MODULE-I

MET 285
MATERIAL SCIENCE AND TECHNOLOGY
LEO A J
 TEXT
BOOKS
• V.Raghavan , Material Science and Engineering, Prentice Hall
• V.Raghavan , Physical Metallurgy, Prentice Hall
• Dr.S.Jose and Dr.E.V.Mathew , Metallurgy and Materials Science,
Pentagon
• William. D Callister., Material Science and Engineering, John Wiley
• O.P.Khanna, Material Science and Metallurgy, Dhanpat Rai Publications
• Van Vlack -Elements of Material Science - Addison Wesley
• George E Dieter, Mechanical Metallurgy, Tata McGraw Hill
 METALLURGY & MATERIAL
SCIENCE
• The study of material science in engineering is confined mainly to
the study of solid materials , useful in engineering applications,
using basic principles of solid state physics and solid state
chemistry
• Metallurgy stands for science and technology of metals and their
alloys
• It is a domain of material science that studies the physical and
chemical behaviour of metallic elements and their alloys
• Extractive metallurgy, physical metallurgy and mechanical
metallurgy are the three predominant areas
 CLASSIFICATION OF ENGINEERING
MATERIALS
• Based on the chemical make up and atomic structure engineering
materials are classified into three major groups
1. Metals
2. Ceramics
3. Polymers
• Metals: elements with 1,2 or 3 valance electrons in the outer shell
• Metals are either pure metals or alloys
• Metals are generally grouped into two major classes: ferrous and
non ferrous
 CLASSIFICATION OF ENGINEERING
MATERIALS (Cont…)

