CHAPTER 3

The mechanical and physical properties of a material are,

ATOMIC STRUCTURE

at the most fundamental level, determined by the

composition and structure of the material.
Composition refers to the types of elements that make up

3.1

THE ATOM

3.2

THE ELECTRONIC STRUCTURE OF ATOMS

3.3

THE PERIODIC TABLE

bonding and forces holding atoms together

3.4

PRIMARY BONDS
3.4.1 Ionic Bonding
3.4.2 Covalent Bonding
3.4.3 Metallic Bonding

as the ways in which atoms/molecules pack together (Chp 4).

3.5

the material and the proportions in which they exist.

The constituent elements will govern the nature of
(Chp. 3),

as well

3.1 THE ATOM

The atom is the smallest unit building block of all matter; it

SECONDARY BONDS
3.5.1 Van der Waals Bonding
3.5.2 Hydrogen Bonding

is the smallest quantity of an element that can take part in

a chemical reaction.
An atom may be thought of as a very small, dense nucleus

3.6

BONDING CHARACTER OF MATERIALS

3.7

BONDING FORCES AND ENERGIES

3.8

BONDING TYPE AND PROPERTIES

3.8.1 Thermal Expansion
3.8.2 Melting Point
3.8.3 Elastic Modulus
3.8.4 Hardness, Ductility and Toughness

surrounded by moving electrons (Fig. 3.1-1).

3-1

Fig. 3.1-1 Schematic

representation
of an atom.

3-2

3 . 2 T HE E LECTRONIC S TRUCTURE OF A TOMS

Each shell may be further divided into subshells s, p, d, f,

, each differing slightly in their energy levels

The electronic structure (arrangement of electrons) of

(Fig. 3.2-2 and

Table 3.2-1).

atoms dictates the nature of bonds and chemical reactions

between atoms, as well as electrical, thermal, magnetic
and optical properties of materials.
Fig. 3.2-2 Schematic
representation of the
relative energies of the
electrons for the various
shells and subshells.

Electrons are held to the nucleus by electrostatic (positivenegative) attraction, the force of which decreases with
distance from the nucleus. Electrons may be thought of as
being arranged in shells of increasing discrete energy
levels with increasing distances from the nucleus. Shells
are designated K, L, M, N, , (K being the closest to the
nucleus) (Fig. 3.2-1).

(a)

Electrons tend towards the lowest energy states (i.e.

(b)

greater stability). The electronic structure of an atom of

Fig. 3.2-1 Schematic representation of (a) the electron configuration; and

(b) the filled energy states for a sodium (Na) atom.

atomic number Z can be specified by putting one electron

in each of the Z lowest energy states.
3-3

3-4

 The most stable (lowest energy) electron configuration is

that in which the electron states within the outermost shell
are completely filled; e.g., He, Ne, Ar (inert gases). Fullyfilled shells are considered closed; electrons in closed
shells do not readily enter into reactions.
Electrons occupying partially-filled outermost shells, known
as the valence electrons, are most likely to enter into
chemical reactions because their distance away from the
nucleus reduces their binding energy to the nucleus. In
addition, the closed inner shells shield the outermost
shells from the positive nuclear charge.

3.3 THE PERIODIC TABLE

Each element is identified by its atomic number, Z, which
is equal to the number of protons in the nucleus. Elements
are arranged in ascending atomic numbers (horizontal
rows) in chemically similar groups (vertical columns) in the
Periodic Table (Fig. 3.3-1).
Elements in the same column (i.e. with similar chemical
behaviour) in the Periodic Table have similar electronic
configurations in the outermost shells of their atoms.
3-5

3-6

3.4 PRIMARY BONDS

Atoms bond because there is a reduction in the overall
energy (i.e. greater stability) when the electrons amongst
the bonding atoms rearrange to achieve the stable
configuration of fully-filled outermost shells.
There are 3 types of primary bonds between atoms: ionic,
covalent and metallic.

Fig. 3.4-1 Ionic bonding in sodium chloride (NaCl).

