U-1

Topics:

Introduction to materials, bonding between atoms: Metallic bonding, ionic bonding, covalent
bonding, Van der Waals bond, thermal co-efficient of expansion, Elastic modulus, Role of
materials selection in design, Structure and property relationship, Miller indices for directions
& planes, Packing of atoms inside solids, Closed-packed structures, structure of ceramics, ionic
solids, glass and polymers, density of various materials

Introduction to materials

Materials are probably more deep-seated in our culture than most of us realize. Transportation,
housing, clothing, communication, recreation, and food production— virtually every segment
of our everyday lives is influenced to one degree or another by materials.
Historically, the development and advancement of societies have been intimately tied to the
members’ ability to produce and manipulate materials to fill their needs.
In fact, early civilizations have been designated by the level of their materials development
(Stone Age, Bronze Age, Iron Age)
 The earliest humans had access to only a very limited number of materials, those that
occur naturally: stone, wood, clay, skins, and so on.
 With time they discovered techniques for producing materials that had properties
superior to those of the natural ones; these new materials included pottery and various
metals.
 it was discovered that the properties of a material could be altered by heat treatments
and by the addition of other substances
 thousands of different materials have evolved with rather specialized characteristics
that meet the needs of our modern and complex society; these include metals, plastics,
glasses, and fibres.
Material Science and Engineering
Sometimes it is useful to subdivide the discipline of materials science and engineering
into materials science and materials engineering subdisciplines.
Materials science involves investigating the relationships that exist between the
structures and properties of materials. Materials engineering is, based on these
structure–property correlations, designing or engineering the structure of a material to
produce a predetermined set of properties.
From a functional perspective, the role of a materials scientist is to develop or synthesize
new materials, whereas a materials engineer is called upon to create new products or
systems using existing materials, and/or to develop techniques for processing materials.
Innovation in engineering often means the clever use of a new material for a specific
application. For example: plastic containers in place of age-old metallic containers. It
is vital that the professional engineer should know how to select materials
which best fit the demands of the design - economic and aesthetic demands, as well as
demands of strength and durability. Beforehand the designer must understand the
properties of materials, and their limitations. Thus, it is very important that every
engineer must study and understand the concepts of Materials Science and Engineering.
This enables the engineer
 To select a material for a given use based on considerations of cost and performance.
• To understand the limits of materials and the change of their properties with use.
• To be able to create a new material that will have some desirable properties.
• To be able to use the material for different application.

structure of a material usually relates to the arrangement of its internal components.

Subatomic structure involves electrons within the individual atoms and interactions
with their nuclei.
Classification of Materials

Why study material science?

Many an applied scientist or engineer, whether mechanical, civil, chemical, or electrical, will
at one time or another be exposed to a design problem involving materials.
For example, an oil refinery component.
A materials problem is one of selecting the right material from the thousands that are available.
The final decision is normally based on several criteria.
Final decision is normally based on several criteria:
 The in-service conditions, for these will dictate the properties required for a material (very
rarely a material has ideal combination of properties so you may have to trade between
characteristics)
 Any deterioration of material properties that may occur during service operation, for
example, significant reductions in mechanical strength may result in elevated temperatures.
 Economics: What will the finished product cost

