Mössbauer studies of phosphate glasses for the immobilisation of toxic and nuclear wastes

Abstract

Various iron-containing phosphate glasses were investigated by Mössbauer spectroscopy. Iron was found to occur predominantly as Fe³⁺ in all glasses, and largely occupied sites with distorted octahedral coordination for both redox states. Using a base glass of nominal composition 60 P₂O₅–40 Fe₂O₃ (mol%), stepwise molar replacement of Fe₂O₃ by (0.67 Na₂O × 0.33 Al₂O₃) increased the redox ratio, Fe²⁺/ΣFe, from 0.13 at 40% Fe₂O₃ to 0.25 at 10% Fe₂O₃. The centre shift increased and quadrupole splitting decreased by up to ∼20% over this range, interpreted as a decrease in the average distortion of Fe sites from cubic symmetry, and an increase in average iron coordination. Literature revealed that recoil-free fraction ratio f (Fe³⁺) / f (Fe²⁺) ≈ 1.3 in iron phosphate glasses, and this was considered when assessing redox. Mössbauer parameters of these and other glasses demonstrated a combination of structural stability and compositional flexibility which makes them so suitable for waste immobilisation.