Oxidation and anion lattice defect signatures of hypostoichiometric lanthanide-doped UO2

Olds, Travis A.; Karcher, Samuel E.; Kriegsman, Kyle W.; Guo, Xiaofeng; McCloy, John S.

doi:10.1016/j.jnucmat.2019.151959

Title: Oxidation and anion lattice defect signatures of hypostoichiometric lanthanide-doped UO₂

Journal Article · 15 December 2019 · Journal of Nuclear Materials

DOI: https://doi.org/10.1016/j.jnucmat.2019.151959 · OSTI ID:1741029

Olds, Travis A. ^[1]; Karcher, Samuel E. ^[2]; Kriegsman, Kyle W. ^[2]; Guo, Xiaofeng ^[2]; McCloy, John S. ^[2]

Washington State Univ., Pullman, WA (United States); Washington State University
Washington State Univ., Pullman, WA (United States)

A series of sintered UO₂ pellets doped with lanthanide (Ce, Nd, Yb) elements were investigated using powder X-ray diffraction, Raman spectroscopy, thermogravimetric analyses and differential scanning calorimetry. A combination of electron microprobe and thermogravimetric analyses, for oxygen content, enabled precise determination of the hypostoichiometry for lanthanide-doped samples at 1 and 5 atom percent. Two Raman laser wavelengths (785 and 455 nm) have afforded greater sensitivity to spectroscopic signatures of the phonon bands (1LO and 2LO) associated with oxidation of (U_1-yM_y)O_2-x and the anion defects introduced by lanthanide substitution. Oxygen hypostoichiometry forces a reduction in the average coordination number surrounding (U,M) sites, which is compensated by a decrease in U-O bond length, and concomitantly the lattice parameter, consistent with the obtained Raman spectra. The evolution of O/M ratio up to (U_1-yM_y)O₂ after oxidation was also examined using Raman spectroscopy, revealing that the ‘defect band’, including a component attributed to oxygen vacancies (~540 cm^-1) and the 1LO phonon (~575 cm^-1) increased in intensity with increasing dopant concentration and upon oxidation. Here, the lanthanide dopants inhibited oxidation to U₃O₈, most prominently for Yb 5 at%, having been delayed by ~180 °C. Thermogravimetric analyses reveal an early oxidation feature that may be related to influx of O to satisfy hypostoichiometry up to (U_1-yM_y)O₂, possibly stabilizing a U₄O₉ or U₃O₇ intermediate, delaying oxidation to U₃O₈.

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Research Organization:: Washington State Univ., Pullman, WA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Nuclear Energy (NE), Nuclear Energy University Program (NEUP)

Contributing Organization:: Washington State University

Grant/Contract Number:: NE0008689

OSTI ID:: 1741029

Journal Information:: Journal of Nuclear Materials, Journal Name: Journal of Nuclear Materials Vol. 530; ISSN 0022-3115

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Oxidation and anion lattice defect signatures of hypostoichiometric lanthanide-doped UO₂