Lecture 3

15D100021

CONTENTS

BONDING FORCES AND ENERGIES

EFFECT OF TEMPERATURE ON MODULUS
CRYSTAL STRUCTURENOF METALS
BRAVAIS LATICES
ATOMIC PACKING FACTOR
STACKING SEQUENCE

GENERAL ATOMIC STRUCTURE

OF METALS
Most of the metals in the periodic table are from the sblock and d-block, with a few from p and f block.
In metals, the outermost electrons experience very less
force from the nucleus. This is because they are shielded
by inner electrons.
Thus they have low ionization energies and low electron
affinities.

GENERAL ATOMIC STRUCTURE

OF METALS

BONDING IN METALS
Metals easily give away their outer-most electrons. So in a
metallic crystal with many such atoms, electrons move freely
over the entire crystal.
Thus all the metals together form a large molecular orbital.
Every metal atom is held in its position by the attractions
between the metal nucleus and delocalized electron cloud.
Due this delocalization metals are good conductors of heat and
electricity.

BONDING IN METALS
As the number of valence electrons increase, more electrons
are available for sharing and thus stronger bonds are formed.
This explains the higher melting points of d-block elements
compared to s-block elements.
Such type of bonding is called metallic bonding and is
responsible for the characteristics of metal like high strength,
high melting points, high thermal and electrical conductivities
etc.

The picture shows

uni-valentmetal but
the principle is
same for multivalentmetals.
With more
electrons, all the
properties become
higher.

CRYSTAL STRUCTURE OF
METALS
Bonding in metals in metallic. This is non-directional in
nature.
Thus metals have very minimum restrictions on number of
neighbours and their positions.
This enables close packing in metals.
This in turn is responsible for their high densities and
strength.

CRYSTAL STRUCTURE OF
METALS
Most of the metals are found in the following lattices :
FCC (face-centered cubic) also called CCP (cubic closed
packing)
BCC (body centered cubic)
HCP (hexagonal closed packing)
We will be looking at their general properties.

UNIT CELL-SOME
PARAMETERS
A unit cell is an element which when repeated in an
ordered way in 3 dimensions gives the entire lattice.
Packing factor (pf) or atomic packing factor (apf):
It is defined as
(volume of metals in the unit cell)/ (volume of the
unit cell)

UNIT CELL-SOME
PARAMETERS
Co-ordination number: It is the number of nearest
neighbour or number of atoms touching a given atom.
This number is same for all the atoms in a unit cell.
The radius of atom is generally represented by R. If the
lattice is cubic then the edge length is denoted by a.

FCC or CCP
In this lattice, the following lattice points of a
cube are occupied by metal atoms:
1. All corners of the cube
2. All centers of the (6) faces of the cube.
Examples: copper, gold , lead , aluminium ,
nickel.

FCC or CCP-Properties
Consider the face diagonal, Length of face diagonal=1.4142x(a). But

in terms of R, length of face diagonal=4R.

Thus 4R=1.4142x(a). Thus:
Packing factor(pf):
pf for a ccp lattice is 0.74. This is the highest pf possible for atoms of
same radius.
Co-ordination number:
Co-ordination number of an atom in ccp lattice is 12.

BCC
In a BCC lattice the following lattice points are occupied
by atoms of metals:
1. All corners of the unit cell
2. The midpoint of body-diagonal ( the center of unit cell)

BCC-Properties
Consider the length of body diagonal. Write it in terms of a
and R. We get the following relation:

Packing factor(pf)= 0.68 (lower than FCC).

Co-ordination number=8.
Examples :chromium, iron, tantalum, molybdenum,
tungsten(wolfram).

HCP
HCP can be visualized by considering 3 layers of atoms.
The bottom and top layers are directly above each other.
The middle layer is placed in complementary positions to
bottom layer.

HCP-PROPERTIES
Inferring to the above figure, a must be equal to 2R. The
relation between a and c in given by c=1.633a.
Packing factor for HCP is same as that of CCP-0.74
Co-ordination number is also the same-12
Examples: cadmium , magnesium , titanium , zinc , cobalt
etc.

BONDING FORCES AND

ENERGIES
To understand physical properties of material, it is
sufficient to study how individual atoms interact when
brought from large separation.
When they are being brought together, there will be 2
types of forces: attractive and repulsive.
Attractive forces: due to interaction between nucleus of
one atom and electrons of other.

