COURSE MATERIAL

II Year B. Tech I- Semester

MECHANICAL ENGINEERING
AY: 2024-25

Materials Engineering
R22A0305

Prepared by:
Dr. Srikar Potnuru
Assoc. Professor

MALLA REDDY COLLEGE OF ENGINEERING & TECHNOLOGY

DEPARTMENT OF MECHANICAL ENGINEERING
(Autonomous Institution-UGC, Govt. of India)
Secunderabad-500100, Telangana State, India.
www.mrcet.ac.in
 B. Tech (ME) R-20

MALLA REDDY COLLEGE OF ENGINEERING AND TECHNOLOGY

II Year B.Tech. ME- I Sem L/T/P/C
3/-/-/3

(R22A0305) Materials Engineering

COURSE OBJECTIVES:

1. To understand the basic structure, properties of metals, mechanism of crystallization and

imperfections in crystals.
2. To study the importance of binary phase diagrams.
3. To acquire knowledge on properties and structure of ferrous and nonferrous alloys and to
select suitable materials for various engineering applications.
4. To learn various methods of heat treatment processes.
5. To gain knowledge on advanced materials and concepts of metallurgy.

UNIT I
Structure of Metals: Bonds in Solids – Metallic bond - crystallization of metals, imperfections, grain
and grain boundaries, effect of grain boundaries on the properties of metal / alloys – determination
of grain size.
Constitution of Alloys: Necessity of alloying, types of solid solutions, Hume Rotherys rules,
intermediate alloy phases, and electron compounds.
UNIT II
Equilibrium Diagrams
Experimental methods of construction of equilibrium diagrams, Isomorphous alloy systems,
equilibrium cooling and heating of alloys, Lever rule, eutectic systems, congruent melting
intermediate phases, peritectic reaction. Transformations in the solid state, allotropy, eutectoid,
peritectoid reactions, phase rule, relationship between equilibrium diagrams and properties of
alloys. Study of binary phase diagram of Fe-Fe3C.
UNIT III
Cast Iron & Steel: Structure and properties of White Cast iron, Malleable Cast iron, Grey cast iron,
Spheroidal graphite cast iron, Alloy cast irons. Classification of steels, structure and properties of
plain carbon steels, Low alloy steels, Had field manganese steels, tool and die steels.
Nonferrous metals & Alloys: Structure and properties of copper and its alloys, Aluminium and its
alloys, Titanium and its alloys.
UNIT IV
Heat treatment of Alloys: Effect of alloying elements on Iron – Iron carbon system, Annealing,
normalizing, Hardening, TTT diagrams, tempering, Harden ability, surface - hardening methods, Age
hardening
Ceramic Materials: Crystalline ceramics, glasses, cermets.

Malla Reddy College of Engineering and Technology (MRCET)

 B. Tech (ME) R-20

UNIT V
Composite Materials: Classification of composites, various methods of component manufacture of
composites, particle – reinforced materials, fiber reinforced materials, metal ceramic mixtures,
metal – matrix composites and Carbon– Carbon composites.
Metallurgy: Steel Making - Introduction, Methods of steelmaking – crucible process, Bessemer
converter process, Open Hearth Process, Introduction to Powder metallurgy.

TEXT BOOKS:

1. Kodgire, Material Science and Metallurgy, 42nd edition Everest Publishing House2017.
2. Donald R.Askeland, Essential of Materials Science and Engineering. Thomson Publications
2014.
3. V.Raghavan, Material Science and Engineering, Prentice –Hall of India Pvt. Ltd., 2007
4. Sidney H. Avner, Introduction to physical metallurgy, Tata Mc-Graw-Hill, Inc. 1997.

REFERENCES:

1. Sidney H. Avener, Introduction to Physical Metallurgy, TMH

2. William and collister, Materials Science and Engineering, wiley pub. 2014.
3. V. Raghavan, Material scienceand engineering, PH Pub. 2015.
4. R.K.Rajput, Engineering materials and metallurgy. S.Chand & Co. 2006.
5. O.P. Khanna, Material Science and Metallurgy. Dhanpatrai Pub. 2014

COURSE OUTCOMES:

1. Understand the mechanism of crystallization, methods of determining grain size and

factors affecting the solid solubility.
2. Use the phase diagrams of binary systems and iron-carbide diagram to select the material
composition.
3. Understand the structure and properties of various cast irons, steels and nonferrous alloys.
4. Apply the various heat treatment processes, TTT diagram, surface hardening methods &
coatings depending on material requirements.
5. Understand the importance of ceramics, composites and concepts of metallurgy

Malla Reddy College of Engineering and Technology (MRCET)

 Materials Engineering

Prof. Satish V. Kailas

Associate Professor
Dept. of Mechanical Engineering,
Indian Institute of Science,
Bangalore – 560012
India

Chapter 1. Introduction

1.1 Historical Perspective and Materials Science

1.1.1 Historical Perspective

Materials are so important in the development of human civilization that the historians have
identified early periods of civilization by the name of most significantly used material, e.g.:
Stone Age, Bronze Age. This is just an observation made to showcase the importance of
materials and their impact on human civilization. It is obvious that materials have affected
and controlling a broad range of human activities through thousands of decades.

From the historical point of view, it can be said that human civilization started with Stone
Age where people used only natural materials, like stone, clay, skin, and wood for the
purposes like to make weapons, instruments, shelter, etc. Thus the sites of deposits for
better quality stones became early colonies of human civilization. However, the increasing
need for better quality tools brought forth exploration that led to Bronze Age, followed by
Iron Age. When people found copper and how to make it harder by alloying, the Bronze
Age started about 3000 BC. The use of iron and steel, a stronger material that gave
advantage in wars started at about 1200 BC. Iron was abundant and thus availability is not
limited to the affluent. This commonness of the material affected every person in many
aspects, gaining the name democratic material. The next big step in human civilization was
the discovery of a cheap process to make steel around 1850 AD, which enabled the
railroads and the building of the modern infrastructure of the industrial world. One of the
most significant features of the democratic material is that number of users just exploded.
Thus there has been a need for human and material resources for centuries, which still
going strong. It’s being said and agreed that we are presently in Space Age marked by many
technological developments towards development materials resulting in
stronger and light materials like composites, electronic materials like semiconductors,
materials for space voyage like high temperature ceramics, biomaterials, etc.

In summary, materials constitute foundation of technology. The history of human

civilization evolved from the Stone Age to the Bronze Age, the Iron Age, the Steel Age,
and to the Space Age (contemporaneous with the Electronic Age). Each age is marked by
the advent of certain materials. The Iron Age brought tools and utensils. The Steel Age
brought railroads, instruments, and the Industrial Revolution. The Space Age brought the
materials for stronger and light structures (e.g., composite materials). The Electronic Age
brought semiconductors, and thus many varieties of electronic gadgets.

1.1.2 Materials Science

As engineering materials constitute foundation of technology, it’s not only necessary but a
must to understand how materials behave like they do and why they differ in properties.
This is only possible with the atomistic understanding allowed by quantum mechanics that
first explained atoms and then solids starting in the 1930s. The combination of physics,
chemistry, and the focus on the relationship between the properties of a material and its
microstructure is the domain of Materials Science. The development of this science
allowed designing materials and provided a knowledge base for the engineering
applications (Materials Engineering).

Important components of the subject Materials Science are structure, properties,

processing, and performance. A schematic interrelation between these four components is
shown in figure 1.1.

Structure

Performance

Properties Processing

Figure 1.1: Interrelation between four components of Materials Science.

1.2 Why Study Materials Science and Engineering? and Classification of Materials?

1.2.1 Why Study Materials Science and Engineering?

All engineers need to know about materials. Even the most "immaterial", like software or
system engineering depend on the development of new materials, which in turn alter the
economics, like software-hardware trade-offs. Increasing applications of system
engineering are in materials manufacturing (industrial engineering) and complex
environmental systems.

Innovation in engineering often means the clever use of a new material for a specific
application. For example: plastic containers in place of age-old metallic containers. It is
well learnt lesion that engineering disasters are frequently caused by the misuse of
materials. So it is vital that the professional engineer should know how to select materials
which best fit the demands of the design - economic and aesthetic demands, as well as
demands of strength and durability. Beforehand the designer must understand the
properties of materials, and their limitations. Thus it is very important that every engineer
must study and understand the concepts of Materials Science and Engineering. This enables
the engineer

• To select a material for a given use based on considerations of cost and

performance.
• To understand the limits of materials and the change of their properties with use.
• To be able to create a new material that will have some desirable properties.
• To be able to use the material for different application.

1.2.2 Classification of Materials

Like many other things, materials are classified in groups, so that our brain can handle the
complexity. One can classify them based on many criteria, for example crystal structure
(arrangement of atoms and bonds between them), or properties, or use. Metals, Ceramics,
Polymers, Composites, Semiconductors, and Biomaterials constitute the main classes of
present engineering materials.

Metals: These materials are characterized by high thermal and electrical conductivity;
strong yet deformable under applied mechanical loads; opaque to light (shiny if polished).
These characteristics are due to valence electrons that are detached from atoms, and spread
in an electron sea that glues the ions together, i.e. atoms are bound together by metallic
bonds and weaker van der Waalls forces. Pure metals are not good enough for many
applications, especially structural applications. Thus metals are used in alloy form i.e. a
metal mixed with another metal to improve the desired qualities. E.g.: aluminum, steel,
brass, gold.

Ceramics: These are inorganic compounds, and usually made either of oxides, carbides,
nitrides, or silicates of metals. Ceramics are typically partly crystalline and partly
amorphous. Atoms (ions often) in ceramic materials behave mostly like either positive or
negative ions, and are bound by very strong Coulomb forces between them. These materials
are characterized by very high strength under compression, low ductility; usually insulators
to heat and electricity. Examples: glass, porcelain, many minerals.
Polymers: Polymers in the form of thermo-plastics (nylon, polyethylene, polyvinyl
chloride, rubber, etc.) consist of molecules that have covalent bonding within each
molecule and van der Waals forces between them. Polymers in the form of thermo-sets
(e.g., epoxy, phenolics, etc.) consist of a network of covalent bonds. They are based on H,
C and other non-metallic elements. Polymers are amorphous, except for a minority of
thermoplastics. Due to the kind of bonding, polymers are typically electrical and thermal
insulators. However, conducting polymers can be obtained by doping, and conducting
polymer-matrix composites can be obtained by the use of conducting fillers. They
decompose at moderate temperatures (100 – 400 C), and are lightweight. Other properties
vary greatly.

Composite materials: Composite materials are multiphase materials obtained by artificial

combination of different materials to attain properties that the individual components
cannot attain. An example is a lightweight brake disc obtained by embedding SiC particles
in Al-alloy matrix. Another example is reinforced cement concrete, a structural composite
obtained by combining cement (the matrix, i.e., the binder, obtained by a reaction known
as hydration, between cement and water), sand (fine aggregate), gravel (coarse aggregate),
and, thick steel fibers. However, there are some natural composites available in nature, for
example – wood. In general, composites are classified according to their matrix materials.
The main classes of composites are metal-matrix, polymer-matrix, and ceramic-matrix.

Semiconductors: Semiconductors are covalent in nature. Their atomic structure is

characterized by the highest occupied energy band (the valence band, where the valence
electrons reside energetically) full such that the energy gap between the top of the valence
band and the bottom of the empty energy band (the conduction band) is small enough for
some fraction of the valence electrons to be excited from the valence band to the conduction
band by thermal, optical, or other forms of energy. Their electrical properties depend
extremely strongly on minute proportions of contaminants. They are usually doped in order
to enhance electrical conductivity. They are used in the form of single crystals without
dislocations because grain boundaries and dislocations would degrade electrical behavior.
They are opaque to visible light but transparent to the infrared. Examples: silicon (Si),
germanium (Ge), and gallium arsenide (GaAs, a compound semiconductor).

Biomaterials: These are any type material that can be used for replacement of damaged or
diseased human body parts. Primary requirement of these materials is that they must be
biocompatible with body tissues, and must not produce toxic substances. Other important
material factors are: ability to support forces; low friction, wear, density, and cost;
reproducibility. Typical applications involve heart valves, hip joints, dental implants,
intraocular lenses. Examples: Stainless steel, Co-28Cr-6Mo, Ti-6Al-4V, ultra high
molecular weight poly-ethelene, high purity dense Al-oxide, etc.

1.3 Advanced Materials, Future Materials, and Modern Materials needs

1.3.1 Advanced Materials

These are materials used in High-Tech devices those operate based on relatively intricate
and sophisticated principles (e.g. computers, air/space-crafts, electronic gadgets, etc.).
These materials are either traditional materials with enhanced properties or newly
developed materials with high-performance capabilities. Hence these are relatively
expensive. Typical applications: integrated circuits, lasers, LCDs, fiber optics, thermal
protection for space shuttle, etc. Examples: Metallic foams, inter-metallic compounds,
multi-component alloys, magnetic alloys, special ceramics and high temperature materials,
etc.

1.3.2 Future Materials

Group of new and state-of-the-art materials now being developed, and expected to have
significant influence on present-day technologies, especially in the fields of medicine,
manufacturing and defense. Smart/Intelligent material system consists some type of sensor
(detects an input) and an actuator (performs responsive and adaptive function). Actuators
may be called upon to change shape, position, natural frequency, mechanical characteristics
in response to changes in temperature, electric/magnetic fields, moisture, pH, etc.

Four types of materials used as actuators: Shape memory alloys, Piezo-electric ceramics,
Magnetostrictive materials, Electro-/Magneto-rheological fluids. Materials / Devices used
as sensors: Optical fibers, Piezo-electric materials, Micro-electro-mechanical systems
(MEMS), etc.

Typical applications: By incorporating sensors, actuators and chip processors into system,
researchers are able to stimulate biological human-like behavior; Fibers for bridges,
buildings, and wood utility poles; They also help in fast moving and accurate robot parts,
high speed helicopter rotor blades; Actuators that control chatter in precision machine
tools; Small microelectronic circuits in machines ranging from computers to
photolithography prints; Health monitoring detecting the success or failure of a product.

1.3.3 Modern Materials needs

Though there has been tremendous progress over the decades in the field of materials
science and engineering, innovation of new technologies, and need for better performances
of existing technologies demands much more from the materials field. More over it is
evident that new materials/technologies are needed to be environmental friendly. Some
typical needs, thus, of modern materials needs are listed in the following:

• Engine efficiency increases at high temperatures: requires high temperature

structural materials
 • Use of nuclear energy requires solving problem with residues, or advances in
nuclear waste processing.
• Hypersonic flight requires materials that are light, strong and resist high
temperatures.
• Optical communications require optical fibers that absorb light negligibly.
• Civil construction – materials for unbreakable windows.
• Structures: materials that are strong like metals and resist corrosion like plastics.

References

1. M. F. Ashby and D. R. H. Jones, Engineering Materials 1, An introduction to

Their Properties and Applications, second edition, Butterworth-Heinemann,
Woburn, UK, 1996
2. William D. Callister, Jr, Materials Science and Engineering – An introduction,
sixth edition, John Wiley & Sons, Inc. 2004.
3. V. Raghavan, Materials Science and Engineering, third edition, Prentice Hall of
India Private Limited, New Delhi, 1990.
Chapter 2. Atomic Structure, Interatomic Bonding and Structure
of Crystalline Solids

2.1 Atomic Structure and Atomic Bonding in Solids

2.1.1 Atomic Structure

Atoms are composed of electrons, protons, and neutrons. Electrons and protons are
negative and positive charged particles respectively. The magnitude of each charged
particle in an atom is 1.6 × 10-19 Coulombs.

The mass of the electron is negligible with respect to those of the proton and the neutron,
which form the nucleus of the atom. The unit of mass is an atomic mass unit (amu) =
1.66 × 10-27 kg, and equals 1/12 the mass of a carbon atom. The Carbon nucleus has Z=6,
and A=6, where Z is the number of protons, and A the number of neutrons. Neutrons and
protons have very similar masses, roughly equal to 1 amu each. A neutral atom has the
same number of electrons and protons, Z.

A mol is the amount of matter that has a mass in grams equal to the atomic mass in amu of
the atoms. Thus, a mole of carbon has a mass of 12 grams. The number of atoms in a mole
is called the Avogadro number, Nav = 6.023 × 1023. Note that Nav = 1 gram/1 amu.

Calculating n, the number of atoms per cm3 of a material of density  (g/cm3):


n = N av
M

where M is the atomic mass in amu (grams per mol). Thus, for graphite (carbon) with a
density  = 1.8 g/cm3, M =12, we get 6 × 1023 atoms/mol × 1.8 g/cm3 / 12 g/mol) = 9 ×
1022 C atoms/cm3.
For a molecular solid like ice, one uses the molecular mass, M(H2O) = 18. With a density of
1 g/cm3, one obtains n = 3.3 × 1022 H2O molecules/cm3. Note that since the water molecule
contains 3 atoms, this is equivalent to 9.9 × 1022 atoms/cm3.

Most solids have atomic densities around 6 × 1022 atoms/cm3. The cube root of that number
gives the number of atoms per centimeter, about 39 million. The mean distance between
atoms is the inverse of that, or 0.25 nm. This is an important number that gives the scale
of atomic structures in solids.

2.1.2 Atomic bonding in solids

In order to understand the why materials behave like they do and why they differ in
properties, it is necessary that one should look at atomic level. The study primarily
concentrates on two issues: what made the atoms to cluster together, and how atoms are
arranged. As mentioned in earlier chapter, atoms are bound to each other by number of
bonds. These inter-atomic bonds are primarily of two kinds: Primary bonds and Secondary
bonds. Ionic, Covalent and Metallic bonds are relatively very strong, and grouped as
primary bonds, whereas van der Waals and hydrogen bonds are relatively weak, and termed
as secondary bonds. Metals and Ceramics are entirely held together by primary bonds - the
ionic and covalent bonds in ceramics, and the metallic and covalent bonds in metals.
Although much weaker than primary bonds, secondary bonds are still very important. They
provide the links between polymer molecules in polyethylene (and other polymers) which
make them solids. Without them, water would boil at -80˚C, and life as we know it on earth
would not exist.

Ionic Bonding: This bond exists between two atoms when one of the atoms is negative
(has an extra electron) and another is positive (has lost an electron). Then there is a strong,
direct Coulomb attraction. Basically ionic bonds are non-directional in nature. An example
is NaCl. In the molecule, there are more electrons around Cl, forming Cl - and fewer
electrons around Na, forming Na+. Ionic bonds are the strongest bonds. In real solids, ionic
bonding is usually exists along with covalent bonding.

Na Cl

Fig.1 Schematic representation of ioning bonding. Here, Na is giving an electron to Cl to

have stable structure
Covalent Bonding: In covalent bonding, electrons are shared between the atoms, to
saturate the valency. The simplest example is the H2 molecule, where the electrons spend
more time in between the nuclei of two atoms than outside, thus producing bonding.
Covalent bonds are stereo-specific i.e. each bond is between a specific pair of atoms, which
share a pair of electrons (of opposite magnetic spins). Typically, covalent bonds are very
strong, and directional in nature. The hardness of diamond is a result of the fact that each
carbon atom is covalently bonded with four neighboring atoms, and each neighbor is
bonded with an equal number of atoms to form a rigid three-dimensional structure.

H H

Figure 2. Schematic representation of covalent bond in Hydrogen molecule (sharing of

electrons)

Metallic Bonding: Metals are characterized by high thermal and electrical conductivities.
Thus, neither covalent nor ionic bondings are realized because both types of bonding
localize the valence electrons and preclude conduction. However, strong bonding does
occur in metals. The valence electrons of metals also are delocalized. Thus metallic
bonding can be viewed as metal containing a periodic structure of positive ions surrounded
by a sea of delocalized electrons. The attraction between the two provides the bond, which
is non-directional.
Electron cloud from
the valence electrons
M M M M

M M M M Core

M M M M

M M M M
 Figure 3. Metallic bonding

Fluctuating Induced Dipole Bonds: Since the electrons may be on one side of the atom
or the other, a dipole is formed: the + nucleus at the center, and the electron outside. Since
the electron moves, the dipole fluctuates. This fluctuation in atom A produces a fluctuating
electric field that is felt by the electrons of an adjacent atom, B. Atom B then polarizes so
that its outer electrons are on the side of the atom closest to the + side (or opposite to the –
side) of the dipole in A.

