Doremus' model of viscosity assumes that viscous flow in amorphous materials is mediated by broken bonds (configurons). The resulting equation contains four coefficients, which are directly related to the entropies and enthalpies of formation and motion of the configurons. Thus by fitting this viscosity equation to experimental viscosity data these enthalpy and entropy terms can be obtained. The non-linear nature of the equation obtained means that the fitting process is non-trivial. A genetic algorithm based approach has been developed to fit the equation to experimental viscosity data for a number of glassy materials including SiO 2 , GeO 2 , B 2 O 3 , anorthite, diopside, xNa 2 O-(1 -x)SiO 2 , xPbO-(1 -x)SiO 2 , soda-limesilica glasses, salol, and α-phenyl-ο-cresol. Excellent fits of the equation to the viscosity data were obtained over the entire temperature range. The fitting parameters were used to quantitatively determine the enthalpies and entropies of formation and motion of configurons in the analysed systems, the activation energies for flow at high and low temperatures as well as fragility ratios using the Doremus criterion for fragility. A direct anti-correlation between fragility ratio and configuron percolation threshold which determines the glass transition temperature in the analysed materials was found. 66.20.1d, 66.10.Cb, 71.55.Jv. PACS:

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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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