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Title: Impact of anharmonicity on the vibrational entropy and specific heat of UO 2

Abstract

The impact of anharmonicity on the vibrational entropy and heat capacity of UO2 has been investigated from 10 K to 1200 K using inelastic neutron scattering measurements of the phonon density of states (PDOS). Small changes in the PDOS are observed from 10 K to 295 K, with more noticeable changes appearing in the 750 K and 1200 K data. The specific heat determined from the PDOS measurements is in agreement with macroscopic specific heat measurements and the overall impact of non-dilation anharmonicity on the specific heat has been shown to be less than 2 percent. An analysis of the phonon measurements shows that the softening of acoustic phonons with temperature is consistent with the quasiharmonic approximation. The optical phonons deviate from the quasiharmonic prediction, with the low energy optical phonons between approximately 20-50 meV softening more than expected, while the higher energy optical phonons between approximately 50-80 meV have no appreciable softening over the temperature range measured. The observation of a small anharmonic specific heat contribution has been shown to be the result of relatively large energy dependent anharmonic effects which have opposite sign, leading to a total contribution near zero.

Authors:
 [1];  [1];  [1];  [2]; ORCiD logo [1];  [3]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Missouri Univ. of Science and Technology, Rolla, MO (United States)
  3. Idaho National Lab. (INL), Idaho Falls, ID (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Idaho National Lab. (INL), Idaho Falls, ID (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1530058
Alternate Identifier(s):
OSTI ID: 1546418; OSTI ID: 1558431
Report Number(s):
INL/JOU-19-54373-Rev000
Journal ID: ISSN 2475-9953; PRMHAR
Grant/Contract Number:  
AC05-00OR22725; AC07-05ID14517
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 3; Journal Issue: 6; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 36 MATERIALS SCIENCE; Specific Heat

Citation Formats

Bryan, M. S., Pang, J. W. L., Larson, B. C., Chernatynskiy, A., Abernathy, D. L., Gofryk, K., and Manley, M. E. Impact of anharmonicity on the vibrational entropy and specific heat of UO2. United States: N. p., 2019. Web. doi:10.1103/PhysRevMaterials.3.065405.
Bryan, M. S., Pang, J. W. L., Larson, B. C., Chernatynskiy, A., Abernathy, D. L., Gofryk, K., & Manley, M. E. Impact of anharmonicity on the vibrational entropy and specific heat of UO2. United States. doi:10.1103/PhysRevMaterials.3.065405.
Bryan, M. S., Pang, J. W. L., Larson, B. C., Chernatynskiy, A., Abernathy, D. L., Gofryk, K., and Manley, M. E. Fri . "Impact of anharmonicity on the vibrational entropy and specific heat of UO2". United States. doi:10.1103/PhysRevMaterials.3.065405. https://www.osti.gov/servlets/purl/1530058.
@article{osti_1530058,
title = {Impact of anharmonicity on the vibrational entropy and specific heat of UO2},
author = {Bryan, M. S. and Pang, J. W. L. and Larson, B. C. and Chernatynskiy, A. and Abernathy, D. L. and Gofryk, K. and Manley, M. E.},
abstractNote = {The impact of anharmonicity on the vibrational entropy and heat capacity of UO2 has been investigated from 10 K to 1200 K using inelastic neutron scattering measurements of the phonon density of states (PDOS). Small changes in the PDOS are observed from 10 K to 295 K, with more noticeable changes appearing in the 750 K and 1200 K data. The specific heat determined from the PDOS measurements is in agreement with macroscopic specific heat measurements and the overall impact of non-dilation anharmonicity on the specific heat has been shown to be less than 2 percent. An analysis of the phonon measurements shows that the softening of acoustic phonons with temperature is consistent with the quasiharmonic approximation. The optical phonons deviate from the quasiharmonic prediction, with the low energy optical phonons between approximately 20-50 meV softening more than expected, while the higher energy optical phonons between approximately 50-80 meV have no appreciable softening over the temperature range measured. The observation of a small anharmonic specific heat contribution has been shown to be the result of relatively large energy dependent anharmonic effects which have opposite sign, leading to a total contribution near zero.},
doi = {10.1103/PhysRevMaterials.3.065405},
journal = {Physical Review Materials},
number = 6,
volume = 3,
place = {United States},
year = {2019},
month = {6}
}

