Nucleation and growth kinetics

¾ Homogeneous nucleation
¾ Critical radius, nucleation rate
¾ Heterogeneous nucleation
¾ Nucleation in melting and boiling
¾ Growth mechanisms
¾ Rate of a phase transformation

Reading: Chapters 4.1and 4.2 of Porter and Easterling,

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

 Nucleation and growth - the main mechanism of
phase transformations in materials

XαB2
B atoms
X0B
XαB1

XαB2
X0B B atoms

XαB1

XαB2
X0B
XαB1
spatial coordinate

liquid

solid

T
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
 Nucleation
Nucleation can be
Heterogeneous – the new phase appears on the walls of
the container, at impurity particles, etc.
Homogeneous – solid nuclei spontaneously appear within
the undercooled phase.
Let’s consider solidification of a liquid phase undercooled
below the melting temperature as a simple example of a
phase transformation.

supercooled
liquid

liquid liquid

solid solid

homogeneous heterogeneous
nucleation nucleation
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
 Homogeneous nucleation

1 2 liquid
supercooled
liquid
solid

Is the transition from undercooled liquid to a solid

spherical particle in the liquid a spontaneous one?
That is, does the Gibbs free energy decreases?

The formation of a solid nucleus leads to a Gibbs free

energy change of ΔG = G2 - G1 = -VS (GvL – GvS) + ASLγSL

negative below Tm
VS – volume of the solid sphere
ASL – solid/liquid interfacial area always
positive
γSL – solid/liquid interfacial energy
ΔGv = GvL – GvS is the difference between free energies per
unit volume of solid and liquid

at T < Tm, GvS < GvL – solid is the equilibrium phase

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
 Reminder: Driving force for solidification (ΔGv)
When a liquid is cooled below the melting temperature,
there is a driving force for solidification, ΔGv = GvL - GvS
At temperature T*
G Lv = H Lv - T *SLv ΔGv
G Sv = H Sv - T *SSv G
GvS
ΔG v = ΔH v - T*ΔSv
GvL
At temperature Tm ΔT

ΔG v = ΔH mv - Tm ΔSmv = 0
T* Tm
ΔH mv
ΔSmv =
Tm
For small undercooling ΔT we can assume that ΔHv and ΔSv are
independent of temperature (neglect the difference in Cp between
liquid and solid) m m
ΔH v ΔH v ΔT
ΔG v ≈ ΔH mv − T* =
Tm Tm
At any temperature below Tm there is a driving force for
solidification. The liquid solidify at T < Tm. If energy is
added/removed quickly, the system can be significantly
undercooled or (supercooled).
As we will see, the contribution of interfacial energy (γSL)
results in a kinetic barrier for the phase transformation.
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
 Origin of the interfacial energy (γSL)
Consider a solid-liquid interface. Depending on the type of
material and crystallographic orientation of the interface, the
interface can be atomically flat (smooth, faceted) or rough
(diffuse).

liquid liquid

solid solid
G Lv = H Lv - TS Lv
free energies of liquid and solid per unit volume:
G Sv = H Sv - TS Sv
H
H Lv
H Sv

- TS
interface

- Tm SSv
- Tm S Lv

G
γSL
G Sv G Lv

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei spatial coordinate
 Homogeneous nucleation
ΔG = G2 - G1 = -VS Δ Gv + ASLγSL
4
For a spherical nucleus with radius r: VS = π r 3
3
4
ΔG r = - π r 3 ΔG v + 4π r 2 γ SL A SL = 4π r 2
3
interfacial
ΔG energy ~ r2

*
ΔG

r*
ΔG r

volume
energy ~ r3

For nucleus with a radius r > r*, the Gibbs free energy will
decrease if the nucleus grows. r* is the critical nucleus
size, ΔG* is the nucleation barrier.
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
 Homogeneous nucleation
dΔ G
At r = r* = -4 π r 2 ΔG v + 8π r γ SL = 0
dr

r* =
2γ SL
ΔG =
16π γ
* ( ) SL 3

3(ΔG v )
2
ΔG v

2 γ SL
ΔG v =
r*
r = r*
G
GvS

ΔT GvL

T* Tm

Temperature of unstable equilibrium

of a solid cluster of radius r* with
undercooled liquid.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

 Homogeneous nucleation

r* =
2γ SL
ΔG =*16π γ ( )
SL 3

3(ΔG v )
2
ΔG v

The difference between the Gibbs free energy of liquid and

solid (also called “driving force” for the phase
transformation) is proportional to the undercooling below
the melting temperature, ΔT = Tm – T:
ΔH m ΔT
ΔG v =
Tm
where Hm is the latent heat of melting (or fusion)

