TRIBHUVAN UNIVERSITY

INSTITUTE OF ENGINEERING

COURSE MANUAL
ON

MATERIAL SCIENCE
(ME 501)

PREPARED BY
KHEM GYANWALI
DEPARTMENT OF MECHANICAL ENGINEERING
THAPATHALI CAMPUS, THAPATHALI
JULY, 2013

MATERIAL SCIENCE Khem Gyanwali

CONTENTS
CHAPTER 1 : INTRODUCTION TO MATERIALS………………………………………………………………………………3

CHAPTER 2 : ATOMIC STRUCTURE AND ARRANGEMENT OF ATOMS...............................................7

CHAPTER 3 : MECHANICAL PROPERTIES AND THEIR TESTS............................................................26

CHAPTER 4 : DEFORMING PROCESS OF MATERIALS.......................................................................46

CHAPTER 5 : SOLIDIFICATION, PHASE RELATIONS AND STRENGTHRNING MECHANISM ...............52

CHAPTER 6 : IRON-IRON CARBIDE DIAGRAM AND HEAT TREATMENT OF STEELS .........................67

CHAPTER 7 : TYPES OF STEELS AND CAST IRON..............................................................................88

CHAPTER 8 : ENVIRONMENTAL EFFECTS........................................................................................95

CHAPTER 9 : NON-FERROUS ALLOYS ..............................................................................................99

CHAPTER 10 : ORGANIC AND COMPOSITE MATERIALS ................................................................105

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 CHAPTER 1
INTRODUCTION TO MATERIALS
Material Science refers to the branch of applied science which is concerned with
investigating the relationship existing between the structures of materials and th eir
properties and their inter-disciplinary study of materials for practical purposes.

1.1 Types of Materials

In material science since we confine our attention to solid materials only so the subject is
related to solid-state physics and solid-solid chemistry. The engineering materials may be
classified as follows:
 Metals  Glasses
 Polymers  Composites
 Ceramics

Metals
Metals are elements that generally have good electrical and thermal conductivity. Many
metals have high strength, high stiffness, and have good ductility. Some metals, such as
iron, cobalt and nickel are magnetic. At extremely low temperatures, some metals and
inter-metallic compounds become superconductors.

Pure metals Metal alloys

Pure metals are elements which come Metal alloys contain more than one
from a particular area of the periodic metallic element. Their properties can be
table. Most pure metals are too soft, changed by changing the elements
brittle and/or chemically reactive. present in the alloy. Examples of metal
Examples of pure metals include copper in alloys include stainless steel which is an
electrical wires and aluminum in cooking alloy of iron, nickel, and chromium; and
foil and beverage cans. gold jewelry which usually contains an
alloy of gold and nickel.

The most important properties of metals include density, fracture toughness, strength and
plastic deformation. The atomic bonding of metals also affects their properties. In metals,
the outer valence electrons are shared among all atoms, and are free to travel everywher e.
Since electrons conduct heat and electricity, metals make good cooking pans and electrical
wires. Many metals and alloys have high densities and are used in applications which
require a high mass-to-volume ratio. Some metal alloys, such as those based on Aluminum,
have low densities and are used in aerospace applications for fuel economy. Many metal
alloys also have high fracture toughness, which means they can withstand impact and are
durable.

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Polymers
A polymer has a repeating structure, usually based on a carbon backbone. The repeating
structure results in large chainlike molecules. Polymers are useful because they are
lightweight, are corrosion resistant, are easy to process at low temperatures, and are
generally inexpensive. Some important characteristics of polymers include their size (or
molecular weight), softening and melting points, crystallinity, and structure. The
mechanical properties of polymers generally include low strength and high toughness.
Their strength is often improved using reinforced composite structures. One of the distinct
properties of polymers is that they are poor conductors of electricity and heat, which
makes them good insulators.

Ceramics
A ceramic is often broadly defined as any inorganic nonmetallic material. Examples of such
materials can be anything from NaCl (table salt) to clay (a complex silicate). Some of the
useful properties of ceramics and glasses include high melting temperature, low density,
high strength, stiffness, hardness; wear resistance, and corrosion resi stance. Many
ceramics are good electrical and thermal insulators. Some ceramics have special
properties: some ceramics are magnetic materials; some are piezoelectric materials; and
a few special ceramics are superconductors at very low temperatures. Ceramics and
glasses have one major drawback: they are brittle.

Glasses
A glass is an inorganic nonmetallic material that does not have a crystalline structure. Such
materials are said to be amorphous. Examples of glasses range from the soda-lime silicate
glass in soda bottles to the extremely high purity silica glass in optical fibres.

Composites
Composites are formed from two or more types of materials. Examples include
polymer/ceramic and metal/ceramic composites. Composites are used because overall
properties of the composites are superior to those of the individual components. For
example: polymer/ceramic composites have a greater modulus than the polymer
component, but aren't as brittle as ceramics.

1.2 Relationship among structures, processing and properties

The important properties of materials are:
Physical properties Chemical properties
Mechanical properties Magnetic properties
Electrical properties

The properties of all materials arise from their structure, i.e. from the manner in which
their atoms aggregate into hierarchies of molecular or crystalline order or into disordered
amorphous structures.

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 The properties of bulk matter of all kinds depend strongly on the nature and
distribution of imperfections, either chemical or architectural, in the main array.
 Most of the properties observed and exploited in materials are co-operative properties
of the aggregate rather than of the constituent atoms and
 The arrangements of outer electrons of the atoms are of primary importance, and
these are strongly modified by the configurations of neighboring ones.

1.3 Material Selection for Design

Material selection is a step in the process of designing any object (physical). In the context
of product design, the main goal of material selection is to minimize cost w hile meeting
product performance goals. Systematic selection of the best material for a given
application begins with properties and costs of candidate materials.
While selecting materials for manufacturing in the initial evaluation of materials
alternatives, many can be rejected on the basis of absolute product parameters such as
strength requirements achievable by the mechanical properties of the selected materials
conductivity by the thermal properties, density, melting point and specifications. Besides
product specifications materials also meet performance specifications. Performance
specifications delineate the basic functional requirements of the product and set out the
basic parameters from which the design can be developed. They are based on the need
the product is intended to satisfy and an evaluation of the likely risk and consequences of
failure.

The performance specification requirements are:

 Function: This is based on the thorough understanding of the product application, the
functions the product must perform in terms of mechanical, physical, electrical and
thermal properties of the material.
 Appearance: The material makes a major contribution to the aesthetics of product.
Compact, nicely shaped, attractive color products jump ahead in the market.
 Reliability : Reliability is gaining greater importance as a criterion for material selection
due to increasing consumer demand for trouble free products.
 Service Life: Larger the length of service life over which the material maintains its
desirable characteristics is important consideration.
 Environment : Environment effects, harmful are to be minimum to which the material is
exposed during the product life.
 Compatibility : When more than one type of material is used in a product or assembly,
material work harmoniously with each other.
 Producibility : The selection of material in relation to the ease of producibility of an item
is an important consideration.

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 Cost: Because cost is so important in selecting materials, it is logical to consider cost at
the outset of the materials selection process. A detailed cost comparison is not possible
at the concept of formulation stage, but it is often possible to set a target cost &
eliminate the materials that obviously are too expensive (e.g. Silver wire for transmiss ion
wire).

Engineering Requirements of Materials

It means that material must be expected to use successfully for making an engineering
components such as crankshaft, spanners etc. The main engineering requirements are as
follows:
 Fabrication Requirements : Material should be able to get shaped (e.g. cast, rolled,
forged) and joined (e.g. welded, brazed etc.) easily.
 Service Requirements: Selected materials must stand up to service demand e.g. proper
strength, wear and corrosion resistant.
 Economic Requirements: The engineering parts should be made with minimum overall
cost.

Steps for selection of materials

 Analysis of the material requirements.
 Screening the candidate materials.
 Selection of candidate material.
 Development of design data.

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 CHAPTER 2
ATOMIC STRUCTURE AND ARRANGEMENT OF ATOMS
2.1 Structure of atom, Periodic Table, Binding Energy and Bonds
All matter is considered to be composed of unit
substances known as chemical elements. These are the
smallest units that are distinguishable on the basis of
their chemical activity and physical properties. The
elements are composed of atoms which have distinct
structure characteristic of each element. The smallest
particle of an element which retains the distinct
structure characteristic of an element is called atom.
Each atom consists of a nucleus and electrons. Figure 2.1
shows the structure of an atom.
Figure 2.1: Structure of an atom
Central nucleus is surrounded by orbital electrons which move in concentric spherical
shells. The weight of the atom and its radioactive properties are associated with the
nucleus. The chemical properties and spectrum on the other hand depend on the planetary
electrons.

Atomic Mass Number

Atomic Mass Number (𝐴) = Number of electrons + Number of neutrons
Or, (𝐴) = Number of protons + Number of neutrons.
If we let 𝐴 = Atomic Mass Number, then
𝐴 = 𝑒 + 𝑛
𝐴 = 𝑝 + 𝑛
Where 𝑝 = Number of protons, 𝑛 = Number of neutrons and 𝑒 = Number of electrons

Atomic Number
Atomic Number (𝑍) = Number of electrons = Number of protons
𝑍 = 𝑒 = 𝑝
If we look at Iron as an example, the atomic number of iron is 26 (𝑍 = 26) and the atomic
mass number is 56 (𝐴 = 56).

Isotopes
Isotopes are the atoms of the same element that have different atomic mass numbers.
Isotopes of an element have the same atomic number but differ in their atomic mass
number because, even though they have the same number of electrons and protons
(electrically neutral), they differ in the number of neutrons. Example: Hydrogen.

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Periodic Table
A periodic table is a tabular display of the chemical elements, organized on the basis of
their atomic numbers, electron configurations, and recurring chemical properties.
Elements are presented in order of increasing atomic number (number of protons). The
standard form of the table comprises an 18-column-by-7-row main grid of elements, with
a double row of elements below. The rows of the table are called periods; the columns are
called groups.

Binding Energy
Binding energy is the mechanical energy required to disassemble a whole into separate
parts. A bound system typically has a lower potential energy than its constituent parts; this
is what keeps the system together—often this means that energy is released upon the
creation of a bound state. The usual convention is that this corresponds to a negative
binding energy.

Atomic Bonds
Primary Bonds: Primary bonds are the strongest bonds which hold atoms together. The
three types of primary bonds are:
 Metallic Bonds  Covalent Bonds  Ionic Bonds

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Secondary Bonds: Secondary bonds are much weaker than primary bonds. They often
provide a "weak link" for deformation or fracture. The examples for secondary bonds are:
 Hydrogen Bond  Van der Waals Bond

2.2 Atomic arrangements

2.2.1 Crystal and Amorphous Substances
All solid substances are either amorphous solids or crystalline solids. In amorphous solids,
the atoms are arranged chaotically i.e., the atoms are not arranged in a systematic order.
The common amorphous solids are wood, plastics, glass, paper, rubber etc. In crystalline
solids, the atoms making up the crystals arrange themselves in a definite and orderly
manner & form. All solid metals such as iron, copper, aluminum etc. are crystalline solids.
The definite and orderly manner & forms of atoms producing a geometrical shape in the
aggregate is called space lattice or crystal lattice.

2.2.2 Crystal Geometry

Crystalline structure is the normal form that metals assume when they are cooled below
their melting points.
To describe basic crystal structure seven different coordinate systems of reference axes
are required which are discussed below:
i) Cubic: All sides equal, all right angles. v) Monoclinic: No sides equal, one right
ii) Tetragonal: Two sides equal, all right angle.
angles. vi) Triclinic: No sides equal, no right angles
iii) Orthorhombic: No sides equal, all right angle.
angles. vii) Trigonal: All sides equal, two right angles.
iv) Hexagonal: Two sides equal, two right angles, one 120 degree angle.

Figure 2.2: Seven Crystal Structures

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2.2.3 Unit cell
A crystal is composed of unit cells. A unit cell contains the
smaller number of atoms, which when taken together
have all the properties of the crystals of the particular
metal. The unit cells are arranged like building blocks in a
crystal i.e. they have same orientation and their similar
faces are parallel.
A unit cell may also be defined as the smallest
parallelepiped which could be transposed in three co-
ordinate directions to build the space lattice.
Figure 2.3: Unit Cell
The space lattices of various substances differ in size and shape of their unit cells.

2.2.4 Lattices, points, directions, planes in a unit cell

Lattice: The three dimensional array formed by the unit cells of a crystal is called lattice.
If each atom in a lattice is replaced by a point; then each point is cal led a lattice point and
the arrangement of the points is referred to as the (three dimensional) lattice array. Thus
a space lattice is defined as an array of points in three dimensions in which every point has
surroundings identical to that every other point in the array. The distance between the
atom- points is called interatomic or lattice spacing. A space lattice is a conventional
geometrical basis by which crystal structures can be destroyed. Each point of a space lattice
has identical surroundings.
The majority of metals have one of three well-packed crystal structures:
Body-Centered Cubic (B.C.C.): In this type
of unit cell of crystal structure the atoms
are located at the corners of the cube and
one atom at its center. This type of unit cell
is found in metals like lithium, sodium,
potassium, barium, vanadium,
molybdenum, alpha-iron, tungsten,
chromium, manganese, tantalum etc.

Face-Centered Cubic (F.C.C.): In this type

of unit cell of crystal structure the atoms
are located at the corners of the cube and
one atom at the center of each face. This
type of unit cell is found in metals like
gamma-iron, aluminum, copper, lead,
silver, nickel, gold, platinum, calcium etc.

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Hexagonal Close Packed (H.C.P): In this
type of crystal structure, the unit cell has
an atom at each of the twelve corners of
the hexagonal prism, one atom at the
center of each of the two hexagonal faces
and three atoms in the body of the cell.
This type of unit cell is found in metals
like zinc, magnesium, cobalt, cadmium,
antimony, bismuth, beryllium, titanium,
zirconium etc.

Atomic Radius
Atomic radius is defined as half the distance between nearest neighbors in a crystal of a
pure element. It is possible to calculate the atomic radius by assuming that atoms are
spheres in contact in a crystal if the structure and the lattice parameters are known.

(i) Simple Cubic (S.C.) Structure

In this structure, atoms touch each other along the lattice.
Therefore, 𝑎 = 2𝑟
𝑎
∴ 𝐴𝑡𝑜𝑚𝑖𝑐 𝑟𝑎𝑑𝑖𝑢𝑠, 𝑟 =
2

(ii) Body Centered Cubic (B.C.C.) Structure

In this structure, the atoms touch each other along the
diagonal of the cube. Therefore, diagonal of the cube (AC) in
this case is 4r.
Also, 𝐴𝐶 = √𝐴𝐵2 + 𝐵𝐶 2
But, 𝐴𝐵 = √𝑎2 + 𝑎2 = 𝑎 √2
2
𝐴𝐶 = 4𝑟 = √(𝑎√2 ) + 𝑎2
𝑎 √3
∴ 𝐴𝑡𝑜𝑚𝑖𝑐 𝑟𝑎𝑑𝑖𝑢𝑠, 𝑟 =
4

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(iii) Face Centered Cubic (F.C.C.) Structure
In this structure, the atoms touch each other along the
diagonal of any face of the cube. The diagonal of the cube (AC)
is 4r.
Also, 𝐴𝐶 2 = 𝐴𝐵2 + 𝐵𝐶 2
𝑜𝑟, (4𝑟 )2 = 𝑎2 + 𝑎2
𝑜𝑟, 16𝑟 2 = 2𝑎 2
𝑎 √2
∴ 𝐴𝑡𝑜𝑚𝑖𝑐 𝑟𝑎𝑑𝑖𝑢𝑠, 𝑟 =
4

Number of atoms per unit cell

The number of atoms possessed in a unit cell can be calculated if the arrangement of atoms
inside the unit cell is known. For three types of cube crystal, the number of atoms can be
calculated as follows:

(i) Simple Cubic (S.C.) Structure

In this case, there are 8 atoms, one at each corner of the
cube and all of them are shared by adjoining or surrounding
cubes. Hence, the share of cube = 1/8 th of each corner atom.
1
∴ 𝑇𝑜𝑡𝑎𝑙 𝑛𝑜. 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 = × 8 = 1
8

(ii)Body Centered Cubic (B.C.C.) Structure

In this case, there are 8 atoms, one at each corner and are
shared by 8 surrounding cubes, plus one center atom at the
center of the cube.
1
∴ 𝑇𝑜𝑡𝑎𝑙 𝑛𝑜. 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 = × 8 + 1 = 2
8

(iii) Face Centered Cubic (F.C.C.) Structure

In this case, there are 8 atoms, one at each corner of
the cube plus 6 face centered atoms at 6 planes of the
cube. Each corner atom is shared by 8 surrounding
cubes, and each face centered atom is shared by two
surrounding cubes.
1 1
∴ 𝑇𝑜𝑡𝑎𝑙 𝑛𝑜. 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 = × 8 + × 6
8 2
= 1+3= 4

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Atomic Packing Factor (APF)
Atomic packing factor (also known as density of facing) is defined as the ratio of the volume
of atoms per unit cell to the total volume occupied by unit cell.

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑣

𝐴. 𝑃. 𝐹. = =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑉

(i) Simple Cubic (S.C.) Structure

Atoms per unit cell = 1
4𝜋𝑟 3
Volume of one atom,𝑣 = where 𝑟 is atomic radius.
3
𝜋𝑎3
Putting 𝑟 = 𝑎/2, we get: 𝑣 =
6
𝜋𝑎3
𝑣 6
∴ Atomic packing factor = = = 0.5238 ≈ 0.52
𝑉 𝑎3

(ii)Body Centered Cubic (B.C.C.) Structure

Atoms per unit cell = 2
4𝜋𝑟 3
Volume of 2 atoms,𝑣 =2× where 𝑟 is atomic radius.
3
𝜋𝑎3 √3
Putting 𝑟 = 𝑎 √3/4, we get: 𝑣 =
8
𝜋𝑎3 √3
𝑣 8
∴ Atomic packing factor = = = 0.68
𝑉 𝑎3

(iv) Face Centered Cubic (F.C.C.) Structure

Atoms per unit cell = 4
4𝜋𝑟 3
Volume of 4 atoms,𝑣 =4× where 𝑟 is atomic radius.
3
𝜋𝑎3 √2
Putting 𝑟 = 𝑎 √2/4, we get: 𝑣 =
6
𝜋𝑎3√2
𝑣 6
∴ Atomic packing factor = = = 0.74
𝑉 𝑎3

(v)Hexagonal Close Packed (H.C.P .) Structure

The unit cell contains one atom at each corner, one atom each at the center of the two
hexagonal faces and three atoms within the body of the cell. The atoms touch each
other along the edge of the hexagon. Thus, 𝑎 = 2𝑟 .

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 The top layer contains seven atoms. Each corner atom is shared by six surrounding
hexagon cells and the center atom is shared by two surrounding cell s. The three atoms
within the body of the cell are fully contributing to the cell.

∴ Total no. of atoms in a unit cell = 3/2 + 3/2 + 3 = 6

Calculation of c/a ratio for an ideal hexagonal close packed structure

Let c be the height of the unit cell and a be the edge of the unit cell.
𝑎√3
In ∆𝐿𝑀𝑃 , 𝐿𝑃 = 𝐿𝑀 cos 30° = 𝑎 cos 30° =
2

In ∆𝐿𝑄𝑆, 𝐿𝑆 2 = 𝐿𝑄 2 + 𝑄𝑆 2 ….. (i)

2 2 𝑎√3 𝑎
Here, 𝐿𝑄 = 𝐿𝑃 = × =
3 3 2 √3

Substituting the appropriate values in equation (i), we get:

2
𝑎 2 𝑐 2 𝑎2 𝑐 2
𝑎 =( ) +( ) = +
√3 2 3 4

𝑐2 2
𝑎2 2𝑎 2
𝑜𝑟, = 𝑎 − =
4 3 3
𝑐2 8
𝑜𝑟, =
𝑎2 3

𝑐 8
∴ =√
𝑎 3

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Volume of unit cell , 𝑉 = 𝐴𝑟𝑒𝑎 𝑜𝑓 𝑡ℎ𝑒 𝑏𝑎𝑠𝑒 × 𝐻𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑒𝑙𝑙

= 𝑆𝑖𝑥 𝑡𝑖𝑚𝑒𝑠 𝑡ℎ𝑒 𝑎𝑟𝑒𝑎 𝑜𝑓 ∆𝐿𝑂𝑀 × 𝑐

1 1 𝑎 √3
= 6 ( × 𝑂𝑀 × 𝐿𝑃) × 𝑐 = 6 ( × 𝑎 × )×𝑐
2 2 2

3√3 2
∴𝑉= 𝑎 𝑐
2
4
Volume of all the atoms in a unit cell, 𝑣 = 6 × 𝜋𝑟3
3

4 𝑎 3
𝑜𝑟, 𝑣 = 6 × 𝜋 ( ) = 𝜋𝑎 3
3 2
𝑣
∴ Atomic packing factor, A.P.F. =
𝑉
𝜋𝑎3
=
3√3 2
𝑎 𝑐
2
2𝜋 𝑎
= ×
3√3 𝑐

2𝜋 8
= ×√
3√3 3

= 0.74
Magnesium, Zinc and Cadmium crystallize in this structure.
The atomic packing facto of F.C.C and H.C.P is 74% and hence they are known as closest
packing structures.

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2.2.5 Millers’ Indices
Millers Indices is a system of notation of planes within a crystal of space lattice. They are
based on the intercepts of plane with the three crystal axes i.e. edges of the unit cell. The
intercepts are measured in terms of the edge lengths or dimensions of the unit cell which
are unit distances from the origin along three
axes.
The Miller indices of a given crystal plane is
determined as follows:
Step 1: Find the intercepts of the plane along
the axes a, b, c (The intercepts are measured as
multiples of the fundamental vector). i.e. 3, 2, 2
Step 2: Take reciprocals of the intercepts i.e.
1/3, 1/2, 1/2
Step 3: Convert into smallest integers in the
same ratio i.e. 2, 3, 3
Figure 2.4: Crystal Plane
Step 4: Enclose in parentheses i.e. (2 3 3)
The factor that results in converting the reciprocals of integers may be indicated outside
the brackets, but it is usually omitted.

In particular, a family of lattice planes is determined by three integers h, k, and ℓ, the Miller
indices. They are written (hkℓ), and each index denotes a plane orthogonal to a direction
(h, k, ℓ) in the basis of the reciprocal lattice vectors. By convention, negative integers are
written with a bar, as in 3 for −3. The integers are usually written in lowest terms, i.e. their
greatest common divisor should be 1. Miller index 100 represents a plane orthogonal to
direction h; index 010 represents a plane orthogonal to direction k, and index 001
represents a plane orthogonal to ℓ.
There are also several related notations:
 The notation {hkℓ} denotes the set of all planes that are equivalent to (hkℓ) by the
symmetry of the lattice.

In the context of crystal directions (not planes), the corresponding notations are:
 [hkℓ], with square instead of round brackets, denotes a direction in the basis of the
direct lattice vectors instead of the reciprocal lattice.
 Similarly, the notation ⟨hkℓ⟩ denotes the set of all directions that are equivalent to [hkℓ]
by symmetry.

Miller indices were introduced in 1839 by the British mineralogist William Hallowes Miller.
The method was also historically known as the Millerian system, and the indices as
Millerian, although this is now rare.

