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田村 由起子*; 荒川 勝利*; 竹中 幹人*; 中西 洋平*; 藤波 想*; 柴田 基樹*; 山本 勝宏*; 宮田 登*; 山田 雅子*; 瀬戸 秀紀*; et al.
Polymer, 333, p.128662_1 - 128662_8, 2025/08
被引用回数：0To investigate the relationship between the mechanical properties of silica-filled styrene-butadiene rubber (SBR) and the amount of bound rubber at the filler/rubber interface, the polymer matrix was extracted from silica-filled SBR using toluene at room temperature. In this study, this extraction process was reproduced by leaching a thermally annealed SBR layer deposited on a Si substrate in toluene at room temperature, where the adsorption layer of the SBR was grown at the interface with the substrate by thermal annealing. The SBR adsorption layer on the Si substrate has two-layer structures consisting of an inner and outer adsorption layers, which correspond to the tightly and loosely bound rubbers on the filler surface of the silica-filled SBR, respectively. For the sample annealed for less than 6 h, the outer adsorption layer, loosely bound to the substrate, was easily leached in toluene for 5 min, leaving only the inner adsorption layer on the substrate. For the samples annealed for more than 24 h, a large portion of the outer adsorption layer remained on top of the inner adsorption layer as a terrace structure. However, even for the sample annealed for 24 h, treating with toluene for 24 h completely leached the outer adsorption layer from the inner adsorption layer, although the inner adsorption layer remained on the substrate. It was found that the loosely bound rubber in the silica-filled SBR could be easily extracted from the filler surface, along with the free polymer chains in the polymer matrix during extraction with toluene at room temperature. In contrast, the tightly bound rubber was not leached by toluene at room temperature. This may be because the interfacial polymer chains within approximately 1 nm of the substrate surface were strongly constrained to the substrate, and even toluene molecules were excluded.
谷崎 志帆*; 久保 智弘*; Bito, Yosuke*; 森 茂樹*; 青木 裕之; 佐藤 浩太郎*
RSC Sustainability (Internet), 3(4), p.1714 - 1720, 2025/04
Catechol is a functional group that is versatile and abundant in nature, exhibiting various functions. In this report, a tert-butoxycarbonyl (Boc)-protected vinyl catechol (VC) monomer was synthesized from caffeic acid, which is a bio-abundant molecule found generally in coffee beans, in order to develop a bio-based adhesive. Reversible addition-fragmentation chain transfer (RAFT) polymerization of the Boc-protected VC afforded well-defined, bio-based catechol-containing polymers with controlled molecular weights and narrow molecular weight distributions. Specifically, it was facile to deprotect the pendent Boc groups quantitatively under acidic or thermal conditions to provide the desired P(VC) without requiring further purification. Consequently, the catechol-containing polymer as a primer showed highly strong adhesion against aluminum when coupled with a commercially available polyurethane adhesive.
田口 美岐*; 宮田 登*; 宮崎 司*; 青木 裕之; Ozawa, Satoru*; 長谷川 龍一 *; 盛満 裕真*; 川口 大輔*; 山本 悟*; 田中 敬二*
Polymer Journal, 7 Pages, 2025/03
被引用回数：0 パーセンタイル：0.00(Polymer Science)Polyrotaxane (PR) exhibits unique mechanical properties due to the ability of its cyclic molecules to move or slide along the axial chain. Thus, to design advanced polymer-based composite materials and organic devices, it is crucial to better understand the aggregation states at the surface and substrate interface in polymer films containing PR. Here, we report the depth profile of PR along the direction normal to the interface when it is mixed with polystyrene (PS). Neutron reflectivity and X-ray photoelectron spectroscopy revealed that PS and PR segregated at the surface and substrate interface, respectively, and that the extent of segregation depended on the length of PS. The surface enrichment of PS is driven by both energy and entropy, whereas the enrichment of PR at the substrate interface is energy driven.
