Isothermal Transformations

Dr A P Singh
UIET, PU Chandigarh
Some of the basic kinetic principles of solid-state
transformations are extended and applied
specifically to iron–carbon alloys in terms of

the relationships among heat treatment,

the development of microstructure,

and mechanical properties.

 In terms of the nucleation rate, the -versus-T curve is
shifted to higher temperatures for heterogeneous.
As shown in figure, much smaller degree of supercooling
(Δ T) is required for heterogeneous nucleation.

Nucleation will continue to occur simultaneously

with growth of the new phase particles

Nucleation cannot occur in regions that have

already transformed to the new phase.
Figure: Nucleation rate versus
temperature for both homogeneous
and heterogeneous nucleation.
Growth process will cease in any region where
Degree of supercooling (Δ T) . particles of the new phase meet, because here
the transformation will have reached completion.

Particle growth occurs by long-range atomic

diffusion—through the parent phase, across a
phase
boundary, and then into the nucleus.
Consequently, the growth rate Ġ is determined

where Q is activation energy) and C is a preexponential are

independent of temperature
The temperature dependence of Ġ is represented by green curves in the
Figure

Red curve is for the nucleation rate, almost the rate for heterogeneous
nucleation).

Now, at a specific temperature, the overall transformation rate is equal to some

product of Growth rate Ġ and Nucleation rate.

The third curve of overall transformation rate, represents this combined effect.

The general shape of this curve is the same as for the nucleation rate, in that it
has a peak
or maximum that has been shifted upward relative to the curve.
Whereas this treatment on transformations has been developed
for solidification,
The same general principles also apply to solid–solid and solid–
gas transformations.
The rate of transformation and the time required for the
transformation to proceed to some degree of completion (e.g.,
time to 50% reaction completion, t0.5) are inversely proportional to
one another (Equation).

Thus, if the logarithm of this transformation time (i.e., log t0.5) is

plotted versus temperature, a curve having the general shape
“C-shaped” curve is a virtual
shown in Figure results mirror image (through a
vertical plane) of the
transformation
rate curve
when a material is cooled very rapidly
through the temperature range
encompassed by the transformation
rate curve to a relatively low
temperature where the rate is extremely
low, it is possible to produce
nonequilibrium phase structures
Consider again the iron–iron carbide eutectoid reaction
(0.76 wt% C) ---cooling/ heating---α(0.022 wt% C) + Fe3C(6.70 wt% C)

which is fundamental to the development of

microstructure in steel alloys.

Upon cooling, austenite, having an intermediate carbon

concentration, transforms to

α ferrite phase, having a much lower carbon content,

and also

cementite, with a much higher carbon concentration.

Phase Transformations in Steels
• Iron has having different crystal structures
at different temperatures.

• It changes from FCC to BCC at 910°C.

• This transformation results in austenite

transforming to pearlite at eutectoid
temperature.

• This transformation of austenite is time

dependant.
Fe-C Equilibrium Diagram:
• Though the Fe-C equilibrium diagram is useful, it does
not provide information about the transformation of
austenite to any structure other than equilibrium
structures, nor does it provide any details about the
influence of cooling rates on the formation of different
structures.

• In other words, Fe-C diagram does not explain the

decomposition of austenite under non-equilibrium
conditions or conditions involving faster rates of cooling
than equilibrium cooling.

• Several structures (e.g. martensite) not appearing on

the equilibrium diagram may be found in the
microstructures in steels.
TTT Diagram
• On the other hand, TTT diagram is a more
practical diagram.

• It shows what structures can be expected after

various rates of cooling.

• It graphically describes the cooling rate required

for the transformation of austenite to pearlite,
bainite or martensite.

• TTT diagram also gives the temperature at

which such transformations take place.
Time-temperature transformation (TTT) diagrams

1. Indicates the amount of transformation at a constant

temperature.

2. Samples are austenitised and then cooled rapidly to

a lower temperature and held at that temperature
whilst the amount of transformation is measured, for
example by dilatometry.

3. Obviously a large number of experiments are

required to build up a complete TTT diagram.
Generate Isothermal transformation diagram: (simple but laborious)
1. Prepare several samples cut from the same bar.

2. Place the samples in a furnace or molten salt bath at the proper

austenizing temperature for long time for the transformation to
complete austenite. For example for 1080 steel it is 780 C.

3. Place the samples in a molten salt bath which is held at

constant subcritical temperature (below A1) say 700 C.

4. After varying time intervals in the salt bath, each sample is

quenched in cold water or iced brine.

