Oxidative Corrosion of the UO 2 (001) Surface by Nonclassical Diffusion
Abstract
Uranium oxide is integral to every stage of the nuclear fuel cycle, from mining through fuel fabrication and use, to waste disposal and environmental cleanup. Its chemical and mechanical stability are intricately linked to the concentration of interstitial O atoms within the structure and the oxidation state of U. We have previously shown that, during corrosion of the UO2 (111) surface under either 1 atm of O2 gas or oxygenated water at room temperature, oxygen interstitials diffuse into the substrate to form a superlattice with three-layer periodicity. In the current study, we used surface X-ray scattering to reveal the structure of the oxygen diffusion profile beneath the (001) surface. The first few layers below the surface oscillate strongly in their surface-normal lattice parameters, suggesting preferential interstitial occupation of every other layer below the surface, which is geometrically consistent with the interstitial network that forms below the oxidized (111) surface. Deeper layers are heavily contracted and indicate that the oxidation front penetrates ~52 Å below the (001) surface after 21 days of dry O2 gas exposure at ambient pressure and temperature. X-ray photoelectron spectroscopy implies U is present as U(IV), U(V), and U(VI).
- Authors:
-
[1];
[4];
- Univ. of Chicago, Chicago, IL (United States)
- Univ. of Michigan, Ann Arbor, MI (United States); Chicago State Univ., Chicago, IL (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- Publication Date:
- Research Org.:
- Univ. of Chicago, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1508051
- Report Number(s):
- DOE-UCHICAGO-14466-12
Journal ID: ISSN 0743-7463
- Grant/Contract Number:
- FG02-94ER14466
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Langmuir
- Additional Journal Information:
- Journal Volume: 33; Journal Issue: 46; Journal ID: ISSN 0743-7463
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 58 GEOSCIENCES
Citation Formats
Stubbs, Joanne E., Biwer, Craig A., Chaka, Anne M., Ilton, Eugene S., Du, Yingge, Bargar, John R., and Eng, Peter J. Oxidative Corrosion of the UO 2 (001) Surface by Nonclassical Diffusion. United States: N. p., 2017.
Web. doi:10.1021/acs.langmuir.7b02800.
Stubbs, Joanne E., Biwer, Craig A., Chaka, Anne M., Ilton, Eugene S., Du, Yingge, Bargar, John R., & Eng, Peter J. Oxidative Corrosion of the UO 2 (001) Surface by Nonclassical Diffusion. United States. https://doi.org/10.1021/acs.langmuir.7b02800
Stubbs, Joanne E., Biwer, Craig A., Chaka, Anne M., Ilton, Eugene S., Du, Yingge, Bargar, John R., and Eng, Peter J. Mon .
"Oxidative Corrosion of the UO 2 (001) Surface by Nonclassical Diffusion". United States. https://doi.org/10.1021/acs.langmuir.7b02800. https://www.osti.gov/servlets/purl/1508051.
@article{osti_1508051,
title = {Oxidative Corrosion of the UO 2 (001) Surface by Nonclassical Diffusion},
author = {Stubbs, Joanne E. and Biwer, Craig A. and Chaka, Anne M. and Ilton, Eugene S. and Du, Yingge and Bargar, John R. and Eng, Peter J.},
abstractNote = {Uranium oxide is integral to every stage of the nuclear fuel cycle, from mining through fuel fabrication and use, to waste disposal and environmental cleanup. Its chemical and mechanical stability are intricately linked to the concentration of interstitial O atoms within the structure and the oxidation state of U. We have previously shown that, during corrosion of the UO2 (111) surface under either 1 atm of O2 gas or oxygenated water at room temperature, oxygen interstitials diffuse into the substrate to form a superlattice with three-layer periodicity. In the current study, we used surface X-ray scattering to reveal the structure of the oxygen diffusion profile beneath the (001) surface. The first few layers below the surface oscillate strongly in their surface-normal lattice parameters, suggesting preferential interstitial occupation of every other layer below the surface, which is geometrically consistent with the interstitial network that forms below the oxidized (111) surface. Deeper layers are heavily contracted and indicate that the oxidation front penetrates ~52 Å below the (001) surface after 21 days of dry O2 gas exposure at ambient pressure and temperature. X-ray photoelectron spectroscopy implies U is present as U(IV), U(V), and U(VI).},
doi = {10.1021/acs.langmuir.7b02800},
journal = {Langmuir},
number = 46,
volume = 33,
place = {United States},
year = {Mon Oct 30 00:00:00 EDT 2017},
month = {Mon Oct 30 00:00:00 EDT 2017}
}
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Works referencing / citing this record:
Direct observation of pure pentavalent uranium in U2O5 thin films by high resolution photoemission spectroscopy
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