堀池 優貴*; 青木 裕之; 大内 誠*; 寺島 崇矢*
Journal of the American Chemical Society, 147(8), p.6727 - 6738, 2025/02
被引用回数：0 パーセンタイル：0.00(Chemistry, Multidisciplinary)Herein, we report water-intercalated and humidity-responsive lamellar materials obtained from the self-assembly of sodium acrylate (ANa)/alkyl acrylate (RA) random copolymers. The random copolymers efficiently absorbed water into the hydrophilic ANa/main chain phase from the outer environment to form lamellar structures consisting of the water-intercalated hydrophilic segments and the hydrophobic side chains. The lamellar formation involves controlling the weight fraction of hydrophilic segments containing water to 40-70 wt% by the RA content, hydrophobic side chains, and the amount of absorbed water. The domain spacing can be controlled in the range of 2-6 nm. More interestingly, the lamellar materials reversibly afford expansion and contraction of the domain spacing in the sub-1 nm level via the absorption and release of water, in response to relative humidity. The multilayered lamellar formation process via the intercalation of water was analyzed in situ by neutron reflectometry and atomic force microscopy measurements under humid conditions. The polymer film further served as a moisture-sensitive actuator that macroscopically induces deformation responsive to humidity.
Liu, Y.*; 宮田 登*; 宮崎 司*; 春藤 淳臣*; 川口 大輔*; 田中 敬二*; 青木 裕之
ACS Applied Materials & Interfaces, 8 Pages, 2025/00
The performance of structural adhesives is strongly influenced by the interfacial structure between the adhesive and adherend. In this study, we developed a nanometric stable interfacial layer derived from an epoxy resin system containing excess hardener. This layer, formed on solid substrates, exhibited excellent structural stability, even after extensive solvent washing. Neutron reflectometry (NR) was employed to investigate its structure under both dry and humid conditions, revealing a robust and well-defined interface that suppressed moisture accumulation at the adherend interface. FT-IR spectroscopy confirmed an excess of unreacted amino groups in the adsorbed layer, enabling further curing reactions with freshly applied epoxy resin. Re-coating experiments demonstrated that the adsorbed layer remained intact after thermal curing, suggesting strong interfacial compatibility. Notably, the presence of the adsorbed layer led to a significant enhancement in adhesive performance. Lap shear tests showed that the adhesion strength of the epoxy resin nearly doubled when the adsorbed layer was introduced at the interface. This approach does not rely on external coupling agents or primers, but instead utilizes a homologous material system to tailor interfacial properties through molecular-level design. The strategy presented here offers a practical and scalable method for improving adhesion in epoxy systems. By directly engineering the adhesive interface using components intrinsic to the epoxy formulation, this method enables reliable and enhanced bonding performance without altering the bulk material.
山本 勝宏*; 今井 達也*; 河合 純希*; 伊藤 恵利*; 宮崎 司*; 宮田 登*; 山田 悟史*; 瀬戸 秀紀*; 青木 裕之
ACS Applied Materials & Interfaces, 16(48), p.66782 - 66791, 2024/11
被引用回数：0 パーセンタイル：0.00(Nanoscience & Nanotechnology)In this study, a silicon-based copolymer, poly(tris(trimethylsiloxy)-3-methacryloxypropylsilane)-co-poly(N,N-dimethyl acrylamide), thin film was subjected to plasma surface treatment to make its surface hydrophilic (biocompatible). Neutron reflectivity (NR) measurement of the plasma-treated thin film showed a decrease in the film thickness (etching width: similar to 20 nm) and an increase in the scattering length density (SLD) near the surface (similar to 15 nm). The region with a considerably high SLD adsorbed water (D
O) from its saturated vapor, indicating its superior surface hydrophilicity. Nevertheless of the hydrophilicity, the swelling of the thin film was suppressed. Hard X-ray photoelectron spectroscopy (HAXPES) performed at various takeoff angles revealed that the thin-film surface (similar to 20 nm depth) underwent extensive oxidation. NR and HAXPES analysis quantitatively yielded the depth profiling of elemental compositions in a few tens of nm scale. Si oxidation and hydrogen elimination (probably CH
groups) in the vicinity of the surface region increased the SLD and decreased the hydrophobicity. A combination of Soft X-ray photoelectron spectroscopy and NR measurements revealed the surface chemical composition and mass density. It was considered that the surface near the film was chemically composed close to SiO, forming a gel-like (three-dimensional network) structure that is hydrophilic and suppresses swelling due to moisture, indicating it can be expected to maintain stable hydrophilicity on the film surface.
宮崎 司*; 宮田 登*; 有馬 寛*; 下北 啓輔*; 山本 勝宏*; 竹中 幹人*; 中西 洋平*; 柴田 基樹*; 青木 裕之; 山田 悟史*; et al.
