Physical Metallurgy

LECTURE NOTES
MM--15
MM 15--019
INTRODUCTION TO PHYSICAL METALLURGY
Revised on 1/1/2016….!
MME -15
15--019
Course Coordinator(s)
Avala Lava Kumar
Department of Metallurgical & Materials Engineering (MME)
Veer Surendra Sai University of Technology (VSSUT), Burla-768018
E-mail : lavakumar.vssut@gmail.com Phone: (+91) (7077110110)
Suneeti Purohit Gautam Behera

Department of MME, VSSUT, Burla – 768018 Department of MME, VSSUT, Burla – 768018
E-mail : suneeti.purohit@gmail.com E-mail : gautamiitkgpian@gmail.com
Phone : (+91) 8339037187 Phone : (+91) 8339037187
The course aims to provide a general introduction to the field of Physical Metallurgy. The
course covers crystal structures, solidification, equilibrium phase diagrams, transformation
diagrams, diffusion, liquid to solid transformations, ferrous and non-ferrous materials, cold
work, recovery and Recrystallization.
Course Overview
The module provides a systematic overview of the major principles of physical
metallurgy. Students successfully completing the module will have a critical
awareness of how these principles relate to current issues in exploiting structural
alloys in engineering applications.
Learning Outcomes
Upon successful completion of the module, students should be able to ►Show a systematic
understanding of the role that crystal structures play in material properties. ►Evaluate
critically the relevance of phase diagrams, isothermal transformation diagrams and continuous
cooling transformation diagrams to understanding real alloys and their microstructure.►
Display a critical awareness of the relevance of key areas, e.g. diffusion, defects,
transformation type, to current problems in designing, processing and exploiting real alloys.
►Show a systematic understanding of the complex interplay between microstructure,
processing and engineering properties in metallic materials.
CONTENTS
S.No Chapter Name Page No.

1 An Introduction 6-31
2 Atomic Structure 32-63
3 Crystal Structure 64-183
4 Solidification 184-207
5.1 Mechanical Properties of Metals 208-241
5
5.2 Crystal Imperfections 242-321
6 Concept of Alloys 323-340
7 Phase Diagrams 341-410
8.1 Iron-Cementite Phase Diagram 411-447
8
8.2 Iron-Graphite Phase diagram 448-477
9.1 Heat Treatment 478-589
9
9.2 Diffusion 585-613
10 Common Alloy Steels & Non-Ferrous Alloys 614-670
References
Introduction to Physical Metallurgy (This is the major reference for this course)
Sidney H. Avner
McGraw Hill Education (India) Private Limited
Materials Science & Engineering E-book (A learners guide) (This is the major reference for this
Notes, we directly taken these slides with slight modifications, our sincere thanks to authors)
Anandh Subramaniam & Kantesh Balani (IITK)
MHRD, Govt. of India through NMEICT
Materials Science and Engineering (5th Edition)
V. Raghavan
Prentice-Hall of India Pvt. Ltd., 2004.
Callister's Materials Science and Engienering
William D Callister (Adapted by R. Balasubramaniam)
Wiley Inida (P) Ltd., 2007.
The Science and Engineering of Materials
Donald. R. Askeland & Pradeep Phulé
Cengage Learning, 2006.
Materials Science & Engineering (NPTEL Course)
Ranjit Bauri (IITM)
Avala Lava Kumar *
Veer Surendra Sai University of Technology (VSSUT), Burla -768018
*E-mail : lavakumar.vssut@gmail.com
Introduction
What is physical metallurgy?
Evolution of structures in solid as it from liquid
Effect of alloy elements/ impurities on the transformation processes
Effect of processing techniques on evolution of structure
Structure property relation.
Objectives
At some point of time or the other an engineering problem involves issues related
to material selection. Understanding the behavior of materials, particularly
structure-property correlation, will help selecting suitable materials for a particular
application.
To provide a basic understanding of the underlying principles that determines the
evolution the evolution of structures in metals and alloys during their processing
and its relation with their properties & performance in service.
Processing/ Structure Properties Performance

Alloying Composition
The Impact of Materials on progress
Revolution in Transportation
By 1890 we had Copper, Bronze, Iron, Steel , Aluminum and Rubber in addition
to Wood. This paved the way for series of inventions leading to a paradigm shift
in the road transport from horse carriages to motorized vehicles.
Ford Motors – The first assembly line for mass production of commercial vehicles
Road Transport before Ford T Model, 1910 The first
affordable automobile. Ford Capri Model, 1962
Benz ‘Velo’ 1894
Advent of new materials like Mg,

polymers and technologies and
innovations. – T to Capri
Audi Q5, 2009
From there to today’s

advanced modern cars
What made it possible?
We have come of ages, developed new

materials and technologies based on them
The application of
these advanced
materials has led to
the modern day cars
Powerful Engines
From Cast iron blocks to more compact, lighter and powerful engine blocks – Material
development has made it all possible
.
Engine components are traditionally made from ferrous alloys. Emphasis on weight
reduction for higher fuel efficiency has increased usage of aluminum for cylinder blocks,
cylinder heads, and other engine components. Some engine covers and intake manifolds
are made of magnesium. Titanium is also used in high-speed engines connecting rods to
reduce reciprocating mass.
Availability of materials like

synthetic rubber, variety of
Interior polymers, foams has provided
new dimension and aesthetic
look to automotive interiors
Invention of Aero plane - 1902
From Wright Brothers’ invention
….. Modern Aviation

Through this to ……………
From the first engine used by Wright brothers to Powerful modern jet engines
Aircraft body structure

Waterways – Transport and Safety RMS Titanic, a classic example…..!
Steel quality – Poor: High S and P and low Mn:S ratio,

compared to high quality modern grade steels
The composition of steels from the titanic, a lock gate and ASTM A36
C Mn P S Si Cu O N MnS
Titanic 0.21 0.47 0.045 0.069 0.017 0.024 0.013 0.0035 6.8:1
Lock Gate 0.25 0.52 0.01 0.03 0.02 - 0.018 0.0035 17.3:1
ASTM A36 0.20 0.55 0.012 0.037 0.007 0.01 0.079 0.0032 14.9:1
Modern cruise : As luxurious as Titanic – Better safety due to use of advanced

materials like fiber reinforced composites (FRP) combined with advanced navigation
system.
The Electronics Revolution Silicon – the heart of every electronic component
Invention high purity Si through zone

refining
1940 - Harvard MarkI Electro- 1959 – IBM Computer, 33

mechanical computer – 5 tons, 8 x 51 feet long
feet and 500 miles of wire
Integrated circuit (IC) or

Silicon chip
Smaller and smaller microchips have brought the whole world on our palm top
Apple I Phone
Display: This relies upon the combination of a liquid crystal
display and a touch screen for communication with the device.
The touch screen is made from a conductive but transparent
material, indium tin oxide, a ceramic conductor.
Integrated Circuits: At the heart of the iPhone are a number
of integrated circuits (Ics) built upon billions of individual
transistors, all of which rely on precise control of the
semiconductor material, silicon, to which has been added
dopant atoms to change the silicon’s electronic properties.
Interconnects: Inter connects that provide the links between
components are now made of copper, not aluminium, for
higher speed and efficiency.
Wireless Microwave circuits need capacitors which are
ceramic insulators whose structure and composition is
carefully controlled to optimize the capacitance.
Battery: The battery is a modern Li-ion battery where the atomic structure of the electrodes
is carefully controlled to enable the diffusion of the Li ions.
Headphones: Most headphones use modern magnetic materials whose structure and
composition has been developed to produce very strong permanent magnets. This is part of a
transducer that turns electrical signals into sound.
A General Classification
The broad scientific and technological segments of Metallurgy & Materials
Science are shown in the diagram below.
To gain a comprehensive understanding of Metallurgy, all these aspects have to be
studied.
METALLURGY & MATERIALS ENGINEERING
Science of Metallurgy
PHYSICAL MECHANICAL ELECTRO- TECHNOLOGICAL

CHEMICAL
• Extractive
• Structure • Deformation • Thermodynamics • Casting
• Physical • Metal Forming
Behaviour • Chemistry
Properties • Corrosion • Welding
• Powder Metallurgy
• Machining
A Broad Overview
We shall start with a broad overview of .. well...almost everything!
(the next slide)
The typical domain of materials science is enclosed in the ellipse. (next slide)
Traditionally materials were developed keeping in view a certain set of properties
and were used for making components and structures.
With the advancement of materials science, materials are expected to perform the
role of an ‘intelligent’ structure or a mechanism.
A good example of this would be applications of shape memory alloys:
● they can be used to make deployable antennas (STRUCTURE) or
● actuators (MECHANISM).
Though it will not be practical to explain all aspects of the diagram (presented in
the next slide) in this elementary course, the overall perspective should be kept at
the back of one’s mind while comprehending the subject.
A point to be noted is that one way of classification does not clash with another.
E.g. from a state perspective we could have a liquid which is a metal from the
band structure perspective. Or we could have a metal (band structure viewpoint)
which is amorphous (structural viewpoint).
Entropic force
UNIVERSE STRONG
WEAK
HYPERBOLIC ELECTROMAGNETIC
EUCLIDEAN SPACE ENERGY GRAVITY
SPHERICAL
nD + t
PARTICLES FIELDS
METAL
SEMI-CONDUCTOR ATOMIC NON-ATOMIC
BAND STRUCTURE
INSULATOR
STATE / VISCOSITY
LIQUID
GAS SOLID LIQUID CRYSTALS
STRUCTURE
AMORPHOUS QUASICRYSTALS RATIONAL CRYSTALS

APPROXIMANTS
SIZE
NANO-QUASICRYSTALS NANOCRYSTALS
A Broad Overview
Based on state (phase) a given material can be Gas, Liquid or Solid
(based on the thermodynamic variables: P, T,…).
Intermediate/coexistent states are also possible (i.e clear demarcations can get blurred).
(Kinetic variables can also affect how a material behaves: e.g. at high strain rates some materials may
behave as solids and as a liquid at low strain rates)
Based on structure (arrangement of atoms/molecules/ions) materials can be
Crystalline, Quasicrystalline or Amorphous.
Intermediate states (say between crystalline and amorphous; i.e. partly crystalline)
are also possible. Polymers are often only partly crystalline.
Liquid Crystals (‘in some sense’) are between Liquids and Crystals.
Based on Band Structure we can classify materials into Metals, Semiconductors
and Insulators.
Based on the size of the entity in question we can Nanocrystals, Nanoquasicrystals
etc.
Faceted glass objects are

Strange? sometimes called
crystals!
A polycrystalline vessel for drinking fluids is sometimes referred to as GLASS!
And, a faceted glass object is sometimes referred to as a crystal!
A Common Perspective
Let us consider the common types of Engineering Materials.
These are Metals, Ceramics, Polymers and various types of composites of these.
A composite is a combination of two or more materials which gives a certain benefit to at least one
property → A comprehensive classification is given in the next slide. The term Hybrid is a superset of
composites.
The type of atomic entities (ion, molecule etc.) differ from one class to another, which in turn gives
each class a broad ‘flavour’ of properties. Bonding and structure are key
● Like metals are usually ductile and ceramics are usually hard & brittle factors in determining the
● Polymers have a poor tolerance to heat, while ceramics can withstand high temperatures properties of materials
● Metals are opaque (in bulk), while silicate glasses are transparent/translucent
● Metals are usually good conductors of heat and electricity, while ceramics are poor in this aspect.
● If you heat semi-conductors their electrical conductivity will increase, while for metals it will decrease
● Ceramics are more resistant to harsh environments as compared to Metals
Biomaterials are a special class of materials which are compatible with the body of an organism
(‘biocompatible’). Certain metals, ceramics, polymers etc. can be used as biomaterials.
Diamond is poor electrical
conductor but a good thermal
Common type of materials conductor!! (phonons are
responsible for this)
Metals Ceramics Polymers

& Glasses
Hybrids (Composites)
Classification of materials
Materials
Composites: have two (or more)
solid components; usually one is a
Monolithic Hybrids
matrix and other is a reinforcement
Metals (& Alloys) Composite
Sandwich structures: have a
Ceramics & Glasses material on the surface (one
Sandwich or more sides) of a core
material
Polymers (& Elastomers)
Lattice* Structures: typically a
Lattice combination of material and space
(e.g. metallic or ceramic forms,
aerogels etc.).
Segment
Segmented Structures: are Hybrids are

designed to improve
divided in 1D, 2D or 3D
certain properties of
(may consist of one or monolithic materials
more materials).
*Note: this use of the word 'lattice' should not be confused with the use of the word in connection with crystallography.
Common materials : with various ‘viewpoints’
Graphite
Glass: amorphous
Ceramics
Crystal
Metals Polymers
Classes of property
Economic Price and Availability, Recyclability

General Physical Density
Modulus, Yield and Tensile strength, Hardness,
Mechanical Fracture strength, Fatigue strength, Creep strength,
Damping
Thermal Thermal conductivity, Specific Heat
Resistivity, Dielectric constant, Magnetic
Electric & Magnetic
permeability
Environmental
Oxidation, corrosion and wear
interactions
Production Ease of manufacturer, joining, finishing
Aesthetic (Appearance) Colour, Texture, Feel.
The Materials Tetrahedron
A materials scientist has to consider four ‘intertwined’ concepts, which are schematically
shown as the ‘Materials Tetrahedron’.
When a certain performance is expected from a component (and hence the material
constituting the same), the ‘expectation’ is put forth as a set of properties.
The material is synthesized and further made into a component by a set of processing
methods
(casting, forming, welding, powder metallurgy etc.).
The structure (at various lengthscales) is determined by this processing.
The structure in turn determines the properties, which will dictate the performance of the
component.
Hence each of these aspects is dependent on the others.
The broad goal of Metallurgy & Materials

Engineering is to understand and ‘Engineer’
this Tetrahedron
The Materials Tetrahedron

What determines the properties of materials?
Cannot just be the composition!
Few 10s of ppm of Oxygen in Cu can degrade its conductivity
Cannot just be the amount of phases present!
A small amount of cementite along grain boundaries can cause the material to have poor impact
toughness
Cannot just be the distribution of phases!
Dislocations can severely weaken a crystal
Cannot just be the defect structure in the phases present!
The presence of surface compressive stress toughens glass
The following factors put together determines the properties of a material:

Composition
Phases present and their distribution
Defect Structure (in the phases and between the phases)
Residual stress (can have multiple origins and one may have to travel across lengthscales)
These factors do NOT act independent of one another (there is an interdependency)
Phases & Their

Distribution
Composition Residual Stress
Defect Structure
Hence, one has to traverse across lengthscales and look at various aspects to understand the properties of materials
Length scales in metallurgy
• Casting
• Metal Forming
Thermo-mechanical • Welding
Treatments • Powder Processing
Crystal
• Machining
Atom Structure Microstructure Component
Electro-
magnetic Phases + Defects + Residual Stress
& their distribution
Structure could imply two types of structure: • Vacancies
Crystal structure
Electromagnetic structure
• Dislocations
Fundamentally these aspects are two sides of the same • Twins
coin • Stacking Faults
Microstructure can be defined as: • Grain Boundaries
(Phases + Defect Structure + Residual Stress) and their
distributions
• Voids
Microstructure can be ‘tailored’ by thermo-mechanical • Cracks
treatments
Processing determines shape and microstructure of a component

Length scales in metallurgy
Let us start with a cursory look at the lengthscales involved in Materials Science
Dislocation Stress fields

Angstroms → Nanometers Microns Centimeters
Unit Cell* Crystalline Defects Microstructure Component
Grain Size
*Simple Unit Cells

Change of properties across lengthscales: polycrystalline copper (CCP structure)
Atomic level (Å) → Unit Cell level (few Å-nm)→ Grain level (nm-µm) → Material level (cm)
At the atomic level there is order only in the average sense (at T > 0K) as the atoms are constantly vibrating about the
mean lattice position. Hence, in a strict sense the perfect order is missing (a). The unit cell level is the level where the
atomic arrangement becomes evident (crystal structure develops) and concepts like Burgers vector emerge, b. It is at
this level that averaging with respect to probabilistic occupation of lattice positions in disordered alloys is made (say
Ni50-Al50 alloy is defined by a 50-50 probability of Ni or Al occupying a lattice position). At the grain level (c, which
is a single crystal), there is nearly perfect order (as the scale of atomic vibrations are too small compared to grain
scale); except for the presence of defects like vacancies, dislocations etc. At this scale the material is also anisotropic
(e.g. with respect to the elastic stiffness, which is represented by three independent numbers: E11, E12 & E44). It is to be
noted that the Cu crystal may be isotropic with respect to other properties. At the material level (d), assuming that the
grains are randomly oriented, there is an averaging of the elastic modulii and the material becomes isotropic. At this
scale, the crystalline order which was developed at the grain level (c) is destroyed at the grain boundaries and there is
no long range order across the sample. When the material is rolled or extruded, it will develop a texture (preferred
directional properties), which arises due to partial reorientation of the grains. That is, we have recovered some of the
inherent anisotropy at the grain scale. As we can see, concepts often get 'inverted' as we go from one lengthscale to
another.
(a) Thermal vibration (b) Unit cell of Cu (c)Grain Structure (d) Sample of Cu
Traversing four lengthscales in a Cu polycrystal: schematic of the changing order and properties. a) instantaneous snapshot of a vibrating atom, b)
crystalline order (unit cell), c), grain level (single crystal- anisotropy) , d) the material level (isotropy due to randomly oriented grains).
Summary
Properties of a material are determined by two important characteristics:
Atomic structure
Electromagnetic structure – the bonding character
(Bonding in some sense is the simplified description of valence electron density distributions)
There are microstructure ‘sensitive’ properties (often called structure sensitive

properties) and microstructure insensitive properties (note the word is sensitive
and not dependent).
Microstructure ‘sensitive’ properties → Yield stress, hardness, Magnetic
coercivity…
Microstructure insensitive properties → Density, Elastic modulus…
Hence, one has to keep in focus:
Atomic structure
Electromagnetic structure/Bonding
Microstructure
to understand the properties.
Questions?
1. What is Physical Metallurgy?
2. Give the broad classification of Materials?
3. Define Metal, Ceramic and Composite.
4. Define Macrostructure and Microstructure?
5. What is Grain and Grain boundary?
6. Give some of important properties of materials.
7. What is composite?
8. What is Bio-materials?
9. What is smart materials?
10. Give some of the types of advanced materials and its applications.
Avala Lava Kumar *
Introduction
In order to understand the structure of materials and its correlation to property, we
have to start form the basic element of matter – The Atom
An atom consists of a nucleus composed of protons and neutrons and electrons
which encircle the nucleus.
Protons and electrons have same and opposite charge of 1.6 x10-19 C.
Atomic number (Z) = Number protons = number of electrons
Atomic mass (A) = proton mass + neutron mass
Isotopes are the same element having different atomic masses. Number of protons
in isotopes remains same while number of neutrons varies.
Atomic mass unit (amu) = 1/12 mass of Carbon 12 (12C)
1 mol of substance contains 6.023 x 1023 (Avogadro’s number) atoms or molecules.
Atomic weight = 1 amu/atom (or molecule) = 1 g/mol = Wt. of 6.023 x 1023 atoms
or molecules.
For example, atomic weight of copper is 63.54 amu/atom or 63.54 g/mole
Role of atomic structure in materials
As we know, common to all materials is that they are composed of atoms.
The properties (whether mechanical, electrical, chemical etc) of all solid materials
are dependent upon the relative positions of the atoms in the solid (in other words
the atomic structure of the material) and their mutual interaction i.e. the nature of
the bonding (whether e.g. covalent, ionic, metallic, van der Waals).
There are examples of where the atom-atom interactions is strongly reflected in the
atomic structure. An example is diamond. Here the carbon-carbon interactions lead
to a very directional covalent bond called a sp3 bond which has tetrahedral
symmetry – this leads to an open structure as shown below.
Role of atomic structure in materials
Of course carbon can also take the form of graphite. Here the carbon atoms are
arranged in a rather different structure and graphite has very different properties to
diamond!
In other solid systems (for example many of the metallic elements) the atomic
structure is dictated by how well we can ‘pack’ the atoms into 3D space – ‘packing
efficiency’ – this leads to dense close-packed structures as we will also discuss in
crystal structure chapter.
So it is vital that to understand the properties of material, and to improve those
properties for example by adding or removing atoms, we need to know the
material’s atomic structure.
As Richard Feynman said….!
“It would be very easy to make an analysis of any

complicated chemical substance; all one would have to do
would be to look at it and see where the atoms are…”
Atomic structure : The Bohr model
Electrons revolve around a positively charged nucleus a
in discrete orbits (K, L, M or n=1, 2, 3 respectively)
with specific levels of energy.
Electrons positions are fixed as such, however, an
electron can jump to higher or lower energy level by
absorption or emission of energy respectively.
b
Limitations of the Bohr Model
Although the Bohr’s model was the first and best

model available at the time of its discovery, it had
certain limitations and could not explain many
phenomena involving electrons
Heisenberg’s uncertainty principle:
The position and momentum of an electron can not be determined simultaneously.

This also disapproves the hypothesis in the Bohr model that electrons revolve around
certain circular orbits
Wave-Mechanical Model
The wave-mechanical or wave-particle model was proposed to address the
limitations in the Bohr model.
The basic premise of this model is the wave-particle duality of electrons i.e.
electrons are considered to have both wave-like and particle-like characteristics.
The position of an electron is defined as the probability of finding it at different
locations in an electron cloud around the nucleus i.e. position of an electron is
described by a probability distribution instead of discrete orbits.
Probability distribution vs. distance from nucleus

Probability of finding an electron is maximum at the Bohr radius
The Bohr radius, r =

Quantum Numbers
Four parameters or numbers called Quantum numbers are needed to describe the
distribution and position of electrons in an atom.
The first three of them (n, l, ml) describe the size, shape, and spatial orientation of
the probability density distribution of electrons
Principal quantum number, n
It describes electron shells as shown in the Bohr model. Values of n can be 1, 2,

3, 4….. Corresponding to electron shells K, L, M, N……. The value of n also
determines the size or distance of the shells from the nucleus.
Number of electrons in a shell = 2n2 for example; number of electrons in K shell
(n=1) = 2 × 12 = 2, and L shell (n=2) = 2 × 22 = 8 and so on.
Azimuthal or Angular quantum number, l
It signifies subshell or electron orbital – s, p, d, f and so on. I can take values of
from 0 to n-1. K shell, n = 1, one ‘s’ orbital. L, n=2, two orbitals, s, p. M, n=3,
three orbitals s, p, d. for N, n=4, four orbital's s, p, d, f and so on.
Quantum Numbers
Azimuthal or Angular quantum number, l
The value of l decides the shape of the orbital as shown in the figure below. ‘s’
orbital (ll =0) – spherical, p (l =1)- polar or dumbbell shaped, d(l
d(l =2) – double-
double-
dumbbell shaped
shaped..
Magnetic quantum number, ml

Orbital's are associated with energy states. Magnetic quantum number determines
the number of energy states in each orbital.
This number depends on the value of l . ml can take values from – l to + l e.g. l = 1
(p orbital) ml = -1, 0, +1 ( three states). Only one state for the s orbital (ll = 0), as
ml can take only one value (0). In general no. of states = 2 l +1
Orbital S p d f
No. of states 1 3 5 7
Quantum Numbers
Spin quantum number, ms
Each electron is associated with a spin moment. The fourth quantum number, ms
is related to this spin moment of electrons. It can have only two values, + ½ and –
½.
Pauli’s exclusion principle
It states that not more than two electrons having opposite spin can occupy the
same energy state.
Based on this principle, number of electrons in different orbital's (s, p, d ….) can
be obtained. For example, ‘s’ orbital has only one energy state, so it can
accommodate only two electrons having opposite spins.
Hund’s rule
It states that, in order to reduce the electron-electron repulsive energy, the number
of electrons of the same spin in p, d or f states should be maximum.
Electron Configuration
The quantum mechanic principles as discussed before allow determination of electron
configuration i.e. the manner in which electron states are occupied in a given atom.Σ
n-1
Σ 2(2 l +1)
l =0
Electron configuration based on quantum numbers. Total number of electrons in a shell is 2n2
or n-1 2(2 l +1)
Σ
l =0
The manner or sequence of filling of electron orbital's is decided a by a set of two
principles / rules:
Aufbau principle
Madelung’s rule
Aufbau principle (German meaning is building up) : it states that lower energy
states will be filled up first.
Madelung’s rule : Orbitals fill in the order of increasing (n+l). 4s (n+l = 4+0 = 4)
will be filled before 3d (n+l= 3+2 = 5) and 5s (n+l = 5+0 = 5)
For orbital with same values of (n+l), the one with lower ‘n’ will be filled first. 3d
will be filled before 4p.
Aufbau principle Madelung rule

Based on the foregoing discussion, it is now possible to find the electron
configuration for a given atom.
For example, sodium Na1123 has 11 electrons – the configuration is shown in the
first figure. The second picture shows the Bohr configuration.
Valence electrons
The electrons in the outer most shell are known as valence electrons. Na has one
valence electron (the 3s electron). These electrons are responsible for chemical
reaction and atomic bonding.
Look at the electron configuration of inert gases (He, Ne, Ar, Kr, Xe) in the
previous table. Their valence electron cell is completely filled unlike any other
element.
Note that the configuration of higher atomic number elements can be expressed by
the previous inert element configuration.
It is the tendency of every element to attain the lowest energy stable configuration
that forms the basis of chemical reactions and atomic bonding.
Electron Configuration of Elements
Ionization Potential, Electron Affinity, Electronegativity
If sufficient energy is supplied, an electron in the outer orbital can break away
completely from the atom and become free. The energy required to remove an
electron in this manner is known as the Ionization potential.
When the extra electron is attracted from infinity to the outer orbital of the neutral
atom, is known as the electron affinity of the atom.
The tendency of an atom to attract electrons to itself during the formation of bonds
with other atoms is measured by the electronegativity of the atom.
Let us start by looking at the relative sizes of some ions in the periodic table
Be2+
Li Li+ Be
1.52 0.68 1.12 0.35
Mg2+
Na Na+ Mg
0.66
1.85 0.97 1.60
1.46 1.31 1.25 1.12 1.24

K K+ Ca Ca2+ Ti V Cr Mn Fe
2.31 1.33 1.96 0.99
Ti4+ V3+ Cr3+ Mn2+ Fe2+ Fe3+

0.68 0.74 0.63 0.83 0.64
0.74
Rb Rb+ Sr Sr2+
1.12 B3+ C4+ 3+ O2−
N N
2.46 1.47 2.15
B C O F F−
0.23 0.2 0.1-0.2 1.33
0.89 0.77 0.74 0.74 1.40 0.72
Cs Cs+ Ba Ba2+
Al3+ Si4+ P5+ S6+
1.67 2.17
1.34 Al Si P S Cl Cl−
2.62
0.42 0.35 0.30
1.26 0.51 1.17 1.10 1.04 1.07 1.81
Values are: Pauling-Ahrens Radii in Å

Atomic Interaction
When two neutral atoms are brought close to each other, they experience attractive
and or repulsive force.
Attractive force is due to electrostatic attraction between electrons of one atom and
the nucleus of the other.
Repulsive force arises due to repulsion between electrons and nuclei of the atoms.
The net force, FN (Fig) acting on the atoms is the summation of attractive and
repulsive forces.
The distance, at which the attraction and repulsion forces are equal and the net
force is zero, is the equilibrium interatomic distance, ro . The atoms have lowest
energy at this position.
Attraction is predominant above ro and

repulsion is dominant below ro.
Atomic Interaction
The interaction energy between the pair of
atoms is given by the Lennard-Jones
potential, Vr or VLJ
σ is the distance at which the interaction

energy is zero.ε is the depth of the
potential well and is a measure of the
Lennard-Jones potential
bonding energy between two atoms.
L-J potential can be also expresses in the simplified form as VLJ = A/r12-B/r6 and
hence, is also known as 6-12 potential.
A/r12 is predominant at short distances and hence, represents the short-range
repulsive potential due to overlap of electron orbital’s and -B/r6 is dominant at
longer distance and hence, is the long range attractive potential.
Atomic Bonding
The mechanisms of bonding between the atoms are based on the foregoing
discussion on electrostatic interatomic interaction.
The types of bond and bond strength are determined by the electronic structures of
the atoms involved.
The valence electrons take part in bonding. The atoms involved acquire, loose or
share valence electrons to achieve the lowest energy or stable configuration of
noble gases.
Atomic bonding can be broadly classified as i) primary bonding ii) secondary
bonding
Primary Bonds Secondary Bonds
Ionic Covalent Metalic Vanderwaals Hydrogen
Majority of the engineering materials consist of one of these bonds. Many

properties of the materials depend on the specific kind of bond and the bond
energy.
Ionic Bond
Ionic bonds are generally found in compounds composed of metal and non-metal
and arise out of electrostatic attraction between oppositely charged atoms (ions).
Number of electron in outer shell is 1 in Na and 7 in Cl . Therefore, Na will tend to
reject one electron to get stable configuration of Ne and Cl will accept one electron
to obtain Ar configuration.
The columbic attraction between Na+ and Cl¯ ions thus formed will make an ionic
bond to produce NaCl.
Cl−
Na+
Some other examples are CaF2 , CsCl, MgO, Al2O3

Covalent Bond
In this type of bonding, atoms share their valence electrons to get a stable
configuration.
Methane (CH4): Four hydrogen atoms share their valence electrons with one
carbon atom and the carbon atom in turn shares one valence electron with each of
the four hydrogen atoms. In the process both H and C atoms get stable
configuration and form a covalent bond.
Covalent bonds are formed between atoms of similar electro negativity.

C atoms in diamond are covalently bonded to each other.
Si also has valency of four and forms SiC through covalent bonding with C atoms.
Metallic Bond
In metals the valence electrons are not really bound to one particular atom, instead
they form a sea or cloud of valence electrons which are shared by all the atoms.
The remaining electrons and the nuclei form what is called the ion core which is
positively charged. The metallic bond arises out of the columbic attraction between
these two oppositely charged species – the electron cloud and the ion cores.
Electron cloud distribution in various kinds of bonding
Characteristics of primary bonds
Ionic and covalent bonds posses high bond energy : 450-1000 KJ/mole
High bond strength in ionic and covalent solids results in high melting point, high
strength and hardness. e.g. diamond
As the electrons are tightly bound to the atoms they are generally poor conductors
of heat and electricity.
Are brittle in nature
Most of the ceramics consist of covalent (SiC) or ionic bonds (Al2O3) or a mix of
both and hence, exhibit all the properties described above.
Metallic bonds on the other hand provide good thermal and electrical
conductivities as the valence electrons are free to move.
The metallic bond energy is 68 kJ/mol (Hg) on the lower side and 850 kJ/mol (W,
tungsten) on the higher side.
Bond strength increases with atomic number as more electrons are available to
form the bonds with the ion cores. As a result melting point, hardness and strength
increases with atomic number.
Metals are ductile as the free moving electrons provides agility to the bonds and
allows plastic deformation.
Vanderwaals bonding
Vanderwaals bonding between molecules or atoms arise due to weak attraction
forces between dipoles.
The natural oscillation of atoms leading to momentary break down of charge
symmetry can generate temporary dipoles.
Dipoles can induce dipoles and attraction between opposites ends of the dipoles
leads to weak bonding.
An ion can also induce a dipole

Some molecules like HCl have permanent dipoles due to asymmetrical
arrangement of +ve and –ve charges.
Vanderwaals bonding
Van der Waals bonding is much weaker compared to primary bonds. Bond energy
lies in the range of 2 – 10 kJ/mol
Molecules in liquid and gas are held by weak Vanderwaals forces.
The atomic layers in graphite are held together by weak vanderwaals bonds.
Therefore, the layers can move easily over each other and this imparts the
lubricating property graphite is known for.
Hydrogen bonding
Hydrogen bond is a type of secondary bond found in molecules containing
hydrogen as a constituent.
The bond originates from electrostatic interaction between hydrogen and another
atom of high electro-negativity such as fluorine or oxygen.
The strength of hydrogen bonds is in the range of 10 - 50 kJ/mol.
Water molecules, for example, are connected by hydrogen bonds (dashed lines in
the picture).
Mixed bonding
Many materials have a mixed bonding characteristics, between covalent and ionic
bonding. Examples are as below.
Oxides: % ionic bonding ~ 70%
Nitrides: % ionic bonding ~ 40%
Carbides: % ionic bonding ~ 15~20%
Metallic-covalent Mixed Bonding: The transition metals are an example where

s,p,d-bonding orbital's lead to high melting points.
Binding Energies of Bonds

Bond Type Energy (eV) Energy (kJ/mole) Energy (kJ/mole)
Ionic ~5-15 (strong) ~500-1500 NaCl: 640
Covalent ~1-10 (strong) ~100-1000 Diamond: ~710
Metallic ~0.5-8.5 (strong) ~50-850 Fe: 406
Hydrogen ~0.05-1.5 ~5-155 H2O: 51
Van der Walls ~0.01-0.5 ~1-50 Ar:7.7

Concept of Thermal Expansion
The length of a bond is defined as the center-to-center distance of the bonding
atoms. Strong bonds pull the bonding atoms closer together and so have smaller
bond lengths as compared to weak bonds.
Primary bonds have lengths in the range 1-2 Å (0.1-0.2 nm). Secondary bond
lengths are larger, in the range 2-5Å (0.2-0.5 nm)
Some ambiguity in this definition arises if the element in question, exhibits
different crystal forms.
For example, the diameter of the iron atom is 2.48 Å when it is surrounded by
eight neighbours in the BCC crystal and 2.54Å when it has 12 nearest neighbours
in the FCC crystal.
If the inter-ionic separation is fixed, it

means the atoms are stationary, and this
can occur only at 0 Kelvin. Therefore the
atoms are at their minimum energy E0,
and inter-ionic separation r0, at 0 Kelvin.
The minimum energy E0, and equilibrium

inter-ionic spacing r0, at 0 Kelvin.
As the temperature of the system is raised to T1, and then further to T2, the solid
becomes consistent with the higher temperatures by having the ions gain energy,
and vibrate with increased amplitudes. Therefore, as shown in Figure(below), at
T1, when the energy is E1, the ions are able to vibrate between the positions “A”
and “B”. Similarly, at T2, when the energy is E2, the ions are able to vibrate
between the positions “C” and “D”.
Effect of increasing temperature on the vibration of the ions and hence on the inter-ionic separation. The
system is raised to temperature T1, and then further to T2. At T1, when the energy is E1, the ions are able to
vibrate between the positions “A” and “B”. Similarly, at T2, when the energy is E2, the ions are able to
vibrate between the positions “C” and “D” .
It is important to note from the Figure (previous slide) that, the midpoint between
“A” and “B”, which represents the mean inter-ionic distance at T1, is r1 which is
greater than r0. This is a direct result of the fact that the solid curve in Figure, is
asymmetric.
It is therefore important to note that thermal expansion occurs as a direct result
of the fact that the ‘E Vs R’ curve is asymmetric.
It is also important to note that while the general approach used here can be
extended to many systems, the exact shape of the resultant curve obtained will
depend on the details of the specific system. In some cases, such as ceramic
materials, the resultant curve will have a very deep and narrow trough, such
materials will have a very low coefficient of thermal expansion. In other cases, the
resultant curve will have a shallow and wide trough, which will cause the material
to display a high coefficient of thermal expansion.
A hypothetical solid, in which the E Vs R curve is exactly

symmetric. In this case when the temperature is raised, E
increases, and the amplitude of vibration of the ions increase, but
there is no thermal expansion since the mean inter-ionic distance
is exactly the same at all temperatures
Questions?
1. Define atom, electron, proton and neutron
2. State the Heisenberg uncertainty principle and Find the minimum uncertainty in
determining the position of a particle, if the uncertainty in its momentum ∆p = 10-
30 kg m s-1 [Ans:1.055×10-4 m]
3. What is Pauli’s exclusion principle.

4. Define a solid. Glass is not considered as true solid
5. Why are noble gases inert?
6. What is Lennard-Jones potential?
7. Briefly explain the primary bonds in solids.
8. How do secondary bonds form? What is hydrogen bond?
9. Why is graphite lubricating?
10. Why are ceramics hard and brittle? Why are they not conductive?
11. Why is boiling point of methane (CH4) lower than water?
12. How many atoms are there in 1 g of copper?
13. Why are some elements known as transition elements
14. Why is Tungsten (74) much stronger than Aluminium (13) though both are
metallic?
Questions?
15. Calculate the attractive force between two K+ and Br- ions that just touch each
other. Atomic radii of K+ and Br- are 0.133 and 0.196 nm respectively.
16. If the attractive force between a pair of Cs+ and I- ions is 2.83 x 10-9 N and the
ionic radius of Cs+ is 0.165 nm, what is the ionic radius of I- ion?
17. Does the size of Na and Cl atoms remain same when they react to from NaCl?
Give reasons for your answer.
18. If energy of an electron, E = - 13.6/n2 eV, find out the energy, wavelength and
frequency of the photon emitted for a jump from M to L shell. h = 4.14 x 10-15
eV.s
19. Explain the arrangement of the elements in the periodic table
20. Show that energy of an electron in hydrogen atom E = 2∏2me4/n2h2 = - 13.6/n2
eV
Avala Lava Kumar*
Why study crystal structures?
When we look around much of what we see is non-crystalline (organic things like
wood, paper, sand; concrete walls, etc. → some of the things may have some crystalline parts!).
But, many of the common ‘inorganic’ materials are ‘usually*’ crystalline:
◘ Metals: Cu, Zn, Fe, Cu-Zn alloys
◘ Semiconductors: Si, Ge, GaAs
◘ Ceramics: Alumina (Al2O3), Zirconia (Zr2O3), SiC, SrTiO3
Also, the usual form of crystalline materials (say a Cu wire or a piece of alumina)
is polycrystalline and special care has to be taken to produce single crystals
Polymeric materials are usually not ‘fully’ crystalline
The crystal structure directly influences the properties of the material
Why study crystallography?
Gives a terse (concise) representation of a large assemblage of species

Gives the ‘first view’ towards understanding of the properties of the crystal
* Many of the materials which are usually crystalline can also be obtained in an amorphous form
Platonic Solids
In 387B.C. scientist called “PLATO” most famous student of Socrates thought that
whole universe is made up of five solids. Whole universe is periodic arrangement
of five solids named as Platonic Solids.
Tetrahedron - 4 faces - Fire He had a some
philosophical thought;
Hexahedron - 6 faces - Earth in the universe we have
Octahedron - 8 faces - Air 5 elements made up of
these five solids
Dodecahedron - 12 faces - GOD
Icosahedron - 20 faces - Water
In icosahedron, we will get best packing as for we concerned. But only problem is,
if we try to translate it in 3D we can’t get continuous structure, without any voids
left. This voids in crystallography is called frustation.
Long back people thought, it is not possible to have solids with Icosahedron
packing; but it is possible when Quasicrystals are discovered in 1984. (Al-Mn)
Ideal Crystals → Real Crystals → Microstructures → Material → Component
Ideal Crystal Ideal Mathematical Crystal

Consider only the Geometrical Entity
or
only the Physical Property
Crystal* Consider only the Orientational
or
Positional Order
Crystal**
Put in Crystalline defects
& Free Surface
& Thermal Vibration
‘Real Crystal’
Put in Multiple Crystals (Phases)
giving rise to interfacial defects
~Microconstituents
Put multiple ~microconstituents
Add additional residual stress
Real materials are
Microstructure usually complex and we
start with ideal
descriptions
Material Material or Hybrid
*, ** Reduced definition of crystals

Component
That which is NOT associated with defects (crystalline or interfacial) → e.g. thermal residual stresses
Ideal Crystals → Real Crystals → Microstructures → Material → Component
Geometrical entity
Ideal Crystal Ideal Mathematical Crystal
Physical Property
Consider only the Geometrical Entity Part of the infinite crystal

or
only the Physical Property
Crystal*
Part of the infinite crystal Consider only the Orientational
or
Positional Order
Crystal**
Part of the infinite crystal
Put in Crystalline defects
& Free Surface
& Thermal Vibration
Vacancy shown as an example of a defect

‘Real Crystal’
*, ** Reduced definition of crystals
How to define a Crystal?
Crystal
A 3D translationally periodic arrangement of atoms in a space is called a crystal.
Lattice
A 3D translationally periodic arrangement of points in a space is called a crystal.
Unit Cell
What is the relation between the two ?
Crystal = Lattice + Motif

Motif or Basis:
typically an atom or a group of atoms associated with each lattice point
Lattice The underlying periodicity of the crystal

Basis Entity associated with each lattice points
Lattice how to repeat

Motif what to repeat
Lattice Crystal
Translationally periodic Translationally periodic
arrangement of points arrangement of motifs
What is the relation between the two ?
Crystal =
Lattice (Where to repeat)+Motif (What to repeat)
∞
Crystal ∞
a
=
∞
Lattice ∞
a
+
Motif Note: all parts of the motif do not sit on the lattice point
a
2
Motifs are associated with lattice points → they need NOT sit physically at the lattice point
Exam
Let us construct the crystal considered before starting with an
ple
infinite array of points spaced a/2 apart
Put arrow marks pointing up and down alternately on the points:
What we get is a crystal of lattice parameter ‘a’ and not ‘a/2’! → as this lattice parameter is a
measure of the repeat distance!
And the
motif is:
↑+↓
Note: we could have alternately chosen the centres of bottom arrows as lattice points!
M.C. Esher : Art with Science
Every periodic pattern (and hence a Crystal) has a unique lattice associate with it.
Water
fall
Interesting Fact…!
Monatomic Body-centered CsCl crystal
cubic (BCC) crystal
Corner and body centered have the same Corner and body centered do not have
neighborhood the same neighborhood
BCC FEYMAN !
Lattice: BCC
Lattice : simple cubic
Motif : 1 atom 000 Motif : Two atom Cl (0,0,0)
Cs (½, ½, ½)
Why study symmetry..?
Crystals are an important class of materials.
Crystals (and in fact quasicrystals) are defined based on symmetry.
The symmetry being referred to in this context is geometrical symmetry.
Symmetry helps reduce the ‘infinite’ amount of information required to describe a
crystal into a finite (preferably small) amount of information.
One obvious manifestation of the symmetry inherent in a crystal, is the external
shape of the crystal.
Symmetry (in conjunction with other elements) helps us define an infinite crystal in
a succinct manner.
In crystallography (the language of describing crystals) when we talk of Symmetry;
the natural question which arises is: Symmetry of What?
The symmetry under consideration could be of one the following entities:
Lattice Crystal Motif Unit cell
(these are distinct and should not be confused with one another!)
Symmetry can be defined as, if an object is brought into self-coincidence after

some operation it said to possess symmetry with respect to that operation.
Broad Classification of Symmetries
Translation Moves a point
Type I
Rotation Does not move a point
Symmetries
Mirror Roto-
Type II reflection
Inversion Roto-
inversion
Certain combination of symmetry operators (without a translational component)

can also leave a finite set of points and these are called the Point Groups
We can have point groups in 1D, 2D, 3D or nD in general.
Certain combination of symmetry operators involving translations can leave a
periodic array of (finite set of) objects in space → the Space Groups
We can have space groups in 1D, 2D, 3D or nD in general.
Translation
The translation symmetry operator (t) moves an point or an object by a
displacement t or a distance t.
A periodic array of points or objects is said to posses translational symmetry.
Translational symmetry could be in 2D or 3D (or in general nD).
If we have translational symmetry in a pattern then instead of describing the entire
pattern we can describe the ‘repeat unit’ and the translation vector(s).
t
∞ ∞
t
∞ ∞
Rotation Axis
Rotation axis rotates a general point (and hence entire space) around the axis by a
certain angle
On repeated operation (rotation) the ‘starting’ point leaves a set of ‘identity-points’
before coming into coincidence with itself.
As we are interested mainly with crystals, we are interested in those rotations axes
which are compatible with translational symmetry → these are the (1), 2, 3, 4, 6 –
fold axis.
If an object come into self-coincidence through smallest non-zero rotation
angle of θ then it is said to have an n-fold rotation axis where:
360 0
n=
θ
Rotational Symmetry
θ=180° n=2 2-fold rotation axis
The rotations compatible with translational symmetry are (1, 2, 3, 4, 6)
⇒ Crystals can only have 1, 2, 3, 4 or 6 fold symmetry

Examples of Rotational Symmetry
Angles
180˚ 120˚ 90˚ 72 ˚ 60˚ 45˚
Fold
2 3 4 5 6 8
Graphic Symbol
Mirror and Inversion
The left hand of a human being cannot be superimposed on the right hand by mere
translations and rotations
The left hand is related to the right hand by a mirror symmetry operation (m)
The right hand is called the enantiomorphic form of the left hand
Another operator which takes objects to enantiomorphic forms is the inversion
operator (i)
m
Inversion operator
Vertical Mirror Horizontal Mirror

Reflection ( or mirror symmetry)
Unit Cells (UC)
An unit cell (also sometimes causally referred to as a cell) is a representative unit
of the structure
Instead of drawing the whole structure I can draw a representative part and specify the
repetition pattern
The term unit should not be confused with ‘having one’ lattice point or motif (The
term primitive or sometimes simple is reserved for that)
If the structure is a lattice the unit cell will be unit of that (hence will have points
only)
If the structure under considerations is a crystal, then the unit cell will also contain
atoms (or ions or molecules etc.)
Note: Instead of full atoms (or other units) only a part of the entity may be present in
the unit cell (a single unit cell)
The dimension of the unit cell will match the dimension of the structure; If the
lattice is 1D the unit cell will be 1D, if the crystal is 3D then the unit cell will be
3D, if the lattice is nD the unit cell will be nD.
If the lattice points are only at the corners, the cell is primitive.
If there are lattice points in the cell other than the corners, the cell is non-
primitive.
1D Unit Cell
Unit cell of a 1D lattice is a line segment of length = the lattice parameter
this is the PRIMITIVE UNIT CELL (i.e. has one lattice point per cell)
Each of these lattice points contributes half a lattice point to the unit cell
Primitive UC
Contributions to the unit cell: Left point = 0.5, Middle point = 1, Right point = 0.5. Total = 2
Doubly Non-
primitive UC
Triply Non-
primitive UC
1D Unit Cell
Unit cell of a 1D crystal will contain Motifs in addition to lattice points
The only kind of motifs possible in 1D are line segments
Hence in ‘reality’ 1D crystals are not possible as Motifs typically have a finite
dimension (however we shall call them 1D crystals and use them for
illustration of concepts)
Though the whole lattice point is

shown only half belongs to the UC
Each of these atoms contributes ‘half-atom’ to the unit cell
Though this is the correct unit cell

Often unit cells will be drawn like this
Unit cell in 1D is described by 1 (one) lattice parameter: a

2D Unit Cell
Some aspects we have already seen in 1D → but 2D many more concepts can be
clarified in 2D
2D crystal = 2D lattice + 2D motif
Unit cell in 2D is described by 3 lattice parameters: a, b, α b

α
a
Special cases include: a = b; α = 90° or 120°
Unit Cell shapes in 2D → Lattice parameters

Square → (a = b, α = 90°)
Rectangle → (a, b, α = 90°)
120° Rhombus → (a = b, α = 120°)
Parallelogram (general) → (a, b, α)
2D
Rectangular
lattice
Note: Symmetry of the Lattice or the crystal is not altered by our choice of unit cell!!
How to choose a unit cell?
Symmetry of the unit cells should be maximum
Size of the unit cell should be minimum.
In this case the primitive (square) and the non-primitive square cell both have the
same symmetry, but the primitive square cell is chosen as it has the smaller size
This is nothing but a

square lattice viewed
at 45°!
Centred square lattice = Simple square lattice Continued…

How to choose a unit cell?
The primitive parallelogram cell is not chosen as it has a lower symmetry
The lattice has 4-fold symmetries as shown
The square cells also have 4-fold symmetry
The parallelogram cell does NOT have 4-fold symmetry (only 2-fold → lower
symmetry)
Note these are symmetries of the UC

and not of the lattice!
3D Unit Cell
In order to define translations in 3-D space, we need 3 non-coplanar vectors
Conventionally, the fundamental translation vector is taken from one lattice point
to the next in the chosen direction
With the help of these three vectors, it is possible to construct a parallelopiped
called a UNIT CELL
Unit Cell shapes in 3D:
Cube → (a = b = c, α = β = γ = 90°)
Square Prism → (a = b ≠ c, α = β = γ = 90°)
Rectangular Prism → (a ≠ b ≠ c, α = β = γ = 90°)
120° Rhombic Prism → (a = b ≠ c, α = β = 90°, γ = 120°)
Parallopiped (Equilateral, Equiangular) → (a = b = c, α = β = γ ≠ 90°)
Paralleogramic Prism → (a ≠ b ≠ c, α = γ = 90° ≠ β)
Parallopiped (general) → (a ≠ b ≠ c, α ≠ β ≠ γ)
Some common names of unit cells are given here → alternate names are also used for these cells
Point groups & Space groups
Point group symmetry

symmetries acting at a point of Lattices → 7
The 7 crystal systems
Symmetries acting
R ⊕ R 32 point groups
at a point
Along with symmetries
having a translation
230 space groups

Space group symmetry of
Lattices →14
symmetries not fixed at a point
The 14 Bravais lattices
R + R → rotations compatible with translational symmetry (1, 2, 3, 4, 6)

What are the symmetries of 7 crystal systems?
We have stated that basis of definition of crystals is ‘symmetry’ and hence the
classification of crystals is also based on symmetry
The essence of the required symmetry is listed in the table
more symmetries may be part of the point group in an actual crystal
Crystal System Symbol Characteristic Symmetry

Cubic Four 3-fold rotation axes
Hexagonal One 6-fold rotation axis
Tetragonal (only) one 4-fold rotation axis
Trigonal (only) one 3-fold rotation axis
Orthorhombic (only) Three ⊥ 2-fold rotation axis
Monoclinic (only) one 2-fold rotation axis
Triclinic None
Symmetry of cube
Pink
2-fold
Blue
3-fold
Yellow
4-fold
Crystal Structures (or) 14 Bravais Lattices
A Symmetry based concept ‘Translation’ based concept
Crystal System Lattice Parameters Bravais Lattices

P I F C
1 Cubic (a = b = c, α = β = γ = 90°)
2 Tetragonal (a = b ≠ c, α = β = γ = 90°)
3 Orthorhombic (a ≠ b ≠ c, α = β = γ = 90°)
4 Hexagonal (a = b ≠ c, α = β = 90°, γ = 120°)
5 Trigonal (a = b = c, α = β = γ ≠ 90°)
6 Monoclinic (a ≠ b ≠ c, α = γ = 90° ≠ β)
7 Triclinic (a ≠ b ≠ c, α ≠ β ≠ γ)
P Primitive
I Body Centred
F Face Centred
C A/B/C- Centred
Bravais Lattice: various viewpoints
A lattice is a set of points constructed by translating a single point in discrete steps
by a set of basis vectors.
In three dimensions, there are 14 unique Bravais lattices (distinct from one
another) in three dimensions. All crystalline materials recognized till now fit in one
of these arrangements.
In geometry and crystallography, a Bravais lattice is an infinite set of points
generated by a set of discrete translation operations.
A Bravais lattice looks exactly the same no matter from which point in the lattice
one views it. An important property of a lattice
Bravais concluded that there are only 14 possible Space Lattices (with Unit Cells
to represent them). These belong to 7 Crystal systems.
There are 14 Bravais Lattices which are the Space Group symmetries of lattices
P I F C
1 Cubic Cube
I
P
a=b=c α = β = γ = 90°
Elements with Cubic structure →

SC: F, O, Po
BCC: Cr, Fe, Nb, K, W, V
FCC: Al, Ar, Pb, Ni, Pd, Pt, Ge
F
Lattice point
P I F C
2 Tetragonal Square Prism (general height)
I
P
a=b≠c
α = β = γ = 90°
Elements with Tetragonal structure → In, Sn

P I F C
3 Orthorhombic Rectangular Prism (general height)
One convention
a<b<c
I
P
Note the position of

‘a’ and ‘b’
a≠b≠c
α = β = γ = 90°
F C
Elements with Orthorhombic structure → Br, Cl, Ga, I, Su

P I F C
4 Hexagonal 120° Rhombic Prism
a=b≠c
α = β = 90°, γ = 120°
A single unit cell (marked in blue)

along with a 3-unit cells forming a
hexagonal prism
Elements with Hexagonal structure → Be, Cd, Co, Ti, Zn
What about the HCP?

Note: there is only one type of hexagonal (Does it not have an additional atom somewhere in the middle?)
lattice (the primitive one)
P I F C
Trigonal /
5 Parallelepiped (Equilateral, Equiangular)
Rhombohedral
a=b=c
α = β = γ ≠ 90°
Note the position of the origin

Elements with Trigonal structure
and of ‘a’, ‘b’ & ‘c’ → As, B, Bi, Hg, Sb, Sm
P I F C
6 Monoclinic Parallogramic Prism
One convention
a<b<c
a≠b≠c
α = γ = 90° ≠ β
Note the position of

‘a’, ‘b’ & ‘c’
Elements with Monoclinic structure → P, Pu, Po

P I F C
7 Triclinic Parallelepiped (general)
a≠b≠c
α ≠β ≠γ
If the definition of Crystals is based on symmetry and the
existence of 7 crystal systems is also base on symmetry
symmetry;; then how
like: a = b = c, α = β = γ = 90°
come we have statements like: 90° is a cubic
crystal?
This is an important point and requires some clarification

Though the definition of crystals (e.g. cubic crystals) are based on symmetry and
NOT on the geometry of the unit cell it is true that if we already have cubic
crystal it is most preferred/logical to use parameters like a = b = c, α = β = γ =
90°
The next slide explains as to why a set of coordinate axis is more preferred for
certain geometrical entities using the example of a circle
Concept of symmetry and choice of axes
( x − a ) + ( y − b) = r
2 2 2
(a,b)
The centre of symmetry
of the object does not
Polar coordinates (ρ, θ)
coincide with the origin
ρ =r
( x) + ( y ) = r
2 2 2
The circle is described equally well by the three

The type of coordinate equations; but, in the polar coordinate system
(with centre of the circle coinciding with the
system chosen is not origin), the equation takes the most elegant
according to the symmetry (simple) form
of the object
Our choice of coordinate axis does not alter the symmetry of the object (or the lattice)!
Preferable way to represent a crystal system
Symmetry Crystal System Conventional unitcell
Symmetry operation Used as UC for crystal: Lattice Parameters

4 Cubic (a = b = c, α = β = γ = 90°)
1 Tetragonal (a = b ≠ c, α = β = γ = 90°)
3 Orthorhombic (a ≠ b ≠ c, α = β = γ = 90°)
1 Hexagonal (a = b ≠ c, α = β = 90°, γ = 120°)
1 Trigonal (a = b = c, α = β = γ ≠ 90°)
1 Monoclinic (a ≠ b ≠ c, α = γ = 90° ≠ β)
None Triclinic (a ≠ b ≠ c, α ≠ β ≠ γ)
Why are some of the entries missing…?
Cubic system Bravais lattices
1. Cubic P I F ?
2. Tetragonal P I
3. Orthorhombic P I F C
4. Hexagonal P
5. Trigonal P
6. Monoclinic P C
7. Triclinic P
Why is there no C-
C-centred cubic lattice?
Why is the F-
F-centred tetragonal lattice missing?
….?
Why not End centre cubic…?
Is this correct way to look…? Why

Cubic F equal to Tetragonal I …?
Really Cubic F = Tetragonal I ???

IMPORTANT
Crystals and Crystal Systems are defined
based on Symmetry
& NOT
Based on the Geometry of the Unit Cell
Example
Cubic Crystal
Does NOT imply a = b = c & α = β = γ
It implies the existence of four 3-fold axis in the structure
IMPORTANT
If lattices are based on just translation
(Translational Symmetry (t))
then how come other Symmetries (especially
rotational) come into the picture while choosing the
Crystal System & Unit Cell for a lattice?
Why do we say that End Centred Cubic Lattice does not exist?
Isn’t it sufficient that a = b = c & α = β = γ to call something cubic?
(why do we put End Centred Cubic in Simple Tetragonal?)
The issue comes because we want to put 14 Bravais lattices into 7 boxes (the 7 Crystal
Systems; the Bravais lattices have 7 distinct symmetries) and further assign Unit Cells
to them
The Crystal Systems are defined based on Symmetries (Rotational, Mirror, Inversion
etc. → forming the Point Groups) and NOT on the geometry of the Unit Cell
The Choice of Unit Cell is based on Symmetry & Size (& Convention)
(in practice the choice of unit cell is left to us! → but what we call the crystal is not!!)
Continued…
Tetragonal symmetry and Cubic symmetry
Cubic C = Tetragonal P Cubic F ≠ Tetragonal

If you try to make End Centered Cubic, the symmetry of cubic will be lost and it will be
turned into tetragonal
ONCE MORE:
When we say End Centred Cubic →
End Centred is a type of Lattice (based on translation)
&
Cubic is a type of Crystal (based on other symmetries)
&
Cubic also refers to a shape of Unit Cell (based on lattice parameters)
To emphasize:
The word Cubic (e.g. in a cubic crystal) refers to 3 things →
A type of Lattice (based on translation)
&
A type of Crystal (based on other symmetries)
&
A shape of Unit Cell (based on lattice parameters)
NaCl Crystal Structure
Face Centred Cubic (FCC) Lattice + Two Ion Motif
Cl− Ion at (0, 0, 0) Na+ Ion at (½, 0, 0)
Note: This is not a close packed crystal Has a packing fraction of ~0.67 (using rigid sphere model)
Diamond Cubic Crystal Structure
Face Centred Cubic (FCC) Lattice + Two Carbon atom Motif
(0,0,0) & (¼, ¼, ¼)
Diamond Cubic Crystal

=
Tetrahedral bonding of C
(sp3 hybridized)
It requires a little thinking to convince yourself that

the two atom motif actually sits at all lattice points!
Solved Does the array of points at the centres of the Carbon atoms in the
Example graphene sheet as shown below form a lattice?
Describe the crystal in terms of a lattice and a motif
What is the unit cell?
Part of the hexagonal array of C atoms which forms

the Graphene structure
The answer is NO!
Not all carbon positions

form a lattice
As atoms A & B do not
have identical
surrounding both cannot
be lattice points
Crystal = Lattice + Motif
Grey atoms sit on the

lattice positions
Motif = 1 grey + 1 green

(in positions as shown)
Primitive unit cell
Arrangement of lattice points in the Unit Cell & No. of Lattice points / Cell
Position of lattice points Effective number of Lattice points / cell
1 P 8 Corners = [8 × (1/8)] = 1
8 Corners
2 I + = [1 (for corners)] + [1 (BC)] = 2
1 body centre
8 Corners
3 F + = [1 (for corners)] + [6 × (1/2)] = 4
6 face centres
A/ 8 corners
4 B/ + = [1 (for corners)] + [2 × (1/2)] = 2
C 2 centres of opposite faces
MILLER INDICES
PLANES
DIRECTIONS
From the law of rational indices developed by French Physicist and mineralogist
Abbé René Just Haüy
and popularized by
William Hallowes Miller
Miller Indices
Miller indices are used to specify directions and planes.
These directions and planes could be in lattices or in crystals.
(It should be mentioned at the outset that special care should be given to see if
the indices are in a lattice or a crystal).
The number of indices will match with the dimension of the lattice or the crystal:
in 1D there will be 1 index and 2D there will be two indices etc.
Some aspects of Miller indices, especially those for planes, are not intuitively
understood and hence some time has to be spent to familiarize oneself with the
notation.
Miller Indices Miller Indices
Directions Planes Lattices Crystals

Miller Indices for directions in 2D
• • • • • • • • • • • • • • • • •
• • • • • • • • • • • • • • • • •
(4,3)
• • • • • • • • • • • • • • • • •
• • • • • • • • • • • • • • • • •
• • • • • • • • • • • • • • • • •
• • • • • • • • • • • • • • • • •
(0,0)
• • • • • • • • • • • • • • • • •
5a + 3b
• • • • • • • • • • • • • • • • •
• • • • • • • • • • • • • • • • •
b
• • • • • • • • • • • • • • • • •
a
Miller indices → [53]
Miller indices for directions in 3D
A vector r passing from the origin to a lattice point can be written as
r = r1 a + r2 b + r3 c r r r
r = r1 a + r2 b + r3 c
Where, a, b, c → basic vectors
Basis vectors are unit lattice translation vectors which define the coordinate axis
(as in the figure below).
Note their length is not 1 unit! (like for the basis vectors of a coordinate axis).
Important directions in 3D represented by Miller Indices (cubic lattice)
[001] [011] Memorize these

Z
[101]
Y [010]
Body diagonal
[100]
[110] [111]
X [110]
Face diagonal
Procedure as before:
• (Coordinates of the final point − coordinates of the initial point)
• Reduce to smallest integer values
Possible coordinates in 3D
[+ + -] [+ - -]
Z
Y
[- + -] [- - -]
X
[+ + +] [+ - +]
[- + +] [- - +]
If you have confusion while selecting origin in negative indices refer this figure
Family of directions
A set of directions related by symmetry operations of the lattice or the crystal is
called a family of directions
A family of directions is represented (Miller Index notation) as: <u v w>
Index Members in family for cubic lattice Number
<100> [100],[100],[010],[0 10],[001],[00 1] 3x2=6
6x2=
<110> [110],[110],[1 10],[1 10],[101],[101],[10 1],[10 1],[011],[0 11],[01 1],[0 1 1]
12
<111> [111],[111],[1 11],[11 1],[1 11],[11 1],[1 1 1],[1 1 1] 4x2=8
the ‘negatives’
Alternate
Symbol (opposite direction)
symbol
[] → Particular direction
<> [[ ]] → Family of directions
Miller Indices for Planes
Miller indices for planes is not as intuitive as
that for directions and special care must be
taken in understanding them
Illustrated here for the cubic lattice
Find intercepts along axes → 2 3 1

Take reciprocal* → 1/2 1/3 1
Convert to smallest integers in the same ratio → 3 2 6
Enclose in parenthesis → (326)
*The reciprocal procedure avoids the intercept of ∞ for a plane parallel to an axis, by making it 0
Important Planes in 3D represented by Miller Indices (cubic lattice)
A set of planes related by symmetry operations of the lattice or the crystal is called a
family of planes
All the points which one should keep in mind while dealing with directions to get the
members of a family, should also be kept in mind when dealing with planes
Family of planes
Intercepts → 1 ∞ ∞ Intercepts → 1 1 ∞
Plane → (100) Plane → (110)
Family → {100} → 6 Family → {110} → 6
Intercepts → 1 1 1
Plane → (111) The purpose of using reciprocal of
Family → {111} → 8 intercepts and not intercepts
(Octahedral plane) themselves in Miller indices becomes
clear → the ∞ are removed
Summary on planes and directions
Unknown direction → [uvw]
Unknown plane → (hkl)
Double digit indices should be separated by commas → (12,22,3)
In cubic lattices/crystals [hkl] ⊥ (hkl)
a
Interplanar spacing (dhkl) in cubic cubic lattice
d hkl =
lattice (& crystals) h2 + k 2 + l 2
Alternate
Symbol
symbols
[] [uvw] → Particular direction
Direction
<> <uvw> [[ ]] → Family of directions
() (hkl) → Particular plane
Plane
{} {hkl} (( )) → Family of planes
Note…!
A direction in 3D can be specified by three angles- or the hree direction cosines.
There is one equation connecting the three direction cosines:
Cos 2α + Cos 2 β + Cos 2γ = 1
This implies that we required only two independent parameters to describe a

direction. Then why do we need three Miller indices?
The Miller indices prescribe the direction as a vector having a particular length (i.e.
this prescription of length requires the additional index)
Similarly three Miller indices are used for a plane (hkl) as this has additional
information regarding interplanar spacing. E.g.: a
=
cubic lattice
d hkl
h2 + k 2 + l 2
Hexagonal crystals → Miller-Bravais Indices : Planes
Directions and planes in hexagonal lattices and crystals are designated by the
4-index Miller-Bravais notation
In the four index notation:
the first three indices are a symmetrically related set on the basal plane
the third index is a redundant one (which can be derived from the first two) and
is introduced to make sure that members of a family of directions or planes have a
set of numbers which are identical
the fourth index represents the ‘c’ axis (⊥ to the basal plane)
Hence the first three indices in a

hexagonal lattice can be permuted to
get the different members of a family; Related to ‘l’ index
while, the fourth index is kept
separate.
Related to ‘i’ index Related to ‘k’ index
Related to ‘h’ index

Hexagonal crystals → Miller-Bravais Indices : PLANES
a3
Intercepts → 1 1 - ½ ∞ (h k i l)
Plane → (1 12 0) i = −(h + k)
a2
a1
In general three indices point is denoted as miller indices i.e., (h k l). But hexagonal crystals we
are using 4 indices point is denoted by miller-bravais indices i.e., (h k i l)The use of the 4 index
notation is to bring out the equivalence between crystallographically equivalent planes and
directions.
a3
a2
Obviously the ‘green’ and
‘blue’ planes belong to the
same family and first three
indices have the same set of
numbers (as brought out by the
a1 Miller-Bravais system)
Intercepts → 1 -1 ∞ ∞ Intercepts → ∞ 1 -1 ∞
Miller → (1 1 0 ) Miller → (0 1 0)
Miller-Bravais → (1 1 0 0 ) Miller-Bravais → (0 11 0)
a3
a2
Intercepts → 1 -2 -2 ∞ a1 Intercepts → 1 1 - ½ ∞
Plane → (2 11 0 ) Plane → (1 12 0)

Intercepts → 1 1 - ½ 1
Plane → (1 12 1)
Both planes contain same

intercepts. The common thing
in these planes is a2 axis is
infinite
Intercepts → 1 ∞ − 1 1
Plane → (1 01 1)
Hexagonal crystals → Miller-Bravais Indices : DIRECTIONS
Drawing the [1120] direction

• Trace a path along the basis vectors as required by the direction. In the current example move
1unit along a1, 1unit along a2 and −2 units along a3.
• Directions are projected onto the basis vectors to determine the components and hence the Miller-
Bravais indices can be determined as in the table.
Drawing the [101 0] direction
Hexagonal crystals → Miller-Bravais Indices : DIRECTIONS
Transformation between 3-index [UVW] and 4-index [uvtw] notations
U = u −t V = v−t
W =w
1
u = (2U − V )
3
t = − (u + v )
1 w =W
v = (2V − U )
3
Directions in the hexagonal system can be expressed in many ways
3-indices:
By the three vector components along a1, a2 and c:
rUVW = Ua1 + Va2 + Wc
In the three index notation equivalent directions may not seem
equivalent; while, in the four index notation the equivalence is
brought out.
Directions ⊥ Planes
Cubic system: (hkl) ⊥ [hkl]
Tetragonal system: only special planes are ⊥ to the direction with same indices:
[100] ⊥ (100), [010] ⊥ (010), [001] ⊥ (001), [110] ⊥ (110)
([101] not ⊥ (101))
Orthorhombic system:
[100] ⊥ (100), [010] ⊥ (010), [001] ⊥ (001)
Hexagonal system: [0001] ⊥ (0001)
(this is for a general c/a ratio; for a Hexagonal crystal with the special c/a ratio =
√(3/2) the cubic rule is followed)
Monoclinic system: [010] ⊥ (010)
Other than these a general [hkl] is NOT ⊥ (hkl)
Coordination Number
Coordination number is defined as the total number of nearest neighboring atoms
Simple cubic
The coordination number of simple cubic

crystal is ‘6’ It is shown in figure. In this figure
we are considered one corner and drawn 3 lines
connecting to six points.
Body Centered cubic
The coordination number of BCC crystal is 8.

The body centered atom is in contact with all the
eight corner atoms. Each corner atom is shared
by eight unit cells and hence, each of these
atoms is in touch with eight body centered
atoms.
Coordination Number
Face Centered cubic
In the FCC lattice each atom is in contact

with 12 neighbor atoms. FCC coordination
number Z = 12 . For example, the face
centered atom in the front face is in contact
with four corner atoms and four other face-
centered atoms behind it (two sides, top and
bottom) and is also touching four face-
centered atoms of the unit cell in front of it.
Hexagonal close pack structure
In Hexagonal lattice Z = 12. The center

atom of the top face is in touch with six
corner atoms, three atoms of the mid layer
and other three atoms of the mid layer of the
unit cell above it.
Average number of atoms per unit cell
Position of atoms Effective number of atoms
1 SC 8 Corners = [8 × (1/8)] = 1
8 Corners
2 BCC + = [1 (for corners)] + [1 (BC)] = 2
1 body centre
8 Corners
3 FCC + = [1 (for corners)] + [6 × (1/2)] = 4
6 face centres
12 corners (6 bottom+6 top)
+
2 atoms at face centers = [12 × (1/6) ] + [2 × (1/2)] + [3
4 HCP
(interior) ] = 6
+
3 atoms in the interior
Atomic packing factor
Atomic packing factor (APF) or packing efficiency indicates how closely atoms are
packed in a unit cell and is given by the ratio of volume of atoms in the unit cell and
volume of the unit cell. Volumeofatoms
APF =
Volumeofunitcell
Simple Cubic
In a simple cubic structures, the atoms are assumed to be placed in such a way that
any two adjacent atoms touch each other. If ‘a’ is the lattice parameter of simple
cubic structure and ‘r’ the radius of atoms. From the figure it is clear that
a
Atomic radius (r) = 2
Avg .noofatomsperunitcell × Volumeofanatom
APF =
Volumeoftheunitcell
4 4
1× ∏ r 3 ∏r3
3 3 4∏
APF = 3
= 3
= × 100 = 0.52 = 52%
a ( 2r ) 24
Body Centered Cubic
In body centered cubic structures the center atom touches
the corner atoms as shown in Figure
c a
From the figure
b a
c = b + a → c = 2a + a
2 2 2 2 2 2
b = a + a = 2a
2 2 2 2
3a 2
c = 3a → (4r ) = 3a → r =
2 2 2 2 2
16
3a 4r r = atomic radius
r= ,a =
4 3 a = lattice parameter
3
4  3a 
2 × ∏ r 3 2 × 3 ∏ 4 
4
3   = 8 × 3 3 ∏ a 3
APF = =
a3 a3 3 × 64a 3
APF = 0.68(or )68%

Face Centered Cubic
From this figure; first we can calculate
atomic radius:
2a 2
(4r ) = a + a → 16r = 2a → r =
2 2 2 2 2 2
16
a 2 a 4r
r= = a= → 4r = 2 a
4 2 2 2
3
4 4  a 
4× ∏ r 3 4 × ∏ 
3 3  2 2  = 16 × 2 2 ∏ a 3
APF = = = 0.74
a 3
a 3
3 × 64a 3
APFFCC = 0.74(or )74%

Hexagonal Close Packed Structure
Consider any one triangle P
Let us consider ∆AOB;
‘P’ is center of triangle Q
a c P R
APOB - Tetrahedron 2
c
A O a
In the ∆ AYB 30 2
30 x
AY a Y x
Cos 30 =
0
a a
AB
B
The distance between any neighboring atoms
is ‘a’ from the figure ‘AB’ = a
a 3
AY = AB cos 300 =
2
From the figure ‘Ax’ is orthocenter; so,
2 2 a 3 a
Ax = AY = × =
3 3 2 3
Hexagonal Close Packed Structure P
Consider ∆ APx a c
2
O
( AP ) 2 = ( Ax) 2 + ( xP ) 2 A 30
30 x
a c 2
a2
c c 2a 2 2 2 2
a Y
a =
2
+ → a2 − = → =
3 4 3 4 4 3 B
c2 8 c 8
2
= → = = 1.633
a 3 a 3
Avg.noofatomsperunitcell × Volumeofanatom
APF =
Volumeoftheunitcell
4
6× ∏ r3
APF = 3
Volumeoftheunitcell
3
In cubic a=b=c, so volume is a but in this case, it is H.C.P so here a=b≠c
Volume of unitcell = Area of base of hexagonal × Height

Hexagonal Close Packed Structure
Volume of unitcell = Area of base of hexagonal × Height
Volumeofunitcell = 6 × areaof∆AOB × c
1
Volumeofun itcell = 6 × × OB × AY × c
2
1 a 3 3 3
Volumeofun itcell = 6 × × a × × c = ca 2
2 2 2
4
6× ∏ r3
APF = 3
2 3 3
ca
2
3
4 4 a
6× ∏ r3 6× ∏×
APF = 3 = 3 8 = 2 ∏ a = 0.74
2 3 3 2 3 3 c×3 3
ca ca
2 2
APFHCP = 0.74(or )74%
Summary on PACKING FRACTION / Efficiency
Volume occupied by atoms
Packing Fraction =
Volume of Cell
SC* BCC* CCP DC HCP
Relation between atomic radius (r) a = 2r 3a = 4 r 3 a = 2r

2 a = 4r a = 2r
and lattice parameter (a) 4 2
c = 4r
3
Atoms / cell 1 2 4 8 2
Lattice points / cell 1 2 4 4 1
No. of nearest neighbours 6 8 12 4 12
Packing fraction π 3π 2π 3π 2π
6 8 6 16 6
~ 0.52 ~ 0.68 ~ 0.74 ~ 0.34 ~ 0.74
* Crystal formed by monoatomic decoration of the lattice

Density
The usual density is mass/volume
In materials science various other kinds of density and occupation ratios are defined. These
include:
Linear density: mass/length [kg/m]
atoms/length [/m] or number/length
length occupied/length [m/m]
Planar(Areal) density: mass/area [kg/m2]
atoms/area [/m2] or number/area
area occupied/area [m2/m2]
Volume density: mass/volume [kg/m3]
atoms/volume [/m3] or number/volume
volume occupied/volume [m3/m3]
The volume occupied/volume of space [m3/m3] is also called the packing fraction
In this context other important quantities include:
Length/area [m/m2] → e.g. length of dislocation lines per unit area of interface (interfacial dislocations)
Length/volume [m/m3] → e.g. length of dislocation lines per unit volume of material
Area/volume [m2/m3] → e.g. grain boundary area per unit volume of material
The ‘useful’ way to write these quantities is to NOT factor out the common terms: i.e. write
[m/m3] ‘as it is’ and not as [1/m2]
Linear density
Linear density (LD) is the number of atoms per unit length along a particular direction
Numberofat omsonthedi rectionvector

LinearDens ity =
Lengthofth edirection vector
<110> directions in the FCC lattice have 2 atoms (1/2 x 2 corner atoms + 1 center
atom) and the length is
2 2
LD[110 ] = =
2a a
This is the most densely packed direction in the FCC lattice

Planar(Areal) density
Planar density (PD) refers to density of atomic packing on a particular plane.
Numberofat omsonaplane
PlanarDensity =
Areaofplan e
For example, there are 2 atoms (1/4 x 4 corner
atoms + 1/2 x 2 side atoms) in the {110} planes in
the FCC lattice. a
Planar density of {110} planes in the FCC crystal
2 2
PD(110 ) = = 2 √2a
a 2a a
In the {111} planes of the FCC lattice there are 2

atoms (1/6 x 3 corner atoms + 1/2 x 3 side atoms).
Planar density of {111} planes in the FCC crystal
2 4
PD(111) = =
1 3 3a 2
2a × 2a
2 2
This is higher than {110} and any other plane. Therefore, {111}
planes are most densely packed planes in the FCC crystal
Theoretical (Volume) density
Theoretical density calculation from crystal structure
nA
Theoretical density ρ =
VC N A n = number of atoms in the unit cell
A = atomic weight
VC = Volume of unitcell
NA = Avogadro’s number (6.023 × 1023)
Calculate the theoretical density of Aluminum (Al)
Given : Al is FCC structure; Lattice parameter is 4.05A0 ; n=4;

Atomic weight of Al is 26.98 g/mol
4 × 26.98
ρ= −8 3
= 2.697 g / cc
(4.05 × 10 ) × 6.023 × 10 23
Atomic Density (atoms/unit area)
(100) (110) (111)
SC
a
2a 2a
FCC a a
2a 2a
BCC
a
2a 2a
Only atoms whose centre of mass lies on the plane included

Atomic Density (atoms/unit area)
SC FCC BCC
(100) 1/a2 = 1/a2 2/a2 = 2/a2 1/a2 = 1/a2
(110) 1/(a2√2) = 0.707/a2 √2/a2 = 1.414/a2 √2/a2 = 1.414/a2
(111) 1/(√3a2) = 0.577/a2 4/(√3a2) = 2.309/a2 1/(√3a2) = 0.577/a2

Order (111) < (110) < (100) (110) < (100) < (111) (111) < (100) < (110)
Only atoms whose centre of mass lies on the

plane included.
In the BCC crystal, the (111) plane partially
intersects the atom at the body centre (½,½,½).
This atom is excluded from the calculation as
above.
CCP=FCC Closed Packed Structures : FCC CCP=FCC
Start with a row of atoms (close packed in 1D)
Monatomic decoration of FCC lattice
Make a 2D hexagonal close packed array (the A layer)
• This is a close packed layer with

close packed directions (like
<110> directions represented
using cubic indices)
• As we shall see this becomes the
{111} plane in the FCC crystal
There is only one way of doing so!
To build the next layer → leading to the 3D structure, there are 2 stable positions where atoms can be put → called
the B and C positions. If atoms are put in the B position than we cannot put atoms in the C position (no space!)
Closed Packed Structures : FCC
Putting atoms in the B position in the II layer and in C positions in the III layer we get a
stacking sequence → ABC ABC ABC…. The CCP (FCC) crystal
+ + =
A B C FCC CCP=FCC
A A
B B
C C
Closed Packed Structures : HCP
An alternate packing (one amongst an infinite possibilities) is where in the III layer
coincides with the I layer → giving rise to a AB AB AB … packing → The
Hexagonal Close Packed Crystal (this arrangement is close packed only for ideal c/a ratio; i.e. for ‘hard
sphere’ packing)
As before we make a 2D hexagonal close packed array (the A layer)
• This is a close packed layer

with close packed directions
(like < 1120 > directions)
• As we shall see this becomes
the {0001} plane in the HCP
crystal
Metals which adopt HCP structure

Mg, Zn, Ti, Co, Be, Cd, Zr, Y, Sc, Tc, Ru, Gd, Tb, Dy, Ho, Er, Tm, Lu, Hf, Re, Os, Tl
Closed Packed Structures : HCP
+ + =
A B A HCP
Shown displaced for clarity
The C position is vacant and we can
pass a line through this position without HCP
intersecting any atoms
As we shall see in one of the upcoming
slides that this is special line
Structure-Property Correlation
Aluminum (Al) is ductile while iron (Fe) and magnesium (Mg) are not. This can be
explained from their crystal structures.
Al is FCC where as Fe is BCC and Mg is HCP.
Plastic deformation in metals takes place mainly by a process called slip. Slip can
broadly be visualized as sliding of crystal planes over one another. Slip occurs on most
densely packed planes in the most closely packed directions lying on that plane.
The slip plane and the direction together is called a Slip system
In FCC, {111} planes are close-packed and there are four unique {111} planes. Each of
these planes contains three closely packed <110> directions. Therefore, there are 4 x 3
= 12 slip systems
In HCP, the basal plane, (0001) is the close-packed and it contains three <11 2 0>
directions. Hence, number of slip system = 1 x 3 = 3
Slip in more number of slip systems allows greater plastic deformation before fracture
imparting ductility to FCC materials.
Close-packed planes are also planes with greatest interplanar spacing and this allows
slip to take place easily on these planes.
BCC structure on the other hand has 48 possible slip systems. However, there is no
close-packed plane. Hence, plastic deformation before fracture is not significant. Slip
might occur in {110}, {112} and {123} planes in the <111> directions.
VOIDS IN CRYSTALS
We have already seen that as spheres cannot fill entire space → the packing
fraction (PF) < 1 (for all crystals)
This implies there are voids between the atoms. Lower the PF, larger the volume
occupied by voids.
These voids have complicated shapes; but we are mostly interested in the largest
sphere which can fit into these voids→ hence the plane faced polyhedron version
of the voids is only (typically) considered.
The size and distribution of voids in materials play a role in determining
aspects of material behavior → e.g. solubility of interstitials and their
diffusivity
In the close packed crystals (FCC, HCP) there are two types of voids → tetrahedral
and octahedral voids (identical in both the structures as the voids are formed
between two layers of atoms)
In the ‘BCC crystal’ the voids do NOT have the shape of the regular tetrahedron or
the regular octahedron
Void in Simple Cube
The simple cubic crystal (monoatomic decoration of the simple cubic lattice) has
large void in the centre of the unit cell with a coordination number of 8.
The actual space of the void in very complicated (right hand figure below) and the
polyhedron version of the void is the cube (as cube is the coordination polyhedron
around a atom sitting in the void)
rx
= ( 3 − 1) = 0.732
r
True Unit Cell of SC crystal Polyhedral model (Cube) Actual shape of the void (space)!
Later on we will talk about tetrahedral and octahedral

voids in FCC, BCC & HCP crystals:
note that there are NO such tetrahedral and octahedral
voids in SC crystals and the only polyhedral void is
CUBIC (i.e. coordination number of 8)
Voids in FCC
Tetrahedral TV Octahedral OV
¼ way along body diagonal At body centre

{¼, ¼, ¼}, {¾, ¾, ¾} {½, ½, ½}
+ face centering translations + face centering translations
1 1
Vtetrahedron = Vcell Voctahedron = Vcell rVoid / ratom = 0.414
rvoid / ratom = 0.225 6
24
Note: Atoms are coloured differently but are the same FCC = CCP
Voids in FCC
TV OV
Tetrahedral Octahedral
Actual shape of the void is as shown

below. This shape is very completed and
we use the polyhedral version of the void-
i.e. tetrahedral and octahedral voids.
Actual shape of void Position of some of the atoms w.r.t to the void
FCC- Octahedral
Once we know the position of a void then we can use the symmetry operations of the crystal to locate the other
voids. This includes lattice translations
Site for octahedral void
{½, ½, ½} + {½, ½, 0} = {1, 1, ½} ≡ {0, 0, ½}

Equivalent site for an octahedral void
Face centering translation
Note: Atoms are coloured differently but are the same

Calculations
There is one octahedral There are eight

site at the centre of the tetrahedral sites in the
FCC cell (½,½,½) and FCC unitcell (¼,¼,¼).
one on each of the twelve
cell edges (½,0,0).
FCC voids Position Voids / cell Voids / atom

¼ way from each vertex of the cube
Tetrahedral along body diagonal <111> 8 2
→ ((¼, ¼, ¼))
• Body centre: 1 → (½, ½, ½)
Octahedral 4 1
• Edge centre: (12/4 = 3) → (½, 0, 0)
Size of the largest atom which can fit into the tetrahedral void of FCC
The distance from the vertex of the tetrahedron to the centroid (DT) is the distance spanned by
radius of the atom and the radius of the interstitial sphere.
DT = r + x Radius of the interstitial atom (sphere)
If ‘e’ is the edge length of the tetrahedron then CV = (√6/4)e → see below in triangle ABC
6
DT = e=r+x e = 2r 6
r=r+x
4 2
x  6 
=  − 1 ~ 0.225
r  2 
In tetrahedron ABCD
In triangle ABC AD 2 = e 2 = AO 2 + DO 2
e2 2 2
e = + AM 2
2 e
e = + DO 2
2 DO = e
4 3 3
3 3
AM = e DT = DO
2 4
2 2 3 e
AO = AM = e= DT =
3 2
e=
6
e
3 3 2 3 4 3 4
Size of the largest atom which can fit into the Octahedral void of FCC
2r + 2x = a Thus, the octahedral void is the bigger one

and interstitial atoms (which are usually
bigger than the voids) would prefer to sit
here
2 a = 4r
x
r
= ( )
2 − 1 ~ 0.414
Voids in BCC crystal
There are NO voids in a ‘BCC crystal’ which have the shape of a regular
polyhedron (one of the 5 Platonic solids)
The voids in BCC crystal are: distorted ‘octahedral’ and distorted tetrahedral
→ the correct term should be non-regular instead of distorted.
However, the ‘distortions’ are ‘pretty regular’ as we shall see
The distorted octahedral void is in a sense a ‘linear void’
→ an sphere of correct size sitting in the void touches only two of the six atoms
surrounding it
Carbon prefers to sit in this smaller ‘octahedral void’ for reasons which we shall
see soon
Voids in BCC Crystal
Distorted TETRAHEDRAL Distorted OCTAHEDRAL**
a√3/2
a
a a√3/2
Coordinates of the void:

{½, 0, ¼} (four on each face) Coordinates of the void:
{½, ½, 0} (+ BCC translations: {0, 0, ½})
Illustration on one face only

** Actually an atom of correct size touches only the top and bottom atoms
Calculations
There is one octahedral site

on each of the six BCC There are four tetrahedral
cell faces (½,½,0) and one sites on each of the six
on each of the twelve cell BCC cell faces (½,¼,0).
edges (½,0,0)
Voids / Voids /
BCC voids Position
cell atom
Distorted
• Four on each face: [(4/2) × 6 = 12] → (0, ½, ¼) 12 6
Tetrahedral
Non-regular • Face centre: (6/2 = 3) → (½, ½, 0)
6 3
Octahedral • Edge centre: (12/4 = 3) → (½, 0, 0)
Calculation of the size of the distorted tetrahedral void
a BCC: Distorted Tetrahedral Void
a√3/2
a2 a2 5
From the right angled triange OCM: OC = + = a=r+x
16 4 4
4r
For a BCC structure: 3a = 4r ( a = )
3
5 4r x  5 
=r+x ⇒ = − 1 = 0.29
4 3 r  3 
Calculation of the size of the distorted octahedral void
Distorted Octahedral Void
a 2a
OB = = 0.5a OA = = .707 a
2 2
As the distance OA > OB the atom in the void

touches only the atom at B (body centre).
a√3/2 ⇒ void is actually a ‘linear’ void*
This implies:
a
a
OB = r + x =
2
4r
r+x= BCC : 3a = 4r
2 3
x 2 3 
* Point regarding ‘Linear Void’ =  − 1 = 0.1547
Because of this aspect the OV along the 3 axes can be r  3 
differentiated into OVx, OVy & OVz
Similarly the TV along x,y,z can be differentiated
Voids in HCP Crystals
TETRAHEDRAL OCTAHEDRAL
This void extends across 3
conventional unit cells and
hence is difficult to visualize
Coordinates : (0,0, 3 8 ), (0,0, 5 8 ), ( 2 3 , 13 , 18 ), ( 2 3 , 1 3 , 7 8 ) Coordinates: (⅓ ⅔,¼), (⅓,⅔,¾)
These voids are identical to the ones found in FCC (for ideal c/a ratio)
When the c/a ratio is non-ideal then the octahedra and tetrahedra are distorted (non-regular)
Important Note: often in these discussions an ideal c/a ratio will be assumed (without stating the same explicitly)
Voids in HCP Crystals
Further views
Octahedral voids
Tetrahedral void

Summary of void sizes
rvoid / ratom
SC BCC FCC
0.155
Octahedral (CN = 6) Not present 0.414
(non-regular)
Tetrahedral 0.29
Not present 0.225
(CN = 4) (non-regular)
Cubic
0.732 Not present Not present
(CN = 8)
Voids should not be confused with vacancies- vacancies are due to missing atoms
or ions in crystals.
Holes should also not be confused with voids- holes are ‘missing electrons’ from
the valence band of a solid.
Voids have complicated shapes- we usually use a polyhedral version – the
coordination polyhedron around a sphere of ‘correct size’.
Sometimes, as in the case of ‘octahedral void’ in the BCC- the second nearest
neighbors are also included in constructing the coordination polyhedron.
Questions?
1. What is unit cell? What is lattice parameter?
2. What is Bravais lattice? How are the Bravais lattices obtained from the primitive
cell? How many types of Bravais lattices are there?
3. Draw two adjacent FCC unit cells and join the top and bottom face centers of
each cell. Also join these four face centers to the nearest common corners.
i. What is the unitcell outlined by this procedure?
ii. Is it in the Bravais list?
iii. If so, the FCC with higher symmetry must be a special case of the outlined
cell. Explain.
4. There is no end-centered tetragonal lattice in the bravais list, but there is an end-
centered orthorhombic lattice. Explain why?
5. Show that packing efficiency of FCC is 74% and that of BCC is 68%.
6. Show that the ideal c/a ratio in a hexagonal unit cell is 1.633 and calculate the
packing efficiency.
7. What is miller index? How is it obtained?
8. Draw the planes ( 1 1 0), (1 2 1), (2 3 4), ( 1 12) and directions [11 1 ], [123], [120], [1 21] in a
cubic unit cell.
Questions?
9. Calculate (i) the packing efficiency, and (ii) the density of diamond [ 1 amu =
1.660×10-27 Kg, a = 0.357 nm]
10. Find the size of the largest sphere that can fit into the tetrahedral void and
octahedral void of a cubic close packed structure without distorting it.
11. Why it is necessary to include a fourth miller index in the hexagonal system?
12. Convert the directions [112], [1 2 3], [110], [111], [130] to four indices in a
hexagonal lattice.
13. Lattice constant of Al is 4.05 Å. What is the atomic radius of Al?
14. Calculate the theoretical density of Mg, Ni and Fe and compare them to the
standard values [for Mg (a = 3.21Å, c = 5.21Å, ρ = 1.74gm/cm3, at.wt – 24.31) for
Ni (a = 3.52Å, ρ = 8.90gm/cm3, at.wt – 58.69) for Fe (a = 2.87Å, ρ = 7.87gm/cm3,
at.wt – 55.85)]
15. A metal has a density of 10.22 g/cc, atomic weight of 95.94 and atomic radius of
0.136 nm. Is it BCC or FCC?
16. Calculate the volume of the unit cell of Zn crystal. a and c of Zn are 266.5 pm and
494.7 pm respectively.
17. Some hypothetical metal has the simple cubic crystal structure. If its atomic weight
is 74.5 g/mol and the atomic radius is 0.145 nm, compute its density.
18. Calculate the planar density of {110} planes in α-Fe (BCC) crystal. a = 0.287 nm.
Questions?
20. Cu has atomic radius of 0.128 nm. The atomic weight of Cu is 63.5 g/mol.
Compute its theoretical density.
21. Find the planar of density {111} planes and linear density of <110> directions in
FCC system.
22. Calculate the inter-planar spacing for the (110), (111), (120), (221) and (123)
planes of copper. Which of the above planes has the greatest inter-planar spacing?
23. What are the miller indices of a plane that intersects the X axis at 2 and the Y
axis at ½ and is parallel to the z axis? The structure is cubic.
24. Determine the indices for the directions shown in the following cubic unit cell:
Questions?
25. Determine the indices for the directions and plane shown in the following
hexagonal unit cell:
26. Derive the planar density expression for the HCP (0001) plane in terms of the
atomic radius R.
27. What is the difference between atomic structure and crystal structure?
28. Show that only four types of rotational symmetry are possible.
29. If the lattice parameter of Alpha iron is 286 pm, what is its atomic radius?
30. Copper has FCC crystal structure and the unit cell with a lattice constant of 0.361
nm. What is the inter-planar spacing of d111 planes?
Avala Lava Kumar
E-mail : lavakumar.vssut@gmail.com
Introduction
Three states of matter are distinguishable: gas, liquid, and solid
In the gaseous state the metal atoms occupy a great deal of space because of their
rapid motion. The atoms move independently and are usually widely separated so
that the attractive forces between atoms are negligible. The arrangement of atoms
in a gas is one of complete disorder.
At some lower temperature, the kinetic energy of the atoms has decreased so that
the attractive forces become large enough to bring most of the atoms together in a
liquid. And there is a continual interchange of atoms between the vapor and liquid
across the liquid surface.
The attractive forces between atoms in a liquid may be demonstrated by the
application of pressure. A gas may be easily compressed into a smaller volume, but
it takes a high pressure to compress a liquid. There is, however, still enough free
space in the liquid to allow the atoms to move about irregularly.
As the temperature is decreased, the motions are less vigorous and the attractive
forces pull the atoms closer together until the liquid solidifies. Most materials
contract upon solidification, indicating a closer packing of atoms in the solid state.
The atoms in the solid are not stationary but are vibrating around fixed points,
giving rise to the orderly arrangement of crystal structures.
Mechanism of Crystallization
Crystallization is the transition from the liquid to the solid state and occurs in two
stages:
Nuclei formation
Crystal Growth
Although the atoms in the liquid state do not have any definite arrangement, it is
possible that some atoms at any given instant are in positions exactly
corresponding to the space lattice they assume when solidified.
These chance aggregates or groups are not permanent but continually break up and
reform at other points.
The higher the temperature, the greater the kinetic energy of the atoms and the
shorter the life of the group. When the temperature, of the liquid is decreased, the
atom movement decreases, lengthening the life of the group, and more groups will
be present at the same time.
Atoms in a material have both kinetic and potential energy. Kinetic energy is related to
the speed at which the atoms move and is strictly a function of temperature. The higher
the temperature, the more active are the atoms and the greater is their kinetic energy.
Potential energy, on the other hand, is related to the distance between atoms. The
greater the average distance between atoms, the greater is their potential energy.
Mechanism of Crystallization
Metals
Thermodynamic ↑ ∆Hfusion High → (10-15) kJ / mole
Crystallization favoured by
Kinetic ↓ ∆Hd ≈∝ Log [Viscosity (η)] Low → (1-10) Poise
Enthalpy of activation for

diffusion across the interface
Difficult to amorphize metals
Very fast cooling rates ~106 K/s are used for the amorphization of alloys
→ splat cooling, melt-spinning.
Solidification (or) Freezing
When metal is poured into the mould,

Pouring Temperature the temperature will be as high as its
inversion temperature.
Temperature →
Superheat
T/t = cooling rate Equilibrium
Freezing
Temperature
Thermal Arrest
Local Solidification time
Total Solidification time
Time →
It gets cooled when poured into the
mould and molten metal in the liquid The solidified metal in the mould (
form will solidify. This time is called called casting) gets cooled in the mould
local solidification time to the temperature of the surroundings
Cooling Curves
Recalescence : The increase in temperature of an undercooled liquid metal as a result of the liberation
of heat during nucleation.
Thermal Arrest : A plateau on the cooling curve during the solidification of a material caused by the
evolution of the latent heat of fusion during solidification.
Total Solidification Time : The time required for the casting to solidify completely after the casting has
been poured.
Local Solidification Time : The time required for a particular location in a casting to solidify once
nucleation has begun.
Cooling curve for a pure metal that has not been well inoculated.
Liquid cools as specific heat is removed (betweens points A and B).
Undercooling is thus necessary (between points B and C). As the
nucleation begins (point C), latent heat of fusion is released causing
an increase in the temperature of the liquid. This process is known
as recalescence (point C to point D). Metal continues to solidify at
a constant temperature (T melting). At point E, solidification is
complete. Solid casting continues to cool from the point.
Cooling curve for a well inoculated, but otherwise pure metal.

No undercooling is needed. Recalescence is not observed.
Solidification begins at the melting temperature
Solidification of pure metal : Super cooling
In a pure metal at its freezing point where both the liquid and solid states are at the
same temperature. The kinetic energy of the atoms in the liquid and the solid must
be the same, but there is a significant difference in potential energy.
The atoms in the solid are much closer together, so that solidification occurs with a
release of energy. This difference in potential energy between the liquid and solid
states is known as the latent heat of fusion.
However, energy is required to establish a surface Cooling Curve for a pure metal
between the liquid and solid. In pure materials at
the freezing point insufficient energy is released
Temperature →
by the heat of fusion to create a stable boundary,
and some under cooling is always necessary to
form stable nuclei.
Subsequent release of the heat of fusion will raise
the temperature to the freezing point. The amount
Under cooling
of undercooling required may be reduced by the
presence of solid impurities which reduce the
amount of surface energy required.
Time →
Solidification of pure metal
When the temperature of the liquid metal has dropped sufficiently below its
freezing point, stable aggregates or nuclei appear spontaneously at various points
in the liquid. These nuclei, which have now solidified, act as centers for further
crystallization.
As cooling continues, more atoms tend to freeze, and they may attach themselves
to already existing nuclei or form new nuclei of their own. Each nucleus grows by
the attraction of atoms from the liquid into its 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 a
characteristic treelike structure which is called a dendrite.
Since each nucleus is formed by chance, the crystal axes are pointed at random and
the dendrites growing from them will grow in different directions in each crystal.
Finally, as the amount of liquid decreases, the gaps between the arms of the
dendrite will be filled and the growth of the dendrite will be mutually obstructed
by that of its neighbors. This leads to a very irregular external shape.
The crystals found in all commercial metals are commonly called grains because of
this variation in external shape. The area along which crystals meet, known as the
grain boundary, is a region of mismatch.
1 2
Liquid to Solid Phase Transformation : Solidification
Growth
of crystal
Solid
3 ↑t
Two crystal going to join
to from grain boundary
Grain boundary
5 6
Growth of nucleated crystal
Solidification Complete
“For sufficient Undercooling”
Solidification of pure metal
This mismatch leads to a noncrystalline
(amorphous) structure at the grain boundary
with the atoms irregularly spaced.
Since the last liquid to solidify is generally
along the grain boundaries, there tends to be
higher concentration of impurity atoms in that
area. Figure (previous page) shows
schematically the process of crystallization
from nuclei to the final grains.
Due to chilling action of mold wall, a thin skin
of solid metal is formed at the wall surface
immediately after pouring.
Grain structure in a casting of a pure metal,
showing randomly oriented grains of small
size near the mold wall, and large columnar
grains oriented toward the center of the
casting.
Solidification of Alloys
Most alloys freeze over a temperature
range
Phase diagram for a Cu-Ni alloy system
and cooling curve for different alloy
systems.
Characteristic grain structure in an alloy
casting, showing segregation of alloying
components in center of casting.
1455 ºC Liquid Solution Pouring Temperature

Liquidus Liquid cooling
Freezing begins
L+S
Temperature
Freezing completed
Solidus
1083 ºC Solid cooling
Total Solidification
Solid solution time
Ni % Cu → Cu Time →
Comparison of cooling curves
Pure metal Alloy
L L Soldification
begins
TL
L S L+ S
Tm
TS
Solidification S
S
complete
Time (t) Time (t)

Cast Structure
Chill Zone: A region of small,
randomly oriented grains that forms
at the surface of a casting as a result
of heterogeneous nucleation.
Columnar Zone: A region of
elongated grains having a preferred
orientation that forms as a result of
competitive growth during the Nucleation begins Chill zone forms
solidification of a casting.
Equiaxed Zone: A region of randomly
oriented grains in the center of a
casting produced as a result of
widespread nucleation.
Figure: Development of the ingot structure preferred growth additional nucleation

of a casting during solidification: produces the creates the equiaxed
columnar zone zone
Nucleation
Solidification = Nucleation + Growth
Nucleation: localized formation of a distinct thermodynamic phase.

