Chapter 4b: Nucleation and Growth

• Homogeneous and heterogeneous

nucleation, and energetic
• Growth of metal crystals and formation of
a grain structure
r*
• Crystal growth in industry: polycrystalline
and single crystal (pp. 133-138)

r*
1. Chapter 4.1-4.2 in Smith & Hashemi
2. Crystal growth for beginners: fundamentals of nucleation, crystal growth, and
epitaxy, by Markov I.V., World Scientific, 1995.

Chapter 4

4.8 Solidification of Metals

Solidification of a metal or alloy can be divided into the following steps:

1. The formation of stable nuclei in the melt – nucleation
2. The growth of nuclei into crystals and formation of a grain structure
(Note that the grains are randomly oriented)

Chapter 4

1
 4.9 Formation of Stable Nuclei in Liquid Metal
Two main mechanisms of solid particle nucleation in liquid metal
- Homogeneous nucleation: the formation of very small region of a new phase
(called nuclei) in a pure metal that can grow until solidification is completed

Embryo Critical size nucleus Nucleus

Nucleus size increases

- Heterogeneous nucleation: the formation of a nuclei of a new solid phase at the

interfaces of solid impurities.
These impurities lower the critical size at a particular T of a stable nuclei
Metal Freezing Heat of fusion Surface Maximum
Temp. (J/cm3) energy undercooling
oC K (×107, J/cm2) observed (∆T [K])

Pb 327 600 280 33.3 80

Cu 1083 1356 1826 177 236
Pt 1772 2045 2160 240 332

Chapter 4

Homogeneous Nucleation
• Even if T <Tm (Tm – the equilibrium phase coexistence temperature or melting point),
it may not occur immediately
• Driving energy for the liquid-to-solid transformation is the difference in the volume
free energy ∆µ of the liquid (L) and that of the solid (S)

V, µL V, µS

Consider a spherical solid “droplet” surrounded by an

Liquid
undercooled melt
solid - if T < Tm, where Tm – the equilibrium phase coexistence
r temperature (or melting point); thus µS < µL

T < Tm - but there is also an energy associated with the interface

(or surface energy, specific surface free energy - γ)
Compared to the homogeneous liquid phase, the presence of the sphere droplet
changes the free energy (∆G) by:
4 Πr 3 The surface area of a sphere of radius r is A = 4 Π r2
∆Gtotal = ∆µ + 4Πr 2γ
3 ν A sphere enclosed volume is 4 Πr 3
V=
∆µ = µ S − µ L 3 ν
Chapter 4

2
 Free-energy change vs radius of nucleus

4 Πr 3
∆Gtotal = ∆µ + 4Π r 2γ
3 ν
∆Gtotal – total free-energy change
r – radius of embryo or nucleus
∆µ – volume free energy
γ - specific surface free energy

Two components: (i) volume free-

energy change (∆GV or ∆µ) and (ii)
surface free-energy change (∆GS)

∆µ = µ S − µ L < 0;
µS < µL
(i) is negative, r* - critical radius
-if r < r*, droplet can shrink or dissolve
(ii) ∆GS is positive -if r > r*, droplet grows

Chapter 4

Critical radius, r*
We can find the value of the critical radius by setting:
∂∆GT ∂ ⎛ 4 Πr 3 ⎞ 4 Πr 2
= 0 = ⎜⎜ ∆µ + 4Πr 2γ ⎟⎟ = 3 ∆µ + 4 × 2Πrγ when r = r*
∂r ∂r ⎝ 3 v ⎠ 3 v
4Π r ∆µ2
= −8Πrγ
v
2γv
r* = −
∆µ
Growth cannot proceed until a droplet with
radius at least as large as r* forms

The energy of this critical nucleus relatively to

the liquid phase is:
16Πγ v
3 2
∆G * =
(∆µ ) 2
The probability of this happening by chance is
∆G * 16 Π γ 3v 2
− −
3 kT ( ∆µ ) 2
Pnucleation ∝ e kT
=e
Chapter 4

3
 r* vs undercooling temperature (∆T)
How big is the critical nucleus? And what determines it’s size?
2γv
r* = −
∆µ
• The greater the degree of undercooling ∆T( = T - Tm), the greater the change
in the volume free energy ∆µ (∆GV)
• γ (∆Gs) - no changes as a function of T

• at T→Tm; ∆T → 0; r* → ∞
• at T<<Tm; r* → 0
The critical-sized nucleus is related to
the amount of ∆T by:
r* = 2 γ Tm / ∆Hf ∆T
where r* - critical radius of nucleus; γ−
– surface free energy; ∆Hf - heat of
fusion; ∆T – amount of undercooling at
Critical radius of Cu nuclei vs degree of undercooling which nucleus is formed

