UNIT-I

ENGINEERING MATERIALS AND CHEMICAL BONDING

Study Material Compiled by Dr. P. Sagayaraj

Head & Associate Professor of Physics, Loyola College, Chennai

Technical Assistance by:

Ms. Marie Rose Jesina Delavictorie, Research Scholar, Department of Physics, Loyola College,
Chennai - 34

Contents

1.1 Classification of engineering materials 2

1.2 Levels of structure 4

1.3 Structure-property relationship in materials 5

1.4 Stability and metastability 5

1.5 Bond energy, bond type and bond length 7

1.6 Ionic and covalent bonding 9

1.7 Variation in bonding character and properties 12

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 Material Science refers to solid materials in Physics and chemistry, while engineering
refers to the engineering usefulness of materials.

1.1 Classification of Engineering Materials

Materials are classified into three broad groups

I) Metals and alloys

II) Ceramics and glasses
III) Organic polymers

Metals and alloys

Metals have a characteristic appearance, capable of changing their shape

permanently and have good thermal and electrical conductivity. Whereas, alloys are
combination of more than one metals.

Ceramics and glasses

They are nonmetallic inorganic substances, which are brittle and have good thermal and
electrical insulating properties.

Organic polymers

These are inert, light and generally have a high degree of plasticity.

The examples of various materials are given below in Fig 1.1

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 Fig 1.1 The three major groups of engineering materials

An alternate way to classify materials is according to the three major areas in which
materials are used.

i) Structures
ii) Machines
iii) Devices

Structures refer to objects without moving parts like a concrete dam, a suspension
bridge. Machines include engines, gas and steam turbines. Devices refer to a transistor,
photoelectric cell and lasers. The block diagram (Fig. 1. 2) below shows the use of all
materials for engineering applications.

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 Fig 1.2 Each category of engineering applications requires materials from any or all the
three groups of materials

1.2 Levels of structure

There are various levels of observing the structure of a material. It can simply be
observed through magnification and resolution. The details of observation vary from one
level to another. Depending on the level, the structure of materials are classified as

i) Macrostructure
ii) Microstructure
iii) Substructure
iv) Crystal structure
v) Electronic structure
vi) Nuclear structure

Macrostructure of a material is examined with naked eye or under a low magnification.

Large crystals are visible to the naked eye.

Microstructure generally refers to the structure as observed under optical microscope. The
optical microscope can magnify upto 1500 times linear and a resolution of about 0.1 µm,
whereas the human eye has a resolution of about 0.1 mm.

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Substructure refers to structures obtained by using a microscope with a much higher
magnification and resolution than an optical microscope. With an electron microscope, a
magnification of 1000000 times linear is possible.

Crystal structure gives details of the atomic arrangement of atoms within a crystal. The
technique used to determine crystal structure is X-ray diffraction.

Electronic structure of a solid refers to the electrons in the outermost orbitals of individual
atoms constituting a solid. Spectroscopic techniques are used here.

Nuclear structure is studied by nuclear spectroscopic techniques, nuclear magnetic

resonance (NMR) and Mossbauer studies.

1.3 Structure- Property Relationships in materials

There exist a correlation between structure of a material and its properties. Among
the various levels of structure, the microstructure, substructure and crystal structure are of
great interest in material science. Also the chemical, mechanical, electrical and magnetic
properties are among the most important engineering properties. These help in relating
structure and property of materials.

Some of the basic concepts relating to the levels of structure are

i) Equilibrium and kinetics

ii) Geometry of crystals
iii) Arrangement of atoms in the unit cell of crystalline materials
iv) Structural imperfections in crystals
v) Microstructure of single phase and multiphase materials

1.4 Stability and Metastability

The concept of stability can be understood by considering a mechanical analog. As seen

from Fig 1.3 shows a rectangular block of square cross-section in various tilted positions.

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 Fig 1.3 Various positions of a tilting rectangular block illustrate the concept of
stability and metastability

In position 1, the square is resting in the square base. The arrow from the centre of
mass indicates the line along which the weight acts. In position 2, the square is slightly tilted
about one of its edges and here the centre of mass moves slightly up due to the lift and the
line along which the weight acts is still within the square base. In position 3, the square is
tilted to such an extent that the line of force is at the edge of the base and the centre of
mass is at its maximum possible height from the base. Tilting the square further makes the
line of force to fall outside the base but within the rectangular base as seen at position 4. At
position 5, the centre of mass is at its lowest position.

