Module 1

METALLURGY & MATERIAL SCIENCE

ELDHO PAUL,
Assistant Professor,
Department of Mechanical Engineering,
Mar Athanasius College of Engineering,
Kothamangalam – 686 666, Kerala
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 Department of Mechanical Engineering
Mar Athanasius College of Engineering

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Preamble
• Understanding of the correlation between the chemical bonds and crystal
structure of metallic materials to their mechanical properties.

• Recognize the importance of crystal imperfections including dislocations in

plastic deformation.

• Learning about different phases and heat treatment methods to tailor the
properties of Fe-C alloys.

• Examine the mechanisms of materials failure through fatigue and creep.

• To determine properties of unknown materials and develop an awareness

to apply this knowledge Mar
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inAthanasius
material design.
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Prerequisite
• PHT 110 Engineering Physics
• CYT 100 Engineering Chemistry

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Course Outcomes
At the end of the course students will be able to,

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 PO 1 Engineering Knowledge PO 7 Environment & Sustainability
PO 2 Problem Analysis PO 8 Ethics
PO 3 Design & Development of Solutions PO 9 Individual & Team work
PO 4 Investigation of Complex Problem PO 10 Communication
PO 5 Modern Tools Usage PO 11 Lifelong Learning
PO 6 Engineer and Society PO 12 Project management & Finance
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 MODULE - 1
• Earlier and present development of atomic structure - Primary bonds: -
characteristics of covalent, ionic and metallic bond - properties based
on atomic bonding: - Secondary bonds: - classification, application.
(Brief review only).
• Crystallography: - SC, BCC, FCC, HCP structures, APF - theoretical
density simple problems – Miller Indices: - crystal plane and direction -
Modes of plastic deformation: - Slip and twinning -Schmid’s law -
Crystallization: Effects of grain size, Hall - Petch theory, simple
problems.

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COURSE CONTENT

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Introduction
History
Historically periods of civilization are divided on the basis of
material development
1. Stone Age
2. Bronze Age
3. Iron Age
4. Plastic Age
5. Silicon Age

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Importance of Materials

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Material Failure

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Structure at different scale

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Atomic Structure
• The atomic structure of an element refers to the constitution of its nucleus and
the arrangement of the electrons around it. Primarily, the atomic structure of
matter is made up of protons, electrons and neutrons.

• The protons and neutrons make up the nucleus of the atom, which is surrounded
by the electrons belonging to the atom. The atomic number of an element
describes the total number of protons in its nucleus.

• Neutral atoms have equal numbers of protons and electrons. However, atoms
may gain or lose electrons in order to increase their stability and the resulting
charged entity is called an ion.

• Atoms of different elements have different atomic structures because they

contain different numbers of protons and electrons. This is the reason for the
unique characteristics of different elements.
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Review of Atomic Structure

1. Earlier concepts of Atomic Models

2. Present atomic model
3. Chemical bonds
(a) Primary bonds
– Ionic bond
– Covalent bond
– Metallic bond
(b) Secondary bonds
4. Mechanical properties

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Atomic Structure (Earlier concepts)

1. Democritus
2. Dalton
3. J J Thomson
4. Millikan
5. Rutherford

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 Democritus (460 –370 BC)
• Greek philosopher
• Can matter be subdivided into fundamental particles?
• Develops the idea of atoms (derived from Greek word atoma - means indivisible)
• All matter can be broken down into indivisible atoms.

According to the early theory of atoms developed by Democritus, Water

atoms would be round and flow over one another while iron atoms would
01-Nov-20 be jagged and stay solidly together.
Mar Athanasius This is not the modern view.
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John Dalton (Dalton’s Atomic Theory (1780))
• Suggested that all matter was made up of tiny spheres that were
able to bounce around with perfect elasticity and called them
ATOMS
• Every matter is made up of atoms.
• Atoms are indivisible.
• Specific elements have only one type of atoms in them.
• Each atom has its own constant mass that varies from element
to element.
• Atoms undergo rearrangement during a chemical reaction.
• Atoms can neither be created nor be destroyed but can be
transformed from one form to another.

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• Dalton’s atomic theory successfully explained the Laws of chemical
reactions, namely, the Law of conservation of mass, Law of constant
properties, Law of multiple proportions and Law of reciprocal
proportions.

Demerits of Dalton’s Atomic Theory

• The theory was unable to explain the existence of isotopes.
• Nothing about the structure of atom was appropriately explained.
• Later, the scientists discovered particles inside the atom that proved, the
atoms are divisible.
• The discovery of particles inside atoms led to a better understanding of
chemical species, these particles inside the atoms are called subatomic
particles. The discovery of various subatomic particles is as follows:
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J J Thompson (1898) (Thomson Atomic Model)
• Thompson pictured atom as uniform spheres of positively charged
substance (positive electric fluid) with negative electrons embedded in it
• Plum Pudding Model
• His work is based on an experiment called cathode ray experiment
• Electrons were supposed to assume certain stable positions inside atomic
body due to – attraction by positive charge and repulsion by other
electrons.

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Cathode Ray Experiment
• A high voltage power supply is connected using electrodes
• When a high voltage power supply is switched on, there were rays
emerging from the cathode towards the anode, called cathode rays
• Thompson concluded that cathode rays are made of negatively
charged particles called “electrons”.
• On applying the electric and
magnetic field upon the cathode
rays (electrons), Thomson found
the charge to mass ratio (e/m) of
electrons. (e/m) for electron:
17588 × 1011 e/bg.
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• Based on conclusions from his cathode ray experiment, Thomson described
the atomic structure as a positively charged sphere into which negatively
charged electrons were embedded.

• It is commonly referred to as the “plum pudding model” because it can be

visualized as a plum pudding dish where the pudding describes the
positively charged atom and the plum pieces describe the electrons.

• Thomson’s atomic structure described atoms as electrically neutral, i.e. the

positive and the negative charges were of equal magnitude.

• Limitations of Thomson’s Atomic Structure: Thomson’s atomic model does

not clearly explain the stability of an atom. Also, further discoveries of
other subatomic particles, couldn’t be placed inside his atomic model.

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Robert Millikan’s Experiment
• Thomson found the charge to mass ratio (e/m) of electrons. (e/m) for electron:
17588 × 1011 C/Kg.
• From this ratio, the charge of the electron was found by Mullikin through oil
drop experiment. [Charge of e– = 1.6 × 10-19 C and Mass of e– = 9.1093 × 10-31
kg].
• Millikan applied electric charge to a tiny drop of oil, and measure how strong
an applied electric field had to be in order to stop the oil drop from falling.
• Since he was able to work out the mass of the oil drop, he could calculate the
force of gravity on one drop. He could then determine the electric charge that
the drop must have.
• By varying the charge on different drops, he noticed that the charge was
always a multiple of 1.6x10-19 C, the charge on a single electron. This meant
that it was electrons carrying
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this unit charge.
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Robert Millikan’s Experiment

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(Rutherford Atomic Theory) Ernest Rutherford

• Rutherford modified the atomic structure with the discovery of

another subatomic particle called “Nucleus”.
• His atomic model is based on the Alpha ray scattering experiment.
• Fired Helium nuclei on a piece of gold foil which was only a few
microns thick.
• Aimed alpha particles at gold foil by drilling a hole in a lead block.
• Expected - Since the mass is evenly distributed in gold atoms, alpha
particles should go straight through.

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Alpha Ray Scattering Experiment
Construction:
• A very thin gold foil of 1000 atoms thick is taken.
• Alpha rays (doubly charged Helium He2+) were made to bombard the
gold foil.
• Zn S screen is placed behind the gold foil.
Observations:
• Most of the rays just went through the gold foil making scintillations
(bright spots) in the ZnS screen.
• A few rays got reflected after hitting the gold foil.
• One in 1000 rays got reflected by an angle of 180° (retraced path) after
hitting the gold foil.
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• Since most rays passed through, Rutherford concluded that most of the
space inside the atom is empty.
• Few rays got reflected because of the repulsion of its positive with some
other positive charge inside the atom.
• 1/1000th of rays got strongly deflected because of a very strong positive
charge in the center of the atom. He called this strong positive charge as
“nucleus”
• He said most of the charge and mass of the atom resides in the Nucleus
• Electrons are supposed to move around nucleus in a dynamically stable
orbit (planetary model)
• Revolving electric charges radiate energy in the form of electromagnetic
waves (electromagnetic theory)
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 Rutherford’s Structure of Atom
• The nucleus is at the center of an atom, where most of the charge and mass
are concentrated.
• Atomic structure is spherical.
• Electrons revolve around the nucleus in a circular orbit, similar to the way
planets orbit the sun.

