ICME Research Lab, Prof.

Alankar, 2022

Structural Materials
Kinetics of Nucleation and Growth

ME 221

Lecture 21
Alankar Alankar
[email protected]; Ph. 9356
Office: S02, ME Building
Lab: ICME Research Lab
www.me.iitb.ac.in/~alankar

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Outline
• Nucleation
• Growth

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Types of Phase Transformations

The transformations are divided into three classifications:

1. In one group are simple diffusion-dependent transformations in which there is

no change in either the number or composition of the phases present. These
include solidification of a pure metal, allotropic transformations, and
recrystallization and grain growth.
2. In another type of diffusion-dependent transformation, there is some alteration
in phase compositions and often in the number of phases present; the final
microstructure ordinarily consists of two phases. The eutectoid reaction is of
this type.
3. The third kind of transformation is diffusionless, wherein a metastable phase is
produced. A martensitic transformation, which may be induced in some steel
alloys, falls into this category.

Callister, 8th Ed. Sec. 10.2, pg. 344

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Kinetics of Phase Transformations

With phase transformations, normally at least one new phase is formed that has
different physical/chemical characteristics and/or a different structure than the
parent phase. Furthermore, most phase transformations do not occur
instantaneously. Rather, they begin by the formation of numerous small particles of
the new phase(s), which increase in size until the transformation has reached
completion.
The progress of a phase transformation may be broken down into two distinct
stages:
Nucleation involves the appearance of very small particles, or nuclei of the new
phase (often consisting of only a few hundred atoms), which are capable of
growing.
During the growth stage these nuclei increase in size, which results in the
disappearance of some (or all) of the parent phase. The transformation reaches
completion if the growth of these new phase particles is allowed to proceed until
the equilibrium fraction is attained.

Callister, 8th Ed. Sec. 10.3, pg. 344

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Nucleation
There are two types of nucleation:
(1) Homogeneous
(2) Heterogeneous.

The distinction between them is made according to the site at

which nucleating events occur. For the homogeneous type,
nuclei of the new phase form uniformly throughout the parent
phase, whereas for the heterogeneous type, nuclei form
preferentially at structural inhomogeneities, such as container
surfaces, insoluble impurities, grain boundaries, dislocations,
and so on.

Callister, 8th Ed. Sec. 10.3, pg. 344

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2019

Homogeneous Nucleation Note that

unit cell will
initially

[
a
show
Consider solidification. r is the size of a up .

spherical nuclei of solid. This surface

will be faceted
wÑ
as
Phase transformation occurs unit cells
time
the
-

then the

¥¥umA
on
cells will
spontaneously when ΔG due to phase myace
transformation is negative. well as
. grow .to a

larger group
For the sake of simplicity, let us first
consider the solidification of a pure
material, assuming that nuclei of the solid
nucleation
phase form in the interior of the liquid as In case
of homogeneous
not
atoms cluster together so as to form a we assume that there are

packing arrangement similar to that found boundaries of the domain . The

in the solid phase. interfaces ) that

exist are

only initial liquid and

between the
solid
nucleating
.

the
Callister, 8th Ed. Sec. 10.3, pg. 345
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Homogeneous Nucleation f

the
solid
tf
n

surface energy of unit area

/ Precisely Yrs the the energy

per
interface beta
The second part is positive
embryo the salrd and
since it represents creation of
an incompatible region i.e.
the liquid .

%kq §
* interface.
nucleus
Gkka•& a•☆

The first part is negative since

as long as the temperature is
below the equilibrium
solidification temperature,
solidification will occur
Da is actually spontaneously.

a → free energy at r = 0 ☐ 9=0

← →
nucleating particle
,

of .

for our discussion

so
we say that AG
is
,
aetadhg
(a) Schematic curves for volume free energy and surface free energy contributions to the total free G.
energy change attending the formation of a spherical embryo/nucleus during solidification. (b)
Schematic plot of free energy versus embryo/nucleus radius, on which is shown the critical free
energy change (ΔG*)
Aaa and the critical nucleus radius (r*).
DG we using G. Callister, 8th Ed. Eq. 10.1, pg. 345-346
Disclaimer : Book is using
are
.

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Homogeneous Nucleation
Baa

For getting r* and Baa

ΔG*, we find the maximum value of Boo
ΔG and the r at which that
occurs. Then that r* value can be replaced in the above equation to getGaa
ΔG*.

Bok

For homogeneous nucleation, critical radius of a stable solid

particle nucleus

For homogeneous nucleation, activation free energy required

for the formation of a stable nucleus Bak

Callister, 8th Ed. pg. 346

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Effect of Temperature on the Free Energy Change

a
☐
Hf is

number .

negative Tm is melting point. ΔHf is latent

heat of fusion.

These equation suggest that:

1. At higher temperature i.e. Tm- T

BB is a small value, r* is large. This
means that at lower
‘supercooling’, the critical size of
embryo is large.
2. Low ‘supercooling’ also leads to
larger critical free energy
• required for nucleation.
•
• 3. The plot indicates the same.
4. At larger degree of
supercooling, the effects are
reversed.

