Effects of modifier additions on the thermal properties, chemical durability, oxidation state and structure of iron phosphate glasses

Modified iron phosphate glasses have been prepared with nominal molar compositions [(1�x)�(0.6P2O5–\ud 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\ud most cases the vast majority or all of the sulfate volatalizes and quarternary P2O5–Fe2O3–FeO–RyOz\ud glasses or partially crystalline materials are formed. Here we have characterized the structure, thermal\ud properties, chemical durability and redox state of these materials. Raman spectroscopy indicates that\ud increasing modifier oxide additions result in depolymerization of the phosphate network such that the\ud average value of i, the number of bridging oxygens per –(PO4)– tetrahedron, and expressed as Qi,\ud decreases. Differences have been observed between the structural effects of different modifier types\ud but these are secondary to the amount of modifier added. Alkali additions have little effect on density;\ud slightly increasing Tg and Td; increasing a and Tliq; and promoting bulk crystallization at temperatures\ud of 600–700 �C. Additions of divalent cations increase density, a, Tg, Td, Tliq and promote bulk crystallization\ud at temperatures of 700–800 �C. Overall the addition of divalent cations has a less deleterious effect\ud on glass stability than alkali additions. 57Fe Mössbauer spectroscopy confirms that iron is present as Fe2+\ud and Fe3+ ions which primarily occupy distorted octahedral sites. This is consistent with accepted structural\ud models for iron phosphate glasses. The iron redox ratio, Fe2+/RFe, has a value of 0.13–0.29 for the\ud glasses studied. The base glass exhibits a very low aqueous leach rate when measured by Product Consistency\ud Test B, a standard durability test for nuclear waste glasses. The addition of high quantities of\ud alkali oxide (30–40 mol% R2O) to the base glass increases leach rates, but only to levels comparable with\ud those measured for a commercial soda-lime-silica glass and for a surrogate nuclear waste-loaded borosilicate\ud glass. Divalent cation additions decrease aqueous leach rates and large additions (30–50 mol%\ud RO) provide exceptionally low leach rates that are 2–3 orders of magnitude lower than have been measured\ud for the surrogate waste-loaded borosilicate glass. The P2O5–Fe2O3–FeO–BaO glasses reported here\ud show particular promise as they are ultra-durable, thermally stable, low-melting glasses with a large\ud glass-forming compositional range.