Hostname: page-component-586b7cd67f-g8jcs Total loading time: 0 Render date: 2024-11-26T07:06:54.810Z Has data issue: false hasContentIssue false

Thermochemistry of New, Technologically Important Inorganic Materials

Published online by Cambridge University Press:  29 November 2013

Get access

Extract

The past decade has seen exciting advances in the discovery, improved synthesis and processing, and molecular level engineering of new inorganic materials having specialized electronic, ceramic, and structural applications. Many such materials share two common characteristics: They are complex in structure and composition (think for example of oxide superconductors), and they must be prepared by a series of steps under carefully controlled conditions (consider the intricacies of zeolite synthesis for example). The use of low-temperature aqueous synthesis conditions, with appropriate attention to pH, inorganic and organic structure-directing agents, and subsequent drying and calcination protocols has led to a wealth of new and often metastable crystalline polymorphs, to amorphous materials, and to fine powders with particles of nanoscale dimensions. Methods such as sol-gel synthesis, chimie douce (soft chemistry), hydrothermal synthesis, chemical vapor deposition, and various beam-deposition and epitaxy techniques produce a wealth of materials not constrained to be in chemical equilibrium with their surroundings and not representing the state of lowest free energy. Modern materials chemists almost have their pet Maxwell Demon to select atoms at will and cause them to assemble in a structure of controllable dimensions. The wealth of possible new structures formed begins to mimic the riches of organic chemistry. In this field, the fact that all complex organic and biochemical molecules are metastable under ambient conditions with respect to a mixture of carbon dioxide, water, and other simple gases is irrelevant except in a conflagration.

Liberation of ceramic science from the tyranny of high-temperature equilibrium is thus leading to new materials synthesized more quickly, at lower cost, and under environmentally more friendly conditions. There is of course a price to pay. First the synthetic procedures are more complex than traditional “mix, grind, fire, and repeat” ceramic processing. Second and more importantly, very little is known about the long-term stability of the materials formed, about their degradation during use, and about materials compatibility. Two examples of such problems are the potential corrosion of high Tc YBCO superconductors by ambient H2O and CO2, and the collapse to inactive phases of complex zeolitic and mesoporous catalysts under operating conditions. Chemical reactions in metastable materials are governed by an intertwined combination of thermodynamic driving forces and kinetic rates. For this rich landscape of new materials, neither the depths of the valleys nor the heights of the mountains are known. Often one cannot even tell which way is energetically downhill.

