Fundamental of

ENGINEERING MATERIALS
for young Engineer

Zaleha Mustafa
Qumrul Ahsan
Zulkifli Mohd Rosli
Zurina Shamsudin
Siti Hajar Sheikh Md Fadzullah

UNIVERSITI TEKNIKAL MALAYSIA MELAKA

 7

CHAPTER 1: INTRODUCTION TO MATERIALS

SCIENCE AND ENGINEERING

1. LEARNING OBJECTIVES:

1. To introduce the field of materials science and engineering

2. To provide introduction to the classifications of materials
3. To introduce the relationship between properties, structure and processing

1.1 WHAT IS MATERIALS SCIENCE AND ENGINEERING?

Materials Science & Engineering stems from a realization concerning every
application of materials. Materials science deals with basic knowledge about the
internal structure, properties, and processing of materials. Materials engineering
is mainly concerned with the use of fundamental and applied knowledge of
materials so that the materials can be converted into suitable products for proper
use. The term materials science and engineering combines both materials science
and materials engineering... Materials make modern life possible—from the
polymers in the chair we are sitting on, the metal ball-point pen we are using. In
order to understand the materials we need to study the relationship between the
structure, the properties, processing and the performance of the materials (Fig.
1.1). Finally we can identify the materials for final usage. The challenge for
materials scientist and engineer is to manipulate their knowledge for creating new
end products out of the materials.

Figure 1.1 Interdependency between structure, properties, processing and

performance of materials [adapted from [Link]

The production and processing of materials into finished goods constitutes a large
part of our present economy. Engineers design most manufactured products and
the processing systems required for their production. Since products require
materials, engineers should be knowledgeable about the internal structure and
properties of materials so that they can choose the most suitable ones for each
application and develop the best processing methods. Research and development
engineers create new materials or modify the properties of existing ones. Design
engineers use existing, modified, or new materials to design and create new
products and systems. Sometimes design engineers have a problem in their
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 8

design that requires a new material to be created by research scientists and

engineers. For example, engineers designing a high-speed civil transport (HSCT)
(Fig. 1.2) will have to develop new high-temperature materials that will withstand
temperatures as high as 1800C (3250F) so that airspeeds as high as Mach 12 to
25 can be attained.

Figure 1.2 High-speed civil transport image shows the Hyper-X at Mach 7 with
the engines operating [Smith and Hashemi, 2011]

1.2 IMPLICATION OF LEARNING MATERIALS SCIENCE.

Materials science syndicates various discipline of science. Figure 1.3 illustrates
how materials science interrelates chemistry, physics, and engineering to make
better, more useful, and more economical and efficient “stuff.”

Figure 1.3 Materials Science and Engineering—A Multidisciplinary Approach

[Matls. Sci & Tech. Teachers Handbook]

Since materials science and engineering is a multidisciplinary field, it becomes a

vital requirement for all scientist, engineers and alike to fully understand the
various aspects of materials knowledge spectrum in order to deal with real world
problem. (Figure 1.4)
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 9

Figure 1.4 Materials knowledge spectrum. [Smith and Hashemi, 2011]

Because of the interdisciplinary nature of materials science, it can be used both as
an introductory course to interest students in science and engineering and also as
an additional course to expand the horizons of students already taking science
and mathematics courses.

1.3 A BRIEF HISTORY OF MATERIALS SCIENCE

Early civilisation started with the use of materials for at least 10,000 years ago but
the real beginning of materials’ use was long before recorded history. The first
materials scientists may well have been Grog or Grogette (a fictional character of
caveman origin) as Table 1.2 shows. In the early civilisation materials were being
used in its pristine form with or without the modification. Later people learned the
application of heat and energy in materials processing to obtain product what they
needed.

Table 1.1 A Short History of Materials Science

1.4 CLASSIFICATION OF MATERIALS

Basically materials are classified in two ways based on their internal structure, viz
crystalline and amorphous. But depending on the physical and mechanical
properties of materials and their engineering applications these two divisions are
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 10

further classified into four ways, i.e. metals, polymers, ceramics and composite.
The interrelationship between these two categories are shown Figure 1.5

Figure 1.5 Interrelationships between classes of materials [Materials Science

and Technology Teachers Handbook]

1.4.1 Metals and its alloys.

Metals, the most widely used materials can be further classified as ferrous and
non-ferrous metals. Although the use of pure metals are prevalent, the wide
application of metals are in the form of alloys which composed of one or more
metallic elements (e.g. iron, aluminium, copper, titanium, nickel) and non-metallic
elements (e.g. carbon, nitrogen and oxygen). From the structure point of view,
atoms in metals and their alloys are arranged in a very orderly manner and in
comparison to the ceramics and polymers, are relatively dense (Fig 1.6).

