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Micheau, C.; 上田 祐生; 元川 竜平; 阿久津 和宏*; 山田 悟史*; 山田 雅子*; Moussaoui, S. A.*; Makombe, E.*; Meyer, D.*; Berthon, L.*; et al.
Journal of Molecular Liquids, 401, p.124372_1 - 124372_12, 2024/05
Supramolecular organization of extractant molecules impacts metal ions separation behavior. Probing bulk and interfacial structures of the relevant systems is expected to provide key insights into the metal ion selectivity and kinetic aspects. The supramolecular features of two solvent extraction systems based on malonamide extractants, N,N,N′,N′-tetrahexylmalonamide (THMA) in toluene and N,N′-dimethyl-N,N′-dibutyl-2-tetradecylmalonamide (DBMA) in n-heptane, were studied using small-angle X-ray scattering for the organic bulk phases, as well as interfacial tension and neutron reflectivity measurements for the interfaces. In the bulk solution, THMA forms dimeric/trimeric associates but no aggregates in toluene, while DBMA forms large aggregates in n-heptane. On the other hand, THMA accumulates in a diffuse layer at the interface at high THMA concentration, whereas DBMA forms a compact but thinner layer. After Pd(II) extraction, the thickness of interfacial layers decreases in the case of THMA, and totally vanishes in the case of DBMA. Based on these new structural information, two mechanisms are proposed for Pd(II) and Nd(III) extraction with malonamides. In toluene, THMA associates slightly accumulate in the vicinity of the interface, then coordinate Pd(II) and diffuse into the organic bulk phase. In n-heptane, DBMA aggregates adsorb at the interface then pick up Nd(III) cations in their polar cores and finally diffuse into the bulk.
下北 啓輔*; 山本 勝宏*; 宮田 登*; 中西 洋平*; 柴田 基樹*; 竹中 幹人*; 山田 悟史*; 瀬戸 秀樹*; 青木 裕之; 宮崎 司*
Soft Matter, 19(11), p.2082 - 2089, 2023/03
被引用回数：0 パーセンタイル：0(Chemistry, Physical)In the case of poly(methyl methacrylate) (PMMA) thin films on a Si substrate, thermal annealing induces the formation of a layer of PMMA chains tightly adsorbed near the substrate interface, and the strongly adsorbed PMMA remains on the substrate, even after washing with toluene (hereinafter called adsorbed sample). Neutron reflectometry revealed that the concerned structure consists of three layers: an inner layer (tightly bound on the substrate), a middle layer (bulk-like), and an outer layer (surface) in the adsorbed sample. When an adsorbed sample was exposed to toluene vapor, it became clear that, between the solid adsorption layer (which does not swell) and bulk-like swollen layer, there was a "buffer layer" that could sorb more toluene molecules than the bulk-like layer. This buffer layer was found not only in the adsorbed sample but also in the standard spin-cast PMMA thin films on the substrate. When the polymer chains were firmly adsorbed and immobilized on the Si substrate, the freedom of the possible structure right next to the tightly bound layer was reduced, which restricted the relaxation of the conformation of the polymer chain strongly. The "buffer layer" was manifested by the sorption of toluene with different scattering length density contrasts.
吉宗 航*; Kikkawa, Nobuaki*; Yoneyama, Hiroaki*; Takahashi, Naoko*; Minami, Saori*; Akimoto, Yusuke*; Mitsuoka, Takuya*; Kawaura, Hiroyuki*; Harada, Masashi*; 山田 悟史*; et al.
ACS Applied Materials & Interfaces, 14(48), p.53744 - 53754, 2022/11
被引用回数：6 パーセンタイル：59.75(Nanoscience & Nanotechnology)Chemically modified carbon supports for the cathode catalyst layers of polymer electrolyte fuel cells (PEFCs) show considerable promise for boosting the oxygen reduction reaction. This study evaluated the ionomer distribution of Nafion ionomer thin films on nitrogen (N)-modified carbon surfaces along their depth direction. Neutron reflectivity (NR) measurements performed using the double-contrast technique with H
O and DO revealed that the introduction of N functional groups to carbon thin films promoted ionomer adsorption onto the surface under wet conditions (22
C, 85% relative humidity). Molecular dynamics (MD) simulations conducted to verify the origin of the robust contact between the ionomer and N-modified carbon surface revealed an ionomer adsorption mechanism on the N-modified carbon surfaces, which involved Coulomb interactions between the positively charged carbon surface and the ionomer side chains with negatively charged sulfonic acid groups. The positive surface charge, which was determined using the contents of the N functional groups estimated by X-ray photoelectron spectroscopy, was found to be sufficient as an impetus for ionomer adsorption. This strategy involving NR measurements and MD simulations can provide insights into the solid-ionomer interfacial structures in a cathode catalyst layer and can therefore be extensively employed in studies on PEFCs.