Callister, 8th Ed. pg. 347

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Number of nuclei
Bro
Frequency of atom attachment from
Number of stable nuclei liquid to solid

Bao

high ,
how Qd
low net ,
high Vd Constant K is related to
1
the total number of
nuclei of solid phase.
Constant K2 is
Book temperature dependent
constant.
K3 the total number of

② how ,
high Qd atoms on the nucleus
surface.
high n* how Ñd
,

For solidification, schematic plots of (a) number of stable nuclei versus temperature, (b) frequency of atomic
attachment versus temperature, and (c) nucleation rate versus temperature (also shown are curves for parts a
and b). Read the next slide for shape of the green curve (shape of nucleation rate).
Callister, 8th Ed. Fig. 10.4, pg. 348
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Shape of Nucleation Curve and Degree of Supercooling

Note that at high temperature (still below Tm),•ΔG* is greater than Qd, which
←
leads to: because it is difficult to
gather at high temperature
exp(-ΔG*/kT
Bae ) << exp(-Qd/kT) atoms lot of additional
,
a atoms already are

energy should be provided diffusing fast diet

high kinetic energy so
.

At temperatures much lower than Tm, BD

ΔG* is very small i.e. smaller as additional

exp(-ΔG*/kT
BB
-6mm
compared to Qd, thus: needed for
aaratroneneFY.fi?!:.snoi-
diffusion
) >> exp(-Qd/kT) low of rs need because atoms
settle down
energy for
more

naturally
"

-
want to .
needed

Thus in the both above conditions, nucleation rate is low. There is an

intermediate region of temperature where nucleation rate is maximum.

Also, note that an appreciable nucleation rate will be there only after
temperature is far below Tm. This difference Tm – T is called degree of
supercooling in homogeneous nucleation. What is meant by appreciable
here ? See the next slide.
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Why the curves are starting from below Tm ?

BBB

Note that circled region

on the plot. It appears
that the amount of
solidification is zero
before the green line
starts. However, it is only
a bad plot. In reality, the
line is asymptotic to the Y
axis. The nucleation is so
low at higher
temperature that it is not
measurable. Statistically
there no significant
solidification at higher
temperatures.
The plot on the right side
shows the correct plot for
better understanding.
Same reasoning works for
lower part as well.

Callister, 8th Ed. Fig. 10.4, pg. 348

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Degree of Supercooling for various metals

Callister, 8th Ed., Table 10.1, pg. 349

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Heterogeneous Nucleation
Although levels of supercooling for homogeneous nucleation may be significant (on
occasion several hundred degrees Celsius), in practical situations they are often on
the order of only several degrees Celsius. The reason for this is that the activation
energy (i.e., energy barrier) for nucleation so
ΔG* is lowered when nuclei form on
preexisting surfaces or interfaces, because the surface free energy.

Heterogeneous nucleation of a solid from a liquid. The solid–surface solid–liquid

and liquid–surface interfacial energies are represented by vectors. The
wetting angle θ is also shown.

Callister, 8th Ed., pg. 351

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Heterogeneous Nucleation

•☒*

•
g.☒

Bak

The S(θ) term of this last equation is a Note that r* is same for heterogeneous
function only of θ (i.e., the shape of the and homogeneous nucleation. But Bak ΔG* is
nucleus), which will have a numerical value much lower for heterogeneous nucleation
between zero and unity. i.e. a much smaller energy barrier needs
to be overcome i.e. not much
Baan Bao supercooling is needed for heterogenous
nucleation.
Callister, 8th Ed., pg. 352
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Heterogeneous Nucleation

Note that much lower supercooling is

needed for heterogeneous nucleation.

Callister, 8th Ed., pg. 352

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Growth

The growth step in a phase transformation begins once an embryo has

exceeded the critical size, r*, and becomes a stable nucleus.

Nucleation will continue to occur simultaneously with growth of the new

phase particles; of course, nucleation cannot occur in regions that have
already transformed to the new phase.

Furthermore, the growth process will cease in any region where particles of
the new phase meet, because here the transformation will have reached
completion.

Particle growth occurs by long-range atomic diffusion, which normally

involves several steps—for example, diffusion through the parent phase,
across a phase boundary, and then into the nucleus.

Callister, 8th Ed., pg. 352

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Growth and Transformation

temperature diffusion is easy
at high
rate high

/
is
growth
.

so

Q is diffusion coefficient.
Note that growth is driven by
long range atomic diffusion.

Note that nucleation is driven

how by short range atomic
←
0 diffusion. The atoms in the
diffusion,
low vicinity of the solid interface
rate participate.
growth
.

Callister, 8th Ed., pg. 353

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matron
Representation of BETWEENS
Growth
Avrami Equation of fraction

Fraction of transformation

Rate is
given by ¥
here

¥
taken
as
the
time
when

50 't tramfmhn
Is complete .

Callister, 8th Ed., pg. 353-355

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Representation of Badakhshan
Growth ation
Avrami Equation of fraction

Avrami equation is an empirical equation that is able to capture the fraction (y) of
transformation in time t.

Time to certain extent of completion can be used for comparing whether one
transformation is faster than the other. E.g. time to 50 % completion could be a
measure.

Inverse of time to completion to certain degree represents the rate of transformation.

i.e. 1/t50 is rate of transformation upto 50 % transformation.

Callister, 8th Ed., pg. 353-354

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