⎛ 2 γ SL
Tm ⎞ 1
Therefore: ⎜
r =⎜
*
⎟⎟
⎝ ΔH m ⎠ ΔT

ΔG *
=⎜
( )
⎛ 16 π γ SL 3 T 2
m
⎞ 1
⎟
⎜ 3 ΔH 2
⎝ ( m ) ⎟ (ΔT )2
⎠

Both r* and G* decrease with increasing undercooling

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

 Homogeneous nucleation

ΔG
ΔG 1*
*
ΔG 2

r2* r1*
ΔG r
T2 < T1 < Tm

⎛ 2 γ SL Tm ⎞ 1
r = ⎜⎜
*
⎟⎟
⎝ ΔH m ⎠ ΔT

ΔG *
=⎜
(
⎛ 16 π γ SL 3 T 2
m ) ⎞ 1
⎟
⎜ 3 ΔH 2
⎝ (m ) ⎟ (ΔT )2
⎠

Both r* and G* decrease with increasing undercooling

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

 MD simulation of laser melting of Au films
laser pulse 20 nm Au films irradiated by 200 fs laser pulse
1.2
6000
Te
1.15

5000
1.1

T/Tm
Temperature (K)
4000 1.05

1
20 ps 500 ps 3000
Tm = 963 K

0.95
0 100 200 300 400 500
Time (ps)
2000
2
Fabs = 45 J/m

two melting fronts propagate from free

1000
Tl

surfaces, temperature drops (energy goes 0 100 200 300 400 500

into ΔHm×Vl). Melting stops when T Time (ps)

approaches Tm.

1.1

nanocrystalline sample with average 1.05

grain diameter of ~8 nm
Tm = 963 K
T/Tm

0.95

0.9
0 100 200 300 400 500
20 ps 100 ps Time (ps)

melting starts at grain boundaries and continues even after T drops below Tm at
30 ps. The last crystalline region disappears at ~250 ps

MSE 3050, Phase Diagrams andJ.Kinetics,

Lin et al., LeonidCZhigilei
Phys. Chem. 114, 5686, 2010
 MD simulation of laser melting of Au films
The continuation of the melting process below Tm can be explained
based on the nucleation theory
2 γ SL ⎛ 2 γ SL Tm ⎞ 1
4 3 r * = =⎜ ⎟
Δ G r = − π r Δ G v + 4 π r 2 γ SL ΔGv ⎜⎝ ΔH m ⎟⎠ ΔT
3
critical radius at ΔT
⎡ 2 γ SL 1 ⎤ - temperature of the equilibrium between the
T = Tm ⎢1 −
*
⎥
⎣ Δ H m r ⎦ cluster of size r and the surrounding liquid

6000
Number of atoms in the crystalline cluster

835 K
5000 820 K 841 K

4000 T* ≈ 845 K

845 K
3000

844 K

2000
850 K 847 K
840 K
843 K
1000
0 50 100 150 200 250 300
Time (ps)

Critical undercooling temperature

of a crystalline cluster surrounded
by undercooled liquid

Lin et al.,
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
J. Phys. Chem. C 114, 5686, 2010
 Homogeneous nucleation
There is an energy barrier of ΔG* for formation of a solid
nucleus of critical size r*. The probability of energy
fluctuation of size ΔG* is given by the Arrhenius
equation and the rate of homogeneous nucleation is

& ⎛ ΔG *
⎞
N ~ ν d exp ⎜⎜ − ⎟⎟ nuclei per m3 per s
⎝ kT ⎠
where νd is the frequency with which atoms from liquid
attach to the solid nucleus. The rearrangement of atoms
needed for joining the solid nucleus typically follows the
same temperature dependence as the diffusion coefficient:

⎛ Qd ⎞
ν d ~ exp ⎜ − ⎟
⎝ kT ⎠

& ⎛ Q ⎞ ⎛ ΔG *
⎞
Therefore: N ~ exp ⎜ − d
⎟ exp ⎜⎜ − ⎟⎟
⎝ kT ⎠ ⎝ kT ⎠
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
 Rate of homogeneous nucleation

& ⎛ Q ⎞ ⎛ ΔG *
⎞
N ~ exp ⎜ − d
⎜
⎟ exp ⎜ − ⎟⎟
⎝ kT ⎠ ⎝ kT ⎠

⎛ Qd ⎞ ⎛ ΔG * ⎞
exp ⎜ − ⎟ exp ⎜⎜ − ⎟⎟
⎝ kT ⎠ ⎝ kT ⎠
N&

Temperature Tm

ΔG* > Qd ( )
exp − ΔG* kT << exp(− Qd kT)
ΔG* is too high - nucleation is suppressed

