Published online by Cambridge University Press: 19 March 2015
Two Mo-bearing glasses considered as candidate forms for high level waste (HLW) a uranium-graphite reactor spent nuclear fuel (SNF) reprocessing were characterized. Incorporation of Mo in sodium aluminophosphate (SAP) glass increases its tendency to devitrification with segregation of orthophosphate phases. Valence state and local environment of Mo in the materials containing ∼2 wt.% MoO3 were determined by X-ray absorption fine structure (XAFS) spectroscopy. In the quenched samples composed of major vitreous and minor AlPO4 nearly all Mo is located in the vitreous phase as [Mo6+О6] units whereas in the annealed samples Mo is partitioned among vitreous and one or two orthophosphate crystalline phases in favor of the vitreous phase. Mo predominantly exists in a hexavalent state in distorted octahedral environment. Four oxygen ions are positioned at a distance of ∼1.71-1.73 Å and two - at a distance of 2.02-2.04 Å. Minor Mo(V) is also present as indicated by a response in EPR spectra with g ≈ 1.911-1.915.