: A cabbage filled with water analogy of the three-
dimensional structure of a single colony of pearlite, an
interpenetrating bi-crystal of ferrite and cementite.
31
Fig. 17: Optical micrograph showing colonies
of pearlite . Courtesy of S. S. Babu.
32
Fig. 18: Transmission electron micrograph of
extremely fine pearlite.
33
Fig.19: Optical micrograph of extremely fine
pearlite from the same sample as used to
create Fig. 18. The individual lamellae cannot
now be resolved.
34
Evolution of microstructure (equilibrium cooling)
Sequence of evolution of microstructure can be described by
the projected cooling on compositions A, B, C, D, E, F.
At composition A
L +L + +I +Cm
III
At composition B
L +L L+
I

I
+
I
+ (P(
ed
+Cm
ed
)

I
(+Cm
III
)+(P(
ed
(
ed
+Cm
III
)+Cm
ed
)
35
At composition C
L
At composition D
L
L+
I

II
+Cm
II P(
ed
+Cm
ed
)+Cm
II
P(
ed
(
ed
+Cm
III
)+Cm
ed
)+Cm
II
L+
I

I
+LB
I
(
II
+Cm
II
)+LB (
eu
(
II
+Cm
II
)+Cm
eu
)
(P(
ed
+Cm
ed
)+Cm
II
)+ LB (P(
ed
+Cm
ed
)+Cm
II
+Cm
eu
)
(P(
ed
(
ed
+Cm
III
)+Cm
ed
) +Cm
II
)+ LB
((P(
ed
(
ed
+Cm
III
)+Cm
ed
)+Cm
II
)+Cm
eu
)
36
At composition E
L
At composition F
L Fe
3
C
L+Cm
I
LB(
eu
+Cm
eu
+Cm
I
LB (
eu
(
II
+Cm
II
)+Cm
eu
)+Cm
I
LB (P(
ed
+Cm
ed
)+Cm
II
)+Cm
eu
)+Cm
I
LB ((P(
ed
(
ed
+Cm
III
)+Cm
ed
) +Cm
II
)+ Cm
eu
)+Cm
I
37
Limitations of equilibrium phase diagram
Fe-Fe
3
C equilibrium/metastable phase diagram
Stability of the phases under equilibrium condition only.
It does not give any information about other metastable phases.
i.e. bainite, martensite
It does not indicate the possibilities of suppression of
proeutectoid phase separation.
No information about kinetics
No information about size
No information on properties.
38
Time Temperature Transformation
(TTT) Diagrams
R. Manna
Assistant Professor
Centre of Advanced Study
Department of Metallurgical Engineering
Institute of Technology, Banaras Hindu University
Varanasi-221 005, India
rmanna.met@itbhu.ac.in
Tata Steel-TRAERF Faculty Fellowship Visiting Scholar
Department of Materials Science and Metallurgy
University of Cambridge, Pembroke Street, Cambridge, CB2 3QZ
rm659@cam.ac.uk
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.
2
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
M
F
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.
3
Fig. 2 : Bath II low-temperature
salt-bath for isothermal treatment.
Fig. 1 : Salt bath I -austenitisation
heat treatment.
4
Fig . 3(a): Sample and
fixtures for dilatometric
measurements
Fig. 3(b) : Dilatometer
equipment
5
In molten salt bath technique two salt baths and one water
bath are used. Salt bath I (Fig. 1) is maintained at austenetising
temperature (780C for eutectoid steel). Salt bath II (Fig. 2) is
maintained at specified temperature at which transformation is
to be determined (below A
e1
), typically 700-250C 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 A
C1
+20-40 C
for eutectoid and hypereutectoid steel, A
C3
+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 t
1
, t
2
, t
3
, t
4
, t
n
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.
6
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).
7
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 ( M
F
).
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
8
Fig.4: Time temperature transformation (schematic) diagram for plain carbon
eutectoid steel
t
1
t
3
t
2
t
4
t
5
M
F
, Martensite finish temperature
M
50,
50% Martensite
M
S,
Martensite start temperature
Metastable austenite +martensite
Martensite
%

o
f

P
h
a
s
e
0
100
T
e
m
p
e
r
a
t
u
r
e
Log time
H
a
r
d
n
e
s
s
A
e1
T
2
T
1
50%
T
2
T
1
Pearlite
Fine pearlite
Upper bainite
Lower bainite
50% very fine pearlite + 50% upper bainite
At T
1
, incubation
period for pearlite=t
2
,
Pearlite finish time
=t
4
Minimum incubation
period t
0
at the nose
of the TTT diagram,
t
0
M
S
=Martensite
start temperature
M
50
=temperature
for 50%
martensite
formation
M
F
= martensite
finish temperature
9
At close to A
e1
temperature, coarse pearlite forms at close to
A
e1
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.
10
Pearlitic transformation is reconstructive. At a given temperature (say
T
1
) the transformation starts after an incubation period (t
2,
at T
1
).
Locus of t
2
for different for different temperature is called
transformation start line. After 50% transformation locus of that time
(t
3
at T
1
)for different temperatures is called 50% transformation line.
While transformation completes that time (t
4
at T
1
) 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
M
S
temperature.
11
Fig. 5(a) : The appearance of a (coarse) pearlitic
microstructure under optical microscope.
12
Fig. 5(b): Acabbage filled with water analogy of the three-
dimensional structure of a single colony of pearlite, an
interpenetrating bi-crystal of ferrite and cementite.
13
Fig. 5(c): Optical micrograph showing colonies
of pearlite . Courtesy of S. S. Babu.
14
Fig. 5(d): Transmission electron micrograph
of extremely fine pearlite.
15
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.
16
Fig. 6: Time Temperature Transformation (schematic) diagram for plain carbon
eutectoid steel
M
F
M
50
M
S
Metastable + M
M
T
e
m
p
e
r
a
t
u
r
e
Log time
H
a
r
d
n
e
s
s
A
e1
P
FP
UB
LB
50% very FP + 50% UB
Metastable