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2.2.6 Allotropic and Polymorphic T ransformation
Polymorphism is a physical phenomenon where a material may have more than one crystal
structure. A material that shows polymorphism exists in more than one type of space
lattice in the solid state. If the change in structure is reversible, then the polymorphic
change is known as allotropy. The prevailing crystal structure depends on both the
temperature and the external pressure.
One familiar example is found in carbon: Graphite is the stable polymorph at ambient
conditions whereas diamond is formed at extremely high pressures.
The best known example for allotropy is iron. When iron crystallizes at 2800 F it is B.C.C.
(delta-iron), at 2554 F the structure changes to F.C.C. (gamma-iron) and at 1670 F it again
becomes B.C.C. (alpha-iron).

Figure 2.5: Cooling curve for pure iron (Allotropic behavior of pure iron)

2.3 Imperfections in the Atomic Arrangement

2.3.1 Imperfections
The perfectly regular crystal structures that have been considered up to now are called
ideal crystals in which atoms are arranged in a regular way. In actual crystals, however,
imperfections or defects are always present and their nature and effects are very
important in understanding the properties of crystals. These imperfections affect the
properties of crystals such as mechanical strength, chemical reactions, electrical properties
etc. to a great extent. By controlling lattice imperfections we create stronger metals and
alloys, more powerful magnets, improved transistors and solar cells, glassware of striking
colors and many other materials of practical importance.
The crystallographic defects are classified as follows:
1. Point Imperfections 2. Line Imperfections 3. Surface Imperfections

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2.3.2 Point Defects, Surface Defects, Dislocations
2.3.2.1 Point Imperfections
These defects are localized disruptions of the lattice involving one or possibly several
atoms. Point defects disturb the perfect arrangement of the surroundings atoms. The
typical size of a point defect is one or two atomic diameters. Point imperfections are always
present in crystals and their presence results in a decrease in the free energy.
The point defects may be created by thermal fluctuations, quenching from higher
temperature, severe deformation of the crystal lattice e.g. hammering or rolling, external
bombardment by atoms or high-energy particle etc. The various types of point defects are
discussed below:
i) Vacancy: Vacancy is produced when an atom is missing from a normal lattice point.
These defects may come up as a result of imperfect packing during the original
crystallization. They may also arise from thermal vibrations of the atoms at high
temperatures.
ii) Interstitial Defect: An Interstitial defect is formed when an extra atom within a crystal
structure is inserted into the lattice structure at a site which is not a normal lattice point.
The addition of an extra atom is particularly due to low atomic packing factor. The vacancy
and interstitial defect are therefore, inverse phenomena.
iii) Substitution Defect: A substitution defect is introduced when a foreign atom substitutes
for a parent atom in the lattice as shown. The substitutional atom remains at the original
normal lattice point.
iv) Frenkel Defect: An ion dislodged from the lattice into an interstitial site is called Frenkel
defect. The interstitial and Frenkel defects are less in number than vacancies because
additional energy is required to force the atom into the new position.
v) Schottky Defect: Whenever a pair of positive and negative ions is missing from a crystal,
the defect caused is called Schottky defect. In such defect, the crystal is electrically neutral.

Figure 2.6: Point defects in a crystal

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2.3.2.2 Line Defects (Dislocations)
A linear disturbance of the atomic arrangement, which can move very easily on the slip
plane through the crystal, is known as dislocation. The dislocation may be caused during
growth of crystals from a melt or from a vapor or they may occur during a slip. It is
important to note that dislocations cannot end inside a crystal. They must end at a crystal
edge or other dislocations, or they must close back on themselves. Two basic types of
dislocations are:
i) Edge Dislocation: Whenever a half plane of atom is inserted between the planes of
atoms in a perfect crystal, the defect so produced is known as edge dislocation. The
imperfection may extend in a straight line all the way through the crystal or it may follow
an irregular path. The symbol ⊥ represents a positive edge dislocation and the symbol T
represents a negative edge dislocation.

Figure 2.7: The perfect crystal in (a) is cut and an extra half plane of atoms is inserted
(b) the bottom edge of the extra half plane is an edge dislocation (c) positive edge dislocation

ii) Screw Dislocation: Whenever the atoms are displaced in two separate planes
perpendicular to each other, the defect so produced is known as screw dislocation. Screw
dislocations can be produced by tearing of the crystal parallel to the slip direction. If a
screw dislocation is followed all the way around a complete circuit, it would show a slip
pattern similar to that of screw thread.

Figure 2.8: The perfect crystal (a) is cut and sheared one atom spacing, (b) and (c) the
line along which shearing occurs is a screw dislocation

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 Figure 2.9: Positive and
negative edge dislocation

Figure 2.10: Geometry of

edge and screw dislocation

2.3.2.3 Surface Imperfections

Surface defects are the two dimensional regions in a crystal. They arise from a change in
the stacking of atomic planes on or across a boundary.
i) External Defects: The external surface of the material is an imperfection itself, because
the atomic bonds do not extend beyond it. The surface atoms have neighbors on one side
only, while atoms inside the crystal have neighbors on either side of them. Since these
surface atoms are not entirely surrounded by others, they possess higher energy than
those of internal atoms.

ii) Internal Defects

a) Grain Boundaries: Grain boundaries are those imperfections which separate crystals or
grains of different orientation in polycrystalline aggregation during nucleation or
crystallization. The mismatch of the orientation of adjacent grain produces a less efficient
packing of atoms at the boundary. Thus, the atoms along the boundary have energy than
those within the grains.

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b) Twin Boundaries: A twin boundary is a special type of grain boundary across which there
is specific mirror lattice symmetry; i.e. atoms on one side of the boundary are located in
mirror-image positions of the atoms on the other side. Twin results from atomic
displacements that are produced from applied mechanical shear forces (mechanical turns)
and also during annealing heat treatments following deformation (annealing twins).
Annealing twins are typically found in crystals that have the F.C.C crystal structure, while
mechanical twins are observed in B.C.C and H.C.P metals.

c) Tilt Boundary: Tilt boundary in reality is a series of aligned dislocations which tend to
anchor dislocation movements normally contributing to plastic deformation. Little energy
is associated with this type of boundary.9841703427

d) Stacking Faults: It is a surface imperfection that arises from the stacking of one atomic
plane out of sequence on another while the lattice on either side of the fault is perfect.
Consider the stacking arrangement of plane in a F.C.C crystal: ….A CBACBACB…. If a C plane
is missing, the stacking sequence becomes ….ACBABACB…. The stacking in the missing
region is ….BABA…. which is H.C.P staking. This thin region is a surface imperfection and is
called stacking fault.

Figure 2.11: Grain Boundaries Figure 2.12: Twin Boundary

Figure 2.13: Tilt Boundary Figure 2.14: Stacking Fault

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2.3.3 Deformation by Slip and Twinning
Slip: Slip is defined as a shear deformation that moves atoms by many interatomic distance
in one crystal plane over the atoms of another crystal plane. By an external force, parts of
the crystal lattice glide along each other, resulting in a changed geometry of t he material.
Depending on the type of lattice, different slip systems are present in the material. The slip
planes are normally the planes with the highest density of atoms, i.e. those which are most
widely spaced, and the direction of the slip is the direction in the slip plane corresponding
to one of the shortest lattice translation vectors. Often this is the direction in which the
atoms are most closely spaced. A slip plane and a slip direction constitute a slip system. A
characteristic shear stress is required to initiate a slip. Slip is an important mode of
deformation mechanism in crystals. Slip induces plasticity in most of the metals.

Figure 2.15: Movement of a dislocation through a crystal

Twinning: Twinning is that process by which a portion of the crystal takes up an orientation
which makes that portion a mirror image of the parent crystal. Deformation by twinning is
most common in H.C.P metals and its effects on others are to move parts of the grains such
that they acquire favorable orientation for the slip to occur. Twinning is produced suddenly
and is accompanied with sound. The well-known cry of twin is the result of twinning. There
are three modes of formation of
twinned crystals. Growth twins are
the result of an interruption or change
in the lattice during formation or
growth due to a possible deformation
from a larger substituting ion.
Annealing or transformation twins are
the result of a change in crystal
system during cooling as one form
becomes unstable and the crystal
structure must re-organize or
transform into another more stable
form. Figure 2.16: (a) Slip Direction (b) Twinning Direction

Deformation or gliding twins are the result of stress on the crystal after the crystal has
formed. Deformation twinning is a common result of regional metamorphism.

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 Figure 2.17: Schematic diagram of Twinning in an F.C.C Lattice

Comparison between Slip and Twinning

Slip Twinning
1. It occurs in discrete multiples of atomic 1. Atom movements are much less than the
spacing. atomic spacing.
2. The orientation of the crystal above and 2. Orientation difference takes place across
below the slip plane is the same after the twin plane.
deformation as before.
3. It occurs over wide planes. 3. Every atomic plane is involved.
4. Slip begins when shearing stress on the 4. There is no critical resolved shear stress
slip plane in the slip direction reaches a for twinning.
threshold value called the critical resolved
shear stress.
5. It takes place in several milliseconds. 5. It takes place in a few micro-seconds.
6. Slip lines do not appear during any heat 6. Twin lines appear during the annealing
treatment. operation of materials.
7. Slip lines disappear after grinding or 7. Twin lines run through the whole depth
other surface finishing operations. of the material and hence do not disappear
on grinding etc.
8. Slip lines may be present in even or odd 8. Twin lines always occur in pairs.
numbers.

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2.3.4 Schmid’s Law
Schmid's law defines the relationship between shear stress, the applied stress, and the
orientation of the slip system. It is an equation for finding the stress in the slip plane given
an axial force and the angle of the slip plane. Schmid's law can help to explain the
differences in behavior of different metals when subjected to a unidirectional force.

Mathematically, Schmid’s law is given by:

𝝉𝒓 = 𝝈 𝐜𝐨𝐬 𝝍 𝐜𝐨𝐬 𝝀
Where, 𝐹 = Unidirectional force, 𝜆 = Angle defining slip direction relative to the force
𝐹𝑟 = Shear force 𝜓 = Angle defining the normal to the slip plane
𝐴 = Area of slip plane 𝜏𝑟 = Resolved shear stress in the slip direction
𝜎 = Unidirectional stress applied to the cylinder

The differences in behavior of metals that have different crystal structures can be
understood by examining the force required to initiate the slip process. Suppose a
unidirectional force F is applied to a cylinder of metal that is a single crystal as shown in
figure above:
The slip plane and slip direction to the applied force can be oriented by defining the angles
𝜆 and 𝜓. 𝜆 is the angle between the slip direction and the applied force, and 𝜓 is the angle
between the normal to the slip plane and the applied force.
In order for the dislocation to move in its slip system, a shear force acting in the slip
direction must be produced by the applied force. This resolved shear force 𝐹𝑟 is given by:
𝑭𝒓 = 𝑭 𝒄𝒐𝒔 𝝀
If the equation is divided by the area of the slip plane, 𝐴 = 𝐴𝑜 /𝑐𝑜𝑠 𝜓, Schmid's law is
obtained:
𝝉𝒓 = 𝝈 𝐜𝐨𝐬 𝝍 𝐜𝐨𝐬 𝝀
Where 𝜏𝑟 = 𝐹𝑟 𝐴 and 𝜎 = 𝐹𝐴𝑜

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2.4 Movement of Atoms in Materials
2.4.1 Fick’s First Law and Second Law
Fick's laws of diffusion describe diffusion and can be used to solve for the diffusion
coefficient, D. They were derived by Adolf Fick in the year 1855.

Fick's first law relates the diffusive flux to the concentration under the assumption of
steady state. It postulates that the flux goes from regions of high concentration to regions
of low concentration, with a magnitude that is proportional to the concentration gradient
(spatial derivative). In one dimension, the law is mathematically represented as:
𝝏∅
𝑱 = −𝑫
𝝏𝒙
Where
𝐽 is the "diffusion flux" [(amount of substance) per unit area per unit time], example
(mol./m2.s). It measures the amount of substance that will flow through a small area during
a small time interval.
𝐷 is the diffusion coefficient or diffusivity in dimensions of [length 2 time−1], example (m2/s)
∅ (for ideal mixtures) is the concentration in dimensions of [amount of substance per unit
volume], example (mol/m3)
𝑥 is the position [length](m)

Fick's second law predicts how diffusion causes the concentration to change with time.
Mathematically,
𝝏∅ 𝝏𝟐 ∅
=𝑫 𝟐
𝝏𝒙 𝝏𝒙
Where
∅ is the concentration in dimensions of [(amount of substance) length −3], (mol./m3)
𝑡 is time (s)
𝐷 is the diffusion coefficient in dimensions of [length2 time−1], (m2/s)
𝑥 is the position [length], (m)

Equations based on Fick's law have been commonly used to model transport processes in
foods, neurons, biopolymers, pharmaceuticals, porous soils, population dynamics, nuclear
materials, semiconductor doping process, etc. Theory of all volumetric methods is based
on solutions of Fick's equation.

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 CHAPTER 3
MECHANICAL PROPERTIES AND THEIR TESTS
The mechanical properties of metals are strength, elasticity, plasticity, ductility,
malleability, toughness, brittleness, hardness, fatigue and creep.
The factors affecting mechanical properties of a metal are grain size, temperature, heat
treatment and atmospheric exposure.

The materials are tested for one or more of the following purposes:
 To assess numerically the fundamental mechanical properties of ductility, malleability,
toughness etc.
 To check chemical composition.
 To determine the suitability of a material for a particular application.
 To determine data i.e. force deformation (or stress) values to draw up sets of
specifications upon which the engineer can base his design.
 To determine the surface or surface defects in raw materials or processed parts.

The tests on materials may be classified as:

1. Non-destructive Tests: In this type of test, the component does not break and so even
after being tested it can be used for the purpose for which it was made. E.g.
Radiography, ultrasonic, inspection etc.
2. Destructive Tests: In this type of test, the component or specimen either breaks or
remains no longer useful for further use. E.g. tensile test, impact test, torsion test etc.

3.1 Tensile Test

Tensile testing, also known as tension testing, is a fundamental materials science test in
which a sample is subjected to uniaxial tension until failure. The results from th e test are
commonly used to select a material for an application, for quality control, and to predict
how a material will react under other types of forces. Properties that are directly measured
via a tensile test are ultimate tensile strength, maximum elongation and reduction in area.
From these measurements the following properties can also be determined: Young's
modulus, Poisson's ratio, yield strength, and strain-hardening characteristics.

3.1.1 Load Deformation Diagrams

(Refer fig. 3.2)During tensile testing of a material sample, the stress-strain curve is a
graphical representation of the relationship between stress derived from measuring the
deformation of the sample, i.e. elongation, compression or distortion. The slope of stress -
strain curve at any point is called the tangent modulus; the slope of the elastic (linear)
portion of the curve is a property used to characterize materials & is known as the Young’s’
modulus. The area under the elastic portion of the curve is known as Modulus of resilience.

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3.1.2 Engineering Stress-Strain Diagram for Ductile and Brittle Materials
3.1.2.1 Ductile Materials
Low carbon steel generally exhibits a very linear stress–strain relationship up to a well-
defined yield point. The linear portion of the curve is the elas tic region and the slope is the
modulus of elasticity or Young's
Modulus. After the yield point,
the curve typically decreases
slightly. As deformation
continues, the stress increases on
account of strain hardening until
it reaches the ultimate strength.
Until this point, the cross-
sectional area decreases
uniformly because of Poisson
contractions. The actual rupture
point is in the same vertical line as
Figure 3.1: Stress-Strain curve for ductile material
the visual rupture point. (structural steel)
In figure 3.1,
1 – Ultimate Strength 5 – Necking region
2 – Yield strength 𝐴 – Apparent stress (𝐹/𝐴𝑜 )
3 – Rupture 𝐵 – Actual stress (𝐹/𝐴
4 – Strain hardening region

However, beyond this point a neck forms where the local cross -sectional area decreases
more quickly than the rest of the sample resulting in an increase in the true s tress as shown
in Fig. On an engineering stress–strain curve this is seen as a decrease in the apparent
stress. However, if the curve is plotted in terms of true stress and true strain the stress will
continue to rise until failure. Eventually the neck becomes unstable and the specimen
ruptures (fractures).

3.1.2.2 Brittle Materials

Brittle materials such as concrete or carbon fibre do not have a yield point, and do not
strain-harden. Therefore the ultimate strength and breaking strength are the same. A
typical stress-strain curve is shown in figure 3.2. Typical brittle materials like glass do not
show any plastic deformation but fail while the deformation is elastic. One of the
characteristics of a brittle failure is that the two broken parts can be reassembled t o
produce the same shape as the original component as there will not be a neck formation
like in the case of ductile materials.

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A typical stress strain curve for a brittle material will be linear. Testing of several identical
specimen, cast iron, or soil, tensile strength is negligible compared to the compressive
strength and it is assumed zero for many engineering applications.

Figure 3.2: Stress-Strain curve for Figure 3.3: Comparison of ductile and
brittle material brittle materials

3.1.3 True Stress-Strain Diagram

True stress-strain curve gives the true indication of deformation characteristics because it
is based on the instantaneous dimension of the specimen. The true stress -stain curve is
also known as flow curve.
In engineering stress-strain curve, stress drops down after necking since it is based on the
original area. In true stress-strain curve, the stress however increases after necking since
the cross sectional area of the specimen decreases rapidly after necking which can be seen
in the figure 3.1.

3.1.4 Properties tested from tensile test, temperature effects

The various properties connected with tensile test are given more elaborately in the
following parts. Refer figure 3.4 where:

1: True elastic limit 2: Proportionality limit

3: Elastic limit 4: Offset yield strength, usually defined at e=0.2%
𝜎: Engineering stress 𝜀: Engineering strain
𝐿: Un-deformed length 𝑙: Elongation
𝐴: Un-deformed cross-sectional area 𝐹: Uniaxial load

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 Figure 3.4: Stress-strain curve showing typical behavior of non-ferrous alloys

1. Modulus of Elasticity : Modulus of elasticity or Young’s modulus is the measure of

material stiffness (given by the slope of stress strain curve). Modulus of elasticity is
determined by the binding forces between atoms (structure intensive property). It is
slightly affected by alloying addition, heat treatment or cold work. Young’s modulus
decreases when there is increase in temperature.

2. True Elastic Limit: The lowest stress at which dislocations move. This definition is rarely
used, since dislocations move at very low stresses, and detecting such movement is very
difficult.

3. Proportionality Limit: It is the maximum stress at which stress remains directly

proportional to strain. The proportional limit is determined from the stress strain curve by
drawing straight line tangent at the origin and noting the first deviation of the plot from
the line.

4. Elastic Limit: The elastic limit is the maximum stress which the material can withstand
without causing permanent deformation which remains after removal of stress.

5. Yield Strength: The yield strength is the stress at which a material exhibits a specified
limiting permanent set. The tensile yield strength indicates resistance to permanent

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deformation by tensile loads. Because of this and the ease of its measurement the tensile
yield strength is used widely as a factor of design.

6. Yield Point: The yield point is the stress at which there first occurs a marked increase in
strain without an increase in stress.

7. Offset Yield Strength: The offset yield strength can be determined by the stress
corresponding to the intersection of the stress strain curve and a line parallel to elastic line
offset by a strain of 0.2 or 0.1% (e = 0.002 or 0.001). In Great Britain, the offset stress is
referred to proof stress either at 0.1 or 0.5% strain. It is used for design and specification
purposes to avoid the practical difficulties of measuring the elastic or proportional limit.

8. Tensile Strength (Ultimate or Maximum S trength): It is calculated by dividing the

maximum load carried by the specimen during a tension test by the original cross -sectional
area of the specimen. Tensile strength is widely used design factor, although there is more
justification for yield strength.

9. Rupture Strength: It is determined by dividing the load at the time of fracture by the
original cross-sectional area. If the rupture load is divided by the actual cross -section at the
time of fracture, the time rupture strength is obtained.

10. Resilience: Resilience is an ability of a material to absorb energy when elastically

deformed and to return it when unloaded. It is usually measured by modulus of resilience
(strain energy per unit volume required to stress the material from zero to yield stress. Coil
springs are examples of resilient materials.

11. Toughness: The toughness of a material refers to that material’s ability to absorb large
amounts of stress, deforming plastically before breaking. Polythene and steel are examples
of tough materials. On the other hand, brittle material, such as glass is elastic over a very
limited range of stresses and undergoes fracture without plastic deformation.

12. Ductility : It measures the amount of deformation that a material can withstand
without breaking. There are two ways of expressing ductility. First, we could measure the
distance the gage marks on our specimen before and after the test. The % elongation
describes the amount that the specimen stretches before fracture.
% Elongation = (𝐿𝑓 – 𝐿 𝑜 )/𝐿 𝑜 ∗ 100
Where, 𝐿𝑓 is the distance between the gage marks after the specimen breaks.

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A second approach is to measure the percent change in cross-sectional area at the point
of fracture before and after the test. This % reduction in area describes the amount of
thinning that the specimen undergoes during the test.
% Reduction in area = (𝐴𝑜 – 𝐴𝑓 )/𝐴𝑜 ∗ 100
Where, 𝐴𝑓 is the first cross-sectional area at the fracture surface.

Temperature strongly affects the stress-strain curve and the flow and fracture properties.
With the increase in temperature, strength of material decreases but the ductility
increases and vice-versa. Thermally activated processes assist deformation (dislocation
motion) and reduce strength at elevated temperatures. Structural changes can occur at
certain temperature ranges (high temp/ long term exposure) to alter the general behavior.

3.1.5 Brittle Behavior and Notch Effects

The behavior of materials can be broadly classified into two categories; brittle and ductile.
Glass and cast iron fall in the class of brittle materials. Brittle materials often have relatively
large Young's moduli and ultimate stresses in comparison to ductile materials. These
differences are a major consideration for design.
The sensitivity of metals and alloys to notch effects is termed as notch sensitivity. This
sensitivity is quantified through the ratio of notch strength to smooth bar tensile strength.
Metals or alloys that are notch sensitive have the ratio less than one. Smooth bar tensile
data for these materials are not satisfactory predictors of material behavior under servi ce
conditions. Tough, ductile metals or alloys frequently are notch-strengthened and have
notch sensitivity ratios greater than one, thus the standard tensile test is a conservative
predictor of performance for these materials.

3.2 Hardness Test

Hardness is the property of a material that enables it to resist plastic deformation, usually
by penetration. However, the term hardness may also refer to resistance to bending,
scratching, abrasion or cutting. Hardness is not an intrinsic material property dictated by
precise definitions in terms of fundamental units of mass, length and time. A hardness
property value is the result of a defined measurement procedure. Hardness tests can be
used for many engineering applications to achieve basic requirement of mechan ical
property. For examples: surface treatments where surface hardness has much been
improved, powder metallurgy, fabricated parts like forgings, rolled plates, extrusions,
machined parts.

3.2.1 Main Hardness Testing Methods

There are three general types of hardness measurements.
1. Scratch Hardness: A. Martens in 1890 defined scratch hardness or the load in grams
under which 90° diamond will produce a scratch 0.01 mm wide. According to Mohr’s test,

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iron and steel range in hardness from 4 to 9 depending upon t he heat treatment and the
alloy content. It is important to mineralogist and not suited for metals.
2. Indentation H ardness: This type of test is carried out in major engineering metals of
interest. This includes Brinell, Rockwell, Vickers, Meyer hardness tes t.
3. Rebound or Dynamic H ardness: The indenter is dropped onto the metal surface and
hardness is expressed as energy of impact. This test was carried out by A.F. shore in 1910.
In this test a steel cylinder hammer is dropped from a height of 25 cm. through a glass tube
on the surface to be tested. The height of the rebound is used as a measure of hardness of
surface. The surface to be tested should be smooth, free from oil and tube should be truly
vertical.
For practical and calibration reasons, each of these methods is divided into a range of
scales, defined by a combination of applied load and indenter geometry.

