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Chapter 1

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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.

and metal-matrix composites (MMC) are mod- ern examples. Figure 1.1 The principal classes of materials (after

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

 

IA

IIA

IIIA

IVA

VA

VIA

VIIA

 

VIII

 

IB

IIB

IIIB

IVB

VB

VIB

VIIB

 

O

 

1

H

 

2

He

1

. 008

4

. 003

 

3

Li

4

Be

 

5 B

6

C

7 N

8 O

9 F

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 !

New IUPAC notation

Previous IUPAC form

Lanthanides

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

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

Actinides

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

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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3.1 Ionic bonding

3.2 Covalent bonding

3.3 Metallic bonding

3.4 Van der Waals bonds

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 model. The atoms of all elements can be visualised as a positively charged nucleus, comprising of one or more positively charged protons and electrically 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 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; however, for our purposes we can disregard their presence. The nucleus of hydrogen, the simplest atom, comprises a single proton, about which a

Atomic structure and interatomic bonding

single electron orbits (Figure 3.1(a)). Helium has a nucleus containing two protons, with two elec- trons in orbit about it (Figure 3.2(b)). The next element, lithium, has a nucleus containing three protons, with three electrons arranged in orbits about it, the third electron being in a separate

1e (a) Hydrogen 3e (c) Lithium
1e
(a) Hydrogen
3e
(c) Lithium
2e (b) Helium 26e (d) Iron
2e
(b) Helium
26e
(d) Iron

FIGURE 3.1 Schematic of the atomic structures of 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
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 Na 2 O. Magnesium has two valence electrons and so the chemical formula for magnesium chloride is MgCl 2 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 e A e B /r where e A and e B 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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KTH/IIP SELECTED MATERIAL FIGURE 3.3 N on-directional nature of the ionic bond: A ions surrounded by

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:

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Cl Cl → Cl Cl (3.1) Where two electrons are required to make up the
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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KTH/IIP SELECTED MATERIAL Schematic structures of elements con- forming to the 8 N rule. (a) Chlorine

Schematic structures of elements con-

forming to the 8 N rule. (a) Chlorine (N 7): indi- vidual molecules; (b) tellurium (N 6): spiral chains; (c) antimony (N 5): corrugated sheets; (d) diamond (N 4): three-dimensional crystal.

FIGURE 3.4

elements (which effectively means the non-metal- lic elements) have poor physical strength, not because the covalent bond itself is weak, but because, with the exception of diamond (one form of carbon), they do not form a three- 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, H 2 O, CH 4 and NH 3 . A large number of compounds show partly ionic and partly covalent bonding, e.g. sulphates such as Na 2 SO 4 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. When elements of high valency combine to form ionic compounds (e.g. the nitrides and carbides of the transition elements), the donor ion may lose

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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.

3.3 Metallic bonding

Metallic atoms possess few valence electrons and thus cannot bond with themselves covalently, 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 3.5). The positive ions are arranged regularly in a crystal lattice, and the electrostatic attraction between the positive ions and the free negative electrons provides the cohesive strength of the metal. The metallic bond may thus be regarded as

of the metal. The metallic bond may thus be regarded as FIGURE 3.5 Schematic ‘free-electron’ structure

FIGURE 3.5 Schematic ‘free-electron’ structure for a monovalent metal. In the absence of an electric field the electrons are in ceaseless random motion, but the overall distribution remains uniform over any period of 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

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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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KTH/IIP SELECTED MATERIAL FIGURE 3.6 W eak Van der Waals linkage between atoms arising from fluctuating

FIGURE 3.6 Weak Van der Waals linkage between atoms arising from fluctuating electronic fields.

The attractive force between two atoms is given by the expression:

F

1 2

r 6

(3.4)

where 1 and 2 are the polarisabilities of the two atoms, i.e. the ease with which their electronic fields can be distorted by a unit electric field to form a dipole, and r is the distance between them. Polarisability increases with atomic number, since 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 (1K) and Xe (133K), or the halogens, fluorine (51K) and iodine (387K). 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 of the hydrogen atom and is known as the hydro- gen bond. When, for example, hydrogen links

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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- ages, but is much weaker (by 10 to 20 times) than 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 molecules, and acts as a bridge between two elec- tronegative oxygen ions. Thus, this relatively insignificant bond is one of the most vital factors for the benefit and survival of mankind. It is

responsible for the abnormally high melting and boiling points of water and for its high specific heat, which affords an essential global tempera- ture control. In the absence of the hydrogen bond, water might well be gaseous at ambient temperatures like ammonia or hydrogen sulphide.

at ambient temperatures like ammonia or hydrogen sulphide. FIGURE 3.7 The hydrogen bond: (a) individual water

FIGURE 3.7 The hydrogen bond: (a) individual water molecule showing dipole resulting from bond angle; (b) structure of water.