A combined calorimetric and computational study of the energetics of rare earth substituted UO2 systems
Abstract
The energetics of rare earth substituted UO2 solid solutions (U1-xLnxO2-0.5x+y, where Ln = La, Y, and Nd) are explored employing a combination of calorimetric measurements and density functional theory based computations. Calculated and measured formation enthalpies agree within 10 kJ/mol for stoichiometric oxygen/metal compositions. To better understand the factors governing the stability and defect binding in rare earth substituted urania solid solutions, systematic trends in the energetics are investigated based on the present results and previous computational and experimental thermochemical studies of rare earth substituted fluorite oxides (A1-xLnxO2-0.5x, where A = Hf, Zr, Ce, and Th). A consistent trend towards increased energetic stability with larger size mismatch between the smaller host tetravalent cation and the larger rare earth trivalent cation is found for both actinide and non-actinide fluorite oxide systems where aliovalent substitution of Ln cations is compensated by oxygen vacancies. Yet, the large exothermic oxidation enthalpy in the UO2 based systems favors oxygen rich compositions where charge compensation occurs through the formation of uranium cations with higher oxidation states.
- Authors:
-
- Univ. of California, Davis, CA (United States)
- Univ. of California, Berkeley, CA (United States)
- Univ. of California, Davis, CA (United States); Univ. of California, Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1370874
- Alternate Identifier(s):
- OSTI ID: 1254764
- Grant/Contract Number:
- SC0001089; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Acta Materialia
- Additional Journal Information:
- Journal Volume: 97; Journal Issue: C; Related Information: MSA partners with University of Notre Dame (lead); University of California, Davis; Florida State University; George Washington University; University of Michigan; University of Minnesota; Oak Ridge National Laboratory; Oregon state University; Rensselaer Polytechnic Institute; Savannah River National Laboratory; Journal ID: ISSN 1359-6454
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Formation enthalpy; Fluorite oxide; Calorimetry; DFT
Citation Formats
Zhang, Lei, Solomon, Jonathan M., Asta, Mark, and Navrotsky, Alexandra. A combined calorimetric and computational study of the energetics of rare earth substituted UO2 systems. United States: N. p., 2015.
Web. doi:10.1016/j.actamat.2015.06.048.
Zhang, Lei, Solomon, Jonathan M., Asta, Mark, & Navrotsky, Alexandra. A combined calorimetric and computational study of the energetics of rare earth substituted UO2 systems. United States. https://doi.org/10.1016/j.actamat.2015.06.048
Zhang, Lei, Solomon, Jonathan M., Asta, Mark, and Navrotsky, Alexandra. Mon .
"A combined calorimetric and computational study of the energetics of rare earth substituted UO2 systems". United States. https://doi.org/10.1016/j.actamat.2015.06.048. https://www.osti.gov/servlets/purl/1370874.
@article{osti_1370874,
title = {A combined calorimetric and computational study of the energetics of rare earth substituted UO2 systems},
author = {Zhang, Lei and Solomon, Jonathan M. and Asta, Mark and Navrotsky, Alexandra},
abstractNote = {The energetics of rare earth substituted UO2 solid solutions (U1-xLnxO2-0.5x+y, where Ln = La, Y, and Nd) are explored employing a combination of calorimetric measurements and density functional theory based computations. Calculated and measured formation enthalpies agree within 10 kJ/mol for stoichiometric oxygen/metal compositions. To better understand the factors governing the stability and defect binding in rare earth substituted urania solid solutions, systematic trends in the energetics are investigated based on the present results and previous computational and experimental thermochemical studies of rare earth substituted fluorite oxides (A1-xLnxO2-0.5x, where A = Hf, Zr, Ce, and Th). A consistent trend towards increased energetic stability with larger size mismatch between the smaller host tetravalent cation and the larger rare earth trivalent cation is found for both actinide and non-actinide fluorite oxide systems where aliovalent substitution of Ln cations is compensated by oxygen vacancies. Yet, the large exothermic oxidation enthalpy in the UO2 based systems favors oxygen rich compositions where charge compensation occurs through the formation of uranium cations with higher oxidation states.},
doi = {10.1016/j.actamat.2015.06.048},
journal = {Acta Materialia},
number = C,
volume = 97,
place = {United States},
year = {Mon Jul 13 00:00:00 EDT 2015},
month = {Mon Jul 13 00:00:00 EDT 2015}
}
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Works referenced in this record:
Stabilization of UO2
journal, December 1961
- Wilson, W. B.; Alexander, C. A.; Gerds, A. F.
- Journal of Inorganic and Nuclear Chemistry, Vol. 20, Issue 3-4
Equilibrium Oxygen Pressures Over Solid Solutions of Urania-Yttria and Urania-Lanthana at 1100o to 14OOoC
journal, November 1967
- Hagemark, K.; Broli, M.
- Journal of the American Ceramic Society, Vol. 50, Issue 11
Thermodynamics and phase relationships of the ternary lanthanum-uranium-oxygen system
journal, August 1974
- Stadlbauer, E.; Wichmann, U.; Lott, U.