3.2.2.1 Brinell Hardness Test

J.A. Brinell introduced the first standardized indentation-
hardness test in 1900. The Brinell hardness test consists in
indenting the metal surface with a 10mm diameter steel
ball at a load range of 500-3000 kg, depending of hardness
of particular materials.
The load is applied for a standard time (30 seconds), and
the diameter of the indentation is measured giving an
average value of two readings of the diameter of the
indentation at right angle.
The Brinell hardness number (BHN or H B ) is expressed as
the load P divided by the surface area of the indentation.
P P
𝑩𝑯𝑵 = 𝜋𝐷 =
( ) (𝐷 − √𝐷 2 − 𝑑 2 ) πDt Figure 3.5: Brinell Hardness Test
2
Where, 𝑃 is applied load (kg), 𝐷 is diameter of ball (mm), 𝑑 is diameter of indentation (mm)
and 𝑡 is depth of impression (mm).

Advantages and Disadvantages of Brinell Hardness Test

 Large indentation averages out local heterogeneities of microstructure.
 Different loads are used to cover a wide range of hardness of commercial metals.
 Brinell hardness test is less influenced by surface scratches and roughness than other
hardness tests.
 The test has limitation on small specimens or in critically stressed parts where
indentation could be a possible site of failure.

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3.2.2.2 Rockwell Hardness Test
Rockwell hardness test is the most
widely used hardness test and
generally accepted due to its
speed, freedom from personal
error, ability to distinguish small
hardness difference and small size
indentation. The hardness is
measured according to the depth
of indentation under a constant
load. Figure 3.6: Rockwell Hardness Test

To carry out this test, firstly the surface area to be measured is positioned close to the
indenter and the minor load is applied and a zero reference position is established. The
major load is applied for a specified time period (dwell time) beyond zero and the major
load is released leaving behind the minor load applied.

The dial contains 100 divisions, each division representing a penetration of 0.002 mm. The
Rockwell number represents the difference in depth from the zero reference position as a
result of the applied major load and deeper the indentation, softer is the material.
Rockwell hardness number (RHN) can be represented in different scale A, B, C… depending
on types of indenters and major loads used. The scale is usable for materials from annealed
brass to cemented carbides. Other scales are available for special purposes.

The instructions for Rockwell hardness test are

listed below:
 Cleaned and well seated indenter and anvil.
 Surface which is clean and dry, smooth and free
from oxide.
 Flat surface, which is perpendicular to the
indenter.
 Cylindrical surface gives low readings, depending
on the curvature.
 Thickness should be 10 times higher
than the depth of the indenter.
 Loading speed should be standardized.
 The spacing between the indentations
should be 3 or 5 times the diameter of the
indentation. Figure 3.7: Rockwell Hardness Tester

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3.2.2.3 Vickers Hardness Test
Vickers hardness test uses a square-
base diamond pyramid as the indenter
with the included angle between
opposite faces of the pyramid of 136°.
The Vickers hardness number (VHN) is
defined as the load divided by the
surface area of the indentation.
𝜃
2𝑃𝑠𝑖𝑛 ( ) 1.854𝑃
𝑽𝑯𝑵 = 2 =
𝐿2 𝐿2
Where, Figure 3.8: Vickers Hardness Test
𝑃 is applied load, kg Specifications
𝐿 is the average length of diagonals, mm
𝜃 is the angle between the opposite faces of diamond = 136°
Vickers hardness test uses the loads ranging from 1-120kgf, applied for between 10 and 15
seconds. A fairly wide acceptance for research work should be provided because it
provides a continuous scale of hardness, for a given load. Since, VHN = 5 -1,500 can be
obtained at the same load level that makes ease for comparison.

3.2.2.4 Knoop Test

The Knoop indenter (diamond-shape) is
used for measuring in a small area, such as
at the cross section of the heat-treated
metal surface. The Knoop Hardness
Number (KHN) is the applied load divided
by the uncovered projected area of the
indentation.
P 𝑃
𝐊𝐇𝐍 = = 2
𝐴𝑃 𝐿 𝐶

Where 𝑃 = applied load, kg

𝐴𝑃 = uncovered projected area of
the indentation, mm2
𝐿 = length of long diagonal, mm
𝐶 = a constant for each indenter
supplied by manufacturer
Figure 3.9: Knoop Hardness Test
specifications

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3.2.3 Micro Hardness Test
Micro Hardness Testing of metals, composites and
ceramics are employed where a 'macro' hardness test is
not usable. Micro hardness tests can be used to provide
necessary data when measuring individual
microstructures within a larger matrix, or testing very
thin foil like materials, or when determining the
hardness gradient of a specimen along a cross section.

The term micro hardness testing usually refers to static

indentations made by loads of 1kgf or less. The Baby
Brinell Hardness Test uses a 1mm carbide ball, while the
Vickers Hardness Test employs a diamond with an apical
angle of 136°, and the Knoop Hardness Test uses a
narrow rhombus shaped diamond indenter. The test
surface usually must be highly polished. The smaller the
force applied, the higher the metallographic finish
Figure 3.10: Micro hardness
required. Tester

Microscopes with a magnification of around 500x are required to accurately measure the
indentations produced.

Hardness Conversion Table

Hardness conversions are empirical relationships for Brinell, Rockwell and Vickers hardness
values. These hardness conversions are applicable to heat-treated carbon and alloy steels
in many heat treatment conditions (or alloys with similar elastic modulus). For soft metals,
indentation of hardness depends on the strain hardening behavior of th e materials.
Hardness at elevated temperatures gives a good indication of potential usefulness of an
alloy for high-temperature strength applications. Hot hardness tester uses a Vickers
indenter made of sapphire and with provisions for testing in either vacuum or an inert
atmosphere. The temperature dependence of hardness could be expressed as follows;

𝐻 = 𝐴𝑒 −𝐵𝑇
Where
𝐻 = Hardness, kgf.mm2 𝑇 = Test temperature, K 𝐴, 𝐵 = constants

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3.3 Impact Test
3.3.1 Toughness
The toughness of a material refers to that material’s ability to absorb large amounts of
stress, deforming plastically before breaking or the ability to withstand occasional stresses
above the yield stress without fracture. It can be simply defined by the area under the
stress-strain curve (amount of work per unit volume that the material can withstand
without failure). Polythene and steel are examples of tough materials. The structural steel
although has a lower yield point but more ductile than high carbon spring steel. So,
structural steel is therefore tougher.
Toughness = Strength + Ductility

3.3.2 Types of Impact Test

Impact test is a method for determining behavior of material subjected to shock loading in
bending tension, or torsion. An impact test signifies toughness of mat erial that is ability of
material, to absorb energy during plastic deformation. The test measures the energy

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necessary to fracture a standard notch bar by applying an impulse load i.e. notch toughness
of material under shock loading.
The pendulum type impact testing machine is generally used for conducting notched bar
impact tests. The following type of impact tests are performed on this machine.
1. Izod Test 2. Charpy Test

1. Izod Test
The test uses a cantilever test piece of 10mm x 10mm section specimen having standard
45° notch 2 mm deep. This is broken by means of a swinging pendulum which is allowed
to fall from a certain height to cause an impact load on the specimen. This angle rise of the
pendulum after rupture of the specimen or energy to rupture the specimen is indicated on
the graduated scale by a pointer. The energy required to rupture the specimen is the
function of the angle of rise.

2. Charpy Test
This test is more common than Izod test and it uses simply supported test piece of 10mm
x 10mm section. The specimen is placed on supports or anvil so that the blow of str iker is
opposite to the notch.

Figure 3.11: Charpy Test

The energy used in rupturing the specimen in both Charpy and Izod tests is calculated as
follows:
Initial energy = 𝑊ℎ = 𝑊(𝑅 – 𝑅𝑐𝑜𝑠𝛼) = 𝑊𝑅 (1 – 𝑐𝑜𝑠𝛼)
Energy after rupture = 𝑊ℎ’ = 𝑊 (𝑅 – 𝑅𝑐𝑜𝑠𝛽) = 𝑊𝑅 (1 – 𝑐𝑜𝑠𝛽)
Energy used to rupture specimen
= 𝑊ℎ – 𝑊ℎ’ = 𝑊𝑅 [(1 − 𝑐𝑜𝑠𝛼) – (1 – 𝑐𝑜𝑠𝛽)] = 𝑊𝑅 (𝑐𝑜𝑠𝛽 – 𝑐𝑜𝑠𝛼)

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Where, ℎ = Height of fall of center of gravity of pendulum/striker
𝛼 = Angle of fall
ℎ’ = Height of rise of center of gravity of pendulum/striker
𝛽 = Angle of rise
𝑅 = Distance from C.G. of pendulum/striker to axis of rotation O.
𝑊 = Weight of pendulum/striker.
The principal advantage of the Charpy V-notch impact test is that it is a relatively simple
test that utilizes a relatively cheap, small test specimen. Tests can readily be carried out
over a range of sub ambient temperatures. Moreover, the design of the test specimen is
well suited for measuring differences in notch toughness in low-strength materials such as
structural steels. The test is used for comparing the influence of alloy studies and heat
treatment on notch toughness. It frequently is used for quality control and material
acceptance purposes.

3.3.3 Significance of Transition -Temperature Curve

The chief engineering use of the Charpy test is in selecting materials which are resistant to
brittle fracture by means of transition-temperature curves. The design philosophy is to
select a material which has sufficient notch toughness when subjected to severe service
conditions so that the load-carrying ability of the structural member can be calculated by
standard strength of materials methods without considering the fracture properties of the
material or stress concentration effects of cracks or flaws.
The transition-temperature behavior of a wide spectrum of materials falls into the three
categories. Medium- and low-strength F.C.C metals and most H.C.P metals have such high
notch toughness that brittle fracture is not a problem unless there is some special reactive
chemical environment. High-strength materials (S0 > E/150) have such low notch
toughness that brittle fracture can occur at nominal stresses in the elastic range at all
temperatures and strain rates when flaws ace present. High-strength steel, aluminum and
titanium alloys fall into this category. At low temperature fracture occurs by brittle
cleavage, while at higher temperatures fracture occurs by low-energy rupture. It is under
these conditions that fracture mechanics analysis is useful and appropriate. The notch
toughness of low- and medium-strength B.C.C metals, as well as Beryllium (Be), Zinc (Zn),
and ceramic materials is strongly dependent on temperature. At low temperature the
fracture occurs by cleavage while at high temperature the fracture occurs by ductile
rupture.
Thus, there is a transition from notch brittle to notch tough behavior with increasing
temperature. In metals this transition occurs at 0.1 to 0.2 of the absolute melting
temperature Tm, while in ceramics the transition occurs at about 0.5 to 0.7 T m. A well-
defined criterion is to base the transition temperature on the temperature at which the
fracture becomes 100 percent cleavage. This point is known as nil ductility temperature

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(NDT). The NDT is the temperature at which fracture initiates with essentially no prior
plastic deformation. Below the NDT the probability of ductile fracture is negligible.

Notch Sensitivity
It is a measure of the reduction in strength of a metal caused by the presence of a notch
or the extent to which the sensitivity of a material to fracture is increased by the presence
of a surface in homogeneity such as a notch, a sudden change in section, a crack, or a
scratch. Low notch sensitivity is usually associated with ductile materials, and high notch
sensitivity with brittle materials.

3.4 Fatigue Test

3.4.1 Fatigue Failure
In materials science, fatigue is the progressive and localized structural damage that occurs
when a material is subjected to cyclic loading. The nominal maximum stress values are less
than the ultimate tensile stress limit, and may be below the yield stress limit of the
material.
Fatigue occurs when a material is subjected to repeated loading and unloading. If the loads
are above a certain threshold, microscopic cracks will begin to form at the stress
concentrators such as the surface, persistent slip bands (PSBs), and grain interfaces.
Eventually a crack will reach a critical size, and the structure will suddenly fracture. The
shape of the structure will significantly affect the fatigue life; square holes or sharp corners
will lead to elevated local stresses where fatigue cracks can initiate. Round holes and
smooth transitions or fillets are therefore important to increase the fatigue strength of the
structure.

Types of Fatigue Loading

Alternating /Reversing Stress
In determining fatigue stress levels
using standard test equipment the
test specimens are subject to
alternative/reversed stress levels.
The cyclic stress varies from 𝜎𝑎 tensile
to 𝜎𝑎 compressive. The mean stress
is equal to zero. The fatigue strength
values for metals are based on this
loading condition with the published
fatigue strength values S' n,
representing the material fatigue strength property, being the 𝜎𝑎𝑚𝑝 value at failure.

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Repeated Stress
In the repeated stress loading condition the stress varies between zero and a maximum
tensile (or compressive) stress in a cyclic manner.

Combined Steady and Cyclic Stress

A stress condition normally experienced in practice is a cyclic stress imposed on a steady
load stress.

3.4.2 S-N Curve

A common method to measure the resistance to fatigue is the rotating cantilever beam
test. One end of a machined cylindrical specimen is mounted in a motor-driven chuck. A
weight is suspended from the other end.

Figure 3.12: Rotating beam fatigue testing machine

The specimen initially has tensile force acting on the top surface, while the bottom surface
is compressed. After the specimen turns 90 o, the locations that were originally in tension
are now in compression. Thus, the stress at any one point goes through a complete cycle
from zero stress to maximum tensile stress to zero stress to maximum compressive stress.

After sufficient number of cycles, the specimen may fail. Generally, a series of specimens
are tested at different applied stresses and the stress plotted versus the number of cycles
at a particular stress and the endurance limit for the material. The fatigue life tells us how
long a component survives when a stress is repeatedly applied to the material.

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 Figure 3.13: (a) S-N Curve, Steel and stainless steel (b) S-N curve, Aluminum

If we are designing a tool steel part that must undergo 100,000 cycles during its lifetime,
then the part must be designed so that the applied stress is lower than 90,000 psi. The
endurance limit is stress below which failure by fatigue never occurs. To prevent the tool
steep part from failing, we must be sure that the applied stress is below 60,000 psi.

Fatigue Strength versus Fatigue Limit

The American Society for Testing and Materials (ASTM) defines fatigue strength (SNf), as
the value of stress at which failure occurs after Nf cycles, and fatigue limit (Sf), as the
limiting value of stress at which failure occurs as N f becomes very large. ASTM does not
define endurance limit, the stress value below which the material will withstand many load
cycles, but implies that it is similar to fatigue limit.

3.4.3 Preventions
The most effective method of improving fatigue performance is improvements in design:
 Eliminate or reduce stress raisers by streamlining the part.
 Avoid sharp surface tears resulting from punching, stamping, shearing, or other
processes.
 Prevent the development of surface discontinuities during processing.
 Reduce or eliminate tensile residual stresses caused by manufacturing.
 Improve the details of fabrication and fastening procedures.

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3.5 Creep Test
Creep is the slow plastic deformation of metals under constant stresses or under prolonged
loading usually at high temperature. It can take place and lead to fracture at static stresses
much smaller than those which will break the specimen by loading it quickly. Creep is
especially taken care of while designing I.C. engines, boilers and turbines.

Figure 3.14: Schematic of Creep Test

The installation for creep test is shown in figure 3.9. The specimen to be tested is placed
in the electric furnace where it is heated to a given temperature and is constantly subjected
to a load. The strain variations are measured with strain gauges. The plot of strain with
time, i.e. the creep curve will be as shown in figure 3.10.

Figure 3.15: Creep Rupture Curve

The creep curve can be studied in the following three stages:
(i) Primary Creep: This is the initial part of the curve. In this part, the curve indicates rapid
extension of the specimen. This part of the curve helps us in providing proper clearances
in the various components of machines. Primary creep represents a transient stage in

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which the resistance of the metal increases due to its own deformation. It forms part of
the total extension reached in a given time affecting clearance.
(ii)Secondary Creep: This state of the curve indicates the period of extension which the
creep occurs at a more or less constant rate having its minimum creep rate. Secondary
creep is the result of balance between processes of strain hardening and recovery. It is the
important part of the curve and covers the whole of estimated service life of the alloy.
(iii) Tertiary Creep: In this stage, the rate of extension or strain rate accelerates, rapidly
leading to rupture finally. In this stage, the uses of alloys should be avoided. Tertiary creep
is considered to be due to necking.

3.5.1 Creep Failure

Creep is more severe in materials that are subjected to heat for long periods, and near
melting point. Creep always increases with temperature. Boilers, gas turbine engines, and
ovens are some of the systems that have components that experience creep. An
understanding of high temperature materials behavior is beneficial in evaluating failures in
these types of systems.
The rate of this deformation is a function of the material properties, exposure time,
exposure temperature and the applied structural load. Depending on the magnitude of the
applied stress and its duration, the deformation may become so large that a component
can no longer perform its function - for example creep of a turbine blade will cause the
blade to contact the casing, resulting in the failure of the blade. Creep is usually of concern
to engineers and metallurgists when evaluating components that operate under high
stresses or high temperatures.

Creep is a deformation mechanism that may or may not constitute a failure mode.
Moderate creep in concrete is sometimes welcomed because it relieves tensile stresses
that might otherwise lead to cracking.
The temperature range in which creep deformation may occur differs in various materials.
For example, tungsten requires a temperature in the thousands of degrees before creep
deformation can occur while ice will creep near 0 °C (32 °F).

3.5.2 Creep and Stress Rupture Curve

If we apply a stress to a material at a high temperature the material may stretch and
eventually fail, even though the applied stress is less than the yield strength at that temp.
Plastic deformation at high temperature is known as creep. To determine the creep
characteristics of a material a constant stress is applied to a cylindrical speci men placed in
a furnace. As soon as stress is applied, the specimen elastically elongates a small amount
E0 depending on the applied stress and the modulus of elasticity of a material at the high
temperature.

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In the initial stage, or primary creep, the strain rate is relatively high, but slows with
increasing time. This is due to work hardening. The strain rate eventually reaches a
minimum and becomes near constant. This is due to the balance between work hardening
and annealing (thermal softening). This stage is known as secondary or steady-state creep.
This stage is the most understood. The characterized "creep strain rate" typically refers to
the rate in this secondary stage. Stress dependence of this rate depends on the creep
mechanism. In tertiary creep, the strain rate exponentially increases with stress because
of necking phenomena.

3.5.3 Effect of temperature and stress level on creep life

Figure 3.16: Effect of temperature or applied stress on creep curve

As the temperature or the applied stress increases, the creep curve shifts upwards and the
time duration of the various stages reduces significantly as shown in figure 3.11. This
indicates that the value of creep increases with the increase in temperature as well as
stress. Therefore, the materials to be used at a high temperature must have high mel ting
point.
Since all mechanisms of steady-state creep are in some way dependent on diffusion, we
expect that creep rate will have this exponential dependence on temperature:

𝜀̇ ∝ 𝑒𝑥𝑝( −𝑄/𝑅𝑇)
Where 𝑄 is the amount of heat due to absolute temperature 𝑇 and 𝑅 is universal gas
constant.
Creep occurs faster at higher temperatures. However, what constitutes a high temperature
is different for different metals.
The applied stress provides a driving force for dislocation movement and diffusion of
atoms. As the stress is increased, the rate of deformation also increases.

In general, it is found that 𝜀̇ = 𝜎 𝑛 , where 𝑛 is the stress exponent.

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3.5.3 Preventions

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 CHAPTER 4
DEFORMING PROCESS OF MATERIALS
4.1 Cold Work
4.1.1 Cold Work and its types
A metal is said to be cold worked, if it is mechanically processed below the recrystallization
temperature of the metal and its grains are in a distorted condition after plastic
deformation is completed. Cold working produces an improved surface finish and closer
dimensional tolerance and because of this characteristic cold working process is generally
used in making end-use products. Since, recrystallization does not take place in cold
working, the grains are permanently distorted. During cold working residual st resses are
set up. As their presence is undesirable a suitable heat treatment is generally necessary to
neutralize these stresses and restore the metal to its original structure.
All the properties of a metal that are dependent on the lattice structure are affected by
plastic deformation or cold working. The following properties are affected by cold work
significantly:
 Tensile Strength  Yield Strength  Work Hardening
 Hardness  Ductility
The various cold working operations are:
 Drawing: Drawing is an operation in which the cross-section of a bar, rod or a wire is
reduced by pulling it through a die opening. Although the presence of tensile stresses is
obvious in drawing, compressive stress also plays a significant role because the metal is
squeezed down as it passes through the die opening.
 Bending: Bending is a sheet-metal operation which is defined as the straining of the
metal around a straight axis. During bending, the metal on the inside of the neutral plane
is compressed, while the metal on the outside of the neutral plane is stretched.
 Shearing: Shearing is a sheet-metal cutting operation along a straight line between two
cutting edges. Shearing is typically used to cut large sheets into smaller sections for
subsequent press-working operations.
 Hobbing: Hobbing is a deformation process in which a hardened steel form is pressed
into a soft steel (or other soft metal) block. The process is often is used to make mold
cavities for plastic molding and die casting. The hardened steel form is called the hob.
 Peening: Peening is the process of working a metal's surface to improve its material
properties, usually by mechanical means such as hammer blows, by blasting with shot (shot
peening), or blasts of light beams with laser peening.
 Cold Extrusion: Extrusion is a compression forming process in which the work metal is
forced to flow through a die opening to produce a desired cross -sectional shape. The
process can be likened to squeezing toothpaste out of a toothpaste tube. Cold extrusion is
done at room temperature or near room temperature.

MATERIAL SCIENCE 46 Khem Gyanwali

4.1.2 Strain Hardening and the Stress Strain Curve
Work (or strain) hardening is a phenomenon which results in an increase in hardening and
strength of a metal (specimen) subjected to plastic deformation at temperature lo wer than
the recrystallization range (cold working). When a material is subjected to plastic
deformation, a certain amount of work done on it is stored internally as strain energy. This
additional energy in a crystal results in strengthening or work hardening of solids. Thus
work hardening may be defined as increased hardness accompanying plastic deformation.
This increase in hardening is accompanied by an increase in both tensile and yield strength.
Work hardening reduces ductility and plasticity. It is used in many manufacturing processes
such as rolling of bars and drawing of tubes.

Tensile strength, yield strength and hardness are increased, while ductility is decreased.
Although both strength and hardness increase, the rate of change is not the same.
Hardness generally increases most rapidly in the first 10 percent reduction (cold work),
whereas the tensile strength increases more or less linearly. The yield strength increases
more rapidly than the tensile strength, so that, as the amount of plastic deformation is
increased, the gap between the yield and tensile strengths decreases. This is important in
certain forming operations where appreciable deformation is required.
In drawing, for example, the load must be above the yield point to obtain appreciable
deformation but below the tensile strength to avoid failure. If the gap is narrow, very close
control of the load is required.

Ductility follows a path opposite to that of hardness. A large decrease in the first 10 percent
reduction and then a decrease at a slower rate is observed. Distortion of the lattice
structure hinders the passage of electrons and decreases electrical conductivity in alloys.
The increase in internal energy, particularly at the grain boundaries, makes the material
more susceptible to inter granular corrosion, thereby reducing its corrosion resistance.
Known as stress corrosion, this is an acceleration of corrosion in certain environments due
to residual stresses resulting from cold working. One of the ways to avoid stress corrosion
cracking is to relieve the internal stresses by suitable heat treatment after cold working
and before placing the material in service.

