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

• Published in: Journal of non-crystalline solids 2009-08, Vol.355 (28), p.1526-1538
• Main Authors: Bingham, P.A., Hand, R.J., Hannant, O.M., Forder, S.D., Kilcoyne, S.H.
• Format: Article
• Language: English
• Subjects: Chemical durability; Composition; Cross-disciplinary physics: materials science; rheology; Exact sciences and technology; Glasses (including metallic glasses); Materials science; Nuclear and chemical wastes; Optical properties; Oxide glasses; Phosphates; Physics; Raman spectroscopy; Specific materials
• ISSN: 0022-3093; 1873-4812
• DOI: 10.1016/j.jnoncrysol.2009.03.008

Modified iron phosphate glasses have been prepared with nominal molar compositions [(1− x)·(0.6P 2O 5–0.4Fe 2O 3)]· xR y SO 4, 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 P 2O 5–Fe 2O 3–FeO–R y O z 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 –(PO 4)– 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 T g and T d; increasing α and T liq; and promoting bulk crystallization at temperatures of 600–700 °C. Additions of divalent cations increase density, α, T g, T d, T liq 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. 57Fe Mössbauer 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% R 2O) 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 P 2O 5–Fe 2O 3–FeO–BaO glasses reported here show particular promise as they are ultra-durable, thermally stable, low-melting glasses with a large glass-forming compositional range.