• Ceramics: inorganic compounds between metals and non metals

• These include oxides, carbides, borides, silicates , etc. of various
metals
• Examples: glass, clay products, refractories, abrasives, etc.
• Polymers: organic compounds that are chemically based on
carbon, hydrogen and other non-metals
• They are either natural materials like rubber or synthetically
processed materials like plastics, pvc, etc.
• Polymers are classified as thermo plastics and thermosetting
plastics
 COMPOSI
TES
• Composites consist of combinations of two or more
different materials
• A number of composite materials have been engineered that
consist of more than one material type.
• Fiberglass is a familiar example, in which glass fibers are
embedded within a polymeric material.
• A composite is designed to display a combination of the best
characteristics of each of the component materials.
• Fiberglass acquires strength from the glass and flexibility from the
polymer.
 ATOMIC
STRUCTURE
• All solid materials are made up of particles of different sizes, held
together by internal cohesive forces
• This cohesive forces between the particles and energies associated
with them determine the properties of the material
• Materials are composed of unit substance known as chemical
elements
• Chemical element is composed of atoms
• Atoms and its internal structure determine the nature ofelement
• Atom is consisting of a nucleus surrounded by electrons
• Entire mass of atom is concentrated in the nucleus which contains
particles termed as nucleons
 ATOMIC STRUCTURE
(Cont…)
• The basic nuclear particles are protons and neutrons
• Protons are positively charged while neutrons carry no charge
• Both have approximately the same mass and their total number
indicates the atomic weight of an element
• Electrons are negatively charged
• To keep the atom electrically neutral, the number of protons and
neutron must be same
• This number is known as atomic number of the element
BHOR ATOMIC
MODEL
 BHOR ATOMIC
MODEL
• Electrons are assumed to revolve around the atomic nucleus in
discrete orbitals or quantum states
• Each quantum state represents a discrete level of energy
• Electrons are permitted to have only specific values of energy
• All electrons revolving around the nucleus do not have the same
energy level
• Electrons or group of electrons with different energy
characteristics are assumed to be confined to specific regions or
shells of different diameters surrounding the nucleus
 WAVE-MECHANICAL
MODEL
• In this model an electron is considered to exhibit both particle-like
and wave-like characteristics
• The position of an electron is specified not in terms of the discrete
orbital, but the position is considered to be the probability of an
electron being at various locations around the nucleus
 ATOMIC
RADIUS
• For the study of properties of materials atoms are assumed to be
hard spherical balls and the electron orbitals are circular
• The distance which is of the order of A0 units from the nucleus to
the outer shell is considered as the atomic radius
• Atomic radius increases as the number of occupied shells increases
and decreases as the number of valence electrons increases
 ATOMIC
BOND
• The process of holding the atoms together in a solid material is
known as atomic bond
• The classification of different types of bond depends on the
electronic structure of atoms concerned
• The type of bond determine properties of a material
• Atomic bonds in the materials are classified into two types namely
primary and secondary bonds
• A primary bond is an inter-atomic bond
• It is strong and more stable
• There are three types of primary bonds (i) ionic bond (ii) covalent
bond and (iii) metallic bond
 IONIC
BOND
• Ionic bond is found in compounds that are composed of both metallic
and non-metallic elements, elements that are situated at the horizontal
extremities of the periodic table.
• Atoms of a metallic element easily give up their valence electrons to the
non-metallic atoms.
• In the process all the atoms acquire stable or inert gas configurations
and, in addition, an electrical charge; they become ions.
• Sodium chloride (NaCl) is an example of ionic bond.
 IONIC BOND
(Cont…)
• The Na atom gives away an electron to
Cl and the Na ion gets a net positive
charge and the Cl ion gets a negative
charge
• By virtue of their net opposite
electrical charges, the two ions attract
one another and bond is formed
• This bond is termed as ionic bond, is
non directional which means that the
magnitude of bond is equal in all
direction around an ion
 COVALENT
BOND
• In covalent bond stable electron
configurations are assumed by the
sharing of electrons between
adjacent atoms.
• Two atoms that are covalently
bonded will each contribute at
least one electron to the bond, and
the shared electrons may be
considered to belong to both
atoms
• Examples of covalent bond are
CH4,Cl2,etc.
 METALLIC
BOND
• Metallic bond is found in metals and their alloys.
• A relatively simple model has been proposed that very nearly
approximates the bonding scheme.
• Metallic materials have one, two, or at most, three valence electrons.
• With this model, these valence electrons are not bound to any
particular atom in the solid and are more or less free to drift
throughout the entire metal.
• They may be thought of as belonging to the metal as a whole, or
forming a ‘‘sea of electrons’’ or an ‘‘electron cloud.’’
• The remaining non valence electrons and atomic nuclei form what are
called ion cores, which possess a net positive charge equal in
magnitude to the total valence electron charge per atom
 METALLIC BOND
(Cont…)
• The free electrons shield the
positively charged ion cores
from mutually repulsive
electrostatic forces, which they
would otherwise exert upon one
another; consequently the
metallic bond is non directional
in character.
• In addition, these free electrons
act as a ‘‘glue’’ to hold the ion
cores together.
 SECONDARY
BOND
• Secondary, van der Waals, or physical bonds are weak in
comparison to the primary or chemical ones
• Secondary bond exists between virtually all atoms or molecules,
but its presence may be obscured if any of the three primary
bonding types is present.
• Secondary bond is evidenced for the inert gases, which have stable
electron structures, and, in addition, between molecules in
molecular structures that are covalently bonded
• Secondary bonding forces arise from atomic or molecular dipoles
an electric dipole exists whenever there is some separation of
positive and negative portions of an atom or molecule.
 SECONDARY
BOND
• The bonding results from the coulombic attraction between the
positive end of one dipole and the negative region of an adjacent
one

