Material Science

CH2008D

Lecture 1: Introduction
1
 SCOPE AND OBJECTIVE OF THE
COURSE
• Write the importance of selection materials for engineering
purposes

• Describe the atomic structure and bonding in solids

• Describe the phase diagrams of some important compounds

• Understanding different failure mechanisms of materials

• Describe the different properties of materials and their

applications

2
 Course Plan
Topics Hours
Classification of materials and crystal properties 11
Phase diagrams and transformations, Mechanical properties
and deformation materials 13
Electrical, magnetic and thermal properties of materials,
processing of materials, selection of materials 15
TOTAL 39
Evaluation Scheme
Weightage
Component Duration Date & Time
(%)
Test 1 1 hour 20 According to Academic Calendar
Test 2 1 hour 20 According to Academic Calendar
Assignment/Review -- 40 -
End Sem 2 hours 20 Class Timings
Examination

Grading: Absolute grading 3

Historical perspective and Material Science

4
Boeing 777 Boeing 787
 What is Materials Science and
Engineering ?

Materials science tetrahedron

Material science is the investigation of the relationship among processing,

structure, properties, and performance of materials.
When utilizing a material, one needs to understand that the structure, properties,
processing, and performance of the material are interrelated. This is represented by the
materials science tetrahedron shown in the figure above. If one alters the processing,
there is a direct connection with the structure, properties, and performance of the
material. Adjusting any one of the factors will have varying degrees of impact on the
other three factors. Characterization is the heart of the tetrahedron, signifying its role
5
in
monitoring the four components.
 Structure
• Subatomic level: Electronic structure of individual
atoms that defines interaction among atoms
(interatomic bonding).

• Atomic level: Arrangement of atoms in materials

(for the same atoms can have different properties,
e.g. two forms of carbon: graphite and diamond)

• Microscopic structure : Arrangement of small grains

of material that can be identified by microscopy.

• Macroscopic structure: Structural elements that

6
may be viewed with the naked eye. Monarch butterfly
~ 0.1 m
7
 Properties
• Properties are the way the material responds to the environment
and external forces.

• Mechanical properties – response to mechanical forces, strength,

etc.
• Electrical and magnetic properties - response electrical and
magnetic fields, conductivity, etc.
• Thermal properties are related to transmission of heat and heat
capacity.
• Optical properties include to absorption, transmission and
scattering of light.
• Chemical stability in contact with the environment - corrosion
resistance.

8
 Processing
• Processing of materials is the application of
heat (heat treatment), mechanical forces, etc.
to affect their microstructure and, therefore,
their properties.

9
 Why Study Materials Science and
Engineering?
• Economics and materials trade-offs

• Innovation, e.g., plastic containers in place of age-old metallic

containers

• Engineering disaster: misuse of materials

• Vital: material selection, designing demand, economic and

aesthetic demands, demands of strength and durability

• Understand the properties of material and their limitations

• Must to study and understand the concept of material science

10
 Ideas from Materials Science and
Engineering
• To select a material for a given use based on
considerations of cost and performance.
• To understand the limits of materials and the change of
their properties with use.
• To be able to create a new material that will have some
desirable properties.
• To be able to use the material for different application

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Classification based on atomic bonds
and structure

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 Classification of Materials
Metals

• High thermal & electrical conductivity

• High mechanical strength
• Opaque to light
• Bounded by metallic bonds and weaker van der Walls
forces
• Pure metals are not good
• A metal mixed with another metal to improve the
desired qualities. E.g.: aluminum, steel, brass, gold

13
 Classification of Materials (contd..)

Ceramics

• Compounds between metallic and non-metallic elements

• Oxides, carbides, nitrides, or silicates of metals

• Partly crystalline and partly amorphous

• Atoms (ions often) in ceramic materials behave mostly like

either positive or negative ions, and are bound by very strong
Coulomb forces between them

• Glass, porcelain
14
 Classification of Materials (contd..)

Polymers
• Thermo-plastics (nylon, polyethylene, polyvinyl
chloride, rubber, etc.) consist of molecules that
have covalent bonding within each molecule and
van der Waals forces between them
• Thermo-sets (e.g., epoxy, phenolics, etc.) consist
of a network of covalent bonds
15
 Classification of Materials (contd..)
Composite materials

• Multiphase materials obtained by artificial combination of different

materials

• e.g., lightweight brake disc obtained by embedding SiCparticles in Al-alloy

matrix

• Reinforced cement concrete, a structural composite obtained by

combining cement (the matrix, i.e., the binder, obtained by a reaction
known as hydration, between cement and water), sand (fine aggregate),
gravel (coarse aggregate), and, thick steel fibers.

