Computational study of the energetics and defect clustering tendencies for Y- and La-doped UO2

Solomon, J. M.; Alexandrov, V.; Sadigh, B.; Navrotsky, A.; Asta, M.

doi:10.1016/j.actamat.2014.06.052

Title: Computational study of the energetics and defect clustering tendencies for Y- and La-doped UO₂

Journal Article · Thu Jul 24 00:00:00 EDT 2014 · Acta Materialia

DOI:https://doi.org/10.1016/j.actamat.2014.06.052· OSTI ID:1305821

Solomon, J. M. ^[1]; Alexandrov, V. ^[2]; Sadigh, B. ^[3]; Navrotsky, A. ^[4]; Asta, M. ^[5]

Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Science Directorate
Univ. of California, Davis, CA (United States). Nanomaterials in the Environment, Agriculture, and Technology Organized Research Unit (NEAT ORU), Peter A. Rock Thermochemistry Lab.
Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Univ. of California, Davis, CA (United States). Dept. of Chemical Engineering and Materials Science

The energetics and defect-ordering tendencies in solid solutions of uoritestructured UO₂ with trivalent rare earth cations (M³⁺=Y, La) are investigated computationally using a combination of ionic-pair-potential and densityfunctional- theory (DFT) based methods. Calculated enthalpies of formation with respect to constituent oxides show higher energetic stability for La solid solutions relative to Y, consistent with the di erences in experimentally measured solubility limits for the two systems. Additionally, calculations performed for di erent atomic con gurations show a preference for reduced (increased) oxygen vacancy coordination around La (Y) dopants. The current results are shown to be qualitatively consistent with related calculations and calorimetry measurements in other trivalent-doped uorite-structured oxides, which show a tendency for increasing stability and increasing preference for higher oxygen coordination with increasing size of the trivalent impurity. The implications of these results are discussed in the context of the e ect of trivalent impurities on oxygen-ion mobilities in UO₂, which are relevant to the understanding of experimental observations concerning the e ect of trivalent ssion products on oxidative corrosion rates of spent nuclear fuel.

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Research Organization:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

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

Grant/Contract Number:: AC52-07NA27344; AC02-05CH11231; SC0001089

OSTI ID:: 1305821

Alternate ID(s):: OSTI ID: 1556437

Report Number(s):: LLNL-JRNL-648918

Journal Information:: Acta Materialia, Vol. 78, Issue C; ISSN 1359-6454

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 16 works

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