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4.2 Treatment after Cold Work
4.2.1 Annealing
As a result of cold working, the hardness, tensile strength, and electrical resistance
increase, while ductility decreases. There is also a large increase in the number of
dislocations, and certain planes in the crystal structure are severely distorted. Most of the
energy used to cold work the metal is dissipated in heat, and a finite amount of energy is
stored in the crystal structure as internal energy associated with the lattice defects created
by the deformation.

Figure 4.1: Effect of annealing on tensile strength, hardness, ductility and gr ain size

Full annealing is the process by which the distorted cold worked lattice structure is changed
back to one which is strain free through the application of heat. This process is carried out
entirely in the solid state and is usually followed by slow cooling in the furnace from the
desired temperature. The annealing process may be divided into three stages:
 Recovery  Recrystallization  Grain Growth

Recovery
This is primarily a low temperature process, and the property changes produced do not
cause appreciable change in microstructure or the properties, such as tensile strength,
yield strength, hardness and ductility. The principal effect of recovery is the relief of
internal stresses due to cold working.

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When the load which causes plastic deformation is released, all the elastic deformation
does not disappear. This is due to the different orientation of crystals, which will not allow
some of them to move back when the load is released. As the temperature is increased,
there is some spring back of these elastically displaced atoms which relieve most of the
internal stresses. Electrical conductivity is also increased appreciably during the recovery
stage.

Since the mechanical properties of the metal are essentially unchanged, the main purpose
of heating in the recovery range is stress relieving cold worked alloys to prevent stress
corrosion cracking or to minimize the distortion produced by residual stresses.
Commercially, this low temperature treatment in the recovery range is known as stress
relief annealing or process annealing.

Recrystallization
As the temperature of the recovery range is reached, minute new crystals appear in the
microstructure. These new crystals have the same composition and lattice structure as the
original un-deformed grains and are not elongated but are uniform in dimensions. The new
crystals generally appear at the most drastically deformed portions of the grain, usually
the grain boundaries and slip planes. The cluster of atoms from which the new grains are
formed is called a nucleus. Recrystallization takes place by a combination of nucleation of
strain free grains and the growth of these nuclei to absorb the entire cold worked material.

Pure metals have low recrystallization temperatures as compared with alloys. Zinc, tin and
lead have recrystallization temperatures below room temperature. This means that these
metals cannot be cold worked at room temperature since they crystallize spontaneously,
reforming a strain free structure.

The greater the prior deformation, the lower the temperature for the start of
recrystallization. Increasing the annealing time decreases the recrystallization temperature
for the start of recrystallization. During recrystallization stage, there is a significant drop in
tensile strength, hardness and a large increase in the ductility of the material.

Grain Growth
In this stage the tensile strength and hardness continue to decrease but at a much less
rate than the recrystallization stage. The major change observed during this stage is the
growth of the grain boundaries and reaching the original grain size.

4.3 Hot Work

4.3.1 Hot-Work Process and its types
Hot working refers to processes where metals are plastically deformed above their
recrystallization temperature. Being above the recrystallization temperature allows the

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material to recrystallizes during deformation. This is important because recrystallization
keeps the materials from strain hardening, which ultimately keeps the yield strength and
hardness low and ductility high. This contrasts with cold working. Hot working process can
be considered as simultaneous combination of cold working and annealing. Any wo rk
hardening effect caused by plastic deformation is neutralized immediately by the effect of
high temperature.

The various hot working operations are:

 Rolling: Rolling is a deformation process in which the thickness of the work is reduced
by compressive forces exerted by two opposing rolls. The rolls rotate in opposite directions
to pull and simultaneously squeeze the work between them.
 Forging: Forging is a deformation process in which the work is compressed between two
dies, using either impact or gradual pressure to form the part. A forging machine that
applies impact an impact load is called a forging hammer, while one that applies gradual
pressure is called a forging press.
 Pipe Welding: Pipe welding is the process of connecting metal pipes by heating them
and joining them together.
 Rotary piercing: Rotary piercing is a hot working metal-working process for forming
thick-walled seamless tubing. The process starts by feeding a blank in between the
opposing rolls. Then, the rolls push the blank over the mandrel to form a uniform inner
diameter of the tubing.
 Hot Extruding: Hot extrusion is a hot working process, which means it is done above the
material's recrystallization temperature to keep the material from work hardening and to
make it easier to push the material through the die. Most hot extrusions are done on
horizontal hydraulic presses.

Advantages and Disadvantages

The advantages of hot-working operations are:

1. Decrease in yield strength, therefore it is easier to work and uses less energy or force.
2. Increase in ductility.
3. Elevated temperatures increase diffusion which can remove or reduce chemical in
homogeneities.
4. Pores may reduce in size or close completely during deformation.
5. In steel, the weak, ductile, face-centered cubic austenite microstructure is deformed
instead of the strong body-centered cubic ferrite microstructure found at lower
temperatures.

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The disadvantages of hot-working operations are:
1. Undesirable reactions between the metal and the surrounding atmosphere (scaling
or rapid oxidation of the work-piece).
2. Less precise tolerances due to thermal contraction and warping from uneven cooling.
3. Grain structure may vary throughout the metal for various reasons.
4. Requires a heating unit of some kind such as a gas or diesel furnace or an induction
heater, which can be very expensive.

4.3.2 Comparison between Cold Working and Hot Working

Cold Working Hot working

1. Cold working is done at a temperature 1. Hot working is done at a temperature

below the value required for above recrystallization temperature, so it
recrystallization, so no appreciable can be regarded as a simultaneous
recovery takes place during deformation. occurrence of deformation and recovery
process.

2. Hardening is not eliminated as working 2. Hardening due to plastic deformation is

is done at a temperature below completely eliminated by recovery and
recrystallization, so it is always recrystallization. This is true, however, only
accompanied by strain hardening. if the rate of crystallization is higher than
rate of deformation.

3. Cold working decreases the value of 3. Mechanical properties like elongation,

elongation, reduction area and impact reduction of area and impact values are
values. improved.

4. Embrittlement does not occur due to 4. Reactive metals get severely embrittled
less diffusion and no reaction of oxygen at by oxygen and hence must be protected
lower temperature. from the action of oxygen by using inert
atmosphere.

5. Surface decarburization in steels does 5. Surface decarburization is likely to occur

not occur. at higher temperatures unless protected by
a proper atmosphere.

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 CHAPTER 5
SOLIDIFICATION, PHASE RELATIONS AND STRENGTHENING MECHANISM
5.1 Solidification
Solidification is a phase change in which a liquid turns into a solid when its temp is lowered
below its freezing point. Almost all metals and alloys, at one point in their processing are a
liquid, when then solidifies as it cools below the freezing temperature the material can be
used in the as-solidified condition or may be further processed by mechanical working or
heat treatment. The structures produced during solidification affect the mechanical
properties and influence the type of further processing needed to achieve the final
properties. In pure metals, the grain size and shape may be controlled by solidification.

5.1.1 Nucleation and Grain Growth

Solidification requires two steps- nucleation and
growth. Nucleation occurs when a small piece of solid
forms from the liquid. Growth of solid occurs as
atoms from the liquid are attached to the tiny solid
until no liquid remains. We expect a material to
solidify when the liquid cools below the freezing
temperature. As the temperature falls below the
freezing temperature, the energy associated with the
crystalline structure of solid is increasingly less than
the energy of the liquid, making the solid more and
more stable. However when the solid forms, an
interface is created, separating the solid from the
liquid; an increase in energy is associated with this Figure 5.1: Free energy versus
interface. temperature plot for a pure metal

The total change in free energy produced when

the solid forms is the sum of the decrease in
volume free energy and the increase in surface
free energy.

Change in free energy in solid-liquid interface,

4
∆𝐺 = 𝜋𝑟3 ∆𝑔 + 4𝜋𝑟2 𝜎
3
2𝜎
Spontaneous growth above radius, 𝑟 ∗ =
∆𝑆𝑓 ∆𝑇
16𝜋𝜎3
Activation energy, ∆𝐺 =
3∆𝑆𝑓 2 (∆𝑇) 2

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The total change in the free energy depends on the size of the solid. The growth of a very
small solid particle, called an embryo, requires an increase in free energy. Instead of
growing, the embryo re-melts; causing the free energy to decrease, and the metal remains
liquid.
Since the liquid is present below the equilibrium freezing temperature, it is under -cooled.
The under-cooling is the equilibrium freezing temperature minus the actual temp of the
liquid. Nucleation has not occurred and growth cannot begin, even though the
temperature is below the equilibrium freezing temperature.
When a large solid particle grows, the free energy decreases. The solid is now stable,
nucleation has occurred, and growth of solid particle, which is now called a nucleus, begins.
Nucleation only occurs when enough atoms spontaneously cluster together to produce a
solid with a radius greater than the critical radius 𝑟 ∗ , corresponding to a maximum on the
total free energy curve.

Homogenous Nucleation
As the liquid cools further below the equilibrium freezing temp, there is a greater
probability that atoms will cluster together to form an embryo larger than the crit ical
radius. In addition, there is a large volume free energy difference between the liquid and
the solid, which reduces the critical size of the nucleus. Homogenous nucleation occurs
when the under-cooling becomes large enough to permit the embryo to exceed the critical
size. As the under-cooling increases, the critical radius required for the nucleation
decreases.
As an approximation, homogenous nucleation occurs when 𝜕𝑇 = 0.2𝑇𝑚
where, 𝑇𝑚 = Equilibrium freezing temperature in K.
𝜕𝑇 = 𝑇𝑚 – 𝑇 is the under-cooling when the liquid temp is T.

5.1.2 Crystal Growth/ Dendrite Formation

Once solid nuclei have formed, growth
occurs as atoms are attached to the solid
surface. In pure metals, growth depends
on how heat is removed from the solid-
liquid system. Two types of heat must be
removed – the specific heat of the liquid
and the latent heat of fusion. The
specific heat must be removed first,
usually by conduction into the
surrounding mold, until the liquid cools
to the freezing temp. The latent heat of
fusion, which represents the energy that
is evolved as the disordered liquid
structure Figure 5.2: Formation of protuberance

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transforms to a more stable crystal structure, must be removed from the solid-liquid
interface before solidification is completed. The manner in which we remove the latent
heat of fusion determines the growth mechanism and final structure.
When a well-inoculated liquid cools slowly under equilibrium conditions, the temp of the
liquid metal is greater than the freezing temp. The latent heat of fusion can only be
removed by conduction from the solid-liquid interface through the solid to the
surroundings.
Any small protuberance (refer fig. 5.2), that begins to grow on the interface is surrounded
by liquid metal above the freezing temperature. This means that the formation of
protuberance begins when the liquid temperature is above the freezing temperature. The
mechanism, known as planar growth, occurs by the movement of a smooth solid-liquid
interface into the liquid.

However, when nucleation is poor, the

liquid may under-cool to a temp below
the freezing temp. Under these
conditions, a small solid protuberance
called a dendrite, which forms at the
interface, is encouraged to grow. As the
solid dendrite grows, the latent heat of
fusion is conducted into the under-cooled
liquid, raising the temp of the liquid
towards the freezing temp. Secondary
and tertiary dendrite arms can also form
on the primary stalks to speed the
evolution of the latent heat. Dendritic
growth continues until the under-cooled
liquid warms to the freezing temp. Any
remaining liquid then solidifies by planar
growth. Figure 5.3: Dendrite formation
In pure metals, dendritic growth normally represents only a small fraction o f the total
growth.

5.1.3 Cooling curve

A cooling curve is a line graph that represents the change of phase of matter, typically from
a gas to a solid or a liquid to a solid. The independent variable (X-axis) is time and the
dependent variable (Y-axis) is temperature. Below is an example of a cooling curve used in
castings.
The initial point of the graph is the starting temperature of the matter, here noted as the
pouring temperature. When the phase change occurs there is a thermal arrest, i.e. the
temperature stays constant. This is because the matter has more internal energy as a liquid

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or gas than in the state that it is cooling to. The amount of energy required for a phase
change is known as latent heat. The cooling rate is the slope of the cooling curve at any
point.

Figure 5.4: Cooling Curve

In the part of the curve where the temperature decreases, the kinetic energy also
decreases while the potential energy stays the same. However, at the phase transition,
where the curve is flat, the kinetic energy stays the same while the potential energy
decreases.

5.1.4 Cast Metal Structure

Figure below summaries four of the dozens of casting processes. The processes are divided
into several groups – sand molds, ceramics molds and metal molds. The process using
metal molds tend to give the highest strength castings due to rapid solidification. Ceramics
molds, because they are good insulators, give the slowest cooling and lowest strength
changes.
a) Green Sand molding in which clay-bonded sand is packed around a pattern. Sand
cores can produce internal cavities in the casting.
b) The permanent mold process in which metal is poured into an iron or steel mold.
c) Die casting in which metal is injected at high pressures into a steel die
d) Investment casting, in which a wax pattern is surrounded by a ceramic; after the
wax is melted and drained, metal is poured into the mold.

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 Figure 5.5: Sand casting
Figure 5.6: Permanent die casting

Figure 5.7: Investment casting

Figure 5.8: Die casting
5.1.5 Solidification Defects
A properly designed casting, a properly prepared mold and correctly melted metal should
result in a defect free casting. However, if proper control is not exercised in the foundry-
sometimes it is too expensive - a variety of defects may result in a casting. These defects
may be the result of:
 Improper pattern design.  Molding and core making materials.
 Improper mold and core pattern.  Improper gating system.
 Improper melting practice.  Improper metal composition.
 Improper pouring practice.  Inadequate melting temperature.

It creates a deficiency or imperfection. Exceeding quality limits imposed by design and

service casting defects are mainly three categories.
They are:
 Surface Defects  Internal Defects  Visible Defects

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5.1.5.1 Surface Defects
Due to design and quality of sand molds and general cause is poor ramming.
1. Blow
Blow is relatively large cavity produced by gases which displace molten metal form.

2. Scar
Due to improper permeability or venting. A scare is a shallow blow. It generally occurs on
flat surf; whereas a blow occurs on a convex casting surface. A blister is a shallow blow like
a scar with thin layer of metal covering it.

3. Scab
This defect occurs when a portion of the face of a mold lifts or breaks down and the recess
thus made is filled by metal. When the metal is poured into the cavity, gas may be
disengaged with such violence as to break up the sand which is then washed away and the
resulting cavity filled with metal. The reasons can fine sand texture, low permeability of
sand, high moisture content of sand and uneven mold ramming.

4. Drop
Drop or crush in a mold is an irregularly shaped projection on the cope surface of a casting.
This defect is caused by the break-away of a part of mold sand as a result of weak packing
of the mold, low strength of the molding sand, malfunctioning of molding equipment,
strong jolts and strikes at the flask when assembling the mold. The loose sand that falls
into the cavity will also cause a dirty casting surface, either on the top or bottom surface
of the casting, depending upon the relative densities of the sand and the liquid.

5. Penetration
It is a strong crust of fused sand on the surface of a casting which results from insuf ficient
refractoriness of molding materials, a large content of impurities, inadequate mold packing
and poor quality of mold washes. When the molten metal is poured into the mold cavity,
at those places when the sand packing is inadequate, some metal will flow between the
sand particles for a distance into the mold wall and get solidified. When the casting is
removed, this lump of metal remains attached to the casting. Of course, it can be removed
afterwards by chipping or grinding.

6. Buckle
A buckle is a long, fairly shallow, broad, vee depression that occurs in the surface of flat
castings. It extends in a fairly straight line across the entire flat surface. It results due to the
sand expansion caused by the heat of the metal, when the sand has insufficient hot
deformation. It also results from poor casting design providing too large a flat surface in
the mold cavity. Buckling is prevented by mixing cereal or wood flour to sand.

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 Figure 5.9: (clockwise from top left) (a) Blow (b) Penetration (c) Scar
(d) Drop (e) Scab (f) Buckle

5.1.5.2 Internal Defects

1. Blow Holes
Blow holes, gas holes or gas cavities are well rounded cavities
having a clean and smooth surface. They appear either on
the casting surface or in the body of a casting. These defects
occur when an excessive evolved gas is not able to flow
through the mold. So, it collects into a bubble at the high
points of a mold cavity ad prevents the liquid metal from
filling that space. This will result in open blows. Closed,
cavities or gas holes are formed when the evolved gases or
the dissolved gases in the molten metal are not able to leave
the mass of the molten metal as it solidifies and get trapped within the casting.

2. Pin Holes
Pin holes are small gas holes either at the surface or just
below the surface. When these are present, they occur in
large numbers and are fairly uniformly dispersed over the
surface. This defect occurs due to gas dissolved in the
alloy and the alloy not properly degassed.

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5.1.5.3 Visible Defects
1. Wash
A cut or wash is a low projection on the drag face of a
casting that extends along the surface, decreasing in height
as it extends from one side of the casting to the other end.
It usually occurs with bottom gating castings in which
the molding sand has insufficient hot strength, and when
too much metal is made to flow through one gate into
the mold cavity.

2. Rat Tail
A rat tail is a long, shallow, angular depression in the surface
of a flat rating and resembles a buckle, except that, it is not
shaped like a broad vee. The reasons for this defect are the
same for buckle.

3. Hot Tear
Hot tears are hot cracks which appear in the form of irregular crevices with a dark oxidized
fracture surface. They arise when the solidifying met does not have sufficient strength to
resist tensile forces produced during solidification. This defect can be avoided by improving
the design of the casting and by having a mold of low hot strength and large hot
deformation.

4. Shrinkage
A shrinkage cavity is a depression or an internal void in a casting that results from the
volume contraction that occurs during solidification.

5. Swell
A swell is a slight, smooth bulge usually found on vertical faces of castings, resulting from
liquid metal pressure. It may be due to low strength of mold because of too high a water
content or when the mold is not rammed sufficiently.

6. Shift
Mold shift refers to a defect caused by a sidewise displacement of the mold cope relative
to the drag, the result of which is a step in the cast product at the parting line. Core shift is
similar to mold shift, but it is the core that is displaced, and (the displacement is usually
vertical. Core shift and mold shift are caused by buoyancy of the molten metal.

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7. Misrun or Cold Sheet or Short R un:
This defect is incomplete cavity filling. The reasons can be inadequate
metal supply, too low mold or melt temperature, improperly designed
gate or length to thickness ratio of the casting is too large. When
molten metal is flowing from one side in a thin section, it may lose
sufficient heat resulting in loss of its fluidity, such that the leading edge
of the stream may freeze before it reaches the end of the cavity.

Figure 5.10: (a) Hot Tear (b) Shrinkage (c) Swell (d) Shift

5.1.6 Solid Solution and S olid Solution Strengthening

The mixture of two or more liquid material i.e. solute and solvent is called solution. The
solution after solidification e.g. Steel (alloy of iron and carbon) is called solid solu tions. The
solute atoms are introduced into the matrix (solvent atoms). Solid solution is
compositionally homogenous; the solute (impurity) atoms are randomly distributed
throughout the matrix. There are two types of solid solutions.
1. Substitutional Solid S olution: The solute and solvent atoms are similar in size, rendering
the solute atoms to occupy lattice point of the solvent atoms.
2. Interstitial Solid S olution: The solute atoms are of similar size than the solvent atom,
rendering the solute atoms to occupy the interstitial sites in the solvent lattice.

Solid solution strengthening is a technique to strengthen and harden metals by alloying

with impurity atoms that go into either substitutional or interstitial solid solution. Solid
solution strengthening distorts the lattice, offers resistance to dislocation movement
which is greater with interstitial elements which cause asymmetric lattice distortion, e.g.,
carbon in steel.

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Factors affecting solubility of Solute A toms
The solubility of the solute atoms in the host matrix (solvent) can be determined by several
factors:
1. Atomic size factor: Solid solution is appreciable when the difference in atomic radii
between the two atoms is ≤ 15%, otherwise it creates substantial lattice distortion.
2. Crystal structure: Similar crystal structure of metals of both atom types are preferred.
3. Electro negativity : The more electropositive one element and the more electronegative
the other, the more tendency to form an inter-metallic compound than solid solution.
4. Valency : A metal will have more of a tendency to dissolve another metal of higher
valency than one of a lower valency.

Effects of Solid Solution Strengthening on properties

1. The yield strength, tensile strength and hardness of the alloy are greater than those of
pure metals.
2. Almost always, the ductility of the alloy is less than the pure metal.
3. Electrical conductivity of the alloy is much lower than that of pure metal.
4. The resistance to creep or loss of strength at elevated temperature is improved by solid
solution strengthening.

5.2 Phase Relation and Equilibrium

The mechanical properties of materials can be controlled by addition of point defects such
as substitutional and intersitial atoms. Particularly in metals, the point defects disturb the
atomic arrangement in the lattice and interfere with the movement of dislocations or slip.
The point defects therefore cause the material to be solid solution strengthened. In
addition, the introduction of point defects changes the composition of the material and
influences solidification behavior. We examine this effect by introducing the equilibrium
phase diagram.

5.2.1 Phase and Phase Rule

Phase: A phase has the following characteristics
a) A phase has the same structure or atomic arrangement throughout
b) A phase has roughly the same composition & properties throughout
c) There is a definite interface between the phase and any surrounding or adjoining
phases. E.g. solid state, liquid state, gaseous state

Solution: It is the mixture of two or more liquid material i.e. (solute + solvent)

5.2.2 Phase Diagram: The properties of a material depend on the type, number, amount,
and form of the phases present, and can be changed by altering these quantities. In order
to make these changes, it is essential to know the conditions under which these quantities

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exist and the conditions under which a change in phase will occur. A phase diagram shows
the state or phase of the solution at various conditions of temp., pressure and composition.
It shows the phases and their compositions at any combination of temperature and alloy
composition.
The best method to record the data related to phase changes in many alloy systems is in
the form of phase diagrams, also known as equilibrium diagrams or constitutional
diagrams. In order to specify completely the state of a system in equilibrium, it is necessary
to specify three independent variables. These variables, which are externally controllable,
are temperature, pressure and composition. With pressure assumed to be constant at
atmospheric value, the equilibrium diagram indicates the structural changes due to
variation of temperature and composition. Phase diagrams show the phase relationships
under equilibrium conditions, that is, under conditions in which there will be no change
with time. Equilibrium conditions may be approached by extremely slow heating and
cooling, so that if a phase change is to occur, sufficient time is allowed.

Phase diagrams are usually plotted with

temperature as the ordinate, and the alloy
composition as the abscissa as shown in
figure alongside. The data for the
construction of equilibrium diagrams are
determined experimentally by a variety of
methods, the most common methods are
metallographic method, X-ray diffraction
technique, thermal analysis, etc.

Cooling Curve of a Pure Metal

Under equilibrium conditions, all metals exhibit a definite melting or freezing point. If a
cooling curve is plotted for a pure metal. It will show a horizontal line at the melting or
freezing temperature.

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Cooling Curve of a Solid Solution
A solid solution is a solution in the solid state and consists of two kinds of atoms combined
in one type of space lattice. A solution is composed of two parts: a solute and a solvent.
The solute is the minor part of the solution or the material which is dissolved, while the
solvent constitutes the major portion of the solution. When solidification of the solution
starts, the temperature may be higher or lower than the freezing point of the pure solvent.
Most solid solutions solidify over a range in temperature. Figure below shows the cooling
curve for the solidification of a solid solution.

