Nucleation and Growth

Homogeneous and heterogeneous nucleation,

thermodynamic barrier for nucleation, nucleation
rate. Structure and energy of interfaces. Strain
energy and its effect on nucleation. Diffusion
controlled and interface controlled growth
mechanisms

1
• System is said to be in equilibrium, when dG=0
• For transformation to occur, ∆G<0,
• Higher humps or energy barrier lowers kinetics
 Order of transformation
Transformations are classified based on how G and its derivatives
with respect to external variables changes with T, P.
1st order phase transformation, G changes continuously at
equilibrium temperature To and pressure Po. However slope of G,
i.e. (∂G/∂T)P or (∂G/∂P)T or [∂(G/T)/∂(1/T)]P is discontinuous.

G=H-TS=U+PV-TS

(∂G/∂T)P=-S,

(∂G/∂P)T=V

[∂(G/T)/∂(1/T)]P=H
First order transformation are associated with entropy change,
volume change and enthalpy changes which are discontinuous.
exp solidification or melting is a first order transformation.
Second order transformation, G, first derivative of G changes
continuously at equilibrium temperature and pressure but second
derivative of G is discontinuous

(∂2G/∂T2)P=-(∂S/∂T)P=-Cp/T=specific heat

(∂ 2G/∂P2)T=(∂V/∂P)T=isothermal compressibility

(∂2G/∂T∂P)=-(∂V/∂T)P=volume coefficient of thermal expansion

In second order transformation derivatives that abruptly change are

heat capacity, isothermal compressibility and volume coefficient of
thermal expansion.
β-brass undergoes a second order order-disorder transformation
at critical temperature. Magnetic transition of Ni.
 Driving force for phase transformation
Negative chemical free energy change is regarded as driving force for
phase transformation in most of the cases.

∆g=gβ-gα=-Ve.

But even when Gibbs free energy change is negative, there can be other
non-chemical factors like interfacial energy (due to creation of interface
between parent and the product phases) and strain energy accommodation
(elastic or plastic or both) arising from volume change/any shape change.
When such nonchemical factors are present, a net free energy change is ∆G.
The negative derivative of ∆G with respect to some size parameter of the
product phase can be called the transformation force.

A phase transformation that occurs spontaneously is accompanied by

a decrease in total free energy or net free energy of the system.
Driving energy is the net free energy change=ΔG, wrongly stated this
driving energy as driving force.

Normally transformation takes place from initial state through an

activated state to final state.

The total free energy change of activated state from the initial state is
called activation barrier energy or activation energy, ΔGa
6
 Nucleation
• Nucleation-formation of tiny volume of a product phase which is
identical in structure and composition to the product

• There is a necessary driving force requirement, i.e. decrease in

free energy for transformation to happen i.e. G2-G1=-Ve but it is
not sufficient.

• Whether transformation to happen or not, is determined by

kinetic factors.

• The beginning of transformation is called nucleation.

• The continuation of transformation is called growth.

7
• First order phase transformations where a metastable phase
transforms to a more stable phase (or phases) normally by
nucleation and growth.

• At any temperature higher than 0K, transitory fluctuations in

density, composition and or structure continuously occur in an
otherwise homogeneous metastable(or stable) phases due to
thermal activation. Fluctuations that corresponds to distinctly
different possible phases are called hetero-phase fluctuations.

• A large fluctuation in density in a small region of a vapor

phase may corresponds to liquid phase, a structural fluctuation
in a liquid phase may corresponds to a crystalline solid phase
and simultaneous fluctuation in structure and or composition
in a solid phase may corresponds to another solid phase.
8
For a fluctuation to be distinguished as a different phase (hetero-
phase fluctuation), it must contain some minimum number of atoms
(~20-25 or less). A hetero-phase fluctuation in a
thermodynamically stable (or metastable) phase normally
increases Gibbs energy of the system.

If thermodynamic properties of a hetero-phase fluctuation are

assumed to be same as of the corresponding bulk phase, then, Gibbs
energy change ∆G’=V∆Gv+Aσ, where V is the volume of
fluctuation, A=interfacial area between fluctuation and the parent
phase. ∆Gv=Volume or chemical free energy change for the
formation of the second phase from parent phase per unit volume of
second phase, σ is the interfacial energy per unit area of the
interface created between the fluctuation (second phase) and the
parent phase.

When ∆G’ is positive, probability Pr of occurrence of the fluctuation

by thermal activation is given by

9
Pr~exp(-∆G’/kT), k=Boltzmann’s constant, ∆Gv=negative for
second phase to be more stable than parent phase and vice
versa. σ is always positive.

Interface area to volume ratio is large when fluctuation is small

(approaches infinity as its size approaches zero) and
continuously decreases with increasing size.

When ∆Gv is positive ∆G’ is always positive and continuously

increases with size of the fluctuation. However when ∆Gv is
negative ∆G’ is initially positive and increases with the size of
the fluctuation due to dominance of positive interfacial energy
term at small sizes, goes through a maximum at a critical size
r* and then continuously decreases as volume Gibbs energy
term becomes more and more dominant.
10
When interfacial energy is isotropic, shape of most probable
fluctuation (also called embryos)would be spherical. For spherical
embryo of radius r , Gibbs energy change

∆G’=(4/3)πr3∆Gv+4πr2σ

Any fluctuation of size less than r* is unstable but fluctuation of

size greater than r* can spontaneously grow with continuous
decrease in Gibbs energy of the system
11
Number of embryos(Nr) of given size r, per unit volume of
parent phase
Nr=Nvexp(-∆G’/kT), Nv is the number of atoms per unit volume
of parent phase.
An embryo of given size may grow(or shrink) by random
thermally activated movement of atoms across the
embryo/matrix interface. Activation energy ∆aGn# is for
growth of an embryo of n atoms to n+1 atoms and Activation
energy ∆aGn+1# is for dissolution or shrinking an embryo of
n+1 atoms to n atoms.
When ∆Gv is positive, ∆G’ continuously increases and the
concentration of embryos exponentially decreases with
increasing r. Embryos in this case never become stable nuclei
of the second phase.
However when ∆Gv is negative an embryo of critical size r*
becomes a stable nuclei of the second phase with the addition of
12
one more atom to it.
13
Beyond this, when r>r*, it grows irreversibly with continuous
decrease in Gibbs energy of the system.

As some of the critical embryos become stable nuclei of the second

phase and grow, steady state concentration of embryos (Nr) in
remaining volume of the parent phase is maintained due to
continuous thermal fluctuations and growth (or shrinkage) of
individual embryos.

