Hostname: page-component-76fb5796d-dfsvx Total loading time: 0 Render date: 2024-04-25T10:10:12.240Z Has data issue: false hasContentIssue false

Why Covalent Ceramics are Hard

Published online by Cambridge University Press:  22 February 2011

John J. Gilman*
Affiliation:
Department of Materials Science and Engineering, University of California, Los Angeles, 405 Hilgard Avenue, Los Angeles, CA 90024-1595
Get access

Abstract

Pure metals with nearly the same elastic properties as hard, covalent ceramics are often very soft, even at low temperatures. Why the difference? “Directed bonds” is the common answer. Or, “the Peierls-Nabarro stress is large”. However, the former is only qualitative, while the latter does not distinguish between covalent and metallic bonding, and is quantitatively incorrect. The rules of quantum chemistry, as developed to account for chemical reaction rates, indicate why dislocation mobilities are low in crystals bonded through hybrid sp and spd orbitals. Resistance to the motion of kinks on dislocation lines arises from the way in which the initial electronic states of these kinks are correlated with the final states (after a unit of motion has occurred). The initial bonding states correlate with the final antibonding states, and vice versa. Thus, the correlation lines cross, creating substantial barriers to the motion. The barrier magnitudes can be calculated from the energy gaps (e.g., for Sic, the HOMO-LUMO gap); together with the quadratic dependencies of bond energy on bond-bending. The calculated results agree with observations. A second prototype, TiC is also discussed.

Type
Research Article
Copyright
Copyright © Materials Research Society 1994

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1. Gilman, J.J., Science, 261, 1436 (1993).Google Scholar
2. Cohen, M.L., Phil. Trans. Roy. Soc. Lon., 334A, 501 (1991).Google Scholar
3. Gavrilenko, V.I., Frolov, S.I., and Klyui, N.I., Physica B, 185, 394 (1993).Google Scholar
4. Corman, G.S., J. Amer. Cer. Soc., 75, 3421 (1992).Google Scholar
5. Woodward, R.B. and Hoffmann, R., The Conservation of Orbital Symmetry, Verlag Chemie Gmbh., Weinheim (1970).Google Scholar
6. Trefilov, V.I. and Mil'man, Yu. V., Soviet Physics - Doklady, 8, 1240 (1992).Google Scholar
7. Gilman, J.J., Phil. Mag. B, 67, 207 (1993).Google Scholar
8. Price, D.L., Cooper, B.R., and Wills, J.M., Phys. Rev. B, 46, 11368 (1992).Google Scholar
9. Gilman, J.J., J. Appl. Phys., 41, 1664 (1970).Google Scholar
10. McColm, I.J., Ceramic Hardness, p. 93, Plenum Press, London (1990).Google Scholar
11. Price, D.L. and Cooper, B.R., Phys. Rev. B, 39, 4945 (1989).Google Scholar
12. This work was supported by the Director, Office of Energy Research, Office of Basic Energy Sciences, Materials Sciences Div., of the U.S. Department of Energy under Contract #DE-AC03-76SF00098.Google Scholar