5.2.3 Inverse Lever Rule

Inverse lever rule is used to determine the percentage of each phase that is present at
various temperatures. The length of line XY represents the sum of the two phases as 100
percent. The inverse lever rule states that liquid phase can be calculated by takin g the
length of the line XZ and dividing this by XY. The solid phase can be calculated by taking the
length of the line ZY and dividing it by XY. To get the percentages, the values are multiplied
by 100.

Sample Calculation:
Alloy with 40 % A and 60 %B at room temperature is heated to a temperature T 1. Calculate
the liquid and solid phase and indicate the composition of each phase.

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 Liquid Phase = (XZ / XY) x 100 = [(40-10) / (70-10)] x100 = 50%
Solid Phase = (ZY / XY) x 100 = [(70-40) / (70-10)] x100 = 50%
At temperature T1, the solid composition is found by the intersection (point X) of
isothermal line T1 and the solidus curve.
Solid composition: 10 % A and 90 % B
The liquid composition at temperature T 1 is found by the intersection (point Y) of
isothermal line T1 and the liquidus curve.
Liquid composition: 70% A and 30 % B

Eutectic System
Eutectic system is a phase transformation that
takes place when a single-phase liquid
transforms directly to a two-phase solid.

𝐿 → 𝑆1 + 𝑆2
𝐿𝑖𝑞𝑢𝑖𝑑 → 𝑆𝑜𝑙𝑖𝑑 1 + 𝑆𝑜𝑙𝑖𝑑 2
This is a reversible phase transformation.

Eutectoid System
The eutectoid phase transformation occurs
when a single-phase solid transforms
directly to two-phase solid.
𝑆1 → 𝑆2 + 𝑆3
𝑆𝑜𝑙𝑖𝑑 1 → 𝑆𝑜𝑙𝑖𝑑 2 + 𝑆𝑜𝑙𝑖𝑑 3
This is a reversible phase transformation.

Peritectic System
The peritectic phase transformation occurs when a liquid and solid phase of fixed
proportions reacts at fixed temperature to yield a single solid phase.
𝑆1 + 𝐿 = 𝑆2 𝑖. 𝑒. , 𝑠𝑜𝑙𝑖𝑑 1 + 𝑙𝑖𝑞𝑢𝑖𝑑 = 𝑠𝑜𝑙𝑖𝑑 2
This transformation exists in the Iron-Iron Carbide System.

Monotectic System
The Monotectic phase transformation occur when a liquid transforms directly to a second
liquid and a solid.
𝐿𝑖𝑞𝑢𝑖𝑑 1 = 𝐿𝑖𝑞𝑢𝑖𝑑 2 + 𝑠𝑜𝑙𝑖𝑑
This transformation is reversible phase transformation and occurs during cooling.

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5.3 Strengthening Mechanism
Since no two elements have the same atomic diameter, solute atoms will be either smaller
or longer than the solvent atoms. Due to the difference in atomic size, lattice distortion is
produced when one element is added to the other. Smaller atoms will produce a local
tensile stress field and larger solute atoms will produce a local compressive field in the
crystal. In both cases, the stress field of a moving dislocation interacts with the stress field
of the solute atom. This increases the stress required to move the dislocation through the
crystal, and hence strengthens the solution.

5.3.1 Alloys strengthening by exceeding solubility limit

When impurities (i.e. the solute atoms) are added into the solution of a metal or an alloy,
the solute atoms go into interstitial or substitutional positions and increase the strength of
the solution. The impurity atoms cause lattice strain which can anchor dislocations. This
occurs when the strain caused by the alloying element compensates that of the dislocation,
thus achieving a state of low potential energy. It costs strain energy for the di slocation to
move away from this state (which is like a potential well). The scarcity of energy at low
temperatures is why slip is hindered and solution is strengthened. Pure metals are almost
always softer than their alloys.

5.3.2 Age Hardening or Precipitation Hardening

Precipitation hardening, also called age hardening, is a heat treatment technique used to
increase the yield strength of malleable materials, including most structural alloys
of aluminum, magnesium, nickel, titanium, and some stainless steels. In super-alloys, it is
known to cause yield strength anomaly providing excellent high temperature strength.
Precipitation hardening relies on changes in solid solubility with temperature to produce
fine particles of an impurity phase, which impede the movement of dislocations, or defects
in a crystal's lattice. Since dislocations are often the dominant carriers of plasticity, this
serves to harden the material. The impurities play the same role as the particle substances
in particle-reinforced composite materials. Just as the formation of ice in air can produce
clouds, snow, or hail, depending upon the thermal history of a given portion of the
atmosphere, precipitation in solids can produce many different sizes of particles, which
have radically different properties. Unlike ordinary tempering, alloys must be kept at
elevated temperature for hours to allow precipitation to take place. This time delay is
called aging.

5.3.3 Residual stress during quenching and heating

Residual stresses are stresses that remain in a solid material after the original cause of the
stresses has been removed. Residual stress may be desirable or undesirable. For example,
laser peening imparts deep beneficial compressive residual stresses into metal
components such as turbine engine fan blades, and it is used in toughened glass to allow

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for large, thin, crack- and scratch-resistant glass displays on smartphones. However,
unintended residual stress in a designed structure may cause it to fail prematurely.
When undesired residual stress is present from prior metalworking operations, the amount
of residual stress may be reduced using several methods. These methods may be classified
into thermal and mechanical (or non-thermal) methods. All the methods involve
processing the part to be stress relieved as a whole.

Thermal method
The thermal method involves changing the temperature of the entire part uniformly, either
through heating or cooling. When parts are heated for stress relief, the process may also
be known as stress relief bake. Cooling parts for stress relief is known as cryogenic stress
relief and is relatively uncommon.

i) Stress relief bake: Most metals, when heated, experience a reduction in yield strength. If
the material's yield strength is sufficiently lowered by heating, locations within the material
that experienced residual stresses greater than the yield strength (in the heated state)
would yield or deform. This leaves the material with residual stresses that are at most as
high as the yield strength of the material in its heated state.
Stress relief bake should not be confused with annealing or tempering, which are heat
treatments to increase ductility of a metal. Although those processes also involve heating
the material to high temperatures and reduce residual stresses, they also involve a change
in metallurgical properties, which may be undesired.
For certain materials such as low alloy steel, care must be taken during stress relief bake
so as not to exceed the temperature at which the material achieves maximum hardness
(See Tempering in alloy steels).

ii) Cryogenic stress relief: Cryogenic stress relief involves placing the material (usually steel)
into a cryogenic environment such as liquid nitrogen. In this process, the material to be
stress relieved will be cooled to a cryogenic temperature for a long period, then slowly
brought back to room temperature.

Non-thermal methods
Mechanical methods to relieve undesirable surface tensile stresses and replace them with
beneficial compressive residual stresses include shot peening and laser peening. Each
works the surface of the material with a media: shot peening typically uses a metal or glass
material; laser peening uses high intensity beams of light to induce a shock wave that
propagates deep into the material.

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 CHAPTER 6
IRON-IRON CARBIDE DIAGRAM AND HEAT TREATMENT OF STEELS
6.1 Iron- Iron Carbide Diagram
Figure 6.1 shows the iron-iron carbide (Fe-Fe3C) phase diagram. In this diagram, the carbon
composition (weight percent) is plotted along the horizontal axis and temperature along
the vertical axis. The diagram shows the phases present at various temperatures for very
slowly cooled iron-carbon alloys with carbon content up to 6.7%. This diagram gives us
information about the following points:
 Solid phases in the phase diagram
 Invariant reactions in the diagram
 Critical temperatures
 Eutectoid, hypo-eutectoid and hyper-eutectoid steels

Figure 6.1: Iron-Iron Carbide phase diagram

Cementite (Fe 3 C):

Cementite is also known as iron carbide which has a chemical formula, Fe 3C. It contains
6.67 % Carbon by weight. It is a typical hard and brittle interstitial compound of low tensile

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strength (approximately 5,000 psi) but high compressive strength. Its crystal structure is
orthorhombic.

Austenite (𝜸 iron):
It is also known as (𝛾) gamma-iron, which is an interstitial solid solution of carbon dissolved
in iron with a face-centered cubic crystal (F.C.C) structure. Average properties of austenite
are:
Tensile strength: 150,000 psi. Hardness Rockwell: C 40
Elongation: 10 % in 2 in gage length. Toughness: High
Austenite is normally unstable at room temperature. Under certain conditions it is possible
to obtain austenite at room temperature.

Ferrite (𝜶 iron):
It is also known as (𝛼 ) alpha -iron, which is an interstitial solid solution of a small amount
of carbon dissolved in iron with a body-centered cubic (B.C.C.) crystal structure. It is the
softest structure on the iron-iron carbide diagram. Average properties are:
Tensile Strength: 40,000 psi Hardness: Less than Rockwell B 90.
Elongation: 40 % in 2 in gage length Toughness: Low

Pearlite (𝜶 + Fe 3 C)
It is the eutectoid mixture containing 0.83 % carbon and is formed at 1333 oF on very slow
cooling. It is very fine plate like or lamellar mixture of ferrite and cementite. The structure
of pearlite includes a white matrix (ferritic background) which includes thin plates of
cementite. Average properties are:

Tensile Strength: 120,000 psi

Elongation: 20 % in 2 in gage length
Hardness: Rockwell C 20 or BHN 250-300

A fixed amount of carbon and a fixed amount of iron are needed to form Cementite (Fe3C).
Also, pearlite needs fixed amounts of cementite and ferrite.

If there is not enough carbon, that is less than 0.83 %, the carbon and the iron will combine
to form Fe3C until all the carbon is consumed. This cementite will combine with the
required amount of ferrite to form pearlite. The remaining amount of ferrite will stay in
the structure as free ferrite. Free ferrite is also known as pro-eutectoid ferrite. The steel
that contains pro-eutectoid ferrite is referred to as hypo-eutectoid steel.
If, however, there is an excess of carbon above 0.83 % in the austenite, pearlite will form,
and the excess carbon above 0.83 % will form Cementite. The excess Cementite deposits
in the grain boundaries. This excess cementite is also known as pro-eutectoid cementite.

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Ledeburite (𝜶 + Fe 3 C)
It is the eutectic mixture of austenite and cementite. It contains 4.3 % Carbon and
represents the eutectic form of cast iron. Ledeburite exists when the carbon content is
greater than 2 %, which represents the dividing line on the equilibrium diagram between
steel and cast iron.

Delta Iron
Delta iron exists between 2552 and 2802oF. It may exist in combination with the melt to
about 0.50 % Carbon, in combination with austenite to about 0.18 % Carbon and in a single
phase state out to about 0.10 % carbon. Delta iron has the body centered cubic (B.C.C)
crystal structure and is magnetic.

6.1.1 Applications and l imitations of Iron-Iron Carbide Diagram

Applications
With the core knowledge gained from the iron-carbon phase, one can investigate different
types of structures derived from heat treatment of steel. The iron-carbon diagram provides
a valuable foundation on which knowledge of both plain carbon and alloy steels in their
immense variety is gained. The iron-iron carbide diagram is useful in finding out what will
be the crystal structure and the physical and chemical properties of iron at known carbon
percentage and temperature.
Limitations
1. Information about transformation of austenite at varying cooling rates is missing.
2. Design of heat treatment for desired properties is not possible.
3. It does not give the answer to the question “How much time is required to start the
transformation or how long does the transformation take to complete?".

6.2 Simple Heat Treatments

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6.2.1 Annealing
Annealing is a heat process whereby a metal is heated to a specific temp/color and then
allowed to cool slowly. This softens the metal which means it can be cut and shaped more
easily. Mild steel, is heated to a red hot state and allowed to cool slowly. However, metals
such as aluminum will melt if heated for too long. Annealed metals are relatively soft and
can be cut and shaped more easily. They bend easily when pressure is applied. As a rule,
they are heated and allowed to cool slowly. The different types of annealing are:

 Full Annealing  Stress-Relief Annealing

 Process Annealing  Spheroidisation

Figure 6.2: Annealing

Full Annealing
Full Annealing is the process of slowly raising the temp about 50 oC (90oF) above the
Austenite temp line A3 or line ACM in the case of hypo-eutectoid steels (steels with less than
0.77%).
It is held at this temp for sufficient time for all the materials to transform into Austenite or
Austenite-Cementite as the case may be. It is then slowly cooled at the rate of about
20oC/hr. (36oF/hr.) in a furnace to about 50 oC (90oF) into the Ferrite-Cementite. At this
point, it can be cooled in a room temp air with natural convection.
The grain structure has coarse Pearlite with Ferrite or Cementite (depending on whether
hypo or hyper-eutectoid). The steel becomes soft and ductile.

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Process Annealing
Process Annealing is used to treat work-hardened parts made out of low carbon steels (less
than 0.25%). This allows the parts to be soft enough to undergo further cold working
without fracturing. Process Annealing is done by raising the temp to just below the Ferrite-
Austenite region, line A1 on the diagram. This temp is about 727 oC (1341 oF) so heating it
to about 700 oC (1292 oF) should suffice. This is held long enough to allow recrystallization
of the ferrite phase, and then cooled in still air. Since the material stays in the same phase
throughout the process, the only change that occurs in the size, shape and distribution of
the grain structure. This process is cheaper than either full annealing or normalizing since
the material is not heated to a very high temp or cooled in a furnace.

Stress-Relief Annealing
Stress-Relief Annealing is used to reduce residual stresses in large castings, welded parts
and cold-formed parts. Such parts tend to have stresses due to thermal cycling or work
hardening. Parts are heated to temp of up to 600-650oC and held for an extended time
about 1 hour and more and then slowly cooled in still air.

Spheroidisation
Spheroidisation is an annealing process used for high carbon steels (carbon more than
0.6%) that will be machined or cold formed subsequently. This is done by one of the
following ways:
1. Heat the part to a temperature just below the Ferrite- Austenite line, line A1 or below
the Austenite - Cementite line, especially below the 727 oC (1340 oF) line. Hold the
temperature for a prolonged time and follow by fairly slow cooling.
2. Cycle multiple times between temperature slightly above and slightly below the 727 oC
(1340 oF) line, say for example between 700 and 750 oC and cool slowly.
3. For tool and alloy steels, heat to 750 to 800 oC (1382 - 1472oF) and hold for several
hours followed by slow cooling.

Figure 6.3: Grain structures of Spheroidite, Austenite and Cementite

All these methods result in a structure in which all the Cementite is in the form of small
globules (spheroids) dispersed throughout the ferrite matrix. This structure allows for

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improved machining in continuous cutting operations such as lathes and screw machines.
Spheroidisation also improves resistance to abrasion.

Applications of Annealing
Annealed metals are relatively soft and can be cut and shaped more easily. They bend
easily when pressure is applied. As a rule they are heated and allowed to cool slowly. Thus
applications include decorative items, Low-friction applications (locks, gears, and
doorknobs), plumbing/electronics, musical instruments for acoustic properties & in bells
and cymbals.

Figure 6.4: Effect of annealing and normalizing on ductility of steel

As indicated in figure 6.3, annealing and normalizing do not present a significant difference
on the ductility of low carbon steels. As the carbon content increases, annealing maintains
the % elongation around 20%. On the other hand, the ductility of the normalized high
carbon steels drop to 1 to 2 % level.

Figure 6.5: Effect of annealing and normalizing on tensile strength of steel

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 Figure 6.6: Effect of annealing and normalizing on yield point of steel
Figures 6.3 and 6.4 show that the tensile strength and the yield point of the normalized
steels are higher than the annealed steels. Normalizing and annealing do not show a
significant difference on the tensile strength and yield point of the low carbon steels.
However, normalized high carbon steels present much higher tensile strength and yield
point than those that are annealed.

Comparison between Annealing and Normalizing

In general, the main purpose of annealing heat treatment is to soften the steel, regenerate
overheated steel structures or just remove internal tensions. It basically consists of heating
to austentising temperature (800ºC and 950ºC depending on the type of steel), followed
by slow cooling. Normalization is an annealing process. The objective of normalization is to
intend to leave the material in a normal state, in other words with the absence of internal
tensions and even distribution of carbon. For the process the high temperatures are
maintained until the complete transformation of austenite with air cooling. It is usually
used as a post-treatment to forging, and pre-treatment to quenching and tempering.
Induction is used in most applications of annealing and normalizing in compared to
conventional ovens.

Applications of Normalizing
By completing the normalization of metal (e.g. steel), the strength of the piece of steel can
be improved, compared to steel that is not normalized or treated with another heating
process. The ductile performance of the steel can also be improved through normalization;
this is possible without reducing the hardness or strength as can happen with other heat
treatments. By using the normalization process, modifications can be made to the grain
structure of the steel to make it usable for specific purposes. Steels with low levels of
carbon do not have their rate of ductility altered by using the normalization process. It is
usually done for steel parts that require maximum amount of impact strength.

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6.2.3 Quenching and its medium
Quenching is the act of rapidly cooling the hot steel to harden the steel.
The various mediums in which quenching can be done are:

 Water: Quenching can be done by plunging the hot steel in water. The water adjacent to
the hot steel vaporizes, and there is no direct contact of the water with the steel. This slows
down cooling until the bubbles break and allow water contact with the hot steel. As the
water contacts and boils, a great amount of heat is removed from the steel. With good
agitation, bubbles can be prevented from sticking to the steel, and thereby prevent soft
spots. Water is a good rapid quenching medium, provided good agitation is done.
However, water is corrosive with steel, and the rapid cooling can sometimes cause
distortion or cracking.
 Salt Water: Salt water is a more rapid quench medium than plain water because the
bubbles are broken easily and allow for rapid cooling of the part. However, salt water is
even more corrosive than plain water, and hence must be rinsed off immediately.
 Oil: Oil is used when a slower cooling rate is desired. Since oil has a very high boiling point ,
the transition from start of martensite formation to the finish is slow and this reduces the
likelihood of cracking. Oil quenching results in fumes, spills, and sometimes a fire hazard.
 Polymer quench: Polymer quenches that will produce a cooling rate in between water
and oil. The cooling rate can be altered by varying the components in the mixture-as these
are composed of water and some glycol polymers. Polymer quenches are capable of
producing repeatable results with less corrosion than water and less of a fire hazard than
oil. But, these repeatable results are possible only with constant monitoring of the
chemistry.
 Cryogenic quench: Cryogenics or deep freezing is done to make sure there is no retained
Austenite during quenching. The amount of martensite formed at quenching is a function
of the lowest temperature encountered. At any given temperature of quenching there is a
certain amount of martensite and the balance is untransformed Austenite. This
untransformed Austenite is very brittle and can cause loss of strength or hardness,
dimensional instability, or cracking. Quenches are usually done to room temperature. Most
medium carbon steels and low alloy steels undergo transformation to 100% martensite at
room temperature. However, high carbon and high alloy steels have retained Austenite at
room temperature. To eliminate retained Austenite, the quench temperature has to be
lowered. This is the reason to use cryogenic quenching.

Hardness and Hardenability

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Hardness is a function of the carbon content of the steel. Hardening of a steel requires a
change in structure from the body-centered cubic structure found at room temperature
to the face-centered cubic structure found in the Austenitic region. The steel is heated to
Austenitic region. When suddenly quenched, the martensite is formed. This is a very strong
and brittle structure.
When slowly quenched it would form Austenite and Pearlite which is a partly hard and
partly soft structure. When the cooling rate is extremely slow then it would be mostly
Pearlite which is extremely soft.
Hardenability, which is a measure of the depth of full hardness achieved, is related to the
type and amount of alloying elements. Different alloys, which have the same amount of
Carbon content, will achieve the same amount of maximum hardness; however, the depth
of full hardness will vary with the different alloys. The reason t o alloy steels is not to
increase their strength, but increase their hardenability — the ease with which full
hardness can be achieved throughout the material.
Usually when hot steel is quenched, most of the cooling happens at the surface, as does
the hardening. This propagates into the depth of the material. Alloying helps in the
hardening and by determining the right alloy one can achieve the desired properties for
the particular application.
Such alloying also helps in reducing the need for a rapid quench cooling — thereby
eliminate distortions and potential cracking. In addition, thick sections can be hardened
fully.

Hardenability and Jominy End Quench Test

The influence of alloy composition on the ability of a steel alloy to transform to martensite
for a particular quenching treatment is related to a parameter called hardenability. For
every different steel alloy there is a specific relationship between the mechanical
properties and the cooling rate. Hardenability is used to describe the ability of an alloy to
be hardened by the formation of martensite as a result of a given heat treatment.
One standard procedure that is widely utilized to determine hardenability is the Jominy
end quench test.

In Jominy test, the standard specimen consists of a

cylindrical rod 4" long 1" in diameter. The test
specimen is first heated to a suitable austentising
temperature and held there long enough to obtain a
uniform austenite structure. It is then placed in a jig
and stream of water is allowed to strike one end of
the specimen. The cooling conditions within the
Jominy bar during quenching changes very little

Figure 6.7: Jominy Test

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across the diameter but vary rapidly at that end and progressively less rapidly at p oints
towards the opposite end.
A plot is made of the hardness reading against the distance from the quenched end of the
bar. Such a plot is shown if figure 6.8.

Figure 6.8: Plot of Rockwell C Hardness versus distance from the quenched end of the bar

The addition of alloys or coarsening of the austenitic grain structure increase the
hardenability of steel. Any steel that has low critical cooling rate will harden deeper than
one that has a high cooling rate of quenching.

Time-Temperature-Transformation (TTT) Diagram

 T (Time) T (Temperature) T (Transformation) diagram is a plot of temperature versus the
logarithm of time for a steel alloy of definite composition. It is used to determine when
transformations begin and end for an isothermal (constant temperature) heat treatment
of a previously austenitized alloy. When austenite is cooled slowly to a temperature below
LCT (Lower Critical Temperature), the structure that is formed is Pearlite. As the cooling
rate increases, the pearlite transformation temperature gets lower. The microstructure of
the material is significantly altered as the cooling rate increases. By heating and cooling a
series of samples, the history of the austenite transformation may be recorded. TTT
diagram indicates when a specific transformation starts and ends and it also shows what
percentage of transformation of austenite at a particular temperature is achieved.
 Cooling rates in the order of increasing severity are achieved by quenching from
elevated temperatures as follows: furnace cooling, air cooling, oil quenching, liquid salts,
water quenching, and brine. If these cooling curves are superimposed on the TTT diagram,
the end product structure and the time required to complete the transformation may be
found.
 In figure 6.8 the area on the left of the transformation curve represents the austenite
region. Austenite is stable at temperatures above LCT but unstable below LCT. Left curve

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indicates the start of a transformation and right curve represents the finish of a
transformation. The area between the two curves indicates the transformation of
austenite to different types of crystal structures. (Austenite to pearlite, austenite to
martensite, austenite to bainite transformation.)

Figure 6.9: Time-Temperature Transformation Curve

Figure 6.10 represents the
upper half of the TTT diagram.
As indicated in figure, when
austenite is cooled to
temperatures below LCT, it
transforms to other crystal
structures due to its unstable
nature. A specific cooling rate
may be chosen so that the
transformation of austenite
can be 50 %, 100 % etc.
Figure 6.10: Upper half of TTT Curve

If the cooling rate is very slow such as annealing process, the cooling curve passes through
the entire transformation area and the end product of this the cooling process becomes
100% Pearlite. In other words, when slow cooling is applied, all the Austenite will transform
to Pearlite. If the cooling curve passes through the middle of the transformation area, the

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end product is 50 % Austenite and 50 % Pearlite, which means that at certain cooling rates
we can retain part of the Austenite, without transforming it into Pearlite.
Figure 6.11 indicates the types of transformation that can be found at higher cooling rates.
If a cooling rate is very high, the cooling curve will remain on the left hand side of the
Transformation Start curve. In this case all Austenite will transform to martensite. If there
is no interruption in cooling the end product will be martensite.

