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Reactivity of Silicates 1. Kinetic Studies of the Hydrolysis of Linear and Cyclic Siloxanes as Models for Defect Structure in Silicates

Published online by Cambridge University Press:  28 February 2011

Carol A. Balfe ,
Kenneth J. Ward ,
David R. Tallant  and
Sheryl L. Martinez
Carol A. Balfe
Affiliation:
Sandia National Laboratories, Albuquerque, NM 87185
Kenneth J. Ward
Affiliation:
Sandia National Laboratories, Albuquerque, NM 87185
David R. Tallant
Affiliation:
Sandia National Laboratories, Albuquerque, NM 87185
Sheryl L. Martinez
Affiliation:
Sandia National Laboratories, Albuquerque, NM 87185
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Abstract

The kinetics of hydrolysis of hexamethylcyclotrisiloxane and di-t-butyldimesitylcyclodisiloxane in tetrahydrofuran solution have been determined and compared to hydrolysis rates of silica defects. In the presence of sufficient excess witer, the first-order rate constant of the cyclotrisiloxine, k= 3.8 × 10−3 min is similar to the rate constant, k = 5.2 × 10−1 min, of the disappearance of the D2 Raman silica defect band it has been proposed to model. Limited hydrolysis rate data for the cyclodisiloxane suggests that it hydrolyzes at least four times faster than does the cyclotrisiloxane. These data are consistent with rate data available for silica crack growth and support the assignment of highly strained siloxane bonds at the crack tip to cyclodisiloxanes. Infrared spectra determined for the cyclodisiloxanes lend further support to this model.

Type
Articles
Information
MRS Online Proceedings Library (OPL) , Volume 73: Symposium H – Better Ceramics Through Chemistry II , 1986 , 619
Copyright
Copyright © Materials Research Society 1986

