Diffusional Diffusional

Transformations Transformations
SOLID STATE SOLID STATE
Introduction Introduction
Phase transformations in solids Phase transformations in solids by by
thermally activated atomic thermally activated atomic
movements movements
Different types of transformations Different types of transformations
divided into following groups divided into following groups
Precipitation Precipitation
Eutectoid Eutectoid
Ordering Ordering
Massive Massive
polymorphic polymorphic
Chapter 9- 5
Tell us about phases as function of T, C
o
, P.
For this course:
--binary systems: just 2 components.
--independent variables: T and C
o
(P = 1atm is always used).
Phase
Diagram
for Cu-Ni
system
2 phases:
L (liquid)
E (FCC solid solution)
3 phase fields:
L
L + E
E
wt% Ni
20 40 60 80 100 0
1000
1100
1200
1300
1400
1500
1600
T(C)
L (liquid)
E
(FCC solid
solution)
L

+

E
l
i
q
u
i
d
u
s
s
o
l
i
d
u
s
Adapted from Fig. 9.2(a), Callister 6e.
(Fig. 9.2(a) is adapted from Phase
Diagrams of Binary Nickel Alloys, P.
Nash (Ed.), ASM International,
Materials Park, OH (1991).
PHASE DIAGRAMS
Development of Development of
Microstructures Microstructures
at Equilibrium at Equilibrium
conditions conditions
Non Non- -
Equilibrium Equilibrium
Conditions Conditions
Chapter 9- 11
C
E
changes as we solidify.
Cu-Ni case:
Fast rate of cooling:
Cored structure
Slow rate of cooling:
E uilibrium structure
First E to solidify has C
E
= wt Ni.
ast E to solidify has C
E
= 5wt Ni.
First E to solidfy:
wt Ni
Uniform C
E
:
5wt Ni
ast E to solidfy:
< 5wt Ni
CORED VS EQUI IBRIUM PHASES
Phase Diagrams Phase Diagrams - - Eutectic Eutectic
Mg Mg- -Pb Pb Phase Diagram Phase Diagram
Fe Fe- -C Phase Diagram C Phase Diagram
Transformations Transformations
Various microstructures could be Various microstructures could be
formed using thermal treatments formed using thermal treatments
Annealing Processes Annealing Processes
Stored Energy of Cold Work (SECW) Stored Energy of Cold Work (SECW)
Recovery Recovery
Recrystallization Recrystallization
Grain Growth Grain Growth
Introduction Introduction
Precipitation Precipitation
+ +
Eutectoid Eutectoid
+ +
Ordering Ordering
(disordered) (disordered) (ordered) (ordered)
Massive Massive

Polymorphic Polymorphic
Single component system Single component system
Homogeneous Nucleation Homogeneous Nucleation
Composition adjustment to form Composition adjustment to form
phase in parent phase in parent
Atoms may rearrange into Atoms may rearrange into crystal crystal
structure structure
/ / interface is created interface is created leads to an leads to an
activation energy barrier activation energy barrier
Homogeneous Nucleation Homogeneous Nucleation
Free energy change associate with Free energy change associate with
the nucleation process have 3 the nucleation process have 3
contributions contributions
Formation of Formation of phase phase causes a volume free causes a volume free
energy reduction energy reduction
Creation of Creation of / / interfacial area interfacial area will give a free will give a free
energy increase energy increase
Transformed volume usually doesnt fit Transformed volume usually doesnt fit
perfectly into available space perfectly into available space misfit strains misfit strains
S V
G V A G V G A + + A = A
Homogeneous Nucleation Homogeneous Nucleation
Equation similar to that derived for solidification Equation similar to that derived for solidification
For liquid For liquid- -solid interface, solid interface, is roughly the same for all is roughly the same for all
interfaces interfaces
Nucleation in solids Nucleation in solids
varies varies
very low for coherent interfaces very low for coherent interfaces
high for incoherent interfaces high for incoherent interfaces
AA term should be replaced by a summation over all surfaces term should be replaced by a summation over all surfaces
of the nucleus, i.e. of the nucleus, i.e.
S V
G V A G V G A + + A = A
i i
A L
Homogeneous Nucleation Homogeneous Nucleation
Ignoring variation of Ignoring variation of and and
assuming spherical nucleus assuming spherical nucleus
) z z
2 3
4
3
4
r G G r G
S
( ( ! (
Effect of the misfit
strain energy is to
reduce the effective
driving force for
transformation.
S V
G G
r
A A
=
2
*
2
3
*
) ( 3
16
S
G G
G
( (
! (
z
Differentiation yields Differentiation yields
Homogeneous Nucleation Homogeneous Nucleation
Concentration of Concentration of
critical critical- -sized nuclei sized nuclei

