Oxygen transport in off-stoichiometric uranium dioxide mediated by defect clustering dynamics

Yu, Jianguo; Bai, Xian -Ming; El-Azab, Anter; Allen, Todd R.

doi:10.1063/1.4914137

Title: Oxygen transport in off-stoichiometric uranium dioxide mediated by defect clustering dynamics

Abstract

In this study, oxygen transport is central to many properties of oxides such as stoichiometric changes, phase transformation and ionic conductivity. In this paper, we report a mechanism for oxygen transport in uranium dioxide (UO₂) in which the kinetics is mediated by defect clustering dynamics. In particular, the kinetic Monte Carlo (KMC) method has been used to investigate the kinetics of oxygen transport in UO₂ under the condition of creation and annihilation of oxygen vacancies and interstitials as well as oxygen interstitial clustering, with variable offstoichiometry and temperature conditions. It is found that in hypo-stoichiometric UO_2-x, oxygen transport is well described by the vacancy diffusion mechanism while in hyper-stoichiometric UO_2+x, oxygen interstitial cluster diffusion contributes significantly to oxygen transport kinetics, particularly at high temperatures and high off-stoichiometry levels. It is also found that diinterstitial clusters and single interstitials play dominant roles in oxygen diffusion while other larger clusters have negligible contributions. However, the formation, coalescence and dissociation of these larger clusters indirectly affects the overall oxygen diffusion due to their interactions with mono and di-interstitials, thus providing a explanation of the experimental observation of saturation or even drop of oxygen diffusivity at high off-stoichiometry.

Authors:

Yu, Jianguo ^[1]; Bai, Xian -Ming ^[1]; El-Azab, Anter ^[2]; Allen, Todd R. ^[3]

Idaho National Lab. (INL), Idaho Falls, ID (United States)
Purdue Univ., West Lafayette, IN (United States)
Idaho National Lab. (INL), Idaho Falls, ID (United States); Univ. of Wisconsin-Madison, Madison, WI (United States)

Publication Date:: Thu Mar 05 00:00:00 EST 2015

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Center for Materials Science of Nuclear Fuel (CMSNF); Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1248176

Alternate Identifier(s):: OSTI ID: 1228119

Report Number(s):: INL/JOU-14-33670
Journal ID: ISSN 0021-9606; JCPSA6

Grant/Contract Number:: AC07-05ID14517

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 142; Journal Issue: 9; Journal ID: ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

Subject:: 11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; uranium dioxide; oxygen transport; kinetic Monte Carlo; diffusion; interstitial defects; vacancies; Monte Carlo methods; cluster analysis

Citation Formats


                    Yu, Jianguo, Bai, Xian -Ming, El-Azab, Anter, and Allen, Todd R. Oxygen transport in off-stoichiometric uranium dioxide mediated by defect clustering dynamics.  United States: N. p., 2015. 
Web.  doi:10.1063/1.4914137.

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                    Yu, Jianguo, Bai, Xian -Ming, El-Azab, Anter, & Allen, Todd R. Oxygen transport in off-stoichiometric uranium dioxide mediated by defect clustering dynamics.  United States.  https://doi.org/10.1063/1.4914137

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                    Yu, Jianguo, Bai, Xian -Ming, El-Azab, Anter, and Allen, Todd R. Thu .  
"Oxygen transport in off-stoichiometric uranium dioxide mediated by defect clustering dynamics".  United States.  https://doi.org/10.1063/1.4914137.  https://www.osti.gov/servlets/purl/1248176.

