On the mechanical stability of uranyl peroxide hydrates: Implications for nuclear fuel degradation
Abstract
The mechanical properties and stability of studtite, (UO2)(O2)(H2O)2·2H2O, and metastudtite, (UO2)(O2)(H2O)2, two important corrosion phases observed on spent nuclear fuel exposed to water, have been investigated using density functional perturbation theory. While (UO2)(O2)(H2O)2 satisfies the necessary and sufficient Born criteria for mechanical stability, (UO2)(O2)(H2O)2·2H2O is found to be mechanically metastable, which might be the underlying cause of the irreversibility of the studtite to metastudtite transformation. According to Pugh's and Poisson's ratios and the Cauchy pressure, both phases are considered ductile and shear modulus is the parameter limiting their mechanical stability. Furthermore, debye temperatures of 294 and 271 K are predicted for polycrystalline (UO2)(O2)(H2O)2·2H2O and (UO2)(O2)(H2O)2, suggesting a lower micro-hardness of metastudtite.
- Authors:
-
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Univ. of Nevada, Las Vegas, NV (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1235916
- Report Number(s):
- SAND-2015-4828J
Journal ID: ISSN 2046-2069; RSCACL; 594908
- Grant/Contract Number:
- AC04-94AL85000
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- RSC Advances
- Additional Journal Information:
- Journal Volume: 5; Journal Issue: 96; Journal ID: ISSN 2046-2069
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Weck, Philippe F., Kim, Eunja, and Buck, Edgar C. On the mechanical stability of uranyl peroxide hydrates: Implications for nuclear fuel degradation. United States: N. p., 2015.
Web. doi:10.1039/c5ra16111h.
Weck, Philippe F., Kim, Eunja, & Buck, Edgar C. On the mechanical stability of uranyl peroxide hydrates: Implications for nuclear fuel degradation. United States. https://doi.org/10.1039/c5ra16111h
Weck, Philippe F., Kim, Eunja, and Buck, Edgar C. 2015.
"On the mechanical stability of uranyl peroxide hydrates: Implications for nuclear fuel degradation". United States. https://doi.org/10.1039/c5ra16111h. https://www.osti.gov/servlets/purl/1235916.
@article{osti_1235916,
title = {On the mechanical stability of uranyl peroxide hydrates: Implications for nuclear fuel degradation},
author = {Weck, Philippe F. and Kim, Eunja and Buck, Edgar C.},
abstractNote = {The mechanical properties and stability of studtite, (UO2)(O2)(H2O)2·2H2O, and metastudtite, (UO2)(O2)(H2O)2, two important corrosion phases observed on spent nuclear fuel exposed to water, have been investigated using density functional perturbation theory. While (UO2)(O2)(H2O)2 satisfies the necessary and sufficient Born criteria for mechanical stability, (UO2)(O2)(H2O)2·2H2O is found to be mechanically metastable, which might be the underlying cause of the irreversibility of the studtite to metastudtite transformation. According to Pugh's and Poisson's ratios and the Cauchy pressure, both phases are considered ductile and shear modulus is the parameter limiting their mechanical stability. Furthermore, debye temperatures of 294 and 271 K are predicted for polycrystalline (UO2)(O2)(H2O)2·2H2O and (UO2)(O2)(H2O)2, suggesting a lower micro-hardness of metastudtite.},
doi = {10.1039/c5ra16111h},
url = {https://www.osti.gov/biblio/1235916},
journal = {RSC Advances},
issn = {2046-2069},
number = 96,
volume = 5,
place = {United States},
year = {Fri Sep 11 00:00:00 EDT 2015},
month = {Fri Sep 11 00:00:00 EDT 2015}
}
Web of Science
Works referenced in this record:
Corrosion of commercial spent nuclear fuel. 1. Formation of studtite and metastudtite
journal, January 2005
- Hanson, Brady D.; McNamara, Bruce; Buck, Edgar C.
- Radiochimica Acta, Vol. 93, Issue 3
Corrosion of commercial spent nuclear fuel. 2. Radiochemical analyses of metastudtite and leachates
journal, January 2005
- McNamara, Bruce; Hanson, Brady D.; Buck, Edgar C.
- Radiochimica Acta, Vol. 93, Issue 3
Alpha-radiolysis effects on UO2 alteration in water
journal, January 2001
- Sattonnay, G.; Ardois, C.; Corbel, C.
- Journal of Nuclear Materials, Vol. 288, Issue 1
Contrary effects of the water radiolysis product H2O2 upon th dissolution of nuclear fuel in natural ground water and deionized water
journal, January 2002
- Amme, M.
- Radiochimica Acta, Vol. 90, Issue 7
Stability of Peroxide-Containing Uranyl Minerals
journal, November 2003
- Kubatko, K. -A. H.
