Basics and application of

phase-field modeling in
materials science
1 : phase transitions, order
parameters
Mathis Plapp

Laboratoire de Physique de la Matière Condensée

CNRS/Ecole Polytechnique, 91128 Palaiseau, France
Branched growth structures
 A snowflake

Ken Libbrecht, www.its.caltech.edu/~atomic/snowcrystals

 Solidification microstructures

Hexagonal
cells (Sn-Pb)

Dendrites (Co-Cr)

Eutectic colonies Peritectic composite (Fe-Ni)

Interfaces: scales and descriptions
Macroscopic view:
Domains are separated
by sharp boundaries
Free-boundary problems

Mesoscopic view:
Fields are continuous but exhibit
interfaces with internal structure
Phase-field models

Microscopic view:
Matter consists of atoms
Each atom is considered individually
Atomistic methods
 Course outline

Monday: Statistical Mechanics, Phase transitions, Ising model

Tuesday: Continuum description of the Ising ferromagnet

Wednesday: Phase separation in binary mixtures

Thursday: Phase-field models for solidification

Friday: Outlook on various aspects of phase-field modeling

 Bottom-up approach:
from the Ising model
to « model A » (Allen-Cahn)
• J. S. Langer, « An introduction to the kinetics of first-order
phase transitions », in Solids far from equilibrium, Cambridge
university press (1991)
• N. Provatas and K. Elder, « Phase-field methods in materials
science and engineering », Wiley-VCH (2010)
• M. Plapp, « Phase-field models », in Multiphase microfluidics:
The diffuse interface method, CISM lectures 538, Springer (2012)
• M. Plapp, « Phase-field models », in Handbook of Crystal
Growth, Elsevier (2015)
 Some statistical physics
• We will consider a system of fixed volume in contact with a
thermostat (constant temperature). The relevant statistical
ensemble is the canonical ensemble, the relevant thermodynamic
potential is the (Helmholtz) free energy F
• At equilibrium, the probabilities for all states obey the
Boltzmann distribution:

Pi  exp  Ei 
1 1

Z k BT

Z   exp  Ei  F  k B T ln Z
i
Magnetic domains

• In magnetic
materials, magnetic
moments can show a
cooperative behavior
• Can change
macroscopic behavior
(ferromagnetism)
The Ising model
• Toy model for
ferromagnetism
• N Atoms carry a single spin
that can have values ±1
• Spins interact only with
their nearest neighbors, and
with an external magnetic
field h

N
H   J  S i S j  h S i
i,j i 1
 Simple : single spin
A single spin can have only two states: + and -

Z  exph   exp h   2 coshh 

Probabilities:
exp h  exp  h 
P  P 
Z Z
Magnetization:
1 
m  S   1P   1P  tanh h   log Z
 h
Paramagnetic behavior

 h 
m  tanh  
 k BT 

• Strong magnetic fields align the

spins
• High temperature creates
disorder (high entropy)
• Competition between energy
and entropy
 Complete partition function:
you can try, but …
A system of N Ising spins has in total 2N microstates.
In the presence of interactions, the energies are not easy to
enumerate
→ the calculation of Z is difficult and complicated !!!!

One possible solution :

Numerical simulations with

the Monte Carlo method
 The Metropolis algorithm
We want to evaluate a partition function (or an energy, or a
magnetization) : how to find the « important » configurations ?

• Choose an arbitrary initial state. Calculate its energy.