=austenite
=ferrite
CP=coarse pearlite
P=pearlite
FP=fine pearlite
UB=upper bainite
LB=lower bainite
M=martensite
M
S
=Martensite start
temperature
M
50
=temperature for
50% martensite
formation
M
F
= martensite finish
temperature
17
On cooling of metastable austenite 1% martensite forms at
about 230C. 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 M
S
.
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 M
F
. Hardness values are
plotted on right Y-axis. Therefore a rough idea about
mechanical properties can be guessed about the phase mix.
18
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
19
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 A
3
decreases, similar is the case
for A
r3
, 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, A
cm
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.
20
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
3
C metastable
equilibriumare shown in Fig. 8.
21
Fig. 7(a) :Schematic TTT diagram for plain carbon hypoeutectoid steel
M
F
M
50
M
S
Metastable + M
M
T
e
m
p
e
r
a
t
u
r
e
Log time
H
a
r
d
n
e
s
s
A
e1
+CP
+P
FP
UB
LB
FP + UB
=austenite
=ferrite
CP=coarse pearlite
P=pearlite
FP=fine pearlite
UB=upper Bainite
LB=lower Bainite
M=martensite
M
S
=Martensite start
temperature
M
50
=temperature for
50% martensite
formation
M
F
= martensite finish
temperature
A
e3
t
0
Metastable
22
Fig. 7(b): Schematic TTT diagram for plain carbon hypereutectoid
steel
M
50
M
S
Metastable
Metastable + M
T
e
m
p
e
r
a
t
u
r
e
Log time
H
a
r
d
n
e
s
s
A
e1
Fe
3
C+CP
Fe
3
C+P
Fe
3
C+FP
UB
LB
very FP +UB
A
ecm
t
0
=austenite
CP=coarse pearlite
P=pearlite
FP=fine pearlite
UB=upper Bainite
LB=lower Bainite
M=martensite
M
S
=Martensite start
temperature
M
50
=temperature for
50% martensite
formation
23
Fig. 8: Schematic Fe-Fe
3
C metastable equilibrium diagram
and TTT diagrams for plain carbon hypoeutectoid, eutectoid
and hypereutectoid steels
M
S
(a) Fe-Fe
3
C
metastable phase
diagram
(b) TTT diagram for
hypoeutectoid steel
(c ) TTT diagram
for eutectoid steel
(d) TTT diagram for
hypereutectoid steel
=austenite
=ferrite
CP=coarse
pearlite
M=martensite
M
S
=Martensite start temperature
M
50
=temperature for 50% martensite
formation
M
F
= martensite finish temperature
P=pearlite
FP=fine pearlite
UB=upper bainite
LB=lower bainite
24
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 ()(Fig.11(a)-
(d)), Widmansttten plate (
W
)(Figs. 12-16), and massive (
M
)
ferrite (Fig.11(f)).
Grain boundary allotriomorphs form at close to A
e3
temperature or extension of A
ecm
line at low undercooling.
Widmansttten plates form at higher undercooling but mainly
bellow Ae
1
. There are overlap regions where both
allotriomorphs and Widmansttten plates are observed.
Equiaxed ferrite forms at lower carbon composition less than
0.29 wt%C.
25
Weight % carbon
T
e
m
p
e
r
a
t
u
r
e
A
e3
0.0218
0.77
Austenite
Pearlite
A
e1
Plate martensite
Mix martensite
Lath martensite
M
S
M
F
Volume % of retained
austenite at room
temperature
V
o
l
u
m
e

%

o
f

r
e
t
a
i
n
e
d

a
u
s
t
e
n
i
t
e
Fig 9: Temperature versus composition in which various morphologies
are dominant at late reaction time under isothermal condition

W
Cm
W

M
Upper bainite
Lower bainite
W=Widmansttten
plate
M=massive
P=pearlite

ub
=upper bainite

lb
=lower bainite
26
There are overlapping regions where both equiaxed ferrite
and Widmansttten 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 A
ecm
or close to
extension of A
e3
line but Widmansttten plates were observed
at wider temperature range than that of hypoeutectoid steel. In
hypereutectoid steel there are overlapping regions of grain
boundary allotrioorph and Widmansttten cementite.
27
Fig. 10: The reconstructive and displacive mechanisms.
28
Fig. 11(a): schematic diagram of grain boundary allotriomoph
ferrite, and intragranular idiomorph ferrite.
29
Fig.11(b): An allotriomorph of ferrite in a sample which is partially
transformed into and then quenched so that the remaining
undergoes martensitic transformation. The allotriomorph grows
rapidly along the austenite grain boundary (which is an easy diffusion
path) but thickens more slowly.
30
Fig. 11(c): Allotriomorphic ferrite in a Fe-0.4C steel which is
slowly cooled; the remaining dark-etching microstructure is fine
pearlite. Note that although some -particles might be identified as
idiomorphs, they could represent sections of allotriomorphs.
Micrograph courtesy of the DoITPOMS project.
31
Fig. 11(d): The allotriomorphs have in this slowly cooled low-
carbon steel have consumed most of the austenite before the
remainder transforms into a small amount of pearlite.
Micrograph courtesy of the DoItPoms project. The shape of
the ferrite is now determined by the impingement of particles
which grow from different nucleation sites.
32
Fig. 11(e): An idiomorph of ferrite in a sample which is partially
transformed into and then quenched so that the remaining
undergoes martensitic transformation. The idiomorph is
crystallographically facetted.
33
Fig. 11(f ): Massive ferrite (
m
) in Fe-0.002 wt%C alloy
quenched into ice brine from 1000C. Courtesy of T. B.
Massalski
34
Fig. 12(a): Schematic illustration of primary Widmansttten
ferrite which originates directly from the austenite grain
surfaces, and secondary
w
which grows from allotriomorphs.
35
Fig. 12(b): Optical micrographs showing white-etching (nital)
wedge-shaped Widmansttten ferrite plates in a matrix quenched to
martensite. The plates are coarse (notice the scale) and etch cleanly
because they contain very little substructure.
36
Fig. 13: The simultaneous growth of two self-
accommodating plates and the consequential tent-like
surface relief.
37
Fig.14: Transmission electron micrograph of what optically appears
to be single plate, but is in fact two mutually accommodating plates
with a low-angle grain boundary separating them. Fe-0.41C alloy,
austenitised at 1200 C for 6 hrs, isothermally transformed at 700 C
for 2 min and water quenched.
38
Fig. 15: Mixture of allotriomorphic ferrite, Widmansttten ferrite
and pearlite. Micrograph courtesy of DOITPOMS project.
39
Fig. 16 (a) Surface relief of Widmansttten ferrite Fe-0.41C
alloy, austenitised at 1200 C for 6 hrs, isothermally
transformed at 700 C for 30 min and water quenced, (b) same
field after light polishing and etching with nital.
40
For eutectoid steel banitic transformation occurs at 550 to
250C. At higher temperature it is upper bainite and at lower
temperature it is lower bainite. As C increases the austenite to
ferrite decomposition becomes increasingly difficult. As
bainitic transformation proceeds by the nucleation of ferrite,
therefore banitic transformation range moves to higher timing
and lower temperature. With increasing percentage of carbon
the amount of carbide in interlath region in upper bainite
increases and carbides become continuous phase. However at
lower percentage of carbon they are discrete particles and
amount of carbide will be less in both type of bainites. For
start and finish temperatures for both types of bainites go
down significantly with increasing amount of carbon (Figs. 8-
9). However increasing carbon makes it easier to form lower
bainite.
41
Fig 17: Summary of the mechanism of the bainite reaction.
42
Fig. 18: Upper bainite; the
phase between the platelets
of bainitic ferrite is usually
cementite.
43
Fig. 19: Transmission electron micrograph of a sheaf of upper bainite in
a partially transformed Fe-0.43C-2Si-3Mn wt% alloy (a) optical
micrograph, (b, c) bright field and corresponding dark field image of
retained austenite between the sub units, (d) montage showing the
structure of the sheaf.
44
Fig. 20 : Corresponding outline of the sub-units near the sheaf tip
region of Fig. 19
45
Fig. 21 : AFMimage showing surface relief due to individual bainite
subunit which all belong to tip of sheaf. The surface relief is
associated with upper bainite (without any carbide ) formed at 350C
for 2000 s in an Fe-0.24C-2.18Si-2.32Mn-1.05Ni (wt% ) alloy
austenitised at 1200C for 120 s alloy. Both austenitisation and
isothermal transformation were performed in vacuum. The
microstructure contains only bainitic ferrite and retained austenite.
The measured shear strain is 0.260.02.
46
Fig. 22: Optical micrograph illustrating the sheaves of lower bainite in
a partially transformed (395C), Fe-0.3C-4Cr wt% ally. The light
etching matrix phase is martensite. (b) Corresponding transmission
electron micrograph illustrating subunits of lower bainite.
a
b
47
Fig. 23 : (a) Optical micrograph showing thin and spiny lower
bainite formed at 190C for 5 hours in an Fe-1.1 wt% C steel. (b)
Transmission electron micrograph showing lower bainite midrib in
same steel. Courtesy of M. Oka
48
Fig. 24 : Schematic illustration of
various other morphologies: (a)
Nodular bainite, (b) columnar bainite
along a prior austenite boundary, (c)
grain boundary allotriomorphic
bainite, (d) inverse bainite
a
b
c
d
49
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.
50
Fig . 26: Acicular ferrite
51
Fig. 27: Replica transmission electron micrograph of
acicular ferrire plates in steel weld. Courtesy of Barritte.
52
For eutectoid steel martensite forms at around 230C. From
230C 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 M
S
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).
53
Weight % carbon
T
e
m
p
e
r
a
t
u
r
e
Austenite +cementite
A
e3
0.0218
0.77
P
e
a
r
l
i
t
e
Austenite
Ferrite + pearlite
Pearlite+cementite
A
e1
Plate martensite Mix martensite Lath martensite
M
S
M
F
Ferrite + austenite
Volume % of retained
austenite at room
temperature
V
o
l
u
m
e

