Abstract
In this and the following chapter, we will describe the most important simple (binary) crystal structures found in ceramic materials. You need to know the structures we have chosen because many other important materials have the same structures and because much of our discussion of point defects, interfaces, and processing will use these materials as illustrations. Some, namely FeS2, TiO2, CuO, and Cu2O, are themselves less important materials and you would not be the only ceramist not to know their structure. We include these oxides in this discussion because each one illustrates a special feature that we find in oxides. These structures are just the tip of the topic known as crystal chemistry (or solid-state chemistry); the mineralogist would have to learn these, those in Chapter 7, and many more by heart. In most examples we will mention some applications of the chosen material.
In traditional ceramic oxides, the anion is usually the larger ion, so we often think of a ceramic crystal structure as a three-dimensional (3D) array of anions with cations inserted in the interstices. Whether or not a particular structure is stable depends on Pauling’s rules. We first review some of the important lattices, paying particular attention to the polyhedra that are formed by groups of anions. As the variety of ceramics being used in today’s high-technology environment increases, some of the above assumptions cease to be valid. In certain oxides, the cation is larger than the anion and covalently bonded oxides and nonoxides cannot be treated as arrays of hard spheres. So we learn the rules and try to understand the exceptions. The concept of crystals being arrays of polyhedra will still work whether the bonding is ionic or covalent and whether the anion or the cation is larger.
In this and the following chapter, the xyz-axes in the schematics of cubic crystal structures lie along the cube edges; the length of the cube edge is the lattice parameter.
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General References
Bragg, W.L. and Claringbull, G.F. (1965) Crystal Structure of Minerals, Cornell University Press, Ithaca, Volume IV of the series The Crystalline State. If you have time to look at the original work, see this in your library.
CrystalMaker. www.crystalmaker.co.uk We repeat this information: you should try it.
Deer, W.A., Howie, R.A., and Zussman, J. (1996) An Introduction to the Rock-Forming Minerals. 2nd edition, Prentice-Hall, Englewood Cliffs, NJ. This is a classic for good reason.
Galasso, F.S. (1970) Structure and Properties of Inorganic Solids, Pergamon, Oxford. A useful reference that surveys a wide range of structures. Not as complete as Wells.
Hyde, B.G. and Anderson, S. (1989) Inorganic Crystal Structures, Wiley, New York. The structures of many crystals are beautifully described and related in this book.
Megaw, H. (1973) Crystal Structures: A Working Approach, W.B. Saunders Co., Philadelphia. This is such a nice text.
O’Keeffe, M. and Hyde, B.G. (1996) Crystal Structures, I. Patterns and Symmetry, Mineralogical Society of America, Washington, D.C. Another treasure.
Putnis, A. (1992) Introduction to Mineral Sciences, Cambridge University Press, Cambridge.
Wells, A.F. (1984) Structural Inorganic Chemistry, 5th edition, Oxford University Press, Oxford. This is the book that you go to first when you want to learn about a new structure. The price may mean that you consult it in the library rather than buying your own copy.
Specific References
Ramsdell, R.S. (1947) “Studies on silicon carbide,” Am. Mineral. 32, 64. The original description of the notation.
Xu, X., Beckman, S.P., Specht, P., Weber, E.R., Chrzan, D.C., Erni, R.P., Arslan, I., Browning, N., Bleloch, A., and Kisielowski, C. (2005) “Distortion and segregation in a dislocation core region at atomic resolution,” Phys. Rev. Lett. 95, 145501.
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(2007). Binary Compounds. In: Ceramic Materials. Springer, New York, NY. https://doi.org/10.1007/978-0-387-46271-4_6
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DOI: https://doi.org/10.1007/978-0-387-46271-4_6
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