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Part of

MATERIALS SCIENCE

& AALearners

LearnersGuide

Guide

ENGINEERING

AN INTRODUCTORY E-BOOK

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

(Photo courtesy: Dr. Sankarasarma Tatiparti)

Video: Dendritic

Video: Dendritic

growth

growthofofcrystal

crystal

from

frommelt

melt

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).

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)

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...

[ (number of atoms) 4Eb]

the surface energy is the

bonded state and not the

free state

[ (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]

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

Except in certain circumstances

Surface Energy

Surface Tension

LIQUID SURFACE

Liquids cannot support shear stresses (hence use of the term surface tension)

Surface Energy

Surface Stress (Tensor)

Surface Torque

SOLID SURFACE

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

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

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

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

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(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

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

(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

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

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

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

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 ( 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

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!

Solids

(from bulk)

Bond Stretching

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

Surface crystal (with different atomic configuration than the bulk)

Forces at the edges to match it with the bulk

Surface viewed from top

Bulk

Relaxed Surface

Crystal

Forces

Crystal

(Solid)

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

of Plane Stress (only )

Symmetry the shear

stresses (xy) are zero

xy = 0

higher Rotational Symmetry the

normal stresses across all lines are

equal and shear stresses (xy) are

zero

3-fold

4-fold

6-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

Symmetry or higher

y

2

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

new surface energy = ( + d)

Work done on stretching W0

Strain on stretching (dx) = dx/1 = dx

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

[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

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

B

Split

[1]

Shear

W 2 W1

[2]

[1] [2]

W W0 2 2d 2 W1

W1 W0 2d 2 xy d xy

xy

d xy

d

x

d x

xy

d xy

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

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 Cos L Sin

AL

ATan AL

A

r 2 R Cos( )

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

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

With diameter (2R) =

2

T

2

L

Centre of Circle O

1

2

T2 L2 , Tan 1

( ) T Cos L Sin

when included the cusps could be less

prominent and could even disappear for high

index planes

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

energy orientation produce a torque on the surface

( )

Torque term

( )

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

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)).

Cos

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

leaf

Water on guava

leaf

Water on lotus

leaf

of the lotus leaf!

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