Thermodynamics of surface and interfaces (Gibbs 1876

-78)
J. W. Gibbs, collected works, Yale Univ. Press, New Haven, vol.1(1957), p. 219 ~ 331.

Define :
Consider to be a force / unit length of surface perimeter.
(fluid systems)

If a portion of the perimeter moves an infinitesimal of distance in the plane

of the surface of area A, the area change dA is a product of that portion of
perimeter and the length moved.

Work term - dA; force x distance, and appear in the combined 1st
and 2nd laws of thermodynamics as

dU TdS pdV i dN i dA
i
Strictly speaking , is defined as the change in internal energy when
the area is reversibly increased at constant S, V and N i (i.e., closed
system).
For a system containing a plane surface this equation can be reading integrated
:
U TS PV i N i A
i

and rearranging for yields.

1
U TS PV i N i
A i

where U TS + PV is the Gibbs free energy of the system.

And N
i
i i
is the Gibbs free energy of the materials comprising the
system.

Thus is an excess free energy due to the presence of the surface.

def Surface Excess Quantities

Macroscopic extensive properties of an interface separating bulk phases

are defined as a surface excess.
There is a hypothetical 2D dividing surface defined for which the
parameters of the bulk phases change discontinuously at the dividing
surface.

The excess is defined as the difference between the actual value of the
def
extensive quantity in the system and that which would have been
present in the same volume if the phases were homogeneous right up to
the Dividing Surface i.e.,

x x
s total
x x


The real value of x in The values of x in the homogeneous
the system and phases
 Solid and liquid Surfaces
In a nn pair potential model of a solid, the surface free energy can be thought
of as the energy/ unit -area associated with bond breaking. :

n
work/ unit area to create new surface = 2
A
where n/A is the # of broken bonds / unit-area and the is the energy per
bond i.e., the well depth in the pair-potential.

Then letting A = a where a lattice spacing
2
2
2a
 pair potential
If the solid is sketched such that
U(r) the surface area is altered

a a da
r A A dA
the energy d

The total energy of the surface U S Asurf .is changed by an amount.

dU dA Ad

and dU d
f A
dA dA
 Surface Stress and Surface Energy

Then in general the relationship between surface stress and surface

energy is given by,

f ij ij i, j 1,2
ij

For a surface with 3-fold or higher rotational symmetry fij is isotropic

and the surface stress can be treated as a scalar.

d
f A
dA
def

f - The surface stress is the reversible work/unit area associated with the
creation of new surface while altering its density by elastic stretching
or
compressing.
dU d
f A for an isotropic surface
dA dA
For an anisotropic surface f is a tensor quantity and

f ij ij
ij
where A A0 (1 ij ) double sum in the strains and dA ij .
A
 The anisotropy of surface energy
Surface energy is a function of orientation crystalline solid. For a liquid is
isotropic and the equilibrium shape minimizes the surface / volume ratio. For
example, the equilibrium hape of a soap bubble is a sphere.

Experimentally it has been found that cuts of crystals off a low index
orientation equilibrate to form stepped structures such that the steps are
composed of low-index surfaces.
broken bond

( 1 0 ) plane
Bond density along direction defined by is greater than the bond density
along a low index direction owing to step structure.

In a nn. central force model, for surfaces forming a stepped structure

is given by:

cos sin
a2 2
where a (lattice parameter) is the unit of length and /2 the bond energy,
is the mis-orientation with respect to a low-index plane.
Polar Plot of

cusps @ 0
(10)

Low-index plane have cusps in

plots at 0 K which tend to get
rounded off at higher temperatures.
Example of a 2D polar plot of
(01)
(11)

(10)

Inner envelope of normals

defining the equilibrium of shape
of crystal.

Equilibrium shape of a crystal obtained when A minimum

planes
i i

and this is given by the Wolffs theorem.

Wulff construction

Wulffs theorem : The equilibrium shape is obtained by taking the inner

envelope of the normals. This envelope defines a shape geometrically
similar to the equilibrium shape of the crystal

Any surface which does not appear in the equilibrium shape can lower
its energy by forming a stepped structure, composed of planes which do
appear in the equilibrium shape.
 Often actual morphologies are determined by kinetic considerations.

Suppose the velocity of the interface is controlled by surface diffusion.

(01)
(11)
Einstein mobility relation

(10) MF

If the temp. dep M is about the same for all the orientation v is determined
by F. Generally the lower , the higher F so: e.g.
 ( 01) (11) ; F( 01) F(11) ; v( 01) v(11)

Faster growth
Slower growth

Faster growth
 The surfaces which grow faster tend to shrink in
size.
Growth of crystals occur by a ledge process.

Fast

Slow

Faster faces grow out; overall growth tends to be limited by slowest faces.
 Types of Interfaces
(a) solid / vapor
(b) liquid / vapor
(c) solid / liquid
chemical

(d) Solid / solid

structural

Estimation of interfacial energies

Recall: Z a / 2
where is the bond energy, Z is the number of near neighbors
and a is the atom density of surface.
For the solid / vapor interface -

Lsublimation Lvap L fusion

sv Z a / 2 Lsub
For the liquid / vapor interface -

Lv Z a / 2 Lvap
For the solid / liquid interface entropic effects dominate.

SL Z a / 2 S fusion T

Note the temperature dependence.