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 Classification of Materials (contd..)
Semiconductors (Electronic Materials)
• Covalent in nature
• Crystalline or amorphous
• High electrical conductivity
• Usually doped in order to enhance electrical conductivity
• Opaque to visible light but transparent to the infrared
• Examples: silicon (Si), germanium (Ge), and gallium arsenide (GaAs,
a compound semiconductor)

17
 Classification of Materials (contd..)
Advanced materials,
• Air-space/crafts
• Electronic gadgets
• Computers
• Integrated circuits
• Fiber-optics
• Lasers
• LCD’s

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 Classification of Materials (contd..)
Future materials

• Used in the field of medicine, defense

– Actuator(performs responsive and adaptive functions)

• Shape memory alloys,
• Piezo-electric ceramics,
• Magnetostrictive materials,
• Electro-/Magneto-rheological fluids
– Sensor (detects an input)
• Optical fibers,
• Piezo-electric materials,
• Micro-electro-mechanical systems (MEMS)

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 Classification of Materials (contd..)
Modern materials

• Engine efficiency increases at high temperatures: requires high temperature

structural materials

• Use of nuclear energy requires solving problem with residues, or advances in

nuclear waste processing.

• Hypersonic flight requires materials that are light, strong and resist high

temperatures.

• Optical communications require optical fibers that absorb light negligibly.

• Civil construction –materials for unbreakable windows.

• Structures: materials that are strong like metals and resist corrosion like plastics 20
 TEXT BOOKS
• Callister, Materials Science and Engineering:
An Introduction, 8th Edition, John Wiley and
sons inc., Jan 2010

• Raghavan V., Material Science and Engineering

Prentice Hall of India, 1996.

21
 Material Science
CH 2008D

Prasanna Kumar S Mural

Assistant professor
NIT Calicut
Lecture 2:
Atomic structure and Atomic
bonding 1
 Atomic structure
• In order to understand the structure of materials and its
correlation to property, we have to start form the basic
element of matter – The Atom
• An atom consists of a nucleus composed of protons and
neutrons and electrons which encircle the nucleus
• Protons and electrons have same and opposite charge of
1.6 x 10-19 C.
• Atomic number (Z) = Number protons = number of
electrons.
• Atomic mass (A) = proton mass + neutron mass.
• Isotopes are the same element having different atomic
masses. Number of protons in isotopes remains same while
number of neutrons varies.

2
 Atomic structure (contd..)
• Atomic mass (M) unit (amu) = 1/12 mass of Carbon 12 (12C)
• 1 mol of substance contains 6.023 x 1023 (Avogadro’s
number) atoms or molecules.
• Atomic weight = 1 amu/atom (or molecule) = 1 g/mol = Wt.
of 6.023 x 1023 atoms or molecules (Avagardros Number,
Nav).
• For example, atomic weight of copper is 63.54 amu/atom
or 63.54 g/mole
• The number of atoms (n) per cm3 of material of density (,
gm/cm3) = Nav * (/M)
• Calculate number of atoms (n) per cm3 Carbon (, gm/cm3
= 1.8)

3
 Atomic structure (contd..)
The Bohr Model
• Electrons revolve around a positively charged
nucleus in discrete orbits (K, L, M or n=1, 2, 3
respectively) with specific levels of energy.
• Electrons positions are fixed as such, however,
an electron can jump to higher or lower
energy level by absorption or emission of
energy respectively

• Limitations:- Although the Bohr’s model was

the first and best model available at the time
of its discovery, it had certain limitations and
could not explain many phenomena involving
electrons. 4
 Atomic structure (contd..)
Heisenberg’s uncertainty principle
• The position and momentum of an electron
can not be determined simultaneously.
• This also disapproves the hypothesis in the
Bohr model that electrons revolve around
certain circular orbits

5
 Atomic structure (contd..)
Laws of Quantum mechanics
• Schröndinger’s wave equation: Whenever a particle is attracted to

a certain region, its energy levels are necessarily quantized (shape

of orbital)