%

o
f

r
e
t
a
i
n
e
d

a
u
s
t
e
n
i
t
e
Fig. 28: Effect of carbon on M
S
, M
F
temperatures and retained austenite in plain carbon
steel
54
Lath
(Fe-9%Ni-0.15%C)
Lenticular
(Fe-29%Ni-0.26%C)
Thin plate
(Fe-31%Ni-0.23%C)
Substructure Dislocation
Dislocation
Twin (midrib)
Twin
Habit plane
{111}
A
{557}
A
{259}
A
{3 10 15}
A
{3 10 15}
A
O.R. K-S
N-W
G-T
G-T
Ms high low
Fig. 29: Morphology and crystallography of (bcc or bct) martensite in
ferrous alloys
Courtesy of
T. Maki
55
Fig. 30: Lath martensite
Courtesy of
T. Maki
56
(T. MakiK. Tsuzaki, I. Tamura: Trans. ISIJ, 20(1980), 207.)
Packet: a group of laths
with the same habit plane
( ~{111} )
Block : a group of laths
with the same orientation
(the same K-S variant)
Fig. 31: effect of carbon
on martensite lath size
57
Fig. 33: Fe-31%Ni-0.28%C
(Ms=192K)
Lenticular martensite
(Optical micrograph)
Fig.32: Fe-29%Ni-0.26%C
(Ms=203K)
Fig.34: schematic diagram for
lenticular martensite
Courtesy of
T. Maki
58
cooling
after polished and etched
Fig. 35: Growth behavior of lenticular martensite
in Fe-30.4%Ni-0.4%C alloy
surface relief surface relief
surface relief
(T. Kakeshita, K. Shimizu, T. Maki, I. Tamura, Scripta Metall., 14(1980)1067.)
Courtesy of
T. Maki
59
midrib twinned region
schematic illustration
Fig. 36: Lenticular martensite in Fe-33%Ni alloy
(Ms=171K)
Optical micrograph
Courtesy of
T. Maki
60
Fig. 37: Optical microstructure of lath martensite (Fe-C alloys)
0.0026%C 0.18%C
0.61%C 0.38%C
Courtesy of
T. Maki
61
Block structure in a single packet (Fe-0.18%C)
Fig.39 : Orientation
image map
Fig. 38: SEM image
Courtesy of
T. Maki
Alloying elements: Almost all alloying elements
(except, Al, Co, Si) increases the stability of supercooled
austenite and retard both proeutectoid and the pearlitic reaction
and then shift TTT curves of start to finish to right or higher
timing. This is due to i) low rate of diffusion of alloying
elements in austenite as they are substitutional elements, ii)
reduced rate of diffusion of carbon as carbide forming
elements strongly hold them. iii) Alloyed solute reduce the rate
of allotropic change, i.e. , by solute drag effect on
interface boundary. Additionally those elements (Ni, Mn, Ru,
Rh, Pd, Os, Ir, Pt, Cu, Zn, Au) that expand or stabilise
austenite, depress the position of TTT curves to lower
temperature. In contrast elements (Be, P, Ti, V, Mo, Cr, B, Ta,
Nb, Zr) that favour the ferrite phase can raise the eutectoid
temperature and TTT curves move upward to higher
temperature.
63
However Al, Co, and Si increase rate of nucleation and growth
of both ferrite or pearlite and therefore shift TTT diagram to
left. In addition under the complex diffusional effect of various
alloying element the simple C shape behaviour of TTT
diagram get modified and various regions of transformation
get clearly separated. There are separate pearlitic C curves,
ferritic and bainitic C curves and shape of each of them are
distinct and different.
64
The effect of alloying elements is less pronounced in bainitic
region as the diffusion of only carbon takes place (either to
neighbouring austenite or within ferrite) in a very short time
(within a few second) after supersaturated ferrite formation by
shear during bainitic transformation and there is no need for
redistribution of mostly substitutional alloying elements.
Therefore bainitic region moves less to higher timing in
comparison to proeutectoid/pearlitic region. Addition of
alloying elements lead to a greater separation of the reactions
and result separate C-curves for pearlitic and bainitic regions
(Fig. 40). Mo encourage bainitic reaction but addition of boron
retard the ferrite reaction. By addition of B in low carbon Mo
steel the bainitic region (almost unaffected by addition of B)
can be separated from the ferritic region.
65
Fig. 40: Effect of boron on TTT diagram of low carbon Mo steel
M
S
Metastable austenite + martensite
T
e
m
p
e
r
a
t
u
r
e
Log time
A
e1
Bainite
Metastable austenite
A
e3
Ferrite C curve in low
carbon Mo steel
Ferrite C curve in low
carbon Mo-B steel
Pearlitic C curve in low
carbon Mo steel
Pearlitic C curve in low
carbon Mo-B steel
Addition of boron
Addition of boron
Bainite start
66
However bainitic reaction is suppressed by the addition of some
alloying elements. B
S
temperature (empirical) has been given by
Steven & Haynes
B
S
( C)=830-270(%C)-90(%Mn)-37(%Ni)-70(%Cr)-83(%Mo)
(elements by wt%)
According to Leslie, B
50
( C)=B
S
-60
B
F
( C)=B
S
-120
Most alloying elements which are soluble in austenite lower M
S
, M
F
temperature except Al, Co.
Andrews gave best fit equation for M
S
:
M
S
(C)=539-423(%C)-30.4Mn-17.7Ni-12.1Cr-7.5Mo+10Co-7.5Si
(concentration of elements are in wt%).
Effect of alloying elements on M
F
is similar to that of M
S
. Therefore,
subzero treatment is must for highly alloyed steels to transform
retained austenite to martensite.
67
Addition of significant amount of Ni and Mn can change the nature of
martensitic transformation from athermal to isothermal (Fig. 41).
T
e
m
p
e
r
a
t
u
r
e
Log time
Fig. 41: kinetics of isothermal martensite in an Fe-Ni-Mn alloy
68
Effect of grain size of austenite: Fine grain size shifts S curve
towards left side because it helps for nucleation of ferrite,
cementite and bainite (Fig. 43). However Yang and Bhadeshia
et al. have shown that martensite start temperature (M
S
) is
lowered by reduction in austenite grain size (Fig. 42).
Fig. 42: Suppression of Martensite
start temperature as a function
austenite grain size L

. M
O
S
is the
highest temperature at which
martensite can form in large
austenite grain. M
S
is the observed
martensite start temperature (at 0.01
detectable fraction of martensite).
Circles represent from low alloy data
and crosses from high alloy data.
69
T= M
S.
a, b are fitting empirial constants,
m =average aspect ratio of martensite=0.05 assumed, V

