Diffusional

Transformations
-2
SOLID STATE

Overall Transformation
Kinetics
Progress
of isothermal
phase transformations can
be represented by plotting
Fraction transformed
(f) as a function of
time (t) and
temperature (T)
TTT Diagrams

(cellular)
+ (cellular)
+
Volume fraction f
varies from 0 to 1

Overall Transformation
Kinetics

f depends on nucleation rate and growth

rate

Factors that
determine f(t, T)

Nucleation rate
Growth rate
Density &
distribution of
nucleation sites
Overlap of diffusion
fields
Impingement of
adjacent
transformed
volumes

f depends on number of nucleation sites and

growth rate

Solid-State Transformation
Kinetics

Many of the reactions of interest to

materials scientists involve
transformations in the solid state.
e.g.
Recrystallization of a cold
worked material
Precipitation of a crystalline
polymer from an amorphous
phase
Growth of an equilibrium
phase from a non-equilibrium
structure

The driving force is usually brought

about by cooling from one temperature
to another.
Lets consider the initial phase
to be and resulting phase to
be .
The total volume of the sample is:
Then the fraction
transformed can be written
as:

V = V + V

V
F
V

Assume that the transformation of to

is controlled by nucleation and growth
i.e. nucleation of phase within and
then growth of .

Let,

N nucleation rate per unit volume

G growth rate in one direction dr
spherical form of )

dt

(assuming

N nucleation rate per unit volume

G growth rate in one direction dr

dt

(assuming

spherical form of )

The equation relating the fraction

transformed to nucleation rate, growth
rate, and time is given by:

3 4
F 1 exp G Nt
3

Johnson-Mehl
equation

similar treatment of the

subject is given by Avrami.
In general, he expresses the fraction transformed as

F 1 exp kt

where n is called the Avrami n

n
n may vary from
1-4

3
k is equivalent to3 G N

Johnson-Mehl
Equation

3 4
F 1 exp G Nt
3

Avrami
Equation

F 1 exp kt n

The variation of n from 4 (as in Johnson-Mehl eqn) can occur

for a number of reasons.
In some solid-state reactions, the nucleation rate is a decaying
function of time. In that case the Avrami n would be 4 early in the
reaction, but decreasing to 3 as the nucleation decreases as a
function of time, and the transformation is governed by the growth rate.

In general, for 3-dimensional solids, the Avrami n is

between 3 and 4.
In case of a growth of a phase in 2-dimensions such
as in a sheet or a film, the Avrami n is between 2 and 3.
In the case of wire, a 1-dimentional solid, the Avrami
n is between 1 and 2.

 Determine

the value of the Avrami n.

F 1 exp kt n

1 F exp kt n

ln 1 F kt

1
ln ln
ln k n ln t
1 F
Thus the Avrami n is the slope of
the plot of the ln ln 1/(1 F) versus
ln t

Overall Transformation
TTT Diagrams
Kinetics

+
Volume fraction f varies
from 0 to 1

4
4
3
V r 3 vt
3
3

f 1 exp Nv 3t 4
3

f 1 exp kt

Value of n is numerical
exponent that varies from ~1

Precipitation in AgeHardening Alloys

Al-4Cu (1.7
at%) alloy

-phase
-phase

Precipitation in AgeHardening Alloys

Transition
Phases
GP zones

Fully coherent
Very low interfacial energy
Two atomic layers thick
10 nm diameter

Precipitation in AgeHardening Alloys

Transition
Phases
GP
zones are
formed as first
ppt during low
temperature
aging of many
technologically
important alloys.

Precipitation in AgeHardening Alloys

Precipitation
GPzones
Transition
Phases
process
o

are fully
coherent platelike ppts
Visible through
coherency-strain
fields
Orientation
relationship with
the matrix

001 " 001

100 " 100

"

3 ' 4

Go G1 G2 G3 G4

Precipitation in
Age-Hardening
Alloys
Activation
energy
barrier

Precipitation in AgeHardening Alloys

Tetragonal

Tetragonal

Composition
approx CuAl2

Bodycentered
tetragonal

Precipitation in
Age-Hardening
Alloys
Nucleation sites

Precipitation in AgeHardening Alloys

Effect of aging temperature on the

sequence of precipitates

Fastest
transformation
rates are
associated with

highest
nucleation rates

and therefore the

finest ppt
distributions

Precipitate Free Zone

(PFZ)

Precipitation Hardening

Under-aged
Peak-aged
Over-aged

Spinodal Decomposition

Transformations having
no barrier to nucleation
Phase diagram with a
miscibility gap
Temperature lowered
from T1 to T2

Alloy will immediately

become unstable
Small fluctuation in
composition can produce Arich and B-rich regions
Up-hill diffusion takes place

Free-energy
d 2G
0
has a negative
2
dX
curvature

Spinodal Decomposition

For spinodal decomposition

the alloy must lie between
the two points of inflection

Locus of the points on the phase

diagram is known as the
chemical spinodal

For alloys outside spinodal

Small variation in composition

will lead to an increase in freeenergy
Thus alloy is metastable
Nucleation & growth process
Down-hill diffusion occurs

Free-energy
has a positive
curvature

d 2G
0
2
dX

Spinodal Decomposition vs
N&G

Particle Coarsening

Microstructure of a 2phase alloy is not

completely stable
unless the total
interfacial free energy
is minimum
High density of fine
ppt will tend to
coarsen into a lower
density of larger ppt

Reduces overall
interfacial area

Gibbs-Thomson effect

Total number of ppts

decreases and the
mean radius r
increases with time

If r0 is the mean radius

at t=0 then

r r kt
3

Where,

3
0

k DX e

Rate of ppt Coarsening