Limitations of Rutherford Atomic Model

• If electrons have to revolve around the nucleus, they will spend energy and
that too against the strong force of attraction from the nucleus, a lot of energy
will be spent by the electrons and eventually, they will lose all their energy
and will fall into the nucleus so the stability of atom is not explained.
• If electrons continuously revolve around the ‘nucleus, the type of spectrum
expected is a continuous spectrum. But in reality, what we see is a line
spectrum.
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Niels Bohr 1915 (Bohr atomic model)
• Bohr refined Rutherford's idea by adding that the electrons are like planets
orbiting the sun.
• Electrons are assumed to revolve around the atomic nucleus in discrete orbitals,
and the position of any particular electron is more or less well defined in terms
of its orbital.

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Strength and Atomic Radius…?

• As the atomic number increases, the number of electrons increases, the

number of shells increases therefore atomic radius increases.
• As a result the valence shell and valence electrons become away from the
nucleus reducing the attraction between outer shell and nucleus which in turn
reduces the strength.
• Thus, as atomic number increases, strength decreases and as atomic number
decreases strength increases.

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Wave Mechanical Model
• Electron is considered to exhibit both wave-like
and particle-like characteristics.
• An electron is no longer treated as a particle
moving in a discrete orbital rather, position is
considered to be the probability of an electron’s
being at various locations around the nucleus.

Comparison of
the (a) Bohr and (b) wave mechanical atom models
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Quantum Numbers

• Using wave mechanics, every electron in an atom is characterized by four

parameters called quantum numbers.
• The size, shape, and spatial orientation of an electron’s probability density are
specified by three of these quantum numbers.
• Principal quantum number n
• Shells are designated by the letters K, L, M, N, O, and so on, which
correspond, respectively, to n = 1, 2, 3, 4, 5, . . . ,
• This quantum number is related to the distance of an electron from the
nucleus, or its position.
• The second quantum number, l, signifies the subshell, which is denoted by a
lowercase letter—an s, p, d, or f; it is related to the shape of the electron
subshell.
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• The number of these subshells is restricted by the magnitude of n.
• Third quantum number ml.
• The number of energy states for each subshell is determined by the third
quantum number.
• For an s subshell, there is a single energy state, whereas for p, d, and f
subshells, three, five, and seven states exist, respectively.

• Fourth quantum number ms. Related to this

spin moment
• Each electron in a subshell has a spin
moment, which must be oriented either up or
down
• Two values are possible (+1/2 and -1/2), one
for each of the spin orientations
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 Schematic representation of the relative energies of
the electrons for various shells and subshells

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Electron Configurations
• Is used to determine the manner in which atoms are filled with electrons.
• The 4 sub shells are s, p, d & f.
• s, p, d and f sub shells accommodates a total of 2, 6, 10, and 14 electrons
respectively.

Notation for Quantum Numbers

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Sub shell
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• Valence electrons are those that occupy the outermost shell
• They participate in the bonding between atoms to form atomic and molecular
aggregates.
• Many of the physical and chemical properties of solids are based on these
valence electrons.
• Stable electron configurations.
• The states within the outermost or valence electron shell are completely filled.
• These elements (ne, ar, kr, and he) are the inert, or noble, gases, which are
virtually unreactive chemically. Some atoms of the elements that have unfilled
valence shells assume stable electron configurations by gaining or losing
electrons to form charged ions, or by sharing electrons with other atoms.

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Aufbau’s principle

• According to Afbau principle, electrons fill orbitals starting at the lowest

available (possible) energy states before filling higher states. (e.g. 1s before 2s)

Pauli exclusion principle

• No two electrons can have all the four quantum numbers to be the same or, if
two electrons have to placed in an energy state they should be placed with
opposite spins.
• The number of electrons that can occupy each orbital is limited by the Pauli
exclusion principle.
• This principle stipulates that each electron state can hold no more than two
electrons, which must have opposite spins. Thus, s, p, d, and f subshells may
each accommodate, respectively, a total of 2, 6, 10, and 14 electrons.
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Atomic Bonding in Solids
BONDING FORCES AND ENERGIES

• The bonding energy for these two atoms, E0, corresponds to the
energy at this minimum point. it represents the energy that would be
required to separate these two atoms to an infinite separation.

• At a state of equilibrium, The centers of the two atoms will remain

separated by the equilibrium spacing r0

• The magnitude of this bonding energy and the shape of the energy-
versus interatomic separation curve vary from material to material,
and they both depend on the type of atomic bonding.
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Bond Length (ro)
• Bond length is the distance between nuclei of two bonded atoms.
ro = 1-2 Å – primary bonds; 2-5 Å–secondary bonds
• Bond length increases & bond energy reduces with increase in
atomic number / radius.

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Deeper energy well bond and shallow energy well bond

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Properties of bonding
1. Melting Temperature (Tm)

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Properties of bonding
2. Modulus of Elasticity (E)

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Properties of bonding
3. Coefficient of Thermal Expansion (α)

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Chemical Bonding
• Chemical Bonding refers to the formation of a chemical bond between two or more
atoms, molecules, or ions to give rise to a chemical compound. These chemical
bonds are what keep the atoms together in the resulting compound.
• Atoms of all elements has a tendency to acquire an electronic configuration similar
to that of inert gases, because it represents the most stable electronic configuration.
(Lewis Octect Rule)
• It is this tendency of atoms to complete and hence stabilize their outermost orbit of
electrons, which is mainly responsible for chemical combination between atoms.
• The attractive force which holds various constituents (atom, ions, etc.) together and
stabilizes them by the overall loss of energy is known as chemical bonding.
• According to a more general rule of electron pairing, atoms of elements have a
tendency to get their electrons paired in all the occupied orbits and thus attain
greater stability.
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Classification of Chemical Bonding

(a) Primary bonds (Strong Bonds :100 -1500 kJ/mole, bond length = 1-2 Å)
• Ionic bond (METAL+ NON METAL)
• Covalent bond (NON METAL+ NON METAL)
• Metallic bond (METAL+ METAL)

(b) Secondary bonds (Weak Bonds :1-50 kJ/mole, bond length = 2-5 Å)
– Inter molecular, gases and liquids
– Feeble and less stable
• Di-pole bond
• Hydrogen bond
• Vander Waals bond

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Ionic Bonding
• Bonding between Metal + Non metal
• Transfer of electrons - easily exchange/ transfer electrons so as to stabilize
their outer shells (i.e. become more inert gas-like)
• Non Directional – over lapping of electrons - magnitude of the bond
equal in all directions around an ion OR bond posses equal strength in all
directions.
• Bond energies : 600 –1500 kJ/mol (6-15 eV/ atom)
• High melting temperature, hard, brittle, electrically and thermally
insulative.
• Example : NaCl

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Properties of Ionic Compounds

• Crystalline structure.
• A regular repeating arrangement of ions in the solid.
• Ions are strongly bonded.
• Structure is rigid.
• High melting points-because of strong forces between ions.

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Covalent bonding

• Bonding Non Metal + Non Metal

• Covalent bond- A bond formed when atoms share electrons equally
• Two atoms share one or more pairs of outer shell electrons
• Strongest of all chemical bonds
• Good overlap of orbital-bring shared electrons close both the nuclei
• Overlapping orbitals are directionally oriented and not spherically
symmetric.

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Covalent bonding
• Directional – magnitude of the bond is not equal in all directions
• Bond energies : 100 –1000 kJ/mol (1-10 eV/ atom)
• High melting temperature, hard, brittle, electrically and thermally insulative

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Metallic Bonding
• Bonding Metal + Metal
• Delocalized electrons/electron cloud/sea of electrons
• Non directional – over lapping of electrons orbitals are spherically
symmetric. Magnitude of the bond equal in all directions around an ion OR
bond posses equal strength in all directions
• Bond energy: wide range:-E (Hg) = 0.7eV/atom to E (W) = 8.8 eV/atom
• Metals are lustrous, Ductile, electrically and thermally conductive

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Metallic bond

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Why metals have high electrical conductivity…?

Metals are good conductors of electricity. This is due to the

mobility of electrons.

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Why metals have high thermal conductivity…?

Metals are good conductors of heat. This is also due to the mobility of
electrons.
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Why metals are malleable & ductile…?

• Metals are malleable (can be flattened to thin sheets) and ductile (can be
drawn into wires).
• This is because positive kernals and electrons can "flow" around each
other, without breaking the crystal structure.
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Why metals are lustrous & opaque…?
• Metals are lustrous - This is due to the uniform way that the valence
electrons of the metal absorb and re-emit light energy.
• Metals are opaque - The free electrons oscillate in the alternating
electric field of the incident light beam, absorbing energy at all
wavelengths and so making the metal opaque.
• In turn the oscillating electrons emit waves and in this way produce the
reflected beam.

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Primary bonds, bond energies & melting temperatures.

