The defect chemistry of UO2±x from atomistic simulations

Cooper, Michael William Donald; Murphy, Samuel T; Andersson, Anders David Ragnar

doi:10.1016/j.jnucmat.2018.02.034

Title: The defect chemistry of $U O_{2 \pm x}$ from atomistic simulations

Abstract

Control of the defect chemistry in UO_2±x is important for manipulating nuclear fuel properties and fuel performance. For example, the uranium vacancy concentration is critical for fission gas release and sintering, while all oxygen and uranium defects are known to strongly influence thermal conductivity. Here the point defect concentrations in thermal equilibrium are predicted using defect energies from density functional theory (DFT) and vibrational entropies calculated using empirical potentials. Electrons and holes have been treated in a similar fashion to other charged defects allowing for structural relaxation around the localized electronic defects. Predictions are made for the defect concentrations and non-stoichiometry of UO_2±x as a function of oxygen partial pressure and temperature. If vibrational entropy is omitted, oxygen interstitials are predicted to be the dominant mechanism of excess oxygen accommodation over only a small temperature range (1265 K to 1350 K), in contrast to experimental observation. Conversely, if vibrational entropy is included oxygen interstitials dominate from 1165 K to 1680 K (Busker potential) or from 1275 K to 1630 K (CRG potential). Below these temperature ranges excess oxygen is predicted to be accommodated by uranium vacancies, while above them the system is hypo-stoichiometric with oxygen deficiency accommodated by oxygen vacancies.more »« less

Authors:

^[1]; Murphy, Samuel T ^[2];

^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Lancaster Univ. (United Kingdom). Dept. of Engineering

Publication Date:: Fri Jun 01 00:00:00 EDT 2018

Research Org.:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Org.:: USDOE Office of Nuclear Energy (NE); USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1524370

Alternate Identifier(s):: OSTI ID: 1550712

Report Number(s):: LA-UR-17-29135
Journal ID: ISSN 0022-3115

Grant/Contract Number:: 89233218CNA000001; AC52-06NA25396

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Nuclear Materials

Additional Journal Information:: Journal Volume: 504; Journal Issue: C; Journal ID: ISSN 0022-3115

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Citation Formats


                    Cooper, Michael William Donald, Murphy, Samuel T, and Andersson, Anders David Ragnar. The defect chemistry of UO2±x from atomistic simulations.  United States: N. p., 2018. 
Web.  doi:10.1016/j.jnucmat.2018.02.034.

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                    Cooper, Michael William Donald, Murphy, Samuel T, & Andersson, Anders David Ragnar. The defect chemistry of UO2±x from atomistic simulations.  United States.  https://doi.org/10.1016/j.jnucmat.2018.02.034

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                    Cooper, Michael William Donald, Murphy, Samuel T, and Andersson, Anders David Ragnar. Fri .  
"The defect chemistry of UO2±x from atomistic simulations".  United States.  https://doi.org/10.1016/j.jnucmat.2018.02.034.  https://www.osti.gov/servlets/purl/1524370.

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@article{osti_1524370,

  title        = {The defect chemistry of UO2±x from atomistic simulations},

  author       = {Cooper, Michael William Donald and Murphy, Samuel T and Andersson, Anders David Ragnar},

  abstractNote = {Control of the defect chemistry in UO2±x is important for manipulating nuclear fuel properties and fuel performance. For example, the uranium vacancy concentration is critical for fission gas release and sintering, while all oxygen and uranium defects are known to strongly influence thermal conductivity. Here the point defect concentrations in thermal equilibrium are predicted using defect energies from density functional theory (DFT) and vibrational entropies calculated using empirical potentials. Electrons and holes have been treated in a similar fashion to other charged defects allowing for structural relaxation around the localized electronic defects. Predictions are made for the defect concentrations and non-stoichiometry of UO2±x as a function of oxygen partial pressure and temperature. If vibrational entropy is omitted, oxygen interstitials are predicted to be the dominant mechanism of excess oxygen accommodation over only a small temperature range (1265 K to 1350 K), in contrast to experimental observation. Conversely, if vibrational entropy is included oxygen interstitials dominate from 1165 K to 1680 K (Busker potential) or from 1275 K to 1630 K (CRG potential). Below these temperature ranges excess oxygen is predicted to be accommodated by uranium vacancies, while above them the system is hypo-stoichiometric with oxygen deficiency accommodated by oxygen vacancies. Our results are discussed in the context of oxygen clustering, formation of U4O9, and issues for fuel behavior. In particular, the variation of the uranium vacancy concentrations as a function of temperature and oxygen partial pressure will underpin future studies into fission gas diffusivity and broaden the understanding of UO2±x sintering.},