下北 啓輔*; 山本 勝宏*; 宮田 登*; 有馬 寛*; 中西 洋平*; 竹中 幹人*; 柴田 基樹*; 山田 悟史*; 瀬戸 秀樹*; 青木 裕之; et al.
Langmuir, 38(41), p.12457 - 12465, 2022/10
被引用回数：0 パーセンタイル：0(Chemistry, Multidisciplinary)We measured the neutron reflectivity (NR) of isotactic polypropylene (PP) thin films deposited on Si substrates modified by hexamethyldisilazane (HMDS) at the saturated vapor pressure of deuterated water at 25C and 60C/85% RH to investigate the effect of HMDS on the interfacial water accumulation in PP-based polymer/inorganic filler nanocomposites and metal/resin bonding materials. We found that the amount of water accumulated at the PP/Si interface decreased with increasing immersion time of the Si substrate in a solution of HMDS in hexane prior to PP film deposition. During the immersion of the Si substrate, the HMDS molecules were deposited on the Si substrate as a monolayer without aggregation. Furthermore, the coverage of the HMDS monolayer on the Si substrate increased with increasing immersion time. At 60C and 85% RH, only a slight amount of interfacial water was detected after HMDS treatment for 1200 min. As a result, the maximum concentration of interfacial water was reduced to 0.1 from 0.3, where the latter corresponds to the PP film deposited on the untreated substrate.
阿久津 和宏*; 山田 悟史*; 上田 祐生; 元川 竜平; 成田 弘一*
Applied Sciences (Internet), 12(3), p.1215_1 - 1215_10, 2022/02
被引用回数：1 パーセンタイル：28.33(Chemistry, Multidisciplinary)液-液系の界面構造を知ることは、二相系の生物・化学反応の理解には必須である。本研究では、界面の層構造を観察できる中性子反射率(NR)測定用の新しいサンプルセルを開発し、典型的な界面活性剤であるドデシル硫酸ナトリウム(SDS)の重トルエン-重水界面への吸着挙動を調べた。開発したセルは、滑らかな界面を作るためにPTFEフレームを底部に配置し、従来のセルに比べて小型化したことが特徴である。得られたNRプロファイルは容易に解析可能であり、重トルエン-重水系と空気-重水系では界面のSDS吸着層構造にわずかな違いがあることがわかった。これは、界面の条件によってSDS分子の吸着挙動が異なることに起因すると考えられる。
structural analysis of an aligning agent additive for the alignment of nematic liquid crystals on solid substrates根本 文也*; 山田 悟史*; 日野 正裕*; 青木 裕之; 瀬戸 秀樹*
Soft Matter, 18(3), p.545 - 553, 2022/01
被引用回数：0 パーセンタイル：0(Chemistry, Physical)Surface aligning agents, such as amphiphilic surfactants, are widely used to control the initial alignment of nematic liquid crystals (NLCs) in liquid crystal displays (LCDs). Generally, these agents are first coated on a substrate prior to NLC introduction. When mixed with NLCs, long alkyl chain amphiphilic agent additives may control the NLC alignment without requiring pretreatment because they may spontaneously form an adsorbed layer at the solid-NLC interface. These self-assembled layers (SALs) appear promising in the effective control of the initial alignment of LCDs. However, direct observation of the adsorbed layer structure in contact with the NLCs is challenging due to probe limitations. Furthermore, the areal densities and alignments of the amphiphiles adsorbed from NLCs at the solid-NLC interface are not previously reported. Herein, the structure of the surface aligning agent 
-hexadecyltrimethylammonium-d
bromide (d-CTAB) was investigated at the silicon-NLC interface using neutron reflectometry (NR), which indicated that the CTAB self-assembled as a monolayer, with its alignment dependent on the amphiphile concentration. At low amphiphile concentrations, the alignment of the SAL and NLCs was parallel to the substrate. With increasing amphiphile concentration, the number of amphiphiles attached to the substrate increased within the framework of the Gibbs monolayer, with the alignment of the amphiphiles and NLCs becoming perpendicular to the substrate. The experimental setup used here is comparable to those of more natural systems, such as those found in the alignment of NLCs in LCDs.