A
=
kT
G
C C
*
hom
0
*
exp
*
hom
fC N =

(
=
k
G
k
G
C N
m
*
0 hom
exp exp [
If each nucleus made supercritical If each nucleus made supercritical
at a rate at a rate ff per second, then per second, then
This depends on surface area of the This depends on surface area of the
nucleus & the rate of nucleus & the rate of diffusion diffusion
Nucleation Nucleation
Rate Rate
AAG G
mm
is activation energy for atomic
migration
[ [ is a factor that include
vibrational frequency of atoms
and area of critical nucleus
C C
00
is the number of atoms per unit volume
Driving Force for Precipitation Driving Force for Precipitation
Alloy X Alloy X
00
is solution treated at is solution treated at
T T
11
and cooled rapidly to T and cooled rapidly to T
22
Supersaturated with B Supersaturated with B will try will try
to ppt to ppt
After complete After complete
transformation, the free transformation, the free- -
energy will decrease by energy will decrease by G G
00
G G
00
is the total driving force for is the total driving force for
transformation transformation
But this ( But this (G G
00
) is NOT the driving ) is NOT the driving
force for NUCLEATION force for NUCLEATION
- Because the first nuclei to appear do
not significantly change the
composition from X
0
.
Driving Force for Precipitation Driving Force for Precipitation
If small amount of material with If small amount of material with
nucleus composition (X nucleus composition (X
BB