Figure 1.6 Bar-chart of room temperature density values for various metals,
ceramics, polymers, and composite materials (William D. Callister)
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 11

Mechanical properties wise, metals are relatively strong (Figure 1.7) and stiff (Fig
1.8). Metals and alloys are also ductile which help them to form into desired shape
without fracture. Most of the metals are also good thermal and electrical
conductor. Therefore various properties of metals and alloys account for their
widespread use from household to engineering applications. Figure 1.9 shows
some objects that are prepared from metallic materials.

Figure 1.7 Bar-chart of room temperature strength (i.e., tensile strength) values
for various metals, ceramics, polymers, and composite materials (William D.
Callister).

Figure 1.8 Bar-chart of room temperature stiffness (i.e., elastic modulus) values
for various metals, ceramics, polymers, and composite materials (William D.
Callister).
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 12

Figure 1.9 Objects are made of metals and metal alloys: (from left to right)
silverware (fork and knife), scissors, coins, a gear, a wedding ring, and a nut and
bolt. (Photography by S. Tanner.)

1.4.2 Ceramics

Ceramics materials are consist of metallic and non-metallic elements and are
available in the form of oxides, nitrides, and carbides. Aluminium oxide (or
alumina,Al2O3), silicon dioxide (or silica, SiO2), silicon carbide (SiC), silicon nitride
(Si3N4) are the most commonly used ceramic materials. Ceramics are hard and
strong not only at room temperature but also retain these properties at high
temperature. One main disadvantage of ceramics is that it tends to be brittle
(which means it can fracture with little or no deformation). However, ceramic
materials are widely used as an insulation material because of it good insulative
property (low electrical conductivities) along with high heat and wear resistance.
Nowadays ceramics are produced with improved properties to diversify its usage
in engineering and can be classified as engineering ceramics, structural ceramics
or advanced ceramics based on its application. Some typical ceramic products are
shown in Figure 1.10.

Figure 1.10 Common objects that are made of ceramic materials: scissors, a china
tea cup, a building brick, a floor tile, and a glass vase. (Photography by S.
Tanner.)
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 13

1.4.3 Polymer

Plastic and rubber, these are the two common names of polymeric materials.
Usually polymeric materials are organic compounds which consists of carbon,
hydrogen, and other non-metallic elements (viz. O, N, and Si). They have long
molecular chains or networks which have a backbone of carbons. Some common
and familiar polymers are polyethylene (PE), nylon, poly(vinyl chloride)(PVC), and
silicone rubber. The polymers or plastics have the widest use because of their low
densities and high process ability. Complex shape parts are easy to form from
polymers. Strength wise polymers are weak as compare to metals and ceramics
and one major disadvantage to the polymer is their tendency to loose strength at
modest temperature. Some articles made of polymer are shown in Figure 1.11.

Figure 1.11 Several common objects that are made of polymeric materials:
plastic tableware (spoon, fork, and knife), billiard balls, a bicycle helmet, two
dice, a lawnmower wheel (plastic hub and rubber tire), and a plastic milk
carton.(Photography by S. Tanner.)
1.4.4 Composites

A composite is a combination of two or more materials (metals, ceramics and

polymers) to form a new one. The design goal of a composite is to achieve a
combination of properties that is not displayed by any single material, and also to
incorporate the best characteristics of each of the component materials. . In most
composites, one type of material will become the base; called ‘matrix’ and the
other material will act as ‘reinforcement’. Furthermore, some naturally-occurring
materials are also considered to be composites—for example, wood and bone.
However, most of those are synthetic (or man-made) composites.

One of the most common and familiar composites is fiberglass, in which small
glass fibres are embedded within a polymeric material (normally an epoxy or
polyester). The glass fibres are relatively strong and stiff (but also brittle), whereas
the polymer is ductile (but also weak and flexible). Thus, the resulting fiberglass is
relatively strong, stiff, (Figures 1.7 and 1.8) flexible, and ductile. In addition, it has
a low density (Figure 1.6). In general the classification of composites is depending
on the type of matrix used, metal matrix composite (MMC), ceramic matrix
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 14

composite (CMC) and polymer matrix composites (PMC). Figure 1.12 shows
schematically where fibre reinforced epoxy composite material was used for the
wings and engines of the C-17 transport plane.

Figure 1.12 Overview of the wide variety of composite parts used in the Air
Force’s C-17 transport (Smith, W.F.).