Ikami, Takaya*; Watanabe, Yuki*; 小川 紘輝*; 竹中 幹人*; 山田 悟史*; 大内 誠*; 青木 裕之; 寺島 崇矢*
ACS Macro Lett (Internet), 10(12), p.1524 - 1528, 2021/12
被引用回数：7 パーセンタイル：48.3(Polymer Science)Making ordered nanostructures in polymers and their thin films is an important technique to produce functional materials. Herein, we report instant yet precise self-assembly systems of amphiphilic random copolymers to build multilayered lamellar structures in bulk materials and thin films. Random copolymers bearing octadecyl groups and hydroxyethyl groups induced crystallization-driven microphase separation via simple evaporation from the solutions to form lamellar structures in the solid state. The domain spacing was controlled in the range between 3.1 and 4.2 nm at the 0.1 nm level by tuning copolymer composition. Interestingly, just by spin-coating the polymer solutions onto silicon substrates, the copolymers autonomously formed thin films consisting of multilayered lamellar structures, where amorphous/hydrophilic parts and crystalline octadecyl domains are alternatingly layered from a silicon substrate to the air/polymer interface at regular intervals. The lamellar domain spacing was tunable by selecting hydrophilic pendants.
宮崎 司*; 下北 啓輔*; 山本 勝宏*; 青木 裕之; 山田 悟史*; 宮田 登*
Langmuir, 36(49), p.15181 - 15188, 2020/12
被引用回数：6 パーセンタイル：31.74(Chemistry, Multidisciplinary)We investigated the polymer chain dynamics in a 2-3 nm thick poly(vinyl acetate) (PVAc) adsorption layer on a Si substrate with a native oxide layer via neutron reflectometry combined with toluene vapor-induced swelling. We can investigate the polymer chain dynamics difference in the film thickness direction by the difference in the degree of swelling of the polymer layers detected by neutron reflectometry. The mobility of the polymer chains depends on the distance from the substrate. The results elucidated that the interfacial layer with a thickness of approximately 1 nm did not swell at all with toluene vapor, which is a solvent for PVAc. Meanwhile, the surface layer excessively swells with toluene vapor compared to the bulk. This indicates that the polymer chain within the interfacial region is immobilized by the substrate through hydrogen-bonding interaction, but in the surface region, the surface effect overcomes this interfacial interaction. We concluded that the polymer chains in the adsorption layer are either strongly constrained to the substrate, owing to hydrogen bonding, or more mobile than the bulk, owing to the surface effect.
伊藤 華苗; 原田 雅史*; 山田 悟史*; 工藤 憲治*; 青木 裕之; 金谷 利治*
Langmuir, 36(43), p.12830 - 12837, 2020/11
被引用回数：13 パーセンタイル：58.64(Chemistry, Multidisciplinary)We performed HO and DO double contrast neutron reflectivity measurements on 
25-nm-thick Nafion thin films on hydrophilic and hydrophobic carbon in water and 80% relative humidity vapor to investigate the depth profile of the water and Nafion distribution. We found a dense Nafion layer at the air or water interface regardless of the carbon hydrophilicity. On the other hand, a water-rich Nafion dense layer was observed at the carbon interface only for hydrophilic carbon. The double contrast measurements provided quantitative information about the depth profile but simultaneously indicated that the sum of the volume occupancies of water and Nafion in the film was less than unity. We assessed the problem based on two possibilities: voids in the film or "residual water", which cannot be exchanged or is difficult to exchange with water outside.