=average volume of austenite. f=detectable fraction of


martensite=0.01 (taken).
It is expected similar effect of grain size on M
F
as on M
S.
Grain size of austenite affects the maximum plate or lath size.
i.e. larger the austenite size the greater the maximum plate size
or lath size
70
Fig. 43 : Effect of austenite grain size on TTT diagram of plain carbon
hypoeutectoid steel
M
F
M
50
M
S
Metastable + M
M
T
e
m
p
e
r
a
t
u
r
e
,

T
Log(time, t)
H
a
r
d
n
e
s
s
A
e1
+CP
+P
FP
UB
LB
50% FP + 50% UB
=austenite
=ferrite
CP=coarse pearlite
P=pearlite
FP=fine pearlite
UB=upper Bainite
LB=lower Bainite
M=martensite
M
S
=Martensite start
temperature
M
50
=temperature at
which 50% martensite
is obtained
M
F
= martensite finish
temperature
A
e3
Metastable
For finer austenite
71
Heterogeinity of austenite: Heterogenous austenite increases
transformation time range, start to finish of ferritic, pearlitic
and bainitic range as well as increases the transformation
temperature range in case of martensitic transformation and
bainitic transformation. Undissolved cementite, carbides act
as powerful inocculant for pearlite transformation. Therefeore
heterogeneity in austenite increases the transformation time
range in diffussional transformation and temperature range of
shear transformation products in TTT diagram.
72
Applications of TTT diagrams
Martempering
Austempering
Isothermal Annealing
Patenting
Martempering : This heat treatment is given to oil hardenable
and air hardenable steels and thin section of water hardenable
steel sample to produce martensite with minimal differential
thermal and transformation stress to avoid distortion and
cracking. The steel should have reasonable incubation period
at the nose of its TTT diagram and long bainitic bay. The
sample is quenched above M
S
temperature in a salt bath to
reduce thermal stress (instead of cooling below M
F
directly)
(Fig. 44)
73
Surface cooling rate is greater than at the centre. The cooling
schedule is such that the cooling curves pass behind without
touching the nose of the TTT diagram. The sample is
isothermally hold at bainitic bay such that differential cooling
rate at centre and surface become equalise after some time.
The sample is allowed to cool by air through M
S
-M
F
such
that martensite forms both at the surface and centre at the
same time due to not much temperature difference and thereby
avoid transformation stress because of volume expansion.
The sample is given tempering treatment at suitable
temperature.
74
Fig. 44: Martempering heatreatment superimposed on TTT diagram
for plain carbon hypoeutectoid steel
M
F
M
50
M
S
Metastable + martensite
Martensite
T
e
m
p
e
r
a
t
u
r
e
Log time
A
e1
+CP
+P
FP
UB
LB
50% FP + 50% UB
=austenite
=ferrite
CP=coarse pearlite
P=pearlite
FP=fine pearlite
t
0
=minimum incubation
period
UB=upper bainite
LB=lower bainite
M=martensite
M
S
=Martensite start
temperature
M
50
=temperature at which
50% martensite is obtained
M
F
= martensite finish
temperature
A
e3
t
0
Metastable
Tempering
Tempered martensite
75
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.
76
Fig. 45: Austempering heatreatment superimposed on TTT diagram
for plain carbon hypoeutectoid steel
M
F
M
50
M
S
Metastable + martensite
Martensite
T
e
m
p
e
r
a
t
u
r
e
Log time
A
e1
+CP
+P
FP
UB
LB
50% FP + 50% UB
=austenite
=ferrite
CP=coarse pearlite
P=pearlite
FP=fine pearlite
t
0
=minimum incubation
period
UB=upper bainite
LB=lower bainite
M=martensite
M
S
=Martensite start
temperature
M
50
=temperature at which
50% martensite is obtained
M
F
= martensite finish
temperature
A
e3
t
0
Metastable
Tempering
Lower bainite
77
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.
78
Fig. 46: Isothermal annealing heat treatment superimposed on TTT
diagram of plain carbon hypoeutectoid steel
M
F
M
50
M
S
Metastable + martensite
Martensite
T
e
m
p
e
r
a
t
u
r
e
Log time
A
e1
+CP
+P
FP
UB
LB
50% FP + 50% UB
=austenite
=ferrite
CP=coarse pearlite
P=pearlite
FP=fine pearlite
t
0
=minimum incubation
period
UB=upper bainite
LB=lower bainite
M=martensite
M
S
=Martensite start
temperature
M
50
=temperature at which
50% martensite is obtained
M
F
= martensite finish
temperature
A
e3
t
0
Metastable
Ferrite and pearlite
79
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 550C(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.
80
Fig. 47: Patenting heat treatment superimposed on TTT diagram of
plain carbon hypoeutectoid steel
M
F
M
50
M
S
Metastable + martensite
Martensite
T
e
m
p
e
r
a
t
u
r
e
Log time
A
e1
+CP
+P
FP
UB
LB
50% FP + 50% UB
=austenite
=ferrite
CP=coarse pearlite
P=pearlite
FP=fine pearlite
t
0
=minimum incubation
period
UB=upper bainite
LB=lower bainite
M=martensite
M
S
=Martensite start
temperature
M
50
=temperature at which
50% martensite is obtained
M
F
= martensite finish
temperature
A
e3
t
0
Metastable
fine pearlite and upper bainite
81
Prediction methods
TTT diagrams can be predicted based on thermodynamic
calculations.
MAP_STEEL_MUCG83 program [transformation start
curves for reconstructive and displacive transformations for
low alloy steels, Bhadeshia et al.], was used for the following
TTT curve of Fe-0.4 wt%C-2 wt% Mn alloy (Fig. 48)
Fig. 48: Calculated
transformation start curve
under isothermal
transformation condition
82
The basis of calculating TTT diagram for ferrous sytem
1. Calculation of A
e3
Temperature below which ferrite
formation become thermodynamically possible.
2. Bainite start temperature B
S
below which bainite
transformation occurs.
3. Martensite start temperature M
S
below which martensite
transformation occurs
4. A set of C-curves for reconstructive
transformation (allotriomorphic ferrite and pearlite).
A set of C-curves for displacive
transformations (Widmansttten ferrite, bainite)
A set of C-curves for fractional transformation
5. Fraction of martensite as a function of temperature
83
1. Calculation of A
e3
temperature for multicomponent
system. [Method adopted by Bhadeshia et al.]
(This analysis is based on Kirkaldy and Barganis and is applicable for total alloying
elements of less than 6wt% and Si is less than 1 wt%)
Where X
i
=mole fraction of component i,
i
=activity coefficient of component i,
R=universal gas constant, assuming 0 for Fe, 1for C, i=2 to n for Si, Mn, Ni,
Cr, Mo, Cu,V, Nb, Co, W respectively.
for A
e3
temperature, low
temperature phase to be
substituted by and high
temperature phase L to be
substituted by )
Where Xo is the mole fraction of iron then
Assume T is the phase boundary temperature at which high
temperature phase L is in equilibrium with low temperature phase .
In case of pure iron then T is given by
General procedure of determination of phase boundary
84
The Wagner Taylor expansion for the activity coefficients
are substituted in the above equations.
and
0
G
L
= standard Gibbs free energy of pure high temperature
phase and
0
G

