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Proton chelating ligands drive improved chemical separations for rhodium

成田 弘一*; Nicolson, R. M.*; 元川 竜平; 伊藤 文之*; 森作 員子*; 後藤 みどり*; 田中 幹也*; Heller, W. T.*; 塩飽 秀啓; 矢板 毅; et al.

Inorganic Chemistry, 58(13), p.8720 - 8734, 2019/07

Current industrial practices to extract rhodium from virgin ores carry a heavy environmental burden. Improving the efficiency of the hydrometallurgical processes to separate and recover rhodium from other precious metals provides an opportunity to improve the materials and energy balances, but the presence of mixed chloride-rhodium species following leaching by acid chloride media complicates the recovery process. In this work we have applied a broad range of analytical techniques (FT-IR spectroscopy, X-ray diffraction, EXAFS, water-transfer analysis, small-angle neutron scattering, NMR spectroscopy, and electrospray mass spectrometry), which together show that the amino-amide reagent preferentially transports chlorido-rhodium species as a 1:2 neutral assembly from aqueous 2.0 M HCl phase into an organic phase. The extractants then ligate in the outer coordination shell of the chloride-rhodium anion, making this an efficient separation process. In this sudy, we found that protonation to the extractants induced to form a proton chelate ring, which pre-organises the ligand to present an array of charge diffuse C-H bonds. This templated arrangement of positive dipoles favors complexation to the charge diffuse chloride-rhodium anion over the more charge-dense chloride anion.


Quantum paramagnet near spin-state transition

富安 啓輔*; 伊藤 菜緒子*; 岡崎 竜二*; 高橋 佑生*; 小野寺 貢*; 岩佐 和晃*; 野島 勉*; 青山 拓也*; 大串 研也*; 石川 喜久*; et al.

Advanced Quantum Technologies (Internet), 1(3), p.1800057_1 - 1800057_7, 2018/12



Effect of porosity distribution on two-phase pressure drop in a packed bed

栗崎 達也*; 伊藤 大介*; 伊藤 啓*; 齊藤 泰司*; 今泉 悠也; 松場 賢一; 神山 健司

Proceedings of 11th Korea-Japan Symposium on Nuclear Thermal Hydraulics and Safety (NTHAS-11) (Internet), 3 Pages, 2018/11



Estimation of porosity and void fraction profiles in a packed bed of spheres using X-ray radiography

伊藤 大介*; 伊藤 啓*; 齊藤 泰司*; 青柳 光裕; 松場 賢一; 神山 健司

Nuclear Engineering and Design, 334, p.90 - 95, 2018/08

 パーセンタイル:100(Nuclear Science & Technology)



Preferred site occupation of 3$$d$$ atoms in Ni$$_{x}$$Fe$$_{4-x}$$N (${it x}$ = 1 and 3) films revealed by X-ray absorption spectroscopy and magnetic circular dichroism

高田 郁弥*; 伊藤 啓太*; 竹田 幸治; 斎藤 祐児; 高梨 弘毅*; 木村 昭夫*; 末益 崇*

Physical Review Materials (Internet), 2(2), p.024407_1 - 024407_5, 2018/02

X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism measurements were performed at the Ni and Fe $$L_{2,3}$$ absorption edges for Ni$$_{x}$$Fe$$_{4-x}$$N (${it x}$ = 1 and 3) epitaxial films. Shoulders at approximately 2 eV above the Ni $$L_{2,3}$$ main peaks in the XAS spectrum of Ni$$_{3}$$FeN were interpreted to originate from hybridization of orbitals between Ni 3$$d$$ at face-centered (II) sites and N 2$$p$$ at body-centered sites, while such features were missing in NiFe$$_{3}$$N film. Similar shoulders were observed at Fe $$L_{2,3}$$ edges in both films. Hence, Ni atoms preferentially occupied corner (I) sites, where the hybridization was weak because of the relatively long distance between Ni at I sites and N atoms. The relatively large magnetic moment deduced from sum-rule analysis of NiFe$$_{3}$$N also showed a good agreement with the presence of Ni atoms at I sites.


New precise measurement of muonium hyperfine structure interval at J-PARC

上野 恭裕*; 青木 正治*; 深尾 祥紀*; 東 芳隆*; 樋口 嵩*; 飯沼 裕美*; 池戸 豊*; 石田 啓一*; 伊藤 孝; 岩崎 雅彦*; et al.