- Science, Vol. 302, Issue 5648
Uranyl peroxide enhanced nuclear fuel corrosion in seawater
journal, January 2012
- Armstrong, C. R.; Nyman, M.; Shvareva, T.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 6
Nuclear Fuel in a Reactor Accident
journal, March 2012
- Burns, Peter C.; Ewing, Rodney C.; Navrotsky, Alexandra
- Science, Vol. 335, Issue 6073
Studtite, [(UO 2 )(O 2 )(H 2 O) 2 ](H 2 O) 2 : The first structure of a peroxide mineral
journal, July 2003
- Burns, Peter C.; Hughes, Karrie-Ann
- American Mineralogist, Vol. 88, Issue 7
On the Reactivity of Uranouranic Oxide, (I) [八三酸化ウランの反応活性に関する研究, (I)]
journal, January 1959
- Ukazi, R.
- Journal of the Atomic Energy Society of Japan / Atomic Energy Society of Japan, Vol. 1, Issue 7
X-ray diffraction data on hydrated uranium peroxide
journal, June 1963
- Debets, P. C.
- Journal of Inorganic and Nuclear Chemistry, Vol. 25, Issue 6
Ab initio study of uranyl peroxides: Electronic factors behind the phase stability
journal, February 2007
- Ostanin, S.; Zeller, P.
- Physical Review B, Vol. 75, Issue 7
Structures of uranyl peroxide hydrates: a first-principles study of studtite and metastudtite
journal, January 2012
- Weck, Philippe F.; Kim, Eunja; Jové-Colón, Carlos F.
- Dalton Transactions, Vol. 41, Issue 32
Energetics of metastudtite and implications for nuclear waste alteration
journal, November 2014
- Guo, Xiaofeng; Ushakov, Sergey V.; Labs, Sabrina
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 50
Thermal decomposition of uranium peroxide hydrate
journal, January 1961
- Sato, Taichi
- Die Naturwissenschaften, Vol. 48, Issue 22
Pseudomorphic decomposition of uranium peroxide into UO3
journal, May 1963
- Cordfunke, E. H. P.; Van Der Giessen, A. A.
- Journal of Inorganic and Nuclear Chemistry, Vol. 25, Issue 5
Thermal decomposition of hydrated uranium peroxides
journal, January 1963
- Cordfunke, E. H. P.; Aling, P.
- Recueil des Travaux Chimiques des Pays-Bas, Vol. 82, Issue 3
Effect of temperature on studtite stability: Thermogravimetry and differential scanning calorimetry investigations
journal, March 2009
- Rey, A.; Casas, I.; Giménez, J.
- Journal of Nuclear Materials, Vol. 385, Issue 2
Determination of the equilibrium formation constants of two U(vi)–peroxide complexes at alkaline pH
journal, January 2011
- Meca, S.; Martínez-Torrents, A.; Martí, V.
- Dalton Transactions, Vol. 40, Issue 31
Physical Characterization and Reactivity of the Uranyl Peroxide [UO 2 (η 2 -O 2 )(H 2 O) 2 ]·2H 2 O: Implications for Storage of Spent Nuclear Fuels
journal, July 2012
- Mallon, Colm; Walshe, Aurora; Forster, Robert J.
- Inorganic Chemistry, Vol. 51, Issue 15
Solubility study and point of zero charge of studtite (UO2O2·4H2O)
journal, October 2014
- Giménez, J.; de Pablo, J.; Casas, I.
- Applied Geochemistry, Vol. 49
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Density Functional Analysis of the Trigonal Uranyl Equatorial Coordination in Hexahomotrioxacalix[3]arene-based Macrocyclic Complexes
journal, February 2010
- Weck, Philippe F.; Kim, Eunja; Masci, Bernardo
- Inorganic Chemistry, Vol. 49, Issue 4
One-dimensional uranium–organic coordination polymers: crystal and electronic structures of uranyl-diacetohydroxamate
journal, January 2011
- Weck, Philippe F.; Gong, Cynthia-May S.; Kim, Eunja
- Dalton Transactions, Vol. 40, Issue 22
On the role of strong electron correlations in the surface properties and chemistry of uranium dioxide
journal, January 2013
- Weck, Philippe F.; Kim, Eunja; Jové-Colón, Carlos F.
- Dalton Transactions, Vol. 42, Issue 13
Layered uranium( vi ) hydroxides: structural and thermodynamic properties of dehydrated schoepite α-UO 2 (OH) 2
journal, January 2014
- Weck, Philippe F.; Kim, Eunja
- Dalton Trans., Vol. 43, Issue 45
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
High-precision sampling for Brillouin-zone integration in metals
journal, August 1989
- Methfessel, M.; Paxton, A. T.
- Physical Review B, Vol. 40, Issue 6
Special points for Brillouin-zone integrations
journal, June 1976
- Monkhorst, Hendrik J.; Pack, James D.
