Hostname: page-component-5c6d5d7d68-wbk2r Total loading time: 0 Render date: 2024-08-22T07:41:21.588Z Has data issue: false hasContentIssue false

Sol-to-Gel and Gel-to-Glass Transitions in the As2S3-Amine system

Published online by Cambridge University Press:  25 February 2011

T. A. Guiton
Affiliation:
Department of Materials Science, The Pennsylvania State University, University Park, PA 16802
C. G. Pantano
Affiliation:
Department of Materials Science, The Pennsylvania State University, University Park, PA 16802
Get access

Abstract

It is proposed that solutions of arsenic trisulfide and ethylenediamine consist of arsenic-sulfur rings (As4S6) which are interlinked through sulfur-sulfur bridges. The Raman spectra of the solutions exhibit an intense band at 438 cm-1 which is attributed to the stretching resonances of these bridges. The bridges are not present in a-As2S3 glass, and thus, the intensity of the band has been used to characterize the molecular connectivity of sols and gels. This band is most intense in the highest viscosity gels, whereas the relative intensity of the band is diminished in the dry gels. The intensity of the band further decreases during vacuum heat-treatment of fibers drawn directly from the gel. TEM analysis of the fibers verify the creation of a dense amorphous structure, while SIMS depth profiles of the films further verify their composition. Altogether, these observations confirm the structural model proposed for the solution, and suggest a relaxation/ recombination process for the molecular gel-to-network glass transition.

Type
Research Article
Copyright
Copyright © Materials Research Society 1988

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

Patel, C. K., SPIE Proceedings 266, 2230 (1981).Google Scholar
2. Arai, T. and Kikuchi, M., Appl. Optics 23 (17), 30173019 (1984).Google Scholar
3. Brandes, R. G., Laming, F. P., Pearson, A. D., Appl. Optics 9 (7), 17121714 (1970).Google Scholar
4. Hartouni, E., Hulderman, F., Guiton, T., SPIE Proceedings 505 (28), (1984).Google Scholar
5. Saito, M. and Takizawa, M., J. Appl. Phys. 59 (5), 14501452 (1986).CrossRefGoogle Scholar
6. Klocek, P. and Kale, B. M., SPIE Proceedings 344 (18) (1980).Google Scholar
7. Keneman, S. A., Thin Solid Films 21, 281285 (1984).CrossRefGoogle Scholar
8. Klocek, P. and Kale, B., SPIE Proceedings 572, (1985).Google Scholar
9. Singh, B., Chern, G. C., Lauks, I., Appl. Phys. Lett. 45 (1), 7476 (1984).CrossRefGoogle Scholar
10. Tanaka, K., Imai, Y., Odajima, A., J. Appl. Phys. 57 (11), 48974900 (1985).CrossRefGoogle Scholar
11. DeNeufville, J. P., Moss, S. C., Ovinshinsky, S. R., J. Non-Cryst. Solids 13, 191223 (1973/1974).Google Scholar
12. Lu, C. S. and Donohue, J., J. Am. Chem. Soc. 66, 818 (1944).Google Scholar
13. Leadbetter, A. J., Apling, A. J., Daniel, M. F., J. Non-Cryst. Solids 21, 47 (1976).Google Scholar
14. Apling, A. J., Leadbetter, A. J., Wright, A. C., J. Non-Cryst. Solids 23, 369 (1977).Google Scholar
15. Solin, S. A., Papatheodorou, G. N., Phys. Rev. B15, 2084 (1977).Google Scholar
16. Takahasi, T. and Harada, Y., Solid State Comm. 35, 191 (1980).CrossRefGoogle Scholar
17. Zallen, R., The Physics of Amorphous Solids (John Wiley and Sons, New York, 1983), pp. 9496.CrossRefGoogle Scholar
18. Wright, A. C., Sinclair, R. N., Leadbetter, A. J., J. Non-Cryst. Solids 71, 295302 (1985).Google Scholar
19. Onari, S., Asai, K., Arai, T., J. Non-Cryst. Solids 76, 243251 (1985).CrossRefGoogle Scholar
20. Guiton, T. A., Soluble Species of Arsenic Trisulfide in Amine Systems, MS Thesis, Pennsylvania State University, 1987.Google Scholar
21. Ward, A. T. and Myers, M. B., J. Phys. Chem. 73, (5), 13741380 (1969).Google Scholar
22. Zallen, R., Slade, M. L., Ward, A. T., Phys. Rev. B3 (12), 42574273 (1971).CrossRefGoogle Scholar
23. Porter, E. J. and Sheldrick, G. M., J. Chem. Soc. 1972, 13471349.Google Scholar
24. Zallen, R. and Slade, M. L., Phys. Rev. B18 (10), 57755798 (1978).CrossRefGoogle Scholar
25. Forneris, R., Am. Mn. 54, 10621074 (1969).Google Scholar
26. Wood, E. A., Bell System Tech. J. 43, 541 (1964).Google Scholar
27. Kobliska, R. J. and Solin, S. A., Phys. Rev. B8 (2), 756768 (1973).Google Scholar
28. Lucovsky, G. and Galeener, F. L., J. Non-Cryst. Solids 37, 5370 (1980).Google Scholar
29. Lucovsky, G. and Martin, R. M., J. Non-Cryst. Solids 8–10, 185 (1972).Google Scholar
30. Daly, F. P. and Brown, Chris W., J. Phys. Chem. 77 (15), 18591861 (1973).Google Scholar