Nucleation takes place by thermal fluctuations

• There are two types of nucleation

– Homogeneous nucleation

– Heterogeneous nucleation 14
 Kinetics of homogeneous nucleation
• Homogeneous nucleation, the probability of nucleation at any
given site is identical to that at any other site within the assembly.
When Gibbs energy of transformation per unit volume of
precipitating phase , ∆Gv, is negative and interfacial energy σ is
isotropic, embryos formed as a result of hetero-phase fluctuation
are spherical. Gibbs energy change

∆G’=(4/3)πr3∆Gv+4πr2σ

A critical embryo of radius r* becomes stable nucleus of the

precipitating phase with the addition of one more atom to it. Rate
of nucleation of the precipitating phase is then the rate at which the
critical embryos of radius r*, formed homogeneously in
untransformed volume of the parent phase, become stable nuclei.15
Radius of critical embryos r* corresponds to the maximum ∆G’, i.e.

(∂∆G’/∂r) r=r* =0

Or, 4/3 π 3r*2∆Gv+4π2r*σ=0

→r*=-2σ/∆Gv,
there will no transformation for positive value of ∆Gv, because r* will be
negative.

∆Gv is negative for a feasible transformation, so that r* has a finite

positive value.
Gibbs energy of formation of critical embryo,
∆G’|r=r*=∆G’*= (4/3)πr*3∆Gv+4πr*2σ,
=(4/3)π(-2σ/∆Gv )3∆Gv+4π(-2σ/∆Gv)2σ
=-(32/3)πσ3/∆Gv2+16 πσ3/ ∆Gv2
=16πσ3/(3(∆Gv)2) =- ∆GvV*/2

Where, V*= (4/3)πr*3=(4/3)π((-2σ/∆Gv )3 =-32/3*πσ3/(∆Gv)3)

V* is the volume of critical embryo. 16
 The driving force for solidification
The free energy decrease (∆G) at a temperature T (∆T) below equilibrium freezing
temperature Tm is called driving force for solidification.
GL=HL-TSL
GS=HS-TSS
Therefore at temperature T, ∆GV=∆H-T∆S, Where ∆H=HS-HL, ∆S=SS-SL.
At equilibrium meting/freezing temperature Tm, ∆GV=0
Therefore at Tm, ∆GV=∆H-Tm∆S=0
Or ∆S=∆H/Tm=L/Tm, ∆S=entropy of fusion≈R for most of metals (Richard’s
Rule)
At small undercoolings (ΔT) the difference in
the specific heats of the liquid and solid
(CPS-CPL) can be ignored. ∆H and ∆S
are therefore approximately independent
of temperature.
Therefore, ∆GV=L-T.L/Tm
Or for small undercooling, ∆GV=L∆T/Tm
Here L is negative.
For positive value of L, ∆Gv=-L∆T/Tm
∆Gv is negative for a feasible transformation and r* has a finite
positive value.
Gibbs energy of formation of critical embryo,
∆G’|r=r*=∆G’*= (4/3)πr*3∆Gv+4πr*2σ,
=(4/3)π(-2σ/∆Gv )3∆Gv+4π(-2σ/∆Gv)2σ
=-(32/3)πσ3/∆Gv2+16 πσ3/ ∆Gv2
=16πσ3/(3(∆Gv)2)
=16πσ3/(3(-L∆T/Tm)2)
=(16πσ3Tm2/3L2).1/∆T2

r*=-2σ/∆Gv
= -2σ/ (-L∆T/Tm)
=(2σTm/L) 1/∆T

V*= (4/3)πr*3
=(4/3)π((-2σ/∆G )3
v

=-32/3*πσ3/(-L∆T/Tm)3)
==(32/3*πσ3 Tm3/L3 )1/∆T3)

V* is the volume of critical embryo. 18

Steady state concentration of critical sized embryos per unit
volume of parent phase
Nr*=Nvexp(-∆G’*/kT)
A critical embryo becomes stable nucleus of second phase when
one more atom is able to be added to it.
Addition of an atom to critical embryo occurs by thermal
activation as shown in fig

19
 Number of attempts per second an atom at the interface in parent phase
makes to cross the interface is equal to vibrational frequency of atoms
normal to interface, kT/h and the probability of an attempt being
successful is exp(-∆GD/KT) where ∆GD is activation energy for atomic
movement across the interface, k=Boltzmann’s constant, h=plank’s
constant
Therefore, rate of homogeneous nucleation (number of nuclei per unit
volume per unit time) Ih may be taken as
Ih=Ns*.(kT/h) (exp(-∆GD/kT)). Nr*
=(kT/h) Ns*Nvexp(- (∆G’*+∆GD)/kT)
where Ns* is number of atoms at the interface of a critical embryo.

Ns*,Nv and kT/h is relatively insensitive to temperature in comparison to

exponential terms and ∆Gv is proportional to undercooling ∆T and
therefore
∆Gv =B∆T, B=constant and ∆G’*= 16πσ3/(3(∆Gv)2= A∆T-2 , where
A=16лб3/(3B2)
Ih=Ih0exp(- (∆G’*+∆GD)/kT) =Ih0exp(- (A/∆T2+∆GD)/kT),
Ih0=constant= =(kT/h) Ns*.Nv 20
Activation energy for movement of atoms across the interface may
be taken as activation energy for interface diffusion.
Taking To=1200K,∆Gv=107∆TJm-3, б=0.45Jm-2, ∆GD=2.49*10-
19J/jump, I 0=1042m-3s-1, [N =1029 m-3, kT/h=1013/s]
h v

at ∆T=0, Ih=0. As ∆T increases, nucleation rate increases sharply,

reaches to a maximum and then decreases. At large ∆T, ∆G’*=
A/∆T2 become negligible in comparison to ∆GD and nucleation
rate is proportional to exp(-∆GD/kT). For transformation to be
observed nucleation rate should have a minimum value ˜ 106m-3s-1.
21
 Time-dependent(transient) nucleation

At temperature To=free energies of both phases(G1, G2) are

equal. ∆G=G2-G1=0.
Let us take T1> To, Transformation temperature T2<To
at Steady state embryo concentration Zn at a given temperature as
a function of their size (n nos of atoms in the embryo) is shown
schematically in Fig.