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Cited by: 2 works
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Works referenced in this record:

Phonon Lifetime Investigation of Anharmonicity and Thermal Conductivity of UO 2 by Neutron Scattering and Theory
journal, April 2013


Origin of Low Thermal Conductivity in Nuclear Fuels
journal, June 2008


Thermodynamic properties of uranium dioxide: A study of the experimental enthalpy and specific heat
journal, June 1981


Anharmonic specific heat of solid UO2
journal, January 1981


The Crystal Dynamics of Uranium Dioxide
journal, August 1965

  • Dolling, G.; Cowley, R. A.; Woods, A. D. B.
  • Canadian Journal of Physics, Vol. 43, Issue 8
  • DOI: 10.1139/p65-135

Enthalpy and heat capacity of the actinide oxides
journal, June 1982

  • Fink, J. K.
  • International Journal of Thermophysics, Vol. 3, Issue 2
  • DOI: 10.1007/BF00503638

Re-analysis of single-crystal neutron-diffraction data on UO2 using third cumulants
journal, July 1980

  • Willis, B. T. M.; Hazell, R. G.
  • Acta Crystallographica Section A: Crystal Physics, Diffraction, Theoretical and General Crystallography, Vol. 36, Issue 4
  • DOI: 10.1107/S0567739480001246

Phonon density of states and anharmonicity of UO 2
journal, March 2014

  • Pang, Judy W. L.; Chernatynskiy, Aleksandr; Larson, Bennett C.
  • Physical Review B, Vol. 89, Issue 11
  • DOI: 10.1103/PhysRevB.89.115132

The lattice dynamics of an anharmonic crystal
journal, October 1963


Anharmonic contributions to vibrational thermodynamic properties of solids
journal, September 1961


Thermodynamics of the UO2+x phase I. Heat capacities of UO2.017 and UO2.254 from 300 to 1000 K and electronic contributions
journal, September 1970

  • Grønvold, Fredrik; Kveseth, Nils Jørgen; Sveen, Arvid
  • The Journal of Chemical Thermodynamics, Vol. 2, Issue 5
  • DOI: 10.1016/0021-9614(70)90042-X

The magnetic transition, heat capacity, and thermodynamic properties of uranium dioxide from 5 to 350 K
journal, January 1971


Design and operation of the wide angular-range chopper spectrometer ARCS at the Spallation Neutron Source
journal, January 2012

  • Abernathy, D. L.; Stone, M. B.; Loguillo, M. J.
  • Review of Scientific Instruments, Vol. 83, Issue 1
  • DOI: 10.1063/1.3680104

A radial collimator for a time-of-flight neutron spectrometer
journal, August 2014

  • Stone, M. B.; Niedziela, J. L.; Loguillo, M. J.
  • Review of Scientific Instruments, Vol. 85, Issue 8
  • DOI: 10.1063/1.4891302

Neutron magnetic form factors of uranium ions
journal, February 1976


Magnetic moment distribution in uranium monosulphide
journal, September 1972


Neutron diffraction study of U O 2 : Antiferromagnetic state
journal, August 1976


Magnetic Excitations in Uranium Dioxide
journal, March 1968


Multipolar, magnetic, and vibrational lattice dynamics in the low-temperature phase of uranium dioxide
journal, September 2011


Magnetic excitations and dynamical Jahn-Teller distortions in UO 2
journal, June 1999


Multiphonon: Phonon Density of States tools for Inelastic Neutron Scattering Powder Data
journal, January 2018

  • Y. Y. Lin, Jiao; Islam, Fahima; Kresh, Max
  • The Journal of Open Source Software, Vol. 3, Issue 21
  • DOI: 10.21105/joss.00440

Neutron scattering lengths and cross sections
journal, January 1992


Evaluation of thermal properties of UO2 and PuO2 by equilibrium molecular dynamics simulations from 300 to 2000K
journal, September 2005


Fast ion diffusion, superionic conductivity and phase transitions of the nuclear materials UO 2 and Li 2 O
journal, September 2007


Quadrupolar Waves in Uranium Dioxide
journal, October 2010


The Spin-Wave Dispersion Relations and the Spin-Wave Contribution to the Specific Heat of Antiferromagnetic UO2
journal, January 1969