- Journal of Solid State Chemistry, Vol. 10, Issue 4
Review and Chemical Thermodynamic Representation of U1-zCezO2+-x> and U1-zLnzO2+-x); Ln = Y, La; Nd, Gd
journal, December 1986
- Lindeme, Terrence B.; Brynestad, Jorulf
- Journal of the American Ceramic Society, Vol. 69, Issue 12
Thermodynamic modeling of the (U,La)O2±x solid solution phase
journal, February 2013
- Shin, Dongwon; Besmann, Theodore M.
- Journal of Nuclear Materials, Vol. 433, Issue 1-3
Phase Relations in the System UO2-UO3- Y2O3
journal, April 1964
- Bartram, S. F.; Juenke, E. F.; Aitken, E. A.
- Journal of the American Ceramic Society, Vol. 47, Issue 4
Behavior of Urania-Rare-Earth Oxides at High Temperatures
journal, November 1969
- Beals, R. J.; Handwerk, J. H.; Wrona, B. J.
- Journal of the American Ceramic Society, Vol. 52, Issue 11
Solid solutions and phase equilibria in (U,Zr,Ln) oxides in the temperature range 1270–1670 K
journal, October 1981
- Schleifer, F.; Naoumidis, A.; Nickel, H.
- Journal of Nuclear Materials, Vol. 101, Issue 1-2
Phase Relations and Crystal Chemistry in the System Uranium Oxide-Lanthanum Oxide
journal, June 1962
- Hill, David C.
- Journal of the American Ceramic Society, Vol. 45, Issue 6
On the relation between lattice parameter and O/M ratio for uranium dioxide-trivalent rare earth oxide solid solution
journal, November 1981
- Ohmichi, Toshihiko; Fukushima, Susumu; Maeda, Atsushi
- Journal of Nuclear Materials, Vol. 102, Issue 1-2
Effect of cations on lattice constants of (MyU1−y)O2.00 (M=Pu, Th, La) at low doped cation concentrations
journal, June 1998
- Tsuji, Toshihide; Iwashita, Mitsushige; Yamashita, Toshiyuki
- Journal of Alloys and Compounds, Vol. 271-273
Electrical conductivity and non-stoichiometry in the (U,Gd)O2±x system
journal, April 2005
- Yang, Jae Ho; Kim, Keon Sik; Kang, Ki Won
- Journal of Nuclear Materials, Vol. 340, Issue 2-3
High-temperature heat capacities and electrical conductivities of UO2 doped with simulated fission products for 2–10 at% burnup
journal, December 1994
- Arita, Yuji; Hamada, Seiichi; Matsui, Tsuneo
- Thermochimica Acta, Vol. 247, Issue 2
The electrical conductivity of doped and undoped uranium oxide
journal, June 1981
- Munir, Z. A.
- International Journal of Thermophysics, Vol. 2, Issue 2
Calorimetric determination of energetics of solid solutions of UO2+x with CaO and Y2O3
journal, February 2008
- Mazeina, Lena; Navrotsky, Alexandra; Greenblatt, Martha
- Journal of Nuclear Materials, Vol. 373, Issue 1-3
Computational study of the energetics and defect clustering tendencies for Y- and La-doped UO2
journal, October 2014
- Solomon, J. M.; Alexandrov, V.; Sadigh, B.
- Acta Materialia, Vol. 78
Energetics and defect clustering trends for trivalent rare earth cations substituted in UO2
journal, February 2015
- Solomon, J. M.; Navrotsky, A.; Asta, M.
- Journal of Nuclear Materials, Vol. 457
Influence of Trivalent-Dopants on the Structural and Electrochemical Properties of Uranium Dioxide (UO 2 )
journal, December 2013
- Razdan, Mayuri; Shoesmith, David W.
- Journal of The Electrochemical Society, Vol. 161, Issue 3
Characterization of the influence of fission product doping on the anodic reactivity of uranium dioxide
journal, October 2007
- He, Heming; Keech, Peter G.; Broczkowski, Michael E.
- Canadian Journal of Chemistry, Vol. 85, Issue 10
Electrical conductivity measurement and thermogravimetric study of lanthanum-doped uranium dioxide
journal, March 1986
- Matsui, Tsuneo; Naito, Keiji
- Journal of Nuclear Materials, Vol. 138, Issue 1
Cooperativity among defect sites in and : Density functional calculations
journal, January 2009
- Andersson, D. A.; Lezama, J.; Uberuaga, B. P.
- Physical Review B, Vol. 79, Issue 2
Stability and migration of large oxygen clusters in UO 2+ x : Density functional theory calculations
journal, June 2012
- Andersson, D. A.; Espinosa-Faller, F. J.; Uberuaga, B. P.
- The Journal of Chemical Physics, Vol. 136, Issue 23
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
- Andersson, D. A.; Baldinozzi, G.; Desgranges, L.
- Inorganic Chemistry, Vol. 52, Issue 5
Nature and strength of defect interactions in cubic stabilized zirconia
journal, January 2003
- Bogicevic, A.; Wolverton, C.
