Interfacial energy

Course: Phase transformations

Level: UG
Author: Satish S Kamath, Department of
Chemical Engineering, NITK-Surathkal
Mentor: M P Gururajan
 Interfacial energy

In materials, the formation of interfaces cost the

system energy. In this animation, we explore the
atomistic origins of the interfacial energy and a
simple model that incorporates the relevant
thermodynamics and geometric factors for
studying the interfaces in a crystalline solid
 Learning objectives
Understand interfacial energy as the excess
free energy associated with the interfaces
Understand the interfacial energy in crystalline
solids in terms of a simple model that
incorporates the relevant thermodynamics and
geometry
Appreciate that interfacial energy is inherently
anisotropic in crystalline solids
 Master layout
Show the soap film stretching define
interfacial energy
Identify the interfacial energy in crystalline
solids as excess free energy associated with
the interface
Build a simple bond-breaking model for
interfacial energy
Show the anisotropy in interfacial energy for a
solid-vapour interface
 Definitions/Key words
Gibbs free energy: G = U + PV T S
Internal energy, U
Pressure, P
Volume, V
Temperature, T
Entropy, S
Enthalpy: H = U + PV
Interfacial energy: excess Gibbs free energy
 Definitions/Key words
Anisotropy: the directional dependence of a
property
Surface tension: interfacial free energy in cases
where the surface energy is independent of
area
 Stepwise description

Soap film F
Area, A

Wire frame

Show a soap film of area A

in a wire frame pulled by a force F
 Stepwise description

Soap film F
Area, A

Wire frame

Increase in area, dA
The area of the film increases by dA
 Work done = Raise in free energy
Free energy of a system with interfacial area A is
G = G0 + A, where is the interfacial energy per
unit area.
dG = dA + A dFdA
Ifinterfacialenergydidnotchangewitharea,
F=thatis,surfacetensionistheexcessfree
energy.However,insolids,becauseshear
stressescanbesupported,interfacialenergycan
changewitharea.So,ingeneral,surfacetension
isnotthesameasinterfacialenergy.

 Stepwise description

Why does the free energy increase at the

surfaces?
Broken bond model

Atom in the bulk:

All bonds are satisfied

Atoms at the surface:

dangling/broken bonds
 Broken bond model

Atom in the bulk:

All bonds are satisfied

Atoms at the surface:

dangling/broken bonds

Broken bonds lead to increase in enthalpy

 Broken bond model

Atom in the bulk:

All bonds are satisfied

Atoms at the surface:

dangling/broken bonds
Broken bonds can also lead to increase in
vibrational entropy
 Broken bond model

Atom in the bulk:

All bonds are satisfied

Atoms at the surface:

dangling/broken bonds
Broken bonds Increase in free energy
 Stepwise description

Let the latent heat of sublimation for a material be

L; let the number of nearest neighbours be z. If an
Avogadro number of atoms (N) evaporate, then, a
total number of zN/2 bonds are borken. Let be
the bond energy. Then, L = zN/2; this implies,
=2L/zN Thus, if a be the number of broken bonds
per unit area of a surface, then the enthalpy
increase is 2aL/zN.
 Interfacial energy anisotropy
In a crystal, the number of broken bonds per
unit area for different planes are different. Thus,
the interfacial free energy for different planes is
different; that is, the interfacial energy is
anisotropic.
With higher temperatures, the contribution from
the interfacial (vibrational) entropy becomes
important; this entropy can overcome the
enthalpy and make the interfacial energy
isotropic.
 Summary
Interfacial energy is the excess free energy
associated with interfaces
Interfacial energy can be understood in terms of
a bond breaking model
Bond breaking model, for a crystalline interface
(with a vapour, for example) indicates that the
interfacial energies are anisotropic
 References/further reading
Phase transformations in metals and alloys,
Porter, Easterling, and Sherif, Third edition,
CRC Press
Materials science and engineering: a first
course, V Raghavan, Fifth edition, Prentice-Hall
of India Pvt Ltd.
 Questions
Calculate the number of atoms per unit area in
(111), (110) and (100) planes of copper (FCC)
with a lattice parameter of 3.61 Angstrom.
19 19 19
Answer: 1.77x10 , 1.08x10 , 1.53x10
The surface energy of a (111) surface of copper
2
is 2.49 J/m ; what is the surface enthalpy of a
(100) surface?

Answer: 2.15 J/m2

 Questions
At low temperatures, the interfacial energy of a
material is anisotropic. As temperature
increases, the anisotropy
(a) increases
(b) decreases
(c) reamins the same

Answer: (b)
 Questions
An atom is on the {100} surface of a bcc crystal.
How many of its bonds are broken?

Answer: 4
 Questions
Consider a cubic lattice of lattice parameter 'a'.
Consider a plane in the lattice described by the
angle that it makes with the x-axis as shown.
Considering the unit length of the interface,
show that the number of broken bonds per unit
area is given by (cos + sin || )/ a 2

a
 Answer
Theanswerfollowsfromthefigurebelowandconsidering
aunitlengthintheperpendiculardirection(tothepage)