The centre of mass for various positions are joined together to form a curve. The
potential energy at different positions is measured by the height of the centre of mass from
the base. This shows that position 5 has the least potential energy of all the configurations
and is considered as the most stable state. A system always tends to go towards the most
stable state. Position 3 has the maximum potential energy and called as unstable state.
Positions 2, 4 are also unstable states but do not have the maximum energy. Position 1 is
called the metastable state.

This analogy can be used to illustrate various equilibrium configurations of a system.

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 Fig 1.4 Potential energy as a function of the configuration coordinate

Fig 1.4 shows the potential energy of a system as a function of configuration. Here
the potential energy curve shows two valleys and a peak. At these positions, the peak has
zero slope, showing that the energy does not vary as a function of configuration for
infinitesimally small perturbations. Such configurations are called equilibrium
configurations. Corresponding to the terminology used for tilting block, we have stable,
unstable and metastable equilibrium. It is also seen that though the potential energy is a
minimum for metastable state, it is not the lowest. However due to the valley position, even
after small perturbations the original configuration is restored in stable and metastable
equilibrium. This restoration is not possible in unstable equilibrium.

The block example used to describe mechanical analogy can be tilted and brought to
the most stable configuration starting from metastable state by an external supply of
energy. This common energy in case of materials is thermal energy. The energy associated
with the vibrations, rotations and translations helps in taking the material from a metastable
state to a stable state.

1.5 Bond energy

The forces between two ions or atoms as a function of their distance of separation r
are shown in Fig 1.5.

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 Fig 1.5 Interatomic forces and potential energy in a system of two atoms, as a
function of their distance of separation r

When the distance of separation is large, the significant force between them is
attractive (negative) force, Fa. As the distance approaches closer, a repulsive (positive) force,
Fr becomes significant and increases rapidly with decreasing distance of separation. At
distance r0 the attractive and repulsive forces exactly balance each other and the net force is
zero. This distance at which potential energy W is minimum corresponds to stable
equilibrium. The magnitude of minimum energy W0 is called bond energy. It is expressed in
kilojoules per mole.

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Bond types

The chemical bonds can be grouped into primary and secondary bonds. Primary
bonds having energy in the range 100-1000 KJ mol-1 include covalent, metallic and ionic
bonds. Among these covalent and ionic bonds are stronger than metallic bonds. However
secondary bonds have energies in the range 1-50 KJ mol-1. Van der Waals bonds and
hydrogen bonds are examples to this among which Van der Waals bonds are very weak.

Bond length

The length of a bond r0 is defined as the centre to centre distance of the bonding
atoms. Strong bonds pull the bonding atoms closer together and hence have smaller bond
lengths when compared to weak bonds. The lengths of primary bonds range from 1-2 Å (0.1-
0.2 nm). Secondary bond lengths are larger in the range 2-5 Å (0.2-0.5 nm).

1.6 Ionic or Electrovalent bonding

Ionic bonds are formed between two oppositely charged ions produced by the
transfer of electrons from one atom to another.

i) Production of ions of opposite sign

Ionic bond formation between sodium and chloride is shown: the sodium atom with an
atomic number Z=11 have one electron in its outermost orbit which can be removed by
supplying suitable energy. This released electron occupies the only vacant state in chlorine
atom to produce a negatively charged ion. The ionic bond is formed between an existing
positive and negative ion, when they are brought into a closer distance.

Na Na+ + e-

Cl + e- Cl-

The ionization potential for sodium is 496 KJ mol-1. And the electron affinity of chlorine is
369 KJ mol-1. Thus the net increase in energy due to transfer of electron from sodium to
chlorine is
ΔE= 496 - 369= 127 KJ mol-1.

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 ii) The Coulomb attraction

The electron transfer results in the inert gas configuration around both the nuclei.
This maintains a spherical symmetry of the electron cloud. Hence the bonding force
between the ions is the same in all directions and the ionic bond is said to be nondirectional.
From Coulomb’s law of electrostatics, the attractive force between two opposite charges
gives the potential energy W = - A’Z1Z2e2 / r.

Where Z1 and Z2 are the valencies of two ions

e - Electronic charge

A’ is conversion factor

iii) The short range repulsion

The assumption that ions are point charges will be valid only when the electron clouds
surrounding the two nuclei do not overlap. If the electron clouds overlap then a repulsive
force occurs due to Pauli’s exclusion principle given as B/r m.