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Secondary Bonding
Secondary / Van der Waals / Physical bonds.
• They are due to van der waals force or inter molecular attractive forces,
which acts between all molecules when they are close to each other.
• They are weak in comparison to the primary bond - bonding energies are
typically in the order of only 10 kJ/mol.
• Secondary bond exists between all atoms or molecules

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Secondary Bonding

1. Dipole – dipole attraction

2. Hydrogen bond

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Polar Molecule / Induced Dipole Bonds
• Permanent dipole moments exist in some molecules by virtue of an
asymmetrical arrangement of positively and negatively charged regions,
such molecules are termed as polar molecules.

Schematic representations of (a) an electrically symmetric atom and (b) an induced atomic dipole.
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Dipole – dipole attraction / bonding

The bonding results from the attraction between the positive

end of one dipole and the negative region of an adjacent one.

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Hydrogen bond
• Hydrogen bonding, a special type of secondary bonding, is found to exist
between some molecules having hydrogen as one of the constituents.
• It is a type of polar covalent bonding between oxygen and hydrogen
wherein the hydrogen develops a partial positive charge. This implies that
the electrons are pulled closer to the more electronegative oxygen atom.
• This creates a tendency for the hydrogen to be attracted towards the
negative charges of any neighboring atom.

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Water
As the second hydrogen atom attaches, now every atom has full energy levels.

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Types of bonding
Classification based on no. of pairs of electrons being shared.

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Bonding Type, Energies and Melting Temperatures for Various Substances

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Crystallography

The structure of materials

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 SOLID MATERIALS

AMORPHOUS
CRYSTALLINE POLYCRYSTALLINE
(Non-crystalline)

Single Crystal
Quasi crystal

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Crystal Structure

Grain boundary

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Classification of Solid materials
Solid materials may be classified according to the regularity with which
atoms or ions are arranged with respect to one another.
1. Crystalline
• A crystalline solid is one in which the atoms are regularly arranged in a
repeating or periodic array over large atomic distances, that is, long-range
order exists.
• Upon solidification, the atoms will position themselves in a repetitive
three-dimensional pattern, in which each atom is bonded to its nearest /
neighbour atom.
• All metals, many ceramic materials, and certain polymers form crystalline
structures under normal solidification conditions.
• Crystalline
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2. Amorphous
• Non crystalline solids lack systematic and regular arrangement of atoms
over relatively large atomic distances or they have short range order.
Such materials are also called amorphous (meaning literally without
form)
• Atomic density is almost similar to that of crystalline solids.

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Crystalline Vs Amorphous

Two-dimensional structure of (a) Crystalline silicon dioxide and (b) Non crystalline silicon dioxide.

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3. Poly crystalline
• A polycrystalline solid is one in which portions of solid are perfect
crystals, but not all of these crystals have the same axis of symmetry.
• Each of the crystals (or grains) have slightly different orientations with
boundaries bordering each other. This borders are called grain
boundaries.

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Crystal Structure

Grain boundary

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 Depending on
which planes are
brought together,
the angle of
alignment will
vary.

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 Short range order

Long range order

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 Single vs Polycrystals
• Single Crystals E (diagonal) = 273 GPa
- Properties vary with Data from Table 3.3, Callister
7e.
direction: anisotropic. (Source of data is R.W.
Hertzberg, Deformation and
-Example: the modulus Fracture Mechanics
Engineering Materials, 3rd
of

of elasticity (E) in BCC iron: ed., John Wiley and Sons,

1989.)

E (edge) = 125 GPa

• Polycrystals
- Properties may/may not 200 mm Adapted from Fig. 4.14(b),
Callister 7e.
vary with direction. (Fig. 4.14(b) is courtesy of
L.C. Smith and C. Brady, the
- If grains are randomly National Bureau of Standards,
Washington, DC [now the
oriented: isotropic. National Institute of Standards
and Technology, Gaithersburg,
(Epoly iron = 210 GPa) MD].)

- If grains are textured,

anisotropic.
AmorphousMarGlass
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- crystalline glass 93
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 Anisotropy of crystals

191.1 GPa

Young’s
modulus of
FCC Cu

130.3 GPa
01-Nov-20 66.7 GPa Mar Athanasius College of Engineering/Mechanical/BCY 94
 WHY POLYCRYSTALLINE MATERIALS ARE ISOTROPIC & SINGLE CRYSTALS ARE
ANISOTROPIC? NARRATE.
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 95
Explain why single crystals are generally anisotropic while poly-crystals are
usually isotropic.

• In a single crystal, the orientation of the crystal structure is uniform

throughout the specimen. Since the properties of the crystal (e.g. linear and
planar atomic densities) vary with the crystallographic plane or direction
considered, the macroscopic properties of a single crystal specimen also
vary with direction; that is, they are anisotropic.

• On the other hand, the many different crystals in a polycrystalline specimen

are all oriented differently, so that the measured properties at a macroscopic
scale represent the average of the properties in all different crystallographic
directions. It doesn’t matter what direction is considered, the average
property is the same, so the polycrystalline specimen will be isotropic.
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 96
Polycrystals
Anisotropic
• Most engineering materials are polycrystals.

Adapted from Fig. K,

color inset pages of
Callister 5e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
1 mm

• Each "grain" is a single crystal. Isotropic

• If grains are randomly oriented,
overall component properties are not directional.
• Grain sizes, range from 1 nm to 2 cm – (normal range 5 - 200
µm) (i.e., from a few to millions of atomic layers).
Nb-Hf-W plate with an electron beam weld.
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 97
• Each "grain" is a single crystal.
Crystals as Building Blocks

• Some engineering applications require single crystals:

--diamond single --turbine blades
crystals for abrasives Fig. 8.33(c), Callister 7e.
(Fig. 8.33(c) courtesy
(Courtesy Martin Deakins, of Pratt and Whitney).
GE Superabrasives,
Worthington, OH. Used with
permission.)

--semiconductor

• Properties of crystalline materials

often related to crystal structure/direction.
--Ex: Quartz fractures more easily along some
crystal planes than others.
(Courtesy P.M. Anderson)

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 98

Single crystal- polycrystalline Structure
Crystalline solid can be single crystal. Where the solid consist of only one
crystal.
An aggregate of many crystals separated by well defined grain boundaries
(irregularly shaped) is said to be polycrystalline.
WHAT IS THE DIFFERENCE BETWEEN - GRAIN AND CRYSTAL?

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 99

Order of atoms

Crystalline solids – Long range order exists

Amorphous solids – Only Short range order exists

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 100
Close packing of atoms
• Closed electron shell that is created when an ionic or metallic bond is
formed can be regarded roughly as a rigid sphere, so that adjacent atoms in a
solid pack together like solid balls.
• The radius of the equivalent rigid sphere is called the ionic radius of the
element.

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 101

Important Terms
• SPACE LATTICE:- its an infinitely regularly spaced array of lattice points in 3
Dimension with translational and rotational symmetry.
• Crystal = lattice + basis
• The location and pattern/ arrangement of atoms in a crystal described by the
term space lattice. There are 14 space lattices possible.
• It’s a 3-dimensional network of lines, the intersection which generates a 3
dimensional array of points which are occupied by the atoms or group of atoms
or about which a group of atoms are clustered, forming the crystalline material.
• UNIT CELL:- While describing crystals structure, it is convenient to subdivide
the structure into small groups of atoms from a repetitive pattern called unit cell.
• Unit cell is the smallest group of atoms that, by repeated translation in three
dimensions, builds up the whole crystal
• Unit cell is the smallest unit which when repeated in space indefinitely will
generate
01-Nov-20
the space lattice. Mar Athanasius College of Engineering/Mechanical/BCY 102
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 103
The Unit Cell

• Crystal: 3D order structure

• Unit cell: smallest repetitive volume which contains the complete lattice
pattern of a crystal.
• The size and shape of the unit cell are described by three lattice vectors
a,b,c, originating from one corner of the unit cell.
• The axial lengths a,b,c and the inter axial angles α, β, and γ are lattice
CONSTANTS of the unit
01-Nov-20 Mar cell.
Athanasius College of Engineering/Mechanical/BCY 104
 Lattice parameters
axial lengths: a, b, c
interaxial angles: a,
 b, g
 
unit vectors: a b c

c
In general: a≠b≠c
 a≠b≠g
b

7 crystal systems

a 14 crystal structures

a, b, and c are the lattice constants

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 105

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 106
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 Unit Cells: Bravais Lattices

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 108

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 109
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 110
Principal Metallic Crystal Structure

90% of metals crystallize into 3 densely packed crystal structures:

• Body-Centered Cubic
• Face-Centered Cubic
• Hexagonal Close-Packed
It is important to understand how small the unit cell really is. The
cube side of BCC Iron is 0.287nm. How many unit cells would
there be if you had 1mm of units cells of pure iron lined up?
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 111
 Coordination Number
• The number of nearest neighbours surrounding any one atom, ion or
molecule is called co-ordination number.
• It depends upon the radii of the atoms or ions in the structure.
• Eg: Simple cubic (SC) – co-ordination number = 6

• Large atoms tend to have large CN,

small atoms usually have small CN

• it’s easier to surround a big atom with

lots of atoms than a smaller one.