  doi          = {10.1016/j.jnucmat.2018.02.034},

  journal      = {Journal of Nuclear Materials},

  number       = C,

  volume       = 504,

  place        = {United States},

  year         = {Fri Jun 01 00:00:00 EDT 2018},

  month        = {Fri Jun 01 00:00:00 EDT 2018}

}

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Figure 1: U-O phase diagram taken from Ref. [75] with experimental data [7, 15, 17, 18, 21, 23, 76–81] shown by points.

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Journal Article Rittman, Dylan R. ; Tracy, Cameron L. ; Chen, Chien-Hung ; ... - Physical Review B

Ultrafast laser irradiation causes intense electronic excitations in materials, leading to transient high temperatures and pressures. Here, we show that ultrafast laser irradiation drives an irreversible cubic-to-monoclinic phase transformation in Ln₂O₃ ( Ln = Er – Lu ) , and explore the mechanism by which the phase transformation occurs. A combination of grazing incidence x-ray diffraction and transmission electron microscopy are used to determine the magnitude and depth-dependence of the phase transformation, respectively. Although all compositions undergo the same transformation, their transformation mechanisms differ. The transformation is pressure-driven for Ln = Tm – Lu , consistent with the material's phasemore »« less
Cited by 3
https://doi.org/10.1103/physrevb.97.024104

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Role of point defects in the electrical and optical properties of ${In}_{2} O_{3}$

Journal Article Chatratin, Intuon ; Sabino, Fernando P. ; Reunchan, Pakpoom ; ... - Physical Review Materials

Using hybrid density-functional calculations we investigate the effects of native point defects on the electrical and optical properties of In₂O₃. We analyze formation energies, transition levels, and local lattice relaxations for all native point defects. We find that donor defects are in general more energetically favorable than acceptor defects, except near O-rich conditions, where oxygen interstitials and indium vacancies have low formation energy in n-type In₂O₃. The oxygen vacancy is the lowest-energy donor defect with transition level (2+/+) slightly below and (+/0) slightly above the conduction-band minimum (CBM), with a predicted luminescence peak at 2.3 eV associated with the transitionmore »« less
Cited by 33
https://doi.org/10.1103/PhysRevMaterials.3.074604

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Predicting Thermochemical Equilibria with Interacting Defects: ${Sr}_{1 - x} {Ce}_{x} {Mn O}_{3 - δ}$ Alloys for Water Splitting

Journal Article Goyal, Anuj ; Sanders, Michael D. ; O’Hayre, Ryan P. ; ... - PRX Energy

Solar thermochemical hydrogen is one of the few potential routes towards direct fuel production from renewable energy sources, but the thermodynamic boundary conditions for efficient and economic energy conversion are challenging. Success or failure of a given oxide working material depends on the subtle balance between enthalpy and entropy contributions in the redox processes. Developing a mechanistic understanding of the behavior of materials on the basis of atomistic models and first-principles calculations is an important part of advancing the technology. One challenge is to quantitatively predict thermochemical equilibria at high concentrations when the redox-active defects start to interact with eachmore »« less
https://doi.org/10.1103/PRXEnergy.3.013008

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Title: The defect chemistry of U O 2 ± x from atomistic simulations

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Figures / Tables:

A comparison of the behaviour of fission gases in UO2±x and α-U3O8−z journal, June 1992