中島 健次; Harjo, S.; 山田 悟史*; 及川 健一; 梶本 亮一
JAEA-Review 2018-032, 43 Pages, 2019/02
JAEA-Review-2018-032.pdf:9.78MB
大強度陽子加速器施設(J-PARC)物質・生命科学実験施設(MLF)では2017年より「MLF将来計画技術検討会」が設置され、MLFの線源や実験装置の将来計画について議論が行われてきた。同検討会では中性子実験装置についても装置カテゴリ毎に現状の問題点や今後目指すべき方向性についての報告がなされた。本報告書は、今後の将来計画の検討の一助とするべく、同検討会におけるMLF中性子実験装置に関する発表資料をまとめたものである。
中島 健次; 川北 至信; 伊藤 晋一*; 阿部 淳*; 相澤 一也; 青木 裕之; 遠藤 仁*; 藤田 全基*; 舟越 賢一*; Gong, W.*; et al.
Quantum Beam Science (Internet), 1(3), p.9_1 - 9_59, 2017/12
J-PARC物質・生命科学実験施設の中性子実験装置についてのレビューである。物質・生命科学実験施設には23の中性子ビームポートがあり21台の装置が設置されている。それらは、J-PARCの高性能な中性子源と最新の技術を組み合わせた世界屈指の実験装置群である。このレビューでは、装置性能や典型的な成果等について概観する。
山田 悟史*; 武田 全康; 山崎 大
波紋, 24(4), p.288 - 295, 2014/11
中性子反射率計は複合高分子界面構造や水面の高分子膜の形態観察、またトンネル磁気抵抗素子等をはじめとする磁性多層膜の界面磁気構造観察など、特にソフトマターの分野において他の方法では決して行うことのできない、ユニークかつインパクトの大きな成果を生み出してきた。しかしながら過去において日本での実験環境は恵まれているとは言い難く、KENSやJRR-3といった既存の施設における中性子反射装置では数インチの大きな基板に作製した試料と、数時間数十時間オーダーの測定時間が必要であった。また、測定可能なダイナミックレンジも5桁程度で、測定時間と共に海外の装置と比較して大きく見劣りするスペックであった。ところが、この状況はJ-PARCの登場により一変した。本稿が、J-PARCに設置された2台の中性子反射率計SOFIAと写楽(SHARAKU)について紹介し、反射率計の利用を検討している研究者の一助となれば幸いである。
塙 悟史; 扇柳 仁; 中村 仁一; 笹島 栄夫; 高佐 明; 細山田 龍二; 中村 武彦
no journal, ,
高燃焼度化,最適運転サイクル対応,炉出力向上などの軽水炉利用の高度化のため、高効率・高負荷での運転が可能な高度化燃料の開発が進められている。こうした燃料の安全性を適切に評価して合理性や説明性の高い許認可を行うために国として必要となるデータを取得することを目的に、JMTRを用いて異常過渡を模擬した条件で燃料の破損限界等を調べる照射試験を実施する計画である。同計画では、出力急昇を伴う異常過渡時における燃料健全性を確認するための試験を、日本への導入が予定されているBWR10
10型燃料を対象に開始する。平成23年度に開始する照射試験に向け、装置整備や試験計画の詳細化等を進めるとともに、試験技術の高度化を目指した新しいタイプの照射キャプセルの検討を進めている。
上田 祐生; Micheau, C.; 元川 竜平; 徳永 紘平; 阿久津 和宏*; 山田 悟史*
no journal, ,
発表者が開発した新規フルオラス抽出系は、優れた抽出分離能力と第三相の抑制能力を有するが、その起源は明らかになっていない。本発表では、フルオラス抽出系と従来の抽出系である有機抽出系における金属イオン抽出能力の違いの起源を明らかにするため、X線吸収微細構造(EXAFS)、中性子反射率法(NR)、及び中性子小角散乱法(SANS)を用いて金属イオン近傍、界面、及び抽出相における構造化学的観点から検証した。EXAFSの結果から、金属イオンの配位構造はフルオラス抽出系と有機抽出系で大きな違いは観られなかったのに対し、NRとSANSの結果から、界面及びバルク抽出相における抽出剤分子の集積構造に及ぼす硝酸分子の影響に違いが観られた。この違いが、フルオラス抽出系の高い抽出能力と第三相生成の抑制に寄与していると推察している。今後は、本研究で得られた知見を基に、フルオラス抽出系の改良を取り組むことを計画している。