• Pauli’s exclusion principle: A given quantam level cannot accept

more than two electrons (why higher energy orbitals are stable and

populated)
• Heisenberg uncertainty principle: It is impossible to simultaneously
know with certainty both the momentum and position of a moving
particle (why an electron does not spiral continually & fall into the
nucleus) 6
 Atomic structure (contd..)
Orbital shape and quantum numbers
• Quantum numbers: principal (n), angular (l) and magnetic (m)

• Principal quantum number : spatial extent and energy of the orbital; n

increases, energy of electron increases & its spatial extent increases

• Angular momentum quantum number :the shape of the orbital for any

given value of n

– e.g., for n = 3, the possible values of l are 0, 1, 2

• Magnetic quantum number :the orientation of the orbital in space

– For a given value of l, m can take on values from -1 to +1
– l= any value, m= 2l+ 1; suppose, l = 2, m = 5 that means m = -2, -1, 0,
+1, +2 7
 Atomic Bonding
• When two neutral atoms are brought close to
each other, they experience attractive and or
repulsive force
• Attractive force is due to electrostatic attraction
between electrons of one atom and the
nucleus of the other.
• Repulsive force arises due to repulsion between
electrons and nuclei of the atoms.
• The net force, FN (Fig. a), acting on the atoms is
the summation of attractive and repulsive
forces
• The distance, at which the attraction and
repulsion forces are equal and the net force is
zero, is the equilibrium interatomic distance, ro.
The atoms have lowest energy at this position.
• Attraction is predominant above ro and
repulsion is dominant below ro
8
 Atomic Bonding (contd..)
Lennard-Jones potential
• The interaction energy between the pair of
atoms is given by the Lennard-Jones potential,
Vr or VLJ
•  is the distance at which the interaction
energy is zero.  is the depth of the potential
well and is a measure of the bonding energy
between two atoms.
• L-J potential can be also expressed in the
simplified form as VLJ = A/r12 – B/r6 and hence,
is also known as 6-12 potential.
• A/r12 is predominant at short distances and
hence, represents the short-range repulsive
potential due to overlap of electron orbitals
and –B/r6 is dominant at longer distance and
hence, is the long range attractive potential.

9
 Atomic Bonding (contd..)
• The mechanisms of bonding between the atoms are
based on the foregoing discussion on electrostatic
interatomic interaction.
• The types of bond and bond strength are determined
by the electronic structures of the atoms involved.
• The valence electrons take part in bonding. The atoms
involved acquire, loose or share valence electrons to
achieve the lowest energy or stable configuration of
noble gases.
• Atomic bonding can be broadly classified as i) primary
bonding ii) secondary bonding

10
 Atomic Bonding (contd..)
Primary Bonds
• Three types primary bonds are found in solids
– Ionic
– Covalent
– Metallic
• Majority of the engineering materials consist
of one of these bonds. Many properties of the
materials depend on the specific kind of bond
and the bond energy.

11
 Atomic Bonding (contd..)
Ionic Bonds
• Ionic bonds are generally found in compounds composed of metal and
non-metal and arise out of electrostatic attraction between oppositely
charged atoms (ions).

• Number of electron in outer shell is 1 in Na and 7 in Cl . Therefore, Na will

tend to reject one electron to get stable configuration of Ne and Cl will
accept one electron to obtain Ar configuration. The columbic attraction
between Na+ and Cl¯ions thus formed will make an ionic bond to produce
NaCl.
• Some other examples are CaF2, CsCl , MgO, Al2O3.
12
 Atomic Bonding (contd..)
Ionic Bonds
Bond Type Ionic Bond
Polarity High
Formation An ionic bond is formed between a metal and a non-metal. Non-
metals(-ve ion) are "stronger" than the metal(+ve ion) and can
get electrons very easily from the metal. These two opposite
ions attract each other and form the ionic bond.
Shape No definite shape
What is it? Ionic bond, also known as electrovalent bond is a type of bond
formed from the electrostatic attraction between oppositely
charged ions in a chemical compound. These kinds of bonds
occur mainly between a metallic and a non metallic atom.
Melting, Boiling point High
Occurs between One metal and one non-metal
Examples Sodium chloride (NaCl), Sulphuric Acid (H2SO4)