Thermophysical properties of uranium dioxide
journal, March 2000


Specific heat of uranium dioxide (UO2) between 0.3 and 50 K
journal, January 1983


Magnon Contribution to the Low-Temperature Specific Heat of UO2
journal, January 1967


5 f -electron states in uranium dioxide investigated using high-resolution neutron spectroscopy
journal, July 1989


Oxidation and crystal field effects in uranium
journal, July 2015


Crystal-field transitions in f -electron oxides
journal, September 1985


Heat capacity measurement of U1−yGdyO2 (0.00 ≦ y ≦ 0.142) from 310 to 1500 K
journal, August 1987


Heat Capacity Measurements of U 1-y Gd y O 2 (y=0–0.27)from 325 to 1,673 K
journal, February 2004


Quadrupole Polarization in Simulations of Ionic Systems:  Application to AgCl
journal, January 1996

  • Wilson, Mark; Madden, Paul A.; Costa-Cabral, Benedito J.
  • The Journal of Physical Chemistry, Vol. 100, Issue 4
  • DOI: 10.1021/jp9512319

Anisotropic multipolar exchange interactions in systems with strong spin-orbit coupling
journal, July 2014


Calculation of Multipolar Exchange Interactions in Spin-Orbital Coupled Systems
journal, February 2014


Heat capacity anomaly in UO2 in the vicinity of 1300K: an improved description based on high resolution X-ray and neutron powder diffraction studies
journal, May 2005

  • Ruello, P.; Desgranges, L.; Baldinozzi, G.
  • Journal of Physics and Chemistry of Solids, Vol. 66, Issue 5
  • DOI: 10.1016/j.jpcs.2004.10.009

High-temperature studies of UO2 and ThO2 using neutron scattering techniques
journal, January 1987

  • Hutchings, Michael T.
  • Journal of the Chemical Society, Faraday Transactions 2, Vol. 83, Issue 7
  • DOI: 10.1039/f29878301083

Analysis of recent measurements of the heat capacity of uranium dioxide
journal, October 1994


Anharmonic contributions to vibrational thermodynamic properties of solids
journal, September 1961


Anharmonic contributions to vibrational thermodynamic properties of solids
journal, May 1963


    Works referencing / citing this record:

    Specific heat of uranium dioxide (UO2) between 0.3 and 50 K
    journal, January 1983


    Magnon Contribution to the Low-Temperature Specific Heat of UO2
    journal, January 1967


    The Spin-Wave Dispersion Relations and the Spin-Wave Contribution to the Specific Heat of Antiferromagnetic UO2
    journal, January 1969


    Enthalpy and heat capacity of the actinide oxides
    journal, June 1982

    • Fink, J. K.
    • International Journal of Thermophysics, Vol. 3, Issue 2
    • DOI: 10.1007/bf00503638

    Anharmonic contributions to vibrational thermodynamic properties of solids
    journal, September 1961


    Thermodynamics of the UO2+x phase I. Heat capacities of UO2.017 and UO2.254 from 300 to 1000 K and electronic contributions
    journal, September 1970

    • Grønvold, Fredrik; Kveseth, Nils Jørgen; Sveen, Arvid
    • The Journal of Chemical Thermodynamics, Vol. 2, Issue 5
    • DOI: 10.1016/0021-9614(70)90042-x

    Thermodynamic properties of uranium dioxide: A study of the experimental enthalpy and specific heat
    journal, June 1981


    Anharmonic specific heat of solid UO2
    journal, January 1981


    Heat capacity measurement of U1−yGdyO2 (0.00 ≦ y ≦ 0.142) from 310 to 1500 K
    journal, August 1987


    Analysis of recent measurements of the heat capacity of uranium dioxide
    journal, October 1994


    Evaluation of thermal properties of UO2 and PuO2 by equilibrium molecular dynamics simulations from 300 to 2000K
    journal, September 2005


    Heat capacity anomaly in UO2 in the vicinity of 1300K: an improved description based on high resolution X-ray and neutron powder diffraction studies
    journal, May 2005

    • Ruello, P.; Desgranges, L.; Baldinozzi, G.
    • Journal of Physics and Chemistry of Solids, Vol. 66, Issue 5
    • DOI: 10.1016/j.jpcs.2004.10.009

    The magnetic transition, heat capacity, and thermodynamic properties of uranium dioxide from 5 to 350 K
    journal, January 1971


