Hostname: page-component-586b7cd67f-dsjbd Total loading time: 0 Render date: 2024-11-29T07:28:28.369Z Has data issue: false hasContentIssue false

Spectrofluorimetric Characterization of an Ionic Conductor: Sodium Sulfate High-Temperature Phases Doped with Europium(III)

Published online by Cambridge University Press:  16 February 2011

Lowell R. Matithews
Affiliation:
Department of Chemistry and Center for Laser Research, Oklahoma State University, Stillwater, Oklahoma, 74078-0447
Edward T. Knobbe
Affiliation:
Department of Chemistry and Center for Laser Research, Oklahoma State University, Stillwater, Oklahoma, 74078-0447
Gamini Dharmasena
Affiliation:
University of Oklahoma, Department of Chemistry, Norman, Oklahoma, 73019
Renée Cole
Affiliation:
University of Oklahoma, Department of Chemistry, Norman, Oklahoma, 73019
Roger Frech
Affiliation:
University of Oklahoma, Department of Chemistry, Norman, Oklahoma, 73019
Get access

Abstract

The highest-temperature polymorph of sodium sulfate, (I), has significant orientational disorder in its structure which allows it to readily accept substitution by di- and trivalent cations. Although Na2SO4 (I) exhibits reasonable ionic conductivity, it cannot be quenched to room temperature without changing phase. However, aliovalent solid solutions of (I) can be quenched to RT and resultant cation vacancies promote conduction via Na+ migration. The closely related but more ordered phase Na2SO4 (III) can also form aliovalent solid solutions which can be quenched to RT.

The europium(III) ion is an extremely sensitive and useful probe of its immediate local environment. The presence, location, and intensity of its fluorescence transitions (particularly the 5D07F0-2 emissions) can provide detailed information about the symmetry, nature, and multiplicity of the individual Eu3+ site which cannot be gained from X-ray or neutron diffraction techniques.

Our research (supported by the National Science Foundation and the State of Oklahoma) involves the structural characterization of two europium-doped sodium sulfate phases via fluorescence spectroscopy.

Type
Research Article
Copyright
Copyright © Materials Research Society 1995

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

references

1. Dharmasena, G. and Frech, R., J. Chem. Phys. 99, 8929 (1993).Google Scholar
2. Careem, M. A. and Mellander, B. E., Solid State Ionics 15, 327 (1985).Google Scholar
3. Prakash, G. and Shahi, K., Solid State Ionics 23, 151 (1987).Google Scholar
4. Eysel, W., Höfer, H. H., Keester, K. L., and Hahn, Th., Acta Cryst. B41, 5 (1985).Google Scholar
5. (a) Höfer, H. H., Eysel, W., and Alpen, U. von, J. Solid State Chem. 36, 365 (1981). (b) H. H. Höfer, U. von Alpen, and W. Eysel, Acta Cryst. A34, S358 (1978).Google Scholar
6. Mehrotra, B. N., Z. Kristallogr. 155, 159 (1981).Google Scholar
7. Lochhead, M. J., Wamsley, P. R., and Bray, K. L., Inorg. Chem., in press.Google Scholar
8. Ribeiro, S. J. L., Hiratsuka, R. S., Massabni, A. M. G., Davolos, M. R., Santilli, C. V., and Pulcinelli, S. H., J. Non-Cryst. Solids 147 & 148, 162 (1992).Google Scholar
9. Buinzli, J.-C. G. and Pradervand, G.-O., J. Chem. Phys. 85, 2489 (1986).Google Scholar
10. Mundy, J. N., in Fast Ion Transport in Solids: Electrodes and Electrolytes, edited by Vashishta, P., Mundy, J. N., and Shenoy, G. K. (Elsevier North Holland, Inc., Amsterdam, 1979), p. 159.Google Scholar
11. Carnall, W. T., Fields, P. R., and Rajnak, K., J. Chem. Phys. 49, 4412 (1968).Google Scholar
12. (a) Judd, B. R., Phys. Rev. 127, 750 (1962). (b) G. S. Ofelt, J. Chem. Phys. 37, 511 (1962). (c) Robert D. Peacock, Struct. Bond. (Berlin) 22, 83 (1975).Google Scholar
13. Reisfeld, R., Chernyak, V., Eyal, M., and Jorgensen, C. K., in The Second International School on Excited States of Transition Elements, edited by Strek, W., Ryba-Romanowski, W., Legendziewicz, J., and Jezowska-Trzebiatowska, B. (World Scientific Publishing Co. Pte. Ltd., Singapore, 1992), p. 247.Google Scholar
14. Judd, B. R., J. Chem. Phys. 44, 839 (1966).Google Scholar
15. Campostrini, R., Carturan, G., Ferrari, M., Montagna, M., and Pilla, O., J. Mater. Res. 7, 745 (1992).Google Scholar
16. Bel'skii, N. K. and Struchkov, Yu. T., , Kristallografiya (Sov. Phys., Cryst.) 10, 21 (Russian) or 15 (English) (1965).Google Scholar
17. Brecher, C., Samelson, H., and Lempicki, A., in Optical Properties of Ions in Crystals, edited by Crosswhite, H. M. and Moos, H. W. (Interscience Publishers Division of John Wiley & Sons, Inc., New York, 1967), p. 73.Google Scholar