Kinetic processes in materials

Chapter 4. phase transformation 1

Nucleation

Prof. Nguyen Hong Hai

Hanoi University of Science and Technology
 Kinetic processes in Materials
4.1. Homo- and hetero-geneous nucleation
4.1.1. Homogeneous Nucleation

 Consider a given volume of liquid at a temperature T below Tm with a

free energy G1
G1 = (VS + VL) GVL
§ If some of the atoms of the liquid
Liquid Liquid
cluster together to form a small sphere
of solid, the free energy of the system
will change to G2: a) b) Solid
G1 G2 = G1 + G
G2 = VSGvS + VLGVL + ASLgSL
G = G2 – G1 = -VS GV + ASLgSL (4.1)
GV = GVL - GVS LV T
GV   S f T 1.12
GV is given by Equation 1.12 as Tm

If the solid particle is sphere of radius r, 4 3

Equation 4.1. becomes:
Gr   r GV  4r 2g SL
3
 Kinetic processes in Materials Interfaces created
4.1.1. Homogeneous Nucleation

 As seen, the creation of small particles of

solid always lead to a free energy increase.

 It is this increase that is able to maintain Nuclei

the liquid phase in a metastable state at
temperature below Tm. Nucleation

 For a given undercooling r* is associated

with a maximum excess free energy.

If r < r* the system can lower its free energy

4
by dissolution of the solid Gr   r 3GV  4r 2g SL
r < r* 3
When r > r* (nuclei) the free energy of the r > r*

system decreases if the solid grows.

When r = r* , dG = 0, the critical nucleus is

in (unstable) equilibrium with the
surrounding liquid
 Kinetic processes in Materials
4.1.1. Homogeneous Nucleation How to find r* and G* ?

4
 By differentiation of Equation Gr   r 3GV  4r 2g SL
3
GV
d G 2g SL GVL
0 r* 
dr GV 4
Gr   r 3 GV  4rr 2=g SLr*
and 3
3 GV
16g SL
G*  2
GVS 2g/r*
3GV 
T
Subtituting r=
LV T
GV  Tm
Tm T

3
 2g SLTm2  1  16g SL Tm2  1
r*    G*   
 3Lv  T 
2 2 2
 3 L v  T 
 Kinetic processes in Materials
4.1.1. Homogeneous Nucleation
The Homogeneous Nucleation Rate

 Because at the melting point the liquid phase has a

volume 2-4% greater than the solid, so there is a great
deal more freedom of movement of atoms in the liquid
resulting on the presence of many small close-packed
clusters (embryos) of atoms which are temporarily in the
same crystalline array as in the solid
The number of spherical clusters of radius r is given by

n0 is the total number of atoms in the system

 Gr  Gr is the excess free energy associated with the
nr  n0 exp   cluster
 kT 
k is Boltzmann’s constant.

nr decreases exponentially with Gr: for example 1 mm3 of copper at its

melting point (~1020 atoms) should on average contain
~ 1014 clusters of 0.3 nm radius (i.e. ~ 10 atoms)
~ 10 clusters with radius of 0.6 nm (~ 60 atoms)
the maximum cluster size is about 100 atoms.
 Kinetic processes in Materials At small undercooling, r* is so large
4.1.1. Homogeneous Nucleation that there will be virtually no chance
The Homogeneous Nucleation Rate of forming a stable nucleus.

 2g SLTm2  1 r
r*    r*
 3Lv  T 
2

3
 16g SL Tm2  1 rmax
G*   2

 2
 3Lv  T 
 As T increases r* and G* decrease

 For supercooling of TN or greater - 0 TN + T

there is a very good chance of some
clusters reaching r* and growing into
stable solid particles. nucleation
barrier
 But before becoming a stable 4
Gr   r 3GV  4r 2g SL
3
nucleus a solid-like cluster must able
to cross the nucleation barrier, which
is proportional to exp (-G*/kT).