Polar Molecule-Induced Dipole Bonds: Another type of secondary bond exists with
asymmetric molecules, also called polar molecules because of positively and negatively
charged regions. A permanent dipole moment arises from net positive and negative charges
that are respectively associated with the hydrogen and chlorine ends of the HCl molecule,
leading to bonding. The magnitude of this bond will be greater than for fluctuating induced
dipoles.

Figure 4. Dipole bond in water

These two kinds of bonds are also called van der Waals bonds. Third type of secondary
bond is the hydrogen bond. It is categorized separately because it produces the strongest
forces of attraction in this category.

Permanent Dipole Bonds / Hydrogen bonding: It occurs between molecules as

covalently bonded hydrogen atoms – for example C-H, O-H, F-H – share single electron
with other atom essentially resulting in positively charged proton that is not shielded any
electrons. This highly positively charged end of the molecule is capable of strong attractive
force with the negative end of an adjacent molecule. The properties of water are influenced
significantly by the hydrogen bonds/bridges. The bridges are of sufficient strength, and as
a consequence water has the highest melting point of any molecule of its size. Likewise,
its heat of vaporization is very high.
2.2 Crystal Structures, Crystalline and Non-Crystalline materials

2.2.1 Crystal structures

All metals, a major fraction of ceramics, and certain polymers acquire crystalline form
when solidify, i.e. in solid state atoms self-organize to form crystals. Crystals possess a
long-range order of atomic arrangement through repeated periodicity at regular intervals in
three dimensions of space. When the solid is not crystalline, it is called amorphous.
Examples of crystalline solids are metals, diamond and other precious stones, ice, graphite.
Examples of amorphous solids are glass, amorphous carbon (a-C), amorphous Si, most
plastics.

There is very large number of different crystal structures all having long-range atomic
order; these vary from relatively simple structures for metals to exceedingly complex
structures for ceramics and some polymers. To discuss crystalline structures it is useful to
consider atoms as being hard spheres, with well-defined radii. In this scheme, the shortest
distance between two like atoms is one diameter. In this context, use of terms lattice and
unit cell will be handy. Lattice is used to represent a three-dimensional periodic array of
points coinciding with atom positions. Unit cell is smallest repeatable entity that can be
used to completely represent a crystal structure. Thus it can be considered that a unit cell
is the building block of the crystal structure and defines the crystal structure by virtue of
its geometry and the atom positions within.

Important properties of the unit cells are

• The type of atoms and their radii R.

• Cell dimensions (Lattice spacing a, b and c) in terms of R and
• Angle between the axis α, β, γ
• a*, b*, c* - lattice distances in reciprocal lattice , α*, β*, γ* - angle in reciprocal
lattice
• n, number of atoms per unit cell. For an atom that is shared with m adjacent unit
cells, we only count a fraction of the atom, 1/m.
• CN, the coordination number, which is the number of closest neighbors to which
an atom is bonded.
• APF, the atomic packing factor, which is the fraction of the volume of the cell
actually occupied by the hard spheres. APF = Sum of atomic volumes/Volume of
cell.

Some very common crystal structures and relevant properties are listed in table 2.1.

Table 2.1: Common crystal structures and their properties.

Unit Cell n CN a/R APF

Simple Cubic 1 6 4/ 0.52

 Body-Centered Cubic 2 8 4/ 3 0.68

Face-Centered Cubic 4 12 4/ 2 0.74

Hexagonal Close Packed 6 12 0.74

Figure 2.1: Common metallic crystal structures.

2.2.2 Crystalline and Non-crystalline materials

Single Crystals: Crystals can be single crystals where the whole solid is one crystal. Then
it has a regular geometric structure with flat faces.

Polycrystalline Materials: A solid can be composed of many crystalline grains, not

aligned with each other. It is called polycrystalline. The grains can be more or less aligned
with respect to each other. Where they meet is called a grain boundary.

Non-Crystalline Solids: In amorphous solids, there is no long-range order. But amorphous

does not mean random, since the distance between atoms cannot be smaller than the size
of the hard spheres. Also, in many cases there is some form of short-range order. For
instance, the tetragonal order of crystalline SiO2 (quartz) is still apparent in amorphous
SiO2 (silica glass).

2.3 Miller Indices, Anisotropy, and Elastic behavior of composites

2.3.1 Miller indices:

It is understood that properties of materials depend on their crystal structure, and many of
these properties are directional in nature. For example: elastic modulus of BCC iron is
greater parallel to the body diagonal than it is to the cube edge. Thus it is necessary to
characterize the crystal to identify specific directions and planes. Specific methods are
employed to define crystal directions and crystal planes.

Methodology to define crystallographic directions in cubic crystal:

 - a vector of convenient length is placed parallel to the required direction.
- the length of the vector projection on each of three axes are measured in unit cell
dimensions.
- these three numbers are made to smallest integer values, known as indices, by
multiplying or dividing by a common factor.
- the three indices are enclosed in square brackets, [uvw]. A family of directions is
represented by <uvw>.

Methodology to define crystallographic planes in cubic crystal:

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

For example, if the x-, y-, and z- intercepts of a plane are 2, 1, and 3. The Miller indices
are calculated as:
- take reciprocals: 1/2, 1/1, 1/3.
- clear fractions (multiply by 6): 3, 6, 2.
- reduce to lowest terms (already there). => Miller indices of the plane are (362).

Figure 2.2 depicts Miller indices for number of directions and planes in a cubic crystal.

Figure 2.2: Miller indices in a cubic crystal.

Some useful conventions of Miller notation:

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

More conventions applicable to cubic crystals only:

- [uvw] is normal to (hkl) if u = h, v = k, and w = l. E.g.: (111) ┴ [111].

- Inter-planar distance between family of planes {hkl} is given by:

a
d{hkl} =
h + k2 + l2
2

- [uvw] is parallel to (hkl) if hu + kv + lw = 0.

- Two planes (h1k1l1) and (h2k2l2) are normal if h1h2 + k1k2 + l1l2=0.
- Two directions (u1v1w1) and (u2v2w2) are normal if u1u2 + v1v2 + w1w2=0
- Angle between two planes is given by:

h1h2 + k1k2 + l1l2

cos =
h12 + k 12 + l12 h22 + k 22 + l 22

The same equation applies for two directions.

Why Miller indices are calculated in that way?

- Using reciprocals spares us the complication of infinite intercepts.
- Formulas involving Miller indices are very similar to related formulas from
analytical geometry.
- Specifying dimensions in unit cell terms means that the same label can be applied
to any plane with a similar stacking pattern, regardless of the crystal class of the
crystal. Plane (111) always steps the same way regardless of crystal system.

2.3.2 Miller-Bravis indices

Though Miller indices can describe all possible planes through any crystal, Miller-Bravis
indices are used in hexagonal crystal systems. This is because they reveal hexagonal
symmetry more clearly. Although partially redundant, they are used exclusively for
hexagonal systems.

Direction indices are obtained as above where first three indices are representative of
projections of the direction over three co-planar axes in the plane called basal plane while
the last index denotes the projection over the axis perpendicular to the basal plane. Miller-
Bravis indices for a plane are denoted as [uvtw], where t = -(u+v)

In the same procedure, planes in a hexagonal crystal are denoted by (hkil), where i = -
(h+k).

2.3.3 Anisotropy

It’s been agreed that many of the materials properties depend on the crystal structure.
However, crystals are not symmetric in all directions, or not the crystal planes same with
respect to atomic density/packing. Different directions in the crystal have different packing.
For instance, atoms along the edge of FCC crystals are more separated than along its face
diagonal. This causes properties to be different in different directions. This directionality
of properties is termed as Anisotropy.

Substances in which measured properties are independent of direction in which they are
measured are called isotropic. Though, in polycrystalline materials, the crystallographic
orientations of individual grains are random, specimen may behave isotropically.

2.3.4 Elastic Behavior of Composites

The idea is that by combining two or more distinct materials one can engineer a new
material with the desired combination of properties (e.g., light, strong, corrosion resistant).
The idea that a better combination of properties can be achieved is called the principle of
combined action.

For example, Pearlitic steel that combines hard and brittle Cementite with soft and ductile
ferrite to get a superior material.

A composite is defined as a artificially made muti-phase material, where constituent phases

are chemically dissimilar and separated by a distinct interface. Thus, composites shall have
at least two or more constituent phases. Many of the composites are made of two phases –
one is termed as matrix, which is continuous and surrounds the other phase, called
dispersed phase. Dispersed phase can exist in many forms like particulates, short-
/long- fibers.

Properties of composites depend on

 - Properties of the constituent phases.
- Geometry of dispersed phase (particle size, size distribution, orientation).
- Amount of each constituent phase.

Classification of composites based on geometry of dispersed phase:

- Particle-reinforced (large-particle and dispersion-strengthened)
- Fiber-reinforced (continuous (aligned) and short fibers (aligned or random)
- Structural (laminates and sandwich panels)

Classification of composites based on matrix phase:

- Metal Matrix Composites.
- Polymer Matrix Composites.
- Ceramic Matrix Composites.

Composite properties can be calculated using rule of mixtures. For example, elastic
modulus of a particle reinforced composite bound by the limits given by

Ec (u) = EmVm + E p V p

E (l) = Em E p
c

E mV p + EpVm

where E and V denote the elastic modulus and volume fraction respectively; c, m, and p
represent composite, matrix, and particulate phases.

However, in case of continuous fiber reinforced composites upper bound is applicable to

condition of longitudinal loading, while the lower bound is applicable to transverse loading
condition. The above equations can be simplified using the following relations:

Vm + V p = 1

When fiber orientation is random, or short and discontinuous fibers are used, rule of
mixtures will be modified as follows to take care of the randomness of fibers:

Ecd = EmVm + KE f V f

where K – is fiber efficiency parameter that depends on Vf and Ef/Em ratio. K’s values are
less than unity, usually attains a value in the range of 0.1 to 0.6.

Many applications, like in aircraft parts, there is a need for high strength per unit weight
(specific strength). This can be achieved by composites consisting of a low-density (and
soft) matrix reinforced with stiff fibers.

2.4 Structure and properties of polymers

Polymers are common in nature, in the form of wood, rubber, cotton, leather, wood, silk,
proteins, enzymes, starches, cellulose. Artificial polymers are made mostly from oil. Their
use has grown exponentially, especially after WW2 (World War-2). The key factor is the
very low production cost and useful properties (e.g., combination of transparency and
flexibility, long elongation, etc.).

Most polymers are organic, and formed from hydrocarbon molecules. These molecules can
have single, double, or triple carbon bonds. A saturated hydrocarbon is one where all
bonds are single, i.e. the number of atoms is maximum (or saturated). Among this type are
the paraffin compounds, CnH2n+2. In contrast, non-saturated hydrocarbons contain some
double and triple bonds.

Isomers are molecules that contain the same molecules but in a different arrangement. An
example is butane and iso-butane. Some physical properties of hydrocarbons depend on
the isomeric state.

2.4.1 Polymer molecules

Polymer molecules are huge, macromolecules that have internal covalent bonds. For most
polymers, these molecules form very long chains. The backbone is a string of carbon atoms,
often single bonded. Polymers are composed of basic structures called mer units. A
molecule with just one mer is a monomer. Within each molecule / mer atoms are bonding
together by strong covalent bonds. When many mers are together, they form polymer. Bi-
functional monomers may bond with two other units in forming 2-D chain- like structures;
while Tri-functional monomers can form three active bonds, and thus 3-D molecular
network. Examples of polymers are polyvinyl chloride (PVC), poly-tetra- fluoro-ethylene
(PTFE or Teflon), polypropylene, nylon and polystyrene. When all the mers are the same,
the molecule is called a homopolymer. When there is more than one type of mer present,
the molecule is a copolymer.

The mass of a polymer is not fixed, but is distributed around a mean value, since not all
polymer chains will grow same extent. The average molecular weight can be obtained by
averaging the masses with the fraction of times they appear (number-average) or with the
weight fraction of the molecules (weight-average). Another representation of average chain
size is degree of polymerization (n) – average number of mer units in a chain. It is obtained
by dividing the average mass of the polymer by the mass of a mer unit. Numbers of
polymer characteristics are affected by the magnitude of the molecular weight. Short chain
polymers usually exist in form of gases or liquids at room temperature; where as medium
range polymers are waxy solids and soft resins. Solid polymers are commonly having
weights ranging between 10K and several million g/mol.

2.4.2 Polymer structures

Polymers consist of large number of molecular chains which are usually not linear; bending
and rotations can occur around single C-C bonds (double and triple bonds are very rigid).
Random kinks and coils in chains along with bending of chains lead to
intertwining and entanglement of neighboring chains, situation like in the spaghetti
structure. These characteristic entanglements are responsible for a number of properties
specific to polymers, e.g.: large elastic extension. However, physical properties of
polymers depend not only on molecular weight and shape, but also on differences in
structure of the chains. It should be remembered that polymers are not usually of only one
distinctive structural type, though they are classified into different groups. Typical polymer
chain structures are: (a) linear, where mer units are joined together end to end in single
chains. E.g.: PVC, nylon. (b) branched, where side-branch chains are connected to main
ones. Branching of polymers lowers polymer density because of lower packing efficiency.
(c) cross-linked, where chains are joined one to another at various positions by covalent
bonds. This cross-linking is usually achieved at elevated temperatures by additive atoms.
E.g.: vulcanization of rubber. (d) network, trifunctional mer units with 3- D networks
comes under this category. E.g.: epoxies, phenol-formaldehyde.

2.4.3 Polymer crystallinity

Crystallinity in polymers is more complex than in metals. Polymer molecules are often
partially crystalline (semicrystalline), with crystalline regions dispersed within amorphous
material. The degree of crystallinity may range from completely amorphous to almost
entirely crystalline; on the other hand metals are almost always crystalline whereas
ceramics are either completely crystalline or noncrystalline. The degree of crystallinity of
a polymer depends on cooling path, and also on chain configuration. For copolymers, the
more irregular and random the mer arrangement, the greater is probability for
noncrystalline nature. Crystalline polymers are denser than amorphous polymers, so the
degree of crystallinity can be obtained from the measurement of density.

Different models have been proposed to describe the arrangement of molecules in

semicrytalline polymers. In the fringed-micelle model, the crystallites (micelles) are
embedded in an amorphous matrix. Polymer single crystals grown are shaped in regular
platelets (lamellae). Spherulites are chain-folded crystallites in an amorphous matrix that
grow radially in spherical shape “grains”. These are considered to be the polymer analogue
of grains in polycrystalline metals and ceramics. Many semicrystalline polymers form
spherulites; each spherulite consists of a collection of ribbonlike chain- folded lamellar
crystallites that radiate outward from its center. E.g.: polyethelene, PVC.

A polymer’s response to mechanical forces under elevated temperatures is related to its

molecular structure. Based on this response, polymers are classified as: thermoplasts
(soften when heated and harden when cooled), and thermosets (become permanently hard
when heat is applied and do not soften upon subsequent heating). Thermosets are generally
harder and stronger than thermoplasts, and have better dimensional stability. Most of the
cross-linked and network polymers are thermosets; whereas linear and some branched
polymers are thermoplasts.

2.4.4 Properties of polymers

Fluids and amorphous solids undergo viscous flow when external forces are applied. It is
well known that polymers exhibit very high viscosity in order of 1012 Pa.s at room
temperature. Polymers are non-Newtonian in nature, and formed into plastic products at a
temperature above their glass-transition temperature. It is evident that temperature has very
strong influence on mechanical behavior of polymers. Elastic strain occurs simultaneously
with viscous flow, resulting in visco-elastic deformation of polymers under externally
applied loads. Below the glass transition temperature elastic deformation dominates and
the material behaves rigid. In the range of glass temperature, the materials is leathery; in
the rubber plateau, polymers deform readily but quickly regain their previous shape if the
stress in removed. At still higher temperatures, under sustained loads, the polymer deforms
extensively by viscous flow. Figure below depicts temperature effect on deformation
behavior of polymers.

Figure 2.3: Dependence of polymer viscosity on temperature and/or loading rate.

2.5 Structure and properties of ceramics

Ceramics are inorganic and non-metallic materials that are commonly electrical and
thermal insulators, brittle and composed of more than one element (e.g., two in Al2O3). As
ceramics are composed of two or more elements, their crystal structures are generally more
complex than those of metals. Ceramic bonds are mixed, ionic and covalent, with a
proportion that depends on the particular ceramics. The ionic character is given by the
difference of electronegativity between the cations (+) and anions (-). Covalent bonds
involve sharing of valence electrons. Very ionic crystals usually involve cations which
are alkalis or alkaline-earths (first two columns of the periodic table) and oxygen or
halogens as anions.

The building criteria for the ceramic crystal structure are as follows:
- maintain neutrality (charge balance dictates chemical formula)
- achieve closest packing

The crystal stability condition i.e. condition of minimum energy implies maximum
attraction and minimum repulsion. This leads to contact and configurations such that anions
have the highest number of cation neighbors (coordination number) and vice versa. The
coordination number is dependent on cation-anion radius ratio, which can be determined
from geometric relations. Table 2.2 presents relevant coordination numbers and radius
ratios.

Table 2.2. Co-ordination number dependency on cation-anion radius ratio.

Cation-anion 0.155 – 0.225 – 0.414 – 0.732 –
< 0.155 > 1.000
radius ratio (rc/ra) 0.225 0.414 0.732 1.000
Coordination
2 3 4 6 8 12
number

Figure-2.4 presents schematic arrangement of cations and anions with respective

coordinate positions for different radius ratios.

Figure 2.4: Ion arrangements for different coordination numbers.

2.5.1 Ceramic crystal structures

AX-type ceramic crystal structures: Most common ceramics are made of equal number of
cations and anions, and are referred to as AX compounds (A-cation, and X-anion). These
ceramics assume many different structures, named after a common material that possesses
the particular structure.
Rock salt structure: here the coordination number is 6, i.e. rc/ra = 0.414-0.732. This
structure can be viewed as an FCC of anions with cations occupying center of each edge
and the center of the cell. Thus it can be said that lattice is made of two interpenetrating
FCC lattices, one composed of cations, and the other of anions. E.g.: NaCl, MgO, FeO.

Cesium Chloride structure: here the coordination number is 8. Crystal structure consists of
anions at corners of a cube while a cation occupies the center, and vice versa. E.g.: CsCl.

Zinc Blende structure: here the coordination number is 4. Unit cell is composed of one kind
of ions occupying corners and face centers of a cube, while the other kind of ions occupies
the interior tetrahedral positions. E.g.: ZnS, SiC.

AmXp- type structures: when the charges of cation and anions are not the same, to maintain
the neutrality, ceramic structures with chemical formula would exist. For example – CaF2
with rc/ra = 0.8, and thus coordination number of 8. It can be expected that crystal structure
could be the same as that of CsCl. However cations are half many as anions, thus only half
the center positions are occupied. One unit cell shall be made of eight cubes. E.g.: UO2,
ThO2, PuO2.

AmBnXp-type structures: it is possible that ceramics do have more than one kind of cations.
E.g.: BaTiO3. unit cell is made of cube where Ba2+ ions occupies all eight corners, T4+
occupies cube center, while O2- are at center of each face. This structure is called perovskite
crystal structure.

It is worth to understand and know more about some common most common ceramic in
nature. For example: silicates and carbon.

2.5.2 Silicates

Oxygen and Silicon are the most abundant elements in Earth’s crust. Their combination
(silicates) occurs in rocks, soils, clays and sand. The bond is weekly ionic, with Si4+ as the
cation and O2- as the anion. However the bonds in silicates are strongly of covalent
character with strong directional Si-O bonds. Basic unit of silicates structures are thus is
SiO44- tetrahedron that consists of four oxygen atoms at corners of tetrahedron, and silicon
atom at the center of it. Various silicate structures consists SiO 4- unit 4bonded in
1-, 2-, and 3- dimensions.