• Hydrogen bonding, a special type of secondary bonding, is found to

exist between some molecules that have hydrogen as one of the
constituents.
• The single hydrogen electron is shared with the other atom,
making the hydrogen atom a positively charged bare proton
• This highly positively charged end of a molecule is capable of
establishing a strong electrostatic attraction to the negative end of
an adjacent molecule
 CRYSTALLOGR
APHY
• Crystalline material is defined as a material in which atoms are
situated in a repeating or periodic array over a large atomic
distance (i.e.. a long range order exists) such that upon
solidification, the atom will position themselves in a repetitive
three dimensional pattern in which each atom is bonded to its
nearest neighbour atoms
• All metals, many ceramic materials, and certain polymers form
crystalline structures under normal solidification conditions.
• For those that do not crystallize, this long-range atomic order is
absent; these noncrystalline or amorphous materials
 SPACE
LATTICE
• Crystalline structures, atoms (or
ions) are thought of as being solid
spheres having well-defined
diameters.
• This is termed the atomic hard
sphere model in which spheres
representing nearest-neighbour
atoms touch one another
• The term lattice is used in the
context of crystal structures; in this
sense ‘‘lattice’’ means a three-
dimensional array of points
coinciding with atom positions (or
sphere centres)
 UNIT
CELLS
• In each type of crystal lattice, a fundamental grouping of atoms, the
repetition of which, will produce the crystal, can be identified
• This fundamental grouping (or the repeated entity) is called a unit
cell
• Unit cell is the basic structural unit or building block of the crystal
structure and defines the crystal structure by virtue of its
geometry and the atom positions within.
 METALLIC CRYSTAL
STRUCTURES
• Though an endless number of crystal structures are possible, it has
been observed that most of the metals fall into three relatively
simple crystal structures
1. Body Centred Cubic (BCC)- e.g.. Cr, Mo, W, α-Fe
2. Face Centred Cubic (FCC)- e.g.. Al, Cu, Ni, γ- Fe
3. Hexagonal Close Packed (HCP)- e.g.. Co, Cd, Zn, Mg
• Crystal structures are characterised by the lattice parameters (a, b,
c, α, β, γ), number of atoms per unit cell (n), co-ordination
number(N) and atomic packing factor (APF)
 NUMBER OF ATOMS PER
UNIT CELL
• Corners of the unit cells are occupied by atoms
• In addition , a unit cell may contain more atoms located either at
the centers of the faces or in the interior of the unitcell
• An atom at the corner of the unit cell is shared by eight
neighbouring unit cell
• An atom at the centre of the face is shared by two unit cells
• An atom within a unit cell belong to that cell only
𝐧𝐜 𝐧𝐟
𝐍𝐮𝐦𝐛𝐞𝐫 𝐨𝐟 𝐚𝐭𝐨𝐦𝐬 𝐩𝐞𝐫 𝐮𝐧𝐢𝐭 𝐜𝐞𝐥𝐥, 𝐧 = + + 𝐧𝐛
𝟖 𝟐
• Where 𝑛𝑐 = Number of corner atoms ,𝑛𝑓= Number of face centred
atoms & 𝑛𝑏=Number of body centred atoms
 CO-ORDINATION
NUMBER & APF
Co-ordination Number (N)
Defined as the number of nearest atoms directly surrounding a
particular atom
Atomic Packing Factor (APF)
Defined as the fraction of volume occupied by the atoms in the unit
cell to the total volume of the unit cell
 SIMPLE CUBIC
STRUCTURE

• The unit cell for simple cubic

structure has eight lattice
points at its corners

n = n c =8 = 1
8 8
• Co-ordination number is 6
 SIMPLE CUBIC
STRUCTURE

a= 2r
Volume of atoms in unit cell
APF =
Volume of unit cell
Volume of atom × n
APF =
Volume of unit cell
4 3 4 3
3ᴫr ×1 3
ᴫr
𝐀𝐏𝐅 = a3
= = 0.52
(2r)3
 BODY CENTERED
CUBIC(BCC)
STRUCTURE
• This type of unit cell has a full
atom positioned at the body
centre in addition to eight
atoms at the corner
nc 8
𝐧 = + nb = + 1 = 𝟐
8 8
• Co-ordination number for
BCC structure is 8
 BODY CENTERED
CUBIC(BCC)
STRUCTURE
Volume of atoms in unit cell
APF =
Volume of unit cell
n=2
Consider right angled triangle PQR
PQ = 4r
PR = a2 + a2= a 2
𝑃𝑄2 = 𝑃𝑅2 + 𝑄𝑅2=2𝑎2 +𝑎2
16r2 = 3a2
a= 𝟒𝐫
𝟑

4 3
ᴫr ×2
𝐀𝐏𝐅 = 3
4r 3 = 0.68
( )
3
 FACE CENTERED
CUBIC(FCC)
STRUCTURE
• This structure consists of
atoms at centers of all six
faces of unit cell in addition to
the atoms at the eight corners
n c nf 8 6
𝐧= + = + =𝟒
8 2 8 2
• The co-ordination number is
12
 FACE CENTERED
CUBIC(FCC)
STRUCTURE
Volume of atoms in unit cell
APF =
Volume of unit cell
n=4
From triangle PQR
PR2 = PQ2 + QR2
(4𝑟)2= 𝑎2 + 𝑎2 = 2𝑎2
𝑎 = 4𝑟
2

