Uncloaking the thermodynamics of the studtite to metastudtite shear-induced transformation

Weck, Philippe F.; Kim, Eunja

doi:10.1021/acs.jpcc.6b05967

Uncloaking the thermodynamics of the studtite to metastudtite shear-induced transformation

Journal Article · Mon Jul 11 00:00:00 EDT 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b05967· OSTI ID:1324610

Weck, Philippe F. ^[1]; Kim, Eunja ^[2]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Univ. of Nevada, Las Vegas, NV (United States)

The interplay between thermodynamics and mechanical properties in the transformation of studtite, (UO₂)(O₂)(H₂O)₂·2H₂O, into metastudtite, (UO₂)(O₂)(H₂O)₂, two important corrosion phases observed on the surface of uranium dioxide exposed to water, is revealed using density functional perturbation theory. Phonon calculations within the quasi-harmonic approximation predict that the standard entropy change for the (UO₂)(O₂)(H₂O)₂·2H₂O → (UO₂)(O₂)(H₂O)₂ + 2H₂O reaction is ΔS⁰ = +80 J·mol^–1·K^–1 for the production of water in the liquid state and +389 J·mol–1·K–1 for water vapor. Similar to bulk H₂O(l), the bulk modulus of (UO₂)(O₂)(H₂O)₂·2H₂O increases with temperature, contrasting with (UO₂)(O₂)(H₂O)₂ which features the typical Anderson–Gruneisen temperature dependence of oxide solids. Upon removal of interstitial H₂O in studtite, the most important changes in the shear modulus, the parameter limiting the mechanical stability, arise in the planes normal to chain propagation directions. Lastly, the present findings have important implications for the dehydration of other hygroscopic materials.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1324610

Report Number(s):: SAND2016-5343J; 641393

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 30 Vol. 120; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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