Phase analysis of simulated nuclear fuel debris synthesized using UO, Zr, and stainless steel and leaching behavior of the fission products and matrix elements

Tonna, Ryutaro*; Sasaki, Takayuki*; Kodama, Yuji*; Kobayashi, Taishi*; Akiyama, Daisuke*; Kirishima, Akira*; Sato, Nobuaki*; Kumagai, Yuta; Kusaka, Ryoji; Watanabe, Masayuki

Nuclear Engineering and Technology, 55(4), p.1300 - 1309, 2023/04

https://doi.org/10.1016/j.net.2022.12.017

Simulated debris was synthesized using UO, Zr, and stainless steel and a heat treatment method under inert or oxidizing conditions. The primary U solid phase of the debris synthesized at 1473 K under inert conditions was UO, whereas a (U,Zr)O solid solution formed at 1873 K. Under oxidizing conditions, a mixture of UO and (Fe,Cr)UO phases formed at 1473 K whereas a (U,Zr)O solid solution formed at 1873 K. The leaching behavior of the fission products from the simulated debris was evaluated using two methods: the irradiation method, for which fission products were produced via neutron irradiation, and the doping method, for which trace amounts of non-radioactive elements were doped into the debris. The dissolution behavior of U depended on the properties of the debris and aqueous medium the debris was immersed in. Cs, Sr, and Ba leached out regardless of the primary solid phases. The leaching of high-valence Eu and Ru ions was suppressed, possibly owing to their solid-solution reaction with or incorporation into the uranium compounds of the simulated debris.

Application of high-energy-resolution X-ray absorption spectroscopy at the U L-edge to assess the U(V) electronic structure in FeUO

Yomogida, Takumi; Akiyama, Daisuke*; Ouchi, Kazuki; Kumagai, Yuta; Higashi, Kotaro*; Kitatsuji, Yoshihiro; Kirishima, Akira*; Kawamura, Naomi*; Takahashi, Yoshio*

Inorganic Chemistry, 61(50), p.20206 - 20210, 2022/12

https://doi.org/10.1021/acs.inorgchem.2c03208

FeUO was studied to clarify the electronic structure of U(V) in a metal monouranate compound. We obtained the peak splitting of HERFD-XANES spectra utilizing high-energy-resolution fluorescence detection-X-ray absorption near edge structure (HERFD-XANES) spectroscopy at the U L-edge, which is a novel technique in the U(V) compounds. Theoretical calculations revealed that the peak splitting was caused by splitting the 6d orbital of U(V). Such distinctive electronic states are of major interest to researchers and engineers working in various fields, from fundamental physics to the nuclear industry and environmental sciences for actinide elements.

Study on the relation between the crystal structure and thermal stability of FeUO and CrUO

Akiyama, Daisuke*; Kusaka, Ryoji; Kumagai, Yuta; Nakada, Masami; Watanabe, Masayuki; Okamoto, Yoshihiro; Nagai, Takayuki; Sato, Nobuaki*; Kirishima, Akira*

Journal of Nuclear Materials, 568, p.153847_1 - 153847_10, 2022/09

https://doi.org/10.1016/j.jnucmat.2022.153847

FeUO, CrUO, and FeCrUO are monouranates containing pentavalent U. Even though these compounds have similar crystal structures, their formation conditions and thermal stability are significantly different. To determine the factors causing the difference in thermal stability between FeUO and CrUO, their crystal structures were evaluated in detail. A Raman band was observed at 700 cm in all the samples. This Raman band was derived from the stretching vibration of the O-U-O axis band, indicating that FeCrUO was composed of a uranyl-like structure in its lattice regardless of its "x"' value. Mssbauer measurements indicated that the Fe in FeUO and FeCrUO were trivalent. Furthermore, FeCrUO lost its symmetry around Fe with increasing electron densities around Fe, as the abundance of Cr increased. These results suggested no significant structural differences between FeUO and CrUO. Thermogravimetric measurements for UO, FeUO, and CrUO showed that the temperature at which FeUO decomposed under an oxidizing condition (approximately 800 C) was significantly lower than the temperature at which the decomposition of CrUO started (approximately 1250 C). Based on these results, we concluded that the decomposition of FeUO was triggered by an "in-crystal" redox reaction, i.e., Fe U Fe U, which would not occur in the CrUO lattice because Cr could never be reduced under the investigated condition. Finally, the existence of Cr in FexCrUO effectively suppressed the decomposition of the FeCrUO crystal, even at a very low Cr content.

Uranium dissolution and uranyl peroxide formation by immersion of simulated fuel debris in aqueous HO solution

Kumagai, Yuta; Kusaka, Ryoji; Nakada, Masami; Watanabe, Masayuki; Akiyama, Daisuke*; Kirishima, Akira*; Sato, Nobuaki*; Sasaki, Takayuki*

Journal of Nuclear Science and Technology, 59(8), p.961 - 971, 2022/08

https://doi.org/10.1080/00223131.2021.2023055

We investigated potential degradation of fuel debris caused by HO, which is the oxidant of major impact from water radiolysis. We performed leaching experiments on different kinds of simulated debris comprising U, Fe, Cr, Ni, and Zr in an aqueous HO solution. Chemical analysis of the leaching solution showed that U dissolution was induced by HO. Raman analysis after the leaching revealed that uranyl peroxides were formed on the surface of the simulated debris. These results demonstrate that uranyl peroxides are possible alteration products of fuel debris from HO reaction. However, the sample in which the main uranium-containing phase was a U-Zr oxide solid solution showed much less uranium dissolution and no Raman signal of uranyl peroxides. Comparison of these results indicates that formation of an oxide solid solution of Zr with UO improves the stability of fuel debris against HO reaction.

Deep groundwater physicochemical components affecting actinide migration

Kirishima, Akira*; Terasaki, Mariko*; Miyakawa, Kazuya; Okamoto, Yoshihiro; Akiyama, Daisuke*

Chemosphere, 289, p.133181_1 - 133181_12, 2022/04

https://doi.org/10.1016/j.chemosphere.2021.133181

no abstracts in English

The Chemistry of thorium, plutonium and MA

Sato, Nobuaki*; Kirishima, Akira*; Watanabe, Masayuki; Sasaki, Takayuki*; Uehara, Akihiro*; Takeda, Shino*; Kitatsuji, Yoshihiro; Otobe, Haruyoshi; Kobayashi, Taishi*

The Chemistry of Thorium, Plutonium and MA, 254 Pages, 2022/03

The chemistry of nuclear materials such as Thorium (Part 1) and Plutonium (Part 2) was described in relation from the fundamentals on solid chemistry and solution chemistry to the practicals on the experiment and evaluation method in detail. Minor actinides such as Neptunium, Americium, Curium and Protoactinium, was introduced the basics on the solid and solution chemistry.

Investigation of chemical state of uranium included in simulated waste glass

Nagai, Takayuki; Akiyama, Daisuke*; Kirishima, Akira*; Sato, Nobuaki*; Okamoto, Yoshihiro

2020-Nendo "Busshitsu, Debaisu Ryoiki Kyodo Kenkyu Kyoten" Oyobi "Hito, Kankyo To Busshitsu O Tsunagu Inobeshion Soshutsu Dainamikku, Araiansu" Kenkyu Seika, Katsudo Hokokusho (CD-ROM), 1 Pages, 2021/11

no abstracts in English

The Kinetics and mechanism of HO decomposition at the UO surface in bicarbonate solution

McGrady, J.; Kumagai, Yuta; Watanabe, Masayuki; Kirishima, Akira*; Akiyama, Daisuke*; Kitamura, Akira; Kimuro, Shingo

RSC Advances (Internet), 11(46), p.28940 - 28948, 2021/08

https://doi.org/10.1039/D1RA05580A

The Chemistry of uranium (II); Method and practice

Sato, Nobuaki*; Kirishima, Akira*; Watanabe, Masayuki; Sasaki, Takayuki*; Uehara, Akihiro*; Takeda, Shino*

Uran No Kagaku (II); Hoho To Jissen, 143 Pages, 2021/03

This book describes necessary facts when readers would have an opportunity to treat Uranium for experiments. In the content, the method section shows experimental facilities and equipment including method, and the practical section mentions solution and solid state experiments using Uranium and/or radioisotopes.

The Chemistry of uranium (I); Basics and application

Sato, Nobuaki*; Kirishima, Akira*; Watanabe, Masayuki

Uran No Kagaku (I); Kiso To Oyo, 184 Pages, 2020/06

This particular book deals with fundamental items related with chemistry of Uranium and consists of basic section and practical section. In the basic section, inorganic and radiochemistry of Uranium was described. On the other hand, in the practical section, the process chemistry related with reprocessing of nuclear fuels and "debris" involved with Fukushima Daiichi Power Plant accident were described. This book is intended for use by scientists, engineers and students in the nuclear industry in their education and/or professional practice.