Metals
Materials in this group are composed of one or more metallic elements (e.g., iron, aluminium,
copper, titanium, gold, and nickel), and often also non-metallic elements (e.g., carbon, nitrogen,
and oxygen) in relatively small amounts.3 Atoms in metals and their alloys are arranged in a
very orderly manner and in comparison, to the ceramics and polymers, are relatively dense
regard to mechanical characteristics, these materials are relatively stiff and strong, yet are
ductile and are resistant to fracture which accounts for their widespread use in structural
applications. A polished metal surface has a lustrous appearance and some metals have
magnetic properties.
Ceramics
Ceramics are compounds between metallic and non-metallic elements; they are most frequently
oxides, nitrides, and carbides. For example, common ceramic materials include aluminium
oxide (or alumina, Al2O3), silicon dioxide (or silica, SiO2), silicon carbide (SiC), silicon
nitride (Si3N4), and, in addition, what some refer to as the traditional ceramics—those
composed of clay minerals (i.e., porcelain), as well as cement and glass.
 Ceramic materials are relatively stiff and strong—stiffnesses and strengths are
comparable to those of the metals also ceramics are relatively hard.
 Ceramics exhibit extreme brittleness (lack of ductility) and are highly susceptible to
fracture.
 Newer ceramics are being engineered to have improved resistance to fracture; these
materials are used for cookware, cutlery, and even automobile engine parts.
 Ceramic materials are typically insulative to the passage of heat and electricity (i.e.,
have low electrical conductivities) and are more resistant to high temperatures and
harsh environments than metals and polymers.
 optical characteristics, ceramics may be transparent, translucent, or opaque
 some of the oxide ceramics (e.g., Fe3O4) exhibit magnetic behaviour.
Polymers
Polymers include the familiar plastic and rubber materials. Many of them are organic
compounds that are chemically based on carbon, hydrogen, and other non-metallic elements.

They have very large molecular structures, often chainlike in nature, that often have a backbone
of carbon atoms. Some of the common and familiar polymers are polyethylene (PE), nylon,
poly (vinyl chloride) (PVC), polycarbonate (PC), polystyrene (PS), and silicone rubber.

 These materials typically have low densities

 Their mechanical characteristics, they are not as stiff nor as strong as other material
types.
 Many of the polymers are extremely ductile and pliable (i.e., plastic), which means they
are easily formed into complex shapes.
 They are relatively inert chemically and unreactive in many environments.
 One major drawback to the polymers is their tendency to soften and/or decompose at
modest temperatures
 have low electrical conductivities and are nonmagnetic.

Composites
A composite is composed of two (or more) individual materials, which come from the
categories previously discussed—metals, ceramics, and polymers.

The design goal of a composite is to achieve a combination of properties that is not displayed
by any single material, and to incorporate the best characteristics of each of the component
materials. Some naturally occurring materials are composites—for example, wood and bone.

 One of the most common and familiar composites is fiberglass, in which small glass
fibres are embedded within a polymeric material, they relatively strong and stiff (also
brittle) where as polymer is more flexible. Thus, fiberglass is relatively stiff, strong and
flexible. In addition, it has a low density.
 Another technologically important material is the carbon fibre–reinforced polymer
(CFRP) composite—carbon fibres that are embedded within a polymer. These materials
are stiffer and stronger than glass fibre–reinforced materials but they are expensive.
Examples, aerospace applications.

ADVANCED MATERIALS
By high technology we mean a device or product that operates or functions using relatively
intricate and sophisticated principles; examples include electronic equipment (camcorders,
CD/DVD players, etc.), computers, fibre-optic systems, spacecraft, aircraft, and military
rocketry.

These advanced materials are typically traditional materials whose properties have been
enhanced, and newly developed, high-performance materials. Advanced materials include
semiconductors, biomaterials, and what we may term “materials of the future”.

Semiconductors
Semiconductors have electrical properties that are intermediate between the electrical
conductors (i.e., metals and metal alloys) and insulators (i.e., ceramics and polymers). the
electrical characteristics of these materials are extremely sensitive to the presence of minute
concentrations of impurity atoms, for which the concentrations may be controlled over very
small spatial regions.

Biomaterials
Biomaterials are employed in components implanted into the human body to replace diseased
or damaged body parts. These materials must not produce toxic substance and must be
compatible with body tissues.

For example, some of the biomaterials that are utilized in artificial hip replacements

Smart Materials
Smart (or intelligent) materials are a group of new and state-of-the-art materials now being
developed that will have a significant influence on many of our technologies. Smart implies
that these materials can sense changes in their environment and then respond to these changes
in predetermined manners.

Components of a smart material (or system) include some type of sensor (that detects an input
signal), and an actuator (that performs a responsive and adaptive function). Actuators may be
called upon to change shape, position, natural frequency, or mechanical characteristics in
response to changes in temperature, electric fields, and/or magnetic fields.