BONDING FORCES AND

ENERGIES
Repulsive forces: due to interactions between electrons of
both atoms.
At some distance these both forces nullify each other. This
distance is called bonding distance-r.
When the atoms are at this distance, the two atom system
is in stable equilibrium.
Studying this two atom system gives an idea of how atoms
in bulk react.

The diagram interaction energy(E) and

inter-atomic force(F) as a function of
separation between the atoms.
Interaction energy is the negative of
energy required to put them apart at
infinite distance.
Inter-atomic force is related to E as:
F=-(dE/dr)
We can see that
If r>r then F>0 which means they both
attract each other
If r<r F<0 which means they repel.
In both the processes, they try to reach
the equilibrium separation r. Such state
of the system is called stable equilibrium.

USES OF THESE PLOTS

Many trends in physical properties can be inferred from these
plots.
For example: materials having large E0have high melting points
(E0is the negative of bonding energy at equilibrium separation)
Modulus of rigidity of a material is high for the materials having
high slope for F vs r curve at r.
The coefficient of thermal expansion of a material depends on
the shape of E vs r plot. The narrower the trough, the lower the
coefficient of thermal expansion.

BRAVAIS LATTICES
Theoretically although there are many kinds of lattices possible,
practically only a few of them are stable in nature.
The set of lattices which are possible are called Bravais lattices.
A 3 co-ordinate axis system is set-up such that
the axes are along the edges of the parallelepiped.
This parallelepiped will be called the unit-cell.
A unit cell is the unit which when repeated in 3-dimensions in an
ordered way gives the entire structure of lattice.

THE SIX PARAMETERS

a= length of the edge of parallelepiped along x-axis.

b= length of the edge of parallelepiped along y-axis.
c= length of the edge of parallelepiped along z-axis.
= angle between y-axis and z-axis.
=angle between x-axis and z-axis.
=angle between x-axis and y-axis.
With these parameters and some other rules, there can be 7
possible lattice systems and 14 lattices in all of them together.

LATTICE SYSTEMS-1
TRICLINIC:
abc; ,,90
degrees
Eg: microcline

MONOCLINIC:
abc; ==90
degrees and
90 degrees.
Eg: orthoclase.

LATTICE SYSTEMS-2
Orthorhombic: ,,=90 degrees, abc.
Eg : olivine, aragonite.

Tetragonal
,,=90 degrees,
a=bc.
Eg: wulfenite.

LATTICE
SYSTEMS-3

Rhombohedral
a=b=c, == 90 degrees.
Eg: quartz, dolomite.

LATTICE SYSTEMS-4
Hexagonal
==90, =120
degrees , a=bc.
Eg: beryl

Cubic

a=b=c , ,,=90 degrees.

Eg: FeS2.

PACKING FACTORS FOR COMMON CRYSTALS

Some basic properties of FCC, BCC and HCP
are given below.

HCP
Packing factor=0.74
Co-ordination
number=12
FCC
Packing factor=0.74
Co-ordination
number=12

BCC
Packing
factor=0.68
Co-ordination
number=8

STACKING SEQUENCE
The order in which individual layers should be arranged

and the sequence in which they must be stacked so that

required lattice is formed.
Studying stacking sequences can help us in understanding
the behaviourof material when it is stretched.
The common examples given to study stacking sequences:
1.FCC. (ABCABC. Type)
2.HCP. (ABAB. Type)

STACKING IN FCC
FCC can be formed by stacking 3 different layers on one
other in same sequence.
These pictures show the arrangement of different layers.

Green-atoms: layer A
blue-atoms: layer B
yellow-atoms: layer C

STACKING IN FCC
These pictures depict the visualization of the unit cell in
the layers. The layers are aligned along the body diagonal.

STACKING IN HCP
HCP follows ABAB type.

EFFECT OF TEMPERATURE ON
MODULI
Increasing the temperature in general decreases the youngs
modulus.
This is because the atoms start vibrating at higher frequencies
causing decrease in bond strength.
The studying this variation is important because:

Modulus decreases
with temperature
Strength
decreases with
temperature

EFFECT OF TEMPERATURE ON
MODULI
1.The temperature of train tracks fluctuates highly due to movement of
trains. One must have a nice idea of the strength of tracks at any
temperature.
2.Many machine parts go to high temperature while working. It is
essential to know their strengths at such temperatures.
3.High temperature analysis of circuit elements is essential while
designing circuits. Otherwise they may just break.
Some materials are there which dont undergo too much change with
rise in temperature. They are of much importance in machines.