1.5 ADVANCED MATERIALS

With the recent advances in materials science and engineering, more and more
revolutionary materials has been created that could bring forward the high-
technology (or high-tech) of the future. These materials are also known as
advanced or functional materials of all material types (e.g., metals, ceramics,
polymers), and are normally expensive. Semiconductors, Biomaterials, and Smart
materials are fall under the advanced material category and they are mainly
applied in electronic, aerospace and medical industries. Some widely used
advanced materials are described below:

1.5.1 Semiconductors

Semiconductors are usually made of Silicon (Si) and Germanium (Ge).

Semiconductors are characterised by their electrical properties that are
intermediate between of conductors (metals & its alloys) and insulators (ceramics
& polymers).—Figure 1.13. The way semiconductors conduct electricity is different
from that of metals. In metals, conductivity comes from the free electron that
moves around in the electron cloud and bond the metal atoms together. In
semiconductor e.g. silicon, at an elevated temperature, some of the Si atoms gain
enough energy to break from
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 15

Figure 1.13 Integrated Circuit (micro-chip) comprises of electronic circuits on

one small plate of semiconductor material
1.5.2 Biomaterials

Biomaterial can be defined as "any substances (other than a drug) or combination

of substances synthetic or natural in origin, which can be used for any period of
time, as a whole or as a part of a system which treats, augments, or replaces any
tissue, organ or function of the body."[14] These materials must not produce toxic
substances and must be compatible with body tissues. [2]. Metal, ceramic
polymer, and composite can be used as biomaterials. For example, biomaterials
are utilized in hip replacement for people with severe hip damage [Figure 1.14].
When a hip replacement required, the surgeon removes damaged cartilage and
bone from hip joint and replaces them with new, man-made parts.

Figure 1.14 A hip joint before and after hip replacement (adapted from
[Link]

1.5.3 Smart materials

Smart materials are what their name says. They are intelligent materials that have
the ability to sense external environmental stimuli (temperature, stress, light,
humidity and electric & magnetic fields); and respond to them by changing their
properties (mechanical, electrical or appearance), structure or functions.

The system for smart materials consists of sensor (to detect input signals) and
actuator (part that responds and adapt to the function). Among the materials that
can serve as an actuator is Shape Memory Alloys (SMA). One of the examples
where SMA is used is in robotic muscles as shown in Figure 1.15 (a). Over the
years scientists have been trying to re-create human anatomy through mechanical
means. However, the functions of human body are so complex; making it very
difficult to imitate by robots even as simple as the grip of your fingers! In this case
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 16

SMA can mimic the tendons and muscles of humans very well as in the Figure
1.15 (b).

(a) (b)
Figure 1.15 (a) robotic hands using SMA and (b) how the SMA wire in the
robotic finger works to create movement. (adapted from
[Link]

1.6 CONCLUSION
Materials science and engineering (MSE) is an interdisciplinary field where
materials science is acquired knowledge about materials, whereas materials
engineering are dealt with application of materials in community. The three main
types of materials are metallic, polymeric, and ceramic materials. Two other types
of materials that are very important for modern engineering technology are
composite and electronic materials. Advanced and smart materials are presented
as new classes of materials with novel and important applications in many
industries.

QUESTIONS
1.1 What are materials? List eight commonly encountered engineering materials.
1.2 Define materials science and materials engineering.
1.3 What are the main classes of engineering materials?
1.4 What are some of the important properties of each of these engineering
materials?
1.5 Define a composite material. Give an example of a composite material.

REFERENCES
1. Askeland, D.R., Fulay, P.P. and Wright, W.J., (2012), the Science and Engineering of Materials,
6th Edition. Thomson.
2. William D. Callister, Jr, Materials Science and Engineering – An introduction, Ninth Edition,
John Wiley & Sons, Inc. 2011.
3. V. Raghavan, Materials Science and Engineering, third edition, Prentice Hall of India Private
Limited, New Delhi, 1990.
4. Smith, W.F. (2011) Principle of Materials Science & Engineering, 5th Edition, Mc. Graw Hill.
5. Shackelford, J.F. (2009) Introduction to Materials Science for Engineering, 7th Edition, Prentice
Hall.
6. Materials Science and Technology Teachers Handbook (2008), Pacific Northwest National
Laboratory Richland, Washington.
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 17

CHAPTER 2: ATOMIC STURCTURE AND BONDING

LEARNING OBJECTIVES:

1. To describe the underlying physical concepts related to structure of matter.

2. To examine the relationships between the structure of atoms-bonds-
properties of engineering materials.

2.1 What is an atom?

Atoms are the basic building block of an element. It can join together to form
molecules or compounds, but specific elements only comprises of entirely one
type of atom. Atoms in an element have its own distinct characteristics that makes
elements different from one another. An atom is composed of a very small nucleus
containing protons and neutrons and the electrons are moving around the nucleus.
Figure 2.1 shows the arrangement of three particles; protons, neutrons and
electrons, in an atom.

