Aging of fuel-containing materials (fuel debris) in the Chornobyl (Chernobyl) Nuclear Power Plant and its implication for the decommissioning of the Fukushima Daiichi Nuclear Power Station

北垣 徹; Krasnov, V.*; 池田 篤史

Journal of Nuclear Materials, 576, p.154224_1 - 154224_14, 2023/04

https://doi.org/10.1016/j.jnucmat.2022.154224

Nuclear fuel debris is a complex material containing a wide range of elements, compounds, and radiation. This complexity renders all the stages of the treatment of nuclear fuel debris extremely difficult and troublesome in the technical context. The whole treatment of nuclear fuel debris is also an extremely long-term process for tens of thousands of years, during which the aging of nuclear fuel debris is an unavoidable but critical issue. This applies to the decommissioning of the damaged reactors of the Fukushima Daiichi Nuclear Power Station (1F). This review article aims at collecting and summarizing the knowledge and information about the aging of materials containing nuclear fuels (fuel-containing materials) formed as a result of the accident at ChNPP-4 in the light of the decommissioning of 1F and assessing the potential effects of aging on the nuclear fuel debris remaining in the damaged 1F reactors.

Lanthanide and actinide ion complexes containing organic ligands investigated by surface-enhanced infrared absorption spectroscopy

平田 早紀子*; 日下 良二; 明地 省吾*; 為国 誠太*; 奥寺 洸介*; 浜田 昇賢*; 坂本 知優*; 本田 匠*; 松下 高輔*; 村松 悟*; et al.

Inorganic Chemistry, 62(1), p.474 - 486, 2023/01

https://doi.org/10.1021/acs.inorgchem.2c03618

A new technique, surface-enhanced infrared absorption (SEIRA) spectroscopy, was used for the structural investigation of lanthanide (Ln) and actinide (An) complexes containing organic ligands. We synthesized thiol derivatives of organic ligands with coordination sites similar to those of diglycolamide (DGA), Cyanex-272, and -tetrakis(2-pyridinylmethyl)-1,2-ethanediamine (TPEN), which have been used for separating Ln and An through solvent extraction. These ligands were attached on a gold surface deposited on an Si prism through S-Au covalent bonds; the gold surface enhanced the IR absorption intensity of the ligands. Aqueous solutions of Ln (Eu, Gd, Tb) and An (Am) ions were loaded onto the gold surface to form ion complexes. The IR spectra of the ion complexes were obtained using FT-IR spectroscopy in the attenuated total reflection mode. In this study, we developed a new sample preparation method for SEIRA spectroscopy that enabled us to obtain the IR spectra of the complexes with a small amount of ion solution (5 L). This is a significant advantage for the IR measurement of radiotoxic Am complexes. In the IR spectra of DGA, the band attributed to C=O stretching vibrations at 1630 cm shifted to a lower wavenumber by 20 cm upon complexation with Ln and An ions. Moreover, the amount of the red-shift was inversely proportional to the extraction equilibrium constant reported in previous studies on solvent extraction. The coordination ability of DGA toward Ln and An ions could be assessed using the band position of the C=O band. The Cyanex-272- and TPEN-like ligands synthesized in this report also showed noticeable SEIRA signals for Ln and An complexes. This study indicates that SEIRA spectroscopy can be used for the structural investigation of ion complexes and provides a microscopic understanding of selective extraction of Ln and An.

Aerosol characterization during heating and mechanical cutting of simulated uranium containing debris; The URASOL project in the framework of Fukushima Daiichi fuel debris removal

Porcheron, E.*; Leblois, Y.*; Journeau, C.*; Delacroix, J.*; Molina, D.*; Suteau, C.*; Berlemont, R.*; Bouland, A.*; Lallot, Y.*; Roulet, D.*; et al.

Proceedings of International Topical Workshop on Fukushima Decommissioning Research (FDR2022) (Internet), 5 Pages, 2022/10

福島第一原子力発電所(1F)の事故炉廃止措置における重要な課題の一つが、燃料デブリの取り出しである。ONET Technologies, CEA, IRSNからなるフランスのコンソーシアムがJAEA/CLADSのために実施したURASOLプロジェクトは、燃料デブリ模擬物質の熱的・機械的加工による放射性エアロゾルの生成と特性に関する科学的基礎データの取得に取り組んでいる。VITAE施設で行われる加熱試験はレーザーによる熱的切断の代表的な条件を模擬している。機械的切断では、FUJISAN施設においてコアボーリング試験を実施した。燃料デブリ模擬物質は、非放射性試験と放射性試験のために開発されている。化学的特性評価と粒径情報の取得は、デブリ取り出しで発生する可能性のある放射性粒子の特性推定のために実施された。これらの情報は1Fにおける燃料デブリ取り出し作業において放射線防護上の対策を評価するうえで重要な情報である。

