NUCLEATION

Control of the properties of alloys is possible by phase transformations

which are accompanied by a change or a rearrangement in the atomic
structure, in addition to produce a composition change and/or a strain
formation.
Major Types of Phase Transformations:
I. Vapor → liquid Condensation of moisture
2. Vapor → solid Formation of frost on a window
3. Liquid → crystal Formation of ice on a lake.
4. Crystal 1 → crystal 2
(a) Precipitation---Formation of Fe3C on cooling austenite
(b) Allotropic--------Fe → γ-Fe at 910°C
(c) Recrystallization----Cold-worked Cu → new grains at high T

Degree of Complexity Involved in Phase Transformations:

(a) Structure change
(b) Structure change + composition change
(c) Structure change + strain formation
(d) Structure change + strain formation+composition change
 (a) Structure change
(b) Structure change+ composition change
(c) Structure change+strain formation
(d) Structure change+strain formation +
a composition change
b

c
d
 Solid State Phase Transformations

Homogeneous Transf’ns Heterogeneous Transf’ns

Spinodal Decomposition
Recovery of CW Structure (Nucleation &Growth)
Few of Martensitic Transf’ns

Diffusion & Heat Transport Controlled Diffusional Shear

Solidification & Melting
Semi-coherent interface
Short Range Diffusion Martensite
Long Range Diffusion
Interface Motion Controlled

Coherent Interface
Continuous Twinning
Discontinuous
Precipitation

Eutectoid Polymorphic
Interface
Controlled
Recrystallization
Discontinuous
precipitation Diffusion
Controlled Order-Disorder
 No.  regions formed/unit time
Nucleation Rate, I =
volume of  phase

Homogeneous nucleation: New phase forms uniformly throughout

bulk of parent phase.
Heterogeneous nucleation: New phase forms preferentially at
inhomogeneities in parent phase.
 HOMOGENEOUS NUCLEATION

Gn=Gsolid –Gliquid<0
Bulk Free Energy

L
Gsolid
S

T
Gliquid
4 4 33 22 
G=
G = rrG
Gnn++44rr 
33
Ttransf. Tm Temperature

4 3
G = r G n + 4r 2 
3
 G (Surface)
4 4 3
G = r 3G n + 4r 2  G = r G n + 4r 2 
3 3
G, Free Energy

G* G (Total) * −2 
r =
r* r G B

G (Bulk)
16 3
4 3
G = r G n + 4r 2  G* =
3 3( G B )2

 Nucleus of n atoms   Nucleus of n+1 atoms 

  + 1 atom →  
 and radius r   and radius r+r 
How can one justify the increase of G up to rcritical ??

It is thought that a size distribution of small clusters of atoms exists in the

liquid at any time and these clusters are considered potential nuclei. Due to
thermal fluctuations these clusters continually gain and lose atoms. A
nucleation event occurs when one of these clusters continues to gain more
atoms than it loses.
 No. of nuclie of critical size r*
Cn =
volume

dn No. of atoms joining a nucleus

=
dt sec

If a nucleation event occurs every time an atom adds to a

cluster of critical size, we may write

dn nucleations
I = Cn =
dt sec.-vol.
 dn
= s  p  e−GA / kT
dt

1. eGA / kT = fraction of liquid atoms with free energy greater than ∆GA;
2. v=vibration frequency of a liquid atom
3. s= number of liquid atoms facing a solid nucleus across the interface
4. p=f .A where f =probability the liquid atom is vibrating toward the nucleus and
A=probability that it does not bounce back by an elastic collision
Equilibrium number of critical sized nuclei, Cn, may be calculated by
an analysis similar to that for vacancies

Gv = nEv - T(nSv+ Sc)

G, Free Energy

Ev Sc=k ln {N!/(N-n)!n!}

= -k{Nln(N-n)/N+nln(n/(N-n))}
G (Total)
nequilubrium

n( # of vacancies)
Gv

-T(nSv+Sc)
ne
Cv= = e−G v / kT
N
 Similar to that in case of vacancies, we imagine that an equilibrium
distribution of clusters exists in the liquid, which increase the configurational
entropy. Then

Cn
= e−G*/ kT
d
where ∆G* is the free energy of formation of critical sized nuclei and d
is a site density.

dn nucleations G A + G * 
I = Cn I v=exp
== K K  −  where Kv=vs*pd
dt 
sec.-vol. kT 

A more detailed analysis shows that,

1/ 2
s * pd  G * 
K =
n *  3kT 
Term e-∆G*/kT is a measure of the driving force and
e-∆GA/kT is a measure of the atomic mobility.