= Standard Gibbs free energy of pure low


temperature phase
Similarly for carbon ( n=1) or component i
85
The Wagner-Taylor expansions for activity coefficients are
Where =0 (assumed)
are the Wagner interaction parameters i.e. interaction between
solutes are negligible. The substitution of Wagner-Taylor
expansions for activity coefficients gives temperature deviation
T for the phase boundary temperature (due to the addition of
substitutional alloying elements
k=1 to 11 in this case
86
In multicomponent system, the temperature deviations due to
individual alloying additions are additive as long as solute
solute interactions are negligible. Kirkaldy and co-workers
found that this interaction are negiligible as long as total
alloying additions are less than 6wt% and Si is less than
1wt%].
Eventually T takes the following form
Where To is the phase boundary
temperature for pure Fe-C system and To
is given by .
87
And where
for which
and
where n=1 or i and H
o
and H
1
are standard molar
enthalpy changes corresponding to Go and G
1
.
88
If the relevant free energy changes
o
G and the interaction
parameters are known then T can be calculated for any
alloy.
Since all the thermodynamic functions used are dependent on
temperature, T cannot be obtained from single application
of all values (used from various sources) but must be deduced
iteratively. Initially T can be set as To, T is calculated. Then
T=T+ T is used for T and T is found. Iteration can be
repeated for a few times (typically five times) about till T
changes by less than 0.1K.
This method obtains A
e3
temperature with accuracy of 10K.
89
2. Bainite start temperature B
S
from Steven and Haynes formula
B
S
( C)=830-270(%C)-90(%Mn)-37(%Ni)-70(%Cr)-83(%Mo)
( %element by wt)
Both bainite and Widmansttten ferrite nucleate by same
mechanism. The nucleus develops into Widmansttten ferrite if
at the transformation temperature the driving force available
cannot sustain diffusionless transformation. By contrast bainite
form from the same nucleus if the transformation can occur
without diffusion. Therefore in principle B
S
=W
S
.
Bainite transformation does not reach completion if austenite
enriches with carbon. But in many steels carbide precipitation
from austenite eliminates the enrichment and allow the
austenite to transform completely. In those cases bainite finish
temperature is given (according to Leslie) by
90
3. M
S
Temperature:
At the M
S
temperature
91
In the above equation, T refers to M
S
temperature in absolute
scale, R is universal gas constant, x=mole fraction of carbon,Yi is
the atom fraction of the ith substitutional alloying element, T
magi
and T
NMi
are the displacement in temperature at which the free
energy change accompanying the transformation in pure
iron (i.e. F
Fe

) is evaluated in order to allow for the changes


(per at%) due to alloying effects on the magnetic and non-
magnetic components of F
Fe
,
respectively. These values were
taken fromAaronson, Zenner. F
Fe

value was from Kaufmann.


92
The other parameters are as follows
(i) the partial molar heat of solution of carbon in ferrite,
H=111918 J mol
-1
(from Lobo) and
H=35129+169105x J mol
-1
(from Lobo)
ii) the excess partial molar non-configurational entropy of
solution of carbon in ferrite S=51.44 J mol
-1
K
-1
(from Lobo)
S=7.639+120.4x J mol
-1
K
-1
(from Lobo)

=the C-C interaction energy in ferrite=48570 J mol


-1
(average
value) (from Bhadeshia)

=the corresponding C-C interaction energy in austenite values


were derived , as a function of the concentrations of various
alloying elements, using the procedure of Shiflet and Kingman
and optimised activity data of Uhrenius. These results were
plotted as a function of mole fraction of alloying elements and
average interaction parameter

was calculated following


Kinsman and Aaronson.
93
f*=Zener ordering term was evaluated by Fisher.
The remaining term, F
Fe
=
free energy change from
austenite to martensite as only function of carbon content.
and is identical for Fe-C and Fe-C-Y steels as structure for
both cases are identical (Calculated by Bhadeshia )=-900 to -
1400 J mol
-1
(for C 0.01 to 0.06 mole fraction, changes are not
monotonic). However Lacher-Fowler-Guggenheim
extrapolation gives better result of -1100 to -1400 J mol
-1
(Carbon mole fraction 0.01-0.06).
The equation was solved iteratatively until the both sides of
the equation balanced with a residual error of <0.01%. The
results underestimate the temperature of 10-20K. The error
may be due to critical driving force for transformation
calculation consider only a function of carbon content.
94
4. Transformation start and finish C curves
The incubation period () can be calculated from the following
equation [Bhadeshia et al.]
Where T is the isothermal transformation temperature in absolute
scale, R is universal gas constant, G
max
is the maximum free energy
change available for nucleation, Q is activation enthalpy for
diffusion, C,p, z=20 are empirical constant obtained by fitting
experimental data of T, G
max
, for each type of transformation
(ferrite start, ferrite finish, bainite start and bainite finish) . By
systematically varying p and plotting ln( G
p
max
/ T
z=20
) against 1/RT
for each type of transformation (reconstructive and displacive) till
the linear regression coefficient R
1
attains an optimum value. Once p
has been determined Q and C follow from respectively the slope
and intercept of the of plot. The same equation can be used to
predict transformation time.
95
Table-I: Chemical compositions, in wt% of the steel
chosen to test the model
96
The optimum values of p and corresponding values of C, Q for
different types of steels (Table-I) where concentrations are in wt% are
summarised below [Bhadeshia et.al.] (Table-II).
Table-II: The optimum values of fitting constants
FS=ferrite start, FF=ferrite finish, BS=bainite start and BF=bainite
finish
97
Based on Q, C and Gmax value it can be predicted that Mo
strongly retard the formation of ferrite through its large
influence on Q. however it can promote bainite via the small
negative coefficient that it has for the Q of the bainitic C-
curve. Cr retard both both bainite and ferrite but net effect is
to promote the formation of bainite since the influence on the
bainitic C-curve is relatively small. Ni has a slight retarding
effect on tranformation rate. Mn has also retarding effect on
ferrite as as well as bainitic transformation
The bainite finish C-curve of the experimental TTT diagram
not only shifts to longer time but also but is also shifts to
lower temperature by about 120C. Therefore this is taken
care by plotting against in
order to determine p, Q and C for the bainitic finish curve.
98
Fractional transformation curves
Fractional transformation time can be estimated from the
following Johnson-Mehl-Avrami equation.
X=transformation volume fraction, K
1
is rate constant which is
a function of temperature and austenite grain size d, n and m
are empirical constants. By selecting steels of similar grain
size, the austenite grain size can be neglected then the above
equation simplifies to