Development of an continuous air monitor for the measurement of highly radioactive alpha-emitting particulates (-aerosols) under high humidity environment

坪田 陽一; 本田 文弥; 床次 眞司*; 玉熊 佑紀*; 中川 貴博; 池田 篤史

Nuclear Instruments and Methods in Physics Research A, 1030, p.166475_1 - 166475_7, 2022/05

https://doi.org/10.1016/j.nima.2022.166475

福島第一原子力発電所(1F)の長期的な廃止措置において、損傷した原子炉に残存する核燃料デブリの取り出しは、技術的に多くの困難を伴う不可避の重要課題である。デブリ取り出しは機械的な切断を伴い、放射性核種を含む微粒子(エアロゾル)が高濃度で発生し、吸入時の健康リスクが大きい。1Fの解体・廃止措置における作業員の放射線被ばくを最小化するためには、粒子の発生場所である原子炉格納容器(PCV)内におけるエアロゾルの濃度を監視することが重要である。このため、エアロゾルのin-situモニタリングシステム(in-situ alpha air monitor: IAAM)を開発し、1Fの実環境で想定される条件下でその技術的性能を検証した。IAAMは次の4つの技術的要求を満たすことが確認された。(1)高湿度下での安定動作、(2)フィルターレス動作、(3)高計数率の線測定能力、(4)高バックグラウンドの/線下でも線が選択的に測定できること。IAAMは、高湿度環境(相対湿度100%)及び/線高バックグラウンド(最大100mSv/hの線)下で、濃度3.3 10 Bq/cm以上のエアロゾルを計数の飽和なしに、選択的に測定することが可能であることが確認された。これらの結果は、IAAMが燃料デブリの解体時及び1Fの長期的な廃止措置全体において、信頼性の高いエアロゾルのモニタリングシステムとして利用できる可能性を示すものである。

Direct temperature measurement for lamp-based heating device

墨田 岳大; 須藤 彩子; 高野 公秀; 池田 篤史

Science and Technology of Advanced Materials; Methods (Internet), 2(1), p.50 - 54, 2022/02

https://doi.org/10.1080/27660400.2022.2035097

Despite a wide variety of its practical applications, handiness, and cost-effectiveness, the advance of lamp-based heating device is obstructed by one technical difficulty in measuring the temperature on a heated material. This difficulty originates in the combination of polychromatic light source and a radiation thermometer that determines temperature from radiation (i.e. light). A new system developed in this study overcomes this intrinsic difficulty by measuring exclusively the radiation from the heated material, allowing us to perform the direct and measurement of temperature in a light-based heating device (an arc image furnace). Test measurements demonstrated the reliability of temperature measurement using the developed system as well as its promising potential for the determination of emissivity at high temperature particularly in the infrared region.

Structure of the {U} polyoxo cluster UOCl(MeO) (x = 2.3, MeO = methoxide)

Fichter, S.*; Radoske, T.*; 池田 篤史

Acta Crystallographica Section E; Crystallographic Communications (Internet), 77(8), p.847 - 852, 2021/08

https://doi.org/10.1107/S2056989021007623

A new type of polyoxo cluster complex that contains thirteen uranium atoms, {U}, was synthesised and characterised as [U(-O)(-O)(-O)Cl(O)] (x = 2.3, MeO = methoxide) (I). The complex crystallises from methanol containing tetravalent uranium (U) with a basic organic ligand. The characterised {U} polyoxo cluster complex possesses a single cubic uranium polyhedron at the centre of the cluster core. The observed shortening of U-O bonds, together with BVS calculations and the overall negative charge (2-) of (I), suggests that the central uranium atom in (I), that forms the single cubic polyhedron, is presumably oxidised to the pentavalent state (U) from the original tetravalent state (U). Complex I is, hence, the first example of a polyoxo cluster possessing a single cubic coordination polyhedron of U.

Solidification and re-melting mechanisms of SUS-BC eutectic mixture

墨田 岳大; 北垣 徹; 高野 公秀; 池田 篤史

Journal of Nuclear Materials, 543, p.152527_1 - 152527_15, 2021/01

https://doi.org/10.1016/j.jnucmat.2020.152527

Fundamental understanding of the high-temperature interaction between stainless steel (SUS) and BC is indispensable for estimating and characterizing the fuel debris generated during severe accidents of boiling water reactors (BWR), such as Fukushima Dai-ichi Nuclear Power Station (FDNPS, also referred to as "1F") in Japan. This study aims at systematically characterizing the solidified products of molten SUS-BC mixtures by powder X-ray diffraction (PXRD), scanning electron microscopy- energy dispersive X-ray spectroscopy (SEM-EDS), and thermogravimetry-differential thermal analysis (TG-DTA) with a range of the BC content relevant to the fuel debris composition expected at 1F, in order to elucidate the solidification and re-melting mechanisms. The results indicated that -Fe and (Cr,Fe)B are the major solidified phases when the BC content is below 3 mass%, while (Cr,Fe)(C,B) is formed as an additional third phase when the BC content exceeds 3 mass%. The solidification of molten SUS-BC mixture and re-melting of solidified SUS-BC melt are eutectic, which is mainly controlled by the pseudo-binary Fe-B system that is influenced by the C and Cr content and additional minor components such as Mo.