22
At transformation temperature (T2) initial (at t=0) concentration of second
phase is zero. It take some time to reach steady state embryo concentration.
In this transient period nucleation rate is time dependent.
If Zn* is steady state embryo concentration of size n*
Then Zn=Zn*exp(-τ/t)where τ is the relaxation time at which
Zn = Zn*/e
And It=Ihexp(-τ/t)

23
 Heterogeneous Nucleation
Nucleation that takes place at certain preferred sites is called
heterogeneous nucleation.
During solidification these sites are container/liquid interface or
inclusion/liquid interfaces. In solid state transformation these are
grain boundaries, free surfaces, inclusion/matrix interfaces, and
dislocations/twin boundaries.
An embryo formed at a heterogeneous nucleation site may either
eliminate the lattice imperfection, i.e reduce surface energy or
replace it by embryo/matrix interface, thereby overall reduction of
Gibbs energy of formation of embryos. Probability of nucleation
at these sites is then higher than that homogeneous nucleation.
However number of heterogeneous nucleation sites in the parent
phase are generally several orders of magnitude lower than for
homogeneous nucleation. Whether nucleation occurs
homogeneously or heterogeneously under given conditions
depends upon the relative effects of these two factors. 24
 Nucleation at impurity surfaces
At walls of containers during solidification and inclusion/liquid
interface or inclusion/matrix interface during solid state phase
transformation
Assume a spherical cap formation at the foreign flat surface.
surface, under equilibrium of surface tension/energies
бαS=бβS+бαβcosθ, (0≤θ≤л), while θ is outside the limit
mentioned, no surface tension equilibrium is possible and either α
phase or β phase completely wets surface. The equilibrium shape of
β phase as truncation of spherical shape like a cap. Radius of sphere
is R, radius of cap is r and half height of cap is c such then r=Rsinθ,
c=R(1-cosθ)
Volume of embryo
V=1/3.лR3(2-3cosθ+cos3θ)
and A=2лR2(1-cosθ)

25
∆G’=V∆Gv+Aбαβ+лr2бβS- лr2 бαS, given бαS=бβS+бαβcosθ
= V∆Gv+Aбαβ-лr2бαβcosθ
=1/3.лR3(2-3cosθ+cos3θ) ∆Gv+ 2лR2(1-cosθ) бαβ
-лR2Sin2θбαβcosθ

For critical R, (∂∆G’/∂R) R=R* =0

Or, 3. 1/3.лR*2(2-3cosθ+cos3θ) ∆Gv+ 2.2лR*(1-cosθ) бαβ
-2лR*Sin2θбαβcosθ=0
Or, R* (2-3cosθ+cos3θ) ∆Gv+4(1-cosθ) бαβ -2(1-cos2θ) бαβcosθ
Or, R* (2-3cosθ+cos3θ) ∆Gv+(4-6cosθ+2 cos3θ) бαβ =0
Or, R*=-2 бαβ/∆Gv
Therefore and radius of critical embryo
R*=-2 бαβ/∆Gv
Thickness of critical embryo, C*=R*(1-cosθ)= -2 (1-cosθ) бαβ/∆Gv

Volume of critical embryo, V*=1/3.л(-2 бαβ/∆Gv )3(2-3cosθ+cos3θ)

=-8л бαβ3(2-3cosθ+cos3θ)/ 3∆Gv3 26
∆Gs’*=V∆Gv+Aбαβ-лr2бαβcosθ
=1/3.л(-2 бαβ/∆Gv)3(2-3cosθ+cos3θ) ∆Gv+ 2л(-2 бαβ/∆Gv)2(1-cosθ) бαβ
–л(-2 бαβ/∆Gv)2Sin2θбαβcosθ

=-8лб3αβ (2-3cosθ+cos3θ)/3∆Gv2+ 4лб3αβ/∆Gv2(2-2cosθ) –

4лб3αβ/∆Gv2(1-cos2θ)бαβcosθ

=-8лб3αβ (2-3cosθ+cos3θ)/3∆Gv2+ 4лб3αβ/∆Gv2(2-2cosθ) –

4лб3αβ/∆Gv2(1-cos2θ)бαβcosθ

=-8лб3αβ (2-3cosθ+cos3θ)/3∆Gv2+ 4лб3αβ/∆Gv2((2-3cosθ+cos3θ)

= 4лб3αβ (2-3cosθ+cos3θ)/3∆Gv2

27
Then Gibbs energy of formation of critical embryo formed at a
planer inclusion surface of α,
∆GS’*=4лб3αβ(2-3cosθ+cos3θ)/(3∆Gv2)
=1/4∆G’*h (2-3cosθ+cos3θ)
=-∆GvV*S/2.
Where V* is the volume of the critical embryo.
And rate of heterogeneous nucleation at impurity surfaces
IS= =(kT/h) Ns*NIexp(-(∆G’S*+∆GD)/kT)
Where Ns* is the number of atoms in parent phase at the interface
of critical embryo and NI is the number of atoms at the foreign
surfaces per unit volume of parent phase, i.e. heterogeneous
nucleation site density. NI depends on number and size of inclusion
per unit volume of parent phase.
∆GS’* varies from 0 to ∆G’*h as θ varies from 0 to л
While inclusion surfaces are flat then its radius of curvature far
exceeds the radius of critical nucleus 28
While surface is of small radius of curvature, the above
relationship does not hold good. бαS=бβS+бαβcosθ
While бβЅ<бαЅ, (i.e. θ<л/2), surface energy change due to
replacement of α/S interface by β/S interface is negative.
Net surface energy contribution can become negative and the
embryo would be stable at temperature higher than α to β
equilibrium transition temperature. This is possible when
embryo is formed at cylindrical cavity (or conical)

29
r=radius of cylinder, h =height of β phase in cylinder
Volume of β=лr2h
Area of α/β interface=2лr2(1-sinθ)/cos2θ
Area of α/S interface has been replaced by β/S interface
=2лrh+лr2
Gibbs energy of formation of such a β embryo
∆G’
=лr2h∆Gv+[2лr2(1-sinθ)/cos2θ]бαβ+(2лrh+лr2)(бβЅ-бαЅ)
=лr2h∆Gv+2лrбαβ[r(1-sinθ)/cos2θ-(h+r/2)cosθ]
When θ<л/2, surface energy term becomes negative at large
value of h. The embryo is then stable even when ∆Gv is
positive.

30
The embryo would be stable as long as ∆G’ increases with
decreasing h. i.e. ∂(∆G’)/∂h<0 or
(лr2∆Gv-2лrбαβcosθ) ≤ 0
Or
r≤2бαβcosθ/∆Gv
The above condition is satisfied for positive ∆Gv while cosθ is
positive (θ<л/2).

31
 At grain boundaries

Let us assume nucleation of β at grain boundaries of α, if

energy of α/β interface is isotropic then equilibrium shape
embryo is a double convex lens shape or that is enclosed by
two identical spherical sections (caps) of radius of curvature R.
radius of cap r and half height c such that
r=Rsinθ, c=R(1-cosθ)
V=2/3.лR3(2-3cosθ+cos3θ)
And A=4лR2(1-cosθ)

θ
To know θ, σαα=2σαβcosθ c
r
90- θ R-C
R

32
Gibbs energy of formation of embryo,
∆G’=V∆Gv+Aбαβ-лr2бαα
= (2-3cosθ+cos3θ)2/3.лR3∆Gv+4лR2(1-cosθ) бαβ- лR2sin2θ.2 б αβcosθ
= (2-3cosθ+cos3θ)2/3.лR3∆Gv+4лR2(1-cosθ) бαβ- лR2(1-
cos2θ).2σαβcosθ
=(2-3cosθ+cos3θ)2/3.лR3∆Gv+4лR2бαβ- 6лR2cosθ бαβ+2лR2cos3θ)σαβ
=(2-3cosθ+cos3θ)(2/3.лR3∆Gv+2лR2 бαβ(2-3cosθ +cos3θ)
=(2-3cosθ+cos3θ)(2/3.лR3∆Gv+2лR2 бαβ)

Radius of critical embryos R* corresponds to the maximum ∆G’, i.e.

