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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-
Figure 1.1 The principal classes of materials (after Rice,
mining effect upon its character, just as cast iron did 1983).
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 Adjectives describing the macroscopic behaviour of
and environmental control each has a substantial and materials naturally feature prominently in any lan-
inescapable ‘materials dimension’. guage. We write and speak of materials being hard,
The engineer is primarily concerned with the func- strong, brittle, malleable, magnetic, wear-resistant, etc.
tion of the component or structure, frequently with Despite their apparent simplicity, such terms have
its capacity to transmit working stresses without risk depths of complexity when subjected to scientific
of failure. The secondary task, the actual choice scrutiny, particularly when attempts are made to relate
of a suitable material, requires that the materials a given property to the internal structure of a material.
scientist should provide the necessary design data, In practice, the search for bridges of understanding
synthesize and develop new materials, analyse fail- between macroscopic and microscopic behaviour is a
ures and ultimately produce material with the desired central and recurrent theme of materials science. Thus
shape, form and properties at acceptable cost. This Sorby’s metallurgical studies of the structure/property
essential collaboration between practitioners of the relations for commercial irons and steel in the late
two disciplines is sometimes expressed in the phrase nineteenth century are often regarded as the beginning
‘Materials Science and Engineering (MSE)’. So far of modern materials science. In more recent times, the
as the main classes of available materials are con- enhancement of analytical techniques for characteriz-
cerned, it is initially useful to refer to the type of ing structures in fine detail has led to the development
diagram shown in Figure 1.1. The principal sectors and acceptance of polymers and ceramics as trustwor-
represent metals, ceramics and polymers. All these thy engineering materials.
materials can now be produced in non-crystalline Having outlined the place of materials science in
forms, hence a glassy ‘core’ is shown in the diagram. our highly material-dependent civilization, it is now
Combining two or more materials of very different appropriate to consider the smallest structural entity in
properties, a centuries-old device, produces important materials and its associated electronic states.
composite materials: carbon-fibre-reinforced polymers
(CFRP) and metal-matrix composites (MMC) are mod-
ern examples.
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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 chloride is NaC1, since chlorine, being able to
atoms, of course, contain increasing numbers of accept one electron, also has a valency of 1.
protons (and neutrons) and electrons (Figure Oxygen, however, has six valence electrons and
3.1 (d)). needs to borrow two. Since sodium can only
In order to emphasise how the electronic struc- donate one electron, the chemical formula for
ture of the elements affects their properties, list- sodium oxide is Na2O. Magnesium has two
ings of all the known elements are usually valence electrons and so the chemical formula for
arranged in a form called the periodic table. This magnesium chloride is MgCl2 and for magnesium
table enables predictions to be made regarding oxide MgO. Hence, it can be seen how the
which elements will form compounds and what number of valence electrons determines how
the properties of the compounds will be. An atoms combine to form compounds. The number
atomic structure of particular stability arises of valence electrons also strongly influences the
whenever the outermost shell contains eight elec- nature of the interatomic bonds.
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.
3.1 Ionic bonding
Consider now the atom of sodium. It contains If an atom (A) with one electron in the outermost
eleven electrons arranged in shells as 2–8–1 shell reacts with an atom (B) with seven electrons
(Figure 3.2). Clearly it can realise the octet con- in the outermost shell, then both can attain the
figuration by losing an electron. In doing so it is octet structure if atom A donates its valence elec-
left with a net positive charge and is known as an tron to atom B. However, the electrical neutrality
ion, in this case a positive ion. Chlorine, on the of the atoms is disturbed and B, with an extra
other hand, contains seventeen electrons arranged electron, becomes a negatively charged ion,
as 2–8–7 (Figure 3.2) and the octet configuration whereas A becomes a positively charged ion. The
can be achieved if it accepts an electron to two ions are then attracted to each other by the
become a negative ion. The electrons in the outer electrostatic force between them and an ionic
shell of an atom are responsible for bonding with compound results, the strength of the bond is
other atoms and are called valence electrons. The proportional to eAeB/r where eA and eB are the
number of these outermost electrons determines charges on the ions and r is the interatomic sepa-
the valency, i.e. the number of bonds which can ration. The bond is strong, as shown by the high
be formed with other atoms. Sodium has a melting point of ionic compounds, and its
valency of 1 and the chemical formula for sodium 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
Electron
transfer
two electrons are involved, is 2640°C; and that of
zirconium carbide, ZrC, where four electrons are
involved, is 3500°C. Although ionic bonding
11e 17e
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
Sodium Chlorine ions, the electrostatic charges are arranged sym-
2–8–1 2–8–7 metrically around each ion, with the result that A
ions tend to surround themselves with B ions and
FIGURE 3.2 Schematic of ionic bonding. vice versa (Figure 3.3). The pattern adopted
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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 (8N) Rule.