Nucleation an occur in a gas, liquid or solid phase. Some examples of phases that may
form via nucleation include:
In gas-creation of liquid droplets in saturated vapor
In liquid-formation of gaseous bubbles crystals (e.g., ice formation from water) or
glassy regions.
In solid-Nucleation of crystalline, amorphous and even vacancy clusters in solid
materials. Such solid state nucleation is important, for example, to the semi
conductor industry.
Most nucleation processes are physical, rather than chemical.
There are two types of nucleation : homogeneous and heterogeneous. This distinction
between them made according to the site at which nucleating events occur. For the
homogeneous type, nuclei of the new phase form uniformly throughout the parent
phase, where as for the heterogeneous type, nuclei form preferentially at structural
inhomogeneities such as container surfaces insoluble impurities grain boundaries,
dislocations and so on
Nucleation
It occurs spontaneously and
Homogenous randomly, but it requires
superheating or supercooling of
the medium.
Nucleation
Liquid → solid
Heterogenous walls of container, inclusions
Solid → solid
inclusions, grain boundaries,
dislocations, stacking faults
The probability of nucleation occurring at point in the parent phase is same

throughout the parent phase
In heterogeneous nucleation there are some preferred sites in the parent phase
where nucleation can occur
Nucleation
Compared to the heterogeneous nucleation (which starts at nucleation sites on
surfaces) homogeneous nucleation occurs with much more difficulty in the interior
of a uniform substance. The creation of a nucleus implies the formation of an
interface at the boundaries of a new phase.
Liquids cooled below the maximum heterogeneous nucleation temperature
(melting temperature) but which are above the homogeneous nucleation
temperature. (pure substance freezing temperature) are cooled super cooled.
An example of supercooling: pure water freezes at -42ºC rather than at its freezing
temperature ºC.
Nucleation - The physical process by which a new phase is produced in a material.

Critical radius (r*) - The minimum size that must be formed by atoms clustering together in the
liquid before the solid particle is stable and begins to grow.
Undercooling - The temperature to which the liquid metal must cool below the equilibrium
freezing temperature before nucleation occurs.
Homogeneous nucleation - Formation of a critically sized solid from the liquid by the clustering
together of a large number of atoms at a high undercooling (without an external interface).
Heterogeneous nucleation - Formation of a critically sized solid from the liquid on an impurity
surface.
Nucleation
There is no change in composition involved as we are considering a pure metal. If we
solidify an alloy this will involve long range diffusion.
When a volume of material (V) transforms three energies have to be considered :
reduction in G (assume we are working at constant T & P),
increase in γ (interface free-energy),
increase in strain energy.
In a liquid to solid phase transformation the strain energy term can be neglected as the
liquid melt can flow to accommodate the volume change (assume we are working at
constant T & P).
The process can start only below the melting point of the liquid (as only below the melting
point the GLiquid < GSolid). I.e. we need to Undercool the system. As we shall note, under
suitable conditions (e.g. container-less solidification in zero gravity conditions), melts can
be undercooled to a large extent without solidification taking place.
New interface created

Bulk Gibbs free energy ↓
Energies involved Interfacial energy ↑
Solid-solid
Volume of transforming material Strain energy ↑ transformation
Solidification of Pure Metal : Homogeneous Nucleation
Consider a pure melt which is cooled below its melting temperature such a liquid is
known as undercooled.
Let a small volume Vs of the liquid turn into solid. If Gs is the free energy per unit
volume of the solid and Gl that of the liquid, if Als is the liquid- solid interfacial
area, and if γls is interfacial free energy, then the total free energy of the system is
given by
GF = Vs Gs + Vl Gl + γ ls Als
Before the small volume of solid formed, the free energy of the system is given by
G I = (Vs + Vl )Gl
Thus, the total free energy change associated with the transformation of a small
volume of liquid vs. into solid is given by
δG = GF − GI
= Vs (Gs − Gl ) + γ ls Als
δG = Vs ∆G + γ ls Als
Free energy change on nucleation =
Reduction in bulk free energy + increase in surface energy + increase in strain energy
δG = (Volume).(∆G ) + (Surface).(γ )
Note that the interfacial energy is always positive. Hence the contribution from the
second term is always positive.
However, depending on whether the liquid is above or below the melting
temperature, ∆G is positive or negative.
Hence, in an under cooled liquid, where ∆G is negative, the system will try to
minimize the shape in such a way that the overall interfacial energy is reduced so
that the maximum reduction in free energy can be achieved.
If we assume interfacial energy to be isotropic, then the volume transformed is a
sphere of radius r (since the maximum volume is enclosed for the minimal surface
area for a sphere), we get
4 3
δG =  πr .(∆Gv ) + 4πr 2 .(γ ls ) ( )
3 
In figure, we show the variation of the
volume free energy, interfacial energy and
overall free energy change as a function of r.
Since the interfacial contribution goes as r2
and that of bulk free energy as r3, at smaller r,
interfacial energy always dominates and
being a positive energy, it actually suppresses
the formation of solid.
Unless the size of the solid is above some
size where in the (negative) bulk free energy
change can more than compensate for the d ∆G
(+ve) interfacial energy, the solid will not be
=0
dr
stable (even if it forms).
Thus one can identify the critical radius of
∆G = 0
the solid that is stable when formed in the
under cooled liquid by minimizing δG with
∆G →
respect to ‘r’. r* r0
 dδG 
 dr  =0 Embryos Supercritical nuclei
r =r *
r →
 dδG 
4 3
( )
δG =  πr .( ∆Gv ) + 4πr 2 .(γ ls ) ⇒  =0
3   dr  r =r *
d 4 3 
 πr ∆G + 4πr 2
γ ls  =0
dr  3  r =r*
[4πr ∆G + 8πrγ ]
2
ls r =r * =0
[4πr ∆G = −8πrγ ]
2
ls r = r * ⇒ r* =
− 2γ ls
∆G
4  − 2γ ls   − 2γ ls 
3 2
δG* = π   ∆ G + 4π   γ ls
3  ∆G   ∆G 
4 8γ ls3 4γ ls2
=− π× ∆G + 4π × γ ls
3 ∆G 3
∆G
 32π 48π  γ ls
3
= − +  16πγ ls3
3  ∆G 2 δG* =
 3 3∆G 2
Rate of Nucleation
There is an energy barrier of ∆G* for formation of a solid nucleus of critical size
r*. The probability of energy fluctuation of size ∆G* is given by the Arrhenius
equation and the rate of homogeneous nucleation is
 ∆G * 
N * = Vd exp − 
 KT 
Where Vd is the frequency with which atoms from liquid attach to the solid
nucleus. The rearrangement of atoms needed for joining the solid nucleus typically
follows the same temperature dependence as the diffusion co-efficient.
Questions..?
1. Differentiate between a crystal, dendrite, and a grain.
2. Why is grain boundary irregular?
3. Is there any difference in the kinetic energy of the atoms in the liquid and the gas at
the boiling point? explain
4. What is supercooling and explain the mechanism of crystallization?
5. Define homogeneous nucleation and heterogeneous nucleation? And derive the
expression for homogeneous nucleation.
6. Calculate the critical free energy of nucleation of ice from water at (i) 0ºC, (ii)-5ºC,
and (iii)-40ºC. Also calculate the critical radius at each temperature. The enthalpy of
fusion of ice is 6.02kJ/mol. The energy of the ice-water interface, 0.076 J m-2 , can be
taken to be independent of temperature. [molar volume of ice = 19 cm3]
7. (a) For the solidification of pure gold, calculate the critical radius r* and the activation
free energy ∆G* if nucleation is homogeneous. Values for the latent heat of fusion and
surface free energy are -1.16× 109 J/m3 and 0.132 J/m2, respectively, assume
supercooling value of gold is 230ºC. (b) And also calculate the number of atoms
found in a nucleus of critical size. Assume a lattice parameter of 0.413 nm for solid
gold at its melting temperature.
8. Name the two stages involved in the formation of particles of a new phase. Briefly
describe each.
Questions..?
9. Rewrite the expression for the total free energy change for nucleation for the case
of a cubic nucleus of edge length a (instead of a sphere of radius r). Now
differentiate this expression with respect to a and solve for both the critical cube
edge length, a*, and also free energy ∆G*. Is ∆G* greater for cube or sphere?
10. Assume for the solidification of nickel that nucleation is homogeneous, and the
number of stable nuclei is 106 nuclei per cubic meter. Calculate the critical radius
and the number of stable nuclei that exist at the following degrees of
supercooling: 200 K and 300 K. and What is significant about the magnitudes of
these critical radii and the numbers of stable nuclei? [rNi – 0.255 J/m2, ΔHf = -
2.53×109 J/m3, Super cooling value for Ni = 319oC]
Avala Lava Kumar*
Introduction
You have been introduced to the lattice structures and types of bonding in
crystalline solids in earlier lectures.
You know that the behavior of electrons determine the way the atoms interact- the
type of bonding (metallic, ionic, covalent and vanderwaals), that holds atoms in a
solid together.
But is the knowledge of bonding and crystal structure is sufficient to predict
the macroscopic properties of materials?
So far in our study of crystalline solids, we have assumed a correspondence
between the abstract three-dimensional lattice and the actual structure of solids.
This implies that crystals are perfect.
Perfect Crystal : A crystal, in which all the atoms are at rest on their correct lattice
position in the crystal.
Such perfect crystals could only exist at absolute zero, and thermal vibrations can
be treated as a form of defect in crystal structures.
For T > 0K, defects always exist in the structure.
REAL CRYSTALS ARE NEVER PERFECT, THERE ARE ALWAYS DEFECTS

Introduction
For example : If a bulk metal (i.e., steel) were a single perfect crystal, it would
have a strength far exceeding the strongest steel ever produced from metallurgical
research. May be this is one of the limitation, in the strength of a metal comes from
the number and type of defect, rather than from the nature of the ideal crystal
lattice.
Many other important properties of materials are due to the imperfections caused
by crystal defects (may be…!)
In this topic we will discuss different types of imperfections or defects in the ideal
arrangement of atoms in a crystal.
For example : When/If you buy a diamond ring, it is mostly the number and type
of defects in the diamond crystal that define the amount of money you pay for a
given crystal size.
Another example : Forging a metal tool introduces defects ….! and increases
strength and elasticity of the tool. Note, that in the case the required properties are
achieved without changes in composition of the material, but just by manipulating
the crystal defects.
“Crystals are like people, it is the defects in them which tend to make them interesting”
- Colin Humphreys
Thermodynamic cause of crystal imperfections
Crystal defects are thermodynamically-controlled phenomena.
To understand how defects come about, consider the effect of probability on
entropy in the following two examples.
A typical single crystal of a large gemstone contains about 1 mole of atoms. Now
compare the effect of adding a single additional defect to
Probability for defect location is 1023
An ideal crystal → 1 defect
There is large increase in the system’s entropy
Probability for defect location is 10

A lattice which → 10% + 1 defect
already has 10% defects There is only a small increase in total entropy
This kind of entropy is called configurational entropy. It is given by the equation

S = K ln(ω) K = Boltzmann constant
ω = Probability
So far the effect of entropy; however, the creation of any kind of defect costs
energy, since the total lattice energy will be reduced. The competing effects of the
energy required to disturb the lattice and the initial large gain in entropy causes a
minimum in the free energy.
Thermodynamic cause of crystal imperfections
G (perfect crystal) T (ºC) n/N

500 1 x 10−10
ibbs free energy)
At a given T
1000 1 x 10−5
∆Gm in 1500 5 x 10−4
2000 3 x 10−3
G (Gibb
Equilibrium ∆Hf = 1 eV/vacancy

concentration
= 0.16 x 10−18 J/vacancy
n (number of vacancies)
Certain equilibrium number of vacancies are preferred at T > 0K

CLASSIFICATION OF DEFECTS BASED ON DIMENSIONALITY
0D 1D 2D 3D
(Point defects) (Line defects) (Surface / Interface) (Volume defects)
Grain Twins
Vacancy Dislocation
boundary
Precipitate
Impurity Disclination Twin
boundary Voids /
Frenkel Cracks
defect Stacking
faults Porosity
Schottky
defect Inclusions
Point Defects
Vacancy
Non-ionic Interstitial
Impurity
crystals
Substitutional
0D
(Point defects) Frenkel defect
Ionic
Other ~
crystals
Schottky defect
Imperfect point-like regions in the crystal about the size of 1-2 atomic
diameters
Point Defects : Non-ionic crystals
Vacancy
Missing atom from an atomic site
Atoms around the vacancy displaced Tensile Stress
Fields ?
Tensile stress field produced in the vicinity
Substitutional Impurity
• Foreign atom replacing the parent atom in the crystal
Interstitial • E.g. Cu sitting in the lattice site of FCC-Ni
Impurity Interstitial Impurity
Substitutional • Foreign atom sitting in the void of a crystal
• E.g. C sitting in the octahedral void in HT FCC-Fe
Relative size
Compressive Stress Fields Tensile Stress Fields

Point Defects : Ionic crystals
Overall electrical neutrality has to be maintained
Frenkel defect
Cation (being smaller get displaced to interstitial voids

E.g. AgI, CaF2
Schottky defect
Pair of anion and cation vacancies

E.g. Alkali halides
Other defects due to charge balance

FeO heated in oxygen atmosphere → FexO (x <1)
Vacant cation sites are present
Charge is compensated by conversion of ferrous to ferric ion:
Fe2+ → Fe3+ + e−
For every vacancy (of Fe cation) two ferrous ions are converted to
ferric ions → provides the 2 electrons required by excess oxygen
How many vacancies are present?
The higher is the temperature, more often atoms are jumping from one equilibrium
position to another and larger number of vacancies can be found in a crystal.
Actually, the number of vacancies, Nv , increases exponentially with the absolute
temperature, T and can be estimated using the equation:
 − EV 
NV = N S exp 
 K BT 
N S = Number of regular lattice sites
K B = Boltzman constant
E V = Energy needed to form a vacant lattice site in a perfect crystal
Using this simple equation we can estimate vacancy per 10n lattice atoms.
Solved Calculate the equilibrium number of vacancies per cubic meter for copper at
Example -1 1000°C. The energy for vacancy formation is 0.9ev/atom; the atomic weight
and density (at 1000°C) for copper are 63.5 g/mol and 8.4 g/cm3 respectively.
This problem may be solved by using following equations

It is first necessary, however, to determine the value of N s , the numberof atomic sites
per cubic meter for copper,
form its atomic weight A Cu , its density ρ and Avogadro' s number N A , according to
NA ρ
NS =
ACu
(6.023 × 10 23 atoms / mol )(8.4 g / cm3 )(106 cm3 / m 3 )
=
63.5 g / mol
= 8.0 ×10 28 atoms / m 3
 − EV 
0
Thus the number of vacancies at 1000 C is equal to N V = N S exp 
 K BT 
 − 0.9e.v 
= (8.0 × 10 28 atoms / m 3 ) exp  −5 
 (8 . 62 × 10 eV / K )(1273 K ) 
= 2.2 × 10 25 vacancies / m 3
1D Defects : DISLOCATIONS
EDGE MIXED SCREW
Usually dislocations have a mixed character and Edge and Screw

dislocations are the ideal extremes
DISLOCATIONS
Random Structural
Geometrically necessary dislocations
Introduction
Dislocation is a boundary between the slipped and the unslipped parts of the crystal
lying over a slip plane
The intersection of the extra half-plane of atoms with the slip plane
defines the dislocation line (for an edge dislocation)
Direction and magnitude of slip is characterized by the Burgers vector
of the dislocation (A dislocation is born with a Burgers vector and expresses it even in
its death!)
The Burgers vector is determined by the Burgers Circuit
Right hand screw (finish to start) convention is used for determining
the direction of the Burgers vector
As the periodic force field of a crystal requires that atoms must move
from one equilibrium position to another ⇒ b must connect one
lattice position to another (for a full dislocation)
Dislocations tend to have as small a Burgers vector as possible
The edge dislocation has compressive stress field above and tensile stress field below
the slip plane.
Dislocations are non-
non-equilibrium defects and would leave the crystal if given an
opportunity
Burgers Vector
Crystal with edge dislocation
Edge dislocation
Perfect crystal
RHFS:
Right Hand Finish to Start convention
r
Direction of t
t vector
dislocation line vector
r
Direction of b
b vector
A dislocation has associated with it two vectors:
r
t → A unit tangent vector along the dislocation line
r
b → The Burgers vector
Compressive stress field
Slipped Unslipped
part part
of the of the
crystal crystal
Dislocation is a boundary between the slipped and

Tensile stress field the unslipped parts of the crystal lying over a slip
plane
Burgers Vector in Edge & Screw dislocations
+ve & -ve edge dislocations
Positive edge dislocation

Negative edge dislocation
Can come together and cancel
one another
ATTRACTION
REPULSION
Motion of dislocations
Conservative Motion of dislocations

(Glide) On the slip plane
Motion of Edge
dislocation
Non-conservative Motion of dislocation
(Climb) ⊥ to the slip plane
For edge dislocation: as b ⊥ t → they define a plane → the slip plane

Climb involves addition or subtraction of a row of atoms below the
half plane
► +ve climb = climb up → removal of a plane of atoms
► −ve climb = climb down → addition of a plane of atoms
Edge Dislocation Glide
Shear stress
Surface
step
Edge Climb
Positive climb Negative climb

Removal of a row of atoms Addition of a row of atoms
Screw dislocation
Screw dislocation cross-slip
Slip plane 2
b
Slip plane 1
The dislocation is shown cross-
cross-slipping from the blue plane to the green plane
The dislocation line ends on

The free surface of the crystal
Internal surface or interface
Closes on itself to form a loop
Ends in a node
A node is the intersection point of more than two dislocations
The vectoral sum of the Burgers vectors of dislocations meeting at a node = 0
Geometric properties of dislocations
Type of dislocation
Dislocation Property
Edge Screw
Relation between dislocation
⊥ ||
line (t) and b
Slip direction || to b || to b
Direction of dislocation line
|| ⊥
movement relative to b
Process by which dislocation
Glide/Climb Cross-slip
may leave slip plane
Mixed dislocations
b
Pure screw Pure Edge

t
We are looking at the plane of the cut (sort of a

semicircle centered in the lower left corner). Blue
circles denote atoms just below, red circles atoms just
above the cut. Up on the right the dislocation is a pure
edge dislocation on the lower left it is pure screw. In
between it is mixed. In the link this dislocation is shown
moving in an animated illustration.
Energy of dislocations
Dislocations have distortion energy associated with them
E per unit length
Edge → Compressive and tensile stress fields
Screw → Shear strains
Elastic E
Energy of dislocation
Non-elastic (Core) ~E/10
1 2 G → (µ) shear modulus

Energy of a dislocation / unit length E ≅ Gb
2 b → |b|
Dislocations will have as small b as possible
Full b → Full lattice translation

Dislocations
(in terms of lattice translation)
Partial b → Fraction of lattice translation
Role of Dislocations
Creep Diffusion
Fatigue (Pipe)
Fracture
Slip
Structural
Incoherent Twin
Grain boundary
(low angle)
Semicoherent Interfaces
Disc of vacancies
~ edge dislocation
Formation of dislocations (in the bulk of the crystal)
Due to accidents in crystal growth from the melt

Mechanical deformation of the crystal
2D Defects : Surface defects
2D in a mathematical sense
The region of distortion is ~ few atomic diameters in thickness
Low
angle
External
Grain boundary
High
angle
2D DEFECTS
(Surface / Interface)
Homophase Twin Boundary
Internal
Stacking Faults
Heteropase
Coherent Incoherent Semi-coherent

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
In an low angle boundary the orientation difference is < 15º
In the low angle boundary the distortion is not so drastic as the
high-angle boundary → can be described as an array of
dislocations
Grain boundary energy is responsible for grain growth on heating
~ (>0.5Tm)
Large grains grow at the expense of smaller ones
The average no. of nearest neighbours for an atom in the grain
boundary of a close packed crystal is 11
Twin Boundary
The atomic arrangement on one side of the twin boundary is related to
the other side by a symmetry operation (usually a mirror)
Twin boundaries usually occur in pairs such that the orientation
difference introduced by one is restored by the other
The region between the regions is called the twinned region
Annealing twins (formed during recrystallization)
Twin
Deformation twins (formed during plastic deformation)

Stacking Fault
Error in the sequence of stacking atomic planes → Stacking fault
Defined by a shift vector
FCC stacking …ABC ABC ABC ABC…
FCC stacking
with a stacking fault …ABC AB AB ABC…
Thin region of HCP type of stacking
In above the number of nearest neighbours remains the same

but next-nearest neighbours are different than that in FCC
Stacking fault energy ~ 0.01 – 0.05 J/m2
Stacking fault in HCP can lead to thin region of FCC kind of stacking
3D Defects : volume defects
Volume defects in crystals are three dimensional aggregates of atoms or vacancies
Volume defects
Precipitates Dispersants Inclusions Voids (or pores)
PRECIPITATES
Precipitates are small particles that are introduced into the matrix by solid state
reactions. While precipitates are used for several purposes, their most common
purpose is to increase the strength of structural alloys by acting as obstacles to the
motion of dislocations. Their efficiency in doing this depends on their size, their
internal properties, and their distribution through the lattice. However, their role in the
microstructure is to modify the behavior of the matrix rather than to act as separate
phases in their own right.
3D Defects : volume defects
DISPERSANTS
Dispersants are larger particles that behave as a second phase as well as influencing the
behavior of the primary phase. They may be large precipitates, grains, or polygranular particles
distributed through the microstructure. When a microstructure contains dispersants such
properties as mechanical strength and electrical conductivity are some average of the
properties of the dispersant phase and the parent.
INCLUSIONS
Inclusions are foreign particles or large precipitate particles. They are usually undesirable
constituents in the microstructure. For example, inclusions have a deleterious effect on the
useful strength of structural alloys since they are preferential sites for failure. They are also
often harmful in microelectronic devices since they disturb the geometry of the device by
interfering in manufacturing, or alter its electrical properties by introducing undesirable
properties of their own.
VOIDS (OR PORES)
Voids (or pores) are caused by gases that are trapped during solidification or by vacancy
condensation in the solid state. They are almost always undesirable defects. Their principal
effect is to decrease mechanical strength and promote fracture at small loads.
Questions..?
1. Differentiate Frenkel and Schottky defects.
2. Find the equilibrium concentration of vacancies in aluminium (eV/vacancy = 0.70,
ΔHf =68 KJ/mol) and nickel (eV/vacancy = 1.74, ΔHf = 168 KJ/mole) at 0K, 300K,
and 900K.
3. Why point defects are called “ Equilibrium defects”. State your reasons
4. Compute the line energy of dislocations in BCC iron. The Burgers vector in iron is
of the ½<111> type. The shear modulus of iron is 80.2 GN m-2 [a BCC Fe = 2.87Å]
5. The surface of copper crystal is of the {111} type. Calculate the surface energy
(enthalpy) of copper. [a FCC Fe = 3.61Å]
6. The surface energy of a single crystal depends on crystallographic orientation. Does
this surface energy increase or decrease with an increase in planar density. Why?
7. Calculate the energy for vacancy formation in silver, given that the equilibrium
number of vacancies at 800°C (1073K) is 3.6× 1023 m-3. The atomic weight and
density (at 800°C) for silver are respectively, 107.9 g/mol and 9.5 g/cm3 .
8. Cite the relative Burgers vector–dislocation line orientations for edge, screw, and
mixed dislocations.
9. For a given material, would you expect the surface energy to be greater than, the
same as, or less than the grain boundary energy? Why?
Questions..?
10. The grain boundary energy of a small angle grain boundary is less than for a high
angle one. Why is this so?
11. For a BCC single crystal, would you expect the surface energy for a (100) plane
to be greater or less than that for a (110) plane? Why?
12. If there are 1010 m-2 of edge dislocations in a simple cubic crystal, how much
would each of these climb down on an average when the crystal is heated from 0
to 1000K? The enthalpy of formation of vacancies is 100 KJ mol-1. The lattice
parameter is 2 Å. The volume of one mole of the crystal is 5.5 × 10-6 m3
13. What is the geometry of edge dislocation? How did the concept arise? What is the
geometry of the screw dislocation? Differentiate Edge and Screw dislocations
14. Write short note on Volume defects
15. What is the Burgers vector of a dislocation? How is the Burgers circuit used to
define the Burgers vector ?
Avala Lava Kumar*
Mechanical properties of metals
The mechanical properties of a material reflects the relationship between its
response or deformation to an applied load or force.
Important mechanical properties are strength, hardness, ductility, and stiffness.
These properties are ascertained by performing carefully designed laboratory
experiments that replicate as nearly as possible the service conditions.
Factors to be considered include the nature of the applied load and its duration, as
well as the environmental conditions.
It is possible for the load to be tensile, compressive, or shear, and its magnitude
may be constant with time, or it may fluctuate continuously. Application time may
be only a fraction of a second, or it may extend over a period of many years.
Service temperature may be an important factor.
What kind of mechanical behavior phenomena does one have to understand?
Phenomenologically mechanical behaviour can be understood as in the flow

diagram below.
Multiple mechanisms may be associated with these phenomena (e.g. creep can
occur by diffusion, grain boundary sliding etc.).
These phenomena may lead to the failure of a material.
Mechanical Behaviour
Elasticity Recoverable deformation
Plasticity Permanent deformation
Fracture Propagation of cracks in a material
Fatigue Oscillatory loading
Creep Elongation at constant load at High temperatures
Note: above is a ‘broad’ classification for ‘convenience’. E.g. Creep is also leads to plastic deformation!
Classification of Deformation Processes
Recoverable
Instantaneous
Elastic
Time dependent Anelasticity
Deformation
Instantaneous
Plastic
Permanent Time dependent
Viscoelasticity
Concepts of Stress & Strain
Solids deform when they are subject to load (can be tensile, compressive or shear).
They can maintain or lose their shape
Tension Tests
Most common mechanical stress–strain tests which is used to ascertain several
mechanical properties of materials.
A specimen is deformed, usually to fracture, with a gradually increasing uniaxial
tensile load applied along the long axis of a specimen.
The tensile testing machine is designed to elongate the specimen at a constant rate,
and to continuously and simultaneously measure the instantaneous applied load
(with a load cell) and the resulting elongations (using an extensometer).
The output of such a tensile test is recorded (usually on a computer) as load or
force versus elongation
A standard tensile specimen with circular cross section

F
Engineering stress : Tensile stress σ= SI Unit: Megapascals
Ao
l − lo ∆l
Engineering strain : Tensile strain ε= =
lo lo
do
d −d ∆d
Lateral Strain : εl = d = d
o
Strain is always dimensionless d
o o
Where lo and do are the original dimensions before any load is

applied; l and d are the instantaneous dimensions; ∆l and ∆d are
changes in dimensions.
Compression Tests
Test is conducted in a manner similar to the tensile test,
except that the force is compressive and the specimen
contracts along the direction of the stress.
By convention, a compressive force is taken to be negative,
which yields a negative stress. Furthermore, since lo is
greater than l, compressive strains is also negative
Shear Tests
For tests performed using a pure shear force, the shear
stress is computed according to
Shear stress τ = F Shear strain γ = tan θ
Ao
Where F is the load or force imposed parallel to the upper

and lower faces, each of which has an area of A0 . The
shear strain γ is defined as the tangent of the strain angle θ.
Torsional Tests
Torsion is a variation of pure shear, wherein a structural
member is twisted about the longitudinal axis of one end
of the member relative to the other end producing a
rotational motion .
Shear stress τ is a function of the applied torque T and
shear strain is related to the angle of twist φ.
Elastic Deformation
Deformation in which stress and strain are proportional is called elastic
deformation.
Elastic deformation is non permanent reversible deformation- i.e. when load/forces
are released the body returns to its original configuration (shape and size). It can be
caused by tension/compression or shear forces.
Usually in metals and ceramics elastic deformation is seen at low strains (< 10–3).
bonds
stretch
return to
initial
δ
F
Elasticity can be linear or Non linear. Metals and ceramics usually show linear
elastic behavior.
Some materials (e.g., gray cast iron, concrete, and many polymers) exhibit non
linear elasticity.
Elastic Stress-Strain Curve
A stress-strain curve is a graph derived from
measuring load (stress - σ) versus extension (strain -
ε) for a sample of a material
For most metals that are stressed in tension and at
relatively low levels, stress and strain are
proportional to each other i.e.
The slope of this linear segment corresponds to the
modulus of elasticity E.
This is known as Hooke’s law, and the constant of
proportionality E (Gpa or psi) is the modulus of
elasticity, or Young’s modulus.
This modulus may be thought of as stiffness, or a
material’s resistance to elastic deformation. The
greater the modulus, the stiffer the material, or the
smaller the elastic strain that results from the
application of a given stress.
Elastic Stress-Strain Curve
For materials showing non

linear elasticity either
tangent or secant modulus
can be used to determine the
modulus of elasticity.
Tangent modulus is taken as
the slope of the stress–strain
curve at some specified
level of stress, while secant
modulus represents the
slope of a secant drawn
from the origin to some
given point of the σ–ϵ
curve.
Young’s Moduli : Comparison
Graphite
Metals Composites
Ceramics Polymers
Alloys fibers
Semicond
1200
10 00 Diamond
8 00
6 00
Si carbide
4 00 Tungsten Al oxide Carbon fibers only
Molybdenum Si nitride
Steel, Ni C FRE(|| fibers)*
2 00 Tantalum <111>
Platinum Si crystal
Cu alloys <100> A ramid fibers only
10 0 Zinc, Ti
80 Silver, Gold
Glass - soda A FRE(|| fibers)*
Aluminum Glass fibers only
60
Magnesium, G FRE(|| fibers)*
40 Tin Eceramics
Concrete
E(GPa) GFRE*
> Emetals
20
CFRE * >> Epolymers
G raphite G FRE( fibers)*
10
8 C FRE( fibers) *
6 AFRE( fibers) *
Polyester
4 PET
PS
PC Epoxy only
2
PP
1 HDP E
0.8
0.6 Wood( grain)
PTF E
0.4
0.2 LDPE
Plastic (Permanent) Deformation
Plastic deformation in the broadest sense means permanent deformation in the
absence of external constraints (forces, displacements).
From an atomic perspective, plastic deformation corresponds to the breaking of
bonds with original atom neighbors and then reforming bonds with new neighbors
as large numbers of atoms or molecules move relative to one another; upon
removal of the stress they do not return to their original positions.
bonds
stretch p lanes
& planes still
shear sheared
δ plastic
δ elastic + plastic
F
For most metallic materials, elastic deformation persists only to strains of about
0.005. As the material is deformed beyond this point, the stress is no longer
proportional to strain (Hooke’s law) and permanent/nonrecoverable/plastic
deformation occurs.
The transition from elastic to plastic is a gradual one for most metals; some
curvature results at the onset of plastic deformation, which increases more rapidly
with rising stress.
Schematic of Stress-Strain diagram showing plastic deformation resulting
from Simple tension test at lower temperatures, i.e. T < Melt/3
Proportional Limit
Elastic + Plastic
at larger stress
engineering stress, s p
Permanent (plastic)
after load is removed
Initially
Elastic
ep engineering strain, e
plastic strain
Tensile Properties
Yielding : Yielding is the beginning of plastic deformation
proportional limit : The point at which there is a deviation from the straight line
‘elastic’ regime
Yield Strength (σy)
Stress at which noticeable plastic deformation has occurred.

The magnitude of the yield strength for a metal is a measure of its resistance to
plastic deformation.
For metals that experience gradual elastic–plastic transition, a curve is drawn parallel
to the elastic line at a given strain like 0.2% (= 0.002) to determine the yield strength.
For materials having a nonlinear elastic region the yield strength is defined as the
stress required to produce some amount of strain (ϵ = 0.005)
Some materials elastic–plastic transition is very well defined and occurs abruptly
(yield point phenomenon). For these materials yield strength is taken as the average
stress that is associated with the lower yield point
Tensile Properties
Typical stress– strain behavior for a metal Representative stress–strain behavior found for
showing elastic and plastic deformations, the some steels demonstrating the yield point
proportional limit P, and the yield strength as phenomenon.
determined using the 0.002 strain offset method.
Yield Strength : Comparison
Graphite/
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
2000
Steel (4140) qt
1000
Room T values
Yield strength, σy (MPa)
Ti (5Al-2.5Sn) a
700 W (pure)
600 a = annealed
Cu (71500) cw
in ceramic matrix and epoxy matrix composites, since

500 Mo (pure) hr = hot rolled
since in tension, fracture usually occurs before yield.
in tension, fracture usually occurs before yield.

400 Steel (4140) a ag = aged
Steel (1020) cd
300 cd = cold drawn
,
Al (6061) ag cw = cold worked
Hard to measure,
200 Steel (1020) hr qt = quenched & tempered
Hard to measure
¨
Ti (pure) a
Ta (pure)
Cu (71500) hr
100
dry
70 PC
60 Nylon 6,6
50 Al (6061) a PET
40 PVC humid σy(ceramics)
PP >>σy(metals)
30 H DPE
>> σy(polymers)
20
LDPE
Tin (pure)
10
Tensile Strength (TS)
The tensile strength TS (MPa or psi) is the stress at the maximum on the
engineering stress–strain curve
TS
F = fracture or
σy
ultimate strength
engineering
stress
Neck – acts as stress

Typical response of a metal concentrator
strain
engineering strain
Metals : This is the point when noticeable necking starts.

Ceramics : Crack propagation starts at this point.
Polymers : Polymer backbones are aligned and about to break at this point.
Tensile Strength: Comparison
Graphite/
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
5000 C fibers
Aramid fib
3000 E-glass fib
(MPa)
2000 Steel (4140) qt
A FRE (|| fiber)
1000 W (pure) Diamond GFRE (|| fiber)
Ti (5Al-2.5Sn) aa C FRE (|| fiber) Room T values
Steel (4140)cw
Cu (71500) Si nitride
Cu (71500) hr Al oxide
a = annealed
Steel (1020) hr = hot rolled
300 Al (6061) ag
Ti (pure) a ag = aged
Tensile strength, TS
200 Ta (pure)
cd = cold drawn
Al (6061) a
100 Si crystal wood(|| fiber) cw = cold worked
<100> Nylon 6,6
Glass-soda PC PET qt = quenched & tempered
40 Concrete PVC GFRE ( fiber) AFRE, GFRE, & CFRE =
PP C FRE ( fiber)
30 aramid, glass, & carbon
A FRE( fiber)
H DPE fiber-reinforced epoxy
20 Graphite
L DPE composites, with 60 vol%
fibers.
10
wood ( fiber)
1
Ductility, %Elongation
Ductility may be expressed quantitatively as either percent elongation or percent
reduction in area.
The percent elongation %EL is the percentage of plastic strain at fracture
Lf − Lo
%EL = x 100
Lo
Engineering Tensile Stress, σ smaller %EL
larger %EL Ao
Lo Af Lf
Engineering tensile strain, ϵ
Another ductility measure: A o - Af

% RA = x 100
Ao
Toughness
Energy required to break a unit volume of material
It can be approximated by the area under the stress-strain curve up to the point of
fracture.
small toughness (ceramics)

Engineering Tensile Stress, σ
large toughness (metals)
very small toughness

(unreinforced polymers)
Engineering tensile strain, ϵ
For Brittle fracture: elastic energy

For Ductile fracture: elastic + plastic energy
Resilience, Ur
Resilience is the capacity of a material to absorb energy when it is deformed
elastically and then, upon unloading, to have this energy recovered.
Modulus of resilience Ur is the strain energy per unit volume required to stress a
material from an unloaded state up to the point of yielding.
εy
Ur = ∫0 σdε
If we assume a linear stress

stress--strain
curve this simplifies to
1
U r ≅ σ yε y
2
Hardness
Resistance to permanently indenting the surface.
Large hardness means:
resistance to plastic deformation or cracking in compression.
better wear properties
True Stress & Strain
F
True stress : σ True =
Ai
li
True strain : ε True = ln
lo
σ T = σ (1 + ε )
ε T = ln (1 + ε )
The relation with Eng. Stress and Eng strain is
Necking begins at point M on the engineering curve, which corresponds to on the

true curve. The “corrected” true stress–strain curve takes into account the complex
stress state within the neck region.
A comparison of typical
tensile engineering
stress–strain and true
stress–strain behaviors
What happens after necking?
Following factors come in to picture due to necking:
Till necking the deformation is ~uniform along the whole gauge length.
Till necking points on the σ-ε plot lie to the left and higher than the s-e plot (as below).
After the onset of necking deformation is localized around the neck region.
Formulae used for conversion of ‘e’ to ‘ε’ and ‘s’ to ‘σ’ cannot be used after the onset of
necking. σ = s( 1 + e) ε = ln ( 1 + e)
Triaxial state of stress develops and uniaxiality condition assumed during the test breaks
down.
Necking can be considered as an instability in tension.
Hence, quantities calculated after the onset of necking (like fracture stress, σF) has to be
corrected for: (i) triaxial state of stress, (ii) correct cross sectional area.
Neck
Fractured surfaces
Mechanisms/modes of plastic deformation
Plastic deformation in crystalline solid is accomplished by means of various
processes mentioned below; among which slip is the most important mechanism.
Plastic deformation of crystalline materials takes place by mechanisms which are
very different from that for amorphous materials (glasses). Plastic deformation in
amorphous materials occur by other mechanisms including flow (~viscous fluid)
and shear banding.
Plastic Deformation in Crystalline Materials
Slip Twinning Phase Transformation Creep Mechanisms

(Dislocation
motion) Grain boundary sliding
+ Other Mechanisms
Vacancy diffusion
Grain rotation
Dislocation climb
Plastic deformation by dislocation Motion (SLIP)
Basic concepts
SLIP is the most important mechanism of plastic deformation . At low temperatures

(especially in BCC metals) twinning may also become important.
At the fundamental level plastic deformation (in crystalline materials) by slip
involves the motion of dislocations on the slip plane (creating a step of Burgers
vector).
Slip is caused by shear stresses (at the level of the slip plane). Hence, a purely
hydrostatic state of stress cannot cause slip.
A slip system consists of a slip direction lying on a slip plane.
Slip is analogous to the mode of locomotion employed by a caterpillar
Shear Stress Edge Dislocation Line Unit Step of Slip

Direction of Dislocation Motion
Edge dislocation line moves parallel to applied stress
Screw dislocation line moves perpendicular to applied stress

Slip systems
Dislocations move more easily on specific planes and in specific directions.
Ordinarily, there is a preferred plane (slip plane), and specific directions (slip
direction) along which dislocations move. The combination of slip plane and slip
direction is called the slip system.
The slip system depends on the crystal structure of the metal.
The slip plane is the plane that has the most dense atomic packing (the greatest planar
density). The slip direction is most closely packed with atoms (highest linear density).
In CCP, HCP materials the slip system consists of a close packed direction on a close
packed plane.
Just the existence of a slip system does not guarantee slip → slip is competing against
other processes like twinning and fracture. If the stress to cause slip is very high (i.e.
CRSS is very high), then fracture may occur before slip (like in brittle ceramics).
For slip to occur in polycrystalline materials, 5 independent slip systems are required.
Hence, materials which are ductile in single crystalline form, may not be ductile in
polycrystalline form. CCP crystals (Cu, Al, Au) have excellent ductility.
At higher temperatures more slip systems may become active and hence
polycrystalline materials which are brittle at low temperature, may become ductile at
high temperature.
Example of slip systems
Crystal Slip plane(s) Slip direction Number of slip systems
FCC {111} ½<110> 12
HCP (0001) <1120> 3
BCC {110}, {112}, {123} ½[111] 48
NaCl (Ionic) {110}
½<110> 6
{111} not a slip plane
C (Diamond
{111} ½<110> 12
cubic)
TiO2(Rutile) {101} <101>
CaF2, UO2, ThO2
{001} <110>
Fluorite
CsCl {110} <001>
NaCl, LiF, MgO
{110} <110> 6
Rock Salt
C, Ge, Si
{111} <110> 12
Diamond cubic
MgAl2O4
{111} <110>
Spinel
Al2O3
(0001) <1120>
Hexagonal
microscopic slip to macroscopic deformation
Step formed
Dislocation
when dislocation
formed by
leaves the crystal
pushing in
a plane r
b
Now visualize dislocations being punched in on successive planes → moving and

finally leaving the crystal
This sequence of events finally leads to deformed shape
Net shape change

Slip in Single Crystal
If a single crystal of a metal is stressed in tension beyond its elastic limit, it
elongates slightly and a step appears on the surface due to the relative displacement
of one part of the crystal with respect to the others and the elongation stops.
Further increase in the load causes movement of another parallel plane, resulting in
another step. Similarly number of small steps are formed on the surface of the
single crystal that are parallel to one another and loop around the circumference of
the specimen.
Each step (shear band) results from the movement of a large number of dislocations
and their propagation in the slip system.
Macroscopic slip in single crystal Slip in a zinc single crystal

Critical Resolved Shear Stress (CRSS)
Extent of slip in a single crystal depends on the magnitude of shearing stress
produced by external loads, geometry of the crystal structure and the orientation of
the active slip planes with respect to the shearing stress.
Slip begins when the shearing stress on slip plane in the slip direction/Resolved
Shear Stress (RSS) reaches a critical value called the Critical Resolved Shear Stress
(CRSS) and plastic deformation starts (The actual Schmid’s law)
Even if we apply an tensile force on the
specimen → the shear stress resolved onto
the slip plane is responsible for slip. σ =
F 
Slip plane 
The stress at which slip starts in a crystal normal  A
depends on the relative orientation of the
stress axis with respect to the slip plane Slip direction
and the slip direction.
When a tensile stress σ is applied to a
crystal, as illustrated in figure, the shear  A 
A' =  
stress τ resolved on a slip plane whose  Cosθ 
normal makes an angle of θ with the stress
axis, along a slip direction inclined at an Externally only
tensile forces are
angle of φ to the stress axis. being applied
Critical Resolved Shear Stress (CRSS)
 Force 
Stress =  
 Area 
 F Cos α 
τ = 
 A / Cos θ 
τ RSS = σ C o sθ C o s ϕ
τ RSS is maximum (P/2A) when ϕ = λ=45o Schmid factor

If the tension axis is normal to slip plane i.e. λ=90o or if it is parallel to the slip
plane i.e. ϕ = 90o then τ RSS = 0 and slip will not occur as per Schmid’s law.
Schmid’s law Slip is initiated when τ R SS ≥ τ C R SS

τCRSS is a material parameter, which is determined from experiments
τ C R SS
Yield strength of a single crystal σy =
C osθ C osϕ
Solved Example 1
Consider a single crystal of BCC iron oriented such that a tensile stress is applied along a [010]
direction.
(a) Compute the resolved shear stress along a (110) plane and in a [111] direction when a
tensile
−
stress of 52 MPa (7500 psi) is applied. If slip occurs on a (110) plane and in a
[1 11 ] direction, and the critical resolved shear stress is 30 MPa (4350 psi), calculate the
magnitude of the applied tensile stress necessary to initiate yielding.
Solution
a. Determine the value of the angle between the normal to the (110) slip plane (i.e., the [110]
direction) and the [010] direction using [u1v1w1] = [110], [u2v2w2] = [010] and the following
equation.
 u1u 2 + v1v2 + w1w2 

θ = cos−1  
 (u1 2 + v1 2 + w1 2 )(u 2 2 + v2 2 + w2 2 ) 
 
 (1)(0) + (1)(1) + (0)(0) 

φ = cos −1 
 [(1) 2 + (1) 2 + (0) 2 ][(0) 2 + (1) 2 + (0) 2 ] 
 
1
= cos−1 ( ) = 45o
2
Solved Example 1
−
Similarly determine the value of λ, the angle between [1 11 ] and [010] directions as
follows:
 (−1)(0) + (1)(1) + (1)(0) 
λ = cos −1  = cos−1 ( 1 ) = 54.7 o
 [(−1) 2 + (1) 2 + (1) 2 ][(0) 2 + (1) 2 + (0) 2 ]  3
 
Then calculate the value of τ RSS using the following expression:

τ RSS = σ cosϕ cosλ
=(52 Mpa)(cos 45)(cos 54.7)
= 21.3 Mpa
= 13060 psi
Yield Strength σY
30 MPa
σy = = 73.4 Mpa
(cos 45)(cos 54.7)
Solved Example 2
−
Determine the− tensile
− −
stress that is applied along the [11 0 ] axis of a silver crystal to cause
slip on the (11 1) [ 0 11] system. The critical resolved shear stress is 6 MPa.
Solution:
− −−
Determine the angle ϕ between the tensile axis [11 0] and normal to (111) using the
following equation.  uu +vv +ww 
cos θ =  
1 2 1 2 1 2
 (u1 + v1 + w1 )(u 2 + v 2 + w2 ) 
2 2 2 2 2 2
 
 (1)(1) + (−1)(−1) + (0)(−1) 
cos φ =  = 1 = 2
 [(1) 2 + (−1) 2 + (0) 2 ][(1) 2 + (−1) 2 + (−1) 2 ]  2 3 6

− −
Determine the angle λ between tensile axis [11 0] and slip direction [011]
 (1)(0) + (−1)(−1) + (0)(−1)  1 1
cos λ =  = =
 [(1) 2 + (−1) 2 + (0) 2 ][(0) 2 + (−1) 2 + (−1) 2 ]  2 2 2
 
Then calculate the Tensile Stress using the expression:
P τRSS 6MPa
σ= = = = 6 6 = 14.7 Mpa
A cosφ cosλ 2 × 1
6 2
Plastic deformation by Twin
In addition to slip (dislocation movement), plastic deformation can also occur by twinning.
Twinning results when a portion of the crystal takes up an orientation that is related to the
orientation of the rest of the untwinned lattice in a definite, symmetrical way.
Twinned portion of the crystal is a mirror image of the parent crystal and the plane of
symmetry between the two portions is called twinning plane.
Twinning may favorably reorient slip systems to promote dislocation movement.
- Atoms that did not move

- Original positions of the atoms
- Final positions of the atoms
Schematic diagram showing how twinning results from an applied shear stress
Twins are generally of two types: Mechanical Twins and Annealing twins
Mechanical twins are generally seen in bcc or hcp metals and produced under conditions of
rapid rate of loading and decreased temperature.
Annealing twins are produced as the result of annealing. These twins are generally seen in
fcc metals.
Annealing twins are usually broader and with straighter sides than mechanical twins.
(a) (b) (c)
(a) Mechanical Twins (Neumann bands in iron), (b) Mechanical Twins in zinc produced by
polishing (c) Annealing Twins in gold-silver alloy
Twinning generally occurs when the slip systems are restricted or when the slip
systems are restricted or when something increases the critical resolved shear
stress so that the twinning stress is lower than the stress for slip.
So, twinning generally occurs at low temperatures or high strain rates in bcc or fcc
metals or in hcp metals.
Twinning occurs on specific twinning planes and twinning directions.
Twin planes and Twin directions
Crystal Typical Twin