Figure 6.11: Lower half of TTT Curve

In the figure 6.12, the cooling rates A and B indicate two rapid cooling processes. In this
case, curve A will cause a higher distortion and a higher internal stresses than the cooling
rate B. The end product of both cooling rates will be martensite. Cooling rate B is also
known as the Critical Cooling Rate, which is represented by a cooling curve that is tangent
to the nose of the TTT diagram. Critical cooling rate is defined as the lowest cooling rate
which produces 100% martensite while minimizing the internal stresses and distortions.

Figure 6.12: Transformation with different cooling rates

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In figure 6.13, a rapid quenching process is interrupted (horizontal line represents the
interruption) by immersing the material in a molten salt bath and soaking at a constant
temperature followed by another cooling process that passes through bainite region of
TTT diagram. The end product is bainite, which is not as hard as martensite. As a result of
cooling rate D; more dimensional stability, less distortion and less internal stresses are
created.

Figure 6.13: Transformation with an interruption

In figure 6.14 cooling curve C represents a slow cooling process, such as furnace cooling.
An example for this type of cooling is annealing process where all the austenite is allowed
to transform to Pearlite as a result of slow cooling.

Figure 6.14: Transformation with a slow cooling process

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 Sometimes the cooling curve may pass through the middle of the Austenite-Pearlite
transformation zone. In figure 6.15, cooling curve E indicates a cooling rate which is not
high enough to produce 100% martensite. This can be observed easily by looking at the
TTT diagram. Since the cooling curve E is not tangent to the nose of the transformation
diagram, austenite is transformed to 50% Pearlite (curve E is tangent to 50% curve). Since
curve E leaves the transformation diagram at the martensite zone, the remaining 50 % of
the austenite will be transformed to martensite.

Figure 6.15: Transformation with an insufficient cooling rate

Figure 6.16: (from left to right) Microstructures of Austenite, Pearlite, Bainite and Martensite

6.2.4 Hardening and Tempering

Steels can be heat treated to high hardness and strength levels. The reasons for doing this
are obvious. Structural components subjected to high operating stress need the high
strength of a hardened structure. Similarly, tools such as dies, knives, cutting devices, and
forming devices need a hardened structure to resist wear and deformation. Hardened
steels are so brittle that even slight impacts may cause fracture. Tempering is a heat
treatment that reduces the brittleness of a steel without significantly lowering its hardness
and strength. All hardened steels must be tempered before use.

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Quench and Tempering Processes
The various hardening methods are:
(1) Conventional Heat, Quench and Temper process
(2) Stepped Quenching or Martempering
(3) Isothermal Quenching or Austempering

Conventional Heat, Quench and Temper Process

In this process, austenite is transformed to martensite as a result of rapid quench from
furnace to room temperature. Then, martensite is heated to a temperature which gives
the desired hardness. One serious drawback is the possibility of distorting and cracking the
metal as a result of severe quenching required to form martensite without transforming
any of the austenite to pearlite. During quenching process, the outer area is cooled quicker
than the center. Thinner parts are cooled faster than parts with greater cross -sectional
areas. What this means is that transformations of the austenite are proceeding at different
rates. As the metal cools, it also contracts and its microstructure occupies less volume.
Extreme variations in size of metal parts complicate the work of the heat treater and should
be avoided in the designing of metal parts. This means there is a limit to the overall size of
parts that can be subjected to such thermal processing.

Stepped Quenching or Martempering (Marquenching)

To overcome the restrictions of
conventional quenching and
tempering, Martempering
process can be used.
Martempering or
Marquenching permits the
transformation of austenite to
martensite to take place at the
same time throughout the
structure of the metal part. This
is shown in Figure. By using
interrupted quench, the cooling
is stopped at a point above the
martensite transformation
region to allow sufficient time
for the center to cool to the
same temperature as the surface. Figure 6.17: Martempering in Eutectoid Steel

Then cooling is continued through the martensite region, followed by the usual tempering.

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Martempering has the following advantages over conventional quenching:
1. Less volume changes occur due to the presence of a large amount of retained
austenite and possibility of self-tempering of martensite.
2. Less warping since the transformations occur simultaneously in all parts of the article.
3. Less chances of quenching cracks appearing in the article.

Isothermal Quenching or Austempering

It is performed in the same manner principally as martempering but with a longer holding
time at hot bath temperature (above the martensite point) to ensure a sufficiently
complete austenite decomposition (usually with a circular troostite or bainite).
This method is used to overcome the restrictions of conventional quench and tempering.
The quench is interrupted at a higher temperature than for Martempering to allow the
metal at the center of the part to reach the same temperature as the surface. By
maintaining that temperature, both the center and the surface are allowed to transform
to bainite and are then cooled to room temperature.
Molten salts are usually used as a medium in martempering and austempering. The lower
the temperature of the salt bath, the higher the cooling rate it provides. .
Austempering process is commercially used for thin steel sections to obtain products free
from cracks and with good impact resistance.

Advantages of Austempering
1. Less distortion and cracking than Martempering.
2. No need for final tempering (less time consuming and more energy efficient).
3. Improvement of toughness (impact resistance is higher than the conventional quench
and tempering).
4. Improved ductility.

6.2.5 Different types of surface hardening processes

6.2.5.1 Carburizing
Carburizing is a heat treatment process in which iron or steel absorbs carbon liberated
when the metal is heated in the presence of a carbon bearing material, such as charcoal
or carbon monoxide, with the intent of making the metal harder. Depending on the
amount of time and temperature, the affected area can vary in carbon content. Longer
carburizing times and higher temperatures lead to greater carbon diffusion into the part
as well as increased depth of carbon diffusion.

When iron or steel is cooled rapidly by quenching, the higher carbon content on the outer
surface becomes hard via the transformation from austenite to martensite, while the core
remains soft and tough as a ferritic and/or pearlite microstructure.

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This manufacturing process can be characterized by the following key points: It is applied
to low-carbon work pieces; work pieces are in contact with a high-carbon gas, liquid or
solid; it produces a hard work piece surface; work piece cores largely retain their toughness
and ductility; and it produces case hardness depths of up to 0.25 inches (6.4 mm).
In some cases it serves as a remedy for undesired decarburization that happened earlier in
a manufacturing process.

There is no technical limit to the depth of hardening with

Depth of
carburizing techniques, but it is not common to carburize to depths
Hardening
in excess of 0.050 inches.
Carburizing time 4 to 10 hours
Carburizing
1750 oF (above the upper critical temperature - Austenite area)
temperature
All of the carburizing processes (pack, gas, liquid) require quenching
from the carburizing temperature or a lower temperature or
Quenching
reheating and quenching. Parts are then tempered to the desired
hardness.

There are three different types of carburizing processes:

1. Pack Carburizing 2. Gas Carburizing 3. Liquid Carburizing

1. Pack Carburizing
In this process, the part that is to
be carburized is packed in a steel
container so that it is completely
surrounded by granules of
charcoal. The charcoal is treated
with an activating chemical such
as Barium Carbonate (BaBO3)
that promotes the formation of
Carbon Dioxide (CO2). This gas in
turn reacts with the excess
carbon in the charcoal to
produce carbon monoxide.
Figure 6.18: Pack Carburizing
Carbon Monoxide reacts with the low-carbon steel surface to form atomic carbon which
diffuses into the steel. Carbon Monoxide supplies the carbon gradient that is necessary for
diffusion. The carburizing process does not harden the steel. It only increases the carbon
content to some predetermined depth below the surface to a sufficient level to allow
subsequent quench hardening.

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Carbon Monoxide reaction:
CO2 + C → 2 CO

Reaction of Cementite to
Carbon Monoxide:
2 CO + 3 Fe → Fe3C + CO2

Figure 6.19: Carburizing depth at different temperatures

It is difficult to quench the part immediately, as the sealed pack has

to be opened and the part must be removed from the pack. One
Quenching
technique that is used often is to slow cool the entire pack and
Process
subsequently harden and temper the part after it is removed from
the sealed pack.
There is no technical limit to the depth of hardening with
Depth of
carburizing techniques, but it is not common to carburize to depths
Hardening
in excess of 0.050 inches.
Carburizing time 4 to 10 hours

2. Gas Carburizing
Gas carburizing can be done with any carbonaceous gas, such as methane, ethane,
propane, or natural gas. Most carburizing gases are flammable and controls are needed to
keep carburizing gas at 1700 oF from contacting air (oxygen). The advantage of this process
over pack carburizing is an improved ability to quench from the carburizing temperature.
Conveyor hearth furnaces make quenching in a controlled atmosphere possible.

3. Liquid Carburizing
Liquid carburizing can be performed in internally or externally heated molten salt pots.
Carburizing salt contains cyanide compounds such as sodium cyanide (NaCN). Cycle times
for liquid cyaniding is much shorter (1 to 4 hours) than gas and pack carburizing processes.
Disadvantage is that the salt has to be disposed, which proves to be very costly and it is
hazardous to environment as well.

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6.2.5.2 Nitriding
In this process, nitrogen is diffused into the surface of the steel being treated. The reaction
of nitrogen with the steel causes the formation of very hard iron and alloy nitrogen
compounds. The resulting nitride case is harder than tool steels or carburized steels. The
advantage of this process is that hardness is achieved without the oil, water or air quench.
As an added advantage, hardening is accomplished in a nitrogen atmosphere that prevents
scaling and discoloration. Nitriding temperature is below the lower critical temperature of
the steel and it is set between 925 oF and 1050 oF. The nitrogen source is usually Ammonia
(NH 3).
At nitriding temperature the ammonia dissociates into Nitrogen and Hydrogen according
to the chemical reaction: 2NH 3 → 2N + 3H 2
The nitrogen diffuses into the steel and hydrogen is exhausted. A typical nitriding setup is
illustrated in figure 6.19.

Figure 6.20: Nitriding

The white layer shown in figure alongside has a

detrimental effect on the fatigue life of nitrided
parts, and it is normally removed from parts
subjected to severe service. Two stage gas-
nitriding processes can be used to prevent the
formation of white layer. White layer thickness
may vary between 0.0003 and 0.002 in. which
depends on nitriding time. The most commonly
nitrided steels are chromium-molybdenum alloy steels and Nitralloys. Nitrided steels are
very hard and grinding operations should not be performed after nitriding. White layer is
removed by lapping.

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6.2.5.3 Carbonitriding
This process involves the
diffusion of both carbon
and nitrogen into the
steel surface. The
process is performed in a
gas atmosphere furnace
using a carburizing gas
such as propane or
methane mixed with
several percent (by
volume) of ammonia. Figure 6.21: Carbonitriding

Methane or propane serve as the source of carbon, the ammonia serves as the source of
nitrogen. Quenching is done in a gas which is not as severe as water quench. As a result of
les severe quench, there is less distortion on the material to be treated. A typical
Carbonitriding system is shown in the following slide. Case hardness of HRC 60 to 65 are
achieved at the surface but not as high as nitrided surfaces. Case depths of 0.003 to 0.030
in can be accomplished by carbonitriding. One of the advantages of this process is that it
can be applied to plain carbon steels which give significant case depths. Carbonitriding
gives less distortion than carburizing. Carbonitriding is performed at temperatures above
the transformation temperature of the steels (1400 oF to 1600 oF).

6.2.5.4 Cyaniding
It is similar to carbonitriding, and involves the diffusion of both carbon and nitrogen into
the surface of the steel. The source of the diffusing element in this method is a molten
cyanide salt such as sodium cyanide. It is a supercritical treatment involving temperatures
in the range of 1400 oF to 1600 oF. Case depths are between 0.010 in. and 0.030 in.
During cyaniding, the cyanide salts are oxidized with the liberation of atomic carbon and
nitrogen, which diffuse into the steel. In medium-temperature cyaniding, the cyanide layer
formed, containing 0.6–0.7 percent C and 0.8–1.2 percent N, has a thickness of 0.15 to 0.6
mm, while in high-temperature cyaniding (a method often used instead of carburizing), the
cyanide layer, containing 0.8–1.2 percent C and 0.2–0.3 percent N, has a thickness of 0.5
to 2 mm.
Diffusion times are less than one hour. Water or oil quench is required to remove residual
cyanide. This type of cases present a significant distortion. Advantage of this method is the
short time it requires to complete the diffusion, otherwise it should be avoided because of
high distortion. The major drawback of cyaniding is that cyanide salts are poisonous and
the process itself is costly.

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Major defects in a metal or alloy due to faulty heat treatment
Following are some of the major defects found in metal or alloy due to faulty heat
treatment:
1. Overheating: Prolonged heating of a metal or alloy above the A 3 line (refer figure 6.1)
leads to the formation of very large actual grains. It is called overheat ing. On cooling a
metal, this yields a structure containing coarse crystalline martensite. Such structure has
reduced ductility and toughness. It is possible to retrieve an overheated metal or alloy by
usual annealing. For considerable overheating, double annealing may be used.
2. Burning: Heating a metal or an alloy to still higher temperatures near melting point for
a longer time leads to burning. This results in the formation of iron oxide inclusions along
the grain boundaries. Burnt metal or alloy has a stoney fracture and such metal or alloy is
irretrievable and is rejected.
3. Oxidation: Sometimes a metal or alloy is oxidized due to oxidizing atmosphere in the
furnace. It is characterized by a thick layer of scale on the surface of a metal or alloy. It can
be prevented by using controlled atmosphere in the furnace or using molten salt baths.
4. Decarburization: It is the loss of carbon in the surface layers of the metal or alloy.
Decarburization results in lower hardness and lower fatigue life. It is caused by t he oxidizing
furnace atmosphere. In order to prevent decarburization, the metal or alloy should be
heated in a neutral or reducing atmosphere or in boxes with cast iron chips or in molten
salt baths.
5. Cracks: The cracks occur in quenching when the internal tensile stresses exceed the
resistance of the metal or alloy to separation. The tendency of a metal or alloy to crack
formation increases with carbon content, hardening temperature and cooling rate in the
temperature interval of martensite transformation. It also increases with the hardenability
of metal or alloy. Another reason of crack formation is the concentration of local stresses.
To prevent the formation of cracks, it is advisable to (i) avoid stress concentrations such as
sharp corners on projections, acute angles, and abrupt changes from thicker to thinner
cross-sections etc., (ii) conduct quenching from lowest possible temperature, (iii) cool the
metal or alloy slowly in the martensite interval of temperatures by quenching in two media
and stepped quenching (i.e. martempering), (iv) apply isothermal quenching.
6. Distortion and warping: Distortion or deformation consisting in changes in the size and
shape of heat-treated work, is due to thermal and structural stresses. Asymmetrical
distortion of work is often called warping in heat-treating practice. It is usually observed in
the case of non-uniform heating or over-heating for hardening, when the work is quenched
in the wrong position and when the cooling rate is too high in the temperature interval of
martensite transformation. An elimination of these causes should substantially reduce
warping.

MATERIAL SCIENCE 87 Khem Gyanwali

 CHAPTER 7
TYPES OF STEELS AND CAST IRON
7.1 Alloy Steel
Steel in itself is an alloy of iron with mainly carbon along with elements like chromium,
manganese, nickel, silicon, vanadium, molybdenum, etc. Alloy steel refers to the alloying
of steel with these different elements in a significant amount. Alloying of steel is done in
order to acquire desired characteristics.
For example:
Alloying of steel with sulphur increases the machinability of steel however it reduces
weldability of steel. Likewise alloying of other elements with steel can improve
hardenability, provide solid solution strengthening of ferrite, improve corrosion resistance,
etc.

Types of Alloy S teels

 HSLA Steel  Stainless Steel  Tool Steel

7.1.1 High Strength Low Alloy Steel s (HSLA)

High Strength Low-Alloy steels or micro-alloyed steels are designed to provide better
mechanical properties, better resistance to environmental corrosion than conventi onal
carbon steels. They are designed to meet the required mechanical properties than acquire
a certain chemical composition. Hence, the composition of the alloy depends on the
mechanical property to be acquired. HSLA in plate or sheet form have low carbon content
(0.05-0.25%) to increase the formability and weldability of steel with manganese content
up to 2%. Chromium, nickel, copper, nitrogen, vanadium, molybdenum, niobium, titanium
are also added in small amounts for various combinations.
HSLA steels are classified as rolled mild carbon steels enhanced with mechanical properties
obtained by the addition of small alloys. HSLA steels are mainly used in pipelines for oils
and gases, heavy duty highway and off road vehicles, storage tanks, power transmission
towers, light poles, etc. The use of HSLA steels is determined on the basis of its purpose
but the most important thing to consider is its favourable strength to weight ratio.

Stainless Steels
All true stainless steels contain a minimum of 11% Chromium which makes them excellent
to corrosion. The secret lies in the protective surface layer of chromium oxide that forms
when the steel is exposed to oxygen. Chromium causes the austenitic region to shrink and
hence the ferrite region increases in size making it a ferrite stabilising agent.

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 Figure 7.1: (a) The effect of 17% chromium on the iron-carbon phase diagram. At low carbon contents,
ferrite is stable at all temperatures. Note that "M" stands for metal such as Cr and Fe or other alloying
additions. (b) A section of the iron-chromium-nickel-carbon phase diagram at a constant 18% Cr - 8% Ni.
At low carbon contents, austenite is stable at room temperature.

Types of Stainless S teels

1. Ferritic Stainless Steels
These contain 12% to 25% Cr and less than 0.1% carbon. Because of B.C.C structure, the
ferritic stainless steels have good strengths and moderate ductility derived from solid
solution strengthening and strain hardening. Ferritic stainless steels are magnetic. They are
not heat treatable. They have excellent corrosion resistance, moderate formability and are
relatively less expensive.

2. Martensitic Stainless Steels

These contain 12% to 25% Cr and 0.1% to 1.0%C. A 17%Cr - 0.5%C alloy heated to 1200 oC
forms 100% austenite, which transforms to martensite on quenching in oil. The martensite
is then tempered to produce high strengths and hardness. The combination of hardness,
strength and corrosion resistance makes the alloy attractive for applications such as high
quality knives, ball bearings and valves.

3. Austenitic Stainless Steels

Nickel, which is an austenite stabilizing element, increases the size of austenite field, while
nearly eliminating ferrite from the iron-chromium-carbon alloys. If the carbon content is
below, about 0.3%, the carbides do not form and the steel is virtually all austenite at room
temperature. The F.C.C austenite stainless steels have excellent ductility, formability and
corrosion resistance. These are non-magnetic, which is an advantage for many

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applications. Unfortunately, the high nickel and chromium contents make the alloy
expensive. The 304 alloy containing 18% Cr and 8% Ni is most widely used grade of stainless
steel.

Figure 7.2: Typical compositions and properties of stainless steels

Tool Steels
Tools steels are high carbon steels that obtain high hardness by quench and temper heat
treatment. Hardenability and stability at high temperatures are the results of alloying
elements. Water hardenable steels must be quenched rapidly to produce martensite and
also soften rapidly even at low temperatures. Oil hardenable steels form martensite more
easily, temper slowly but still soften at high temperatures. The alloy carbides are
particularly stable, resist growth for spheroidisation and are important in establishing the
high temperature resistance of steels. Tool steels are mainly used in making cutting tools
for machining, die casting as high strength, hardness, toughness and temperature
resistance is needed off them. With a carbon content between 0.7% and 1.5%, tool steels
are manufactured under carefully controlled conditions to produce the required quality.
The manganese content is often kept low to minimize the possibility of cracking.

7.1.2 Weldability of S teels

Weldability of steels refers to the ability of steels to be joined by welding. As steels are
used as important structural components along with the strength of steels, joints must also
be strong for the integrity of structures. Many low carbon steels weld easily. Welding of

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medium and high carbon steel is comparatively more difficult since martensite can form in
the heat affected zone rather easily, thereby causing a weld with poor toughness. Several
strategies such as preheating the material or minimizing incorporation of hydrogen have
been developed to counter these problems. In low carbon steels the strength of the
welded zones is higher than the base material itself. This occurs as a result of formation of
pearlite microstructure during cooling. Retained austenite along the ferrite grain
boundaries prevents recrystallization and thus helps retain a finer grain size which
contributes to the strength of the welded joints. During welding, metal near the weld starts
to heat up above the A 1 temperature (refer fig. 6.1) and austenite forms.

During cooling, austenite transforms to a new structure depending on the cooling rate.
We should not weld steels in quenched or tempered conditions because the portion of the
heat affected zone that heats above the A1 temperature forms martensite on cooling and
the portion of steels below A1 temperature may over tempering.

Embrittlement of S teel
Embrittlement is the complete loss or partial loss of ductility in material where an
embrittled product characteristically fails by fracture without appreciable deformation.
The most common embrittlement is usually encountered in galvanized steel related to
aging phenomena, cold working, and absorption of hydrogen. Embrittlement or loss of
ductility in steel is often associated with strain-aging. Strain-aging refers to the delayed
increase in hardness and strength, and loss of ductility and impact resistance which occur
in susceptible steels as a result of the strains induced by cold working. The aging changes
proceed slowly at room temperature, but proceed at an accelerated rate as the aging
temperature is raised and may occur rapidly at the galvanizing temperature of
approximately 455°C (850°F).

Hydrogen Embrittlement may also occur due to the possibility of atomic hydrogen being
absorbed by the steel. The susceptibility to hydrogen Embrittlement is influenced by the
type of steel, its previous heat treatment, and degree of previous cold work. In the case
of galvanized steel, the acid pickling reaction prior to galvanizing presents a potential
source of hydrogen. However, the heat of the galvanizing bath partially expels hydrogen
that may have been absorbed. In practice hydrogen Embrittlement of galvanized steel is
usually of concern only if the steel exceeds approximately 1100 MPa (150 ksi) in ultimate
tensile strength, or if it has been severely cold worked prior to pickling. Loss of ductility of
cold-worked steels is dependent on many factors including the type of steel (strength level,
aging characteristics), thickness of steel, and degree of cold work, and is accentuated by
areas of stress concentration such as caused by notches, holes, fillets of small radii, sharp
bends, etc.

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7.2 Cast Iron and its types
Cast Irons are iron, carbon, silicon alloys mostly containing 2-4% carbon, 0.5-3% silicon that
pass through the eutectic reaction during solidification. Cast iron make excellent casting
alloys since they are easily melted, are very fluid in the liquid state, and do not form
undesirable surface. These alloys have wide range of strength and hardness and in most
cases easy to be machined.

Figure 7.3: Schematic drawings of five types of cast iron: (a) Grey iron, (b) White iron,
(c) Malleable iron, (d) Ductile iron and (e) Compacted graphite iron

Grey Cast Iron

Grey cast iron contains small, interconnected graphite flakes which results in low strength
and ductility. When fractured, the break in this type of cast iron appears gr ey and hence
it’s called grey cast iron. It contains many clusters and eutectic cells of interconnected
graphite flakes which are connected at the graphite nucleus. High strength in grey cast iron
is achieved by reducing carbon content by alloying or heat treating. Although graphite
flakes concentrate stresses and lower ductility and strength, they have high compressive
strength, good machinability, good resistance to sliding ware, good resistance to thermal
fatigue, good thermal conductivity and good vibration damping.