5. After cooling, each sample’s hardness and microstructure is

studied.
6. Above steps are repeated at different sub critical temperatures
until sufficient points are determined to plot the curves on the
diagram.
Temperature plays important role in austenite to pearlite transformation
Incubation Time at which Transformation
Temp.( 0C) Starts/Begins Ends
700 S1 E1
650 S2 E2
600 S3 E3
550 S4 E4
500 S5 E5
450 S6 E6
400 S7 E7
350 S8 E8
----- S E
----- Sn En
----- Sr Er
 STABLE AUSTENITE

Near
A1

Sluggish 550
transformation
Austinite to Bianite in

Coarse Pearlite feather 550-220

shaped
Greater time for patches
diffusion Slow rate of
Degree of diffusion of Carbon
under cooling atoms retards
high increased tendency
of Austenite
transformation
Transformation
V/s logarithm
of Time plot

Isothermal
Transformation
diagram plot
4000C -6000C range
Temperature

1 sec

1000 sec
Time (on logarithmic Scale)
 Transformation Transformation
starts/begins ends
Stable Austenite

Coarse Pearlite
Unstable Austenite

Fine Pearlite
4000C -6000C range

Feathery Bainite

Unstable Austenite Acicular Bainite

Ms ≈ 2500C
M 90% at 1100C Austenite + Martensite

Mf ≈-500C
Martensite Time-Temperature Transformation Curves
 Photomicrographs of (a) coarse pearlite and (b) fine pearlite. 3000X. (From K. M. Ralls et al., An
Introduction to Materials Science and Engineering, p. 361. Copyright ©1976 by John Wiley &
Sons, New York. Reprinted by permission of John Wiley & Sons, Inc.)

Thickness of ferrite and cementite layers in pearlite depends on the

transformation temp
A high temp carbon can diffuse long distances and hence form thick layers
leading to coarse pearlite
Ferrite nucleates first, over which layer of Cementite (Iron Carbide)-
Growth is quick.
Spheroidite
If a steel alloy having either pearlitic or bainitic microstructures is heated to, and left at, a
temperature below the eutectoid for a sufficiently long period of time— for example, at
about 700C for between 18 and 24 h—yet another microstructure will form. It is called
spheroidite.

Instead of the alternating ferrite and cementite lamellae (pearlite), or the microstructure
observed for bainite, the Fe3C phase appears as spherelike particles embedded in a
continuous α-phase matrix.

This transformation has occurred by additional carbon diffusion with no change in the
compositions or relative amounts of ferrite and cementite
phases.

Photomicrograph of a steel having a spheroidite microstructure. The

small particles are cementite; the continuous phase is -ferrite. 1000.
(Copyright 1971 by United States Steel Corporation.)
Transmission electron micrograph showing the structure of
bainite. A grain of bainite passes from lower left to upper right
corners; it consists of elongated and needle-shaped particles of
Fe3C within a ferrite matrix. The phase surrounding the bainite is
martensite. (Reproduced with permission from Metals Handbook,
8th edition, Vol. 8, Metallography, Structures and Phase
Diagrams, American Society for Metals, Materials Park, OH,
1973.)
Photomicrograph showing the martensitic microstructure.
The needleshaped grains are the martensite phase, and
the white regions are austenite that failed to transform
during the rapid quench. 1220X (Photomicrograph
courtesy of United States Steel Corporation.)
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.
 Complete Isothermal
Transformation diagram
for
EUTECTOID composition

A- Austenite
B- Bainte
M- Martensite
P- Pearlite
 A- Austenite
B- Bainite
P- Peralite
M- Martensite
F- pro-eutectoid ferrite

Isothermal Transformation Diagram for

alloy steel (with 0.40%C, Ni, Cr & Mo small %)
Isothermal heat treatments are useful but not the most
practical to conduct because an alloy must be rapidly
cooled to and maintained at an elevated temperature
from a higher temperature above the eutectoid.

Most heat treatments for steels involve the continuous

cooling of a specimen to room temperature.

An isothermal transformation diagram is valid only for

conditions of constant temperature

This diagram (IT) must be modified for:

transformations that occur as the temperature is
constantly changing
Most heat treatments for steels involve
continuous cooling of specimen to room
temperature

For continuous cooling, the time required for a

reaction to begin and end is delayed

Thus Isothermal curves are shifted to longer

times and lower temperatures as shown in figure
Continuous cooling transformation (CCT)
diagrams
1. Indicates the extent of transformation as a
function of time for a continuously decreasing
temperature.
2. Samples are austenitised and then cooled at
a predetermined rate and the degree of
transformation is measured, for example by
dilatometry.
3. In this case also a large number of
experiments are required to build up a complete
CCT diagram also
Transformation Diagrams
• CCT diagrams are generally more
appropriate for engineering applications

Components are continuously cooled (air

cooled, furnace cooled, quenched etc.) from
a processing temperature.

