Energetics of a uranothorite (Th1–xUxSiO4) solid solution

Guo, Xiaofeng; Szenknect, Stephanie; Mesbah, Adel; Clavier, Nicolas; Poinssot, Christophe; Wu, Di; Xu, Hongwu; Dacheux, Nicolas; Ewing, Rodney C.; Navrotsky, Alexandra

doi:10.1021/acs.chemmater.6b03346

Title: Energetics of a uranothorite (Th_1–xU_xSiO₄) solid solution

Journal Article · Wed Sep 14 00:00:00 EDT 2016 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.6b03346· OSTI ID:1329910

Guo, Xiaofeng ^[1]; Szenknect, Stephanie ^[2]; Mesbah, Adel ^[2]; Clavier, Nicolas ^[2]; Poinssot, Christophe ^[3]; Wu, Di ^[4]; Xu, Hongwu ^[5]; Dacheux, Nicolas ^[2]; Ewing, Rodney C. ^[6]; Navrotsky, Alexandra ^[7]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of California, Davis, CA (United States)
CNRS/CEA/Univ. of Montpellier/ENSCM, Bagnols sur Ceze cedex (France)
CEA, Bagnols sur Ceze (France)
Washington State Univ., Pullman, WA (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Stanford Univ., Stanford, CA (United States)
Univ. of California, Davis, CA (United States)

High-temperature oxide melt solution calorimetric measurements were completed to determine the enthalpies of formation of the uranothorite, (USiO₄)_x–(ThSiO₄)_1–x, solid solution. Phase-pure samples with x values of 0, 0.11, 0.21, 0.35, 0.71, and 0.84 were prepared, purified, and characterized by powder X-ray diffraction, electron probe microanalysis, thermogravimetric analysis and differential scanning calorimetry coupled with in situ mass spectrometry, and high-temperature oxide melt solution calorimetry. This work confirms the energetic metastability of coffinite, USiO₄, and U-rich intermediate silicate phases with respect to a mixture of binary oxides. Furthermore, variations in unit cell parameters and negative excess volumes of mixing, coupled with strongly exothermic enthalpies of mixing in the solid solution, suggest short-range cation ordering that can stabilize intermediate compositions, especially near x = 0.5.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES)

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

OSTI ID:: 1329910

Report Number(s):: LA-UR-16-26227

Journal Information:: Chemistry of Materials, Vol. 28, Issue 19; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 28 works

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Title: Energetics of a uranothorite (Th_1–xU_xSiO₄) solid solution