Since electrostatic attraction is omnidirectional and long3.4.1

Ionic Bonding

ranged, ionic bonds are non-directional. The (usually)

Ionic bonding involves the transfer of electrons from the

nearly-empty outermost shell of one element to the nearly-

smaller positive ions are surrounded by as many negative

ions as possible and vice versa (Fig. 3.4-2).

full outermost shell of another element, resulting in

complete outermost shells in both (Fig. 3.4-1).
Ionic bonds form between elements located at the
horizontal extremities of the Periodic Table; e.g. between
Group I (metal) and Group VII elements (non-metal); e.g.
NaCl (Fig. 3.4-1).
Fig. 3.4-2 Ionic bonding is non-directional.

The bond arises from electrostatic (Coulombic) attraction

between the positive and negative ions (Fig. 3.4-1).

Ionic bonding is found in many ceramics; e.g. alumina

(Al2O3), titanium carbide (TiC), and zirconia (ZrO2).

3-7

3-8

3.4.2

Covalent Bonding

The bond arises from the electrostatic attraction between

the negatively-charged pair of shared electrons and the

Atoms with difficulty in gaining or losing electrons in their

two positively-charged atomic cores (Fig. 3.4-4).

outermost shells tend towards sharing of electrons in

pairs to complete their outermost shells; e.g. C, Si (Fig. 3.4-3).

Due to strong mutual repulsion, each negatively-charged

valence electron cloud assumes equilibrium positions as far
from one another as possible. Covalent bonds therefore
have a fixed directional relationship with one another

(Fig.

3.4-5).

Fig. 3.4-3 Covalent bonding in silicon.

Each pair of shared electrons orbit about both atomic

cores, mainly traversing the space between the two atomic
cores (Fig. 3.4-4).

Fig. 3.4-5 Directional covalent bonding in diamond.

Fig. 3.4-4 Electron orbital
penetrating two atomic cores.

Materials with covalent bonding include: semiconductors

(Si, Ge, GaAs), some ceramics (SiC, Si3N4), and diamond.

3-9

3-10

3.4.3

Metallic Bonding

Metallic bonding is confined to metals and near-metals

with few valence electrons in their outermost shells; e.g. in
Groups I, II and III of the Periodic Table.
Valence electrons, which are weakly-bound to the nucleus,
become easily detached and move freely around the ion
cores. These electrons are delocalized from their nucleus,
forming a randomly-moving sea of electrons surrounding
the ion cores.
The electrostatic attraction between the negativelycharged electron sea and the positive ion cores acts as a
glue that bonds the metallic structure. (Fig. 3.4-6).

Fig. 3.4-6 Schematic

illustration of metallic bonding
showing positive ion cores
immersed in a randomlymoving sea of negative
electrons.

Metallic bonds are non-directional.

3-11

3-12

3.5.2

3.5 SECONDARY BONDS

Secondary bonds are formed between molecules; no
change in the electronic structure is involved.

Hydrogen Bonding

Hydrogen bonding is a special type of van der Waals

bonding that involves the attraction between molecular
dipoles with hydrogen as a constituent.

Secondary bonds are weaker than primary bonds.

Covalent bonding between hydrogen and an element with

3.5.1

a nearly-full outermost shell concentrates the electron

Van der Waals Bonding

Van der Waals bonding involves the attraction between

atomic or molecular dipoles.

away from the hydrogen nucleus, leaving a positive charge

at the hydrogen end of molecule; this forms a permanent
dipole (Fig. 3.5-3).

A dipole arises when the centres of positive and negative

charge in an atom or molecule do not coincide.

The bond arises from electrostatic attraction between the

positive and negative ends of permanent dipoles (Fig. 3.5-3).

Due to the constant motion of

electrons, the negative charge is
sometimes

not

symmetric

with

Fig. 3.5-3 Hydrogen

bonding between water
molecules.

respect to the positive nucleus,

forming a temporary dipole.
A dipole may induce a similar dipole in an adjacent atom
or molecule. The bond arises from weak electrostatic
attraction between the positive end of one dipole to the
negative end of the other dipole (Fig. 3.5-2).
Fig. 3.5-2 Van der Waals bonding
between two temporary dipoles.

3-13

Hydrogen bonds are stronger than van der Waals bonds

between fluctuating induced dipoles because the dipoles
involved in the bonding are permanent.
Hydrogen bonds are important in polymers and biological
molecules; e.g. cellulose, DNA.
3-14

 Van der Waals bonding may be found between the layers

of covalently-bonded C atoms in graphite
between

chains

of

thermoplastic

(Fig. 3.5-4),

polymers;

polyethylene (PE), polyvinyl chloride (PVC)

(Fig.

and
e.g.
3.5-5),

polystyrene, and nylon.