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White Cast Iron
White cast iron is formed as a result of the eutectic reaction of Fe-C alloys that occurs at
1140°C. White cast iron produced by this reaction contains Fe3C and Pearlite. This is the
metastable state and in true equilibrium the reaction results in graphite. When Chromium
and Bismuth are added it results in white cast iron as it prevents the formation of graphite.
Thus, white cast iron has a light appearance.

A more advanced form of white cast iron is chilled cast iron. When an area of grey cast iron
is chilled rapidly from the melt, cast iron is formed at the melt that has been cooled called
the chilled cast iron. The depth of chill decreases and the hardness of the chilled zone
increases with increasing carbon content. As chromium supresses the formation of
graphite and increases hardness and abrasion resistance, it is added in amount, 1 -4%.
Chilled cast iron is used in railway car wheels, crushing rolls, stamp shoes and dies and
heavy duty machinery parts.

Malleable Cast Iron

Malleable cast iron is formed by heat treatment of white cast iron (2.5% C and 1.5% Si)
which forms clumps of graphite. It has better ductility and machinability than white or grey
cast iron. During heat treatment the cementite formed during solidification decomposes
and graphite clumps or nodules are produced. Malleable Cast Iron is therefore used for
connecting rods and universal joint yokes, transmission gears, differential cases and certain
gears, compressor crankshafts and hubs, flanges, pipe fittings and valve parts for railroad,
marine and heavy duty applications. The major drawback of malleable cast iron is
shrinkage.

Ductile Cast Iron

Ductile cast iron is also called nodular cast iron because it contains spheroidal graphite
particles. Ductile cast iron is formed by treating liquid iron with 4.3% magnesium which
causes spheroidal graphite to grow during solidification without lengthy heat treatment
process. Compared to grey cast iron ductile cast iron has excellent strength and ductility.
Due to higher Silicon ductile iron is strong but not as tough as malleable cast iron. Ductile
cast iron is preferred because of its versatility and high performance at low cost. Ductile
cast iron doesn’t shrink during solidification reducing its material requir ement and thus
making it cheaper.

Ductile Cast iron is used when strength, toughness combined with good machinability and
low cost is required. It is used to make crankshafts, engine connecting suspension system
parts, power transmission yokes, high security valves and cast iron pipes.

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Compacted Graphite Iron
Compacted graphite iron(CGI), also known as vermicular graphite iron is a metal which is
gaining popularity in applications that require either greater strength, or lower weight than
cast iron. The graphite in compacted graphite iron differs in structure from that in grey iron
because the graphite particles are shorter and thicker. This results in stronger adhesion
between the graphite and the iron giving the material a greater tensile strength.

The first commercial application for compacted graphite iron was for the brake di scs for
high speed rail trains. More recently compacted graphite iron has been used for diesel
engine blocks. It has proven to be useful in the manufacture of V topology diesel engines
where the loading on the block is very high between the cylinder banks, and for heavy
goods vehicles which use diesel engines with high combustion pressures.
It is also used for turbo housings and exhaust manifolds. In the latter case to reduce
corrosion.

7.2.2 Applications of Cast Iron

 Cookware, such as skillets, pots and pans, is one of the common uses of cast iron.
Once the cookware is cured, it seals in the seasoning of the foods cooked in them and
even adds iron to the diet.
 Cooking utensils for stove-top and outdoor cooking are also constructed of cast iron.
Many of these cast-iron cooking utensils include spoons, grill presses and tongs.
 Designers use cast iron to build furniture, particularly outdoor patio pieces. Cast -iron
furniture includes chairs and glass-top tables.
 Welded barbecue grills use heavy cast-iron materials and stainless steel. Larger models
of these grills are often so heavy that two people have to carry them.
 Industrial and residential construction used cast iron on buildings, especially for beams
and posts that hold up architectural structures. Cast iron is also used in pipe plumbing.
 In the late 1700s, bridges constructed in Europe and the United States used cast iron
as their primary building material.

MATERIAL SCIENCE 94 Khem Gyanwali

 CHAPTER 8
ENVIRONMENTAL EFFECTS
8.1 Corrosion
It is the gradual destruction of material, usually metals, by chemical reaction with its
environment. In the most common use of the word, this means electrochemical oxidation
of metals in reaction with an oxidant such as oxygen. Rusting, the formation of iron oxides,
is a well-known example of electrochemical corrosion. This type of damage typically
produces oxide(s) or salt(s) of the original metal. Corrosion can also occur in materials
other than metals, such as ceramics or polymers, although in this context, the term
degradation is more common. Corrosion degrades the useful properties of materials and
structures including strength, appearance and permeability to liquids and gases.
Many structural alloys corrode merely from exposure to moisture in air, but the process
can be strongly affected by exposure to certain substances. Corrosion can be concentrated
locally to form a pit or crack, or it can extend across a wide area more or less uniformly
corroding the surface. Because corrosion is a diffusion-controlled process, it occurs on
exposed surfaces. As a result, methods to reduce the activity of the exposed surface, such
as passivation and chromate conversion, can increase a material's corrosion resistance.
However, some corrosion mechanisms are less visible and less predictable.

8.2 Galvanic Corrosion

Galvanic corrosion occurs when two different metals have physical or electrical contact
with each other and are immersed in a common electrolyte, or when the same metal is
exposed to electrolyte with different concentrations. In a galvanic couple, the more active
metal (the anode) corrodes at an accelerated rate and the more noble metal (the cathode)
corrodes at a retarded rate. When immersed separately, each metal corrodes at its own
rate. The type of metal(s) to be used is readily determined by the galvanic series. For
example, zinc is often used as a sacrificial anode for steel structures. Galvanic corrosion is
of major interest to the marine industry and also anywhere water (containing salts)
contacts pipes or metal structures.
Factors such as relative size of anode, types of metal, and operating conditions
(temperature, humidity, salinity, etc.) affect galvanic corrosion. The surface area ratio of
the anode and cathode directly affects the corrosion rates of the materials. Galvanic
corrosion is often utilized in sacrificial anodes.
A potential difference usually exists between two dissimilar metals when they are
immersed in a corrosive or conductive solution. If these metals are placed in contact (or
otherwise electrically connected), this potential difference produces electron flow
between them. Corrosion of the less corrosion-resistant metal is usually increased and
attack of the more resistant material is decreased, as compared with the behavior of these
metals when they are not in contact. The less resistant metal becomes anodic and the

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more resistant metal cathodic. Usually the- cathode or cathodic metal corrodes very little
or not at all in this type of couple. Because of the electric currents and dissimilar metals
involved, this form of corrosion is called galvanic, or two-metal, corrosion. It is
electrochemical corrosion, but we shall restrict the term galvanic to dissimilar -metal
effects for purposes of clarity.

8.3 Stress Corrosion

Stress-corrosion cracking refers to cracking caused by the simultaneous presence of tensile
stress and a specific corrosive medium. Many investigators have classified all cracking
failures occurring in corrosive mediums as stress-corrosion cracking, including failures due
to hydrogen embrittlement. However, these two types of cracking failures respond
differently to environmental variables. To illustrate, cathodic protection is an effective
method for preventing stress-corrosion cracking whereas it rapidly accelerates hydrogen-
embrittlement effects. Hence, the importance of considering stress-corrosion cracking and
hydrogen embrittlement as separate phenomena is obvious. For this reason, the two
cracking phenomena are discussed separately in this chapter.
During stress-corrosion cracking, the metal or alloy is virtually unattacked over most of its
surface, while fine cracks progress through it. This cracking phenomenon has serious
consequences since it can occur at stresses within the range of typical design stress.
Exposure to boiling MgCl 2 at 310 °F (154 °C) is shown to reduce the strength capability to
approximately that available at 1200 °F.

The two classic cases of stress-corrosion cracking are "season cracking" of brass, and the
"caustic embrittlement" of steel. Both of these obsolete terms describe the environmental
conditions present which led to stress-corrosion cracking. Season cracking refers to the
stress-corrosion cracking failure of brass cartridge cases. During periods of heavy rainfall,
especially in the tropics, cracks were observed in the brass cartridge cases at the point
where the case was crimped to the bullet. It was later found that the important
environmental component in season cracking was ammonia resulting from th e
decomposition of organic matter.

Many explosions of riveted boilers occurred in early steam-driven locomotives.

Examination of these failures showed cracks or brittle failures at the rivet holes. These
areas were cold-worked during riveting operations, and analysis of the whitish deposits
found in these areas showed caustic, or sodium hydroxide, to be the major component.
Hence, brittle fracture in the presence of caustic resulted in the term caustic
embrittlement. While stress alone will react in ways well known in mechanical metallurgy
(i.e., creep, fatigue, tensile failure) and corrosion alone will react to produce characteristic
dissolution reactions; the simultaneous action of both sometimes produces the disastrous
results.

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8.4 Corrosion Protection
1. Applied Coatings
Plating, painting, and the application of enamel are the most common anti-
corrosion treatments. They work by providing a barrier of corrosion-resistant material
between the damaging environment and the structural material. Aside from cosmetic and
manufacturing issues, there are tradeoffs in mechanical flexibility versus resistance to
abrasion and high temperature. Platings usually fail only in small sections, and if the plating
is more noble than the substrate (for example, chromium on s teel), a galvanic couple will
cause any exposed area to corrode much more rapidly than an unplated surface would.
For this reason, it is often wise to plate with active metal such as zinc or cadmium. Painting
either by roller or brush is more desirable for tight spaces; spray would be better for larger
coating areas such as steel decks and waterfront applications. Flexible polyurethane
coatings, like Durabak-M26 for example, can provide an anti-corrosive seal with a highly
durable slip resistant membrane. Painted coatings are relatively easy to apply and have
fast drying times although temperature and humidity may cause dry times to vary.

2. Reactive Coatings
If the environment is controlled (especially in re-circulating systems), corrosion
inhibitors can often be added to it. These form an electrically insulating or chemically
impermeable coating on exposed metal surfaces, to suppress electrochemical reactions.
Such methods obviously make the system less sensitive to scratches or defects in the
coating, since extra inhibitors can be made available wherever metal becomes exposed.
Chemicals that inhibit corrosion include some of the salts in hard water (Roman water
systems are famous for their mineral deposits), chromates, phosphates, polyaniline,
other conducting polymers and a wide range of specially-designed chemicals that
resemble surfactants (i.e. long-chain organic molecules with ionic end groups).

3. Anodization
This climbing descender is anodized with a yellow finish. Aluminum alloys often undergo a
surface treatment. Electrochemical conditions in the bath are carefully adjusted so that
uniform pores several nanometers wide appear in the metal's oxide film. These pores allow
the oxide to grow much thicker than passivating conditions would allow. At th e end of the
treatment, the pores are allowed to seal, forming a harder-than-usual surface layer. If this
coating is scratched, normal passivation processes take over to protect the damaged area.
Anodizing is very resilient to weathering and corrosion, so it is commonly used for building
facades and other areas that the surface will come into regular contact with the elements.
Whilst being resilient, it must be cleaned frequently. If left without cleaning, panel edge
staining will naturally occur.

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4. Bio-film Coatings
A new form of protection has been developed by applying certain species of bacterial films
to the surface of metals in highly corrosive environments. This process increases the
corrosion resistance substantially. Alternatively, antimicrobial-producing biofilms can be
used to inhibit mild steel corrosion from sulfate-reducing bacteria.

5. Controlled Permeability Formwork

Controlled permeability formwork (CPF) is a method of preventing the corrosion
of reinforcement by naturally enhancing the durability of the cover during concrete
placement. CPF has been used in environments to combat the effects of carbonation,
chlorides, frost and abrasion.

6. Cathodic Protection
Cathodic protection (CP) is a technique to control the corrosion of a metal sur face by
making that surface the cathode of an electrochemical cell. Cathodic protection systems
are most commonly used to protect steel, water, and fuel pipelines and tanks; steel
pier piles, ships, and offshore oil platforms.

7. Sacrificial Anode Protect ion

Sacrificial anode in the hull of a ship. For effective CP, the potential of the steel surface is
polarized (pushed) more negative until the metal surface has a uniform potential. With a
uniform potential, the driving force for the corrosion reaction is halted. For galvanic CP
systems, the anode material corrodes under the influence of the steel, and eventually it
must be replaced. The polarization is caused by the current flow from the anode to the
cathode, driven by the difference in electrochemical potential between the anode and the
cathode.

8. Impressed Current Cathodic Protection

For larger structures, galvanic anodes cannot economically deliver enough current to
provide complete protection. Impressed current cathodic protection (ICCP) systems use
anodes connected to a DC power source (such as a cathodic protection rectifier). Anodes
for ICCP systems are tubular and solid rod shapes of various specialized materials. These
include high silicon cast iron, graphite, mixed metal oxide or platinum coated titanium or
niobium coated rod and wires.

9. Anodic Protection
Anodic protection impresses anodic current on the structure to be protected (opposite to
the cathodic protection). It is appropriate for metals that exhibit passivity (e.g., stainless
steel) and suitably small passive current over a wide range of potentials. It is used in
aggressive environments, e.g., solutions of sulfuric acid.

MATERIAL SCIENCE 98 Khem Gyanwali

 CHAPTER 9
NON-FERROUS ALLOYS
9.1 Aluminium Alloys
Aluminium alloys are alloys in which aluminium (Al) is the predominant metal. The typical
alloying elements are copper, magnesium, manganese, silicon and zinc. There are two
principal classifications, namely casting alloys and wrought alloys, both of which are further
subdivided into the categories heat-treatable and non-heat-treatable.
Aluminium alloys can be classified into wrought and casting alloys on the basis of method
of fabrication. Wrought alloys are formed by plastic deformation while casting alloys are
formed by using casting process. Wrought alloys can be classified as heat treatable and
non-heat treatable alloys. Non-heat treatable alloys include aluminium alloys with
magnesium, manganese and silicon. While heat treatable wrought alloys are aluminium
alloys with Copper, Lithium, Silicon and Zinc

Properties
 Aluminium and its alloys are easily formable and can be worked upon by rolling,
extruding, drawing, machining and other mechanical processes.
 They have high thermal and electrical conductivity and do not show ductile to brittle
transition at low temperatures.
 Cast aluminium alloys have low melting point, although they generally have lower tensile
strengths than wrought alloys.
 Aluminium and its alloys lend themselves to a huge variety of surface treatments, which
enhances its intrinsic qualities. For example, an anodization of a few micrometres is
enough to preserve the optical or decorative properties of the materials, while improving
resistance, especially to corrosion and stress.
 The tensile strength of pure aluminum is around 90 MPa but this can be increased to
over 690 MPa for some heat-treatable aluminum alloys.

Uses
 Non-heat treatable aluminum alloys are used for making electrical components, foil,
food packaging, beverage can bodies, architectural uses, filler metal welding, beverage can
tops and marine components while heat treatable aluminum alloys are used for truck
wheels, aircraft skins, pistons, canoes, railroad cars and aircraft frames.
 Casting alloys contain high amount of silicon to cause the eutectic reaction giving the
alloys low melting points, good fluidity and good castability
 Aluminium alloys are widely used in engineering structures and components where light
weight or corrosion resistance is required.
 Advanced aluminum alloys have enabled the design of high-speed ships, by lightening
hulls by 40% to 50% over steel.

MATERIAL SCIENCE 99 Khem Gyanwali

9.2 Magnesium Alloys
Magnesium alloys are mixtures of magnesium with other metals, often aluminium, zinc,
manganese, silicon, copper, rare earths metals and zirconium. Magnesium alloys have a
hexagonal lattice structure, which affects the fundamental properties of these alloys.
Plastic deformation of the hexagonal lattice is more complicated than in cubic latticed
metals like aluminium, copper and steel. Therefore magnesium alloys are typically used as
cast alloys.

Properties
 Magnesium is the lightest structural metal and its alloys containing Lithium have
extremely light weight.
 Magnesium has low modulus of elasticity and poor resistance to fatigue, creep and
wear.
 Magnesium alloys can be strengthened either by dispersion strengthening or age
hardening.
 Some age hardened alloys such as those containing Zirconium, Thorium, Silver, and
Cerium have good resistance to over aging temperatures.
 Magnesium alloys with less impurities and high Cerium content form a protective layer
of MgO making it corrosion resistant.
 The machinability of magnesium alloys is the best of any commercial metal, and in many
applications, the savings in machining costs more than compensate for the increased cost
of the material.
 Magnesium alloys are easily machined, cast, forged, and welded.

Uses
 Magnesium alloys are used for aerospace applications, high speed machinery and
materials handling equipment.
 Cast magnesium alloys are used for many components of modern cars, and magnesium
block engines have been used in some high-performance vehicles.
 Magnox (alloy), whose name is an abbreviation for 'magnesium non-oxidising', is 99%
magnesium and 1% aluminium, and used in the cladding of fuel rods in some nuclear power
stations.
 They are now also used in jet-engine parts, rockets and missiles, luggage frames,
portable power tools, and cameras and optical instruments .
 They is also used in pyrotechnics, especially in incendiary bombs, signals, and flares, and
as a fuse for thermite.

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9.3 Copper Alloys
Copper alloys have higher densities than that of steels. Copper based alloys benefit by
strengthening mechanisms as they improve the mechanical properties of copper alloys.
Copper containing 0.1% impurities is used for electrical and microelectronics applications .
Small amounts of cadmium, silver and Aluminium oxide improve their hardness without
impairing conductivity. Cold working is used for strengthening of single phase copper
based alloys.

Properties
 Even though their yield strength is higher than that of aluminium and magnesium alloys,
they have low specific strengths.
 They are better resistant to creep, fatigue, and wear.
 Most of high ductility, corrosion resistance, electrical and thermal conductivity and can
be joined and fabricated into complex shapes easily.
 The face centred cubic structure of copper provides excellent ductility and high strain
hardening coefficient.
 Copper alloy corrode easily by reacting with sulphur and forms a green layer on the
surface.

Uses
 Copper based alloys are used in pumps, valves and plumbing parts where their
properties are used as advantages.
 Copper based alloys are used as decorative items because of the changing colours as it
reacts with different elements.
 Copper and its alloys are widely used in deep draw and flat stamped products because
they have excellent electrical and thermal performance, good resistance to corrosion, high
ductility and relatively low cost.
 Integrated circuits and printed circuit boards use copper and its alloys in place of
aluminum because of its superior electrical conductivity.

Types of Copper alloys

1. Brass
Brass is an alloy made of copper and zinc; the proportions of zinc and copper can be varied
to create a range of brasses with varying properties. Brass is a substitutional copper alloy.
The relatively low melting point of brass (900 to 940 °C, depending on composition) and
its flow characteristics make it a relatively easy material to cast. Different grades of brass,
with different amounts of zinc, have different characteristics in surface smoothness,
corrosion-resistance, ease and quality of machining, response to plating, ductility levels,
chemical and temperature limits.

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Uses: It is used for decoration for its bright gold-like appearance; for applications where
low friction is required such as locks, gears, bearings, doorknobs, ammunition casings and
valves; for plumbing and electrical applications; and extensively in brass musical
instruments such as horns and bells for its acoustic properties. It is also used in zippers.
Brass is often used in situations where it is important that sparks not be struck, as in fittings
and tools around explosive gases.

2. Bronze
Bronze is principally an alloy of copper and tin. Bronze does not necessarily contain tin, and
a variety of alloys of copper, including alloys with arsenic phosphorus, aluminum,
manganese, and silicon, are commonly termed "bronze". Bronze is generally harder
than wrought iron, with Vickers hardness of 60–258. Bronze is softer, weaker and less stiff
than steel. Bronze resists corrosion (especially seawater corrosion) and metal fatigue more
than steel and is a better conductor of heat and electricity than most steels.
Uses: Bronze was especially suitable for use in boat and ship fittings prior to the wide
employment of stainless steel owing to its combination of toughness and resistance to salt
water corrosion. Bronze is still commonly used in ship propellers and submerged bearings.
It is also widely used for cast bronze sculpture. Many common bronze alloys have the
unusual and very desirable property of expanding slightly just before they set, thus filling
in the finest details of a mold. Bronze parts are tough and typically used for bearings, clips,
electrical connectors and springs. Bronze is also used to make bronze wool for
woodworking applications where steel wool would discolor oak.

9.4 Nickel and Cobalt Alloys

Nickel and Cobalt have high strengths and high melting points and thus are used for
corrosion protection and high temperature resistance. Solidified powders of nickel and
cobalt based super alloys can be formed by using spray atomization followed by hot
isostatic pressing which are then used for making rings that retain the turbine blades. Since
Iron, Nickel and Cobalt are magnetic, they form very good magnetic materials.

Solidified powders of nickel and cobalt based super alloys can be formed by using spray
atomization followed by hot isostatic pressing which are then used for making rings that
retain the turbine blades. Since Iron, Nickel and Cobalt are magnetic, they for m very good
magnetic materials. Because of their biocompatibility, cobalt alloys are used for prosthetic
devices.

A Ni-Fe alloy Invar displays approximately no expansion during heating and are hence used
in producing bimetallic composite materials. Cobalt is used for absorbing shocks and
vibrations in cutting tools.

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Copper added nickel alloy called Monel is used for its strength and corrosion resistance in
salt water and at elevated temperatures.
Solid solution strengthening, dispersion strengthening and precipitation hardening are
used to make super alloys which basically consist of Iron, Nickel and Cobalt. These
strengthening measures produce high strength at elevated temperatures, resistance to
corrosion and resistance to creep up to 1000°C. Thus made super alloys are used in making
vanes and blades for turbines and jet engines, heat exchangers, chemical reaction vessel
components and heat treating equipment.
Typical alloys and their applications are listed in the table below:

Figure 9.1: Compositions, properties and applications for selected Nickel and Cobalt alloys

9.5 Titanium Alloys

Titanium alloys are metals which contain a mixture of titanium and other chemical
elements. Such alloys have very high tensile strength and toughness (even at extreme
temperatures). They are light in weight, have extraordinary corrosion resistance and the
ability to withstand extreme temperatures. However, the high cost of both raw materials
and processing limit their use to military applications, aircraft, spacecraft, medical devices,
connecting rods on expensive sports cars and some premium sports equipment and
consumer electronics.
Auto manufacturers Porsché and Ferrari also use titanium alloys in engine components due
to its durable properties in these high stress engine environments.

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Although "commercially pure" titanium has acceptable mechanical properties and has
been used for orthopaedic and dental implants, for most applications titanium is alloyed
with small amounts of aluminium and vanadium, typically 6% and 4% respectively, by
weight. This mixture has a solid solubility which varies dramatically with temperature,
allowing it to undergo precipitation strengthening. This heat treatment process is carried
out after the alloy has been worked into its final shape but before it is put to use, allowing
much easier fabrication of a high-strength product.
Titanium has excellent mechanical properties. An adherent TiO 2 layer on the surface
provides excellent resistance to corrosion and contamination below 535°C but above this
temperature the oxide film breaks down and small atoms such as carbon, oxygen,
hydrogen and nitrogen make titanium brittle.
Excellent corrosion resistance makes titanium suitable for chemical processing equipment,
marine components and biomedical implants. Titanium alloys are also used in making
airframes and jet engine components. When combined with niobium, it forms a
superconductive intermetallic compound (mixture of elements producing its own crystal
structure and mechanical properties). Titanium alloys are used for sports equipment such
as the head of the golf club.