(∂∆G’/∂R) R=R* =0→
2/3.л.3R2∆Gv+2л.2R бαβ=0
That gives R*= -2 бαβ/∆Gv

33
Thus radius of curvature of spherical section of the critical
embryo in heterogeneous nucleation is same as radius of critical
embryos during homogeneous nucleation
Then Gibbs energy of formation of critical embryo formed at a
planer grain boundary of α,
∆G’*gb= ∆G’=V∆Gv+Aбαβ-лr2бαα
=2/3.лR*3(2-3cosθ+cos3θ) ∆Gv+4лR*2(1-cosθ) бαβ- л R*2sin2θ.
2бαβ cosθ
= 2/3.л (-2 бαβ/∆Gv)3(2-3cosθ+cos3θ) ∆Gv+4л(-2 бαβ/∆Gv)2(1-cosθ)
бαβ- л(-2 бαβ/∆Gv)2sin2θ. 2бαβ cosθ
=8лб3αβ(2-3cosθ+cos3θ)/(3∆Gv2)
=(1/2). 16лб3αβ /(3∆Gv2) (2-3cosθ+cos3θ)
=1/2. ∆G*h. (2-3cosθ+cos3θ)
= -∆GvV*gb/2.
34
When cosθ=0, бαα/бαβ is negligible. Grain boundary does not affect.
∆G’*gb=∆Gh*
As cosθ increases, ∆G’*gb decreases continuously, and
∆G’*gb becomes zero when cosθ approaches one.
Then бαα/бαβ is 2 , While бαα/бαβ is >2, surface tension
equilibrium is not possible but cosθ remains 1, ∆Ggb*=0,

Nucleation rate at grain boundaries, Igb= =(kT/h) Ns*Ngbexp(-

(∆G’*gb+∆GD)/kT)
Where Ns*=number of atoms at the surface of critical embryo in
parent phase α, Ngb =number of atoms per unit volume of α at grain
boundaries of α
Ngb is orders of magnitude lower than Nv therefore lower ∆G’*gb
than ∆G’*h does not necessarily mean a higher rate of
heterogeneous nucleation rate than that of homogeneous nucleation.
35
Equilibrium shape at grain edge (triple junction, three grain
boundaries meet along a line). Assuming surface tension
equilibrium and isotropic grain boundaries three grain
boundaries meet along a line at an angle of 120˚ to each other.
An embryo at a grain edge is bounded by three intersecting
spherical surfaces or caps of equal radius. Radius R* is still
given by R*=-2 бαβ/∆Gv as for homogeneous nucleation and
∆G’*ge can be obtained from volume and area of critical
embryo. This is very complicated calculation.

36
Equilibrium shape at grain corner by four intersecting
spherical surfaces or caps of equal radius (four grains are
meeting at a point with tetrahedral angles.).

37
38
Conditions for maximum contribution to overall nucleation rate are given below. A
parameter is defined RB=kTln(L/δ) where L= average grain size, δ=average grain
boundary thickness. Curve abcde shows just perceptible nucleation rate(106/m3/s
when δ/L=10-6.
Highest Nucleation Rate Conditions
Ih RB>(ΔG*h-ΔG*gb)
Igb (ΔG*h-ΔG*gb)>RB>(ΔG*gb-ΔG*ge)
Ige (ΔG*gb-ΔG*ge)>RB>(ΔG*ge-ΔG*gc)
Igc (ΔG*ge-ΔG*gc)>RB

39
Nucleation in solid state considering strain energy
During solid state phase transformation volume change (if
present) is partly or completely accommodated by strains in the
system without much flow or creep. It is assumed no plastic
deformation. Strain redistribute between α and β till internal
equilibrium is established.

The associated strain energy affects energetics and kinetics of

nucleation in solid state.

Let us first consider formation of a β embryo with incoherent

α/β interface formed homogeneously in a α matrix during α to β
transformation. α/β interface energy is isotropic.

40
 Nabarro treated this problem and assumed following:
(i) All volume changes are accompanied by elastic strain only
in α matrix, ii) no plastic flow occurs, iii) α is elastically
isotropic, iv) embryo is an ellipsoid of radius r and semi-
thickness c
[strain energy is a function of embryo shape]
The strain energy of embryo due to volume change
∆GVS=2/3μα(∆V/V)2ϕ(c/r)
Where (∆V/V) is total volume strain, μα is shear modulus of α
matrix. Φ(c/r) is a factor that depends on shape of embryo

41
Φ(c/r) is a factor that depends on shape of embryo particle
shown in the Fig

or rod

ϕ(c/r) =(3л/4)(c/r) for c/r<<1 for disc

Φ(c/r)=0-1 for 0<c/r<1 and shape is ellipsoid
Φ(c/r)=1 for c/r=1 for sphere,
ϕ(c/r) =0.75 for c/r>1 for needle and c/r>>1(for rod)
42
Gibbs energy of formation of embryo
∆G’=V(∆Gv+∆GVS)+ Aσαβ,
where V is volume of embryo, ∆Gv and ∆GVS are Gibbs energy of
transformation and strain energy respectively, per unit volume of
embryo, A and σαβ are area and interface energy per unit area of α/β
interface.

Strain energy and interfacial energy terms increase Gibbs energy

of formation of embryo.

For ellipsoidal β embryo of given volume, surface area is

minimum when (c/r)=1 (spherical embryo) and strain energy is
maximum but strain energy is lowest when (c/r→0) (disc
shaped embryo)

43
• Equilibrium shape of an embryo would therefore be an ellipsoid
of (c/r) ratio between 0 and 1, depending on the relative
magnitudes of surface and strain energy terms.

• When surface energy is dominant equilibrium shape of embryo is

close to spherical and nucleation is governed by homogeneous
nucleation.

• However when strain energy is dominant embryo will be disc

shaped ellipsoid whose strain energy is proportional to c/r ratio.

44
 Strain energy due to shape change
• Fisher, Hollomon and Turnbull had calculated strain energy
due to shape change.
• Let a disc or plate like particle of a product phase form in the
parent matrix.

