A combined calorimetric and computational study of the energetics of rare earth substituted UO2 systems

Zhang, Lei; Solomon, Jonathan M.; Asta, Mark; Navrotsky, Alexandra

doi:10.1016/j.actamat.2015.06.048

A combined calorimetric and computational study of the energetics of rare earth substituted UO₂ systems

Journal Article · Mon Jul 13 00:00:00 EDT 2015 · Acta Materialia

DOI:https://doi.org/10.1016/j.actamat.2015.06.048· OSTI ID:1370874

Zhang, Lei ^[1]; Solomon, Jonathan M. ^[2]; Asta, Mark ^[3]; Navrotsky, Alexandra ^[1]

Univ. of California, Davis, CA (United States)
Univ. of California, Berkeley, CA (United States)
Univ. of California, Davis, CA (United States); Univ. of California, Berkeley, CA (United States)

The energetics of rare earth substituted UO₂ solid solutions (U_1-xLn_xO_2-0.5x+y, where Ln = La, Y, and Nd) are explored employing a combination of calorimetric measurements and density functional theory based computations. Calculated and measured formation enthalpies agree within 10 kJ/mol for stoichiometric oxygen/metal compositions. To better understand the factors governing the stability and defect binding in rare earth substituted urania solid solutions, systematic trends in the energetics are investigated based on the present results and previous computational and experimental thermochemical studies of rare earth substituted fluorite oxides (A_1-xLn_xO_2-0.5x, where A = Hf, Zr, Ce, and Th). A consistent trend towards increased energetic stability with larger size mismatch between the smaller host tetravalent cation and the larger rare earth trivalent cation is found for both actinide and non-actinide fluorite oxide systems where aliovalent substitution of Ln cations is compensated by oxygen vacancies. Yet, the large exothermic oxidation enthalpy in the UO₂ based systems favors oxygen rich compositions where charge compensation occurs through the formation of uranium cations with higher oxidation states.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)

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

Grant/Contract Number:: SC0001089; AC02-05CH11231

OSTI ID:: 1370874

Alternate ID(s):: OSTI ID: 22453084
OSTI ID: 1254764

Journal Information:: Acta Materialia, Journal Name: Acta Materialia Journal Issue: C Vol. 97; ISSN 1359-6454

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited By (2)

Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La) Solomon, Jonathan M.; Shamblin, Jacob; Lang, Maik Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep38772	journal	December 2016
Dependency of f states in fluorite-type XO ₂ (X = Ce, Th, U) on the stability and electronic state of doped transition metals Ding, Qian; Qiu, Ruizhi; Ao, Bingyun Physical Chemistry Chemical Physics, Vol. 21, Issue 47 https://doi.org/10.1039/c9cp04371c	journal	January 2019

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