    Thermophysical properties of uranium dioxide
    journal, March 2000


    Quadrupole Polarization in Simulations of Ionic Systems:  Application to AgCl
    journal, January 1996

    • Wilson, Mark; Madden, Paul A.; Costa-Cabral, Benedito J.
    • The Journal of Physical Chemistry, Vol. 100, Issue 4
    • DOI: 10.1021/jp9512319

    High-temperature studies of UO2 and ThO2 using neutron scattering techniques
    journal, January 1987

    • Hutchings, Michael T.
    • Journal of the Chemical Society, Faraday Transactions 2, Vol. 83, Issue 7
    • DOI: 10.1039/f29878301083

    Design and operation of the wide angular-range chopper spectrometer ARCS at the Spallation Neutron Source
    journal, January 2012

    • Abernathy, D. L.; Stone, M. B.; Loguillo, M. J.
    • Review of Scientific Instruments, Vol. 83, Issue 1
    • DOI: 10.1063/1.3680104

    A radial collimator for a time-of-flight neutron spectrometer
    journal, August 2014

    • Stone, M. B.; Niedziela, J. L.; Loguillo, M. J.
    • Review of Scientific Instruments, Vol. 85, Issue 8
    • DOI: 10.1063/1.4891302

    The lattice dynamics of an anharmonic crystal
    journal, October 1963


    Neutron scattering lengths and cross sections
    journal, January 1992


    Heat Capacity Measurements of U 1-y Gd y O 2 (y=0–0.27)from 325 to 1,673 K
    journal, February 2004


    Magnetic moment distribution in uranium monosulphide
    journal, September 1972


    Fast ion diffusion, superionic conductivity and phase transitions of the nuclear materials UO 2 and Li 2 O
    journal, September 2007


    Magnetic Excitations in Uranium Dioxide
    journal, March 1968


    Neutron magnetic form factors of uranium ions
    journal, February 1976


    Neutron diffraction study of U O 2 : Antiferromagnetic state
    journal, August 1976


    Crystal-field transitions in f -electron oxides
    journal, September 1985


    5 f -electron states in uranium dioxide investigated using high-resolution neutron spectroscopy
    journal, July 1989


    Magnetic excitations and dynamical Jahn-Teller distortions in UO 2
    journal, June 1999


    Multipolar, magnetic, and vibrational lattice dynamics in the low-temperature phase of uranium dioxide
    journal, September 2011


    Phonon density of states and anharmonicity of UO 2
    journal, March 2014

    • Pang, Judy W. L.; Chernatynskiy, Aleksandr; Larson, Bennett C.
    • Physical Review B, Vol. 89, Issue 11
    • DOI: 10.1103/physrevb.89.115132

    Anisotropic multipolar exchange interactions in systems with strong spin-orbit coupling
    journal, July 2014


    Oxidation and crystal field effects in uranium
    journal, July 2015


    Origin of Low Thermal Conductivity in Nuclear Fuels
    journal, June 2008


    Quadrupolar Waves in Uranium Dioxide
    journal, October 2010


    Phonon Lifetime Investigation of Anharmonicity and Thermal Conductivity of UO 2 by Neutron Scattering and Theory
    journal, April 2013


    Calculation of Multipolar Exchange Interactions in Spin-Orbital Coupled Systems
    journal, February 2014


    Re-analysis of single-crystal neutron-diffraction data on UO2 using third cumulants
    journal, July 1980

    • Willis, B. T. M.; Hazell, R. G.
    • Acta Crystallographica Section A: Crystal Physics, Diffraction, Theoretical and General Crystallography, Vol. 36, Issue 4
    • DOI: 10.1107/s0567739480001246

    The Crystal Dynamics of Uranium Dioxide
    journal, August 1965

    • Dolling, G.; Cowley, R. A.; Woods, A. D. B.
    • Canadian Journal of Physics, Vol. 43, Issue 8
    • DOI: 10.1139/p65-135

    Multiphonon: Phonon Density of States tools for Inelastic Neutron Scattering Powder Data
    journal, January 2018

    • Y. Y. Lin, Jiao; Islam, Fahima; Kresh, Max
    • The Journal of Open Source Software, Vol. 3, Issue 21
    • DOI: 10.21105/joss.00440