- Physical Review B, Vol. 67, Issue 2
First-principles computational study of defect clustering in solid solutions of with trivalent oxides
journal, November 2010
- Alexandrov, Vitaly; Grønbech-Jensen, Niels; Navrotsky, Alexandra
- Physical Review B, Vol. 82, Issue 17
Enthalpy of formation of cubic yttria-stabilized hafnia
journal, June 2004
- Lee, Theresa A.; Navrotsky, Alexandra
- Journal of Materials Research, Vol. 19, Issue 6
Enthalpy of Formation of Yttria-Doped Ceria
journal, January 2005
- Chen, Weiqun; Lee, Theresa A.; Navrotsky, Alexandra
- Journal of Materials Research, Vol. 20, Issue 1
Calorimetric measurements of energetics of defect interactions in fluorite oxides
journal, January 2007
- Navrotsky, Alexandra; Simoncic, Petra; Yokokawa, Harumi
- Faraday Discuss., Vol. 134
Enthalpies of formation and insights into defect association in ceria singly and doubly doped with neodymia and samaria
journal, October 2012
- Buyukkilic, Salih; Shvareva, Tatiana; Navrotsky, Alexandra
- Solid State Ionics, Vol. 227
Thermochemistry of Lanthana- and Yttria-Doped Thoria: Thermochemistry of Lanthana- and Yttria-Doped Thoria
journal, September 2010
- Aizenshtein, Michael; Shvareva, Tatiana Y.; Navrotsky, Alexandra
- Journal of the American Ceramic Society, Vol. 93, Issue 12
Systematics of Phase Transition and Mixing Energetics in Rare Earth, Yttrium, and Scandium Stabilized Zirconia and Hafnia
journal, July 2007
- Simoncic, Petra; Navrotsky, Alexandra
- Journal of the American Ceramic Society, Vol. 90, Issue 7
Energetics of rare-earth-doped hafnia
journal, April 2007
- Simoncic, Petra; Navrotsky, Alexandra
- Journal of Materials Research, Vol. 22, Issue 4
The alloy theoretic automated toolkit: A user guide
journal, December 2002
- van de Walle, A.; Asta, M.; Ceder, G.
- Calphad, Vol. 26, Issue 4
Multicomponent multisublattice alloys, nonconfigurational entropy and other additions to the Alloy Theoretic Automated Toolkit
journal, June 2009
- van de Walle, Axel
- Calphad, Vol. 33, Issue 2
The extent of zinc oxide solution in zinc chromate spinel
journal, September 1995
- Grimes, Robin W.; Binks, D. Jason; Lidiard, A. B.
- Philosophical Magazine A, Vol. 72, Issue 3
Disorder in Pyrochlore Oxides
journal, August 2000
- Minervini, Licia; Grimes, Robin W.; Sickafus, Kurt E.
- Journal of the American Ceramic Society, Vol. 83, Issue 8
Defect cluster formation in M2O3-doped CeO2
journal, January 1999
- Minervini, L.
- Solid State Ionics, Vol. 116, Issue 3-4
Solution Mechanisms for Dopant Oxides in Yttria
journal, June 1999
- Busker, Gerdjan; Chroneos, Alex; Grimes, Robin W.
- Journal of the American Ceramic Society, Vol. 82, Issue 6
Nonstoichiometry in A2B2O7 Pyrochlores
journal, November 2002
- Stanek, Christopher R.; Minervini, Licia; Grimes, Robin W.
- Journal of the American Ceramic Society, Vol. 85, Issue 11
Computational study of the energetics of charge and cation mixing in U Ce O
journal, August 2011
- Hanken, B. E.; Stanek, C. R.; Grønbech-Jensen, N.
- Physical Review B, Vol. 84, Issue 8
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
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
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
journal, February 1997
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 78, Issue 7
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
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998
- Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
- Physical Review B, Vol. 57, Issue 3, p. 1505-1509
Method for locating low-energy solutions within
journal, November 2010
- Meredig, B.; Thompson, A.; Hansen, H. A.
- Physical Review B, Vol. 82, Issue 19
calculations of the ground state and metastable states of uranium dioxide
journal, June 2009
- Dorado, Boris; Amadon, Bernard; Freyss, Michel
- Physical Review B, Vol. 79, Issue 23
Thermodynamics of rare earth sesquioxides
journal, May 2007
- Zinkevich, M.
- Progress in Materials Science, Vol. 52, Issue 4
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976
- Shannon, R. D.
- Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767
Works referencing / citing this record:
Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La)
journal, December 2016
- Solomon, Jonathan M.; Shamblin, Jacob; Lang, Maik
- Scientific Reports, Vol. 6, Issue 1
Dependency of f states in fluorite-type XO 2 (X = Ce, Th, U) on the stability and electronic state of doped transition metals
journal, January 2019
- Ding, Qian; Qiu, Ruizhi; Ao, Bingyun
- Physical Chemistry Chemical Physics, Vol. 21, Issue 47