9.6 Refractory Metals

Refractory metals are metals with really high melting points normally above 2000°C. This
category consists of tungsten, molybdenum, tantalum and niobium. These metals are
therefore used for their high temperature service such as filaments in light bu lbs, rocket
nozzles, nuclear power generators, tantalum and niobium based electronic capacitors and
chemical processing equipment. However, their high densities limit their specific strengths.
Refractory metals rapidly oxidize between 200 and 425°C and are therefore contaminated
or embrittled. Hence, special precautions are required during casting, welding, hot working
or powder metallurgy. For tungsten filaments, preserving in vacuum protects it from
oxidization.

Some metals can be coated with a silicide or aluminium coating. These coating materials
are selected on the basis of their high melting temperature, compatibility with refractive
metals, ability to form a diffusion barrier so that contaminants can’t reach the underlying
metals, and their coefficient of thermal expansion which is required to be similar to that of
refractory metals. As refractory metals have B.C.C crystal structure, they have low ductile
to brittle transition temperature. For niobium and tantalum this temperature is below
room temperature whereas for molybdenum and tungsten, it’s above room temperature.
Therefore, niobium and tantalum can be easily formed while molybdenum and tungsten
are hot worked to produce a fibrous micro structure improving their forming
characteristics. Further alloying of refractory metals produces improved mechanical
properties along with improving high temperature properties.

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 CHAPTER 10
ORGANIC AND COMPOSITE MATERIALS
10.1 Polymers
Polymers are materials consisting of giant macromolecules which are built of many units
joined by chemical bonding. The process by which polymers are formed is called
polymerization. Polymers are used in many applications including clothing, toys, home
appliances, structural and decorative items, paints, adhesives, automobile tyr es, car
bumpers, biomedical devices, interiors, foams and packaging. Polymers are also used to
make electrical components as they possess insulating ability and low dielectric constant.
Polymers can also be used as substitutes for glass when they are trans parent. Because of
their lightweight, corrosion resistant property and their inexpensiveness they are used in
several applications. Engineering polymers are therefore designed to improve strength at
elevated temperatures but are expensive to manufacture.

10.1.1 Types of Polymers

Polymers can be classified into three groups and their comparison can be done as follows:
1) Thermoplastic
2) Thermosetting
3) Elastomers
Thermoplastic polymers have flexible linear chain whether straight or branched while
thermosetting polymers have rigid three dimensional network. Elastomers on the other
hand are a mixture of thermosetting and thermoplastic polymers with spring like
molecules. Polyethylene, polyurethane and rubber are examples of thermoplastic,
thermosetting and elastomer respectively.

Thermoplastics
Thermoplastics behave in a ductile manner and are composed of long chains produced by
joining together of monomers. The individual chains may be branched or single. The
Vander Waals forces between atoms of each chain is very weak. Therefore, these chains
tangle up in order to form a material and can be untangled by the application of tensile
stress. They soften and melt upon heating and can therefore be easily recycled.

Thermosetting Polymers
Thermosetting polymers are composed of long chains of molecules, single or branched
that are cross linked to each other to form a three dimensional network. Thermosetting
polymers are therefore stronger but brittle when compared to thermoplastics. Unlike
thermoplastics they do not melt on heating, they decompose and the cross links break
making it harder for them to be recycled.

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Elastomers
Elastomers are basically rubbers which can be plastically deformed up to 200%. The
polymer chains consist of coil like molecules which can reversibly stretch by applying a
force. Thermoplastic polymers have the ease of processing of thermoplastics and elastic
behaviours of elastomers.

10.1.3 Addition and Condensation Polymerisation

The polymer is the only product in addition polymerisation. An addition polymer is
a polymer which is formed by an addition reaction, where many monomers bond together
via rearrangement of bonds without the loss of any atom or molecule. It involves the
opening out of a double bond. The conditions of the reaction can alter the properties of
the polymer. Reaction proceeds by a free radical mechanism. Oxygen is often used as the
initiator in many reactions.
An example of addition reaction is given below:
In this reaction vinyl chloride monomer is changed to polyvinyl chloride by addition
reaction. Condensation polymerisation uses monomers that have two functional groups
per molecule. These are said to be di-functional. Polymerisation occurs when these
monomers react ‘head-to-tail’ to form a new bond that will eventually join the monomers
together. A small molecule (often water) is eliminated during the reaction.

An example of condensation polymerization is given below:

Figure 10.1: Condensation reaction for polyethylene terephthalate (PET)

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10.1.4 Degree of Polymerization
The degree of polymerization, or DP, is usually defined as the number of monomeric units
in a macromolecule or polymer or oligomer molecule.
For a homopolymer, there is only one type of monomeric unit and the number-average
degree of polymerization is given by,
𝑎𝑣𝑒𝑟𝑎𝑔𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑜𝑙𝑦𝑚𝑒𝑟
𝐷𝑃𝑛 =
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑟𝑒𝑝𝑒𝑎𝑡𝑖𝑛𝑔 𝑢𝑛𝑖𝑡
For most industrial purposes, degrees of polymerization in the thousands or tens of
thousands are desired.
International Union of Pure and Applied Chemistry (IUPAC) defines degree of
polymerization as "the number of monomeric units in a macromolecule an oligomer
molecule, a block, or a chain."

10.1.5 Forming of Polymers

Thermoplastics are melted from a solid and reshaped before cooling. Common forming
methods include injection moulding, blow moulding and extrusion. Thermosets are not
fully polymerised before forming. They are formed into the desired shape and then made
into a solid through a chemical reaction to create cross-links in the polymer chains.
Common forming methods include injection moulding, compression moulding and transfer
moulding.

Injection Moulding
Injection moulding is by far the most important method of forming plastic materials. Plastic
pellets are fed into a rotating auger. The auger moves the pellets down a path towards the
mould. As the pellets move they are pushed against the heated outer walls and are melted
into a viscous liquid. At the end of the moulding machine the polymer liquid is injected into
a fashioned mould and cooled until solid.

Figure 10.2: Injection Moulding

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Compression Moulding
Compression moulding is principally used for thermosetting plastics. Preheated resin is
placed into a hot mould cavity. The upper section of the mould is subsequently forced
down onto the resin to create the desired product shape. The applied pressure and heat
forces the liquefied polymer to fill the cavity. Following the compression, a period of
heating is required to force cross-linking of the thermosetting polymer.

Figure 10.3: Compression Moulding

Transfer Moulding
Transfer Moulding is similar to compression moulding in that a carefully calculated, pre-
measured amount of uncured moulding compound is used for the moulding process. The
difference is, instead of loading the polymer into an open mould, the plastic material is
pre-heated and loaded into a holding chamber called the pot. The material is then
forced/transferred into the pre-heated mould cavity by a hydraulic plunger through a
channel called sprue. The mould remains closed until the material inside is cured.

Figure 10.4: Transfer Moulding

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10.1.6 Additives to Polymers
Additives to polymers are materials that are added to polymers in order to improve or
change the visual, process, or environmental resistance and degradation properties.
Additives to polymers can be categorized based on their primary purpose, which will be
either to add bulk or volume while controlling properties and costs, or modify the chemical
or physical properties of the polymer or reinforce the mechanical properties of the
polymer, making it stronger or higher in impacts strength.

10.1.7 Adhesives to P olymers

Adhesives are materials, typically liquid or semi-liquid, that adhere or bond items together.
Adhesives come from either natural or synthetic sources. Adhesives cure (harden) by
either evaporating a solvent or by chemical reactions that occur between two or more
constituents. Adhesives are also very useful for joining thin or dissimilar materials,
minimizing weight, and providing a vibration-damping joint. A disadvantage of most
adhesives is that most do not form an instantaneous joint, unlike many other joining
processes, because the adhesive needs time to cure.

Types of Adhesives
1. Non-reactive adhesives : white glue, rubber cement, natural rubber, polychloroprene
2. Reactive adhesives : polyester resin, polyurethane resin, polyols, acrylic polymers
3. Natural adhesives : animal glue, Casein,
4. Artificial adhesives : epoxy, polyurethane, cyanoacrylate

10.2 Ceramics
Ceramic is an inorganic, non-metallic solid prepared by the action of heat and subsequent
cooling. Ceramic materials may contain ionic, covalent or both bonds. The building criteria
for the crystal structure are:
 maintain neutrality
 charge balance dictates chemical formula
 achieve closest packing (refer figure below)
 the condition for minimum energy implies maximum attraction and minimum
repulsion. This leads to contact, configurations where anions have the highest
number of cation neighbours and vice versa.

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10.2.1 Imperfections in Ceramics
Imperfections include point defects and impurities. The columbic forces are very large and
any charge imbalance has a strong tendency to balance itself. To maintain charge neutrality
several point defects can be created.
Non-stoichiometry (composition deviates from the one predicted by chemical formula)
may occur when one ion type can exist in two valence states. To minimize energy, the
effect of non-stoichiometry is a redistribution of the atomic charges. E.g. Fe 2+, Fe3+
For example, in FeO, usual Fe valence state is 2+. If two Fe ions are in 3+ state, then a Fe
vacancy is required to maintain charge neutrality which means there'll be fewer Fe ions
and hence leads to non-stoichiometry.

Charge neutral defects include the Frenkel and Schottky defects.

Frenkel defect is a pair of cation (positive ion) vacancy and a cation interstitial. It may also
be an anion (negative ion) vacancy and anion interstitial. However, anions are larger than
cations and 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.

Figure 10.5: Frenkel and Schottky Defect

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Impurity atoms can exist as either substitutional or interstitial solid solutions.
 Substitutional ions substitute for ions of like type.
 Interstitial ions are small compared to host structure - anion interstitials are unlikely.
 Solubility is higher if ion radii and charges match closely.
 Incorporation of ion with different charge state requires compensation by point
defects.

10.2.2 Silicate Ceramics

Silicate is mainly composed of silicon and oxygen, the two most
abundant elements in earth’s crust (rocks, soil, clay, sand). The
basic building block is SiO 4 4- tetrahedron. Si-O bonding is
largely covalent, but overall SiO4 block has charge of –4.

Figure 10.6: 3D network of SiO4

tetraherdra in cristobalite
10.2.3 Glass
Glass is a non-crystalline (amorphous) ceramic. Fused silica
is SiO2 to which no impurities have been added. Other
common glasses contain impurity ions such as Na +, Ca2+,
Al3+, and B3+.
Basic unit of glass is shown in figure 10.7.

Figure 10.7: Basic unit of glass

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A special characteristic of glasses is that solidification is gradual, through a viscous stage,
without a clear melting temperature. The specific volume does not have an abrupt
transition at a temperature but rather shows a change in slope at the glass-transition
temperature. The melting point, working point, softening point and annealing point are
defined in terms of viscosity, rather than temperature, and depend on glass composition.

Sheet Glass Forming

Sheet forming is a continuous casting process where sheets of glass (float glass) are formed
by floating the molten glass on a pool of molten tin or lead or any other alloy with low
melting point. This method gives the sheet uniform thickness and very flat surfaces.
Modern windows are made of float glass, which are mostly soda-lime glass.

Figure 10.8: Sheet Glass Forming

10.2.4 Deformation and Failure

The brittle fracture of ceramics limits 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 formation,
and crack propagation (perpendicular to the applied stress) is usually transgranular, along
cleavage planes. The flaws cannot be closely controlled in manufacturing; this leads to a
large variability (scatter) in the fracture strength of ceramic materials.

The compressive strength is typically ten times the 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.

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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). Viscosity decreases strongly with increases temperature.

Processing of Ceramics
Ceramic processing is used to produce commercial products that are very diverse in size,
shape, detail, complexity, and material composition, structure, and cost. The purpose of
ceramics processing to an applied science is the natural result of an increasing ability to
refine, develop, and characterize ceramic materials.
Ceramics are typically produced by the application of heat upon processed clays and other
natural raw materials to form a rigid product. Ceramic products that use naturally
occurring rocks and minerals as a starting material must undergo special processing in
order to control purity, particle size, particle size distribution, and heterogeneity. These
attributes play a big role in the final properties of the finished ceramic. Chemically
prepared powders also are used as starting materials for some ceramic products. These
synthetic materials can be controlled to produce powders with precise chemical
compositions and particle size.

The next step is to form the ceramic particles into a desired shape. This is accomplished by
the addition of water and/or additives such as binders, followed by a shape forming
process. Some of the most common forming methods for ceramics include extrusion, slip
casting, pressing, tape casting and injection moulding. After the particles are formed, these
"green" ceramics undergo a heat-treatment (called firing or sintering) to produce a rigid,
finished product. Some ceramic products such as electrical insulators, dinnerware and tile
may then undergo a glazing process. Some ceramics for advanced applications may
undergo a machining and/or polishing step in order meet specific engineering design
criteria.

Applications of ceramics
Most ceramics materials do not exhibit a non-linear plastic region before failure. Instead,
ceramics are known to be brittle and fail catastrophically. Their application in engineering
applications has certainly been limited by their lack of toughness.
Ceramics are used in an array of applications:
 Compressive strength makes ceramics good structural materials (e.g., bricks in houses,
stone blocks in the pyramids).
 High voltage insulators and spark plugs are made from ceramics due to its electrical
conductivity properties. E.g. Due to good thermal insulation, ceramic tiles are used in

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 ovens and as exterior tiles on the Shuttle orbiter. Some ceramics are transparent to
radar and other electromagnetic waves and are used in transmitters.
 Hardness, abrasion resistance, imperviousness to high temperatures and extremely
caustic conditions allow ceramics to be used in special applications where no other
material can be used.
 Chemical inertness makes ceramics ideal for biomedical applications like orthopaedic
prostheses and dental implants.
 Glass-ceramics, due to their high temperature capabilities, leads to uses in optical
equipment and fibre insulation.
 Ceramic materials that contain alumina and silicon carbide are ext remely rigid and are
used to sand various surfaces, cut metals, polish, and grind. Ceramics that consists of
silica, zirconium oxide, magnesium oxide, silicon carbide & alumina are used in making
refractories.

10.3 Composite materials

Sometimes two or more materials are combined together to produce a new material,
which possesses much superior properties than any one of the constituent materials. Such
a material is known as composite material. The common example of a natural composite
is wood, which consists of long cellulose fibre held together by amorphous lignin. Some of
the artificial (or synthetic) composite materials are cement concrete, glass, reinforced
plastic, plywood, etc.
A type of composite that has been discussed is pearlitic steel, which combines hard, brittle
cementite with soft, ductile ferrite to get a superior material.
Usually composites have two phases: matrix phase (continuous) or dispersed phase
(particulates, fibres). Properties of composites depend on properties of phases, geometry
of dispersed phase (particle size, distribution, orientation) and amount of phase.

10.3.1 Dispersion-Strengthened Composites

It is the process of use of very hard, small particles to strengthen metals and metal alloys.
The effect is like precipitation hardening but not so strong. In dispersion strengthened
composites, small particles on the order of 10-5 mm to 2.5 x 10-4 mm in diameter are
added to the matrix material. These particles act to help the matrix resist deformation. This
makes the material harder and stronger. Consider a metal matrix composite with a fine
distribution of very hard and small secondary particles. The matrix material is carrying most
of the load and deformation is accomplished by slip and dislocation movement. The
secondary particles impede slip and dislocation and, thereby, strengthen the material. The
mechanism is that same as precipitation hardening but effect is not quite as strong.
However, particles like oxides do not react with the matrix or go into solution at high
temperatures so the strengthening action is retained at elevated temperatures.

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Classification of compos ites
The composite materials are of the following three types:
10.3.2 True particulate composites ( Particle-Reinforced Materials or Agglomerated
Materials): The materials in which the particles are condensed together to form an integral
mass, are known as agglomerated materials. A common example of agglomerated material
is cement concrete, which is formed by mixing coarse aggregate, fine aggregate, cement
and water in different proportions. Other useful agglomerated material is grinding wheel
(abrasive) which is formed by mixing asphalt, stone and resin of different sizes.
Agglomerated materials are usually dispersion strengthened to increase their strength
than the normal composites. The particles in these composite are larger than in dispersion
strengthened composites. The particle diameter is typically on the order of a few microns.
In this case, the particles carry a major portion of the load. The particles are used to
increase the modulus and decrease the ductility of the matrix. Another example of particle
reinforced composite is an automobile tire which has carbon black particles in a matrix of
polyisobutylene elastomeric polymer. Particle reinforced composit es are much easier and
less costly than making fibre reinforced composites. With polymeric matrices, the particles
are simply added to the polymer melt in an extruder or injection molder during polymer
processing. Similarly, reinforcing particles are added to a molten metal before it is cast.

10.3.3 Fibre-Reinforced Materials : The materials which are produced by combining some
suitable material to provide additional strength which does not exist in a single material,
are known as reinforced materials. The common example of reinforced material is
reinforced cement concrete (R.C.C), glass fibre, reinforced plastics, etc. Fibre-reinforced
composites use short or long fibre as their prime component, which are usually interwoven
using appropriate binder to give a stiff product.
Fibreglass is likely the best known fibre reinforced composite but carbon-epoxy and other
advanced composites all fall into this category. The fibres can be in the form of long
continuous fibres, or they can be discontinuous fibres, particles, whiskers and even weaved
sheets. Fibres are usually combined with ductile matrix materials, such as metals and
polymers, to make them stiffer, while fibres are added to brittle matrix materials like
ceramics to increase toughness. The length-to diameter ratio of the fibre, the strength of
the bond between the fibre and the matrix, and the amount of fibre are variables that
affect the mechanical properties. It is important to have a high length-to-diameter aspect
ratio so that the applied load is effectively transferred form the matrix to the fibre.

10.3.4 Laminar Composite Materials (Structural Materials): The materials which are
produced by bonding two or more layers of different materials completely to each other,
are known as laminated materials or laminates. The materials, constituting a laminated
material, may be metallic or non-metallic depending upon the type of application. Sheets
(panels) with different orientation of high strength directions are stacked and glued

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together, producing a material with more isotropic strength in the plane. Plywood, Tufnol
are some of the examples of laminates. Strong, stiff end sheets are bonded to lightweight
core structure, for instance honeycomb which provides strength to shear. It is used in
roofs, walls, and aircraft structures.

10.3.5.1 Wood
Wood is a natural composite material made of
complex array of cellulose called lignin. It has high
tangential strength along longitudinal axis of tree
trunk. Wood is used to make other composites like
plywood and paper. Wood is machined according
to different applications.

Properties
 Wood is a complex structure with no uniformity.
 Diagram of the cross-section of a tree trunk
shows the following:
 Outer bark : Composed of dry, dead tissues Figure 10.9: Transverse section of
 Inner bark : Moist & soft layer a tree trunk
 Sapwood : Light colored outer wood; contains
some living cells
 Heartwood : Dark, older wood that forms inner part of stem; contains non-living cells
 Pith : Soft tissue at center of the wood
 Classified as softwood and hardwood.
 Annual growth rings determine the age of trees.
 Moisture content is a parameter of wood. i.e.
 Wood moisture (wt. %) = (wt. of water in sample/ wt. of dry wood sample) X 100%
 At green condition, moisture content ranges form 60-150% while at dry condition, it
comes down to around 20-30%.
 Young’s Modulus = 9 to 11 X 10 9 N/m2

Applications
 Wood is extensively used for making doors and window frames.
 Extensively used in in-door furniture.
 Used as floors and walls
 Used in aircrafts and water boats as major components plus decorative items.
 Used during construction for scaffolding purpose.
 Used for making musical instruments plus sports equipment.

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10.3.5.2 Concrete
Concrete is a mixture of cement (or lime), sand, brick or stone ballast and water, which
when placed in forms and allowed to cure, becomes hard like stone. The hardening is
caused by the chemical reaction between cement and water. The cement and water form
a paste which, upon hardening, binds the aggregates to a permanent mass. Cement is
called the binding material. The stone or brick ballast is called the coarse aggregate as
distinguished from the fine aggregate which is sand. The mortar used in concrete is called
matrix. Cement concrete when used by itself is known as mass concrete.

Cement (Portland cement)

 Raw materials: CaO, Sio2, Al2O3, Fe2O3 are mixed in a rotatory kiln at temperature around
1400oC.
 Gypsum is added to cement controls its setting time.
 Different proportions of aforesaid ingredients differ grade of cement (Classified as Type
I to Type V)

Aggregate
 Source include rocky mountains.
 Big rocks are cut using manpower, machines or explosives.
 Aggregates of standard sizes (coarse and fine) are sieved using appropriate sieves.
 With the components of concrete manufactured, they are mixed in different
proportions.
 Ratio of 1:2:4 for cement: water: aggregate is the usual ratio for a concrete mixture.
 Sand is also mixed in most cases to be economical.

Properties
 Aggregate size, cement types and water content plus use of sand in concrete differs its
 Quality in terms of reactance with sulfate, strength and setting time.
 Concrete has high compressive strength relative to its tensile strength.
 Steel reinforcing bars are used within the concrete structure to increase its tensile
strength. Such concrete is called RCC (Reinforced Concrete Cement).
 Steel bars are first applied with tensile force.
 Concrete paste is poured on the steel bars.
 Tensile force is removed from the steel bar.
 Steel tries to be compressed which introduces compressive force which concrete can.

Applications
 Making beams, pillars and roofs for buildings.
 Construction of septic tanks, water pipes and water reserve tanks.
 Concrete blocks are used widely for making pavements and making walls.

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 Used in making bank vaults because of immense strength.
 Used in water proofing of floors.

10.3.5.3 Asphalt
Asphalt is a black colored composite in liquid or semi-liquid phase. It is highly viscous and
sticky. It is a petroleum product. It is also called bitumen or pitch. It is heated and mixed
with fine aggregate to form asphalt aggregate. Asphalt aggregate is used extensively in
road construction and waterproofing purpose.

Properties
 A petroleum product.
 A hydrocarbon with some oxygen, sulfur and other impurities.
 Highly viscous liquid/ semi-solid substance.
 Viscosity decreases with increase in temperature.
 Mechanical properties resemble with that of thermoplastic.
 Aggregate mix behaves like a strong bonded mass when set.
 Glossy but provides friction on road surfaces.

Applications
 Mixed with fine aggregate in 5%-95% ratio to form asphalt concrete which is rolled onto
road to form hard surface.
 Used to make runways for airplanes.
 Mastic asphalt is used to waterproof underground tanks and floors.
 Asphalt is also used to make lacquers and emulsions.
 Used to seal batteries during manufacture.

10.3.6 Nano-Composites
A nano-composite is a multiphase solid material where one of the phases has one, two or
three dimensions of less than 100 nanometres (nm), or structures having nano-scale
repeat distances between the different phases that make up the material. In the broadest
sense this definition can include porous media, colloids, gels and copolymers, but is more
usually taken to mean the solid combination of a bulk matrix and nano-dimensional
phase(s) differing in properties due to dissimilarities in structure and chemistry. These
materials have high surface to volume ratio.The mechanical, electrical, thermal, optical,
electrochemical, catalytic properties of the nano-composite will differ markedly from that
of the component materials. Nano-composites have enhanced electrical, thermal,
magnetic, optical plus mechanical properties with respect to macro-composites and can
be made of ceramic, polymer or metal.

MATERIAL SCIENCE 118 Khem Gyanwali

 Size limits for these effects have been proposed, <5 nm for catalytic activity, <20 nm for
making a hard magnetic material soft, <50 nm for refractive index changes, and <100 nm
for achieving super paramagnetism, mechanical strengthening or restricting matrix
dislocation movement. Nano-composites are found in nature, for example in the structure
of the abalone shell and bone. The use of nanoparticle-rich materials long predates the
understanding of the physical and chemical nature of these materials.
Carbon-reinforced composite is one of its most useful example of nano composite.

MATERIAL SCIENCE 119 Khem Gyanwali