U and Xe transport in UO 2 ± x : Density functional theory calculations journal, August 2011

Molecular Dynamics Simulation of Thermal Transport in UO 2 Containing Uranium, Oxygen, and Fission-product Defects journal, October 2016

Relations between the Concentrations of Imperfections in Crystalline Solids book, January 1956

The low temperature oxidation of UO2 and U4O9 journal, March 1961

Metallographic determination of the UO2-U409 phase diagram journal, June 1960

System UO3+ U3O8: dissociation pressure of ?-UO3 journal, January 1965

High‐Temperature Thermodynamic Properties of Oxygen‐Deficient Urania journal, December 1968

Thermodynamic study of hypostoichiometric urania journal, June 1972

Étude thermodynamique des oxydes UO 2+x journal, January 1965

N° 57. — Détermination des limites de phases du système U —O par « transfert d’oxygène ». — Diagramme de phase pour la région 2,19 < O/U < 2,63 et 1080 < 0 °C < 1200 journal, January 1968

Equilibrium oxygen pressures over the nonstoicheiometric uranium oxides UO2+x and U3O8−z at higher temperatures journal, December 1966

Oxygen Dissociation Pressures over Uranium Oxides journal, August 1958

Equilibrium pressures and phase relations in the uranium oxide system journal, December 1961

Nonstoichiometry in uranium dioxide journal, May 1974

High-Temperature Electrochemical Study of Uranium Oxides in the UO2-U3O8 Region. journal, January 1962

Thermodynamic study of UO2 +x by solid state emf technique journal, June 1987

The defect structure of hyper-stoichiometric uranium dioxide journal, January 1978

First-principles DFT + U modeling of actinide-based alloys: Application to paramagnetic phases of UO 2 and (U,Pu) mixed oxides journal, May 2013

First-principles calculations of uranium diffusion in uranium dioxide journal, July 2012

First-principles study of noble gas impurities and defects in UO 2 journal, October 2011

Role of di-interstitial clusters in oxygen transport in UO 2 + x from first principles journal, August 2009

First-Principles Calculation of Point Defects in Uranium Dioxide journal, January 2006

First-principles study with charge effects of the incorporation of iodine in UO2 journal, October 2012

Erratum: DFT + U investigation of charged point defects and clusters in UO 2 (2014 J. Phys.: Condens. Matter 26 325501) journal, August 2014

Stability of oxygen point defects in UO 2 by first-principles DFT + U calculations: Occupation matrix control and Jahn-Teller distortion journal, July 2010

Plane-wave pseudopotential study of point defects in uranium dioxide journal, August 2001

Charge states of point defects in uranium oxide calculated with a local hybrid functional for correlated electrons journal, May 2011

First-principles study of defects and phase transition in UO 2 journal, October 2009

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

Thermophysical properties and oxygen transport in the (U ,Pu1−)O2 lattice journal, June 2015

Vacancy mediated cation migration in uranium dioxide: The influence of cluster configuration journal, November 2014

Determination of Krypton Diffusion Coefficients in Uranium Dioxide Using Atomic Scale Calculations journal, December 2016

Point defects and non-stoichiometry in thoria journal, December 2014

Ab initio molecular dynamics for open-shell transition metals journal, November 1993

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal, October 1996

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal, July 1996

Projector augmented-wave method journal, December 1994

From ultrasoft pseudopotentials to the projector augmented-wave method journal, January 1999

Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators journal, August 1995

Effect of Mott-Hubbard correlations on the electronic structure and structural stability of uranium dioxide journal, May 1997

Method for locating low-energy solutions within DFT + U journal, November 2010

DFT + U calculations of the ground state and metastable states of uranium dioxide journal, June 2009

Magnetism of actinide compounds journal, September 1999

Special points for Brillouin-zone integrations journal, June 1976

Accurate prediction of defect properties in density functional supercell calculations journal, November 2009

Anisotropic charge screening and supercell size convergence of defect formation energies journal, March 2013