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 112

 Range radius
ratio for which
Ion element A surrounding
CN is expected Coordination
a smaller ion element C Packing
to be stable polyhedron
CN
(rC/rA )

2 0 to 0.155 line Linear

3 0.155 to 0.225 Triangle Triangular

4 0.225 to 0.414 Tetrahedron Tetrahedral

6 0.414 to 0.732 Octahedron Octahedral

8 0.732 to 1.0 Cube Cubic

Twinned Cubo
12 1.0
Octahedron
HCP

Cubo
12 1.0
Octahedron
FCC

01-Nov-20 CN calculated as aCollege

Mar Athanasius function of radius ratio
of Engineering/Mechanical/BCY 113
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 114
Number of atoms in a unit cell

Simple cubic
(no metals except
Polonium Po – N is 84)
a
8 atoms but each atom is shared by
8 unit cells.

In each cubic unit cell has 8 octants.

ie,1/8 x 8 =1 atom
a
→ 1 atom per unit cell
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 115
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 116
 Atomic Packing Factor (APF) – Simple Cubic

Volume of atoms in unit cell*

APF =
Volume of unit cell

• APF for a simple cubic structure = 0.52

volume
atoms atom
4
a = 2r a unit cell 1 p (0.5a) 3
3
R=0.5a APF =
r+r a3 volume
close-packed directions unit cell
contains 8 x 1/8 = 1 atom/unit cell

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 117

• Eight corner atoms and one atom at center.
• Corner atoms do not touch each other, but each corner atoms touches the
center atom.
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 118
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 119
 From Callister 6e resource CD.

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 120

 Body-Centered Cubic (BCC)

LATTICE CONSTANT (a) = Atoms

2a at the corners of the cube
+
Atom at the center of the cube

( )
2
= ( 4R )
2
a +2
2a
a 4R Pythagoras theorem
4R
a=
3

Body diagonal (b.d) of the unit cell = 4R = abcc 3

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 121

 Number of atoms in a BCC unit cell

• Each corner atom contributes

as 1/8.
There are 8 corner atoms in an
FCC unit cell.

• The center atom

contributes as 1.
There is only 1 center atom.

1
 8( corner _ atoms ) + 1 1( center _ atom ) = 2 atoms / unit _ cell
8
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 122
 Coordination number for BCC

2 3

1 4
Total 8 nearest neighbor atoms
Coordination number = 8

6 7

5 8

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 123

 Atomic packing factor (APF) for BCC
4 
2a Vatoms = 2  p R3 
3 
a 2 + ( 2a) 2 = (4 R) 2
4R
a=
3
a 4R
4 R 3 64 R 3
Vunit _ cell = a = ( ) =
3

3 3 3

8 3
 pR 
APF =
Vatoms
=
3  = 3p = 0.68
Vunit _ cell 64 R3 8
3 3

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 124

 Summary for BCC

2a 4R
||unit vector|| = a=
3

2 atoms/unit cell
a 4R
Coordination number = 8 = CN
APF = 0.68

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 125

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 126
 Face Centered Cubic (FCC)

• Atoms touch each other along face diagonals.

--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

ex: Al, Cu, Au, Pb, Ni, Pt, Ag - DUCTILE

• Coordination no. = 12

Adapted from Fig. 3.1, Callister 7e.

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 127
 Coordination number for FCC

2 2R
6
2R 9 10
5
2 2R 2 3
1 4
7
12 11
8

Total 12 nearest neighbor atoms

01-Nov-20
Coordination number = 12
Mar Athanasius College of Engineering/Mechanical/BCY 128
 Face-Centered Cubic (FCC)

Atoms at the corners of the cube

+
Atoms at the center of each face

a a = ||unit vector||
4R
R = atomic radius

a 2 + a 2 = (4 R) 2
Pythagoras theorem
a a = 2 2R

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 129

 Atomic packing factor (APF) for FCC

2 2R

2R

2 2R

a 4R

4 
Vatoms = 4  p R3 
3 
a Vunit _ cell = a3 = (2 2R)3 = 16 2R3

 16 3 
 pR 
APF =
Vatoms
=
3  = p = 0.74 Independent of R and a!
Vunit _ cell 16 2 R3 3 2
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 130
Summary for FCC

||unit vector|| = a = 2 2 R
4 atoms/unit cell
Coordination number = 12 =N
a 4R APF = 0.74

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 131

 FCC Stacking Sequence
• ABCABC... Stacking Sequence
• 2D Projection
B B
C
A
A sites B B B
C C
B sites B B
C sites

A
• FCC Unit Cell B
C

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 132

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Hexagonal Close-Packing (HCP)

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 135

 Middle layer = 3 atoms

Top layer =½x1 = ½ atom

= 1/6 x 6 = 1 atom = 1 ½ atom

Bottom layer =½x1 = ½ atom

= 1/6 x 6 = 1 atom = 1 ½ atom

Total atoms in HCP = 6 atoms

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 136
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 137
 600
L
L

J K J K J K

JKL

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 138

 L

J K

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 139

 1
Area Δ JKL = × base × height
2
1
= × 2r × a sin60
2
1
= × 2r × 2r sin60
2
1
Total base area = 6 × × 2r × 2r cos60
2
= 6 × 2r 2 sin60
Total volume of HCP unit cell = total base area × height
= 6 × 2r 2 sin60 × c
= 6×2r 2 sin60 ×1.633 × 2r Lattice parameter a and c
of HCP unit cell related by
c=1.633a =1.633 x 2r
4 3
6× πr
APF= 3 = 0.74
2
6×2×r sin60×1.633×2r
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 140
 Structures of Elemental Metals [Ref.Callister 3.4]

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 141

Polymorphism and Allotropy
• Existence of more than one equilibrium crystallographic form for
elements or compounds at different conditions of temperature and
pressure is called Polymorphism.
• i.e., two or more different crystal structures for the same material
exists…
• If the change in in crystal structure is reversible, then the polymorphic
change is called Allotropy.
• Polymorphisam :- more than one element or compound eg. Fe3C
• Allotropy:- only one element
• eg. C - Diamond (sp3), graphite (sp2), polymer(sp1), fullerene (C66).

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 142

Example: Polymorphism

• Iron is liquid above 1539⁰C

➢δ- Iron (BCC) between 1394 and 1539⁰C
➢γ- Iron (FCC) between 912 and 1394⁰C
➢α- Iron (BCC) between -273 and 912⁰C

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 143

Crystallographic Points,Directions, and Planes
• When dealing with crystalline materials, it often becomes necessary to
specify a particular point within a unit cell, a crystallographic direction, or
some crystallographic plane of atoms.
• Three numbers or indices are used to designate point locations, directions,
and planes.

POINT COORDINATE
• The position of any point located within a unit cell may be specified in
terms of coordinates as fractional multiples of the unit cell edge lengths
(i.e., in terms of a, b, and c).
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 144
• Position of P in terms of the generalized coordinates q, r, and s where
q is some fractional length of a along the x axis, r is some fractional
length of b along the y axis, and similarly for s.
• Thus, the position of P is designated using coordinates q r s with
values that are less than or equal to unity.

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 145

• For the unit cell shown in the accompanying sketch, locate the point P
coordinates.
• a=0.48 nm , b= 0.46 nm, c = 0.40 nm
• For point P , x coordinate = 0.12 nm, y coordinate = 0.46 nm, z coordinate =
0.20 nm
• q = 0.12/.48 = ¼
• r = 0.46/.46 = 1
• s = 0.20/0.40= 1/2

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 146

CRYSTALLOGRAPHIC DIRECTIONS ( Miller Indices of Directions)

• Certain directions and planes within a unit cell carry particular significance
• Ex, crystallographic directions are used to indicate a particular orientation
of a crystal.
• A crystallographic direction is defined as a line or a vector between two
points.
• Following are the steps for determination of the Miller Indices of
Directions.
• Determine the coordinates of two points that lie on the direction , using a right
handed coordinate system.
• Subtract the coordinates of tail point from those of the head point and express the
same in terms of the unit cell dimensions.
• Multiply or divide these numbers by a common factor to reduce them to the
smallest integer
• The three indices are enclosed in square brackets as [uvw]. A negative integer is
represented with a bar over
01-Nov-20 the number.
Mar Athanasius College of Engineering/Mechanical/BCY 147
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01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 150
(CRYSTALLOGRAPHIC PLANES) Miller Indices
• Metals deform along the planes of atoms which are most tightly packed.
• Miller Indices are a symbolic vector representation for the orientation of
an atomic plane in a crystal lattice.
• It is defined as the reciprocals of the fractional intercepts which the plane
makes with the crystallographic axes.
• Miller indices are represented by a set of 3 integer numbers (hkl).
• Any two planes parallel to each other are equivalent and have identical
indices. The procedure employed in determination of the h, k, and l index
numbers is as follows:
• If the plane passes thorough the origin of coordinate system , the origin must be
moved to another corner of unit cell
• Identify the points at which the plane intercepts the x,y,z axis and express the
intercepts in terms of the lattice parameters
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 151
 • Take reciprocals of these numbers. Intercepts for a plane parallel to an axis to be taken as
infinity with reciprocal equal to zero.
• Change the number to a set of smallest integer by multiplication or division by a
common factor.
• Enclose the integer indices within parentheses as (hkl)