In silica (SiO2) every oxygen atom is shared by adjacent tetrahedra. Silica can either be
crystalline (e.g., quartz) or amorphous, as in glass. Crystalline forms of silica are known to
be complicated and comparatively open, thus of low densities compared with amorphous
glasses. Soda glasses melt at lower temperature than amorphous SiO2 because the addition
of Na2O (soda) that act as network modifier breaks the tetrahedral network. Addition of
intermediates such as Al2O3, TiO2 substitute of silicon atoms and become part of stabilized
network. Addition of network modifiers and intermediates lowers melting point, and thus
it is easy to form glass, for instance, bottles.
In complicated silicate structure, corner oxygen atom of basic unit is shared by other
tetrahedra, resulting in formulas such as SiO44-, Si2O76-, Si3O96-, etc. The repeating unit of
2-D sheet or layered structure is represented as Si2O52-. Such layered structures are
characteristics of clays and other minerals.

2.5.3 Carbon

Carbon is not really a ceramic, but one of its allotropic form, diamond may be considered
as a ceramic. Diamond has very interesting and even unusual properties such as:
- possesses diamond-cubic structure (like Si, Ge)
- consists covalent C-C bonds
- having highest hardness of any material known
- very high thermal conductivity (unlike ceramics)
- transparent in the visible and infrared, with high index of refraction
- semiconductor (can be doped to make electronic devices)
- meta-stable (transforms to carbon when heated)

Synthetic diamonds are made by application of high temperatures and pressures or by

chemical vapor deposition. Future applications of this latter, cheaper production method
include hard coatings for metal tools, ultra-low friction coatings for space applications, and
microelectronics.

Graphite, another allotropic form of carbon, has a layered structure with very strong
hexagonal bonding within the planar layers (using 3 of the 3 bonding electrons) and weak,
van der Waals bonding between layers using the fourth electron. This leads to easy inter-
planar cleavage and applications as a lubricant and for writing (pencils). Graphite is a good
electrical conductor and chemically stable even at high temperatures. Applications include
furnaces, rocket nozzles, electrodes in batteries, etc.

Recently (1985) discovered allotropic form of carbon is the C60 molecule, also known as
fullerene or bucky-ball (after the architect Buckminster Fuller who designed the geodesic
structure that C60 resembles.). Structure of this form resembles a hallow spherical cluster
of 60 atoms, and is found to consist of 20 hexagons and 12 pentagons where no two
pentagons share a common edge. Fullerenes and related structures like nanotubes are
exceptionally stiff, strong, and ductile. Future applications of fullerenes are as a structural
material and possibly in microelectronics, due to the unusual properties that result when
fullerenes are doped with other atoms.

2.5.4 Imperfections in ceramics

Imperfections in ceramics include point defects and impurities. Their formation is strongly
affected by the condition of charge neutrality (creation of unbalanced charges requires the
expenditure of a large amount of energy). Both vacancies and interstitials are possible in
ceramics as in metals; however as ceramics have more then one element these defects can
be associated with each of these elements. Neutral charge defects include the Frenkel and
Schottky defects. A Frenkel-defect is a vacancy- interstitial pair of cations
(placing large anions in an interstitial position requires a lot of energy in lattice distortion).
A Schottky-defect is a pair of nearby cation and anion vacancies.

Non-stoichiometry refers to a change in composition so that the elements in the ceramic

are not in the proportion appropriate for the compound (condition known as stoichiometry).
To minimize energy, the effect of non-stoichiometry is a redistribution of the atomic
charges. Introduction of impurity atoms in the lattice is likely in conditions where the
charge is maintained. This is the case of electronegative impurities that substitute lattice
anions or electropositive substitutional impurities. This is more likely for similar ionic radii
since this minimizes the energy required for lattice distortion. Defects will appear if the
charge of the impurities is not balanced.

2.5.5 Mechanical response of ceramics

Brittle Fracture of Ceramics: The brittle fracture of ceramics limits their engineering
applications. It occurs due to the unavoidable presence of microscopic flaws (micro-
cracks, internal pores, and atmospheric contaminants) that result during cooling from the
melt. The flaws need to crack initiation, and crack propagation (perpendicular to the
applied stress) is usually trans-granular, along cleavage planes. The flaws cannot be closely
controlled in manufacturing; this leads to a large scatter in the fracture strength of ceramic
materials.

Under compressive stresses, however, flaws do not associate with amplification of stress.
Hence, the compressive strength of ceramics is typically ten times to their tensile strength.
This makes ceramics good structural materials under compression (e.g., bricks in houses,
stone blocks in the pyramids), but not in conditions of tensile stress, such as under flexure.

Plastic deformation in crystalline ceramics is by slip, which is difficult due to the structure
and the strong local (electrostatic) potentials. There is very little plastic deformation before
fracture. Non-crystalline ceramics, like common glass, deform by viscous flow (like very
high-density liquids) as deformation can not occur by slip because of absence of regular
atomic structure, which occurs in metals. Characteristic property of viscous flow, viscosity,
is a measure of non-crystalline material’s resistance to deformation. It was found to
decrease with increasing temperature. At room temperature, the viscosity of many non-
crystalline ceramics is extremely high.

References

1. William D. Callister, Jr, Materials Science and Engineering – An introduction,

sixth edition, John Wiley & Sons, Inc. 2004.
2. B. D. Cullity and S. R. Stock, Elements of X-Ray Diffraction, Third Edition,
Prentice Hall, Upper Saddle River, NJ, 2001
3. Lawrence H. Van Vlack, Elements of Materials Science and Engineering, sixth
edition, Addison Wesley Longman, Inc. New York, 1998
Crystal Structure
 Preface
Crystal structure is one of the most important aspects of
materials science and engineering as many properties of
materials depend on their crystal structures. The basic
principles of many materials characterization techniques
such as X-ray diffraction (XRD), Transmission electron
microscopy (TEM) are based on crystallography. Therefore,
understanding the basics of crystal structures is of
paramount importance.
 Atomic arrangement
Solid

Crystalline Amorphous

Crystalline – periodic arrangement of atoms: definite

repetitive pattern
Non-crystalline or Amorphous – random arrangement of
atoms.
The periodicity of atoms in crystalline solids can be
described by a network of points in space called lattice.
 Space lattice
➢ A space lattice can be defined as a three dimensional array
of points, each of which has identical surroundings.
➢ If the periodicity along a line is a, then position of any point
along the line can be obtained by a simple translation, ru = ua.
➢ Similarly ruv = ua + vb will repeat the point along a 2D plane,
where u and v are integers.
a

b
Symmetry
 Symmetry
➢ Symmetry refers to certain pattern or arrangement. A body is
symmetrical when it is reproduced by certain operation.

➢ The symmetry word (somewhat distorted) itself shows 2-fold

rotation symmetry (restored by 180o rotation)
➢ In the picture below the plane looks identical after a 90o
rotation. The plane has 4 fold rotation symmetry as it repeats
itself 4 times (shown by the red dot) in a full 360o rotation.
Symmetry operations

1. Translation
2. Rotation
3. Reflection
4. Inversion
 Translation
uT

The first point is repeated at equal distances along a line by a

translation uT, where T is the translation vector and u is an
integer.

Translation on a point with coordinates xyz → x+a y+b z+c

where, a, b and c are the unit vectors in x, y and z directions
respectively.
 Symmetry operations
Rotation
A rotation can be applied on the translation vector T in all
directions, clock or anti-clock wise, through equal angles 
in the 2D space.
If two rotation operations, one each in clock and anti-clock
direction, are applied on the translation vector T, it will
create two more lattice points. Because of the regular
pattern, the translation between these two points will be
some multiple of T (pT).


 Symmetry operations
Rotation
T = T cos + pT + T cos = pT +2T cos
T T cos  = (1 – p)/2
 
p  n-fold Symbol
pT 0 60 6
Tcos Tcos 1 90 4
T
2 120 3
3 180 2
-1 0/360 1

An n-fold rotation symmetry means rotation through an

angle of 2/n will repeat the object or motif n times in a full
360o rotation. n =1 means no symmetry.
 Rotation

1- Fold Rotation Axis - An object that

requires rotation of a full 360o to repeat
itself has no rotational symmetry.

2- fold Rotation Axis - If an object appears identical after

a rotation of 180o, that is twice in a 360o rotation, then it is
said to have a 2-fold (2/180) rotation symmetry

2 2 2
 Rotation
Similarly we have 3, 4 and 6-fold rotational symmetry

3 fold – 2/120

4 fold – 2/90

6 fold – 2/60
 Rotation
Is it possible to have 5, 7 or 8-fold rotation symmetry?
Objects with 5, 7 and 8 or higher order symmetry do exist in
nature, e.g. star fish (5-fold), flowers with 5 or 8-fold symmetry.

However, these are not possible in crystallography as they

cannot fill the space completely

5 fold 8 fold
 Reflection or Mirror symmetry
An object with a reflection symmetry will be a mirror image of
itself across a plane called mirror plane (m).

y
-xy m xy

Reflection operation: xyz → -x y z (x y z ) across a mirror

plane perpendicular to x axis
 Symmetry and Space lattice
Symmetry elements discussed so far define five types of 2D
space lattices. When a translation is applied to the third
direction these lattices create a total of 7 crystal systems.

a2 2-fold 3, 6-fold
Parallelogram Hexagonal
a = a ,  = 120
 
a1  a2,  = Any 1 2
a1

4-fold: Square Centered-Rectangular Primitive-Rectangular

a1 = a2,  = 90 a1  a2,  = 90 a1  a2,  = 90
 Inversion – Center of symmetry
In this operation, every part of the object is reflected through
an inversion center called center of symmetry which is
denoted as i. The object is reproduced inverted from its
original position.
1 4

2 5
6 i 3
i i
3 6

5 2

4 1
xyz →i -x -y -z (xyz)
 Combined operations
Combined symmetry operations also exist. For example,
rotation can be combined with inversion which is called
roto-inversion. The roto-inversion axis is denoted as n.
For example, a 6-fold roto-inversion (6 ) involves rotating
the object by 60o (360/6), and inverting through a symmetry
center.
6

Inversion
center

Rotation axis
 Point and Space groups
Symmetry operations generate a variety of arrangements of
lattice points in three dimensions. There are 32 unique ways
in which lattice points can be arranged in space. These
non-translation elements are called point-groups.

A large number of 3D structures are generated when

translations [linear translation, translation + reflection (glide
plane) and translation + rotation (screw axis)] are applied to
the point groups. There are 230 unique shapes which can
be generated this way. These are called space groups.
 Hermann-Mauguin Symbols
➢ The 32 point groups are denoted by notations called
Hermann-Mauguin symbols. These symbols basically
describe the unique symmetry elements present in a body.
➢ The shape in Fig.(a) contains 1 4-fold axis, 4 2-fold axes, 5
mirror planes. 3 mirror planes and 2 2-fold axes are unique as
others can be produced by a symmetry operation. Therefore,
point group symbol for this shape is 4/m2/m2/m. The “/”
between 4 or 2 and m indicates that they are perpendicular to
each other.

m
m

4/m2/m2/m (b)
(a)
2/m2/m2/m
 Summary
❑ Space lattice is arrangement of points with each point having
exactly same surroundings.
❑ Symmetry operations restore a body to its original position.
❑ There are four symmetry operations – Translation, reflection,
rotation and inversion.
❑ There are 32 point groups and 230 space groups.
❑ Hermann-Mauguin symbols are used to denote point groups.

References
http://www.tulane.edu/~sanelson/eens211/index.html#Lecture
Notes
http://www.tulane.edu/~sanelson/eens211/introsymmetry.pdf
http://www.tulane.edu/~sanelson/eens211/32crystalclass.pdf
 Crystal Systems
➢ The space lattice points in a crystal are occupied by atoms.
➢ The position of any atom in the 3D lattice can be described
by a vector ruvw = ua + vb + wc, where u, v and w are integers.

(a) (b)

Unit Cell
The three unit vectors, a, b, c can define a cell as shown by the
shaded region in Fig.(a) This cell is known as unit cell (Fig. b)
which when repeated in the three dimensions generates the
crystal structure.
 Crystal Systems
Bravais Lattice

The unit vectors a, b and c are called lattice parameters.

Based on their length equality or inequality and their
orientation (the angles between them, ,  and ) a total of 7
crystal systems can be defined. With the centering (face,
base and body centering) added to these, 14 kinds of 3D
lattices, known as Bravais lattices, can be generated.
 Crystal Systems
Cubic: a = b = c,  =  =  = 90o

Simple Body-centered Face-centered

cubic cubic (BCC) cubic (FCC)

Tetragonal: a = b  c,  =  =  = 90o

Simple Body-centered
Tetragonal Tetragonal (BCT)
 Crystal Systems
Orthorhombic: a  b  c,  =  =  = 90o

Simple Body-centered Base-centered Face-centered

Monoclinic: a  b  c,  =  = 90o  

Simple Base-centered
monoclinic monoclinic
 Crystal Systems

Triclinic
Rhombohedral Hexagonal
abc
a=b=c a=bc
      90o
 =  =   90o  =  = 90  = 120
o o
 Crystal Systems

Crystal system Example

Triclinic K2S2O8,K2Cr2O7
Monoclinic As4S4, KNO2,CaSO4.2H2O, -S
Rhombohedral Hg, Sb, As, Bi, CaCO3
Hexagonal Zn, Co, Cd, Mg, Zr, NiAs
Orthorhombic Ga, Fe3C, -S
Tetragonal In, TiO2, -Sn
Cubic Au, Si, Al, Cu, Ag, Fe, NaCl
 Point Coordinates
Position of any point in a unit cell is given by its coordinates
or distances from the x, y and z axes in terms of the lattice
vectors a, b and c.
Thus the point located at a/2 along x axis, b/3 along y axis
and c/2 along z axis, as shown in the figure below, has the
111
coordinates
232
 Crystal Planes
Miller Indices
Planes in a crystal are described by notations called Miller
indices
❖ Miller indices of a plane, indicated by h k l, are given by the
reciprocal of the intercepts of the plane on the three axes.

❖ The plane, which intersects X axis at 1 (one lattice

parameter) and is parallel to Y and Z axes, has Miller indices
h = 1/1 = 1, k = 1/ = 0, l = 1/ = 0. It is written as (hkl) =
(100).

❖ Miller indices of some other planes in the cubic system are

shown in the figures in the next slide
 Crystal Planes

To find the Miller Indices of a plane, follow these steps:

▪ Determine the intercepts of the plane along the crystal axes
▪ Take the reciprocals
▪ Clear fractions
▪ Reduce to lowest terms and enclose in brackets ()
Ex: Intercepts on a, b, c : ¾, ½, ¼ (h k l) = (4/3, 2, 4) = (2 3 6)
 Crystal Planes
Planes can also have negative intercept e.g. 1, -1/2, 1
−
h k l = 1 -2 1. This is denoted as ( 121 )

Family of planes {hkl}

Planes having similar indices are equivalent, e.g. faces
of the cube (100), (010) and (001). This is termed as a
family of planes and denoted as {100} which includes
all the (100) combinations including negative indices.
Some other equivalent planes are shown in the next
slide.
 Equivalent Planes

Note the shift of origin from blue to red circle for the negative indices
 Planes in Hexagonal system

➢ In the cubic system all the faces of the cube are equivalent,
that is, they have similar indices.
➢ However, this is not the case in the hexagonal system. The
six prism faces for example have indices (1 0 0), (0 1 0),
(1 1 0 ), (1 0 0 ), (01 0), (11 0 ), which are not same.

In order to address this, a fourth axis (a3) (1 1 0 )

which is opposite to the vector sum of a1

and a2 is used and a corresponding fourth

(010)
(100)
index i is used along with hkl. Therefore
the indices of a plane is given by (hkil)
whre i = -(h+k). Sometime i is replaced
with a dot and written as (h k . l)
 Planes in Hexagonal system

The indices of six faces now become (1 01 0), (0 11 0),
(1 1 0 0), (1 0 1 0), (01 1 0), (11 0 0 ) which are now
equivalent and belong to the {1 01 0 } family of planes.

(1 1 0 0)

(0 11 0)
(1 01 0)
 Interplanar spacing
The spacing between planes in a crystal is known as
interplanar spacing and is denoted as dhkl
In the cubic system spacing between the (hkl) planes is
1 1 2 2 2
given as
2
= ︵ + +
2

/
For example, dhkl of {111} planes d111 = 3
1 1 2 1
In Tetragonal system 2
= 2 + 2
+ 2
2

1 1 1 1
In Orthorhombic system 2
= 2
2
+ 2
2
+ 2
2

1 4 1
In Hexagonal system = 2
+ + 2
+ 2
2

2 2
3
 Crystal Directions
The directions in a crystal are given by specifying the
coordinates (u, v, w) of a point on a vector (ruvw) passing
through the origin. ruvw = ua + vb + wc. It is indicated as
[uvw]. For example, the direction [110] lies on a vector r110
whose projection lengths on x and y axes are one unit (in
terms of unit vectors a and b).
Directions of a form or family like [110], [101], [011] are
written as <110>

<100> and <110> family <111> family

 Crystal Directions
➢ The line which passes through uvw will also pass through
2u2v2w and ½ u ½ v ½ w. Hence [uvw], [2u2v2w] and
[½ u ½ v ½ w] are same and written as [uvw].

➢ Fractions are converted in to integers (as shown in the

figure below) and reduced to lowest terms.
 Crystal Directions
To determine a direction of a line in the crystal:

❑ Find the coordinates of the two ends of the line and

subtract the coordinates (Head – Tail) OR draw a line from
the origin parallel to the line and find its projection lengths on
x, y and z axis in terms of the unit vectors a, b and c.

❑ Convert fractions, if any, in to integers and reduce to

lowest term.

❑ Enclose in square brackets [uvw]

 Directions in Hexagonal Crystal
Like planes, directions in the hexagonal system are also
written in terms of four indices as [uvtw].

If [UVW] are indices in three axes then it can be

converted to four-axis indices [uvtw] using the following
relations.
U=u–t V=v–t W=w
u = (2U-V)/3 v = (2V-U)/3 t = -(u + v) = -(U + V)/3
w=W

Ex: [100] = [211 0], [210] = [1 0 1 0]

 Relationship between direction and planes
In the cubic system planes and directions having same
indices are perpendicular to each other i.e. if [uvw] direction
is perpendicular to (hkl) plane then h = u, k = v and l = w
Ex: {100} planes and <100> directions are perpendicular to
each other.

If [uvw] direction is parallel to (hkl), that is if [uvw] lies in the

plane (hkl) then hu + kv + lw = 0. For example, [1 1 0 ] lies
in the plane (111) since 1.(-1) + 1.1 + 1.0 = 0
 Coordination number
Coordination number is the number of nearest neighbor
to a particular atom in the crystal

In the FCC lattice each atom is in contact with 12 neighbor

atoms. FCC coordination number Z = 12
For example, the face centered atom in the front face is in
contact with four corner atoms and four other face-centered
atoms behind it (two sides, top and bottom) and is also
touching four face-centered atoms of the unit cell in front of
it.
 Coordination number

The coordination number of BCC crystal is 8.