Chapter 4

Q.: (a) Calculate the critical radius (in cm and in nm) of a homogeneous nucleus that forms when
pure liquid Cu solidifies. Consider two cases: ∆T (undercooling) = 0.2 Tm, and (ii) ∆T
(undercooling) = 0.02Tm. Use data from Table 4.1 (Tm=1083oC; γ = 177×10-7J/cm3, ∆Hf =
1826J/cm3)
(b) For both undercooling conditions calculate the number of atoms in the critical-sized nucleus

Chapter 4

4
 4.10 Heterogeneous Nucleation
Heterogeneous nucleation: the formation of a nuclei of a new solid phase on
the surface of its container, insoluble impurities, and other structural material
that lower the critical free energy required to form a stable nucleus
2γ × v
r* = −
∆µ
Requirements: (a) The solid nucleating agent (impurity or container) must
be wetted by the liquid metal (similar to wetting process by liquid)
(b) liquid should solidify easily on the nucleating agent

Wetting - low contact angle ( α)

γL
γS α γSL Liquid γ is lower for heterogeneous
nucleation → the total free-
Nucleating agent energy change is lower →
Equilibrium shape and wetting angle → r* is smaller
of the solid on a nucleating agent
Chapter 4

Contact Angle

γL γ L , γ S– surface free energy of liquid (solid)

γS α γSL Liquid γSL – interface energy
Surface tension exerts force along surface at
Nucleating agent
line of intersection
Equilibrium shape and wetting angle
of the solid on a nucleating agent At equilibrium: γL cos α = γ S – γSL (Young’s eq.)

γS > (γSL + γL) complete wetting

γSL > (γS + γL) no wetting, α > 90o

Liquid −γL < (γS + γSL) < γ wetting

Chapter 4

5
 Anisotropy of surface free energy, γ
Consider stepped or (vicinal) surface of 2D solid:
α Starting from plane, addition of
each step adds energy
a n×a
Define β – energy per step
a 1
tan α ~ = steps 1 tan α α
na n = = ≈
unit _ cell na a a
β
γ (α ) = γ (0) + α
a
γ (α) has discontinuous derivative at α = 0; i.e., there is a cusp

A cusp exists at every direction

corresponding to a rational Miller index
(i.e., low index plane, for example:
(100), (111), (110)

Chapter 4

Anisotropy of the γ -plot

• A plot of surface tension has many “cusps”
γ -plot

γ1
γ2

Crystal will seek an equilibrium crystal shape (ECS) determined by

minimum surface e free energy at constant volume
Use Wulff’s Theorem to determine ECS

Chapter 4

6
 Wulff’s theorem
• For a crystal at equilibrium, there exists a point in the interior such that its
perpendicular distance hi from the ith face is proportional to γi

2D ECS

h1 γ1
h2 γ2 γ1 γ2
= = ...
h1 h2

Procedure:
1. given γ(n), draw a set of vectors from a common origin with length hi
proportional to γi, and with directions normal to plane in question
2. construct planes perpendicular to each vector
3. find the geometric figure having the smallest size with non-intersecting
planes
4. this is the ECS (in practice - in 3D)
Chapter 4

ECS
•In equilibrium, shape of a given amount of crystal minimizes the total surface
energy
• For Liquids: spherical shape
• For Solids: Equilibrium Crystal Shape (ECS) has facets

Chapter 4

7
 Example of ECS for a 2D crystal

∫ γdl = minimum for constant area

Suppose γ-plot has only two types of cusps: (10) and (11)
γ10 = 250 ergs/cm; γ11 = 225 ergs/cm

Chapter 4

Consequences for planar surfaces

• There is a tendency for stepped (vicinal) surface to form facets by step bunching
α Driving force → minimize edge energy
a n×a

2n×a
2a
Double step O/Ir(210) → Ir{311} and Ir (110) facets

• Impurity-induced faceting: adsorb

impurities (oxygen, metallic films)
e.g. bcc W(111) → Pt/W{011} and {112}

T.E.Madey, C.-H.Nien, K.Pelhos, Surf. Sci.

438 (1999)191-206 Chapter 4

8
4.11 Growth and formation of a grain structure
When solidification of the metal is finally completed, the crystals (grains) join
together in different orientation and form crystal boundaries (grain
boundaries)

Such solidified metal containing many crystals is said to be polycrystalline

# of nucleation sites → different grain structure (e.g.: fewer nucleation sites

produces a coarse, large grain structure)

1. Equiaxed grains
2. Columnar grains

Chapter 4

4.12 Industrial Growth Processes

• Metals and alloys are cast into various shapes

• Different growth processes for polycrystalline and single-crystal metals

Polycrystal Polycrystal Single

equiaxed columnar crystal
Chapter 4