The structure of liquid UO2− x in reducing gas atmospheres

• Published in: Applied physics letters 2017-02, Vol.110 (8)
• Main Authors: Alderman, O. L. G., Benmore, C. J., Weber, J. K. R., Skinner, L. B., Tamalonis, A. J., Sendelbach, S., Hebden, A., Williamson, M. A.
• Format: Article
• Language: English
• Subjects: Applied physics; Atmospheric temperature; Coordination numbers; Correlation analysis; Elongation; ENVIRONMENTAL SCIENCES; Floating structures; Gas mixtures; Laser beam heating; Liquid metals; Melts; Nonstoichiometric compounds; Nuclear energy; Nuclear reactors; Organic chemistry; Oxidation; Periodic variations; Position measurement; Uranium; Uranium dioxide; X-ray absorption near edge structure; X-ray diffraction
• ISSN: 0003-6951; 1077-3118
• DOI: 10.1063/1.4977035

High energy X-ray diffraction experiments performed on hypostoichiometric UO2− x liquids in reducing gas mixtures of 95%Ar:5%CO and 95%Ar:5%H2 are compared to that conducted in a pure Ar atmosphere [Skinner et al., Science 346, 984 (2014)]. The measurements are pertinent to severe accident scenarios at nuclear reactors, where core melts can encounter reducing conditions and further shed light on the oxide chemistry of the low valence states of uranium, particularly U(III), which become stable only at very high temperatures and low oxygen potentials. The radioactive samples were melted by floating small spheres of material using an aerodynamic levitator and heating with a laser beam. In the more reducing environments, a 1.7% shift to lower Q-values is observed in the position of the principal peak of the measured X-ray structure factors, compared to the more oxidizing Ar environment. This corresponds to an equivalent elongation in the U-U nearest neighbor distances and the U-U periodicity. The U-O peak (modal) bond-length, as measured from the real-space total correlation functions, is also observed to expand by 0.9–1.6% under reducing conditions, consistent with the presence of 15–27% U3+ cations, assuming constant U-O coordination number. The slightly larger U-U elongation, as compared to the U-O elongation, is interpreted as a slight increase in U-O-U bond angles. Difficulties concerning the determination of the hypostoichiometry, x, are discussed, along with the future directions for related research.