The body centered atom is in contact with all the eight

corner atoms. Each corner atom is shared by eight unit
cells and hence, each of these atoms is in touch with
eight body centered atoms.
 Coordination number

In Hexagonal lattice Z = 12. The center atom of the top

face is in touch with six corner atoms, three atoms of the
mid layer and other three atoms of the mid layer of the
unit cell above it.
 Atomic packing factor

Atomic packing factor (APF) or packing efficiency

indicates how closely atoms are packed in a unit cell and
is given by the ratio of volume of atoms in the unit cell
and volume of the unit cell
V
o u
l
m e
e o
oP f
fFu
a n
t
o t
m c
s e
=
A
m

ll
 Atomic packing factor
FCC lattice
In the FCC unit cell effective number of atoms = 8 corner
atoms x (1/8) (each atom is shared by 8 unit cells) + 6 face-
centered atoms x1/2 (each shared by two unit cells) = 4

The corner atom C is shared

1
F 2 by unit cells 1, 2, 3, 4 and
four more in front of each of
3
C them. The face-centered
atom, F is shared between
cells 1 and 2.
4

Click here for animation

 Atomic packing factor
FCC lattice
Considering the atoms as hard spheres of radius R
4 3
= 4  R
u
m
e
o
f
a
t
o
m
s
3
The relation between R and the FCC cell side a as shown in
the figure below is 2a = 4R

4
4   R3
3 16  2 2 a3
APF (FCC) = = 3
= 0.74
a3 3 64a
 Atomic packing factor
BCC
For BCC crystals effective number of atoms per unit cell is
8 x 1/8 + 1 = 2 and the relation between R and a is
3a = 4R

4
2   R3
3 8 3 3 a
3

APF (BCC) = = 3
= 0.68
a3 3 64a
 Atomic packing factor
Hexagonal lattice
In the Hexagonal unit cell, number of atoms = 12 corner
atoms x 1/6 (shared by six unit cells) + Two face atoms x 1/2
+ 3 interior = 6.
2R = a
Unit cell volume = (6 x ½ x a x h) x c = (3 x a x a sin60) x c
= 3a2 c sin60
 Atomic packing factor

The face-centered atom and the three

mid-layer atoms form a tetrahedron
MNOP which has sides equal to a (as
atoms at vertices touch each other) and
height of c/2. Using this tetrahedron it
can be shown that for an ideal
hexagonal crystal c/a ratio = 1.633
4
6   R3 8 3

3 = a
APF (HCP) = 2 3
= 0.74
3a c sin 60 3 81.414a
 Planar density
Planar density (PD) refers to density of atomic packing
on a particular plane.
fa
an
tar
or e
mDa
se
oy f
n p
a l
p a
l
a e
n
e
=
n
st io
A

n
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.
Planar density of {110} planes in the FCC crystal
2
PD = = 2
(110) a 2a a2

2a
 Planar density
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 3a2
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

2a
 Linear Density
Linear density (LD) is the number of atoms per unit
length along a particular direction
e
d
i L
r
en
cy g
t
i
o o
n f
v
e
c
t
o
r
=
n
e
a
r
D
e
st it
d
i
r
e
cn

it
o
h
n
v
e
c
t
o
r
<110> directions in the FCC lattice have 2 atoms (1/2 x 2
corner atoms + 1 center atom) and the length is 2a
2
LD = = 2
[110] 2a a
This is the most densely packed direction in the FCC lattice
 Close-Packed Structure
➢ FCC and hexagonal crystal structures are most highly
packed with packing efficiency of 74% (APF= 0.74). Such
structures can be described in terms of close-packed
atomic planes.
➢ In FCC, {111} planes are close-packed and the basal
plane (0001) is the close-packed one in hexagonal
close-packed (HCP) system. Therefore, both of these
structures can be generated by stacking of these planes.
A portion of such a stack is shown in the picture below.
 Close-Packed Structure
➢ There are two types of voids between the atoms –
vertex up (b), and vertex down (c). The atoms in the next
layer sit on the b sites (See animation below).
➢ In FCC, atoms in the third layer sit over the c sites and this
repeats giving rise to ABC ABC ABC type of stacking.
 Close-Packed Structure
➢ In HCP system, centers of atoms of the third layer lie
directly over centers of atoms of the first layer (a positions)
giving rise to AB AB AB type of stacking.
 Structure-Property correlation
Aluminium (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
 Structure-Property correlation
❑ 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 <1 1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
 Structure-Property correlation
❑ 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.
 Evaluation
At the end of this chapter on crystallography, one should be
able to
➢ Understand Space lattice, Unit cells,7 crystal structure
and 14 Bravais lattices.
➢ Understand atomic arrangement and packing in different
unit cells.
➢ Derive point coordinates
➢ Find out miller indices of crystallographic planes and
directions.
➢ Correlate some properties to crystal structure.
 Web References

http://www.youtube.com/watch?v=qh29mj6uXoM&feature=relmfu
http://www.youtube.com/watch?v=8zWySdeXB0M&feature=relmfu
http://www.youtube.com/watch?v=Rm-i1c7zr6Q&feature=related
http://www.youtube.com/watch?v=PWQ89UoxOK8&feature=related
http://www.youtube.com/watch?v=mQy2CdKYqX0&feature=related

Key words: Symmetry; Space lattice; Crystal structure; Miller

indices; Close pack structure; Slip system
 Examples
Ex. 1: Theoretical density calculation from crystal structure.
nA
Theoretical density,  =
V N
C A

n = number of atoms in the unit cell

A = atomic weight
VC = volume of unit cell
NA = Avogadro’s number (6.023 x 1023 atoms/mol)
Calculate the theoretical density of Al.
Al is FCC, lattice parameter, a = 4.05 Å, n = 4.
Atomic weight of Al is 26.98 g/mol
4  26 98
.

= = 2 697
.

/
︵4 05 10−8 ︶  6 023 1023
.

3
 Examples
Ex. 2: Show the point having coordinates 1/2, 1, 1/3 .
Solution: Select one of the corners of the unit cell as the
origin. Move a/2 from the origin along the x axis and mark
this point. From this point move b units along the y axis
and then c/3 units along the z axis.
Ex. 3: Draw the plane ( 31 2) in a cubic unit cell.
z

c/2
y
a/3

‐b
x
 Examples
Ex. 4: Draw the directions [236] and [203] and [21 1] in a
cubic unit cell.

[211]

c/2

-b/2

Ex. 5: The atomic radius of Fe is 0.124 nm. Find the

lattice parameter of Fe.
Solution: Fe is BCC at room temperature. Therefore,
4  0 124
.

4
3 = 4 and = = = 0 286 nm
3 3 .
 Quiz
1. Show that only four types of rotational symmetry are
possible.
2. Why it is not possible to have 5, 7 or higher order
symmetry in crystallography?
3. What is point group? How many point-groups are possible?
4. Find out the Hermann-Mauguin symbol for a cube.
5. For a point at xyz write a translation, a reflection and an
inversion operation.
5. What is unit cell? What is lattice parameter?
6. What is Bravais lattice? How are the Bravais lattices
obtained from the primitive cell? How many types of Bravais
lattices are there?
7. What is the effective number of atoms in a simple cubic unit
cell?
 Quiz
8. What is coordination number (CN)? Show that CN for FCC
and HCP structure is 12 while it is 8 for BCC.
9. Show that packing efficiency of FCC is 74% and that of
BCC is 68%.
10. Show that the ideal c/a ratio in a hexagonal unit cell is
1.633 and calculate the packing efficiency.
11. What are the coordinates of the center atom in the BCC
unit cell.
12. What is miller index? How is it obtained?
13. Draw the planes (11 0), (12 1), (23 4), (1 12 ) and
directions[1 11], [123], [120], [1 2 1] in a cubic unit cell.
14. Why it is necessary to include a fourth miller index in the
hexagonal system?
15. Convert the directions [112], [12 3], [110], [111], [130] to
four indices in a hexagonal lattice.
 Quiz
16. What is family of planes? Draw the {111} family of planes
in cubic system?
17. What is linear density? What is planar density?
18. Find the planar of density {111} planes and linear density
of <110> directions in FCC system.
19. What is the linear density of <111> directions in the
BCC crystal.
20. What is interplanar spacing? Find the interplanar spacing
of the vertical planes in the HCP system?
21. What is the stacking sequence of FCC and HCP crystals?
22. What is slip system?
23. Why FCC metals are ductile while BCC and HCP metals
are not?
24. Calculate the theoretical density of Cu from its crystal
structure.
 Quiz
25. Lattice constant of Al is 4.05 Å. What is the atomic
radius of Al?
26. Calculate the theoretical density of Mg, Cu and Fe and
compare them to the standard values.
27. 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?
28. Calculate the volume of the unit cell of Zn crystal. a and
c of Zn are 266.5 pm and 494.7 pm respectively.
29. Calculate the planar density of {110} planes in -Fe
(BCC) crystal. a = 0.287 nm.
30. Calculate the linear density of [110] direction in a Cu
crystal. a = 0.361 nm.
Perovskites
The terms "perovskite" and "perovskite structure" are often used interchangeably. Technically, a
perovskite is a type of mineral that was first found in the Ural Mountains and named after Lev
Perovski who was the founder of the Russian Geographical Society. A perovskite structure is any
compound that has the same structure as the perovskite mineral.
True perovskite (the mineral) is composed of calcium, titanium and oxygen in the form CaTiO 3.
Meanwhile, a perovskite structure is anything that has the generic form ABX3 and the same
crystallographic structure as perovskite (the mineral). However, since most people in the solar cell
world aren’t involved with minerals and geology, perovskite and perovskite structure are used
interchangeably.
The perovskite lattice arrangement is demonstrated below. As with many structures in
crystallography, it can be represented in multiple ways. The simplest way to think about a
perovskite is as a large atomic or molecular cation (positively-charged) of type A in the centre of
a cube. The corners of the cube are then occupied by atoms B (also positively-charged cations)
and the faces of the cube are occupied by a smaller atom X with negative charge (anion).

A generic perovskite crystal structure of the form ABX3. Note however that the two structures are equivalent
– the left hand structure is drawn so that atom B is at the <0,0,0> position while the right hand structure
is drawn so that atom (or molecule) A is at the <0,0,0> position. Also note that the lines are a guide to
represent crystal orientation rather than bonding patterns.

Depending on which atoms/molecules are used in the structure, perovskites can have an impressive
array of interesting properties including superconductivity, giant magnetoresistance, spin-
dependent transport (spintronics) and catalytic properties. Perovskites therefore represent an
exciting playground for physicists, chemists and material scientists.
In the case of perovskite solar cells, the most efficient devices so far have been produced with the
following combination of materials in the usual perovskite form ABX3:
• A = An organic cation - methylammonium (CH3NH3)+
• B = A big inorganic cation - usually lead(II) (Pb2+)
• X3= A slightly smaller halogen anion – usually chloride (Cl-) or iodide (I-)
Since this is a relatively general structure, these perovskite-based devices can also be given a
number of different names, which can either refer to a more general class of materials or a specific
combination. As an example of this, we’ve created the below table to highlight how many names
can be formed from one basic structure.

A B X3

Organo Metal Trihalide (or trihalide)

Methylammonium Lead Iodide (or triiodide)

Plumbate Chloride (or trichloride)

Diamond Structure
Diamond Crystal Structure is a metastable allotrope of carbon where the each carbon atom is
bonded covalently with other surrounding four carbon atoms and are arranged in a variation of the
face centered cubic crystal structure called a diamond lattice. Diamond is a transparent crystal of
tetrahedrally bonded carbon atoms (sp3) that crystallizes into the diamond lattice which is a
variation of the face centered cubic structure. Each carbon atom joins four other carbon atoms in
regular tetrahedrons (triangular prisms). Based on the cubic form and its highly symmetrical
arrangement of atoms, diamond crystals can develop into several different shapes, known as
'crystal habits'.
Graphite Structure
Graphite is a greyish black opaque substance. It is lighter than diamond and is soft and slippery to
touch. It conduct electricity. It is made up of carbon atoms only. The structure of graphite is very
different from that of diamond. It consists of layers of carbon atoms or sheet of carbon atoms.
Each carbon atoms in a graphite layer is joined to three other carbon atoms by strong covalent
bonds to form flat hexagonal rings. The various layers of carbon atoms in graphite are held together
by weak van der waals forces.
The structure of graphite is very different from that of diamond. It consists of layers of carbon
atoms or sheet of carbon atoms. Each carbon atoms in a graphite layer is joined to three other
carbon atoms by strong covalent bonds to form flat hexagonal rings. The various layers of carbon
atoms in graphite are held together by weak van der waals forces. Due to the sheet like structure,
graphite is comparatively soft substance. Graphite is good conductor of electricity because due to
the presence of free electrons.

Uses of Graphite:
• Graphite can be used for lubricating those machine parts which operate at very high
temperature.
• Graphite is used for making graphite electrodes in dry cells and electric arcs.
• Graphite is used for making the cores of our pencils called pencil leads.

Hexagonal Closed Packed Structure

• It consists of three layers of atoms.

• The bottom layer has six corner atoms and one face centred atom.
• The middle layer has three full atoms.
• The upper layer has six corner atoms and one face centred atom.
• Each and every corner atom contributes 1/6 of its part to one unit cell.
• The number of total atoms contributed by the corner atoms of both top and bottom layers
is 1/6  12 = 2.
 • The face centred atom contributes 1/2 of its part to one unit cell.
• Since there are 2 face centred atoms, one in the top and the other in the bottom layers,
the number of atoms contributed by face centred atoms is 1/2 2 = 1.
• Besides these atoms, there are 3 full atoms in the middle layer.
• Total number of atoms present in an HCP unit cell is 2+1+3 = 6.

CO-ORDINATION NUMBER (CN)

• The face centered atom touches 6 corner atoms in its plane.
• The middle layer has 3 atoms.
• There are three more atoms, which are in the middle layer of the unit cell.
• Therefore the total number of nearest neighbours is 6+3+3=12.

ATOMIC RADIUS (R)

• Consider any two corner atoms.
• Each and every corner atom touches each other.
Therefore a = 2r. i.e., The atomic radius, r = a/2.

ATOMIC PACKING FACTOR (APF)

APF =
v = 6  4/3 r3
Substitute r = ,
v = 6  4/3 
v = a3
 C

a
O

30 
A

30 

AB = AC = BO = ‘a’. CX = where c → height of the hcp unit cell.

Area of the base = 6  area of the triangle – ABO
= 6  1/2  AB  OO
Area of the base = 6  1/2  a  OO

O ' O B = 30
In triangle OBO
cos30º =

 OO = a cos 30º = a

Now, substituting the value of OO,
Area of the base = 6  0.5  a 0.866 a

3 3a 2

= 2

V = Area of the base × height

CALCULATION OF c/a RATIO
A 'AB = 30
In the triangle ABA,

AA '

Cos 30º = AB

 AA = AB cos 30º = a

But AX = AA =

i.e. 2AX =
c  1 c2
= a2 1 − =
8 c 8
=
  3
4  3 a2 3 a
Now substituting the value of to calculate APF of an hcp unit cell,
2
APF =

2
=

 APF =

Packing Fraction =74%

 IMPERFECTIONS IN CRYSTALS

➢ ISSUES TO ADDRESS...

• How do defects affect material properties?

• What types of defects arise in solids?
• Are defects undesirable?
 Crystalline Imperfections
There is no such thing as a perfect crystal!
• Thermodynamically “impossible”
• “defects” lower the energy of a crystal & make it more stable
• always have vacancies and impurities, to some extent
Defect does not necessarily imply a bad thing
• addition of C to Fe to make steel
• addition of Cu to Ni to make thermocouple wires
• addition of Ge to Si to make thermoelectric materials
• addition of Cr to Fe for corrosion resistance
• introduction of grain boundaries to strengthen materials
…… and so on
“Defect” (in this context) can be either desirable or undesirable.
In general, a defect simply refers to a disruption in the crystalline
order of an otherwise periodic material.
Crystal imperfections are broadly classified
into four major classes as below:
1) Point defects (Zero dimensional)
2) Line defects (One dimensional)
3) Planar or surface defects (Two dimensional)
4) Volume defects
1) Point Defects
➢ Atoms in solid possess vibrational energy, some
atoms have sufficient energy to break the bonds
which hold them in eqbm position. Hence once the
atoms are free they give rise to Point Defects.
Classes of point defects:
1. Vacancy/Schottky
2. Interstitial/Frenkel
➢ Impurities
1. Substitution
2. Interstitial
Vacancies
➢ A lattice position that is vacant because the atom is
missing
➢ There are naturally occurring vacancies in all crystals
➢ The concentrations of vacancies increase with:
⚫ increasing temperature
⚫ decreasing activation energy
 Vacancies

⚫ -vacant atomic sites in a structure.

Vacancy

distortion
of planes
Self-Interstitial

⚫ If the matrix atom occupies its own interstitial site, the

defect is called Self Interstitial.

⚫ Self-interstitials in metals introduce large distortions in

the surrounding lattice.

self-
interstitial
distortion
of planes
 For Ionic Solids, Frenkel and Schottky defects are
likely to form.
➢ Schottky Defects
When cation vacancy is associated with anion vacancy, the
defect is called Schottky Defect.
➢ Frenkel Defects
When an atom leaves its regular site and occupy nearby
interstitial site it gives rise to two defects i.e. one vacancy
and other self interstitial these two defects are called as
Frenkel Defects.
 DEFECTS IN CERAMIC
STRUCTURES
• Frenkel Defect
--a cation is out of place.
• Shottky Defect
--a paired set of cation and anion vacancies.

Adapted from Fig. 13.20,

Callister 5e. (Fig. 13.20 is
from W.G. Moffatt, G.W.
Pearsall, and J. Wulff, The
Structure and Properties
of Materials, Vol. 1,
Structure, John Wiley and
Sons, Inc., p. 78.) See Fig.
12.21, Callister 6e.

− Q D / kT
~e 8
• Equilibrium concentration of defects
2.Line Defects (One dimensional)
➢ A dislocation is a line discontinuity in the regular crystal
structure.
➢ A part of the line will be missing from its regular site and this
missing row is dislocation. The dislocation is centered along a
line and hence the line defect is called dislocation.
The dislocation is a boundary between the slipped and
unslipped region and lies in the slip plane
➢ The structure and behaviour of dislocations affect many of the
properties of engineering materials.
➢ There are two basic types:
1) Edge dislocations
2) Screw dislocations.
1) Edge dislocation
➢ An Edge dislocation in a metal may
be regarded as the insertion (or removal)
of an extra half plane of atoms in the
crystal structure.
➢ In Ionic and Covalent solids edge
dislocations involve extra half planes
of unit cells.

➢ If we consider a perfect crystal to be made up of vertical

planes parallel to one another and to the side faces. If one of
these vertical planes does not extend from the top to
the bottom of crystals but ends part way within crystal, it is
called as edge dislocation.
⚫ Berger vector is perpendicular to dislocation
line.
Movement of an Edge Dislocation
2) Screw dislocation
➢ In screw dislocation ,there is transformation of successive
atomic planes into the surface of helix around dislocation line
due to shear stress i.e. it follows
helical or screw path.
➢ A screw dislocation can be imagined as being produced by
cutting the crystal partway through with a knife and then
shearing one part of the crystal with respect to the other parallel
to the cut.
• Berger vector is parallel to dislocation line.
Linear/Line Defects – (Dislocations)
🞂 Line imperfection or dislocation are defects that cause lattice
distortions.

🞂 Dislocation are created during:

➢ Solidification
➢ Permanent deformation of crystalline solid
➢ Vacancy condensation
➢ Atomic mismatch in solid solution

🞂 Different types of line defects are:

➢ Edge dislocation
➢ Screw dislocation
➢ Mixed dislocation

17
🞂 An edge dislocation is created in a crystal by insertion of extra half
planes of atoms. Edge Dislocation

Positive edge Negative edge

dislocation dislocation

🞂 In figure 4.18, a linear defect occurs in the region just above the
inverted T, where an extra half plane of atoms has been wedged in.

18
 Figure 4.18 : Positive edge dislocation in a crystalline lattice.

19
 Screw Dislocation
🞂 The screw dislocation can be formed in a perfect crystal by
applying upward and downward shear stresses to regions of a
perfect crystal that have been separated by a cutting plane as
shown in Figure 4.20a.

Figure 4.20a
Formation of a screw dislocation:
A perfect crystal is sliced by a cutting plane, and up and
down shear stresses are applied parallel to the cutting
plane to form the screw dislocation as in (b).