3.6 BONDING CHARACTER OF MATERIALS

Bonding between atoms may involve more than one type
of primary bond and can also involve secondary bonds.
The transition from pure ionic to pure covalent bonding is
gradual and many ceramics display mixed ionic/covalent
bonding.
The transition metals (e.g. Fe, Cr, Mo, W, Pt) display mixed
metallic/covalent bonding because partially-filled inner
shells result in some covalent bonding.

Fig. 3.5-4 Structure of graphite showing covalent bonding between carbon atoms in
each layer, and van der Waals bonding between the layers.

Fig. 3.5-5 Atoms within each chain of polyvinyl chloride (PVC) are covalently bonded,
while van der Waals (hydrogen) bonding exists between the chains.

3-15

Fig. 3.6-1 Tetrahedron

representing the relative
contribution of different
bond types to the four
fundamental categories of
engineering materials.

3-16

3.7 BONDING FORCES AND ENERGIES

Equilibrium spacing (bond-length), ro, occurs when

When two atoms are brought close together, an attractive

force, FA, is set up, which increases with decreasing atomic
separation (Fig. 3.7-1a).
At short separations, a repulsive force, FR, arises due to the
resistance of the closed inner shells to mutual penetration
(Fig. 3.7-1a).

FN = FA + FR = 0
Potential energy due to the interaction between the atoms,
UN, is such that:

or

FN =

dUN
dr

UN =

#"FN dr

! When r = r0, potential energy is a minimum (Fig. 3.7-1b):

dU N %'
$ dr ''
#
&
"

FN = $$

=0
r=r0

! Mechanical model of a solid: a solid may be envisaged as

an array of particles (atoms) with each particle linked to its
neighbours by springs (bonds) (Fig. 3.7-2).
Fig. 3.7-1 The variation of (a)
forces and (b) energies with
interatomic separations. C and K
in FA and FR are constants,
and m < n.

(a)

3-17

(b)

Fig. 3.7-2 Mechanical model of a solid showing (a) atoms linked by atomic bonds that
behave like springs, and (b) the variation in forces and energies with atomic separation.
3-18

 The energy-separation curve is also known as the potential

By convention, the potential energy is set at zero when the

well; it represents the potential energy of an atom due to

interatomic separation is infinite (i.e. r = !), since the

the influence of its neighbouring atom. The bottom of the

atoms would have zero interaction (Fig. 3.7-4).

well (minimum of the curve) corresponds to the total

energy of the atom at absolute zero (0 Kelvin). At this
temperature, the atom has potential energy only, without

Fig. 3.7-4 By convention,

potential energy is set at
zero for r = !.
[Note that mathematically,

any kinetic energy.

Above 0 K, the atom also possesses kinetic energy, which
must be added above the potential energy curve

(Fig. 3.7-3a).

(Fig.3.7-3b),

" N

As the temperature increases, the atom may be seen as

moving up the potential well

F dr also leads to
negative potential energy.]

vibrating back and

forth the distance dictated by the width of the well at any

particular temperature.

If the temperature of the solid rises such that the total

energy becomes greater than zero (i.e. interatomic
separation approaches infinity), the material exists in the
gaseous state (Fig. 3.7-4).
However, the energy-separation curve does not provide a
basis for discussing the liquid state, since the phase change
from solid to liquid or from liquid to gas requires a supply
of energy (latent heat) that is unrelated to a rise in

(a)

temperature.

(b)

Fig. 3.7-3 (a) Potential and kinetic energy components of the total energy of an atom.
(b) The atom moves up the potential well as temperature increases.
[Note that in these diagrams, the potential energy is set at zero when r=r0;
the usual convention is to set potential energy to zero when r = !.]

3-19

3-20

3.8 BONDING TYPE AND PROPERTIES

Materials that are ionically and/or covalently bonded; e.g.

The type of bonding in a material determines several

ceramics, tend to have deep and narrow wells, and thus,

properties, some of which may be related to the shape of

good thermal stability. Metals experience slightly greater

the force-separation and energy-separation curves.

expansion. Materials containing secondary bonding, e.g.

polymers, have very large coefficients of expansion.

