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-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)
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
1
U TS PV i N i
A i
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
f ij ij i, j 1,2
ij
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.
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)
(10)
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.
(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
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 -
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
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)
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
d sdT vdP s
T p
and for metals s 10 3 J / m 2 oK weak T dependence
Solid / Solid Interfaces
chemical structural
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.
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
so U i ~ 10 1 J / m 2
x
x
y (distance)
a
a
interplaner spacing
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
D y
A
Tilt boundary x Twist boundary
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
s LV =0 Complete wetting
s 0 < 90
s 0 > 90