Raman spectra, structural units and durability of nuclear waste glasses with variations in composition and crystallization: Implications for intermediate order in the glass network

Abstract

Abstract The Raman spectra of nuclear waste glasses are composed of large variations in half-width and intensity for the commonly observed bridging (Q0) and non-bridging (Q1 to Q4) bands in silicate structures. With increase in waste concentration in a boroaluminosilicate melt, the bands of quenched glasses are distinctly localized with half-width and intensity indicative of increase in atomic order. Since the nuclear waste glasses contain disparate components, and since the bands depart from the typical random network, a systematic study for the origin of these bands as a function of composition and crystallization was undertaken. From a comparative study of Raman spectra of boroaluminosilicate glasses containing Na2O-ZrO2, Na2O-MgO, MgO-Na2O-ZrO2, Na2O-CaO-ZrO2, Na2O-CaO, and Na2O-MgO-CaF2 component sets and orthosilicate crystals of zircon and forsterite, intermediate order is inferred. An edge-sharing polyhedral structural unit is proposed to account for narrow bandwidth and high intensity for Q2 antisymmetric modes, and decreased leaching of sodium with ZrO2 concentration in glass. The intense Q4 band in nuclear waste glass is similar to the intertetrahedral antisymmetric modes in forsterite. The Raman spectra of zircon contains intratetrahedral quartz-like peaks and intertetrahedral non-bridging silicate peaks. The quartz-like peaks nearly vanish in the background of forsterite spectrum. This difference between the Raman spectra of the two orthosilicate crystals presumably results from their biaxial and uniaxial effects on polarizability ellipsoids. The results also reveal formation of 604, 956 and 961 cm−1 defect bands with composition and crystallization.