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上田 祐生; Micheau, C.; 元川 竜平
ファインケミカル, 54(5), p.53 - 60, 2025/05
持続可能な社会を実現するためには金属資源のリサイクルが重要である。高濃度の金属イオンを取り扱う抽出操作では、プロセスの安全な運転を阻害する油相の相分離(第三相の生成)が長年の課題であった。本稿では、フルオラス化合物の強力な疎水性を利用した、第三相を生成させない新たな抽出系開発におけるこれまでの成果をまとめた。
上田 祐生; Micheau, C.; 阿久津 和宏*; 徳永 紘平; 山田 雅子*; 山田 悟史*; Bourgeois, D.*; 元川 竜平
Langmuir, 40(46), p.24257 - 24271, 2024/11
被引用回数：0 パーセンタイル：0.00(Chemistry, Multidisciplinary)本研究では、パーフルオロヘキサン中のフルオラスリン酸エステル(TFP)からなるフルオラス抽出系において、n-ヘキサン中の有機リン酸エステル(THP)からなる類似の有機抽出系と比較して、より高い金属イオン抽出性能に寄与する主要因を分子レベルで理解するために、硝酸溶液からのZr(IV)イオンの抽出の巨視的挙動を微視的構造情報と相関させた。拡張X線吸収微細構造、中性子反射率測定、中性子小角散乱により、それぞれZr(IV)イオン周辺の局所配位構造、界面における抽出剤分子の蓄積、バルク抽出相における抽出剤分子の構造が明らかになった。その結果、いずれの抽出系においても、界面には抽出剤分子はあまり蓄積しなかった。フルオラス抽出系では、硝酸との接触により凝集体が形成され、Zr(IV)抽出後も残存した。一方、有機抽出系では、二量体のみが形成された。Zr(IV)イオン周辺の局所的な配位構造とバルク抽出相における抽出剤分子の構造の違いが、フルオラス抽出系における高いZr(IV)抽出性能に寄与していると推測している。特に、フルオラス相中のZr(IV)濃度が増加しても凝集体の大きさはほとんど変化せず、これはフルオラス抽出系で相分離が起こらないことと密接に関係していると考えられる。
杉田 剛; 吉田 博和*; 児玉 弘人*; 石垣 徹*; 大場 洋次郎*
Journal of the Ceramic Society of Japan, 132(9), p.548 - 554, 2024/09
被引用回数：1 パーセンタイル：31.17(Materials Science, Ceramics)気孔率はセラミックスの性能に不可欠な役割を果たしている。本研究では、セラミックスの気孔径分布に及ぼす粘土組成と焼成温度の影響を中性子小角散乱(SANS)測定により評価した。石英に富む純粋な笠間粘土と比較して、ムライトに富む笠間粘土ブレンドは熱処理後に細孔が小さくなった。D
Oを吸収した試料のSANS測定から、数十ナノメートルから約1マイクロメートルの大きさの開孔が水の吸収に寄与していることがわかった。閉気孔と開気孔は焼成温度の上昇とともに粗大化し、全気孔率は低下した。
熊田 高之
四季, 63, p.2 - 5, 2024/07
中性子はX線や電子線とは異なり水素に対して比較的大きな散乱長を持ち、その散乱長は軽水素Hと重水素Dで大きく異なる。そのため、ソフトマテリアルとよばれる化学・生物系複合材料の構造を解析するにあたり、特定成分を重水素ラベルすることにより散乱曲線は大きく変化し、その変化から特定成分の形状(部分構造)と多成分との絡み合い状態を決定できる。しかし、3成分以上の複合材料ともなると、部分構造を決定するには何種類もの重水素ラベル試料を用意する必要が生じる。材料科学の進歩に伴い中性子施設に持ち込まれる試料もますます複雑化する昨今において、重水素ラベル試料を複数用意するには多大な労力と困難を伴う。そこで我々は、最新の核偏極技術を採り入れることでスピンコントラスト変調実験のハードルを下げ、構造研究を展開することに成功している。本稿では最近行われた2つの研究を紹介する。
熊田 高之; 元川 竜平; 岩瀬 裕希*
Journal of Applied Crystallography, 57(Part 3), p.728 - 733, 2024/06
被引用回数：2 パーセンタイル：73.34(Chemistry, Multidisciplinary)We found that intensity of small-angle neutron scattering (SANS) from ultrahigh-purity aluminium (5N-Al) was lower than that from aluminium alloys by a factor of 40 in maximum, and thus replaced a 500 mm-diameter aluminium alloy neutron window by the 5N-Al window at SANS-J. We succeeded in decreasing the intensity of background in range of the magnitude of scattering vector Q between 0.02 and 0.2 nm
by a factor of 10 in maximum. This result indicates that, the 5N-Al window, which is made thicker to compensate lower tensile strength, generates much lower background than the aluminium alloy windows. The 5N-Al window is suitable for large-diameter neutron window in SANS diffractometers and windows in their environmental apparatus, which cannot be made of single crystalline silicon due to its poor fracture strength, processability, and/or affinity with metallic materials.