Twin Plane
Structure Examples Direction
BCC α-Fe, Ta (112) [111]
Zn, Cd, Mg, − −

HCP (10 1 2) [1 011]
Ti
FCC Ag, Au, Cu (111) [112]
Difference between Slip and Twin
Slip Twin
• The crystallographic orientation above • Orientation difference is seen across
and below the slip plane is the same the twin plane
both before and after the deformation • the atomic displacement for twinning is
• Slip occurs in distinct atomic spacing less than the inter-atomic separation
multiples • Twinning leaves small but well defined
• Slip Leaves a series of steps (lines) regions of the crystal deformed
• Normally slip results in relatively large • Only small deformations result for
deformations twinning
• Mostly seen in FCC and BCC structure, • Is most important for HCP structure ,
as they have more slip systems because of its small number of slip
system
Plastic deformation of Polycrystalline Materials
Plastic deformation in polycrystalline materials is very complex than those in the
single crystals due to the presence of grain boundaries, different orientation of
neighboring crystals, presence of several phases etc.
Due to random crystallographic orientations, the slip planes and slip direction
varies from one grain to another
As a result the resolved shear stress τRSS will vary from one crystal to another and
the dislocations will move along the slip systems with favorable orientation (i.e.
the highest resolved shear stress).
When a polished polycrystalline specimen of
copper is plastically deformed, two slip systems
operate for most of the grains (evidenced by two
sets of parallel yet intersecting sets of lines).
Slip lines are visible, and the variation in grain
orientation is indicated by the difference in
alignment of the slip lines for several grains.
Slip lines
Plastic deformation of Polycrystalline Materials
During deformation, mechanical integrity and coherency are maintained along the
grain boundaries; i.e. the grain boundaries usually do not come apart or open up.
As a consequence, each individual grain is constrained, to some degree in the
shape it may assume by its neighboring grains.
Alteration of the grain structure of a polycrystalline metal as a result of plastic deformation (a)
Before deformation the grains are equiaxed. (b) After deformation elongated grains are produced
Strengthening Mechanisms
The ability of a metal to deform depends on the ability of the dislocations to move
and the slip of dislocations weakens the crystal. Hence we have two strategies to
strengthen the crystal/material:
completely remove dislocations → difficult, but dislocation free whiskers have been
produced (however, this is not a good strategy as dislocations can nucleate during
loading)
Increase resistance to the motion of dislocations or put impediments to the motion of
dislocations → this can be done in many ways as listed below.
Strengthening mechanisms
Solid solution Precipitate & Dispersoid Strain hardening Grain boundary
by adding introduce precipitates or increase point grain boundaries

interstitial and inclusions in the path of defect and provide an
substitutional dislocations which dislocation impediment to
alloying impede the motion of density the motion of
elements). dislocations dislocations
Solid Solution Strengthening
The introduction of solute atoms into solid solution in the solvent-atom lattice
invariably produces an alloy which is stronger than the pure metal
Two types of solid solutions:
Substitutional solid solutions → Solute atoms occupy lattice points in the
solvent lattice (Hume Rothery’s rules are to be satisfied)
Interstitial solid solutions → Solute atoms occupy interstitial positions in the
solvent lattice (Carbon, Nitrogen, Boron, Oxygen, Hydrogen are the common
interstitial solutes)
The stress fields around solute atoms interact with the stress fields around the
dislocation.
This interaction provides frictional resistance to dislocations motion and static
locking of dislocations
The factors playing an important role on strengthening effect:
Size of the solute
Concentration of solute
Elastic modulus of the solute (higher the elastic modulus of the solute greater
the strengthening effect)
Nature of distortion produced by solute atoms (Spherical or Non-spherical)
Effect of Size and Concentration of Solute
For the same size difference the
Size difference smaller atom gives a greater
strengthening effect
Size effect depends on:
Concentration of the solute (c)
~c
σy ∝
200 Sn (1.51)
Matrix: Cu (r = 1.28 Å) More the size difference, more
the intensity of stress field
Be (1.12)
150 around solute atoms and more is
the hardening effect.
σy (MPa) →
Large the concentration

difference, more obstacles to
100
dislocations motion and strength
Zn (1.31) increases (Increase in σY is
proportional to concentration of
50 the solute).
(Values in parenthesis are atomic radius values in Å)
Solute Concentration (Atom %) → Solute strengthening of Cu crystal

10 20 30 40 by solutes of different sizes
0
By ↑ σi (lattice friction)
X
↑ σy
σ →
Solute atoms ↑ level of σ - ε curve
ε →
Often produce Yield Point Phenomenon
σ →
ε →
Relative strengthening effect of Interstitial and Substitutional atoms
Interstitial solute atoms have a non-spherical distortion field and can elastically interact
with both edge and screw dislocations. Hence they give a higher hardening effect (per
unit concentration) as compared to substitutional atoms which have (approximately) a
spherical distortion field.
Interstitial
Substitutional
Relative strengthening effect / unit concentration
Non− spherical distortion field

Interstitial
 → 3Gsolute
Solute atoms
Substitutional   →
Spherical distortion field Gsolute / 10
Hardening of Precipitates
Precipitates may be coherent, semi-coherent or incoherent. Coherent (& semi-coherent)
precipitates are associated with coherency stresses.
Dislocations cannot glide through incoherent precipitates.
Inclusions behave similar to incoherent precipitates in this regard (precipitates are part of the
system, whilst inclusions are external to the alloy system).
A pinned dislocation (at a precipitate) has to either climb over it (which becomes favourable
at high temperatures) or has to bow around it.
Glide through the precipitate → If the precipitate is coherent with the matrix
Dislocation
Get pinned by the precipitate
Only if slip plane is continuous from the matrix through the precipitate ⇒ precipitate is coherent with
the matrix.
Stress to move the dislocation through the precipitate is ~ that to move it in the matrix (though it is
usually higher as precipitates can be intermetallic compounds).
Usually during precipitation the precipitate is coherent only when it is small and becomes incoherent on
growth.
Small Large
 Growth
→  Growth
→
Coherent Partially coherent Incoherent
Glide of the dislocation causes a displacement of the upper part of the precipitate w.r.t the lower part by
b → ~ cutting of the precipitate.
Schematic views
→ edge dislocation glide through a coherent precipitate
b Precipitate particle
b
If the particle is sheared, then how does the hardening effect come about?
We have seen that as the dislocation glides through the precipitate it is sheared.
If the precipitate is sheared, then how does it offer any resistance to the motion of
the dislocation? I.e. how can this lead to a hardening effect?
The hardening effect due to a precipitate comes about due to many factors (many of
which are system specific). The important ones are listed in the tree below.
Glide through the precipitate → If the precipitate is coherent with the matrix
Dislocation
Get pinned by the precipitate
Increase in surface area due to particle shearing
Hardening effect
Part of the dislocation line segment (inside the
precipitate) could face a higher PN stress
Orowan bowing mechanism : Pinning effect
Dislocations can bow around widely separated inclusions. In this process they leave
dislocation loops around the inclusions, thus leading to an increase in dislocation
density. This is known as the Orowan bowing mechanism as shown in the figure
below. (This is in ‘some sense’ similar to the Frank-Read mechanism).
The next dislocation arriving (similar to the first one), feels a repulsion from the
dislocation loop and hence the stress required to drive further dislocations increases.
Additionally, the effective separation distance (through which the dislocation has to
bow) reduces from ‘d’ to ‘d1’.
Precipitate Hardening effect
The hardening effect of precipitates can arise in many ways as below:
Lattice Resistance: the dislocation may face an increased lattice friction stress in
the precipitate.
Chemical Strengthening: arises from additional interface created on shearing
Stacking-fault Strengthening: due to difference between stacking-fault energy
between particle and matrix when these are both FCC or HCP (when dislocations
are split into partials)
Modulus Hardening: due to difference in elastic moduli of the matrix and particle
Coherency Strengthening: due to elastic coherency strains surrounding the particle
Order Strengthening: due to additional work required to create an APB in case of
dislocations passing through precipitates which have an ordered lattice
Strengthening by Dispersoids
In dispersion hardening, the hard particles are mixed with matrix powder and
consolidated and processed by powder metallurgy techniques.
Example: Thoria dispersed Nickel → Fine particles of Thoria are dispersed in the
nickel matrix and the inter particle distance is enough to hinder the dislocation
movement thereby increasing the strength up to 0.9 times Tm (Tm in 0C).
In dispersion hardening, dispersoids are incoherent with the matrix and
dislocations cannot glide through these dispersoids and gets pinned.
A pinned dislocation (at a precipitate) has to either climb over it (which becomes
favorable at high temperatures) or has to bow around it (Orowan’s Mechanism of
Dispersion Hardening)
Dislocation loop exert a back stress on dislocation which needs to be overcome for
additional slip to take place and this causes hardening.
Dislocation
Direction of
Dislocation Dispersoid
Motion Dislocation
Loop
Strain Hardening : Forest Dislocations
What causes Strain hardening? → multiplication of dislocations
Strain hardening
Annealed material Stronger material
   →
Cold work
ρ dislocatio n ~ (10 − 10 )
6 9
ρ dislocatio n ~ (10 12 − 10 14 )
Why increase in dislocation density ?
Why strain hardening ? X
If dislocations were to leave the surface

of the crystal by slip / glide then the
dislocation density should decrease
σ →
on plastic deformation →
but observation is contrary to this
This implies some sources of dislocation

multiplication / creation should exist ε →
Some specific sources/methods of formation/multiplication of dislocations include
It is difficult to obtain crystals without dislocations (under special conditions whiskers
have been grown without dislocations).
Dislocation can arise by/form:
Solidification (errors in the formation of a perfect crystal lattice)
Plastic deformation (nucleation and multiplication)
Irradiation
High stresses
► Heterogeneous nucleation at second phase particles
► During phase transformation
Frank-Read source
Orowan bowing mechanism
Strain hardening
We had noted that stress to cause further plastic deformation (flow stress) increases
with strain → strain hardening. This happens at
Dislocations moving in non-parallel slip planes can intersect with each other →
results in an increase in stress required to cause further plastic deformation ⇒
Strain Hardening / work hardening
One such mechanism by which the dislocation is immobilized is the Lomer-
Cottrell barrier.
Strengthening by Grain Boundary
Grain boundary is the boundary between two grains in a polycrystalline aggregate and
this is the region of a disturbed lattice which is of few atomic diameters distance.
There are two important ways in which grain boundary acts as a barrier to the
dislocation
Difficulty for a dislocation to pass through two different grain orientations (need to
change the direction)
The atomic disorder within a grain boundary region contributes to a discontinuity of
slip planes from one grain to other.
Dislocation pile-up at grain boundaries

Hall – Petch Relation
A fine grained material is harder and stronger than one that is coarse grained since greater
amounts of grain boundaries in the fine grained materials impede dislocation motion.
The general relationship between yield stress (tensile strength) and grain size was proposed
by Hall and Petch, which is known as Hall-Petch relation.
1
−
σ Yield = σ o + k yd 2
Where,
σyield = Yield stress

σo = Friction stress or resistance
to dislocation motion
ky = Locking parameter or the
hardening contribution
from the grain boundary
d = Grain diameter
Influence of grain size on yield strength of 70Cu-30Zn Brass
Yield-Point Phenomenon
Many metals, particularly low carbon steel, show a localized, heterogeneous type of
transition from elastic to plastic deformation which produces a yield point in the stress-
strain curve.
For these metals, load increases steadily
with elastic strain, drops suddenly,
fluctuates around a certain value (Plateau Upper Yield Yield Elongation
region) and then rises with further strain. Point
The load at which sudden drop occurs
corresponds to the upper yield point, the
constant load is called the lower yield
Lower Yield
point, and the elongation that occurs at Point
constant load is called the yield-point
elongation.
At the upper yield point, plastic
deformation is initiated forming a
discrete band of deformed metal, known Lüders bands
as Lüders band/Hartmann lines or
stretcher strains Unyielded
Metal
Then these bands propagate to cover the
entire length of the specimen.
Explanation of Yield-Point Phenomenon in terms of Dislocation Behavior
Solute atoms in a solution (Carbon or Nitrogen atoms in iron) readily diffuse into the
minimum energy positions (distorted regions near the dislocations line) while the material is
stress-free.
The interaction between the solute atoms and the dislocation line is very strong and some
breakaway stress is needed to pull a dislocation line away from the line of solute atoms.
When external stress is applied, the dislocations ‘tears off’ its pinning points and the stress
required for this defines the upper yield strength.
After the dislocation has left its pinning points, it is more mobile than before, and the yield
strength reduces (lower yield strength).
The dislocations released into the slip planes pile up at the grain boundaries and produces a
stress concentration at its tip which in turn increases the stress in the neighboring grain,
allowing dislocations there to become mobile as well.
This results in the formation of narrow bands of localized deformation, so-called Lüders
bands within the material.
This alternation between local hardening by dislocation pile-up and removal of this
deformation obstacle by tearing off dislocations in the neighboring grain causes a strongly
serrated flow curve (yield point elongation).
Only after the Lüders bands have spread throughout the material and all dislocations are
removed from their pinning points, the yield strength increases beyond the lower yield
strength by work hardening.
Preferred Orientation (Texture)
In Latin, textor means weaver and in materials science, texture is the way in which a
polycrystalline material is woven.
Polycrystalline material is constituted from a large number of small crystallites (limited

volume of material in which periodicity of crystal lattice is present). Each of these crystallites
has a specific orientation of the crystal lattice .
A fully textured sheet the cube texture

A texture-less sheet
(001) ║ ND (Sheet Normal Direction)
(Configuration like a powder aggregate)
[100] ║ RD (Sheet Rolling Direction)
When a metal undergoes a severe amount of deformation, its crystallographic planes tend to
orient themselves in a preferred manner with respect to the direction of maximum strain; in
which case the material is said to have a “texture”.
The type of preferred orientation which is developed depends mainly on number and type of
slip systems available, principal strains, temperature of deformation and type of texture
present prior to deformation.
For uniaxial deformation or other processes, texture is expressed in terms of miller indices
of directions [uvw] aligned along the specimen axis, also called Fiber texture.
Fiber texture is symmetrical to the wire axis. BCC metals have a fiber texture with <110>
direction parallel to the wire axis. FCC metals have double fiber texture with both <111>
and <100> directions parallel to the fiber axis.
Texture develops or changes due to: (i) Crystallization/ solidification (from a non-
crystalline / liquid state) (ii) Plastic deformation (by slip and twinning) (iii) Annealing
(from the same phase) (iv) Phase transformation (from a different phase)
Texture resulting from plastic deformation is strongly dependent on available slip and
twinning systems but is not affected by processing variables like die angle, roll diameter,
speed etc. Thus, same texture is produced whether a rod is made by rolling or drawing.
Recrystallization of a cold worked metal produces a texture which is different from and
stronger than that existing in the deformed metal. This is called an annealing or
Recrystallization texture.
Preferred Orientations are determined by X-Ray Methods.
Diffraction patterns from a single crystal is in the form of isolated spots, while for a
randomly oriented polycrystalline material, the diffraction pattern is in the form of
concentric rings (Debye-Scherrer rings) corresponding to different planes and the intensity
of rings will be uniform for all angles.
Textured polycrystalline materials are somewhat in-between. Here the diffraction pattern
consists of Debye-Scherrer rings, but the intensity distribution is non-uniform along the
circumference of the rings.
Diffraction pattern from the crystals of materials

Hot Working
Plastic deformation which is carried out under conditions of temperature and strain rate
such that recovery processes occur substantially so that large strains can be achieved with
essentially no strain hardening.
Normally performed at temperature >0.6Tm & at high strain rates in the range of 0.5-500 s-1
Advantages of Hot Working
Larger deformation can be accomplished and more rapidly by hot working since the metal
is in plastic state.
Porosity of the metal is considerably minimized.
Concentrated impurities, if any in the metal are disintegrated and distributed throughout the
metal.
Grain structure of the metal is refined and physical properties is improved.
No residual stresses in the material
Disadvantages of Hot Working

Poor surface finish and loss of metal due to rapid oxidation or scale formation on the metal
surface
Close tolerances cannot be maintained.
It involves excessive expenditure on account of high cost of tooling. This, however, is
compensated by the high production rate and better quality of products.
Warm Working
Warm working is the plastic deformation of a meta at temperature below the temperature
range of recrystallization and above the room temperature i.e. intermediate to hot and cold
working.
Advantages compared to Cold Working

Combines the advantages of both hot and cold working into one operation.
Fewer number of annealing operation ( because of less strain hardening )
Lesser loads on tooling and equipment
Greater metal ductility
Advantages compared to Hot Working

Improved dimensional control,
Lower energy costs.
Better precision of components
Lesser scaling and decarburization on parts
Better surface finish
Lesser thermal shock on tooling
Lesser thermal fatigue to tooling, and so greater life of tooling.
Cold Working
Plastic deformation which is carried out in a temperature region and over a time interval
such that the strain hardening is not relieved is called cold work.
Normally performed at room temperature but in general < 0.3Tm, where recovery is limited
and recrystallization does not occur.
Advantages of Cold Working
Due to work hardening Strength and hardness of the metal are increased.
It is an ideal method for increasing hardness of those metals which do not respond to the
heat treatment.
Better dimensional control is possible because the reduction in size is not much.
Provide fine grain size and good surface finish (No oxidation takes place).
Handling is easier because of low operating temperature.
Directional properties can be imparted.
Disadvantages of Cold Working
Only ductile metals can be shaped through cold working.
Over-working of metal results in brittleness and it has to be annealed to remove the same.
Subsequent heat treatment is mostly needed to remove the residual stresses set up during
cold working.
Higher forces and heavier and more powerful equipment are required for deformation.
Recovery, Recrystallization & Grain Growth
Introduction
Plastic deformation in the temperature range (0.3 – 0.5) Tm → COLD WORK
Point defects and dislocations have strain energy associated with them
(1 -10) % of the energy expended in plastic deformation is stored in the form of
strain energy (in these defects) → The material becomes battery of energy..!
The cold worked material is in a micro structurally metastable state.
Depending on the severity of the cold work the dislocation density can increase 4-6
orders of magnitude more. The material becomes stronger, but less ductile.
The cold worked material is stronger (harder), but is brittle.
Heating the material (typically below 0.5Tm) is and holding for sufficient time is a
heat treatment process called annealing.
Depending on the temperature of annealing processes like Recovery at lower
temperatures) or Recrystallization (at higher temperatures) may take place. During
these processes the material tends to go from a micro structurally metastable state to
a lower energy state (towards a stable state).
Further ‘annealing’ of the recrystallized material can lead to grain growth.
Annealed material Stronger material
Cold
 →
work
ρ dislocation ~ (106 − 109 ) ρ dislocation ~ (1012 − 1014 )

Introduction
↑ point defect density

Material tends to lose
Cold work Anneal
the stored strain energy
↑ dislocation density
Increase in strength Softening of the material

of the material
During cold work the point defect density (vacancies, self interstitials…) and dislocation
density increase. Typical cold working techniques are rolling, forging, extrusion etc.
Cold working is typically done on ductile metals (e.g. Al, Cu, Ni)
Low temperature
Recovery
Cold work Anneal
Recrystallization
High temperature
Overview of processes taking place during annealing of cold
worked material and the driving force for these processes
Driving force is free energy stored in point defects

Cold work Anneal Recovery
and dislocations
Driving force is free energy stored in dislocations Recrystallization
Driving force is free energy stored in grain boundaries Grain growth
Cold work
↑ Strength ↑ Hardness ↑ Electrical resistance ↓ Ductility
Changes occur to almost all physical and mechanical properties

Recovery
Recovery takes place at low temperatures of annealing
“Apparently no change in microstructure”
Excess point defects created during Cold work are absorbed:
► at surface or grain boundaries
► by dislocation climb
Random dislocations of opposite sign come together and annihilate each other
Dislocations of same sign arrange into low energy configurations:
► Edge → Tilt boundaries
► Screw → Twist boundaries
POLYGONIZATION
Overall reduction in dislocation density is small
At the early stage of annealing of cold formed metals, external thermal energy
permits the dislocations to move and form the boundaries of a polygonized subgrain
structure while the dislocation density stays almost unchanged.
This process also removes the residual stresses formed due to cold working
significant. The recovering of physical and mechanical properties varies with the
temperature and time.
POLYGONIZATION
Bent crystal
Low angle grain boundaries

Recrystallization
Trecrystallization ∈ (0.3 – 0.5) Tm
“Nucleation” and growth of new, strain free crystals
Nucleation of new grains in the usual sense may not be present and grain boundary
migrates into a region of higher dislocation density
∆G (recrystallization) = G (deformed material) – G (undeformed material)
TRecrystallization is the temperature at which 50 % of the material recrystallizes in 1
hour
Region of lower
Region of higher dislocation density
dislocation density
Direction of grain
boundary migration
Recrystallization
Deformation ↑ ⇒ recrystallization temperature (Trecrystallization) ↓
Initial grain size ↓ ⇒ recrystallization temperature ↓
High cold work + low initial grain size ⇒ finer recrystallized grains
↑ cold work temperature ⇒ lower strain energy stored
⇒ ↑ recrystallization temperature
Rate of recrystallization = exponential function of temperature
Trecrystallization = strong function of the purity of the material
Trecrystallization (very pure materials) ~ 0.3 Tm
Trecrystallization (impure) ~ (0.5 – 0.6) Tm
► Trecrystallization (99.999% pure Al) ~ 75oC

Trecrystallization (commercial purity) ~ 275oC
The impurity atoms segregate to the grain boundary and retard their motion →
Solute drag (can be used to retain strength of materials at high temperatures)
Second phase particles also pin down the grain boundary during its migration
Hot Work and Cold Work
Often the range is further subdivided into Hot, Cold and Warm working as in the figure
Hot Work Plastic deformation above TRecrystallization

Cold Work Plastic deformation below TRecrystallization
Hot Work
− 0.9 Tm
When a metal is hot worked. The conditions of deformation are
− 0.8 Tm such that the sample is soft and ductile. The effects of strain
− 0.7 Tm hardening are negated by dynamic and static processes (which keep
the sample ductile)
− 0.6 Tm
The lower limit of temperature for hot working is taken as 0.6 Tm
Warm − 0.5 Tm
Working − 0.4 Tm Recrystallization temperature (~ 0.4 Tm)
− 0.3 Tm
Cold Work
− 0.2 Tm The effects of strain hardening is not negated. Recovery

mechanisms involve mainly motion of point defects.
− 0.1 Tm
Upper limit ►0.3 Tm
Grain Growth
Large grains have lower free energy than small grains. This is associated with the
reduction of the amount of grain boundary.
Therefore, under ideal conditions, the lower energy state for a metal would be as a
single crystal. This is driving force for grain growth.
Opposing this force is the rigidity of the lattice. As the temperature increases, the
rigidity of the lattice decreases and the rate of grain growth is more rapid.
At any given temperature there is a maximum grain size at which these two effects are
in equilibrium
↓ Heating Time↓
↓ Degree of prior deformation ↑
Grain size →
Grain growth ↓ Time at temperature↑
↓ Annealing temperature↓
↓ Insoluble impurities↑ Temperature →
Effect of temperature on recrystallized grain size

Summary
Electical conductivity
Internal stress
Ductility
Tensile strength
Cold work Recovery Recrystallization Grain growth

Questions ?
1. Cite the primary differences between elastic, anelastic, and plastic deformation
behaviors.
2. Define Slip and Slip system. Give the slip systems of BCC, FCC and HCP
3. Define Twinning. Give the preferred twinning plane and twinning directions of
BCC, FCC and HCP
4. It is possible to have both slip and twinning occur in the same grain? Explain
5. Which properties would be affected by preferred orientation and why?
6. Explain the reason for the increase in ductility of most metals as the temperature
is raised.
7. A piece of copper originally 305 mm (12 in.) long is pulled in tension with a
stress of 276 MPa (40,000 psi). If the deformation is entirely elastic, what will be
the resultant elongation? [E for copper is 110 Gpa]
8. Make a schematic plot showing the tensile engineering stress–strain behavior for
a typical metal alloy to the point of fracture. Now superimpose on this plot a
schematic compressive engineering stress–strain curve for the same alloy. Explain
any differences between the two curves.
Questions ?
9. Which of the following is the slip system for the simple cubic crystal structure?
Why? {100} <110>, {110} <110>, {100} <010>, {110} <111>.
10. Explain the difference between resolved shear stress and critical resolved shear
stress. Derive the expression for critical resolved shear stress.
11. Would you expect a crystalline ceramic material to strain harden at room
temperature? Why or why not?
12. Briefly explain why some metals (i.e., lead and tin) do not strain harden when
deformed at room temperature.
13. Sometimes cosφ cosλ in CRSS equation is termed the Schmid factor. Determine
the magnitude of the Schmid factor for an FCC single crystal oriented with its
[120] direction parallel to the loading axis.
14. Consider two edge dislocations of opposite sign and having slip planes that are
separated by several atomic distances as indicated in the diagram. Briefly describe
the defect that results when these two dislocations become aligned with each
other.
Questions ?
15. Is it possible for two screw dislocations of opposite sign to annihilate each other?
Explain your answer.
16. For each of edge, screw, and mixed dislocations, cite the relationship between the
direction of the applied shear stress and the direction of dislocation line motion.
17. Consider a single crystal of nickel oriented such that a tensile stress
−
is applied
along a [001] direction. If slip occurs on a (111) plane and in a [1 01 ] direction
and is initiated at an applied tensile stress of 13.9 Mpa. Compute the critical
resolved shear stress.
18. A single crystal of a metal that has the BCC crystal structure is oriented such that
a tensile stress is applied in the [100] direction. If the
−
magnitude of this stress is
4.0 MPa, compute the− resolved shear stress in the [111] direction on each of the
(110), (011), and (10 1) planes. On the basis of these resolved shear stress values,
which slip system(s) is (are) most favorably oriented.
19. List four major differences between deformation by twinning and deformation by
slip relative to mechanism, conditions of occurrence, and final result.
20. Briefly explain why HCP metals are typically more brittle than FCC and BCC
metals.
Questions ?
21. Describe in your own words the three strengthening mechanisms discussed in this
chapter (i.e., grain size reduction, solid-solution strengthening, and strain
hardening). Be sure to explain how dislocations are involved in each of the
strengthening techniques.
22. Two previously undeformed cylindrical specimens of an alloy are to be strain
hardened by reducing their cross-sectional areas (while maintaining their circular
cross sections). For one specimen, the initial and deformed radii are 15 mm and
12 mm, respectively. The second specimen, with an initial radius of 11 mm, must
have the same deformed hardness as the first specimen; compute the second
specimen’s radius after deformation.
23. Briefly cite the differences between recovery and recrystallization processes.
24. Explain the differences in grain structure for a metal that has been cold worked
and one that has been cold worked and then recrystallized.
25. What is the driving force for recrystallization? And for grain growth?
Avala Lava Kumar
E-mail : lavakumar.vssut@gmail.com
Introduction
An alloy is a substance that has metallic properties and is composed of two or
more chemical elements, of which at least one is a metal.
An alloy system contains all the alloys that can be formed by several elements
combined in all possible proportions. If the system is made up of two elements, it
is called a binary alloy system; three elements, a ternary alloy system; etc.
Taking only 45 of the most common metals, any combination of two gives 990
binary systems. Combinations of three give over 14,000 ternary systems.
However, in each system, a large number of different alloys are possible. If the
composition is varied by 1 percent, each binary system will yield 100 different
alloys.
Since commercial alloys often contain many elements, it is apparent that the
number of possible alloys is almost infinite.
Alloys may be homogeneous (uniform) or mixtures. If the alloy is homogeneous it
will consist of a single phase, and if it is a mixture it will be a combination of
several phases.
The uniformity of an alloy phase is not determined on an atomic scale, such as the
composition of each unit lattice cell, but rather on a much larger scale.
Phase
A phase is anything which is homogeneous and physically distinct.
Any structure which is visible as physically distinct microscopically may be
considered as a phase
For most pure elements the term phase is synonymous with state. There is,
therefore, for pure elements, a gaseous, liquid, and solid phase.
Some metals are allotropic in the solid state and will have different solid
phases. When the metal undergoes a change in crystal structure, it undergoes a
phase change since each type of crystal structure is physically distinct.
In a pure material when other elements are added intentionally they are called
alloying elements*
Alloying elements are added to improve certain properties of the pure element
The alloying element can be accommodated in one of the three possibilities as
shown in the figure below
* When added small quantity it is often called doping

‘In Principle’ there is no difference between an ‘impurity’ and ‘alloying’
Classification of alloys
Segregation / phase separation
1
Interstitial
Disordered
Element Added 2 Solid solution
Ordered
Substitutional
3
Compound /Intermediate structure
(new crystal structure)
1 Segregation / phase separation
The added element does not dissolve* in the parent/matrix phase →

in may form a separate phase**
in a polycrystal it may go to the grain boundary
in may segregate to other defects like dislocation cores etc.
The solubility in the case of a substitutional solid solution is given by Hume-
Rothery rules (considered soon)
2 Solid Solutions
Any solution is composed of two parts: a solute and a solvent. The solute is the
minor part of the solution or the material which is dissolved, while the solvent
constituents the major portion of the solution.
The most common solutions involve water as the solvent, such as sugar or salt
dissolved in water.
There are three possible conditions for a solution: unsaturated, saturated, and
supersaturated.
If the solvent is dissolving less of the solute than it could dissolve at a given
temperature and pressure, it is said to be unsaturated.
If it is dissolving the limiting amount of solute, it is saturated.
If it is dissolving more of the solute than it should, under equilibrium conditions,
the solution is supersaturated.
The supersaturated condition is an unstable one, and given enough time or a little
energy, the solution tends to become stable or saturated by rejecting or
precipitating the excess solute.
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.
There are two types solid solutions, substitutional and interstitial.
Mechanical Equilibrium of a Rectangular Block
A Ball on a plane
Neutral Equilibrium
Centre B
Of
Gravity
C1 C2 C3
CG)→
B
Potential Energy = f(height of CG
Unstable
Stable
A
Lowest CG of all possible
states
Metastable state C
Configuration→
Substitutional Solid Solution
In this type of solution, the atoms of the solute substitute for atoms of the solvent
in the lattice structure of the solvent.
For example, silver atoms may substitute for gold atoms without losing the f.c.c
structure of gold, and gold atoms may substitute for silver atoms in the f.c.c lattice
structure of silver.
All alloys in the silver-gold system consist of an f.c.c lattice with silver and gold
atoms distributed at random through the lattice structure. This entire system
consists of a continuous series of solid solutions.
Several factors are now known, largely through the work of Hume-Rothery, that
control the range of solubility in alloy systems.
Empirical (precise) rules for the formation of substitutional solid solution
The solute and solvent atoms do not differ by more than 15% in diameter
The electro-negativity difference between the elements is small
The valency and crystal structure of the elements is same
Additional rule
Element with higher valency is dissolved more in an element of lower valency
rather than vice-versa
Hume Rothery Rules
CRYSTAL-STRUCTURE FACTOR : complete solid solubility of two elements is
never attained unless the elements have the same type of crystal lattice structure.
RELATIVE-SIZE FACTOR : The size factor is favorable for solid solution
formation when the difference in atomic radii is less than about 15%
r −r 
mismatch =  solute solvent  × 100 ≤ 15
 rsolvent 
VALENCY RULE : a metal will dissolve a metal of higher valency to greater
extent than one of lower valency. The solute and solvent atoms should typically
have the same valance in order to achieve maximum solubility.
ELECTRONEGATIVITY RULE : Electro negativity difference close to ‘0’ gives
maximum solubility. The more electropositive one element and the more
electronegative the other, the greater is the likelihood that they will form an inter
metallic compound instead of a substitutional solid solution. The solute and the
solvent should lie relatively close in the electrochemical series.
Hume Rothery Rules
Examples of pairs of elements satisfying Hume Rothery rules and forming complete solid
solution in all proportions
Crystal Radius of
System Valency Electronegativity
structure atoms (Å)
Ag FCC 1.44 1 1.9
Ag-Au
Au FCC 1.44 1 2.4
Cu FCC 1.28 1 1.9

Cu-Ni
Ni FCC 1.25 2 1.8
Ge DC 1.22 4 1.8
Ge-Si
Si DC 1.18 4 1.8
A continuous series of solid solutions may not form even if the above conditions are satisfied
e.g. Cu-γ Fe
Interstitial Solid Solutions
The second species added goes into the voids of the parent lattice
E.g. Octahedral and tetrahedral voids in CCP, HCP (& BCC) crystals
(E.g. of solvents: Fe, Mo, Cr etc.)
E.g. B (r = 0.97 Å) C (r = 0.77 Å), N (r = 0.71 Å), O (r = 0.66 Å), H (r = 0.46 Å)
If the solute atom has a diameter < 0.59 rhost then extensive solubility is expected
(may or may not happen!)
Solubility for interstitial atoms is more in transition elements (Fe, Ti, V, Zr, Ni, W,
U, Mn, Cr) → due to electronic structure (incomplete inner shell)
C is especially insoluble in most non-transition elements
FCC OV FCC TV
BCC TV BCC OV
o
B r = 0.81 A
B
o o o o
C r = 0.77 A
C
N r = 0.71 A
N
O r = 0.66 A
O
H r = 0.46 A
H
3 Compound /Intermediate structure
Chemical compounds are combination of positive and negative valence elements.
Intermetallic compounds can be very different from the normal chemical
compounds (e.g. H2O).
Most compounds like pure metals, the cooling curve for a compound is similar to
that for a pure metal.
Valency compounds (or)

Intermetallic compounds
Mg2Sn, Mg2Pb, MgS etc.
A
Interstitial compounds: Hägg
Determined by Rx / RM ratio
B
W2C, VC, Fe4N etc.
Chemical
compounds Electron compounds
C
specific e/a ratio [3:2, 21:13, 7:4]
AgZn, Cu9Al4, Au3Sn
D
Others
Laves phases, Sigma Phases etc.,
A Valency compounds (Intermetallic compounds)
The following includes features distinguishing them from solid solutions
Different crystal lattice as compared to the components

Most chemical compounds have complex crystal structures
Each component has a specific location in the lattice
Composition can be specified by a simple formula → AnBm : Mg2Sn, Mg2Pb, Ni3(Al,Ti)
(m,n are small whole numbers)
Different properties than the components
Constant melting point and dissociation temperature
Accompanied by substantial thermal effect
Typically formed by elements with very different electronic and crystal structures
The bonding in intermetallic compounds is usually metallic
The bonding between a metal and a non-metal could also be metallic
A large number of intermetallic compounds do not obey valency rules or have a
constant composition (thus distinguishing them from usual chemical compounds)
In some sense the tendency to form compounds is opposite of that to form solid solutions!
B Interstitial compounds: Hägg Phases
Transition metals form compounds with elements with small atomic size (H, C, N, B)
Formulae:
M4X → Fe4N, Mn4N
M2X → W2C, Mo2C, Fe2N
MX → WC, VC, TiC, NbC, TiN
The crystal structure depends on Rx /RM ratio
If Rx /RM < 0.59 → Simple crystal lattices (Cubic, Hexagonal)
Non-metal occupies specific interstitial sites in the cubic or hexagonal crystal
If Rx /RM > 0.59 → Complex crystal structures (e.g. Fe3C)
Apart from size factor valency of the interstitial atom also seems to play some role
Typically interstitial phases have a variable composition (the chemical formula indicates the
maximum amount of non-metal in the structure)
Properties include:
High electrical conductivity (with decreasing conductivity with increasing temperature as for a metal)
Metallic lustre
Many of the interstitial phases are hard (e.g. WC, VC)
The carbides have high melting point
Some covalent character to the bonding in some of these phases
Interstitial solid solutions on the other hand have much lower content of the interstitial atoms and the
crystal structure of the parent is retained
C Electron Compounds
It have a definite ratio of valence electrons to atoms and are therefore called electron
compounds.
These compounds are formed usually in:
Monovalent metals (Cu, Ag, Au, Li, Na)
Transition metals (Fe, Co, Mn)
Other metals with a valency values between 2-5
Alloys of Cu, Ag, Au frequently form electron compounds
These compounds have specific ratios for: number of valence electrons/atoms →
3:2 - B.C.C → (E.g. AgCd, AgZn, Cu3Al, FeAl etc.,)
21:13 – complex CUBIC → (E.g. Ag5Cd8, Cu9Al4, Fe5Zn21, Ni5Zn21 etc.,)
7:4 – H.C.P → (E.g. AuZn3, AgCd3, Cu3Si, Ag3Sn)
These compounds can form over a wide range of compositions
For example, in the compound AgZn, the atom of silver has one valence electron while that
of zinc has two valence electrons so that the two atoms of the compound will have three
valence electrons, or an electron-to-atom ration of 3:2.
Consider, In the compound Cu9Al4, each atom of copper has one valence electron and each
atom of aluminium three valence electrons, so that the 13 atoms that make up the
compound have 21 valence electrons, or an electron-to-atom ration of 21:13.
D Others..!
Laves Phases
Laves phases have a general formula of AB2 , for exmple MgCu2(cubic), MgZn2
(hexagonal), MgNi2 (hexagonal).
Sigma Phases
Sigma phases has a very complex crystal structure and is very brittle. This phase can act as
a source of embrittlement in some alloys such as steels.
Summary
Alloy Structure
Homogeneous Mixture
Solid solution Intermediate

alloy phase Any combination of solid phases
segregation
Solid solution
Substitutional Interstitial
Intermediate alloy
Intermetalic Interstitial Electron

Questions..?
1. What is an ALLOY?
2. What is a solid solution?
3. How many types of solid solutions are there? Give examples for each of them?
4. What are Hume-Rothery rules?
5. If two metals have very different electronegetavity will they form a solid solution?
6. How does valence of an element affect the solid solubility?
7. What is an ideal solution?
8. What is an intermetallic compound?
9. What is Hume-Rothery phase?
10. The atomic radius of Cu is 0.128 nm and electronegativity is 1.8. What is the
probability of lead, Pb (atomic radius 0.175 nm, electronegativity 1.6) and zinc, Zn
(atomic radius 0.133 nm, electronegativity 1.7) forming solid solution with
copper?
11. Nickel, Aluminium & Copper have face cantered cubic structure yet Ni is soluble
in copper whereas Al has only a limited solubility. Explain why it is so?
Questions..?
12. Predict the relative degree of solid solubility of the following elements in Fe (r = 0.124 nm,
electronegativity 1.7). Ni (atomic radius, r = 0.125 nm, electronegativity 1.8), Cr (r = 0.125
nm, electronegativity 1.6), Ti (r = 0.147 nm, electronegativity 1.3)
13. What kind of metals form carbides?
14. FCC crystals have more packing density than BCC crystal, yet why solubility of carbon in
FCC form of iron is higher than in its BCC form?
15. What is the effect of plastic deformation on lattice parameter?
Avala Lava Kumar*
Introduction
Phase diagrams are an important tool in the armory of an materials scientist
In the simplest sense a phase diagram demarcates regions of existence of various
phases. (Phase diagrams are maps)
Phase diagrams are also referred to as “equilibrium diagrams” or “constitutional
diagrams”. This usage requires special attention: through the term used is
“equilibrium”, in practical terms the equilibrium is not global equilibrium but
Microstructural level equilibrium.
Broadly two kinds of phase diagrams can be differentiated*→ those involving time
and those which do not involve time.
In this chapter we shall deal with the phase diagrams not involving time.
This type can be further sub classified into:
Those with composition as a variable (e.g. T vs. %Composition)
Those without composition as a variable (e.g. P vs. T)
Time-Temperature-Transformation (TTT) diagrams and Continuous-Cooling-
Transformation (CCT) diagrams involve time. These diagrams will be considered
in the chapter on Heat treatment.
*This is form a convenience in understanding point of view

Definitions
Components of a system
Independent chemical species which comprise the system. These could be Elements, Ions,
Compounds
Example: Au-Cu system : Components →Au, Cu (elements)
Ice-water system : Component→H2O (compound)
Al2O3-Cr2O3 system : Components→Al2O3, Cr2O3
Phase
A physically homogeneous and distinct portion of a material system (e.g. gas, crystal,
amorphous…)
Gases : Gaseous state always a single phase → mixed at atomic or molecule level.
Liquids: Liquid solution is a single phase → e.g. Nacl in H2O and Liquid mixtures consists
of two or more phases → e.g. Oil in water (no mixing at the atomic level)
Solids: In general due to several compositions and crystals structures many phases are
possible.
For the same composition different crystal structures represent different phases. E.g. Fe
(BCC) and Fe (FCC) are different phases
Definitions
What kinds of phases exist?
Based on state → Gas, Liquid, Solid

Based on atomic order → Amorphous, Quasi-crystalline, Crystalline
Based on band structure → Insulating, Semi-conducting, Semi-metallic, Metallic
Based on Property → Para-electric, Ferromagnetic, Superconducting
Based on stability → Stable, Metastable, Unstable
Also sometimes- Based on size/geometry of an entity → Nanocrystalline, mesoporous,
layered.
Phase transformation
Phase transformation is the change of one phase into another. For example
Water → Ice and α-Fe (BCC) → γ-Fe (FCC)
Grain
The single crystalline part of polycrystalline metal separated by similar entities by a grain
boundary
Definitions
Solute
The component of either a liquid or solid solution that is present to a lesser or minor extent;
the component that is dissolved in the solvent.
Solvent
The component of either a liquid or solid solution that is present to a greater or major
extent; the component that dissolves the solute.
System
System, has two meanings. First, ‘‘system’’ may refer to a specific body of material or
object. Or, it may relate to the series of possible alloys consisting of the same components,
but without regard to alloy composition
Solubility Limit
For many alloy systems and at some specific temperature, there is a maximum
concentration of solute atoms that may dissolve in the solvent to form a solid solution; this
is called a Solubility Limit.
Definitions
Microstructure
(Phases + defects + residual stress) & their distributions
Structures requiring magnifications in the region of 100 to 1000 times. (or) The distribution
of phases and defects in a material.
Phase diagram
Map that gives relationship between phases in equilibrium in a system as a function of T, P

and composition. Map demarcating regions of stability of various phases
Variables/Axis of phase diagrams
The axes can be:

Thermodynamic (T, P, V)
Kinetic (t) or Composition variables (C, %X)
In single component systems (unary systems) the usual variables are T & P
In phase diagrams used in materials science the usual variable are T & %X
In the study of phase transformation kinetics TTT diagrams or CCT diagrams are also used
where the axis are T & t
Definitions
System Components
Phase diagrams and the systems they describe are often classified and named for the
number (in Latin) of components in the system:
Number of components Name of system or diagram

One Unary
Two Binary
Three Ternary
Four Quaternary
Five Quinary
Six Sexinary
Seven Septenary
Eight Octanary
Nine Nonary
Ten Decinary
Coordinates of Phase Diagrams
Phase diagrams are usually plotted with temperature, in degrees centigrade or
Fahrenheit, as the ordinate and the alloy composition in weight percentage as the
abscissa.
The weight % of component A: weight of component A
WA = × 100
Σ Weight of all components
The atom (or mol)% of component A

number of atoms (or mols) of component A
XA = × 100
Σ number of atoms (or mols) of all components
The Conversion from weight percentage to atomic percentage may be made by the
following formulas:
M 
X Y 
Atomic percent of A = × 100 N
M  Atomic percent of B = ×100
X +Y  M 
N  X +Y 
N 
M = atomic weight of metal A & N = atomic weight of metal B

X = weight percentage of metal A & Y = weight percentage of metal B
Experimental Methods
Thermal Analysis
A plot is made of temperature vs. time, at constant composition, the resulting cooling curve will
show a change in slope when a phase change occurs because of the evolution of heat by the
phase change. This method seems to be best for determining the initial and final temperature of
solidification. Phase changes occurring solely in the solid state generally involve only small
heat changes, and other methods give more accurate results.
Metallographic Methods
This method consists in heating samples of an alloy to different temperatures, waiting for
equilibrium to be established, and then quickly cooling to retain their high temperature
structure. The samples are then examined microscopically. This method is difficulty to apply to
metals at high temperatures because the rapidly cooled samples do not always retain their high
temperature structure, and considerable skill is then required to interpret the observed
microstructure correctly.
X-ray diffraction
Since this method measures lattice dimensions, it will indicate the appearance of a new phase
either by the change in lattice dimension or by the appearance of a new crystal structure. This
method is simple, precise, and very useful in determining the changes in solid solubility with
temperature
Gibbs Phase Rule
The phase rule connects the Degrees of Freedom, the number of components in a
system and the number of phases present in a system via a simple equation.
To understand the phase rule one must understand the variables in the system along
with the degrees of freedom.
We start with a general definition of the phrase “degrees of freedom”.
Degrees of Freedom
The degree of freedom, F, are those externally controllable conditions of temperature,
pressure, and composition, which are independently variable and which must be
specified in order to completely define the equilibrium state of the system.
F=C–P+2 F – Degrees of Freedom

For a system in or C – Number of Components
equilibrium
F-C+P=2 P – Number of Phases
The degrees of freedom cannot be less than zero so that we have an upper limit to the
number of phases that can exist in equilibrium for a given system.
Gibbs Phase Rule
Variables in a phase diagram
o C – No. of components
o P – No. of phases
o F – No. of degrees of freedom
o Variables in the system = Composition variables + Thermodynamic variables
o Composition of a phase specified by (C – 1) variables (If the composition is expressed in
%ages then the total is 100% → there is one equation connecting the composition variables and we
need to specify only (C - 1) composition variables)
o No. of variables required to specify the composition of all phases: P(C – 1) (as there
are P phases and each phase needs the specification of (C – 1) variables)
o Thermodynamic variables = P + T (usually considered) = 2 (at constant pressure (e.g.
atmospheric pressure) the thermodynamic variable becomes 1)
o Total no. of variables in the system = P (C – 1) + 2
o F < no. of variables → F < P (C – 1) + 2
Gibbs Phase Rule
o For a system in equilibrium the chemical potential of each species is same in all the
phases
If α, β, γ… are phases, then: μA (α) = μA (β) = μA (γ)…..
Suppose there are 2 phases (α and β phases) and 3 components (A, B, C) in each phase then : μA(α) =
μA(β), μB(α) = μB(β), μC(α) = μC(β) → i.e. there are three equations. For each component there are (P –
1) equations and for C components the total number of equations is C(P – 1). In the above example the
number of equations is 3(2 – 1) = 3 equations.
F = (Total number of variables) – (number of relations between variables)
= [P(C – 1) + 2] – [C(P – 1)] = C – P + 2
In a single phase system F = Number of variables F=C–P+2
P↑ → F↓ (For a system with fixed number of components as the number phases
increases the degrees of freedom decreases.
It is worthwhile to clarify a few terms at this stage:

Components ‘can’ go on to make a phase (of course one can have single component phases as well e.g. BCC
iron phase)
Phases ‘can’ go on to make a microconstituent.
Microconstituents ‘can’ go on to make a microstructure (of course phases can also directly go on to make a
microstructure)
Gibbs Phase Rule
A way of understanding the Gibbs Phase Rule : P + F = C + 2
The degrees of freedom can be thought of as the difference between what you (can)
control and what the system controls
F = C+2 - P
Degrees of freedom = What you can control - What the system controls
Can control the no. of System decided how many
components added and P&T phases to produce given the
conditions
Variation of the number of degrees of freedom with number of components and number of phases
C=2 No. of Total Variables Degrees of freedom Degrees of freedom

Phases P(C-1)+2 C-P+2 C-P+1
1 3 3 2
2 4 2 1
3 5 1 0
4 6 0 Not possible
Unary Phase Diagram
Let us start with the simplest system possible: the unary system wherein there is just one
component.
Though there are many possibilities even in unary phase diagram (in terms of the axis and
phases), we shall only consider a T-P unary phase diagram.
Let us consider the water (H2O) unary

phase diagram
The Gibbs phase rule here is: F=C-P+2
(2 is for T&P) (no composition variables
here)
Along the 2 phase co-existence (at B & C) C
lines the degree of freedom (F) is 1 → i.e. B
we can chose either T or P and the other A
will be automatically fixed.
D
The 3 phase co-existence points (at A) are
invariant points with F=0. (Invariant point
implies they are fixed for a given system).
The single phase region at point D, T and P
can both be varied while still being in the
single phase region with F = 2.
Unary Phase Diagram
1600
δ
1200
Temperature ((ºC) 800 γ
400
α ε
0
50 100 150
Pressure / kbar
The above figure represents the phase diagram for pure iron. The triple point
temperature and pressure are 490ºC and 110 kbars, respectively. α, γ and ε
refer to ferrite, austenite and ε-iron, respectively. δ is simply the higher
temperature designation of α.
Binary Phase Diagram
Binary implies that there are two components.
Pressure changes often have little effect on the equilibrium of solid phases (unless
of course we apply ‘huge’ pressures).
Hence, binary phase diagrams are usually drawn at 1 atmosphere pressure.
The Gibbs phase rule is reduced to:
Variables are reduced to : F = C – P + 1 (1 is for T).
T & Composition (these are the usual variables in materials phase diagrams)
Phase rule for condensed phases F=C–P+1

For T
In the next page we consider the possible binary phase diagrams. These have been
classified based on:
Complete solubility in both liquid & solid states
Complete solubility in both liquid state, but limited solubility in the solid state
Limited solubility in both liquid & solid states
Overview of possible Binary Phase Diagram
Liquid State Solid State
Isomorphous Solid state analogue

of isomorphous
Complete Solubility in both Isomorphous with
liquid & Solid states ordering
Isomorphous with
Phase separation
Eutectic Eutectoid
Complete solubility in liquid
state but limited solubility
in the solid state
Peritectic Peritectoid
Monotectic Monotectoid
Limited solubility in both liquid

Syntectic
& Solid states
Metatectic
Isomorphous Phase Diagram
Isomorphous phase diagrams form when there is complete solid and liquid
solubility.
Complete solid solubility implies that the crystal structure of the two components
have to be same and Hume-Rothery rules to be followed.
Examples of systems forming isomorphous systems: Cu-Ni, Ag-Au, Ge-Si, Al2O3-
Cr2O3
Both the liquid and solid contain the components A and B.
In binary phase diagrams between two single phase regions there will be a two
phase region → In the isomorphous diagram between the liquid and solid state
there is the (Liquid + Solid) state.
The Liquid + Solid state is NOT a semi-solid state → it is a solid of fixed
composition and structure, in equilibrium with a liquid of fixed composition.
In some systems (e.g. Au-Ni system) there might be phase separation in the solid
state (i.e.,the complete solid solubility criterion may not be followed) → these will
be considered as a variation of the isomorphous system (with complete solubility
in the solid and the liquid state.
cooling curves : Isomorphous system
L
L S
L
L TL
L TL TNi
L+ S
Temperature (ºC)
ºC)
L S L+ S
Pure Ni
TS
S
TCu S TS S
Pure Cu Cu-20%Ni
Cu-10%Ni
t
Time (t)
Revision : Solidification (cooling) curves
Pure metal Alloy
L L Soldification
begins
TL
L S L+ S
Tm
TS
Solidification S
S
complete
Time (t) Time (t)

Isomorphous Phase Diagram
T and Composition can both be
varied while still being in the single C=1
phase region
P=2
C=2 F=0
P=1 (liquid) Liquidus 1457ºC
F=2 Liquid (L)
C=2
L+ S P=2 (L+S)
Temperature →
F=1
In the two phase
Solidus region, if we fix T
(and hence exhaust
1080ºC our DOF), the
composition of liquid
and solid in
equilibrium are
Solid (S) automatically fixed
(i.e. we have no
choice over
them).Alternatively
C=2 we can use our DOF
P=1 (Solid) to chose CL then T
F=2 Cu % Ni → Ni and Cs are
automatically fixed.
T and Composition can both be
varied while still being in the single
phase region
Tie line and Lever rule
Chemical Composition of Phases Tie Line Rule
To determine the actual chemical composition of the phases of an alloy, in

equilibrium at any specified temperature in a two phase region, draw a horizontal
temperature line, called a tie line, to the boundaries of the field . These points of
intersection are dropped to the base line, and the composition is read directly.
Relative Amounts of Each Phase Lever Rule
To determine the relative amounts of the two phases in equilibrium at any specified
temperature in a two phase region , draw a vertical line representing the alloy and a
horizontal temperature line to the boundaries of the field.
The vertical line will divide the horizontal line into two parts whose lengths are
inversely proportional to the amount of the phases present. This is also known as
Lever rule.
The point where the vertical line intersects the horizontal line may be considered
as the fulcrum of a lever system.
The relative lengths of the lever arms multiplied by the amounts of the phases
present must balance.
We draw a horizontal line (called the Tie Line)at the temperature of interest (say
T0). Let Tie line is XY.
Solid (crystal) of composition C 1 coexists with liquid of composition C 2
Note that tie lines can be drawn only in the two phase coexistence regions (fields).
Though they may be extended to mark the temperature.
To find the fractions of solid and liquid we use the lever rule.
The portion of the horizontal line in the Arm of the lever

proportional to the
Arm of the lever
proportional to the
two phase region is akin to ‘lever’ with the Liquid Cooling Solid
fulcrum at the nominal composition (C0)
Temperature →
The opposite arms of the lever are Y
proportional to the fraction of the solid and X
liquid phase present (this is lever rule)
Fulcrum of the lever
C0 − C1 C 2 − C0
f liquid = f Solid =
C2 − C1 C2 − C1
A C1 C0 C2 B
% B→
Example
Cu – Ni System
At Co = 35 wt% Ni TA A
tie line
1300 L (liquid)
Temperature ((ºC)
At T A : Only Liquid (L)
W liquid = 100 wt%, Wsolid = 0 B
TB
R S
a
At T D: Only Solid ( S ) 1200 S (solid)
D
W L = 0, W solid = 100 wt% TD
At T B : Both S and L 20 3032 35 40 4 3 50

C LC o Ca
WL =
S 43 − 35 % Ni→
= = 73 wt %
R +S 43 − 32 Notice: as in a lever “the opposite leg” controls with
a balance (fulcrum) at the ‘base composition’ and
R+S = tie line length = difference in composition
R
WS = = 27 wt% limiting phase boundary, at the temp of interest
R +S
Variations of Isomorphous System
An alloy typically melts over a range of temperatures. However, there are special compositions which
can melt at a single temperature like a pure metal. There is no difference in the liquid and solid
composition. It begins and ends solidification at a constant temperature with no change in
composition, and its cooling curve will show a horizontal line. Such alloys are known as a
congruent-melting alloys, sometimes known as a pseudo-eutectic alloy. Ex: Cu-Au, Ni-Pd.
Congruently melting alloys → just like a pure metal

Is the DOF 1? No: in requiring that we have exhausted the degree of freedom. Hence T is
automatically fixed → DOF is actually Zero..!
Variations of Isomorphous System
Elevation in the MP means that the solid state is ‘more stable’ (crudely speaking the ordered
state is more stable) → ordering reaction is seen at low T.
Depression in MP ‘means’ the liquid state (disordered) is more stable → phase separation is
seen at low T. (phase separation can be thought of as the opposite of ordering. Ordering
(compound formation) occurs for –ve values for ΔH mix).
A – B bonds stronger than A – A and B – B bonds A – A and B – B bonds stronger than A-B bonds
Solid Stabilized → Ordered Solid Formation Liquid Stabilized → Phase separation in the solid
Case 1 Case 2
Examples of Isomorphous System with phase separation
Equilibrium Cooling
Figure: The above figure represents the very slow cooling , under equilibrium conditions, of a
particular alloy 70A-30B will now be studied to observe the phase changes that occur .
Equilibrium Cooling
This alloy at temperature T0 is a homogeneous single-phase liquid solution (a) and
remains so until temperature T1is reached. Since T1is on the liquidus line, freezing or
solidification now begins.
The first nuclei of solid solution to form α1 will be very rich in the higher melting point
metal A and will be composed of 95A-5B (by tie line rule). Since the solid solution in
forming takes material very rich in A from the liquid, the liquid must get richer in B. Just
after the start of solidification, the composition of the liquid is approximated as 69A-31B
(b).
When the lower temperature T2 is reached, the liquid composition is at L2. The only solid
solution in equilibrium with L2 and therefore the only solid solution forming at T2 is α2.
Applying tie line rule, α2 is composed of 10B. Hence, as the temperature is decreased,
not only does the liquid composition become richer in B but also the solid solution.
At T2 ,crystals of α2 are formed surrounding the α1 composition cores and also separate
dendrites of αz (see figure in below).
Equilibrium Cooling
In order for equilibrium to be established at T2, the entire solid phase must be a
composition α2. This requires diffusion of B atoms to the A-rich core not only from
the solid just formed but also from the liquid. This is possible in crystal growth (c).
The composition of the solid solution follows the solidus line while the
composition of liquid follows the liquidus line, and both phases are becoming
richer in B.
At T3 (d), the solid solution will make up approximately three-fourths of all the
material present.
Finally, the solidus line is reached at T4, and the last liquid L4, very rich in B,
solidifies primarily at the grain boundaries (e).
However, diffusion will take place and all the solid solution will be of uniform
composition α(70A-30B), which is the overall composition of the alloy (f).
There are only grains and grain boundaries. There is no evidence of any difference
in chemical composition inside the grains, indicating that diffusion has made the
grain homogeneous.
Equilibrium Cooling
The very slow cooling , under Cu-Ni Phase Diagram
equilibrium conditions, of
L (liquid) L: 35wt%Ni
particular alloy 65Cu - 35Ni will
now be studied.
1300 A
A – Homogeneous single phase L: 35 wt% Ni
(Liquid) a: 46 wt% Ni B 35 B
46
C
32
Temperature ((ºC)
B - ‘B’ is on the liquidus line, C 43
solidification now begins. D
24 36 L: 32 wt% Ni
C – Solid surrounded by liquid a : 43 wt% Ni
crystals. 1200 E E
L: 24 wt% Ni
D – ‘D’ is on the solidus line, a : 36 wt% Ni
solidification now ends.
S (solid)
E – Homogeneous single phase
(Solid)
1100
20 30 35 40 50
Cu Ni
Co
% Ni→
Non Equilibrium Cooling - Coring
In actual practice it is extremely difficult to cool under equilibrium conditions.
Since diffusion in the solid state takes place at a very slow rate, it is expected that
with ordinary cooling rates there will be some difference in the conditions as
indicated by the equilibrium diagram.
Consider again 70A-30B alloy,

solidification starts at T1 forming
a solid solution of composition
α1 .
At T2 the liquid is L2 and the
solid solution now forming is of
composition α2 . Since diffusion
is too slow to keep pace with
crystal growth, not enough time
will be allowed to achieve
uniformity in the solid, and the
average composition will be
between α1 and α2, say α’2.
As the temperature drops, the average composition of the solid solution will depart
still further from equilibrium conditions. It seems that the composition of the solid
solution is following a “nonequilibrium” solidus line α1 to α’5, shown dotted lines
in figure.
The liquid, on the other hand, has essentially the composition given by the liquidus
line, since diffusion is relatively rapid in liquid. At T3 the average solid solution
will be of composition α’3 instead of α3.
Under equilibrium cooling, solidification should be complete at T4 ; however, since
the average composition of the solid solution α’4 has not reached the composition
of the alloy, some liquid must still remain. Applying lever rule at T4 gives α’4 =
75% and L4 = 25%.
Therefore, solidification will continue until T5 is reached. At this temperature the
composition of the solid solution α’5 coincides with the alloy composition, and
solidification is complete. The last liquid to solidify, L5, is richer in B than the last
liquid to solidify under equilibrium conditions.
The more rapidly the alloy is cooled the greater will be the composition range in the
solidified alloy. Since the rate of chemical attack varies with composition, proper
etching will reveal the dendritic structure microscopically (see below figure). The
final solid consists of a “cored” structure with a higher-melting central portion
surrounded by the lower-melting, last-to-solidify shell. The above condition is
referred to as coring or dendritic segregation.
Dendritic Structure
To summarize, nonequilibrium cooling results in an increased temperature range

over which liquid and solid are present; Since diffusion has not kept pace with
crystal growth, there will be a difference in chemical composition from the center to
the outside of the grains. The faster the rate of cooling, the greater will be the above
effects.
Cored vs. Equilibrium Phases
Consider Cu-Ni phase diagram case
First a to solidify has Csolid = 46 wt% Ni.

Last a to solidify has Csolid = 35 wt% Ni.
On Fast rate of cooling On Slow rate of cooling

Cored structure Equilibrium structure
First a to solidify: Uniform Csolid

46 wt% Ni 35 wt% Ni
Last a to solidify:
< 35 wt% Ni
Homogenization
Cored structures are most common in as-cast metals. From the earlier discussion of
the origin of a cored structure, it is apparent that the last solid formed along the
grain boundaries and in the inter-dendritic spaces is very rich in the lower-melting-
point metal.
Depending upon the properties of the lower-melting-point metal, the grain
boundaries may act as a plane of weakness. It will also result in a serious lack of
uniformity in mechanical and physical properties and, in some cases, increased
susceptibility to intergranular corrosion because of preferential attack by corrosive
medium. Therefore, for some applications a cored structure is objectionable.
There are two methods for solving the problem of coring. One is to prevent its
formation by slow freezing from the liquid, but this result in large grain size and
requires a very long time. The preferred method industrially is to achieve
equalization of composition or homogenization of the cored structure by diffusion
in the solid state.
At room temperature, for most metals, the diffusion rate is very slow; but if the
alloy is reheated to a temperature below the solidus line, diffusion will be more
rapid and homogenization will occur in a relatively short time.
Eutectic Phase Diagram
Very few systems exhibit an isomorphous phase diagram (usually the solid
solubility of one component in another is limited).
Often the solid solubility is severely limited – through the solid solubility is never
zero (due to entropic reasons).
In a Simple eutectic system (binary), there is one composition at which the liquid
freezes at a single temperature. This is in some sense similar to a pure solid which
freezes at a single temperature (unlike a pure substance the freezing produces a
two solid phases both of which contain both the components).
The term Eutectic means easy melting → The alloy of eutectic composition freezes
at a lower temperature than the melting point s of the constituent components.
This has important implifications → e.g. the Pb-Sn eutectic alloy melts at 183ºC,
which is lower than the melting points of both Pb (327ºC) and Sn (232ºC) → Can
be used for soldering purposes (as we want to input least amount of heat to solder
two materials).
In the next page we consider the Pb-Sn eutectic phase diagram.
Eutectic Phase Diagram
Liquidus
327ºC
Eutectic
L→α+β L+β
α+L
Temperature ((ºC)
232ºC
α 183ºC
β
Solidus
Solvus
α+β
Pb 18% % Sn → 62% 97% Sn
Eutectic reaction at 183ºC L → α + β

62%Sn → 18%Sn + 97%Sn
Example : Cu-Ag Eutectic System
Raoult’s law states that the freezing point of a pure substance will be lowered by
the addition of a second substance provided the latter is soluble in the pure
substance when liquid and insoluble when solidified. The amount of lowering of
the freezing point is proportional to the molecular weight of the solute.
1200
• Limited solubility: L (liquid)
Temperature ((ºC)
α: mostly Cu 1000
α L+ α TE L+ β
β: mostly Ag 800 779°C β
8.0 71.9 91.2
• TE : No liquid below TE
600
• CE : Min. melting TE α +β
400
Three single phase regions – (L, α, β)
exist at 71.9% Ag at 779°C commonly 200
known as Eutectic. The reaction is as 0 20 40 60 CE 80 100
Cu wt% of Ag→ Ag
follows…!
L(CE) α(CαE) + β(CβE)
Microstructural Characteristics of Eutectic System
L: Co wt% Sn L: Co wt% Sn
400 400
L L
α L
300 L 300 α
Temperature ((ºC)
Temperature ((ºC)
L+ α
L+ α α: Co wt% Sn
200
α α
200
TE α: Co wt% Sn TE
α
β
100 100
α +β α+ β
Co
Co
0 10 20 30 0 10 20 30
Pb 2% wt% Sn→ , Pb wt% Sn→
To reiterate an important point: Phase diagram do not contain microstructural information
(i.e. they cannot tell you what is the microstructures produced by cooling. Often
microstructural information is overlaid on phase diagram for convenience. Hence, strictly
cooling is not in the domain of phase diagram – but we can overlay such information
keeping in view the assumptions involved.
18.3 wt% Sn < Co < 61.9 wt% Sn
Microstructure consists a crystals and a eutectic microstructure
L: Co wt% Sn
α L →Just above TE :
L
α C α = 18.3 wt% Sn
300 L
CL = 61.9 wt% Sn
L+α
Temperature ((ºC)
α Wα = S = 50 wt%
200 R S L+ β β R+S
TE WL = (1- W α ) = 50 wt%
R S
100 α +β → Just below TE :

primary α
eutectic α C α = 18.3 wt% Sn
eutectic β
C β = 97.8 wt% Sn
0 20 40 60 80 97.8100
Pb 18.3 61.9 Sn Wα = S = 72.6 wt%
wt% Sn→
R+S
W β = 27.4 wt%
Co = CE
Microstructure represents Eutectic microstructure (lamellar structure) alternating
layers (lamellae) of a and b crystals.
Pb-Sn Eutectic Microstructure

L: Co wt% Sn
300 L
L+ α
Temperature ((ºC)
200
α 183°C L+β β
TE
160µm
100
α+β β: 97.8 wt% Sn
α: 18.3 wt%Sn
0 20 40 60 80 97.8100
Pb 18.3 CE Sn
61.9
→wt% Sn
45.1% α and 54.8% β

Hypo Eutectic – Eutectic – Hyper Eutectic
300
L
α L+ α
200 L+β β
TE
α + β
100
Pb0 20 40 60 80 100
eutectic (61.9%Sn) Sn
Hypoeutectic Hypereutectic
Eutectic
α β
α β
α α β β
α β
α β
160 mm
175 mm 175 mm
eutectic micro-constituent
Special Eutectic Systems
Consider the eutectic system without terminal solid solubility : Bi-Cd
Technically it is incorrect to draw eutectic phase diagrams with zero solid solubility.
This would imply that a pure component (say Bi in the example considered) melts over
a range of temperatures (from ‘p’ to 271 ºC) → which is wrong.
Also let us consider an example of a point ‘p’ (which lies on the ‘eutectic line’ PQ). At
‘p’ the phase rule becomes : F = C-P+1 = 1-3+1 = -1 !!!
Special Eutectic Systems
Note that the above is an alternate way of arriving at the obvious contradiction that at ‘P’
on one hand we are saying that there is a pure component and on the other hand we are
considering a three phase equilibrium (which can happen only for Bi-Cd alloys.
In Eutectic systems, at Eutectic point E → 3 phases co-exist : L, α &β
The number of components in a binary phase diagram is 2→ the number of DOF F=0
This implies that the Eutectic point is an Invariant Point → For a given system it occurs
at a fixed composition and temperature.
Application of Lever rule in Eutectic System
For a 40 wt% Sn-60 wt% Pb alloy at 150°C, find the phases present: α
Solved
and β, Composition of phases
Example
CO = 40 wt% Sn Pb-Sn Phase Diagram

Ca = 11 wt% Sn
Cb = 99 wt% Sn 300 L (liquid)
Temperature ((ºC)
The relative amount of each phase L+ α
α
by using lever rule 200 183°C L+ β β
18.3 61.9 97.8
S Cβ - CO 150 R S
Wa = =
R+S Cβ - Cα 100 α+β
99 - 40 59
= = = 67 wt%
99 - 11 88
C -C 0 11 20 40 60 80 99100
Wβ = R = O α Cα Co Cβ
R+S Cβ - Cα
wt% Sn→
40 - 11 29
= = = 33 wt%
99 - 11 88
Application of Lever rule in Eutectic System
For a 40 wt% Sn-60 wt% Pb alloy at 220°C, find the phases present: α
Solved
and Liquid, Composition of phases
Example
CO = 40 wt% Sn Pb-Sn Phase Diagram

Ca = 17 wt% Sn
CL = 46 wt% Sn
300 L (liquid)
L+ α
Temperature ((ºC)
The relative amount of each phase
220 α
by using lever rule 200 R S L+ β β
183°C
CL - CO 46 - 40
Wa = = 100
CL - Cα 46 - 17 α +β
6
= = 21 wt%
29
0 17 20 40 46 60 80 100
CO - Cα 23 Cα Co CL
WL = = = 79 wt%
CL - Cα 29 Wt% Sn→
During the solidification of a off eutectic (Pb-Sn) composition (C0 ), 90
Solved
vol.% of the solid consisted of the eutectic mixture and 10vol.% of the
Example
proeutectic β phase. What is the value of C0 ?
Density data for β and α Let us start with some observations: ♦Pb is heavier than Sn and hence the density
of α is more than that of β ♦Since the proeutectic phase is β → the composition is
ρα = 10300 Kg/ m3 hypereutectic (towards the Sn side) ♦ The volume fraction (in %) are usually
ρβ = 7300 Kg/ m3 calculated by taking the area fractions by doing metallography (microstructure) and
Eutectic Data then converting it into volume fractions (usually volume fraction is assumed to be
183 ºC equal to area fraction
62 wt% Sn L α β
+
62%Sn 18%Sn 97%Sn
Using the fact that there is 10 Vol% β phase :
Vol%
 Wt .ofβ  0.1× 7300
Wt . fractionof proeutecti cβ =  =
 (0.1× 7300) + (0.9 × ρ
 Wt .ofthealloy  eutecticmi x )
97 − 62 62 − 18
Where, ρ eutecticmix = 10300( ) + 7300( ) = 4563 + 4066 = 8629 Kg / m 3
97 − 18 97 − 18
Substituting in equation (1): Wt. fraction of proeutectic β = 0.086
C0 − 0.62
U sin gleverrule : 0.086 = , C0 = 0.650 = 65.0%
0.97 − 0.62
Peritectic Phase Diagram
1772ºC
Peritectic
L+α→β
L+α
Liquid (L)
Temperature ((ºC)
(Pt) 1186ºC
TP
α L+β
961.9ºC
(Ag)
α+β
β
Pt 10.5 42.4 66.3 90 Ag

Weight Percent Silver Ag→
Peritectic L α Cool β
+
Reaction 66.3%Ag 10.5%Ag 1186ºC
42.4%Ag
Peritectic Phase Diagram
Like the eutectic system, the Peritectic reaction is found in systems with complete
liquid solubility but limited solid solubility.
In the Peritectic reaction the liquid (L) reacts with one solid (α) to produce another
solid (β). L+α → β
Since the solid β forms at the interface between the L and the α, further reaction is
dependent on solid state diffusion. Needless to say this becomes the rate limiting
step and hence it is difficult to ‘equilibrate’ peritectic reactions (as compared to say
eutectic reactions).
In some Peritectic reactions (e.g. the Pt-Ag system – previous page). The (pure) β
phase is not stable below the Peritectic temperature (TP = 1186 ºC for Pt- Ag
system) and splits into a mixture of (α+β) just below TP.
Monotectic Phase Diagram
In all the types discussed previously, it was assumed that there was complete
solubility in the liquid state. It is quite possible, however, that over a certain
composition range two liquid solutions are formed that are not soluble in each
other.
Another term for solubility is miscibility. Substances that are not soluble in each
other, such as oil and water, are said to be immiscible. Substances that are partly
soluble in each other are said to show a miscibility gap, and this is related to
Monotectic Systems.
When one liquid forms another liquid, plus a solid, on cooling, it is known as a
Monotectic Reaction.
It should be apparent that the Monotectic reaction resembles the eutectic reaction,
the only difference being that one of the products is a liquid phase instead of a
solid phase.
An example of an alloy system showing a Monotectic reaction is that between
copper and lead given in next page. Notice that in this case the L1 + L2 is closed.
Also, although the terminal solids are indicated as α and β, the solubility is actually
so small that they are practically the pure metals, copper and lead.
Monotectic Phase Diagram
1100
1083 L1
991.6
1000 36 87
953 L2
900
α+L1 L1 + L2
800
Monotectic
Temperature ((ºC)
700 L1 → L2+α
600
α+L2
500
400
326 327.5
300 99.94
←α β→
200
30 40 50 60 70 80
Cu 10 20 90 Pb
Weight Percent Lead Pb→
In Cu-Zn Phase diagram the eutectoid reaction occurs
At 560 ºC with 75% Zn
The Eutectoid Reaction
This is a common reaction in the solid state. It is very similar to the eutectic
reaction but does not involve the liquid . In this case, a solid phase transforms on
cooling into two new solid phases. The general equation may be written as..!
Cooling
Solid1 Solid2 + Solid3
Heating
The resultant Eutectoid mixture is extremely fine, just like the eutectic mixture.
Under the microscope both mixtures generally appear the same, and it is not
possible to determine microscopically whether the mixture resulted from a eutectic
reaction or eutectoid reaction.
An equilibrium diagram of Cu-Zn, illustrating the eutectoid reaction is shown in
figure (see in next page).
In copper (Cu) – Zinc (Zn) system contains two terminal solid solutions i.e. these
are extreme ends of phase diagram α and η, with four intermediate phases called β,
γ, δ and ε. The β’ phase is termed an ordered solid solution, one in which the
copper and zinc atoms are situated in a specific and ordered arrangement within
each unit cell.
Cu-Zn Phase Diagram - Eutectoid Reaction
1200
α+L Liquid (L)

1000 β+L
Eutectoid
δ → γ+ε
Temperature ((ºC)
800
γ+L
α β
γ
+ β δ+L
+δ
600 β + δ
598ºC
560ºC
γ η+ L
α γ ε+L
β’ ε
400 α β’ γ+ε η
+ + ε+η
β’ γ
200
0 20 40 60 80 100
Cu Zn
Composition (Wt% Zn→)
Cu-Zn Phase Diagram - Eutectoid Reaction
In the diagram, some phase boundary lines near the bottom are dashed to indicate
that there positions have not been exactly determined. The reason for this is that at
low temperatures, diffusion rates are very slow and inordinately long times are
required for the attainment of equilibrium.
Again only single- and two- phase regions are found on the diagram, and the same
and we can utilize the lever rule for computing phase compositions and relative
amounts.
The commercial material brasses are copper-rich copper-zinc alloys: for example,
cartridge brass has a composition of 70 wt% Cu-30 wt% Zn and a microstructure
consisting of a single α phase.
In Cu-Zn Phase diagram the eutectoid

reaction occurs at 560 ºC with 75% Zn
Cooling
δ γ + ε
Heating
Cu 70, Zn 30 (wt%),
recrystallied
annealing twins
The Peritectoid Reaction
This is a fairly common reaction in the solid state and appears in many alloy
systems. The peritectoid reaction may be written as
Cooling
Solid1 + Solid2 Solid3
Heating
The new solid phase is usually an intermediate alloy, but it may also be a solid
solution .The peritectoid reaction has the same relationship to the peritectic
reaction as the eutectoid has to the eutectic. Essentially, it is the replacement of a
liquid by a solid.
The peritectoid reaction occurs entirely in the solid state and usually at lower
temperatures than the peritectic reaction, the diffusion rate will be slower and there
is less likelihood that equilibrium structures will be reached.
Consider Silver (Ag) – Aluminium (Al) phase diagram (in next page) containing a
peritectoid reaction.
If a 7% Al alloy is rapidly cooled from the two phase area just above the
peritectoid temperature the two phases will be retained, and the microstructure will
show a matrix of γ with just a few particles of α. When we cool at below the
peritectoid temperature by holding we get single phase μ.
Peritectoid Reaction : Ag-Al Phase Diagram
Weight percent aluminium →
10 20
1000 0 30 40 50 60 80 100
960.5
Cooling
900 Solid1 + Solid2 Solid3
Heating
800 780
727 Liquid
700 β
660
Temperature ((ºC)
600 610
566
αAg αAg+γ αAl
γ
500
448 6.8% Al
400
Peritectoid
300 μ αAg+γ → μ
αAg
μ +
200 +μ γ
100
0 10 20 30 40 50 60 70 80 90 100
Ag Atomic percent aluminium → Al
Monotectoid Reaction : Al-Zn Phase Diagram
800
700 Monotectoid
Liquid
660
α→ α‫׳‬+β
600
L+α
500 L+β
Temperature ((ºC)
400 Al (α) 420

381
351 83.1 94 β
α+β
300 277 α+α‫׳‬
32.4 96.3
77.7
200
α‫׳‬+β Zn→
100
0 10 20 30 40 50 60 70 80 90 100
Al Zn
Weight percent Zinc →
Syntectic Reaction : Ga – I Phase Diagram
Weight Percent Iodine
0 10 20 30 40 50 60 70 80 90 100
L1
L2
Temperature ((ºC) L 1+L 2
271ºC
211ºC 214ºC
205ºC
Syntectic
L 1+L 2↔GaI 160ºC
70.2
113.6ºC
GaI3
GaI2
29.7ºC GaI (I)
(Ga)
0 50 65.5 75 100
Ga Atomic Percent Iodine I
Metatectic Reaction : Fe - Sc Phase Diagram
Metatectic
In the above Fe-Sc system represents a Metatectic reaction,

δ Fe ↔ γFe + L at 1360 ºC
Summary of Invariant reactions
Name of reaction Phase equilibrium Schematic representation

L+S1 L L+S2
Eutectic L ↔ S1 + S2 S1 S2
S1 +S2
S1 L+S1 L
Peritectic S1 + L ↔ S2 S1 +S2 L+S2
S2
L+S1 L1 L1+L2
Monotectic L1 ↔ S1 + L2 S1 L2
L+S2
S1+S2 S1 S1+S3
Eutectoid S1 ↔ S2 + S3 S2 S3
S2+S3
S1+S2
Peritectoid S1 + S2 ↔ S3 S1 S2
S1+S3 S3 S3+S2
S1b+S1a S1a S +S
Monotectoid S1a ↔ S1b + S2 1a 2
S1b S2
S1b+S2
S2+S1 S1 S +L
Metatectic S1 ↔ S2 + L 1
S2 L
S2+L
L1+L2
Syntectic L1 + L2 ↔ S L1 L2
L1+S S S+L2
Allotropic Transformations
As we discussed earlier that several metals may exist in more than one type of crystal
structure depending upon temperature , Iron, Tin, Manganese and Cobalt are examples
of metals which exhibit this property , known as Allotropy.
On an equilibrium diagram, this allotropic change is indicated by a point or points on
the vertical line which represents the pure metal. This is illustrated in below figure. In
this diagram, the gamma solid solution field is ‘looped’. The pure metal Fe and alloys
rich in Fe undergo two transformations.
2000
Liquid 1907
1800
Temperature (ºC)
1538
1600
Liquid + α
1400
1200
γ α
1000 γ+α
912
800
α+σ σ
600
α+σ
0 10 20 30 40 50 60 70 80 90 100
Weight Percent Chromium →
Allotropic Transformations: Fe-Fe3C System
Peritectic L
Eutectic
L+δ→γ 1493ºC
δ L → γ + Fe3C
L+ γ
0.1 %C γ 2.06 1147ºC
Eutectoid γ + Fe3C
γ → α + Fe3C
723ºC
α
0.025 %C α + Fe3C
T →
Fe Fe3C
0.16 0.8 4.3 6.7
Fe-Cementite diagram %C →
Order-disorder Transformations
Ordinarily in the formation of substitutional type of solid solution the solute atoms do not
occupy any specific position but are distributed at random in the lattice structure of the
solvent. The alloy is said to be in a ‘disordered’ condition.
Some of these random solid solutions, if cooled slowly, undergo a rearrangement of the
atoms where the solute atoms move into definite positions in the lattice. This structure is
known as an ordered solid solution or superlattice.
Ordering is most common in metals that are completely soluble in the solid state, and
usually the maximum amount of ordering occurs at a simple atomic ratio of the two
elements.
For this reason, the ordered phase is sometimes given a chemical formula, such as AuCu
and AuCu3 in the gold-copper alloy system. On the equilibrium diagram, the ordered
solutions are frequently designated as α‫ ׳‬, β‫ ׳‬, etc. or α‫ ׳‬, α‫ ״‬, etc., and the area in which they
are found is usually bounded by a dot-dash line.
CuAu Cu3Au Fe3Al

Order-disorder Transformations
When the ordered phase has the same lattice structure as the disordered phase, the
effect of ordering on mechanical properties is negligible. Hardening associated
with the ordering process is most pronounced in those systems where the shape of
the unitcell is changed by ordering.
Regardless of the structure formed as a result of ordering, an important property
change produced, even in the absence of hardening, is a significant reduction in
electrical resistance. Notice the sharp decrease in electrical resistivity at the
compositions which correspond to the ordered phases AuCu and AuCu3.
Figure : Effect of (a) temperature, (b) composition, and (c) deformation on the resistivity of
copper-gold alloys
Note
Some of the equilibrium diagrams discussed under the simple types are
the same as actual ones. Many alloy systems have diagrams which show
more than one type of reaction and are generally more complex than the
simple types.
However, even the most complex diagrams show mainly the reactions
that have been covered. The student should be able to label a phase
diagram completely; understand the significance of every point, line and
area; determine the various reactions that occur at the horizontal lines;
and describe the slow cooling and microstructure of any alloy on a
binary equilibrium diagram.
Questions..?
1. What is Gibbs phase rule? And state the application of it in phase diagrams.
2. Two metals A (melting point 800 ºC) and B (melting point 600 ºC) form a binary
isomorphous system. An alloy having 35% B has 75% solid and rest liquid whereas an alloy
having 55%B has 25% solid at 700 ºC. Estimate the composition of solidus and liquidus at
the above temperature.
3. Apply phase rule to the two phase field of a binary isomorphous diagram. What conclusion
can be drawn?
4. What is the difference between the states of phase equilibrium and metastability?
5. Is it possible to have a copper–nickel alloy that, at equilibrium, consists of an phase of
composition 37 wt% Ni–63 wt% Cu, and also a liquid phase of composition 20 wt% Ni–80
wt% Cu? If so, what will be the approximate temperature of the alloy? If this is not
possible, explain why.
6. What thermodynamic condition must be met for a state of equilibrium to exist?
7. Briefly describe the phenomenon of coring and why it occurs. Cite one undesirable
consequence of coring.
8. A binary alloy having 28 wt % Cu & balance Ag solidifies at 779⁰C. The soild consists of
two pahses α & β. Phase α has 9% Cu whereas phase β has 8% Ag at 779⁰C. At room
temperature these are pure Ag & Cu respectively. Sketch the phase diagram. Label all fields
& lines. Melting points of Cu & Ag are 1083⁰C & 960⁰C respectively. Estimate the amount
of α & β in the above alloy at 779⁰C & at room temperature.
Questions..?
9. The figure on the below is the hafnium–vanadium phase diagram, for which only single-
phase regions are labeled. Specify temperature–composition points at which all eutectics,
eutectoids, peritectics, and congruent phase transformations occur. Also, for each, write the
reaction upon cooling.
10. Briefly explain why, upon solidification, an alloy of eutectic composition forms a
microstructure consisting of alternating layers of the two solid phases.
11. What is the difference between a phase and a microconstituent?
Questions..?
12. What is the principal difference between congruent and incongruent phase transformations?
13. A molten Ag‐Cu (20%) alloy is allowed to cool slowly till room temperature. Refer to the
diagram in problem 8 and plot its cooling curve. Estimate % α just after it has solidified at
779⁰C & room temperature. Sketch its microstructure and find % Eutectic .
14. Two alloys belonging to a binary system have the following microstructures. One having
25% B consists of 50% α & 50% eutectic and the other having 0.75%B has 50% β & 50%
eutectic. Microstructrural examination shows that eutectic is made of 50% α & 50% β.
Estimate the composition of α,β & eutectic.
15. Draw the phase diagram for a binary alloy system having following features. Melting point
of the two metals (A & B) are widely different. These are partially soluble in each other.
There is one three phase reaction isotherm at a temperature higher than the melting point of
B but lower than that of A. Write down the equation representing the 3 phase reaction. What
is it commonly known as?
16. Sketch a binary phase diagram showing 2 peritectic and 1 eutectic reaction isotherm.
Assume both metal A & B have nearly same melting point & there are two & terminal two
intermediate soild solutions.
17. Draw a binary phase diagram where A undergoes an allotropic transformation (but not B)
and there are one eutectic and one eutectoid transformation.
18. Cooling curve of a binary alloy looks exactly similar to that of a pure metal. Is this
possible?
Questions..?
19. Why the eutectic structure does not exhibit coring?
20. In below figure is shown the pressure– temperature phase diagram for Apply the Gibbs
phase rule at points A,B, and C; that is, specify the number of degrees of freedom at each of
the points—that is, the number of externally controllable variables that need be specified to
completely define the system.
Avala Lava Kumar*
History
Figure 1
Iron – carbon (Fe-C) diagram and
first phase diagram of any alloy to be
established, done by Roberts –Austen
in 1898 after whom austenite came to Figure 2
be named. (Figure 1)
The Iron Carbon diagram, adjusted by Bakhuis-Roozeboom in 1900. Notice line A-a and
the temperature range between 1000 and 1100ºC, where carbide formation was suppose to
take place as the result of a chemical reaction between graphite and austenite (at that time
called martensite! (Figure 2)
Allotropic Transformations in Iron
Iron is an allotropic metal, which means that it can exist in more than one type of
lattice structure depending upon temperature. A cooling curve for pure iron is
shown below:
Liquid
1539ºC
δ (delta) Fe - B.C.C
1400ºC
Temperature ºC →
γ (gamma) Fe - F.C.C
Non Magnetic
910ºC
Non Magnetic α (alpha) Fe - B.C.C
768ºC
α (alpha) Fe - B.C.C
Magnetic
Time →
Allotropic Transformations in Iron
There are three more allotropes for pure iron that form under different
conditions
ε-iron
The iron having hexagonal close packed structure. This forms at extreme
pressure,110 k bars and 490°C. It exists at the centre of the Earth in solid
state at around 6000°C and 3 million atmosphere pressure.
FCT-iron
This is face centered tetragonal iron. This is coherently deposited iron
grown as thin film on a {100} plane of copper substrate
Trigonal-iron
Growing iron on mis-fiting {111} surface of a face centered cubic copper
substrate.
Iron – Cementite Phase Diagram
The Fe-C (or more precisely the Fe-Fe3C) diagram is an important one. Cementite
is a metastable phase and ‘strictly speaking’ should not be included in a phase
diagram. But the decomposition rate of cementite is small and hence can be
thought of as ‘stable enough’ to be included in a phase diagram. Hence, we
typically consider the Fe-Fe3C part of the Fe-C phase diagram.
A portion of the Fe-C diagram – the part from pure Fe to 6.67 wt.% carbon
(corresponding to cementite, Fe3C) – is technologically very relevant.
Cementite is not a equilibrium phase and would tend to decompose into Fe and
graphite. This reaction is sluggish and for practical purpose (at the microstructural
level) cementite can be considered to be part of the phase diagram. Cementite
forms as it nucleates readily as compared to graphite.
Compositions upto 2.1%C are called steels and beyond 2.1% are called cast irons.
In reality the calssification should be based on ‘castability’ and not just on carbon content.
Heat treatments can be done to alter the properties of the steel by modifying the
microstructure → we will learn about this in coming chapters.
0.1 0.16 0.51
Peritectic Liquid (L)
Eutectic
L+δ→γ 1493ºC
L → γ + Fe3C
δ (Ferrite)
L+ γ L + Fe3C
Temperature →
δ+ γ γ (Austenite) 1147ºC
Hypo Eutectic Hyper Eutectic
910ºC 2.11
[γγ(Austenite) + Fe3C(Cementite)] = Ledeburite
723ºC
α (Ferrite)
Eutectoid 4.3
Eutectoid
Hyper
Hypo
0.025 %C
Eutectoid α (Ferrite) + Fe3C (Cementite)] = Pearlite

[α
γ → α + Fe3C Steels Cast Irons
0.008 0.8 6.7
Fe % Carbon → Fe3C
Carbon Solubility in Iron
Solubility of carbon in Fe = f (structure, temperature)
Where is carbon located in iron lattice ?
Octahedral
sites
Octahedral
sites
6 faces sharing with two sides (6/2)=3 One interstitial site in center plus
12 edges sharing with four sides (12/4)=3 12 edges sharing with four sides (12/4)=3
Total sites is (3+3), 6 per unit cell Total sites is (1+3), 4 per unit cell
Every one Fe atom we have 3 interstitial sites Every one Fe atom we have 1 interstitial site
Surprising facts…!
C dissolves more in the close packed structure (FCC, γ-Fe) (albeit at higher temperatures at
1 atm. pressure− where FCC is stable) than in the open structure (BCC-Fe).
C sits in the smaller octahedral void in BCC in preference to the larger tetrahedral void in
BCC.
Some relevant explanation…!
The octahedral void in FCC is the larger one and less distortion occurs when
carbon sits there → this aspect contributes to a higher solubility of C in γ-Fe.
The distorted octahedral void in BCC is the smaller one → but (surprisingly)
carbon sits there in preference to the distorted tetrahedral void (the bigger one). (we
will see in coming slides)
Due to small size of the voids in BCC the distortion caused is more and the
solubility of C in α-Fe is small
this is rather surprising at a first glance as BCC is the more open structure
but we have already seen that the number of voids in BCC is more than that in
FCC → i.e. BCC has more number of smaller voids.
FCC
o
= 1.292 A
Fe Void (Oct) Void (Tet)
Size of Fe atom
CCP crystal rFCC
o FeFCC C
Size of the OV
Fe
xFCC (oct ) = 0.534 A
o
r = 0.77 A
C Relative sizes of voids w.r.t atoms
Size of Carbon atom
Note the difference in size of the atoms

BCC
o
Size of Fe atom
BCC crystal r Fe
BCC = 1.258 A Void (Oct) Void (Tet)
o
(d .tet ) = 0.364 A
Fe FeBCC C
Size of the TV
x BCC
o Relative sizes of voids w.r.t atoms
Size of the OV x Fe
BCC (d .oct ) = 0.195 A
Remember
FCC Size of the largest atom which can fit into the tetrahedral is 0.225 and octahedral void is 0.414
BCC Size of the largest atom which can fit into the d.tetrahedral is 0.29 and d.octahedral void is 0.154
Why carbon preferentially sits in the apparently smaller octahedral void in BCC ?
Ignoring the atom sitting at B and assuming the interstitial atom touches the atom at A
o
2a
OA = r + x A = r Fe
BCC = 1.258 A
2
2 6r BCC : 3a = 4 r
r + xA =
3
xA  2 6 
=  − 1  = 0.6329
r  3 
o o o
OX = x A = 0.796 A OY = xB = 0.195 A x Fe
BCC ( d .tet ) = 0.364 A
Actually the octahedral void in BCC is a linear one (interstitial atom
actually touches only two out of the 6 atoms surrounding it)
This implies for x/r ratios between 0.15 and 0.63 the interstitial atom has to
push only two atoms
(xcarbon/rFe)BCC ~ 0.6
This explains why Carbon preferentially sits in the apparently smaller
octahedral void in BCC
Characteristics of phases appeared in
Fe-Fe3C phase diagram
Ferrite (α)
It is an interstitial solid solution of a small amount

of carbon dissolved in α iron. The maximum
solubility is 0.025%C at 723ºC and it dissolves
only 0.008%C at room temperature. It is the
softest structure that appears on the diagram
The crystal structure of ferrite (α) is B.C.C
Tensile strength – 40,000 psi or 275 Mpa
Elongation – 40% in 2 in.
Hardness - < 90 HRB
α(Ferrite) contains
B.C.C structure
α (Ferrite) – 90X
Cementite (Fe3C)
Cementite or iron carbide, chemical formula Fe3C, contains 6.67%C by weight and
it is a metastable phase.
It is typically hard and brittle interstitial compound of low tensile strength (approx.
5000 psi) but high compressive strength.
It is the hardest structure that appears on the diagram.
Its crystal structure is orthorhombic
Cementite network
Carbon
(4 atoms)
Iron
(12 atoms)
a≠b≠c
Orthorhombic α = β = γ = 90º
α + Fe3C)
Pearlite (α
Pearlite is the eutectoid mixture containing 0.80
%C and is formed at 723ºC on very slow
cooling.
It is very fine platelike or lamellar mixture of
ferrite and cementite. The fine fingerprint
Eutectoid
mixture called pearlite is shown in below figure.
Hypo Hyper
Eutectoid Eutectoid
Fine Pearlite Coarse
α + Fe3C
Remember…!
Pearlite is a not a
phase but combination
Tensile strength – 120,000 psi or 825 Mpa of two phases (ferrite
+ cementite)
Elongation – 20 percent in 2 in.
Hardness – HRC 20, HRB 95-100, or BHN 250-300
Austenite (γ)
It is an interstitial solid solution of a small amount of carbon dissolved in γ iron.
The maximum solubility is 2.1%C at 1147ºC.
The crystal structure of Austenite (γ) is F.C.C
Tensile strength – 150,000 psi or 1035 Mpa
Elongation – 10% in 2 in. Fe
Hardness - 40 HRC and Toughness is high.
1539ºC
1495ºC
1400ºC
γ(Austenite) – 325X
Ledeburite (γ+ Fe3C)
Ledeburite is the eutectic mixture of austenite
and cementite. It contains 4.3%C and is formed
at 1147ºC
Structure of ledeburite contains small islands of
austenite are dispersed in the carbide phase.
Not stable at room temperature 6.7
The pearlite is resolved in some

regions where the sectioning plane
makes a glancing angle to the lamellae.
The ledeburite eutectic is highlighted
by the arrows. At high temperatures
this is a mixture of austenite and
cementite formed from liquid. The
austenite subsequently decomposes to
pearlite.
Ferrite (δ)
Interstitial solid solution of carbon in iron of body
centered cubic crystal structure. (δ iron ) of higher lattice
parameter (2.89Å) having solubility limit of 0.09 wt% at
1495°C with respect to austenite. The stability of the
phase ranges between 1394-1539°C.
This is not stable at room temperature in plain carbon steel. However it can be
present at room temperature in alloy steel specially duplex stainless steel.
δ-ferrite in dendrite form

in as-cast Fe-0.4C-2Mn-
0.5Si-2 Al0.5Cu
Microstructures involved in
eutectoid mixture
Eutectoid reaction
Phase changes that occur upon passing from the γ
region into the α+ Fe3C phase field.
Consider, for example, an alloy of eutectoid
composition (0.8%C) as it is cooled from a temperature
within the γ phase region, say 800ºC – that is,
beginning at point ‘a’ in figure and moving down
vertical xx’. Initially the alloy is composed entirely of
the austenite phase having composition 0.8 wt.% C and
then transformed to α+ Fe3C [pearlite]
The microstructure for this eutectoid steel that is slowly
cooled through eutectoid temperature consists of
alternating layers or lamellae of the two phases α and
Fe3C
The pearlite exists as grains, often termed “colonies”;
within each colony the layers are oriented in essentially
the same direction, which varies from one colony to
other.
The thick light layers are the ferrite phase, and the
cementite phase appears as thin lamellae most of which
appear dark.
Eutectoid structure
Pearlite in SEM
Schematic representation of the formation of pearlite from

austenite; direction of carbon diffusion indicated by arrows
Pearlite in AFM
Pearlite in optical microscope 500X

Hypo eutectoid region
Hypo eutectoid region – 0.008 to 0.8 %C
Consider vertical line yy’ in figure, at
about 875ºC, point c, the microstructure
will consist entirely of grains of the γ
phase.
In cooling to point d, about 775ºC, which
is within the α+γ phase region, both these
phases will coexist as in the schematic
microstructure Most of the small α
particles will form along the original γ
grain boundaries.
Cooling from point d to e, just above the
eutectoid but still in the α+γ region, will
produce an increased fraction of the α
phase and a microstructure similar to that
also shown: the α particles will have
grown larger.
Hypo eutectoid region
Just below the eutectoid temperature, at point f, all the γ phase that was present at
temperature e will transform pearlite. Virtually there is no change in α phase that existed at
point e in crossing the eutectoid temperature – it will normally be present as a continuous
matrix phase surrounding the isolated pearlite colonies.
Thus the ferrite phase will be present both in the pearlite and also as the phase that formed
while cooling through the α+γ phase region. The ferrite that is present in the pearlite is
called eutectoid ferrite, whereas the other, is termed proeutectoid (meaning pre- or before
eutectoid) ferrite.
Pearlite
Pro-eutectoid ferrite
Hyper eutectoid region
Hyper eutectoid region – 0.8 to 2.1 %C
Consider an alloy of composition C1 in figure
that, upon cooling, moves down the line zz’. At
point g only the γ phase will be present and the
microstructure having only gamma grains.
Upon cooling into the γ+ Fe3C phase field –
say to point h – the cementite phase will began
to form along the initial γ grain boundaries,
similar to the α phase in point d. this cementite
is called proeutectoid cementite that which
forms before the eutectoid reaction.
As the temperature is lowered through the
eutectoid to point I, all remaining austenite of
eutectoid composition is converted into
pearlite; thus the resulting microstructure
consists of pearlite and proeutectoid cementite
as microconstituents.
Hyper eutectoid region
Pearlite
Cementite network
Application of Lever rule in
Fe-Fe3C phase diagram
Solved For a 99.6 wt% Fe-0.40 wt% C at a temperature just below the
Example eutectoid, determine the following:
a) The amount of Fe3C, ferrite (α) and pearlite
b) The amount of pearlite and proeutectoid ferrite (α)
0.025 0.4 6.67

a) The amount of Fe3C and ferrite (α)
Ferrite Cementite
Percentage of Fe3C =
Percentage of Fe3C in 0.4 %C steel is 5.64 %
Percentage of Ferrite (α) in 0.4 %C steel = (100- 5.64)%
Percentage of ferrite in 0.4 %C steel = 94.36%

or
Percentage of ferrite= = 94.36%

b) Phase fraction of pearlite and proeutectoid ferrite (α)
0.025 0.4 0.8

Percentage of pearlite = 48 %
Ferrite Pearlite
Percentage of proeutectoid ferrite (α) in 0.4 %C steel = (100- 48)%
Percentage of proeutectoid ferrite (α) = 52 % or

