The ambient- and high-temperature oxidation behaviour of U3+N and Ln3+N compounds relevant to spent nuclear fuel
Source abstract
Abstract
Abstract Actinide and lanthanide binary nitrides ( An N, Ln N), are isostructural cubic compounds relevant to next-generation nuclear fuels which require detailed understanding regarding their oxidative degradation for safe disposal, yet a systematic comparative description remains. Herein, the room- and high-temperature oxidation behaviour of U 3+ N and Ln 3+ N ( Ln = Pr, Nd, Gd, Tb, Dy, Ho, Tm and Lu) compounds is examined via a combination of X-ray diffraction, electron microscopy, thermogravimetric, and X-ray absorption spectroscopy analysis. At room temperature, UN was found to undergo an oxygen mediated oxidising mechanism, which contrasted chemically and microstructurally to the Ln N’s , which followed a consistent hydrolysis mechanism. At high temperature, more congruent behaviour is determined with direct occurrence of oxide products, where the onset temperature of oxidation was found to correlate with the ionic radii of examined Ln /U cations. The results provide insight into the behaviour of these compounds in UN-based spent fuel, particularly phase separation variability and incongruent behaviour during inadvertent oxidation.
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OpenAlex topics: Nuclear Materials and Properties · Radioactive element chemistry and processing · Nuclear reactor physics and engineering
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References (61)
Show source-provided references
1. Kelly, J. E. Generation IV international forum: a decade of progress through international cooperation. Prog. Nucl. Energy 77, 240–246 (2014).10.1016/j.pnucene.2014.02.010 ↗
2. Dehlin, F., Wallenius, J. & Bortot, S. An analytic approach to the design of passively safe lead-cooled reactors. Ann. Nucl. Energy 169, 108971 (2022).10.1016/j.anucene.2022.108971 ↗
3. Elkhawas, N. A., Reda, S. M., Amin, E. A. & Anwar, D. Deployment study of accident tolerant fuels in small modular advanced high temperature reactor. Phys. Scr. 100, 095307 (2025).10.1088/1402-4896/ae05d3 ↗
4. Degueldre, C., Goddard, D., Berhane, G., Simpson, A. & Boxall, C. Simulation of uranium mononitride spent fuel: a thermodynamic approach. J. Nuclear Mater., 154900 (2024).10.1016/j.jnucmat.2024.154900 ↗
5. Degueldre, C., Goddard, D. T., Berhane, G., Simpson, A. & Boxall, C. Simulation of uranium mononitride spent fuel: A crystallographic approach. J. Nucl. Mater. 562, 153612 (2022).10.1016/j.jnucmat.2022.153612 ↗
6. Dehadraya, J. V. et al. The oxidation of uranium-cerium mononitride microspheres. J. Alloy. Compd. 257, 313–321 (1997).10.1016/S0925-8388(97)00010-8 ↗
7. Vinograd, V. L., Bukaemskiy, A. A., Deissmann, G. & Modolo, G. Thermodynamic model of the oxidation of Ln-doped UO2. Sci. Rep. 13, 17944 (2023).10.1038/s41598-023-42616-x ↗
8. Murphy, G. L. et al. Probing the long- and short-range structural chemistry in the C-type bixbyite oxides Th0.40Nd0.48Ce0.12O1.76, Th0.47Nd0.43Ce0.10O1.785, and Th0.45Nd0.37Ce0.18O1.815 via synchrotron X-ray diffraction and absorption spectroscopy. ACS Omega 9, 27397–27406 (2024).10.1021/acsomega.4c02200 ↗
9. Shirokiy, D. et al. Speciation and radiation stability of Cr and Ln “Grey-Phases” within Cr-doped (Ln,U)O2 spent fuel model materials. npj Mater. Degrad. https://doi.org/10.1038/s41529-026-00752-5 (2026).10.1038/s41529-026-00752-5 ↗
