Influence of the heat treatment procedure and irradiation on the structure of the anionic motif and crystallization of uranium-containing phosphate glasses

Resumo

The solubility of UO₃ in sodium almino(ferro)phosphate (SAFP) glasses prepared by quenching of melts reaches almost 50 wt %. The structure of the anionic motif of the network of such glasses is formed by polyanions and consists of alumino(ferro)phosphate and uranium–oxygen constituents. Irradiation with electrons of up to 8 MeV energy to an absorbed dose of 10⁶ Gy does not lead to appreciable changes in the glass structure, except insignificant increase in the fraction of octahedrally coordinated aluminum. After annealing, samples of sodium aluminophosphate glasses with low content of uranium oxides (up to 10 wt %) partially crystallize with the formation of phosphotridymite, whereas high-uranium glasses (up to ~50 wt % UO₃) remain X-ray amorphous. Samples of SAFP glasses at low concentrations of uranium oxides remain amorphous and at high concentrations undergo phase segregation with the formation of a SAFP glass phase enriched in uranium oxides and crystalline phase of sodium aluminum iron orthophosphate Na₃(Al,Fe)₂(PO₄)₃ containing impurity amounts of uranium ions. The incorporation of uranium ions is most probably due to the occurrence of redox processes between uranyl and iron ions.