Critical temperature lines
A5
A4
A3
A2 Acm A0
767ºC
A1,3
210ºC
A1
In general, A0 – Subcritical temperature, A1 - lower critical temperature, A3 - upper

critical temperature, A4 – Eutectic temperature, A5 – Peritectic temperature and Acm
- γ/γ+cementite phase field boundary.
While heating we denoted as Ac1, Ac2, Ac3 etc., ‘c’ stands for chauffage (French
word), which means heating and while cooling we denoted as Ar1, Ar2, Ar3 etc., ‘r’
stands for refroidissement, (French word) which means cooling.
Critical temperature lines
The upper – and lower critical temperature lines are shown as single lines under equilibrium
conditions and are sometimes indicated as Ae3, Ae1 etc. When the critical lines are actually
determined, it is found that they do not occur at the same temperature.
The critical line on heating is always higher than the critical line on cooling. Therefore, the
upper critical line of a hypo eutectoid steel on heating would be labeled AC3 and the same
line on cooling Ar3. The rate of heating and cooling has a definite effect on the temperature
gap between these lines.
The results of thermal analysis

of a series of carbon steels with
an average heating and cooling
rate of 11ºF/min are shown in
figure.
Final word…! with infinitely slow

heating and cooling they would
probably occur at exactly the same
temperature.
Properties of
carbon steels
Classification of metal alloys
Technically steels contain

2.1% but actually in many
applications we are using
carbon limited to 1.2%.
Plain stands for only Fe-c with out any alloying element
Classification of steels
Based on method of manufacturer
This gives rise to bessemer steel, open hearth steel, electric – furnace steel, crucible steel,
etc.
Based on method application
This is generally the final use for the steel, such as machine steel, spring steel, boiler steel,
structural steel, or tool steel.
Based on % of Carbon
Low carbon alloys - (0.025-0.3)%C

Medium carbon alloys – (0.3-0.6)%C
High carbon alloys – (0.6-1.2)%C
Based on Specifications
BIS (Burue Indian Standard)
These standard specifications
AISI (American Iron and Steel Institute)
given by different societies, and
SAE (Society of Automotive Engineering)
they developed different series of
JIS ⇨Japanese Standard
(Fe-c) alloys based on different
DIN ⇨German Standard
compositions. For each type they
TIS ⇨ Thai Standard
given a standard series number…!
AISI –SAE Steel Specification
Series Steel type
10xx Plain carbon steel
11xx Plain carbon steel (high S, low P)
12xx Plain carbon steel (high S, high P)
13xx Mn-Steel (Mn 1.75%)
23xx Ni-Steel (Ni 3.00%)
25xx Ni-Steel (Ni 5.00%)
31xx Ni-Cr Steel (Ni 1.25%, Cr 0.60%)
33xx Ni-Cr Steel (Ni 3.50%, Cr 1.50%)
40xx Molybdenum steel (Mo 0.20 or 0.25)
41xx Chrom – Moly steel (Cr 0.50, 0.80, or 0.95. Mo 0.12,0.20 or 0.30
43xx No-Cr-Mo steel
44xx Molybdenum 0.53
92xx Silicon steel (Si 2.0%) ……etc.
AISI –SAE Steel Specification
Steel type 10XX Carbon content/100
% of alloying element
Nickel steel 2520 20/100 = 0.20% C
5% of Nickel
Questions..?
1. Sketch the microstructure of 0.2% C steel. Calculate %Pearlite % cementite, % proeutectoid
ferrite and % total ferrite.
2. Estimate the ratio of the widths of ferrite and cementite plates in lamellar pearlite.
3. Sketch the temperarture – time diagram during the heating cycle of a 0.8% C steel. Use
standard Fe- Fe3C phase diagram.
4. Estimate %Cm in Ledeburite just below eutectic and just above eutectoid temeratures. What
is its structure at room temperature?
5. If an eutectoid steel is kept at 700⁰C
⁰ what change do you expect?
6. What is the limitation of phase diagram?
7. Which microstructure in eutectoid steel has maximum hardenss? Give reason.
8. Is it possible to have an iron-carbon alloy for which the mass fractions of total cementite
and pro-eutectoid ferrite are 0.057 and 0.36, respectively? Why or why not?
9. Briefly explain why a proeutectoid phase (ferrite or cementite) forms along austenite grain
boundaries.
10. Draw the Fe- Fe3C phase diagram and label all the phases.
Avala Lava Kumar*
Iron – Graphite Phase Diagram
The true equilibrium diagram for iron and carbon is generally considered as iron-
graphite phase diagram (next slide). Earlier we learn about iron-iron carbide phase
diagram and it is not a true equilibrium diagram, generally it is called metastable
iron - iron carbide phase diagram.
Cementite (Fe3C) is a metastable compound, and under some circumstances it can
be made to dissociate or decompose to form ferrite and graphite, according to the
reaction
Fe3C 3Fe + C
For explain of cast irons we will refers to both Iron-Iron carbide phase diagram
and Iron-Graphite phase diagram.
Cast irons are a class of ferrous alloys with carbon contents above 2.14 wt%; in
practice, however, most cast irons contain between 3.0 and 4.5 wt% C and, in
addition, other alloying elements .
The ductility of cast iron is very low and brittle, it cannot be rolled, drawn, or
worked at room temperature. However they melt readily and can be cast into
complicated shapes which are usually machined to final dimensions. Since casting
is the only suitable process applied to these alloys, they are known as cast irons.
Iron – Graphite Phase Diagram
δ 0.51 Stable
1539 L
1493
1395 L + Graphite
L+γ
1153
γ
Temperature ºC →
0.09 %C 1.98 4.2

Metastable
912 γ + Graphite
740
0.69
α
0.021 α + Graphite (C)
Fe C
0.16 6.7 100
% Carbon →
A brief history of cast irons
Cast iron has its earliest origins in china between 700 and 800B.C. until this period
ancient furnaces could not reach sufficiently high temperatures.
The use of this newly discovered form of iron varied from simple tools to a
complex chain suspension bridge erected approximately 56A.D.
The next significant development in cast iron was the first use of coke in 1730 by
an English founder named Darby.
Due to this revolution, better casts were available for more versatile roles, such as
James Watt’s first steam engine, constructed in 1794.
In 1810, Swedish chemist Bergelius, and German physicists Stromever discovered
that by adding silicon to the furnace, along with scrap and pigiron, consistently
cast iron is produced.
In 1885 Turner added ferrosilicon to white iron to produce stronger gray iron
castings.
In the late 20th century the major use of cast irons consisted of pipes, thermal
containment units, and certain machine or building entities which were necessary
to absorb continuous vibrations.
Classification of cast irons
White CI
Grey CI Malleabilize
Ductile/Nodular CI Stress concentration

at flake tips avoided
CAST IRONS
Malleable CI
Compacted Graphite CI
Alloy CI
Good castability ⇒ C > 2.4%

White Cast Iron
In which all the C is in the combined form as Fe3C (Cementite)
The typical microstructure of white cast iron (see next slide), consisting of dendrites
of transformed austenite (pearlite) in a white interdendritic network of cementite.
Microstructure → Pearlite + Ledeburite + Cementite
White cast iron contains a relatively large amount of cementite as a continuous
interdendritic network, it makes the cast iron hard and wear-resistant but extremely
brittle and difficult to machine.
‘completely white’ cast irons are limited in engineering applications because of this
brittleness and lack of machinability. mainly used in liners for cement mixers, ball
mills and extrusion nozzles.
A large tonnage of white cast iron is used as a starting material for the
manufacturer of malleable cast iron.
Hardness : 375 to 600 BHN
Tensile strength : 135-480 Mpa, Compressive strength: 1380 -1725 Mpa
White Cast Iron
Pearlite
400 X
White cementite network

Grey Cast Iron
This group is one of the most widely used alloys of iron, containing between 2.5 to
4 percent of carbon with other alloying elements.
In the manufacture of gray cast iron the tendency of cementite to separate into
graphite and austenite or ferrite is favored by controlling alloy additions and
cooling rates.
These alloys solidify by first forming primary austenite. The initial appearance of
combined carbon is in the cementite resulting from the eutectic reaction. With
proper control of carbon content, temperature and the proper amount of
graphitizing elements notably silicon, magnesium cerium and, alloy will follow the
stable iron – graphite equilibrium diagram.
For most of these cast irons, the graphite exists in the form of flakes (similar to
corn flakes), which are normally surrounded by an α-ferrite or pearlite matrix.
Mechanically, gray iron is comparatively weak and brittle in tension as a
consequence of its microstructure; the tips of graphite flakes are sharp and pointed,
and may serve as points of stress concentration when an external tensile stress is
applied. Strength and ductility are much higher under compressive loads.
Grey Cast Iron
Gray irons are very effective in damping vibrational energy. Base structures for
machines and heavy equipment that are exposed to vibrations are frequently
constructed of this material. In addition, gray irons exhibit a high resistance to wear.
Furthermore, in the molten state they have a high fluidity at casting temperature, which
permits casting pieces having intricate shapes; also, casting shrinkage is low. Finally,
and perhaps most important, gray cast irons are among the least expensive of all
metallic materials.
Gray irons having different type of microstructures, it may be generated by adjustment
of composition and/or by using an appropriate heat treatment. For example, lowering
the silicon content or increasing the cooling rate may prevent the complete dissociation
of cementite to form graphite. Under these circumstances the microstructure consists of
graphite flakes embedded in a pearlite matrix.
Comparison of the relative

vibrational damping capacities
of (a) steel and (b) gray cast
iron.
Grey Cast Iron
Role of silicon
Silicon increases fluidity and influences the solidification of the molten metal and
it decreases Eutectivity i.e., the eutectic composition is shifted to the left
approximately 0.30% carbon for each 1% silicon, which effectively depresses the
temperature at which the alloy begins o solidify.
Si promotes graphitization → ~ effect as ↓ cooling rate
As the silicon content is increased, the austenite field decreases in area, the
eutectoid carbon content is lowered, and the eutectoid transformation occurs over a
broadening range.
Solidification over a range of temperatures permits the nucleation and growth of
Graphite flakes
Change in interfacial energy between γ/L & Graphite/L brought about by Si
Careful control of the silicon content and cooling rate is required to graphitize the
eutectic and proeutectoid cementite, but not the eutectoid cementite, in order to
end up with a pearlitic gray iron of high strength.
Grey Cast Iron
Role of Sulfur
Most commercial gray irons contain between 0.06 and 0.12% sulfur. The effect of
sulfur on the form of carbon is the reverse of silicon. The higher the sulfur content, the
greater will be the combined carbon, thus tending to produce a hard, brittle white iron.
Role of Manganese
Manganese is a carbide stabilizer, tending to increase the amount of combined carbon,
but it is much less potent than sulfur. Excess manganese (>1.25%) has little effect on
solidification and only weakly retards primary graphitization. On eutectoid
graphitization, however, Mn is strongly carbide stabilizing.
Role of Phosphorus
Most gray irons contain between 0.10 to 0.90% phosphorus. Most of the ‘P’ combines
with the iron to form iron phosphide (Fe3P).This iron phosphide forms a ternary
eutectic known as steadite, contains cementite and austenite (at room temperature
pearlite).
Fluidity ↑, Primary graphitization ↑ and extends the range of eutectic freezing
Grey Cast Iron
∈ [2.4% (for good castability), 3.8 (for OK mechanical propeties)]
< 1.25% → Inhibits graphitization
< 0.1% → retards graphitization; ↑ size of Graphite flakes
Fe-C-Si + (Mn, P, S)
→ Invariant lines become invariant regions in phase diagram
Si ∈ (1.2, 3.5) → C as Graphite flakes in microstructure (Ferrite matrix)
↑ volume during solidification ⇒ better castability
L → γ + ( Fe3C ) → α + Fe3C + ( Fe3C ) suuuuuuuu

Si ↑ ⇒ Ceutectoid
14243 1424 3
Ledeburite Pearlite
Grey Cast Iron
Graphite flakes
500 X
Ferrite matrix Pearlite matrix

Ductile Cast Iron
Ductile cast iron also called as Nodular cast iron, Spheroidal graphite cast
iron, and Spherulitic cast iron.
Graphite nodules instead of flakes (in 2D section)
Mg, Ce, Ca (or other spheroidizing) elements are added
The elements added to promote spheroidization react with the solute in the
liquid to form heterogeneous nucleation sites
The alloying elements are injected into mould before pouring
It is thought that by the modification of the interfacial energy the ‘c’ and ‘a’
growth direction are made comparable leading to spheroidal graphite
morphology
The graphite phase usually nucleates in the liquid pocket created by the
proeutectic γ
Ductile Cast Iron
Ferrite Graphite nodules
10 µm
With Ferritic Matrix
With (Ferrite + Pearlite) Matrix
With Pearlitic matrix

Ductile Cast Iron
Ferrite (White)
Graphite (black)
Bull’s Eye
Ferrite
5 µm
Pearlite (grey)
Malleable Cast Iron
As we discussed earlier that cementite is actually a metastable phase. There
is a tendency for cementite to decompose into iron and carbon. This
tendency to form free carbon is the basis for the manufacture of malleable
cast iron.
The reaction of Fe3C 3Fe + C is favored by elevated temperatures, the
existence of solid nonmetallic impurities, higher carbon contents, and the
presence of elements that aid the decomposition of Fe3C.
White Cast Iron → Malleable Cast Iron

Malleabilize
To Increase Ductility
> 48 hrs
Fe3C (WCI)  
2 stage heat treatment
→ Graphite Temper Nodules (Malleable Iron)
Malleable Cast Iron
• (940-960)°C (Above eutectoid temperature)
Stage I • Competed when all Cementite → Graphite
A: Low T structure (Ferrite + Pearlite + Martensite) → (γ + Cementite)
B: Graphite nucleation at γ/Cementite interface

(rate of nucleation increased by C, Si)
(Si ↓ solubility of C in γ ⇒ ↑ driving force
for growth of Graphite)
C: Cementite dissolves → C joining growing Graphite plates
Spacing between Cementite and Graphite →

↓ spacing ⇒ ↓ time (obtained by faster cooling of liquid)
Time for Addition of Alloying elements

Graphitization → which increase the nucleation rate of Graphite temper nodules
in Stage I
Si ↑ ⇒ t ↓
Malleable Cast Iron
• (720-730)°C (Below eutectoid temperature)
Stage II • After complete graphitization in Stage I → Further Graphitization
Slow cool to the lower temperature such that γ does not form Cementite
C diffuses through γ to Graphite temper nodules (called Ferritizing
Anneal)
Full Anneal in Ferrite + Graphite two phase region
Partial Anneal (Insufficient time in Stage II Graphitization) γ → Ferrite is
partial and the remaining γ transforms to Pearlite ⇒ γ → Pearlite + Ferrite
+ Graphite
If quench after Stage I ⇒ γ → Martensite (+ Retained Austenite(RA))
(Graphite temper nodules are present in a matrix of Martensite and RA)
Malleable Cast Iron
Pearlitic Matrix Ferrite (White)
Graphite (black)
Pearlite (grey)
Ferritic Matrix
Partially Malleabilized Iron
→ Incomplete Ferritizing Anneal
Ferrite (White)
Graphite (black)
Fully
10 µm Malleabilized Iron
→Complete Ferritizing Anneal
Compacted Graphite Cast Iron
A relatively recent addition to the family of cast irons is compacted
graphite (CGI).
Micro structurally, the graphite in CGI alloys has a worm-like (or
vermicular) shape; a typical CGI microstructure. In a sense, this
microstructure is intermediate between that of gray iron and ductile iron
and, in fact, some of the graphite (less than 20%) may be as nodules.
The chemistries of CGIs are more complex than for the other cast iron
types; compositions of Mg, Ce and other additives must be controlled so as
to produce a microstructure that consists of the worm-like graphite
particles, while at the same time limiting the degree of graphite nodularity,
and preventing the formation of graphite flakes. Furthermore, depending
on heat treatment, the matrix phase will be pearlite and/or ferrite.
CGI are now being used in a number of important applications – these
include: diesel engine blocks, exhaust manifolds, gearbox housings, brake
discs for high speed trains and flywheels.
Compacted Graphite Cast Iron
Ferritic Matrix
Vermicular shape
Graphite Nodules
Alloy Cast Iron
Cr, Mn, Si, Ni, Al
↑ the range of microstructures
Beneficial effect on many properties
↑ high temperature oxidation resistance
↑ corrosion resistance in acidic environments
↑ wear/abaration resistance
Graphite free
Alloy Cast Irons
Graphite bearing
Chromium addition (12- 35 wt %)
Excellent resistance to oxidation at high temperatures
High Cr Cast Irons are of 3 types:
12-28 % Cr matrix of Martensite + dispersed carbide
29-34 % Cr matrix of Ferrite + dispersion of alloy carbides [(Cr,Fe)23C6,
(Cr,Fe)7C3]
15-30 % Cr + 10-15 % Ni stable γ + carbides [(Cr,Fe)23C6, (Cr,Fe)7C3]
Ni stabilizes Austenite structure
29.3% Cr, 2.95% C

Nickel Hard Cast Iron
Stabilizes Austenitic structure
↑ Graphitization (suppresses the formation of carbides)
(Cr counteracts this tendency of Ni for graphitization)
↓ Carbon content in Eutectic
Moves nose of TTT diagram to higher times ⇒ easy formation of Martensite
Carbide formation in presence of Cr increases the hardness of the eutectic
structure → Ni Hard Cast Irons (4%Ni, 2-8% Cr, 2.8% C)
Good abrasion resistance
Needles of Martensite
Transformation sequence
Crystallization of primary γ
Eutectic liquid → γ + alloy carbide
4%Ni, 2-8% Cr, 2.8% C γ → Martensite
Nickel Resist Cast Iron
Ni Resist Iron: 15-30% Ni + small amount of Cr:
Austenitic Dendrites + Graphite plates/flakes + interdendritic carbides due
to presence of Cr
Resistant to oxidation (used in chemical processing plants, sea water, oil
handling operations…)
Graphite plates
Dendrites of γ
Silicon (Silal) Cast Iron
Silal Iron (trade name): Alloy CI with 5% Si
Si allows solidification to occur over larger temperature range → promotes
graphitization
Forms surface film of iron silicate → resistant to acid corrosion
Some other types…!
Chilled Cast Iron
Chilled –iron castings are made by casting the molten metal against a metal
chiller, resulting in a surface of white cast iron. This hard, abrasion-resistant white
iron surface or case is backed up by a softer gray iron core.
This case-core structure is obtained by careful control of the overall alloy
composition and adjustment of the cooling rate.
Mottled Cast Iron
Solidifying at a rate with extremes between those for chilled and gray irons, thus
exhibiting micro structural and metallurgical characteristics of both
High-Alloy Graphitic Irons

Produced with microstructures consisting of both flake and nodule structures.
Mainly utilized for applications requiring a combination of high strength and
corrosion resistance.
Graphite flake - Gf
Graphite nodules - Gn
Graphite rosettes - Gr
Questions..?
1. Give the broad classification of cast irons.
2. Cite three reasons why ferrous alloys are used so extensively. And cite three characteristics
of ferrous alloys that limit their utilization.
3. Compute the volume percent of graphite VGr in a 2.5 wt% C cast iron, assuming that all the
carbon exists as the graphite phase. Assume densities of 7.9 and 2.3 g/cm3 for ferrite and
graphite, respectively.
4. On the basis of microstructure, briefly explain why gray iron is brittle and weak in tension.
5. Compare gray and malleable cast irons with respect to (a) composition and heat treatment,
(b) microstructure, and (c) mechanical characteristics.
6. Compare white and nodular cast irons with respect to (a) composition and heat treatment,
(b) microstructure, and (c) mechanical characteristics.
7. Is it possible to produce malleable cast iron in pieces having large cross-sectional
dimensions? Why or why not?
8. Differentiate between free and combined carbon?
9. Why should the iron-iron carbide diagram not be used to determine the structures in gray
iron?
10. Assume that a C clamp is to made of cast iron. Select a suitable a type of cast iron and
explain the reasons for the selection.
Avala Lava Kumar*
Definition of Heat treatment
Physical
Heat treatment is an operation or

combination of operations involving
heating at a specific rate, soaking at
a temperature for a period of time
Magnetic and cooling at some specified rate. Electrical
The aim is to obtain a desired
microstructure to achieve certain
predetermined properties.
Mechanical
Objectives of Heat Treatment Processes
To increase strength, hardness and wear resistance (bulk hardening, surface
hardening)
To increase ductility and softness (Tempering, Recrystallization Annealing)
To increase toughness (Tempering, Recrystallization annealing)
To obtain fine grain size (Recrystallization annealing, Full annealing,
Normalizing)
To remove internal stresses induced by differential deformation by cold working,
non-uniform cooling from high temperature during casting and welding (Stress
relief annealing)
To improve machinability (Full annealing and Normalizing)
To improve cutting properties of tool steels (Hardening and Tempering)
To improve surface properties (surface hardening, high temperature resistance-
precipitation hardening, surface treatment)
To improve electrical properties (Recrystallization, Tempering, Age hardening)
To improve magnetic properties (Hardening, Phase transformation)
Classification
HEAT TREATMENT
BULK SURFACE
Annealing Tempering
Normalizing Hardening Thermal Thermo-Chemical
Flame
Induction Carburizing
Full Annealing Martempering
Laser Nitriding
Recrystallization Annealing Austempering
Stress Relief Annealing Electron Beam Cyaniding
Spheroidization Annealing
Annealing
Full Annealing
The steel is heated above A3 (for hypo-eutectoid steels) | A1 (for hyper-eutectoid
steels) →(hold) →then the steel is furnace cooled to obtain Coarse Pearlite
Coarse Pearlite has ↓ Hardness, ↑ Ductility
Not above Acm →to avoid a continuous network of proeutectoid cementite along
grain boundaries (→path for crack propagation)
No
910oC Ful
rma
liz a a tion
lA tion a liz Acm
nne rm
alin No
A3 g
Full Annealing
723oC
Spheroidization A1
Recrystallization Annealing
Stress Relief Annealing
T
0.8 %
Wt% C
Annealing
The Heat below A1 → Sufficient time → Recrystallization
Cold worked grains → New stress free grains

Used in between processing steps (e.g. Sheet Rolling)
No n
rma tio
910oC Ful liza a
lA tion a liz Acm
nne r m
A3 alin
g No
Full Annealing
723oC
Spheroidization A1
T
0.8 %
Wt% C
Annealing
Residual stresses → Heat below A1 → Recovery
→ Differential cooling Annihilation of dislocations,

polygonization
→ Martensite formation
No n
rma tio
→ Machining and cold working 910oC Ful
lA
nne
liza
tion
mali
za
Acm
r
A3 aling No
Full Annealing
→ Welding 723oC
Spheroidization A1
T
0.8 %
Wt% C
Annealing
Spheroidization Annealing
Heat below/above A1 (Prolonged holding*)

Cementite plates → Cementite spheroids → ↑ Ductility
Used in high carbon steel requiring extensive machining prior to final hardening and
tempering
Driving force is the reduction in interfacial energy
The spheroidized structure is desirable when minimum hardness, maximum

ductility, or(in high-carbon steels) maximum machinability is important.
Low-carbon steels are seldom spheroidized for machining, because in the
spheroidized condition they are excessively soft and “gummy”.
Medium-carbon steels are sometimes spheroidization annealed to obtain maximum
ductility.
*If the steel is kept too long at the spheroidized-annealing temperature, the cementite particles will coalesce and become elongated thus reducing
machinability
Normalizing
Heat above A3 | Acm → Austenization → Air cooling → Fine Pearlite (Higher hardness)
No
Refine grain structure prior to hardening rma on
910oC Ful liza izati
lA
nne tion al Acm
alin N orm
A3 g
Full Annealing
723oC
Spheroidization A1
Purposes To harden the steel slightly
T
To reduce segregation in casting or forgings 0.8 %

Wt% C
In hypo-eutectoid steels normalizing is done 50oC above the annealing temperature

In hyper-eutectoid steels normalizing done above Acm → due to faster cooling
cementite does not form a continuous film along GB
Ranges of temperature where Annealing, Normalizing and Spheroidization
treatment are carried out for hypo- and hyper-eutectoid steels.
Acm
910oC A3
Temperature →
A1 Full Annealing
723oC
Spheroidization Stress Relief Annealing
0.8 %
Wt % Carbon →
Hardening
Heat above A3 | Acm → Austenization → Quench (higher than critical cooling rate)
Under slow cooling rates, the carbon atoms are able to diffuse out of the austenite
structure and it leads to gamma to alpha transformation . This process involves
nucleation and growth and it is time dependent.
With a still further increase in cooling rate, insufficient time is allowed for the
carbon to diffuse out of solution, and although some movement of the iron atoms
takes place, the structure cannot become B.C.C. while the carbon is trapped in
solution.
The resultant structure is called Martensite, is a supersaturated solid solution of
carbon trapped in a body-centered tetragonal structure and it is a metastable
phase.
The highly distorted lattice structure is the prime reason for the high hardness of
martensite.
After drastic cooling, martensite appears microscopically as a white needlelike or
acicular structure or lenticular, sometimes described as pile of straw.
Characteristics of Martensite
Shape of the Martensite formed →Lenticular (or thin parallel plates)
Associated with shape change (shear)
This condition requires:
1) Bain distortion → Expansion or contraction of the lattice along certain
crystallographic directions leading to homogenous pure dilation
2) Secondary Shear Distortion →Slip or twinning
3) Rigid Body rotation
Martensitic transformation can be understood by first considering an alternate unit cell for
the Austenite phase as shown in the figure below.
If there is no carbon in the Austenite (as in the schematic below), then the Martensitic
transformation can be understood as a ~20% contraction along the c-axis and a ~12%
expansion of the a-axis → accompanied by no volume change and the resultant structure
has a BCC lattice (the usual BCC-Fe) → c/a ratio of 1.0.
γ ( FCC ) α ' ( BCT )

Quench
→
0 .8 % C 0 .8 % C
In Pure Fe after
FCC Austenite alternate choice of Cell the Martensitic transformation
c=a
FCC → BCC
~20% contraction of c-axis

~12% expansion of a-axis
In the presence of Carbon in the octahedral voids of CCP (FCC) γ-Fe (as in the schematic below)
→ the contraction along the c-axis is impeded by the carbon atoms. (Note that only a fraction of
the octahedral voids are filled with carbon as the percentage of C in Fe is small).
However the a1 and a2 axis can expand freely. This leads to a product with c/a ratio (c’/a’) >1
In this case there is an overall increase in volume of ~4.3% (depends on the carbon content) →
the Bain distortion*.
Bain distortion C along the c-axis

obstructs the contraction
Tetragonal
Austenite to Martensite → ~4.3 % volume increase Martensite
* Homogenous dilation of the lattice (expansion/contraction along crystallographic axis) leading to the formation of a new lattice is called
Bain distortion. This involves minimum atomic movements.
Microstructures of Martensite
Fe-0.6%C steel Fe, C 0.8 (Wt%)

Martensite plates Martensite plates
The Martensitic transformation occurs without composition change
The transformation occurs by shear without need for diffusion and is called
diffusion less transformation
The atomic movements (shearing) required are only a fraction of the inter atomic
spacing
The shear changes the shape of the transforming region
→ results in considerable amount of shear energy
→ plate-like shape of Martensite
The amount of martensite formed is a function of the temperature to which the
sample is quenched and not of time
Hardness of martensite is a function of the carbon content
→ but high hardness steel is very brittle as martensite is brittle
Steel is reheated to increase its ductility
→ this process is called TEMPERING
60
Ms
Hardness (Rc) →
40
Temperature
Hardness of Martensite as a
function of Carbon content
20
Mf
0 % Martensite → 100 0.2 0.4 0.6
Martensite start - Ms and Martensite finish - Mf % Carbon →
Properties of 0.8% C steel

Constituent Hardness (Rc) Tensile strength (MN / m2)
Coarse pearlite 16 710
Fine pearlite 30 990
Bainite 45 1470
Martensite 65 -
Martensite tempered at 250 oC 55 1990
0.95 1.90 2.85 3.80 4.75 5.70 6.65
3.70
3.66
1000
3.62 a – parameter of fcc austenite
Temperature oF →
Lattice parameter, Ao
800
3.58
3.54 600
Ms
3.50
Mf
400
3.02 c – parameter of bct martensite 200
2.98
0.4 0.8 0.12 0.16
2.94 % Carbon →
2.90 Influence of carbon on the
a – parameter of bct martensite
2.86
martensite range
2.82
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
% Carbon →
Effect carbon on lattice parameters of
austenite and martensite
The martensite transformation, for many years, was believed to be unique for steel.
However, in recent years, this martensite type of transformation has been found in
a number of other alloy systems, such as iron-nickel, copper-zinc, and copper-
aluminum.
The basic purpose of hardening is to produce a fully martensitic structure, and the
minimum cooling rate ( per second) that will avoid the formation of any of the
softer products of transformation is known as the critical cooling rate.
The critical cooling rate, determined by chemical composition and austenitic grain
size, is an important property of a steel since it indicates how fast a steel must be
cooled in order to form only martensite
More structures of martensitic structure

Time-Temperature-Transformation
(TTT) Diagrams
Davenport and Bain were the first to develop the TTT diagram of eutectoid steel.
They determined pearlite and bainite portions whereas Cohen later modified and
included MS and MF temperatures for martensite.
There are number of methods used to determine TTT diagrams. The most
popular method is salt bath techniques combined with metallography and hardness
measurement with addition of this we have other techniques like dilatometry,
electrical resistivity method, magnetic permeability, in situ diffraction techniques
(X-ray, neutron), acoustic emission, thermal measurement techniques, density
measurement techniques and thermodynamic predictions.
TTT diagrams, also called as Isothermal (temperature constant) Transformation
diagrams.
TTT diagrams give the kinetics of isothermal transformations.
For every composition of steel we should draw a different TTT diagram.
Equipments for determination of TTT Diagrams
Salt bath I Salt bath II

Austenitisation heat treatment Low-temperature for isothermal treatment
Sample and fixtures

for dilatometric measurements Dilatometer equipment
Determination of TTT diagram for eutectoid steel
For the determination of isothermal transformation (or) TTT diagrams, we
consider molten salt bath technique combined with metallography and hardness
measurements.
In molten salt bath technique two salt baths and one water bath are used. Salt bath
I is maintained at austenising temperature (780˚C for eutectoid steel). Salt bath II
is maintained at specified temperature at which transformation is to be
determined (below Ae1), typically 700-250°C for eutectoid steel. Bath III which is
a cold water bath is maintained at room temperature.
In bath I number of samples are austenite at A1+20-40°C for eutectoid, A3+20-
40°C for hypo-eutectoid steel and ACm+20-40°C for hyper-eutectoid steels for
about an hour.
Then samples are removed from bath I and put in bath II and each one is kept for
different specified period of time say t1, t2, t3, t4,…..........,tn etc. After specified
times, the samples are removed and quenched in cold water. The microstructure of
each sample is studied using metallographic techniques. The type, as well as
quantity of phases, is determined on each sample.
Simple experimental arrangement for determining

The kinetics of isothermal austenitic transformation Eutectoid section of the iron - carbon diagram
The progress of austenite transformation

A-austenite, P-pearlite, M-martensite TTT curve of austenite to pearlite for 1080 steel
% of pearlite
100
T2 At T1, incubation
50% T1
period for pearlite=t2,
Pearlite finish time =t4
0
Ae1 Minimum incubation

period t0 at the nose of
T2
the TTT diagram,
T1
t1 t2 t3 t4 t5 Important points to be
t0 Nose noted:
α + Fe3C The x-axis is log scale.
‘Nose’ of the ‘C’ curve is
Temperature
in ~sec and just below

TE transformation times
may be ~day.
The starting phase

(left of the C curve) has
MS, Martensite start temperature to γ.
M50,50% Martensite
To the right of finish C
Metastable austenite +martensite curve is (γ+ Fe3C) phase
MF, Martensite finish temperature
field. This phase field
Martensite has more labels included.
Log time
Isothermal Transformation diagram for eutectoid steel
Important points to be
800
noted: Eutectoid temperature
The x-axis is log 723
scale. ‘Nose’ of the Austenite
‘C’ curve is in ~sec Pearlite
and just below TE 600
transformation times
may be ~day. α + Fe3C
Temperature →
500 Pearlite + Bainite
The starting phase
(left of the C curve)
has to γ.
400 Bainite
To the right of
finish C curve is (γ+
300
Fe3C) phase field. Ms
This phase field has 200
more labels included.
Mf
100
Martensite
0.1 1 10 102 103 104 105
t (s) →
Possible phases in TTT diagram for eutectoid steel
Ae1
Coarse Pearlite R/C 15

Medium Pearlite R/C 30
Nose Fine Pearlite (F.P) R/C 40

50% F.P + 50% U.B
Temperature
Hardness
Upper bainite (U.B) R/C40
50% Transformation
Lower bainite R/C 60
MS, Martensite start temperature

M50,50% Martensite
Metastable austenite +martensite
MF, Martensite finish temperature
Martensite R/C 64
Log time
As pointed out before one of the important utilities of the TTT diagrams comes
from the overlay of micro-constituents (microstructures) on the diagram.
Depending on the T, the (γ+ Fe3C) phase field is labeled with micro-constituents
like Pearlite, Bainite.
The time taken to 1% transformation to, say pearlite or bainite is considered as
transformation start time and for 99% transformation represents transformation finish.
We had seen that TTT diagrams are drawn by instantaneous quench to a
temperature followed by isothermal hold.
Suppose we quench below (~225°C, below the temperature marked Ms), then
Austenite transforms via a diffusionless transformation (involving shear) to a (hard)
phase known as Martensite. Below a temperature marked Mf this transformation to
Martensite is complete. Once γ is exhausted it cannot transform to (γ + Fe3C).
Hence, we have a new phase field for Martensite. The fraction of Martensite
formed is not a function of the time of hold, but the temperature to which we quench
(between Ms and Mf).
Strictly speaking cooling curves (including finite quenching rates) should not be
overlaid on TTT diagrams (remember that TTT diagrams are drawn for isothermal
holds!).
Isothermal hold at: (i) 800
T1 gives us Pearlite, (ii) Eutectoid temperature Eutectoid steel (0.8%C)
T2 gives Pearlite+Bainite, 723
(iii) T3 gives Bainite. Note
that Pearlite and Bainite
Austenite Coarse
are both α+Fe3C (but their T1 Pearlite
morphologies are 600 Fine
different).
Temperature →
500 T2 Pearlite + Bainite
To produce Martensite
we should quench at a rate
such as to avoid the nose
of the start ‘C’ curve.
400 T3 Bainite
Called the critical cooling
rate.
300
If we quench between Austenite
Ms and Mf we will get a Ms
mixture of Martensite and 200
γ (called retained
Austenite). Mf
100
Martensite
Not an isothermal 1 102 103 104
0.1 10 105
transformation t (s) →
In principle two curves exist for Pearlitic and Bainitic transformations

→ they are usually not resolved in plain C steel
(In alloy steels they can be distinct)
TTT diagram for Hypo eutectoid steel
In hypo- (and hyper-) eutectoid steels (say composition C1) there is one more branch to the
‘C’ curve-NP (next slide: marked in red).
The part of the curve lying between T1 and TE (marked in fig : next slide) is clear, because in
this range of temperatures we expect only pro-eutectoid α to form and the final microstructure
will consist of α and γ. (E.g. if we cool to Tx and hold).
The part of the curve below TE is a bit of a
‘mystery’ (since we are instantaneously undercooling wrt A cm w.r.t
cooling to below TE, we should get a mix of (formation of pro-eutectoid α)
α+ Fe3C what is the meaning of a ‘pro’-
eutectoid phase in a TTT diagram?
(remember ‘pro-’ implies ‘pre-’)
Suppose we quench instantaneously an
hypo-eutectoid composition C1 to Tx we
should expect the formation of α+Fe3C (and
undercooling wrt A 1 line
not pro-eutectoid α first). (formation of α+ Fe3C)
The reason we see the formation of pro-
eutectoid α first is that the undercooling w.r.t
to Acm is more than the undercooling w.r.t to C1
A1. Hence, there is a higher propensity for
the formation of pro-eutectoid α.
TTT diagram for Hypo eutectoid steel
T1
P
TE
Hypo-Eutectoid steel
TTT diagram for Hyper eutectoid steel
Similar to the hypo-eutectoid case, hyper-eutectoid compositions C2 have a γ+Fe3C branch.
For a temperature between T2 and TE (say Tm (not melting point- just a label)) we land up
with γ+Fe3C.
For a temperature below TE (but above the nose of the ‘C’ curve) (say Tn), first we have the
formation of pro-eutectoid Fe3C followed by the formation of eutectoid γ+Fe3C.
T2
TE
C2
Transformation to Pearlite
The transformation product above the nose region is pearlite. The pearlite
microstructure is the characteristic lamellar structure of alternate layers of ferrite
and cementite.
As the transformation temperature decreases, the characteristic lamellar structure is
maintained, but the spacing between the ferrite and carbide layers becomes
increasingly smaller until the separate layers cannot be resolved with the light
microscope.
As the temperature of transformation and the fineness of the pearlite decreases, it
is apparent that the hardness will increase.
Transformation to Pearlite
Initial Fe3C nucleus Fe3C plate full grown, α-Fe plates are now grown
α-Fe is nucleus new Fe3C plates nucleated
γ → α + Fe3C
new Fe3C plates nucleated

on different orientation New colony of advanced stage of growth
Nucleation and growth

Heterogeneous nucleation at grain boundaries
Interlamellar spacing is a function of the temperature of transformation
Lower temperature → finer spacing → higher hardness
Pearlitic structure
Pearlite in SEM
Schematic representation of the formation of pearlite from

austenite; direction of carbon diffusion indicated by arrows
500X
Pearlite in AFM Pearlite in optical microscope

Transformation to Bainite
In between the nose region of approximately 510˚C and the Ms temperature, a new,
dark-etching aggregate of ferrite and cementite appears. This structure, named after
E.C.Bain, is called bainite.
At upper temperatures of the transformation range, it resembles pearlite and is known
as upper or feathery bainite. At low temperatures it appears as a black needlelike
structure resembling martensite and is known as lower or acicular banite.
Upper or Feathery bainite Lower or Acicular bainite

Transformation to Bainite
Bainite formed at 348°C Bainite formed at 278°C
γ → α + Fe3C**
Pearlite is nucleated by a carbide crystal, bainite is nucleated by a ferrite crystal, and

this results in a different growth pattern.
Acicular, accompanied by surface distortions
** Lower temperature → carbide could be ε carbide
Bainite plates have irrational habit planes
Ferrite in Bainite plates possess different orientation relationship relative to the parent
Austenite than does the Ferrite in Pearlite
Microstructures in a eutectoid steel
Pearlite formed at
720˚C
Bainite obtained
by isothermal
transformation at
290˚C
Bainite obtained
by isothermal
transformation at
180˚C
Martensite
Cooling curves and the I-T diagram
Austenite (stable)
Ae1
x2 1 x1
x3
x4 x*1
x5 x*2 2
x*3
3
x*4
Temperature
x*5 α + Fe3C
4
x*8
8 x8
CCR
Austenite 5
(Unstable) 6
x6 x**5
7
x*6
Time, log scale

Curve 1
Cooling curve 1 shows a very slow cooling rate typical of conventional annealing
transformation will start at x1, ends at x*1, and there is a slight temperature difference in
temperature between the beginning and end of transformation, there will be a slight difference
in the fineness of pearlite formed at the beginning and at the end.
Curve 2
Cooling curve 2 shows ‘isothermal’ cooling and was developed directly from the IT diagram.
The process is carried out by cooling the material rapidly from above the critical range to a
predetermined temperature in the upper portion of the I-T diagram and holding for the time
indicate to produce complete transformation. In contrast to conventional annealing, this
treatment produces a more uniform microstructure and hardness.
Curve 3
Cooling curve 3 is a faster cooling rate than annealing and may be considered typical of
normalizing. The diagram indicates that transformation will start at x3, with the formation of
coarse pearlite, and ends at x*3, with the formation of medium pearlite. Here, we are clearly
observing the temperature difference between x3 - x*3 and x1 - x*1, so that microstructure will
show a greater variation in fineness of pearlite.
Curve 4
Cooling curve 4, typical of a slow oil quench, is similar to the one just described, and the
microstructure will be a mixture of medium and fine pearlite.
Curve 5
Cooling curve 5, typical of an intermediate cooling rate, will start to transform at x5 to fine
pearlite in a relative short time. After some temperature, the cooling curve is going in a
direction of decreasing percent transformed. Since pearlite cannot form austenite on cooling,
the transformation must stop at x*5. The microstructure at this point will consists, fine pearlite
surrounding with austenitic grains. It will remain in this condition until the Ms line is crossed
x**5. The remaining austenite now transforms to martensite. The final microstructure consists,
martensite and fine nodular pearlite largely concentrated along the original austenite grain
boundaries.
Curve 6
Cooling curve 6, typical of drastic quench, is rapid enough to avoid transformation in the nose
region. It remains austenitic until the Ms line is reached at x6. Transformation to martensite will
take place between the Ms and MF lines. The final microstructure will be entirely martensite of
high hardness.
Curve 7
Cooling curve 7, which is tangent to the nose, would be the approximate critical cooling rate
(CCR) for the steel. Any cooling rate slower than the one indicated will cut the curve above the
nose and form some softer transformation product. Any cooling rate faster than the one
illustrated will form only martensite. To obtain a fully Martensitic structure it is necessary to
avoid transformation in the nose region.
Curve 8
It is possible to form 100 % pearlite or 100% martensite by continuous cooling, but it is not
possible to form 100% bainite. A complete bainitic structure may be formed only by cooling
rapidly enough to miss the nose of the curve and then holding in the temperature range at
which bainite is formed until transformation is complete. This is illustrated by cooling curve 8.
It is apparent that continuously cooled steel samples will contain only small amounts of
bainite, and this is probably the reason why this structure was not recognized until the
isothermal study.
Factors affecting on TTT diagram
Composition of steel
carbon wt%,
alloying element wt%
Grain size of austenite
Heterogeneity of austenite
Composition
.
With some limitations, an increase in carbon or alloy content or in grain size of the
austenite always retards transformation (moves curves to the right), at least at
temperatures at or above the nose region. This in turn slows up the critical cooling rate,
making is easier to form martensite.
This retardation is also reflected in the greater hardenability, or depth of penetration of
hardness, of steel with higher alloy content or larger austenitic grain size.
I.T diagram of a 1035 steel
This is a hypo-eutectoid steel, notice the presence of the austenite to ferrite region. The nose of the curve is
not visible, indicating that it is very difficult to cool this steel fast enough to obtain only martensite. The
microstructure of a low carbon steel water quenched shows a white ferrite network surrounding the gray
low carbon martensite areas.
The microstructure of a medium carbon steel water quenched, shows dark areas of fine pearlite that seem to
outline some of the previous austenite grain boundaries, some dark feathery bainite, and substantially more
martensite as the matrix than appeared in the low carbon steel.
Alloy additions tend in general to delay the start of transformation and to increase the time for
its completion, they differ greatly in both magnitude and nature of their effects. Above diagram
shows the 1335 manganese steel.
Heterogeneity of austenite
Heterogenous austenite increases transformation time range, start to finish of
ferritic, pearlitic and bainitic range as well as increases the transformation
temperature range in case of martensitic transformation and bainitic
transformation. Undissolved cementite, carbides act as powerful inocculant for
pearlite transformation. Therefeore heterogeneity in austenite increases the
transformation time range in diffussional transformation and temperature range of
shear transformation products in TTT diagram.
TTT diagram for

hypo-eutectoid steel TTT diagram for TTT diagram for
eutectoid steel hyper-eutectoid steel
Continuous Cooling Transformation diagrams
The TTT diagrams are also called Isothermal Transformation Diagrams, because
the transformation times are representative of isothermal hold treatment (following
a instantaneous quench).
In practical situations we follow heat treatments (T-t procedures/cycles) in which
(typically) there are steps involving cooling of the sample. The cooling rate may or
may not be constant. The rate of cooling may be slow (as in a furnace which has
been switch off) or rapid (like quenching in water).
Hence, in terms of practical utility TTT curves have a limitation and we need to
draw separate diagrams called Continuous Cooling Transformation diagrams
(CCT), wherein transformation times (also: products & microstructure) are noted
using constant rate cooling treatments. A diagram drawn for a given cooling rate
(dT/dt) is typically used for a range of cooling rates (thus avoiding the need for a
separate diagram for every cooling rate).
However, often TTT diagrams are also used for constant cooling rate experiments-
keeping in view the assumptions & approximations involved.
The CCT diagram for eutectoid steel is considered next.
Important difference between the CCT & TTT transformations is that in the CCT
case Bainite cannot form.
Determination of CCT diagram for eutectoid steel
CCT diagrams are determined by measuring some physical properties during
continuous cooling. Normally these are specific volume and magnetic
permeability. However, the majority of the work has been done through specific
volume change by dilatometric method. This method is supplemented by
metallography and hardness measurement.
In dilatometry the test sample is austenitised in a specially designed furnace and
then controlled cooled. Sample dilation is measured by dial gauge/sensor. Slowest
cooling is controlled by furnace cooling but higher cooling rate can be controlled
by gas quenching
Sample and fixtures

for dilatometric measurements Dilatometer equipment
Cooling data are plotted as temperature versus time (Fig. a). Dilation is recorded
against temperature (Fig. b). Any slope change indicates phase transformation.
Fraction of transformation roughly can be calculated based on the dilation data as
explained below.
a
X
c
Temperature
Dilation
b
V
d Z
IV
I II III TF TS
Temperature
Time
Fig. b : Dilation-temperature plot
Fig. a : Schematic cooling curves
for a cooling curve
In Fig. a curves I to V indicate cooling curves at higher cooling rate to lower
cooling rate respectively. Fig. b gives the dilation at different temperatures for a
given cooling rate/schedule.
In general slope of dilation curve remains unchanged while amount of phase or the
relative amount of phases in a phase mixture does not change during cooling (or
heating) however sample shrink or expand i.e. dilation takes place purely due to
thermal specific volume change because of change in temperature.
Therefore in Fig. b dilation from a to b is due to specific volume change of high
temperature phase austenite. But at TS slope of the curve changes. Therefore
transformation starts at TS. Again slope of the curve from c to d is constant but is
different from the slope of the curve from a to b. This indicates there is no phase
transformation between the temperature from c to d but the phase/phase mixture is
different from the phase at a to b.
Slope of the dilation curve from b to c is variable with temperature. This indicates
the change in relative amount of phase due to cooling. The expansion is due to the
formation of low density phase(s). Some part of dilation is compensated by purely
thermal change due to cooling. Therefore dilation curve takes complex shape. i.e first
slope reduces and reaches to a minimum value and then increases to the
characteristic value of the phase mixture at c.
Therefore phase transformation start at b i.e. at temperature TS and transformation
ends or finishes at c or temperature TF. The nature of transformation has to be
determined by metallography. When austenite fully transforms to a single product
then amount of transformation is directly proportional to the relative change in
length. For a mixture of products the percentage of austenite transformed may not
be strictly proportional to change in length, however, it is reasonable and generally
is being used.
Cumulative percentage of transformation at in between temperature T is equal to
YZ/XZ*100 where X, Y and Z are intersection point of temperature T line to
extended constant slope curve of austenite (ba), transformation curve (bc) and
extended constant slope curve of low temperature phase (cd) respectively.
So at each cooling rate transformation start and finish temperature and
transformation temperature for specific amount (10 %, 20%, 30% etc.) can also be
determined. For every type of transformation, locus of start points, isopercentage
points and finish points give the transformation start line, isopercentage lines and
finish line respectively and that result CCT diagram. Normally at the end of each
cooling curve hardness value of resultant product at room temperature and type
of phases obtained are shown.
CCT curves for eutectoid steel
800
Eutectoid temperature
723
600 Pearlite
Temperature →
500
Original TTT lines
400
Austenite
300
Ms
200
Mf
100
Martensite
0.1 1 10 102 103 104 105
t (s) →
Different cooling treatments for eutectoid steel
800
723
Process Cooling rate (K/s)
Annealing 10−5 – 10−3 600

