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3. Kinetics
Rongshan QIN
http://cml.postech.ac.kr/rqin
1
In this lecture:
• Homogeneous nucleation
• Heterogeneous nucleation
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
• Nucleation
r
r
• Growth
Homogeneous nucleation
– Inclusion, …
Local free energy change
Spherical nucleus:
4 3
G r GL GS 4r 2 SL
3
Single nucleus
Critical radius
dG / dr 0
2 SL
r*
GL GS
16 SL 3
G*
3 GL GS 2
(GL-GS) vs. supercooling
Gc ni G TS
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
Using IL IN NL cos
Thermodynamic barriers
Heterogeneous
nucleation barrier
Homogeneous
nucleation barrier
Thermodynamic barrier vs. wetting angle
Number of nuclei with critical radius
• Surface refinement
• Solidification
– Nucleation
– Growth