Hyperfine Interactions, 238(1), p.14_1 - 14_6, 2017/11

 被引用回数:1 パーセンタイル:17.79

MuSEUM is an international collaboration aiming at a new precise measurement of the muonium hyperfine structure at J-PARC (Japan Proton Accelerator Research Complex). Utilizing its intense pulsed muon beam, we expect a ten-fold improvement for both measurements at high magnetic field and zero magnetic field. We have developed a sophisticated monitoring system, including a beam profile monitor to measure the 3D distribution of muonium atoms to suppress the systematic uncertainty.


Experiments on gas entrainment phenomena due to free surface vortex induced by flow passing beside stagnation region

江連 俊樹; 伊藤 啓; 田中 正暁; 大島 宏之; 亀山 祐理*

Proceedings of 17th International Topical Meeting on Nuclear Reactor Thermal Hydraulics (NURETH-17) (USB Flash Drive), 9 Pages, 2017/09



Reduction and resource recycling of high-level radioactive wastes through nuclear transmutation; Isolation techniques of Pd, Zr, Se and Cs in simulated high level radioactive waste using solvent extraction

佐々木 祐二; 森田 圭介; 伊藤 圭祐; 鈴木 伸一; 塩飽 秀啓; 高橋 優也*; 金子 昌章*; 大森 孝*; 浅野 和仁*

Proceedings of International Nuclear Fuel Cycle Conference (GLOBAL 2017) (USB Flash Drive), 4 Pages, 2017/09

高レベル廃液中のPd, Zr, Se, Csは長半減期核種のPd-107, Zr-93, Se-79, Cs-135を有している。高レベル廃液から除去し、核変換により処分することで、環境負荷低減に役立てることができる。これら元素について、PdはMIDOA, NTAアミド、Csはクラウンエーテル、ZrはTODGA, HDEHP, Seはフェニレンジアミンで抽出可能である。それぞれ元素の回収条件について検討した成果について述べる。


Extraction and separation of Se, Zr, Pd, and Cs including long-lived radionuclides

佐々木 祐二; 森田 圭介; 鈴木 伸一; 塩飽 秀啓; 伊藤 圭祐; 高橋 優也*; 金子 昌章*

Solvent Extraction Research and Development, Japan, 24(2), p.113 - 122, 2017/06

硝酸溶液からオクタノールまたはドデカン溶媒へのSe, Zr, Pd, Csの溶媒抽出を行った。これら元素は長半減期の核種を含み、高レベル廃液の処理にとってこれら元素の簡便な分離方法の開発が不可欠である。Seはフェニレンジアミン、ZrはHDEHP又はTODGA、PdはMIDOA又はNTAアミドで抽出可能である。CsはDtBuDB18C6を用いて、抽出溶媒を水相の10倍を用いることで90%回収を達成できることを確認した。


New muonium HFS measurements at J-PARC/MUSE

Strasser, P.*; 青木 正治*; 深尾 祥紀*; 東 芳隆*; 樋口 嵩*; 飯沼 裕美*; 池戸 豊*; 石田 啓一*; 伊藤 孝; 岩崎 雅彦*; et al.

Hyperfine Interactions, 237(1), p.124_1 - 124_9, 2016/12

 被引用回数:3 パーセンタイル:10.17

At the Muon Science Facility (MUSE) of J-PARC (Japan Proton Accelerator Research Complex), the MuSEUM collaboration is planning new measurements of the ground state hyperfine structure (HFS) of muonium both at zero field and at high magnetic field. The previous measurements were performed both at LAMPF (Los Alamos Meson Physics Facility) with experimental uncertainties mostly dominated by statistical errors. The new high intensity muon beam that will soon be available at MUSE H-Line will provide an opportunity to improve the precision of these measurements by one order of magnitude. An overview of the different aspects of these new muonium HFS measurements, the current status of the preparation, and the results of a first commissioning test experiment at zero field are presented.