• All the strains due to the shape change are assumed to reside in
the matrix within a sphere circumscribed about the disc
shaped particle. It is assumed that the strain is uniformly
distributed within the sphere. 45
If φ is the shear angle, then tan φ=δ/c

The shear strain within the sphere is

Tan ψ~=δ/r,
Therefore tanψ=ctanφ/r= c/r.tanφ
The shear strain energy per particle stored in the spherical
volume

The shear strain(SS) energy per unit volume of the particle

∆GSS= ε =4/3 лr31/2 μm c2/r2 tan2φ/(4/3 лr2c)
=1/2 μmtan2φ.c/r=Ashearc/r

46
Gibbs energy of formation of a disc shaped β embryo or radius
r and semi-thickness c may be written as
∆G’=4/3лr2c{(∆Gv)+AT.(c/r)}+2лr2σαβ
Where 4/3лr2c is volume and 2лr2 is area of embryo
AT.c/r=Total strain energy/unit volume of particle.
AT=Adil+Ashear
Adil.(c/r) is strain energy per unit volume of embyro due to
dilation and ∆GVS =Adil c/r= 2/3μα(∆V/V)2ϕ(c/r)
= 2/3μα(∆V/V)2 3π /4.c/r
= л /2. μα(∆V/V)2 .c/r
Adil =(л/2)μα(∆V/V)2
and ∆GSS =Ashear .c/r=shear strain energy per unit volume of
embryo=1/2 μmtan2φ.c/r
shear= ½.μmtan φ
Or, A 2

47
∆G’=4/3лr2c{(∆Gv)+AT.(c/r)}+2лr2σαβ
= 4/3лr2c∆Gv+ 4/3лrc2 AT.c+2лr2σαβ
For critical embryo, (∂∆G’/∂c)=0 and (∂∆G’/∂r)=0
Or, (∂∆G’/∂c)=0 gives,
4/3лr2∆Gv+ 4/3лr.2c AT=0
Or, r ∆Gv+2cAT=0
Or, r=- 2ATc/∆Gv
Or, (∂∆G’/∂r)=0 gives,
4/3л.2rc∆Gv+ 4/3лc2 AT+2л.2rσαβ=0, Or, 2rc∆Gv+c2AT+3rσαβ=0
Or, 2c(- 2ATc/∆Gv) ∆Gv+ATc2+3 σαβ(- 2ATc/∆Gv)=0
Or, 2c(-2ATc/∆Gv) ∆Gv+ATc2+3 σαβ(- 2ATc/∆Gv)=0
or, -4cAT+Ac2-6σαβ ATc/∆Gv=0
Or, -4c+c- 6σαβ /∆Gv=0
Or, c=-2σαβ /∆Gv
Or, r=- 2AT(-2σαβ /∆Gv)/∆Gv=4ATσαβ/∆Gv2 48
 Therefore, c*= -2 σαβ/∆Gv and r*=4ATσαβ/(∆Gv)2, and
As, ∆G’=4/3лr2c{(∆Gv)+AT.(c/r)}+2лr2σαβ
Or, ∆G’* = 4/3л(4AT σαβ/(∆Gv)2)2(-2 σαβ/∆Gv)∆Gv+ 4/3л(4AT
σαβ/(∆Gv)2)(-2 σαβ/∆Gv)2 AT+2л(4AT σαβ/(∆Gv)2)2σαβ
=(-128/3)лAT2σαβ3/∆Gv)4+(64/3)лAT2σαβ3/∆Gv)4+32 лAT2σαβ3/∆Gv)4
∆G’*=32лAT2σαβ3/(3(∆Gv)4)
Rate of homogeneous nucleation considering strain energy
I=Nr*Ns*(kT/h) exp(-∆GD/kT)
=(kT/h) Ns*Nvexp (- (∆G’*+∆GD)/kT)
where Ns* is number of atoms at the interface of critical embryo,
Nr*=Steady state concentration of critical embryos per unit volume
of parent phase, Nv= number of atoms per unit volume of the parent
phase.
The above treatment is valid for homogeneous nucleation
when c/r<<1 and αβ interface is incoherent.
49
When αβ interface is coherent or semi-coherent, nature
of elastic strain due to volume change is quite different.
A coherent β phase may be considered to form
natural misfit, δ°=(a°m-a°p)/a°m
Actual misfit, δ= (am-ap)/am
Coherency strain in the matrix=em =(am-a°m)/a°m
Coherency strain in the particle=ep=(ap-a°p)/a°p

The resulting strain energy ε per unit volume of particle depends

on relative stiffness of the matrix and the particle.
[Eshelby’s model predicts coherency strain energy/unit vol of
product that is independent of particle shape]

50
For rigid matrix, Ym>Yp, all strains are stored in the particle
ε=3Ypep2/(2(1-νp)
For rigid particle(Ym<Yp), all strains are in matrix
ε=3Ymem2/((1+νm)

51
• Semicoherent interface:
• For sufficiently large atomic misfit, coherent interface is
replaced by semicoherent interface where disregistry is
periodically taken up by misfit dislocations. There are two
types of semicoherent interfaces epitaxial/sessile and
glissile interface. While the Burger vector is parallel to
interface the interface is called epitaxial type.
• Epitaxial type is shown below where glide of dislocation
cannot cause the interface to advance and therefore the
interface is sessile.

52
 If transformation involves pure dilation, then strain energy per
unit volume of embryo is independent of its shape and is in
general given by
ε=ΔGpd=Ece2, Where Ec is a function of elastic constants of α and β
and e is lattice mismatch across the coherent interface.

For equal stiffness, Ym=Yp, Y=Young’s modulus

ε=Ye2/(1-ν), e=lattice mismatch
For rigid matrix, Ym>Yp, all strains are stored in the particle
ε=3Ypep2/(2(1-νp)
For rigid particle (Ym<Yp), all strains are in matrix
ε=3Ymem2/((1+νm)

53
Embryos would be spherical during homogeneous nucleation
if interface energy is isotropic. Strain energy then only reduces
the effective driving force for nucleation from │ΔGv│ to
(│ΔGv│- ΔGpd).

r*=-2σ/(∆Gv+ε)
∆G*=16πσ3/(3(∆Gv+ε)2=- (∆Gv+ε)V*/2

Coherent precipitates during most solid state phase

transformation are generally observed to be plate shaped,
because interface coherency is generally possible only across
specific crystallographic planes of the two phases.
Equilibrium shape of embryo is dictated by anisotropy in
interfacial energy.

54
Spherical coherent precipitates are, however, when coherency is
possible in all directions (example-both phases have same crystal
structure).

At large lattice mismatch e across the interface and or with increasing

embryo size, interface becomes semi-coherent with part, or all, of the
mismatch being taken up by interface dislocations. Volume strain
energy is then reduced, but the interface energy is increased.

As long as interface is coherent or semi-coherent, shape of the

embryo/precipitates is dictated by anisotropy in interfacial
energy.

At still larger embryo/precipitate size, total energy may be lowered if

interface becomes incoherent and embryo/precipitate takes an
ellipsoid/spherical shape. This normally occurs during growth 55
of
precipitates.
56
 Heterogeneous nucleation at dislocations
Nucleation may also occur at dislocations.
An embryo formed at a dislocation eliminates part of elastic
strain energy of dislocation contained within the volume of
embryo. Cahn assumed embryo to lie along the dislocation
with a circular cross section perpendicular to dislocation line.
A small length of embryo is effectively a cylinder of radius r
centered on the dislocation and its Gibbs energy of formation
per unit length.