Four types of materials are commonly used for actuators:

shape-memory alloys: Shape-memory alloys are metals that, after having been deformed, revert
to their original shape when temperature is changed.

piezoelectric ceramics: expand and contract in response to an applied electric field (or voltage);
conversely, they also generate an electric field when their dimensions are altered.

magneto strictive materials: They are analogous to piezoelectric materials but responsive to
magnetic fields.

Electrorheological/magnetorheological fluids: That experience dramatic changes in viscosity

upon the application of electric and magnetic fields.

Nanomaterials
One new material class that has fascinating properties and tremendous technological promise
is the nanomaterials. Nanomaterials may be any one of the four basic types—metals, ceramics,
polymers, and composites.

Unlike these other materials, they are not distinguished based on their chemistry, but rather,
size; the Nano-prefix denotes that the dimensions of these structural entities are on the order of
a Nano-meter (10–9 m)—as a rule, less than 100 Nano-meters (equivalent to approximately
500 atom diameters). Some of the physical and chemical characteristics exhibited by matter
may experience dramatic changes as particle size approaches atomic dimensions.

Materials that are opaque in the macroscopic domain may become transparent on the nanoscale;
some solids become liquids, chemically stable materials become combustible, and electrical
insulators become conductors.

Applications:

 Catalytic converters for automobiles

 Carbon nanotubes—Materials of Importance box
 Particles of carbon black as reinforcement for automobile tires
 Nanocomposites in tennis balls—Materials of Importance box
 Magnetic Nano size grains that are used for hard disk drives

Need of modern materials:

 Nuclear energy holds some promise, but the solutions to the many problems that remain
will necessarily involve materials, such as fuels, containment structures, and facilities
for the disposal of radioactive waste.
 Significant quantities of energy are involved in transportation. Reducing the weight of
transportation vehicles (automobiles, aircraft, trains, etc.), as well as increasing engine
operating temperatures, will enhance fuel efficiency. New high strength, low-density
structural materials remain to be developed.
 There is a recognized need to find new, economical sources of energy and to use present
resources more efficiently. Materials will undoubtedly play a significant role in these
developments.
 Furthermore, environmental quality depends on our ability to control air and water
pollution. Pollution control techniques employ various materials. In addition, materials
processing and refinement methods need to be improved so that they produce less
environmental degradation—that is, less pollution and less de-spoilage of the landscape
from the mining of raw materials. Also, in some materials manufacturing processes,
toxic substances are produced, and the ecological impact of their disposal must be
considered.
 Non-renewable resources are gradually becoming depleted: which needs (1) the
discovery of additional reserves, (2) the development of new materials having
comparable properties with less adverse environmental impact, and/or (3) increased
recycling efforts and the development of new recycling technologies.
  Because of the economics of not only production but also environmental impact and
ecological factors

Bonding between atoms:

Ionic Bonding

It is always 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. In the process all
the atoms acquire stable or inert gas configurations and, in addition, an electrical charge; that
is, they become ions. Sodium chloride (NaCl) is the classic ionic material. For two isolated
ions, the attractive energy EA is a function of the interatomic distance according to

EA =-A/r

An analogous equation for the repulsive energy is

ER = B/𝑟 𝑛

In these expressions, A, B, and n are constants whose values depend on the particular ionic
system. The value of n is approximately 8.

Bonding energies, which generally range between 600 and 1500 kJ/mol (3 and 8 eV/atom), are
relatively large, as reflected in high melting temperatures.

Ionic materials are characteristically hard and brittle and, furthermore, electrically and
thermally insulative. these properties are a direct consequence of electron configurations and/or
the nature of the ionic bond.

Covalent Bonding:
In covalent bonding, 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.

Schematic representation of covalent bonding in a molecule of methane (CH4)

The covalent bond is directional; that is, it is between specific atoms and may exist only in the
direction between one atom and another that participates in the electron sharing. Many non-
metallic elemental molecules (H2, Cl2, F2, etc.) as well as molecules containing dissimilar
atoms, such as CH4, H2O, HNO3, and HF, are covalently bonded. Furthermore, this type of
bonding is found in elemental solids such as diamond (carbon), silicon, and germanium and
other solid compounds composed of elements.

