This action might not be possible to undo. Are you sure you want to continue?
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 literally the stuff of our civilization and have a determining 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 inﬂuence 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 function 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 failures 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 concerned, 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 modern examples.
Figure 1.1 The principal classes of materials (after Rice, 1983).
Adjectives describing the macroscopic behaviour of materials naturally feature prominently in any language. 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 characterizing structures in ﬁne detail has led to the development and acceptance of polymers and ceramics as trustworthy 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.
1 90 Th 140.62 56 Ba 88.91 75 Re 101.2 192.10 37 Rb 40.0 237.47 55 Cs 87.37 48 Cd 69.9 87 Fr 137.71 46 Pd 63.00 17 Cl 20.01 14 Si 14.8 83 Bi 127.5 104 Unq 180.93 45 Rh 58.22 72 Hf 92.012 12 Mg 10. 1986.9 101 Md 173.9 89 Ac 178.9 105 Unp 183.85 44 Ru 58.45 35 Br 39.2 209.01 15 P 16.7 82 Pb 121.0 227 s-block ! d-block ! p-block ! 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 138.91 57 La 91.941 11 Na 9.6 84 Po 126.45 34 Se 35.4 78 Pt 107.97 33 Ge 32.0 238.94 43 Tc 55.9 97 Bk 162.KTH/IIP SELECTED MATERIAL Page 2 Table 1.99 19 K 24.9 91 Pa 144.94 41 Nb 52.96 39 Y 47.0 103 Lr Actinides 227 232.3 100 Fm 168.9 106 Unh 186.3 88 Ra 138.2 195.0 231.1 76 Os 102.4 207.8 81 Tl 118.0 102 No 175.18 18 A 22.0 95 Am 157.2 92 U 147 93 Np 150.6 204.09 32 Ge 30.72 49 In 72.31 20 Ca 21 Sc 22 Ti 23 V 24 Cr 25 Mn 26 Fe 27 Co 28 Ni 29 Cu 30 Zn 26.95 36 Kr 39.90 53 I 83.92 50 Sn 74.96 52 Te 79.9 85 At 131.9 99 Es 167.00 16 S 19.1 197.2 The Periodic Table of the elements (from Puddephatt and Monaghan.0 242 243 248 247 251 254 253 256 254 257 f-block .98 31 Ga 28.00 42 Mo 54.4 94 Pu 152.9 89 Ac 140.08 38 Sr 44.81 13 Al 12.91 73 Ta 95.5 98 Cf 164.94 74 W 98.2 107 Uns 190.0 210 210 222 223 226.92 51 Sb 78.0 200.80 54 Xe 85.3 86 Rn 132.90 40 Zr 50.4 80 Hg 114.9 79 Au 112.3 96 Cm 158. by permission of Oxford University Press) 1 IA 1H 2 IIA 3 IIIA 4 IVA 5 VA 6 VIA 7 VIIA 8 9 VIII 10 11 IB 12 IIB 13 IIIB 14 IVB 15 VB 16 VIB 17 VIIB 18 O 2 He New IUPAC notation Previous IUPAC form 1.008 3 Li 4 Be 5B 6C 7N 8O 9F 4.9 77 Ir 106.55 47 Ag 65.003 10 Ne 6.
about which a single electron orbits (Figure 3. In order to discuss these forces some understanding of the structure of the atom is required.KTH/IIP SELECTED MATERIAL Page 3 Atomic structure and interatomic bonding 3. for our purposes we can disregard their presence. Helium has a nucleus containing two protons. The electrical charges on the proton ( e) and electron ( e) are equal and opposite. The following uses a simpliﬁed model.2 3. the incorporation of neutrons in the nucleus is essential for stability. with two electrons in orbit about it (Figure 3. comprising of one or more positively charged protons and electrically neutral neutrons.4 Ionic bonding Covalent bonding Metallic bonding Van der Waals bonds It will be clear that the differences between solids and liquids.1 3.3 3. are a consequence of the bonding forces between the atoms of which they are composed.2 (b)). indicated earlier. The next element. in their normal state. contain equal numbers of protons and electrons and are electrically neutral.1 Schematic of the atomic structures of the ﬁrst three elements of the periodic table and iron. the third electron being in a separate 1e 2e (a) Hydrogen (b) Helium 3e 26e (c) Lithium (d) Iron FIGURE 3. the simplest atom. All atoms.1 (a)). lithium. has a nucleus containing three protons. Except in the case of hydrogen. with three electrons arranged in orbits about it. surrounded by orbiting negatively charged electrons. comprises a single proton. however. . The atoms of all elements can be visualised as a positively charged nucleus. The mass of the proton is about 2000 times that of the electron. The nucleus of hydrogen.
