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Chapter 1
The structure and bonding of atoms

1.1 The realm of materials science

In everyday life we encounter a remarkable range of
engineering materials: metals, plastics and ceramics
are some of the generic terms that we use to describe
them. The size of the artefact may be extremely small,
as in the silicon microchip, or large, as in the welded
steel plate construction of a suspension bridge. We
acknowledge that these diverse materials are quite lit-
erally the stuff of our civilization and have a deter-
mining effect upon its character, just as cast iron did
during the Industrial Revolution. The ways in which
we use, or misuse, materials will obviously also influ-
ence its future. We should recognize that the pressing
and interrelated global problems of energy utilization
and environmental control each has a substantial and
inescapable ‘materials dimension’.
The engineer is primarily concerned with the func-
tion of the component or structure, frequently with
its capacity to transmit working stresses without risk
of failure. The secondary task, the actual choice
of a suitable material, requires that the materials
scientist should provide the necessary design data,
synthesize and develop new materials, analyse fail-
ures and ultimately produce material with the desired
shape, form and properties at acceptable cost. This
essential collaboration between practitioners of the
two disciplines is sometimes expressed in the phrase
‘Materials Science and Engineering (MSE)’. So far
as the main classes of available materials are con-
cerned, it is initially useful to refer to the type of
diagram shown in Figure 1.1. The principal sectors
represent metals, ceramics and polymers. All these
materials can now be produced in non-crystalline
forms, hence a glassy ‘core’ is shown in the diagram.
Combining two or more materials of very different
properties, a centuries-old device, produces important
composite materials: carbon-fibre-reinforced polymers
(CFRP) and metal-matrix composites (MMC) are mod-
ern examples.
Figure 1.1 The principal classes of materials (after Rice,
1983).
Adjectives describing the macroscopic behaviour of
materials naturally feature prominently in any lan-
guage. We write and speak of materials being hard,
strong, brittle, malleable, magnetic, wear-resistant, etc.
Despite their apparent simplicity, such terms have
depths of complexity when subjected to scientific
scrutiny, particularly when attempts are made to relate
a given property to the internal structure of a material.
In practice, the search for bridges of understanding
between macroscopic and microscopic behaviour is a
central and recurrent theme of materials science. Thus
Sorby’s metallurgical studies of the structure/property
relations for commercial irons and steel in the late
nineteenth century are often regarded as the beginning
of modern materials science. In more recent times, the
enhancement of analytical techniques for characteriz-
ing structures in fine detail has led to the development
and acceptance of polymers and ceramics as trustwor-
thy engineering materials.
Having outlined the place of materials science in
our highly material-dependent civilization, it is now
appropriate to consider the smallest structural entity in
materials and its associated electronic states.
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Table 1.2 The Periodic Table of the elements (from Puddephatt and Monaghan, 1986; by permission of Oxford University Press)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 New IUPAC notation

IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB VIIB O Previous IUPAC form

1H 2 He
1.008 4.003

3 Li 4 Be 5B 6C 7N 8O 9F 10 Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18

11 Na 12 Mg 13 Al 14 Si 15 P 16 S 17 Cl 18 A
22.99 24.31 26.98 28.09 30.97 32.45 35.45 39.95

19 K 20 Ca 21 Sc 22 Ti 23 V 24 Cr 25 Mn 26 Fe 27 Co 28 Ni 29 Cu 30 Zn 31 Ga 32 Ge 33 Ge 34 Se 35 Br 36 Kr
39.10 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65.37 69.72 72.92 74.92 78.96 79.90 83.80

37 Rb 38 Sr 39 Y 40 Zr 41 Nb 42 Mo 43 Tc 44 Ru 45 Rh 46 Pd 47 Ag 48 Cd 49 In 50 Sn 51 Sb 52 Te 53 I 54 Xe
85.47 87.62 88.91 91.22 92.91 95.94 98.91 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3

55 Cs 56 Ba 57 La 72 Hf 73 Ta 74 W 75 Re 76 Os 77 Ir 78 Pt 79 Au 80 Hg 81 Tl 82 Pb 83 Bi 84 Po 85 At 86 Rn
132.9 137.3 138.9 178.5 180.9 183.9 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 210 210 222

87 Fr 88 Ra 89 Ac 104 Unq 105 Unp 106 Unh 107 Uns

223 226.0 227

s-block !  d-block !  p-block !