13
 Atomic Bonding (contd..)
Covalent Bonds
• In this type of bonding, atoms share their
valence electrons to get a stable
configuration.
• Methane (CH4): Four hydrogen atoms
share their valence electrons with one
carbon atom and the carbon atom in turn
shares one valence electron with each of
the four hydrogen atoms. In the process
both H and C atoms get stable
configuration and form a covalent bond.
• Covalent bonds are formed between
atoms of similar electronegativity.
• C atoms in diamond are covalently bonded
to each other.
• Si also has valency of four and forms SiC
through covalent bonding with C atoms

14
 Atomic Bonding (contd..)
Covalent Bonds
• Dispersion forces between molecules are much weaker than
the covalent bonds within molecules
• How molecular size affects the strength of the dispersion
forces
• The boiling points of the noble gases are
neon xenon
Noble Gas Boiling Point
• B.P. increases, as we go down the group, the number of
helium -269 °C electron increases, so does the radius of the atom
neon -246 °C • The more electrons you have, more distance over which
they can move, the bigger the possible temporary dipoles
argon -186 °C and the bigger the dispersion forces
krypton -152°C • Due to greater temporary dipoles, xenon molecules are
xenon -108°C "stickier" than neon molecules. Neon molecules will break
away from each other at much lower temperatures than
radon -62°C xenon molecules -hence neon has the lower boiling point.
15
 Atomic Bonding (contd..)
Covalent Bonds
Bond Type Covalent Bond
Polarity Low
Formation A covalent bond is formed between two non-metals that have
similar electro negativities. Neither atom is "strong" enough to
attract electrons from the other. For stabilization, they share
their electrons from outer molecular orbit with others.
Shape Definite shape
What is it? Covalent bonding is a form of chemical bonding between two
non metallic atoms which is characterized by the sharing of pairs
of electrons between atoms and other covalent bonds.
Melting, Boiling point low
Occurs between Two non-metals
Examples Methane (CH4), Hydro Chloric acid (HCl)

16
 Atomic Bonding (contd..)
Metallic Bonds
• In metals the valence electrons are not really bound to one
particular atom, instead they form a sea or cloud of valence
electrons which are shared by all the atoms. The remaining
electrons and the nuclei form what is called the ion core
which is positively charged. The metallic bond arises out of
the columbic attraction between these two oppositely
charged species – the electron cloud and the ion cores.

17
 Atomic Bonding (contd..)
Metallic Bonds
Bond Type Metallic Bond
Polarity Polar/non-polar
Formation An metallic bond is formed between a +ve-ly charged metal and
a conduction electron (the form of an electron cloud of
delocalized electrons).
Shape No definite shape
What is it? Metallic bonding occurs as a result of electromagnetism. It may
be described as the sharing of free electrons among a lattice of
positively charged ions (cations). In a more quantum-mechanical
view, the conduction electrons divide their density equally over
all atoms that function as neutral (non-charged) entities.
Melting, Boiling point High
Occurs between One metal and a conduction electron

18
 Atomic Bonding (contd..)
Structure-property correlation
• Ionic and covalent bonds posses high bond energy – 450 – 1000 kJ/mole
• High bond strength in ionic and covalent solids results in high melting
point, high strength and hardness. e.g. diamond
• As the electrons are tightly bound to the atoms they are generally poor
conductors of heat and electricity
• Are brittle in nature
• Most of the ceramics consist of covalent (SiC) or ionic bonds (Al2O3) or a
mix of both and hence, exhibit all the properties described above.
• Metallic bonds on the other hand provide good thermal and electrical
conductivities as the valence electrons are free to move.
• The metallic bond energy is 68 kJ/mol (Hg) on the lower side and 850
kJ/mol (W, tungsten) on the higher side.
• Bond strength increases with atomic number as more electrons are
available to form the bonds with the ion cores. As a result melting point,
hardness and strength increases with atomic number.
• Metals are ductile as the free moving electrons provides agility to the 19
bonds and allows plastic deformation.
 Atomic Bonding (contd..)
Secondary Bonds
• Van der Waals bonding
• Van der Waals bonding between molecules or atoms
arise due to weak attraction forces between dipoles
• The natural oscillation of atoms leading to momentary
break down of charge symmetry can generate
temporary dipoles

• Dipoles can induce dipoles and attraction between

opposites ends of the dipoles leads to weak bonding

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 Atomic Bonding (contd..)
Van der Waals bonding
• An ion can also induce a dipole

• Some molecules like HCl have permanent dipoles due to

asymmetrical arrangement of +ve and –ve charges.