江連 俊樹; 伊藤 啓; 亀山 祐理*; 上出 英樹; 功刀 資彰*

日本原子力学会和文論文誌, 15(3), p.151 - 158, 2016/09



Study on behavior of vortex cavitation around suction pipes in sodium-cooled fast reactor geometry

江連 俊樹; 伊藤 啓; 上出 英樹; 功刀 資彰*

Thermal Science and Engineering, 24(3), p.31 - 38, 2016/07

Vortex cavitation behavior is studied using a 1/22 scaled upper plenum water model of advanced loop-type sodium-cooled fast reactor. Vortex cavitation occurrences are quantitatively grasped through visualization measurements including its transient behavior under various conditions of inlet velocity of suction pipe, water temperature and system pressure. In addition, the relation between local velocity around vortex and vortex cavitation occurrences are investigated based on results from visualization and Particle Image Velocimetry measurements. Experimental results show the difficulty of evaluation of vortex cavitation occurrences simply based on cavitation factor. And also, vortex evaluation with local circulation shows the effectiveness to organize the vortex cavitation occurrences via the evaluation of pressure decrease using vortex model.


Experimental measurement of vortex cavitation around a suction pipe inlet

江連 俊樹; 伊藤 啓; 亀山 祐理*; 栗原 成計; 功刀 資彰*

混相流, 30(2), p.189 - 196, 2016/06

In this study, experiments on vortex cavitation are carried out using a simple water cylindrical vessel with a suction nozzle. In order to understand the fundamental behavior of vortex cavitation, its instantaneous occurrence behavior is grasped by visualization using high speed camera. Velocity distribution around vortex, which causes cavitation, is also quantitatively grasped by means of Particle Image Velocimetry. From visualization measurements, vortex cavitation is considered to be triggered by the wall nuclei and the cavity develops immediately toward the suction nozzle once triggering occurs on the bottom wall. In addition, distribution of pressure decrease along vortex center estimated based on Burgers model and measured velocity distribution shows monotone increase from the bottom wall toward the suction nozzle. As the results, the cavity is thought to develop toward the suction nozzle intake immediately, if some triggering of cavitation occur on the bottom wall.


Physics-basis simulation of bubble pinch-off

伊藤 啓; 小泉 安郎; 大島 宏之; 河村 拓己*

Mechanical Engineering Journal (Internet), 3(3), p.15-00671_1 - 15-00671_9, 2016/06

The authors are developing a high-precision CFD code with an interface tracking method to simulate the gas entrainment (GE) phenomena in sodium-cooled fast reactors (SFRs), which might be caused by a highly-intensified free surface vortex. To simulate the complicated GE phenomenon, the authors' CFD code has physics-basis algorithms which model accurately the interfacial dynamic behavior, the pressure jump condition at an interface and the surface tension. Several verification problems, e.g. the slotted-disk problem, have been already solved and the accuracy of each individual algorithm is confirmed. In this paper, a basic experiment of the GE is simulated to validate the developed CFD code. In the experiment, the entrained gas flow rate is measured by image processing with a high-speed video camera. The simulation result of the entrained flow rate shows comparable value to the experimental data, that is, our CFD code is considered applicable to the evaluation of the GE in SFRs.


高速実験炉「常陽」における原子炉容器内保守・補修技術開発; 「常陽」炉心上部機構の交換

伊藤 裕道*; 大田 克; 川原 啓孝; 小林 哲彦; 高松 操; 長井 秋則

JAEA-Technology 2016-008, 87 Pages, 2016/05




高速実験炉「常陽」の原子炉容器内観察・補修技術開発; 炉心上部機構の交換作業

高松 操; 川原 啓孝; 伊藤 裕道; 宇敷 洋; 鈴木 信弘; 佐々木 純; 大田 克; 奥田 英二; 小林 哲彦; 長井 秋則; et al.

日本原子力学会和文論文誌, 15(1), p.32 - 42, 2016/03

高速実験炉「常陽」では、平成19年に「計測線付実験装置との干渉による回転プラグ燃料交換機能の一部阻害」が発生し、原子炉容器内において、計測線付実験装置(以下、MARICO-2(MAterial testing RIg with temperature COntrol 2nd))試料部が炉内ラック内の移送用ポットから突出した状態で変形していること、MARICO-2試料部と炉心上部機構(以下、UCS(Upper Core Structure))の接触により、UCS下面に設置されている整流板等が変形していることが確認された。当該燃料交換機能復旧作業の一環として、「常陽」では、平成26年5月よりUCS交換作業を開始し、同年12月に終了した。高放射線・高温環境のSFRにおける原子炉容器内補修(観察を含む)には、軽水炉にはない技術開発が必要であり、その技術レベルを高め、供用期間中の運転・保守に反映することはSFRの信頼性の向上に寄与することができる。SFRにおけるUCSの交換実績は世界でも数少なく、30年以上使用した原子炉容器内の大型構造物の交換作業の完遂により蓄積された経験・知見は、「常陽」のみならず、SFRにおける原子炉容器内観察・補修技術開発に大きく資するものと期待される。


