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

Temperature

liquid

Glass formation
Metal casting solid
time
Temperature vs. time during solidification
Solidification

Molecular/atom arrangements in (a) Glass. (b) Crystal.

Metal solidification

• Nucleation

r
r

• Growth
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

G  Gafter  Gbefore  V GS  GL   A SL

Spherical nucleus:

4 3
G   r GL  GS   4r 2 SL
3
Single nucleus
Critical radius

dG / dr  0
2 SL
r* 
GL  GS 
16  SL 3

G* 
3 GL  GS 2
(GL-GS) 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

• ni particles with each contains i atoms
• n particles with each contains 1 atom

Gc  ni G  TS
  ni   n 
S  k ni ln    n ln  
  n  ni   n  ni 
Number of nuclei

• At equilibrium

Gc / ni  0

G  ni 
  ln  
kT  n  ni 
Number of nuclei

when n  ni

 G 
Boltzmann formula: ni  n exp   
 kT 

 G * 
Critical nuclei: ni *  n exp   
 kT 
Heterogeneous nucleation

• Nucleation site
– Mold walls
– Inclusion
– Interface
– Surface
– Impurity
Heterogeneous nucleation

Liquid
NL

h
Nucleus  R IL

IN
a

Inclusion r


Heterogeneous nucleation

Force equilibrium

 IL   IN   NL cos

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.
Free energy change
Free energy change

Using  IL   IN   NL cos
 Thermodynamic barriers

Heterogeneous
nucleation barrier
Homogeneous
nucleation barrier
Thermodynamic barrier vs. wetting angle
Number of nuclei with critical radius

where ns 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.