is 801°C. The electrons in the outer shell of an atom are responsible for bonding with other atoms and are called valence electrons. listings of all the known elements are usually arranged in a form called the periodic table. and that of zirconium carbide. The number of valence electrons also strongly inﬂuences the nature of the interatomic bonds. when a crystal is built up of large numbers of ions. The ionic bond is always non-directional. The two ions are then attracted to each other by the electrostatic force between them and an ionic compound results. and its strength increases. ZrC. Chlorine. . Sodium has a valency of 1 and the chemical formula for sodium chloride is NaC1. MgO. An atomic structure of particular stability arises whenever the outermost shell contains eight electrons. However. where two or more electrons are donated. as they are known. The pattern adopted Electron transfer 11e 17e Sodium 2–8–1 FIGURE 3.3). krypton. Clearly it can realise the octet conﬁguration by losing an electron. in this case a positive ion. the inert gases. xenon. where four electrons are involved. since chlorine. contains seventeen electrons arranged as 2–8–7 (Figure 3. contain increasing numbers of protons (and neutrons) and electrons (Figure 3. i.1 (c)). These octets. is 3500°C. of course. This table enables predictions to be made regarding which elements will form compounds and what the properties of the compounds will be. Although ionic bonding involves the transfer of electrons between different atoms. It contains eleven electrons arranged in shells as 2–8–1 (Figure 3. Since sodium can only donate one electron. Magnesium has two valence electrons and so the chemical formula for magnesium chloride is MgCl2 and for magnesium oxide MgO. the electrical neutrality of the atoms is disturbed and B. Heavier atoms. Hence. In doing so it is left with a net positive charge and is known as an ion. becomes a negatively charged ion.2 Chlorine 2–8–7 Schematic of ionic bonding. the number of bonds which can be formed with other atoms. as shown by the high melting point of ionic compounds. with an extra electron. has six valence electrons and needs to borrow two. with the result that A ions tend to surround themselves with B ions and vice versa (Figure 3. it can be seen how the number of valence electrons determines how atoms combine to form compounds. also has a valency of 1. that is. however. the electrostatic charges are arranged symmetrically around each ion. that is.KTH/IIP SELECTED MATERIAL Page 4 shell from the ﬁrst two (Figure 3. 3.e. on the other hand. In order to emphasise how the electronic structure of the elements affects their properties. the overall neutrality of the material is maintained. so-called because they are just that. Thus the melting point of sodium chloride. etc. is 2640°C.2) and the octet conﬁguration can be achieved if it accepts an electron to become a negative ion. argon. that of magnesium oxide.. Consider now the atom of sodium. being able to accept one electron. whereas A becomes a positively charged ion. are found in neon. where two electrons are involved. Oxygen.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.1 (d)). as might be expected. the chemical formula for sodium oxide is Na2O. 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 separation. The number of these outermost electrons determines the valency. The bond is strong. then both can attain the octet structure if atom A donates its valence electron to atom B. NaCl.2).