Figure 2.1 Image of an atom showing its particles of proton, neutron and
electron [[Link]

Protons – are positively charged particles. All atoms of an element (radioactive

and non-radioactive) have the same number of protons. The mass of proton is
1.673 x 10-24 g and its electrical charge q is +1.602 x 10-19 coulomb (C).

Neutrons - have no electrical charge, and like protons, are about 1800 times as
heavy as an electron. The mass of neutron is 1.675 x 10 -24 g. Since neutron is
neutral in charge, it will not electrically attract to either protons or electrons.

Electrons- The particles that orbit the nucleus as a cloud are called electrons.
They are negatively charged and are held to the nucleus by an electrostatic
attraction of the positive electrical charge of the protons in the nucleus.
Interactions with electrons in the outer orbits affect an atom's chemical properties.
The mass of an electron is 9.109 x 10-28g and its electrical charge q is –1.602 x
1019. Coulomb (C).
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 18

Each element is characterized by the atomic number (Z) which is number of

protons in the nucleus of an atom. The atomic number also equals the number of
electrons. Therefore an atom as a whole is electrically neutral because the number
of protons and electrons are equal.

The atomic mass (A) of a specific atom is the sum of the masses of protons and
neutrons within the nucleus. The atomic weight of an element or the molecular
weight of a compound may be specified on the basis of amu per atom (molecule)
or mass per mol of material. In one mol of a substance there are (Avogadro’s
number 6.022 x 1023) atoms or molecules. These two atomic weight schemes are
related as

1 amu/atom (1or molecule) = 1 g/mol.

For example, the atomic weight of iron is 55.85 amu/atom, or 55.85 g/mol.

Example 2-1 illustrates how to calculate the number of atoms for 100 g
silver.
Calculate the number of atoms in 100 g of silver (Ag).

SOLUTION

The atomic mass, or weight, of silver is 107.868 g mol.

The number of Ag atoms is = (Amount of Ag x Avogadro’s number)/Atomic mass

= (100 g x 6.022 x 1023 atoms/mol)/107.868 g/mol

= 5.58 x 1023

2.2 The electronic structure of the atom

The atomic model that is known today is based on the study of quantum
mechanics. Quantum mechanics is a set of scientific principles describing the
known behaviour of energy and matter that predominate at the atomic and sub-
atomics scales. Scientists that are responsible for the atomic models in quantum
mechanics are Rutherford, Bohr, De Broglie, Heisenberg and Schrodinger for a
clear understanding of the behaviour of electrons in atoms and crystalline solids

2.2.1 Bohr’s atomic model.

Bohr’s atomic model expresses that electrons in an atom will orbit (go around) the
nucleus in a planetary manner (just imagine the planets orbiting the sun). These
electrons could only exist at certain energy levels from the nucleus in a discrete
orbital. The further it gets from the nucleus, the weaker is the attraction of
electrons to it and the higher is the energy of the electrons (Figure. 2.2).
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 19

Figure 2.2 Bohr’s planetary orbital model

According to Bohr, energies of each electron are quantized so that electrons can
only have specific energy values. However, its energy can be changed by making
a quantum jump from one energy level (orbit) to another if we provide enough
external energy that exceeded the energy of the particular There are two ways in
which quantum jump can occur (Figure 2.3):

i. When atoms absorbed energy, the electrons become excited and jumped
from low energy levels (close to the nucleus) to high energy levels (farther
from the nucleus).

ii. Energy is emitted during the same transition from high energy level to lower
energy level.

Figure 2.3 Electron quantum jump from higher to lower energy level

The major advantages of Bohr’s model are that it explained several things:

i. Each electron orbit (or energy shell) of the same size can only hold distinct
number of electrons. For example, first shell (n=1) can hold up to 2
electrons and second shell (n=2) can hold up to 8 electrons.

ii. Once the shell with lower energy was filled up with electron, the remaining
electrons were found at higher energy levels.

iii. Chemical properties were based on the number of electrons in the

outermost shell (valence electrons). Element with full outer shells do not
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 20

react (chemically inert) and element with certain number of valence electron
will take or give up their electron in a chemical reaction to get a full outer
shell.

2.2.2 De Broglie’s model

Even though Bohr’s model already explained certain aspects of electrons orbiting
the nucleus, it still has certain flaws. Louis De Broglie comes out with explanation
for limitation in Bohr’s model. Broglie suggested that like light, electrons could act
as both particles and waves while orbiting the nucleus (Figure 2.4).

