EMA5001 Lecture 13

Solidification via
Heterogeneous Nucleation,
Growth of Pure Solid from Liquid
 Heterogeneous Nucleation (1)

❑Actual solidification often involves mold wall, insoluble oxides, etc.,

which become substrates for heterogeneous nucleation
Assuming SL
Liquid
▪ ML is isotropic Solid

▪ Mold wall flat
Mold r SM ML
 ML =  SM +  SL Cos
Free energy change in heterogeneous nucleation

Ghet = −VS Gv + ASL SL + ASM  SM − ASM  ML Assuming sphere-cap geometry

Therefore,
4
VS = r 3 
(2 + Cos )(1 − Cos )
2

3 4
 4 
Ghet = − r 3 Gv + 4r 2 SL   S ( )
 3  ASL = 2r 2 (1 − Cos )

S ( ) =
(2 + Cos )(1 − Cos )
2
ASM = r 2 Sin 2
4

EMA 5001 Zhe Cheng 13 Heterogeneous Nucleation 2

 Heterogeneous Nucleation (2)

❑Continue from previous G

 4 
Ghet = − r 3Gv + 4r 2 SL   S ( )
 3 
Remember for homogeneous nucleation
4 Ghom
*

Ghom = − r 3 Gv + 4r 2 SL Ghet

*
3
r
We have Ghet = Ghom  S ( )

0  S ( ) =
(2 + Cos )(1 − Cos )
2
1
4
Same critical nucleus radius Heterogeneous nucleation has the same
2 SL critical nucleus radius as for
*
rhet = rhom
*
=
Gv homogeneous nucleation, but lower
nucleation barrier (activation energy)

EMA 5001 Zhe Cheng 13 Heterogeneous Nucleation 3

 Heterogeneous Nucleation (3)

❑Continue from previous S ( )

2 1.0
*
rhet = rhom
*
= SL
Gv 0.8
Critical nucleation energy
0.6  = 10o, S() = 0.00017
Ghet
*
= Ghom
*
 S ( ) 0.4
 = 30o, S() = 0.013
 = 60o, S() = 0.16
S ( ) =
(2 + Cos )(1 − Cos )
2
1 0.2  = 90o, S() = 0.50
4 0.0  (o )
SL 0 20 40 60 80 100 120 140 160 180
Liquid
Solid
 Heterogeneous nucleation,
Mold r SM ML especially those on mold wall
that is similar to solid (i.e. low
𝛾𝑀𝐿 = 𝛾𝑆𝑀 + 𝛾𝑆𝐿 𝐶𝑜𝑠𝜃 γSM), has much lower nucleation
𝛾𝑀𝐿 − 𝛾𝑆𝑀 = 𝛾𝑆𝐿 𝐶𝑜𝑠𝜃 barrier than homogeneous
SM  Cos    or better “wetting” nucleation
EMA 5001 Zhe Cheng 13 Heterogeneous Nucleation 4
 Heterogeneous Nucleation Rate

❑Define
C1 Number of atoms contacting heterogeneous
nucleation sites per unit liquid volume
Ghet
*
Heterogeneous nucleation energy
f1 Frequency of adding one atom to a
heterogeneous nucleus with critical size
Heterogeneous nucleation rate (m-3s-1)
 Ghet *

N het = f1C1 exp − 
 kT 
Since
Ghet*
= Ghom
*
 S ( )
16 SL
3
Tm2 1
G *
= 
T 2
hom 2
3Lv Phase Transformations in Metals & Alloys, Porter,
3rd Ed, 2008, p. 199
We have
 A  S ( )  Heterogeneous nucleation occurs at
N het = f1C1 exp − 
  T 2
 much smaller undercooling than
homogenous nucleation
EMA 5001 Zhe Cheng 13 Heterogeneous Nucleation 5
 Other Factors Influencing
Heterogeneous Nucleation Rate
❑Surface tension & contact angle
S ( ) =
(2 + Cos )(1 − Cos )
2
1
Smaller solid-mold (or impurity) 4
 ML −  SM
interfacial energy SM → Smaller  Cos = 𝛾𝑀𝐿 = 𝛾𝑆𝑀 + 𝛾𝑆𝐿 𝐶𝑜𝑠𝜃
Smaller S() → Faster nucleation  SL
❑Mold surface microstructure
Concave
▪ In general, no matter what shape
nucleation energy 
1  Flat
G* = V *Gv 
2
▪ Concave mold (or impurity) surface
and certain micro-cracks facilitate Convex
nucleation by decreasing V* and Over mold or
In micro-cracks
nucleation energy impurity surface

❑Impurity density
▪ Adding seeds or inoculants increases nucleation rate
− Also decreases grain size
EMA 5001 Zhe Cheng 13 Heterogeneous Nucleation 6
 Growth of Pure Element Solid from Liquid

❑Growth of pure element solid from liquid for different types of solid-
liquid interfaces
Liquid Liquid
Diffuse Flat