3.8.1

T he rm al Expansion, !

As temperature rises above 0 K, kinetic energy results in

the atom shifting up the potential well. Due to the
asymmetrical shape of the well, the mean position of the
atom changes with temperature and the atoms tend to
move apart as temperature increases (Fig. 3.8-1a).

Thermal expansion becomes an important consideration

when there are temperature changes during service.
Nonuniform dimensional changes, as well as expansion or
contraction that is constrained, would generate stresses,
and may lead to distortion or cracking. Low expansion
coefficients are generally preferred in such applications.

For a material with a deep and narrow well, the change in

interatomic distance for a given rise in temperature (i.e.

Assemblies containing two or more different materials

would require careful matching of expansion coefficients.

the thermal expansion coefficient) is smaller than that for a

material with a broader, shallower well (Fig. 3.8-1b).

3.8.2

M e l ti n g Poi n t

The melting point is a measure of bond strength, given by

the depth of the potential well. The deeper the well, the
greater the thermal energy required to reach levels where
bonding energy is low (liquid) or zero (gas).
Materials with primary bonds (ionic, covalent, metallic)

T3 > T2 > T1

(a)

generally have deep wells and high melting points, while

(b)

secondary bonding gives rise to low melting points.

Fig. 3.8-1 (a) Increase in interatomic separation with temperature.

(b) Comparison of the energy-separation curves for two materials: !A < !B.
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3.8.3

Elastic Modulus

(see also Sec. 2.2.1)

The elastic modulus (Youngs modulus) is a measure of a

materials stiffness or resistance to elastic deformation. It is
related to the slope of the force-separation curve near the
equilibrium separation distance, r0; the steeper the slope,
the greater the force required to move the atoms from
their equilibrium positions, and the higher the modulus
(the stiffer the material) (Fig. 3.8-2).

Fig. 3.8-3 Mechanical model of a solid where the spring stiffness

is a reflection of the elastic modulus.

Note that atomic bonds, like springs, have breaking points

(Fig. 3.8-4).
Fig. 3.8-2 A steep
gradient indicates a
high elastic modulus.

If the atoms are pulled with a force greater than

the peak on the force-separation curve, i.e. Fmax, the atomic

bond breaks and the attractive force between the atoms
will fall to zero as they separate further and further until
they no longer have an effect on each other. (See also Sec. 3.8.2)

In the mechanical model of a solid

(Fig. 3.8-3),

a higher elastic

modulus may be thought of as having stiffer springs

linking the particles, resisting their movement.
Materials containing primary bonds (ionic, covalent,
metallic) tend to have high stiffness, while those with
secondary bonds are less rigid.
3-23

Fig. 3.8-4 Atomic bond strength is measured by the peak of the force-separation curve
when a tensile force greater than Fmax is applied, the atomic bond breaks.

3-24

3.8.4

Hardness, Ductility and Toughness

Although hardness, ductility and toughness are different

In metals, the sea of electrons shield the positive ion cores

from one another and the ion cores can slip without
regard to electrical-charge constraints

(Fig.

3.8-5b).

The

mechanical properties, they may all be related to a

delocalized nature of the electrons also allows that the ions

materials ability to deform plastically (permanently) under

to slide past one another without interrupting the inter-

an externally applied stress. The plastic deformation of a

atomic bonding. Metals are relatively ductile and tough.

material requires atoms to slip and slide past one another.

In ionic solids, a displacement of the ions might lead to like
charges moving into adjacent positions

(Fig. 3.8-5a),

causing

repulsion. In covalent solids, strong mutual repulsion

between the negatively-charged electron clouds limits
atomic movement. Ionic and covalent solids are very hard,

In conclusion, understanding the chemical composition

(type of atoms), the nature of atomic bonding and the
property trends of various classes of materials enables us to
select and design materials more efficiently.
TABLE 3.8-1

but have low ductility and toughness.

Uo = depth of energy-separation curve at equilibrium separation, ro (bonding energy)

Ey = Elastic modulus (Youngs modulus)
! = coefficient of thermal expansion

Fig. 3.8-5 (a) Slip in ionic solids lead to repulsion of like charges.
(b) Ionic cores in metals are shielded by the electron sea.
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