Figure 2.4 De Broglie’s electron wave model

2.2.3 Heisenberg Uncertainty Principles

Heisenberg, German scientist, gives an answer to the issues raised by De

Broglie’s atomic model. In his theory called the Uncertainty Principle, he proved
that we can NEVER know both the momentum and position of an electron in an
atom. He also stressed out that we shouldn’t view electrons as moving in well-
defined orbits about the nucleus.

2.2.4 Schrodinger modification on Bohr’s Model

Erwin Schrodinger is an Austrian physicist who derived a set of equations or wave

functions for electrons. His modification compliment Bohr’s model, De Broglie’s
and Heisenberg principle. According to him, we could only describe the probability
of where the electron could be (meaning you can pin point the location of the
electron at a time). The distributions of the probabilities formed regions of space
about the nucleus called orbitals. In other word, orbital can be described as the
electron density cloud area that has greatest probability of finding electron.

2.3 Quantum numbers

According to Bohr’s model, each orbit in the atomic model is associated with a
definite energy that is known as energy level or energy shell. Within each or the
energy level, the electrons separate into subshells. Quantum numbers are
representing energy levels to which each electron belongs. Basically there are four
quantum numbers, namely principal quantum number n, secondary or orbital
quantum number l, the magnetic quantum number ml, and the spin quantum
number ms.
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 21

2.3.1 2.3.1 The principal quantum number, n

The principal quantum number, n is related to the size of the shell. It determines
the principal energy levels and it takes only positive integer value of n ≥ 1 (i.e. n =
1, 2, 3, 4...). As ‘n’ increase, orbital become larger and the electrons occupying
that particular level has higher energy. Electrons with higher energy is easier to
ionize (easier to jump from shell to shell) since larger shell means it is further away
from the nucleus and less tightly bound to it. Sometimes these shells are also
designated as K, L, M and N accordingly to ascending order of n as shown in
Figure 2.5 and Table 2.1.
4

Nucleus of an atom
(protons + neutrons) +

Figure 2.5 Principal quantum number, n in an atom

Table 2.1 The Number of Available Electron States in Some of the Electron
Shells and Subshells

2.4 The secondary or orbital quantum number, l

The secondary or orbital quantum number, l, refers to the subshell, within the
principle shell, which is denoted by a lowercase letter—an s, p, d, or f and it is
related to the shape of the electron subshell.. Each of this subshell can contain
certain distinct number of electrons. In addition, the number of these subshells is
restricted by the magnitude of n and the secondary quantum numbers are
assigned l= 0,1,2………., n-1. . For an atom, when n = 1, it can only have 1
subshell. However, as the number or shell increase to n= 2, there will be 2
possible subshells. Allowable subshells for the several n values are also presented
in Table 2.1.
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 22

2.4.1 The magnetic quantum number, ml

Magnetic quantum number is the third quantum number ml and it represents the
orientation of the orbitals within each subshell (secondary quantum number). The
total number of magnetic quantum numbers for each l is 2l+1. The values for ml
are given by whole numbers between -l and +l. For example, if l = 2, there are
2(2)+1= 5 magnetic quantum numbers with values -2, -1, 0, 1, and 2. The
combination of l and ml specifies a particular orbital in a shell.

2.4.2 The spin quantum number, ms

The last quantum number is used to further specify each electron in the subshell.
For example; if the atomic number for helium is 2, then both electron in helium
atom is having the same n (n = 1) and lies in l = 0 (s subshell). In order to
differentiate these two electrons spin quantum number, ms is introduced. The spin
of electron has to be either up and down; no other position is allowed. In order to
avoid any confusion, we follow the Pauli’s exclusion principle that says ‘no more
than two electrons can occupy the same orbital of an atom and the two electrons
must have the opposite spin. The two values possible for ms is + ½ and - ½ .

2.4.3 Energy State of an Orbit

Thus, the Bohr model was further refined by wave mechanics, in which the
introduction of three new quantum numbers gives rise to electron subshells within
each shell. A complete energy level diagram for the various shells and subshells
using the wave-mechanical model is shown in Figure 2.6. Several features of the
diagram are worth noting. First, the smaller the principal quantum number, the
lower the energy level; for example, the energy of a 1s state is less than that of a
2s state, which in turn is lower than the 3s. Second, within each shell, the energy
of a subshell level increases with the value of the l quantum number. For example,
the energy of a 3dstate is greater than a 3p, which is larger than 3s. Finally, there
may be overlap in energy of a state in one shell with states in an adjacent shell,
which is especially true of d and f states; for example, the energy of a 3d state is
greater than that for a 4s.