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 152

Miller Indices

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 153

Miller Indices

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 154

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 155
• Following are some important aspects of the Miller indices for planes.
• Planes and their negatives are identical; (0 1 0) = (0 1 0) unlike the case of
directions. By Changing the signs of all the indices of a plane, we obtain a
Plane located at the same distance on the other side of the origin.
• Planes and their multiples are not identical (unlike the case of directions)
• The planes defined by Miller indices obtained by changing the order and
sign of indices represent a family of planes. This group of similar planes are
denoted with curly brackets. Eg., The family {1 1 0 } in cubic system.
• In cubic system, a plane and a direction having the same indices are
perpendicular to each other. Hence the direction [110] is perpendicular to
the plane (1 1 0), in a cubic unit cell.
• Parallel planes have the same Miller indices. Distance between two adjacent
parallel planes with same Miller index (hkl) is called interplanar spacing.
Interplanar spacing in cubic crystals is given by
𝑎
d=
01-Nov-20 ℎ2 + 𝑘 2 + 𝑙2
Mar Athanasius College of Engineering/Mechanical/BCY 156
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 157
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01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 160
Atomic Arrangements
• The atomic arrangement for a crystallographic plane, which is often of
interest, depends on the crystal structure.
• The (110) atomic planes for FCC and BCC crystal structures are represented
in Figures, Note that the atomic packing is different for each case.

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 161

 • A “family” of planes contains all those planes that are crystallographically
equivalent—that is, having the same atomic packing.

LINEAR AND PLANAR DENSITIES

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 162

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 163
Deformation in Metals
• When a material is subjected to an external force or load, the material
suffers a change in shape, which is called deformation.
• If the deformation is temporary, (if the deformation disappears on
removal of the load) it is elastic deformation
• if permanent, (if the deformation persists even after removal of the load),
it is called plastic deformation.
• Both deformations take place due to adjustments or displacement in
atomic arrangement within the crystal.
• The mechanical behavior of a material reflects the relationship between
its response or deformation to an applied load or force.
• Factors to be considered, while evaluating the properties are nature of the
applied load and its duration, as well as the environmental conditions.
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 164
Elastic Deformation
• When a solid material is subjected to an applied
force, the atoms within the crystal are displaced
from their normal positions of equilibrium.

• Thus, when a solid bar is loaded axially in

tension, it becomes slightly longer. If, on
removal of the load, the bar returns to its original
dimensions, the deformation is elastic in nature.

• This is because the displacement of the atoms is

by relatively small amounts and the removal of
the applied load allows the atoms to return to
their normal equilibrium positions. Thus the
elastic deformation is reversible.
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 165
Elastic Deformation

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 166

Plastic deformation
• Yielding involves the possibility that some of the atoms, under the
distortion produced by the applied load, move to new equilibrium
positions.
• Since the atoms form new bonds in their new positions, the material is
not weakened and also there is no tendency for the atoms to return to
their original positions.
• Thus the deformation is inelastic or irrecoverable. Such a deformation is
permanent and known as plastic deformation. There are two common
mechanisms of plastic deformation
(i) by slip and
(ii) by twinning.

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 167

Plastic deformation by slip
• Most metals are significantly weaker in shear than in tension or
compression and hence yielding or plastic deformation occurs under the
action of a shear force.

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 168

Plastic deformation by slip
• Under the influence of a shear force, atoms move relative to each other
on certain planes from one position of equilibrium to another position of
equilibrium, causing a permanent deformation.
• Some atoms are said to have slipped past the other atoms on a certain
plane in a certain direction. This process is called slip, the plane on
which slip takes place is known as the slip plane and the direction along
which the atoms move is known as the slip direction.
• Even when the material is subjected to a tensile or compressive load, it is
the shear component that causes plastic deformation.
• Slip occurs more readily along certain crystal directions and planes
within the crystal. A set of such favored plane and direction together is
called a slip system.
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 169
Plastic deformation by slip
• For a particular crystal structure, the slip plane is the plane that has the
most dense atomic packing—that is, has the greatest planar density.
• The slip direction corresponds to the direction, in this plane, that is most
closely packed with atoms—that is, has the highest linear density.

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 170

Brittleness and Ductility
• When stressed, some materials are capable of undergoing extensive plastic
deformation before breakage or rupture occurs. Such materials are said to be
ductile.
• Some other materials break up abruptly with very little or no plastic
deformation. Such materials are termed brittle.
• In crystalline materials dominant mode of plastic deformation is slip, which
is dependent on the available number of slip systems within the crystal.
• Slip occurs easily on planes and in directions of maximum atomic density.
• In FCC crystals the {111} planes and <110> directions have maximum
atomic density and there are 12 easy slip systems available in FCC crystals.
These slip systems are well distributed in space and therefore it is possible to
have at least one slip system oriented in a favorable position for slip to take
place. Hence, slip and thereby plastic deformation is initiated easily in FCC
crystals. Materials having FCC structure are therefore ductile in nature.
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 171
Brittleness and Ductility
• BCC crystals also have 12 easy slip systems with the {110} planes and
<111> directions. However, the {110} planes of BCC have lesser atomic
density compared to the {111} planes of FCC. Therefore, the stress
required to cause unit atomic displacement will be more in BCC crystals.
So BCC materials are less plastic (or less ductile) compared to FCC.

• In HCP crystals, the planes having maximum atomic density are the
basal planes {0001} and the directions <1120>. Only 3 common slip
systems are available in HCP. Having only a few active slip systems,
HCP materials are normally brittle.

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 172

Resolved Shear Stress and Critical Resolved Shear
Stress ( Schmid’s Law)
• Consider a single crystal cylindrical bar as shown in to which an axial load
F is applied.
• Let the angle between slip direction and applied force be α , inclination of
the normal to slip plane with the applied force be β.
• For the dislocation to move along its slip system, a shear force acting along
the slip direction must be produced by the applied force.
Shear force Fr = F cos α

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 173

 • If the area of the cross section of the cylindrical bar is A0, then area of the
slip plane is,

• This equation is called Schmid’s Law

• τr is called resolved shear stresses, and their magnitudes depend not only on the
applied force, but also on the orientation of both the slip plane and direction
within
01-Nov-20 that plane. Mar Athanasius College of Engineering/Mechanical/BCY 174
• A metal single crystal has a number of different slip systems that are capable of
operating. The resolved shear stress normally differs for each one because the
orientation of each relative to the stress axis (β and α angles) also differs
• However, one slip system is generally oriented most favorably—that is, has the
largest resolved shear stress,
τr (max) = σ (cos α cos β ) max
• In response to an applied tensile or compressive stress, slip in a single crystal
commences on the most favorably oriented slip system when the resolved shear
stress reaches some critical value, termed the critical resolved shear stress τcr; it
represents the minimum shear stress required to initiate slip, and is a property of
the material that determines when yielding occurs.
• The single crystal plastically deforms or yields when
Condition for yielding, τr (max) = τcr
• And the magnitude of the applied stress required to initiate yielding (i.e., the
yield strength σy)

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 175

• The minimum stress necessary to introduce yielding occurs when a single
crystal is oriented such that (β and α = 450 under these conditions,
σy = 2 τcr
• For a single-crystal specimen that is stressed in tension, deformation will
be as in Figure, where slip occurs along a number of equivalent and most
favorably oriented planes and directions at various positions along the
specimen length.
• This slip deformation forms as small steps on the surface of the single
crystal that are parallel to one another and loop around the circumference
of the specimen.

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Plastic deformation by twinning.
• In certain materials, when a shear stress is applied, planes of atoms in the
lattice move parallel to a specific plane so that the lattice is divided into
two symmetrical parts which are differently oriented. This phenomenon
is known as twinning .
• Planes parallel to which atomic movement has taken place are known as
twinning planes. The differently oriented region within the crystal and
between the twinning planes is known as the twinned region.