Air Cooling 1 – 10
Oil Quenching ~100 500

Temperature →
Water Quenching ~500
Splat Quenching 105

400
Melt-Spinning 106 – 108
Evaporation,
109 (expected)
300
sputtering
200
Coarse P
100
M + +P
M Fine P
0.1 1 10 102 103 104 105

M = Martensite P = Pearlite t (s) →
Transformation diagram for cast iron
Homogeneity of austenite
This refers to the uniformity in carbon content of the austenite grains. If a hypo-eutectoid
steel is heated for hardening, when the A1 line is crossed, the austenite grains formed from
pearlite will contain 0.8 percent carbon.
With continued heating, the austenite grains formed from pro-eutectoid ferrite will contain
very little carbon, so that when the A3 line is crossed, the austenite grains will not be
uniform in carbon content.
Upon quenching, the austenite grains leaner in carbon, having a fast critical cooling rate,
tend to transform to nonmartensitic structures, while those richer in carbon, having a slower
critical cooling rate, tend to form martensite. This results a non uniform microstructure with
variable hardness . This condition may be avoided by very slow heating, so that uniformity
is established by carbon diffusion during heating. It is recommended that the material be
held at the austenitizing temperature 1hour for each inch of thickness or diameter
The recommended austenitizing temperature for hypo-eutectoid steels is about 30˚C above
the A3 line. This same as the recommended annealing temperature.
For hyper-eutectoid steels the recommended austenitizing temperature is usually between
the Acm and A3,1 lines.
The Acm line rises so steeply that an excessively high temperature may be required to
dissolve all the proeutectoid cementite in the austenite. This tends to develop undesirable
coarse austenitic grain size, with danger of cracking on cooling.
Quenching
Mechanism
The properties of materials alter by different heat treating processes by varying the cooling
rate followed by quenching. If the actual cooling rate (ACR) exceeds the critical cooling
rate, only martensite will result. If the actual cooling rate is less than the critical cooling
rate (CCR), the part will not completely harden. So that, difference in cooling rates leads to
variation in properties. At this point, it is necessary to understand the mechanism of heat
removal during quenching.
A cooling curve shows the variation of temperature with time during quenching. A
cooling rate, however, shows the rate of change of temperature with time.
The cooling rate at any temperature may be obtained from the cooling curve by drawing a
tangent to the curve at that temperature and determining the slope of the tangent. It is
apparent that the cooling rate is constantly changing with time.
a- Vapor-blanket cooling stage

b- Vapor-transport cooling stage
c- Liquid cooling stage
a b c
Quenching
Vapor-blanket cooling stage
In this stage, quenching medium is vaporized at the surface of the metal and forms a thin
stable layer.
Cooling is by conduction and radiation.
Cooling rate is relatively slow
Vapor-transport cooling stage
This stage starts when the metal has cooled to a temperature at which the vapor
film is no longer stable. Wetting of the metal surface by the quenching medium
and violent boiling occur. Heat is removed from the metal very rapidly as the
latent heat of vaporization. This is the fastest stage of cooling.
Liquid cooling stage
This stage starts when the surface temperature of the metal reaches the boiling
point of the quenching liquid .
Vapor no longer forms, so cooling is by conduction and convection through the
liquid. The rate of cooling is slowest in this stage.
Factors affecting on Quenching
Many factors determine the actual cooling rate. The most important are the type of quenching
medium, the temperature of the quenching medium, the surface condition of the part, and the
size and mass of the part.
Quenching Medium
Brine solution (Water solution of 10% sodium chloride)

Tap water
Fused or liquid salts
Soluble oil and water solutions
Oil
Air
Temperature of Quenching Medium
Generally, as the temperature of the medium rises, the cooling rate decreases. This is due to
the increase in persistence of the vapor-blanket stage. This is particular true of water and brine.
In another case, an increase in cooling rate with a rise in temperature of the medium. In the
case of oil, as the temperature of the oil rises there is a tendency for the cooling rate to
decrease due to the persistence of the vapor film. However, as the temperature of the oil rises
it also become more fluid, which increase the rate of heat conduction through the liquid.
Severity of quench values of some typical quenching conditions
Process Variable H Value If the increase in rate of heat
Air No agitation 0.02 conduction is greater than the
Oil quench No agitation 0.2
decrease due to persistence of the
vapor film, the net result will be an
" Slight agitation 0.35
increase in the actual cooling rate.
" Good agitation 0.5 However if the reverse is true, then the
" Vigorous agitation 0.7 result will be decrease in cooling rate.
Water quench No agitation 1.0
Severity of Quench as indicated by the heat
" Vigorous agitation 1.5 transfer equivalent H
Brine quench f
(saturated Salt water)
No agitation 2.0 H= [ m −1 ]
K
" Vigorous agitation 5.0
f → heat transfer factor
Ideal quench ∞
K → Thermal conductivity
Note that apart from the nature of the quenching medium, the vigorousness of the shake determines the severity of the
quench. When a hot solid is put into a liquid medium, gas bubbles form on the surface of the solid (interface with medium).
As gas has a poor conductivity the quenching rate is reduced. Providing agitation (shaking the solid in the liquid) helps in
bringing the liquid medium in direct contact with the solid; thus improving the heat transfer (and the cooling rate). The H
value/index compares the relative ability of various media (gases and liquids) to cool a hot solid. Ideal quench is a conceptual
idea with a heat transfer factor of ∞ (⇒ H = ∞)
Surface condition
When the steel is exposed to an oxidizing atmosphere, because of the presence of

water vapor or oxygen in the furnace a layer of iron oxide called scale is formed.
Experiments have shown that a thin layer of scale has very little effect on the
actual cooling rate, but that a thick layer of scale (0.005 inch in deep) retards the
actual cooling rate.
There is also the tendency for parts of the scale to peel off the surface when the
piece is transferred from the furnace to the quench tank, thus giving rise to a
variation in cooling rate at different points on the surface. The presence of scale is
need to be considered only if the actual cooling rate is very close to critical
cooling rate.
To minimize the formation of scale, we have different methods depend upon part
being heat treated, type of furnace used, availability of equipment and cost.
Copper plating
Protective atmosphere
Liquid salt pots
Cast iron chips
Size and mass
The ratio of surface area to mass is an important factor in determining the actual cooling
rate, because only the surface of a part which is in contact with the quenching medium.
Thin plates and small diameter wires have a large ratio of surface area to mass and
therefore rapid cooling rates.
Surface area  πDL 
For Cylinder =  
 (π / 4) D Lρ 
2
Mass
The calculation shows that the ratio is inversely proportional to diameter if the diameter
is increased, the ratio of surface area to mass decreases, and the cooling rate decreases.
The heat in the interior of the piece must be removed by conduction, through the body of
the piece, eventually reaching the surface and the quenching medium. Therefore the
cooling rate in the interior is less than that at the surface.
If such variation in cooling rates exists across the radius of a bar during cooling, it is to
be anticipated that variations in hardness would be evident when the bars are cut and
hardness surveys made on the cross section. A considerable temperature difference
between the surface and the center during quenching (see in next slide).
This temperature difference will give rise to stresses during heat treatment called residual
stresses, which may result in distortion and cracking of the piece.
Hardness profile in a cylinder from surface to interior
Schematic showing variation in cooling

Typical hardness test survey made along rate from surface to interior leading to
a diameter of a quenched cylinder different microstructures
Hardenability
From the earlier study, we seen that, hardness profile various from case to core. It leads to
an important conclusion that, by varying the diameter of cylinder with same composition
will give the different hardness profiles, i.e., depth of hardness is different from different
size of samples. Generally this diagrams called as hardness-penetration diagrams or
hardness-traverse diagrams.
Hardenability is the ability of a steel to partially or completely transform from austenite to
some fraction of martensite at a given depth below the surface, when cooled under a given
condition.
For example, a steel of a high hardenability can transform to a high fraction of martensite to
depths of several millimeters, under relatively slow cooling, such as an oil quench, whereas
a steel of low hardenability may only form a high fraction of martensite to a depth of less
than a millimeter, even under rapid cooling such as a water quench. Hardenability therefore
describes the capacity of the steel to harden in depth under a given set of conditions.
Hardenability
Increase in the hardenability or depth of penetration of the hardness may be
accomplished by either of two methods:
1. With the actual cooling rates fixed, slow up the critical cooling rate (shift the
I-T curve to the right) by adding alloying elements or coarsening the
austenitic grain size.
2. With the I-T curve fixed, increase the actual cooling rates by using a faster
quenching medium or increasing circulation.
Since increasing cooling rates increase the danger of distortion or cracking, the
addition of alloying elements is the more popular method of increasing
hardenability.
Steels with high hardenability are needed for large high strength components, such
as large extruder screws for injection moulding of polymers, pistons for rock
breakers, aircraft undercarriages etc.
Steels with low hardenability may be used for smaller components, such as chisels
and gears etc.
The most widely used method of determining hardenability is the end-quench
hardenability test or the Jominy test, commonly called as Jominy End Quench
test.
Jominy End Quench Test
In conducting this test, a 1 inch round specimen 4 inch long is heated uniformly to the
proper austenising temperature. It is then removed from the furnace and placed on a fixture
where a jet of water impinges on the bottom face of the sample.
After 10 min. on the fixture, the specimen is removed, and to cut along the longitudinal
direction. And then Rockwell C scale hardness readings are taken at 1/16 inch, intervals
from the quenched end. The results are expressed as a curve of hardness values Vs. distance
from the quenched end. A typical hardenability curve shown below for eutectoid steel.
Jominy Sample Variation of hardness along a Jominy bar

Jominy End Quench Test
A number of Jominy end quench samples are first end- quenched for a series of different
times and then each of them (whole sample) is quenched by complete immersion in
water to freeze the already transformed structures.
Cooling curves are generated putting thermocouple at different locations and recording
temperature against cooling time during end quenching. Microstructures at the point
where cooling curves are known, are subsequently examined and measured by
quantitative metallography. Hardness measurement is done at each investigated point.
Based on metallographic information on investigated point the transformation start and
finish temperature and time are determined. The transformation temperature and time are
also determined for specific amount of transformation.
These are located on cooling curves plotted in a temperature versus time diagram. The
locus of transformation start, finish or specific percentage of transformation generate
CCT diagram (see next slide).
A, B, C, D, E, F are six different locations on the Jominy sample shown in Figure (before
slide) that gives six different cooling rates. The cooling rates A, B, C, D, E, F are in
increasing order. The corresponding cooling curves are shown on the temperature log
time plot. At the end of the cooling curve phases are shown at room temperature.
Variation in hardness with distance from Jominy end is also shown in the diagram.
Hardness, HRC
Jominy sample
FE D C B A
Distance from quench end
TE
to=Minimum incubation
A period at the nose of the
TTT diagram,
t0 tꞌo=minimum incubation
tꞌ0 period at the nose of the
B CCT diagram
Temperature
F C
E D M – Martensite
P – Pearlite
F.P – Fine pearlite
C.P – Coarse pearlite
MS MS – Martensite start
MF – Martensite finish
M50 TE – Eutectoid temp.
MF
M M P+M F.P P C.P
Log time
Tempering
Tempering is the re-heat treatment processes, to relieve the residual stresses and
improve the ductility and toughness of steel. In other words, tempering is a
processes to optimize the strength and toughness of steel.
With the increase in temperature, carbon diffusion becomes appreciable and the
metastable martensite decomposes to more stable products. Four stages of
tempering are known.
Stage I
Stage I of temperature extends from room temperature to 200°C. During this stage,
the martensite decomposes to two phases: a low carbon martensite with 0.2%C
some times known as black martensite, and ε (HCP, Fe2.4C), a transition carbide.
With increase in the carbon content of the steel, more ε-carbide forms. It
precipitates very fine form and resolves only under the electron microscope. The
hardening effect due to this precipitation is usually offset by the softening effect
associated with the loss of carbon in martensite.
Tempering
Stage II
Stage II tempering occurs in the range of 250-400°C changes the epsilon carbide to
orthorhombic cementite, the low-carbon martensite becomes BCC ferrite, and any retained
austenite is transformed to lower bainite as a function of time. The carbide are too small to
be resolved by the optical microscope, and the entire structure etches rapidly to a black
mass formerly called troostite.
Stage III
Stage III tempering in the range of 400-650°C continues the growth of the cementite
particles. This coalescence of the carbide particles allows more of the ferrite matrix to be
seen, causing the sample to etch lighter than the low temperature product. In this structure
formerly known as sorbite, it is resolvable above 500X, under electron microscopy it is
clearly visible.
Stage IV
Stage IV tempering in the range from 650-720°C produces large, globular cementite
particles. This structure is very soft and tough and is similar to the spheroidized cementite
structure. Spheroidite is the softest yet toughest structure that steel may have.
Tempering
For many years , metallurgists divided the tempering processes into definite stages.
For microstructures appearing in these stages was given names like Black
Martensite, troostite and sorbite. However, the changes in microstructures are so
gradual that it is more realistic to call the product of tempering at any temperature
simply tempered martensite.
A schematic of possible transformations involving austenite decomposition

Tempering
Tempering of some steels may result in a reduction of toughness what is known as
temper embrittlement.
This may be avoided by (1) compositional control, and/or (2) tempering above
575°C or below 375°C, followed by quenching to room temperature.
The effect is greatest in Martensite structures, less severe in bainite structures and
least severe in pearlite structures.
It appears to be associated with the segregation of solute atoms to the grain
boundaries lowering the boundary strength.
Impurities responsible for temper brittleness are: P, Sn, Sb and As. Si reduces the
risk of embrittlement by carbide formation. Mo has a stabilizing effect on carbides
and is also used to minimize the risk of temper brittleness in low alloy steels.
α ' ( BCT ) α ( BCC ) Fe3C (OR)

Summary →
Temper
+
Martensite Ferrite Cementite
Martempering
This heat treatment is given to oil hardenable and air hardenable steels and thin
section of water hardenable steel sample to produce martensite with minimal
differential thermal and transformation stress to avoid distortion and cracking.
The steel should have reasonable incubation period at the nose of its TTT
diagram and long bainitic bay.
The sample is quenched above MS temperature in a salt bath to reduce thermal
stress (instead of cooling below MF directly) Surface cooling rate is greater than at
the centre.
The cooling schedule is such that the cooling curves pass behind without touching
the nose of the TTT diagram. The sample is isothermally hold at bainitic bay such
that differential cooling rate at centre and surface become equalize after some
time.
The sample is allowed to cool by air through MS-MF such that martensite forms
both at the surface and centre at the same time due to not much temperature
difference and thereby avoid transformation stress because of volume expansion.
The sample is given tempering treatment at suitable temperature.
Martempering
Ae3
Ae1 γ=austenite
α=ferrite
α+CP CP=coarse pearlite
α+P P=pearlite
t0 FP FP=fine pearlite
t0=minimum incubation
50% FP + 50% UB period
Temperature
UB=upper bainite
UB LB=lower bainite
M=martensite
MS=Martensite start
Tempering temperature
M50=temperature at which
MS LB 50% martensite is
obtained
M50 MF= martensite finish
Metastable γ + martensite temperature
MF
Martensite Tempered martensite
Log time
Austempering
Austempering heat treatment is given to steel to produce lower bainite in high
carbon steel without any distortion or cracking to the sample.
The heat treatment is cooling of austenite rapidly in a bath maintained at lower
bainitic temperature (above Ms) temperature (avoiding the nose of the TTT
diagram) and holding it here to equalize surface and centre temperature and till
bainitic finish time.
At the end of bainitic reaction sample is air cooled. The microstructure contains
fully lower bainite. This heat treatment is given to 0.5-1.2 wt%C steel and low
alloy steel.
The product hardness and strength are comparable to hardened and tempered
martensite with improved ductility and toughness and uniform mechanical
properties. Products do not required to be tempered.
Austempering
Ae3
Ae1
γ=austenite
α+CP α=ferrite
α+P CP=coarse pearlite
t0 FP P=pearlite
FP=fine pearlite
t0=minimum incubation
Temperature
50% FP + 50% UB
period
UB UB=upper bainite
LB=lower bainite
Metastable γ M=martensite
MS=Martensite start
temperature
MS LB M50=temperature at which
50% martensite is
M50 obtained
Metastable γ + martensite MF= martensite finish
MF temperature
Martensite
Lower bainite
Log time
Comparison between Martempering & Austempering
800
Eutectoid temperature
723
Austenite
Pearlite
600
α + Fe3C
500 Pearlite + Bainite
T →
400 Bainite
300
Martempering Ms
200
Mf
100 Austempering
Martensite
0.1 1 10 102 103 104 105

t (s) →
Alloy Steels
Various elements like Cr, Mn, Ni, W, Mo etc are added to plain carbon
steels to create alloy steels
The alloys elements move the nose of the TTT diagram to the right
→ this implies that a slower cooling rate can be employed to obtain
martensite → increased HARDENABILITY
The ‘C’ curves for pearlite and bainite transformations overlap in the
case of plain carbon steels → in alloy steels pearlite and bainite
transformations can be represented by separate ‘C’ curves
Role of Alloying Elements
Segregation / phase separation Interstitial
Element Added Solid solution
Compound (new crystal structure) Substitutional
• + Simplicity of heat treatment and lower cost

• − Low hardenability
Plain Carbon Steel • − Loss of hardness on tempering
• − Low corrosion and oxidation resistance
• − Low strength at high temperatures
• ↑ hardenability
• Provide a fine distribution of alloy carbides during tempering
• ↑ resistance to softening on tempering
• ↑ corrosion and oxidation resistance
• ↑ strength at high temperatures
• Strengthen steels that cannot be quenched
Alloying elements • Make easier to obtain the properties throughout a larger section
• ↑ Elastic limit (no increase in toughness)
• Alter temperature at which the transformation occurs
• Alter solubility of C in α or γ Iron
• Alter the rate of various reactions
Sample elements and their role
P ►Dissolves in ferrite, larger quantities form iron phosphide → brittle (cold-shortness)
S ►Forms iron sulphide, locates at grain boundaries of ferrite and pearlite poor ductility
at forging temperatures (hot-shortness)
Si ► (0.2-0.4%) increases elastic modulus and UTS
Cu ►0.8 % soluble in ferrite, can be used for precipitation hardening
Pb ►Insoluble in steel
Cr ►Corrosion resistance, Ferrite stabilizer, ↑ hardness/strength, > 11% forms passive
films, carbide former
Ni ► Austenite stabilizer, ↑ strength ductility and toughness,
Mo► Dissolves in α & γ, forms carbide, ↑ high temperature strength,
↓ temper embrittlement, ↑ strength, hardenability
Mn +0.1% C
Brinell Hardness →
180
Mn
Cr + 0.1%C
140
100 Cr
60
v
0 2 4 6 8 10
Alloying Element (%) →
Alloying elements increase hardenability but the major contribution to hardness comes
from Carbon
Mn, Ni are Austenite stabilizers
Temperature →
0.35% Mn
6.5% Mn
0 0.4 0.8 1.2 1.6

C (%) →
Temperature →
Outline of the γ phase field

15% Cr 12% Cr
5% Cr 0% Cr
Cr is Ferrite stabilizer
Shrinking γ phase field with ↑ Cr
0 0.4 0.8 1.2 1.6

C (%) →
TTT diagram of low alloy steel (0.42%
C, 0.78% Mn, 1.79% Ni, 0.80% Cr,
0.33% Mo)
U.S.S Carilloy Steels, United States Steel Corporation,
Pittsburgh, 1948)
Surface Hardening Treatments
Numerous industrial applications require a hard wear resistant surface called the
case, and a relatively soft, tough inside called the core. Example: Gears
They are two different categories. They are thermo chemical and thermo
mechanical treatments. Thermo chemical treatment is related to change in
chemical composition and In Thermo mechanical treatment, there is no change of
chemical composition of the steel and are essentially shallow- hardening methods.
A detailed flow chart is given below related to surface hardening treatments.
SURFACE
Thermal Thermo-Chemical
Flame
Induction Carburizing
Laser Nitriding
Electron Beam Cyaniding

Thermo Chemical Treatments
Carburizing
Carburizing is the most widely used method of surface hardening. Here, the
surface layers of a low carbon steel (<0.25) is enriched with carbon up to 0.8-
1.0%. The source of carbon may be a solid medium, a liquid or a gas.
In all cases, the carbon enters the steel at the surface and diffuses into the steel as a
function of time at an elevated temperature. Carburizing is done at 920-950°C. at
this temperature the following reaction takes place
Fe + 2CO → Fe( c ) + CO2
Where Fe(c) represents carbon dissolved in austenite. the rate of diffusion of carbon
in austenite, at a given temperature is dependent upon the diffusion coefficient and
the carbon concentration gradient.
The carburizing equation given previously, Fe+2CO Fe(c) + CO2 is reversible
and may proceed to the left, removing carbon from the surface layer if the steel is
heated in an atmosphere containing carbon dioxide (CO2). This is called
decarburization.
Carburizing
Decarburization may be prevented by using an endothermic gas atmosphere in the

furnace to protect the surface of the steel from oxygen, carbon dioxide and water
vapor.
An endothermic gas atmosphere is prepared by reacting relatively rich mixtures of
air and hydrocarbon gas (usually natural gas) in an externally heated generator in
the presence of a nickel catalyst.
Liquid Carburizing
Liquid carburizing is a method of case hardening steel by placing it in a bath (8%

NaCN, 82% BaCl2 and 10% NaCl) of molten cyanide so that carbon will diffuse
from the bath into the metal and produce a case comparable to one resulting from
pack or gas carburizing.
Liquid carburizing may be distinguished from cyaniding by the character and
composition of the case produced. The cyanide case is higher in nitrogen and
lower in carbon; the reverse is true of liquid carburized cases.
BaCl2 + 2NaCN 
→ Ba(CN)2 + 2NaCl
Ba(CN ) 2 + Fe 
→ Fe(C ) + Ba(CN ) 2
Pack Carburizing
In pack carburizing, the article s to be carburized are packed in a box, embedding

them in a powdery mixture of 85% charcoal and 15% of energizers such as BaCO3.
The box is sealed with fireclay and loaded into the furnace kept at 930°C. The
residual air in the box combines with carbon to produce CO. The energizer
decomposes as below : BaCO 3  → BaO + CO 2
CO2 + C 
→ 2CO
The carbon enters the steel through the following reaction:
Fe + 2CO 
→ F e (c) + CO 2
If selective carburization is to be done, copper is electroplated to a thickness of

~0.05 mm in regions where carburization is not desired. Alternatively, a refractory
paste of fireclay mixed with asbestos can be applied. Control of temperature and
penetration depth is less in pack carburizing as compared to liquid and gas
carburizing. Also, direct quench from the carburizing temperature to harden the
surface is not possible.
Gas Carburizing
The steel is heated in contact with carbon monoxide and/or a hydrocarbon which is
readily decomposed at the carburizing temperature.
A mixture consisting of 5-15% methane (or propane) in a neutral carrier gas is used.
The methane decomposes according to the following reaction:
CH 4 + Fe 
→ 2 H 2 + Fe(c)
The carbon potential of the gas mixture increases with increasing concentration of
methane. Too large a concentration or too high a gas velocity releases carbon faster
than it can be absorbed and may result in soot formation on the surface.
Closer control of temperature and case depth is possible in gas carburizing, as
compared to pack carburizing. Also, post quenching can be done directly.
Heat treatment after carburizing
Since steel is carburized in the austenite region, direct quenching from the carburizing
temperature will harden both the case and core will harden both the case and core if the
cooling rate is greater than the critical cooling rate. Direct quenching of coarse grained
steels often leads to brittleness and distortion, so that this treatment should be applied only
to fine grained steels. A diagrammatic representation of various hardening treatments for
carburized steels shown in next slide.
Heat treatment after carburizing
TREATMENT CASE CORE

A – best adapted to fine
Refined; Excess carbide not dissolved Unrefined; soft and machinable
grained steels
B-best adapted to fine Slightly coarsened; some solution of excess Partially refined; stronger and tougher than
grained steels carbide A
Somewhat coarsened; solution of excess Refined: maximum core strength and
C-best adapted to fine
carbide favored; austenite retention promoted hardness; better combination of strength and
grained steels
in highly alloyed steels. ductility than B
D-best treatment for Refined solution of excess carbide favored; Refined; soft and machinable; maximum
coarse grained steels austenite retention minimized toughness and resistance to impact
E-adapted to fine grained Unrefined with excess carbide dissolved;
Unrefined but hardened
steels only austenite retained; distortion minimized
F-adapted to fine grained Refined; solution of excess carbide favored;
Unrefined; fair toughness
steels only austenite retention minimized
Relation of time and temperature to
case depth
Carburizing
Carbon-concentration gradient in a
Carbon
carburized steel
Nitriding
In contrast to the processes described before, nitriding is carried out in the ferrite
region. Consequently, no phase change occurs after nitriding .
This part to be nitrided should possess the required core properties prior to
nitriding. Pure ammonia decomposes to yield nitrogen which enters the steel:
2 NH 3 
→ 2 N + 3H 2
The solubility of nitrogen in ferrite is small. Most of the nitrogen that enters the
steel forms hard nitrides (e.g. Fe3N). A typical nitriding steel contains alloying
elements of 1%Al, 1.5%Cr and 0.2%Mo. Al, Cr, and Mo form very hard and wear
resistant nitrides.
The temperature of nitriding is 500-590°C. the time for a case depth of 0.02mm is
about 2 hour. In addition with wear resistance, it also increases the resistance of a
carbon steel to corrosion in moist atmospheres.
A common problem encountered in nitriding is the formation of γꞌ nitride (Fe4N)
on the outer layers of the case , known as the “white layer”, as it looks white under
the microscope. This layer is very brittle and tends to crack. It must be removed by
final grinding operation. Its formation can be minimized by maintaining the correct
ratio of NH3/ H2 in the gas mixture during the heat treatment.
Cyaniding and Carbonitriding
In this case that contain both carbon and nitrogen are produced in liquid salt baths
(cyaniding) or by use of gas atmospheres (carbonitriding). The temperatures used
are generally lower than those used in carburizing, being between 750-900°C.
Exposure is for a shorter time, and thinner cases are produced, up to 0.010in. For
cyaniding and up to 0.030in. For carbonitriding.
In Cyaniding is done in a liquid bath of NaCN, with the concentration varying
between 30 and 97%. Both carbon and nitrogen enter the steel via the following
reactions:
2 NaCN + O2 
→ 2 NaCNO
3 NaCNO 
→ NaCN + Na2CO3 + C + 2 N
The temperature used for cyaniding is lower than that for carburizing and in the
range of 800-870°C. the time of cyaniding is 0.5-3 hour to produce a case depth of
0.25 mm or less.
Cyaniding and Carbonitriding
Carbonitriding is a case-hardening process in which a steel is heated in a gaseous

atmosphere of such composition that carbon and nitrogen are absorbed
simultaneously.
This process is also known as dry cyaniding or gas cyaniding. It is the gas
carburizing process modified by the addition of anhydrous ammonia.
The decomposition of ammonia provides the nitrogen, which enters the steel along
with carbon.
A typical gas mixture consists of 15% NH3, CH4, and 80% of neutral carrier gas.
The temperature used is 750-900°C. With increasing temperature, a greater
proportion of carbon enters the steel.
The presence of nitrogen in the austenite accounts for the major differences
between carbonitriding and carburizing. Carbon-nitrogen austenite is stable at
lower temperatures than plain-carbon austenite and transforms more slowly on
cooling. Carbonitriding therefore can be carried out at lower temperatures and
permits slower cooling rates than carburizing in the hardening operation
Thermal Energy Treatments
Flame Hardening
For large work pieces, such as mill rolls, large gears and complicated cross
sections, in such cases, flame hardening is done by means of an oxyacetylene
torch. Heating should be done rapidly by the torch and the surface quenched,
before appreciable heat transfer to the core occurs.
Four methods are generally use for

Flame Hardening
Stationary (Spot): Torch and
work is stationary
Progressive: Torch moves over
a work piece
Spinning: Torch is stationary
while work piece rotates
Progressive-spinning: Torch
moves over a rotating work
piece.
Induction Hardening
Here, an alternating current of high frequency passes through an induction coil
enclosing the steel part to be heat treated. The induced emf heats the steel. the
depth up to which the heat penetrates and rises the temperature above Ac3 is
inversely proportional to the square root of the AC frequency.
Correspondingly, the hardened depth decreases with increasing frequency in
induction hardening, the heating time is usually a few seconds. Immediately after
heating water jets are activated to quench the surface . Martensite is produced at
the surface, making it hard and wear resistant. The microstructure of the core
remains unaltered. Induction hardening is suitable for mass production of articles
of uniform cross section
Five basic designs of work coils with the heat patterns developed by each are shown below
A Simple Solenoid for

external heating
Induction Hardening
A coil to be used internally

for heating bores
A “pie-plate” type of coil

designed to provide high
current densities in a
narrow band for scanning
applications.
A Single turn coil for scanning

a rotating surface, provided
with a contoured half turn that
will aid in heating the fillet
A ‘Pancake’ coil for spot

heating.
Laser Hardening
Laser hardening treatment is widely used to harden localized areas of steel and cast
iron machine components. This process is sometimes referred to as laser
transformation hardening to differentiate it from laser surface melting phenomena.
There is no chemistry change produced by laser transformation hardening, and the
process, like induction and flame hardening, provides an effective technique to
harden ferrous materials selectively.
As laser beams are of high intensity, a lens is used to reduce the intensity by
producing a defocused spot of size ranging from 0.5 to 25 mm. proper control of
energy input is necessary to avoid melting.
Laser transformation hardening produces thin surface zones that are heated and
cooled very rapidly, resulting in very fine Martensitic microstructures, even in steels
with relatively low hardenability. High hardness and good wear resistance with less
distortion result from this process.
Laser hardening has the advantage of precise control over the area to be hardened, an
ability to harden reentrant surfaces, very high speed of hardening and no separate
quenching step (the quench is effected by the mass of the unheated material).
The disadvantage is that the hardening is shallower than in induction and flame
hardening.
Electron Beam (EB) Hardening
Electron Beam (EB) hardening is like laser treatment, is used to harden the
surfaces of steels. The EB heat treating process uses a concentrated beam of high-
velocity electrons as an energy source to heat selected surface areas of ferrous
parts. Electrons are accelerated and are formed into a directed beam by an EB gun.
After exiting the gun, the beam passes through a focus coil, which precisely
controls beam density levels (spot size) at the work piece surface and then passes
through a deflection coil.
To produce an electron beam, a high vacuum of 10-5 torr is needed in the region
where the electrons are emitted and accelerated. This vacuum environment
protects the emitter from oxidizing and avoids scattering of the electrons while
they are still traveling at a relatively low velocity.
Like laser beam hardening, the EB process eliminates the need for quenchants but
requires a sufficient work piece mass to permit self quenching.
A mass of up to eight times that of the volume to be EB hardened is required
around and beneath the heated surfaces. Electron beam hardening does not require
energy absorbing coatings, as does laser beam hardening.
Relative benefits of common surface-
surface-hardening processes
PROCESS BENEFITS
Hard, highly wear-resistant surface (medium case depths); excellent capacity for contact load; good
Carburizing bending fatigue strength; good resistance to seizure; excellent freedom from quench cracking; low-to-
medium cost steels required; high capital investment required
Hard, highly wear-resistant surface (shallow case depths); fair capacity for contact load; good bending
fatigue strength; excellent resistance to seizure; excellent dimensional control possible; good freedom from
Nitriding
quench cracking (during pretreatment); medium-to-high-cost steels required; medium capital investment
required; improved salt corrosion resistance
Hard, highly wear-resistant surface (deep case depths); good capacity for contact load; good bending
Induction
fatigue strength; fair resistance to seizure; fair dimensional control possible; fair freedom from quench
hardening
cracking; low-cost steels usually satisfactory; medium capital investment required
Hard, highly wear-resistant surface (deep case depths); good capacity for contact load; good bending
Flame
fatigue strength; fair resistance to seizure; fair dimensional control possible; fair freedom from quench
hardening
cracking; low-cost steels usually satisfactory; low capital investment required
Residual Stresses
These are stresses that remain in the part after the force has disappeared. Residual
stresses always arise from a nonuniform plastic deformation.
In the case of heat treatment, this nonuniform plastic deformation may be caused
by the temperature gradient or the phase change or usually a combination of both
factors during cooling.
Residual stresses are a very serious problem in heat treatment, since they often
result in distortion or cracking and in some cases in premature failure of the part in
service.
Consider the effect of temperature gradient alone . It was shown earlier, under the
effect of size and mass, that during quenching the surface is cooled more rapidly
than the inside.
Almost all solids expand as they are heated and contract as they are cooled. This
means that at the end of 10 s ( for example) the surface, since it is at a much lower
temperature, should have contracted much more than inside.
However since the outside and inside are attached to each other, the inside, being
longer, will prevent the outside from contracting as much as it should. It will
therefore elongates the outside layer, putting them in tension while the inside in
turn will be in compression.
Residual Stresses
Thermal stresses may by calculated from the following formula:
S = α . E . ∆Τ
Where S = Thermal stress, psi
α = Coefficient of linear expansion in./(in.)(°F)
E = Modulus of elasticity, psi
∆T = Difference in temperature, °F
The stress distribution is plotted schematically in below figure.
Tension
150
100
The stress distribution The area in tension
across the dia. Due to
Stress 103 psi
50 must balance the

temperature gradient. area in compression
Dotted curve indicates in order for the
a truer representation 0
stresses to be in
of the stress
Compression
equilibrium across
distribution
distribution. 50 the cross section
Diameter
100
Residual Stresses
In general, the tensile stress on the surface may reach a very high value. If this
stress exceeds the ultimate strength of the material, cracking will occur.
In the case of steel, however, thermal stresses alone very rarely lead to cracking. If
the stress is below the yield strength of the steel, the stress will be borne
elastically.
When the entire piece has reached room temperature, ∆T = 0, and therefore, since
the thermal stress will be zero, there will be no distortion.
If the stress exceeds the yield strength, the surface layer will be plastically
deformed or permanently elongated. At room temperature the surface will have
residual compressive stress and the inside, residual tensile stress.
Let us consider the combined effect of temperature gradient and phase change for
two possibilities: (1) Through-Hardened steel and (2) Shallow-Hardened steel
The next two slides shows the surface- and center- cooling curves superimposed
on the I-T diagram for the through hardened steel and shallow hardened steel.
In many applications, the tensile stress developed by the external force is
maximum at or near the surface. For these applications, shallow hardened or case-
hardened parts are preferred.
Residual Stresses
Through-Hardened Condition
Ae1 STRESS CONDITION
Center cooling curve STAGE
SURFACE CENTER
First Temperature
Tension Compression
gradient
Second
Compression Tension
A+F+C F+C A →M of surface
Temperature
Third
Tension Compression
A→M of center
Crack
Surface
cooling
curve
Ms
Mf
1st stage 2nd stage 3rd stage
Compression Tension
t1 t2 layers layers
Time, log scale
Possible fracture in Through-Hardened steel
Residual Stresses
Shallow-Hardened Condition
Ae1 STRESS CONDITION

STAGE
Center cooling curve SURFACE CENTER
First
Tension Compression
Temperature gradient
Second
A+F+C F+C A →M of surface Compression Tension
A→P of center
Temperature
Third
Greater Greater
Cooling of center to Compression Tension
room temperature
Crack
Surface
cooling
curve
Ms
Mf
1st stage 2nd stage 3rd stage
Tension Compression
t1 t2 layers layers
Time, log scale
Possible fracture in Shallow-Hardened steel
Questions..?
1. If a piece of steel having 0.2% carbon is quenched after soaking at a temperature just above
A1 what type of structure will you get? Estimate approximate constituents of phases present
and their compositions.
2. Carbon atoms occupy octahedral interstitial sites in austenite and ferrite. Estimate fraction
of these sites that are occupied in these if carbon contents are 0.1 and 0.01wt% respectively.
3. Show that the inter-lamellar spacing of pearlite is inversely proportional to the degree of
under cooling.
4. Which is the more stable, the pearlitic or the spheroiditic microstructure? Why?
5. Microstructure of isothermally transformed pearlite should have identical spacing in all
colonies. However often its microstructure often shows that lamellar spacing varies from
colony to colony. Why is it so?
6. Cite two major differences between martensitic and pearlitic transformations.
7. Use the concept of Bain distortion to estimate maximum displacement experienced by iron
atom during martensitic transformation. Lattice parameters of austenite and ferrite are
0.356nm & 0.286 respectively. Assume c/a ratio of martensite to be 1.15.
8. Name three most important characteristics of martensitic transformation in steel.
9. Explain why bainite does not form during continuous cooling in plain carbon steel.
10. Why do not you have long carbide plates like Pearlite in Baintite?
Questions..?
11. Suggest a simple experimental method for determination of Ms temperature of steel if you
have only facility for heat treatment and metallographic examination.
12. Which of the two would require more severe cooling rate to get fully hardened structure?
(a) 0.8 % carbon steel (b) 1.0 % C steel.
13. Briefly describe the simplest continuous cooling heat treatment procedure that would be
used to convert a 4340 steel from (martensite + bainite) to (ferrite + pearlite).
14. A piece of steel which was quenched after prolonged holding at 700⁰C was found to have
ferrite martensite structure. Explain when would you expect this to happen?
15. List the factors that determine the strength of properly hardened steel.
16. 0.2 % plain carbon steel in annealed condition has 25% coarse pearlite. If it is normalized
(heat treatment) what changes would you expect in its microstructure?
17. A thin strip of 1.2% carbon steel is quenched in water from its fully austenitic state. What
structure would you expect in this steel?
18. List the factors that determine hardenability of steel. Which of these are preferred? Give
reasons.
19. What is meant by severity of quench? List the factors that determine this. What is its
dimension?
20. Give example of a shallow hardening and a deep hardening steel.
21. A hardened steel has become embrittled on tempering. Can this be de-embrittled?
Questions..?
22. In terms of heat treatment and the development of microstructure, what are two major
limitations of the iron–iron carbide phase diagram?
23. Briefly describe the phenomena of superheating and supercooling. Why do these occur?
24. Make a copy of the isothermal transformation diagram for an iron–carbon alloy of eutectoid
composition and then sketch and label time–temperature paths on this diagram to produce
the following microstructures:
25. Cite two important differences between continuous cooling transformation diagrams for
plain carbon and alloy steels.
26. What is the white layer on steel that forms during nitriding?
27. Cite three main reasons for surface hardening of steel.
28. Explain why core refining heat treatment may not be required for case carburized
aluminium killed steel.
29. Can steel having 0.1% carbon be case carburized at 850⁰C?
30. Explain the construction of TTT diagram. Why it is called S – Curve? And Draw a CCT
diagram for eutectoid steel. Which one is more important industrially and why?
Avala Lava Kumar*
Introduction
Diffusion is defined as, random movement of atoms/ molecules in solid, liquid and
gas. For example dissolution of ink in water and smoke in air
It can also defined as, Diffusion is a process of mass transport by atomic
movement under the influence of thermal energy and a concentration gradient.
To comprehend many materials related phenomenon one must understand
diffusion.
Role of Diffusion
Oxidation Creep
Sintering Aging
Doping Carburizing
Many More...!
Materials Joining : Diffusion Bonding
Diffusion Phenomena
Mass flow process by which species change their position relative to their
neighbors.
Driven by thermal energy and a gradient
Thermal energy → thermal vibrations → Atomic jumps
Atoms move from higher to lower concentration region. If this movement is from
one element to another e.g. Cu to Ni, then it is termed as Inter-diffusion. If the
movement is within similar atoms as in pure metals, it is termed self-diffusion.
Gradient
Electric Stress
Magnetic Chemical potential

Diffusion Mechanism
Diffusion of atoms involves movement in steps from one lattice site to the another.
An empty adjacent site and breaking of bonds with the neighbor atoms are the two
necessary conditions for this.
Vacancy Mechanism
This mechanism involves movement of atoms (we are interested in substitutional

atoms) from a regular lattice site to an adjacent vacancy. Since vacancy and atoms
exchange position, the vacancy flux is in the opposite direction.
Diffusion Mechanism
Interstitial Mechanism
This mechanism Involves migration of atoms from one interstitial site to a

neighboring empty interstitial site.
Usually the solubility of interstitial atoms (e.g. carbon in steel) is small. This
implies that most of the interstitial sites are vacant. Hence, if an interstitial species
wants to jump, ‘most likely’ the neighboring site will be vacant and jump of the
atomic species can take place.
This mechanism is more prevalent for impurity such a hydrogen, carbon, nitrogen,
oxygen which are small enough to fit into an interstitial position.
Interstitial
Interstitial
atom
atom
Diffusion Mechanism
Atom Interchange Mechanism
It is possible for movement to take place by a direct interchange between two
adjacent atoms or by a four –atom ring interchange.
However, these would probably occur only under special conditions, since the
physical problem of squeezing between closely packed neighboring atoms would
increase the barrier for diffusion.
Note: The rate of diffusion is much greater in a rapidly cooled alloy than in the
same alloy slow cooled. The difference is due to the larger number of vacancies
retained in the alloy by fast cooling.
Kirkendall effect
If the diffusion rates of two metals A and B into each other are different, the
boundary between them shifts and moves towards the faster diffusing metal.
This is known as kirkendall effect. Named after the inventor Ernest Kirkendall
(1914-2005). It can be demonstrated experimentally by placing an inert marker at
the interface
A B
Materials A and B welded together with inert Marker

marker and given a diffusion anneal motion
Usually the lower melting component diffuses
faster (say B)
Inert Marker – thin rod of a high melting material which is

basically insoluble in A & B
Kirkendall effect
Zn diffuses faster into Cu than Cu in Zn. A diffusion couple of Cu and Zn will lead
to formation of a growing layer of Cu-Zn alloy (Brass).
Same will happen in a Cu-Ni couple as copper diffuses faster in nickel than nickel
in copper.
Since this takes place by vacancy mechanism, pores will form in cu (of the Cu-Ni
couple as the vacancy flux in the opposite direction (towards Cu) will condense to
form pores.
steady and non-steady state diffusion
Diffusional processes can be either steady-state or non-steady-state. These two
types of diffusion processes are distinguished by use of a parameter called flux.
It is defined as net number of atoms crossing a unit area perpendicular to a given
direction per unit time. For steady-state diffusion, flux is constant with time,
whereas for non-steady-state diffusion, flux varies with time.
A schematic view of concentration gradient with distance for both steady-state and
non-steady-state diffusion processes are shown below.
Flux (J) (restricted definition) → Flow / area / time [Atoms / m2 / s]

Steady state diffusion Non-Steady state diffusion
C1 C1
Concentration →
Concentration →
D ≠ f(c)
Steady state
D = f(c)
J ≠ f(x,t) t1
t2
C2 t3
Non-steady state C2
J = f(x,t)
Distance, x → Distance, x →
steady and non-steady state diffusion
Steady State : Concentration profile not changing with time.
Concentration ‘C’ in the box

J (left) J (right) doesn’t change with time
Steady State
X J(x) Left = J(x) Right
Non--Steady State : Concentration profile changes with time.

