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Surface Energy,

Surface Tension & Shape of Crystals

Part of

MATERIALS SCIENCE
& AALearners
LearnersGuide
Guide
ENGINEERING
AN INTRODUCTORY E-BOOK

Anandh Subramaniam & Kantesh Balani


Materials Science and Engineering (MSE)
Indian Institute of Technology, Kanpur- 208016
Email: anandh@iitk.ac.in, URL: home.iitk.ac.in/~anandh
http://home.iitk.ac.in/~anandh/E-book.htm

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

Note the facets

Electrodeposited nanocrystalline Al-Mg alloy powders


(Photo courtesy: Dr. Sankarasarma Tatiparti)
Video: Dendritic
Video: Dendritic
growth
growthofofcrystal
crystal
from
frommelt
melt

KDP crystals grown from solution

What is a surface and what is an interface?


A cut through an infinite crystal creates two surfaces.
The joining of two phases creates an interface.
(Two orientations of the same crystalline phase joined in different orientation also creates an interface called a
grain boundary).

Cut and Separate

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)

How to understand surface energy?

We use a crystal to understand the concept

Consider the following dialogue:


Kantesh: I suffered a loss of 4 crore rupees!
Anandh: How did that happen?
Kantesh: Last year I got a profit of 14 crores and this year I got a profit of only 10 crores- that is a loss
of 4 crores!!
Did Kantesh really suffer a loss?!!
The accounting leading to the concept of surface energy is similar to the dialogue above (in some
sense).
To understand this further let us do the following ideal thought experiment:
(i) start with atoms far apart (upcoming figure)
such that there is no bonding (interactions) between them
(ii) bring the atoms close to form a bonded state with a surface
Let the energy of the unbonded state be zero. Let the energy lowering on bond formation be E b per
bond.
Each bulk atom is bonded to 4 atoms (as in the upcoming figure)
Energy lowering of bulk atoms = 4Eb this is negative energy w.r.t to the unbonded state
Each surface atom is bonded to 3 other atoms only
Energy lowering of bulk atoms = 3Eb this is also negative energy w.r.t to unbonded state!
Cotd...

Energy lowering on the formation of infinite crystal/unit volume =


[ (number of atoms) 4Eb]

This is the surface energy!

The reference state for


the surface energy is the
bonded state and not the
free state

Energy of a crystal with a free surface/unit volume =


[ (number of atoms) 4Eb] + [(number of surface atoms) 1Eb]
An alternate calculation without invoking surface energy
Energy of a crystal with a free surface/unit volume =
[ (number of bulk atoms) 4Eb] [(number of surface atoms) 3Eb]

Schematic not to scale

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

What is a broken bond?

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.

Partly bonded surface atoms

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

Surface Energy Surface Tension

SOLIDS

Surface Energy Surface Tension


Except in certain circumstances

+ Surface energy is Anisotropic

A comparison of the solid and liquid surfaces


Surface Energy
Surface Tension

LIQUID SURFACE

Characterized by one number the surface density

Liquids cannot support shear stresses (hence use of the term surface tension)
Surface Energy
Surface Stress (Tensor)
Surface Torque

SOLID SURFACE

Has a structure and hence more numbers may be needed


to characterize a solid surface
Crystalline surfaces all the lattice constants will be required
Amorphous surfaces Density + a Short Range Order parameter

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

Liquid surfaces are characterized by a single parameter: the density (atoms /


area)
The short range order in liquids (including their surfaces) is spatio-temporally
varying hence no structure (and no other characteristic) can be assigned to the
surface
Crystalline solids have a definite structure in 3D and hence additional parameters
are required to characterize them
The order at the surface of a crystal can be different from the bulk
Amorphous solids have short-range order, but NO long-range order. Under low
temperature conditions and short times (i.e. low atomic mobility regimes) the
atomic (entity) positions are temporally fixed

Funda Check

What leads to an increased interface energy?

We will try to make heuristic arguments to understand interface energy.


As we have already noted surface is a special kind of interface between material and
vacuum/air.
If the material on the two sides are similar, then the interface energy is low.
More the difference in the nature of the two materials more will be the interface
energy.
Similarity can be based on: (i) atomic structure (including crystal structure, mismatch in
atomic planes, etc.), (ii) bonding nature (including valence electron concentration), (iii)
electronegativity difference etc.
Low energy interface if:
Same crystal structure on both sides of the interface, Interface is coherent
(continuation of atomic planes from one side to another), Similar bonding (say metals
on both sides with similar valence electron concentration) or in more general terms
similar electromagnetic structure, Atoms with similar electronegativity on both sides,
etc. (The orientation of the crystals and interface also plays an important role).
High energy of interface if:
Bonding is different, Crystal structure is different, Interface is incoherent.
We have focused on interface between crystalline materials above. Interfaces can be
between amorphous and crystalline, crystalline and quasicrystalline etc.