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Plastic deformation by twinning.
• Twinning is produced suddenly (within a few micro seconds) and is
accompanied with sound. In both slip and twinning the lattice is sheared.
• In slip, the deformation or shear is uniformly distributed over a volume,
rather than localized on a discrete number of slip planes.
• In contrast to slip, here the atoms move only a fraction of an interatomic
distance relative to each other.
• The amount of movement of each plane of atoms in the twinned region is
proportional to its distance from the twinning plane, so that a mirror image
is formed across the twin plane.
• Twinning is not a significant deformation mechanism for cubic metals.
However, it is a significant mode of deformation in HCP crystals.

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Deformation by slip & twinning

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Slip & Twinning

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 MECHANISM OF CRYSTALLISATION

Solidification
• CASTING - One of the oldest manufacturing processes – 4000
B.C. with stone and metal molds for casting copper

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 185

• Single crystal.
• Crystalline solids are composed of a collection of many small crystals
known as grains. Such materials are termed polycrystalline.
• Grain structure and the defects develop during solidification of the liquid
material.
• Solidification of pure metals, also known as Crystallisation is the
transition from liquid state to solid state.
• Crystallization is a Phase Transformation process.
• The stages of Phase Transformation divided in to two,
• Nucleation
• Homogeneous nucleation
• Heterogeneous nucleation

• Growth
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 186
 Mechanism of Crystallization

1. Nuclei formation
• Nuclei – not center of an atom, is the center of few atoms together

2. Crystal growth

• At freezing point B, K.E (L) = K.E. (S)

• = ʃ (TEMPERATURE)
• But P.E (L) = P.E (S) = AVERAGE DISTANCE BETWEEN
ATOMS
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 187
Ref:- Avner
Nucleation
• Two Type
• Homogeneous nucleation
• Heterogeneous nucleation
• Homogeneous nucleation
• No preferred nucleation sites
• Spontaneous
• Random
• Heterogeneous nucleation
• Those of preferred sites
• Boundary, mould walls,
• Surface, interface
• Inclusion, impurity
• Multiphase
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Homogeneous nucleation

• In the liquid state, atoms of any material will be in constant motion due to
their high kinetic energy
• The atoms do not have any definite arrangement in liquid state.
• When the temperature of the molten metal is brought down, it is possible
that some atoms, at any given instant, may group together in positions
exactly corresponding to the space lattice.
• These chance aggregates or groups are not permanent; but continually,
break up and regroup at other points. How long they last is determined by
the temperature and the size of the group.
• When the temperature of liquid is sufficiently decreased, the atomic
movement also decreases. This lengthens the life of the group and also
promotes the formation of more groups within the liquid. Such groups are
known
01-Nov-20 as embryos. Mar Athanasius College of Engineering/Mechanical/BCY 190
• As the temperature of the liquid metal drops, a stage is reached where the
embryos (more like solid) and the surrounding liquid co-exist. This
temperature is known as the solidification point or freezing point.
• At this point, both the liquid and solid states are at the same temperature
and hence have the same kinetic energy for the respective atoms. But there
is significant difference in the potential energy.
• The atoms in the solid are much closer together resulting in lowering of
potential energy. Thus, solidification occurs with release of energy. The
difference in potential energy between the liquid and solid states is known
as latent heat (heat of fusion or heat of solidification).
• At the freezing point, energy is required to establish a surface between the
solid and the liquid.
• In pure materials, at freezing point, insufficient energy is released by the
heat of fusion to create a stable boundary surface. Hence some
undercooling
01-Nov-20 (super cooling) is necessary to form a stable solid region. 191
 Homogeneous nucleation: very pure metal, nuclei form uniformly
throughout the parent phase; requires considerable supercooling (typically
80-300°C/ 0.2Tm).
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Solidification of Pure Metals

Pure metals solidify at a constant temperature. During freezing the latent heat of
solidification is given off. Most metals shrink on solidification and shrink
further (Ice) as the solid cools
01-Nov-20
to room temperature.
Mar Athanasius College of Engineering/Mechanical/BCY 193
 Cooling curve for a pure metal; ABDE ideal, ABCDE actual.
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 Ref.-Bailey

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• This kind of nucleation occurs uniformly throughout the liquid. The
nucleus grows further by adding more and more atoms to it which leads
to a small solid region.
• Such stable solid regions within the liquid are known as nuclei.
• Subsequent to the formation of nuclei, release of heat of fusion takes
place and the temperature will be raised to the freezing point again. But
loss of heat to the surroundings lowers the temperature again making
more atoms to freeze.
• These atoms may attach themselves to already existing nuclei or form
new nuclei of their own. Thus the process of solidification continues
apparently at constant temperature till the entire liquid is transformed
into solid.

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 Supercooling
• During the cooling of a liquid, solidification (nucleation) will begin only
after the temperature has been lowered below the equilibrium
solidification (or melting) temperature Tm. This phenomenon is termed
supercooling (or undercooling.

• The driving force to nucleate increases as T increases

• Small supercooling → slow nucleation rate - few nuclei - large crystals

• Large supercooling → rapid nucleation rate - many nuclei - small crystals

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 Nucleation of a spherical solid particle in a liquid
• The change in free energy DG (a function of the internal energy
and enthalpy of the system) must be negative for a transformation
to occur. Liquid

• Assume that nuclei of the solid phase form in the interior of the
liquid as atoms cluster together-similar to the packing in the solid
phase.
• Also, each nucleus is spherical and has a radius r.
• Free energy changes as a result of a transformation: 1) the
difference between the solid and liquid phases (volume free
energy, DGV); and 2) the solid-liquid phase boundary (surface
free energy, DGS).
• Transforming one phase into another takes time.
G = GS + GV
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 Homogeneous Nucleation & Energy Effects
Surface Free Energy- destabilizes
the nuclei (it takes energy to make
an interface)
GS = 4pr 2 g
g = surface tension

GT = Total Free Energy

= GS + GV

Volume (Bulk) Free Energy –

stabilizes the nuclei (releases energy)
4
GV = pr 3 G
3
volume free energy
G =
unit volume
r* = critical nucleus: for r < r* nuclei shrink; for r >r* nuclei grow (to reduce energy)
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 205
Heterogeneous nucleation
• Nucleation is also facilitated by the presence of some impurity atoms, an
inoculant (grain refiner), an imperfection or a grain boundary. This type of
preferential nucleation is called heterogeneous nucleation.
• Form at structural inhomogeneities (container surfaces, impurities, grain
boundaries, dislocations) in liquid phase much easier since stable “nucleating
surface” is already present; requires slight supercooling (0.1-10ºC).
• A much lower level of undercooling is sufficient for this type of nucleation to
occur. Even the wall of the container promotes heterogeneous nucleation.
• Addition of a grain refiner to molten metal can produce fine grained grains. Nb
• The grain refiners solidify earlier and form a large number of small solid
particles in the liquid.
• Solidification of the liquid is initiated by heterogeneous nucleation around these
solid particles.
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 Growth (Dendritic Growth)
• During the process of solidification, each
nucleus grows by attracting atoms from the
liquid into the space lattice.
• Crystal growth continues in three dimensions,
the atoms attaching themselves in certain
preferred directions, usually along the axes of
the crystal. This gives rise to the characteristic
treelike structure which is called a dendrite.
• Since each nucleus is formed by chance, the
crystal axes are pointed at random, and
dendrites growing from them will grow in
different directions in each crystal.
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 208
• This is a sort of crystal skeleton from which arms begin to grow in all
directions depending upon the lattice pattern.
• From the primary arms, secondary, tertiary etc. arms begin to sprout,
somewhat similar to branches and twigs growing out of the trunk of a
tree, leading to the formation of a rather elongated skeleton.
• In the case of metallic dendrites, these branches and twigs conform to
a rigid geometrical pattern. The dendritic arms continue to grow and
thicken at the same time, until ultimately the space between them will
become filled with solid.
• Meanwhile the outer arms of one dendrite begin to make contact with
those of neighboring dendrites, which have been developing
independently at the same time.

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• If the material is pure, there shall be no evidence of dendritic growth
once the solidification is complete, since all the atoms are identical.
• If the material is impure, dissolved impurities will often tend to remain
in the molten portion of the metal, which ultimately solidifies in the
spaces between the dendrites.
• Since their presence will often cause a slight alteration in colour of the
parent metal, the dendritic structure will be easily revealed on
microscopical examination.
• The areas containing impurity will appear as patches between the
dendrite arms.