- Physical Review B, Vol. 13, Issue 12, p. 5188-5192
Symmetry-general least-squares extraction of elastic data for strained materials from ab initio calculations of stress
journal, February 2002
- Le Page, Yvon; Saxe, Paul
- Physical Review B, Vol. 65, Issue 10
Crystal structures and elastic properties of superhard and from first principles
journal, August 2007
- Wu, Zhi-jian; Zhao, Er-jun; Xiang, Hong-ping
- Physical Review B, Vol. 76, Issue 5
Hashin‐Shtrikman bounds on the effective elastic moduli of polycrystals with monoclinic symmetry
journal, March 1980
- Watt, J. Peter
- Journal of Applied Physics, Vol. 51, Issue 3
Necessary and sufficient elastic stability conditions in various crystal systems
journal, December 2014
- Mouhat, Félix; Coudert, François-Xavier
- Physical Review B, Vol. 90, Issue 22
Theoretical predictions of structure and related properties of intermetallics
journal, April 1992
- Pettifor, D. G.
- Materials Science and Technology, Vol. 8, Issue 4
Berechnung der Fließgrenze von Mischkristallen auf Grund der Plastizitätsbedingung für Einkristalle .
journal, January 1929
- Reuss, A.
- ZAMM - Zeitschrift für Angewandte Mathematik und Mechanik, Vol. 9, Issue 1
The Elastic Behaviour of a Crystalline Aggregate
journal, May 1952
- Hill, R.
- Proceedings of the Physical Society. Section A, Vol. 65, Issue 5
XCII. Relations between the elastic moduli and the plastic properties of polycrystalline pure metals
journal, August 1954
- Pugh, S. F.
- The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, Vol. 45, Issue 367
Universal Elastic Anisotropy Index
journal, August 2008
- Ranganathan, Shivakumar I.; Ostoja-Starzewski, Martin
- Physical Review Letters, Vol. 101, Issue 5
Works referencing / citing this record:
Infrared and Raman spectroscopy of α-ZrW 2 O 8 : A comprehensive density functional perturbation theory and experimental study
journal, May 2018
- Weck, Philippe F.; Gordon, Margaret E.; Greathouse, Jeffery A.
- Journal of Raman Spectroscopy, Vol. 49, Issue 8
Periodic density functional theory study of the Raman spectrum of the hydrated uranyl oxyhydroxide mineral becquerelite
journal, March 2019
- Colmenero, Francisco; Cobos, Joaquín; Timón, Vicente
- Theoretical Chemistry Accounts, Vol. 138, Issue 3
Extreme negative mechanical phenomena in the zinc and cadmium anhydrous metal oxalates and lead oxalate dihydrate
journal, September 2019
- Colmenero, Francisco; Timón, Vicente
- Journal of Materials Science, Vol. 55, Issue 1
Mechanical properties of anhydrous oxalic acid and oxalic acid dihydrate
journal, January 2019
- Colmenero, Francisco
- Physical Chemistry Chemical Physics, Vol. 21, Issue 5
Monitoring bromide effect on radiolytic yields using in situ observations of uranyl oxide precipitation in the electron microscope
journal, January 2018
- Buck, Edgar C.; Wittman, Richard S.; Soderquist, Chuck. Z.
- RSC Advances, Vol. 8, Issue 33
Becquerelite mineral phase: crystal structure and thermodynamic and mechanical stability by using periodic DFT
journal, January 2018
- Colmenero, Francisco; Fernández, Ana María; Timón, Vicente
- RSC Advances, Vol. 8, Issue 43
Crystal structure, hydrogen bonding, mechanical properties and Raman spectrum of the lead uranyl silicate monohydrate mineral kasolite
journal, January 2019
- Colmenero, Francisco; Plášil, Jakub; Cobos, Joaquín
- RSC Advances, Vol. 9, Issue 27
Structural, mechanical, spectroscopic and thermodynamic characterization of the copper-uranyl tetrahydroxide mineral vandenbrandeite
journal, January 2019
- Colmenero, Francisco; Plášil, Jakub; Cobos, Joaquín
- RSC Advances, Vol. 9, Issue 69
Anomalous mechanical behavior of the deltic, squaric and croconic cyclic oxocarbon acids
journal, January 2019
- Colmenero, Francisco
- Materials Research Express, Vol. 6, Issue 4
Combined experimental and first-principles studies of a hydrated uranyl carbonate: Insight into phonon spectra for a core environmental class of uranium materials
journal, March 2020
- Kalashnyk, N.; Perry, D. L.; Ivanov, V. G.
- Journal of Physics and Chemistry of Solids, Vol. 138
First-Principles Structural, Mechanical, and Thermodynamic Calculations of the Negative Thermal Expansion Compound Zr 2 (WO 4 )(PO 4 ) 2
journal, November 2018
- Weck, Philippe F.; Kim, Eunja; Gordon, Margaret E.
- ACS Omega, Vol. 3, Issue 11