 So, the nucleation will only become

possible when G* is reduced below
some critical value (~ 78 kT)
 Kinetic processes in Materials
4.1.1. Homogeneous Nucleation
The Homogeneous Nucleation Rate

The number of clusters

 Gr  that have reached the *
 Ghom  clusters
nr  n0 exp   N *  N 0 exp  
 kT  critical size (N*) can be m-3
 kT 
obtained as
N0 is number of atoms per unit volume in the liquid, ~1029 atoms m-3.

The addition of one more atom to each of

these clusters will convert them into stable
nuclei and, if this happens with a frequency Nhom
f0 (~1011) , the homogeneous nucleation rate
will be given by 0,2 Tm How to reduce
this TN ?
*
 Ghom 
N hom  f 0 N 0 exp  
 kT  0 TN T

A critical undercooling for nucleation

A reasonable nucleation rate (1 cm-3 s-1 ) TN, which is ~0.2 Tm for most metals (i.e.
is obtained when G* ~ 78 kT ~ 200 K).
 Kinetic processes in Materials
4.1. Homo- and hetero-geneous nucleation
4.1.2. Heterogeneous Nucleation
Nucleation will be
made easier at small
Liquid G = G2 – G1 = -VS GV + ASLgSL undercoolings if the
total interfacial
energy term ASLgSL
b) Solid
must be reduced.
A simple way of effectively achieving
this is if the nucleus forms in contact
with the mould wall
For a given volume of solid the total
interfacial energy of the system is
minimized if the embryo has the
shape of a spherical cap with
“wetting” angle q given by the
condition that the interfacial
tensions balance in the plane of the cosq = ( gML - gSM ) / gSL
mould wall: gML = gSM + gSL cosq
 Kinetic processes in Materials
4.1.2. Heterogeneous Nucleation
Liquid Liquid Solid
For homogeneous nucleation
Grain
Ghom = -VS GV + ASLgSL Solid refiner

For heterogeneous nucleation

Ghet = - VS GV + ASL gSL + ASM gSM - ASM gML

VS is the volume of the spherical cap,
(or grain
ASL and ASM are the aeras of the solid/liquid refiner)
and solid/mould interfaces.
Ghom

The above equation can be re-

 4 3 
written in term of the wetting angle Ghet   r GV  4r g SL  S q 
2

q and the cap radius r as  3 

2
S q  
2  cos q 1  cos q  Ghet  Ghom S q 
4
 Kinetic processes in Materials
4.1.2. Heterogeneous Nucleation
 4 3 
 By differentiation of Equation G het   r GV  4r 2 g SL S q 
 3 
3
2g SL The same as for 16g SL
r*  homogeneous G*  2
S q 
GV nucleation 3GV
Note:
1. The activation energy barrier against
heterogeneous nucleation (G*het) is smaller
than G*hom by the shape factor S(q):

G*het = G*hom S(q)

2
2  cosq 1  cosq  q =100, S(q) ~ 10-4
S q   q =300, S(q) = 0.02
4
q =900, S(q) = 0.5
2. The critical nucleus radius remains the same
and depends only on the undercooling.
 Kinetic processes in Materials
4.1.2. Heterogeneous Nucleation

Assuming that critical value of

G* is again 78 kT, it can be
seen that heterogeneous
nucleation will be possible at
much lower undercoolings than
are necessary for
homogeneous nucleation.

The volume rate of

heterogenous nucleation:
*
 Ghet 
N het  f1 N1 exp  
 kT 

N1 is number of atoms in contact *

with heterogeneous sites per  Ghom 
N hom  f 0 N 0 exp  
unit volume of liquid  kT 
 Kinetic processes in Materials

4.1.2. Heterogeneous Nucleation

Mold wall can supply many good heterogenous nucleation sites

 Kinetic processes in Materials
4.1.2. Heterogeneous Nucleation

The heterogeneous nucleation in mould-wall cracks is able to

occur at very small undercoolings, however for the crack or
crevices to be effective the crack opening must be large enough
to allow the solid to grow out with the radius of the solid/liquid
interface equal to or larger than r*.
 Kinetic processes in Materials
4.2. Growth of a pure solid

It was known that there are basically two

different types of solid/liquid interface:
an atomically rouge or diffuse interface
associated with metallic systems,

and an atomically flat or

sharply defined interface often
associates with non-metals.