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 (a) (b)
Nuclei – not center of an atom, is the center of few atoms
together

Schematic representation of the process of crystallization by

01-Nov-20
nucleation and dendrite growth.
Mar Athanasius College of Engineering/Mechanical/BCY 212
 (c) Orientation of atoms in each crystal

Schematic representation of the process of crystallization by

nucleation and dendrite growth.
01-Nov-20 Why grain boundaries
Mar Athanasius are irregular?
College of Engineering/Mechanical/BCY 213
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01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 215
The secondary dendrite arm spacing controls strength, very similar to
the Hall Petch relation (1/sqrt d) in the case of grain size strengthening.
Thus, in castings, this is an important microstructural parameter to
consider.
01-Nov-20
The arm spacing is proportional to cooling rate.
Mar Athanasius College of Engineering/Mechanical/BCY 216
 Type of boundary Energy (J/m2)
Grain boundary between BCC crystals 0.89
Grain boundary between FCC crystals 0.85
Interface between BCC and FCC crystals 0.63

Grain boundaries in
SrTiO3

Mar Athanasius College of

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 Automobile - 45, 30 turn, hairpin, straight

Depending on
which planes are
brought together,
the angle of
alignment will
vary.

WHY

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Dendrite – Dendrum (Greek word)- tree

Direction of
dendrite growth
shows direction
of cooling

The early stages in the growth of a metallic dendrite

01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 222
Metallic Structures

Growth of metal
dendrite

Copper
dendrites
Mar Athanasius College of
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Magnesium dendrites growing from liquid
Engineering/Mechanical/BCY
Dendrites in a

Cobalt-Samarium-
Copper alloy

-SEM

-Why grain boundaries

are irregular shape?

Mar Athanasius College of

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 Dendrites of water in ice
01-Nov-20 Mar Athanasius College of Engineering/Mechanical/BCY 226
 Dendrites of zinc rescued from
partially solidified melt
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 Dendrites of ice on window, Harbin, China (-25 oC)
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 01-Nov-20

Mar Athanasius College of

229
Dendrites forming in Fe82Si4B14 metallic glass.
Engineering/Mechanical/BCY
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Dendrites forming in Fe82Si4B14 metallic glass
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 Mar Athanasius College of
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Dendrites forming in Fe82Si4B14 metallic glass
Engineering/Mechanical/BCY
231
Grain
• The randomly formed nuclei will be having different crystallographic
orientations. The nuclei grow into crystals by the successive addition of atoms
from the surrounding liquid.
• All these neighboring crystals (or grains) will be oriented differently due to their
independent formation.
• As these grow, the outer arms of the neighboring crystals meet similar extremities
of other neighboring grains. Finally at a certain stage, further growth outwards
becomes impossible, the remaining liquid is used up in thickening the existing
dendrite arms and solidification will be completed.
• This independent formation of each crystal leads to the irregular shape of the
crystal. These crystals are commonly called grains.
• A grain is a portion of the material within which the atomic arrangement is
nearly identical. But the orientation of the atomic arrangement may be
different for adjoining grains.
• The area, along which the grains meet is known as grain boundary, is a region of
mismatch, because atoms at the grain boundary are irregularly placed.
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Metallic Structures

• This crystalline structure gives metals their properties (strength,

stiffness, ductility, conductivity & toughness).
• Each dendrite grows in a geometric pattern consistent with the lattice
structure until each one touches its neighbour. At this point the dendrites
begin to thicken to form a totally solid grain of metal.
• The grain boundaries between are visible under a microscope, each grain
having the same structure but a different orientation. This boundary is a
narrow zone (perhaps three atoms) in which the atoms are not properly
spaced according to the lattice structure.
Single Crystal & Poly crystals
• When a liquid is cooled slowly in equilibrium with the surroundings, the
solid that form contains tiny crystals called grains.
• The number of grains formed during solidification depends on the number
of nuclei formed.
• If all nucleation sites except one are suppressed, the liquid solidifies into a
single grain. Even the orientation of grain can be engineered to be in a
specific direction. Single crystals show excellent high temperature
properties because of the absence of grain boundaries.
• When the liquid is normally cooled under equilibrium condition, there
would be abundant nucleation sites and the liquid solidifies into a large
number of small grains.
• Although these grains look alike, the crystallographic orientations are
different and the orientation changes randomly from one grain to other.
Such a solid is called polycrystalline.
Nuclei – not center of an atom, is the center of few
atoms together
 Microstructure of a casting
• Polygonal crystal growth also explains the typical three-
zone microstructure of a solidified casting block
(primary microstructure). Such a casted block is also
called ingot.
• In the vicinity of the mold wall, a very fine-grained
structure with roundish grains (globulites) forms due to
the strong isotropic undercooling caused by the cool
mold wall (zone I).

• Subsequently, a zone with elongated grains (columnar crystals) is obtained due to the
strongly directed, anisotropic heat dissipation towards the mold wall (transcrystalline zone
II).
• The relatively low (isotropic) cooling or undercooling inside the casting block produces a
very coarse-grained microstructure (zone III).
• By subsequent heat treatment, this heterogeneous structure can be transformed into a
homogeneous structure with the desired properties (secondary microstructure).
241
 The grain refiners
solidify earlier and form
a large number of small
solid particles in the
liquid.

Solidification of the
liquid is initiated by
heterogeneous
nucleation around these
solid particles.

Mar Athanasius College of

01-Nov-20
Engineering/Mechanical/BCY
 Heat Flow, Interface Stability and Dendritic Growth

(a)
(b)

(c)

The development of dendrites: (a) a spherical

nucleus; (b) the interface becomes unstable; (c)
primary arms develop in crystallographic
directions (<100> in cubic crystals); (d)
secondary and tertiary arms develop (after R.E.
Reed-Hill, Physical Metallurgy Principles, 2nd. (d)
Edn., Van Nostrand, New York, 1973.)
Modification of grain size
• The rate of cooling and the amount of impurities in the molten metal will
affect grain size:
• Gradual cooling - a few nuclei are formed – leads to large grain size
• Rapid cooling - many nuclei formed - small grain size.
• Reheating a solid metal / alloy allows the grain structure to re-align itself.
• Directional cooling in a structure is achieved by selectively cooling one
area of a solid.
• The effect of impurities (or additives) in a molten metal can induce a large
number of fine grains that will give a stronger and harder metal. This
addition must be carefully controlled as too many impurities may cause an
accumulation at the grain boundaries, which will weaken the material.
• Walls of mold is cold - large under cooling - fine grains form at
walls of the mold.
• Cubic lattice – some grains grows faster than other grains – Easy
grow direction -cooling rate is faster in <100> / fastest growth
direction - <100> is parallel to heat flow – coarse structure -
columnar structure.
• Presence of dirt particles at center portion of molten pool lead to
form equiaxed structure.
Features of Grains
GRAIN SIZE DISTRIBUTION;
GRAIN SHAPE and
GRAIN ORIENTATION
GRAIN SIZE
• Size of the crystal formed depends on the rate at which a molten metal is
cooled.
• A slow fall in temperature, which leads to a small degree of undercooling
at the onset of solidification, promotes the formation of relatively few
nuclei, so that the resultant crystal size will be large.

Nuclei – not center of an atom, is the

center of few atoms together
• Grain size is having effect on material properties
• There are methods to control the nucleation process and thereby the
material properties.
• Grain size in materials is also controlled by the combination of
controlled deformation and thermal treatments, called thermo
mechanical treatments.

(a) grain size (20 - 50mm – small (b) 100 - 200mm - large)
Orientation of grains –Random
Equiaxed (approximately equal dimensions in the three coordinate directions)
EFFECT OF GRAIN SIZE
Hall – Petch equation
The Hall-Petch equation gives a general relationship between the yield stress
and grain size of a material.

where σ y is the yield strength (the stress needed to cause plastic

deformation), d is the average diameter of grains, σ i and K are constants for
the material. It is to be noted that the dislocation density has been
experimentally observed as an inverse function of grain size.
Constants indicating the extent to which dislocations are piled up at barriers (such as grain boundaries)
σ 0 Basic yield stress that can be regarded as the stress opposing the motion of dislocations
Valid for many materials but not for nano-structures and very large grain material !!
• Hall-Petch equation finds application in design of components made of
metallic materials.
• Using this relationship, yield stress, σ y of a material for a given grain
size or the grain size to be developed for obtaining a required yield
stress can be evaluated.
• An estimation of the yield stress for the materials can be made by
determining the grain size using a micrograph.
Effect of Grain size on Material Strength

• Smaller grain size – More number of grains!!!

• More number of grains – More barriers for slip!!!
• More barriers for slip - Increased material strength!!!

• Influence of grain boundaries in dislocation movement

- restricting or hindering dislocation motion makes
material harder and stronger.
 How is grain size measured?
1. Counting the grains in a given area
2. Counting number of grains that intersect a length of a
line (microscopic)
3. Determined by comparing to a standard chart (ASTM
Chart)
The effects of grain size on yield strength
• A change in grain size affects the yield strength due to the dislocations
interacting with the grain boundary as they move.
• The boundaries act as obstacles, hindering the dislocation glide along the
slip planes. As subsequent dislocations move along the same slip plane the
dislocations pile-up at the grain boundaries.
• The dislocations repel each other, so as the number of dislocations in the
pile-up increases the stress on the grain boundary increases.
• In a larger grain there will be more dislocations within the grain, so there
will be more dislocations in the pile-up.
• Therefore a lower applied stress is required to produce a local stress great
enough to cause the grain boundary to collapse.
• A fine-grained material (one that has small grains) is harder and stronger
than one that is coarse grained, since the former has a greater total grain
boundary area to impede dislocation motion.

