Impact of anharmonicity on the vibrational entropy and specific heat of UO2

Bryan, M. S.; Pang, J. W.  L.; Larson, B. C.; Chernatynskiy, A.; Abernathy, D. L.; Gofryk, K.; Manley, M. E.

doi:10.1103/PhysRevMaterials.3.065405

Title: Impact of anharmonicity on the vibrational entropy and specific heat of ${UO}_{2}$

Journal Article · 27 June 2019 · Physical Review Materials

DOI: https://doi.org/10.1103/PhysRevMaterials.3.065405 · OSTI ID:1530058

Bryan, M. S. ^[1]; Pang, J. W. L. ^[1]; Larson, B. C. ^[1]; Chernatynskiy, A. ^[2];

^[1]; Gofryk, K. ^[3];

^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Missouri Univ. of Science and Technology, Rolla, MO (United States)
Idaho National Lab. (INL), Idaho Falls, ID (United States)

The impact of anharmonicity on the vibrational entropy and heat capacity of ${UO}_{2}$ has been discovered from 10 to 1200 K using inelastic neutron-scattering measurements of the phonon density of states (PDOS). Small changes in the PDOS are observed from 10 to 295 K, with more noticeable changes appearing in the 750- 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 nondilation anharmonicity on the specific heat has been shown to be less than 2%. 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 and 50 meV softening more than expected, while the higher-energy optical phonons between approximately 50 and 80 meV have no appreciable softening over the temperature range measured. The observation of a small anharmonic specific heat contribution has been demonstrated to be the result of relatively large energy-dependent anharmonic effects which have opposite sign, leading to a total contribution near zero.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Thermal Energy Transport under Irradiation (TETI); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1530058

Alternate ID(s):: OSTI ID: 1546418; OSTI ID: 1558431

Journal Information:: Physical Review Materials, Journal Name: Physical Review Materials Journal Issue: 6 Vol. 3; ISSN PRMHAR; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

References (45)

