Abstract
Of the three states of matter, solids possess the most structural diversity. Whereas gases and liquids consist of discrete molecules that are randomly distributed due to thermal motion, solids consist of molecules, atoms, or ions that are statically positioned. To fully understand the properties of solid materials, one must have a thorough knowledge of the structural interactions between the subunit atoms, ions, and molecules. This chapter will outline the various types of solids, including structural classifications and nomenclature for both crystalline and amorphous solids. The material in this key chapter will set the groundwork for the rest of this textbook, which describes a variety of materials classes.
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References and Notes
Zallen, R. The Physics of Amorphous Solids, John Wiley and Sons: New York, 1983.
Electrons in an s-orbital have a finite probability of being found at the nucleus. As the principal quantum number increases, the s-orbitals become more diffuse, leading to electrons being found at distances further from the nucleus. With less attraction toward the nucleus, these electrons are able to orbit the nucleus at speeds approaching the speed of light. When objects move at such high speeds, an increase in relativistic mass occurs, whereby the s-electrons behave as though they were more massive than electrons moving at slower speeds. This mass increase causes the orbiting electrons to be slightly contracted toward the nucleus, decreasing their availability to participate in chemical reactions.
Schroers, J.; Johnson, W. L. “History Dependent Crystallization of Zr41 Ti14 Cu12 Ni10 Be23 Melts” J. Appl. Phys. 2000, 88(1), 44-48, and references therein. More information may be obtained from http://www.liquidmetal.com.
There is an ongoing debate whether the term “pseudopolymorph” should be abandoned, instead designating these compounds as “solvates”. Two viewpoints may be found at: (a) Bernstein, J. Cryst. Growth Design 2005, 5, 1661. (b) Nangia, A. Cryst. Growth Design 2006, 6, 2.
Note: the Miller indices for the (211) plane may also be visualized by extending the unit cell beyond a cell volume of 1 cubic unit. For instance, this plane would also pass through (2,0,0), (0,2,0), and (0,0,2), as well as other extended coordinates. For the (001) plane, the zeroes indicate that the plane does not intercept either the a or b axes).
Cullity, B. D. Elements of X-ray Diffraction, 2nd ed., Addison-Wesley: Reading, Massachusetts, 1978.
The effective nuclear charge is defined as the actual nuclear charge felt by a particular valence electron. It is expressed as Z eff = Z −σ, where Z is the nuclear charge for the atom and σ is the “screening constant.” This latter term corresponds to the number of core electrons, and the effectiveness of the orbitals to shield core electron density.
Willard, M. A.; Nakamura, Y.; Laughlin, D. E.; McHenry, M. E. J. Am. Ceram. Soc. 1999, 82(12), 3342.
Nakamura, Y.; Smith, P. A.; Laughlin, D. E.; De Graef, M.; McHenry, M. E. IEEE Trans. Magn. 1995, 31(6),4154.
(a) Jansen, M.; Letschert, H. P. Nature 2002, 404, 980. (b) Kasahara, A.; Nukumizu, K.; Hitoki, G.; Takata, T.; Kondo, J. N.; Hara, M.; Kobayashi, H.; Domen, K. J. Phys. Chem. A 2002, 106, 6750. (c) Hitoki, G.; Takata, T.; Kondo, J. N.; Hara, M.; Kobayashi, H.; Domen, K. Chem. Commun. 2002, 1698.
(a) Honle, W. J. Solid State Chem. 1983, 49, 157. (b) Perrin, et al. Acta Crystallogr. 1983, C39, 415.
A nice updated website for past/recent superconductor discoveries is found at http://superconductors.org/type2.htm
The d notation indicates a diamond glide plane, found in diamond or zinc blende extended crystal structures. Whereas glide planes are found in many inorganic-based crystals, screw axes are found predominantly in protein structures.
Garlick, G. D.; Kamb, W. B. J. Geol. Educ. 1991, 39, 398.
For a thorough treatment of crystal field theory, see Cotton, F. A.. Wilkinson, G.; Murillo, C. A.; Bochmann, M. Advanced Inorganic Chemistry, 6th ed., Wiley: New York, 1999.