) is ) is
removed from the removed from the phase phase
Then total free energy of the system Then total free energy of the system
will decrease by will decrease by G G
11
(per mole of (per mole of
removed) removed)
G G
11
is represented by point P is represented by point P
F E F E
Q Q
B B A A
X X G ! (
1
F F F F
Q Q
B B A A
X X G ! (
2
Atoms are then rearranged into Atoms are then rearranged into
crystal structure crystal structure
Per mole of Per mole of formed formed
G G
22
is represented by point Q is represented by point Q
Driving force for Nucleation Driving force for Nucleation
1 2
G G G
n
( ( ! (
Homogeneous Nucleation Homogeneous Nucleation
Volume free energy Volume free energy
decrease associated with decrease associated with
nucleation event is nucleation event is
therefore, therefore,
m
n
V
V
G
G
(
! (
For dilute solutions For dilute solutions
X G
V
A A
e
X X X = A
0
where where
Homogeneous Nucleation Homogeneous Nucleation
Homogeneous Nucleation Homogeneous Nucleation
Assumed Assumed nuclei are spherical with nuclei are spherical with
equilibrium composition & structure equilibrium composition & structure
However, in practice, nucleation will be However, in practice, nucleation will be
dominated by whatever nucleus has minimum dominated by whatever nucleus has minimum
activation energy barrier. activation energy barrier.
Most effective is to form nucleus with smallest Most effective is to form nucleus with smallest
total interfacial energy total interfacial energy
This will mostly dominate nucleation This will mostly dominate nucleation
Incoherent nuclei have very high Incoherent nuclei have very high
energy energy virtually impossible virtually impossible
Homogeneous Nucleation Homogeneous Nucleation
Coherent nuclei with orientation Coherent nuclei with orientation
relationship with matrix relationship with matrix reduced reduced
energy energy
Coherent nuclei Coherent nuclei high strain energy high strain energy
Lowering of interfacial energy compensates for Lowering of interfacial energy compensates for
the increase in the strain energy the increase in the strain energy
Homogeneous Nucleation Homogeneous Nucleation
Homogeneous nucleation can occur Homogeneous nucleation can occur
in very few systems in very few systems
e.g. Cu e.g. Cu- -Co system Co system
Both are FCC with only 2% difference in lattice Both are FCC with only 2% difference in lattice
parameter parameter
Very low coherency strains Very low coherency strains
Ni Ni- -Superalloys Superalloys
Precipitation of Ni Precipitation of Ni
33
Al Al
Most other examples are limited to metastable Most other examples are limited to metastable
phases (usually GP zones) phases (usually GP zones)
Gamma-Prime PPts
Extremely small Extremely small ' precipitates always ' precipitates always
occur as spheres. occur as spheres.
In fact, for a given volume of precipitate, a sphere has In fact, for a given volume of precipitate, a sphere has
less surface area than a cube, and less surface area than a cube, and
thus is the preferred shape to minimize surface energy. thus is the preferred shape to minimize surface energy.
With a coherent particle, however, the With a coherent particle, however, the
interfacial energy can be minimized by interfacial energy can be minimized by
forming cubes and allowing the forming cubes and allowing the
crystallographic planes of the cubic matrix crystallographic planes of the cubic matrix
and precipitate to remain continuous. and precipitate to remain continuous.
Thus as the Thus as the ' grows, the morphology can change from ' grows, the morphology can change from
spheres to cubes (as shown in this figure) or plates spheres to cubes (as shown in this figure) or plates
depending on the value of the matrix/precipitate lattice depending on the value of the matrix/precipitate lattice
mismatch. mismatch.
Heterogeneous Nucleation Heterogeneous Nucleation
Nucleation is mostly heterogeneous Nucleation is mostly heterogeneous
Suitable nucleation sites Suitable nucleation sites
Defects like excess vacancies, dislocations, Defects like excess vacancies, dislocations,
grain boundaries, stacking faults, inclusions grain boundaries, stacking faults, inclusions
and free surfaces and free surfaces
Creation of a nucleus results in the destruction Creation of a nucleus results in the destruction
of a defect of a defect some free energy ( some free energy ( G G
d d
) will be ) will be
released released
This will reduce the activation energy barrier This will reduce the activation energy barrier
)
S V het
G A G G V G ( ( ( ! ( K
Nucleation on GBs Nucleation on GBs
Optimum embryo shape would be one that Optimum embryo shape would be one that
minimize total interfacial free energy minimize total interfacial free energy
EF
EE
K
K
U
2
cos !
EE EE EF EF
K K A A G V G
V
+ + A = A
Nucleation on GBs Nucleation on GBs
Critical radius of the Critical radius of the
spherical caps spherical caps
V
G
r
(
!
EF
K 2
*
Activation energy Activation energy
barrier barrier
) U S
V
V
G
G
het het
! !
(
(
*
hom
*
*
hom
*
where
) ) )
2
cos 1 cos 2
2
1
U U U ! S
Nucleation on GBs Nucleation on GBs
If matrix and precipitate are sufficiently If matrix and precipitate are sufficiently
compatible compatible
Low energy (coherent) facets can be formed Low energy (coherent) facets can be formed
Nucleus may have orientation relationship with one of the Nucleus may have orientation relationship with one of the
grains grains
Nucleation on Dislocations Nucleation on Dislocations
Lattice distortion Lattice distortion
in the vicinity of in the vicinity of
dislocations can dislocations can
assist nucleation assist nucleation
Nucleation on Dislocations / Nucleation on Dislocations /
Stacking Faults Stacking Faults
In FCC crystals, unit dislocations
usually dissociate to produce two
partial-dislocations
Creates a ribbon of stacking fault
Stacking fault is, in fact, 4 close-packed layers
of HCP crsystal (ABAB stacking)
This is a very potent site for nucleation of an HCP
precipitate
Rate of Heterogeneous Nucleation Rate of Heterogeneous Nucleation
In order of decreasing In order of decreasing
AAG G
**
Homogeneous sites Homogeneous sites
Vacancies Vacancies
Dislocations Dislocations
Stacking faults Stacking faults
Grain boundaries / Grain boundaries /
interphase interphase boundaries boundaries
Free surfaces Free surfaces
Overall rate of Overall rate of
transformation also transformation also
depends on the depends on the
relative relative
concentration of concentration of
these sites these sites
Rate of Heterogeneous Nucleation Rate of Heterogeneous Nucleation
If concentration If concentration
of heterogeneous of heterogeneous
sites is C sites is C
11
per unit per unit
volume, then volume, then

(
!
k
G
k
G
C N
m
het
*
1
exp exp [
Nuclei m
-3
s
-1
Rate of Heterogeneous Rate of Heterogeneous
Nucleation Nucleation
Relative magnitudes Relative magnitudes
of heterogeneous of heterogeneous
and homogeneous and homogeneous
volume nucleation volume nucleation
rates rates
(Differences in (Differences in [ [
and and AAG G
mm
are not so are not so
important and so important and so
ignored.) ignored.)