Because of the differences in atomic

structure these two types of interface
migrate in quite different ways:
rough interfaces migrate by a
continuous growth process
flate interfaces migrate by a lateral
growth process involving ledges.
 Kinetic processes in Materials
4.2. Growth of a pure solid
4.2.1. Continuous Growth
 The migration of a solid/liquid
interface can be treated in a similar
way to the migration of a random Free
high-angle grain boundary. energy
G Ga
§ The free energy of an atom crossing
the S/L interface will vary as shown in
Fig. 4.23, except one grain will be G
replaced by liquid phase 
0
The activation energy barrier G* Distance
Liquid Solid
should be approximately the
same as that for diffusion in the The driving force for solidification
liquid phase G will then be given by
3
16g SL L
G*  2
G  Ti
3GV  Tm
 Kinetic processes in Materials
T
4.2.1. Continuous Growth

 The net rate of solidification should

be given by an equation of the form
v = k1 Ti
k1 is the properties of boundaries
mobility and has such a high value
that normal rates of solidification can
be achieved with interfacial
undercooling Ti of only a fraction of
a degree K.

For most purposes therefore Ti can be ignored and the solid/liquid surface
is assumed to be at the equilibrium melting temperature.
In other words the solidification of metals is usually a diffusion controlled
process (heat diffusion for pure metals and solute diffusion for alloys).
So, it can be assumed that atoms can be received at any site on the solid
surface and for this reason it is known as continuous growth.
 Kinetic processes in Materials
4.2. Growth of a pure solid What happens if the S-L
4.2.2. Lateral growth interface is flat (faceted)?

 Materials with a high entropy of melting prefer to form atomically

smooth, close-packed interfaces

a  0,3 a2 a >> 2

a is dimentionless entropy of fusion and a = Sf / R

 Kinetic processes in Materials
Addition of a single atom onto a flat
4.2.2. Lateral growth interfaces increases the number of
“broken bonds” by four
 The probability of an atom
remaining ledges and jogs is much
greater than for an atom joining
attached to the solid at a facet.

Since the ledges and jogs are a non-

equilibrium feature of the interface,
growth will be very dependent on
how the ledges can be supplied.
It is thought that there are basically
three different ways in which this can
be achiveved:
Addition to a ledge (L) At a jog in a
i) by repeated surface nucleation ledge (J)
only increases the
ii) by spiral growth number of broken there is no
iii) from twin boundaries. bonds by two increase
 Kinetic processes in Materials
4.2.2. Lateral growth
Surface Nucleation

 A single atom solidifying on to a flat

solid surface will be unstable and
tend to rejoin the melt.
v
However, if a sufficently large number
of atoms can come together to form a
disk-shaped layer it is possible for the
arrangement to become self-stabilized
and continue to grow.

Once nucleated the disc will spread rapidly over the surface and the rate of
growth normal to the interface will be governed by the surface nucleation rate v:

v  exp ( - k2 / Ti) k2 roughly constant.

This mechanism is very ineffective at small undercooling where r* is very large.

 Kinetic processes in Materials
4.2.2. Lateral growth
Spiral Growth

 Consider a screw dislocation into a

block of perfect crystal. The effect will
be to create a step or ledge in the
surface of the crystal.

§ The addition of atoms to the ledge will

cause it to rotate about the point
where the dislocation emerges, i.e. the
ledge will never run out of the
interface.
§ Consequently as growth proceeds the
ledge will develop into a growth spiral.

• A steady state is reached when the spiral appears to be rotating with a

constant angular velocity.
• For spiral growth the normal growth rate v and the undercooling of the
interface Ti are related by an expression:
v = k3 ( Ti )2 k3 is a materials constant.
 Kinetic processes in Materials
4.2.2. Lateral growth

 Growth from Twin Intersections Another permanent source of steps

can arise where two crystals in defferent orientations are in contact.

Si-
twin
re-entrant edges
 Kinetic processes in Materials
4.2.2. Lateral growth

§ Growth rates for continuous and lateral growths

For a given solid growth rate the necessary undercooling at the interface is
least for the continuous growth of rough interface.

v = k1 Ti

v = k3 ( Ti )2

v  exp ( - k2 / Ti)
 Kinetic processes in Materials

4.2.3. Heat flow and Interface stability

 In pure metals solidification is controlled by the rate at which the latent heat
of solidification can be conducted away from the solid/liquid interface.

 Conduction can take place either through the solid or the liquid depending
on the temperature gradients at the interface;

 The heat balance is as follow: KST’S = KLT’L + vLV (Fourier law: q = - KT’)

K is the thermal conductivity,

T’ is the temperature gradient (dT/dx),
v is the growth velocity of a planar interface into a superheated liquid,
LV is the latent heat of fusion per unit volume.
 Kinetic processes in Materials
4.2.3. Heat flow and Interface stability
 Case 1: a solid grows into a superheated liquid
(positive temperature gradient in liquid) – a)

A planar solid/liquid interface can be

formed and stable – b)

Suppose that as a result of a local

increase in v a small prostrusion forms
at the interface – c)

more heat is conducted into the protruding

Heat flow is
solid and less away so that the growth rate converging
will decrease below that of the planar regions
and the protrusion will disapear,

 The solid/liquid interface remains planar

and stable.
(d)
 Kinetic processes in Materials
4.2.3. Heat flow and Interface stability

Planar solid/liquid interface.

The recesses are the grain
boundary
 Kinetic processes in Materials
4.2.3. Heat flow and Interface stability

 Case 2: a solid grows into a supercooled liquid

(negative temperature gradient in liquid)

 Heat is remove more effectively from the tip

of protrusion than from surrounding regions

 This allow the protrusion to grow

preferentially

 The solid/liquid interface advancing into

Heat flow is
supercooled liquid is inherently unstable diverging
 Kinetic processes in Materials
4.2.3. Heat flow and Interface stability

 An originally spherical solid

particle will therefore develop arm
in many directions. This shape of
solid is known as a dendrite (from
the Greek for tree).

 Dendrites in pure metals are

usually called thermal dendrites
to distinguish them from
dendrites in alloys.
 Kinetic processes in Materials
4.2.3. Heat flow and Interface stability

 A closer look at the tip of the growing dendrite in the case a solid growing
into supercooled liquid
Temperature profile

Assume that the solid is isothermal

(T’S = 0) and T’L is approximately
given by TC / r

TC is constitutional undercooling, i.e. the

difference between the interface
temperature (Ti) and the temperature of the
supercooled liquid far from dendrite (T)

KST’S = KLT’L + vLV

TC is
with T’S = 0 and
 K LTL' K L TC driving
v  . force for
T’L  TC / r LV LV r
growth
 Kinetic processes in Materials
4.2.3. Heat flow and Interface stability

 K LTL' K L TC T: total undercooling

v  . TC for growth
LV LV r Tr for curvrture
Tr = K G
Tc is not independent of r and is Tr is known as Gibbs-
Thomson undercooling
related with an undercooling Tr below
Tm due to Gibbs-Thomson effect. K - curvature of solid-liquid
interface K= dA/dV = 1/r1 + 1/ r2
If r1 = r2, K = 2 / r

G - Gibbs-Thomson coefficient
G = g / sf
 sf – volume entropy of
fusion = L /Tm

2 gTm
Tr  .
r LV
 Kinetic processes in Materials
4.2.3. Heat flow and Interface stability 2 gTm 2 gTm
Tr  . r .
 The minimum possible radius of curvature
r LV Tr LV
of the tip is when Tr equals the total
undercooling Tr = T0 = Tm - T
Tr(max)
This is just the critical = T0
2 gTm
nucleus radius r* r*  .
given by substituting T0 LV
Tr = T0
r*
Therefore in general Tr is given by Tr  T0
r

Finally since T0 = Tc + Tr or

TC = T0 - Tr equation

K L TC K L T0  r * 
v . v . 1  
LV r LV r  r 
The tip velocity tends to zero as r  r* due to Gibbs-Thomson effect and as r  
due to slower heat conduction. The maximum velocity is obtained when r = 2r*.
 Kinetic processes in Materials

4.3. Diffusional transformations in solids

4.3.1. Homogeneous Nucleation in Solids

Consider the precipitation of B-rich b

from a supersaturated A-rich a solid
solution.

 The free energy change associated with

the nucleation process will have the
following three contributions:
1. The creation of a volume V of b will
cause a volume free energy reduction of
VGV (b phase is stable).
2. The creation of an area A of interface
will give a free energy increases of Ag.
3. A misfit strain energy GS per unit
volume of b increases free energy.
 Kinetic processes in Materials

4.3. Diffusional transformations in solids

4.3.1. Homogeneous Nucleation in Solids

 So, the total free energy change is:

G = - VGV + Ag + VGS
 Equation above is very similar to that derived
for the formation of a solid nucleus in a liquid,
ecxept two differences:
1. The misfit strain energy
2. g can vary widely from very low values for which is very similar to
coherent interfaces to high values for the expressions for
incoherent interfaces. solidification, ecxept the
chemical driving force is
§ If we ignore the variation of g and assume the
reduced by a positive
nucleus is spherical:
strain energy term.

4 3 4 3
G   r GV  G S   4r 2 g Gr   r GV  4r 2g SL
3 3
 Kinetic processes in Materials
4.3. Diffusional transformations in solids
4.3.1. Homogeneous Nucleation in Solids

4 3
G   r GV  GS   4r 2g
3

Differentiation of Equation above yields:

2g 2 g SL
r*  r* 
GV  GS  GV
3
16g 3 16g SL
 G*  G*  2
3GV  G S 
2
3GV 
 is a factor that includes the vibration
frequency of the atoms and the area of the
The nucleation rate critical nucleus

C0 is the number of atoms per unit volume

 Gm   G * 
N hom  C 0 exp   exp   in the phase
 kT   kT  Gm is the activation energy for atomic
migration (per atom)
 Kinetic processes in Materials
4.3. Diffusional transformations in solids
4.3.1. Homogeneous Nucleation in Solids

4
G   r 3 GV  GS   4r 2g 4 42 3
3 G   r 3 GV G
Gr S 4 rgr  GV  4r 2g SL
3 3
 Kinetic processes in Materials
4.3.1. Homogeneous Nucleation in Solids
Driving force for transformation

4
G   r 3 GV  GS   4r 2g
3

 The main factor controlling G is the

driving force for precipitation GV, the
magnitude of which must be obtained from
the free energy-composition diagram.
 If the alloy X0 is solution treated at T1 and
then cooled rapidly to T2 it will become
supersaturated with B and will try to
precipitate b.
 When the transformation to a + b is
complete the free energy of the alloy will
have decreased by an amount G0 per
mole.
 G0 therefore is the total driving force for How to find the driving force for nucleation?
the transformation, but not the driving
force for nucleation.
 Kinetic processes in Materials
4.3.1. Homogeneous Nucleation in Solids
Driving force for nucleation

If small amount of material with the

nucleus composition (XBb ) is removed
from the a phase, the total free energy of
the system will decrease by G1 (per
mole b removed – point P):

G1   aA X Ab   Ba X Bb
If these atoms are now rearranged into
the b crystal structure and replaced, the
total free energy of the system will
increase by an amount (per mole b
formed – point Q):

G 2   Ab X Ab   Bb X Bb
Therefore the driving force for
nucleation Gn = G2 - G1 per mole
of b which is just the length PQ
 Kinetic processes in Materials
4.3.1. Homogeneous Nucleation in Solids
Driving force for precipitation

 The volume free energy decrease

associated with the nucleation event
(per unit volume of b) is therefore
given by
Gn
GV 
Vm
Vm is the molar volume of b.

§ For dilute solutions it can be

shown that approximately
GV  X
where X = X0 – Xe

§ The driving force for precipitation

increases with increasing
undercooling T
 Kinetic processes in Materials
4.3.1. Homogeneous Nucleation in Solids
4
Rate of nucleation G *   r 3 GV  GS   4r 2g
3
 Evaluate now Equation for nucleation rate
for alloy X0 as a function of temperature.