• Van der Waals bonding is much weaker compared to primary

bonds. Bond energy lies in the range of 2 – 10 kJ/mol.
• Molecules in liquid and gas are held by weak Van der Waals forces
• The atomic layers in graphite are held together by weak van der
Waals bonds. Therefore, the layers can move easily over each other
and this imparts the lubricating property graphite is known for

21
 Atomic Bonding (contd..)
Hydrogen bonding
• Hydrogen bond is a type of secondary
bond found in molecules containing
hydrogen as a constituent.
• The bond originates from electrostatic
interaction between hydrogen and
another atom of high electronegativity
such as fluorine or oxygen.
• The strength of hydrogen bonds is in the
range of 10 – 50 kJ/mol.
• Water molecules, for example, are
connected by hydrogen bonds (dashed
lines in the picture).

22
 Van Der Waals or Intermolecular
bonding: Dispersion forces
How molecular shape affects the strength of the
dispersion forces
– The shapes of the molecules also matter
– Long thin molecules can develop bigger temporary dipoles
due to electron movement
– Long thin molecules can also lie closer together
– e.g., butane and 2-methylpropane

• Butane has a higher b.p. because the dispersion forces

are greater. The molecules are longer (and so set up
bigger temporary dipoles) and can lie closer together
than the shorter, fatter 2-methylpropane molecules.

23
 Van Der Waals or Intermolecular
bonding: Dipole-dipole interaction
• HCl has a permanent dipole because chlorine is more electronegative than
hydrogen
• All molecules have dispersion forces
• Dipole-dipole interactions are not an alternative to dispersion forces -they
occur in addition to them
• Molecules which have permanent dipoles will therefore have boiling
points rather higher than molecules which only have temporary
fluctuating dipoles

Comparing dipole-dipole attractions with dispersion forces

Two molecules with the same number of electrons and the same size
e.g., the boiling points of ethane, CH3CH3, and fluoromethane, CH3F, are
– higher b.p. of fluoromethane
– large permanent dipole on the molecule
– high electronegativity of fluorine

24
 Problem
• How many Fe atoms are there in 1 g of Fe?
Solution: Atomic mass of Fe = 55.85 g/mol.
1 mol of substance has 6.023 x 1023 atoms
(Avogadro’s number). Therefore, 1 mol or 55.85
g of Fe has 6.023 x 1023 atoms. Hence, 1 g Fe
has (6.023 x 1023) / 55.85 = 10.78 x 1021 atoms

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 Material Science
CH 2008D

Prasanna Kumar S Mural

Assistant professor
NIT Calicut
Lecture 3:
Crystal Structures, Crystalline
and Non-Crystalline materials 1
 Crystal structure
• Crystal structure is one of the most important
aspects of materials science and engineering
as many properties of materials depend on
their crystal structures. The basic principles of
many materials characterization techniques
such as X-ray diffraction (XRD), Transmission
electron microscopy (TEM) are based on
crystallography. Therefore, understanding the
basics of crystal structures is of paramount
importance.
2
 Atomic arrangement
• Crystalline – periodic arrangement of atoms: definite
repetitive pattern, Long-range order (LRO): Atoms or ions
form a regular repetitive, grid like pattern in 3D
• Non-crystalline or Amorphous – random arrangement of
atoms. Short-range order (SRO): a certain regularity in the
• arrangement of the neighboring atoms
• The periodicity of atoms in crystalline solids can be described
by a network of points in space called lattice.

3
 Fundamental concepts
• Large number of different crystal structures
• Metals: simple structures, ceramics and
polymers: complex structures
• To discuss crystalline structures it is useful to
consider atoms as being hard spheres, with well-
defined radii
• The shortest distance between two like atoms is
one diameter.
• Use of terms lattice and unit cell will be handy.
• Lattice is used to represent a 3D periodic array
of points coinciding with atom positions.
• Unit cell is smallest repeatable entity that can be
used to completely represent a crystal structure
by virtue of its geometry and the atom positions
within

4
 Crystal Systems
• The space lattice points in a crystal are
occupied by atoms.
• The position of any atom in the 3D lattice can
be described by a vector ruvw= ua + vb + wc,
where u, v and w are integers

The three unit vectors, a, b, c can define a cell as shown by the shaded region in Fig.(a) This cell
is known as unit cell (Fig. b) which when repeated in the three dimensions generates the crystal
5
structure.
 Crystal Systems
Bravais Lattice
• The unit vectors a, b and c are called lattice
parameters. Based on their length equality or
inequality and their orientation (the angles
between them, ,  and ) a total of 7 crystal
systems can be defined. With the centering
(face, base and body centering) added to
these, 14 kinds of 3D lattices, known as
Bravais lattices, can be generated.