ΔG* ≤ Qd ( )
exp − ΔG* kT > exp(− Qd kT)
ΔG*~ 1/ΔT2 – decreases with T – sharp rise of
homogeneous nucleation (diffusion is still active)

exp(− Qd kT) – too small – low atomic mobility

suppresses the nucleation rate
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
 Rate of Homogeneous Nucleation
In many phase transformations, it is difficult to achieve the
level of undercooling that would suppress nucleation due to
the drop in the atomic mobility (regime 3 in the previous
slide). The nucleation typically happens in regime 2 and is
defined by the probability of energy fluctuation sufficient
to overcome the activation barrier ΔG*r:

& ⎛ ΔG *
⎞
N ~ exp ⎜⎜ − ⎟⎟
⎝ kT ⎠

Using ΔG *
=⎜
( )
⎛ 16 π γ SL 3 T 2
m
⎞ 1
⎟
r
⎝ ( )
⎜ 3 ΔH m 2
v
⎟ (ΔT )2
⎠
⎛ A ⎞ where A has a relatively weak
N = I 0 exp ⎜⎜ −
& ⎟
2 ⎟ dependence on temperature (as
⎝ (ΔT ) ⎠ compared to ΔT2)
very strong temperature &
dependence! N

There is critical undercooling for

homogeneous nucleation ΔTcr ⇒
there are virtually no nuclei until
ΔTcr is reached, and there is an
“explosive” nucleation at ΔTcr.
0 ΔTcr ΔT
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
Computer simulation of laser overheating and explosive boiling

rate of homogeneous nucleation (explosive

boiling) increases sharply in a very narrow
temperature range at ~0.9Tspin ⇒ sharp
threshold for laser ablation

Phys. Rev. E 68, 041501 (2003)

overheating and rapid

decomposition into a mixture of gas 50 ps 250 ps
phase molecules and liquid droplets
Appl. Phys. A 114, 11, 2014
http://www.faculty.virginia.edu/CompMat/ablation/animations/
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
 Heterogeneous nucleation

liquid
supercooled
liquid
solid

the new phase appears on the walls of the container, at

impurity particles, grain boundaries, etc.

Let’s consider a simple example liquid

of heterogeneous nucleation of solid
a nucleus of the shape of a nucleus
spherical cap on a wall of a
container. Three interfacial θ γLS
energies: γLC
γLC – liquid container interface, γSC
γLS – liquid-solid interface,
γSC – solid-container interface.

Balancing the interfacial tensions in the plane of the

container wall gives γLC = γSC + γLS cos(θ) and the wetting
angle θ is defined by cos(θ) = (γLC - γSC)/ γLS

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

How about the out-of-plane component of the liquid-
vapor surface tension?

γLS = γSV + γLV cos(θ)

θ = 90º
↓
γLS = γSV

The out-of-plane component of the liquid-vapor

surface tension is expected to be balanced by the
elastic response of the solid, but theoretical analysis is
not straightforward due to an apparent divergence of
stress at the contact line.

See [Physical Review Letters 106, 186103, 2011] for

extracurricular reading

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

 Heterogeneous Nucleation

liquid solid
nucleus

θ γLS
γLC
γSC

The formation of the nucleus leads to a Gibbs free energy

change of ΔGrhet = -VS ΔGv + ASLγSL + ASCγSC - ASCγLC

VS = π r3 (2 + cos(θ)) (1 – cos(θ))2/3
ASL = 2π r2 (1 – cos(θ)) and ASC = π r2 sin2(θ)

One can show that

⎧ 4 ⎫
ΔG het
r = ⎨ - π r 3 ΔG v + 4π r 2 γ SL ⎬ S (θ ) = ΔG hom
r S (θ )
⎩ 3 ⎭

S (θ ) = (2 + cos θ )(1 − cos θ ) /4

2

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

 Heterogeneous nucleation

⎧ 4 ⎫
ΔG het
r = ⎨ - π r 3 ΔG v + 4π r 2 γ SL ⎬ S (θ ) = ΔG hom
r S (θ )
⎩ 3 ⎭
where S (θ ) = (2 + cos θ )(1 − cos θ )2 /4 ≤ 1

At r = r* dΔ G r
dr
(
= - 4π r 2 ΔG v )
+ 8π r γ SL S (θ ) = 0

* 2 γ SL
r = - same as for homogeneous nucleation
ΔG v

ΔG *
= S (θ )
16 π γ SL( ) 3

= S (θ )ΔG *

3 (ΔG v )
het 2 hom

S ( θ ) can be small ⇒ if θ = 10 o
S (θ ) = (2 + cos θ )(1 − cos θ ) / 4 ≈ 10 - 4
2