Dielectric Constant of UO 2 at 9.4 GHz journal, November 1969

Understanding and correcting the spurious interactions in charged supercells journal, August 2011

GULP: A computer program for the symmetry-adapted simulation of solids journal, January 1997

Solution Mechanisms for Dopant Oxides in Yttria journal, June 1999

A many-body potential approach to modelling the thermomechanical properties of actinide oxides journal, February 2014

The Crystal Dynamics of Uranium Dioxide journal, August 1965

Thermophysical properties of uranium dioxide journal, March 2000

THE OXIDATION OF NIAL: What Can We Learn from Ab Initio Calculations? journal, August 2005

Point Defects and Non-stoichiometry in Li 2 TiO 3 journal, February 2014

Effect of stoichiometry on diffusion of xenon in UO2 journal, March 1972

Density Functional Theory Calculations of UO 2 Oxidation: Evolution of UO 2+ x , U 4 O 9– y , U 3 O 7 , and U 3 O 8 journal, February 2013

Computer simulation of defect clusters in UO2 and their dependence on composition journal, January 2015

Accommodation of excess oxygen in fluorite dioxides journal, December 2013

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

Les equilibres des composes oxygenes de l'uranium entre 1500 ET 2000° K journal, September 1963

On the phase limits of U4O9 journal, December 1970

X-ray study on a phase transition and a phase diagram in the U4O9 phase journal, May 1970

High-temperature X-ray study of uranium oxides in the UO2U3O8 region journal, December 1955

Electronic transitions, crystal field effects and phonons in UO2 journal, August 1980

Optical properties and electronic structure of UO 2 journal, March 1978

Atomistic description of self-diffusion in molybdenum: A comparative theoretical study of non-Arrhenius behavior journal, January 2020

Nanoscale oxygen defect gradients in UO 2+ x surfaces journal, August 2019

Title: The defect chemistry of $U O_{2 \pm x}$ from atomistic simulations

A comparison of the behaviour of fission gases in UO2±x and α-U3O8−z
journal, June 1992

U and Xe transport in UO $_{2 \pm x}$ : Density functional theory calculations
journal, August 2011

Molecular Dynamics Simulation of Thermal Transport in ${UO}_{2}$ Containing Uranium, Oxygen, and Fission-product Defects
journal, October 2016

Relations between the Concentrations of Imperfections in Crystalline Solids
book, January 1956

The low temperature oxidation of UO2 and U4O9
journal, March 1961

Metallographic determination of the UO2-U409 phase diagram
journal, June 1960

System UO3+ U3O8: dissociation pressure of ?-UO3
journal, January 1965

High‐Temperature Thermodynamic Properties of Oxygen‐Deficient Urania
journal, December 1968

Thermodynamic study of hypostoichiometric urania
journal, June 1972

Étude thermodynamique des oxydes UO _2+x
journal, January 1965

N° 57. — Détermination des limites de phases du système U —O par « transfert d’oxygène ». — Diagramme de phase pour la région 2,19 < O/U < 2,63 et 1080 < 0 °C < 1200
journal, January 1968

Equilibrium oxygen pressures over the nonstoicheiometric uranium oxides UO2+x and U3O8−z at higher temperatures
journal, December 1966

Oxygen Dissociation Pressures over Uranium Oxides
journal, August 1958

Equilibrium pressures and phase relations in the uranium oxide system
journal, December 1961

Nonstoichiometry in uranium dioxide
journal, May 1974

High-Temperature Electrochemical Study of Uranium Oxides in the UO2-U3O8 Region.
journal, January 1962

Thermodynamic study of UO2 +x by solid state emf technique
journal, June 1987

The defect structure of hyper-stoichiometric uranium dioxide
journal, January 1978

First-principles DFT $+ U$ modeling of actinide-based alloys: Application to paramagnetic phases of UO $_{2}$ and (U,Pu) mixed oxides
journal, May 2013

First-principles calculations of uranium diffusion in uranium dioxide
journal, July 2012