 G m   G * 
N hom  C 0 exp   exp  
 kT   kT 

Essentially the potential Essentially the

concentration of nuclei atomic mobility

Note
Critical
1. At undercooling smaller than TC , N is
under-
negligible bacause the driving force GV
cooling
is too smal

2. At very high undercooling N is negligible

because diffusion is too slow.

3. A maximum nucleation rate is obtained at

intermediate undercoolings.
 Kinetic processes in Materials
4.3.1. Homogeneous Nucleation in Solids
Rate of nucleation

 For alloys containing less solute the

critical supercooling TC will not be
reached until lower absolute
temperature where diffusion is slower.
 In most systems the a and b phases
have such different crystal structures
that it is impossible to form coherent
low-energy intefaces and
homogeneous nucleation of the The nucleation rate in alloy 2 is
equilibrium b phase is then always less than in alloy 1.

impossible.
 However, it is often possible to form § There are a few systems in which the
a coherent nucleus of some other, equilibrium phase may nucleate
metastable phase (b’) which is not homogeneously, for example in the Cu-Co
present in the equilibrium phase system containing 1-3% Co or the
diagram. The most common example precipitation of Ni3Al in many Ni-rich alloys.
of this is the formation of GP zone.
 Kinetic processes in Materials

4.3. Diffusional transformations in solids

4.3.2. Heterogeneous Nucleation

 Nucleation in solids, as in liquids, is almost always heterogeneous.

 Suitable nucleation sites are non-equilibrium defects such as excess

vacancies, dislocations, grain boundaries, stacking faults, inclusions
and free surfaces, all of which increase the free energy of the material.

 If creation of a nucleus results in the destruction of a defect, some free

energy (Gd) will be released thereby reducing (or even removing) the
activation energy barrier.

 The equivalent to Equation for homogeneous nucleation

(G = - VGV + Ag + VGS), equation for heterogeneous nucleation is:

Ghet = -V (GV - GS) + Ag - Gd

 Kinetic processes in Materials
4.3.2. Heterogeneous Nucleation
Nucleation on Grain Boundary

 The optimum embryo shape should be that

which minimizes the total interfacial free energy.
 The optimum embryo shape for an incoherent
grain-boundary nucleus will consequently be
two abutted spherical caps, with q given by: 2g ab
r* 
cosq = gaa / 2gab GV

§ The excess free energy associated with the embryo will be given by

G = - GV + Aab gab - Aaa gaa

V is the volume of the embryo
Aab is the area of a/b interface of energy ggb created
Aaa is the area of a/a grain boundary of energy gaa destroyed.
 Kinetic processes in Materials
4.3.2. Heterogeneous Nucleation Aaa
Nucleation on Grain Boundary

G = - GV + Aab gab - Aaa gaa

The last term (Aaa gaa) of the above equation is simply Gd in equation for
Ghet.
Ghet = -V (GV - GS) + Ag - Gd
 It can be seen that grain boundary nucleation is analoguos to solidification
on a substrate and the same results will apply.

2g SL
r* 
GV
 Kinetic processes in Materials
4.3.2. Heterogeneous Nucleation
Nucleation on Grain Boundary

 V* and G* can be reduced futher by

nucleation on a grain edge or grain
corner.
 The ratio G*het / G*hom depends on
cosq

* *
G het Vhet
*
 *  S q 
Ghom Vhom

2
S q  
 
2  cos q 1  cos q 
4
 Kinetic processes in Materials
4.3.2. Heterogeneous Nucleation
Nucleation on Grain Boundary

§ High-angle grain boundary are particularly effective nucleation sites

for incoherent precipitates with high gab.

§ If the matrix and precipitate are sufficiently compatible to allow the

formation of lower energy facets then V* and G* can be futher reduced.

