Modified iron phosphate glasses have been prepared with nominal molar compositions [(1−x)·(0.6P2O5-0.4Fe2O3)]·xRySO4, where x = 0-0.5 in increments of 0.1 and R = Li, Na, K, Mg, Ca, Ba, or Pb and y = 1 or 2. In most cases the vast majority or all of the sulfate volatalizes and quarternary P2O5-Fe2O3-FeO-RyOz glasses or partially crystalline materials are formed. Here we have characterized the structure, thermal properties, chemical durability and redox state of these materials. Raman spectroscopy indicates that increasing modifier oxide additions result in depolymerization of the phosphate network such that the average value of i, the number of bridging oxygens per -(PO4)-tetrahedron, and expressed as Q i , decreases. Differences have been observed between the structural effects of different modifier types but these are secondary to the amount of modifier added. Alkali additions have little effect on density; slightly increasing Tg and Td; increasing α and Tliq; and promoting bulk crystallization at temperatures of 600-700 °C.Additions of divalent cations increase density, α, Tg, Td, Tliq and promote bulk crystallization at temperatures of 700-800 °C. Overall the addition of divalent cations has a less deleterious effect on glass stability than alkali additions.57 FeMössbauer spectroscopy confirms that iron is present as Fe 2+ and Fe 3+ ions which primarily occupy distorted octahedral sites. This is consistent with accepted structural models for iron phosphate glasses. The iron redox ratio, Fe 2+/ΣFe, has a value of 0.13-0.29 for the glasses studied. The base glass exhibits a very low aqueous leach rate when measured by Product Consistency Test B, a standard durability test for nuclear waste glasses. The addition of high quantities of alkali oxide (30-40 mol% R2O) to the base glass increases leach rates, but only to levels comparable with those measured for a commercial soda-lime-silica glass and for a surrogate nuclear waste-loaded borosilicate glass. Divalent cation additions decrease aqueous leach rates and large additions (30-50 mol% RO) provide exceptionally low leach rates that are 2-3 orders of magnitude lower than have been measured for the surrogate waste-loaded borosilicate glass. The P2O5-Fe2O3-FeO-BaO glasses reported here show particular promise as they are ultra-durable, thermally stable, lowmelting glasses with a large glass-forming compositional range.

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Mössbauer spectroscopy and X-ray absorption spectroscopy (XAS) have been used to obtain information on the redox and coordination of iron in glasses made by the vitrification of simulated and actual sewage sludge combustion ashes. Mössbauer spectra have been deconvoluted using three extended Voigt-based profiles to allow quantitative analysis of multiple Fe 3+ coordination environments. XAS Fe pre-K-edge absorption peaks have been analysed and fitted against reference standards to yield complementary analyses and provide validation of the Mössbauer results. Correlations are noted between the iron redox and the Fe 3+ coordination. Tetrahedral Fe 3+ is much more likely to take part in any redox reaction whilst octahedral Fe 3+ appears to be more resistant to reduction to the ferrous state. Results from XAS also suggest that Fe 2+ ions occupy both four-and six-fold coordination environments. Neither technique has provided any clear evidence for the existence of Fe 2+ or Fe 3+ in five-fold symmetry in the glasses studied.

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Role of ilmenite micro-inclusion on