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Iron Redox Reactions in Model Nuclear Waste Glasses and Melts

Published online by Cambridge University Press:  01 February 2011

Benjamin Cochain
Affiliation:
cochain@ipgp.jussieu.fr, CEA, DEN, DTCD, SECM, LDMC, Bagnols-sur-Cèze, France
Daniel R. Neuville
Affiliation:
&@ipgp.jussieu.fr, CNRS-IPGP, Physique des Minéraux et des Magmas, Paris, France
Jacques Roux
Affiliation:
2@ipgp.jussieu.fr, CNRS-IPGP, Physique des Minéraux et des Magmas, Paris, France
Dominique De Ligny
Affiliation:
3@ipgp.jussieu.fr, LPCML, UCBL, Lyon, France
Denis Testemale
Affiliation:
4@ipgp.jussieu.fr, Institut Néel, MCMF, Grenoble, France
Olivier Pinet
Affiliation:
pinet@ipgp.jussieu.fr, CEA, DEN, DTCD, SECM, LDMC, Bagnols-sur-Cèze, France
Pascal Richet
Affiliation:
prich@ipgp.jussieu.fr, CNRS-IPGP, Physique des Minéraux et des Magmas, Paris, France
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Abstract

The influence of boron on the kinetics of oxidation of iron in silicate melts relevant to nuclear waste storage has been investigated by XANES experiments. The measurements have been performed isothermally as a function of time at the iron K-edge. The redox kinetics become slower with increasing B2O3 content either close to the glass transition range, where the redox kinetics are controlled by diffusion of network-modifying cations, or at superliquidus temperatures where oxygen diffusion is the rate-limiting factor. In both ranges the kinetics can be interpreted in terms of boron speciation and interaction with alkali cations. Below the liquidus, however, the long times needed to reach redox equilibrium allow sintering of the powders investigated to take place so that the resulting changes in sample geometry prevent determinations of oxidation kinetic parameters from being made.

Type
Research Article
Copyright
Copyright © Materials Research Society 2009

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