20
🞂 These shear stresses introduce a region of distorted crystal lattice
in the form of a spiral ramp of distorted atoms or screw dislocation
as Figure 4.20b.

Figure 4.20b
Formation of a screw dislocation:
A screw dislocation is shown with its slip or Burgers
vector b parallel to the dislocation.

21
🞂 The region of distorted crystal is not well defined and is at least
several atoms in diameter.

🞂 A region of shear strain is created around the screw dislocation in

which energy stored.

🞂 The slip or Burgers vector of the screw dislocation is parallel to

the dislocation line as shown in Figure 4.20b.

22
🞂 Most crystal have components of both edge and screw dislocation.
Mixed Dislocation

🞂 Dislocation, since have irregular atomic arrangement will appear as

dark lines when observed in electron microscope.

Dislocation structure of iron deformed

14% at –1950C

23
 3. Planar or Surface defects
(Two dimensional)
➢ Planar defects arise due to change in the stacking of atomic
planes during mechanical and thermal treatments.The change
may be of the orientation or of the stacking sequence of the
planes.

➢ Planar defects are of following types:

A. Grain boundaries
B. Tilt boundaries
C. Twin boundaries
 A) Grain Boundaries
➢ A Grain Boundary is a general planar defect that separates
regions of different crystalline orientation (i.e. grains) within a
polycrystalline solid . Grain boundaries are
usually the result of uneven growth when the solid
is crystallizing.
B) Tilt Boundaries

➢ When the angle between two crystals is less than 10 ,the

distortion is not so drastic as to be compared with a non
crystalline material .They are also called low angle boundaries.
➢ It can be described as set of parallel, equally spaced edge
dislocation of same sign located
one above other.
➢ A Tilt Boundary, between two slightly
mis-aligned grains appears
as an array of edge
dislocations.
 C) Twin Boundaries
➢ These are the boundaries in the grains at which the atomic
arrangement on one side of the boundary is the mirror image of
the atoms on the other side .The volume of material which has
an orientation similar to the mirror image of the matrix
orientation is called a twin.

➢ The plane is called

twinning plane.
4. Volume Defects

➢ Volume defects such as stacking faults may arise when there is

only small dissimilarity between the stacking sequence of close
packed planes in FCC and HCP metals.
➢ Stacking faults are of two types called as intrinsic and extrinsic
.Intrinsic fault results in one break whereas extrinsic fault
results in two breaks in the sequence
➢ The volume defects may affect their mechanical, electrical and
optical properties.
Solid Solutions
◾ Solid Solutions
◾ Substitutional Solid Solution
◾ Hume-Rothery Rules
◾ Interstitial Solid solution
◾ Intermediate Phases

2
8
◾ Solid Solution or an Alloy is a phase, where two or more elements
are completely soluble in each
other.
◾ Solid solutions have important commercial and industrial applications, as such
mixtures often have superior properties to pure materials.
◾ Many metal alloys are solid solutions.
◾ Ex: Cu-Ni, Au-Ag etc.
◾ In a solid solution, the metal in the major proportion is called the
solvent (host or parent or matrix) and the metal in the minor
proportion is called the solute

2
9
◾ There are two types of Solid Solutions:
i. Substitutional Solid Solution
ii. Interstitial Solid Solution

3
0
Substitutional Solid Solution
◾ In this type of solid solution, the solute atoms substitute the atoms
of solvent in the crystal structure of the solvent.
The substitutional solid solution are generally ordered at lower temperatures
and at higher disordered temperatures.
◾ Temperature is the deciding factor.

3
1
◾ There are two types of substitutional solid solutions:
i. Ordered Substitutional Solid Solution (OSSS)
ii. Disordered Substitutional Solid Solution (DSSS)
OSSS: In this type, the solute atoms substitute the solvent atoms in an
orderly manner, taking up fixed positions of symmetry in lattice. This solid
solution has uniform distribution of solute and solvent atoms.
DSSS: In this type, the solute atoms do not occupy any fixed positions but are
distributed at random in the lattice structure of solvent. The concentration
of solute atoms vary considerably through out lattice structure.

3
2
RULES FOR FORMATION OF SOLID SOLUTION
HUME-ROTHARY RULES:
➢ These are the rules which govern the formation of Solid Solutions.
➢ In other words, only when these rules are satisfied,a substitutional solid solution is formed.

1. Crystal Structure Factor:

◾ For complete solubility of two elements, they should have the same type of crystal lattice.
◾ For example,Au-Ag solution, both should have FCC structure.

2. Relative Size Factor:

◾ The atoms of the solute and solvent should have the same atomic size approximately.
3
◾ This factor is satisfied if the difference of atomic radii of two elements is less than 15%. 3
3. Electro-negativity:
◾ Higher the electro-negativity, greater is the chance of forming an
intermediate phase rather than a solid solution.
◾ Electro-negativity is the tendency to acquire electrons.

4. Relative Valence Factor:

◾ Among two metals, which have satisfied all the above rules, the
metal with lower valency tends to dissolve more of a metal 3of
higher valency and vice-versa. 4
Interstitial Solid Solution
◾ These are formed when atoms of small
atomic radii fit into the
interstitial spaces of larger solvent atoms.
◾ Atoms of elements such as carbon, nitrogen,
boron, hydrogen, etc. which have radii less than
1 Ao are likely to form interstitial solute atoms
and may dissolve more readily in transition
metals such as Fe, Ni, Mn, Cr, etc. than in other
metals.

3
5
Intermediate Phases
◾ Intermediate phases are those phases whose chemical
compositions are intermediate between the two pure metals
and generally have crystal structure different from those of
the base (parent) metals.
◾ An alloy can be made up of a solid solution phase entirely or
can exist along with an intermediate phase.
◾ An intermediate phase here is nothing but a
compound and is made up of two or more elements
of which at least one of them is a metal.
3
6
◾ A compound is a chemical combination of positive and negative valence elements.
i.e., atoms of different elements are combined in different proportions and are
expressed by chemical formulae like H2O, NaCl, etc.
◾ When a compound or intermediate phase is formed, the elements lose their
individual identity and properties to a good extent and the compound will have its
own characteristic physical, mechanical and chemical properties.

3
7
◾ There are three most common
intermediate alloy phases:
i. Intermetallic orValency Compounds
ii.Interstitial Compounds
iii.Electron Compounds

3
8
Intermetallic or Valence Compounds
◾ When alloy phase are exclusively metal-metal systems, they are called
intermetallic compounds.
◾ These are formed between chemically dissimilar metals and are combined by
following the rules of chemical valence.
◾ The combination is usually non-metallic and show poor ductility and poor electrical
conductivity and have complex crystal structure.

◾ Examples for intermetallic compounds: Mg2Pb,Mg2Sn,CaSe, Cu2Se

3
9
Interstitial Compounds
◾ These are similar to interstitial solid solutions except that they have more or less a
fixed composition.
◾ Example:Fe3C.
◾ The interstitial compounds are metallic in nature, have high melting points and are
extremely hard.

4
0
Electron Compounds
◾ These are of variable compositions and do not obey the valence law, but have a definite
electron to atom ratio.
Example:Cu9Al4
◾ Each Cu atom has 1 valence electron and each Al atom has 3 valence electrons.
◾ So 13 atoms which make up the compound have 21 valence electrons with electron to
atom ratio being 21:13
◾ Electron compounds have properties same as those of solid solutions – wide range of
compositions, high ductility and
low hardness.

4
1
 DEFINITION OF PHASE

Phase is Homogenous, physically distinct and mechanically

separable part of the system

Pure substance- It is a substance constant

Chemical composition throught its mass .
it may exist in one phase or more than one phase

If you look at the diagram, you will see

that there are three lines, three areas
marked "solid", "liquid" and “Vapour", and
two special points marked "C" and "T".
Three areas

At point 1 in the diagram, the substance would

be a solid because it falls into that area of the
phase diagram. At 2, it would be a liquid; and at
3, it would be a Vapour (a gas)

Moving from solid to liquid by changing the temperature:

(fusion line)

If increases the temperature while keeping

the pressure constant - as shown in the
figure. As the temperature increases to the
point where it crosses the line, the solid will
turn to liquid
(solid melts at higher temperature)
 Moving from solid to liquid by changing the pressure:

Moving from liquid to Vapour:

(Vapourisation line)

The liquid will change to a Vapour - it boils

- when it crosses the boundary line
between the two areas

As the pressure increases, so the boiling

point increases.
Critical point
In liquid-vapour equilibrium curve has a top limit at that
point C in the phase diagram. It is called critical point.
The temperature and pressure corresponding to this
are known as the critical temperature and critical
pressure.

If you increase the pressure on a gas (Vapour) at a

temperature lower than the critical temperature, you will
eventually cross the liquid-Vapour equilibrium line and
the Vapour will condense to give a liquid

Shortcut Def
the intersection of saturated
liquid line and saturated Vapour
line
 Moving from solid to Vapour (sublimation line)

If the temperature and pressure fell exactly on same line, there

would be solid and Vapour in equilibrium with each other - the
solid would be subliming. (Sublimation is the change directly
from solid to Vapour or vice versa without going through the
liquid phase.)

The triple point

At point T on the diagram is called the triple point.

The combination of temperature and pressure

where all three phases are in equilibrium
together. That's why it is called a triple point.

Def-
The intersection of fusion line, Vapourisation line and sublimation line
Is called triple point
2-D Representation of phase diagram
Phase Diagrams of Water and Carbon
Dioxide
 Types of phase diagrams

1) ISOMORPHOUS SYSTEMS

2) EUTECTIC SYSTEMS

1) ISOMORPHOUS SYSTEMS

THESE diagrams are loop type and are obtained for two metals
Having complete solubility in the liquid state as well as solid state

Ex – cu/Ni, au/ag
Examples

Cu-Ni phase diagram

Temperature- Composition
Binary isomorphous diagram
Lever rule
⚫ Used to find the composition of phases.

⚫ Ws = Wo-Wl
Ws-Wl
⚫ Wl = Ws-Wo
Ws-Wl
Binary phase diagram
On a two component or binary diagram three variables
can be represented. These are generally pressure (P),
temperature (T) and compositional changes (X)

To graphically represent a Binary diagram one variable

must be kept constant, which is usually P, and the phase
diagram is plotted as a T-X diagram for a specific
Pressure.Ex- isomorphous systems
Eutectic systems –
These diagrams are obtained for having complete solubility in the
liquid state and complete insolubility in the solid state
Ex- Pb/As ,bi-cd, th -ti
The Iron-Iron Carbide Diagram
⚫ A map of the temperature at which different phase changes
occur on very slow heating and cooling in relation to
Carbon, is called Iron- Carbon Diagram.
⚫ Iron- Carbon diagram shows
⚫ the type of alloys formed under very slow cooling,
⚫ proper heat-treatment temperature and
⚫ how the properties of steels and cast irons can be
radically changed by heat-treatment.
Cooling curve for pure iron
 IRON-CARBON (Fe-C) PHASE DIAGRAM
Pure iron: 3 solid phases
BCC ferrite (α)
FCC Austenite (γ)
BCC δ
Beyond 6.7% C
cementite (Fe3C)
Eutectic: 4.3% C
L - γ + Fe3C
(L -solid + solid)
Eutectoid: 0.76% C
γ + α + Fe3C
(solid - solid + solid
 How to read the Fe-C phase diagram
Eutectic
eutectoid
Pearlite and
Cementine

Austenite

Ferrite
Pearlite and
Carbide
Pearlite

Steel Cast iron

 Definition of structures
Various phases that appear on the Iron-
Carbon equilibrium phase diagram are
as under:
• Ferrite
• Pearlite
• Austenite
• Cementite
• Ledeburite
• Martensite
Definition of structures
⚫ Ferrite is known as α solid solution.
⚫ It is an interstitial solid solution of a small amount of
carbon dissolved in α (BCC) iron.
⚫ stable form of iron below 912 deg.C
⚫ The maximum solubility is 0.025 % C at 723C and it
dissolves only 0.008 % C at room temperature.
⚫ It is the softest structure that appears on the diagram.
Definition of structures
⚫ Pearlite is the eutectoid mixture
containing 0.80 % C and is formed at
723°C on very slow cooling.
⚫ It is a very fine platelike or lamellar
mixture of ferrite and cementite.
⚫ The white ferritic background or matrix
contains thin plates of cementite (dark).
 Definition of structures
⚫ Austenite is an interstitial solid solution of Carbon
dissolved in  (F.C.C.) iron.
⚫ Maximum solubility is 2.0 % C at 1130°C.
⚫ High formability, most of heat treatments begin with
this single phase.
⚫ It is normally not stable at room temperature. But,
under certain conditions it is possible to obtain
austenite at room temperature.
 Definition of structures
⚫ Cementite or iron carbide, is very hard, brittle
intermetallic compound of iron & carbon, as Fe3C,
contains 6.67 % C.
⚫ It is the hardest structure that appears on the diagram,
exact melting point unknown.
⚫ Its crystal structure is orthorhombic.
⚫ It is has
⚫ low tensile strength (approx. 5,000 psi), but
⚫ high compressive strength.
Definition of structures
⚫ Ledeburite is the eutectic mixture of
austenite and cementite.
⚫ It contains 4.3 percent C and is formed at
1130°C.
Definition of structures
Martensite - a super-saturated solid solution of carbon in
ferrite.
It is formed when steel is cooled so rapidly that the change
from austenite to pearlite is suppressed.
The interstitial carbon atoms distort the BCC ferrite into a
BC-tetragonal structure (BCT).; responsible for the
hardness of quenched steel
Microstructure of different phases of steel
 Various Features of Fe-C diagram
Phases present
• Liquid(l)
• BCC structure,Paramagnetic
•  ferrite:BCC structure,
Ferromagnetic,Fairly ductile
•  austenite:FCC structure, Non-
magnetic,Ductile
• Fe3C cementite:Orthorhombic,Hard, brittle

Reactions Max. solubility of C in ferrite=0.022%

Peritectic L +  = 
Max. solubility of C in austenite=2.11%
Eutectic L =  + Fe3C

Eutectoid  =  + Fe3C
Three Phase Reactions
A horizontal line always indicates an invariant reaction
in binary phase diagrams
⚫ Peritectic reaction at 1495˚C and 0.18%C,
⚫ -ferrite + L↔ -iron (austenite)
⚫ (almost no engineering importance).
⚫ Eutectic reaction at 1147˚C and 4.3 %C,
⚫ L ↔ -iron + Fe3C (cementite) [ledeburite]
⚫ alloys called cast irons
⚫ Eutectoid reaction at 727˚C and 0.77%C,
⚫ -iron ↔ –ferrite+Fe3C (cementite) [pearlite]
⚫ They are steels
 The Iron-Iron Carbide Diagram
The diagram shows three horizontal lines which indicate
isothermal reactions (on cooling / heating):
⚫ First horizontal line is at 1490°C, where peritectic reaction
takes place:
Liquid +  ↔ austenite
⚫ Second horizontal line is at 1130°C, where eutectic
reaction takes place:
liquid ↔ austenite + cementite
⚫ Third horizontal line is at 723°C, where eutectoid reaction
takes place:
austenite ↔ pearlite (mixture of ferrite &
cementite)
 Cast Irons
-Iron-Carbon alloys of 2.11%C or
more are cast irons.
-Typical composition: 2.0-
4.0%C,0.5-3.0% Si, less than
1.0% Mn and less than 0.2% S.
-Si-substitutes partially for C and
promotes formation of graphite
as the carbon rich component
instead Fe3C.
The Austenite to ferrite / cementite transformation in
relation to Fe-C diagram
 The Austenite to ferrite / cementite
transformation in relation to Fe-C diagram

⚫ The iron wants to change crystal structure from

the FCC austenite to the BCC ferrite, but the
ferrite can only contain 0.02% carbon in solid
solution.
⚫ The excess carbon is rejected and forms the
carbon-rich intermetallic known as cementite.
The Austenite to ferrite / cementite transformation in
relation to Fe-C diagram

Hypo-eutectoid steel showing primary cementite along grain boundaries

pearlite
The Austenite to ferrite / cementite transformation in relation
to Fe-C diagram

⚫ Hypo-eutectoid steels: Steels having less than 0.8% carbon

are called hypo-eutectoid steels (hypo means "less than").
⚫ Consider the cooling of a typical hypo-eutectoid alloy
along line y-y‘.
⚫ At high temperatures the material is entirely austenite.
⚫ Upon cooling it enters a region where the stable phases are
ferrite and austenite.
⚫ The low-carbon ferrite nucleates and grows, leaving the
remaining austenite richer in carbon.
The Austenite to ferrite / cementite transformation in
relation to Fe-C diagram

⚫ Hyper-eutectoid steels (hyper means "greater than")

are those that contain more than the eutectoid amount of
Carbon.
⚫ When such a steel cools, as along line z-z' , the process
is similar to the hypo-eutectoid steel, except that the
primary or pro-eutectoid phase is now cementite instead
of ferrite.
 Principal phases of steel and their
Characteristics

Crystal
Phase Characteristics
structure
Ferrite BCC Soft, ductile, magnetic

Soft, moderate strength,

Austenite FCC
non-magnetic

Compound of Iron &

Cementite Hard &brittle
Carbon Fe3C
 Applications
⚫ It is used tailor properties of steel and to heat treat them.
⚫ It is also used for comparison of crystal structures for
metallurgists in case of rupture or fatigue
 LECTURE NOTES ON

MM-1515--015015 : HEAT
TREATMENT
6th Semester, MME

1
 MM-15-15-015015
HEAT TREATMENT

Couroursse Cooroordidinanattoror
Avala Lava Kumar
Department of Metallurgical & Materials Engineering (MME)
Veer Surendra Sai University of Technology (VSSUT), Burla-768018
E-mail : [email protected] Phone: (+91) (7077110110)

D.K.Mishra Dr. S.K.Badjena

Department of MME, VSSUT, Burla – 768018 Department of MME, VSSUT, Burla – 768018
E-mail : [email protected] E-mail : [email protected]
2
Phone : (+91) 7377483380 Phone : (+91) 8455938473
 HEAT TREATMENT
Course Objective
The aim of this course is to gain an understanding of the role of heat treatment on the
development of microstructure and properties of metallic materials. The course will highlight a
number of commercially-significant applications where heat treatment are important.

Course Overview
This course covers the theory of heat treatment including the kinetic principles of solid state
transformations. The influence of time on phase transformation is investigated. The
interpretation of IT and CT diagrams to predict transformations and resulting microstructures is
covered. Hardenability of steel is studied including factors influencing hardenability and the use
of hardenability curves in the selection of steels for given applications. The effect of thermal
gradients and phase transformations on distortion and residual stress in heat treated products is
studied. With addition of this it covers heat treatment of some selected non-ferrous alloys and
ferrous alloys.