Some more mathematical looking concepts!


Some readers may want to skip the pages with too much math and get to pages of interest.

(Surface : Volume) is large

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

The thickness of the interface layer is determined from the equilibrium


constraint that the chemical potential of each species present is constant
throughout the system
Any variation in chemical potential will tend to lead to mass transport

F A nv [ f (c ) k

dc
] dx
dx

Gradient term:
Contribution due to variation
in composition

F Helmholtz free energy


f(c) F per molecule of a homogenous
system of composition c
nv No. of atoms per unit volume
A Cross sectional area
k Constant for small gradients

Geometrical dividing surface


Instead of the diffuse interface a geometrical dividing surface can be used if:
the radius of curvature >> thickness of the transition layer (or dimension of crystal)
The dividing layer is positioned within the transition layer such that each point
on the dividing layer has the same surrounding as the neighbouring points which
lie on the interface
Gibbs method of locating the dividing surface:
chose surface such that surface density of atoms is zero in a one component
system Ns = 0 & N = N1 + N2
In a Multi-component system the surface density of the principal component is
made zero by the choice of the surface

dW the reversible work done at constant (T, V, ) to increase the area by dA


(without changing the volumes (V1 & V2) or states of each phase

d S
dW

dA T ,V , i dA T ,V , i

d d (F G)

Interface

is the change in thermodynamic


potential which characterizes
reversible work at constant (T,V,i)

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

Creation of interface under the constraint of constant chemical potentials


implies the flow of species in and out of the control volume bound by ABCD
If dNi is added or removed from the interface:

dN i
Surface Excess i

dA

+ve or ve depending on if the species


segregates or depletes at the interface

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

Liquid vapor interface (or Liquid-liquid interface)


A Liquid film has equilibrium surface configuration of atoms (or entities)
specified by a certain concentration of atoms (surface density) with a surface
energy
When a Liquid film is stretched, the surface will try to maintain this equilibrium
configuration atoms from the bulk will move to the surface to accommodate
this increase in area (and maintain a constant surface density) possible in
liquid due to high atomic mobility
Additionally, the thickness of the film can adjust freely to avoid any volume
strains in the liquid

Work done in stretching the LIQUID film by dx

In terms of surface tension ()

In terms of surface energy ()

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

The surface atoms show an increased separation as compared to the bulk


This is equivalent to a negative pressure (parallel to surface) surface
tension
The atomic displacements of surface atoms is such that stress to surface
(z = 0) Liquid surface is in a Plane Stress Condition
Increased separation
compared to the bulk

Crude schematic!

Increase in surface area

Solids

Addition of surface atoms


(from bulk)
Bond Stretching

Work required to increase area of a Liquid


Create additional surface having same configuration
Work required to increase area of a Solid
Create additional surface having same configuration
Stretch bonds

Liquids

Solids
Taking the example of crystals

Crystal = Bulk crystal +


Surface crystal (with different atomic configuration than the bulk)

Surface crystal = Relaxed 2D crystal +


Forces at the edges to match it with the bulk
Surface viewed from top

Bulk

Relaxed Surface
Crystal

Forces

Crystal
(Solid)

The forces can be tensile, compressive or shear (any general force)


Force required is reduced by adjustment of atoms in 2 nd and other layers below
the surface crystal ( some tangential forces have to be applied to the layers
below to maintain equilibrium)
The real surface is a few layers deep!
The sum of all the forces (per unit length of edge)
gives the surface tension of the solid
If the surface structure is an extension of the bulk planar structure no stresses
are required for matching the 2D crystal to the remaining bulk
Surface Energy Surface Stress


Components of Surface Stress

x
y
xy yx

Solid surface in condition


of Plane Stress (only )

Effect of Symmetry of the Surface on the Stress Components

Across a line of Mirror


Symmetry the shear
stresses (xy) are zero

xy = 0

For a crystal surface with 3-fold or


higher Rotational Symmetry the
normal stresses across all lines are
equal and shear stresses (xy) are
zero