Figure 2.6 Energy state for each orbital within a subshell

CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 23

2.4.4 Electron configuration

All the electrons in a particular atom can arrange according to Pauli’s exclusion
principle for four quantum numbers. Electrons in an atom will occupy the lowest
energy states in the energy level and subshells. Refer back to Figure 2.6, in terms
of energy, 4s orbital has lower energy than 3d orbital. That means, when electrons
are arranged to build up its configuration, 4s will fill up first then come back to 3d
orbital. When all the lowest energy state is filled with electron, the atom is said to
be in its ground state. To assist the electron configuration, Figure 2.7 shows the
method for arrangement of electrons in the orbitals.

Figure 2.7 Method of arrangement for electrons in orbitals within subshells

Electron configuration of an atom tells us about the valence electrons. Valence

electrons are those that occupy the outermost shell. The knowledge about valence
electrons is so significant in understanding the structure and properties of
materials because they take part in chemical reaction during bonding process. If
you refer back to Example 2.1, the valence electron for sodium (Na) is 1 since that
is the amount of electron occupying n = 3.
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 24

EXAMPLE 2.1
For calcium with Z = 20, write down its electron configuration.
ANSWER
The way to write the electron configuration:

Therefore, by referring to Figure 2.7; the electron configuration for calcium (Ca)
will be:
1s2 2s2 2p6 3s23p64s2

2.4.5 Electronegativity

We already knew that valence electrons are those electrons that take part in
chemical reaction during bonding process. Electronegativity can be defined as the
ability of an atom to attract electrons from other atom/s. If the element has more
tendencies to attract electrons during a chemical reaction, this type element is
known as electronegative element.

EXAMPLE 2.3
Between Natrium (Sodium) and Chlorine, which one will
become electropositive ion and which one will become
electronegative ion in a chemical reaction?
Given that the electronegativity value for Na = 0.9 and that
of Cl = 3.0

ANSWER
Natrium is tends to give up its electron because of the lower
electronegativity value compared to chlorine. Chlorine will
have more tendency of attracting electrons towards its atom
in a chemical reaction with Natrium. So, Natrium will be
electropositive ion and chlorine will be electronegative ion.

2.5 Periodic table

All the elements have been classified according to electron configuration in the
periodic table (Figure 2.8). Here, the elements are situated, with increasing
atomic number. The elements in periodic table are arranged in term of periods
(rows) and columns. Each of the 7 rows is filling sequentially by atomic number of
the elements. Group that build up the column include elements having the same
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 25

electron configuration in the outer shell (valence electrons) which results in group
elements sharing similar physical and chemical properties.

Figure 2.8 The periodic table of the elements. The numbers in parentheses are
the atomic weights of the most stable or common isotopes. (Callister, 2012)

If we take a look at one element from the periodic table, it provides the atomic
number, (Z) and the atomic weight, (A) of that particular element (Figure 2.9).

Figure 2.9 The value of atomic number, Z and atomic mass, A of copper excerpt
from periodic table.

2.6 PRIMARY INTERATOMIC BONDING

Most of the physical properties of the materials are predicted by the interatomic
forces between two atoms that help to bind the atoms together. The bonding
energy for any two atoms, corresponds to the energy that would be required to
separate these two atoms to an infinite separation. Electrons inside an atom can
actually interact with electrons from another atom hence creating the attraction
that lead to the formation of compounds/ chemical substances. But this interaction
is different from one compound to another. That is why we have few types of
bonding. Those that are strongly attracted to each other falls under primary
bonding and the less attracted to each other will be under secondary bonding.
There are three types of primary bonding or chemical bonding that can be found in
solids. Under this category we have:
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 26

2.6.1 Ionic bonding

It represents the bond between metallic and non-metallic elements to form a

compound. The capability of giving and accepting valence electrons depends on
electronegativity of each element. Usually electropositive elements give up its
valence electrons while electronegative elements prone to accept valence
electrons. In the periodic table, elements that easily give up their valence electrons
are metallic elements and those that easily accept electrons are non-metallic
elements.

After the process of giving up and accepting electrons, atoms will become ions.

 Electropositive atoms  give up electron/s  positive ions  cations

 Electronegative atoms  accept electron/s  negative ions  anions

The oppositely charged ions are then attracted to one another and produce the
ionic bond. For example, the attraction between sodium and chloride ions
(Figure 2-10) produces sodium chloride (NaCl), or table salt

Figure 2.10 An ionic bond is created between two unlike atoms with different
electronegativities. When sodium donates its valence electron to chlorine, each
becomes an ion, attraction occurs, and the ionic bond is formed.