Learning Outcomes
the course is to supply the student with a basic understanding of the modern heat treatment
processes and reheating principles. Upon completing the required coursework, the student can
explain the reasons for the heat treatment and its effects on the final properties of the product.
With the help of a short theoretical background. 3
 MM-15-015 : HEAT TREATMENT
CONTENTS
Chapter Chapter Name Slide No
1 Foundation 6-55
2 Principles of heat treatment of steels 56-133
3 Heat treatment processes for steels 134-170
4 Hardenability 171-196
5 Quenching technology 197-231
6 Surface hardening treatment of steels 232-241
7 Thermo chemical treatments of steels 242-259
8 Thermo mechanical treatment 260-272
9 Cast irons 273-308
10 Heat treatment of selected steels 309-334
11 Heat treatment of non ferrous alloys 335-395

4
 MM-15-015 HEAT TREATMENT
REFERENCES

❑ Steel heat treatment : Metallurgy and Technologies

Geroge E. Totten
CRC Press , Taylor & Francis Group
❑ Heat Treatment : Principles and Techniques
T.V.Rajan, C.P.Sharma and Ashok Sharma
PHI Learning Private Limited
❑ Heat Treatment of Materials
Vijendra Singh
Standard Publishers Distributors, Delhi
❑ Phase Transformations & Heat Treatment
Prof. M.P.Gururajan
NPTEL web course
❑ Practical Heat Treating
Howard E. Boyer
American society for metals
❑ Introduction to Physical Metallurgy
Sidney H. Avner
McGraw Hill Education (India) Pvt Ltd 5
 Avala Lava Kumar : D.K.Mishra : Dr.S.K.Badjena
Department of Metallurgical & Materials Engineering (MME)
Veer Surendra Sai University of Technology (VSSUT), Burla -768018
*E-mail : [email protected]
6
 Objective

Physical

Heating and cooling a solid metal or

Magnetic alloy in a way so as to obtain specific Electrical
conditions and/or properties

Mechanical

7
 Objective
❑ 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)

Temperature

Holding time
Heat Treatment Process variables
Heating rate

Cooling rate
8
Furnace atmosphere
 Classification of steels
❑ Compositions, such as carbon (or non alloy ), low -alloy, and alloy steels
❑ Manufacturing methods , such as converter, electric furnace, or electroslag
remelting methods
❑ Application or main characteristic, such as structural , tool, stainless steel, or
heatresistant steels.
❑ Finishing methods, such as hot rolling, cold rolling, casting, or controlled rolling
and controlled cooling.
❑ Product shape, such as bar, plate, strip, tubing, or structural shape
❑ Oxidation practice employed, such as rimmed, killed, semikilled, and capped
steels.
❑ Microstructure, such as ferritic, pearlitic, martensitic, and austenitic
❑ Required strength level, as specified in the American Society for Testing and
Materials (ASTM) standards.
❑ Heat treatment, such as annealing, quenching and tempering, air cooling
(normalization), and thermo-mechanical processing.
❑ Quality descriptors and classifications, such as forging quality and commercial
quality.
9
 Classification of steels
Steels
Low Alloy High Alloy
low carbon Med carbon high carbon
<0.25 wt% C 0.25-0.6 wt% C 0.6-1.4 wt% C

heat austenitic
Name plain HSLA plain plain tool
treatable stainless

Cr,V Cr, Ni Cr, V,

Additions none none none Cr, Ni, Mo
Ni, Mo Mo Mo, W
Example 1010 4310 1040 4340 1095 4190 304
Hardenability 0 + + ++ ++ +++ 0
TS - 0 + ++ + ++ 0
EL + + 0 - - -- ++
Uses auto bridges crank pistons wear drills high T
struc. towers shafts gears applic. saws applic.
sheet press. bolts wear dies turbines
vessels hammers applic. furnaces
blades V. corros.
resistant
increasing strength, cost, decreasing ductility
10
 Allotropic Transformation 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
 (delta) Fe - B.C.C
1400ºC
γ (gamma) Fe - F.C.C
Temperature ºC →

Non Magnetic
910ºC
Non Magnetic α (alpha) Fe - B.C.C
768ºC

α (alpha) Fe - B.C.C
Magnetic

Time →
Can be other allotropic structures are possible….? 11
 Effect of pressure on allotropy of Iron
This line slopes upward as at constant T
if we increase the P the gas will liquefy
as liquid has lower volume (similarly
the reader should draw horizontal lines
to understand the effect of pressure on
the stability of various phases- and
rationalize the same).

Phase fields of non-close packed

structures shrink under higher pressure

Phase fields of close packed structures

expand under higher pressure

These lines slope downward as: Under

higher pressure the phase with higher
packing fraction (lower volume) is
preferred

The face centered tetragonal (FCT) iron is coherently deposited iron grown as thin film on a
{100} plane of copper substrate. Growing Trigonal iron on mis-fiting {111} surface of a face
12
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.
❑ In the phase diagram, temperature is plotted against composition. Any point on the diagram
therefore represents a definite composition and temperature. The phase diagram indicates
the phases present and the phase changes that occur during heating and cooling. The relative
amounts of the phases that exist at any temperature can also be estimated with the help of
lever rule.
❑ 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.
13
 Fe-Fe3C metastable phase diagram
0.1 0.16 0.51
Peritectic Liquid (L)
Eutectic
L+→ 1493ºC
L →  + Fe3C
 (Ferrite)
L+ L + Fe3C

→
1147ºC
+   (Austenite)

Temperature
Hypo Eutectic Hyper Eutectic
910ºC 2.11

[(Austenite) + Fe3C(Cementite)] = Ledeburite

723ºC
 (Ferrite) 4.3
Eutectoid
Eutectoid

Hyper
Hypo

0.025 %C

Eutectoid [ (Ferrite) + Fe3C (Cementite)] = Pearlite

 →  + Fe3C Steels Cast Irons

0.008 0.8 F
e
%Fe-Fe
Carbon3C metastable6 phase diagram
→ .
7
F
e
3
C
1
4
 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
15
Why concentration of carbon in α-Fe with BCC structure
is less than γ-Fe with FCC structure?
❑ FIRST LET US CONSIDER FCC STRUCTURE (γ-Fe)
❑ Packing factor of FCC lattice 0.74
❑ This indicates the presence of voids. Let us discuss it more elaborately.
❑ In a FCC crystal there are mainly two types of voids:
❑ Tetrahedral: coordination number (CN) is 4. That means the void is surrounded by 4 atoms.
❑ Octahedral: CN is 6. That means the void is surrounded by 6 atoms.
❑ There are 8 tetrahedral voids in a unit cell. That means 2 voids per atom.
❑ There are 4 octahedral voids in a unit cell. That means 1 void per atom.
❑ However, impurities prefer to occupy octahedral voids.
❑ Because the ratio of the radius of the tetrahedral void to atom is 0.225 and the same for the
octahedral void is 0.414.
❑ The ratio of the radius of the carbon atom (size is 77 pm) to Fe (when it has FCC crystal) is
0.596.
❑ So when a carbon atom occupies any void, lattice will be distorted to increase the enthalpy.
❑ Distortion will be less if it occupies the octahedral voids.
❑ Although it increases the enthalpy, carbon atoms will be present up to a certain extent
because of the gain in entropy, as explained previously, which decreases the free energy.
16
 Carbon Solubility in Iron
FCC Void (Oct) Void (Tet)
∘
Size of Fe atom
CCP crystal
r
Fe
FCC = 1.292 A FeFCC C
∘

Size of the OV
Fe
xFCC (oct) = 0.534 A Relative sizes of voids w.r.t atoms
∘

Size of Carbon atom

r C = 0.77 A Note the difference in size of the atoms

BCC
∘

Size of Fe atom
BCC crystal
Fe
rBCC = 1.258 A Void (Oct) Void (Tet)

∘
FeBCC
(d.tet) = 0.364 A
Fe C
Size of the TV
x BCC
Fe ∘ Relative sizes of voids w.r.t atoms

Size of the OV
xBCC (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 .1 5147
Why concentration of carbon in α-Fe with BCC structure is less
than γ-Fe with FCC structure?
❑ NOW LET US CONSIDER THE BCC UNIT CELL (α - Fe)
❑ Packing factor of BCC lattice 0.68. So total void in a BCC unit cell is higher than FCC cell.
❑ However, there are 12 (6 per atom) tetrahedral and 6 (3 per atom) octahedral voids present. This
number is higher than the number of voids present in a FCC unit cell.
❑ Unlike voids in FCC lattice, in a BCC lattice the voids are distorted. That means if an atom sits
in a void, it will not touch all the host atoms.
❑ The ratio of the radius of tetrahedral void to atom is 0.29 and the radius of octahedral void to
atom is 0.155.
❑ The ratio of the radius of the C atom (size is 77 pm) to Fe (when it has BCC crystal) is 0.612.
So it is expected that in a BCC unit cell, impurities should prefer tetrahedral voids.
❑ However, although the octahedral void size is small, planar radius which has 4 atoms on the
same plane is 79.6 pm, which is larger that the C atom size. That means it needs to distort only
other two atoms.
❑ On the other hand if C sits in the tetrahedral void it has to distort all four atoms. So in α – Fe
with BCC unit cell C occupies the octahedral voids
❑ Now the octahedral void size in g-Fe (FCC) is higher than a-Fe (BCC). So naturally the
distortion in a BCC cell will be higher and the activation energy for impurities to occupy a void
in a BCC cell also will be higher.
❑ This is the reason that we find much lower solubility limit of C in a-Fe. 18
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
∘
2a
OA = r + xA = rFe
BCC = 1.258 A
2
2 6r BCC : 3a = 4r
r + xA =
3
xA 2 6 
= −1 = 0.6329
r  3 
 

x Fe (d.tet ) =
∘ ∘ ∘ 19
OX = xA = 0.796 A OY = xB = 0.195 A BCC
0.364 A
Characteristics of phases appeared in
Fe-Fe3C phase diagram

20
 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.
❑ Ferrite is ferromagnetic at low temperatures but loses its magnetic properties with the rise of
temperatures with major loss at curies temperatures, 768ºC and above this temperature, it
becomes non magnetic (paramagnetic).
❑ The crystal structure of ferrite (α) is B.C.C
❑ Tensile strength – 245 Mpa, Yield strength 118 Mpa
❑ Elongation – 40-50% in 2 in.
❑ Hardness - 95 VPN

(Ferrite) contains
B.C.C structure  (Ferrite) – 90X 21
 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 (35 Mpa) but
high compressive strength and high hardness ~800VPN.
❑ It is the hardest structure that appears on the diagram.
❑ It has a complex orthorhombic crystal structure with 12 iron atoms and 4 carbon atoms per
unitcell.
❑ It is slightly ferromagnetic up to 210ºC and paramagnetic above it. Melting point around
1227ºC.

Cementite network
Carbon
(4 atoms)

Iron
(12 atoms)

abc
22
Orthorhombic  =  =  = 90º
 Pearlite (α+Fe3C)
❑ 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 mixture called
pearlite is shown in below figure.
❑ The weight % of these two phases are thus in ratio 8:1

Eutectoid
❑ Tensile strength – 120,000 psi or 825 Mpa Hypo Hyper
❑ Elongation – 20 percent in 2 in. Eutectoid Eutectoid
❑ Hardness – HRC 20, HRB 95-100, or BHN 250-300
α + Fe3C

Fine Pearlite Coarse

Remember…!
Pearlite is a not a
phase but combination
of two phases (ferrite
+ cementite)

23
 Austenite (γ)
❑ It is an interstitial solid solution of a small amount of carbon dissolved in γ iron and has
FCC crystal structure. The maximum solubility is 2.1%C at 1147ºC.
❑ Austenite is soft, ductile tough and malleable (FCC structure) and non magnetic
(paramagnetic).
❑ Steels are commonly rolled and forged above about 1100ºC when they are in austenite state
due to its high ductility and malleability, which is also due to its FCC structure.
❑ Tensile strength – 150,000 psi or 1035 Mpa
❑ Elongation – 10% in 2 in.
❑ Hardness - 395 VPN and Toughness is high.

Fe

γ(Austenite) – 325X
24
 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.

25
 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.
❑ It is a high temperature phase and is a high temperature
manifestation of α ferrite.

❑ 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

26
Invariant Reactions in Fe-Fe3C
Phase Diagram

27
 Peritectic Reaction
❑ The invariant peritectic reaction in Fe-Fe3C diagram is given by

L δ-ferrite Cool
+ Austenite (γ)
0.51%C 0.1 %C 1495ºC
0.17%C

❑ Thus Liquid, wt% is 0.16 − 0.1

L= 100 = 14.63%
0.51− 0.1

0.51− 0.16
❑ Thus δ ferrite, wt % is =  =
0.51− 0.1

❑ Fe-0.16%C steel is a peritectic steel because only this steel undergoes above reaction
completely.
❑ Peritectic reaction is of some importance during freezing of steels (carbon from 0.1 to 0.51%
particularly under fast cooling conditions, when micro segregation may result, otherwise no
commercial heat treatment is done in this region.
❑ Unfortunately these temperatures are attained during heating of steels for forging or rolling
etc., then severe overheating and burning results in steels turning them to scrap form.

28
 Eutectic Reaction
❑ The invariant Eutectic reaction in Fe-Fe3C diagram is given by

Liquid (L) Cool Austenite (γ) Cementite

+
0.17%C 1147ºC 2.11%C 6.67 %C

6.67 − 4.3
❑ Thus Austenite, wt% is  = 100 = 51.97%
6.67 − 2.11

4.3 − 2.11
❑ Thus cementite, wt % is Fe3C = 100 = 48.03%
6.67 − 2.11

❑ Fe-4.3%C alloy is called eutectic cast iron as it is the lowest melting point alloy, which is
single phase liquid (100%) of 4.3% carbon at the eutectic temperature, 1147°C just attained
and undergoes eutectic reaction completely at this constant eutectic temperature to give a
mixture of two different solids, namely austenite and cementite, solidifying simultaneously.
The eutectic mixture called Ledeburite.
❑ As Fe-C alloys having more than 2.11% carbon are classed as cast irons, the Fe-C alloys
having carbon between 2.11 and 4.3% are called hypo eutectic cast irons, where as those
having carbon between 4.3% and 6.67% are called hypereutectic cast irons. Alloys of Fe with
4.3% carbon is called eutectic cast iron.
Eutectic Reaction 29
 Eutectoid Reaction
❑ The invariant Eutectoid reaction in Fe-Fe3C diagram is given by

Austenite (γ) Cool Ferrite (α) Cementite

+
0.8%C 727ºC 0.02%C 6.67 %C

6.67 − 0.8
❑ Thus Ferrite, wt% is = 100 = 88%
6.67 − 0.02

0.8 − 0.02
❑ Thus cementite, wt % is Fe3C = 100 = 12%
6.67 − 0.02

❑ During cooling austenite of 0.8% at constant eutectoid temperature, 727°C undergoes

eutectoid transformation to form a mixture of ferrite (C%=0.02%) and cementite i.e., there
are alternate lamellae of ferrite and cementite .
❑ This eutectoid mixture of ferrite and cementite is called PEARLITE, because of its pearly
appearance under optical microscope.
❑ The weight % of these phases are thus 8:1. The densities are (α-7.87 gm/cm3) and (Fe3C- -
7.70 gm/cm3) are quite comparable. Thus the Volume % also approx 8:1. Thus ferrite lamilla
is 8 times thicker than cementite lamilla. as the two boundaries of cementite plate are close
together, they may not resolved separately under the microscope, instead of two lines, it
appears a single dark line.
 30
Eutectoid Reaction
 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.
31
 Eutectoid Structure

Pearlite in SEM

Schematic representation of the formation of pearlite from

austenite; direction of carbon diffusion indicated by arrows

Pearlite in AFM

32
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.
33
 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

34
 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.

35
Hypo Eutectoid Region

Pearlite

Cementite network 36
 Concept of Primary Ferrite & Primary Cementite
❑ When the carbon content of steels is much away from the eutectoid carbon, then distinction
can easily be made between hypoeutectoid steels and the hypereutectoid steel. Nital is the
common etching agent.

Shahapepof
Shape e of
of phases
the thehe
phaphases
❑ Proeutectoid ferrite appears as grains which are quite wide, polyhedral and the grain
boundaries in between neighboring ferrite grains can be seen.
❑ The films of pro eutectoid cementite generally are much thinner, have irregular outlines and
bounded by sharp lines. These are present as network of needles or platelets. Cementite looks
much brighter and sharp because of its hardness and etching characteristics.
❑ Major difference is cementite is present as network at the grain boundaries of pearlite (at
RT), whereas ferrite is present as grains (equiaxed polyhedral grains) with grain boundaries
in between ferrite grains (if etched properly).

Microstructu
res of (a) b
Hypereutecto
id steel (b)
Hypoeutectoi
d steel
37
a
 Concept of Primary Ferrite & Primary Cementite
RelativeveHardness
Relative
Hardnednesss
❑ Cementite is very hard (~800 VPN) and ferrite is (~95 VPN). Micro hardness testing can be
done to distinguish between ferrite and cementite.
❑ A simple scratch test can be done. Make a scratch on the polished and etched surface of the
steel and then, examine the point of the scratch where it enters the white proeutectoid phase
from the pearlite.
❑ If the scratch widens on entering, it is the soft phase ferrite, and if it thins in white phase, then
the white phase is much harder than pearlite, i.e, it is cementite.

a b
Relative hardness of ferrite
and cementite distinguishes
them (a) Hypereutectoid
steel (b) Hypoeutectoid steel

SpepeccialEtchants
Special
Etchahantntss
❑ Nital etching causes cementite as well as ferrite to look white under microscope
❑ A sodium picrate solution used either boiling or electrolytically, darkens Fe3C but not ‘α’
❑ Another etchant based on sodium thiosulphate and ammonium nitrate gives colors but
not cementite. 38
Fe-Fe3C phase diagram (microstructural aspects)
L=liquid, Cm=cementite, LB=ledeburite, δ=delta ferrite, α=
1539˚C δ+L L alpha ferrite, α’= alpha ferrite(0.00005 wt%C) γ=austenite,
δ A5=1495˚C P=pearlite, eu=eutectic, ed=eutectoid, I=primary,
0.09 0.53 II=secondary, III=tertiary
δ+γ 0.17 1227˚C

1394˚C
L+γI
LB+Cm L+CmI
4.30
γ +LB

γ 2.11 I I A4=1147˚C
Temperature, °C

γI’(γII+CmII)+LB’ (γ’eu(γII LB’ (γeu(γII

+CmII)+Cmeu)
+CmII)+Cmeu)
A B +CmI
C

Ledeburite=LB(γeu+Ceu)
910˚C D E F
A2 A3
=668/ Cm
770˚C 0.77
αI+γ γII+CmII
0.0218 A1=727˚C
α P(α +Cm ) (P(α +Cm )+Cm )+ LB’ (P(α +Cm ) LB’ (P(α +Cm )
αI+ (P(αed ed ed
Pearlite

ed ed II ed ed ed ed

+Cmed) +CmII +CmII+Cmeu) +CmII)+Cmeu)+CmI

αI(α’+CmIII)+ P(α (α’ (P(αed(α’ed+CmIII)+Cmed) +CmII)+ LB’

(P(αed(α’ed+C ed ed
+CmIII)+Cmed) LB’ ((P(αed(α’ed+CmIII)+Cmed) ((P(αed(α’ed+CmIII)+Cmed)
mIII)+Cmed)
+CmII +CmII)+Cmeu) +CmII)+ Cmeu)+CmI
Ao=210˚C
α’+CmIII
 6.67
0.00005
Weight percent carbon
39
Evolution of Microstructures on equilibrium cooling
❑ Sequence of evolution of microstructure can be described by the projected cooling on
compositions A, B, C, D, E, F.
❑ At composition A

L →  + L →  →  +  →  →  + I →  →  ' + Cm III

❑ At composition B

L →  + L → L +  I →  →  I +  → I + (P(ed + Cmed ) → I ( ' + Cm III ) + P(ed '

+ Cm III ) + Cmed )
( ed

❑ At composition C

L → L +  I →  →  II + CmII → P(ed + Cmed ) + CmII → P(ed '

+ Cm III ) + Cmed ) + CmII
( ed

❑ At composition D

L → L +  I →  I + LB →  ' ( + CmII ) + LB' ( eu' ( II + CmII ) + Cmeu )

I II

→ (P(ed + Cmed ) + CmII ) + LB' (P( ed + Cmed ) + CmII + Cmeu

( ed'
→ (P(ed ( ed' + Cm III ) + Cmed ) + CmII ) + LB' ((P( ed + Cm III ) + Cmed ) + CmII ) + Cmeu )
Evolution of Microstructures on equilibrium cooling
40
Evolution of Microstructures on equilibrium cooling
❑ Sequence of evolution of microstructure can be described by the projected cooling on
compositions A, B, C, D, E, F.
❑ At composition E
L → L + CmI → LB(eu + Cmeu + Cm ) → LB' ( ( + CmII ) + Cmeu ) + CmI
I eu II

→ LB' (P( ed + Cmed ) + CmII ) + Cmeu ) + CmI

→ LB' ((P( ed ( ed' + Cm III ) + Cmed ) + CmII ) + Cmeu ) + CmI

❑ At composition F

L → Fe3C
 41
Evolution of Microstructures on equilibrium cooling
Application of Lever rule in
Fe-Fe3C phase diagram

42
 For a 99.6 wt% Fe-0.40 wt% C at a temperature just below the
Solved
eutectoid, determine the following:
Example
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%

43
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

44
 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. 45
 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.