3-fold

4-fold

6-fold

Illustrated here for the case of 4-fold


A cubic crystal having the same
symmetry on the surface as in the bulk:
4-fold {100} & 3-fold {111} surfaces
have no shear surface stresses and equal
normal surface stresses

For Surfaces with 3-fold


Symmetry or higher

Surface Stress SurfaceTension ( )

y
2

Relation between surface stress and surface energy in solids


Consider the following experiment
1+dx

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

Change in surface energy () on stretching d


new surface energy = ( + d)
Work done on stretching W0
Strain on stretching (dx) = dx/1 = dx

Total Work Done Work Done to Stretch Work Done to Split


W W0 2( d ) (1 dx ) 1 W0 2( d )(1 d x )
B 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

W1 W0 is the work done by the 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

Due to this additional term x

For shearing process (area does not change during shearing)

Shear

Split

Total Work Done Work Done to Shear Work Done to Split


W W0 2( d )(1) W0 2 2d
B

Split

[1]

Shear

Total Work Done Work Done to Split Work Done to Shear

W 2 W1

[2]

Work done by the surface stresses W1 W0 2 xy d xy


[1] [2]

W W0 2 2d 2 W1
W1 W0 2d 2 xy d xy

xy

d xy

This term does not appear for liquids

d
x

d x

xy

d xy

Surface Energy Surface Stress only if does not change with


the stretching process
The equality of and depends on the ability of the surface to maintain its
configuration while stretching i.e. on the mobility of the atoms and the
relaxation time required for the surface atoms to regain their undistorted
configuration by atomic migration
Liquids: trelaxation << tstretch
In crystals for some disordered boundaries: trelaxation ~ tstretch
the boundaries behave as liquid films

Anisotropy in Surface Energy


A crystal plane at a angle to a close packed plane will have will have additional
bonds broken as compared to the close packed plane
Such a surface can be described in terms of ledges and terraces
A general surface described interms of two orientations ( & ) will consist of
ledges and kinks (in the ledges)
Any general orientation within the stereographic triangle (Euler triangle) can be
constructed with a ledges and kinks of certain density in an appropriate terrace
orientation

A
A
Cos
S
S
Cos

( )

Tan

Energy T AT L AL

Area
S

T A L ATan

( )

A Cos

( ) T L Tan Cos T Cos L Sin


( ) T Cos L Sin

Note: the origin of is due to broken bonds!

AL
ATan AL
A

Equation of circle passing through origin

r 2 R Cos( )

r 2 R(Cos Cos Sin Sin )


(2 R Cos ) Cos (2 R Sin ) Sin

r (2 R Cos ) Cos (2 R Sin ) Sin

Comparing with:

( ) T L Tan Cos T Cos L Sin

T (2 R Cos )
L (2 R Sin )

L
Tan
T

The diameter of the circle:

T2 L2 (4 R 2 Cos 2 ) (4 R 2 Sin 2 ) 4 R 2

T2 L2 2 R

( ) T Cos L Sin is the equation of a circle passing through the origin


With diameter (2R) =
2
T

2
L

Centre of Circle O

1
2

T2 L2 , Tan 1

-plot or Wulff plot

( ) T Cos L Sin

Entropy effects are ignored so far


when included the cusps could be less
prominent and could even disappear for high
index planes

In this simplistic model the energy of the ledge L is assumed independent of


the ledge spacing
In reality some ledge interaction will be present L will be a function of
ledge spacing (and thus of the surface orientation)
ledges will be observed for all rational orientations

The orientation dependence of will tend to rotate the surface to a low


energy orientation produce a torque on the surface

( )
Torque term
( )

From -plot to EQUILIBRIUM SHAPE OF CRYSTAL the Wulff construction


Draw radius vectors from the origin to intersect the Wulff plot (OA in Figure)
Draw lines to OA at A (line XY)
The figure formed by the inner envelope of all the perpendiculars is the
equilibrium shape

Wulff plot Equilibrium shape


From the equilibrium shape it is not uniquely possible to construct a Wulff
plot
Wulff plot with sharp cusps equilibrium shape = polyhedron
Width of the crystal facets 1/(surface energy)
largest facets are the ones with lowest energy

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)).

Surface tension force balance



Cos

Cos

(2)

(1)

is the contact angle

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 upper side of banana


leaf

Water on guava
leaf

Water on lotus
leaf

Water on lower side of pipal

A closer look at the upper side


of the lotus leaf!