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@article{osti_1248176,

  title        = {Oxygen transport in off-stoichiometric uranium dioxide mediated by defect clustering dynamics},

  author       = {Yu, Jianguo and Bai, Xian -Ming and El-Azab, Anter and Allen, Todd R.},

  abstractNote = {In this study, oxygen transport is central to many properties of oxides such as stoichiometric changes, phase transformation and ionic conductivity. In this paper, we report a mechanism for oxygen transport in uranium dioxide (UO2) in which the kinetics is mediated by defect clustering dynamics. In particular, the kinetic Monte Carlo (KMC) method has been used to investigate the kinetics of oxygen transport in UO2 under the condition of creation and annihilation of oxygen vacancies and interstitials as well as oxygen interstitial clustering, with variable offstoichiometry and temperature conditions. It is found that in hypo-stoichiometric UO2-x, oxygen transport is well described by the vacancy diffusion mechanism while in hyper-stoichiometric UO2+x, oxygen interstitial cluster diffusion contributes significantly to oxygen transport kinetics, particularly at high temperatures and high off-stoichiometry levels. It is also found that diinterstitial clusters and single interstitials play dominant roles in oxygen diffusion while other larger clusters have negligible contributions. However, the formation, coalescence and dissociation of these larger clusters indirectly affects the overall oxygen diffusion due to their interactions with mono and di-interstitials, thus providing a explanation of the experimental observation of saturation or even drop of oxygen diffusivity at high off-stoichiometry.},

  doi          = {10.1063/1.4914137},

  journal      = {Journal of Chemical Physics},

  number       = 9,

  volume       = 142,

  place        = {United States},

  year         = {Thu Mar 05 00:00:00 EST 2015},

  month        = {Thu Mar 05 00:00:00 EST 2015}

}

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Title: Oxygen transport in off-stoichiometric uranium dioxide mediated by defect clustering dynamics

Abstract

Citation Formats

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Kinetics of precipitation of U4O9 from hyperstoichiometric UO2+x journal, July 2007

Crystallographic studies of anion-excess uranium oxides journal, January 1987

Local Structure and Charge Distribution in the UO 2 −U 4 O 9 System journal, November 2004

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A review of kinetic data on the rate of U3O7 formation on UO2 journal, June 1997

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Oxygen and uranium diffusion in uranium dioxide (a review) journal, April 1969

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Atomic transport properties in UO2 and mixed oxides (U, Pu)O2 journal, January 1987

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Oxygen self-diffusion in non-stoichiometric uranium dioxide journal, December 1975

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Kinetic Monte Carlo Study of Ambipolar Lithium Ion and Electron–Polaron Diffusion into Nanostructured TiO 2 journal, July 2012

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The solubility of uranium in urania journal, January 1968

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Comparison of interatomic potentials for UO2. Part I: Static calculations journal, June 2007

Kinetics of Materials
book, September 2005

Kinetics of precipitation of U4O9 from hyperstoichiometric UO2+x
journal, July 2007

Crystallographic studies of anion-excess uranium oxides
journal, January 1987

Local Structure and Charge Distribution in the UO ₂ −U ₄ O ₉ System
journal, November 2004

Neutron Diffraction Study of the in Situ Oxidation of UO ₂
journal, August 2009

A review of kinetic data on the rate of U3O7 formation on UO2
journal, June 1997

Thermal conductivity of hyperstoichiometric SIMFUEL
journal, May 1995

Thermal Transport in Off-Stoichiometric Uranium Dioxide by Atomic Level Simulation
journal, April 2009

Kinetic Study of the Oxidation of Uranium Dioxide
journal, July 1957

Oxygen diffusion in UO2−x
journal, November 1981

Oxygen and uranium diffusion in uranium dioxide (a review)
journal, April 1969

Autodiffusion de l'oxygene dans le dioxyde d'uranium surstoechiometrique
journal, January 1972

Uranium and oxygen self-diffusion in UO2
journal, April 1969

Atomic transport properties in UO2 and mixed oxides (U, Pu)O2
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Oxygen diffusion in UO2, ThO2 and PuO2. A review
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Oxygen self-diffusion in non-stoichiometric uranium dioxide
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Migration mechanisms of oxygen interstitial clusters in UO ₂
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Temperature accelerated dynamics study of migration process of oxygen defects in UO2
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Computer simulation of defects formation and equilibrium in non-stoichiometric uranium dioxide
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Solving the Puzzle of $⟨ 100 ⟩$ Interstitial Loop Formation in bcc Iron
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Assessment of structures and stabilities of defect clusters and surface energies predicted by nine interatomic potentials for UO2
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