57 La 58 Ce 59 Pr 60 Nd 61 Pm 62 Sm 63 Eu 64 Gd 65 Tb 66 Dy 67 Ho 68 Er 69 Tm 70 Yb 71 Lu
Lanthanides
138.9 140.1 140.9 144.2 147 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0

89 Ac 90 Th 91 Pa 92 U 93 Np 94 Pu 95 Am 96 Cm 97 Bk 98 Cf 99 Es 100 Fm 101 Md 102 No 103 Lr

Actinides
227 232.0 231.0 238.0 237.0 242 243 248 247 251 254 253 256 254 257

f-block
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Atomic
structure and
interatomic
bonding

single electron orbits (Figure 3.1 (a)). Helium has

3.1 Ionic bonding
3.2 Covalent bonding a nucleus containing two protons, with two elec-
3.3 Metallic bonding trons in orbit about it (Figure 3.2 (b)). The next
3.4 Van der Waals bonds element, lithium, has a nucleus containing three
protons, with three electrons arranged in orbits
about it, the third electron being in a separate
It will be clear that the differences between solids
and liquids, indicated earlier, are a consequence
of the bonding forces between the atoms of which
they are composed. In order to discuss these
forces some understanding of the structure of the
atom is required. The following uses a simplified
1e 2e
model.
The atoms of all elements can be visualised as a
positively charged nucleus, comprising of one or
more positively charged protons and electrically (a) Hydrogen (b) Helium
neutral neutrons, surrounded by orbiting nega-
tively charged electrons. The electrical charges on
the proton (e) and electron (
e) are equal and
opposite. All atoms, in their normal state, contain
equal numbers of protons and electrons and are 3e 26e
electrically neutral. The mass of the proton is
about 2000 times that of the electron. Except in
the case of hydrogen, the incorporation of neu-
trons in the nucleus is essential for stability; (c) Lithium (d) Iron
however, for our purposes we can disregard their
presence. The nucleus of hydrogen, the simplest FIGURE 3.1 Schematic of the atomic structures of
atom, comprises a single proton, about which a the first three elements of the periodic table and iron.
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shell from the first two (Figure 3.1 (c)). Heavier
atoms, of course, contain increasing numbers of
protons (and neutrons) and electrons (Figure
3.1 (d)).
In order to emphasise how the electronic struc-
ture of the elements affects their properties, list-
ings of all the known elements are usually
arranged in a form called the periodic table. This
table enables predictions to be made regarding
which elements will form compounds and what
the properties of the compounds will be. An
atomic structure of particular stability arises
whenever the outermost shell contains eight elec-
trons. These octets, as they are known, are found
in neon, argon, krypton, xenon, etc.; that is, the
inert gases, so-called because they are just that.
Consider now the atom of sodium. It contains
eleven electrons arranged in shells as 2–8–1
(Figure 3.2). Clearly it can realise the octet con-
figuration by losing an electron. In doing so it is
left with a net positive charge and is known as an
ion, in this case a positive ion. Chlorine, on the
other hand, contains seventeen electrons arranged
as 2–8–7 (Figure 3.2) and the octet configuration
can be achieved if it accepts an electron to
become a negative ion. The electrons in the outer
shell of an atom are responsible for bonding with
other atoms and are called valence electrons. The
number of these outermost electrons determines
the valency, i.e. the number of bonds which can
be formed with other atoms. Sodium has a
valency of 1 and the chemical formula for sodium
Electron
transfer
11e 17e
Sodium Chlorine
2–8–1 2–8–7
FIGURE 3.2 Schematic of ionic bonding.
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chloride is NaC1, since chlorine, being able to
accept one electron, also has a valency of 1.
Oxygen, however, has six valence electrons and
needs to borrow two. Since sodium can only
donate one electron, the chemical formula for
sodium oxide is Na2O. Magnesium has two
valence electrons and so the chemical formula for
magnesium chloride is MgCl2 and for magnesium
oxide MgO. Hence, it can be seen how the
number of valence electrons determines how
atoms combine to form compounds. The number
of valence electrons also strongly influences the
nature of the interatomic bonds.
3.1 Ionic bonding
If an atom (A) with one electron in the outermost
shell reacts with an atom (B) with seven electrons
in the outermost shell, then both can attain the
octet structure if atom A donates its valence elec-
tron to atom B. However, the electrical neutrality
of the atoms is disturbed and B, with an extra
