Phase transformations

Felipe Castro Cerda, Ph.D.

Bernd Schulz, Ph.D.

1 – Nucleation I

1
1. Overview of nucleation
Nucleation in liquids
Solidification is a process that occurs by
nucleation and growth of a new phase.
Pure element: Equilibrium
G

GS
GL

Tm T 2
1. Overview of nucleation
Pure element: Nucleation
Below Tm, very small crystals will start
forming. Some of them are dissolving into
the liquid phase and some others are going
to grow. The Gibbs free energy of such
particles can be written as

ΔG(r) = ΔGV + ΔGS

3
1. Overview of nucleation
Pure element: Nucleation of spheres

ΔG(r) = 4/3πr3ΔGV + 4πr2γS L

Corresponds to the free

energy of a sphere of radius r
forming in a liquid.

1
.
1

4
 1. Overview of nucleation
Pure element: Nucleation of spheres

ΔG(r) = 4/3πr3ΔGV + 4πr2γS L

For a given undercooling
G ΔT = Tm - T, T < Tm

G(r)S 1
GS .
1
GL

TN Tm T 5
 1. Overview of nucleation
Pure element: Nucleation of spheres

ΔG(r) = 4/3πr3ΔGV + 4πr2γS L

For a given undercooling
G ΔT = Tm - T, T < Tm
ΔG(r)

G(r)S 1
GS .
1
GL

TN Tm T 6
1. Overview of nucleation Task 1:
Plot for T > Tm
and T = Tm

Pure element: Nucleation of spheres

For a given undercooling
ΔT = Tm - T, T < Tm
ΔG(r) = 4/3πr3ΔGV + 4πr2γ S
G
There will be a size for which
4πr2γ S ΔG(r) starts decreasing.
Such value can be determined
by calculating the value of r
for which

dΔG(r)/dr = 0

r
ΔG(r) 7
4/3πr3ΔGV
1. Overview of nucleation Task 2:
Calculate the
derivative and
solve for r
Pure element: Nucleation of spheres
For a given undercooling
ΔT = Tm - T
r = -2γS/ΔGV = r*
G
r* is the critical radius
at which the free
4πr2γ S energy of the sphere
start decreasing, i.e. the
bulk free energy term is
equal to the surface
free energy term.
ΔG(r*)
r* r
ΔG(r) 8
4/3πr3ΔGV
1. Overview of nucleation Task 3:
Calculate
ΔG(r*)

Pure element: Nucleation of spheres

For a given undercooling
ΔT = Tm - T
r = -2γS/ΔGV = r*
G ΔG(r*) is thus the
energy barrier for the
formation of a stable
4πr2γ S nucleus of r > r*.

A sphere of r < r* is
called embryo, whereas
a sphere of r > r* is a
ΔG(r*) nucleus.

r* r
ΔG(r) 9
4/3πr3ΔGV
 1. Overview of nucleation
Pure element: Nucleation of spheres
Example: ΔT = Tm – T1 , T1 > T2 > T3
L
G r > r*1

1
.
ΔG*1 1
r*1 r
ΔG(r, T1) 10
 1. Overview of nucleation
Pure element: Nucleation of spheres
Example: ΔT = Tm – T2 , T1 > T2 > T3
L
G r > r*2

1
ΔG*2 .
ΔG*1 1
r*1 r
r*2

ΔG(r, T1) 11
ΔG(r, T2)
 1. Overview of nucleation
Pure element: Nucleation of spheres
Example: ΔT = Tm – T3 , T1 > T2 > T3
L
G r > r*3
There is a variation of the
critical size and energy
barrier for nucleation as
ΔT is increased.

ΔG*3 1
ΔG*2 .
ΔG*1 1
r*3 r*2 r*1 r
ΔG(r, T1) 12
ΔG(r, T3) ΔG(r, T2)
1. Overview of nucleation
Pure element: Nucleation
The former analysis applies only to
nucleation in the absence of any foreign
particle or surfaces, which is called
Homogeneous Nucleation.

The case when nucleation takes place in the

surface of a substrate (such as impurities, the
mold wall, etc.) is called Heterogeneous
Nucleation.
13
2. Solid-state nucleation
Pure element: Nucleation of spheres

ΔG(r) = 4/3πr3(ΔGV + ΔGε) + 4πr2γS

ΔGε: strain energy associated to elastic strain

14
2. Solid-state nucleation
Pure element: Nucleation of spheres in
absence of volume change
ΔG(r) = 4/3πr3ΔGV + 4πr2γ S
G

4πr2γ S

ΔG(r*)
r* r
ΔG(r) 15
4/3πr3ΔGV
2. Solid-state nucleation Task 4:
Calculate r*
and ΔG(r*)

Pure element: Nucleation of spheres

ΔG(r) = 4/3πr3(ΔGV + ΔGε) + 4πr2γ S

G

4πr2γ S

ΔG(r*)
ΔG(r*)
r*r* r
ΔG(r) 16
4/3πr3ΔGV 4/3π(ΔGV + ΔGε)
2. Solid-state nucleation Task 4:
Calculate r*
and ΔG(r*)

