Sulfur incorporation in high level nuclear waste glass: a S K-edge XAFS investigation

We perform X-ray absorption fine structure (XAFS) spectroscopy measurements at the sulfur K-edge to elucidate the electronic and geometric bonding of sulfur atoms in borosilicate glass used for the vitrification of high level radioactive liquid waste. The sulfur is incorporated as sulfate, most probably as sodium sulfate, which can be deduced from the X-ray absorption near edge structure (XANES) by fingerprint comparison with reference compounds. This finding is backed up by Raman spectroscopy investigation. In the extended XAFS data, no second shell beyond the first oxygen layer is visible. We argue that this is due to the sulfate being present as small clusters located into voids of the borosilicate network. Hence, destructive interference of the variable surrounding prohibits the presence of higher shell signals. The knowledge of the sulfur bonding characteristics is essential for further optimization of the glass composition and to balance the requirements of the process and glass quality parameters, viscosity and electrical resistivity on one side, waste loading and sulfur uptake on the other side

Roentgenabsorptionsspektroskopie an Phosphorsalzperlen Bestimmung der geometrischen und elektronischen Struktur von metalloxid-dotierten Natriumphosphatglaesern

Sodium metaphosphate glasses doped with transition metal oxides show characteristic colors. X-ray absorption spectroscopy (XAS) investigations provide information whether the coloration stems from different electronic transitions or changes in the geometrical structure of the glasses. Even though the violet color of MnO_y-doped glasses is considered as an evidence for Mn"3"+-ions, Mn K-XAS reveals that the majority of the manganese ions are in the oxidation state +II and have a mixed coordination of four and six oxygen atoms, respectively. The oxygen coordination around the nickel ions in NiO-doped glasses with different metall oxide concentrations is always six. The change of color from citreous to auburn with increasing nickel oxide content is attributed to a systematic change in the bonding characteristic from mainly ionic-like to a small but significant contribution of covalent-like bonding. Analysis of higher coordination shells provides no indication of the formation of metal oxide clusters. (orig.)SIGLEAvailable from TIB Hannover: RN 4852(2004-03) / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekDEGerman