Phase Transformations

Kinetics and Phase Transformations

• Phase diagrams show which phases are in equilibrium

under certain conditions, such as temperature
– A change in the external conditions makes the
phases unstable and drives phase transformation

• A system cannot change instantaneously, i.e. phase

transformations occur over a period of time.
• Kinetics deals with the rates of transformations
– A diffusion controlled process involves the
movement of atoms over “long” distances (more than
a few lattice constant lengths) to form the new more
stable phase(s)
 Phase Transformations

• When the external conditions (e.g. temperature) is

changed, the stable phase(s) may change
• Transformation typically occurs in two steps
– Nucleation : Formation of stable nuclei of the more
stable phase
– Growth of nuclei : Increase in size of the nuclei to
form a grain structure
Solidification = Nucleation + Growth
• Nucleation can occur in one of two ways
– Homogeneous nucleation occurs in the bulk
– Heterogeneous nucleation occurs at grain
boundaries and other defects
 Phase Transformation: Solidification

• Homogenous Nucleation:
– As temperature is reduced below the melting point,
the liquid becomes more and more unstable
– The atoms in the liquid, as they are moving around,
may locally arrange themselves to form clusters of the
solid and establish a solid-liquid interface
• The interface has a higher energy than the bulk
• The additional energy required to form the
interface must be overcome by the energy
released when the liquid changes to solid
– The smallest viable particle of the solid phase is
called a nucleus.
 Nucleation during Solidification

Volume free energy Gv Surface energy Gs

• Released by liquid to solid • Required to form new solid

transformation. surface
• ΔGv is the change in free • ΔGs is energy needed to
energy per unit volume create a surface
between liquid and solid • γ is the surface free energy per
– ΔGv is negative unit area, then
– This is the energy that G s  4r 2
drives the transformation
• The free energy change for a
spherical cluster of radius r is
given by

4 3
r Gv
3
 Homogeneous Nucleation

Total free energy change is given by • As the size of the cluster of atoms
increases, total free energy change
(ΔGT) increases up to a size r* (Blue
4
GT   r 3 Gv  4r 2 curve)
3 • Any further increase in size results in a
decrease in free energy change (ΔGv)
• A cluster of critical size (r*) is called a
ΔGs nucleus
+ – Smaller clusters will redissolve
into the liquid
– Once a cluster reaches critical
ΔGT size it can grow
• At the critical cluster size

ΔGT GT
r 0
r* r
or
2
r* 
GV
and
- ΔGv
16 3
GT * 
3GV 
2
 Homogeneous Nucleation

• The magnitude of GV increases as temperature decreases

below the melting point, while  does not change significantly
• It can be shown that the radius, r*, of the cluster of critical size
at a transformation temperature T decreases as T decreases,
i.e., with increasing undercooling
2  2 T m  1   2 T m  1 
  
r *= =   
GV  L  Tm  T    L  T 
where Tm is the melting temperature in Kelvin, L is the latent
heat of fusion and T is the under-cooling
• As a result, it becomes easier to form nuclei and the number
of nuclei per unit volume increases as the temperature T
drops further and further below the melting point
 Effect of undercooling on nucleation
Tm

Decreasing G*

Decreasing r*
G →

r →
Decrease in critical nucleus size
Decrease in activation energy to form nuclei
Increase in nucleation rate
 Heterogeneous Nucleation

• Occurs at a preexisting imperfection, such as a grain boundary

(during solid state transformation) or the mold wall (during
solidification of an ingot)
• During nucleation, two types of interfaces that require energy are
formed
– Solid-liquid (SL) and Solid-Imperfection (SI)
• One type of interface, the Liquid-Imperfection (IL) interface is
removed. This provides additional energy to drive the transformation
Homo- and Heterogeneous Nucleation Rates
• At low under-cooling, the additional
energy provided by the removal of the
IL interfaces aids heterogeneous
nucleation
• At higher under-cooling, the
homogeneous nucleation rate
becomes higher than heterogeneous
nucleation rate because there are
many more potential sites for
homogeneous nucleation to occur
• At very high under-cooling, the
nucleation rate drops off because
atoms are not able to diffuse fast
enough for nucleation to occur
 Diffusion controlled growth

• Once stable nuclei have formed, they grow by diffusion

of atoms to the interface, and their migration across the
interface from the liquid to the solid phase
• It can be shown that the radius of a spherical particle will
increase according to the equation below, where D is the
diffusion coefficient
r =  Dt
where
  Qd 
D  D0 exp  
 RT 
• As the temperature T decreases, the diffusion coefficient
(D) decreases exponentially. This results in a rapid
decrease in growth rate
Overall Transformation Kinetics
• The overall rate of
transformation
depends on both
nucleation and growth
• At low under-cooling,
nucleation rate is low
resulting in a low
transformation rate
• At high under-cooling,
the growth rate is low,
also resulting in a low
transformation rate
• The fastest
transformation occurs
at an intermediate
temperature
 Transformation rate and time

• The time that a transformation takes is proportional to the inverse of

the transformation rate
• The figure above shows schematically, the rate and time for 50% of
the transformation to complete
– i.e., half of the liquid has solidified
• The time-temperature-transformation curve shows a characteristic
“C” shape
 Isothermal Transformation Diagram OR
TTT(Time-Temp.-Transformation) Diagram
• The isothermal transformation diagram (for eutectoid composition)
has the typical “C” shape because
– At high temperatures, close to the transformation temperature
(melting point, solvus temperature, eutectoid temperature, etc)
the nucleation rate is low because T is small, while growth rate
is high. Transformation is slow because there simply aren’t
enough nuclei to grow.
– At low temperatures well below the transformation temperature,
nucleation rate is very high, and a large number of small nuclei
will form, but growth rate is low. The nuclei are generally too
small to be observed, and the transformation is therefore
sluggish
– At an intermediate temperature, nucleation rate is high, and the
growth rate is also sufficiently high that the overall transformation
occurs rapidly
 Diffusion controlled transformation
• The extent of
transformation varies
with time in a sigmoidal
fashion
• Avrami equation is
often used to describe
such transformations


y  1  exp  kt n 
• where k and n are time
independent constants
that depend on the
temperature and 1
geometry of the rate of transformation  r 
t0.5
transformation process.
 Kinetics of transformation
 Rate of a transformation occurs depends upon temperature
 Q 
r  A exp   Arrhenius Equation
 RT 
 Q = activation energy for transformation
 T = absolute temperature (in Kelvin)
 R = universal gas constant

Recrystallization of rolled copper

t0.5
 Isothermal transformation Diagram

• The Iron-Carbon system is very significant for industrial

applications, and has been widely studied.
• The formation of pearlite from austenite has been
extensively investigated under both isothermal
transformation and continuous cooling conditions
– Isothermal transformation: samples are held at
constant temperature below the eutectoid
temperature and the transformation is observed
– Continuous cooling: samples are allowed to cool
continuously from a temperature above the eutectoid
temperature
Isothermal Transformation Diagram (TTT diagram)
• Several samples are first austenitized above eutectoid temperature,
quickly transferred to a salt bath held at the desired temperature and
then quenched in water after different time intervals.

Repeat
procedure
at
727ºC

727ºC
progressive
lower
0.76%
temperatures
0.76%

Quenching stops any diffusional

transformation that is occurring, and
the extent of transformation can be
observed under a microscope
 Isothermal Transformation Diagram

Also called
Time Temperature Transformation or
T-T-T diagrams

Diffusion Controlled Processes

Nucleation – rate increases as T decreases
Growth – rate decreases as T decreases
Time- Temperature-Transformation (TTT) Curves – Isothermal Transformation
Eutectoid steel (0.8%C)
800
Eutectoid temperature
723
Austenite Coarse
600 Pearlite
Fine

500 Pearlite + Bainite

T →

400 Bainite

Not an isothermal
300

200
 Ms
Austenite

transformation
Mf
100
Martensite
0.1 1 10 102 103 104 105
t (s) →
Pearlite

[1] [1]

 →  + Fe3C

 Nucleation and growth

 Heterogeneous nucleation at grain boundaries
 Interlamellar spacing is a function of the temperature of transformation
 Lower temperature → finer spacing → higher hardness
 Bainite

[1] [1]
Bainite formed at 348oC Bainite formed at 278oC
 →  + Fe3C**
 Nucleation and growth
 Acicular, accompanied by surface distortions
** Lower temperature →
carbide could be ε carbide (hexagonal structure, 8.4% C)
 Bainite plates have irrational habit planes
 Ferrite in Bainite plates possess different orientation relationship
relative to the parent Austenite than does the Ferrite in Pearlite
 Isothermal Transformation Diagram

Diffusion Controlled Processes

Nucleation – rate increases as T decreases
Growth – rate decreases as T decreases
 Martensite

Bainite

Bainite forms below the “nose” or “knee”

Very rapid cooling produces Martensite

Diffusion Controlled Processes

Nucleation – rate increases as
temperature drops below Teutectic
Growth – rate decreases as T decreases

Initially the transformation rate increases

due to increased nucleation rate, but then
slows down due to decreased growth rate
giving the TTT curve a characteristic “C”
shape
 Formation of Martensite

• Very fast cooling results in the formation of a new phase called

Martensite

• For the eutectoid composition, 0.76wt% C is dissolved in the fcc

austenite phase.

• Limit of solid solubility in the bcc ferrite phase is 0.022wt%C

• Upon “slow cooling” below the eutectoid temperature, the excess

carbon forms Fe3C or cementite in a diffusion controlled process

• During quenching, the carbon does not have time to get out of the
fcc matrix, and the alloy transforms to Martensite in a diffusion-less
or athermal transformation.
 Formation of Martensite
• The carbon position remains
unchanged
• Instead of the bcc ferrite phase, a
new phase with a body centered Austenite unit cell
tetragonal (bct) structure is
formed
• This can be thought of as a bcc
structure that has been stretched
in one direction by the trapped
carbon atoms
• During quenching, austenite starts Ferrite unit cell
changing to martensite at the
M(start) temperature and the
extent of transformation depends
on how far below this temperature
the sample is quenched and not
on how long it is held at a Martensite unit cell
particular temperature
• Martensite is a very hard phase
 60
Hardness (Rc) →

Hardness of Martensite as a
function of Carbon content
40

20
% Carbon →
0.2 0.4 0.6

Properties of 0.8% C steel

Constituent Hardness (Rc) Tensile strength (MN / m2)
Coarse pearlite 16 710
Fine pearlite 30 990
Bainite 45 1470
Martensite 65 -
Martensite tempered at 250 oC 55 1990
 TTT curves for different steels

Hypereutectoid steel

Alloy steel type 4340

Microstructure can be controlled
by changing the heat treatment
process

A = Austenite
P = Pearlite
B = Bainite
M = Martensite
F = Ferrite
C = Cementite
 Continuous Cooling Transformation
• The sample is withdrawn from the
furnace and allowed to cool
continuously
• The cooling rate depends upon the
cooling medium
– Furnace cooling
– Air cooling (still air or forced air)
– Oil quenching
– Water quenching
– Iced brine quenching
– …
– The start and finish lines for
pearlite transformation get
shifted to lower temperatures
and longer times
• Bainite transformation is not
observed for eutectoid PC steel
because it occurs below the “nose”
or “knee”
 Continuous Cooling Transformation

•Fast cooling produces martensite

•Slow to moderate cooling produces •Quenching at rates > than critical
coarse or fine pearlite cooling rate of 140ºC/s produces
100% Martensite