Effects of melting and coagulating conditions on the structure of simulated waste glasses

Nagai, Takayuki  ; Aoyama, Yusuke; Okamoto, Yoshihiro  ; Hasegawa, Takehiko*; Sato, Seiichi*; Kikuchi, Tetsuya*; Hatakeyama, Kiyoshi*

In the vitrification process study of high-level radioactive waste liquids, precipitates present in the simulated waste glasses are detected by X-ray diffraction (XRD), but due to the state of the precipitates (fine size, extremely small amount), precipitate peaks cannot be observed in the XRD pattern. We have evaluated the glass structure of simulated waste glasses prepared under different melting and coagulated conditions using Raman spectroscopy and other methods, in this study. The simulated waste glass, which does not show any precipitate peaks in the XRD pattern, was subjected to Raman spectroscopy, and it was confirmed that precipitate particles in the glass phase could be detected. And it was confirmed that in glass preparation, stirring the molten glass and increasing the cooling rate from the molten state are likely to suppress the formation of precipitate particles in the glass phase. The evaluation of the Si-O bridging structure of the glass revealed no difference in the Si-O bridging structure between areas with and without precipitates. The precipitates detected by Raman spectroscopy are not ceria (CeO) or calcium molybdate (CaMoO), but they are presumed to be compounds such as spinel. In experiments using synchrotron radiation, X-ray transmission images of the internal state of glasses were observed, and it was confirmed that stirring molten glass is effective in reducing bubbles present in the glass phase. The XAFS measurements of Mo K-edge, Ce L-edge, and Si K-edge confirmed that stirring the molten glass does not affect the chemical state of Mo, Ce, and Si contained in the glass.