Thermochemistry and Crystallization of Glass-Forming Y-Substituted Sr-Analogues of Fresnoite (Sr2TiSi2O8)
Abstract:Strontium titanosilicate (Sr2TiSi2O8) is the Sr-analogue of fresnoite (Ba2TiSi2O8). It may provide useful properties due to the unusual five-coordinate titanium in its structure. Sr2TiSi2O8 is also a possible oxide form for the immobilization of short-lived fission products in radioactive waste. Through decay, strontium decays to yttrium and then to zirconium. Therefore, not only the stability of Sr-loaded waste forms but also that of a potential decay product series with charge-balance in a naturally occurring mineral or ceramic is of fundamental importance. To incorporate the reaction 3Sr2+=2Y3++vacancy in the fresnoite composition, Y-substituted Sr-analogues of fresnoite, (Sr2−xY2/3x)TiSi2O8 (x=0, 0.5, 0.75, 1, 1.25, and 1.5) were prepared by a high-temperature synthesis and were found to form glass upon cooling. The Y-end-member (Y1.33TiSi2O8, x=2) crystallized to a mixture of Y2TiSiO7, TiO2, and SiO2 upon quenching in air. The enthalpies of formation of Y-substituted Sr-fresnoite glasses were obtained from drop solution calorimetry in a molten lead borate (2PbO·B2O3) solvent at 702°C. The enthalpies of formation from constituent oxides were exothermic but become less so with increasing Y content. The enthalpy of vitrification of Sr2TiSi2O8 composition was measured to be 68.5 ± 6.2 kJ/mol. The thermodynamic stability of the Y-substituted Sr-analogue of crystalline fresnoite may become marginal with increasing yttrium content. Their ready glass formation, even in the absence of radiation, suggests that amorphous phases may dominate as the Sr- and Cs-containing waste forms decay.
Document Type: Research Article
Affiliations: Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California at Davis, Davis, California 95616
Publication date: 2010-07-01