6
Crystal Systems

7
Crystal Systems

8
9
Unit cell geometry for the
seven crystal systems
showing inter axial angles
Axial relationships
Cubic, a = b = c
Tetragonal, a = b ≠ c
Orthorhombic, a ≠ b ≠ c
Hexagonal, a = b ≠ c
Rhombohedral, a = b = c
Monoclinic, a ≠ b ≠ c
Triclinic, a ≠ b ≠ c

10
11
How to define
• Points (atomic positions)
• Vectors (defines a particular direction - plane
normal)
• Miller Indices (defines a particular plane)
relation to diffraction
• 3-index for cubic and 4-index notation for HCP

12
 Miller Indices
• Definition of Miller index : any of a set of
three numbers or letters used to indicate the
position of a face or internal plane of a crystal
and determined on the basis of the reciprocal
of the intercept of the face or plane on the
crystallographic axes.

13
 Crystallographic points
• To define a point within a unit
cell….
• Express the coordinates u, v, w
as fractions of unit cell vectors
a, b, and c (so that the axes x,
y, and z do not have to be
orthogonal).

14
 Crystallographic directions
X (a), Y(b) Z(c)
Procedure: 1 1 0
• Any line (or vector direction) is specified by 2 points.
• The first point is, typically, at the origin (000).
• Determine length of vector projection in each of 3
axes in units (or fractions) of a, b, and c.

• Multiply or divide by a common factor to reduce the

lengths to the smallest integer values, u v w.
• Enclose in square brackets: [u v w]: [110] direction.
• Designate negative numbers by a bar [1 1 0]
• Pronounced “bar 1”, “bar 1”, “zero” direction.
• “Family” of [110] directions is designated as <110>.

15
 Symmetry Equivalent Directions
Note: for some crystal structures,
different directions can be equivalent.

e.g. For cubic crystals, the directions are

all equivalent by symmetry:
[1 0 0], [0 1 0], [0 0 1]

Families of crystallographic directions

e.g. <1 0 0>

16
 Designating Lattice Planes
Why are planes in a lattice important?
(A) Determining crystal structure
Diffraction methods measure the distance between parallel lattice planes of
atoms. This information is used to determine the lattice parameters in a
crystal.
Diffraction methods also measure the angles between lattice planes.

(B) Plastic deformation

– Plastic deformation in metals occurs by the slip of atoms past each other in the crystal.
– This slip tends to occur preferentially along specific crystal-dependent planes.

(C) Transport Properties

– In certain materials, atomic structure in some planes causes the transport of electrons
and/or heat to be particularly rapid in that plane, and relatively slow not in the plane.
– Example: Graphite: heat conduction is more in sp2-bonded plane.
17
 Families of Lattice planes
• Given any plane in a lattice, there is a infinite set of parallel lattice
planes (or family of planes) that are equally spaced from each
other.
• One of the planes in any family always passes through the origin.

Methodology to define crystallographic planes in cubic crystal:

– determine the intercepts of the plane along the crystallographic axes,
in terms of unit cell dimensions. If plane is passing through origin,
there is a need to construct a plane parallel to original plane.
– take the reciprocals of these intercept numbers.
– clear fractions.
– reduce to set of smallest integers.
– The three indices are enclosed in parenthesis, (hkl). A family of planes
is represented by {hkl}.

18
 Designating Lattice Planes
• Planes intersects axes at:
a axis at r= 2
b axis at s= 4/3
c axis at t= 1/2
How do we symbolically designate planes in a lattice?
Solution:
1. Take the reciprocal of r, s, and t.
Here: 1/r = 1/2 , 1/s = 3/4 , and 1/r = 2
2. Find the least common multiple that converts all reciprocals
to integers.
With LCM = 4, h = 4/r = 2 , k= 4/s = 3 , and l= 4/r = 8
3. Enclose the new triple (h,k,l) in parentheses: (238)
4. This notation is called the Miller Index.