ΔG*
Active nucleation
starts
ΔG * ΔG *hom
het

cr
ΔT het cr
ΔT hom ΔT

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

 Heterogeneous Nucleation

SL
2 γ
r* = ΔG *
het = S (θ )ΔG *
hom
ΔG v

ΔG

ΔG *hom
ΔG *het

r*

heterogeneous nucleation starts at a lower undercooling

& ⎛ ΔG *hom ⎞
N hom
~ exp ⎜⎜ − ⎟⎟
⎝ kT ⎠ & & het
N & hom
N
N
& het ⎛ ΔG *het ⎞
N ~ exp ⎜⎜ − ⎟⎟
⎝ kT ⎠

& het >> N

N & hom

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

ΔT
 Pre-melting
For solid/liquid/vapor interfaces, often
γSolid-Vapor > γSolid-Liquid + γLiquid-Vapor

in this case, no superheating is needed for nucleation of liquid

and surface melting can take place below Tm ⇒ pre-melting

cross-section of an atomic cluster close to Tm

(simulations by J. Sethna, Cornell University)

Why ice is slippery?

Physics Today,
Dec. 2005, pp. 50-55

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

 Two-step nucleation in solid–solid phase transitions
(extracurricular - not tested)

Fortini & Dijkstra, J. Phys. Condens. Matter 18, L371, 2006

microgel colloidal
spheres with σ ~ 0.7 μm

packing fraction

phase transformations in a system of hard spheres (colloidal particles)

confined between parallel hard plates: 1∆ → 2□ → 2∆ → 3□ → ... →
n∆ → (n + 1)□ → (n + 1) ∆ → ..., where where n is the number of
crystal layers, and the phases have triangular (∆) or square (□) symmetry

single-particle resolution Yi Peng et al. Nature Mater. 14, 101, 2015

video microscopy of a
transition from square to
triangular lattice in a
colloidal film

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

 Two-step nucleation in solid–solid phase transitions
(extracurricular - not tested)
two-step nucleation with an intermediate liquid phase when γS-L < γS1-S2

Yi Peng et al. Nature

Mater. 14, 101, 2015

single-particle resolution video

microscopy of a transition
from square to triangular
lattice in a colloidal film

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

 γLV (T, C) → Marangoni effect (extracurricular - not tested)

The decrease of surface energy of

a liquid with increasing T can be
described by a semiempirical
equation:
γ LV ≈ γ LV (1 − T / Tc )
0 n

γ 0LV − value of γ LV extrapolat ed to 0 K

n ≈ 1.2 for metals
γ LV → 0 when T → Tc
liquid becomes indistinguishable from gas

T + ΔT
gradient of chemical
composition
or temperature

gradient of
surface tension
alcohol high γ
Marangoni effect - evaporation
low γ
flow along the gradient
of surface tension

tears of wine: flow from regions with higher concentration of

alcohol (lower γLV) to regions where concentration of alcohol
decreased due to evaporation (higher γLV)
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
γLV (T, C) → Marangoni effect (extracurricular - not tested)
Marangoni effect in laser synthesis of TiN: surface-tension-driven
convection has to be accounted for to explain experimental observations
Höche & Schaaf, Heat and
Mass Transfer 47, 519, 2011

strong dependence of Tm on XN
N concentration gradient
⎛ ∂γ LV ⎞ resolidification starts at surface
⎟ ≈ 0.24 mJ m K
-2 -1
⎜
⎝ ∂T ⎠ P

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

 Growth mechanisms

The next step after the nucleation is growth. Atomically

rough (diffuse) interfaces migrate by continuous growth,
whereas atomically flat interfaces migrate by ledge
formation and lateral growth.

liquid liquid

solid solid

The rate of the continuous growth (typical for metals) is

typically controlled by heat transfer to the interfacial
region for pure materials and by solute diffusion for alloys.

Growth in the case of atomically flat interfaces can proceed

from existing interfacial steps (e.g. due to the screw
dislocations or twin boundaries) or by surface nucleation
and lateral growth of 2D islands.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

 Growth mechanisms

Smooth solid-liquid interfaces

typically advance by the
lateral growth of ledges.
Ledges can result from
surface nucleation or from
dislocations that is
intersecting the interface.

Spiral growth on dislocations

AFM images of growing crystal
of KDP (potassium dihydrogen
phosphate) by De Yoreo and
Land, LLNL and Malkin and
Kuznetsov, University of California

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

 Growth: Temperature dependence
In multi-component systems, non-congruent phase
transformations typically involve long-range diffusion of
components necessary for achieving the equilibrium phase
composition.