Non
dx
Concentration accumulating
in the box
J (left) J (right)
Non-Steady State
J(x) Left ≠J(x) Right
Fick’s I law
Steady-state diffusion is described by Fick’s first law which states that flux, J, is
proportional to the concentration gradient.
The constant of proportionality is called diffusion coefficient (diffusivity), D
(cm2/sec). diffusivity is characteristic of the system and depends on the nature of
the diffusing species, the matrix in which it is diffusing, and the temperature at
which diffusion occurs.
Thus under steady-state flow, the flux is independent of time and remains the same
at any cross-sectional plane along the diffusion direction. for the one-dimensional
case, Fick’s first law is given by
J ≡ atoms / area / time ∝ concentration gradient

dc dc 1 dn dc
J∝ J = −D J= = −D
Steady state
dx dx A dt dx
J ≠ f(x,t)
No. of atoms crossing Concentration gradient
dn dc
= − DA
area A per unit time
Diffusion coefficient/ Cross-sectional area
diffusivity dt dx The minus sign in the equation means that
diffusion occurs down the concentration gradient
Fick’s I law
In Ficks I law, minus sign comes from the fact that matter flows down the concentration
gradient. It is not necessarily true in all the cases.
Matter may also diffuse up the concentration gradient, which is called uphill diffusion.
Fick’s first law can directly be applied in the case of
steady state, as shown in the example below.
Steady state means that there will not be any change in
the composition profile with time.
If we pass carburizing gas through the pipe as shown in
the figure and decarburizing gas outside the pipe, a
steady composition profile may develop.
Concentration gradient can be calculated following:
dc C − C0 C − Ci
=− i =− 0
dx d d
From this, one can calculate the flux from the known
diffusion coefficients of carbon or the diffusion
coefficient from the flux determined.
The steady-state diffusion is found in the purification of hydrogen gas.
Solved Compute the number of kilograms of hydrogen that pass per hour through a
Example -1 6-mm-thick sheet of palladium having an area of 0.25 m2 at 600°C. Assume a
diffusion coefficient of 1.7 × 10-8 m2 / s, that the concentrations at the high-
and low-pressure sides of the plate are 2.0 and 0.4 kg of hydrogen per cubic
meter of palladium, and that steady-state conditions have been attained.
This Problem calls for the mass of hydrogen, per hour, that diffuses through a pd sheet.
From the Fick’s I law:
∆c
M = JAt = − DAt
∆x
−8  0.4 − 2.0kg / m 3 
= −(1.7 × 10 m / s )(0.25m )(3600 s / h) 
2 2
−3 
 6 × 10 s 
= 4.1×10 −3 kg / h
A sheet of BCC iron 2 mm thick was exposed to a carburizing gas atmosphere on one
Solved side and a decarburizing atmosphere on the other side at 675ºC. After having reached
Example -2 steady state, the iron was quickly cooled to room temperature. The carbon
concentrations at the two surfaces of the sheet were determined to be 0.015 and 0.0068
wt%. Compute the diffusion coefficient if the diffusion flux is 7.36 × 10-9 kg/m2-s
(Hint : convert the concentrations from weight percent to kilograms of carbon per
cubic meter of iron.
This problem calls for computation of the diffusion coefficient for a steady-state diffusion
situation. Let us first convert the carbon concentrations from weight percent to kilograms
carbon per meter cubed using below equation.
For 0.015 wt% C    
 C   0.015 
C 'C =  C
× 10 
3 C 'C =  × 10 3  = 1.18kgC / m 3
C C 0.015 99.985
 C+ C   + 
 ρ C ρ Fe   2.25 7.87 
Similarly, for 0.0068 wt% C  

 0.0068 
C '' C = ×103  = 0.535kgC / m3
0.0068 99.9932
 + 
 2 . 25 7 .87 
X − XB  − 2 × 10 −3 m 
D = −J A −9
= −(7.36 × 10 Kg / m − s ) 2
3
C A − CB 1.18 Kg / m − 0.535 Kg / m 
3
= 2.3 ×10−11 m 2 / s
Fick’s II law
Most interesting cases of diffusion are non-steady-state processes since the
concentration at a given position changes with time, and thus the flux changes with
time.
This is the case when the diffusion flux depends on time, which means that a type
of atoms accumulates in a region or depleted from a region (which may cause them
to accumulate in another region). Fick’s second law characterizes these processes,
which is expressed as:
 Atoms 1    Atoms 
∆x  m 3 s .m  =  m 2 s  ≡ [J ]
Accumulati on = J x − J x + ∆x     
 ∂J   ∂c   ∂J 
Jx Jx+∆x Accumulation = J x −  J x + ∆x   ∆x = J x −  J x + ∆x 
 ∂x   ∂t   ∂x 
Non-steady state
 ∂c  ∂  ∂c   ∂c  ∂  ∂c   ∂c  ∂J
  = D    = −  −    ∆ = − ∆x
J = f(x,t)
D x
 ∂t  ∂x  ∂x   ∂t  ∂x  ∂x   ∂t  ∂x
 ∂c  ∂ 2c
 =D 2 Fick’s II law
 ∂t  ∂x
Solutions to Fick’s II law
 ∂c  ∂ 2c
 =D 2
 ∂t  ∂x
Solution to the above expression is possible when meaningful boundary conditions
are specified. One common set of boundary conditions can be written as:
For t = 0, C = Co at 0 ≤ x ≤∞
Cs
For t > 0, C = Cs at x = 0
Concentration →
C = Co at x = ∞
Cs - Co
Cx
C ( x, t ) − C o  x 
= 1 − erf   Cx - Co
C s − Co  2 Dt  Co
Distance, x →
Where Cx represents the concentration at depth x after time t. The term erf stands for Gaussian
error function. Corresponding error function values for a variable are usually found from
standard mathematical tables. The above equation demonstrates the relationship between
concentration, position, and time. Thus the equation can be used to explain many practical
industrial problems like corrosion resistance of duralumin, carburization and decarburization of
steel, doping of semi conductors etc.
Summary on Fick’s II law
Process Solution
 x  Cs = Surface concentration
Carburisation C = CS − (C S − C0 )erf  
 2 Dt  C0 = Bulk concentration
 x 
Decarburisation C = C0 erf   C0 =Initial Bulk concentration
 2 Dt 
 C + C2   C1 − C2   x  C1 = Concentration of steel 1
Diffusion couple C = 1 − erf   C2 = Concentration of steel 2
 2   2   2 Dt 
 πx   t Cmean = Mean concentration

C = Cmean + β 0 sin   exp −  β0 = Initial concentration amplitude
Homogenisation λ  τ λ = half wavelength
t = relaxation time
An FCC iron–carbon alloy initially containing 0.55 wt% C is exposed to an
Solved oxygen-rich and virtually carbon-free atmosphere at 1325 K (1052ºC).
Example - 3 Under these circumstances the carbon diffuses from the alloy and reacts at
the surface with the oxygen in the atmosphere; that is, the carbon
concentration at the surface position is maintained essentially at 0 wt% C.
(This process of carbon depletion is termed decarburization.) At what
position will the carbon concentration be 0.25 wt% after a 10-h treatment?
The value of D at 1325 K is 4.3 × 10-11 m2/s.
This problem asks that we determine the position at which the carbon concentration is 0.25 wt%
after a 10-h heat treatment at 1325 K when Co = 0.55 wt% C.
C x − Co 0.25 − 0.55  x 
= = 0.5455 = 1 − erf  
C s − Co 0 − 0.55  2 Dt  Z Erf (Z)
 x  0.40 0.4284
erf   = 0.4545
 2 Dt  Z 0.4545
Using tabulation of error function values and linear interpretation
0.45 0.4755
Z − 0.40 0.4545 − 0.4284
= Z = 0.4277
0.45 − 0.40 0.4755 − 0.4284
 x 
  = 0.4277 x = 2(0.4277) Dt = (0.8554) (3.6 × 10 4 s )(4.3 × 10 −11 m 2 / s )
 2 Dt 
= 1.06 ×10 −3 m = 1.06mm
Solved Nitrogen from a gaseous phase is to be diffused into pure iron at 675ºC. If
Example - 4 the surface concentration is maintained at 0.2 wt% N, what will be the
concentration 2 mm from the surface after 25 h? The diffusion coefficient
for nitrogen in iron at 675ºC is 1.9× 10-11 m2/s .
This problem asks us to compute the nitrogen concentration Cx at the 2 mm position after a 25
h diffusion time, when diffusion is non steady-state.
C x − Co C x − 0  x 
= = 1 − erf  
Cs − Co 0.2 − 0  2 Dt 
 2 × 10 −3
m 
= 1 − erf   = 1 − erf (0.765)
 2 (1.9 × 10 −11 m 2 / s )(25h)(3600 s / h) 
 
Using tabulation of error function values and linear interpretation Z Erf (Z)
0.750 0.7112
0.765 − 0.750 y − 0.7112 y = erf (0.765) = 0.7205
=
0.800 − 0.750 0.7421 − 0.7112 0.765 y
Cx − 0 0.800 0.7421
= 1.0 − 0.7205
0.2 − 0
C x = 0.056wt % N
Factors affecting Diffusion
Ease of a diffusion process is characterized by the parameter D, diffusivity. The value
of diffusivity for a particular system depends on many factors as many mechanisms
could be operative.
Diffusing species
If the diffusing species is able to occupy interstitial sites, then it can easily diffuse
through the parent matrix. On the other hand if the size of substitutional species is
almost equal to that of parent atomic size, substitutional diffusion would be easier.
Thus size of diffusing species will have great influence on diffusivity of the system.
Lattice structure
Diffusion is faster in open lattices or in open directions than in closed directions.
Presence of defects
As mentioned in earlier section, defects like dislocations, grain boundaries act as

short-circuit paths for diffusing species, where the activation energy is diffusion is
less. Thus the presence of defects enhances the diffusivity of diffusing species.
Factors affecting Diffusion
Temperature
Temperature has a most profound influence on the diffusivity and diffusion rates. It
is known that there is a barrier to diffusion created by neighboring atoms those
need to move to let the diffusing atom pass. Thus, atomic vibrations created by
temperature assist diffusion.
Empirical analysis of the system resulted in an Arrhenius type of relationship
between diffusivity and temperature.
 Q 
− 
D = D0 e  kT 
Where D0 is a pre-exponential constant, Q is the activation energy for diffusion, R

is gas constant (Boltzmann’s constant) and T is absolute temperature.
From the above equation it can be inferred that large activation energy means
relatively small diffusion coefficient. It can also be observed that there exists a
linear proportional relation between (lnD) and (1/T). Thus by plotting and
considering the intercepts, values of Q and D0 can be found experimentally (see in
next slide for clear understanding).
Diffusion paths with lesser resistance
Experimentally determined activation energies for diffusion…!
Qsurface < Qgrain boundary < Qpipe < Qlattice

Lower activation energy automatically implies higher diffusivity
Core of dislocation lines offer paths of lower resistance PIPE DIFFUSION
Diffusivity for a given path along with the available cross-section for the path will
determine the diffusion rate for that path
Comparison of Diffusivity for
Log (D) →
self-diffusion of Ag → Single Polycrystal
crystal vs. polycrystal
Single
Qgrain boundary = 110 kJ /mole crystal
QLattice = 192 kJ /mole 1/T →

← Increasing Temperature
Solved Using the following diffusion data, compute the value of D for the
Example - 5 diffusion of magnesium in aluminum at 400ºC.
Do(Mg in Al) =1.2 × 10-4 m2/s Qd=131 KJ/mol
This problem asks us to compute the magnitude of D for the diffusion of Mg in Al at

400ºC (673K).
−4  131,000 J / mol 
D = (1.2 × 10 m / s ) exp −
2

 (8.31J / mol − k )( 673k ) 
= 8.1×10 −15 m 2 / s
Solved At what temperature will the difusion coefficient for the diffusion of
Example - 6 zinc in copper have a value of 2.6 × 10-16 m2/s
Do =2.4 × 10-5 m2/s Qd=189 KJ/mol
We are asked to calculate the temperature at which the diffusion coefficient for the
diffusion of Zn in Cu has a value of 2.6 × 10-16 m2/s. Solving for T from below
equation
Qd
T =−
R (ln Do − ln D )
By using the given data we can get
 189,000 J / mol 
T = − −16 −5 
 (8.31J / mol − k )[ln(2.6 × 10 m 2
/ s ) − ln( 2.4 × 10 m 2
/ s ) 
= 901K = 6280 C
Solved The diffusion coefficients for nickel in iron are given at two
Example - 7 temperatures:
At 1473K 2.2 × 10-15 m2/s
At 1673K 4.8 × 10-14 m2/s
a) Determine the values of Do and the activation energy Qd.
b) What is the magnitude of D at 1300ºC (1573K)
Qd
T =− From this equation we can compute two simultaneous
R (ln Do − ln D ) equations they are
ln D1 − ln D2
Q 1 Q 1 Qd = − R
ln D1 = ln D0 − d { } ln D2 = ln D0 − d { } 1 1
−
R T1 R T2 T1 T2
[ln(2.2 × 10 −15 ) − ln(4.8 × 10 −14 )

Qd = −(8.314 J / mol − K )
1 1
−
1473 K 1673 K
= 315,700 J / mol
 Qd 
Now we can solve Do from this equation  − 
D0 = D1 e  RT1 
−15  315,700 J / mol 

= (2.2 ×10 2
m / s ) exp 
 (8.31J / mol − k )(1473k ) 
= 3.5 ×10 −4 m 2 / s
(b) Using these values of Do and Qd, D at 1573K is just
−4  315,700 J / mol 
D = (3.5 ×10 m / s ) exp −2

 (8.31J / mol − k )(1573k ) 
= 1.1× 10 −14 m 2 / s
Summary
Diffusion Faster for Diffusion Slower for
Open crystal structures Close packed structures
Lower melting temperature materials. Higher melting temperature materials
Smaller diffusing atoms Larger diffusing atoms
Cations Anions
Materials with secondary bonding Materials with covalent bonding
Lower density materials Higher density materials
Questions..?
1. Briefly explain the difference between selfdiffusion and interdiffusion.
2. Compare interstitial and vacancy atomic mechanisms for diffusion.
3. Briefly explain the concept of steady state as it applies to diffusion.
4. Briefly explain the concept of a driving force. And what is the driving force for steady-state
diffusion?
5. A sheet of steel 2.5 mm thick has nitrogen atmospheres on both sides at 9000C and is
permitted to achieve a steady-state diffusion condition. The diffusion coefficient for
nitrogen in steel at this temperature is 1.2×10-10 m2/s, and the diffusion flux is found to be
1.0×10-7kg/m2-s. Also, it is known that the concentration of nitrogen in the steel at the high-
pressure surface is 2 kg/m3. How far into the sheet from this high pressure side will the
concentration be 0.5 kg/m3? Assume a linear concentration profile.
6. If iron is kept at 1200˚K in a carburizing atmosphere for 8hrs to obtain a carbon
concentration of 0.75 at a depth of 0.5mm. Find the time it would take to reach same carbon
concentration at depth of 7.5mm at 1250˚K. (Given D0 = 0.2x10-4 m2/s & Q =
143kJ/mole/˚K)
7. The concentration of carbon on the surface of iron is maintained at 1.00% at 1175˚K for
2hours. Estimate the depth at which % C would be 0.5%. Use the diffusivity values given
D0 = 0.2x10-4 m2/s & Q = 143kJ/mole/˚K. Assume initial carbon content of iron to be
negligible.
Questions..?
8. It is often thought that that species having lower activation energy diffuses faster than the
one having higher activation energy. Is this always true?
9. Rank the following samples in order of increasing self diffusion coefficients (a) Aluminium
single crystal, (b) Polycrystalline aluminium whose average grain size is 5micron (c)
Polycrystalline aluminium whose average grain size is 10micron.
10. For a steel alloy it has been determined that a carburizing heat treatment of 15 h duration
will raise the carbon concentration to 0.35 wt% at a point 2.0 mm from the surface.
Estimate the time necessary to achieve the same concentration at a 6.0-mm position for an
identical steel and at the same carburizing temperature.
Avala Lava Kumar*
Stainless Steels
Stainless Steels are a large group of special alloys developed primarily to withstand
corrosion. These steels contain chromium in excess of 12% by weight which imparts
“stainless” characteristics to iron alloys.
Types of stainless steels:
Stainless Steels
Martensitic SS Duplex SS
Ferritic SS Austenitic SS Precipitation

Hardened SS
AISI Grades of stainless steels:
Series Designation Groups
2xx Chromium-Nickel-Manganese; Nonhardenable,
Austenitic, Nonmagnetic
3xx Chromium-Nickel; Nonhardenable, Austenitic,
Nonmagnetic
4xx Chromium; Hardenable, Martensitic, Magnetic
4xx Chromium; Nonhardenable, Ferritic, Magnetic
5xx Chromium; Low chromium; Heat-Resisting
Martensitic Stainless Steel
These are primarily straight chromium steels with 11.5 to 18% Cr, 0.15% C, 1.25% Mn,
and 1%Si.
Common examples are 403, 410, 416, 420, 440A, 501 & 502 (AISI grades).
Used for turbine blades and corrosion resistant applications
Heat Treatment
Process Annealing → 650 - 760 o C, ↑ ductility and machinability
Austenitizing → 925 -1065 o C followed by oil quenching or air cooling, ↑ corrosion resistance
and strength
Sulfide particles
(Improves machinability) Lath martensite
Microstructure of annealed 416 stainless steel Microstructure of hardened type 403 stainless
etched with Vilella’s reagant steel etched with 4% picral-HCl
Austenitic Stainless Steel
These are chrome-nickel (3xx type) or chrome -nickel- manganese(2xx type) alloys.
Total content of Ni and Cr is at least 23%.
Difficult to machine but can be improved by addition of selenium of sulfur.
Best high temperature strength and scaling resistance. Hence shows best corrosion
resistance
Used in chemical industry and for household and sanitary fittings.
Heat Treatment
Cold working causes work hardening but hot working can easily be done.
Annealing at high temperatures → Recrystallization and carbide solution
Solution treatment → Dissolution of chromium carbides
Equiaxed grains
Annealing twins
Microstructure of annealed type 316L austenitic stainless

steel etched in 20% HCl, 2% NH4FHF, 0.8% PMP
Ferritic Stainless Steel
These are primarily straight chromium steels with 14 to 27% Cr. Carbon is restricted both to
maintain high toughness and ductility and to prevent austenite formation (As carbon
expands the gamma loop)
These steels can be cold formed easily and hence are used for deep drawn parts such as
vessels for food and chemical industries and for architectural and automotive trim.
Heat Treatment
Can be cold or hot worked.
Annealing → 760 - 966oC, Recrystallization of cold-worked structures → achieves maximum
softness, ductility and corrosion resistance.
Single-phase microstructure of an
annealed ferritic stainless steel
Microstructure of annealed ferritic stainless steel containing

26% Cr and 1% Mo, etched electrolytically in 60% HNO3-H2O
Precipitation Hardened Stainless Steel
Contains Mo, Nb, Ti or Al in addition to basic composition. Ni content is generally less to
reduce the stability of austenite.
Common Grades are: 630/17-4 PH (17% Cr, 4%), 631/17-7 PH,15-5 PH etc.
Provides high strength and toughness while maintaining the corrosion resistance of stainless
steels. Also shows excellent elevated-temperature performance and are widely used in the
aerospace industry.
Strengthening is accomplished by the precipitation of intermetallic compounds such as
Ni3Al in austenitic or ductile low-carbon martensitic matrices.
Heat Treatment
These steels are usually solution – annealed followed by air cooling with the resultant
transformation of austenite to martensite. After forming ageing (480-620 o C) is carried out
to cause precipitation effect.
More is the ageing temperature, better is the ductility, toughness and resistance to stress
corrosion.
Tempered Fine, disc-shaped
Martensite γ’ precipitates
Microstructure of 17-4PH alloy solution Microstructure of an aged austenitic

treated at1038 o C and aged at 495 o C precipitation-hardening stainless steel
Duplex Stainless Steel
Duplex stainless steels by design have nearly balanced amounts of ferrite and austenite.
Compositions of duplex stainless steels range from 17 to 30% Cr and 3 to 13% Ni. Molybdenum,
a ferrite stabilizer, is also typically present.
Shows higher strength and better resistance to stress corrosion. Decrease in ductility at low
temperature is compensated by increased rates of strain hardening due to strain-induced
transformation of austenite to martensite
Used in petrochemical industry (for handling wet an dry CO2, sour gas and oil products), heat
exchanges (welded tubing), chemical, industries etc.
Heat Treatment
Thermomechanical processing is accomplished in the two-phase ferrite austenite fields.
Amounts of ferrite and austenite formed during hot working or annealing are a function of temperature.
Higher temperatures produce larger amounts of ferrite. Hence, hot working temperatures must be kept
between 1000 - 1200 oC
Ferrite
Austenite
Microstructure of duplex stainless Microstructure of cold worked and

steel 7Mo-Plus annealed duplex stainless steel Al 2205
Tool Steel
Tool steel refers to a variety of carbon and alloy steels that are particularly well-suited to be
made into tools.
Characteristics include high hardness, resistance to abrasion (excellent wear), an ability to
hold a cutting edge, resistance to deformation at elevated temperatures (red-hardness).
Tool steel are generally used in a heat-treated state.
AISI-SAE tool steel grades

Defining property AISI-SAE grade Significant characteristics
Water-hardening W
O Oil-hardening
Cold-working A Air-hardening; medium alloy
D High carbon; high chromium

Shock resisting S
T Tungsten base
High speed
M Molybdenum base
H1-H19: chromium base
Hot-working H H20-H39: tungsten base
H40-H59: molybdenum base
Plastic mold P
L Low alloy
Special purpose
F Carbon tungsten
Tool Steel and their Uses
Shock resisting tool steels → Intended for applications requiring toughness and resistance to
shock-loading such as hammers, chisels, punches, driver bits and others.
Water hardening tool steels → Shallow hardened and relatively low resistance to softening.
They are suitable for woodworking tools, hand-metal cutting tools such as taps and reamers
and cutlery.
Steels for Room Temperature Use (Classified according to their quenching media)
Water hardened grades (W) → Plain carbon steels with 0.6-1.0 %C. These have a low
hardenability, ie., martensite only to a depth of 0.5 in. V can be added (forms V4C3)to
improve the hardness and wear resistance of these steels.
Shock resistant grades (S) → Contain small amounts of Cr or Mo and are quenched in oil.
They have lower C contents (0.5%) to improve impact strength.
Oil hardened grades (O) → Small percentages of Cr and W with 0.9 %C. The have medium
hardness and are used to short run cold forming dies.
Air hardening grades (A) → Greater amounts of Cr and Mo and 1 %C. Used for
complicated shapes and thread rolling. Mo and W are relatively expensive so they are only
added in small amounts to give much improved hardenability.
High carbon, high Cr grades (D grade) → 12 %Cr and 1.5-2.25 %C are extremely wear
resistant and used for long run dies and for gauges. Chromium is a relatively low cost
addition for increasing hardenability with the excess Cr, Cr23C6 is also formed, which
improves wear resistance.
Tool Steel : Steels for High Temperature Use
Chromium hot working steels (H grades) → 5-7 % Cr, 0.4-1.0% V, 1.5-7.0% W, 1.5% Mo,
0.35% C. Medium hot working for Mg and Al extrusion die-casting dies.
Tungsten hot working steels (H ) → 9.5-12 % W, 3.5-12.0 % Cr, 0.35 % C. Hot working,
extrusion and forging dies for brass, nickel and steel.
Tungsten high speed steel (T) → 12-18 % W, 4.0 % Cr, 1-5 % V, 0.7-1.5 % C. Original high
speed (HS) cutting steel with excellent HT wear resistance.
Molybdenum HS steel (M) → 3.5-8.0 % Mo, 1.5-6.0 % W, 4.0 % Cr, 1-5 % V, 5 % Co, 0.8-
1.5 % C. Used for 85% of US cutting steels before the advent of ceramic cutting tools.
Heat Treatment Processes
Schematic diagram of
tool steel processing up
to the final hardening
heat treatment
High Speed Steel (HSS)
HSS is a subset of tool steel, commonly used in tool bits and cutting tools. It is often used in
power saw blades and drill bits.
They are characterized by high carbon contents, sometimes up to 1.5%, and major additions
of strong carbide forming elements such as chromium, molybdenum, tungsten and
vanadium. Up to 12% Co is also included in some of the more complex grades.
It can withstand higher temperatures without losing its temper (hardness) which allows it to
cut faster than high carbon steel, hence the name.
Other characteristics include high hardness, resistance to abrasion (excellent wear), an
ability to hold a cutting edge, resistance to deformation at elevated temperatures (red-
hardness).
Modulus Of elasticity: 221GPa, Density : 8767 kg/m3 (↑ durability & hardness), Thermal
Conductivity: 21W/m/K
HSS are mainly of two types: Tungsten based ones (T grades), Molybdenum based ones (M
grades)
Three popular grades of high-speed steel
AISI-SAE grade C% W% Mo% Cr% V%

T1 0.75 18 4 1
M1 0.8 2 8 4 1
M2 0.85 6 5 4 2
High Speed Steel (HSS)
Heat Treatment
Schematic diagram of the

heat treatment of High
Speed Steel
Microstructure of KMnO4
etched M2 high-speed steel
showing Feathery, MC
eutectics (M, maybe Fe,
Mn, Cr with a little W, Mo,
V).
High Strength Low Alloy Steel (HSLA)
HSLA steels are low carbon steels that contain up to 10 % alloying additions of the strong
carbide- or nitride-forming elements niobium, titanium or vanadium, separately or together.
The alloying elements enable martensite and bainite to form during quenching and increases
strength and impact toughness.
ASTM Zr Cu
C% Mn% P% S% Ni% Cr% Mo% V% B%
Grade % %
A533
0.22 1.25 0.015 0.015 0.20 0.50
grade B
A517
0.15 0.80 0.015 0.015 0.20 0.50 0.50 0.1 0.002 0.3
grade F
A543
class 1
0.15 0.35 0.010 0.010 0.25 1.75 0.50 0.02
A542
0.12 0.45 1.020 1.020 0.25 2.25 1.00
class 1
A 203
0.12 0.45 0.015 0.015 0.25
grade D
A553
0.10 0.65 0.010 0.010 0.25
type 1
A533 grade B
Contains small amounts of Ni and Mo, ↑ hardenability,
forms ferrite plus bainite microstructure on quenching.
Tempering of bainite ↑ toughness, strength & similar
ductility to the hot worked low-carbon plain-carbon
steels.
Used for nuclear vessels and steam generators
Microstructure of A533 grade B quenched

from 900 oC and tempered at 620 oC
Grades A543 class 1 and A517 grade F showing ferrite and tempered bainite
Contains Ni, Cr, Mo with further additions of V, Zr, and B.

Very high yield and tensile strengths in addition to good toughness
Ni, Cr, Mo + V forms a mixture of martensite and bainite on quenching, while the additional
Zr and B enables 100% martensite to form on quenching to give even greater strength.
Zr + B → Forms precipitate at high temperatures, ↑ strength
Tempering of bainite and martensite → 600-650 oC, ↑ toughness
Used in plates, shapes, forgings and for weld constructions including bridges and nuclear
pressure vessels etc.
HSLA
Microstructure of A543 class 1 quenched Microstructure of A517 grade F

from 850 oC and tempered at 650 oC quenched from 925 oC and tempered at
showing tempered bainite and martensite. 650 oC showing Tempered martensite.
A203 grade D and A553 type 1

Ni improves low temperature notch toughness.
3.5 %Ni in Steel A203 does not improve the strength but after tempering ductile-brittle
transition temperature is lowered to below -20 oC.
9% Ni content of A533 improves the strength by “solid solution strengthening” up to the
level of the Ni-Cr-Mo HSLA steel and also gives A533 a higher ductility so that its ductile
to brittle transition temperature is lowered to below –200 OC.
A 203 is used for a variety of relatively low-stress, low temperature applications and A533
is used for high-stress low-temperature applications such as pressure vessels and for the
transport of liquified natural gas (-170 oC)
A542 class1
Contains Cr and Mo which increases its resistance to high temperature creep (Due to
interphase precipitation hardening) and corrosion resistance.
Quenching and Tempering ↑ strength with good ductility similar to A543
Used for high pressure chemical reactors and refinery vessels.
Microstructure of 0.15C–0.75V HSLA

Steel showing interphase precipitation at
the α/γ boundary
Microalloyed Steel
Microalloyed steel → Contains small amounts (< 0.2%) of strong carbide forming elements
such as niobium, vanadium, titanium, molybdenum, zirconium, boron, and rare earth metals
→ refines the grain microstructure (Grain size of ferrite ASTM 12-14) & facilitates
precipitation hardening (by forming fine dispersion of alloy carbides).
These steels have improved strength and excellent weldability compared to mild steel. In
terms of performance and cost, these steels lie between carbon steel and low alloyed steel.
Typical mechanical properties of Microalloyed steel are: Yield Strength → 400-500 Mpa,
Tensile Strength → 600-650 Mpa, % Elongation → 20-22.
Used in vehicles/transportation, tubular components, heavy equipment, rails, off-
shore/platforms, bridges, suspension components, building structures etc.
Acicular Ferrite
Precipitate phase
Grain Boundary Ferrite

Widmanstätten
Ferrite
Microstructure of Nb-Ti steel obtained from plane Microstructure of low carbon microalloyed steel
strain compression tests after soaking at 1200ºC produced by thermo-mechanical processing
Heat Treatment
In order to realize the full strengthening potential of micro-alloying additions, it is necessary
to use a soaking temperature prior to forging that is high enough to dissolve all vanadium-
bearing precipitates. A soaking temperature above 1100°C is generally preferred.
For Nb–Ti microalloyed steel the single step austenite reheating temperature at 1150°C
provides better austenite conditioning than the higher reheating temperature at 1240°C.
Finishing temperature for rolling also plays an important in determining the grain size and,
hence the strength level.
If rolling is done through the transformation into the completely ferritic condition, fine
ferrite is seen in subgrain structures.
Alternatively, If rolling is finished above the γ/α transformation, the nature of the
transformation is altered by increasing the cooling rate. Slow rates of cooling obtained by
coiling at a particular temperature will give lower strengths than rapid rates imposed by
water spray cooling following rolling. Rapid cooling rate results in transformation of equi-
axed ferrite to Widmanstätten ferrite with a much higher dislocation density.
Avala Lava Kumar*
Introduction
Metallic materials, when considered in abroad sense, may be divided into two large
groups, ferrous and non ferrous.
The ferrous materials are iron-based, and the non ferrous materials have some
element other than iron as the principle constituent .
The bulk of the nonferrous materials is made up of the alloys of copper,
aluminum, magnesium, nickel, tin, lead, titanium and zinc.
Other nonferrous metals and alloys that are used to a lesser extent include
cadmium, molybdenum, cobalt, zirconium, beryllium, tantalum, and the precious
metals gold, silver and the platinum group.
→ This chapter will be concerned with the more important nonferrous metals and
alloys These are as follows.
Copper and copper alloys (Bronze and Brass)
Aluminum and aluminum alloys
Copper and Copper Alloys
Pure Cu Cu- alloys
Brasses Cupronickel Brasses
Deformable alloys Cast alloys

Introduction
The properties of copper that are most important are high electrical and thermal
conductivity, good corrosion resistance, machinability, strength, and easy fabrication.
Most of the copper that is used for electrical conductors contains over 99.9 percent
copper and is identified as electrolytic tough-pitch copper (ETP) or oxygen-free
high-conductivity copper (OFHC).
ETP copper contains from 0.02 to 0.05 percent oxygen, which is combined with
copper as the compound cuprous oxide (Cu2O). As cast, copper oxide and copper
form an inter dendritic mixture. After working and annealing, the inter dendritic
network is destroyed, and the strength is improved.
Oxygen-free copper is used in electronic tubes or similar applications because it
makes a perfect seal to glass.
Arsenical copper : 0.3 % arsenic has improved resistance to special corrosive
conditions.
Free cutting copper : 0.6 % tellurium excellent machining properties.
Silver – bearing copper : 7 to 30 oz/ton. Silver raises the Recrystallization
temperature of copper, thus preventing softening during soldering of commutators.
Introduction
Brasses are essentially alloys of copper zinc. Some of these alloys have small
amounts of other elements such as lead, tin, or aluminum.
The portion of the binary copper zinc phase

diagram which is applicable to commercial
alloys is shown in Fig.
The solubility of zinc in the alpha (α) solid
solution increases from 32.5 % at 910 ºC to
about 39 % at 455 ºC.
Since copper is F.C.C , the α solid solution is
F.C.C the beta (β) phase is B.C.C electron
compound and undergoes ordering, indicated
by a dot-dash line, in the region of 455 to 470
ºC.
On cooling in this temperature range the
B.C.C β phase, with copper and zinc atoms
randomly dispersed at lattice points, changes
continuously to the ordered structure β’ ,
which is still B.C.C.
Alpha Brasses
But with the copper atoms at the corners and zinc atoms at the centers of the unit
cubes. The ordering reaction is so rapid that it cannot be retarded or prevented by
quenching. The best combination of strength and ductility is obtained in 70Cu-
30Zn brass.
The commercial brasses may be divided into two groups, brasses for cold working
(α brasses) and brasses for hot working (α plus β brasses)
1. These contain 20-36 % Zn
2. It is common practice to stress relief anneal these brasses
after severe cold working to prevent season cracking.
3. Season cracking or stress corrosion cracking is due to the
high residual stresses left in the brass as a result of cold
working.
Yellow Brasses 4. Dezincification and Plug-type dezincification
5. Most widely used yellow α brasses are cartridge brass
(70Cu-30Zn) and yellow brass (65Cu-35Zn)
Alpha Brasses
(upto 36% Zn)
Red Brasses
1. These contain between 5 and 20 percent zinc.
2. The most common low zinc brasses are gliding metal
(95Cu-5Zn), commercial , commercial bronze (90Cu-
10Zn), red brass (85Cu-15Zn) and low brass (80Cu-
20Zn)
Alpha plus Beta Brasses
These contain from 54 to 62 % copper. And this alloy consist of two phases, α and
β’. The β’ phase is harder and more brittle at room temperature than α; therefore,
these alloys are more difficult to cold work than the α brasses.
At elevated temperatures the β phase becomes very plastic, and since most of these
alloys may be heated into the single phase β region, they have excellent hot-working
properties.
The most widely used α+β’ brass is muntz metal (60Cu-40Zn), which has high
strength and excellent hot-working properties.
200X muntz metal

Muntz metal is used in condenser heads, perforated metal and architectural work.
Alpha plus Beta Brasses
Free-cutting brass (61.5Cu-35.5Zn-3Pb) has the best machinability of any brass
combined with good mechanical and corrosion resistant properties.
Forging brass (60Cu-38Zn-2Pb) has the best hot working properties of any brass and
is used for hot forgings, hardware and plumbing parts.
Architectural bronze (57Cu-40Zn-3Pb) has excellent forging and free matching
properties.
Naval brass (60Cu-39.25Zn-0.75Sn), also known as tobin bronze, has increased
resistance to salt water corrosion and is used for condenser plates, welding rod,
propeller shafts, piston rods, and valve systems.
Manganese bronze (58.5Cu-39Zn-1.4Fe-1Sn-0.1Mn), really a high-zinc brass, has
high strength combined with excellent wear resistance and is used for clutch disks,
extruded shapes, forgings, pump rods, shafting rod, valve stems, and welding rod.
Cast brasses The previous discussion was concerned primarily with wrought brasses,
which are mainly binary alloys of copper and zinc. The cast brasses are similar in
name to the wrought brasses but usually contain appreciable amounts of other
alloying elements. Tin may be present from 1 to 6 percent and lead from 1 to 10
percent; some alloys may contain iron, manganese, nickel and aluminium.
Introduction
The term bronze was originally applied to the copper-tin alloys; however, the term is
now used for any copper alloy, with the exception of copper-zinc alloys, that contains
up to approximately 12% of the principle alloying element.
Bronze, as a name, conveys the idea of a higher-class alloy than brass, and it has
been incorrectly applied to some alloys that are really special brasses
Commercial bronzes are primarily alloys of copper and tin, aluminum, silicon, or
beryllium. In addition, they may contain phosphorus, lead, zinc or nickel.
Tin Bronzes
These are generally referred to as phosphor bronzes since phosphorous is always

present as a deoxidizer in casting.
The usual range of phosphorus content is between 0.01 and 0.5%, and of tin between
1 and 11 percent.
The copper- rich portion of the copper-tin alloy system is shown in next page. The β
phase forms as the result of a peritectic reaction at 798 ºC. At 586 ºC, the β phase
undergoes a eutectoid reaction to form the eutectoid mixture (α+γ). At 520ºC,
gamma (γ) also undergoes a eutectoid transformation to (α+δ).
Tin Bronzes
The diagram also indicates the

decomposition of the δ phase. This takes
place by a eutectoid reaction at 350 ºC
forming (α+ε). This reaction is so
sluggish that in commercial alloys, the
epsilon (ε) phase is nonexistent.
The slope of the solvus line below 520
ºC shows a considerable decrease in the
solubility of tin in the α phase.
The precipitation of the δ and ε phase
due to this change in solubility is slow
that, for practical purposes, the solvus
line is indicated by the vertical dotted
line below 520 ºC. Copper-rich portion of the copper tin phase diagram
For this reason, slow cooled cast tin bronzes containing below 7% tin generally show
only a single phase, the α solid solution. There is some of the δ phase in most
castings containing over 7 percent tin. The phosphor bronzes are characterized by
high strength, toughness, high corrosion resistance and freedom for season cracking .
Silicon Bronzes
The copper-rich portion of the copper-

silicon alloy system is shown in Fig.
The solubility of silicon in the α phase
is 5.3% at 850ºC and decreases with
temperature.
The eutectoid reaction at 555ºC is very
sluggish, so that commercial silicon
bronzes, which generally contain less
than 5% Si, are single phase alloys.
Copper-rich portion of the copper Silicon phase diagram
Silicon bronzes are the strongest of the work-hardenable copper alloys. They have
mechanical properties comparable to those of mild steel and corrosion resistance
comparable to that of copper.
They are used for tanks, pressure vessels, marine construction, and hydraulic pressure lines.
Aluminum Bronzes
The maximum solubility of aluminum in

the α solid solution is approximately 9.5%
at 565ºC to form the (α+γ2) mixture.
Most commercial aluminum bronzes
contain 4 and 11 percent aluminum. Those
alloys containing up to 7.5% Al are
generally single-phase alloys, while those
containing between 7.5 and 11% aluminum
are two phase alloys. Other elements such
as iron, nickel, manganese, and silicon are
frequently added to aluminum bronzes
The single-phase aluminum bronzes show
good cold working properties with good
corrosion resistance to atmospheric and
water attack.
The α+β aluminum bronzes are interesting
because they can be heat treated to obtain
structures similar to those in steel.
Copper-rich portion of the copper aluminum phase diagram

Cupronickels
These are copper-nickel alloys that contain up to 30% nickel. The copper-nickel
binary phase diagram shows complete solubility, so that all cupronickels are
single-phase alloys. They are not susceptible to heat treatment and may have their
properties altered only by cold working.
The cupronickel alloys have high resistance to corrosion fatigue and also high
resistance to the corrosive and erosive action of rapidly moving sea water. They are
widely used for condenser, distiller, evaporator and heat exchanger tubes for naval
vessels and coastal power plants.
“ Where ever weight is the enemy
Where ever appearance matters
Where ever durability is required”
The answer is Aluminum & its alloys

Introduction
Aluminum and its alloys possess many attractive characteristics including light weight,
high thermal and electrical conductivities, a nonmagnetic nature, high reflectivity, high
resistance to corrosion, reasonably high strength with good ductility and easy fabrication.
Nevertheless, probably the most important characteristic of aluminum is its low density,
which is about one-third that of steels and copper alloys. Because of this, certain
aluminum alloys have a better strength-to-weight ratio than high-strength steels.
Among the many alloying elements added to aluminum, the most widely used are copper,
silicon, magnesium, zinc, and manganese. These are used in various combinations, and in
many cases they are used together with other additions to produce classes of age
hardening, casting, and work hardening alloys.
All age hardening alloys contain alloying elements that dissolve in aluminum at elevated
(solution treatment) temperatures and precipitate at lower (aging) temperatures. An
example of an age hardening alloy is Al-Cu (which will discussed in coming slides).
Most casting alloys contain silicon, which improves the fluidity and mold-filling capacity
of aluminum alloys and reduces their susceptibility to hot cracking and the formation of
shrinkage cavities during solidification. Work hardening alloys frequently contain Mn and
Mg, which form a fine dispersion of inter metallic phases and/or impart solid-solution
strengthening.
Major Aluminum alloy systems
Al-Cu
Zn Al-Cu-Mg
Age-Hardening
Al-Mg-Si alloys
Mg
Al-Zn-Mg
Al Cu Al-Zn-Mg-Cu
Mn Al-Si
Casting alloys
Al-Si-Cu
Si
Al-Mg
Work Hardening
alloys
Al-Mn
ALUMINIUM ALLOY DESIGNATION SYSTEM
.
ALLOY MAJOR ALLOYING EXAMPLE
GROUP ELEMENTS
AA 1XXX Min. 90% pure Al. AA 1050

AA 2xxx Copper AA 2014, AA2024
AA 3XXX Manganese AA 3003
AA 4XXX Silicon AA 4030
AA 5XXX Magnesium AA 5083
AA 6XXX Magnesium+Silicon AA 6061
AA 7XXX Zinc AA 7075, AA 7175
AA 8XXX Others AA 8020

Heat treatment
The most important heat treating process for non ferrous alloys is age hardening,
or precipitation hardening.
In order to apply this heat treatment, the equilibrium diagram must show partial
solid solubility, and the slope of the solvus line must be such that there is greater
solubility at a higher temperature than at a lower temperature.
The purpose of precipitation hardening treatment is to improve strength of the
materials. It can explained by with respect to dislocations.
The presence of dislocation weakens the crystal → easy plastic deformation
Putting hindrance to dislocation motion increases the strength of the crystal
Fine precipitates dispersed in the matrix provide such an impediment.
For example: Strength of Al → 100 MPa
Strength of Duralumin (Al + 4% Cu + other alloying elements) → 500 Mpa
Two stages are generally required in heat treatment to produce age hardening:
Solution treatment
Aging
Age-Hardening
L
600
α
T ((ºC) →
400
θ
Sloping Solvus line
⇒ high T → high solubility
200
low T → low solubility
of Cu in Al
Al 15 30 45 60
% Cu →
Al rich end of the Al-Cu phase diagram
Age-Hardening
On Equilibrium cooling
α→α+θ
Slow equilibrium cooling gives rise to
α coarse θ precipitates which is not good
in impeding dislocation motion.*
α
α+θ
θ
4 % Cu
α ( FCC )   α ( FCC )  θ CuAl 2 (Tetragonal ) 

  slow cool    
 4 % Cu    → 0.5 % Cu  +  52 % Cu 
 550 o C   RT   RT 
     
Age-Hardening
To obtain a fine distribution of precipitates
the cycle A → B → C is used α
B
Solution treating at high temperature, then
quenching (second phase is in solid solution) A C
→Cycle A and B
α+θ
A Heat (to 550oC) → solid solution α
4 % Cu
supersaturated solution
B Quench (to RT) →
Increased vacancy concentration
Ageing at room temperature or slightly higher temperature (Precipitation of second
phase, giving strengthening effect) →Cycle C
C Age (reheat to 200oC) → fine precipitates

Note: Treatments A, B, C are for the same composition
Age-Hardening
180oC Peak-aged
100oC
Hardness →
Dispersion of Coarsening
Hardness →
fine precipitates of precipitates

(closely spaced) with increased
180oC interparticle spacing
20oC Underaged Overaged
Log(t) →
Log(t) → Region of solid solution

Region of precipitation
hardening (but little/some
strengthening solid solution
(no precipitation hardening) strengthening)
Higher temperature ⇒ less time of aging to obtain peak hardness

Lower temperature ⇒ increased peak hardness
⇒ optimization between time and hardness required
A complex set of events are happening parallely/sequentially during the aging process
→ These are shown schematically in the figure below
180oC Peak-aged
Hardness →
Log(t) →
Increasing size of precipitates with increasing interparticle (inter-precipitate) spacing
Interface goes from coherent to semi-coherent to incoherent
Precipitate goes from GP zone → θ’’ → θ’ → θ

Age-Hardening
Due to large surface to volume ratio the fine
precipitates have a tendency to coarsen → small
precipitates dissolve and large precipitates grow
Coarsening
⇒ ↓ in number of precipitate
⇒ ↑ in interparticle (inter-precipitate) spacing
⇒ reduced hindrance to dislocation motion
At higher temperatures the stable θ phase is

produced directly
At slightly lower temperatures θ’ is produced
first
At even lower temperatures θ’’ is produced

first
The normal artificial aging is usually done in

this temperature range to give rise to GP
zones first
Coherent lattice theory
The strengthening of a heat-treatable alloy by aging is not due merely to the
presence of a precipitate. It is due to both the uniform distribution of a finely
dispersed submicroscopic precipitate and the distortion of the lattice.
There are several theories of precipitation hardening, to explain in what manner
precipitate particles harden the matrix or solvent lattice, the most useful theory is
coherent lattice theory.
After solution treatment and quenching, the alloy is in a supersaturated condition,
with the solute atoms distributed at random in the lattice structure (Fig A).
During an incubation period, the excess solute atoms tend to migrate to certain
crystallographic planes, forming clusters or embryos of the precipitate.
During aging, these clusters form an intermediate crystal structure, or transitional
lattice, maintaining registry (coherency) with the lattice structure of the matrix.
The excess phase will have different lattice parameters from those of the solvent,
and as a result of the atom matching (coherency), there will be considerably
distortion of the matrix (Fig B).
Coherent lattice theory
The distortion of the matrix extends over a larger volume than would be the case if
the excess phase were a discrete particle. Eventually the equilibrium excess phase
is formed with its own lattice structure (Fig C).
This causes a loss of coherency with the matrix and less distortion hardness and
strength will decrease, and the alloy is ‘over-aged’. There will now be a boundary
between the excess phase and the matrix so that the precipitated particle will be
visible under the microscope.
Solid-Solid Interfaces
Consider an interface between two solid phases, α and θ, arising when θ nucleates and grows in
α . The interface can be of various types:
Coherent, with strain. It is likely that a

coherent interface will have some elastic
Coherent. There is perfect alignment of strain. The strain energy increases with
the lattices. the size of the growing particle and there
will be a transition to a semi coherent
interface.
Solid-Solid Interfaces
Semi-coherent. The introduction of

dislocations (defects in the way the
Incoherent. There is no matching at the
crystal is organized) reduces the overall
interface
elastic strain, although they themselves
contribute to the energy of the system.
Microstructures of common aluminum alloys
Al-Mg-Fe-Si Duralumin
Al-Si Al-Si
Corrosion Resistance of Al and Al-alloys
The high corrosion resistance of aluminum is due to the self-protecting, thin,
invisible oxide film that forms immediately on exposing surfaces to the
atmosphere.
This film protects the metal from further corrosion. If the oxide film is removed, in
many environments, a new film will form immediately and the metal remains fully
protected.
In certain strongly acid or alkaline solutions, or in contact with moist corrosive
materials that prevent access of oxygen to the aluminum surface, the protective
film does not form readily. Therefore, the aluminum should be adequately
protected or not used at all.
A relatively thick oxide coating on aluminum and aluminum alloys may be
produced by placing the metal into an aqueous solution containing 15 to 25%
sulfuric acid. This process, known as anodizing, produces a clear, transparent
coating containing submicroscopic pores that are usually sealed before use to
prevent absorption and staining. Sealing may be accomplished by suitable heating
in hot water.
Corrosion Resistance of Al and Al-alloys
The corrosion resistance of Al-Cu alloys and Al-Zn alloys is satisfactory for most
applications but is generally lower than that of the other aluminum alloys. Under
certain corrosive conditions they are subject to intergranular corrosion.
Therefore, these alloys in the form of sheet are usually clad with a high-purity
alloy such as commercial aluminum or a magnesium-silicon alloy.
The coating slabs are mechanically attached to the alloy core ingot, and the
bonding is accomplished by hot rolling. The nominal cladding thickness per side is
usually 1½ or 2½ percent of thickness of the base material.
Alclad alloys are extensively used for aircraft applications because of the excellent
combination of high strength and high resistance to corrosion.
Questions..?
1. Which lead – tin alloy will be ideal for joining electronic assemblies? Give reason.
2. Why is Al-12% Si alloy a very popular casting material for automotive applications?
3. Cartridge brass is easily cold worked but Muntz metal can not be cold worked. Explain why
it is so.
4. Explain the applications of Bronze and Brasses.
5. What is the diffrence between disordered & ordered AuCu3 alloy? How is the presence of
ordered structure detected?
6. Name three common grades of steel produced by ingot route. Which of these has higher
yield?
7. Why does compressive stress develops at the surface in a case carburized and subsequently
case hardened steel?
8. Why low carbon content is preferred in most structural application? Is high strength not a
major criterion?
9. What is the composition of the steel designated as 25Mn1S14? What is the role of sulfur in
this steel?
10. Why is it possible to get much finer grain structure in steel than in aluminum?
11. How is ausforming different from austempering? Is this a hot working process?
12. What is the effect of micro-alloy addition on rolling load?
Questions..?
13. How is the mechanism of strengthening in maraging steel different from that in
conventional ultra high strength steel?
14. Explain why commercial steels / alloys having lower stacking fault energy exhibit higher
creep resistance.
15. Does all steel suitable for ausforming exhibit transformation induced plasticity?
16. High speed cutting tools are made of 18W4Cr1V0.6C and it is used in hardened and
tempered condition. Unlike normal hardened and tempered plain carbon tool steel it does
not lose its cutting ability even when it is red hot. Explain why it is so.
17. Briefly explain why ferritic and austenitic stainless steels are not heat treatable.
18. What is the main difference between brass and bronze?
19. Explain why, under some circumstances, it is not advisable to weld a structure that is
fabricated with a 3003 aluminum alloy.
20. On the basis of melting temperature, oxidation resistance, yield strength, and degree of
brittleness, discuss whether it would be advisable to hot work or to cold work (a) aluminum
alloys, and (b) magnesium alloys.
21. What types of alloys would respond to precipitation hardening?
22. Why Aluminium alloy rivets are strored in refigerator?
23. A batch of age hadrenable alloy has been overagred by mistake. Is there any way to slavage
these?
Questions..?
24. Why non-age hardenable aluminium alloys are chosen for beverage can?
25. When can you get more than one peak in the hardness versus aging time plot of a given
alloy at a given temperature?
26. Ag rich GP zones can form in a dilute Al-Ag alloy. Given that the lattice parameters of Al
and Ag are 0.405nm and 4.09nm respectively. What is likely shape of these zones?
27. Under what heat treatment condition an age harden-able alloy can be machined?
28. What the principal difference is between wrought and cast alloys?
29. Give the distinctive features, limitations, and applications of the following alloy groups:
titanium alloys, refractory metals, superalloys, and noble metals.
30. What is Duralumin? Give its alloy number and uses. What is the recent development in
alloy for aircraft bodies and application?

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LECTURE NOTES

INTRODUCTION TO PHYSICAL METALLURGY

Suneeti Purohit Gautam Behera

S.No Chapter Name Page No.

Processing/ Structure Properties Performance

Benz ‘Velo’ 1894

Advent of new materials like Mg,

From there to today’s

What made it possible?

We have come of ages, developed new

Availability of materials like

From Wright Brothers’ invention

….. Modern Aviation

Aircraft body structure

Steel quality – Poor: High S and P and low Mn:S ratio,

Modern cruise : As luxurious as Titanic – Better safety due to use of advanced

Invention high purity Si through zone

1940 - Harvard MarkI Electro- 1959 – IBM Computer, 33

Integrated circuit (IC) or

METALLURGY & MATERIALS ENGINEERING

PHYSICAL MECHANICAL ELECTRO- TECHNOLOGICAL

AMORPHOUS QUASICRYSTALS RATIONAL CRYSTALS

Faceted glass objects are

Metals Ceramics Polymers

Segmented Structures: are Hybrids are

Economic Price and Availability, Recyclability

The broad goal of Metallurgy & Materials

The Materials Tetrahedron

The following factors put together determines the properties of a material:

Phases & Their

Atom Structure Microstructure Component

Processing determines shape and microstructure of a component

Dislocation Stress fields

*Simple Unit Cells

There are microstructure ‘sensitive’ properties (often called structure sensitive

As Richard Feynman said….!

“It would be very easy to make an analysis of any

Although the Bohr’s model was the first and best

Heisenberg’s uncertainty principle:

The position and momentum of an electron can not be determined simultaneously.

Probability distribution vs. distance from nucleus

The Bohr radius, r =

It describes electron shells as shown in the Bohr model. Values of n can be 1, 2,

Magnetic quantum number, ml

Aufbau principle Madelung rule

1.46 1.31 1.25 1.12 1.24

Ti4+ V3+ Cr3+ Mn2+ Fe2+ Fe3+

Values are: Pauling-Ahrens Radii in Å

Attraction is predominant above ro and

σ is the distance at which the interaction

Ionic Covalent Metalic Vanderwaals Hydrogen

Majority of the engineering materials consist of one of these bonds. Many

Some other examples are CaF2 , CsCl, MgO, Al2O3

Covalent bonds are formed between atoms of similar electro negativity.

An ion can also induce a dipole

Metallic-covalent Mixed Bonding: The transition metals are an example where

Binding Energies of Bonds

Covalent ~1-10 (strong) ~100-1000 Diamond: ~710