Thermal conductivity evaluation of Am-doped oxide fuels

Yokoyama, Keisuke; Watanabe, Masashi; Onishi, Takashi; Yano, Yasuhide; Tokoro, Daishiro*; Sugata, Hiromasa*; Kato, Masato*

JAEA-Research 2025-002, 18 Pages, 2025/05

JAEA-Research-2025-002.pdf:1.73MB

It is advocated as a development target of fast reactors (FRs) to allow for the of use of mixed oxide (MOX) fuels containing minor actinide (MA) separated and recovered from spent fuels with the aim of reducing the volume and toxicity of high-level radioactive waste generated from nuclear reactors. In the development of MAMOX fuels, it is important behavior to understand the thermal properties such as thermal conductivity for fuel design and analysis of the irradiation. However, there are only a few reports on the thermal properties of MA-MOX fuels, and neither the effects of MA contents nor of oxygen non-stoichiometry in MOX fuels on their thermal conductivities have been fully understood. In this study, the thermal conductivities of MOX fuels with up to 15% Am content were measured at near-stoichiometric composition and the relationship between thermal conductivity and Am content was evaluated. Moreover, the thermal conductivities of Am-doped UO fuels were also measured and evaluated by comparison with Am-MOX to evaluate the effect of Am content. The fuel samples used in this study were three types of MOX with a Pu content of 30% and different Am contents (5%, 10%, and 15%), and UO containing 15% Am. The thermal conductivities of specimens were calculated from the thermal diffusivities measured by the laser flash method, the density of the specimens and, the heat capacity at constant pressure. The oxygen partial pressure during the measurement was controlled at that of the targeted near-stoichiometric composition. The thermal conductivities of all specimens exhibited a decline with increasing temperature and Am content, with a particularly pronounced reduction observed below 1,173 K. The results of the classical phonon scattering model analysis of the measured thermal conductivities showed that the effect of lattice strain due to the Am addition was significant on the thermal resistivity change, and the effect was comparable for both MOX and UO.

Oxygen potential measurement of UAmO at 1473, 1573, and 1673 K

Watanabe, Masashi; Yokoyama, Keisuke; Vauchy, R.; Kato, Masato; Sugata, Hiromasa*; Seki, Takayuki*; Hino, Tetsushi*

Journal of Nuclear Materials, 599, p.155232_1 - 155232_5, 2024/10

https://doi.org/10.1016/j.jnucmat.2024.155232

Oxygen potential data of UAmO were measured at 1473, 1573, and 1673 K by thermogravimetry. In UAnO, where An stands for Pu or Am, and for a given value of y and Oxygen/Metal ratio, the oxygen potential of UAmO is higher than that of UPuO. The valence of cations in the hypostoichiometric region is similar to that of Nd-doped UO. At the stoichiometric composition, it is estimated to be Am, U, and U (for charge compensation of Am). The experimental data were analyzed using a defect chemistry model, and a relationship connecting the oxygen-to-metal ratio, the temperature, and the equilibrium oxygen partial pressure was proposed.

Experimental visualization of water/ice phase distribution at cold start for practical-sized polymer electrolyte fuel cells

Higuchi, Yuki*; Yoshimune, Wataru*; Kato, Satoru*; Hibi, Shogo*; Setoyama, Daigo*; Isegawa, Kazuhisa*; Matsumoto, Yoshihiro*; Hayashida, Hirotoshi*; Nozaki, Hiroshi*; Harada, Masashi*; et al.

Communications Engineering (Internet), 3, p.33_1 - 33_7, 2024/02

https://doi.org/10.1038/s44172-024-00176-6

Breaking the hard-sphere model with fluorite and antifluorite solid solutions

Vauchy, R.; Hirooka, Shun; Watanabe, Masashi; Kato, Masato

Scientific Reports (Internet), 13, p.2217_1 - 2217_8, 2023/02

https://doi.org/10.1038/s41598-023-29326-0

Oxygen potential, oxygen diffusion, and defect equilibria in UO

Watanabe, Masashi; Kato, Masato

Frontiers in Nuclear Engineering (Internet), 1, p.1082324_1 - 1082324_9, 2023/01

https://doi.org/10.3389/fnuen.2022.1082324

Since the oxygen potential and the oxygen coefficient of UO have a significant impact on fuel performance, many experimental data have been obtained. However, experimental data of the oxygen potential and the oxygen diffusion coefficient in the high temperature region above 1673 K are very limited. In the present study, we aimed to obtain these data and analyze them by defect chemistry. The oxygen potentials and the oxygen chemical diffusion coefficient of UO were measured by the gas equilibrium method in the near stoichiometric region at temperatures ranging from 1673 to 1873 K. A data set of oxygen potentials was made together with literature data and analyzed by defect chemistry. The oxygen potential of UO was determined as a function of O/U ratio and temperature, and an equation representing the relationship was derived. The oxygen chemical diffusion coefficient values obtained in this study were reasonably close to the literature values. The oxygen partial pressure dependence of the oxygen chemical diffusion coefficients was predicted from the evaluated results of the oxygen potential data, but no clear dependence was observed.