⎛ E ⎞
D = D 0 exp ⎜ − d ⎟
⎝ RT ⎠

The atomic rearrangements necessary for growth of a one-

component phase or growth in a congruent phase
transformation also involve thermally-activated elementary
processes (diffusion). When growth is diffusion
controlled, it slow down with decreasing temperature.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

 Rate of phase transformations

Total rate of a phase transformation induced by cooling is a

product of the nucleation rate (driving force increases
with undercooling but diffusion needed for atomic
rearrangement slows down with T decrease) and
growth rate (diffusion controlled - slows down with T
decrease).

overall transformation rate

growth
rate

nucleation rate

temperature Tm
high T (close to Tm): low nucleation and high growth rates
Æ coarse microstructure with large grains
low T (strong undercooling): high nucleation and low
growth rates Æ fine structure with small grains
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
 Surface energy of crystals, γSV
directional dependence of the surface energy in crystals: the
number of broken bonds in an fcc crystal increases from {111} to
{100} to {110} faces and, in general, Hs can be expected to be
higher for high {hkl} index of the crystal face.

{111} {100} {110}

θ
a face at an angle θ
to a low-energy
close-packed plane
energy per unit
surface area:
a
E SV = (cos θ + sin | θ |)ε / a 2
E SV
where ε is the surface energy of
close-packed plane per area of a2

although surface entropy

contribution may smooth the
energy cusps, the cusps are still
0 θ
present in γ(θ)
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
 Growth mechanisms – directional dependence
The shape of a growing crystal can be affected by the fact that
different crystal faces have different growth rates. Close-packed
low-energy faces tend to grow slower and, as a result, they are
the ones that are mostly present in a growing crystallite.

For example, water ice I(h) has

hexagonal crystal symmetry
that is reflected in the
symmetry of snow crystals.
The growth rate is fast parallel
to the basal {0001} and prism
{1010} faces. As a result, very
small snow crystals have shape
of hexagonal prisms. As they
grow, growth instabilities
result in more complex shapes
of larger snow crystals.

MSE 3050, Phase Diagrams and Kinetics, Leonid

P. V. Hobbs, Zhigilei
Ice Physics, Oxford Univ. Press, Oxford, 1974.
 Growth instabilities, dendrites
Material and heat diffusion limits the rate at which a crystal can
grow, often greatly affecting the shape of the growing crystals.

An example is the Mullins-Sekerka supersaturated

instability. Consider a flat solid surface vapor
growing into a supersaturated vapor. If
a small bump appears on the surface, crystal
then the bump sticks out farther into the
supersaturated medium, and hence
tends to grow faster than the
surrounding surface.

As a result the flat

growth is unstable, and
a crystal tend to grow
into more complex
shapes, e.g. snowflakes

MSE 3050, Phase Diagrams and Kinetics,http://www.its.caltech.edu/~atomic/snowcrystals/

Leonid Zhigilei
 Patterns of snow crystals:
“A letter from the sky”

Nakaya diagram: The shape of snow crystals

depends on the temperature and humidity of the
atmosphere in which they have grown.
Vertical axis shows the density of water vapor in
excess of saturation with respect to ice.
The black curve shows the saturation with
respect to liquid water as a function of
temperature.
Physics Today, Dec. 2007, pp. 70-71, 2007

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

http://www.lowtem.hokudai.ac.jp/ptdice/english/aletter.html
 Two-dimensional ice dendrites on windows

by Harry Bhadeshia

by Nadezhda Bulgakova
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
 Water dendrites in ice

http://www.msm.cam.ac.uk/

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Crystal growth and heat flow during solidification
Thermal dendrites

Bragard et al., Interfacial

Science 10, 121, 2002

microstructure of a metal ingot

http://www.msm.cam.ac.uk/phase-trans/
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
 Crystal growth and heat flow during solidification
Thermal dendrites

liquid
metal

cold
mould

heat flow

What are the processes leading to the

formation of the microstructure
schematically shown in this figure?

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

 Summary
Make sure you understand language and concepts:

¾ Homogeneous nucleation
¾ Interfacial energy
¾ Critical radius, nucleation rate
¾ Heterogeneous nucleation
¾ Temperature dependence homogeneous and
heterogeneous nucleation rates
¾ Nucleation in melting and boiling
¾ Nucleation in solidification
¾ Growth mechanisms
¾ Rate of a phase transformation
¾ Growth instabilities, dendrites

H. Imai and Y. Oaki, MRS Bulletin 35, February issue, 138-144 (2010)

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei