Bonding in Solids

and
Metallic Bond
Presented By:
Rajnish Kumar Singh
Assistant Professor
Mechanical Engineering Department
Lecture Details: GIET(A), Rajahmundry
Unit- I, Topic- 2
Subject – Metallurgy and Material Science
ME, I Year/ II Semester
 Lesson Objectives
After studying this chapter you should be able to do the following:
 Revisit the concept of atomic structure and different atomic models.
 Describe the concept atomic interactions and define bond energy.
 Differentiate between different types of bonds and describe each of them.
 Describe how metallic bonds form and their nature.
 Understand the co-relation between bonding and properties of solids.
 Importance of Atomic Structure and
Bonding
• Atomic Structure determine type of bonding and bonding decides properties of
materials
• E.g.; Graphite and Diamond shows different properties due to different structures.

Material Bonding and structure Properties

Graphite Within Plane – Covalent Soft as

bonds Layers can
Across Plane – Van-der wall slide
Diamond Carbon atoms in covalent Hardest
Bond with other 4 atoms Material
 Atomic Interactions
• Attractive Force- Electrons of one atom to
𝐹𝑎

Force →
nucleus of another 𝐹𝑡 r→
• Repulsive Force- Repulsion b/w electrons 𝑟0

and nuclei. 𝐹𝑟

• 𝑟0 - Equilibrium Distance, where repulsive

and attractive forces are equal.

Potential energy →
• 𝑊0 - Measurement of bonding energy. r→

• Higher 𝑊0 , Higher melting point. 𝑊0

Higher elastic modulus 𝑟0

 Bonding in Solid
Stronger Bonds Weaker Bonds
Mostly Interatomic Atomic Mostly Intermolecular
Bonding

Primary Secondary
Bonds Bonds

Ionic Covalent Metallic Van-der

Hydrogen
wall
 Ionic Bonds
IONIC BOND
• It forms between a metal and a non metal.

• The transfer of electrons is done to attain stabilised outermost electronic

configuration or inert gas configuration.

• Bonding forces ⇒ F electrostatic attraction between opposite charged ions.

 Ionic Bonds-Properties
• It is non directional bond.
• Bonding energy is very high as electrostatic force is one of the strongest force.
• Ionic solids are hard, brittle and crystalline in nature because of strong forces.
• These solids have high melting and boiling points because of high bonding energy.

• Good insulators of electricity in

solid state but good conductor in
molten state.
• Ionic solids are soluble in water and
slightly soluble in organic solvents.
 Covalent Bonds
Covalent Bond
• Generally it forms between the non metallic elements of the periodic table
• A covalent bond is formed, when two or more electrons of an atom, in its outermost
energy level, are shared by other to attain nearest inert gas configuration.
• Example:- Many nonmetallic elemental molecules- 𝐻2 , 𝐶𝑙2 , 𝐹2 etc.
Molecules containing dissimilar atoms - 𝐶𝐻4 , 𝐻2 𝑂, 𝐻𝑁𝑂3 etc.
Elemental solids- Diamond (carbon), Silicon, and Germanium etc.
 Covalent Bonds
• When two dissimilar atoms share electron in a covalent
bond, there is a separation of charge as one of the atoms
will have high electronegativity.

• Due to this covalent bonds like this formed are polar in

nature.

• Dipole Moment (𝞵)= Q x r,

Where, Q= Charge
r= distance between atoms
1
• % Ionic character =( 1 − 1 ) x 100 %, where 𝑋𝐴 − 𝑋𝐵 is difference of
(𝑋𝐴 −𝑋𝐵
𝑒4
electronegativity.
• More the difference in electronegativity more will be ionic character of bond.
 Covalent Bonds
Properties
• Relatively weaker bond but in some cases these form strong bond (as in diamond)
• May exist in solid state but mostly these are liquid and gaseous state.
• Covalent compounds are bad conductors of electricity.
• Covalent compounds are having low melting and boiling points.
• Insoluble- in water but Soluble- in organic solvents like Benzene.
• Most molecules are partially ionic and partially covalent.
• These are directional bonds.
 Metallic Bonds
Electron Sea Model
 Metals have more than one valance electron which is not bound to positive nucleus.
 These are called free electrons, as they are free to drift throughout the metal
 The remaining positive nuclei, which is
surrounded by sea of free electrons, and
vibrate around their position.
 This sea of free electron acts as a glue to hold
positive ions together and also act as shield
to avoid repulsion between positive ions.
 Metallic Bonds
• Non directional Bond
• Due to presence of free electron sea these are very
good conductors of electricity.
• Since positive ions can vibrate easily around their
positions and they are in closed proximity, they are
also good conductors of heat.
• Charged ions are strongly bonded with sea of
electrons, hence boiling and melting point are high.
• These are highly ductile and malleable as atoms can
slip slide past in sea of electrons.
 Van-der Wall Bonds
Dipole- dipole forces
• These exist between polar covalent molecules, such as HCl.
• Because of dipole moment, more electronegative atom (Cl) becomes partially
negatively charged while other atom becomes partially positively charged.
• Because of this, Negative pole of a polar molecule gets attracted towards positive pole
of other molecule and vice versa.
• This dipole-dipole bond are much weaker
than covalent or ionic bonds.
 Van-der Wall Bonds
Ion- Dipole forces
• Polar molecules and ions both exhibit poles of different
charges.
• Polar molecules when comes in vicinity of ionic molecules,
opposite poles of those molecules gets attracted.
• This forms Ion-dipole forces between ions and polar
molecule
Dispersion or London Forces
• A non polar molecule, in vicinity of ion or polar molecule
develops a non-permanent polarity.
• This is called induced polarity, which attracts opposite
poles of ion or polar molecule
• This is the weakest force in the nature
 Hydrogen Bond
• This is a special case of Dipole-Dipole Bonding.
• When in a polar bond, one atom is hydrogen atom while other atom is an
electronegative atom, the bond exhibit a polar nature.
• Opposite poles of different atoms attracted towards each other, creating Hydrogen
Bonding.
• Example- Water, HCl etc.
 Summary
• Electrons can be transferred from an electropositive atom to an electronegative atom,
producing ions of opposite sign and giving rise to the non-directional ionic bond.
• Sharing of electrons between neighboring atoms results in a covalent bond, which is
directional.
• A metal is an array of positive ions which are held together in a cloud of free
electrons. The metallic bond is non-directional and generally weaker than ionic and
covalent bonds.
• Melting and boiling points of materials increase with increasing bond strength. Strong
and directional bonds result in hard and brittle solids.
• Free electrons are responsible for the high thermal and electrical conductivities of
metals.
Thank You
 Crystal Structure

Presented By:
Rajnish Kumar Singh
Assistant Professor
Mechanical Engineering Department
Lecture Details: GIET(A), Rajahmundry
Unit- I, Topic- 3
Subject – Metallurgy and Material Science
ME, II Year/ I Semester
 Lesson Objectives
After studying this chapter you should be able to do the following:
 Distinguish between crystal and lattice structure.
 Different parameters of a lattice structure.
 Describe 7 crystal system and Bravais Lattices.
 Understand the principle of X-ray Crystallography and Bragg’s Law.
 Determine the structure of a crystal lattice with help of a diffractometer pattern.
 Crystalline and Amorphous
Solids can be classified in Crystals and Non-Crystals, depending upon their structure
Crystalline Solid
• A Crystalline Solid is the solid form of a substance in
which the atoms or molecules are arranged in a definite,
repeating pattern in three dimensions..
• Anisotropic in nature.
Single crystal
Crystalline
Polycrystalline
 Crystalline and Amorphous
Non- Crystalline or Amorphous Solid
• These are composed of randomly orientated atoms, ions, or molecules.
• No form defined patterns or lattice structures.
• Varying degrees of short range order.
• Examples of amorphous material
include amorphous silicon, plastics, &
glasses
• Isotropic in nature
 Single Crystals
Single Crystal
• A Single Crystal has an atomic structure that repeats periodically across its whole
volume.
• Even at infinite length scales, each atom is related to every other equivalent atom in
the structure by translational symmetry
• Single crystals are very rare, only with cutting edge technology we are able to create
single crystals in metals.
• Mostly single crystal structure are found in semiconductors and some carbon
allotropes like diamond.
 Polycrystalline material
Polycrystalline
• A Polycrystalline Solid is made up of an aggregate of many small single crystals
(crystallites or grains).

• Polycrystalline materials have a

periodic array of atoms over many
atomic or molecular dimensions.
• Grains are separated by Grains
Boundaries.
 Crystal Structure
• All metals are crystalline in nature.
• A Crystalline material has atoms arranged in
periodic fashion.
Crystal Structure
• Three dimensional and periodic array of atoms
in space is called Crystal structure.
• Any solid which have such crystal structure is
called a crystal.
• To visualize this array we use a geometric framework called lattice.
 Lattice
Lattice
• A lattice is just a geometrical term, which represents only an array of points. When
these points are replaced by atoms, ions or particles, it forms a Crystal Structure.
• Such atoms, ions or particles are called Basis or Motif.
• A basis or Motif is an atom or group of atoms associated with each lattice points.

Lattice Motif Crystal

(Basis)

• Geometry or periodicity • Group of atoms to be • Periodic arrangement

of crystal. repeated of group of atoms
• How to repeat • What to repeat
 Relationship between Lattice and Motif

• Space Lattice: A lattice is also called a space lattice.

• One important property of lattice or space lattice is that it is an array of points
such that every point has identical surroundings.
 Lattice Structure
Unit Cell
• The smallest group of points in lattice which has the overall symmetry of a lattice, and
which when repeated over and again in 3D, produces a complete crystal lattice.
• A unit cell contains complete information of crystal structure.
• The lattice constant, or lattice
parameter, refers to the physical
dimension of unit cells in a crystal
lattice.
• Axial lengths a, b and c, and Axial
angles α, β and γ are lattice
constant.
 7 crystal system
• A unit cell, when stacked together over and again, should be able to fill the space.
• Bravais found that only 7 lattice unit cell fulfil this criteria.
• These are called 7 crystal system.
 Primitive and Non-Primitive Lattices
Primitive Lattices
• In primitive cell lattice
points are only possible at
corners
Simple unit cell Face Centred unit cell
Non primitive unit
• These cell may have lattice
point at face centre or
body centre or end centre.

Body Centred unit cell End centred unit cell

 Bravais Lattices
Crystal System Lattice Parameters S B F E Total
Cubic 𝑎 = 𝑏 = 𝑐, 𝛼 = 𝛽 = 𝛾 = 90° √ √ √ 3
Tetragonal 𝑎 = 𝑏 ≠ 𝑐, 𝛼 = 𝛽 = 𝛾 = 90° √ √ 2
Orthorhombic 𝑎 ≠ 𝑏 ≠ 𝑐, 𝛼 = 𝛽 = 𝛾 = 90° √ √ √ √ 4
Monoclinic 𝑎 ≠ 𝑏 ≠ 𝑐, 𝛼 = 𝛽 = 𝛾 = 90° √ √ 2
Hexagonal 𝑎 = 𝑏 ≠ 𝑐, 𝛼 = 𝛽 = 90°, 𝛾 = 120° √ 1
Rhombohedral 𝑎 = 𝑏 = 𝑐, 𝛼 = 𝛽 = 𝛾 ≠ 90° √ 1
Triclinic 𝑎 ≠ 𝑏 ≠ 𝑐, 𝛼 ≠ 𝛽 ≠ 𝛾 ≠ 90° √ 1
• Why are some of the entries missing?
 Why is there no edge- centred cubic lattice?
 Why is the F- centred tetragonal lattice missing?
Bravais Lattices
 XRD- Crystallography
• X-ray diffraction techniques are very useful for crystal structure analysis and
identification of different types of crystals.
• Diffraction occurs when waves traveling through an object whose dimensions are
order of wavelength.
  2d
• Typical inter atomic spacing in crystals is 2-5°A.
• The x-rays have wavelengths (0.02°A to 100°A) in this range . Hence x-ray diffraction
is utilized to study the crystal structures
 XRD- Crystallography
Application of XRD crystallography
1. Differentiation between crystalline and amorphous materials;
2. Determination of the structure of crystalline materials;
3. Calculate lattice parameters;
4. Determination of the orientation of single crystals;
5. Determination of the texture of poly-grained materials;
6. Measurement of strain and small grain size.
 Bragg’s Law
• proposed by William Lawrence Bragg and
A C
William Henry Bragg in 1913.
A’ C’
• W. L. Bragg explained this by modeling the
crystal as a set of discrete parallel planes
𝜽 B 𝜽
separated by a constant parameter d.
D 𝜽 𝜽
d F
• The incident X-ray radiation would
produce a Bragg peak if their reflections B’
d
off the various planes interfered Atomic scale crystal lattice planes

constructively.
 Bragg’s Law
• For constructive interference,
Path difference = nλ
But path difference = DB’ + FB’ = d sin𝜃 + d sin𝜃
= 2d sinϴ
So, 2d sinϴ = nλ.
This is called Bragg’s Law.
d = interplanar distance.
n = integer value, order of reflection
λ = wavelength of X-ray used
 Structure Determination
• In a diffractometer, the intensity of
diffracted light from the sample is
plotted against 2ϴ.
• Peaks in the diffractometer recording
correspond to positions where the
Bragg condition is satisfied.
• d spacing can be calculated from
Braggs’ law by taking value of ϴ at
these peaks (and wavelength of X-ray
used)
 Summary
• A space lattice is an infinite array of points, all with identical surroundings.
• A crystal structure is obtained by combining a space lattice with a basis.
• Space lattices are limited to fourteen, but known crystal structures run into
thousands.
• X-ray diffraction is used for crystal structure and interplanar spacing determinations.
A beam of x-rays directed on a crystalline material may experience
diffraction (constructive interference) as a result of its interaction with a series
of parallel atomic planes.
• The Bragg law gives the condition for diffraction by a crystal.
Thank You
 Miller Indices

Presented By:
Rajnish Kumar Singh
Assistant Professor
Mechanical Engineering Department
Lecture Details: GIET(A), Rajahmundry
Unit- I, Topic- 4
Subject – Metallurgy and Material Science
ME, II Year/ I Semester
 Lesson Objectives
After studying this chapter you should be able to do the following:
 Determine the Miller indices for Crystallographic direction and plane in a crystal
structure.
 Draw the direction vector or planes in crystal for given miller indices.
 List out the different features of miller indices.
 Determine the family crystallographic directions/ planes related to certain
crystallographic directions/ planes by symmetry of crystal.
 Miller Indices
• To study crystals, we need to specify directions or planes in the crystals.
• William miller, a scientist, a set of specific notations to specify the directions or planes
in crystal.
• These are called Miller Indices.
• Miller indices can be defined for directions as well as for planes in crystals.
• Rules and techniques to find these indices are explained in the next slides separately
for directions and then for planes.
 Miller Indices for Directions
z
1. Choose a point on the direction vector as the origin.
2. Choose a coordinate system with axes parallel to
the unit cell edges.
3. A crystallographic direction is defined as a line
between two points, or a vector.
4. Find the coordinates of another point on the
direction in terms of a, b and c.
1, 0, 0
y 5. These three numbers are multiplied or divided by a
common factor to reduce them to the smallest
x integer values. 1, 0, 0
1a+0b+0c 6. Put in square bracket [u v w].
[1 0 0]
 Determination of Direction Indices
1 Q. Find the miller indices of given direction

Example 1: 0a+ 0b + 1c Example 2: 1a+ 1b + 0c

3 001 110
z [0 0 1] [1 1 0]
y 1
Example 3: 0a+ 1b + 1c Example 4: a+ 1b + 0c
x 2
4 011 1
2
1 0
2 [0 1 1]
120
[1 2 0]
Determination of Direction Indices
Q. Find the miller indices of given direction
a) 1a + (-1b) + 0c
z
b) 1 -1 0
y
x c) [1 1 0]
-ve indices are shown as a bar over the number

Q. Find the miller indices of given direction

 Features of miller Indices for Direction
1. Miller Indices of direction represents only the
orientation of the line corresponding to the direction
and not its position or sense.
2. All parallel directions have the same miller indices. z
3. In case a vector not passing through origin, it can be x
repositioned by drawing a parallel vector through origin. y
4. Miller indices for are always shown in lowest integer
values and are enclosed in square brackets [u v w] (no
commas).
 Family of Crystal Directions
• <u v w> = [u v w] and all other directions related to [u v w]
by symmetry of the crystal.

• For simple cubic cell, direction corresponding to cube

edges have following family of directions
<1 0 0> = [1 0 0], [0 1 0], [0 0 1]
[1 0 0], [0 1 0], [0 0 1]

• For simple tetragonal, direction corresponding to cube

edges have following family of directions
<1 0 0> = [1 0 0], [0 1 0], [0 0 1]
[1 0 0], [0 1 0], [0 0 1]
 Miller Indices for Planes
Steps to find Miller Indices
z
1. Choose a coordinate system with origin (not on the
plane)
2. Determine the intercepts of the plane along the
crystal axes. 1∞∞
y 3. Take the reciprocals of those intercepts, which may
be fractions. 1 0 0
x
4. Convert the reciprocals into smallest integers.
5. Enclose in parenthesis. (1 0 0)
 Determination of Miller Indices for planes

z Q. Find the miller indices of given planes.

Example 1: Example 2:
Origin 0 Origin 0
Coordinates xyz Coordinates xyz
0 Intercepts ∞∞1 Intercepts ∞1∞
y Reciprocals 001 Reciprocals 010
x Smallest Integers 001 Smallest Integers 010
Miller Indices (0 0 1) Miller Indices (0 1 0)
 Determination of Miller Indices for planes

z Q. Find the miller indices of given planes

Example 3:
Origin 0
Coordinates xyz
Intercepts 111
y Reciprocals 111
Smallest Integers 111
x
Miller Indices (1 1 1)
 Negative Miller Indices for planes
Q. Find the miller indices Example 3:
of given planes
Origin 0
z
Coordinates xyz
Intercepts 1 -1∞
Reciprocals 1 -1 0
Smallest Integers 1 -1 0
y Miller Indices (1 𝟏 0)

x -ve indices are shown as a bar over the number

 Features of Miller Indices
• Miller indices of a plane specifies only its orientation in space
and not its position.
• All parallel planes have same miller indices. (h k l) = (ℎ 𝑘 𝑙)
• In case any plane passes through origin, it can be repositioned (0 0 1)
by drawing a parallel plane.
• The interplanar spacing between adjacent planes of Miller
indices (hkl), 𝑑ℎ𝑘𝑙 , is defined as the spacing between the first
such plane and a parallel plane passing through the origin.
𝑎
𝑑ℎ𝑘𝑙 = , (Cubic)
ℎ2 +𝑘 2 +𝑙 2
• Miller indices for are always shown in lowest integer values
and are enclosed in parenthesis (h k l). (no commas). (0 0 1)
 Interplanar Spacing and Diffraction Angle
For BCC iron, Compute. (a) the interplanar spacing and
(b) the diffraction angle for the (220) set of planes.
The lattice parameter for Fe is 0.2866 nm. Also, assume that monochromatic radiation
having a wavelength of 0.1790 nm is used, and the order of reflection is 1.

Given, 𝑎 0.2866 𝑛𝑚
𝑑ℎ𝑘𝑙 = = = 0.1013 𝑛𝑚
(hkl) = (220) ℎ2 +𝑘 2 +𝑙 2 22 + 22 + 02

a = 0.2866 nm.
𝑛λ 1 𝑥 0.1790𝑛𝑚
λ = 0.1790 nm 𝑠𝑖𝑛𝜃 = = = 0.884
2𝑑 2 𝑥 0.1013 𝑛𝑚
n=1 𝑜𝑟, 𝜃 = 62.13°
𝑜𝑟, 2 𝜃 = 124.26° (diffraction angle)
 Family of Crystal Plans
• {h k l} = (h k l) and all other plans related to [h k l] by symmetry
of the crystal.

• For simple cubic cell, plans corresponding to cubic faces have

following family of plans
{1 0 0} = (1 0 0), (0 1 0), (0 0 1)
(1 0 0), (0 1 0), (0 0 1)

• For simple tetragonal cell, plans corresponding to tetragonal

faces have following family of plans.
{1 0 0} = (1 0 0), (0 1 0), (0 0 1)
(1 0 0), (0 1 0), (0 0 1)
 Summary
• Crystal directions and crystal planes are denoted by the Miller indices.
• Crystallographic points, directions, and planes are specified in terms of indexing
schemes.
• The basis for the determination of each index is a coordinate axis system
defined by the unit cell for the particular crystal structure.
• Directional indices are computed in terms of the vector projection on each
of the coordinate axes.
• Miller Indices of direction represents only the orientation of the line corresponding to
the direction and not its position or sense.
 Summary
• Planar (or Miller) indices are determined from the reciprocals of axial intercepts.
• Miller indices of a plane specifies only its orientation in space and not its position.
• Miller indices, directional or planar, can be both positive and negative.
• A negative index is always shown with a bar over it.
Miller Indices Notation
Directional indices [u v w]
Family of directional indices <u v w>
Planar Indices (h k l)
Family of Planar indices {h k l}
Thank You
 BCC, FCC, HCP Unit Cells

Presented By:
Rajnish Kumar Singh
Assistant Professor
Mechanical Engineering Department
Lecture Details: GIET(A), Rajahmundry
Unit- I, Topic- 5
Subject – Metallurgy and Material Science
ME, II Year/ I Semester
 Lesson Objectives
After studying this chapter you should be able to do the following:
 Describe the difference in simple cubic, FCC, BCC and HCP unit cells.
 Determine the relationships between lattice parameter and atomic radius for these
crystal structures.
 Calculate Packing efficiency and co-ordination number of FCC, BCC and HCP unit cell
crystal structures.
 Calculate the planar and volumetric density for different crystals.
 Most common Unit Cells
Unit Cell
• The atomic order in crystalline solids indicates that small groups of atoms form a
repetitive pattern.
• Thus, in describing crystal structures, it is often convenient to subdivide the structure
into small repeat entities called unit cells.
• Most Solids Crystallize in following forms of crystal structures.
 Face Centered Cubic cell
 Body Centered Cubic Cell
 Hexagonal Close- Packed Structure
 Simple Cubic Cell
Simple Cubic Unit Cell
• A Simple Cubic Cell consists of Eight corner atoms.
• The adjacent corner atoms touches each other.
• Because this structure is inefficient, only one element -polonium- crystallizes in a
simple cubic structure

Space filling model Open Structure Hard- Solid Structure

 Face Centred Cubic (FCC)
Face Centred Cubic Unit Cell
• A FCC consists of eight corner atoms and one atom at the centre of each face.
• Example- Aluminium, Copper, Nickel, Gamma Iron (𝛾 − Fe), Gold, and Silver.

Hard- Solid Structure Open Structure Space filling model

 Body Centred Cubic (BCC)
Body Centred Cubic Unit Cell
• A BCC consists of eight corner atoms and one atom at centre of cubic cell.
• Example- lithium, sodium, barium, vanadium, Alpha Iron (𝛼 − Fe).

Hard- Solid Structure Open Structure Space filling Model

 Hexagonal Closed-Packed Structure (HCP)
Hexagonal Closed-Packed Structure (HCP)
• The top and bottom faces of the unit
cell consist of six atoms that form
regular hexagons and surround a single
atom in the center.

• Another plane that provides three additional atoms to the unit cell is situated
between the top and bottom planes.
• Example- lithium, sodium, potassium, chromium, barium, vanadium.
 Number of atoms per unit cell
Unit Cell Description No of atoms/ unit cell

Simple 8 corners = [8 × (1/8)] = 1

FCC 8 corners + 6 face centred = 1 (for corners) + [6 × (1/2)] = 4

BCC 8 corners + 1 body centred = 1 (for corners) + 1 (Center)= 2

HCP 12 corners (6 bottom+6 top) + 2 atoms = 12 × (1/6)

at face centers + 3 atoms in the interior + 2 × (1/2) + 3 (interior) = 6
 Co ordination Number
Number of nearest or immediate neighboring
atoms, which directly surrounds a given atom in a
crystal lattice.

Unit Cell Coordination Number

Simple 6
FCC 12
BCC 8
HCP 12
 Packing Efficiency or Packing Factor
Packing Efficiency or Packing Factor
• It is the ratio of volume of atoms in a unit cell to total volume of unit cell.
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
• Packing Factor = ,
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

4
𝑛. 𝜋 𝑟3
3
= 3 , ( for cubic cell)
𝑎
Where n = effective number of atoms in unit cell
r = atomic radii
a = lattice constant
 Simple Cubic Cell
Atomic Radii
• In a simple cubic lattice, a corner atom touches with another corner atom.
𝑎
• Therefore, 2r=a. So, the atomic radius of an atom in a simple cubic unit cell is .
2
Packing Efficiency of Simple Cubic
• For Simple cubic cell,
4 4
𝑛. 3 𝜋 𝑟 3 1. 3 𝜋 𝑟 3
• Packing Factor = 3 =
𝑎 2𝑟 3
= 0.52
• It means, 52% of the volume of the unit cell
is occupied by atoms
 Face Centred Cubic (FCC)
Atomic Radii (r) and lattice constant (a)
• As can be seen in figure,
a2 + a2 = (4r)2
2a2 = 16r2
a=2 2𝑟

Packing Efficiency of FCC

• For Simple cubic cell,
• effective number of atoms in unit cell = 4
• Atomic radii, a = 2 2 𝑟
4
𝑛. 3 𝜋 𝑟 3 4. 4 𝜋 𝑟 3 It means, 74% of the volume of
3 the unit cell is occupied by atoms
• Packing Factor = = = 0.74
𝑎3 16 2𝑟 3
 Body Centred Cubic (BCC)
G
Atomic Radii (r) and lattice constant (a)
F
• As can be seen in figure, H
E
AF2 = FC2 + AC2
O
But AB2 + BC2 = AC2
So, AF2 = FC2 + AB2 + BC2
(4r)2 = 3 a2 D C

Packing Efficiency of BCC A B

• Effective number of atoms in unit cell = 2 It means, 68% of the volume of the
• Atomic radii, (4r)2 = 3 a2 unit cell is occupied by atoms
4
𝑛. 3 𝜋 𝑟 3
• Packing Factor = = 0.68
𝑎3
 HCP – c/a Ratio
• c = spacing between two successive A layers.
• B layer lies midway between two successive A layers

• For a tetrahedron,
2
Height = x edge
3
2 a a
c/2 = xa
3
c/2
2 2
c/a = 3 a
a
c/a ≈ 1.633 For ideal HCP
 Hexagonal Closed-Packed Structure (HCP)
Packing Efficiency
• From figure, a = 2r
• Also c/a = 1.633
√3
• In a hexagon, Base Area = 6 x ( x a2)
4
• Total Volume of unit cell = Area x Ht.
√3
= 6 x ( x a2) x c
4
= 4.24 a3
4
• V(sphere) = 3 πr3 x 6
8𝜋 r3 It means, 74% of the volume of the unit
• Packing Fraction = = 0.74 cell is occupied by atoms
4.24 a3
 Density of a Crystal
Theoretical (volumetric) Density of a Crystal
nA
• 𝜌 = VC NA ,
Where, NA = Avogadro’s number = 6.022 x 1023 atoms/ mole
VC = volume of the unit cell
A = atomic weight
n = number of atoms associated with each unit cell

Q. Al is FCC structure; Lattice parameter is 4.05𝐴0 ; Atomic weight of Al is 26.98 g/mol.

Calculate the theoretical density of Aluminum (Al).
Summary
Thank You
 Crystallization of metals
and
Grain Boundaries
Presented By:
Rajnish Kumar Singh
Assistant Professor
Mechanical Engineering Department
Lecture Details: GIET(A), Rajahmundry
Unit- I, Topic- 6
Subject – Metallurgy and Material Science
ME, II Year/ I Semester
 Lesson Objectives
After studying this chapter you should be able to do the following:
 Understand the concept of supercooling and driving force for crystallisation.
 Explain in detail the steps involved in crystallisation of metals.
 Describe atomic structure within grains and grain boundaries.
 Establish relation between grain boundaries and properties of materials.
 Describe different methods to determine grain size and relation between grain size
and material properties.
 Crystallisation
• Crystallization or solidification is the process of transformation of a metal from liquid
state to solid state in which the crystal lattice is formed.
• Crystallization occurs in three stages:
i. Supercooling/ Undercooling
ii. Nucleation
iii. Crystal Growth
 Supercooling/ Undercooling
• Thermodynamically both liquid and solid are
equally stable at melting point.
• To start solidification, temperature has to bring
down below melting point. This lowering of
temperature is called undercooling or
supercooling.
• It provides driving force for next step, i.e.,
nucleation.
• Low supercooling → slow nucleation rate → few nuclei → large crystals
• Large supercooling → rapid nucleation rate → many nuclei → small crystal
 Nucleation and Growth
Nucleation – It is initial formation of nuclei of a distinct thermodynamic phase.
• At temperatures near to solidification, groups of atoms (clusters) start coming
together due to lowering in temperature.
• These groups or clusters may appear, exist for a certain time and then fall apart to
appear again at some other place.
• So mostly these clusters are very unstable and only become stable after they become
greater than a certain size. This size is called critical size.
• The critical size is the minimum size of the crystal that must be formed by the
clustering atoms in a liquid so that solid particle becomes stable and begins to grow.
 Nucleation and Growth
• The solid is called an “Embryo” (unstable), if it’s radius is less than the critical radius
and is a “Nucleus” (stable), if its radius is greater than the critical radius.
Growth
• As cooling continues more atoms get attached to pre-existing stable nuclei and nuclei
continues to grow in size. This stage is called growth.
• Atoms attach themselves onto pre-existing nuclei as per crystal structure of solid.
• Once stable nuclei keeps growing and only ceases to grow when it meets other
growing nuclei.
 Grain and Grain Boundaries
• As cooling continues, more atoms attach themselves to nuclei and nuclei grows into
small crystals.
• The crystallographic orientation varies from crystal to crystal.
• So after solidification each nuclei grows into a crystal having distinct orientation of
atoms.
• These small crystals are called grains & are separated from one another by grain
boundaries.
• Such material made up of grains of different orientation is called Polycrystalline.
Grain and Grain Boundaries
 Homogenous and Heterogeneous Nucleation
• Occurs spontaneously and randomly.
Homogeneous • Requires supercooling/ undercooling
Nucleation • Liquid→Solid walls of container, inclusions.
Heterogeneous
• Solid→Solid walls of container, inclusions,
Grain boundaries, Staking Faults

• For the homogeneous type, nuclei of the new phase form uniformly throughout the parent phase
due to effect of undercooling.
• Whereas for the heterogeneous type, nuclei form preferentially at structural inhomogeneities
such as container surfaces insoluble impurities grain boundaries, dislocations and so on.
 Effect of Grain size on properties of metals
Hall–Petch equation
• Relation between yield stress and

Mechanical properties →
grain size

1
σy = σ 0 + K
d
σy = Yield stress/ strength
σ0 = Constant (represent resistance to
dislocation motion)
K = Co efficient
d = Average diameter of grains Increasing grain size→
 Effect of Grain size on properties of metals
Effect of grain size on mechanical properties
• Metals and alloys are stronger if the grain size is reduced.
• Metals with fine grain structure possess high strength and hardness.
• Also they possess high fatigue strength and toughness (i.e., resistance to impact).
• Metals with coarse grains are less tough and less hard.
• Coarse grains structure gives high ductility, good machinability and formability.
• Large grain size is also improve the hardenability.
 Determination of Grain Size
Intercept method
1. Straight lines all the same length are drawn through several photomicrographs.
2. The grains intersected by each line segment are counted as follows.
• Line cutting a boundary- 1
• Line touching a boundary- ½
1
• Line cutting through a triple point- 12
3. Mean intercept length = 𝐿
𝐿𝑖𝑛𝑒 𝑙𝑒𝑛𝑔𝑡ℎ
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 x 𝑀𝑎𝑔𝑛𝑖𝑓𝑖𝑐𝑎𝑡𝑖𝑜𝑛
 Determination of Grain Size
Comparison method
• The ASTM (E112-13 standard) has prepared several
standard comparison charts, all having different
average grain sizes having grain number ranging
from 1 to 10.
• A specimen is photographed at a magnification of
100.
• Grain size is expressed as the grain size number of
the chart that most nearly matches the grains in the micrograph.
 Determination of Grain Size

How grain size number is assigned for ASTM grain Number of grains per
size number square inch at
standard ASTM charts (n) magnification of 100x (N)
• Let n represent the grain size number, 1 1

• And N the average number of grains per 2 2

3 4
square inch at a magnification of 100.
4 8
• Then,
5 16
𝑁= 2𝑛−1
6 32

7 64
 Summary
• Based on their grain structure materials can be divided in crystalline and amorphous.
• Crystalline material can be further divided into single crystal and polycrystalline.
• A polycrystalline material is made up of grains, which is result of simultaneous
nucleation and grain growth during solidification.
• Relation between grain size and yield stress is given by Hall- Petch equation.

• Grain size can be determine by mostly two methods: Intercept method and
Comparison Method.
Thank You
 Constitution of Alloys

Presented By:
Rajnish Kumar Singh
Assistant Professor
Mechanical Engineering Department
Lecture Details: GIET(A), Rajahmundry
Unit- I, Topic- 7
Subject – Metallurgy and Material Science
ME, II Year/ I Semester
Topic Outcomes
After studying this chapter you should be able to do the following:
 Familiarise with alloys, alloy system and their classification based upon their
structure.
 Acquaint with necessity of alloying.
 Classify alloys bases upon their atomic structure and arrangement.
 Describe different types of solid solutions and properties.
 Describe ordered and disordered solid solutions.
 Alloying of Metals
Alloys
Base
• It is a substance that has metallic properties and is Metal

composed of two or more chemical elements, of

which at least one is a metal. Alloy
• If the system is made up of two elements, it is
Alloying
Element
called a Binary alloy system; three elements, a
Ternary alloy system; etc.
• Ex.:- Aluminum is alloyed with zinc, copper etc. to gain strength, Iron is alloyed with
carbon to gain strength and ductility
 Why alloying is done?
Alloying helps to make a metal suitable for service
• To improve hardness and wear resistance.
• To improve corrosion resistance.
• To improve strength and toughness.
• To improve machinability, weldability and hardenability.
• To retain properties at elevated temperature.
• To improve magnetic and electrical properties.
 Classification of Alloys
Substitutional
Solid Solution
Homogeneous Interstitial
Alloys

Only single phase

is present
Intermetallic
Compounds

When more than one

phase is present Compounds/ Interstitial
Intermediate alloy phase Compounds
Mixture
Electron
Compounds
 Solid solution
• A solid solution is simply a solution in the solid state and consists of two kinds of
atoms combined in one type of space lattice.
• A solid solution is homogeneous.
• Component of higher composition is called solvent while all other components are
called solute.
• Solid solution depending upon their solubility limit can be – unsaturated, saturated
and supersaturated.
• Example: Austenite – Solid solution of C in 𝛾 − 𝐹𝑒(FCC)
Ferrite – Solid solution of C in 𝛼 − 𝐹𝑒(BCC)
 Freezing of Metals and Solid solutions
Temperature →

Temperature →
𝑻𝒎 --

Time→ Time→

A pure metal melts/ freezes at a single temperature while alloys mostly melts/freezes over a
temperature range.
 Types of Solid solution
Solid Solution

Substitutional solid solution Interstitial Solid solution

• The solute atoms substitute the solvent • Solute atoms (small atomic radii) fit into
atoms in the lattice of solvent. the spaces or interstices of the lattice
structure of the larger solvent atoms
• 𝛼 − 𝑏𝑟𝑎𝑠𝑠(Cu in Zn) • Austenite (C in FCC-Iron)

𝑟𝑠𝑜𝑙𝑢𝑡𝑒 ≈ 𝑟𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑟𝑠𝑜𝑙𝑢𝑡𝑒 ≪ 𝑟𝑠𝑜𝑙𝑣𝑒𝑛𝑡

 Substitutional solid solutions
𝛂 − 𝐁𝐫𝐚𝐬𝐬

Cu (CCP) Zn (HCP) Solid solution of Cu and Zn

Structure: CCP (same as Cu)
Crystal structure of a substitutional solid solution same as that of one of it’s components
 Interstitial Solid solution
Austenite: Interstitial solid solution of C in FCC-iron. C- atoms occupies octahedral sites.