Systematic comparison of the structure of homoleptic tetradentate NO-type Schiff base complexes of tetravalent f-elements (M(IV) = Ce, Th, U, Np, and Pu) in solid state and in solution

Radoske, T.*; Kloditz, R.*; Fichter, S.*; Mrz, J.*; Kaden, P.*; Patzschke, M.*; Schmidt, M.*; Stumpf, T.*; Walter, O.*; 池田 篤史

Dalton Transactions (Internet), 49(48), p.17559 - 17570, 2020/12

https://doi.org/10.1039/d0dt03405c

A series of tetradentate NO-type Schiff base complexes with tetravalent 4f- and 5f-block metals, [M(salpn)] (Hsalpn = -disalicylidene-1,3-diaminopropane; M = Ce, Th, U, Np, and Pu), were prepared to systematically investigate their solid state structure, and their complexation behaviour in solution with the goal to investigate the subtle differences between 4f- and 5f-elements. X-ray diffraction revealed that all investigated metal cations form [M(salpn)] complexes. All the complexes show the same ligand arrangement with meridional conformation, amongst which only Ce(IV) exhibits unique behaviour upon crystallisation. [Ce(salpn)] crystallises in two less symmetric systems ( or 2/), whilst all the other [M(salpn)] crystallise in a more symmetric orthorhombic system (ban). Quantum chemical calculations suggest that the observed structural peculiarity of Ce(IV) stems from the geometrical flexibility due to the more "ionic" nature of bonds to the 4f element. H NMR measurements revealed that [M(salpn)] forms two different species in solution with and without an additional solvent molecule, where the relative distribution of the two species depends mainly on the ionic radius of the metal centre. Again, Ce(IV) behaves differently from the tetravalent actinides with a higher ratio of the solvent-molecule-coordinated species than the ratio expected from its ionic radius. Hence, this study is successful in observing subtle differences between 4f- ( Ce) and 5f-elements (actinides; Th, U, Np, and Pu) both in the solid state and in solution on an analytically distinguishable level, and in relating the observed subtle differences to their electronic structure.

Impact of ferrous iron dosing on iron and phosphorus solids speciation and transformation in a pilot scale membrane bioreactor

Wu, H.*; Wang, Y.*; 池田 篤史; Miller, C. J.*; Waite, T. D.*

Environmental Science; Water Research & Technology, 5(8), p.1400 - 1411, 2019/08

AA2019-0201.pdf:0.72MB

https://doi.org/10.1039/C9EW00225A

排水プロセスにおける燐成分回収等の目的のため、パイロットスケールの膜分離活性汚泥排水装置に二価鉄(Fe(II))を添加した際の排水装置各部位の鉄・燐の溶存化学種をX線吸収分光(XANES/EXAFS)と因子分析法を組み合わせて検討した。

Electronic structure of the high- ferromagnetic semiconductor (Ga,Fe)Sb; X-ray magnetic circular dichroism and resonance photoemission spectroscopy studies

坂本 祥哉*; Tu, N. T.*; 竹田 幸治; 藤森 伸一; Hai, P. N.*; Anh, L. D.*; 若林 勇希*; 芝田 悟朗*; 堀尾 眞史*; 池田 啓祐*; et al.

Physical Review B, 100(3), p.035204_1 - 035204_8, 2019/07

https://doi.org/10.1103/PhysRevB.100.035204

The electronic structure and the magnetism of the ferromagnetic semiconductor (Ga,Fe)Sb, whose Curie temperature can exceed room temperature, were investigated by means of X-ray absorption spectroscopy (XAS), X-ray magnetic circular dichroism (XMCD), and resonance photoemission spectroscopy (RPES). The line-shape analyses of the XAS and XMCD spectra suggest that the ferromagnetism is of intrinsic origin. The orbital magnetic moments deduced using XMCD sum rules were found to be large, indicating that there is a considerable 3 contribution to the ground state of Fe. From RPES, we observed a strong dispersive Auger peak and nondispersive resonantly enhanced peaks in the valence-band spectra. The latter is a fingerprint of the correlated nature of Fe 3 electrons, whereas the former indicates their itinerant nature. It was also found that the Fe 3 states have a finite contribution to the density of states at the Fermi energy. These states would be responsible for the ferromagnetic order in this material.