Guerinoni, E.*; Giusti, F.*; Dourdain, S.*; Dufr
che, J.-F.*; 元川 竜平; 上田 祐生; 青柳 登; Zemb, T.*; Pellet-Rostaing, S.*
Journal of Molecular Liquids, 403, p.124820_1 - 124820_11, 2024/06
被引用回数：0 パーセンタイル：0.00(Chemistry, Physical)In uranium production, liquid-liquid extraction using the AMEX (AMine EXtraction) process employs tertiary amines solubilized in an aliphatic diluent. Practical constraints as phase stability problems and co-extraction of competitive elements highlight the need for in-depth investigation and optimization. Modifying gradually the alkyl chain structure of tertiary amines, we investigate here the large variation in extraction performance in terms of Gibbs free energy of transfer using the ienaic decomposition taking into account long range interactions. We show hereby that structuration of the solvent phase can change uranium distribution by 2 orders of magnitude, which is incompatible with standard complexation theory of liquid-liquid extraction. We observe that co-extracted water is required to obtain extraction while extraction is quenched and no pair core can be formed when less than four as effective aggregation number. We conclude that the film term in the ienaic decomposition of the Gibbs energy of transfer, is the one that governs extraction performance. It shows that metal transfer is beyond complexation, and that organization of the solvent phase must be considered to quantitatively interpret the distribution coefficients.
中西 洋平*; 柴田 基樹*; 澤田 諭*; 近藤 寛朗*; 元川 竜平; 熊田 高之; 山本 勝宏*; 三田 一樹*; 宮崎 司*; 竹中 幹人*
Polymer, 306, p.127209_1 - 127209_7, 2024/06
被引用回数：2 パーセンタイル：50.19(Polymer Science)Adding silane coupling agents to rubber/silica particles systems improves their mechanical properties and the dispersion of the particles. The improvement is believed to be attributed to the enhanced adsorption of rubber molecules on the surface of silica particles by the silane coupling agent. However, the enhancement of the adsorption by silane coupling agent has not been clarified quantitatively yet. In this study, we have investigated the difference in (i) the adsorption of rubber on silica surfaces and (ii) the aggregation of silica particles in rubber/silica particle systems with and without silane coupling agents by using contrast variation neutron scattering (CV-SANS). The CVSANS results quantitatively clarified the adsorption layer's thickness and the degree of aggregation for both systems. In the case of the system without silane coupling agents, the adsorption layers do not exist around the particles, and the particles tend to aggregate. On the other hand, the adsorption layers of about 5.3 nm are formed on the surface of the particles in the system with silane coupling agents, and the addition of silane coupling agents suppressed the aggregation.
熊田 高之; 中川 洋; 三浦 大輔; 関根 由莉奈; 元川 竜平; 廣井 孝介; 稲村 泰弘; 奥 隆之; 大石 一城*; 森川 利明*; et al.