how many B ions can be comfortably accommodated around A ions whilst preserving the correct ratio of A to B ions. i.3) FIGURE 3. is known as the sodium chloride (NaCl) or rock salt structure.4. or: S S S S . B ions surrounded by A ions. and with carbon (N 4) a three-dimensional network can form. and it will be seen that only carbon can achieve a three-dimensional pattern in which all the bonds are covalent.e. two chlorine atoms can bond together and achieve the octet structure by each contributing one electron to share with the other atom. 3. Thus chlorine (N 7) has only one nearest neighbour and the atoms pair off as diatomic molecules. is structurally self-sufﬁcient and there is no extension of the covalent bonding between molecules. . octet structures can be built up by the sharing of two or more valence electrons between the atoms. 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. is saturated by the individual atoms participating in it. unlike the ionic bond. .→ S S S S (3. the elements showing covalent bonding obey what is known as the (8 N) Rule. Thus. which consists of two chlorine atoms. with sulphur. They would require at least ﬁve nearest neighbours. The interaction may be written: as in one form of sulphur. Structurally. i.3 Non-directional nature of the ionic bond: A ions surrounded by B ions. Atoms with values of N less than 4 cannot show covalent bonding with their own species. with arsenic. selenium and tellurium (N 6) long chains occur. The chlorine molecule. This reveals the major structural difference between ionic and covalent bonding: the covalent bond. the interaction may either be: O O → O O (3. where each species of ion taken by itself lies on the sites of a face-centred cubic structure.2 Covalent bonding An obvious limitation of the ionic bond is that it can only occur between atoms of different elements. This particular arrangement.e. as in diamond.2) as in the oxygen molecule. the chains of sulphur and the sheets of bismuth are really large molecules but there is little bonding between the chains or sheets. Where both atoms are of the electron acceptor type. and therefore it cannot be responsible for the bonding of any of the solid elements. The possible arrangements of atoms are shown schematically in Figure 3. The result is that the covalent . antimony and bismuth (N 5) sheets of atoms occur. depends on the relative sizes of the A and B ions. Similarly. where there is an obvious tendency for the atoms to form up in long chains. with close to eight outermost electrons.KTH/IIP SELECTED MATERIAL Page 5 Cl Cl → Cl Cl (3.1) Where two electrons are required to make up the octet. whilst only having three or fewer electrons available for making up the shared bonds.
The bond thus acquires some of the characteristics of the covalent linkage. Compounds of this sort are usually extremely hard and have very high melting points. the hardness and high melting point of diamond (3500°C) show that the covalent bond is extremely strong. In a metallic crystal the valence electrons are detached from their atoms and can move freely between the positive metallic ions (Figure 3. (d) diamond (N 4): three-dimensional crystal. The vast ﬁeld of industrial polymers is also predominantly concerned with covalent compounds. H2O.4 Schematic structures of elements conforming to the 8 N rule. they do not form a threedimensional lattice.KTH/IIP SELECTED MATERIAL Page 6 The result is a strong polarising pull (electrostatic force) exerted by the donor ion on the electrons of the acceptor ion. (b) tellurium (N 6): spiral chains. FIGURE 3.g. rather.g. sulphates such as Na2SO4 in which the sulphate ion is covalently bonded whilst the bond to the sodium is ionic. many compounds are covalent. A large number of compounds show partly ionic and partly covalent bonding. The positive ions are arranged regularly in a crystal lattice. since they combine to some extent the strength of the covalent bond and the non-directionality of the ionic bond. Covalent bonding is not limited to elements. some simple examples being HCl.5). there is in fact no sharp line of demarcation between them. they obey what is termed the free-electron theory. 3. The metallic bond may thus be regarded as elements (which effectively means the non-metallic elements) have poor physical strength.3 Metallic bonding Metallic atoms possess few valence electrons and thus cannot bond with themselves covalently. so that the electrons are sucked back towards the donor and spend more time between the two ions than circling each individually. not because the covalent bond itself is weak. the nitrides and carbides of the transition elements).5 Schematic ‘free-electron’ structure for a monovalent metal. Individual bonds may exhibit hybrid qualities akin to both ionic and covalent bonding. (a) Chlorine (N 7): individual molecules. with the exception of diamond (one form of carbon). 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. although in the pure form the two bond types represent different modes of linkage. and the electrostatic attraction between the positive ions and the free negative electrons provides the cohesive strength of the metal. e. the donor ion may lose FIGURE 3. but because. In fact. (c) antimony (N 5): corrugated sheets. CH4 and NH3. . When elements of high valency combine to form ionic compounds (e.