Type
Technical Features
Copyright
Copyright © Materials Research Society 1997

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.Navrotsky, A., Phys. Chem. Minerals 2 (1977) p. 89.CrossRefGoogle Scholar
2.Navrotsky, A., Phys. Chem. Minerals 2 (1977) p. 89, in press.CrossRefGoogle Scholar
3.Ito, E., Akaogi, M., Topor, L., and Navrotsky, A., Science 249 (1990) p. 1275.CrossRefGoogle Scholar
4.Liu, J., Topor, L., Zhang, J., Navrotsky, A., and Liebermann, R.C., Phys. Chem. Minerals 23 (1996) p. 11.CrossRefGoogle Scholar
5.Topor, L., Navrotsky, A., Wang, Y., Zhang, J., and Fei, Y., EOS Trans. AGU 77 (1996) p. F754.Google Scholar
6.Navrotsky, A., Weidner, D.J., Liebermann, R.C., and Prewitt, C.T., MRS Bulletin XVII (1992) p. 30.CrossRefGoogle Scholar
7.Navrotsky, A., Rapp, R.P., Smelik, E., Burnley, P., Circone, S., Chai, L., Bose, K., and Westrich, H.R., Am. Mineral. 79 (1994) p. 1099.Google Scholar
8.Chai, L. and Navrotsky, A., Am. Mineral. 79 (1994) p. 921.Google Scholar
9.Smelik, E.A., Jenkins, D.M., and Navrotsky, A., Am. Mineral. 79 p. 1110.Google Scholar
10.Kiseleva, I., Navrotsky, A., Belitsky, L.A., and Fursenko, B.A., Am. Mineral. 81 (1996) p. 656.Google Scholar
11.McHale, J.M., Navrotsky, A., and Perrotta, A.J., J. Phys. Chem. B101 (1997) p. 603.CrossRefGoogle Scholar
12.Zhou, Z. and Navrotsky, A., J. Mater. Res. 7 (1992) p. 2920.CrossRefGoogle Scholar
13.Elder, S.H., DiSalvo, F.J., Topor, L., and Navrotsky, A., Chem. Mater. 5 (1993) p. 1545.CrossRefGoogle Scholar
14.Takayama-Muromachi, E. and Navrotslu, A.. J. Solid State Chem. 106 (1993) p. 349.CrossRefGoogle Scholar
15.Bolech, M., Cordfunke, E.H.P., Janssen, J.J.G., and Navrotsky, A., J Am. Ceram. Soc. 78 (1995) p. 2257.CrossRefGoogle Scholar
16.Xirouchakis, D., Fritsch, S., Putnam, R.L., Navrotsky, A., and Lindsley, D.H., Am. Mineralogist (in press).Google Scholar
17.Ellison, A.J.G. and Navrotsky, A., J. Am. Ceram Soc. 75 (1992) p. 1430.CrossRefGoogle Scholar
18.Putnam, R.L., Cordfunke, E., and Navrotsky, A., unpublished manuscript.Google Scholar
19.Ying, J.Y., Benziger, J.B., and Navrotsky, A., J. Am. Ceram. Soc. 76 (1993) p. 1465.Google Scholar
20.Petrovic, I., Navrotsky, A., Davis, M.E., and Zones, S.I., Chem. Mater. 5 (1993) p. 1805.CrossRefGoogle Scholar
21.Hu, Y., Navrotsky, A., Chen, C-Y., and Davis, M.E., Chem. Mater. 7 (1995) p. 1816.CrossRefGoogle Scholar
22.Petrovic, I., Navrotsky, A., Chen, C-Y., and Davis, M.E., “Zeolites and Related Microporous Materials: State of the Art 1994,” edited by Weitkamp, J., Karge, H.G., Pfeifer, H., and Holderich, W. (Elsevier, New York, 1994) p. 677.Google Scholar
23.Petrovic, I. and Navrotsky, A., Microporous Mater, in press.Google Scholar
24.Fritsch, S. and Navrotsky, A., J. Am. Ceram. Soc. 779 (1996) p. 1761.CrossRefGoogle Scholar
25.Fritsch, S., Post, J.E., and Navrotsky, A., Geochim. Cosmochim. Acta in press.Google Scholar
26.Navrotsky, A., Am. Mineral. 79 (1994) p. 589.Google Scholar
27.Molodetsky, I. and Navrotsky, A., unpublished manuscript.Google Scholar
28.Ohtaka, O., Yamanaka, Y., Kume, S., Ito, E., and Navrotsky, A., J. Am. Soc. Ceram. Soc. 74 (1991) p. 505.CrossRefGoogle Scholar
29.Ellsworth, S., Navrotsky, A., and Ewing, R.C., Phys. Chem. Minerals 21 (1994) p. 140.CrossRefGoogle Scholar
30.Liang, J.J., Navrotsky, A., and Mitomo, M., unpublished manuscript.Google Scholar
31.Geilfuss, J., Kniaz, K., Davis, M.E., and Navrotsky, A., unpublished manuscript.Google Scholar
32.Petrovic, I., Heaney, P.J., and Navrotsky, A., Phys. Chem. Minerals 23 (1996) p. 119.CrossRefGoogle Scholar
33.Navrotsky, A., unpublished.Google Scholar
34.Kanke, Y. and Navrotsky, A., unpublished manuscript.Google Scholar