Adsorption mechanism of Eu onto newly synthesized fluorous-compound-impregnating adsorbent

荒井 陽一; 渡部 創; 渡部 雅之; 新井 剛*; 勝木 健太*; 吾郷 友宏*; 藤川 寿治*; 武田 啓佑*; 福元 博基*; 保科 宏行*; et al.

Nuclear Instruments and Methods in Physics Research B, 554, p.165448_1 - 165448_10, 2024/09

https://doi.org/10.1016/j.nimb.2024.165448

Radioactive aqueous and organic liquid wastes contaminated by U and radioactive materials have been generated through solvent extraction experiments on nuclear fuel materials. Although incineration and denitrification / conversion processes are promising for treatment of such liquid wastes, installation of large equipment is essential. Treatment of liquid wastes generated from the reprocessing experiments is one of important tasks of Systematic Treatments of RAdioactive liquid wastes for Decommissioning (STRAD) project, and the recovery technologies of nuclear materials from the spent solvent has been developed. However, recovery of trace amounts of nuclear fuel material from aqueous solutions with wide pH range is still a challenging task. In our previous study, the porous silica particles with a high specific surface area bearing the iminodiacetic acid (IDA) functional group were revealed to be applicable to recover cations. Although the IDA group introduced adsorbents showed an excellent adsorption reaction from the aqueous solution, further improvement related to the adsorption amount is indispensable for application to the radioactive liquid treatment. In this study, fluorous ligands with IDA group were newly synthesized, and its complexation behavior with cations was investigated in order to understand the adsorption mechanism.

Quantum critical behavior of the hyperkagome magnet MnCoSi

山内 宏樹; Sari, D. P.*; 安井 幸夫*; 坂倉 輝俊*; 木村 宏之*; 中尾 朗子*; 大原 高志; 本田 孝志*; 樹神 克明; 井川 直樹; et al.

Physical Review Research (Internet), 6(1), p.013144_1 - 013144_9, 2024/02

https://doi.org/10.1103/PhysRevResearch.6.013144

-Mn-type family alloys Mn have three-dimensional antiferromagnetic (AFM) corner-shared triangular network. The antiferromagnet MnRhSi shows magnetic short-range order (SRO) over a wide temperature range of approximately 500 K above the Nel temperature = 190 K. MnCoSi has the smallest lattice parameter and the lowest in the family compounds. The quantum critical point (QCP) from AFM to the quantum paramagnetic state is expected near a cubic lattice parameter of 6.15 of MnCoSi is only 140 K, quantum critical behavior is observed in MnCoSi as the enhancement of the electronic specific heat coefficient . We study how the magnetic SRO appears in MnCoSi by using neutron scattering, SR, and physical property measurements. The experimental results show that the neutron scattering intensity of the magnetic SRO does not change much regardless of the suppressed magnetic moment in the long-range magnetic ordered state compared to those of MnRhSi. The initial asymmetry drop ratio of SR above becomes small, and the magnetic SRO temperature is suppressed to 240 K. The results suggest that the MnCoSi is close to the QCP in the Mn system.

Decontamination and solidification treatment on spent liquid scintillation cocktail

渡部 創; 高畠 容子; 小木 浩通*; 大杉 武史; 谷口 拓海; 佐藤 淳也; 新井 剛*; 梶並 昭彦*

Journal of Nuclear Materials, 585, p.154610_1 - 154610_6, 2023/11

https://doi.org/10.1016/j.jnucmat.2023.154610

Treatment of spent scintillation cocktail generated by analysis of radioactivity is one of important tasks for management of nuclear laboratories. This study proposed a procedure consists of adsorption of radioactivity and solidification of residual liquid wastes, and fundamental performance of each step was experimentally tested. Batch-wise adsorption showed excellent adsorption performance of Ni onto silica-based adsorbent, and chelate reaction was suggested as the adsorption mechanism by EXAFS analysis. Alkaline activate material successfully solidified the liquid waste, and TG/DTA and XRD analyses revealed that the organic compounds exist inside the matrix. Only 1% of the loaded organic compounds were leaked from the matrix by a leaching test, and most of the organic compounds should be stably kept inside the matrix.