A A
=
kT
G G
C
C
N
N
het het
* *
hom
0
1
hom
exp
Although Although AAG G
**
is always is always
smallest for heterogeneous smallest for heterogeneous
nucleation , the factor nucleation , the factor C C
11
/C /C
00
must also be taken into must also be taken into
account account
i.e. the number of atoms on the i.e. the number of atoms on the
heterogeneous sites relative to heterogeneous sites relative to
the number of atoms within the number of atoms within
the matrix the matrix
At small driving forces, At small driving forces,
heterogeneous nucleation is always heterogeneous nucleation is always
dominate dominate
At large driving forces, homogeneous At large driving forces, homogeneous
nucleation may also occur because of nucleation may also occur because of
the the CC
11
/C /C
00
ratio ratio

( (
!
k
G G
C
C
N
N
het het
* *
hom
0
1
hom
exp
Precipitate Growth Precipitate Growth
Coherent interfaces Coherent interfaces Slow Slow
Incoherent interfaces Incoherent interfaces Fast Fast
Shape is determined by the relative Shape is determined by the relative
migration rates of the interfaces migration rates of the interfaces
Formation of disk or plate shape Formation of disk or plate shape Widmanstatten Widmanstatten
morphology morphology
Slow Slow
VV
**
Fast Fast
Growth Behind Planar Incoherent Growth Behind Planar Incoherent
Interfaces Interfaces
Assume a slab Assume a slab
of of - -phase phase
forms by forms by
combining combining
several nuclei several nuclei
formed on a formed on a
grain boundary grain boundary
Relationships for the interface
migration velocity v and distance
x defining the region where
adjustment of concentration occurs
Note the following:
(i)
(ii)
(iii)
) Dt x
) Dt x
0
X v A
t
D
v
ppt thickening obeys a parabolic growth law
For a given time the growth rate is
proportional to the supersaturation
Concentration Profiles Concentration Profiles
Grain Boundary Diffusion Grain Boundary Diffusion
Usually g.b. ppts do not form as Usually g.b. ppts do not form as
continuous layer continuous layer
Grain boundary diffusion can lead to Grain boundary diffusion can lead to
rapid lengthening and thickening of rapid lengthening and thickening of
ppts. ppts.
Diffusion Diffusion- -Controlled Lengthening of Controlled Lengthening of
Plates or Needles Plates or Needles
Consider the ppt is a plate with Consider the ppt is a plate with
Constant thickness and Constant thickness and
curved incoherent edge with radius curved incoherent edge with radius r r
rr
Due to Gibbs-Thomson effect, the
equilibrium concentration in the
matrix adjacent to the edge will be
increased to CC
r r
.
The concentration The concentration
gradient avialable gradient avialable
to drive the diffusion to drive the diffusion
to the advancing to the advancing
edge is therefore edge is therefore
reduced to reduced to AAC/L C/L
Where, Where,
AAC = C C = C
00
CC
r r
L = Characteristic L = Characteristic
diffusion distance diffusion distance
The lengthening rate is given by:
kr
C
C C
D
v
r
A

=
F
k is numerical constt ~1
Composition difference available to Composition difference available to
drive diffusion will depend on the tip drive diffusion will depend on the tip
radius radius
With certain simplifying assumptions, With certain simplifying assumptions,
it can be shown that it can be shown that

( ! (
r
r
X X
*
0
1
Where,
AX=X
0
X
r
AX
0
= X
0
X
e
r* = critical nucleus
radius
Assuming constant molar volume, we Assuming constant molar volume, we
can write: can write:
)

A
=
r
r
r X X k
X D
v
r
*
0
1
1
F
This equation applies
as long as there is no
decrease in
supersaturation far
from the interface
due to other ppts.
Thickening of Plate-Like PPts
Thickening proceeds by lateral
movement of linear ledges.

B B
u u
v v