For a recent review, see Cheetham, A. K.; Mellot, C. F. Chem. Mater. 1997, 9, 2269. It should be noted that the hydrolytic condensation of trifunctional organosilicon monomers (e.g., RSiCl3 or RSi(OMe)3 ) results in polyhedral oligomeric silsesquioxanes (POSS) - see: http://www.azonano.com/details.asp?ArticleID=1342#POSSTMPolymersPolymerization/Gr. These structures represent the smallest forms of silica, often being denoted as “molecular silica”. Since particle diameters range from 0.07 to 3 nm, these are important architectures for nanoapplications (e.g., see http://www.reade.com/Products/Polymeric/poss.html
A supercritical fluid has intermediate properties of liquid and gas. Typically, the alcogel is placed in an autoclave filled with ethanol. The system is pressurized to 750-850 psi with CO2 and cooled to 5-10霂C. Liquid CO2 is then flushed through the vessel until all the ethanol has been removed from the vessel and from within the gels. When the gels are ethanol-free, the vessel is heated to a temperature above the critical temperature of CO2 (31◦C). As the vessel is heated, the pressure of the system rises. The pressure of CO2 is carefully monitored to maintain a pressure slightly above the critical pressure of CO2 (1050 psi). The system is held at these conditions for a short time, followed by the slow, controlled release of CO2 to ambient pressure. The length of time required for this process is dependent on the thickness of the gels; this process may last anywhere from 12 h to 6 days.
For a recent review on the synthesis, properties, and applications of aerogels see: Pierre, A. C.; Pajonk, G. M. “Chemistry of Aerogels and Their Applications”, Chem. Rev. 2002, 102, 4243.
The γ-Al2 O3 crystal structure is best described as a defect spinel structure; an FCC array of O2− ions, with Al3+ ions in 21 3 of the 16 octahedral and eight tetrahedral sites. By contrast, α-Al2 O3 is an HCP array of O2− , with Al3+ in 2/3 of the octahedral sites.
For a comprehensive database of zeolite structures refer to: http://www.iza-structure.org/databases/21 Some remaining stock of safe, weakly radioactive glass items such as ceramic plates, ore, marbles, etc. may still be acquired online from http://www.unitednuclear.com/
Richardson, T. J.; Slack, J. L.; Armitage, R. D.; Kostecki, R.; Farangis, B.; Rubin, M. D.; Appl. Phys. Lett. 2001, 78, 3047.
Asphalt is a black, sticky, viscous liquid that is obtained from crude petroleum. It comprises almost entirely a form of tar called bitumen. The structure of asphalt is actually a colloidal suspension, with small particulates called asphaltenes dispersed through the petroleum matrix. More environmentally friendly aqueous-based asphalt emulsions are currently being used for road repair applications.
For more details regarding the role of C4AF in the hardening mechanisms of Portland cement, see: Meller, N.; Hall, C.; Jupe, A. C.; Colston, S. L.; Jacques, S. D. M.; Barnes, P.; Phipps, J. J. Mater. Chem. 2004, 14, 428, and references therein.
Further Reading
Pogge, H. B. Electronic Materials Chemistry, Marcel-Dekker: New York, 1996.
Glusker, J. P.; Lewis, M.; Rossi, M. Crystal Structure Analysis for Chemists and Biologists, VCH: New York, 1994.
Larminie, J.; Dicks, A. Fuel Cell Systems Explained, 2nd ed., Wiley: New York, 2003.
West, A. R. Solid State Chemistry and Its Applications, Wiley: New York, 1987.
West, A. R. Basic Solid State Chemistry, 2nd ed., Wiley: New York, 1999.
Moore, E.; Smart, L. Solid State Chemistry: An Introduction, 2nd ed., CRC Press: New York, 1996.
Hurd, C. M. Electrons in Metals, Wiley: New York, 1975.
Elliott, S. The Physics and Chemistry of Solids, Wiley: New York, 1998.
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Fahlman, B.D. (2007). Solid-State Chemistry. In: Materials Chemistry. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-6120-2_2
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DOI: https://doi.org/10.1007/978-1-4020-6120-2_2
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