electron, becomes a negatively charged ion,
whereas A becomes a positively charged ion. The
two ions are then attracted to each other by the
electrostatic force between them and an ionic
compound results, the strength of the bond is
proportional to eAeB/r where eA and eB are the
charges on the ions and r is the interatomic sepa-
ration. The bond is strong, as shown by the high
melting point of ionic compounds, and its
strength increases, as might be expected, where
two or more electrons are donated. Thus the
melting point of sodium chloride, NaCl, is
801°C; that of magnesium oxide, MgO, where
two electrons are involved, is 2640°C; and that of
zirconium carbide, ZrC, where four electrons are
involved, is 3500°C. Although ionic bonding
involves the transfer of electrons between differ-
ent atoms, the overall neutrality of the material is
maintained.
The ionic bond is always non-directional; that
is, when a crystal is built up of large numbers of
ions, the electrostatic charges are arranged sym-
metrically around each ion, with the result that A
ions tend to surround themselves with B ions and
vice versa (Figure 3.3). The pattern adopted
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FIGURE 3.3 Non-directional nature of the ionic
bond: A
ions surrounded by B ions, B ions sur-
rounded by A
ions. This particular arrangement,
where each species of ion taken by itself lies on the sites
of a face-centred cubic structure, is known as the
sodium chloride (NaCl) or rock salt structure.
depends on the relative sizes of the A and B ions,
i.e. how many B ions can be comfortably accom-
modated around A ions whilst preserving the
correct ratio of A to B ions.
3.2 Covalent bonding
An obvious limitation of the ionic bond is that it
can only occur between atoms of different ele-
ments, and therefore it cannot be responsible for
the bonding of any of the solid elements. Where
both atoms are of the electron acceptor type, i.e.
with close to eight outermost electrons, octet
structures can be built up by the sharing of two
or more valence electrons between the atoms.
Thus, two chlorine atoms can bond together
and achieve the octet structure by each contribut-
ing one electron to share with the other atom.
The interaction may be written:
Page 5
Cl  Cl → Cl Cl (3.1)
Where two electrons are required to make up the
octet, the interaction may either be:
O  O → O O (3.2)
as in the oxygen molecule, or:
S  S  S  S . . .→ S S S S (3.3)
as in one form of sulphur, where there is an
obvious tendency for the atoms to form up in
long chains.
Structurally, the elements showing covalent
bonding obey what is known as the (8
N) Rule.
This states that the number of nearest neighbours
to each atom is given by 8
N where N is the
number of electrons in the outermost shell. Thus
chlorine (N  7) has only one nearest neighbour
and the atoms pair off as diatomic molecules;
with sulphur, selenium and tellurium (N  6) long
chains occur; with arsenic, antimony and bismuth
(N  5) sheets of atoms occur, and with carbon
(N  4) a three-dimensional network can form, as
in diamond. Atoms with values of N less than 4
cannot show covalent bonding with their own
species. They would require at least five nearest
neighbours, whilst only having three or fewer
electrons available for making up the shared
bonds.
The possible arrangements of atoms are shown
schematically in Figure 3.4, and it will be seen
that only carbon can achieve a three-dimensional
pattern in which all the bonds are covalent. This
reveals the major structural difference between
ionic and covalent bonding: the covalent bond,
unlike the ionic bond, is saturated by the indi-
vidual atoms participating in it.
The chlorine molecule, which consists of two
chlorine atoms, is structurally self-sufficient and
there is no extension of the covalent bonding
between molecules. Similarly, the chains of
sulphur and the sheets of bismuth are really large
molecules but there is little bonding between the
chains or sheets. The result is that the covalent
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The result is a strong polarising pull (electrostatic

force) exerted by the donor ion on the electrons
of the acceptor ion, so that the electrons are
sucked back towards the donor and spend more
time between the two ions than circling each indi-
vidually. The bond thus acquires some of the
characteristics of the covalent linkage. Com-
pounds of this sort are usually extremely hard
and have very high melting points, since they
combine to some extent the strength of the cova-
lent bond and the non-directionality of the ionic
bond.

