A Raman spectroscopy study of bicarbonate effects on UO

McGrady, J.  ; Kumagai, Yuta   ; Watanabe, Masayuki   ; Kirishima, Akira*; Akiyama, Daisuke*; Kimuro, Shingo   ; Ishidera, Takamitsu 

Raman spectroscopy was used to investigate the effect of bicarbonate solution on the hyperstoichiometric UO surface oxide of UO pellets. The hyperstoichiometry causes distortion of the UO lattice, leading to the formation of defect peaks which arise in the Raman spectrum due to a loss of symmetry. By deconvolution of the defect peaks, the extent of oxygen inclusion and defect formation in the surface oxide as a function of bicarbonate concentration was investigated. Immersion in solution caused a reduction in the amount of interstitial oxygen due to dissolution U(V) and U(VI) in the UO oxide surface. The defect concentration increased upon immersion due to the formation of an equilibrium between dissolution and reprecipitation. The bicarbonate concentration affected the defect content which was attributed to different forms of U in solution (hydrolysed UO and UO(CO)) leading to different rates of reduction and precipitation.