Uncloaking the thermodynamics of the studtite to metastudtite shear-induced transformation
Abstract
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.
- Authors:
-
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Univ. of Nevada, Las Vegas, NV (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE Office of Nuclear Energy (NE)
- OSTI Identifier:
- 1324610
- Report Number(s):
- SAND2016-5343J
Journal ID: ISSN 1932-7447; 641393
- Grant/Contract Number:
- AC04-94AL85000
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 120; Journal Issue: 30; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Weck, Philippe F., and Kim, Eunja. Uncloaking the thermodynamics of the studtite to metastudtite shear-induced transformation. United States: N. p., 2016.
Web. doi:10.1021/acs.jpcc.6b05967.
Weck, Philippe F., & Kim, Eunja. Uncloaking the thermodynamics of the studtite to metastudtite shear-induced transformation. United States. https://doi.org/10.1021/acs.jpcc.6b05967
Weck, Philippe F., and Kim, Eunja. Mon .
"Uncloaking the thermodynamics of the studtite to metastudtite shear-induced transformation". United States. https://doi.org/10.1021/acs.jpcc.6b05967. https://www.osti.gov/servlets/purl/1324610.
@article{osti_1324610,
title = {Uncloaking the thermodynamics of the studtite to metastudtite shear-induced transformation},
author = {Weck, Philippe F. and Kim, Eunja},
abstractNote = {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.},
doi = {10.1021/acs.jpcc.6b05967},
journal = {Journal of Physical Chemistry. C},
number = 30,
volume = 120,
place = {United States},
year = {Mon Jul 11 00:00:00 EDT 2016},
month = {Mon Jul 11 00:00:00 EDT 2016}
}
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