Coherent
a

b
q
a
Incoherent
 4.3.2. Heterogeneous Nucleation
Nucleation on Grain Boundary

Al2Cu

AlN
Al15Mn3Si2

a-Al dendrites

Aluminum
alloy A380
reinforced by
AlN particles.
Heated to
5400 for 8h,
aging at 1800
for 5 h
 Kinetic processes in Materials
4.3.2. Heterogeneous Nucleation
Nucleation on Dislocations

The lattice distortion in the vicinity of a

dislocation can assist nucleation in several
ways:

 Main effect is to reduce the GS by reducing the

total strain energy of the embryo

 A coherent nucleus with a negative misfit, i.e. a

smaller volume than matrix, can reduce its G*
by forming in the region of compressive strain
above an edge dislocation, with positive misfit -
below.
Rows of niobium carbonitride
 By solute segregation which can raise the precipitates on dislocations in
composition of the matrix to nearer that of the ferrite (x108,000).
precipitate. (Dark-field electron micrograph in
which the precipitates show up
 By the providing a diffusion pipe with a lower
bright)
Gm
 Kinetic processes in Materials
4.3.2. Heterogeneous Nucleation
Excess Vacancies

 The vacancies can assist nucleation by increasing diffusion rates or

by relieving misfit strain energies.

Ghet = -V (GV - GS) + Ag - Gd

 Since Gd is relatively small for vacancies, nucleation will only take
place when a reasonable combination of the following conditions
(essentially the same conditions that must be fulfilled for
homogeneous nucleation) is met:

+ Low interfacial energy (i.e. fully coherent nuclei)

+ Small volume strain energy

+ High driving force

 Kinetic processes in Materials

4.3.2. Heterogeneous Nucleation

Rate of Heterogeneous Nucleation

A sequence for various nucleation sites in order of

increasing Gd, i.e. decreasing G*:

homogeneous sites Highest

vacancies G*
dislocations
stacking faults
Highest

Gd grain boundaries and interface boundaries

free surfaces

Nucleation should always occur most rapidly on sites near the

bottom of the list.

However the relative importance of these sites also depends on

the relative concentrations of the sites.
 Kinetic processes in Materials

4.3.2. Heterogeneous Nucleation

Rate of Heterogeneous Nucleation
 If the concentration of heterogeneous nucleation sites is C1 per unit volume, the
heterogeneous nucleation rate will be given by an equation of the form :

*
 Gm   Ghet 
N het  C1 exp   exp   nuclei m-3s-1
 kT   kT 

§ For comparison with the homogeneous

nucleation rate

*
 Gm   Ghom 
N hom  C0 exp   exp 
  
 kT   kT 

§ So, the relative magnitudes of the heterogeneous and homogeneous volume

nucleation rates
* *
N het C1  Ghom  Ghet 
 
exp 
N hom C0  kT 
 Kinetic processes in Materials

4.3.2. Heterogeneous Nucleation * *

N het C1  Ghom  Ghet 
Rate of Heterogeneous Nucleation
 exp 
N hom C0  kT 
The factor C1/ C0 , i.e. the number of atoms on heterogeneous sites
relative to the number of atoms within matrix, for grain boundary
nucleation:
C1   is the boundary thickness
 D is the grain size.
C0 D

For a 50 m grain size taking  as 0.5 nm gives  / D = 10-5.

 Grain boundary nucleation will dominate over homogeneous

nucleation if the boundary is sufficiently potent to make the
exponential term in Equation
* *
N het C1  G hom  G het 
 exp 

N hom C 0  kT 
greater than 105.
 Kinetic processes in Materials

4.3.2. Heterogeneous Nucleation

Rate of Heterogeneous Nucleation

 In order of increasing driving force GV and decreasing gaa / gab

the types of site which gives the highest volume nucleation rate would be:

GV gaa / gab

grain corner
grain edge cosq = gaa / 2gab
boundary
homogeneous nucleation

C1 
 C1 / C0 for Various Heterogeneous Nucleation Sites
C0 D
Grain Grain edge Grain corner Dislocation Excess
boundary, vacancies
D = 50 m D = 50 m D = 50 m
105 mm-2 108 mm-2 XV = 10-6
10-5 10-10 10-15 10-8 10-5 10-6