波紋, 34(2), p.50 - 53, 2024/05
本研究では、スピンコントラスト変調小角散乱法を用いてグルコース濃厚糖溶液を急冷すると氷結晶は平面上になり、その厚みは氷晶生成臨界半径と同程度の数ナノメートルしかないことを明らかにした。本研究は、グルコース分子が氷結晶の特定面に付着してその方向の成長を完全に止めてしまうことを示唆している。
関根 由莉奈; 南川 卓也; 杉田 剛; 永川 栄泰*; 柴山 由樹; 元川 竜平; 深澤 倫子*
Nanoscale, 16(19), p.9400 - 9405, 2024/05
被引用回数：3 パーセンタイル：70.50(Chemistry, Multidisciplinary)凍結架橋法により強靱なカルボキシメチルセルロースナノファイバー(CMF)/ジルコニウム(Zr)複合ハイドロゲルを開発した。本ハイドロゲルは、Zrを含むHCl溶液を凍結CMFに添加し、それを解凍することによって調製した。作製したハイドロゲルはフッ化物に対して高い吸着性を示した。本研究により、ハイドロゲルと金属の複合体の開発に有用な知見を得た。
-phenylmaleimide山崎 駿*; 金子 直矢*; 加藤 敦也*; 渡邉 航平*; 青木 大輔*; 谷口 竜王*; 唐津 孝*; 上田 祐生; 元川 竜平; 大倉 滉生*; et al.
Polymer, 298, p.126846_1 - 126846_11, 2024/04
被引用回数：5 パーセンタイル：74.19(Polymer Science)Synthesis of heat-resistant, living polymer particles via one-step reversible addition-fragmentation chain transfer precipitation polymerization (RAFTPP) of styrene and -phenylmaleimide is reported. Gel permeation chromatography and nuclear magnetic resonance spectroscopy confirmed that the polymerization proceeded in a living manner. The scanning electron microscopy results showed that the monodisperse P(St-PhMI) RAFTPP particles with a diameter of 1.88 micrometer were successfully synthesized. The P(St-PhMI) RAFTPP showed excellent thermal stability with a high glass transition temperature and a 5 percent weight loss temperature. The surface concentration of the RAFT groups was determined to be 0.181 groups/square-nanometer due to fragmentation of the RAFT groups exposed on the particles. The small-angle neutron scattering measurements showed the particle formation mechanism, in which the swollen, growing polymer chains were consumed for particle formation. The introduction of grafted chains by surface-initiated RAFT polymerization demonstrated the possibility of further functionalization of P(St-PhMI) RAFTPP particles by exploiting their living nature.
He spin filter and small-angle X-ray scattering領木 研之*; 渡部 史*; 奥平 琢也*; 高橋 慎吾*; 奥 隆之; 廣井 孝介; 元川 竜平; 中村 洋*
Journal of Chemical Physics, 160(11), p.114907_1 - 114907_9, 2024/03
被引用回数：2 パーセンタイル：37.13(Chemistry, Physical)Small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS) measurements were performed for deuterated and non-deuterated poly(ethylene glycol) (d-PEG and h-PEG, respectively) in DO and a DO/HO mixed solvent (Mix) to compere the scattering profiles. To determine the coherent scattering intensity of SANS, a He spin filter was utilized. The scattering profiles determined by SANS measurements were analyzed in terms of the wormlike chain model with touched beads along the contour of the chain. However, the SAXS profiles were not explained by the same model with uniform beads but with beads each consisting of a core and a shell having different electron densities. To explore the chain thickness determined form the SANS profile, scattering intensities for different combinations of d-PEG/DO, d-PEG/Mix, h-PEG/DO, and h-PEG/Mix were also examined.
熊田 高之; 元川 竜平; 大場 洋次郎; 中川 洋; 関根 由莉奈; Micheau, C.; 上田 祐生; 杉田 剛; 美留町 厚; 佐々木 未来; et al.
Journal of Applied Crystallography, 56(6), p.1776 - 1783, 2023/12
被引用回数：18 パーセンタイル：97.57(Chemistry, Multidisciplinary)既存のメイン検出器および高位置分解能フォトマル検出器に加えて新規に導入した前面検出器を組み合わせることにより、波数0.002nmから6nmにわたる散乱を3つの光学機器配置により切れ目なく測定できるようになった。またグラフィカルユーザーインターフェースの導入と併せて装置のユーザビリティが大幅に向上した。
辻 勇人*; 中畑 雅樹*; 菱田 真史*; 瀬戸 秀紀*; 元川 竜平; 井上 大傑*; 江川 泰暢*
Journal of Physical Chemistry Letters (Internet), 14(49), p.11235 - 11241, 2023/12
被引用回数：6 パーセンタイル：61.28(Chemistry, Physical)This work investigates the water-fraction dependence of the aggregation behavior of hydrophobic solutes in water-tetrahydrofuran (THF) and the elucidation of the role of THF using fluorescence microscopy, dynamic light scattering, neutron and X-ray scattering, as well as photoluminescence measurements. Based on the obtained results, the following model is proposed: hydrophobic molecules are molecularly dispersed in the low-water-content region (10-20 vol %), while they form mesoscopic particles upon increasing the water fraction to 
30 vol percent. This abrupt change is due to the composition fluctuation of the water-THF binary system to form hydrophobic areas in THF, followed by THF-rich droplets where hydrophobic solutes are incorporated and form loose aggregates. Further increasing the water content prompts the desolvation of THF, which decreases the particle size and generates tight aggregates of solute molecules. This model is consistent with the luminescence behavior of the solutes and will be helpful to control the aggregation state of hydrophobic solutes in various applications.
柴田 基樹*; 中西 洋平*; 阿部 淳*; 有馬 寛*; 岩瀬 裕希*; 柴山 充弘*; 元川 竜平; 熊田 高之; 高田 慎一; 山本 勝宏*; et al.
Polymer Journal, 55(11), p.1165 - 1170, 2023/11
被引用回数：2 パーセンタイル：17.57(Polymer Science)Marine ecosystem degradation due to micro plastics is a significant environmental problem, as acknowledged by Sustainable Development Goal 14. Decomposition of plastics using near critical or supercritical water is one of the promising methods to reduce micro plastics. To attain the optimization of the method for improving environmental friendliness, it is necessary to clarify the structural change of materials during the process. We, thus, investigated the decomposition processes of polystyrene particles dispersed in deuterated water (DO) during heating under near critical or supercritical conditions by using in situ small-angle neutron scattering. Under subcritical conditions, the PS particles were swollen by DO due to increased compatibility with temperature. Near the critical point in subcritical conditions, the cleavage of PS chains in the particles occurred, so that the swollen ratio was much enhanced though the PS particles kept their shapes. In a supercritical condition, the PS particles were degraded into oil including oligomers or monomers and the phase-separated structures with styrene-rich and DO-rich regions.
Micheau, C.; 上田 祐生; 元川 竜平; Bauduin, P.*; Girard, L.*; Diat, O.*
Langmuir, 39(31), p.10965 - 10977, 2023/07
被引用回数：11 パーセンタイル：75.59(Chemistry, Multidisciplinary)Understanding clay flotation mechanisms has become a major concern because of the increasing level of environmental contamination of soil and ground water by heavy metals and radionuclides. Clays are often used as sorbents for extracting metals in indirect flotation processes but can function simultaneously as defoamers. However, how foam generation and stability depend on the molecular interactions between the clays and surfactant is still controversial. In the present study, an amine polyethoxylated surfactant was used as a bifunctional surfactant that collected clay particles and acted as a foaming agent in the flotation process. The pH conditions strongly affected the surfactant physicochemical properties, allowing the clay extraction efficiency to be tuned. The interfacial recovery factor of the clays almost reached 100 percent under acidic (pH lower than 6) and neutral (pH 6-10) conditions, whereas it was negative under alkaline conditions (pH higher than 10), contrary to expectations. To elucidate the mechanisms involved in the particle flotation process for each of the pH conditions, the bulk and foam phases were analyzed. The effects of electrostatic interactions between the solutes and multiscale structure on the clay extraction behavior were investigated by electrophoretic measurements, dynamic light scattering, small-angle neutron scattering, and image analysis. Based on these results, three flotation processes were found depending on pH range: surfactant foam fractionation at pH higher than 10; clay particle foam flotation at pH 6-10; and particle froth flotation at pH lower than 6.
microphase separation磯崎 祐嘉*; 東原口 誠也*; 金子 直矢*; 山崎 駿*; 谷口 竜王*; 唐津 孝*; 上田 祐生; 元川 竜平
Chemistry Letters, 51(6), p.625 - 628, 2022/06
被引用回数：4 パーセンタイル：28.02(Chemistry, Multidisciplinary)Polymer photonic crystals (PPCs) that selectively reflect visible light were prepared by triblock polymerization-induced microphase separation via reversible addition-fragmentation chain transfer polymerization. The addition of homopolymer to the polymerization system swelled a specific phase of the microdomains, enabling the preparation of PPCs with long-wavelength structural colors. Small-angle neutron scattering confirmed the increase in the domain spacing of the lamellar microdomains with the addition of homopolymer, while maintaining their morphology.
