Introduction to Solidification

3. Kinetics
Rongshan QIN
http://cml.postech.ac.kr/rqin
1
In this lecture:
Homogeneous nucleation
Heterogeneous nucleation
Solidification
Two types of solidification
Viscosity vs. temperature in: (a) Glass formation. (b) Metal casting.

Solidification
time
Temperature
Glass formation
Metal casting
Temperature vs. time during solidification
liquid
solid
Solidification
Molecular/atom arrangements in (a) Glass. (b) Crystal.
Metal solidification
Nucleation
Growth
r
r
Homogeneous nucleation
No preferred nucleation sites
Spontaneous
Random
Those of preferred sites
Boundary
Surface
Inclusion,
Local free energy change
1. Liquid to solid 2. Interface
Local free energy change
( )
SL L S before after
A G G V G G G o + = = A
( )
SL S L
r G G r G o t
t
2 3
4
3
4
+ = A
Spherical nucleus:
Single nucleus
Critical radius
0 / = A dr G d
( )
S L
SL
G G
r

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

= A
o
t
(G
L
-G
S
) vs. supercooling
Free energy density vs. temperature
Parameters
For FCC Copper, r*~1 nm, which contains 310 Cu atoms in
each nucleus.
System free energy
Ideal solution: Particle of different sizes
n
i
particles with each contains i atoms
n particles with each contains 1 atom
S T G n G
i c
A A = A
(

|
|
.
|

\
|
+
+
|
|
.
|

\
|
+
= A
i i
i
i
n n
n
n
n n
n
n k S ln ln
Number of nuclei
At equilibrium

0 / = c A c
i c
n G
|
|
.
|

\
|
+
=
A

i
i
n n
n
kT
G
ln
i
n n >>
|
.
|

\
|
A
=
kT
G
n n
i
exp
|
.
|

\
|
A
=
kT
G
n n
i
*
exp *
when
Number of nuclei
Boltzmann formula:
Critical nuclei:
Heterogeneous nucleation
Nucleation site
Mold walls
Inclusion
Interface
Surface
Impurity
Heterogeneous nucleation
Liquid
Inclusion
Nucleus u o
IL

o
NL

o
IN

R
r
h
a
u
Heterogeneous nucleation
u o o o cos
NL IN IL
+ =
Force equilibrium
where o
IL
, o
IN
and o
NL
are the interface energies of
inclusion-liquid, inclusion-nucleus and nucleus-liquid,
respectively. u is the nucleus-inclusion wetting angle. The
nucleus is a spherical cap of radius r.
Free energy change
Free energy change
Using
u o o o cos
NL IN IL
=
Thermodynamic barriers
Heterogeneous
nucleation barrier
Homogeneous
nucleation barrier
Thermodynamic barrier vs. wetting angle
Number of nuclei with critical radius
where n
s
is the total number of atom around the
incubating agents surface in liquid.
Inoculating agents
Small interface energy
Similar crystal structure
Similar lattice distance
Same physical properties
Same chemical properties
Effect of surface geometry
Casting refinement
Adding inoculating agents
Overheat might melt the agents
Surface refinement
Coat agents on mold walls
Pattern induced solidification

In summary
Two types of solidification
Glass formation
crystallization
Solidification
Nucleation
Growth
Homogeneous and heterogeneous nucleation
References
1. M.C. Flemings, Solidification processing, 1974.
2. A. L. Greer, Kinetics, Cambridge.