Covalent bonds may be very strong, as in diamond, which is very hard and has a very high
melting temperature, > 35500C (64000F), or they may be very weak, as with bismuth, which
melts at about 2700C (5180F)

Metallic bonding

Is found in metals and their alloys. Metallic materials have one, two, or at most, three valence
electrons which are not bonded to any atom in the solid and are free to drift throughout the
entire metal 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.
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
nondirectional in character In addition, these free electrons act as a “glue” to hold the ion cores
together. Bonding may be weak or strong; energies range from 68 kJ/mol (0.7 eV/atom) for
mercury to 849 kJ/mol (8.8 eV/atom) for tungsten. Their respective melting temperatures are -
39 and 34100C (-38 and 61700F). For example, metals are good conductors of both electricity
and heat, because of their free electrons. contrast, ionically and covalently bonded materials
are typically electrical and thermal insulators because of the absence of large numbers of free
electrons.

Metallic bonding

Secondary, van der Waals, or physical bonds are weak in comparison to the primary or
chemical ones; bonding energies are typically on the order of only 10 kJ/mol (0.1 eV/atom).
Secondary bonding exists between virtually all atoms or molecules, but its presence may be
obscured if any of the three primary bonding types is present. Secondary bonding is evidenced
for the inert gases, which have stable electron structures,

Hydrogen bonding, a special type of secondary bonding, is found to exist between some
molecules that have hydrogen as one of the constituents.

Ionic solids:

The constituent units which make up ionic solids are oppositely charged ions

 The force of attraction between the ions is called an ionic bond. These crystals are
formed between constituents which have very large differences in electron attracting
 power to allow complete transfer of electrons from one constituent to another. The force
of attraction between the ions is purely electrostatic.
 Examples of ionic solids are: NaCl, CsCl and ZnS. Since these ions are held in fixed
positions, there, ionic solids do not conduct electricity in the solid state.
 They conduct electricity in the fused state.
 The forces of attraction in ionic solids are very strong and therefore they exhibit high
melting points and cleave only if force is applied along certain directions. All ionic
solids are hard and brittle.
 It may be observed that movement of layers of ions brings ions of the same charge near
each other and this causes strong repulsions which lead to the breakdown of the crystal.

Crystal Geometry and Structure Determination

A crystal structure is known as a unique arrangement of atoms, ions or molecules in
a crystalline liquid or solid. It describes a highly ordered structure, occurring due to the
intrinsic nature of its constituents to form symmetric patterns. A crystalline material is one in
which the atoms are situated in a repeating or periodic array over large atomic distances upon
solidification, the atoms will position themselves in a repetitive three-dimensional pattern, in
which each atom is bonded to its nearest-neighbour atoms.
Crystal lattice is the depiction of three-dimensional arrangements of constituent particles
(atoms, molecules, ions) of crystalline solids as points. Or the geometric arrangement of
constituent particles of crystalline solids as point in space is called crystal lattice.

Characteristics of crystal lattice:

 Each constituent particle is represented by one point in a crystal lattice.

 These points are known as lattice point or lattice site.
 Lattice points in a crystal lattice are joined together by straight lines.

By joining the lattice points with straight lines, the geometry of the crystal lattice is formed

The box can be thought of as an array of 'small boxes' infinitely repeating in all three
spatial directions. Such a unit cell is the smallest unit of volume that contains all of the
structural and symmetry information to build-up the macroscopic structure of the lattice
by translation.
Patterns are located upon the points of a lattice, which is an array of points repeating
periodically in three dimensions. The lengths of the edges of a unit cell and the angles between
them are called the lattice parameters. The symmetry properties of the crystal are embodied in
its space group.
A crystal structure and symmetry play an important role in determining many of its physical
properties, such as cleavage, electronic band structure, and optical transparency.