99
Assuming x=0.01 for transformation start and x=0.99 for
transformation finish. For a given temperature transformation
start time and finish time can be calculated then K
1
and n can
be solved for each transformation product an a function of
temperature.
Then fractional transformation curves for arbitary values of x
can therefore be determined using
100
Representation of intermediate state of transformation
between 0% and 100% can be derived by fitting to the
experimental TTT diagram as follows:
Where x refers to the fraction of transformation.
In most of TTT diagrams of Russell has a plateau at its
highest temperature. Therefore a horizontal line can be drawn
at B
S
and joining it to a C-curve calculated for temperatures
below B
S
.
101
Relation between observed and predicted values for ferrite start
(FS), ferrite finish (FF), bainite start (BS) and bainite finish
(BF) are shown in Fig. 49. Predicted value closely matches the
observed values for selected low alloy steels. Predicted TTT
diagrams are projected on experimental diagrams (Figs. 50-52).
The model correctly predicts bainite bay region in low alloy as
well as in selected high alloy steels. The model reasonably
predicts the fractional C curves (Fig. 52). Mo strongly retard the
formation of ferrite through its large influence on Q. however it
can promote bainite via the small negative coefficient that it
has for the Q of the bainitic C-curve. Cr retard both both bainite
and ferrite but net effect is to promote the formation of bainite
since the influence on the bainitic C-curve is relatively small. Ni
has a slight retarding effect on transformation rate. Mn has also
retarding effect on ferrite as as well as bainitic transformation
The model is impirical in nature but it can nevertheless be
useful in procedure for the calculation of microstructure in steel.
102
Fig. 49: Relation between observed and predicted Q(Jmol
-1
)
value for: (a) FS-ferrite start, (b) FF-ferrite finish, (c) BS-bainite
start and (d) BF-bainite finish curves.
103
Fig. 50: Comparison of experimental and predicted TTT diagram
for BS steel:(a) En14, (b) En 16, (c) En 18 and (d) En 110.
104
Fig. 51: Comparison of experimental and predicted TTT diagram for
US steel:(a) US 4140, (b) US 4150, (c) US 4340 and (d) US 5150
105
Fig. 52: Comparison of the experimental and predicted TTT
diagrams including fractional transformation curves at 0.1, 0.5
and 0.9 transform fractions: (a)En 19 and (b) En24.
106
Limitations of model
The model tends to overestimate the transformation time at
temperature just below A
e3
. This is because the driving force
term G
max
is calculated on the basis of paraequilibrium and
becomes zero at some temperature less than A
e3
temperature.
The coefficients utilized in the calculations were derived by
fitting to experimental data, so that the model may not be
suitable for extrapolation outside of that data set. Thus the
calculation should be limited to the following concentration
ranges (in wt%):C 0.15-0.6, Si 0.15-0.35, Mn 0.5-2.0, Ni 0-
2.0, Mo 0-0.8 Cr 0-1.7.
107
5. Fraction of martensite as a function of temperature
Volume fraction of martensite formed at temperature T =f and
f=1-exp[BVpdGv)/dT(M
S
-T)]
Where, B=constant, Vp=volume of nucleus, Gv=driving force
for nucleation, M
S
=martensite start temperature. Putting the
measured values
the above equation becomes
f=1-exp[-0.011(M
S
-T)] [Koistinen and Marburger equation].
The above equation can be used to calculate the fraction of
martensite at various temperature.
108
Continuous Cooling Transformation (CCT)
Diagrams
R. Manna
Assistant Professor
Centre of Advanced Study
Department of Metallurgical Engineering
Institute of Technology, Banaras Hindu University
Varanasi-221 005, India
rmanna.met@itbhu.ac.in
Tata Steel-TRAERF Faculty Fellowship Visiting Scholar
Department of Materials Science and Metallurgy
University of Cambridge, Pembroke Street, Cambridge, CB2 3QZ
rm659@cam.ac.uk
Continuous cooling transformation (CCT) diagram
There are two types of CCT diagrams
I) Plot of (for each type of transformation) transformation start,
specific fraction of transformation and transformation finish
temperature against transformation time on each cooling curve
II) Plot of (for each type of transformation) transformation start,
specific fraction of transformation and transformation finish
temperature against cooling rate or bar diameter for each type of
cooling medium 2
Definition: Stability of phases during continuous
cooling of austenite
Determination of CCT diagram type I
CCT diagrams are determined by measuring some physical
properties during continuous cooling. Normally these are
specific volume and magnetic permeability. However, the
majority of the work has been done through specific volume
change by dilatometric method. This method is supplemented
by metallography and hardness measurement.
In dilatometry the test sample (Fig. 1) is austenitised in a
specially designed furnace (Fig. 2) and then controlled cooled.
Sample dilation is measured by dial gauge/sensor. Slowest
cooling is controlled by furnace cooling but higher cooling rate
can be controlled by gas quenching.
3
Fig. 1: Sample and fixtures for
dilatometric measurements
Fig. 2 : Dilatometer equipment
4
Cooling data are plotted as temperature versus time (Fig. 3).
Dilation is recorded against temperature (Fig. 4). Any slope
change indicates phase transformation. Fraction of
transformation roughly can be calculated based on the dilation
data as explained below.
I
II
III
IV
V
T
e
m
p
e
r
a
t
u
r
e
Time
D
i
l
a
t
i
o
n

Temperature
a
c
b
d
For a cooling
schedule
T
S
T
F
Fig. 3: Schematic cooling curves
Fig. 4: Dilation-temperature plot
for a cooling curve
X
Y
Z
T
5
In Fig. 3 curves I to V indicate cooling curves at higher
cooling rate to lower cooling rate respectively. Fig. 4 gives the
dilation at different temperatures for a given cooling
rate/schedule. In general slope of dilation curve remains
unchanged while amount of phase or the relative amount of
phases in a phase mixture does not change during cooling (or
heating) however sample shrink or expand i.e. dilation takes
place purely due to thermal specific volume change because of
change in temperature. Therefore in Fig. 4 dilation from a to b
is due to specific volume change of high temperature phase
austenite. But at T
S
slope of the curve changes. Therefore
transformation starts at T
S
. Again slope of the curve from c to
d is constant but is different from the slope of the curve from a
to b. This indicates there is no phase transformation between
the temperature from c to d but the phase/phase mixture is
different from the phase at a to b.
6
Slope of the dilation curve from b to c is variable with
temperature. This indicates the change in relative amount of phase
due to cooling. The expansion is due to the formation of low
density phase(s). Some part of dilation is compensated by purely
thermal change due to cooling. Therefore dilation curve takes
complex shape. i.e first slope reduces and reaches to a minimum
value and then increases to the characteristic value of the phase
mixture at c.
Therefore phase transformation start at b i.e. at temperature T
S
and transformation ends or finishes at c or temperature T
F
. The
nature of transformation has to be determined by metallography.
When austenite fully transforms to a single product then amount
of transformation is directly proportional to the relative change in
length. For a mixture of products the percentage of austenite
transformed may not be strictly proportional to change in length,
however, it is reasonable and generally is being used.
7
Cumulative percentage of transformation at in between
temperature T is equal to YZ/XZ*100 where X, Y and Z are
intersection point of temperature T line to extended constant
slope curve of austenite (ba), transformation curve (bc) and
extended constant slope curve of low temperature phase (cd)
respectively.
So at each cooling rate transformation start and finish
temperature and transformation temperature for specific
amount (10 %, 20%, 30% etc.) can also be determined. For
every type of transformation, locus of start points,
isopercentage points and finish points give the transformation
start line, isopercentage lines and finish line respectively and
that result CCT diagram. Normally at the end of each cooling
curve hardness value of resultant product at room temperature
and type of phases obtained are shown.
8
Fig. 5 shows the five different cooling curves a to e employed
to a hypoeutectoid steel. Fig. 5(a) to (e) show the type of
corresponding dilatometric plots drawn against dilation versus
temperature. Fig. 6 shows the corresponding transformation
temperature and time in a temperature versus log time plot
against each corresponding cooling rate. At the end of each
cooling rate curve normally hardness value and type of phases
obtained at room temperature are shown. Symbols F, P, B, M
stand for ferrite, pearlite, bainite and martensite respectively.
Subscripts S and F stand for reaction start and reaction
finish respectively. In cooling a schedule martensite starts at
M
S
and finishes at M
F
and therefore 100% martensite results.
While in cooling schedule b bainite starts at B
S
but reaction
does not complete and retained austenite enriched in carbon
transforms at lower M
S
but completes at lower M
F
. Cooling
schedule b results bainite and martensite.
9
a
b c d
e
T
e
m
p
e
r
a
t
u
r
e
D
i
l
a
t
i
o
n
temperature
Time
Temperature
Temperature
Temperature
Temperature
d
i
l
a
t
i
o
n
d
i
l
a
t
i
o
n
d
i
l
a
t
i
o
n
D
i
l
a
t
i
o
n
Ae
3
Ae
1
a b
c
d
e
M
S
M
F
B
S
B
F
F
S
P
S
M
S
M
F
B
S
M
S
M
F
F
S
F
F
B
S
M
S
M
F
F
S
F
F
B
S
B
F
F
S
P
S
P
F
T
e
m
p
e
r
a
t
u
r
e
Log time
HV
HV HV HV
HV
M
M+B
F+B
F+B
F+P
Fig. 5: Schematic dilatometric plots for five different cooling rates where F,
P, B and M stands for ferrite, pearlite, bainite and martensite respectively
and subscript S and F stands for transformation start and transformation
finish for respective products for a hypoeutectoid steel
Fig. 6: Schematic CCT diagram constructed
from data of Fig 3(for the hypoeutectoid
steel). Dotted line is 25% of total
transformation.
a
b
c
d
e
10
In cooling schedule c ferrite starts at F
S
and finishes at F
F
.
Quantity of ferrite is about 15% but rest of austenite enriched
in carbon transforms to bainite at B
S
and just finishes at B
F
.
Therefore cooling c results ferrite and bainite at room
temperature. Similarly cooling schedule d results increased
ferrite and rest bainite. During cooling schedule e ferrite start
at F
S
and pearlite starts at P
S
but pearlite reaction finishes at P
F
.
Therefore cooling schedule e results increased ferrite and rest
pearlite. The locus of all start points and finish points result the
CCT diagram. This diagram is not a unique diagram like TTT
diagram for a material. It depends on type of cooling. This
diagram can predict phase transformation information if
similar cooling curves had been used during its determination
or if equivalent cooling schedule are used during process of
production.
11
The two cooling curves are considered equivalent if
(i) the times to cool from A
e3
to 500C are same.
(ii) the times to cool from A
e3
to a temperature halfway
between Ae
3
and room temperature , are same.
(iii) the cooling rates are same.
(iv) the instant cooling rates at 700C are same.
Therefore to make it useful different types of CCT diagrams
need to be made following any one of the above schedule that
matches with heat treatment cooling schedule.
12
End-quench test method for type I CCT diagram
A number of Jominy end quench samples are first end- quenched
(Fig.7) for a series of different times and then each of them (whole
sample) is quenched by complete immersion in water to freeze the
already transformed structures. Cooling curves are generated putting
thermocouple at different locations and recording temperature
against cooling time during end quenching. Microstructures at the
point where cooling curves are known, are subsequently examined
and measured by quantitative metallography. Hardness
measurement is done at each investigated point. Based on
metallographic information on investigated point the transformation
start and finish temperature and time are determined. The
transformation temperature and time are also determined for specific
amount of transformation. These are located on cooling curves
plotted in a temperature versus time diagram. The locus of
transformation start, finish or specific percentage of transformation
generate CCT diagram (Fig. 8). 13
1(29 mm)
diameter
1
2
(26.2 mm)
1(25.4 mm)
diameter
(3.2 mm)
(12.7 mm)
4(102 mm)
long
2(64 mm)
Free height
of water jet
(12.7 mm)
(12.7 mm) diameter
Fig 7(a): Jominy sample with fixture and water jet
Water
umbrella
Nozzle
14
Fig.7: Figures show (b) experimental set up, (c ) furnace for
austenitisation, (d) end quenching process. Courtesy of
DOITPoMS of Cambridge University.
d
c
b
15
M
F
, Martensite finish temperature
M
50,
50% Martensite
M
S,
Martensite start temperature
Metastable austenite +martensite
Martensite
H
a
r
d
n
e
s
s
,