Ionic bonding is considered as nondirectional bonding because the magnitude of

the bond is equal in all directions around an ion. After the reaction takes place,
notice how atoms gain or lose just the right number of electrons to produce an
ion with a complete outer shell of electrons. This is sometimes called a stable
octet.

We already knew how the reaction takes place between one sodium atom and one
chlorine atom. But to make a spoonful of salt would take more than just this one
set of ions attracted to each other. We might need millions of it!

TRY IT YOURSELF THIS TIME!

Question 1
Try to work out the ionic bonding process between
magnesium (Z=12) and oxygen (Z=8).

General properties of ionic compound:

CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 27

i. Strong electrostatic attraction means high melting and evaporation points.

Ionic bonds are very strong and a lot of energy is needed to break them, so
ionic compounds have high melting points and boiling points.

ii. Usually hard and brittle solid at room temperature.

iii. It does not conduct electricity except for in molten state or when dissolve in
water because ionic compounds can only conduct electricity if their ions are
free to move (Figure 2.11).

iv. Ionic compounds are mostly water soluble.

Figure 2.11 Conductivity of ionic compounds

2.6.2 Covalent bonding

Materials with covalent bonding are differ from ionic bonding. Instead of donating
or accepting, covalent bonds are formed by sharing of valence electrons among
two or more atoms.

Consider the bond of a silicon atom. It has a valence of four [Figure 2.12(a)]. Now
it will share its four valence electrons with four surrounding silicon atoms for which
the silicon atom will have eight electrons in its outer energy shell and adjacent four
atoms would follow the same if they encounter other silicon atoms. In addition the
bonds have a fixed directional relationship with one another because, atoms in a
covalently bonded material form specific angles [Figure 2. 12(c)], depending on
the material.
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 28

Figure 2.12(a) and (b). Each instance of sharing represents one covalent bond;
thus, each silicon atom is bonded to four neighbouring atoms by four covalent
bonds. (c) Covalent bonds are directional. In silicon, a tetrahedral structure is
formed with angles of 109.5° required between each covalent bond.

 A covalent bond is formed between non metal atoms, which combine

together by sharing electrons.
 Covalent compounds have no free electrons and no ions so they don't
conduct electricity.
 Covalently bonded materials are very strong and hard. For example,
diamond (C), silicon carbide (SiC), silicon nitride (Si3N4), and boron nitride
(BN) all have covalent bonds.
 These materials also exhibit very high melting points, which means they
could be useful for high-temperature applications. On the other hand, the
high temperature needed for processing presents a challenge.
 The electrical conductivity of many covalently bonded materials (i.e., silicon,
diamond, and many ceramics) is not high since the valence electrons are
locked in bonds between atoms and are not readily available for
conduction.

EXAMPLE 2.3
How Do Oxygen and Silicon Atoms Join to Form Silica?
Assuming that silica (SiO2) has 100% covalent bonding, describe how oxygen
and silicon atoms in silica (SiO2) are joined.

SOLUTION
Silicon has a valence of four and shares electrons with four oxygen atoms, thus giving a total of
eight electrons for each silicon atom. Oxygen has a valence of six and shares electrons with two
silicon atoms, giving oxygen a total of eight electrons. Figure 2-13 illustrates one of the possible
structures. Similar to silicon (Si), a tetrahedral structure is produced. We will discuss later in this
chapter how to account for the ionic and covalent nature of bonding in silica

2.6.3 Metallic bonding

When metals bond with themselves, they bond in a different way than when they
bond with other elements. It isn't ionic or molecular or covalent. It is its own metal
bond. Each metal atom in a metallic material gives up their valence electrons and
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 29

these electrons are not bound to any particular atom instead as a whole forms a
“sea of electrons” or an “electron cloud”. The remaining nonvalence electrons and
atomic nuclei form what are called ion cores. The attraction between the free
electrons and the positively charged ion cores produces a strong metallic bond.
Figure 2.13 shows the free electrons in sea model.

Figure 2.13 Free electrons in metallic bonding

Some general behaviours of the metals may be explained by bonding type.

 Metals are good conductors of both electricity and heat, as a consequence

of their free electrons. Metals contain electrons that are free to move in the
metal structure, carrying charge from place to place and allowing metals to
conduct electricity/heat well.

 Metals are good reflectors (opaque) because when light incident on the sea
of electrons, these electrons start vibrating e by absorbing the light energy
and immediately reflect the light rather than transmit the light through metal.

 Metals are malleable i.e. they can be formed easily by the application of the
load because of the non-directionality of the metallic bond.