Types of Unit Cell: - There are two types of unit cells – Primitive (simple cubic) and centred
Unit Cells.

Primitive Unit Cells: – When particles in unit cell are present only at the corners, it is called
the primitive unit cell.

Centred Unit Cells: – When particles are present at other positions in addition to those at
corners in a unit cell, it is called a centred Unit Cell.

There are three types of centred Unit Cell.

(a) Body centred Unit Cells: – If one constituent particle lies at the centre of the body of a unit
cell in addition to the particles lying at the corners, it is called Body-centred Unit Cell.

(b) Face-centred Unit Cells: – If one constituent particle lies at the centre of each face besides
the particles lying at the corner, it is known as Face-centred Unit Cells.

(c) End-centred Unit Cell: – If one constituent particle lies at the centre of any two opposite
faces besides the particles lying at the corners, it is known as End-centred Unit Cell. It is also
known as base-centred unit cell.

Lattice systems
These lattice systems are a grouping of crystal structures according to the axial system used to
describe their lattice. Each lattice system consists of a set of three axes in a geometric
arrangement. There are seven lattice systems. They are like but not quite the same as the seven
crystal systems and the six crystal families.

The 7 lattice systems

(From least to most The 14 Bravais Lattices
symmetric)

1. triclinic
(none)

simple base-centered

2. monoclinic
(1 diad)

simple base-centered body-centered face-centered

3. orthorhombic
(3 perpendicular diads)

4. rhombohedral
(1 triad)

simple body-centered

5. tetragonal
(1 tetrad)

6. hexagonal
(1 hexad)
 body- face-
simple (SC)
centered (bcc) centered (fcc)

7. cubic
(4 triads)

Bravais Lattices
There are only 14 possible crystal lattices, which are called Bravais Lattices.

14 Bravais Lattices divided into 7 Crystal Systems

Crystal
Shape of UC Bravais Lattices
System
P I F C
1 Cubic Cube   
2 Tetragonal Square Prism (general height)  
3 Orthorhombic Rectangular Prism (general height)    
4 Hexagonal 120 Rhombic Prism 
5 Trigonal Parallelepiped (Equilateral, Equiangular) 
6 Monoclinic Parallogramic Prism  
7 Triclinic Parallelepiped (general) 

P Primitive
I Body Centered
F Face Centered
C A/B/C- centered
 Crystal system Bravais lattices
1. Cubic P I F C
2. Tetragonal P I (F=I)
3. Orthorhombic - P I F C
4. Hexagonal P
5. Trigonal P
6. Monoclinic P C
7. Triclinic P
Number of atoms in Primitive Cubic Unit Cell –

In primitive unit cell, atoms are present at corners only. In a crystal lattice every corner is
shared by eight adjacent unit cells. Therefore, only 1/8 of an atom, or other constituent particles,
belong to a unit cell.

Therefore,

Since, there are 8 atoms present in a unit cell on every corner,

Thus, 1 atom is present in a Primitive Cubic Unit Cell.

Body centred Cubic (bcc) Unit Cell – There are eight atoms at each corner and one atom present
at the centre of body in a body centred cubic (bcc) unit cell.
Therefore, the number of atoms present in a Body centred Cubic (bcc) Unit Cell

Face – centred Cubic (fcc) Unit Cell –

In a face centred cubic unit cell, there are eight atoms present at each corner. A cube has six
faces, therefore total six atoms are present at the centre of each of the face.

Each atom present at corners is shared by adjacent eight atoms and each atom present at the
centre of face is shared between adjacent two atoms.

Therefore, number of atoms in an fcc unit cell –

Packing Factor
In crystallography, atomic packing factor (APF), packing efficiency or packing fraction is the
fraction of volume in a crystal structure that is occupied by constituent particles. It is
dimensionless and always less than unity.

In atomic systems, by convention, the APF is determined by assuming that atoms are rigid
spheres. The radius of the spheres is taken to be the maximal value such that the atoms do not
overlap. For one-component crystals (those that contain only one type of particle), the packing
fraction is represented mathematically by

Where Nparticle is the number of particles in the unit cell, Vparticle is the volume of each particle,
and Vunit cell is the volume occupied by the unit cell.

