ABSTRACT
Iron-phosphate glasses are a wide group of materials with a wide range of applications. Among others, they are promising materials in toxic waste vitrification because of their high chemical durability and relatively low processing temperature and time. They are a novel group of glasses that are considered in the vitrification of radioactive waste, especially those that cannot be treated using conventional borosilicate ones. Since strontium isotopes are one of the main fission products present in the waste, the influence of Sr on the structural properties of the glasses is an important factor. Strontium-containing iron-phosphate glasses were subjected to structural studies using FT-IR and Raman spectroscopies. The obtained spectra were described, and appropriate band assignments were done. Based on the research conducted, the structural features of the phosphate network and their changes were determined. The results obtained showed that strontium in relatively low content up to 20 mol% acts as the glass network charge compensator and can stabilize the network. Above this threshold, SrO can be treated as a pure modifier, leading to gradual depolymerization. Thus, this point may be treated as the maximum waste loading for effective strontium immobilization.
ABSTRACT
Vitrification is the most effective method for the immobilization of hazardous waste by incorporating toxic elements into a glass structure. Iron phosphate glasses are presently being considered as matrices for the storage of radioactive waste, even of those which cannot be vitrified using conventional borosilicate waste glass. In this study, a structural model of 60P2O5-40Fe2O3 glass is proposed. The model is based on the crystal structure of FePO4 which is composed of [FeO4][PO4] tetrahedral rings. The rings are optimized using the DFT method and the obtained theoretical FTIR and Raman spectra are being compared with their experimental counterparts. Moreover, the proposed model is in very good agreement with X-ray absorption fine structure spectroscopy (XANES/EXAFS) and Mössbauer spectroscopy measurements. According to the calculations the Fe(3+) is in tetrahedral and five-fold coordination. The maximal predicted load of waste constituents into the glass without rebuilding of the structure is 30 mol%. Below this content, waste constituents balance the charge of [FeO4](-) tetrahedra which leads to their strong bonding to the glass resulting in an increase of the chemical durability, transformation and melting temperatures and density.