4 3
ᴫr ×4 16𝑟 3
3
APF = 3
a
= 4 = 0.74
3(𝑟 )3
2
 HEXAGONAL CLOSE PACKED (HCP)
STRUCTURE

• HCP crystal structure is commonly

observed in metallic materials
• Three atoms are located at the
middle layer between the end faces
of the hexagonal structure
• There are 12 atoms located at the
12 corners and two at the centre of
the hexagonal end faces
 HEXAGONAL CLOSE PACKED (HCP)
STRUCTURE

• Number of atoms , n = Corner atoms × +

1
6
1
Face centeratoms × × Mid palne atoms × 1
2
1 1
𝐧 = 12 × + 2 × + 3 × 1
6 2

=6
• The Co-ordination number for HCP crystal is 12
 HEXAGONAL CLOSE PACKED (HCP)
STRUCTURE

• APF = Volume of atoms in unit cell

Volume of unit cell

• Volume of unit cell = Cross sectional area× Height

• Consider the hexagon consisting of 6 triangular parts
• Area of hexagon = area of triangle × 6

= 1 × base × altitude × 6
2

=1 × a × h × 6
2

= 3ah
 HEXAGONAL CLOSE PACKED (HCP)
STRUCTURE

In right angled triangle PQR

PR2 = QR2 + PQ2
a
a2 = h2 + ( ) 2
2
2 2
a 3a
h2 = a2 − =
4 4
a 3
h = 2
2
3 3𝑎 3
Area of hexagonal face = 3𝑎(𝑎 ) =
2 2
The lattice parameter a and c of HCP unit cell are related by
c= 1.633 a
a= 2r
 HEXAGONAL CLOSE PACKED (HCP)
STRUCTURE

2
3a 3
Volume of hexagonal unit cell= × 1.633 a = 4.242a3
2
4 3
ᴫr 8ᴫr3 8ᴫr3
3
APF= ×6= = = 𝟎. 𝟕𝟒
4.242a3 4.242a3 4.242×8r3
 RADIUS
RATIO
• The metallic ions, or cations, are positively charged, because they have
given up their valence electrons to the non-metallic ions, or anions, which
are negatively charged
• Let the sizes or ionic radii of the cations and anions, 𝐫𝐜and 𝐫𝐚
• Because the metallic elements give up electrons when ionized, cations
are ordinarily smaller than anions and the radius ratio 𝐫𝐜/𝐫𝐚 is less
than unity.
• Each cations prefers to have as many nearest-neighbour anions as
possible and the anions also desire a maximum number of cation
nearest neighbours
• The coordination number (i.e., number of anion nearest neighbours
for a cation) is related to the cation–anion radius ratio.
• For a specific coordination number, there is a critical or minimum
𝐫𝐜/𝐫𝐚 ratio for which this cation–anion contact is established
 RADIUS RATIO & CO-
ORDINATION
NUMBER

Stable and unstable anion–cation coordination configurations.

Open circles represent anions; colored circles denote cations.
 THEORETICAL DENSITY OF
UNIT CELL
𝐴
Mass of an atom= gm
𝑁𝐴

where A= Atomic weight

N A= Avogadro's number=6.023 × 1023

Mass of a unit cell having ‘n’ number of atoms= A × n gm

NA

Mass of one unit cell = volume of unit cell× density(ρ)

Mass of one unit cell = 𝑉𝑐× ρ
A
𝑉𝑐× ρ = ×n
NA
𝑨×𝒏
𝝆=
𝑵𝑨 × 𝑽𝒄
 POLYMORPHISM AND
ALLOTROPY
• Some metals, as well as non-metals, may have more than one crystal
structure, a phenomenon known as polymorphism.
• When found in elemental solids, the condition is termed allotropy.
• The prevailing crystal structure depends on both the temperature and
the external pressure.
• One example is found in carbon, graphite is the stable polymorph at
ambient conditions, whereas diamond is formed at extremely high
pressures.
• Pure iron has a BCC crystal structure at room temperature, which
changes to FCC iron at 912 ̊ C and reverts back to BCC at 1394 ̊C and
melts at a temperature of 1539 ̊ C.
• Modification of the density and other physical properties accompanies
a polymorphic transformation