440
Effect of alloying elements on Fe-Fe3C phase diagram
Based on stabilizing Austenite

❑ Mn, Ni, Co, Cu, Zn increase the range in which γ-phase, or austenite is stable [by raising A4
and lowering A3 temperature and also tend to retard the separation of carbides.
❑ These elements have γ-phase FCC crystal structure (or similar structure) in which these
elements are more soluble than ferrite, and that is why, in the (α+γ) two phase equilibrium,
these segregate in austenite in preference to ferrite.
❑ Elements like carbon and nitrogen (interstitial solid solution forming elements) are also
austenite stabilizers.

Based on stabilizing Ferrite

❑ Cr, W, Mo, V, Si, Al, Be, Nb, P, Sn, Ti, Zr increase the range of α-phase (by lowering A4 and
raising A3 temperatures).
❑ These elements have α phase BCC crystal structure (or similar structure) and thus in (α+γ)
two phase equilibrium , these elements segregate in ferrite in preference to austenite. These
elements decrease the amount of carbon soluble in austenite, and thus tend to increase the
volume of the free carbide in the steel for a given carbide content.
❑ Chromium is a special case of these elements as at low concentrations , chromium lowers A3
temperature and raises A4 , but at high concentrations raises A3 temperature. Overall, the
stability of austenite is continuously decreased.
47
Effect of alloying elements on Austenite phase region Mn, Cr

Temperature →
0.35% Mn
▪ Mn is Austenite stabilizer
▪ Expansion of  phase field with ↑ Mn

Outline of the  phase field

6.5% Mn
0 0.4 0.8 1.2 1.6
C (%) →
Temperature →

Outline of the  phase field

15% Cr 12% Cr

5% Cr 0% Cr
▪ Cr is Ferrite stabilizer
▪ Shrinking  phase field with ↑ Cr

0 0.4 0.8 1.2 1.6 48

C (%) →
Effect of alloying elements on Fe-Fe3C phase diagram
Carbide forming elements

❑ Important elements, in this class, are arranged in order of increasing affinity for carbon, and
thus the carbide forming potential of the element :
Fe → Mn → Cr → W → Mo → V → Ti → Nb → Ta → Zr
❑ For example, vanadium is added in steel having chromium and molybdenum with insufficient
carbon, then vanadium first removes carbon from chromium carbide, the remaining vanadium
then removes carbon from molybdenum carbide and forms its own carbide. The released Cr
and Mo dissolve to form solid solution in austenite.

Graphitising elements

❑ Si, Ni, Cu, Al are common graphitizes. Small amount of these elements in steel can graphitise
it and thus, impair the properties of steel unless elements of austenite stabilizers are present
to counteract the effect.

Neutral element

❑ Co is the only element which neither forms carbide, nor causes graphitisation.

49
 Effect of alloying elements on Fe-Fe3C phase diagram
Effect on Eutectoid composition

❑ All the elements lower the eutectoid carbon content. Titanium and molybdenum are the
most effective in lowering it.
❑ For example, a steel with 5% Cr has its eutectoid point at 0.5%C as compared to 0.8% in
carbon steels. High speed steel has eutectoid point at 0.25% carbon.

Effect on Eutectoid temperature

❑ Elements like Ni, Mn i.e., the austenite stabilizers lower the eutectoid temperature (727°C).
Ferrite stabilizers like Cr, V, W etc. raise the eutectoid temperature.

Effect of alloying element on eutectoid temperature Effect of alloying element on effective carbon conte5 n0 t
 Limitations on Fe-Fe3C phase diagram
❑ Fe-Fe3C diagram represents behavior of steels under equilibrium conditions, whereas the
actual heat treatments of steels are normally under non-equilibrium conditions.
❑ The diagram does not indicate the character of transformation of austenite such as to
bainite, or martensite.
❑ The diagram does not indicate the presence of metastable phases like martensite, or bainite.
❑ It does not indicate the temperature of start of martensite Ms or bainite Bs .
❑ It does not indicate the kinetics of the transformation of austenite to martensite, bainite or
even pearlite.
❑ It does not indicate the possibilities of suppressing the pearlitic or bainitic transformations.

51
 Strengthening Mechanisms in Steels
Solid Solution Strengthening
❑ Solid solution strengthening is a phenomenon that occurs when the number of impurity atoms
in the lattice of the basic element is so small that they are incapable of forming both stable
and metastable precipitation phases under any thermal treatment conditions.
❑ Consider the influence of carbon, which is statistically uniformly distributed in the lattice of
the α-iron, on the structure and properties of a-iron. Solubility of carbon in α-iron is much
lower than in the γ-iron. It forms interstitial solid solutions with both irons.
❑ However, whereas the γ-iron lattice has sufficiently large pores for implantation of carbon
atoms, the cubic lattice of the α-iron suffers, upon introduction of carbon atoms, a tetragonal
distortion similar to the one of the martensite lattice, except that in the former case the
distortion is much smaller.
❑ In addition, implantation of carbon atoms causes the entire lattice of the α-iron to expand
somewhat. For example, at a carbon content of 0.015% the lattice constant increases at room
temperature by 0.025c.
❑ The yield stress rises most dramatically with an increase in the carbon concentration from 10-
7 to 10-4 -10-3 %. The influence that carbon exerts on plastic deformation resistance of the α-

phase is due to both its strong interaction with dislocations and pinning of the dislocations
and elastic deformations arising as a result of the tetragonal distortion of the a-phase lattice
after implantation of carbon atoms.
❑ Dissolution of part of the carbon in the α-phase and suggests that the solid solution strengthening of the phaseis one of
the factors providing the high strength properties of intermediate transformation products. 52
 Strengthening mechanisms in steels
Grain Size Refinement

❑ Austenite passes to other phases during cooling, its grain size represents an important
characteristic of steel. This is due to the fact that all structural components are formed within
each separate crystal.
❑ The smaller the austenite grains, the finer the network of excess ferrite at their boundaries and
the smaller the pearlite colonies and martensite crystals. Therefore, a fine grain corresponds
to a fine crystal fracture of steel and vice versa at the temperatures where austenite has already
precipitated.
❑ Impact strength is especially sensitive to the austenite grain size, and it decreases with grain
enlargement. A decrease in the dimensions of pearlite colonies inside the initial austenite
grain favors a rise in impact strength also.
❑ Although the grain size has a considerable effect on impact strength, its influence is small if
any on the statistical characteristics of mechanical properties such as hardness, fracture stress,
yield stress, and specific elongation. Only the actual grain size affects steel properties, the
inherited size has no effect.
❑ However, the technological process of heat treatment is determined by the inherited grain.
For example, a hereditarily fine-grained steel may be deformed at a higher temperature with
the assurance that the coarse-grained structure will not occur.

53
 Strengthening mechanisms in steels
Dispersion strengthening
❑ In the majority of metal alloys, precipitation of supersaturated solid solutions formed during
quenching is followed by precipitation of disperse particles enriched in atoms of the alloying
components. It was found that the strength (hardness) of the alloys increases with the
precipitation of these particles. The increment in the value of these characteristics increases
as the dispersion and volume fraction of the particles increase. This phenomenon has been
referred to as dispersion strengthening.
❑ When a solid solution of carbon in α-iron is cooled be low point A1, carbon should precipitate
as cementite with lowering of the carbon solubility and a decrease in temperature. This
process is realized under sufficiently slow cooling, which is accompanied by diffusion
processes, leading to the formation of cementite.
❑ In the case of abrupt cooling , e.g. , water quenching, carbon has no time toprecipitate. A
supersaturated a solid solution appears. At room temperature the retained amount ofcarbon can
correspond to its maximum solubility of 0.018%. During subsequent storage atroom temperature
(natural aging) carbon tends to precipitate from the solid solution.Carbon enriched regions
appear predominantly in defective sections of the matrix.Precipitation of carbon from a
supersaturated solid solution during natural aging results inimprovement of its strength
characteristics and hardness. However, plasticcharacteristics—reduction of area, specific
elongation, and impact strength are impaired. A clearly pronouncedyield stress appears after a
long natural aging. Hardness may increase by 50% over that ofthe as quenched stat e. The
phenomenon of dispersion strengthening is observed. 54
 Strengthening mechanisms in steels
Work Hardening

❑ An important method used to strengthen steels is deformation strengthening. Strengthening

achieved with crystal deformation can be judged from the shape of stress–strain curves.
❑ The actual shape of these curves largely depends on the crystal lattice type of the metal, its
purity, and thermal treatment.
❑ In the case of cubic lattice metals, strengthening curves are parabolic, whereas for hexagonal
lattice metals a nearly linear dependence is observed between the stress and the strain.
❑ This fact suggests that plastic deformation strengthening is determined mainly by the
interaction of dislocations and is associated with the structural changes that impede the
movement of dislocations.
❑ Metals with a hexagonal lattice are less prone to deformation strengthening than cubic lattice
metals because the hexagonal lattice has fewer easy slip systems.
❑ In cubic lattice metals, the slip proceeds in several intersecting planes and directions.

55
 Classification
HEAT TREATMENT

BULK SURFACE

Annealing Tempering

Normalizing Hardening Thermal Thermo-Chemical

Full Annealing Flame Carburizing

Recrystallization Annealing Nitriding

Induction

Stress Relief Annealing Cyaniding

Laser
Spheroidization Annealing Boronizing
Electron Beam
Diffusion Annealing Chromizing

Partial Annealing
 135
Process 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)

Acm
A3
Full Annealing
Spheroidization A1
Recrystallization Annealing
Stress Relief Annealing

136
 Annealing
Recrystallization Annealing
❑ The Heat below A1 → Sufficient time → Recrystallization

Cold worked grains → New stress free grains

❑ Used in between processing steps (e.g. Sheet Rolling)

910oC
A
A3
Full Annealing
723oC
Spheroidization A1
Recrystallization Annealing
Stress Relief Annealing
T

0.8 %
Wt% C 137
 Annealing
Stress Relief Annealing

Residual stresses → Heat below A1 → Recovery

→ Differential cooling Annihilation of dislocations,

polygonization
→ Martensite formation

→ Machining and cold working 910oC

Acm
A3
Full Annealing
→ Welding 723oC
Spheroidization A1
Recrystallization
Recrystallization Annealing
Stress Relief Annealing
T

0.8 %
Wt% C
138
 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
139
 Annealing
Diffusion Annealing
❑ This process also known as homogenizing annealing, is employed to remove any structural
non-uniformity.
❑ Dendrites, columnar grains and chemical inhomogeneities are generally observed in the case
of ingots, heavy plain carbon steel casting, and high alloy steel castings. These defects
promote brittleness and reduce ductility and toughness of steel.
❑ In diffusion annealing treatment, steel is heated sufficiently above the upper critical
temperature (say, 1000-1200°C), and is held at this temperature for prolonged periods, usually
10-20 hours, followed by slow cooling.
❑ Segregated zones are eliminated and a chemically homogeneous coarse grain steel is obtained
by this treatment as a result of diffusion.
❑ The coarse grained structure can be refined either by plastic working for ingots or by
employing a second heat treatment for castings.
❑ Hypoeutectoid and eutectoid steel castings are given full annealing treatment, whereas
hypereutectoid steel castings are either normalized or partially annealed for this purpose.

140
 Annealing

Diffusion
annealing

Partial
annealing

Process
annealing

141
Temperature ranges for various types of annealing processes
 Annealing
Partial Annealing
❑ Partial annealing is also referred to as intercritical annealing or incomplete annealing. In this
process, steel is heated between the A1 and the A3 or Acm. It is followed by slow cooling.
❑ Generally, hypereutectoid steels are subjected to this treatment. Resultant microstructure
consists of fine pearlite and cementite. The reason for this is that grain refinement takes place
at a temperature of about 10 to 30C above Ac1 for hypereutectoid steels.
❑ As low temperature are involved in this process, so it is cost effective than full annealing

Process Annealing
❑ In this treatment steel is heated to a temperature below the lower critical temperature, and is
held at this temperature for sufficient time and then cooled. Since it is a subcritical annealing,
cooling rate is of little importance
❑ The purpose of this treatment is to reduce hardness and to increase ductility of cold-worked
steel so that further working may be carried out easily. It is an Intermediate operation and is
sometimes referred to as in process annealing. The process is less expensive than
Recrystallization annealing.

142
 Normalizing
Heat above A3 | Acm → Austenization → Air cooling → Fine Pearlite (Higher hardness)
910oC
Refine grain structure prior to hardening Acm
A3

Full Annealing
Purposes To harden the steel slightly 723oC
Spheroidization A1
Recrystallization Annealing
Stress Relief Annealing
To reduce segregation in casting or forgings T

00.88 %

❑ In hypo-eutectoid steels normalizing is done 50oC above the annealing temperature

Wt% C

❑ In hyper-eutectoid steels normalizing done above Acm → due to faster cooling

cementite does not form a continuous film along GB
Annealed Vs Normalized
Annealed Normalized
Less hardness, tensile strength and toughness Slightly more hardness, tensile strength and toughness
Pearlite is coarse and usually gets resolved by Pearlite is fine and usually appears unresolved with
the optical microscope optical microscope
Grain size distribution is more uniform Grain size distribution is slightly less uniform
Internal stresses are least Internal stresses are slightly more 143
 Hardening
Heat above A3 | Acm → Austenization → Quench (higher than critical cooling rate)
❑ Certain applications demand high tensile strength and hardness values so that the components
may be successfully used for heavy duty purposes. High tensile strength and hardness values
can be obtained by a processes known as Hardening.
❑ hardening process consists of four steps. The first step involves heating the steel to above A3
temperature for hypoeutectoid steels and above A1 temperature for hypereutectoid steels by
500C.
❑ The second step involves holding the steel components for sufficient socking time for
homogeneous austenization.
❑ The third step involves cooling of hot steel components at a rate just exceeding the critical
cooling rate of the steel to room temperature or below room temperature.
❑ The final step involves the tempering of the martensite to achieve the desired hardness.
Detailed explanation about tempering is given in the subsequent sections. In this hardening
process, the austenite transforms to martensite. This martensite structure improves the
hardness.
❑ In the hardening process, which involves quenching and tempering. During quenching outer
surface is cooled quicker than the center. In other words the transformation of theaustenite is
proceeding at different rates. Hence there is a limit to the overall size of the part in this
hardening process. 144
 Hardening
A few salient features in hardening of steel

❑ Proper quenching medium should be used such that the component gets cooled at a rate just
exceeding the critical cooling rate of that steel.
❑ Alloy steels have less critical cooling rate and hence some of the alloy steels can be
hardened by simple air cooling.
❑ High carbon steels have slightly more critical cooling rate and has to be hardened by oil
quenching.
❑ Medium carbon steels have still higher critical cooling rates and hence water or brine
quenching is necessary.

145
 Hardening
Factors affecting Hardening Processes
Chemical composition of steel
Size and shape of the steel part
Hardening cycle (heating/cooling rate, temp, soak time
Homogeneity and grain size of austenite
Quenching media
Surface condition of steel part

Hardening Methods
Conventional or direct quenching
Quenching in stages in sequence in different media
Spray Quenching
Quenching with self tempering
Austempering or Isothermal Quenching
Martempering
146
 Retained Austenite
❑ Austenite that is present in in the ferrous alloys even after the completion of the heat treatment
process is referred to as retained austenite. In simple words, retained austenite is the
untransformed austenite.
❑ Austenite transforms to martensite between Ms and Mf temperatures as it is essentially an
athermal transformation. However, this transformation never goes to completion, i.e., 100%
martensite (Mf temperature line is illustrated as dotted line in TTT diagrams).
❑ This is because at Mf , a small amount of (~1%) of austenite is present in highly stressed state
along with ~99% martensite, and can not transform to martensite because unfavourable stress
conditions.
❑ Both Ms and Mf temperatures decrease with increase in carbon content. Therefore amount of
retained austenite in hardened steels increase with increase in carbon content.
❑ All alloying elements, except Al and Co, lower the Ms temperature and hence enhance the
amount of retained austenite. Therefore, both high carbon steels and high alloy steels are more
prone to the presence of retained austenite.
❑ The substructure of retained austenite differs from that of the original austenite as it has as a
higher density of imperfections like dislocations, stacking faults, etc. which are created by
local plastic deformation of the austenite by martensite crystals.
❑ Tool steels may have retained- austenite in the range of 5-35%. At the surface of aquenched steel,
that restrains are minimum. R.A is less at surface than center of the part. 147
 Retained Austenite
Advantages
❑ Ductility of austenite can help to relieve some internal stresses developed due to hardening,
to reduce danger of distortion and cracks. 10% retained austenite along with martensite is
desirable.
❑ The presence of 30-40% retained austenite makes straightening operation of the components
possible after hardening. Straightening increases the hardness slightly.
❑ Non-distorting steels owe their existence to retained austenite. Here enough austenite is
retained to balance the transformational contracting during heating, on the formation of
austenite from ferrite carbide aggregate on the one hand, and the expansion corresponding to
the formation of martensite during cooling, on the other, Here, the basis of dimensional
stability of non-distorting steels is the presence of retained austenite.

disadvantages

❑ The soft austenite if present, in large amounts, decreases the hardness of hardened steels.
❑ As retained austenite may transform to lower bainite, or to martensite, there takes place
increase in dimensions of the part. Not only it creates problems in precision gauges, or dies,
the neighboring parts may be put under stress by it. In the component itself, stresses may be
created to cause distortion or cracking.
❑ Retained austenite decreases the magnetic properties of the steel. 148
 Sub-Zero treatment
❑ The retained austenite is generally undesirable, sub-zero treatment is one of the method to
eliminate retained austenite.
❑ As the room temperature lies between Ms and Mf temperatures of steel, quenching to room
temperature results in retained austenite.
❑ Subzero treatment consists in cooling the hardened steel to a temperature below 0C. The
temperature of the sub zero treatment depends on the position of Mf temperature of the steel.
❑ A steel can be cooled much below the Mf temperature, but it, evidently achieves nothing,
because it cannot bring about any additional increase of hardness, or any additional increase
of martensite, because the Martensitic transformation ends at Mf temperature.
❑ Sub-zero treatment is more effective, if it is carried out immediately after quenching
operation. Any lapse of time between hardening and the cold treatment causes the
stabilization of austenite, makes the retained austenite resistant to further transformation.
❑ Most steels can be cooled by subzero treatment in a low cooling unit with one of the mediums
as given in table (next page) .
❑ The low-cooling unit consists of two vessels, the interior one of copper, where the parts or
tools to be deep frozen, are placed and the exterior one of steel provided with a good heat
insulation.
149
 Sub-Zero treatment
Table : Subzero Coolants with
Temperature of Application
Minimum
Coolant
temperature C
Dry ice (solid Co2)
-78
+ Acetone
Ice + Salt (NaCl) -23
Ice + Salt (CaCl2) -55
Liquid air -183
Liquid Nitrogen -196
Liquid Pentane -129
Freon -111

Figure : Liquid cooled (liquid N2 ) system.

Components are immersed in a bath of alcohol,
or trichloro ethylene, which is cooled by a
submerged liquid nitrogen spray (-150C
), cooling rates can be controlled.

150
 Sub-Zero treatment
❑ The space in between the vessels is filled with one of the chosen medium, or a system (figure
in previous page) which is inexpensive and can be used.
❑ Usually the temperature range used is in range of -30C to -150C, and total time of cooling
and holding at that temperature (Mf) varies from ½ - 1 hour. The hardness increased by 2-4
HRc.
❑ As the amount of martensite increases by sub-zero treatment, it increases hardness, abrasion
resistance, fatigue resistance and eliminates the danger of developing grinding cracks.
❑ As the newly formed martensite may add further to unfavorable stresses to cause distortion
and cracks, the complicated, or intricate shaped components may be first tempered at 150-
160C immediately after first quenching and then given the sub-zero treatment.