FIGURE 3.4 Schematic structures of elements con- 3.3 Metallic bonding

forming to the 8
N rule. (a) Chlorine (N  7): indi-
vidual molecules; (b) tellurium (N  6): spiral chains;
Metallic atoms possess few valence electrons and
(c) antimony (N  5): corrugated sheets; (d) diamond thus cannot bond with themselves covalently,
(N  4): three-dimensional crystal. rather, they obey what is termed the free-electron
theory. In a metallic crystal the valence electrons
are detached from their atoms and can move
freely between the positive metallic ions (Figure
elements (which effectively means the non-metal- 3.5). The positive ions are arranged regularly in a
lic elements) have poor physical strength, not crystal lattice, and the electrostatic attraction
because the covalent bond itself is weak, but between the positive ions and the free negative
because, with the exception of diamond (one electrons provides the cohesive strength of the
form of carbon), they do not form a three- metal. The metallic bond may thus be regarded as
dimensional lattice. In fact, the hardness and high
melting point of diamond (3500°C) show that the
covalent bond is extremely strong. Covalent
bonding is not limited to elements; many com-
pounds are covalent, some simple examples being
HCl, H2O, CH4 and NH3. A large number of
compounds show partly ionic and partly covalent
bonding, e.g. sulphates such as Na2SO4 in which
the sulphate ion is covalently bonded whilst the
bond to the sodium is ionic.
The vast field of industrial polymers is also pre-
dominantly concerned with covalent compounds.
Individual bonds may exhibit hybrid qualities
akin to both ionic and covalent bonding;
although in the pure form the two bond types
represent different modes of linkage, there is in
fact no sharp line of demarcation between them. FIGURE 3.5 Schematic ‘free-electron’ structure for
a monovalent metal. In the absence of an electric field
When elements of high valency combine to form the electrons are in ceaseless random motion, but the
ionic compounds (e.g. the nitrides and carbides of overall distribution remains uniform over any period of
the transition elements), the donor ion may lose time.
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a very special case of covalent bonding, in which
the octet structure is satisfied by a generalised
donation of the valence electrons to form a
‘cloud’ which permeates the whole crystal lattice,
rather than by electron sharing between specific
atoms (true covalent bonding) or by donation to
another atom (ionic bonding).
Since the electrostatic attraction between ions
and electrons is non-directional, i.e. the bonding
is not localised between individual pairs or
groups of atoms, metallic crystals can grow easily
in three dimensions, and the ions can approach
all neighbours equally to give maximum struc-
tural density.
Crystallographically, these structures are
known as ‘close-packed’ (see Section 8.2). They
are geometrically simple by comparison with the
structures of ionic compounds and naturally
occurring minerals, and it is this simplicity that
accounts in part for the ductility (ability to
deform non-reversibly) of the metallic elements.
Metallic bonding explains the high thermal and
electrical conductivity of metals. Since the valence
electrons are not bound to any particular atom,
they can move through the lattice under the
application of an electric potential, causing a
current flow, and can also, by a series of colli-
sions with neighbouring electrons, transmit
thermal energy rapidly through the lattice (see
Chapter 7). Optical properties are also explained
by the theory. If a ray of light falls on a metal, the
electrons (being free) can absorb the energy of the
light beam, thus preventing it from passing
through the crystal and rendering the metal
opaque. The electrons which have absorbed the
energy are excited to high energy levels and sub-
sequently fall back to their original values with
the emission of the light energy. In other words,
the light is reflected back from the surface of the
metal, and the high reflectivity of metals can be
accounted for.
The ability of metals to form alloys (of extreme
importance to engineers) is also explained by the
free-electron theory. Alloys are discussed in
Chapter 8.
Since the electrons are not bound, when two
metals are alloyed there is no question of electron
Page 7
exchange or sharing between atoms in ionic or
covalent bonding, and hence the ordinary valency
laws of combination do not apply. The principal
limitation then becomes one of atomic size, and
providing there is no great size difference (see
Section 2.4.2), two metals may be able to form a
continuous series of alloys or solid solutions from
100 per cent A to 100 per cent B.
3.4 Van der Waals bonds
The three strong primary types of atomic bond
(ionic, covalent and metallic) all occur because of
the need for atoms to achieve a stable electron
configuration. However, even when a stable con-
figuration exists already, as in the case of the
inert gases, some form of bonding force between
the molecules must be present since these ele-
ments will all liquefy and ultimately solidify at
sufficiently low temperatures.
Bonds of this nature are universal to all atoms
and molecules, but are normally so weak that
their effect is overwhelmed when primary bonds
are present. They are known as Van der Waals
bonds, and are one reason why real gases deviate
from the ideal gas laws. They arise as follows.
Although in Figure 3.1 we represented the orbit-
ing electrons in discrete shells, the true picture is
that of a cloud, the density of the cloud at any
point being related to the probability of finding
an electron there. Such a picture implies that the
electron charge is ‘spread’ around the atom, and,
over a period of time, the charge may be thought
of as symmetrically distributed within its particu-
lar cloud.
However, the electronic charge is moving, and
this means that on a scale of nanoseconds the
electrostatic field around the atom is continuously
fluctuating, resulting in the formation of a
dynamic electric dipole, i.e. the centres of positive
charge and negative charge are no longer coinci-
dent. When another atom is brought into proxim-
ity, the dipoles of the two atoms may interact
co-operatively with one another (Figure 3.6) and
the result is a weak non-directional electrostatic
bond.
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covalently with oxygen to form water, the elec-