Measurements of thermal conductivity for near stoichiometric (UPuAm)O (z = 0.05, 0.10, and 0.15)

Yokoyama, Keisuke; Watanabe, Masashi; Tokoro, Daishiro*; Sugimoto, Masatoshi*; Morimoto, Kyoichi; Kato, Masato; Hino, Tetsushi*

Nuclear Materials and Energy (Internet), 31, p.101156_1 - 101156_7, 2022/06

https://doi.org/10.1016/j.nme.2022.101156

In current nuclear fuel cycle systems, to reduce the amount of high-level radioactive waste, minor actinides (MAs) bearing MOX fuel is one option for burning MAs using fast reactor. However, the effects of Am content in fuel on thermal conductivity are unclear because there are no experimental data on thermal conductivity of high Am bearing MOX fuel. In this study, The thermal conductivities of near stoichiometric (UPuAm)O solid solutions(z = 0.05, 0.10, and 0.15) have been measured between room temperature (RT) and 1473 K. The thermal conductivities decreased with increasing Am content and satisfied the classical phonon transport model ((A+BT)) up to about 1473 K. A values increased linearly with increasing Am content because the change in ionic radius affects the conduction of the phonon due to the solid solution in U and Am. B values were independent of Am content.

Oxygen self-diffusion in near stoichiometric (U,Pu)O at high temperatures of 1673-1873 K

Watanabe, Masashi; Kato, Masato; Sunaoshi, Takeo*

Journal of Nuclear Materials, 542, p.152472_1 - 152472_7, 2020/12

https://doi.org/10.1016/j.jnucmat.2020.152472

The oxygen self-diffusion coefficients in near stoichiometric (U,Pu)O at high temperatures were successfully measured by thermogravimetry combined with the oxygen isotope exchange method. The activation energy for oxygen diffusion in the stoichiometric composition of (U,Pu)O was evaluated from experimental data, and the value was determined to be 248 kJ/mol. In addition, the defect migration energies of (U,Pu)O were derived, and the oxygen self-diffusion coefficients were evaluated using these. As a result, good agreement was found between the experimental data and the oxygen self-diffusion coefficients calculated using the defect migration energies.

Physical properties of non-stoichiometric (U,Pu)O

Watanabe, Masashi; Matsumoto, Taku; Hirooka, Shun; Morimoto, Kyoichi; Kato, Masato

2018 GIF Symposium Proceedings (Internet), p.315 - 320, 2020/05

Recently, a research group studying at Plutonium Fuel Development Facility (PFDF) in Japan Atomic Energy Agency has systematically measured vast amounts of physical properties in the non-stoichiometric (U, Pu)O. Lattice parameter, elastic modulus, thermal expansion, oxygen potential, oxygen chemical diffusion coefficient and thermal conductivity were successfully measured as function of Pu content, O/M ratio and temperature, and the effects of Pu content and O/M ratio on their physical properties were evaluated. In this work, those experimental data are reviewed, and latest experimental data set on the non-stoichiometric (U, Pu)O are presented. The data set would be available in development of a fuel performance code.

Density Functional Theory (DFT)-based bonding analysis correlates ligand field strength with Ru Mssbauer parameters of ruthenium-nitrosyl complexes

Kaneko, Masashi; Kato, Akane*; Nakashima, Satoru*; Kitatsuji, Yoshihiro

Inorganic Chemistry, 58(20), p.14024 - 14033, 2019/10

https://doi.org/10.1021/acs.inorgchem.9b02024

We applied density functional theory calculations to ruthenium-nitrosyl complexes, which are known to exist in high-level radioactive waste, to give a theoretical correlation between Ru Mssbauer spectroscopic parameters ( and ) and ligand field strength () for the first time. The structures of the series of complexes, [Ru(NO)L] (L = Br, Cl, NH, CN), were modeled based on the corresponding single-crystal X-ray coordinates. The comparisons of the geometries and total energies between the different spin states suggested that the singlet spin state of [Ru(II)(NO)L] complexes were the most stable. The calculated results of both the and values reproduced the experimental results by reported previously and increased in the order of L = Br, Cl, NH, CN. Finally, we estimated the ligand field strength () based on molecular orbitals, assuming C symmetry and showed the increase of values in that order, being consistent with well-known spectrochemical series of ligands. The increase attributes to the strengthening of the abilities of -donor and -acceptor of the L-ligands to the Ru atom, resulting in the increase of the values.

Defect chemistry and basic properties of non-stoichiometric PuO

Kato, Masato; Nakamura, Hiroki; Watanabe, Masashi; Matsumoto, Taku; Machida, Masahiko

Defect and Diffusion Forum, 375, p.57 - 70, 2017/05

http://doi.org/10.4028/www.scientific.net/DDF.375.57

The basic properties of PuO were reviewed, and the equilibrium defects in PuO were evaluated from the experimental data of the oxygen potential and electrical conductivity as well as the Ab-initio calculation results. Consistency among various properties was confirmed, and the mechanistic models for thermal property representations were derived.