The lattice dynamics of an anharmonic crystal Cowley, R. A. Advances in Physics, Vol. 12, Issue 48 https://doi.org/10.1080/00018736300101333	journal	October 1963
Enthalpy and heat capacity of the actinide oxides Fink, J. K. International Journal of Thermophysics, Vol. 3, Issue 2 https://doi.org/10.1007/BF00503638	journal	June 1982
Heat Capacity Measurements of U _1-y Gd _y O ₂ (y=0–0.27)from 325 to 1,673 K Amaya, Masaki; Une, Katsumi; Hirai, Mutsumi Journal of Nuclear Science and Technology, Vol. 41, Issue 2 https://doi.org/10.1080/18811248.2004.9715466	journal	February 2004
Phonon Lifetime Investigation of Anharmonicity and Thermal Conductivity of UO 2 by Neutron Scattering and Theory Pang, Judy W. L.; Buyers, William J. L.; Chernatynskiy, Aleksandr Physical Review Letters, Vol. 110, Issue 15 https://doi.org/10.1103/PhysRevLett.110.157401	journal	April 2013
Calculation of Multipolar Exchange Interactions in Spin-Orbital Coupled Systems Pi, Shu-Ting; Nanguneri, Ravindra; Savrasov, Sergey arXiv https://doi.org/10.48550/arxiv.1308.1488	text	January 2013
Magnetic moment distribution in uranium monosulphide Wedgwood, F. A. Journal of Physics C: Solid State Physics, Vol. 5, Issue 17 https://doi.org/10.1088/0022-3719/5/17/018	journal	September 1972
The Crystal Dynamics of Uranium Dioxide Dolling, G.; Cowley, R. A.; Woods, A. D. B. Canadian Journal of Physics, Vol. 43, Issue 8 https://doi.org/10.1139/p65-135	journal	August 1965
A radial collimator for a time-of-flight neutron spectrometer Stone, M. B.; Niedziela, J. L.; Loguillo, M. J. Review of Scientific Instruments, Vol. 85, Issue 8 https://doi.org/10.1063/1.4891302	journal	August 2014
Magnetic excitations and dynamical Jahn-Teller distortions in UO 2 Caciuffo, R.; Amoretti, G.; Santini, P. Physical Review B, Vol. 59, Issue 21 https://doi.org/10.1103/PhysRevB.59.13892	journal	June 1999
Design and operation of the wide angular-range chopper spectrometer ARCS at the Spallation Neutron Source Abernathy, D. L.; Stone, M. B.; Loguillo, M. J. Review of Scientific Instruments, Vol. 83, Issue 1 https://doi.org/10.1063/1.3680104	journal	January 2012
Neutron magnetic form factors of uranium ions Freeman, A. J.; Desclaux, J. P.; Lander, G. H. Physical Review B, Vol. 13, Issue 3 https://doi.org/10.1103/PhysRevB.13.1168	journal	February 1976
Phonon Density of States and Anharmonicity of UO2 Pang, Judy W. L.; Chernatynskiy, Aleksandr; Larson, Bennett C. arXiv https://doi.org/10.48550/arxiv.1401.1788	text	January 2014
Heat capacity measurement of U1−yGdyO2 (0.00 ≦ y ≦ 0.142) from 310 to 1500 K Inaba, Hideaki; Naito, Keiji; Oguma, Masaomi Journal of Nuclear Materials, Vol. 149, Issue 3 https://doi.org/10.1016/0022-3115(87)90536-8	journal	August 1987
Anharmonic specific heat of solid UO2 Hyland, G. J.; Stoneham, A. M. Journal of Nuclear Materials, Vol. 96, Issue 1-2 https://doi.org/10.1016/0022-3115(81)90211-7	journal	January 1981
Magnetic Excitations in Uranium Dioxide Cowley, R. A.; Dolling, G. Physical Review, Vol. 167, Issue 2 https://doi.org/10.1103/PhysRev.167.464	journal	March 1968
Evaluation of thermal properties of UO2 and PuO2 by equilibrium molecular dynamics simulations from 300 to 2000K Arima, Tatsumi; Yamasaki, Sho; Inagaki, Yaohiro Journal of Alloys and Compounds, Vol. 400, Issue 1-2 https://doi.org/10.1016/j.jallcom.2005.04.003	journal	September 2005
High-temperature studies of UO2 and ThO2 using neutron scattering techniques Hutchings, Michael T. Journal of the Chemical Society, Faraday Transactions 2, Vol. 83, Issue 7 https://doi.org/10.1039/f29878301083	journal	January 1987
The Spin-Wave Dispersion Relations and the Spin-Wave Contribution to the Specific Heat of Antiferromagnetic UO2 Cracknell, A. P.; Joshua, S. J. physica status solidi (b), Vol. 36, Issue 2 https://doi.org/10.1002/pssb.19690360237	journal	January 1969
Neutron diffraction study of U O 2 : Antiferromagnetic state Faber, J.; Lander, G. H. Physical Review B, Vol. 14, Issue 3 https://doi.org/10.1103/PhysRevB.14.1151	journal	August 1976
Anisotropic multipolar exchange interactions in systems with strong spin-orbit coupling Pi, Shu-Ting; Nanguneri, Ravindra; Savrasov, Sergey Physical Review B, Vol. 90, Issue 4 https://doi.org/10.1103/PhysRevB.90.045148	journal	July 2014
5 f -electron states in uranium dioxide investigated using high-resolution neutron spectroscopy Amoretti, G.; Blaise, A.; Caciuffo, R. Physical Review B, Vol. 40, Issue 3 https://doi.org/10.1103/PhysRevB.40.1856	journal	July 1989
Oxidation and crystal field effects in uranium Tobin, J. G.; Yu, S. -W.; Booth, C. H. Physical Review B, Vol. 92, Issue 3 https://doi.org/10.1103/PhysRevB.92.035111	journal	July 2015
Phonon density of states and anharmonicity of UO 2 Pang, Judy W. L.; Chernatynskiy, Aleksandr; Larson, Bennett C. Physical Review B, Vol. 89, Issue 11 https://doi.org/10.1103/PhysRevB.89.115132	journal	March 2014
Quadrupole Polarization in Simulations of Ionic Systems: Application to AgCl Wilson, Mark; Madden, Paul A.; Costa-Cabral, Benedito J. The Journal of Physical Chemistry, Vol. 100, Issue 4 https://doi.org/10.1021/jp9512319	journal	January 1996
