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ENGINEERING
AN INTRODUCTORY E-BOOK
Shape of Crystals
Let us start with a few observations:
Crystals (which are well grown) have facets
Under certain conditions of growth we may observe tree like patterns known as
dendritic growth
Two kinds of shapes of crystals are important: (i) growth shape and (ii) equilibrium shape
Surface/interface energy plays an important role in determining the shape of a crystal.
Dendritic growth of
crystals
Close to
equilibrium shape
Creation
of a
surface
(or materials)
Creation
of an
interface
Join
(or materials)
Note: Surface can also be thought of a vacuum-material interface (or even a air-material interface)
Hence, we have seen that surface energy is not really an energy in the truest sense it is a correction
coming about because we had over counted the number of fully bonded atoms. (Sir Richard Feynman
may say that all forms of energy are accountants book keeping terms).
However, the effects of surface energy is very real and it is nice to hang on to the concept!
Funda Check
The electron distribution in a material can be viewed in a simplified manner using the language of
bonds. I.e. isolated atoms have a higher energy as compared to the atoms in a solid (we restrict
ourselves to solids for now) and this lowering of energy can be visualized as a bond.
The lowering of energy can be reported as bond energy/bond.
The number and types of bonds an atom forms in the solid state depends on:
broadly speaking the electronic configuration of the constituent atoms
Atoms on the surface have a lower coordination number as compared to atoms in the bulk of the solid.
The missing coordination can be viewed as a broken bond.
The surface need not be a mere termination of the bulk and may undergo relaxation or reconstruction
to lower its energy.
Also the surface may be considered a few atomic layers thick (i.e. it need not just be a monolayer of
atoms).
Surface Energy
Surface Energy and Surface Tension are concepts associated with liquids and solids.
If the Gibbs Free Energy (G) of the solid or liquid is lower than a given gaseous state
under certain thermodynamic parameters (wherein the atoms are far apart without any
interatomic forces), then the gas will condense (and form a solid or liquid).
The lowering in the Gibbs Free Energy is due to the cohesive forces in the liquid or the
bonding forces in the solid.
The lowering in energy is calculated for an atom (or entity) fully bonded.
The atoms on the surface are not fully bonded.
The atoms on the surface have a higher energy than the bulk atoms (in the regime where
the solid or the liquid have a lower energy than the gaseous state).
Hence the reference state for the surface is the bulk and not the gaseous state.
When the calculation of the lowering of the energy of the system on the
formation of the condensed state was done all the atoms were taken into account
(assumed to be bulk atoms) i.e. an over-counting was done
The higher energy of the surface is with respect to the bulk and not with respect
to the gaseous (non-interacting) state
Hence the reference state for the surface is the bulk and not the gaseous state
Hence, it costs energy to put an atom on the surface as compared to the bulk
origin of Surface Energy ()
The surface wants to minimize its area (wants to shrink) origin of Surface
Tension ()
Let us look at the units of these two quantities
Force F
[N ]
Length L
[ m]
Energy E
[ J ] [ Nm] [ N ]
2
2
Area
A [ m ] [ m ] [ m]
Dimensionally and are identical Physically they are different type of quantities
is a scalar while is a second order tensor
LIQUIDS
SOLIDS
LIQUID SURFACE
Liquids cannot support shear stresses (hence use of the term surface tension)
Surface Energy
Surface Stress (Tensor)
Surface Torque
SOLID SURFACE
In the case of solids the term surface tension (which actually should be avoided) refers to
surface stresses
Surface Energy () is the reversible work required to create an unit area of surface
(at constant V, T & i)
Surface Tension () is the average of surface stresses in two mutually
perpendicular directions
x y
Surface stress at any point on the surface is the force acting across any line on the
surface which passes through this point in the limit the length of the line goes to
zero
The definition of surface tension in 2D is analogous to the definition of
hydrostatic pressure in 3D
Funda Check
Surface/Interface Effects
become important
Interface has large curvature
When surface effects are important it is not advantageous to use pressure to
characterize the state of the system as pressure is different across a curved
interface
T and (Chemical potential) are have the same value across the system and
should be used to describe the state of the system
Variation of thermodynamic
function across the interface
Interface
F A nv [ f (c ) k
dc
] dx
dx
Gradient term:
Contribution due to variation
in composition
d S
dW
dA T ,V , i dA T ,V , i
d d (F G)
Interface
Total SurfaceWork S dA
S
V1 V2
C
Phase-1 Phase-2
(AB & CD) S
The equilibrium shape of the interface will be given by the minimum value of
the integral; such that no work is done on the bulk phases
dN i
Surface Excess i
dA
Surface Energy
Pressure is not the same in two phases separated by a curved interface
An equilibrated system have two phases separated by a curved interface is
characterized by T, V and (chemical potential)
Surface energy has a unique value only under equilibrium conditions
Is the reversible work required to create a unit area of the surface at
constant T, V, increase in Helmholtz surface free energy.
FA E A T S A
Work ( L dx ) 2
2 L dx
Work ( x L dx ) 2
2 x L dx
F ( x L)
W ( Force displacement )
Area L dx
L
dx
Crude schematic!
Solids
Liquids
Solids
Taking the example of crystals
Bulk
Relaxed Surface
Crystal
Forces
Crystal
(Solid)
Components of Surface Stress
x
y
xy yx
xy = 0
3-fold
4-fold
6-fold
y
2
Stretch
1+dx
Split
A z y
dx
dx
1+dx
z y
x
Stretch
dx
1
Split
Assume:
Length in y direction is
constant during stretching
Centre of symmetry in the
crystal and the halves to be
equivalent
Stretch
Split
[1]
Stretch
Total Work Done Work Done to Split Work Done to Stretch [2]
W 2 W1
Work done on stretching the split haves W1
is different from the work done in stretching the unsplit haves due to surface stresses
[1] W W0 2( d d x d d x )
[2] W 2 W1
From
[1] [2]
W W0 2( d )(1 d x ) 2 W1
W1 W0 2 d 2 d x ) Work done by the surface stresses 2 x d x
d
x
d x
d
y
Similarly
d y
Shear
Split
Split
[1]
Shear
W 2 W1
[2]
W W0 2 2d 2 W1
W1 W0 2d 2 xy d xy
xy
d xy
d
x
d x
xy
d xy
A
A
Cos
S
S
Cos
( )
Tan
Energy T AT L AL
Area
S
T A L ATan
( )
A Cos
AL
ATan AL
A
r 2 R Cos( )
Comparing with:
T (2 R Cos )
L (2 R Sin )
L
Tan
T
T2 L2 (4 R 2 Cos 2 ) (4 R 2 Sin 2 ) 4 R 2
T2 L2 2 R
2
L
Centre of Circle O
1
2
T2 L2 , Tan 1
( ) T Cos L Sin
( )
Torque term
( )
FCC
Contact Angle
The picture below shows a water droplet on a plant leaf. Note that the droplet has beaded
up. A schematic of the picture is shown in the diagram, with surface (interface) tension
forces included. There are 3 interfaces and correspondingly 3 forces.
The angle that the tangent to the droplet lens at the triple line is called the contact angle
and this angle can be calculated using force balance as below (eq. (1)).
Cos
(2)
(1)
The contact angle changes depending on the substrate (keeping the liquid constant- water
for now).
For most leaves the upper side (adaxial) is less hydrophobic (with a lower contact angle)
as compared to the lower side (abaxial) which is more hydrophobic (with a higher
contact angle). In lotus leaf the upper side is more hydrophobic.
Water on glass
slide
Water on lower side of banana
leaf
Water on guava
leaf
Water on lotus
leaf