tron contributed by the hydrogen atom spends
the greater part of its time between the two
atoms. The bond acquires a definite dipole with
hydrogen becoming virtually a positively charged
ion.
Since the hydrogen nucleus is not screened by
any other electron shells, it can attract to itself
other negative ends of dipoles, and the result is
the hydrogen bond. It is considerably stronger
(roughly 10) than other Van der Waals link-
FIGURE 3.6 Weak Van der Waals linkage between ages, but is much weaker (by 10 to 20 times) than
atoms arising from fluctuating electronic fields.
any of the primary bonds. Figure 3.7 shows the
resultant structure of water, where the hydrogen
bond forms a secondary link between the water
The attractive force between two atoms is molecules, and acts as a bridge between two elec-
given by the expression: tronegative oxygen ions. Thus, this relatively
12 insignificant bond is one of the most vital factors
F  (3.4) for the benefit and survival of mankind. It is
r6 responsible for the abnormally high melting and
where 1 and 2 are the polarisabilities of the two boiling points of water and for its high specific
atoms, i.e. the ease with which their electronic heat, which affords an essential global tempera-
fields can be distorted by a unit electric field to ture control. In the absence of the hydrogen
form a dipole, and r is the distance between them. bond, water might well be gaseous at ambient
Polarisability increases with atomic number, since temperatures like ammonia or hydrogen sulphide.
the outermost electrons, which are responsible for
the effect, are further removed from the nucleus
and therefore more easily pulled towards neigh-
bouring atoms. This is shown by a comparison of
the freezing points of the inert gases He (1 K) and
Xe (133 K), or the halogens, fluorine (51 K) and
iodine (387 K).
As well as this fluctuating dipole, many mole-
cules have permanent dipoles as a result of
bonding between different species of atoms.
These can play a considerable part in the struc-
ture of polymers and organic compounds, where
side chains and radical groups of ions can lead to
points of predominantly positive or negative
charges. These will exert an electrostatic attrac-
tion to other oppositely charged groups.
The strongest and most important example of
dipole interaction occurs in compounds between
hydrogen and nitrogen, oxygen or fluorine. It
occurs because of the small and simple structure FIGURE 3.7 The hydrogen bond: (a) individual
of the hydrogen atom and is known as the hydro- water molecule showing dipole resulting from bond
gen bond. When, for example, hydrogen links angle; (b) structure of water.