First-principles study of noble gas impurities and defects in UO $_{2}$
journal, October 2011

Role of di-interstitial clusters in oxygen transport in ${UO}_{2 + x}$ from first principles
journal, August 2009

First-Principles Calculation of Point Defects in Uranium Dioxide
journal, January 2006

First-principles study with charge effects of the incorporation of iodine in UO2
journal, October 2012

Erratum: DFT + U investigation of charged point defects and clusters in UO ₂ (2014 J. Phys.: Condens. Matter 26 325501)
journal, August 2014

Stability of oxygen point defects in ${UO}_{2}$ by first-principles $DFT + U$ calculations: Occupation matrix control and Jahn-Teller distortion
journal, July 2010

Plane-wave pseudopotential study of point defects in uranium dioxide
journal, August 2001

Charge states of point defects in uranium oxide calculated with a local hybrid functional for correlated electrons
journal, May 2011

First-principles study of defects and phase transition in UO ₂
journal, October 2009

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

Thermophysical properties and oxygen transport in the (U ,Pu1−)O2 lattice
journal, June 2015

Vacancy mediated cation migration in uranium dioxide: The influence of cluster configuration
journal, November 2014

Determination of Krypton Diffusion Coefficients in Uranium Dioxide Using Atomic Scale Calculations
journal, December 2016

Point defects and non-stoichiometry in thoria
journal, December 2014

Ab initio molecular dynamics for open-shell transition metals
journal, November 1993

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Projector augmented-wave method
journal, December 1994

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators
journal, August 1995

Effect of Mott-Hubbard correlations on the electronic structure and structural stability of uranium dioxide
journal, May 1997

Method for locating low-energy solutions within $DFT + U$
journal, November 2010

$DFT + U$ calculations of the ground state and metastable states of uranium dioxide
journal, June 2009

Magnetism of actinide compounds
journal, September 1999

Special points for Brillouin-zone integrations
journal, June 1976

Accurate prediction of defect properties in density functional supercell calculations
journal, November 2009

Anisotropic charge screening and supercell size convergence of defect formation energies
journal, March 2013

Dielectric Constant of UO ₂ at 9.4 GHz
journal, November 1969

Understanding and correcting the spurious interactions in charged supercells
journal, August 2011

GULP: A computer program for the symmetry-adapted simulation of solids
journal, January 1997

Solution Mechanisms for Dopant Oxides in Yttria
journal, June 1999

A many-body potential approach to modelling the thermomechanical properties of actinide oxides
journal, February 2014

The Crystal Dynamics of Uranium Dioxide
journal, August 1965

Thermophysical properties of uranium dioxide
journal, March 2000

THE OXIDATION OF NIAL: What Can We Learn from Ab Initio Calculations?
journal, August 2005

Point Defects and Non-stoichiometry in Li ₂ TiO ₃
journal, February 2014

Effect of stoichiometry on diffusion of xenon in UO2
journal, March 1972

Density Functional Theory Calculations of UO ₂ Oxidation: Evolution of UO _{2+ x} , U ₄ O _{9– y} , U ₃ O ₇ , and U ₃ O ₈
journal, February 2013

Computer simulation of defect clusters in UO2 and their dependence on composition
journal, January 2015

Accommodation of excess oxygen in fluorite dioxides
journal, December 2013

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

Les equilibres des composes oxygenes de l'uranium entre 1500 ET 2000° K
journal, September 1963

On the phase limits of U4O9
journal, December 1970

X-ray study on a phase transition and a phase diagram in the U4O9 phase
journal, May 1970

High-temperature X-ray study of uranium oxides in the UO2U3O8 region
journal, December 1955

Electronic transitions, crystal field effects and phonons in UO2
journal, August 1980

Optical properties and electronic structure of UO ₂
journal, March 1978

Atomistic description of self-diffusion in molybdenum: A comparative theoretical study of non-Arrhenius behavior
journal, January 2020

Nanoscale oxygen defect gradients in UO _{2+ x} surfaces
journal, August 2019