On the product phases and the reaction kinetics of carbothermic reduction of UO2+C at relatively low temperatures

Silva, Chinthaka M.; Kondrat, Kyle J.; Childs, Bradley C.; Ferrier, Maryline G.; Greenough, Michelle M.; Holliday, Kiel S.; McCormack, Scott J.

doi:10.1016/j.jnucmat.2024.155495

Title: On the product phases and the reaction kinetics of carbothermic reduction of UO₂+C at relatively low temperatures

Journal Article · 02 November 2024 · Journal of Nuclear Materials

DOI: https://doi.org/10.1016/j.jnucmat.2024.155495 · OSTI ID:2481161

^[1]; Kondrat, Kyle J. ^[2];

^[3];

^[3]; McCormack, Scott J. ^[4]

Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Univ. of California, Davis, CA (United States)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Univ. of California, Davis, CA (United States)

The synthesis of UC using carbothermic reduction of UO₂ and C mixtures has been well studied at high temperatures. However, the product phase behavior of carbothermic reduction at low temperatures (≤1773 K) is not well studied. Such a study is important as low temperatures permit single phase UC synthesis without forming secondary higher carbides, and it further supports the knowledge base of the process that needs to be used for transuranic elements such as plutonium that have high vapor pressures at elevated temperatures. Therefore, a low temperature carbothermic reduction of two different C/UO₂ molar ratios under inert and reducing environments have been studied here. Two different sample holding crucibles, alumina (Al₂O₃) and graphite, were also used here to differentiate the hypostoichiometric (UC_1-a) and oxygen dissolved (UC_1-xO_x) uranium monocarbide phases adding more details on the two systems. Also, the reaction kinetics involved in the formation of UC via the carbothermic reduction of UO₂+C using product phases instead of evolved gases such as carbon monoxide is reported here. Under inert atmospheres but with significant oxygen partial pressures, the low temperature carbothermic reduction of UO₂+C produced up to 90 wt.% UC_1-xO_x type oxycarbides as was confirmed by Xray powder diffraction. Reducing Ar-4%H₂ environments at these temperatures were not successful in synthesizing UC as it reduces the amount of C required for the carbothermic reduction, leaving UC phase at a non-equilibrium state. Inert atmospheres with low or negligible oxygen partial pressures on the other hand produced near stoichiometric UC at high phase purity, especially at 1673 – 1773 K temperature range. An activation energy of 377±75 kJmol^-1 was also calculated using product phase concentrations of the carbothermic reduction of UO₂+C under these inert Ar_(g) atmospheres.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 2481161

Report Number(s):: LLNL--JRNL-866636; 1086849

Journal Information:: Journal of Nuclear Materials, Journal Name: Journal of Nuclear Materials Vol. 604; ISSN 0022-3115

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (39)

Reaktionen im festen Zustande bei höheren Temperaturen. Reaktionsgeschwindigkeiten endotherm verlaufender Umsetzungen Jander, Wilhelm Zeitschrift für anorganische und allgemeine Chemie, Vol. 163, Issue 1 https://doi.org/10.1002/zaac.19271630102	journal	June 1927
Uranium carbide dissolution in nitric acid: speciation of organic compounds Legand, S.; Bouyer, C.; Dauvois, V. Journal of Radioanalytical and Nuclear Chemistry, Vol. 302, Issue 1 https://doi.org/10.1007/s10967-014-3409-2	journal	August 2014
Reaction between beryllium and uranium monocarbide Murdock, J. F. Journal of Nuclear Materials, Vol. 7, Issue 2 https://doi.org/10.1016/0022-3115(62)90164-2	journal	November 1962
The uranium monocarbide-plutonium monocarbide system Rosen, S.; Nevitt, M. V.; Mitchell, A. W. Journal of Nuclear Materials, Vol. 9, Issue 2 https://doi.org/10.1016/0022-3115(63)90129-6	journal	July 1963
The carbides of uranium Frost, B. R. T. Journal of Nuclear Materials, Vol. 10, Issue 4 https://doi.org/10.1016/0022-3115(63)90181-8	journal	December 1963
Diffusion in uranium monocarbide Chubb, W.; Getz, R. W.; Townley, C. W. Journal of Nuclear Materials, Vol. 13, Issue 1 https://doi.org/10.1016/0022-3115(64)90068-6	journal	January 1964
The volatility of plutonium carbides Potter, P. E. Journal of Nuclear Materials, Vol. 12, Issue 3 https://doi.org/10.1016/0022-3115(64)90093-5	journal	January 1964
Note on the reported high-temperature solubility of uranium in uranium monocarbide Ervin, G.; Korst, W. L. Journal of Nuclear Materials, Vol. 19, Issue 2 https://doi.org/10.1016/0022-3115(66)90112-7	journal	May 1966
The secondary creep behaviour of uranium monocarbide in compression I: Hypostoichiometric uranium monocarbide Killey, N. M. Journal of Nuclear Materials, Vol. 41, Issue 2 https://doi.org/10.1016/0022-3115(71)90078-X	journal	November 1971
The uranium-plutonium-carbon-oxygen systems Potter, P. E. Journal of Nuclear Materials, Vol. 42, Issue 1 https://doi.org/10.1016/0022-3115(72)90002-5	journal	January 1972
The chemical thermodynamic properties of nuclear materials Oetting, F. L.; Navratil, J. D.; Storms, E. K. Journal of Nuclear Materials, Vol. 45, Issue 4 https://doi.org/10.1016/0022-3115(73)90161-X	journal	January 1973
Kinetics of the carbothermic reduction of a ThO2 + UO2 + C mixture to prepare (Th, U)C Namba, Takashi; Koyama, Tadafumi; Imada, Goro Journal of Nuclear Materials, Vol. 150, Issue 2 https://doi.org/10.1016/0022-3115(87)90077-8	journal	October 1987
Kinetic study of the carbothermic synthesis of uranium monocarbide microspheres Mukerjee, S. K.; Dehadraya, J. V.; Vaidya, V. N. Journal of Nuclear Materials, Vol. 172, Issue 1 https://doi.org/10.1016/0022-3115(90)90007-A	journal	June 1990
The uranium monocarbide-uranium mononitride system Williams, J.; Sambell, R. A. J. Journal of the Less Common Metals, Vol. 1, Issue 3 https://doi.org/10.1016/0022-5088(59)90030-X	journal	June 1959
The variation of unit-cell edge of uranium monocarbide in ARC melted uranium-carbon alloys Williams, J.; Sambell, R. A. J.; Wilkinson, D. Journal of the Less Common Metals, Vol. 2, Issue 5 https://doi.org/10.1016/0022-5088(60)90043-6	journal	October 1960
Characteristics of uranium carbonitride microparticles synthesized using different reaction conditions Silva, Chinthaka M.; Lindemer, Terrence B.; Voit, Stewart R. Journal of Nuclear Materials, Vol. 454, Issue 1-3 https://doi.org/10.1016/j.jnucmat.2014.08.038	journal	November 2014
In situ synthesis and characterization of uranium carbide using high temperature neutron diffraction Reiche, H. Matthias; Vogel, Sven C.; Tang, Ming Journal of Nuclear Materials, Vol. 471 https://doi.org/10.1016/j.jnucmat.2015.12.044	journal	April 2016
Effect of carbon vacancies and oxygen impurities on the dynamical and thermal properties of uranium monocarbide Wdowik, Urszula D.; Buturlim, Volodymyr; Havela, Ladislav Journal of Nuclear Materials, Vol. 545 https://doi.org/10.1016/j.jnucmat.2020.152547	journal	March 2021
Preparation of microspheres of carbon black dispersion in uranyl-ascorbate gels as precursors for uranium carbide Brykala, Marcin; Rogowski, Marcin Progress in Nuclear Energy, Vol. 89 https://doi.org/10.1016/j.pnucene.2016.02.015	journal	May 2016
Unconventional Pathways to Carbide Phase Synthesis via Thermal Decomposition of UI₄(1,4-dioxane)₂ Ferrier, Maryline G.; Childs, Bradley C.; Silva, Chinthaka M. Inorganic Chemistry, Vol. 61, Issue 44 https://doi.org/10.1021/acs.inorgchem.2c02590	journal	October 2022
The Structures of the Carbides, Nitrides and Oxides of Uranium ¹ Rundle, R. E.; Baenziger, N. C.; Wilson, A. S. Journal of the American Chemical Society, Vol. 70, Issue 1 https://doi.org/10.1021/ja01181a029	journal	January 1948
Preparation and Structure of the Carbides of Uranium¹ Litz, Lawrence M.; Garrett, A. B.; Croxton, Frank C. Journal of the American Chemical Society, Vol. 70, Issue 5 https://doi.org/10.1021/ja01185a015	journal	May 1948
Carbides in Nuclear Energy Nature, Vol. 201, Issue 4914, p. 27-30 https://doi.org/10.1038/201027b0	journal	January 1964
Atomic Radii in Crystals Slater, J. C. The Journal of Chemical Physics, Vol. 41, Issue 10 https://doi.org/10.1063/1.1725697	journal	November 1964
Hydrolysis of Uranium Carbonitrides Sugihara, Sunao; Imoto, Shosuke Journal of Nuclear Science and Technology, Vol. 7, Issue 2 https://doi.org/10.1080/18811248.1970.9734646	journal	February 1970
Studies on the Uranium Dicarbide Phase Tagawa, Hiroaki; Fujii, Kimio; Sasaki, Yasuichi Journal of Nuclear Science and Technology, Vol. 8, Issue 5 https://doi.org/10.1080/18811248.1971.9735324	journal	May 1971
Fabrication of Uranium-Plutonium Mixed Carbide Pellets Suzuki, Yasufumi; Sasayama, Tatsuo; Arai, Yasuo Journal of Nuclear Science and Technology, Vol. 18, Issue 1 https://doi.org/10.1080/18811248.1981.9733223	journal	January 1981
Carbothermic Synthesis of Uranium-Plutonium Mixed Carbide Suzuki, Yasufumi; Arai, Yasuo; Sasayama, Tatsuo Journal of Nuclear Science and Technology, Vol. 20, Issue 7 https://doi.org/10.1080/18811248.1983.9733437	journal	July 1983
Mechanism of Carbothermic Reduction of (U, Pu)0₂to (U, Pu)C Suzuki, Yasufumi; Arai, Yasuo; Sasayama, Tatsuo Journal of Nuclear Science and Technology, Vol. 20, Issue 10 https://doi.org/10.1080/18811248.1983.9733481	journal	October 1983
Carbon positions in uranium carbides Austin, A. E. Acta Crystallographica, Vol. 12, Issue 2 https://doi.org/10.1107/S0365110X59000445	journal	February 1959
The crystal structure of UC₂ Bowman, A. L.; Arnold, G. P.; Witteman, W. G. Acta Crystallographica, Vol. 21, Issue 5 https://doi.org/10.1107/S0365110X66003670	journal	November 1966
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
The preparation and structure of barium uranium oxide BaUO _{3+ x} Barrett, S. A.; Jacobson, A. J.; Tofield, B. C. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 38, Issue 11 https://doi.org/10.1107/S0567740882009935	journal	November 1982
The UZrC Ternary Phase Diagram above 2473 K Butt, Darryl P.; Wallace, Terry C. Journal of the American Ceramic Society, Vol. 76, Issue 6 https://doi.org/10.1111/j.1151-2916.1993.tb03919.x	journal	June 1993
The Uranium-Carbon System Mallett, M. W.; Gerds, A. F.; Nelson, H. R. Journal of The Electrochemical Society, Vol. 99, Issue 5 https://doi.org/10.1149/1.2779702	journal	January 1952
Training for An Industrial Society Scott, Marshal L. Theology Today, Vol. 13, Issue 2 https://doi.org/10.1177/004057365601300208	journal	July 1956
Carbides in Nuclear Energy Chubb, Waiston Nuclear Science and Engineering, Vol. 22, Issue 4 https://doi.org/10.13182/NSE65-A20647	journal	August 1965
Development of carbide--carbon composite fuel elements for Rover reactors Davidson, K. V.; Martin, W. W.; Schell, D. H. https://doi.org/10.2172/4454241	report	October 1972
Laser Heating Study of the High-Temperature Interactions in Nanograined Uranium Carbides Chowdhury, Sanjib; Manara, Dario; Dieste-Blanco, Oliver Materials, Vol. 14, Issue 19 https://doi.org/10.3390/ma14195568	journal	September 2021

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36 MATERIALS SCIENCE
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Title: On the product phases and the reaction kinetics of carbothermic reduction of UO2+C at relatively low temperatures

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Title: On the product phases and the reaction kinetics of carbothermic reduction of UO₂+C at relatively low temperatures