Fundamentals of Solidification

Lecture 4: Nucleation and growth

 Outline

• Introduction
• Homogeneous nucleation
• Heterogeneous nucleation
• Growth and microstructure
• Summary
 Introduction

• There are two types of solidification

– Glass formation
• Physical properties such as viscosity change
smoothly across the solidifying region
– Phase transition
• Some physical properties change abruptly,
such as viscosity, heat capacity
Temperature vs. time in glass solidification and
phase transition solidification
Viscosity vs. temperature in glass solidification
and phase transition solidification

(a) Glass solidification (b) Phase-transition solidification

Density vs. temperature in glass solidification and
phase transition solidification
Heat capacity of Fe
 Introduction

• Solidification by phase transition is

modelled as two stage
– Nucleation
• Homogeneous nucleation
• Heterogeneous nucleation

– Growth
Homogeneous nucleation

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

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* 
 G L  GS 
3
16  SL
G* 
3  GL  GS  2
(GL-GS) vs. supercooling

solid
Free energy density

liquid

temperature

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
 Casting refinement
• Adding inoculating agents
– Overheat might melt the agents

• Surface refinement
– Coat agents on mold walls

• Pattern induced solidification

Growth and microstructure

T. F. Brower and M.C. Flemings, Trans. AIME, 239, 1620 (1967)

Growth and microstructure

H.B. Dong and P.D. Lee, Acta Mater. 53 (2005) 659

Outer chilled zones
Outer chilled zones
Outer chilled zones
 Outer chilled zones

Pure metals: Formation of shell because temperature

gradient is the key factor in grain growth.
Outer chilled zones

Pouring temperature

re-melted?

survived?
 Microstructure of ingot
• Chilled zone
– Fine equiaxed grains.
– Pure substance: Continuous shell.
– Solution: Particles
– Particles flushed away from wall into the
central
• Re-melted
• Survived – nucleus
Intermediate columnar zone

The grain is overtaken by neighbors.

Columnar grains grows

Intermediate columnar zone

Growth and overtaken

Intermediate columnar zone

Columnar growth blocked

 Central equiaxed zone
• Equiaxed grain
– Nucleation:
• Supercooling
• Falling particles
• Dendrite fragments
– Elevated pouring
temperature:
• Larger equiaxed
grains
 Structure and properties
• More columnar zone
– Anisotropic properties
• Magnetic materials
• Turbo blade.

• More equiaxed zone

– Isotropic properties
– Less segregation
 Summary

• Casting
• Heat management
• Thermodynamics
• Nucleation and growth