Pure element: Nucleation of spheres

4.00E-10

ε) + 4πr γ S
ΔG(r) = 4/3πr3(ΔGV + ΔGDelta_Gr 2
3.00E-10
G Delta_Gr_e

2.00E-10 Delta_Gs
4πr2γ S Delta_Gv
1.00E-10
Delta_Gv_e

0.00E+00
-1.00E-05 6.00E-20
ΔG(r*) 1.00E-05 2.00E-05 3.00E-05 4.00E-05 5.00E-05
ΔG(r*)
-1.00E-10
r*r* r
-2.00E-10
sigma 0.2ΔG(r)
Delta-Ge 1000 Delta_Gv -20000 17
4/3πr3ΔGV 4/3π(ΔGV + ΔGε)
Summary
A barrier must be overcome
Undercooling is needed for nucleation
The size of the critical nucleus depends on
the temperature

18
Phase transformations
Felipe Castro Cerda, Ph.D.
Bernd Schulz, Ph.D.

1 – Nucleation II

19
 The KS orientation relationship

Atom positions projected onto a Atom positions projected onto a

{111}FCC plane {110}BCC plane

J.M. Rigsbee, H.I. Aaronson, Acta Met. 27, 351-363, 1979 20

 The KS orientation relationship

Atom positions projected onto a Atom positions projected onto a

{111}FCC plane {110}BCC plane

J.M. Rigsbee, H.I. Aaronson, Acta Met. 27, 351-363, 1979 21

 The KS orientation relationship

Atom positions projected onto a Atom positions projected onto a

{111}FCC plane {110}BCC plane

J.M. Rigsbee, H.I. Aaronson, Acta Met. 27, 351-363, 1979 22

2. Solid-state nucleation Task 5:
Calculate nC as
a function of
ΔT
Kinetics: Nucleation of spheres
Let nC be the number of embryos of critical
size in a given volume, it can be showed that

nC = N·exp(-ΔG*/kT)
N: sites per unit volume at which embryos can
form
k: Boltzmann constant

23
2. Solid-state nucleation
Kinetics: Nucleation of spheres
If each nucleus can be made supercritical at a
given frequency f, the rate of nucleation I
can be written as:

I = f·nC
An embryo of size r* will become a nucleus
when it gains one or more atoms.

24
2. Solid-state nucleation
Kinetics: Nucleation of spheres
If the activation energy for the migration of
atoms is ΔGm, the frequency at which the
embryos become stable is

f = w·exp(-ΔGm /kT)

w: factor related to the vibrational frequency

25
2. Solid-state nucleation
Kinetics: Nucleation of spheres
The number of nuclei that appears per unit
volume per unit time is thus

I = f·nC = w·exp(-ΔGm /kT)·N·exp(-ΔG*/kT)

I = A·exp(- (ΔGm +ΔG*)/kT)

26
 2. Solid-state nucleation
Kinetics: Nucleation of spheres

ΔG* increases with ΔT,

related to the density of nuclei
whereas ΔGm is almost
constant. The other pre-
exponential terms are
negligible compared to the
exponential. The rate of
nucleation shows a
maximum at an
intermediate temperature.

,N≈I
related to atomic mobility

Fig 5.4, D. Porter and K. Easterling, “Phase transformations in metals and alloys” 27
 3. Interfaces
Coherent: Occurs when the atoms at the
interface are common to both grains
Incoherent: no match between atoms at the
interface

Fig. 6-2, P. Shewmon, “Transformations in metals” 28

 3. Interfaces Task 6:
Find the K-S
OR in a hard-
ball model
Semi-coherent: The interface has
regions of complete coherency separated by
dislocations An example in Fe: the
Kurjumov-Sachs orientation
relationship

{111}γ {110}α
Fig. 6-3, P. Shewmon, “Transformations in metals”

Fig. 5.15c, J. Burke, “The kinetics of phase transformations in metals” 29

3. Interfaces
What´s the most favorable interface for
nucleation?
ΔG(r) = 4/3πr3(ΔGV + ΔGε) + 4πr2γ S
G

4πr2γ S

ΔG(r*)
r* r
ΔG(r) 30
4/3π(ΔGV + ΔGε)
 4. Heterogeneous nucleation
Nucleation at grain boundaries: The role of
interfacial energy

ΔG(r) = V(ΔGV + ΔGε) + Aγαβ + Aγαα

Fig 5.6, D. Porter and K. Easterling, “Phase transformations in metals and alloys” 31
 4. Heterogeneous nucleation
Nucleation at grain boundaries: The role of
interfacial energy

ΔG(r) = V(ΔGV + ΔGε) + Aγαβ + Aγαα

Fig 6-5, P. Shewmon, “Transformations in metals” 32

 4. Heterogeneous nucleation Task 7:
What is
wetability?

Nucleation at grain boundaries: The role of

interfacial energy

ΔG(r) = V(ΔGV + ΔGε) + Aγαβ + Aγαα

Fig 6-5, P. Shewmon, “Transformations in metals” 33

Summary
Certain ΔT must be attained for rendering
nucleation observable
The kinetics of nucleation follows a “C”
shape
Coherent, semicoherent and incoherent
interfaces will have an impact on nucleation
Nucleation sites, such as grain boundaries,
can reduce ΔG* and the critical volume of
the nucleus.
r*, for a given ΔT, do not depend on the
position of the nucleus 34