Synthesis of heat-resistant living polymer particles by one-step reversible addition-fragmentation chain transfer precipitation polymerization of styrene and -phenylmaleimide

Yamazaki, Shun*; Kaneko, Naoya*; Kato, Atsuya*; Watanabe, Kohei*; Aoki, Daisuke*; Taniguchi, Tatsuo*; Karatsu, Takashi*; Ueda, Yuki; Motokawa, Ryuhei; Okura, Koki*; et al.

Polymer, 298, p.126846_1 - 126846_11, 2024/04

https://doi.org/10.1016/j.polymer.2024.126846

Two-dimensional metal-organic nanosheets composed of single-molecule magnets; Structural modulation and enhanced magnetism utilizing the steric hindrance effect

Aratani, Ikumi*; Horii, Yoji*; Kotani, Yoshinori*; Osawa, Hitoshi*; Tanida, Hajime; Ina, Toshiaki*; Watanabe, Takeshi*; Yano, Yoko*; Mizoguchi, Akane*; Takajo, Daisuke*; et al.

Journal of Materials Chemistry C, 12(2), p.724 - 735, 2024/01

https://doi.org/10.1039/D3TC03360K

UO dissolution in bicarbonate solution with HO; The Effect of temperature

McGrady, J.; Kumagai, Yuta; Kitatsuji, Yoshihiro; Kirishima, Akira*; Akiyama, Daisuke*; Watanabe, Masayuki

RSC Advances (Internet), 13(40), p.28021 - 28029, 2023/09

https://doi.org/10.1039/D2RA08131H

Upon nuclear waste canister failure and contact of spent nuclear fuel with groundwater, the UO matrix of spent fuel will interact with oxidants in the groundwater generated by water radiolysis. Bicarbonate (HCO) is often found in groundwater, and the HO induced oxidative dissolution of UO in bicarbonate solution has previously been studied under various conditions. Temperatures in the repository at the time of canister failure will differ depending on the location, yet the effect of temperature on oxidative dissolution is unknown. To investigate, the decomposition rate of HO at the UO surface and dissolution of U in bicarbonate solution (0.1, 1, 10 and 50 mM) was analysed at various temperatures (10, 25, 45 and 60 C). At [HCO] 1 mM, the apparent equilibrium concentration of U decreased with increasing temperature. This was attributed to the formation of U-bicarbonate species at the surface and a change in the mechanism of HO decomposition from oxidative to catalytic. At 0.1 mM, no obvious correlation between temperature and U dissolution was observed, and thermodynamic calculations indicated this was due to a change in the surface species. A pathway to explain the observed dissolution behaviour of UO in bicarbonate solution as a function of temperature was proposed.

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.

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.

A Study of HO-induced oxidative degradation of simulated fuel debris

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

Hoshasen Kagaku (Internet), (113), p.61 - 64, 2022/04

The severe accident at TEPCO's Fukushima Daiichi Nuclear Power Station resulted in generation of fuel debris. The fuel debris is in contact with water and the radiolysis of water can accelerate degradation of the debris. The analysis of particles sampled from inside or near the damaged reactors indicates the complicated compositions of the fuel debris. It is challenging to estimate the effect of water radiolysis on such a complicated material. Therefore, in this study, we investigated the potential degradation process by leaching experiments of simulated fuel debris in aqueous HO solution. The results show that the reaction of HO induced uranium dissolution from most of the samples and then formation of uranyl peroxides. In contrast, a sample that had U-Zr oxide solid solution as the major phase exhibited remarkable resistance to HO. These findings revealed that the degradation of the simulated debris reflects the reactivity and stability of the uranium phase in the matrices.

Improving the safety of the high temperature gas-cooled reactor "HTTR" based on Japan's new regulatory requirements

Hamamoto, Shimpei; Shimizu, Atsushi; Inoi, Hiroyuki; Tochio, Daisuke; Homma, Fumitaka; Sawahata, Hiroaki; Sekita, Kenji; Watanabe, Shuji; Furusawa, Takayuki; Iigaki, Kazuhiko; et al.

Nuclear Engineering and Design, 388, p.111642_1 - 111642_11, 2022/03

https://doi.org/10.1016/j.nucengdes.2021.111642

Following the Fukushima Daiichi Nuclear Power Plant accident in 2011, the Japan Atomic Energy Agency adapted High-Temperature engineering Test Reactor (HTTR) to meet the new regulatory requirements that began in December 2013. The safety and seismic classifications of the existing structures, systems, and components were discussed to reflect insights regarding High Temperature Gas-cooled Reactors (HTGRs) that were acquired through various HTTR safety tests. Structures, systems, and components that are subject to protection have been defined, and countermeasures to manage internal and external hazards that affect safety functions have been strengthened. Additionally, measures are in place to control accidents that may cause large amounts of radioactive material to be released, as a beyond design based accident. The Nuclear Regulatory Commission rigorously and appropriately reviewed this approach for compliance with the new regulatory requirements. After nine amendments, the application to modify the HTTR's installation license that was submitted in November 2014 was approved in June 2020. This response shows that facilities can reasonably be designed to meet the enhanced regulatory requirements, if they reflect the characteristics of HTGRs. We believe that we have established a reference for future development of HTGR.

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

Hydrochemical investigation at the Mizunami Underground Research Laboratory; Compilation of groundwater chemistry data in the Mizunami Group and the Toki Granite (fiscal year 2019)

Fukuda, Kenji; Watanabe, Yusuke; Murakami, Hiroaki; Amano, Yuki; Aosai, Daisuke*; Hara, Naohiro*

JAEA-Data/Code 2020-012, 80 Pages, 2020/10

JAEA-Data-Code-2020-012.pdf:3.55MB

Japan Atomic Energy Agency has been investigating groundwater chemistry to understand the influence of excavation and maintenance of underground facilities as part of the Mizunami Underground Research Laboratory (MIU) Project in Mizunami, Gifu, Japan. In this report, we compiled data of groundwater chemistry and microbiology obtained at the MIU in the fiscal year 2019. In terms of ensuring traceability of data, basic information (e.g. sampling location, sampling time, sampling method and analytical method) and methodology for quality control are described.