H
R
C
T
e
m
p
e
r
a
t
u
r
e
Log time
A
e1
t
o
=Minimum
incubation period at
the nose of the TTT
diagram,
t
o
=minimum incubation
period at the nose of the
CCT diagram
t
0
A
F
E
D
C
B
Distance from quench end
A B
C
D
E
F
Jominy
sample
Martensite
Pearlite+Martensite
Fine pearlite
pearlite
Coarse
pearlite
a
b
c
d
Fig. 8: CCT
diagram ( )
projected on
TTT diagram
( ) of eutectoid
steel
t
0
16
Fig. 7. shows the Jominy test set up and Fig. 6 shows a schematic
CCT diagram. CCT diagram is projected on corresponding TTT
diagram.
A, B, C, D, E, F are six different locations on the Jominy sample
shown at Fig.8 that gives six different cooling rates. The cooling
rates A, B, C, D, E, F are in increasing order. The corresponding
cooling curves are shown on the temperature log time plot. At the
end of the cooling curve phases are shown at room temperature.
Variation in hardness with distance from Jominy end is also
shown in the diagram.
For cooling curve B, at T
1
temperature minimum t
1
timing is
required to nucleate pearlite as per TTT diagram in Fig. 8. But
material has spent t
1
timing at higher than T
1
temperature in
case of continuous cooling and incubation period at higher
temperature is much more than t
1
. The nucleation condition
under continuous cooling can be explained by the concept of
progressive nucleation theory of Scheil.
17
Scheils concept of fractional nucleation/progressive
nucleation
Scheil presented a method for calculating the transformation
temperature at which transformation begins during continuous
cooling. The method considers that (1) continuous cooling occurs
through a series of isothermal steps and the time spent at each of
these steps depends on the rate of cooling. The difference between
successive isothermal steps can be considered to approach zero.
(2) The transformation at a temperature is not independent to cooling
above it.
(3) Incubation for the transformation occurs progressively as the
steel cools and at each isothermal step the incubation of
transformation can be expressed as the ratio of cooling time for the
temperature interval to the incubation period given by TTT diagram.
This ratio is called the fractional nucleation time.
18
Scheil and others suggested that the fractional nucleation time are
additive and that transformation begins when the sum of such
fractional nucleation time attains the value of unity.
The criteria for transformation can be expressed
t
1
/Z
1
+t
2
/Z
2
+t
3
/Z
3
+.+t
n
/Z
n
=1
Where t
n
is the time of isothermal hold at Temperature T
n
where
incubation period is Z
n
. This is called additive reaction rule of
Scheil (1935). The reactions for which the additive rule is justifiied
are called isokinetic, implying that the fraction transform at any
temperature depends only on time and a single function of
temperature. This is experimentally verified by Krainer for
pearlitic transformation.
19
Therefore though nucleation has progressed to some fraction of the
event but time is not sufficient for pearlite nucleation at a. If time is
allowed in continuous cooling while summation of fractional
nucleation time becomes unity (at b), pearlite is to nucleate but by
that time temperature drops down as it is continuously cooling.
This concept of progressive nucleation is not strictly valid for
bainite transformation where austenite get enriched with carbon at
higher temperature. As transformation at higher temperature
enriches the austenite by carbon, the transformation characteristic
changes. i.e. transformation slows down at lower temperature.
By continuous cooling transformation temperature moves towards
down and incubation moves toward right. Similar is the case for
pearlite finish temperature and time. Pearlitic region takes the
shape as shown in the diagram. The bainitic region moves so right
that entire region is sheltered by the pearlitic curve.
20
So there is no chance of bainitic tranformation in eutectoid
plain carbon steel under continuous cooling condition. There is
untransformed region where earlier was bainitic region. Under
such circumtances split transformation occurs. However
martensitic region remain unaffected.
Various cooling rates give various combination of phases.
Cooling A indicates very slow cooling rate equivalent to
furnace cooling of full annealing process and that results
coarse pearlite. Cooling B is faster cooling can be obtained
by air cooling. This type of cooling can be obtained by
normalising and that results finer pearlite. Cooling C: just
touches the finishing end of nose that gives fully fine pearlite.
Cooling D is faster cooling that can be obtained by oil
quenching. This is a hardening heat treatment process and that
produces fine pearlite and untransformed austenite transforms
to martensite below M
S
.
21
Cooling curve E just touches the nose of CCT diagram and that
produces almost fully martensite.
Cooling curve F avoid nose of C curve in CCT but touches the
nose of TTT gives entirely martensite. Notice the critical cooling
rate to avoid nose of CCT diagram i.e. diffusional
transformations is lower than that to TTT diagram.
22
General features of CCT diagrams
1. CCT diagram depends on composition of steel, nature of cooling,
austenite grain size, extent of austenite homogenising, as well as
austenitising temperature and time.
2. Similar to TTT diagrams there are different regions for different
transformation (i.e. cementite/ferrite, pearlite, bainite and
martensite). There are transformation start and transformation finish
line and isopercentage lines. However depending on factors
mentioned earlier some of the transformation may be absent or some
transformation may be incomplete.
3. In general for ferrite, pearlite and bainite transformation start and
finish temperature moves towards lower temperature and
transformation time towards higher timing in comparison to
isothermal transformation. Transformation curve moves down and
right.
23
4. The bainite reaction can be sufficiently retarded such that
transformation takes shelter completely under pearlitic transformation
in case of eutectoid plain carbon steel and therefore bainite region
vanishes. However in other steel it may be partially sheltered.
Therefore bainitic region observed in non eutectoid plain carbon steel
or alloy steels.
5. C curves nose move to lower temperature and longer time. So actual
critical cooling rate required to avoid diffusional transformation
during continuous cooling is less than as prescribed by TTT diagram.
Actual hardenability is higher than that predicted by TTT.
6. M
S
temperature is unaffected by the conventional cooling
rate,however, it can be lowered at lower cooling rate if cooling curves
such that austenite enriches with carbon due to bainite or ferrite
formation (in hypoeutectoid steel). On the other hand M
S
can go up
for lower cooling rate such that austenite become lean in carbon due
to carbide separation (in hypereutectiod steel).
24
7. Large variety of microstructure like ferrite/cementite/carbide
+pearlite+bainite+martensite can be obtained in suitable cooling
rate. It is not feasible or limited in case of isothermal
transformation.
25
Determination of type II CCT diagram
This procedure was developed by Atkins. In this process round
samples of different diameters were quenched in three different
media air, oil and water. The cooling curves were recorded at the
centre of each bar. Later these cooling curves were simulated in
dilatometer test in order to identify the transformation
temperature, microstructure and hardness. The transformation
information is plotted against temperature and bar diameter
cooled in specific medium. These are bar diameter cooled in air,
quenched in oil and quenched in water. A scale cooling rate
(usually at 700C) in C/min is added.
At the bottom of the same diagram another plot is added for
hardness (in HRC) and with same cooling rate axis/bardiameter.
These diagrams have to be read along vertical lines (from top to
bottom), denoting different cooling rates. Fig. 9 shows a
schematic CCT diagram for hypoeutectoid plain carbon steel.
26
Bar diameter, in mm
Air cooled
Oil quench
Water quench
T
e
m
p
e
r
a
t
u
r
e
,