This is more economic than transferring to a

separate furnace for an isothermal
treatment.
 Complete Isothermal
Transformation diagram for
EUTECTOID composition
With
Continuous Cooling
Transformation diagram-
CCT
superimposed

Main difference between TTT and CCT

diagrams:
no space for bainite in CCT diagram as
continuous cooling always results in
formation of pearlite
 Transformation Transformation
starts/begins ends

A- fine Pearlite

Continuous cooling Transformation

EFFECT OF
DIFFERENT
COOLING
RATES
A - 50C/sec(normalising)

B- M + little Au B - Rapid 4000C/sec (water quench)

C D
C - 1400C/sec- Martensitic
Continuous Cooling
D - 500C/sec- P + M + Au
Transformation diagram
Normally Bainite will not form when an alloy of Eutectoid composition or, for that
matter, any plain carbon steel is continuously cooled to room temperature.

All the Austenite will have transformed to Pearlite by the time the Bainite
transformation has become possible.

Thus the region representing A-P transformation terminated just below the nose
by curve AB.

Any cooling curve passing through AB, the transformation ceases at the point of
intersection; with continued cooling, the un-reacted Austenite transforms to
Martensite upon crossing Ms(start) line.

For continuous cooling of steel, there is CCR that produces complete

Martensite

CCR is diminished by presence of Carbon.

Fe-C alloy containing less than 0.25% C are not heat treated to form Martensite
because quenching rates required are too rapid to be practical.
Martensite transformation
Is diffusionless transformation on rapid cooling from austenite range

Its non-equilibrium single phase BCT structure, hence not visible of Fc-C diagram

Shape memory alloys involve the martensitic phase transformation- Nitinol alloy
 [2]
Full
Annealing

[1]
Normalising

Moderately
rapid [1] and
slow cooling [2]
curves
superimposed
on continuous
cooling
transformation
diagram for
EUTECTOID
CCT: Dependence
of final
microstructure on
transformations
occurring during
cooling
Martensite:
quenching rates
greater than the
critical cooling rate
 Quenching Medium
Media, arranged In order of quenching speed:

– 5% Caustic Soda - highest

– 5-20% Brine
– Cold Water
– Warm Water
– Mineral Oil
– Animal Oil
– Vegetable Oil - least
 COOLING CURVES
LARGE STEEL
PART WHEN
COOLED

CORE WITH FINE

PEARLITE,
BAINITE SURFACE
MARTENSITIC-
SURFACE CORE
CALLED
MASS EFFECT OF
HEAT TREATMENT

MARTENSITE
QUENCH CRACKS
MAY FORM, EVEN IF
COOLING RATE
INCREASED
 Quenched in bath of
temperature E, kept for
long, removed and cooled
E – martensite forms

Air Cool Also called

MARQUENCHING

Transformation Complete

MARTEMPERING
 Transformation Complete at G
FINE BAINITE FORMS,
G AIR COOLED
STRUCTURE AS OF
TEMPERED MARTENSITE
Air Cool GOOD FOR INTRICATE
SHAPES. BY REPLACING
QUENCHING AND
TEMPERING, CRACKS
AVOIDED
AUSTEMPERING
Possible transformations involving
the decomposition of Austenite.

Solid arrows: Transformation by Diffusion

Dashed arrow: Diffusionless transformation

Classification scheme for various ferrous alloys
Microstructural Determinations for Three
Isothermal Heat Treatments
Using the isothermal transformation diagram for an iron–carbon alloy of eutectoid
composition (Figure 10.22), specify the nature of the final microstructure
(in terms of micro constituents present and approximate percentages) of
a small specimen that has been subjected to the following time–temperature
treatments. In each case assume that the specimen begins at 760C (1400F)
and that it has been held at this temperature long enough to have achieved a
complete and homogeneous austenitic structure.
(a) Rapidly cool to 350C (660F), hold for 104 s, and quench to room temperature.
(b) Rapidly cool to 250C (480F), hold for 100 s, and quench to room temperature.
(c) Rapidly cool to 650C (1200F), hold for 20 s, rapidly cool to 400C (750F),
hold for 10 s, and quench to room temperature.
3
(a) 100% of the specimen is bainite, and
no further transformation is possible,
even though the final quenching line
passes through the martensite region of
the diagram.

(b) In this case it takes about 150 s at

250C for the bainite transformation to
begin, so that at 100 s the specimen is
still 100% austenite. As the specimen is
cooled through the martensite region,
beginning at about 215C, progressively
more of the austenite instantaneously
transforms to martensite. This
transformation is complete by the time
room temperature is reached, such
that the final microstructure is 100%
martensite
(c) Upon quenching to room
temperature, any further transformation
is not possible inasmuch as no austenite
remains; and so the final microstructure
at room temperature consists of 50%
pearlite and 50% bainite