the dipoles of the two atoms may interact co-operatively with one another (Figure 3. but are normally so weak that their effect is overwhelmed when primary bonds are present. these structures are known as ‘close-packed’ (see Section 8. Such a picture implies that the electron charge is ‘spread’ around the atom. the charge may be thought of as symmetrically distributed within its particular cloud. . They arise as follows. transmit thermal energy rapidly through the lattice (see Chapter 7). thus preventing it from passing through the crystal and rendering the metal opaque. i. and the high reﬂectivity of metals can be accounted for. resulting in the formation of a dynamic electric dipole.KTH/IIP SELECTED MATERIAL Page 7 a very special case of covalent bonding.2). causing a current ﬂow. They are geometrically simple by comparison with the structures of ionic compounds and naturally occurring minerals. Since the valence electrons are not bound to any particular atom. and providing there is no great size difference (see Section 2. over a period of time. Bonds of this nature are universal to all atoms and molecules.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. and. and this means that on a scale of nanoseconds the electrostatic ﬁeld around the atom is continuously ﬂuctuating. the electrons (being free) can absorb the energy of the light beam. the true picture is that of a cloud. rather than by electron sharing between speciﬁc atoms (true covalent bonding) or by donation to another atom (ionic bonding). by a series of collisions with neighbouring electrons. the electronic charge is moving. and the ions can approach all neighbours equally to give maximum structural density. Alloys are discussed in Chapter 8. 3. Although in Figure 3. Metallic bonding explains the high thermal and electrical conductivity of metals. When another atom is brought into proximity. If a ray of light falls on a metal. i. Since the electrons are not bound. the light is reﬂected back from the surface of the metal. even when a stable conﬁguration exists already. they can move through the lattice under the application of an electric potential. the centres of positive charge and negative charge are no longer coincident. when two metals are alloyed there is no question of electron exchange or sharing between atoms in ionic or covalent bonding. 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.1 we represented the orbiting electrons in discrete shells. as in the case of the inert gases. the bonding is not localised between individual pairs or groups of atoms. The ability of metals to form alloys (of extreme importance to engineers) is also explained by the free-electron theory. metallic crystals can grow easily in three dimensions. They are known as Van der Waals bonds.6) and the result is a weak non-directional electrostatic bond. The electrons which have absorbed the energy are excited to high energy levels and subsequently fall back to their original values with the emission of the light energy. 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.e. Crystallographically. some form of bonding force between the molecules must be present since these elements will all liquefy and ultimately solidify at sufﬁciently low temperatures. the density of the cloud at any point being related to the probability of ﬁnding an electron there. and are one reason why real gases deviate from the ideal gas laws. Since the electrostatic attraction between ions and electrons is non-directional. and it is this simplicity that accounts in part for the ductility (ability to deform non-reversibly) of the metallic elements. Optical properties are also explained by the theory.2).4. and hence the ordinary valency laws of combination do not apply.e. The principal limitation then becomes one of atomic size. However. However. In other words. and can also.
and r is the distance between them. the ease with which their electronic ﬁelds can be distorted by a unit electric ﬁeld to form a dipole. Polarisability increases with atomic number.KTH/IIP SELECTED MATERIAL Page 8 FIGURE 3. which affords an essential global temperature control.6 Weak Van der Waals linkage between atoms arising from ﬂuctuating electronic ﬁelds. When. since the outermost electrons. water might well be gaseous at ambient temperatures like ammonia or hydrogen sulphide. this relatively insigniﬁcant bond is one of the most vital factors for the beneﬁt and survival of mankind.4) where 1 and 2 are the polarisabilities of the two atoms. but is much weaker (by 10 to 20 times) than any of the primary bonds. or the halogens. many molecules have permanent dipoles as a result of bonding between different species of atoms. The bond acquires a deﬁnite dipole with hydrogen becoming virtually a positively charged ion. These can play a considerable part in the structure of polymers and organic compounds. Thus. As well as this ﬂuctuating dipole.7 shows the resultant structure of water. (b) structure of water. where side chains and radical groups of ions can lead to points of predominantly positive or negative charges. it can attract to itself other negative ends of dipoles. are further removed from the nucleus and therefore more easily pulled towards neighbouring atoms. hydrogen links covalently with oxygen to form water. ﬂuorine (51 K) and iodine (387 K). Since the hydrogen nucleus is not screened by any other electron shells. These will exert an electrostatic attraction to other oppositely charged groups. FIGURE 3. In the absence of the hydrogen bond. the electron contributed by the hydrogen atom spends the greater part of its time between the two atoms. oxygen or ﬂuorine. for example. This is shown by a comparison of the freezing points of the inert gases He (1 K) and Xe (133 K). The strongest and most important example of dipole interaction occurs in compounds between hydrogen and nitrogen. which are responsible for the effect. It is responsible for the abnormally high melting and boiling points of water and for its high speciﬁc heat. Figure 3. It occurs because of the small and simple structure of the hydrogen atom and is known as the hydrogen bond. where the hydrogen bond forms a secondary link between the water molecules. It is considerably stronger (roughly 10) than other Van der Waals linkages.7 The hydrogen bond: (a) individual water molecule showing dipole resulting from bond angle. i.e. . and acts as a bridge between two electronegative oxygen ions. and the result is the hydrogen bond. The attractive force between two atoms is given by the expression: F 1 2 r6 (3.