• A fine grain size in shaped castings ensures the following:

(i) Mechanical properties that are uniform throughout the material
(ii) Distribution of second phases and microporosity on a fine scale
(iii) Improved machinability because of (ii)
(iv) Improved ability to achieve a uniformly anodizable surface
(v) Better strength, toughness, and fatigue life, and
(vi) Better corrosion resistance
(MPa)
Grain Size Effect • Grain boundaries present obstacles to dislocation
propagation. Therefore, it is generally found that
the yield strength of a material increase with
decreasing grain size according to the Hall-Petch
equation.
• However at low strain rate and close to Tm,
dislocation is resolved by diffusion. Material
deforms by sliding of grains or reshaping of grains.
Both processes are easier if grain size is small.
 (c) 2003 Brooks/Cole Publishing / Thomson Learning
Figure 4.17 The effect of grain size on the yield
strength of steel at room temperature.
 Example 1 Design of a Mild Steel

The yield strength of mild steel with an average grain size of 0.05 mm is 20,000 psi. The yield stress
of the same steel with a grain size of 0.007 mm is 40,000 psi. What will be the average grain size of
the same steel with a yield stress of 30,000 psi? Assume the Hall-Petch equation is valid and that
changes in the observed yield stress are due to changes in dislocation density.
Example 1 SOLUTION

Thus, for a grain size of 0.05 mm the yield stress is

20  6.895 MPa = 137.9 MPa.
(Note:1,000 psi = 6.895 MPa). Using the Hall-Petch equation
Example 1 SOLUTION (Continued)

For the grain size of 0.007 mm, the yield stress is 40  6.895 MPa = 275.8
MPa. Therefore, again using the Hall-Petch equation:

Solving these two equations K = 18.43 MPa-mm1/2, and σ0 = 55.5

MPa. Now we have the Hall-Petch equation as
σy = 55.5 + 18.43 d-1/2
If we want a yield stress of 30,000 psi or 30  6.895 = 206.9 MPa, the
grain size will be 0.0148 mm.
Example 2
The yield strength of mild steel with an average grain size of 0.05mm is 138MPa. The yield
strength of the same steel with a grain size of 0.007mm is 276MPa. What will be the grain
size of the same steel with a yield stress of 207MPa. Assume the HallPetch equation is valid
and that the changes in yield stress are due to changes in grain size.
Example 3

• Assume that a metal has a yield stress of 20 ksi if the grain size is 10-4 mm, and
32 ksi if the grain size is 10-6 mm. What will be the yield stress if the grain size
was 10-5 mm, all other things being equal?

20 =  0 + k 10000

32 =  0 + k 1000000

Solving, we find that k=0.01333 and 0 = 18.67

 y = 18.67 + 0.01333 100000 = 22.9 ksi

Example 4 Calculation of ASTM Grain Size Number

Suppose we count 16 grains per square inch in a photomicrograph taken

at magnification  250. What is the ASTM grain size number?
Example 4 SOLUTION
If we count 16 grains per square inch at magnification  250, then at
magnification  100 we must have:
N = (250/100)2 (16) = 100 grains/in.2 = 2n-1
Log 100 = (n – 1) log 2
2 = (n – 1)(0.301)
n = 7.64
Grain Shape
• Three separate zones can be distinguished in an
ingot solidified in a large mould.
• First zone is near to the mould walls where fine grains
are observed,
• Followed by a zone of long columnar grains
• At the center of mould having coarse, equi-axed grains.
• Nature of the container in which the liquid metal
cools, will affect the shape and number of grains

Microstructure
of ingots
 (a) Equiaxed (c) Columnar shape
Grain shape – equiaxed (approximately equal dimensions in the three coordinate
Directions therefore properties are same in all directions)
• When the molten metal first strike the mould, the mould is cold and has a
chilling effect. This results in the formation of a large number of nuclei and
consequently large number of fine grains along the surface of the solidifying
metal.
• As the mould is warmed up, the chilling effect is reduced, so that nuclei
formation is retarded as the solidification progresses. Thus the crystals
formed towards the center of the mould will be larger in size.
• In the intermediate portion, the rate and nature of cooling are favorable to
the formation of elongated columnar grains.
• Metallic mould tends to produce a fine grained structure, while sand mould
a coarse grained structure.
• Thin sections are subjected to relatively larger rate of cooling, resulting in
fine grains.
Al. Ingot
equiaxed
pipe
grains

coarse grains

Fine grains
Schematic illustration of three cast structures of metals solidified in a
square mold (a) pure metals (b) solid solution alloys (c) structure
obtained by using nucleating agents.
 MORPHOLOGY OF SOLIDIFICATION
Heat Flow
Equiaxed dendrite;
growth is radial and along
heat flow direction
Growth

Columnar dendrite;
growth is opposite heat
flow direction
Initially, small nuclei nucleate near mold walls, and mutual competition makes them grow in an
equiaxed manner. Then, those crystals (dendrites) which can grow parallel and opposite to the heat
flow direction become dominant, and produce the columnar structure. With time, some of the dendrite
branches break off. These are then forced to grow into an undercooled melt, with growth along the
direction of heat flow. The heat flow is now radial and forces these crystals to take on an equiaxed
morphology. Stirring is often used, such as in continuous casting, to break of the columnar branches
and produce more equiaxed structure.
Columnar -ferrite grains, with austenite (light phase)
allotriomorphs growing at the grain boundaries.
 Mar Athanasius College of
Columnar microstructure
Engineering/Mechanical/BCY
Plate-like W,
8mm/h

Microstructure of unidirectionally solidified Ni-W alloy Kagami

Memorial Research Institute for Materials Science and
Mar Athanasius College of
Technology,Waseda University,
Engineering/Mechanical/BCY
since 1882, private independent University, Tokyo.
Microstructure of Ta target fabricated by thermomechanical
processing of 300 mm ingot revealing a uniform and equiaxed
grain structure. Metallurgical homogeneity is desirable for
consistent performance through the life of the tantalum sputtering
target.
Orientation of Grains
• Usually, the grains formed are having random crystallographic
orientations. But there are metallurgical techniques with which the
grains can be made oriented along some specified direction.
• As an example, the [100] directions of iron have a higher magnetic
permeability (ability of a magnetic material to support magnetic field
development) than do the other directions. Therefore, if the grains within
a polycrystalline transformer sheet are not random, but are processed to
have preferred orientation such that the [100] direction is preferentially
aligned with magnetic field, the transformer will operate with greater
efficiency. The metallurgist has learned how to develop this orientation,
with the result of billions of dollars worth of savings in electrical-power
distribution
(a) Orientation of grains are random (d) preferred orientation (atoms are arranged to a
desired direction)
[100] of iron - high magnetic permeability- Transformer efficiency – high Savings.
Grain Boundary
• The grain boundary region may be distorted with atoms belonging to neither crystal
• The thickness may be of the order of few atomic diameters
• The crystal orientation changes abruptly at the grain boundary
• Orientation difference of atoms in adjacent grains are the grain boundary.
• Grain boundary are area of mismatch.
• Along the grain boundary imperfections, impurities are present therefore grain boundary
area are considered as area of weakness.
• Grain boundary has 2 to 3 atomic thickness
• Grain boundary containing atoms are randomly oriented and these atoms are not
belongs to adjacent neither of grains.
• In an low angle boundary the orientation difference is < 10º
• Grain boundary energy is responsible for grain growth on heating ~ (>0.5Tm)
• Large grains grow at the expense of smaller ones
Grain boundaries are barriers to slip:

- Owing to misalignment of the slip planes in adjacent grains, a

dislocation passing the grain boundary have to change its direction and
thus lose its energy.

-low angle boundaries are less effective in blocking than high angle
ones.
-How strength is related to fine and coarse grain?
 Type of boundary Energy (J/m2)
Grain boundary between BCC crystals 0.89
Grain boundary between FCC crystals 0.85
Interface between BCC and FCC crystals 0.63

Grain boundaries in
SrTiO3

Mar Athanasius College of

01-Nov-20 283
Engineering/Mechanical/BCY
 Mar Athanasius College of
01-Nov-20 284
Engineering/Mechanical/BCY
 Depending on
which planes are
brought together,
the angle of
alignment will
vary.

WHY

Mar Athanasius College of

286
Engineering/Mechanical/BCY
SP