Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

11. Kinetics of solidification 1


11.1 Homogeneous nucleation

Nucleation is the starting of a phase transition in a small region. In solidification,
nucleation is the formation of solid from liquid phase. Nucleation without
preferential nucleation sites is homogeneous nucleation. Homogeneous
nucleation occurs spontaneously and randomly.

The free energy change during nucleation contains two parts: Bulk free energy
difference between solid and liquid phase and the surface energy, as expressed
as
( )
SL L S before after
A G G V G G G V + = = A (11.1)

where V is the volume of the nucleus. G
S
and G
L
are free energy of solid and
liquid phases per volume, respectively. A is the surface area. o
SL
is the interface
energy between solid and liquid. For the spherical nucleus as illustrated in figure
1, the free energy change of equation (11.1) is expressed into


Figure 1. A spherical particle of r radius forms in liquid

( )
SL S L
r G G r G V S
S
2 3
4
3
4
+ = A (11.2)

r
Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)


Figure 2. Free energy change during solidification

The first term and second term of the right hand of equation (11.2), and their
addition which gives the total free energy change during solidification is given in
figure 2. It shows that AG achieves maximum AG* when r=r*, which means that
the nucleus will certainly grow when r>r*. The particle of radius r* is termed the
critical nucleus. The critical radius can be obtained by equation (11.2) via
0 / = A dr G d

( ) T H
V T
G G
r
m
m SL
S L
SL
A A
=

=
V V 2 2
* (11.3)

Metal Supercooling qC Surface energy erg/cm
-2

Al
Mn
Fe
Co
Ni
Cu
Pt
Ag
Pb
Sn
Bi
195
308
295
330
319
236
332
227
80
118
90
121
206
204
234
255
177
209
126
33
59
54
Table 1. Suprcooling of some liquid metals, [after Hollomon and Turnbull]
Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

where AT is the supercooling. Equation (11.3) shows that the critical radius for
nucleus is reciprocal proportional to the undercooling. Insulting equation (11.3)
into (11.2) one gets AG*

2 2
2 2 3
3
16
*
T H
V T
G
m
m sl
A A
= A
SV
(11.4)

AG* is the maximum of AG during solid formation.

Following Turnbull, liquid with nuclei can be considered as an ideal solution of
various size clusters, each contains i atoms or molecules. Let n denotes the
number of particles containing only 1 atom or molecules and n
i
denotes the
number of particles containing i>1 atoms or molecules in per unit volume of liquid.
The Gibbs energy change per unit volume of liquid on forming the particles is
given by

S T G n G
i c
A A = A (11.5)

AS is the entropy of mixing n
i
nuclei with n atoms, which for an ideal solution is
simply given by

1
]
1

|
|

\
|
+
+
|
|

\
|
+
= A
i i
i
i
n n
n
n
n n
n
n k S ln ln (11.6)

At equilibrium one has 0 / = c A c
i c
n G . One gets

|
|

\
|
+
=
A

i
i
n n
n
kT
G
ln (11.7)

when
i
n n >> , it turns into

|

\
| A
=
kT
G
n n
i
exp (11.8)

Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

Equation (11.8) is Boltzmann formula. The number of embryos with critical radius,
r*, is given by


|

\
| A
=
kT
G
n n
i
*
exp * (11.9)

For FCC Copper, r*=1 nm, which contains 310 Cu atoms in each nucleus.

11.2 Nucleation rate

Nucleation rate means the nuclei formed per unit volume and per unit time
duration, i.e., the rate of formation of nuclei per unit volume. By two assumptions
of that: (a) the concentration of critical nuclei remains that at predicted by
equilibrium considerations even after nucleation begins. (b) The addition of a
single atom to a critical nucleus makes that nucleus supercritical and able to
grow rapidly. Then, the nucleus rate I is given by


Figure 3. One atom jumps into critical nucleus and make the nucleus a supercritical.

LS i
n I Q Z* * = (11.10)

where e* is the number of atoms surrounding a critical nucleus. v
LS
is the
frequency of atom jump across the liquid-solid interface. For a spherical nucleus,
e* is approximately given by

2
2
* 4
*
a
r S
Z = (11.11)

where a is the average distance between two nearest-neighbored atoms in liquid.
The diffusivity is given by

Critical
nucleus
Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

2
6
1
O I =
L
D (11.12)

where I is the jump frequency of an atom in liquid and i is the jump distance of
atom in liquid. Taking a ~ O and considering that the atom jumping along one
direction is one-sixth of all possible jumping, it has

2
a
D
L
SL
= Q (11.13)

Bring equations (11.9), (11.11) and (11.13) into (11.10), one has

|

\
| A
=
kT
G
D
a
r
n I
L
*
exp
* 4
4
4
S
(11.14)

The diffusivity D
L
changes with the liquid temperature in a relationship of

|

\
| A
=
kT
G
D D
A
L
exp
0
(11.15)

where AG
A
is the activation energy which barely depends on temperature. When
the temperature drops largely the nucleation rate drops because of the smaller
diffusivity. Equation (11.14) shows that when the nucleation rate approaches to
zero when supercooling is to disappear because AG* 1/AT
2
which makes
A * G when 0 AT . Increasing of supercooling will increase the nucleation
rate. The above discussion describes an image of the nucleation rate will initially
increase as the increasing of supercooling, but will decrease because of the
lower diffusivity at low temperature. The image is schematically illustrated in
figure 4.

Figure 4. Schematic diagram of nucleation rate with respect to supercooling.
Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)


For many materials such as glass and polymers, the nucleation rate and supercooling
relationship agrees with figure 4. However, for majority of metals especially pure metals,
the dropping tail of nucleation rate at low temperature has not been found. It is proved
that the relationship between nucleation rate and supercooling in pure metal is like the
schematic diagram in figure 5. The diffusivity-temperature relationship has not play the
expected role.


Figure 5. Nucleation vs. supercooling in metals.

For alloys, the diffusivity plays the important role and metal glasses are made by
rapid quench.


References

1. M.C. Flemings, Solidification processing, 1974.