∆G’=лr2∆Gv.1-Blnr.1+2лr.1.σαβ
where Blnr is elastic strain energy of dislocation per unit
57
length.
 B=constant =μb2/(4л) for screw dislocation,
= μb2/(4л(1-ν)) for edge dislocation
where, μ=shear modulus, b=magnitude of Burger vector,
ν=Poisson’s ratio.
At small values of r dislocation energy term is dominant and at large
value of r volume free energy term is dominant, at intermediate
value of r surface energy term may lead to an activation barrier
energy. However this may not happen necessarily.
For critical embryo
(∂∆G’/∂r)=0 gives, 0=л2r∆Gv-B/r+2лσαβ
Or, ∆Gv r2-B/(2л)+σαβ.r=0
Or, ∆Gv r2+ σαβ.r –B/(2л) =0
r=[- σαβ± √[(σαβ2-4. ∆Gv (-B/(2л))]]/(2∆Gv)
r=-σαβ.[1±√[1+2BΔGv/(лσ2αβ)] /(2ΔGv)
=-σαβ.[1±√[1+αD] /(2ΔGv), Where αD = 2BΔGv/(лσ2αβ) and is
58
always negative
r is real when │αD│<1 and r is imaginary if │αD│>1
At low undercooling when │αD│<1, there are two r’s.
At r=ro, ΔG’ is minimum, a subcritical nucleus is metastable. and
at r=r*, ΔG’ is maximum, critical nucleus r=r* is related to an
activation energy which is the difference in energy of formation at
r=r* and r=ro. ΔG*d= Activation energy for nucleation at
dislocation.
At high undercooling when │αD│>1,
ΔG’ decreases continuously,
therefore nucleation takes place
spontaneously.
Transformation is controlled by
a growth only.
Variation of ∆Gv at low undercooling (A)
when │αD│<1 ,
At high undercooling (B) when │αD│>1
59
At equilibrium temperature, ΔGv=0 and αD =0, ΔGd*=infinite.

As temperature is lowered below equilibrium temperature, ΔGv

becomes increasingly negative, absolute value of αD increases.

An appreciable amount of nucleation occurs when, αD is between

0.4-0.7.
At high undercooling,spontaneous nucleation would occur only
when |αD| >1.

Rate of nucleation I=Id=(kT/h) Ns*Ndexp(- (∆Gd*+∆GD)/kT)

Where Nd =number of atoms at dislocations per unit volume of
parent phase α.
Ns* is number of atoms at the interface of critical embryo,
60
 Quench-in-vacancies

Excess vacancies(Quench-in vacancies) can assist in the nucleation

process if transformation takes place at low temperature by
relieving the strain energy due to volume change when the
interface of β is incoherent.

Excess vacancies also increase diffusivity of solutes in α and the

nucleation would be assisted if composition of β phase is different
than of α

61
 Interfaces and their energies
Creation of interfaces increases Gibbs energy of the system. This
increase in energy leads to an activation barrier for nucleation of new
phase. However heterogeneous nucleation is added by interface.

Free surfaces of crystal (solid/vapor interface) in all solids important

for vaporisation or condensation

Grain boundaries (α/α) interfaces, of two crystals of same composition

and crystal structure) but a different orientation
Important for recrystallisation. Transformation of deformed crystal
into non deformed or strain free grains.

Interphase interfaces (α/β interfaces)

Interphase interface plays important role for growth of stable nuclei,
hetero 62
Growth occurs by movement of product/parent phase interface
and the mobility of the interface depends to a large extent on
its nature of structure. Nucleation of product phase may occur
heterogeneously at internal/external interfaces in parent phase
(grain boundaries, stacking faults, free surfaces etc). But they
may also assist or hinder growth of product phase.

63
 Interfacial energy and surface tension
Surface energy of an interface is the reversible work required to create
unit area of interface at constant temperature, volume and chemical
potentials of components

γ=(∂W/∂A)T,V,µi

Surface tension (σ) is the force acting on surface edge per unit length
to contract the volume. This is equivalent to hydrostatic pressure in
bulk materials.

In general in liquid γ=σ,

but in solid surface area of an interface can be increased by adding
new surface of same atomic configuration or by stretching of inter
atomic bonds at the surface as solid can support stresses and strains.
64
Surface tension in solid is not always equal in magnitude to its
surface energy. Surface tension of interface in solid can be
different in different direction due to anisotropy.

Solid vapor interface:

Energy of a free surface is primarily due to unsatisfied atomic
bonds at the surface, corrected for relaxation of atoms at and
near the surface. Energy of a free surface of a condensed
phase is equal to enthalpy of evaporation or sublimation
multiplied by ratio of average number of missing nearest
neighbour bonds at the surface to number of nearest
neighbour bonds in material.
Energy of free surface in a crystalline solid also depends on its
crystallographic orientations.

65
In the surfaces with relatively low indices, the surface planes
have lower energy than surfaces with irrational high indice
planes, due to lower number of unsatisfied atomic bonds at the
surface in more closely packed low indices surface planes.

A convenient method of plotting the variation of γ with

surface orientation in three dimension is to construct a surface
about an origin such that the free energy of any plane is equal
to the distance between the surface and the origin when
measured along the normal to the plane in question.

For an isolated crystal bounded by several planes A1, A2, etc

with energies γ1, γ2 etc, the equilibrium shape has the
property that ΣAiγi is a minimum.

66
67
Under equilibrium conditions, a solid phase must be bounded
by low energy surfaces to minimise its total surface energy.

However generally it is not possible to attain complete

eqilibrium shapes in solids, due to various constraints.

When crystallographic orientation of a solid surface does not

correspond to a low energy plane, it may consist of a terrace-
ledge structure of low energy surface planes.

68
At high temperature the energy increases due to entropy
cosideration. Crystallographic effect does not exist in liquid
and their surface energies are isotropic. Free surface energies
in metals are normally in the range of 1-2 J/m2.

69
 Grain boundaries
Low angle boundary: Tilt boundary, twist boundary

70
Tilt boundary

71
Twist boundary
• Pure tilt boundary consists of parallel edge dislocations where
as pure twist boundary consists of screw dislocations.
Normally low angle boundaries consist of both types so both
type of dislocations are there.
• The energy of low angle boundary is simply the total energy of
dislocations within the unit area of boundary. This depends on
spacing of dislocations. D=b/sinθ=~b/θ, b=Burger vector, θ is
the angle of misorientation. At small values of θ dislocation
spacings are large. The gb energy is proportional to density of
dislocations in the boundary(1/D). i.e.
• γ α θ, Energy is in the range 0-0.2J/m2.
• However as θ increases the strain field of dislocations
progressively cancel out so the γ increases at a decreasing rate.
When θ exceeds 10-15° the spacing is so small dislocation
core overlap and dislocations are not identifiable physically
and the energy is almost independent of misorientation. 72
When the angle θ>10-15°, the boundary is called high angle
boundary

Random high angle boundaries:

The atoms in the boundary are completely random(non-
crystalline, non-periodic) in one or two atomic thickness and
independent relative orientation of the adjacent grains. Large
angle grain boundaries are essentially isotropic. Structure is
73
close to liquid structure. Grain boundary energy 0.4-1J/m2.
74
 Special high angle grain boundary

Not all high angle boundaries have open random(non periodic)

structure. These occur at some particular misorientations and
boundary planes which allow the two adjoining lattices to fit
together with relatively little distortion of interatomic bonds.

