Effect of Added Gadolinium Oxide on the Thermal Air Oxidation of Uranium Dioxide

Scheele, Randall D.; Hanson, Brady D.; Casella, Andrew M.

doi:10.1016/j.jnucmat.2021.153008

Effect of Added Gadolinium Oxide on the Thermal Air Oxidation of Uranium Dioxide

Journal Article · 15 August 2021 · Journal of Nuclear Materials

DOI:https://doi.org/10.1016/j.jnucmat.2021.153008· OSTI ID:1809078

Scheele, Randall D. ^[1]; Hanson, Brady D. ^[2]; ^[2]

PNNL
BATTELLE (PACIFIC NW LAB)

To develop a more reliable and stable UO2-based nuclear fuel, the Pacific Northwest National Laboratory (PNNL) investigated modifying fuel with several soluble lanthanides and zirconium. This article provides the results of these studies investigating gadolinium doping at levels up to 10 mass%. The authors characterized and compared commercially- and PNNL-prepared gadolinium-doped UO2 to determine the oxygen-to-metal ratio, elemental distribution, chemical composition, physical appearance, lattice parameters, and grain structure using atomic force microscopy, scanning electron microscopy coupled with energy dispersive spectroscopy, and X-ray diffractometry. After confirming PNNL-prepared UO2 and (Gd,U)O2 were similar to commercially prepared UO2 and (Gd,U)O2, we measured the thermal behavior of these gadolinium-doped UO2 materials to air oxidation using differential scanning calorimetry and thermogravimetric analysis. Addition of gadolinium stabilized the first oxidation product U4¬O9/U3O7 and slowed the subsequent oxidation to U3O8. Comparison of our measured two-step oxidation of UO2 to U3O8 at 325°C to common gas/solid kinetic reaction models found that each oxidation step is best described as a convolution of kinetic behaviors; the gadolinium insertion into the UO2 lattice enforces a significant alteration in mechanism and oxidation rate. Noticeable changes in mechanism become apparent between 1% and 3% gadolinium content.

Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1809078

Report Number(s):: PNNL-SA-158705

Journal Information:: Journal of Nuclear Materials, Vol. 552

Country of Publication:: United States

Language:: English

References (41)

Stabilization of UO2 No authors listed Journal of Inorganic and Nuclear Chemistry https://doi.org/10.1016/0022-1902(61)80273-X		December 1961
Phase Relations and Crystal Chemistry in the System Uranium Oxide-Lanthanum Oxide No authors listed Journal of the American Ceramic Society https://doi.org/10.1111/j.1151-2916.1962.tb11140.x		June 1962
Oxidation Behavior of Spent UO ₂ Fuel No authors listed Nuclear Technology https://doi.org/10.13182/NT89-A34186		February 1989
Effect of fission products on air-oxidation of LWR spent fuel No authors listed Journal of Nuclear Materials https://doi.org/10.1016/0022-3115(93)90187-4		May 1993
The effect of rare-earth fission products on the rate of U3O8 formation on UO2 No authors listed Journal of Nuclear Materials https://doi.org/10.1016/S0022-3115(97)00286-9		January 1998
Effect of a trivalent dopant, Gd3+, on the oxidation of uranium dioxide No authors listed Journal of Nuclear Materials https://doi.org/10.1016/S0022-3115(01)00639-0		September 2001
Oxidation kinetic changes of UO2 by additive addition and irradiation No authors listed Journal of Nuclear Materials https://doi.org/10.1016/S0022-3115(99)00160-9		February 2000
A review of the oxidation of uranium dioxide at temperatures below 400°C No authors listed Journal of Nuclear Materials https://doi.org/10.1016/S0022-3115(97)00343-7		April 1998
Characterization of the influence of fission product doping on the anodic reactivity of uranium dioxide No authors listed Canadian Journal of Chemistry https://doi.org/10.1139/v07-056		October 2007
The effect of fission products on the rate of U3O8 formation in SIMFUEL oxidized in air at 250°C No authors listed Journal of Nuclear Materials https://doi.org/10.1016/0022-3115(96)80022-5		June 1996
Oxidation and anion lattice defect signatures of hypostoichiometric lanthanide-doped UO2 No authors listed Journal of Nuclear Materials https://doi.org/10.1016/j.jnucmat.2019.151959		March 2020
Raman and X-ray Studies of Uranium-Lanthanum-Mixed Oxides Before and After Air Oxidation No authors listed Journal of the American Ceramic Society https://doi.org/10.1111/jace.13559		March 2015
Studies on the Air-oxidation Behavior of Uranium Dioxide I. Phase transformation from (U _1-y Gd _y )O ₂ to (U _l-y Gd _y ) ₃ O _S No authors listed Journal of Nuclear Science and Technology https://doi.org/10.1080/00223131.2002.10875581		November 2002
Accurate lattice parameter measurements of stoichiometric uranium dioxide No authors listed Journal of Nuclear Materials https://doi.org/10.1016/j.jnucmat.2015.01.029		April 2015
Low-Temperature Oxidation of Fine UO ₂ Powders: A Process of Nanosized Domain Development No authors listed Inorganic Chemistry https://doi.org/10.1021/acs.inorgchem.6b00127		March 2016
Solution of trivalent cations into uranium dioxide No authors listed Journal of Nuclear Materials https://doi.org/10.1016/j.jnucmat.2011.10.006		January 2012
Evaluation of burnable absorber rods effect on neutronic performance in fuel assembly of WWER-1000 reactor No authors listed Annals of Nuclear Energy https://doi.org/10.1016/j.anucene.2015.10.012		January 2016
Pore size distributions in uranium dioxide and uranium dioxide-gadolinium oxide fuel kernel produced by sol-gel technique No authors listed Journal of Nuclear Materials https://doi.org/10.1016/0022-3115(91)90388-N		February 1991
Swelling due to fission products and additives dissolved within the uranium dioxide lattice No authors listed Journal of Nuclear Materials https://doi.org/10.1016/j.jnucmat.2012.03.037		August 2012
Thermal conductivity variation in uranium dioxide with gadolinia additions No authors listed Journal of Nuclear Materials https://doi.org/10.1016/j.jnucmat.2020.152258		November 2020
Dopant solubility and lattice contraction in gadolinia and gadolinia–chromia doped UO2 fuels No authors listed Journal of Nuclear Materials https://doi.org/10.1016/j.jnucmat.2012.02.014		May 2012
The Combined Influence of Gadolinium Doping and Non-stoichiometry on the Structural and Electrochemical Properties of Uranium Dioxide No authors listed Electrochimica Acta https://doi.org/10.1016/j.electacta.2017.07.023		September 2017
Phase studies in the UO2–Gd2O3 system No authors listed Journal of Nuclear Materials https://doi.org/10.1016/j.jnucmat.2010.03.001		May 2010
Powder characteristics and microstructure of uranium dioxide and uranium dioxide-gadolinium oxide fuel No authors listed Journal of Nuclear Materials https://doi.org/10.1016/0022-3115(96)00349-2		July 1996
Heat Capacity and Thermal Expansion of Uranium-Gadolinium Mixed Oxides No authors listed Journal of Nuclear and Radiochemical Sciences https://doi.org/10.14494/jnrs.10.1_19		January 2009
Thermal conductivities of irradiated UO2 and (U,Gd)O2 pellets No authors listed Journal of Nuclear Materials https://doi.org/10.1016/S0022-3115(01)00704-8		January 2002
The effect of fuel chemistry on UO2 dissolution No authors listed Journal of Nuclear Materials https://doi.org/10.1016/j.jnucmat.2016.04.025		August 2016
Numerical Data for Some Commonly Used Solid State Reaction Equations No authors listed Journal of the American Ceramic Society https://doi.org/10.1111/j.1151-2916.1966.tb13289.x		July 1966
Modeling of Gas-Solid Reactions: Kinetics, Mass and Heat Transfer, and Evolution of the Pore Structure No authors listed Chemical Engineering & Technology https://doi.org/10.1002/(SICI)1521-4125(200001)23:1<75::AID-CEAT75>3.0.CO;2-V		January 2000
Reaction Kinetics in Differential Thermal Analysis No authors listed Analytical Chemistry https://doi.org/10.1021/ac60131a045		November 1957
Kinetics of Solid-Gas Reactions and Their Application to Carbonate Looping Systems No authors listed Energies https://doi.org/10.3390/en12152981		August 2019
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides No authors listed Acta Crystallographica Section A https://doi.org/10.1107/S0567739476001551		September 1976
Vegard’s law No authors listed Physical Review A https://doi.org/10.1103/PhysRevA.43.3161		March 1991
Lattice contraction and lattice deformation of UO 2 and ThO 2 doped with Gd 2 O 3 No authors listed Journal of Nuclear Materials https://doi.org/10.1016/j.jnucmat.2015.09.018		December 2015
A detailed study of UO2 to U3O8 oxidation phases and the associated rate-limiting steps No authors listed Journal of Nuclear Materials https://doi.org/10.1016/j.jnucmat.2006.03.015		September 2006
Neutron Diffraction Study of the in Situ Oxidation of UO ₂ No authors listed Inorganic Chemistry https://doi.org/10.1021/ic9000889		August 2009
Thermoanalytical study on the oxidation of uranium dioxides derived from uranyl nitrate, uranyl acetate and ammonium diuranate No authors listed Thermochimica Acta https://doi.org/10.1016/0040-6031(79)87029-X		October 1979
Oxidation reactions and dopants in non-stoichiometric UO2 No authors listed Journal of Nuclear Materials https://doi.org/10.1016/0022-3115(79)90114-4		February 1979
Thermal studies on fluorite type ZryU1−yO2 solid solutions No authors listed Journal of Nuclear Materials https://doi.org/10.1016/j.jnucmat.2008.10.015		February 2009
Influence of Trivalent-Dopants on the Structural and Electrochemical Properties of Uranium Dioxide (UO ₂ ) No authors listed Journal of The Electrochemical Society https://doi.org/10.1149/2.047403jes		December 2013
A review of kinetic data on the rate of U3O7 formation on UO2 No authors listed Journal of Nuclear Materials https://doi.org/10.1016/S0022-3115(96)00733-7		June 1997

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Thermal Air Oxidation

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