Effects of local bonding between solute atoms and vacancy on formation of nanoclusters in Al-Mg-Si alloys

栗原 健輔*; Lobzenko, I.; 都留 智仁; 芹澤 愛*

Materials Transactions, 64(8), p.1930 - 1936, 2023/08

https://doi.org/10.2320/matertrans.MT-L2023006

Al-Mg-Si合金で形成されたナノクラスターは、形成温度に応じて合金の時効挙動に影響を与える。本研究では、第一原理計算を用いて、Mg、Si原子、およびAlマトリックス中の空孔間の2体および3体相互作用を評価し、ナノクラスターの形成に対する局所結合構造の影響を評価した。まず、モンテカルロ計算を行い、Al-Mg-Si合金で形成されたナノクラスターの安定した構造を評価した。Alマトリクス中ではMg-Si結合とSi-Vac結合が安定していることが確認された。その結果、Al中の溶質原子は異種元素が凝集しやすく、Si原子は空孔と強い引力相互作用を持っていることがわかった。また、Al中のMg-Si空孔三体結合は、Mg-Si二体結合およびSi空孔二体結合よりも安定であることがわかった。したがって、MgとSi原子からなる安定した局所結合により、空孔はクラスター領域内に強くトラップされると考えられる。これは、Alマトリックス内のナノクラスターが溶質原子と空孔の間の安定した結合によって熱的に安定化されることを示している。これらの結果は、ナノクラスターの内部結合が、熱安定性だけでなく、低温での時効中のナノクラスターの形成と成長挙動にも重要な役割を果たすことを示唆している。

Design of MA(III)/Ln(III) separation process of extraction chromatography technology

阿久澤 禎*; Kim, S.-Y.*; 久保田 真彦*; Wu, H.*; 渡部 創; 佐野 雄一; 竹内 正行; 新井 剛*

Journal of Radioanalytical and Nuclear Chemistry, 331(12), p.5851 - 5858, 2022/12

https://doi.org/10.1007/s10967-022-08658-7

In this work, we have examined Ln(III) and MA(III) separation conditions by the extraction chromatography using HONTA adsorbent to decide the Ln(III)/MA(III) separation process fow. From the research results, we found the simulated element of Am(III) for HONTA adsorbent and the conditions to use it. In addition, Ln(III) and Am(III) (simulated element) separation experiments were carried out using the HONTA adsorbent packed column, we have determined the column separation conditions for Am(III) such as order of fow solution and fow rate.

Acid dissociation constant of bis(2-ethylhexyl) hydrogen phosphate impregnated in a polymer layer coated on silica microparticles

宮川 晃尚*; 竹内 正行; 新井 剛*; 渡部 創; 佐野 雄一; 中谷 清治*

Bulletin of the Chemical Society of Japan, 95(4), p.566 - 568, 2022/04

https://doi.org/10.1246/bcsj.20220011

高分子相に含浸させた抽出剤のpKaが、架橋度や他の抽出剤の共存によって変化し、高分子相の疎水性が変化することを実証した。本成果は、新規な固体抽出吸着剤の開発に役立つと考えられる。

Development of a membrane reactor with a closed-end silica membrane for nuclear-heated hydrogen production

Myagmarjav, O.; 田中 伸幸; 野村 幹弘*; 野口 弘喜; 今井 良行; 上地 優; 久保 真治; 竹上 弘彰

Progress in Nuclear Energy, 137, p.103772_1 - 103772_7, 2021/07

https://doi.org/10.1016/j.pnucene.2021.103772

Hydrogen production from nuclear energy has attracted considerable interest as a clean energy solution to address the challenges of climate change and environmental sustainability. With respect to the large-scale and economical production of hydrogen using nuclear energy, the thermochemical water-splitting iodine-sulfur (IS) process is a promising method. The IS process uses sulfur and iodine compounds to decompose water into its elemental constituents, hydrogen and oxygen, by using three coupled chemical reactions: the Bunsen reaction; sulfuric acid decomposition; and hydrogen iodide (HI) decomposition. The decomposition of HI is the efficiency-determining step of the process. In this work, a membrane reactor with a silica membrane closed on one end was designed, and its potential for hydrogen production from HI decomposition was explored. In the reactor-module design, only one end of the membrane tube was fixed, while the closed-end of the tube was freely suspended to avoid thermal expansion effects. The closed-end silica membranes were prepared for the first time by a counter-diffusion chemical vapor deposition of hexyltrimethoxysilane. In application, HI conversion of greater than 0.60 was achieved at a decomposition temperature of 400C. Thus, the membrane reactor with closed-end silica membrane was shown to produce a successful equilibrium shift in the production of hydrogen via HI decomposition in the thermochemical IS process.