Coherent twin boundary: atoms are in undistorted position

boundary is parallel to twinning plane. Energy of boundary is
extremely low. 20 mJ/m2.

Incoherent twin boundary: boundary is at some angle of

twinning plane atoms are not in perfect fit to adjoining grains.
Boundary energy is higher than coherent twin boundary but
much lesser than random grain boundary energy. 0.2-0.4J/m2.
75
76
Inter-phase interfaces:
Coherent, semicoherent and incoherent interfaces
Coherent interface: at the interface there is usually a change in
composition so that each atom is partly bonded to wrong
neighbours across the interface. This increases the energy of the
interfacial atoms and leads to a chemical contribution to the
interfacial energy and that is the only contribution.
Energy varies 1-200mJ/m2.

However the interface experiences coherency strains. Depending

on Young’s modulus of two phases this energy is stored in both or
either of the phases.

For equal stiffness, Ym=Yp, Y=Young’s modulus

ε=Ye2/(1-ν), e=lattice mismatch, shared in both.
77
For rigid matrix, Ym>Yp, all strains are stored in the particle
ε=3Ypep2/(2(1-νp)
For rigid particle(Ym<Yp), all strains are in matrix
ε=3Ymem2/((1+νm)

78
• Semicoherent interface:
• For sufficiently large atomic misfit, coherent interface is
replaced by semicoherent interface where disregistry is
periodically taken up by misfit dislocations. There are two
types of semicoherent interfaces epitaxial/sessile and
glissile interface. While the Burger vector is parallel to
interface the interface is called epitaxial type.
• Epitaxial type is shown below where glide of dislocation
cannot cause the interface to advance and therefore the
interface is sessile.

79
Lattice misfit can be completely eliminated by without any long range
strain field by a set of edge dislocations with a spacing D
Where D=dβ/δ, where misfit between two lattices= δ=(dβ-dα)/dα,
d=unstressed interplanar spacing

For small δ, D= b/δ, b=burger vector of dislocation= (dβ+dα)/2

Normally misfit exists in two direction and misfit can be eliminated by
two sets non parallel dislocations of spacings
D1= b1/δ1 and D2= b2/δ2. If spacing are greater than D= b/δ the misfit
is partially eliminated and long range strain field exists.

The surface energy has two components –a chemical contribution due

to neighbour of different atoms and structural distortions due to misfit
dislocations.
Surface energy ranges 0.2-0.5J/m2
while δ>0.25, dislocations strainfields overlaps and are not clearly
80
identifiable.
 Glissile Interface
Semicoherent interface between two phases containing matching slip
planes across the interface but continuous between two phases and not
necessarily parallel. Slip planes contain dislocation whose Burger
vector lie on the slip plane but not on interface.

These dislocations are partial dislocation type because Burger vector

does not connect lattice points of parent phase. They are Shockley
partial dislocation.

Glide of dislocation shear one lattice to other by Burger vector and the
macroscopic interface plane moves towards parent phase.

This interfacial plane can be irrational and lies at an angle to close

packed planes of both the lattices.
81
82
Incoherent interface:

When δ>0.25, one dislocation for every four interplanar

spacings, regions of poor fit around dislocation core overlap
and the interface becomes incoherent. Energy ranges 0.5-
1J/m2.

83
Solid/Liquid boundaries
Faceted/smooth/sharp: an atomically flat close packed
interface, one atomic layer thick, forms for those alloys
whether Lf/Tm >>4R/mol, some intermetallics, Si, Ge, Sb,
non-metals.

Non-faceted/diffuse/rough: a few atomic layer thick, Entropy

Lf/Tm <4R/mol. For most of metals Lf/Tm=R

Solid liquid interfacial energies-0.15-0.4J/m2.

84
85
 Structure of interfaces and their energies

Category Type Energy Level

Solid Vapor interface Free surface 1-2 J/m2
Grain boundary Low angle boundary 0-0.2J/m2
Random high angle 0.4-1 J/m2
boundary
Special HAB Coherent twin 20 mJ/m2
Incoherent twin 0.2-0.4 J/m2
Inter-phase Interfaces Coherent 1-200 mJ/m2
Semi-coherent 0.2-0.5 J/m2
incoherent 0.5-1 J/m2
Solid-Liquid 0.15-0.4 J/m2

86
 Growth
Critical nucleus becomes supercritical by addition of one more
atom to it.
Growth is the further addition of atoms to supercritical nucleus.

Interface controlled growth

Transformation involving the rate controlling step of growth by
the transfer of atoms across the interface but no change in
composition though diffusion controlled, are interface controlled
growth processes.

87
 Growth rate at constant T
The net rate of atomic jumping from α to β per unit area of
interface,
=forward rate-reverse rate
(dnα→β/dt)net=s ν exp(-∆GD/kT )-s ν exp[-(∆GD-V∆g)/kT]
= s ν exp(-∆GD/kT )[1- exp(V∆g/kT)]
Where s is the number of interfacial atoms in each
phase per unit area of the interface and ν is the
lattice vibration frequency. V=volume per atom,
V∆g=change in chemical free energy.

88
The growth rate of β phase,
U (m/s)=dr/dt(m/s)=dv/dt(m/s) (per m2 of the interface), specific
volume=v/unit area (m3/m2)
=(dnα→β/dt)net.V, where, dn/dt=nos of atomic movements/unit
area of interface, V=volume of atom
= s ν exp(-∆GD/kT )[1- exp(V∆g/kT)].V
=λj ν exp(-∆GD/kT )[1- exp(V∆g/kT)]
Where λj is the jump distance across the interface., λj=sV
The diffusivity in the boundary between the two phases
Db=λj2ν exp(-∆GD/kT ),
at To, ∆g=0, therefore growth rate U=0
Just below To , ∆g is negative but small and
For small driving force
-V∆g<<kT, exp (V∆g/kT)≈1+ V∆g/kT,
U≈ λjν exp(-∆GD/kT). (1-1-V∆g/kT)=λj2ν exp (-∆GD/kT ) (-V∆g/kT)/λj.
=(Db/ λj )(-V∆g/kT) 89
At temperatures where the driving force is large
-V∆g>>kT or V∆g/kT<<1 or
Or, exp (V∆g/kT)<<1 and, ~0
Therefore, forU=λjν exp(-∆GD/kT )[1- exp(V∆g/kT)]
or, U≈ λjν exp(-∆GD/kT ).(1-0)
=λj2ν exp(-∆GD/kT )/λj
=Db/λj
Thus the growth rate U increases approximately linearly with ∆g
for small degree of suppercooling or small ΔT. However as the
suppercooling increases the growth rate is proportional to Db. But
Db term decreases rapidly as Δg increases or undercooling ΔT.
Therefore, the growth rate after reaching a maximum, decreases
exponentially with temperature.
Polymorphic transformation, massive transformation and
recrystallisation and grain growth follow the interface controlled
growth kinetics. 90
91
 Diffusion controlled growth
• Diffusion controlled growth refers to the growth process, where
there is a change in composition and the rate is controlled by the
long-range diffusion of one of the component atoms through the
matrix phase.
• Exp: Precipitation of theta (θ) from supersaturated α. Al-Cu system

