Abstract
Complex sodium-aluminum-iron phosphate glassy materials with various Al2O3 to Fe2O3 ratio containing high level waste (HLW) surrogate were characterized by X-ray diffraction and scanning electron microscopy and studied in details by Fourier transform infrared (FTIR) spectroscopy. The samples with high Al2O3 content and not containing Fe2O3 were predominantly amorphous but subjected to devitrification under annealing. Addition of B2O3 and partial Fe2O3 substitution for Al2O3 in the materials increases their resistance to devitrification whereas further substitution and NiO incorporation significantly increase the tendency to devitrification. FTIR spectra demonstrate changes in the structure of glassy materials caused by both structural variations in the anionic motif and occurrence of crystalline phases in the materials. According to Mössbauer spectroscopy data, iron in the glassy samples is present as octahedrally coordinated Fe3+ ions while in the partly devitrified samples iron is partitioned among vitreous and crystalline phases entering the vitreous phase mainly as Fe3+O6 units and crystalline phases as major Fe3+ and minor Fe2+ ions in a magnetically ordered state and participating in a “fast” electronic exchange.
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