Anharmonic contributions to vibrational thermodynamic properties of solids Maradudin, A. A.; Flinn, P. A.; Coldwell-Horsfall, R. A. Annals of Physics, Vol. 15, Issue 3 https://doi.org/10.1016/0003-4916(61)90189-0	journal	September 1961
The magnetic transition, heat capacity, and thermodynamic properties of uranium dioxide from 5 to 350 K Huntzicker, James J.; Westrum, Edgar F. The Journal of Chemical Thermodynamics, Vol. 3, Issue 1 https://doi.org/10.1016/S0021-9614(71)80067-8	journal	January 1971
Multiphonon: Phonon Density of States tools for Inelastic Neutron Scattering Powder Data Y. Y. Lin, Jiao; Islam, Fahima; Kresh, Max The Journal of Open Source Software, Vol. 3, Issue 21 https://doi.org/10.21105/joss.00440	journal	January 2018
Heat capacity anomaly in UO2 in the vicinity of 1300K: an improved description based on high resolution X-ray and neutron powder diffraction studies Ruello, P.; Desgranges, L.; Baldinozzi, G. Journal of Physics and Chemistry of Solids, Vol. 66, Issue 5 https://doi.org/10.1016/j.jpcs.2004.10.009	journal	May 2005
Neutron scattering lengths and cross sections Sears, Varley F. Neutron News, Vol. 3, Issue 3 https://doi.org/10.1080/10448639208218770	journal	January 1992
Magnon Contribution to the Low-Temperature Specific Heat of UO2 De Batist, R.; Gevers, R.; Verschueren, M. physica status solidi (b), Vol. 19, Issue 1 https://doi.org/10.1002/pssb.19670190108	journal	January 1967
Origin of Low Thermal Conductivity in Nuclear Fuels Yin, Quan; Savrasov, Sergey Y. Physical Review Letters, Vol. 100, Issue 22 https://doi.org/10.1103/PhysRevLett.100.225504	journal	June 2008
Anharmonic contributions to vibrational thermodynamic properties of solids Maradudin, A. A.; Flinn, P. A.; Coldwell-Horsfall, R. A. Annals of Physics, Vol. 15, Issue 3 https://doi.org/10.1016/0003-4916(61)90188-9	journal	September 1961
Quadrupolar Waves in Uranium Dioxide Carretta, S.; Santini, P.; Caciuffo, R. Physical Review Letters, Vol. 105, Issue 16 https://doi.org/10.1103/PhysRevLett.105.167201	journal	October 2010
Thermodynamics of the UO2+x phase I. Heat capacities of UO2.017 and UO2.254 from 300 to 1000 K and electronic contributions Grønvold, Fredrik; Kveseth, Nils Jørgen; Sveen, Arvid The Journal of Chemical Thermodynamics, Vol. 2, Issue 5 https://doi.org/10.1016/0021-9614(70)90042-X	journal	September 1970
Crystal-field transitions in f -electron oxides Kern, S.; Loong, C. -K.; Lander, G. H. Physical Review B, Vol. 32, Issue 5 https://doi.org/10.1103/PhysRevB.32.3051	journal	September 1985
Origin of Low Thermal Conductivity in Nuclear Fuels Yin, Quan; Savrasov, Sergey Y. arXiv https://doi.org/10.48550/arxiv.0802.2006	text	January 2008
Multipolar, magnetic, and vibrational lattice dynamics in the low-temperature phase of uranium dioxide Caciuffo, R.; Santini, P.; Carretta, S. Physical Review B, Vol. 84, Issue 10 https://doi.org/10.1103/PhysRevB.84.104409	journal	September 2011
Fast ion diffusion, superionic conductivity and phase transitions of the nuclear materials UO2 and Li2O Goel, Prabhatasree; Choudhury, N.; Chaplot, S. L. Transactions of the Indian Institute of Metals, Vol. 62, Issue 2 https://doi.org/10.1007/s12666-009-0019-8	journal	April 2009
Specific heat of uranium dioxide (UO2) between 0.3 and 50 K Khattak, G. D. Physica Status Solidi (a), Vol. 75, Issue 1 https://doi.org/10.1002/pssa.2210750136	journal	January 1983
Analysis of recent measurements of the heat capacity of uranium dioxide Ronchi, C.; Hyland, G. J. Journal of Alloys and Compounds, Vol. 213-214 https://doi.org/10.1016/0925-8388(94)90897-4	journal	October 1994
Fast ion diffusion, superionic conductivity and phase transitions of the nuclear materials UO ₂ and Li ₂ O Goel, Prabhatasree; Choudhury, N.; Chaplot, S. L. Journal of Physics: Condensed Matter, Vol. 19, Issue 38 https://doi.org/10.1088/0953-8984/19/38/386239	journal	September 2007
Thermophysical properties of uranium dioxide Fink, J. K. Journal of Nuclear Materials, Vol. 279, Issue 1 https://doi.org/10.1016/S0022-3115(99)00273-1	journal	March 2000
Re-analysis of single-crystal neutron-diffraction data on UO2 using third cumulants Willis, B. T. M.; Hazell, R. G. Acta Crystallographica Section A: Crystal Physics, Diffraction, Theoretical and General Crystallography, Vol. 36, Issue 4 https://doi.org/10.1107/S0567739480001246	journal	July 1980
Calculation of Multipolar Exchange Interactions in Spin-Orbital Coupled Systems Pi, Shu-Ting; Nanguneri, Ravindra; Savrasov, Sergey Physical Review Letters, Vol. 112, Issue 7 https://doi.org/10.1103/PhysRevLett.112.077203	journal	February 2014
Thermodynamic properties of uranium dioxide: A study of the experimental enthalpy and specific heat Browning, P. Journal of Nuclear Materials, Vol. 98, Issue 3 https://doi.org/10.1016/0022-3115(81)90161-6	journal	June 1981

Cited By (1)

Ultrastable phonon frequencies in α -quartz-type BPO ₄ at high temperature Le Parc, R.; Buixaderas, E.; Levelut, C. Applied Physics Letters, Vol. 115, Issue 14 https://doi.org/10.1063/1.5111621	journal	September 2019