This states that the number of nearest neighbours
to each atom is given by 8N where N is the
FIGURE 3.3 Non-directional nature of the ionic
number of electrons in the outermost shell. Thus
bond: A ions surrounded by B ions, B ions sur- chlorine (N  7) has only one nearest neighbour
rounded by A ions. This particular arrangement, and the atoms pair off as diatomic molecules;
where each species of ion taken by itself lies on the sites with sulphur, selenium and tellurium (N  6) long
of a face-centred cubic structure, is known as the chains occur; with arsenic, antimony and bismuth
sodium chloride (NaCl) or rock salt structure.
(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
depends on the relative sizes of the A and B ions, species. They would require at least five nearest
i.e. how many B ions can be comfortably accom- neighbours, whilst only having three or fewer
modated around A ions whilst preserving the electrons available for making up the shared
correct ratio of A to B ions. bonds.
The possible arrangements of atoms are shown
schematically in Figure 3.4, and it will be seen
3.2 Covalent bonding
that only carbon can achieve a three-dimensional
An obvious limitation of the ionic bond is that it pattern in which all the bonds are covalent. This
can only occur between atoms of different ele- reveals the major structural difference between
ments, and therefore it cannot be responsible for ionic and covalent bonding: the covalent bond,
the bonding of any of the solid elements. Where unlike the ionic bond, is saturated by the indi-
both atoms are of the electron acceptor type, i.e. vidual atoms participating in it.
with close to eight outermost electrons, octet The chlorine molecule, which consists of two
structures can be built up by the sharing of two chlorine atoms, is structurally self-sufficient and
or more valence electrons between the atoms. there is no extension of the covalent bonding
Thus, two chlorine atoms can bond together between molecules. Similarly, the chains of
and achieve the octet structure by each contribut- sulphur and the sheets of bismuth are really large
ing one electron to share with the other atom. molecules but there is little bonding between the
The interaction may be written: 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 exchange or sharing between atoms in ionic or
the octet structure is satisfied by a generalised covalent bonding, and hence the ordinary valency
donation of the valence electrons to form a laws of combination do not apply. The principal
‘cloud’ which permeates the whole crystal lattice, limitation then becomes one of atomic size, and
rather than by electron sharing between specific providing there is no great size difference (see
atoms (true covalent bonding) or by donation to Section 2.4.2), two metals may be able to form a
another atom (ionic bonding). continuous series of alloys or solid solutions from
Since the electrostatic attraction between ions 100 per cent A to 100 per cent B.
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
3.4 Van der Waals bonds
all neighbours equally to give maximum struc- The three strong primary types of atomic bond
tural density. (ionic, covalent and metallic) all occur because of
Crystallographically, these structures are the need for atoms to achieve a stable electron
known as ‘close-packed’ (see Section 8.2). They configuration. However, even when a stable con-
are geometrically simple by comparison with the figuration exists already, as in the case of the
structures of ionic compounds and naturally inert gases, some form of bonding force between
occurring minerals, and it is this simplicity that the molecules must be present since these ele-
accounts in part for the ductility (ability to ments will all liquefy and ultimately solidify at
deform non-reversibly) of the metallic elements. sufficiently low temperatures.
Metallic bonding explains the high thermal and Bonds of this nature are universal to all atoms
electrical conductivity of metals. Since the valence and molecules, but are normally so weak that
electrons are not bound to any particular atom, their effect is overwhelmed when primary bonds
they can move through the lattice under the are present. They are known as Van der Waals
application of an electric potential, causing a bonds, and are one reason why real gases deviate
current flow, and can also, by a series of colli- from the ideal gas laws. They arise as follows.
sions with neighbouring electrons, transmit Although in Figure 3.1 we represented the orbit-
thermal energy rapidly through the lattice (see ing electrons in discrete shells, the true picture is
Chapter 7). Optical properties are also explained that of a cloud, the density of the cloud at any
by the theory. If a ray of light falls on a metal, the point being related to the probability of finding
electrons (being free) can absorb the energy of the an electron there. Such a picture implies that the
light beam, thus preventing it from passing electron charge is ‘spread’ around the atom, and,
through the crystal and rendering the metal over a period of time, the charge may be thought
opaque. The electrons which have absorbed the of as symmetrically distributed within its particu-
energy are excited to high energy levels and sub- lar cloud.
sequently fall back to their original values with However, the electronic charge is moving, and
the emission of the light energy. In other words, this means that on a scale of nanoseconds the
the light is reflected back from the surface of the electrostatic field around the atom is continuously
metal, and the high reflectivity of metals can be fluctuating, resulting in the formation of a
accounted for. dynamic electric dipole, i.e. the centres of positive
The ability of metals to form alloys (of extreme charge and negative charge are no longer coinci-
importance to engineers) is also explained by the dent. When another atom is brought into proxim-
free-electron theory. Alloys are discussed in ity, the dipoles of the two atoms may interact
Chapter 8. co-operatively with one another (Figure 3.6) and
Since the electrons are not bound, when two the result is a weak non-directional electrostatic
metals are alloyed there is no question of electron 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.