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References

REFERENCES

1. Gaskell, P.H., Phys. Chem. Glasses 8, 69 (1976).Google Scholar
2. Stolen, R.H., Krause, J.T., Kurkjian, C.R., Disc. Faraday Soc. 50, 103 (1970).CrossRefGoogle Scholar
3. Stolen, R.H., Walrafen, G.E., J. Chem. Phys. 64, 2623 (1976).CrossRefGoogle Scholar
4. Galeener, F.L., in Lattice Dynamics, Bablanski, M., ed. (Flammarion, Paris) 1978, p. 345.Google Scholar
5. Galeener, F.L., Phys. Rev. B19, 1292 (1979).Google Scholar
6. A) Morrow, B.A. and Devi, A., J. Chem. Soc., Faraday Trans. 1, 163, 403 (1972). b) Morrow and I.A. Cody, J. Phys. Chem. 79, 761 (1975).Google Scholar
7. Compton, W.D., Arnold, G.W., Disc. Farady Soc. 31, 130 (1961).Google Scholar
8. Griscom, D.L., Phys. Rev. B22, 4192 (1980).Google Scholar
9. Friebele, E.J., Griscom, D.L., Stapelbrock, M., and Weeks, R.A., Phys. Rev. Lett. 42, 1346 (1979).Google Scholar
10. Silin, A.R., Bray, P.J., Mikkelsen, J.C. Jr, J. Non-Crystalline Sol. 37, 71 (1981).Google Scholar
11. Subramanian, B., Halliburton, L.E., Martin, J.J., J. Phys. Chem. Solids 45, 575 (1984).Google Scholar
12. Phillips, J.C., J. Non-Crystalline Solids 63, 347 (1984).Google Scholar
13. Bertoluzza, A., Fagnano, C., Marzelli, M.A., Gottardi, V., Guglielmi, M., J. Non-Crystalline Solids 48, 117 (1982).CrossRefGoogle Scholar
14. Krol, D.M., van Lierop, J.G., J. Non-Crystalline Solids, 63, 131 (1984).Google Scholar
15. Bunker, B.C., Sandia National Laboratories, Albuquerque, NM, unpublished results.Google Scholar
16. Laughlin, R.B., Joannapoulous, J.D., Murray, C.A., Hartnett, K.J., and Greytak, T.J., Phys. Rev. Lett. 40, 461 (1978).Google Scholar
17. Lucovsky, G., Phil. Mag. 39, 513 (1979).Google Scholar
18. Brinker, C.J., Roth, E.P., Scherer, G.W., and Tallant, D.R., J. Non- Crystalline Solids 71, 171 (1985).Google Scholar
19. Galeener, F.L., J. Non-Crystalline Solids, 49, 53 (1982).Google Scholar
20. O'Keefe, M. and Gibbs, G.V., J. Chem. Phys., 81, 876 (1984).Google Scholar
21. Griffith, W.P., J. Chem. Soc. (A), 1372 (1959).Google Scholar
22. Morrow, B.A. and Cody, I.A., J. Phys. Chem. 80, 1997, (1976).Google Scholar
23. Morrow, B.A. and Cody, I.A., J. Phys. Chem. 80, 1998, (1976).Google Scholar
24. Morrow, B.A. and Cody, I.A., J. Phys. Chem. 80, 2761, (1976).Google Scholar
25. Weiss, V.A. and Weiss, A., Anorg., Z. Allg. Chem. 276, 95 (1954).Google Scholar
26. Michalczyk, M.J., West, R., and Michl, J., J. Chem. Soc., Chem. Commun., 1525 (1984).CrossRefGoogle Scholar
27. Fink, M.J., Haller, K.J., West, R., and Michl, J., J. Am. Chem. Soc., 106, 822 (1954).Google Scholar
28. a) Brinker, C.J., Tallant, D.R., Roth, E.P., and Ashley, C.S., J. Non- Crystalline Solids, in press; b) C.J. Brinker, D.R. Tallant, E.P. Roth and C.S. Ashley, Proc. of the Fall 1985 MRS Symposium: Defects in Glass, eds. F.L. Galeener, D.L. Griscom, M. Weber, in press.Google Scholar
29. Kudo, T. and Nagase, S., J. Am. Chem. Soc., 107, 2589 (1985).Google Scholar
30. Binkley, J.S. and Melius, C.F., Sandia National Laboratories, Livermore, CA, unpublished results.Google Scholar
31. Michalske, T.A. and Bunker, B.C., J. Appl. Phys. 56, 2686 (1984).Google Scholar
32. Galeener, F.L., in Proceedings of the Second International Conference on the Structure of Non-Crystalline Materials, eds. Gaskell, P.H., Parker, J.M., Davis, E.A., Taylor and Francis, Ltd., London, 1983.Google Scholar
33. Shriver, D.F., The Manipulation of Air-sensitive Compounds, New York, McGraw-Hill, 1969.Google Scholar
34. Haaland, D.M., Easterling, R.G., and Vopicka, D.A., Appl. Spectrosc., 39, 73 (1985).Google Scholar
35. Smith, A.L. and Anderson, D.R., Appl. Spectrosc., 38, 822 (1984).Google Scholar
36. Conway, B.E., Angerstein-Kowzlowska, H., Sharp, W.B.A., and Criddle, E.E., Anal. Chem., 45, 1131 (1973).Google Scholar
37. Tallant, D.R., Higgins, K.L., L.I.A., 42, 12 (ICALEO 1983).Google Scholar
38. Fogarasi, G., Hacker, H., Hoffman, V., Dobos, S., Spectrochim. Acta, 30A, 629 (1974).CrossRefGoogle Scholar
39. Kovalev, I.F., Shevchenko, I.V., Voronkov, M.G., and Kozlova, N.V., Dokl. Akad, Nauk. S.S.S.R., 212, 01 (1973).Google Scholar
40. Tallant, D.R., Bunker, B.C., Brinker, C.J. and Balfe, C.A., “Raman Spectra of Rings in Silica Materials”, to be published in this proceedings.Google Scholar
41. Tallant, D.R., unpublished results.Google Scholar