Thermodynamic studies of studtite thermal decomposition pathways via amorphous intermediates UO3, U2O7, and UO4

Guo, Xiaofeng; Wu, Di; Xu, Hongwu; Burns, Peter C.; Navrotsky, Alexandra

doi:10.1016/j.jnucmat.2016.06.014

Thermodynamic studies of studtite thermal decomposition pathways via amorphous intermediates UO₃, U₂O₇, and UO₄

Journal Article · Thu Sep 01 00:00:00 EDT 2016 · Journal of Nuclear Materials

DOI:https://doi.org/10.1016/j.jnucmat.2016.06.014· OSTI ID:1304726

Guo, Xiaofeng ^[1]; Wu, Di ^[2]; Xu, Hongwu ^[1]; Burns, Peter C. ^[3]; Navrotsky, Alexandra ^[4]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Earth and Environmental Sciences Division
Univ. of California, Davis, CA (United States). Peter A. Rock Thermochemistry Lab. and NEAT ORU; Washington State Univ., Pullman, WA (United States). Gene and Lina Voiland School of Chemical Engineering and Bioengineering
Univ. of Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences; Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry
Univ. of California, Davis, CA (United States). Peter A. Rock Thermochemistry Lab. and NEAT ORU

The thermal decomposition of studtite (UO₂)O₂(H₂O)₂·2H₂O results in a series of intermediate X-ray amorphous materials with general composition UO_3+x (x = 0, 0.5, 1). As an extension of a structural study on U₂O₇, this work provides detailed calorimetric data on these amorphous oxygen-rich materials since their energetics and thermal stability are unknown. These were characterized in situ by thermogravimetry, and mass spectrometry. Ex situ X-ray diffraction and infrared spectroscopy characterized their chemical bonding and local structures. This detailed characterization formed the basis for obtaining formation enthalpies by high temperature oxide melt solution calorimetry. The thermodynamic data demonstrate the metastability of the amorphous UO_3+x materials, and explain their irreversible and spontaneous reactions to generate oxygen and form metaschoepite. Thus, formation of studtite in the nuclear fuel cycle, followed by heat treatment, can produce metastable amorphous UO_3+x materials that pose the risk of significant O₂ gas. Quantitative knowledge of the energy landscape of amorphous UO_3+x was provided for stability analysis and assessment of conditions for decomposition.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC52-06NA25396; SC0001089

OSTI ID:: 1304726

Alternate ID(s):: OSTI ID: 1325346
OSTI ID: 22592715
OSTI ID: 1387907

Report Number(s):: LA-UR-16-23089

Journal Information:: Journal of Nuclear Materials, Journal Name: Journal of Nuclear Materials Journal Issue: C Vol. 478; ISSN 0022-3115

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO ₂ Guo, Xiaofeng; Boukhalfa, Hakim; Mitchell, Jeremy N. Review of Scientific Instruments, Vol. 90, Issue 4 https://doi.org/10.1063/1.5093567	journal	April 2019
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