He spin filter at a pulsed neutron source奥平 琢也; 上田 祐生; 廣井 孝介; 元川 竜平; 稲村 泰弘; 高田 慎一; 奥 隆之; 鈴木 淳市*; 高橋 慎吾*; 遠藤 仁*; et al.
Journal of Applied Crystallography, 54(2), p.548 - 556, 2021/04
被引用回数：5 パーセンタイル：50.64(Chemistry, Multidisciplinary)Heスピンフィルタを中性子スピン解析子として使用することにより、パルス中性子源での中性子小角散乱実験において、偏極解析を行うことに成功した。本実験に使用したHeスピンフィルタは中性子小角散乱実験を行うために十分な立体角をカバーすることができ、He偏極緩和時間も数日と長く、これは実験を完遂するために十分な性能である。水素原子による非干渉性散乱は非常に大きく、試料の組成から計算によって非干渉性散乱量を見積もる試みが行われていたが、正確に非干渉性散乱量を決定することは難しかった。しかし本研究では試料内での中性子の多重散乱を考慮した偏極解析実験を行うことで、干渉性散乱と非干渉性散乱を正確に分離することが可能となった。現在までパルス中性子源での中性子小角散乱では、偏極解析の手法が確立されていなかったが、本成果によって、様々な種類の試料に対して干渉性散乱と非干渉性散乱を正確に分離することができるようになると予想される。
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
被引用回数：21 パーセンタイル：75.49(Chemistry, Inorganic & Nuclear)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 study, 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.
元川 竜平; 小林 徹; 遠藤 仁; Mu, J.*; Williams, C. D.*; Masters, A. J.*; Antonio, M. R.*; Heller, W. T.*; 長尾 道弘*
ACS Central Science, 5(1), p.85 - 96, 2019/01
被引用回数：56 パーセンタイル：85.91(Chemistry, Multidisciplinary)We present a hierarchical aggregate model of an organic phase containing a coordination species that acts as a fundamental building unit of higher-order structures formed in the organic phase. We aimed to elucidate the fundamental aspects of the microscopic structure and phase separation occurring in ionic separation and recovery systems during solvent extraction. The coordination species aggregate through a hydrogen-bonding network formed by interaction between the hydrophilic part of the coordination species with extracted water and acid molecules. This reduces the hydrophilic surface area, resulting in subsequent formation of small primal clusters of 2 to 3 nm in diameter. The primal clusters further aggregate due to van der Waals interaction to form large aggregates of 
10 nm in diameter. The size of the primal cluster does not depend on the concentration of the coordination species, whereas the size of the large aggregate increases as the aggregation number of the primal clusters increases. We conclude that hybrid interaction is a key driving force in the formation and growth of the hierarchical aggregate and the induction of phase separation of the organic phase.
中島 多朗*; 稲村 泰弘; 伊藤 崇芳*; 大石 一城*; 大池 広志*; 賀川 史敬*; 吉川 明子*; 田口 康二郎*; 加倉井 和久*; 十倉 好紀*; et al.
Physical Review B, 98(1), p.014424_1 - 014424_5, 2018/07
被引用回数：9 パーセンタイル：37.26(Materials Science, Multidisciplinary)MnSi中に発生する磁気スキルミオンの相転移の挙動を中性子小角散乱ストロボスコピック測定により観測した。温度を50K/秒という速度で急激に変化させている間に13マイクロ秒の時間分解能で中性子小角散乱パターンの時間変化を測定することに成功し、その結果、温度の上昇によって磁気スキルミオンが消滅する様子や、急速な冷却過程で生成されたスキルミオンが本来存在できない低温まで過冷却状態で残る様子などが明らかとなった。