C
H
a
r
d
n
e
s
s
,

H
R
C
H
a
r
d
n
e
s
s
,

H
V
Cooling rate at 700C, C per min
M
s
0%
50%
90%
100%
M
50
M
f
M
90
Fig. 9: CCT
diagram for
hypoeutectoid
steel
Hardness after transformation at room temperature
27
Conversion of TTT to CCT diagram, Scheils
method (1935)
Scheils method is based on the assumption that the continuous
cooling curve is a combination of sufficiently large number of
isothermal reaction steps. Incubation for the transformation
occurs progressively as the steel continuously cools.
Transformation begins when the sum of fractional nucleation
time attains the value of unity.
The criteria for transformation can be expressed
t
1
/Z
1
+t
2
/Z
2
+t
3
/Z
3
+.+t
n
/Z
n
=1
Where t
n
is the time of isothermal hold at temperature T
n
where incubation period is Z
n
. The rule can be justified if
reaction rate solely depends on volume fraction and
temperature.
28
Conversion of TTT to CCT, Grange and Kiefer Method
(1941)
During continuous cooling along a given cooling curve which
intercepts the TTT start curve at temperature T
1
, the
transformation will start at temperature T
2
, such that the time of
cooling between T
1
and T
2
is equal to the time for the start of
transformation during isothermal holding at temperature T
3
=
(T
1
+T
2
)/2 (as shown in Fig. 10).
t
3
=t
2
-t
1
Similar rule can be applied for a isopercentage curve and finish
curves.
Assumptions are not strictly valid, however, the method gives
reasonable result. The method is particularly suitable for ferrite-
pearlite region
29
t
3
t
1
t
2
T
1
T
2
T
3
T
e
m
p
e
r
a
t
u
r
e
Log time
T
3
=(T
1
+T
2
)/2
and t
3
=t
2
-t
1
or t
2
=(t
1
+t
3
)/2
Ae
3
Fig. 10: Graphic method of converting TTT diagram to CCT diagram
[Grange and Kiefer method]
30
Conversion of TTT to CCT, Avrami method (1939)
Let
TTT
(T) be time required to obtain a given percentage of
transformation, X at temperature T during isothermal
transformation.
Then time required(
CCT
) to obtain the same percentage of
transformation, X, on continuous cooling at T
CCT
is given by the
condition
X=
Ae
3
T
CCT
dX=
Ae
3
T
CCT
dX/dt.dt=
Ae
3
T
CCT g-
dt-------1
g-=time average transformation rate (at any temperature T)=X/
IT
(T).
Substituting this in equation 1
We get
Ae
3
T
CCT
dt/
TTT
(T) =1--------2,
By rewriting equation 2 we get

Ae
3
T
CCT
dT/(
TTT
(T) dT/dt)=1----------3
Both these integrals are called Avrami integral. Any one of these
integrals has to be evaluated for each cooling curve to get the
CCT
at
T
CCT 31
Conversion of CCT to TTT diagram, Kirkaldy and
Sharma method (1982)
Let
CCT
(T
CCT
) be the time required to obtain a given
percentage of transformation, X at temperature T
CCT
during
continuous cooling. If it is assumed that CCT diagram was
constructed using constant cooling rate(linear cooling),
Then
dT/dt=-(A
e3
-T
CCT
)/(
CCT
(T
CCT
)----4
Substituting equation 4 in equation 3, cross multiplying and
differentiating with respect to T
CCT
We get

TTT
(T
CCT
)=1/(d/dT
CCT
[(A
e3
-T
CCT
)/
CCT
(T
CCT
)])---5
Where
TTT
is the time required for the given percentage
transformation, X, when carried out isothermally at T
CCT
.
32
While rate of cooling is not constant but cooling rate can be
expressed analytically or empirically as
dT/dt=f
1
(x)f
2
(T)=f
1
(T
CCT
)f
2
(T) ---6 (Exp: Jominy cooling
curve can be expressed in this form)
where x is the distance from the surface of a continuouly cooled
sample.
Substituting equation 6 in equation 3, cross multiplying and
differentiating
We get

TTT
(T
CCT
)=1/(f
2
(T
CCT
) df
1
/dT
CCT
)-----7
Equation 5 or 7 can be used for the conversion of CCT diagram to
TTT diagram depending on constant cooling rate or case of cooling
rate that can be expressed in analytical or empirical form.
Jominy cooling curves can be expressed in equation 6 form and the
using equation 7, CCT diagram can be converted to TTT diagram.
33