Solid Solid
Lf Lf
R S  R ~ 4 R S  ~ 4 R
Tm Tm
• Microscopically diffuse • Microscopically flat
• Macroscopically flat or branch-like • With stepped or zig-zagged Features
• Most metals: • Si, Ge, and nonmetals
Ni: Tm =1455 oC Si: Tm =1414 oC
Lf =298 kJ/kg=17.4 kJ/mol, CN=12 Lf =1790 kJ/kg=50.26 kJ/mol, CN=4
→ Lower bonding energy → Much higher bonding energy
Continuous growth Lateral growth
• Microscopically, growth of solid (into • Microscopically, growth of solid occurs
liquid) occurs by adding individual along the solid-liquid interface at
atoms, randomly to the interface specific locations/sites
EMA 5001 Zhe Cheng 13 Heterogeneous Nucleation 7
 Continuous Growth

❑Low bonding energy (i.e., easier to create broken bonds)

▪ High vacancy concentration at the solid-liquid Liquid
interface
▪ Activation energy ΔGa  diffusion activation
energy in liquid (very small)
Solid
▪ Fast interface “reaction” or L → S conversion
▪ Driving force for solidification (solid growth) G
L
Gv =  Ti
Tm ΔGa
L Latent heat of melting/fusion ΔGv
Ti Undercooling at the solid-liquid interface
▪ Velocity of the solid-liquid interface (growth Liquid Solid x
rate of solid)
v  Gv  Ti
▪ Mobility of diffuse solid-liquid interface is extremely high
▪ For normal rate of metal solidification, Ti < 1 oC →
Solid-liquid “diffuse” interface is at close to equilibrium Tm in solidification
EMA 5001 Zhe Cheng 13 Heterogeneous Nucleation 8
 Lateral Growth

❑If high bonding energy (e.g. for Si) Liquid

▪ A single atom attached to a flat surface creates
multiple broken bonds and tend to dissolve back, Solid
leading to limited perpendicular growth
Liquid
▪ Atoms prefer to attach to solid at existing ledge or
jog positions, leading to lateral growth Solid
❑Possible growth geometries
Surface Nucleation Spiral Growth Continuous growth
(diffuse interface)

Growth rate v
Spiral
growth
Surface
nucleation

http://encyclopedia2.thefreedictionary.com/Crystallization
Ti
▪ Lateral growth slower than continuous growth due to fewer geometric locations
EMA 5001 Zhe Cheng 13 Heterogeneous Nucleation 9
 Examples of Lateral Growth:
Surface Nucleation & Spiral Growth
Glucose isomerase
SiC crystal Graphite crystal
crystal

S. AMELINCKX
Mike Sleutel Dr. Victor N. Kvasnitsa
https://www.nature.com/physics/looking-
https://www.pnas.org/content/11 https://pages.mtu.edu/~jaszczak/compspirals.html
back/verma/index.html
1/5/E546

EMA 5001 Zhe Cheng 13 Heterogeneous Nucleation 10

 Temperate Profile & Growth of
a Pure Element Solid (1) - Planar Growth
❑Solidification rate of pure element solid determined by heat conduction
❑Solid grows into superheated liquid (TS < TL)
▪ Example
Solid Liquid
− Solidification of liquid in a mold and
mold wall is colder than liquid Ti v
▪ Balance of heat flow Solid Liquid
Heat
S Thermal conductivity of solid Ti=Tm
L Thermal conductivity of liquid
If local protrusion
TS ’ Temperature gradient in solid
Solid Liquid
TL’ Temperature gradient in liquid
v
Lv Latent heat of melting
Assuming NO
v Solid growth rate temperature change Heat
deep in S, L, and at
 S TS ' =  LTL '+ vLv the S/L interface

▪ Shape of the solid-liquid interface TS’ ↓ TL’  v ↓

− Planar (macroscopically) solid-liquid interface
is stable (i.e., local protrusions are NOT stable)
EMA 5001 Zhe Cheng 13 Heterogeneous Nucleation 11
 Temperate Profile & Growth of
a Pure Element Solid (2) - Dendritic Growth
❑Solid grows into supercooled liquid (TS > TL) Solid Liquid
v
▪ Example Ti
Solid Liquid
− Beginning stage of solidification of Heat
supercooled liquid Ti=Tm
▪ Balance of heat flow If local protrusion
 S TS '+ vLv =  LTL ' Solid Liquid
▪ Shape of the solid-liquid interface v
− Planar solid-liquid interface is unstable Assuming NO
temperature change
Heat
(protrusions tend to grow even faster!)
− Form dendrite (branch-like) structures deep in S, L, and at
the S/L interface
TS’ ↓ TL’  v 
▪ Tip growth rate increases as tip radius
decreases
▪ Growth rate approaches zero as
− r increases towards  (i.e., flat)
− r decreases towards r*

EMA 5001 Zhe Cheng 13 Heterogeneous Nucleation 12

 Dendrites in (Metal) Solidification

Ni dendrites (simulated)

Zn
dendrites

H. K. D. H. Bhadeshia
http://www.phase-trans.msm.cam.ac.uk/dendrites.html

Cu
dendrites
http://www.scielo.br/scielo.php?script=sci_art
text&pid=S1516-14392006000400002

https://en.wikipedia.org/wiki/Dendrite_(metal)

EMA 5001 Zhe Cheng 13 Heterogeneous Nucleation 13