10. Holmes-Hewett, W. F., Miller, J. D., Ahmad, H. G., Granville, S. & Ruck, B. J. Rare-earth nitrides: fundamental advances and applications in cryogenic electronics. J. Phys. D: Appl. Phys. 58, 343001 (2025).10.1088/1361-6463/adf1b2 ↗
11. Xiao, K., Shi, X., Zhang, X., Ping, Q. & Du, L. The emergence of novel magnetic properties in ternary iron nitrides toward spintronics: first-principles calculations. Phys. Chem. Chem. Phys. PCCP 27, 6677–6686 (2025).10.1039/D5CP00405E ↗
12. Kwon, H. R., Yang, J. W. & Jang, H. W. Metal nitride catalysts for photoelectrochemical and electrochemical catalysis. Exploration 5, 20240013 (2025).10.1002/EXP.20240013 ↗
13. Porter, W. N., Turaczy, K. K., Yu, M., Mou, H. & Chen, J. G. Transition metal nitride catalysts for selective conversion of oxygen-containing molecules. Chem. Sci. 15, 6622–6642 (2024).10.1039/D4SC01314J ↗
14. Fahrenholtz, W. G. & Hilmas, G. E. Ultra-high temperature ceramics: materials for extreme environments. Scr. Mater. 129, 94–99 (2017).10.1016/j.scriptamat.2016.10.018 ↗
15. Wan, Y. et al. A nitride-reinforced NbMoTaWHfN refractory high-entropy alloy with potential ultra-high-temperature engineering applications. Engineering 30, 110–120 (2023).10.1016/j.eng.2023.06.008 ↗
16. Kneisel, K. et al. Synthesis, structural, and Raman investigation of lanthanide nitride powders (Ln = La, Ce, Nd, Sm, Gd, Tb, Dy, Er, Lu). ACS omega 9, 47842–47847 (2024).10.1021/acsomega.4c08638 ↗
17. Dell, R. M., Wheeler, V. J. & McIver, E. J. Oxidation of uranium mononitride and uranium monocarbide. Trans. Faraday Soc. 62, 3591 (1966).10.1039/tf9666203591 ↗
18. Watkins, J. K., Gonzales, A., Wagner, A. R., Sooby, E. S. & Jaques, B. J. Challenges and opportunities to alloyed and composite fuel architectures to mitigate high uranium density fuel oxidation: Uranium mononitride. J. Nucl. Mater. 553, 153048 (2021).10.1016/j.jnucmat.2021.153048 ↗
19. Lawrence Bright, E. et al. Oxidation and passivation of the uranium nitride (001) surface. Corrosion Sci. 110705 (2022).
20. Sole, M. J. & Van Der Walt, C. M. Oxidation and deformation studies of uranium nitride by electron microscopy. Acta Metall. 16, 501–510 (1968).10.1016/0001-6160(68)90124-7 ↗
21. Paljević, M. & Despotović, Z. Oxidation of uranium mononitride. J. Nucl. Mater. 57, 253–257 (1975).10.1016/0022-3115(75)90208-1 ↗
22. Goncharov, V. G. et al. Energetics of oxidation and formation of uranium mononitride. J. Nucl. Mater. 569, 153904 (2022).10.1016/j.jnucmat.2022.153904 ↗
23. Vinograd, V. L., Bukaemskiy, A. A., Modolo, G., Deissmann, G. & Bosbach, D. Thermodynamic and structural modelling of non-stoichiometric Ln-doped UO2 solid solutions, Ln={La, Pr, Nd, Gd}. Front. Chem. 9, 705024 (2021).10.3389/fchem.2021.705024 ↗
24. Liu, J. et al. Thermal expansion and steam oxidation of uranium mononitride analysed via in situ neutron diffraction. J. Nucl. Mater. 575, 154215 (2023).10.1016/j.jnucmat.2022.154215 ↗
25. Rundle, R. E., Baenziger, N. C., Wilson, A. S. & McDonald, R. A. The structures of the carbides, nitrides and oxides of uranium. J. Am. Chem. Soc. 70, 99–105 (1948).10.1021/ja01181a029 ↗
26. Kai, H., Katsura, M. & Sano, T. Nitrogen pressure region for monophase UC -UN solid solution and relation of its lattice parameter and composition. (1969).
27. Shannon, R. D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr. Sect. A 32, 751–767 (1976).10.1107/S0567739476001551 ↗
28. Baur, W. H. Effective ionic radii in nitrides. Crystallogr. Rev. 1, 59–83 (1987).10.1080/08893118708081679 ↗
29. Olcese, G. L. Interconfiguration fluctuation of cerium in CeN as a function of temperature and pressure. J. Phys. F: Met. Phys. 9, 569–578 (1979).10.1088/0305-4608/9/3/018 ↗
30. Kappler, J. P. et al. Anomalous behaviour of X-ray absorption observed on the highly correlated cerium nitride (CeN) compound. J. de. Phys. I 1, 1381–1387 (1991).
31. Natali, F. et al. Rare-earth mononitrides. Prog. Mater. Sci. 58, 1316–1360 (2013).10.1016/j.pmatsci.2013.06.002 ↗
32. Wan, Y. et al. Structure and oxidation properties of CeN thin films prepared by DC reactive magnetron sputtering. Surf. Coat. Technol. 381, 125168 (2020).10.1016/j.surfcoat.2019.125168 ↗
33. Ikawa, K. & Taketani, K. Room temperature oxidation of UN powder. J. Nucl. Sci. Technol. 7, 433–438 (1970).10.1080/18811248.1970.9734717 ↗
34. Beňadik, A. Atmospheric corrosion of uranium monocarbide, mononitride, and carbonitrides. Collect. Czechoslovak Chem. Commun. 35, 988–993 (1970).10.1135/cccc19700988 ↗
35. Murphy, G. L. et al. Deconvoluting Cr states in Cr-doped UO2 nuclear fuels via bulk and single crystal spectroscopic studies. Nat. Commun. 14, 2455 (2023).10.1038/s41467-023-38109-0 ↗
36. Ramanantoanina, H. et al. High-energy resolution X-ray spectroscopy reveals bonding characteristics of La3+ homologues of actinium radiopharmaceuticals. Commun. Chem. https://doi.org/10.1038/s42004-026-01929-4 (2026).10.1038/s42004-026-01929-4 ↗
37. Gouder, T., Seibert, A., Rebizant, J., Huber, F. & Havela, L. Comparative photoemission study of actinide (Am, Pu, Np and U) metals, nitrides, and hydrides. MRS Proceedings 986 https://doi.org/10.1557/proc-986-0986-oo01-02 (2006).10.1557/proc-986-0986-oo01-02 ↗
38. Irber, W. The lanthanide tetrad effect and its correlation with K/Rb, Eu/Eu∗, Sr/Eu, Y/Ho, and Zr/Hf of evolving peraluminous granite suites. Geochim. Cosmochim. Acta 63, 489–508 (1999).10.1016/S0016-7037(99)00027-7 ↗
39. Fleming, P., Farrell, R. A., Holmes, J. D. & Morris, M. A. The rapid formation of La(OH) 3 from La2O3 powders on exposureto water vapor. J. Am. Ceram. Soc. 93, 1187–1194 (2010).10.1111/j.1551-2916.2009.03564.x ↗
40. Rao, G. A. R., Mukerjee, S. K., Vaidya, V. N., Venugopal, V. & Sood, D. D. Oxidation and hydrolysis kinetic studies on UN. J. Nucl. Mater. 185, 231–241 (1991).10.1016/0022-3115(91)90340-D ↗
41. Kulyukhin, S. A., Nevolin, Y. M., Gordeev, A. V. & Bessonov, A. A. Gas-phase volume oxidation of uranium mononitride. Radiochemistry 61, 146–155 (2019).10.1134/S1066362219020036 ↗
42. Arai, Y., Maeda, A., Shiozawa, K. -i & Ohmichi, T. Chemical forms of solid fission products in the irradiated uranium—plutonium mixed nitride fuel. J. Nucl. Mater. 210, 161–166 (1994).10.1016/0022-3115(94)90233-X ↗
43. Uno, M., Kurosaki, K., Yamanaka, S. & Minato, K. Thermal properties of simulated high burn up nitride fuels and nitride ADS targets. MRS Proc. 1043. https://doi.org/10.1557/proc-1043-t13-03.10.1557/proc-1043-t13-03 ↗
44. Smailos, E. Reactions of fission products in carbide and nitride fuel based on simulated experiments. Report No. KFK 1953, (Kernforschungszentrum Karlsruhe, 1974).
45. Holleck, H., Smailos, E. & Thümmler, F. Zur Mischkristallbildung von UN mit den Nitriden der Seltenen Erden CeN und NdN. J. Nucl. Mater. 28, 105–109 (1968).10.1016/0022-3115(68)90061-5 ↗
46. Holleck, H., Smailos, E. & Thümmler, F. Zur Mischphasenbildung der Mononitride in den Systemen U- (Y, La, Pr)-N. J. Nucl. Mater. 32, 281–289 (1969).10.1016/0022-3115(69)90077-4 ↗
47. Giacchetti, G., Sari, C. & Walker, C. T. Actinides and fission products distribution in fast breeder nitride fuel. Nucl. Technol. 28, 216–225 (1976).10.13182/NT76-A31562 ↗
48. Schnick, W., Huppertz, H. & Lauterbach, R. High temperature syntheses of novel nitrido- and oxonitrido-silicates and sialons using rf furnaces. J. Mater. Chem. 9, 289–296 (1999).10.1039/a803900c ↗
49. Toby, B. H. & Dreele, R. B. v. GSAS-II: the genesis of a modern open-source all purpose crystallography software package. J. Appl. Crystallogr. 46, 544–549 (2013).10.1107/S0021889813003531 ↗
50. Schacherl, B. et al. Implementation of cryogenic tender X-ray HR-XANES spectroscopy at the ACT station of the CAT-ACT beamline at the KIT Light Source. J. Synchrotron Radiat. 29, 80–88 (2022).10.1107/S1600577521012650 ↗
51. Solé, V. A., Papillon, E., Cotte, M., Walter, P. & Susini, J. A multiplatform code for the analysis of energy-dispersive X-ray fluorescence spectra. Spectrochim. Acta Part B At. Spectrosc. 62, 63–68 (2007).10.1016/j.sab.2006.12.002 ↗
52. Schacherl, B. et al. Resonant inelastic X-ray scattering tools to count 5 f electrons of actinides and probe bond covalency. Nat. Commun. 16, 1221 (2025).10.1038/s41467-024-54574-7 ↗
53. Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using Ifeffit. J. Synchrotron Radiat. 12, 537–541 (2005).10.1107/S0909049505012719 ↗
54. Scheinost, A. C. et al. ROBL-II at ESRF: a synchrotron toolbox for actinide research. J. Synchrotron Radiat. 28, 333–349 (2021).10.1107/S1600577520014265 ↗
55. Brown, R. C. & Clark, N. J. Composition limits and vaporization behaviour of rare earth nitrides. J. Inorg. Nucl. Chem. 36, 2507–2514 (1974).10.1016/0022-1902(74)80462-8 ↗
56. Ettmayer, P., Waldhart, J., Vendl, A. & Banik, G. Über die Mischkristallbildung von ThN mit LaN, CeN, PrN, NdN, SmN, GdN, DyN und ErN. Monatshefte f.ür. Chem. 111, 945–948 (1980).10.1007/BF00899260 ↗
57. Klesnar, H. & Rogl, P. F. Phase relations in the ternary systems rare-earth metal (RE)-boron-nitrogen, where RE=Tb. Dy Ho Er Tm. Lu Sc. Y. high. Temp.High. Press. 22, 453–457 (1990).
58. Mullica, D. F., Milligan, W. O. & Beall, G. W. Crystal structures of Pr(OH)3, Eu(OH)3 and Tm(OH)3. J. Inorg. Nucl. Chem. 41, 525–532 (1979).10.1016/0022-1902(79)80438-8 ↗
59. Beall, G. W., Milligan, W. O., Dillin, D. R., Williams, R. J. & McCoy, J. J. Refinement of neodymium trihydroxide. Acta Crystallogr. Sect. B Struct. Crystallogr. Cryst. Chem. 32, 2227–2229 (1976).10.1107/S0567740876007437 ↗
60. Desgranges, L., Baldinozzi, G., Rousseau, G., Nièpce, J.-C. & Calvarin, G. Neutron diffraction study of the in situ oxidation of UO2. Inorg. Chem. 48, 7585–7592 (2009).10.1021/ic9000889 ↗
61. Sasa, Y. & Atoda, T. Nonstoichiometric hexagonal close-packed uranium sesquinitride. J. Am. Ceram. Soc. 53, 102–105 (1970).10.1111/j.1151-2916.1970.tb12020.x ↗