Where B, m are constants with m> 1

Summing the three terms above we get

W = - A’Z1Z2e2 / r + B/ rm + ΔE

The minimum potential energy W0 can be obtained by setting dW/dr = 0 which yields bond
energy W0 and equilibrium bond length r0

Covalent bonding

Covalent bonding occurs by the sharing of electrons between neighboring atoms.

This is in contrast to the transfer of electrons from one atom to another in ionic bonding.
This bonding occurs when there are vacant electron states in the outermost orbital of the
bonding atoms and sharing of electrons results in lowering the potential energy of the
system.

Consider the formation of a hydrogen molecule. When two hydrogen atoms are very
far apart, they do not interact and the lone electrons of the atom stay in their respective

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ground states. But when the atoms come closer, the electron probability clouds of 1s states
overlap. As the 1s orbitals can have two electrons of opposite sign, the sharing of electrons
between the two atoms takes place, without having to promote the electrons to higher
energy levels. The hydrogen molecule has bond energy of 436 K J mol-1 and a bond length of
0.74 Å. Sharing of electrons and formation of covalent bonds readily occurs between atoms
which have unfilled p orbitals.

(a) End-to-end overlap gives rise to a σ bond

(b) Lateral overlap gives rise to a π bond

This is an example of an end-to-end overlap of p orbitals giving rise to σ bond. When there is
lateral overlap of p orbitals then π bonds are said to form.

Metallic bonding

We know that in metals, each atom losses all its valence electrons and becomes a
positively charged ion. These free and mobile electrons form an electron cloud or gas which
permeates all atoms. These valence electrons are not bonded to an individual atom but
move freely in the sphere of influence of other atoms. Thus a metallic bond results from
sharing of variable number of electrons by variable number of atoms. This seems to be
contrast to covalent bonding in which the electrons are localized. Hence metallic bonds are
nondirectional.

Secondary bonding

Hydrogen bonds

Usually in molecules where hydrogen takes part in covalent bonding, the centres
of positive and negative charges do not coincide. Considering the example of water
molecule, the electronegativity of oxygen is more when compared to hydrogen. Hence the

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oxygen atom pulls the bonding electrons to itself more strongly than hydrogen. This leads to
a net negative charge at the oxygen end and a net positive charge at hydrogen end of the
molecule. The bond formed between the positively charged hydrogen end of the molecule
and negatively charged oxygen end of the molecule is called hydrogen bond. Hence
hydrogen bonds are directional.

The hydrogen bonds between water molecules are strong enough to persist in the liquid
state responsible properties of water and ice (Fig 1.6).

Fig. 1.6 Hydrogen bond between water molecules

Van der Walls bonding

Inert gas atoms have spherically symmetric electron probability cloud around
them and hence no permanent dipole moments. Yet these atoms form solid molecules at
low temperatures. The bonding in such solids is called the Van der Waals bonding. Eg;
Helium and Neon

1.7 Variation in bonding character and properties

There lies a relationship between properties and bonding character of a material.

The atoms in solid state are considered to vibrate about their mean positions at the atomic
sites. In liquid state, the atoms also have translational motion and the bonds between
atoms are broken and reformed. However in gaseous state, the bonds are totally broken.
The higher the bond strength, the more will be the thermal energy required to break the

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bonds. Hence strongly bonded materials tend to have high melting and boiling
temperatures. The covalent and ionic bonds are stronger than metallic bonds. Also the
thermal and electrical conductivities of a solid are to a great extent dependent on the
presence of free electrons in the solid. Ionic and covalent materials are good thermal and
electrical insulators because the electron transfer and sharing of electrons occurring results
in inert gas configuration, thereby having no free electron. Solids having secondary bonds
are also good insulators.

With regard to thermal expansion occurring due to asymmetry of potential energy

verses distance, deep potential wells are more symmetric than shallow curves indicating
that strongly bonded materials undergo less expansion than weakly bonded materials.
Depending on the strength and directional nature of bonding, mechanical properties of
solids are decided. Covalently bonded materials are hard, example diamond, while presence
of metallic bonds in metals makes them soft and malleable capable to change their shape.
Ionic solids fall in between covalent and ionic bonding with limited amount of ductility.

From the periodic table, the presence of elements from left to right show a decrease
in metallic character of bonding and increase in covalent character. This resembles the
increased bond energy and decreasing bond length of the elements from left to right. Eg:
transition metals are hard than Cu and Al but less thermal and electrical conductivity than
Cu and Al.

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