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CRYSTALLOGRAPHY


the striae on crystal-faces are due to repeated lamellar twinning, as in the plagioclase felspars. The directions of the striations are very characteristic features of many crystals: e.g. the faces of the hexagonal prism of quartz are always striated horizontally, whilst in beryl they are striated vertically. Cubes of pyrites (fig. 89) are striated parallel to one edge, the striae on adjacent faces being at right angles, and due to oscillatory combination of the cube and the pentagonal dodecahedron (compare fig. 36); whilst cubes of blende (fig. 90) are striated parallel to one diagonal of each face, i.e. parallel to the tetrahedron faces (compare fig. 31). These striated cubes thus possess different degrees of symmetry and belong to different symmetry-classes. Oscillatory combination of faces gives rise also to curved surfaces. Crystals with twisted surfaces (see Dolomite) are, however, built up of smaller crystals arranged in nearly parallel position. Sometimes a face is entirely replaced by small faces of other forms, giving rise to a drusy surface; an example of this is shown by some octahedral crystals of fluorspar (fig. 2) which are built up of minute cubes.

Fig. 89.—Striated Cube of
Pyrites.
Fig. 90.—Striated Cube of
Blende.

The faces of crystals are sometimes partly or completely replaced by smooth bright surfaces inclined at only a few minutes of arc from the true position of the face; such surfaces are called “vicinal faces,” and their indices can be expressed only by very high numbers. In apparently perfectly developed crystals of alum the octahedral face, with the simple indices (111), is usually replaced by faces of very low triakis-octahedra, with indices such as (251·251·250); the angles measured on such crystals will therefore deviate slightly from the true octahedral angle. Vicinal faces of this character are formed during the growth of crystals, and have been studied by H. A. Miers (Phil. Trans., 1903, Ser. A. vol. 202). Other faces with high indices, viz. “prerosion faces” and the minute faces forming the sides of etched figures (see below), as well as rounded edges and other surface irregularities, may, however, result from the corrosion of a crystal subsequent to its growth. The pitted and cavernous faces of artificially grown crystals of sodium chloride and of bismuth are, on the other hand, a result of rapid growth, more material being supplied at the edges and corners of the crystal than at the centres of the faces.

(i) Theories of Crystal Structure.

The ultimate aim of crystallographic research is to determine the internal structure of crystals from both physical and chemical data. The problem is essentially twofold: in the first place it is necessary to formulate a theory as to the disposition of the molecules, which conforms with the observed types of symmetry—this is really a mathematical problem; in the second place, it is necessary to determine the orientation of the atoms (or groups of atoms) composing the molecules with regard to the crystal axes—this involves a knowledge of the atomic structure of the molecule. As appendages to the second part of our problem, there have to be considered: (1) the possibility of the existence of the same substance in two or more distinct crystalline forms—polymorphism, and (2) the relations between the chemical structure of compounds which affect nearly identical or related crystal habits—isomorphism and morphotropy. Here we shall discuss the modern theory of crystal structure; the relations between chemical composition and crystallographical form are discussed in Part III. of this article; reference should also be made to the article Chemistry: Physical.

The earliest theory of crystal structure of any moment is that of Haüy, in which, as explained above, he conceived a crystal as composed of elements bounded by the cleavage planes of the crystal, the elements being arranged contiguously and along parallel lines. There is, however, no Haüy. reason to suppose that matter is continuous throughout a crystalline body; in fact, it has been shown that space does separate the molecules, and we may therefore replace the contiguous elements of Haüy by particles equidistantly distributed along parallel lines; by this artifice we retain the reticulated or net-like structure, but avoid the continuity of matter which characterizes Haüy’s theory; the permanence of crystal form being due to equilibrium between the intermolecular (and interatomic) forces. The crystal is thus conjectured as a “space-lattice,” composed of three sets of parallel planes which enclose parallelopipeda, at the corners of which are placed the constituent molecules (or groups of molecules) of the crystal.

The geometrical theory of crystal structure (i.e. the determination of the varieties of crystal symmetry) is thus reduced to the mathematical problem: “in how many ways can space be partitioned?” M. L. Frankenheim, in 1835, determined this number as fifteen, but A. Bravais, Franken-heim; Bravais. in 1850, proved the identity of two of Frankenheim’s forms, and showed how the remaining fourteen coalesced by pairs, so that really these forms only corresponded to seven distinct systems and fourteen classes of crystal symmetry. These systems, however, only represented holohedral forms, leaving the hemihedral and tetartohedral classes to be explained. Bravais attempted an explanation by attributing differences in the symmetry of the crystal elements, or, what comes to the same thing, he assumed the crystals to exhibit polar differences along any member of the lattice; for instance, assume the particles to be (say) pear-shaped, then the sharp ends point in one direction, the blunt ends in the opposite direction.

A different view was adopted by L. Sohncke in 1879, who, by developing certain considerations published by Camille Jordan in 1869 on the possible types of regular repetition in space of identical parts, showed that the lattice-structure of Bravais was unnecessary, it being sufficient Sohncke. that each molecule of an indefinitely extended crystal, represented by its “point” (or centre of gravity), was identically situated with respect to the molecules surrounding it. The problem then resolves itself into the determination of the number of “point-systems” possible; Sohncke derived sixty-five such arrangements, which may also be obtained from the fourteen space-lattices of Bravais, by interpenetrating any one space-lattice with one or more identical lattices, with the condition that the resulting structure should conform with the homogeneity characteristic of crystals. But the sixty-five arrangements derived by Sohncke, of which Bravais’ lattices are particular cases, did not complete the solution, for certain of the known types of crystal symmetry still remained unrepresented. These missing forms are characterized as being enantiomorphs consequently, with the introduction of this principle of repetition over a plane, i.e. mirror images. E. S. Fedorov (1890), A. Schoenflies (1891), and W. Barlow (1894), independently and by different methods, showed how Sohncke’s theory of regular point-systems explained the whole thirty-two classes of crystal symmetry, 230 distinct types of crystal structure falling into these classes.

By considering the atoms instead of the centres of gravity of the molecules, Sohncke (Zeits. Kryst. Min., 1888, 14, p. 431) has generalized his theory, and propounded the structure of a crystal in the following terms: “A crystal consists of a finite number of interpenetrating regular point-systems, which all possess like and like-directed coincidence movements. Each separate point-system is occupied by similar material particles, but these may be different for the different interpenetrating partial systems which form the complex system.” Or we may quote the words of P. von Groth (British Assoc. Rep., 1904): “A crystal—considered as indefinitely extended—consists of n