19
 Some useful conventions of Miller
notation
• If a plane is parallel to an axis, its intercept is at infinity and its Miller index will be
zero.
• If a plane has negative intercept, the negative number is denoted by a bar above
the number. Never alter negative numbers. For example, do not divide -1, -1, -1 by
-1 to get 1,1,1. This implies symmetry that the crystal may not have!
• The crystal directions of a family are not necessarily parallel to each other.
Similarly, not all planes of a family are parallel to each other.
• By changing signs of all indices of a direction, we obtain opposite direction.
Similarly, by changing all signs of a plane, a plane at same distance in other side of
the origin can be obtained.
• Multiplying or dividing a Miller index by constant has no effect on the orientation
of the plane.
• The smaller the Miller index, more nearly parallel the plane to that axis, and vice
versa.
• When the integers used in the Miller indices contain more than one digit, the
indices must be separated by commas. E.g.: (3,10,13)

20
 More conventions applicable to cubic
crystals only
• [uvw] is normal to (hkl) if u = h, v = k, and
w = l. E.g.: (111) ┴ [111].
• Inter-planar distance between family of
planes {hkl} is given by:
• [uvw] is parallel to (hkl) if hu + kv + lw =
0.
• Two planes (h1k1l1) and (h2k2l2) are
normal if h1h2 + k1k2 + l1l2=0.
• Two directions (u1v1w1) and (u2v2w2) are
normal if u1u2 + v1v2 + w1w2=0
• Angle between two planes is given by:
The same equation applies for two
directions.
21
 Why Miller indices are calculated in
that way?

• Using reciprocals spares us the complication of

infinite intercepts.
• Formulas involving Miller indices are very similar
to related formulas from analytical geometry.
• Specifying dimensions in unit cell terms means
that the same label can be applied to any plane
with a similar stacking pattern, regardless of the
crystal class of the crystal. Plane (111) always
steps the same way regardless of crystal system.
22
 Material Science
CH 2008D

Prasanna Kumar S Mural

Assistant professor
NIT Calicut
Lecture 4:
Crystal Structures, Crystalline
and Non-Crystalline materials 1
Index Number in
the family for
cubic lattice
<100> → 3x2=6
<110> → 6 x 2 = 12
<111> → 4x2=8
 Planes in Hexagonal system
• In the cubic system all the faces of the
cube are equivalent, that is, they have
similar indices.
• However, this is not the case in the
hexagonal system. The six prism faces
for example have indices (1 0 0), (0 1
0),(1̅ 1 0 ), (1̅ 0 0 ), (01̅ 0), (11 0
̅ ),
which are not same.
• In order to address this, a fourth axis
(a3) which is opposite to the vector
sum of a1 and a2 is used and a
corresponding fourth index i is used
along with hkl. Therefore the indices
of a plane is given by (hkil) whre i = -
(h+k). Sometime i is replaced with a
dot and written as (h k . l)
 Directions in Hexagonal Crystal
• Like planes, directions in the hexagonal
system are also written in terms of four
indices as [uvtw].
• If [UVW] are indices in three axes then it can
be converted to four-axis indices [uvtw] using
the following relations.
 Planes in Hexagonal system
• The indices of six faces
now become (1 01̅ 0),
(0 11̅ 0), (1̅ 1 0 0), (1̅ 0 1
0), (01̅ 1 0), (11̅ 0 0 )
which are now
equivalent and belong
to the {1 01̅ 0 } family of
planes.
 Coordination number
• Coordination number is the
number of nearest neighbor to a
particular atom in the crystal
• In the FCC lattice each atom is in
contact with 12 neighbor atoms.
FCC coordination number Z = 12
• For example, the face centered
atom in the front face is in contact
with four corner atoms and four
other face-centered atoms behind
it (two sides, top and bottom) and
is also touching four face-centered
atoms of the unit cell in front of it.
 Coordination number
• The coordination number
of BCC crystal is 8
• The body centered atom
is in contact with all the
eight corner atoms. Each
corner atom is shared by
eight unit cells and hence,
each of these atoms is in
touch with eight body
centered atoms.
 Coordination number
• In Hexagonal lattice Z =
12. The center atom of
the top face is in touch
with six corner atoms,
three atoms of the mid
layer and other three
atoms of the mid layer
of the unit cell above it.
 Atomic packing factor
• Atomic packing factor (APF) or packing
efficiency indicates how closely atoms are
packed in a unit cell and is given by the ratio
of volume of atoms in the unit cell and
volume of the unit cell