2.7 SECONDARY BONDING or VAN DER WAALS

BONDING
van der Waals bonding are forces of attraction which exist between all atoms and
molecules. van der Waals bonds are much weaker than all other previously
mentioned bond types. The strength of the van der Waals bond is related to the
size of atoms and molecules. The bigger the atom or molecule the bigger the van
der Waals force types of bonding.
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 30

The origin of van der Waals forces between atoms and molecules is the secondary
bonding forces arise from atomic or molecular dipole. Dipole exists if positive part
(+q) and negetive part(-q) of charges are separated by a distance. Usually atoms
are electrically neutral, therefore, a neutral atom has no dipole moment. But when
a neutral atom is exposed to an internal or external electric field, the atom may
become polarized (i.e., the centers of positive and negative charges separate).
The momentary attraction between two opposite charges of two dipoles is known
as the van der Waals force (Figure 2.14).

Figure 2.14 Schematic illustration of van der Waals bonding between two
dipoles.

There are three types of van der Waals interactions: Dipole interactions occur
between induced dipoles, between polar molecules (which have permanent
dipoles), and between induced dipoles and polar molecules.

2.8.1 Induced Dipole Bonds

The interactions between two dipoles that are induced in atoms or
molecules are refer to induced dipole bonds. A dipole may be induced in an atom
or molecule that is normally electrically symmetric [Figure 2.15 (a)]. When atoms
or molecules are bring together their symmetry experiences distortion resulted
from constant vibrational motion which ultimately induce small electric dipoles
[Figure 2.15 (b)].

Figure 2.15 Schematic representations of (a) an electrically symmetric atom and

(b) an induced atomic dipole.

2.8.2 Permanent Dipole Bonds

When van der Waals forces exists between adjacent molecules that are
permanently polarized (Permanent dipole moments exist in some molecules by
virtue of an asymmetrical arrangement of positively and negatively charged
regions; such molecules are termed polar molecules.). For example, when water
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 31

molecules are attracting other water molecules or other polar molecules, we refer
to these as permanent dipole bonds. The associated bonding energies are
significantly greater than for bonds involving induced dipoles. The attraction
between the positively charged regions of one water molecule and the negatively
charged regions of a second water molecule provides an attractive bond between
the two water molecules (Figure 2-16).

Figure 2.16 The Permanent Dipole Bonds is formed as a result of polarization of

molecules or groups of atoms. In water, electrons in the oxygen tend to
concentrate away from the hydrogen. The resulting charge difference permits
the molecule to be weakly bonded to other water molecules.

2.8.3 Polar Molecule-Induced Dipole Bonds

Polar Molecule-Induced Dipole Bonds refers when an induced dipole (a non-

polar atom or molecule) interacts with a permanent dipole moment molecule. An
example of this interaction would be forces between water molecules and carbon
tetrachloride. Figure 2.17 represents a hydrogen chloride molecule which shows a
permanent dipole moment arises from hydrogen (net positive) and chlorine
(negative) charges. Polar molecules can also induce dipoles in adjacent nonpolar
molecules, and a bond will form as a result of attractive forces between the two
molecules. Furthermore, the strength of this bond will be greater than for
fluctuating induced dipoles.

Figure 2.17 Schematic representation of a polar hydrogen chloride (HCl)

molecule
CHAPTER I-2 ATOMIC STRUCTURE AND BONDING 32

2.7.1 Hydrogen bonding

Hydrogen bonding, a special type of secondary bonding, is found to exist between

some molecules that have hydrogen as one of the constituents. Hydrogen bonds
are permanent dipole-permanent dipole interactions. Hydrogen bonds are
electrostatic forces of attraction between molecules which contain these highly
polar bonds. Bonds consisting of a hydrogen atom bonded to an atom of a strongly
electronegative element such as fluorine, oxygen or nitrogen are highly polar. This
highly positively charged end of the molecule is capable of a strong attractive force
with the negative end of an adjacent molecule, as demonstrated in Figure 2.18 for
HF

Figure 2.18 Hydrogen bonding in hydrogen fluoride (HF).

A hydrogen bond is stronger than other forms of permanent dipole-permanent
dipole interactions but weaker than a covalent bond.

2.9 CONCLUSION
This chapter started with particles in atom and their characteristics. Electron
energy was highlighted with the help of quantum number and presented wave-
mechanical models of electrons in atoms. Electron energy states are specified in
terms of quantum numbers that give rise to electron shells and subshells. Atomic
bonding in solids may be considered in terms of attractive and repulsive forces
and energies of charge particles . The three types of primary bond in solids are
ionic, covalent,and metallic. Both van der Waals and hydrogen bonds are termed
secondary, being weak in comparison to the primary ones.

1.