Common sphere packings taken on by atomic systems are listed below with their corresponding
packing fraction.

• Hexagonal close-packed (hcp): 0.74

• Face-centred cubic (fcc): 0.74 (also called cubic close-packed (ccp))
• Body-centred cubic (bcc): 0.68
• Simple cubic: 0.52
• Diamond cubic: 0.34

BCC:
By geometry, the length of the diagonal is a√3. Therefore, the length of each side of the BCC
structure can be related to the radius of the atom by

Knowing this and the formula for the volume of a sphere, it becomes possible to calculate the
APF as follows:

Hexagonal close-packed
HCP structure
For the hexagonal close-packed structure the derivation is similar. Here the unit cell (equivalent
to 3 primitive unit cells) is a hexagonal prism containing six atoms. Let a be the side length of
its base and c be its height. Then: a=2r

It is then possible to calculate the APF as follows:

Coordination Number
In chemistry, crystallography, and materials science the coordination number of a central atom
in a molecule or crystal is the number of its near neighbours. This number is determined
somewhat differently for molecules than for crystals.
In a body-centred cubic (BCC) crystal, the bulk coordination number is 8, whereas, for the
(100) surface, the surface coordination number is 4.
α-aluminium has a regular cubic close packed structure, fcc, where each aluminium atom has
12 nearest neighbours, 6 in the same plane and 3 above and below and the coordination
polyhedron is a cuboctahedron. α-iron has a body centred cubic structure where each iron atom
has 8 nearest neighbours situated at the corners of a cube.
A graphite layer, carbon atoms and C-C bonds shown in black.
The two most common allotropes of carbon have different coordination numbers. In diamond,
each carbon atom is at the centre of a regular tetrahedron formed by four other carbon atoms,
the coordination number is four, as for methane. Graphite is made of two-dimensional layers
in which each carbon is covalently bonded to three other carbons. Atoms in other layers are
further away and are not nearest neighbours, giving a coordination number the carbon atom in
graphite is 3.

Properties of the Common Structures of Metals

 Percentage of Space Coordination
Structure
Occupied by Atoms Number
simple cubic 52 6
body-centred cubic 68 8
hexagonal close packed 74 12
cubic close packed (identical to
74 12
face-centred cubic)

Density Computations
A knowledge of the crystal structure of a metallic solid permit computation of its theoretical
density (for metals) through the relationship
𝑛𝐴
𝜌=𝑉
𝐶 𝑁𝐴

n = number of atoms associated with each unit cell

A =atomic weight
VC = volume of the unit cell
NA = Avogadro’s number (6.022 * 1023 atoms/mol)

Linear and Planar Densities

Linear density (LD) is defined as the number of atoms per unit length whose centres lie on the
direction vector for a specific crystallographic direction; that is,

the units of linear density are reciprocal length (e.g., nm-1, m-1).

In an analogous manner, planar density (PD) is taken as the number of atoms per unit area
that are centred on a crystallographic plane, the units for planar density are reciprocal area
(e.g., nm-2, m-2).

Close-Packed Crystal Structures

• Both FCC and HCP crystal structures may be generated by the stacking of close packed
planes of atoms on top of one another. With this scheme A, B, and C denote possible atom
positions on a close-packed plane.
The stacking sequence for HCP is ABABAB. . . .
For FCC the stacking sequence is ABCABCABC. . . .
• Close-packed planes for FCC and HCP are {111} and {0001}, respectively.

Ceramics are intermediate in density between polymers (lower) and metals (higher) in the
range of 2-6 gms/cm3. Non-crystalline materials are less dense than crystalline ones.
Compositions with several Allotropes such as SiO2 will have minor differences in density.
For most polymers’ density is a constant; polypropylene is 0.90 g/cm3, polycarbonate is 1.2
g/cm3, etc. Adding filler such as talc or glass will increase the density; incorporating an
impact modifier may lower it slightly; but the density of the base polymer does not change.