Metal closest-packed crystal structures

HGURE 11.56 Closest-Packed Crystal Structures in Metals Nickel crystallizes in the cubic closest-packed structure. Zinc crystallizes in the hexagonal closest-packed structure. 

The structure of crystals can be investigated by the electron-diffraction method as well as by the x-ray-diffraction method. The electron-diffraction method has been especially useful in studying the strueture of very thin films on the surface of a crystal. For example, it has been shown that when argon is adsorbed on a clean face of nickel crystal the argon atoms occupy only one-quarter of the positions formed by triangles of nickel atoms (in the octahedral face of the cubic closest-packed crystal Figure 2-7). The structure of very thin films of metal oxide that are formed on the surface of metals, and that protect them against further corrosion, has been studied by this method. 

I shall take the simple view that most metal oxide structures are derivatives of a closest packed 02 lattice with the metal ions occupying tetrahedral or octahedral holes in a manner which is principally determined by size, charge (and hence stoichiometry) and d configuration (Jj). The presence of d electrons can lead to pronounced crystal field effects or metal-metal bonding. The latter can lead to clustering of metal atoms within the lattice with large distortions from idealized (ionic) geometries. 

Some metals crystallize in more than one structural type, which means that there are two alio tropic modifications. The metals marked do not conform precisely to the closest-packed structure, but deviate slightly from it. Uranium, manganese, gallium and indium have very abnormal structures, and the last two are transitional between metallic and non-metallic elements of the carbon group. The picture presented by the metallic structures is utterly different from that of elements of the four last groups of the periodic system. The homopolar bonds of these latter strive to produce a state in which the number of neighbours of each atom is determined by its valency. In the other elements, however, forces appear to be acting that tend to surround each atom with as many other atoms as possible. 

Closest-packed Structures.—If the stability of a metal crystal were determined by the number of bonds formed at a minimum interatomic distance, with no contribution of longer bonds, the structures with closest packing would be the most stable for the metallic elements. These structures, which have been described in the preceding section, involve contact between each atom and the 12 nearest neighbor. (The next interatomic distances are 41 percent larger and presumably have little significance.)... 

The close approximation of metal atoms in these crystals to mutually attracting spheres is further shown by the values observed for the axial ratio c/aot the hexagonal closest-packed structures, as tabulated below. 

V3 = 1.633 that makes the twelve smallest interatomic distances egual the two exceptional substances, zinc and cadmium, are discussed below, together with several other metals that crystallize with structures obtained from closest-packed arrangements by a deformation that shortens some of the twelve small interatomic distances at the expense of others. 

This brings us to a class of compounds too often overlooked in the discussion of simple ionic compounds the transition metal halides. In general, these compounds (except fluorides) crystallize in structures that are hard to reconcile with the structures of simple ionic compounds seen previously (Figs. 4.1-4.3). For example, consider the cadmium iodide structure (Fig. 7.8). It is true that the cadmium atoms occupy octahedral holes in a hexagonal closest packed structure of iodine atoms, but in a definite layered structure that can be described accurately only in terms of covalent bonding and infinite layer molecules. 

Many simple minerals, especially simple salts like halite, NaCl, sulfides, sulfosalts and oxides, have structures based upon cubic or hexagonal closest-packed arrays of either cations or anions. Coordination geometries of metal ions in many of these kinds of minerals are thus confined to more or less regular octahedra and tetrahedra. The occupancy of the two types of sites is dictated by the stoichiometry of the mineral, the radius of the ions involved and their preferred coordination geometries. Coordination of cations in mineral species in terms of bonding and crystal field effects has been extensively reviewed.16-21 Comprehensive lists of ionic radii relevant to cation coordination geometries in minerals have also been compiled.16,21... 

The 17 rare-earth metals are known to adopt five crystalline forms. At room temperature, nine exist in the hexagonal closest packed structure, four in the double c-axis hep (dhep) structure, two in the cubic closest packed structure and one in each of the body-centered cubic packed and rhombic (Sm-type) structures, as listed in Table 18.1.1. This distribution changes with temperature and pressure as many of the elements go through a number of structural phase transitions. All of the crystal structures, with the exception of bep, are closest packed, which can be defined by the stacking sequence of the layers of close-packed atoms, and are labeled in Fig. 18.1.1. 

A metallic crystal can be pictured as containing spherical atoms packed together and bonded to each other equally in all directions. We can model such a structure by packing uniform, hard spheres in a manner that most efficiently uses the available space. Such an arrangement is called closest packing (see Fig. 16.13). The spheres are packed in layers in which each sphere is surrounded by six others. In the second layer the spheres do not lie direotlv over those in the first layer. Instead, each one occupies an indentation (or dimple) formed by three spheres in the first layer. In the third layer the spheres can occupy the dimples of the second layer in two possible ways. They can occupy positions so that each sphere in the third layer lies directly over a sphere in the first layer (the aba arrangement), or they can occupy positions... 

Examples of metals that are cubic closest packed are aluminum, iron, copper, cobalt, and nickel. Magnesium and zinc exhibit hexagonal closest packing. Calcium and certain other metals can crystallize in either structure. 

---