Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

3. Kinetics

There are two types of solidification. The first is that the viscosity of liquid increases
gradually as the decreasing of the temperature. Examples are wax solidification and
glass formation. Instead of having a melting point, this type of solidification has a melting
zone. The second is that the viscosity of liquid increases suddenly as the decreasing of
the temperature. Metal casting is an example for this solidification. The solidification
happens at the melting point. The change of viscosity regarding to temperature for both
solidification is illustrated in figure 1. The molecular arrangements in glass and crystal
are demonstrated in figure 2.


Figure 1. Viscosity vs. temperature in: (a) Glass formation. (b) Metal casting.


Figure 2. Molecular/atom arrangements in (a) Glass. (b) Crystal.
Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

The second type of solidification is modeled as two steps: Nucleation and growth. There
are two types of nucleation: homogeneous nucleation and heterogeneous nucleation.


3.1 Homogeneous nucleation

Nucleation is the starting formation of solid from liquid phase. Nucleation without
preferential nucleation sites is called homogeneous nucleation. Homogeneous
nucleation occurs spontaneously and randomly. Figure 3 shows a nucleation of
spherical solid from liquid.


Figure 3. A spherical particle of r radius forms in liquid

The free energy change during nucleation contains two parts: Bulk free energy
difference between solid and liquid phase and the surface energy

( )
SL L S before after
A G G V G G G + = = (3.1)

where V is the volume of the nucleus. G
S
and G
L
are free energy density of solid and
liquid phases, respectively. A is the surface area.
SL
is the interface energy between
solid and liquid. For the spherical nucleus as illustrated in figure 3, the free energy
change of equation (3.1) is expressed into

( )
SL S L
r G G r G

2 3
4
3
4
+ = (3.2)

r
Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

Figure 4. Free energy change during solidification

The first term and second term of the right hand of equation (3.2), and their addition
which gives the total free energy change during solidification is given in figure 2. It
shows that G achieves maximum G* 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 (3.2) via 0 / = dr G d

( )
S L
SL
G G
r

=
2
* (3.3)


Figure 5. Free energy density vs. temperature

Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

Bring equation (3.3) into (3.2) one gets the maximum nucleation barrier

( )
2
3
3
16
*
S L
SL
G G
G

=

(3.4)

As illustrated by figure 5 where T is the supercooling, the free energy density depends
on the temperature. Supercooling is needed for nucleation to overcome the extra energy
bring out by interface energy. Table one lists the maximum supercooling can be
achieved for various pure metals.

Table 1. Suprcooling of some liquid metals, [after Hollomon and Turnbull]
Metal Supercooling C 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

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
= (3.5)

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

Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)
(

|
|

\
|
+
+
|
|

\
|
+
=
i i
i
i
n n
n
n
n n
n
n k S ln ln (3.6)

At equilibrium one has 0 / =
i c
n G . Equation (3.5) turns into

|
|

\
|
+
=

i
i
n n
n
kT
G
ln (3.7)

when
i
n n >> , it turns into

|

\
|
=
kT
G
n n
i
exp (3.8)

Equation (3.8) is Boltzmann formula. The number of embryos with critical radius r* is
given by


|

\
|
=
kT
G
n n
i
*
exp * (3.9)

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


3.2 Heterogeneous nucleation

In engineering practice, many liquid metals start solidification in a few degrees of
supercooling. The thermodynamic barrier for nucleation in this case is smaller than
calculated critical free energy change G* by homogeneous nucleation theory. The
solidification begins on impurity particles, e.g. inclusions, mold walls, surfaces and
interfaces. The nucleation occurs on preferential sites and is named heterogeneous
nucleation.

To calculate the thermodynamic barrier for heterogeneous nucleation, we consider the
case illustrated in figure 6, where a spherical cap shaped nucleus is forming in a flat
inclusion surface.

Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

Figure 6. Nucleation on Inclusion surface

Force balance at position R gives

cos
NL IN IL
+ = (3.10)

where
IL
,
IN
and
NL
are the interface energies of inclusion-liquid, inclusion-nucleus
and nucleus-liquid, respectively. is the nucleus-inclusion wetting angle. The nucleus is
a spherical cap of radius r. The volume of the nucleus is given by

( )
3 3
cos cos 3 2
3
1
+ = r V (3.11)

The surface area of the spherical cap is

( ) cos 1 2
2
= r A
s
(3.12)

The surface area of nucleus-inclusion contacting area is

( )
2 2 2 2
cos 1 sin = = r r A
c
(3.13)

The free energy change during the heterogeneous nucleation is

( ) ( )
( ) ( )
IL IN
NL S L he
r r
r G G r G


2 2 2 2
2 3 3
cos 1 cos 1
cos 1 2 ) ( cos cos 3 2
3
1
+
+ + =
(3.14)

Liquid
Inclusion
Nucleus
IL

NL

IN

R
r
h
a

Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)
By using equation (3.1), it changes into

( ) ( )
( )



f G
r G G r
r G G r G
ho
NL S L
NL S L he
=
|
|

\
| +
(

+ =
+ + + =
4
cos cos 3 2
4 ) (
3
4
cos cos 3 2 ) ( cos cos 3 2
3
1
3
2 3
3 2 3 3
(3.15)

where we defined

( )
4
cos cos 3 2
3

+
= f (3.16)

The critical radius of nucleus, r*, is the same as defined in homogeneous nucleation.
However, the free energy to form a cap of this size on the substrate
*
he
G is smaller by a
factor of f().

) (
* *
f G G
ho he
= (3.17)

where ( ) f goes to zero as the wetting angle decreases to zero. This means that the
nucleation barrier decreases, ultimately vanishing, as the wetting between forming
particle and substrate (walls, inclusions, interface, etc) improves.

Figure 7.
* *
/
ho he
G G vs. wetting angle

Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)
In the case of ( ) 0 = f when 0 = , liquid can solidify without any supercooling. ( ) 1 = f
when
o
180 = , in which the inclusion does not play any role and
* *
ho he
G G = . The
relation ship between
* *
/
ho he
G G and wetting angle is plotted in figure 7.

The number of nucleus at critical radius
*
he
n in heterogeneous nucleation can be derived
in the same way as for the homogeneous nucleation, it takes the format of

( ) kT G
s he
he
e n n
/ *
*

= (3.9)

where
s
n is the total number of atom around the incubating agents surface in liquid.

Heterogeneous nucleation needs small supercooling to stimulate. The smaller the
wetting angle is the smaller supercooling needed. However, heterogeneous nucleation is
limited by the surface area of the inclusions and walls, which is basically different from
homogeneous nucleation where nucleation can happen at anywhere in the liquid. When
the solid growth rate is large, one can assume that each inoculating particle can act as
one nucleus only. The cast grain refinement can be estimated by the number of
nucleation agents.


3.3 Inoculating agents

Figure 7 and equation (3.10) demonstrate the principle of choosing inoculating agents to
stimulate the heterogeneous nucleation. To make the wetting angle minimum
IN

should be as small as possible or
IL
should be as large as possible. Normally, interface
energy between two substances with similar crystal structure, lattice distance, physical
and chemical properties is smaller. The wetting angle also depends on the roughness
and geometry of the surface. For example, in cavities nucleation can occur at very low
supercooling.

In commercial practice, inoculating agents are added into many liquid metals to produce
small grain-sized alloys, e.g. to add titanium and boron for refinement of microstructures
of aluminum alloys.

References

1. M.C. Flemings, Solidification processing, 1974.
Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)
2. A. L. Greer, Kinetics, Cambridge.
3. K.T. Kashyap and T. Chandrashekar, Bull. Mater. Sci. 24 (2001) 345-353