• Choose a possible move (for example, return a spin). Calculate
the change in energy DE between initial and final state.
• If DE is negative, accept the move
• If DE is positive, accept the move with a probability
P  exp DE
• In practice, draw a random number between 0 and 1, and
complete the move if it is smaller than P
• Repeat. After enough steps, the correct equilibrium is reached
Example: Ising model

kBT/J = 4
Example: Ising model

kBT/J = 1
Ising model: phase diagram

There is a phase transition between paramagnetic

and ferromagnetic state !
 Interacting spins:
mean-field approximation
• A single spin in the average field created by the neighbors
• Each neighbor has a magnetization m, so the effective field is

h eff  h  zJm
• Self-consistent treatment: m must also be the result of

m  tanhheff   tanhh  zJm 

• For h=0, 3 solutions for T<Tc, 1 solution for T>Tc with

k B Tc  zJ
 Alternative approach
Let us calculate directly the free energy as a function of m
F  U  TS
The internal energy U is the average of the Hamiltonian:

U  H   J  S iS j  h S i
i,j i

If we neglect the correlations between the spins, we get

Nz 2
U  J m  hNm
2
 Entropy
Boltzmann : the thermodynamic entropy is given by the log
of the number of microstates

S  k B log W
N N!  1 m 
W     N   N 
 N   N  ! N  N  !  2 
Stirling’s formula, log N! ~ N log N for large N, yields

 1  m   1  m   1  m   1  m 
log W   N   log    log  
 2   2   2   2 
 Free energy
Putting all parts together, we obtain

F zJ 2  1  m   1  m   1  m   1  m 
  m  hm  k B T  log    log  
N 2  2   2   2   2 

A Taylor expansion of all the log terms up to 4th order yields

F zJ 2  1 2 1 4
 f   m  hm  k B T  ln 2  m  m 
N 2  2 12 

f
kB
T  Tc m 
2 k BT 4
m  hm
2 12
 Landau theory
The free energy can be written as

f  T  Tc m  m  hm , a, b  0
a 2 b 4
2 4

• Similar expressions can be written for all phase transitions

if the right order parameters are identified.
• The form of the polynomial depends only on the dimensionality
of the order parameter and the symmetries of the Hamiltonian
• Can predict singular behavior at the critical point
 Critical behavior
The equilibrium magnetization minimizes the free energy:

f ' m  0  aT  Tc m  bm  h3

For h=0, solutions are m*=0 for T>Tc and

m 0
* m*

aTc  T
m 
*

b Tc T

for T<Tc
 Magnetic susceptibility
The equilibrium magnetization depends on h !
For small magnetic fields, the equation can be linearized

m h   m 0   m 0 
h h
 
* * *

2aTc  T f ' ' m 0

*

The magnetic susceptibility is given by

m *
T  
1 1
 
h h0

2aTc  T  f ' ' m 0 
*

Inhomogeneous systems

 • The magnetization
varies between different
domains
• Idea: coarse-graining
• Need to take into
account interactions
between neighboring
cells
1
mI   Si
   i incellI
 Gradient square term
• We suppose that ℓ is big enough to do thermodynamics
(entropy …)
• We need to re-evaluate the internal energy. For cell I:

U  J  I J
m 2

inner pairs
m m I
boundary pairs
J

• We use:

2 2
 m I m J  m I  m J  
1 m m

2 I J
2 2 2
 Total free energy
J
F    f m I  
2
 mI  m J 2

I 2 I ,J
In the continuum limit: Ginzburg-Landau free energy
functional

K 
F    m   f m  dV
J
K
2

V 
2 

!! Attention !! Supposes that there is a scale hierarchy:

Lattice spacing << ℓ << scales of interest

 Dynamics
• There is no conservation law or constraint attached to spins,
they can flip freely → the magnetization is non-conserved
• From linear response theory (or the master equation) we can
obtain that the rate of change is proportional to the
thermodynamic force, and the system evolves toward a
minimum of F

m
t
 
F
m

  K m  f m 
2

Allen-Cahn equation or model A
 Summary
• The Ising model is a simple top model for the ferromagnetic
to paramagnetic transition
• Can be studied by computer simulations with the Monte
Carlo method
• Mean-field theory gives a qualitative explanation for the
phase transition
• Similar theories can be formulated for any phase transition
if the right order parameters are identified (Landau theory)
• For inhomogeneous (polydomain) systems, coarse-graining
yields a Ginzburg-Landau free energy functional with a square
gradient term and a double-well potential