Microscopic analyses on Zr adsorbed IDA chelating resin by PIXE and EXAFS

荒井 陽一; 渡部 創; 大野 真平; 野村 和則; 中村 文也*; 新井 剛*; 瀬古 典明*; 保科 宏行*; 羽倉 尚人*; 久保田 俊夫*

Nuclear Instruments and Methods in Physics Research B, 477, p.54 - 59, 2020/08

https://doi.org/10.1016/j.nimb.2019.10.028

Used PUREX process solvent generated from reprocessing process of spent nuclear fuel contains a small amount of U and Pu complexed with tributyl phosphate (TBP) or dibutyl phosphate (DBP). The radioactive nuclides should be removed from the solvent for safety storage or disposal. The iminodiacetic acid (IDA) type chelating resin was proposed as promising procedures for efficient recovery of the trapped cations in the solvent. In order to reveal the distribution and amount of Zr in the particle and local structure of Zr complex formed in the adsorbent, PIXE and EXAFS analyses on the Zr adsorbed chelating resin were carried out. Micro-PIXE analysis proved that it is an effectual method for quantitative analysis of trace adsorbed elements. Moreover, some of the adsorption sites were possibly occupied by the molecules. On the other hand, Zr-K edge EXAFS analysis suggested that extraction mechanism of Zr from the aqueous solution and the solvent was different.

放射性核種の長期安定化を指向した使用済みゼオライト焼結固化技術の開発(委託研究); 平成30年度英知を結集した原子力科学技術・人材育成推進事業

廃炉国際共同研究センター; 芝浦工業大学*

JAEA-Review 2019-028, 71 Pages, 2020/03

JAEA-Review-2019-028.pdf:6.46MB

日本原子力研究開発機構(JAEA)廃炉国際共同研究センター(CLADS)では、平成30年度英知を結集した原子力科学技術・人材育成推進事業(以下、「本事業」という)を実施している。本事業は、東京電力ホールディングス福島第一原子力発電所の廃炉等をはじめとした原子力分野の課題解決に貢献するため、国内外の英知を結集し、様々な分野の知見や経験を、従前の機関や分野の壁を越えて緊密に融合・連携させた基礎的・基盤的研究及び人材育成を推進することを目的としている。平成30年度の新規採択課題から実施主体を文部科学省からJAEAに移行することで、JAEAとアカデミアとの連携を強化し、廃炉に資する中長期的な研究開発・人材育成をより安定的かつ継続的に実施する体制を構築した。本研究は、研究課題のうち、平成30年度「放射性核種の長期安定化を指向した使用済みゼオライト焼結固化技術の開発」について取りまとめたものである。本研究は、継続して発生するCs等の放射性核種を吸着したゼオライト(使用済みゼオライト)の焼結固化法の開発を目的とする。焼結固化法は、使用済みゼオライトにガラスをバインダーとして添加し、それらを焼結することで核種を固定化する新たな固化法である。本法は、ガラス固化と比較して固化体の大幅な減容や焼成固化と同程度の安定な固化体の形成が期待できる。本事業では、コールド試験により焼結固化に適したガラスの選定、焼結温度等の最適化を図りホット試験で実証する。平成30年度においてバインダーの候補ガラスの熱特性、及び加熱雰囲気が焼結固化に及ぼす影響について調査した。また、放射性核種を含む模擬汚染水を作成するための照射済燃料を選定し、試料の状態を確認した。さらに、ゼオライトの固化、焼成固化等に関する既存の研究成果及び最新の研究動向を調査した。

Improvement in flow-sheet of extraction chromatography for trivalent minor actinides recovery

渡部 創; 先崎 達也; 柴田 淳広; 野村 和則; 竹内 正行; 中谷 清治*; 松浦 治明*; 堀内 勇輔*; 新井 剛*

Journal of Radioanalytical and Nuclear Chemistry, 322(3), p.1273 - 1277, 2019/12

https://doi.org/10.1007/s10967-019-06808-y

Extraction chromatography flow-sheet employing octyl(phenyl)--diisobutylcarbonoylmethylphosphine oxide (CMPO) and (2-ethylhexyl) hydrogen phosphate (HDEHP) extractants for trivalent minor actinide recovery was modified to improve column separation performance. Excellent trivalent minor actinides recovery performance was obtained by column separation experiments on nitric acid solution containing the trivalent minor actinides and representative fission product elements, i.e. recovery yields 93% with sufficient decontamination factors against the fission products. Those are the best performance which we have ever obtained by experiments inside hot cell.