Sub-zero treatment has been most extensively used for…!

❑ Alloyed tool steels – like high speed steel, which now shall need only single stage
tempering.
❑ Tools and components which need exact dimensions – gauges
❑ Carburized steels, especially alloy steels (having elements like Ni in it) to increase their
hardness and wear resistance
❑ Steels having 0.8 to 1.1%C as hardness increases by 1-3 HRc
151
 Tempering
❑ The hardened steel is not readily suitable for engineering applications. It possesses
following three drawbacks.
✓ Martensite obtained after hardening is extremely brittle and will result in failure of
engineering components by cracking.
✓ Formation of martensite from austenite by quenching produces high internal stresses in
the hardened steel.
✓ Structures obtained after hardening
consists of martensite and retained
austenite. Both these phases are
metastable and will change to stable
phases with time which subsequently
results in change in dimensions and
properties of the steel in service.
❑ Tempering helps in reduce these problems.
Tempering is the process of heating the
hardened steel to a temperature maximum up
to lower critical temperature (A1), soaking at
this temperature, and then cooling, normally
very slowly.
152
Variation in properties with tempering temperature
 Tempering
Objective

Relieve Internal Restore ductility To improve To improve magnetic

stresses and toughness dimensional stability properties

Structure in as Quenched state

Highly supersaturated martensite

Retained austenite

Undissolved carbides

Rods, or plates of carbide particles produced during ‘auto-tempering’

Segregation of carbon
153
 Tempering of plain carbon steels
First stage of Tempering

❑ First Stage of tempering temperature extends from room temperature to 200°C. The
tempering reactions in steels, containing carbon less than 0.2%, differ somewhat from the
steels containing more than 0.2% carbon.
❑ In the former, if carbon atoms have not yet segregated (during quenching) to dislocations,
these diffuse and segregate around the dislocations and lath boundaries in the first stage of
tempering. No ε-carbide forms as all the carbon gets locked up to the dislocations (defects).
❑ Martensite in steels with more than 0.2% carbon is highly unstable because of super
saturation, and interstitial diffusion of carbon in BC martensite can occur. Thus in the first
stage of tempering, the decomposition of martensite into low-tetragonality martensite
(containing ~0.2%C, c/a ~ 1.014) and ε-carbide, Fe2.4C occurs. (There are reports of
precipitation of eta-carbide, Fe2C and Haggs carbide, Fe2.2C.
❑ ε-carbide is a separate phase and is not a preliminary step in the formation of cementite, but
it nucleates and grows more rapidly than cementite. It has HCP structure with c = 4.33A°, a
= 2.73A°, c/a = 1.58A° and forms as small (0.015-0.02 μm) platelets, or needles observed
under electron microscope.
❑ The structure at this stage referred to as tempered martensite, which is double phase mixture
of low tetragonal martensite and ε-carbide.
❑ In this stage volume ↓ because specific volume of martensite ↓ due to rejecting of C at1o54ms.
 Tempering of plain carbon steels
Second stage of Tempering
❑ Second Stage of tempering temperature lies between 200-300°C. The amount of retained
austenite in the as-quenched steel depends mainly on the composition of the steel, and the
temperature to which steel is quenched.
❑ In the second stage of tempering retained austenite transforms to lower bainite (the carbide in
bainite is ε-carbide). The matrix in lower bainite is cubic ferrite (c/a = 1), where as in tempered
martensite, the low tetragonal martensite has c/a ~ 1.014
❑ When retained austenite changes to lower bainite, their takes place increase in volume.

Third stage of Tempering

❑ Third Stage of tempering temperature lies between 200-350°C. In this stage of tempering, ε-
carbide dissolves in matrix, and low tetragonal martensite losses its completely its carbon and
thus, the tetragonality to become ferrite .
❑ Cementite forms as rods at interfaces of ε-carbide and matrix, twin boundaries, interlath
boundaries, or original austenite grain boundaries.
❑ During this stage, volume decreases just as in stage one, due to complete loss of tetragonality.
In a 1% carbon steel , the total decrease in length in the first and third stages in around 0.25%
155
 Tempering of plain carbon steels
Fourth stage of Tempering

❑ Fourth Stage of tempering temperature lies between 350-700°C.

❑ Growth and spheroidisation of cementite, as well as recovery and Recrystallization of ferrite
occur. Though the growth of cementite starts above 300°C, its spheroidisation starts above
400°C to 700°C.
❑ Spheroidisation takes place due to reduction in interfacial energy of ferrite-cementite
interfaces. As quenched martensite has high concentration of lattice defects. Though their
annealing out starts in the third stage of tempering, but the cementite precipitates retard the
recovery processes.
❑ Substantial recovery processes starts occurring only above 400°C. original lathe boundaries
are stable up to 600°C, but above this, these are replaced by equiaxed-ferrite grain boundaries
– the process, which is best described as ‘Recrystallization’.
❑ In the end, the optical microstructure consists of equiaxed ferrite grains with coarse
Spheroidal particles of cementite, and then the structure is called globular pearlite, or
spheroidized cementite.
❑ The structure perhaps is the most stable of all ferrite- cementite aggregates, and is the softest
with highest ductility with best machinability.

156
 Effect of carbon on Tempering

Effect of tempering temperature( 1 hour at each temperature) on hardness and reactio1n57s

 Tempering of alloy steels
❑ The presence of alloying elements, steels can change their nature and properties effectively.
❑ Most common elements (except cobalt) shift the CCT curve to longer times, which essentially
result in the increase of hardenability of the steels, so that pearlitic transformation can be
avoided easily to obtain Martensitic structure, even at a slower trate of cooling and in thicker
parts.
❑ Alloying elements also lower Ms and Mf temperatures, increasing further the amount of
retained austenite. The decomposition of retained austenite on tempering, plays quite a
significant role on the properties of tempered steels, specially having high carbon and high
alloying elements.
❑ Some elements, that are not found in carbides, but are present as solid solution in ferrite, are
Al, Cu, Si, P, Ni, and Zr. Some elements arranged in order of increasing tendency to form
carbides are Mn, Cr, W, Mo, V and Ti. These carbide forming elements retard most
effectively the rate of softening during tempering of the steel.
❑ The first stage of tempering does not appear to be effected by the presence of the alloying
elements. However, most of the alloying elements in steels tends to increase the hardness
after tempering than a plain carbon steel with the same carbon content.
❑ At smaller concentration, they merely retard the tempering processes hence the softening,
particularly at higher temperature (> 500°C), where these elements have good diffusivity to
take part in tempering reactions.
158
 Tempering of alloy steels
❑ When alloy carbides are formed, the drop in hardness during tempering is not only retarded
but is significantly increased. The steel is then said to secondary hardening.
❑ Thus, 0.5% chromium , or less than 0.5% Mo resists softening but secondary hardening is
produced by either 12% chromium, or 2 % Mo.. Stronger the carbide, the more potent is the
secondary hardening.

Effect of increasing Mo on tempering of as

quenched 0.1%C steel Effect of increasing chromium in 0.35%C steel on te1 m
5 9pering
 Tempering of alloy steels
❑ Element, such as, silicon dissolves in ε-carbide to stabilize it. Steels with 1-2% silicon have
ε-carbide present even after tempering at 400°C, which means that the formation of cementite
is delayed considerably, and thus, resisting the softening. Otherwise, the effect of silicon is
essentially due to solid solution strengthening.
❑ Nickel has a small, but constant effect on tempered hardness at all temperatures due to solid
solution strengthening as it is not a carbide former.
❑ Manganese has little effect on softening at low tempering temperatures, but at high
temperatures, has a strong effect on due to its faster diffusion then, and thus, it resists
cementite coarsening as it is present in cementite as (Fe, Mn)3C.
❑ Martensite in plain carbon steels losses its tetragonality by 300°C, but the tetragonality is seen
at 450°C, or even at 500°C if the steels have elements like Cr, W, Mo, Ti, V and Si.
❑ The basic cause of steep softening in carbon steels on tempering above 400°C, is the
coagulation of the cementite particles. Alloying elements notably Si, Cr, Mo, V, when present
in steels, retard the coalescence and the coarsening of cementite particles., resulting in
enhanced hardening over and above the solid solution hardening effect.
❑ Elements like Cr, Si, Mo, or W delay coarsening to temperature range of 500-550°C. up to
tempering temperature 500°C, the carbides formed are of iron with proportional alloying
elements in it, but above 500°C, alloying elements can form their own carbides and thus,
coarse cementite particles are replaced by fine dispersion of more stable alloy carbides.
160
 Tempering of alloy steels
❑ An Fe-10 Ni alloy shows constant
hardness on tempering up to 450°C and
then, there takes place some decrease in
strength (curve I).
❑ Addition of 0.12% carbon increases the
as quenched strength to almost double,
and slow decrease of hardness occurs on
tempering to fall to 0.7 GPa at 500°C.
❑ A 8% cobalt addition, which doesn’t
enter the carbide, delays the softening to
have strength of 0.8 GPa at 500°C .
❑ Addition of 2% Cr almost continuously
but slowly ↑ hardness to start falling at
above ~450°C to become 1.1 GPa at
500°C by fine dispersion of Cr carbide.
❑ Addition of Mo causes secondary
hardening, as it is very strong carbide
Effect of C, Co, Cr, and Mo on tempering of
forming element, to attain a hardness of
Fe-10Ni steels
1.3 Gpa at 500°C
161
 Tempering of alloy steels : Secondary Hardening
❑ In alloy steels, having larger amounts of strong carbide forming elements like Mo, Ti, V, Nb,
W, Cr etc., and carbon , a peculiar phenomena occurs, the hardness of the as-quenched
martensite (called primary hardness) on tempering, decreases initially, as the tempering
temperatures is raised, but starts increasing again to often become higher than the as quenched
hardness, with much improved toughness, when tempered in the range of 500 to 600°C. This
increase in hardness is called secondary hardness (also called red hardness).
❑ This is great importance in high speed steels, as these are able to continue machining, at high
speeds (as these are able to resist fall in hardness and thus, the cutting property ) even when
they become red hot.
❑ Secondary hardening is a process, similar to age hardening, in which coarse cementite
particles are replace by a new and much finer alloy carbide dispersion of V4C3, Mo2C, W2C
(which normally form on dislocations). As in aging a critical dispersion causes a peak in the
hardness and strength of the alloy, and as over aging takes place, i.e., carbide dispersion
slowly coarsens, the hardness decreases.
❑ Secondary hardening is best shown in steels containing Mo, V, W, Ti and also in Cr steels at
high chromium concentrations.
❑ The amount of secondary hardening in an alloy steel is directly proportional to thevolume fraction
of the alloy carbides, and thus is directly proportional to the concentration ofstrong carbide
forming elements present in steels. The alloy carbides must precipitate as fine dispersion in
ferrite matrix rather than massive carbide particles. 162
Time and Temperature relationship in Tempering
❑ For a given steel, a heat treater might like to choose some convenient tempering time, say
over night, otherwise different than 1 hour, and thus, wants to calculate the exact temperature
required to achieve the constant hardness.
❑ Hollomon and Jaffe’s “tempering parameter” may be used for this purpose as it relates the
hardness, tempering temperature and tempering time. For a thermally activated process, the
usual rate equation is : Rate 1 −Q / RT

= = Ae
t
❑ Where, t is the time of tempering to develop a given hardness, and Q is the ‘empirical
activation energy’ . ‘Q’ is not constant in the complex tempering processes but varies with
hardness. Thus, hardness was assumed to be a function of time and temperature:
H = f [te−Q/ RT ]
❑ Interestingly, [te−Q / RT ] is a constant, and let it be t0. Equating activation energies of eq (1)

Q = T ln t − ln t0  = f (H )
and (2) gives,
❑ As t0 constant then

H = f T (C + ln t)
❑ Where, C is a constant, whose value depends on the composition of austenite. The single
parameter which expresses two variables time and the temperature i.e., T (C + ln t) is called
the Hollomon and Jaffe tempering parameter. (hardness in vickers is preferable)
163
Temperature and colours for Heating and Tempering of Steel

Colours of Hot Solid metal °C Process of Heat treatment

White 1500
Yellow white 1300 High speed steel hardening (1230-1300°C)
HEAT COLOURS

Yellow 1100
Orange Red 1000 Alloy steel hardening (800-1100°C)
Light-Cherry-Red 900
Cherry-red 800 Carbon steel hardening
Dark-red 700
Vary dark-red 500 High speed steel tempering (500-600°C)
Black red in dull light, or darkness 400
Steel gray 300 Carbon steel tempering (150-575°C)
Colour of Oxide film °C Parts Heat treated
Steel Gray 327 Cannot be used for cutting tools
TEMPER COLOURS

Pale-light blue 310 For springs

Purple 282 Spring and screw drivers
Brown 270 Axes, wood cutting tools
Gold 258 Shear blades, hammer faces, cold chisels
Dark-straw-light-brown 240 Punches and Dies
Light-Straw-Yellow 220 Steel cutting tools, files, paper cutters
164
 Embrittlement during Tempering
❑ Normally, as the tempering progresses, the hardness and the strength decreases, but the
ductility and impact strength increase. But in certain steels, there is an unexpected decrease
of the impact strength in certain ranges of temperatures. This indicates that there are two main
types of embrittlement during tempering.
➢ Tempered Martensite Embrittlement (TME)
➢ Temper Embrittlement
❑ Both these embrittlement raise the impact transition temperature (ITT) to higher temperature.
Figure (below) indicates the increase in impact transition temperature, Δ(ITT) due to TE in
SAE 3140 steel.

unembrittled
Temper-embrittlement in SAE 3140
embrittled
steel shifts the impact transition
temperature to higher temperature .
Δ(TTT) indicates the amount of
increase.

165
 Embrittlement during Tempering
❑ Normally, the degree of both type of embrittlement is expressed in terms of relative
displacements of ITT i.e., by Δ (ITT) illustrated in figure (in previous slide).
❑ In both the transgranular fracture mode is replaced by an intergranular (IG) mode below the
transition temperature, i.e., these show bright inter crystalline fracture along original austenite
grain boundaries.
❑ Inspite of these similar effects, the two types of embrittlement are two separate phenomena,
which occur in two different temperature ranges. Moreover, TME is a much faster process
usually occurring in one hour, where as TE takes many hours.
❑ Temper embrittlement is of mush greater concern from practical point of view, as the rotors
and shafts of power generating equipment even after tempering above 600°C, develop it when
thick section cool very slowly through the range (450-600°C)

Schematic illustration of effect of

tempering temperature on impact
strength in steels prone to
embrittlement during tempering.

166
 Tempered Martensite embrittlement
❑ As TME develops after tempering in range 260°C to 370°C, it is called as “350°C”
embrittlement, or 500°F embrittlement. It is called ‘one-step embrittlement’ as during heating
only in this range, TME develops. It is also called ‘irreversible embrittlement because a steel
embrittled by tempering in this range , if heated further to above 400°C (above the critical
range), becomes tougher, and the tempered martensite embrittlement does not occur again if
cooled down to or tempered in the range of 260°C to 370°C again.
❑ All steels, including the plain carbon steels are prone to irreversible embrittlement to some
extent, and that is why tempering range of 260°C- 370°C is avoided in all steels, though it is
a malady of low alloy steels.
❑ The embrittlement is associated with the change in the structure of carbide from epsilon (ε)
to cementite in the form of a film at the grain boundaries.
❑ On tempering at higher temperatures, this film disappears and can not be restored, on repeated
heating in 260°C-370°C temperature range.
❑ Although, tempered martensite embrittlement is concurrent with the precipitation of
cementite, but such precipitation is not in itself the cause of loss of impact toughness, as the
embrittlement is does not occur if P, Sb, Sn, As, or N are not present in steel.
❑ Addition of sufficient silicon to the steel inhibits the formation of cementite in the critical
range, as silicon dissolved in epsilon carbide, increases its stability, and thus embrittlement
does not occur
167
 Temper embrittlement
❑ The sickness of alloy steels occurs when they are tempered in the range 450°C to 600°C. it is
also called reversible embrittlement (as well as two step embrittlement), because it occurs,
when steels are tempered in this range, but gets removed, when heated to high temperatures,
but occurs again on slow continuous cooling through this range from that high temperature
(>600°C). The degree of embrittlement depends on the rate of cooling in the range 600-
450°C.
❑ The phenomena of temper embrittlement results in loss of toughness as measured by notched
impact test (without affecting very much the hardness, Y.S, UTS, elongation and fatigue
properties), and a rise in ductile to brittle transition temperature occurs, with an intergranular
(IG) fracture, below the transition temperature along the original austenitic grain boundaries.
❑ Carbon steels in general, but with less than 0.5% Mn, do not show temper embrittlement.
Alloy steels of high purity do not show it. It is caused primarily by Sb and P and secondarily
by Sn or As (even in amounts as low as 0.01%) in presence of elements like Ni, Mn, Cr, Si in
steels. The highest effect is in Ni-Cr and Mn-Cr steels. Presence of elements like Mo, Ti, Zr
delay, or remove embrittlement.
❑ The characteristic features of temper embrittlement are best explained by the concept of co-
segregation. The impurity solutes are the surface active elements in iron, i.e., these reduce the
grain boundary energy, and thus reduce the cohesion. Elements like Sb, P, As, Sn, interact
with certain elements like Ni and Mn in steels.
168
 Temper embrittlement
❑ These interactions leads to co-segregation of alloying elements and the impurity elements
such as between Ni-Sb, Ni-P-Ni-Sn and Mn-Sb. The reason of co-segregation is the stronger
interaction between them than, between either of these and iron.
❑ If the interaction is very strong then, co-segregation does not occur, but a scavenging effect
is got, as happens between Mo-P, Ti-P, which is the cause of elimination of embrittlement by
0.5% Mo in such steels. If larger amount of Mo, Ti, Zr are present , then these elements slowly
react with carbon to form stable carbides releasing the impurity atoms to segregate to the
boundaries.
❑ Additional segregation may take place, when two alloying elements are present
simultaneously, such as Ni and Cr. At high temperatures (>600°C), thermal vibrations make
the equilibrium segregation low enough not to cause embrittlement., and at lower temperature
(<450°C), the diffusion of the elements is too low to cause enough co- segregation with in the
normal tempering time.
❑ The following methods are normally recommended to minimize the effect of Temper
embrittlement
✓ Keep the impurities such as Sb, P, Sn, As as low as possible
✓ Alloy the steel with Mo (0.5-0.75%)
✓ Quench from tempering at higher temperatures
169
 Heat Treatment Defects
❑ Heat treatment of steels or aluminum can lead to several defects. The principal types of
defects found in quenching of steels are internal and external cracks in the work, distortion
and warping.
❑ CRACK : When the internal tensile stresses exceed the resistance of the steel to separation
the crack occurs. The insertion of the tools in the furnace without preheating for tempering is
one of the main causes of crack propagation. The crack formation is reduced by preheating
the tool between 2000Cto 3000C.
❑ DISTORTION : Distortion occurs due to uneven heating, too fast cooling, part incorrectly
supported in furnace, incorrect dipping in quenching and stresses present before preheating.
Distortion can be prevented by preheating the tool or check furnace capacity, reduce the
hardening temperature, and by reviewing the method of dipping.
❑ WARPING : Asymmetrical distortion of the work is often called warping in heat-treating
practice. Warping is usually observed upon non-uniform heating or over heating for
hardening. It also occurs when the work is quenched in the wrong position and when the
cooling rate is too high in the temperature range of the martensite transformation. An
elimination of these causes should subsequently reduce warping.
❑ The properties required in the heat treated part are obtained without the parts being distorted
beyond the acceptable limits.
❑ The ideal design for a heat treatable part is the shape that when heated (or cooled)would have the
same temperature at every point with in the part. 170