Hostname: page-component-586b7cd67f-t7czq Total loading time: 0 Render date: 2024-11-29T10:54:27.831Z Has data issue: false hasContentIssue false
  • English
  • Français

Affinity Rate Law Failure to Describe Sodium Borosilicate Glass Alteration Kinetics

Published online by Cambridge University Press:  01 February 2011

P. Frugier ,
S. Gin  and
C. Jégou
P. Frugier
Affiliation:
Commissariat à l'Énergie Atomique - CEA Valrhô DIEC/SESC, BP 17171, 30207 Bagnols-sur-Cèze Cedex, France
S. Gin
Affiliation:
Commissariat à l'Énergie Atomique - CEA Valrhô DIEC/SESC, BP 17171, 30207 Bagnols-sur-Cèze Cedex, France
C. Jégou
Affiliation:
Commissariat à l'Énergie Atomique - CEA Valrhô DIEC/SESC, BP 17171, 30207 Bagnols-sur-Cèze Cedex, France
Get access

Abstract

Simplified glass compositions were chosen to improve our knowledge of the alteration kinetics of complex glasses dedicated to the confinement of high-level waste. Since 1998, the sodium borosilicate glass system is at the center of a passionate debate between an affinity-based kinetic rate law and a protective surface layer theory. All the authors who have investigated ternary 68/14/18 SiO2–B2O3–Na2O glass agree on the fact that the affinity law cannot satisfactorily account for its alteration kinetics. Some authors explained that these discrepancies between classical kinetic rate law and experimental findings could be due to macromolecular amorphous separation in the 68/14/18 sodium borosilicate system and that this simplified glass could be divided into 90% reedmergnerite (NaBSi3O8) and 10% diborate (Na2O–2B2O3). This article provides evidence of the homogeneity of ternary 68/18/14 SiO2–B2O3–Na2O glass at nanometric scale and shows that even phase separation at less than nanometric scale could not explain the inability of hydrated glass-solution affinity laws to describe its alteration. The relative simplicity of the SiO2–B2O3–Na2O chemical system allows a critical examination of the macroscopic alteration laws developed over the last twenty years based only on the hydrated glass-solution chemical affinity without taking into account the formation and reactivity of the gel or its passivating properties.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 807: Symposium Scientific Basis for Nuclear Waste Management XXVII , 2003 , 127
Copyright
Copyright © Materials Research Society 2004

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. Aagard, P. and Helgeson, H.C., American Journal of Science 282, 237–285 (1982).Google Scholar
2. Grambow, B., in Scientific Basis for Nuclear Waste Management VII, edited by Jantzen, C.M., Stone, J.A. and Ewing, R. C., 44, Mat. Res. Soc. (1985) pp. 15–27.Google Scholar
3. McGrail, B.P., Icenhower, J. and Rodriguez, E.A., Origins of Discrepancies Between Kinetic Rate Law Theory and Experiments in the Na2O–B2O3–SiO2 System. Material Research Society (2002).Google Scholar
4. Gin, S., in Scientific Basis for Nuclear Waste Management XXIV, edited by Hart, K. and Lumpkin, G. R., Mater. Res. Soc. (2000) pp. 207–216.Google Scholar
5. Vernaz, E., Gin, S., Jégou, C., and Ribet, I., Journal of Nuclear Materials 298(1,2), 27–36 (2001).Google Scholar
6. Vernaz, E. and Gin, S., in Scientific Basis for Nuclear Waste Management XXIV, edited by Hart, K. and Lumpkin, G. R., Mater. Res. Soc. (2001) pp. 217–226.Google Scholar
7. Gin, S., Jégou, C., C, and Minet, Y., CEA report RT/DRRV/N°98–004. (1998).Google Scholar
8. Valle, N., PhD thesis, INPL, Nancy, France. CNRS. 260 p. (2001).Google Scholar
9. Jégou, C., Gin, S. and Larché, F., Journal of Nuclear Materials 280(2), 216–229 (2000).Google Scholar
10. Polyakova, I.G., Glass Physics and Chemistry 23(1), 45–57 (1997).Google Scholar
11. Polyakova, I.G., Physics and Chemistry of Glasses 41(5), 247–258 (2000).Google Scholar
12. Deruelle, O., et al., Morphology of altered layers of glasses. Méjannes-Le-Clap, France. (1997) pp. 393–402.Google Scholar
13. Deruelle, O., Spalla, O., Barboux, P. and Lambard, J., Journal of Non-Crystalline Solids 261, 237–251 (2000).Google Scholar
14. Spalla, O. et al. Alteration of Glasses: Study of the Interfacial Porous Layer by Small X-Ray Scattering, (2001).Google Scholar
15. Spalla, O., General Theorems in Small-Angle Scattering. Neutrons, X-Rays and Light (Chapter 3), 49–71(2002).Google Scholar
16. Lasaga, A.C., Soler, J.M., Ganor, J., Burch, T.E. and Nagy, K.L., Geochimica et Cosmochimica Acta 58(10), 2361–2386 (1994).Google Scholar
17. Grambow, B. and Muller, R., Journal of Nuclear Materials 298(1,2), 112–124 (2001).Google Scholar
18. Linard, Y., PhD thesis, Université Denis Diderot - UFR des Sciences de la Terre (2000).Google Scholar