Local electronic states of Fe$$_{4}$$N films revealed by X-ray absorption spectroscopy and X-ray magnetic circular dichroism

伊藤 啓太*; 都甲 薫*; 竹田 幸治; 斎藤 祐児; 小口 多美夫*; 末益 崇*; 木村 昭夫*

Journal of Applied Physics, 117(19), p.193906_1 - 193906_6, 2015/05

 被引用回数:4 パーセンタイル:67.17(Physics, Applied)

We performed XAS and XMCD measurements at Fe L$$_{2,3}$$ and N K-edges for Fe$$_{4}$$N epitaxial films grown by MBE. We compared experimental XAS and XMCD spectra with those simulated by a combination of a first-principles calculation and Fermi's golden rule. We revealed that the shoulders observed at Fe L$$_{2,3}$$-edges in the XAS and XMCD spectra were due to the electric dipole transition from the Fe 2p core-level to the hybridization state generated by $$sigma$$$$^{ast}$$ anti-bonding between the orbitals of N 2p at the body-centered site and Fe 3d on the face-centered (II) sites. Thus, the observed shoulders were attributed to the local electronic structure of Fe atoms at II sites. As to the N K-edge, the line shape of the obtained spectra was explained by the dipole transition from the N 1s core-level to the hybridization state formed by $$pi$$$$^{ast}$$ and $$sigma$$$$^{ast}$$ anti-bondings between the Fe 3d and N 2p orbitals.


Replacement of upper core structure in experimental fast reactor Joyo, 1; Existing damaged upper core structure jack-up test

伊藤 裕道; 鈴木 信弘; 小林 哲彦; 川原 啓孝; 長井 秋則; 坂尾 龍太*; 村田 長太郎*; 田中 淳也*; 松坂 康智*; 立野 高寛*

Proceedings of 2015 International Congress on Advances in Nuclear Power Plants (ICAPP 2015) (CD-ROM), p.1058 - 1067, 2015/05



Physics-basis simulation of bubble pinch-off

伊藤 啓; 小泉 安郎*; 大島 宏之; 河村 拓己*

Proceedings of 23rd International Conference on Nuclear Engineering (ICONE-23) (DVD-ROM), 6 Pages, 2015/05



A Preliminary evaluation of unprotected loss-of-flow accident for a prototype fast-breeder reactor

鈴木 徹; 飛田 吉春; 川田 賢一; 田上 浩孝; 曽我部 丞司; 松場 賢一; 伊藤 啓; 大島 宏之

Nuclear Engineering and Technology, 47(3), p.240 - 252, 2015/04

 被引用回数:11 パーセンタイル:10.49(Nuclear Science & Technology)

In the original licensing application for the prototype fast-breeder reactor, MONJU, the event progression during an unprotected loss-of-flow (ULOF), which is one of the technically inconceivable events postulated beyond design basis, was evaluated. Through this evaluation, it was confirmed that radiological consequences could be suitably limited even if mechanical energy was released. Following the Fukushima-Daiichi accident, a new nuclear safety regulation has become effective in Japan. The conformity of MONJU to this new regulation should hence be investigated. The objectives of the present study are to conduct a preliminary evaluation of ULOF for MONJU, reflecting the knowledge obtained after the original licensing application through CABRI experiments and EAGLE projects, and to gain the prospect of In-Vessel Retention (IVR) for the conformity of MONJU to the new regulation. The preliminary evaluation in the present study showed that no significant mechanical energy release would take place, and that thermal failure of the reactor vessel could be avoided by the stable cooling of disrupted-core materials. This result suggests that the prospect of IVR against ULOF, which lies within the bounds of the original licensing evaluation and conforms to the new nuclear safety regulation, will be gained.

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