L fus
S fusion
Tm
For many situations, these values provide reasonable estimates.
 Values of SV Values of LV

SV ( J / m2 ) SV ( J / m2 ) T (C) LV ( J / m2 )
near Tm @ 25C
H2O 25 0.072
Sn 0.68 MgO 1.0
Pb 350 0.442
CaF2
Ag 1.12 0.45 Cu 1120 1.270
(111)
CaCo3 Ag 1000 0.920
Pt 2.28 0.23
(1010) Pt 1770 1.865
LiF NaPO 620 0.209
Cu 1.72 0.34
(100)
FeO 1420 0.585
NaCl
Au 1.39 0.30 Al2O3 2080 0.700
(100)

Note that near Tm, lv ~ sv.

 Values of SL (inferred from nucleation exp)

SL ( J / m2 ) near Tm
Al 0.093
Cu 0.177
Fe 0.204
Pb 0.033
C2H2(CN)2 [succinonitrile] 0.009
Nylon 0.020

Temperature dependence of ( solid / vapor, liquid / vapor ) recall that

for a 1 component system:

d sdT vdP s
T p
and for metals s 10 3 J / m 2 oK weak T dependence
 Solid / Solid Interfaces

Consider a general inter-phase / boundary. can be thought of as being

composed of 2 terms :
(i) Chemical bonding
(ii) Structural bonding ( say phases have different crystal structure)

chemical structural

Chemical contribution to chemical :

x x is the mole fraction of A in

x x is the mole fraction of A in

y (distance)
 Regular solution model of an interfaces (Becker 1938)

Let U(x1, x2) be the sum of the bond energy per unit area between
planes of composition x1 and x2

U x1, x2 Z a / 2 x xVAA 1 x 1 x VBB x 1 x 1 x x VAB
where VAA, VBB, and VAB are the bond energy.

In analogy with the regular solution model we define an excess energy,

Ui, due to the interface:

U i U x , x 1/ 2 U x , x U x , x a / 2 x x
2

where Z V AB 1 / 2V AA VBB

can be estimated from /2R = T critical (see Reg. Sol. Theory)

 For metal / metal interfaces :

a / 2 1019 / m 2 ~ 0.1 eV / atom 10-20 J / at

For close to pure metal interfaces :

x 1, x 0

so U i ~ 10 1 J / m 2

Typical values of lattice matched (coherent) interfaces energies range from 10 -3 ~

10-1 J/m2.
 * The diffuse chemical interface (1-D estimates)

x
x

y (distance)
a

a
interplaner spacing

x variation in the mole fraction of A atom 1 plane to the next

U i a / 2 x x
2
generalize to a continuum

2
xi x ,i1
U i a / 2 a
2

i
a

x i x ,i 1 dx a dy

2 2
dx dx
Ui a a2
/ 2
K1
dy dy
composition gradient
K1 Gradient energy coefficient in 1D

* important in spinodal decomposition

 Cahn Hilliard Free Energy (1958)

Consider a small region of material with a chemical inhomogeneity. :

The free energy per unit volume can be thought of as being composed of
two terms:
(i) g0(C) homogeneous free energy per unit volume, if the material was of
homogeneous composition ( Regular sol. Model)
(ii) g i(C) inhomogeneous free energy owing to the presence of the
compositional gradient K(C)2

The total free energy is expressed as a functional ( a function of a

function) i.e.,
G g 0 (c) K (C ) 2 dV
V

for metals K 10-19 J/m

 Structural Interfacial energy:
( to be discussed in more detail later, see coherence)

Classification of structural interfaces:

(i) Coherent (i i) Incoherent
lattice matched systems
some xtal structure or
( 1 1 1 )fcc / ( 0 1 1 )hcp
or ( 1 1 1 )fcc / ( 1 1 0 )bcc and etc.

The structural misfit energy is most easily accommodated by forming

misfit dislocation in the interface.
 a a
Def misfit m
a
For large m misfit dislocations form.

Grain boundaries, twin boundaries, stacking faults are examples of

structural interfaces which can have ( 1 component ) no chemical term.
 Grain boundaries
Gbs are incoherent interfaces defined by the relative misoreintation between
grains.
To specify a gb define the orientation of the crystallites with respect to one
another and the orientation of the boundary with respect to one of the
crystallites.
In 3D the specification of 3 angles ( with respect to the coordinate axes) is
necessary to describe the relative orientation between crystals and 2 angles
specify the boundary orientation with respect to one of the crystal axes. ( see
Bollman, 1970, crystal defects and interfaces)
 Cut ABCD
z
Rot @ x-axis Rot @ y-axis
B C

D y
A
Tilt boundary x Twist boundary

Consider the triple point of a gb junction:

13 Grain 1

Grain 3 23 12
12
13 Grain 2
23
Herring (1951) showed that by balancing the forces for a virtual change in
the orientation of the triple junction :

13
d 23

12

d 13
23
23 13
12 23 cos 13 13 cos 23 sin 23 sin 13
23 13
i
where the terms are called surface torque terms.

i
For high angle gb the torque terms can be neglected and

12 13 23

sin 12 sin 13 sin 23
 Wetting (Contact) Angle
Force Balance
LV
SV SL LV cos
SV SL

Def
s SL SV
solid
s
cos
LV

is called the wetting or contact angle.

 s
s SL SV cos
LV

s LV =0 Complete wetting

s 0 < 90

s 0 > 90

s LV > 180 No wetting