Sulfur behavior in silicate glasses and melts: Implications for sulfate incorporation in nuclear waste glasses as a function of alkali cation and V2O5 content

International audiencehe presence of sulfur in radioactive waste to be incorporated in borosilicate glasses entails difficulties mainly due to the relatively low solubility of sulfates in the vitreous phase. In this work a study is presented on the effects of the ratio R = [Na2O]/[B2O3], the type of sulfate added and the addition of V2O5 on the incorporation of sulfates in borosilicate glasses. Glass samples were prepared at the laboratory scale (up to 50–100 g) by melting oxide and sulfate powders under air in Pt/Au crucibles. XRF and ICP/AES chemical analysis, SEM/EDS, microprobe WDS and Raman spectroscopy were employed to characterize the fabricated samples. The main experimental results confirm that the incorporation of sulfates in borosilicate glasses is favored by the network depolymerization, which evolves with the ratio R. The addition of V2O5 seems to accelerate the kinetics of sulfur incorporation in the glass and, probably, increase the sulfate solubility by modifying the borate network and fostering the formation of voids of shape and size compatible with the sulfur coordination polyhedron in the glassy network. The kinetics of X2SO4 incorporation in the glass seems to be slower when X = Cs