92
93
age hardening
 Diffusion controlled growth
• Diffusion controlled growth refers to the growth process, where
there is a change in composition and the rate is controlled by the
long-range diffusion of one of the component atoms through the
matrix phase.
• Exp: Continuous precipitation of β from supersaturated α. where β
grows continuously is called continuous precipitation.

95
As the composition at the interface remains independent of
time, the number of B atoms that arrive from the matrix at
the interface (flux) must be equal to the number of B atoms
that are added to the growing particle (grown amount per
area per unit time)
So , Dα(∂cα/∂y)y=r, =U(cβα-cαβ)
where U=dr/dt=growth rate
Dα=diffusion coefficient of B in the α matrix
Dα(∂cα/∂y)y=r,=flux of B at interface due to concentration
gradient at the interface
Hence,
U= (Dα(∂cα/∂y)y=r)/(cβα-cαβ)

96
For large spherical particle,
it is assumed solubility of B atoms in α matrix at the interface cαβ is
independent of r, The concentration profile (cα) in the matrix can be
approximated to
(𝐶ҧ -cαβ)r= (𝐶ҧ -cα)y, Or cα= 𝐶ҧ -(r/y)(𝐶ҧ -cαβ)
This yields cα= cαβ, while y=r and
cα= 𝐶ҧ when y=∞,
At ∞>y>r, cαvaries between 𝐶ҧ and cαβ
by differentiating,
(∂c/∂y)y=r=(r/y2)(𝐶ҧ -cαβ)=(r/r2)(𝐶ҧ -cαβ)
(∂c/∂y)y=r= (𝐶ҧ -cαβ)/r
U= (Dα(∂cα/∂y)y=r, )/(cβα-cαβ)=(Dα (𝐶ҧ -cαβ)/((cβα-cαβ)r) =dr/dt
By intergrating above, r2=2 (Dα (𝐶ҧ -cαβ)t/(cβα-cαβ) Or, r α t1/2, Or, U α t-1/2
The radius of particle increases as square root of time, signifying
parabolic growth and growth rate decreases with inverse square root
of time.
97
Growth of spherical particles while particles are small.
cαβ depends on r, The Thomson-Freundlich equation describe this
dependence
cαβr = cαβ ∞ exp(2Vσ/(RTr))
Where cαβr , cαβ ∞ are solute(B) concentration in the α matrix in
equilibrium with a β particle of radius r and ∞ (infinity) respectively.
V=molar volume of the precipitate, σ=specific interface energy
while 2Vσ/RTr <<1
cαβr ≈ cαβ ∞(1+2Vσ/(RTr))
If we take cαβ= 𝐶ҧ at r=r*=critical size of nucleus
Then
(𝐶ҧ - cαβr )/(𝐶ҧ - cαβ ∞)=(cαβ ∞ exp(2Vσ/(RTr*)) - cαβ ∞ exp(2Vσ/(RTr)))/
((cαβ ∞ exp(2Vσ/(RTr*)))- cαβ ∞)
=( cαβ ∞ (1+2Vσ/(RTr*)) - cαβ ∞ (1+2Vσ/(RTr)))/ (cαβ ∞ (1+
2Vσ/(RTr*))-cαβ ∞)
98
(𝐶ҧ - cαβr )/(𝐶ҧ - cαβ ∞)
=( cαβ ∞ 2Vσ/(RTr*)) - cαβ ∞ 2Vσ/(RTr)))/ (cαβ ∞ 2Vσ/(RTr*))
= (1/r*-1/r)/1/r*
=(1-r*/r)
Then U= (Dα(∂cα/∂y)y=r, )/(cβα-cαβ)=(Dα (𝐶ҧ -cαβr)/(r (cβα-cαβ))
=Dα /r ((𝐶ҧ -cαβr) /(𝐶ҧ -cαβ ∞)* (𝐶ҧ -cαβ ∞) /( (cβα-cαβ))
=Dα /r (1-r*/r) (𝐶ҧ -cαβ ∞)/(cβα-cαβ)
Now
1. U=negative when r<r*, subcritical particles tend to dissolve
2.U=0 for r=r*, such particles are in stable equilibrium with 𝐶ҧ
3. U =positive for r>r*, particles are stable and tend to grow.
For Umax, dU/dr=0
0=-1/r2+2r*/r3. Dα(𝐶ҧ -cαβ ∞)/(cβα-cαβ)
that gives rmax=2r*=radius at which growth rate is maximum, i.e
Umax= Dα (𝐶ҧ -cαβ ∞)/(4r*(cβα-cαβ))) 99
100
The temperature dependence of Umax
Assumption: solvus is linear, (𝐶ҧ -cαβ ∞) α (T0-T)
From nucleation equation, r* α 1/(T0-T)
Umax= Dα (𝐶ҧ -cαβ ∞)/(4r*(Cβα-Cαβ)))
Or, Umax α (T0-T)2exp(-Q/RT)
Umax=0 at T=T0 and also very small at low temperature.
Temperature dependence of maximum value of max growth rate can
be obtained by setting dU/dTr=2r*=0 that yields
-2(T0-T)exp(-Q/RT)+(T0-T)2. (Q/RT2). exp(-Q/RT)=0
Or, -2(T0-T)+(T0-T)2. (Q/RT2)=0
Or, -2+(T0-T). (Q/RT2)=0, Or, -2T2+QTo/R-QT/R=0
Or, 2T2+QT/R-QT0/R=0,
Solution of this equation gives the temperature at which max growth
rate is maximum.
Precipitation, dissolution follow diffusion controlled growth process
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For plane front growth
The interface is planar and the radius of curvature is infinite. So
the concentration of B in the matrix in contact with precipitate
is cαβ∞ and is independent of the growth distance r and time t.
It can also be proven that, r α t1/2,
And U=dr/dt α t-1/2
This indicates parabolic growth rate as the case of growth of
spherical particles with r>>r*

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