Carbon atom
• 1 OHV per atom (for FCC)
Ferrous Atom

• Interstitial Spaces in lattice structure are restricted in size.

• So only small atoms like hydrogen, boron, carbon, nitrogen and oxygen can form
interstitial solid solution
 Solubility Limit
• Maximum amount of solute that can be dissolved in a solid solution.
• Cu in Zn 2.8%
Both are substitutional solid
solution { • Cu in Ni 100%
Solubility in Interstitial Solid Solution
 Geometrical limit – only those solute atoms which can fit in voids.
 No of voids available
 Strain in lattice – Solution energy increases with number of solute atoms
 Electronegativity – Difference should not be large
Interstitial solid solution can never exhibit unlimited solid solubility
 Hume Rothery’s Rule
• Unlike interstitial solid solution there is no Geometric solubility limit for substitutional
solid solution, nor is there any limit on number of solute atoms that can be dissolved.
• But as seen in example of Cu-Zn in previous slide, solubility limit is also present in
many of the substitutional solid solution.
• Solubility of a substitutional solid solution is explained by Hume – Rothery Rules.
Rule 1: Crystal Structure Factor
 Complete solid solubility of two elements is never obtained unless the elements have
the same types of the crystal structure.
Cu (CCP) Complete solubility not Cu (CCP)
100% solubility
Zn (HCP) possible Ni (CCP)
 Hume Rothery’s Rule
Rule 2: Size Factor
• The difference of the atomic diameter between solute atoms and solvent atoms
should be not more than 15%.

Cu (r = 1.28Å) Cu (r = 1.28Å) Low Cu (r = 1.28Å) Very Low

100% solubility
Ni (r = 1.25Å) Zn (r = 1.38Å) Solubility Cd (r = 1.54Å) solubility
Rule 3: Electronegativity Factor
Rule 4: Valancy Factor
• Electronegativities and valances of solute and solvent atoms should be close
(difference should be small)
Large difference in electronegativity or Valancy indicates a tendency towards formation
of compounds
 Intermediate alloy phase/ Compounds
• The isomorphous and eutectic phase diagrams discussed thus far are relatively
simple.
• Those for many binary alloy systems are much more complex as they contain
Intermediate solid Phases.
• The most common intermediate alloy phases are:-
 Intermetallic Compounds or Valence Compounds
 Interstitial Compounds
 Electron Compounds
 Intermediate alloy phase/ Compounds
Intermetallic Compounds or Valence Compounds
• They are generally formed between chemically dissimilar metals.
• Metallic Bonding. Examples:-𝑀𝑔2 𝑃𝑏, 𝐶𝑢2 𝑆𝑒 etc.
• Have a fixed composition but doesn’t follow Valancy rule as seen in normal chemical
compounds
Interstitial Compounds
• The word interstitial means between the spaces.
• They are formed between the transition metals such as Sc, Ti, Ta, W and Fe with
hydrogen, oxygen, carbon, boron and nitrogen.
• Variable composition. Examples are 𝐹𝑒4 𝑁, 𝐹𝑒3 𝐶, 𝑊2 𝐶, 𝐶𝑟𝑁 etc.
 Intermediate alloy phase/ Compounds
Electron Compounds
• In alloys of copper, gold, silver, iron and nickel with the metals cadmium, magnesium,
tin, zinc, and aluminum, a number of compounds are formed.
• They have a definite ratio of valence electrons to atoms and are therefore called
electron compounds.

Compound Valance Electron/Atom Ratio Crystal Structure

AgCd 3:2 Body centered cubic
Ag5Cd8 21:13 Complex cubic
AgCd3 7:4 Close packed hexagonal
 Summary
• Alloys is a substance that has metallic properties and is composed of two or more
chemical elements, of which at least one is a metal.
• A solid solution is simply a solution in the solid state and consists of two kinds of
atoms combined in one type of space lattice.
• Two types of solid solutions may be formed – Substitutional and Interstitial.
• In substitutional solid solution, the solute atoms substitute the solvent atoms in the
lattice of solvent.
• Interstitial solid solution are formed when atoms of small atomic radii fit into the
spaces or interstices of the lattice structure of the larger solvent atoms.
 Summary
• Cu-Zn or Cu-Ni is great example of substitutional solid solution, while Carbon and
iron forms interstitial solid solution.
• Solubility of interstitial solution is always limited by size of solute atoms and number
of voids available per solvent atom.
• Solubility of substitutional solid solution is determined by Hume Rothery Rules.
• 4 Hume Rothery rule –
 Crystal Structure factor
 Size factor
 Electronegativity factor
 Valancy factor
Thank You