Hostname: page-component-586b7cd67f-vdxz6 Total loading time: 0 Render date: 2024-11-25T17:59:40.857Z Has data issue: false hasContentIssue false
  • English
  • Français

Dissolution Kinetics of a Simple Analogue Nuclear Waste Glass as a Function of Ph, Time and Temperature

Published online by Cambridge University Press:  21 February 2011

Kevin G. Knauss ,
William L. Bourcier ,
Kevin D. McKeegan ,
Celia I. Merzbacher ,
Son N. Nguyen ,
Frederick J. Ryerson ,
David K. Smith ,
Homer C. Weed  and
Leon Newton
Kevin G. Knauss
Affiliation:
Lawrence Livermore National Laboratory, Livermore, CA 94550
William L. Bourcier
Affiliation:
Lawrence Livermore National Laboratory, Livermore, CA 94550
Kevin D. McKeegan
Affiliation:
Lawrence Livermore National Laboratory, Livermore, CA 94550
Celia I. Merzbacher
Affiliation:
Lawrence Livermore National Laboratory, Livermore, CA 94550
Son N. Nguyen
Affiliation:
Lawrence Livermore National Laboratory, Livermore, CA 94550
Frederick J. Ryerson
Affiliation:
Lawrence Livermore National Laboratory, Livermore, CA 94550
David K. Smith
Affiliation:
Lawrence Livermore National Laboratory, Livermore, CA 94550
Homer C. Weed
Affiliation:
Lawrence Livermore National Laboratory, Livermore, CA 94550
Leon Newton
Affiliation:
Lawrence Livermore National Laboratory, Livermore, CA 94550
Get access

Abstract

We have measured the dissolution rate of a simple five-component borosilicate glass (Na2O, CaO, Al2O3, B2O3, SiO2) using a flow-through system. The experiments were designed to measure the dissolution rate constant over the interval pH 1 through pH 13 at 3 temperatures (25°, 50° and 70°C). Dilute buffers were used to maintain a constant pH. Analyses of solutions and solid surfaces provided information that is used to develop a kinetic model for glass dissolution.

Under all conditions we eventually observed linear dissolution kinetics. In strongly acidic solutions (pH 1 to pH 3) all components but Si were released in their stoichiometric proportions and a thick, Si-rich gel was formed. In mildly acidic to neutral solutions the gel was thinner and was both Si- and Al-rich, while the other components were released to solution in stoichiometric proportions. In mildly to strongly alkaline solutions all components were released to solution in stoichiometric proportions. By varying the flow rate at each pH we demonstrated a lack of transport control of the dissolution rate.

The dissolution rates were found to be lowest at near-neutral pH and to increase at both low and high pH. A rate equation based on transition-state theory (TST) was used to calculate dissolution rate constants and reaction order with respect to pH over two pH intervals at each temperature. At 250C between pH 1 and pH 7 based on the Si release rate the log rate constant for glass dissolution (g glass/m20d) was −0.77 and the order with respect to pH was −0.48. Between pH 7 and pH 13 the log rate constant for glass dissolution was −8.1 and the order with respect to pH was +0.51. The measured simple glass dissolution rate constants compare very well with constants estimated by fitting the same TST equation to experimental results obtained for SRL-165 glass and to dissolution rate estimates made for synthetic basaltic glasses.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 176: Symposium U – Scientific Basis for Nuclear Waste Management XIII , 1989 , 176
Copyright
Copyright © Materials Research Society 1990

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. White, A.F., J. Non-Cryst. Sol. 67, 225 (1984).Google Scholar
2. Wicks, G.G., Mosley, W.C., Whitkop, P.G. and Saturday, K.A., J. Non-Cryst. Sol. 49, 413 (1982).Google Scholar
3. Sales, B.C. and Boatner, L.A., in Radioactive Waste Forms for the Future, edited by Lutze, W. and Ewing, R.C. (Elsevier Science Publishers, N.Y., 1988), p. 193.Google Scholar
4. EI-Shamy, T.M. and Douglas, R.W., Glass Technol. 13, 77 (1972).Google Scholar
5. EI-Shamy, T.M., Lewis, J. and Douglas, R.W., Glass Technol. 13, 81 (1972).Google Scholar
6. Paul, A. and Youssefi, A., J. Mat. Sci. 13, 97 (1978).Google Scholar
7. Lee, C.-T., PhD Thesis, U. Florida, 1986.Google Scholar
8. Mazer, J.J., PhD Thesis, Northwestern U., 1987.Google Scholar
9. White, W.B., Advances in Ceramics. 20, 431 (1986).Google Scholar
10. Knauss, K.G. and Wolery, T.J., Geochim. Cosmochim. Acta 53, 1493 (1989).Google Scholar
11. Knauss, K.G. and Wolery, T.J., Geochim. Cosmochim. Acta 50, 2481 (1986).Google Scholar
12. Crovisier, J.L., Honnorez, J. and Eberhart, J.P., Geochim. Cosmochim. Acta 51, 2977 (1987).Google Scholar
13. Lanford, W.A., Davis, K., Lamarche, P., Laursen, T., Groleau, R. and Doremus, R.H., J. Non-Cryst. Sol. 33, 249 (1979).Google Scholar
14. Zhou, Z. and Fyfe, W.S., Am. Miner. 74, 1045 (1989).Google Scholar
15. Bourcier, W.L., Peifer, D.W., Knauss, K.G., McKeegan, K.D. and Smith, D.K., this issue.Google Scholar
16. Stolper, E., Contrib. Mineral. Petrol. 81, 1 (1982).Google Scholar
17. Engelhardt, G., Nofz, M., Forkel, K., Wihsmann, F.G., Magi, M., Samonson, A. and Lippmaa, E., Phys. Chem. Glasses 26, 157 (1985).Google Scholar
18. Oestrike, R., Yang, W.-H., Kirkpatrick, R.J., Hervig, R.L., Navrotsky, A. and Montez, B., Geochim et Cosmochim. Acta 51, 2199 (1987).Google Scholar
19. Dupree, R., Holland, D. and Williams, D.S., Phys. Chem. Glasses, 26, 50 (1985).Google Scholar
20. Risbud, S.H., Kirkpatrick, R.J., Taglialavore, A.P. and Montez, B., J. Am. Ceram. Soc. 70, C10 (1987).Google Scholar
21. Kirkpatrick, R.J., Dunn, T., Schramm, S., Smith, K.A., Oestrike, R. and Turner, G., in Structure and Bonding in Noncrystalline Solids, edited by Walrafen, G.E. and Revesz, A.G. (Plenum Press, N.Y., 1986), p 303.Google Scholar
22. Maciel, G.E. and Sindorf, D.W., J. Am. Chem. Soc. 102, 7606 (1980).Google Scholar
23. Bourcier, W.L., Lawrence Livermore Laboratory National Laboratory Report UCRL-101621 (1989).Google Scholar