Structural role of molybdenum in nuclear glasses: an EXAFS study.

The Mo environment has been investigated in inactive nuclear glasses using extended X-ray absorption spectroscopy (XAS). Mo is present in a tetrahedron coordinated to oxygen in the form of molybdate groups [MoO4]2− (d(Mo–O)=1.78 Å). This surrounding is not affected by the presence of noble metal phases in the nuclear glass. Relying on the XAS results, on the bond-valence model and on molecular dynamics simulations of a simplified borosilicate model glass, we show that these groups are not directly linked to the borosilicate network but rather located within alkali and alkaline-earth rich domains in the glass. This specific location in the glass network is a way to understand the low solubility of Mo in glasses melted under oxidizing conditions. It also explains the possible phase separation of a yellow phase enriched in alkali molybdates in molten nuclear glasses or the nucleation of calcium molybdates during thermal aging of these glasses. Boron coordination changes in the molten and the glassy states may explain the difference in the composition of the crystalline molybdates, as they exert a direct influence on the activity of alkalis in borosilicate glasses and melts