Volume of atoms in a unit cell

APF =
Total unit cell volume
 Atomic packing factor
FCC lattice
• In the FCC unit cell effective
number of atoms = 8 corner
atoms x (1/8) (each atom is
shared by 8 unit cells) + 6 face
centered atoms x 1/2 (each
shared by two unit cells) = 4
• The corner atom C is shared by
unit cells 1, 2, 3, 4 and four
more in front of each of them.
The face-centered atom, F is
shared between cells 1 and 2.
 Atomic packing factor
FCC lattice
• Considering the atoms Total volume of atoms = 4  4   R 3
3
as hard spheres of
radius R
2a = 4 R
• The relation between R
and the FCC cell side a
as shown in the figure
below is

4  4    R 3 16  2 2    a 3
APF ( FCC ) = 3 = = 0.74
3 3
a a
 Atomic packing factor
BCC lattice
• For BCC crystals effective number of atoms per
unit cell is 8 x 1/8 + 1 = 2 and the relation between
R and a is 3a = 4R
4
2     R3
3 8  3 3 a 3
APF ( BCC ) = = = 0.68
a3 a3
 Atomic packing factor
Hexagonal lattice
• In the Hexagonal unit cell, number of atoms =
12 corner atoms x 1/6 (shared by six unit cells)
+ Two face atoms x ½ + 3 interior = 6.
2𝑅 = 𝑎
• Unit cell volume = (6 x ½ x a x h) x c = (3 x a x a
sin 60) x c = 3a2 c sin 60
 Atomic packing factor
Hexagonal lattice
• The face-centered atom and
the three mid-layer atoms
form a tetrahedron MNOP
which has sides equal to a (as
atoms at vertices touch each
other) and height of c/2.
Using this tetrahedron it can
be shown that for an ideal
hexagonal crystal c/a ratio =
1.633 4
6     R3
3 8 a 3
APF ( HCP ) = = = 0.74
2
3a c sin 60 3  8 1.41 a 3
 Density computation

• Problem: Copper has an atomic radius of

0.128 nm, an FCC crystal structure, and an
atomic weight of 63.5 g/mol. Compute its
theoretical density ?
• Problem: Copper has an atomic radius of 0.128 nm,
an FCC crystal structure, and an atomic weight of
63.5 g/mol. Compute its theoretical density ?
• Solution:- nA
Density =
Vc N A

• Where, n = number of atoms associated with each

unit cell, A = atomic weight, V= volume of the unit
cell, N= Avogadro’s no. (atoms/mol)

• For FCC, n = 4, ACu=63.5 g/mol, Vc = 16R3 2, and R

=0.128
• =8.89 g/cc
 Factors affecting structure
• Crystal stoichiometry
• Radius ratio
• Propensity for covalency and tetrahedral
coordination
 Crystal stoichiometry
• Electrically neutral
• Sum of the +ve charges must be balanced by
an equal number of –ve charges
• Example: Al2O3
• Limitations: AX2 compound can’t crystallize in
the rock salt structure
 Radius ratio
• State of lowest energy: attractions between
cations & anions should be high
• Maximum attraction: each cation surrounds
itself with as many anions as possible
• Radius ratios ≥: 0.155 (triangle), 0.225
(tetrahedron), 0.414 (octahedron), 0.732
(cube), 1.00 (cubotahedron)
 Coordination number
• Coordination number: the number of atoms
or ligands directly bonded to the metal atom
• Figure. Ion arrangements for different
coordination numbers
 Anisotropy
• Many of the materials properties depend on the crystal
structure
• Crystals are not symmetric in all directions the crystal
planes same with respect to atomic density/packing
• Different directions in the crystal have different packing
e.g., atoms along the edge of FCC crystals are more separated
than along its face diagonal
• causes properties to be different in different directions.
This directionality of properties is termed as Anisotropy
• substances in which measured properties are independent
of direction in which they are measured are called isotropic