While GA is independent of temperature, G* is

proportional to 1 / GB
−G*/ kT −1/ TG 2B
[e ][e ]
Nucleation TTT curves has the same form as the
curves used to describe the kinetics of phase
transformations, which will be discussed later.
 HETEROGENEOUS NUCLEATION

G( surf ) = [ A   + A w  w ] − A w  w

  w =   w +   cos 
Letting S = cosδ and recognizing that Aβw, = πR2

G ( surf ) = A   −  R (   s )
2

dihedral angle, δ
G = G (bulk ) + G ( surf )
= V GB + ( A −  R 2 S ) 
dihedral angle, δ
 2 − 3S + S 
3
V =  r3  


volume and surface area  3 
of a spherical cap A = 2 r2 [1 − S ]
R = r sin 

 2 − 3S + S 3 
G =  r 
3
  GB + [2 r 2
 (1 − S ) −  r 2
 (sin 2
 )S ] 
 3 
Recognizing that sin2δ is 1-S2 where S = cosδ

4 3  2 − 3S + S 3

G = [  r  GB + 4 r   ] 
2

3  4 
 2  Same as in homogeneous
r = −
* nucleation but r is defined
GB differently, i.e., as cap radius.

 2 − 3S + S 3 
G *(het ) = G *(hom)  
 4 

   2 − 3S + S 3

G *(het ) = G *(hom) 
V (het) = V (hom)  G* differs from that
 4  for homogeneous
nucleation by this term

2 
R* = − sin  = r* sin 
GB
Rainmaking.
Clouds consist of small drops of water plus water vapor. When the
cloud temperature is below 0°C the water droplets become
supercooled and ice crystals nucleate in the cloud and grow at the
expense of the droplets. When the ice crystals are sufficiently large
they fall as snow or are converted to rain or sleet depending on the
temperature of the atmosphere. Causing a supercooled cloud to
release its water content as rain is essentially a nucleation problem.
One desires to seed the cloud with particles that will cause nucleation
to occur with a minimum of supercooling. Consequently one desires a
seed material that has a very small dihedral angle δ with ice. This
requires a small value of γice_seed. Interfaces of small γ are
characterized by a fairly good crystal matching at the interface.
Hence, we need a seed crystal having a crystal structure that
contains crystal planes similar in structure and lattice spacing to the
lattice planes of ice. Crystals of silver iodide have proven effective in
seeding clouds, and these crystals satisfy this crystal-matching
requirement.
Bubbles in a glass of beer
A pleasant example illustrating heterogeneous nucleation
involves the formation of bubbles of CO2 in a glass of beer or
champagne or soft drink. Observation reveals that the bubbles
originate from certain selected points, frequently on the glass
wall. These points are probably small invisible cracks or other
inhomogeneities on the wall that act as heterogeneous
nucleation sites. We will be concerned with different types of
solid-solid phase transformations and in these cases it is almost
always true that nucleation occurs heterogeneously at grain
boundaries or dislocation clusters in the metal.
 Nucleation from a solid
Suppose that a second-phase β nucleates from a primary phase in a polycrystalline
metal. Consider two possible sites for nucleation of the second phase.
(a) It nucleates as a sphere within the bulk of a
grain.
(b) It nucleates as a double spherical cap at a
grain boundary. The following relations
apply to both case (a) and (b):

VV** −2
GG**== − GGB
 r* =
2G2B
B GB
To form a critical nucleus, a small cluster grows
by fluctuations until it attains a critical radius of
curvature that is independent of its shape.
However, the critical volume will not be
independent of shape.
Problem:
(a) Determine an expression for the ratio of
ΔG*(sphere)/ΔG*(double spherical cap).
(b) If the dihedral angle δ were 120° would you expect the β
nucleus to form first at the grain boundaries or in the bulk?
Explain. When would you expect the nucleus to form first within
the bulk?