Colloids and Surfaces A; Physicochemical and Engineering Aspects, 701, p.134928_1 - 134928_8, 2024/11
被引用回数：0 パーセンタイル：0.00(Chemistry, Physical)Isotactic polypropylene (PP) thin films deposited on Si substrates were subjected to neutron reflectivity (NR) measurements under various humidity conditions to evaluate the isothermal adsorption of water accumulated between the PP layer and Si substrate, with focus on the temperature-dependence of the adsorption isotherm. The adsorption of accumulated water followed a single type II isotherm according to the Brunauer-Emmett-Teller (BET) classification, regardless of temperature. This can be attributed to the weak interactions between the PP layer and Si substrate, and between the PP layer and water molecules. Hydrophobic PP does not significantly interact with water molecules and the hydrophilic Si surface. Therefore, the interfacial water molecules are simply adsorbed on the native oxide layer on Si via simple interaction between the water molecules and the silicon oxide surface without being affected by the PP layer. Consequently, the adsorption isotherm of the accumulated water follows the single type II adsorption isotherm regardless of temperature, similar to the adsorption isotherm of water simply adsorbed on exposed silica surfaces. These weak interactions of the PP layer with the Si surface and water molecules also lead to fast diffusion kinetics for the accumulated water along the interface.
沖田 将一朗; 青木 健; 深谷 裕司; 橘 幸男
Proceedings of 31st International Conference on Nuclear Engineering (ICONE31) (Internet), 5 Pages, 2024/11
We have been developing a methodology for nuclide production and annihilation and decay heat evaluations for High Temperature Gas-cooled Reactors (HTGRs). We are planning to perform validation of the evaluation method with isotopic composition data obtained from HTGR type fuel irradiation tests (AGR tests) performed at the Idaho National Laboratory. As a first step of this plan, preliminary validation of a calculation code and a nuclear data library to be used in the evaluation methodology should be conducted. We made a calculation model of the Advanced Test Reactor (ATR) with a continuous-energy Monte Carlo code MVP-3 and the latest nuclear data library in Japan JENDL-5 on the basis of a calculation input for another Monte Carlo code MCNP5 documented in the International Handbook of Evaluated Reactor Physics Benchmark Experiments (IRPhE). We also calculated effective multiplication factors and relative power densities for the ATR calculation model. As a result of comparison with measured values reported in the IRPhE handbook, the JENDL-5 and the calculation model built with MVP-3 shows an enough calculation accuracy in the ATR. Our results will help us to perform our planned validation of our nuclide production and annihilation and decay heat evaluation methodology with the AGR test data.
佐藤 修彰*; 亀尾 裕; 佐藤 宗一; 熊谷 友多; 佐藤 智徳; 山本 正弘*; 渡邉 豊*; 永井 崇之; 新堀 雄一*; 渡邉 雅之; et al.
廃止措置・廃炉化学入門, 251 Pages, 2024/09
原子力施設の廃止措置と過酷事故炉の廃炉を対象とし、第1部では燃料化学、分析化学、放射線化学、腐食、除染化学から、廃棄物処理・処分にわたる基礎的な分野について紹介する。第2部では、種々の原子力関連施設の廃止措置に関わる化学を学びながら、東京電力福島第一原子力発電所の廃炉にはどのような化学的アプローチが必要かつ可能か、廃炉の在り方やそれに必要な研究開発・人材育成などについて触れる。
内田 和杜*; 増田 造*; 原 伸太郎*; 松尾 陽一*; Liu, Y.*; 青木 裕之; 浅野 吉彦*; 宮田 一輝*; 福間 剛士*; 小野 俊哉*; et al.
ACS Applied Materials & Interfaces, 16(30), p.39104 - 39116, 2024/07
被引用回数：1 パーセンタイル：30.18(Nanoscience & Nanotechnology)Zwitterionic MPC polymer coatings effectively deter blood coagulation and protein buildup on medical devices. Researchers synthesized MPC copolymers containing a cross-linking unit (MPTMSi) plus one of four hydrophobic anchoring groups (MPTSSi, BMA, EHMA, LMA) and applied them to PDMS, PP, and PMP. These treatments yielded uniformly hydrophilic, electrically neutral surfaces. Protein adsorption tests showed that PMBSi (BMA) best resisted fluorescently labeled BSA, while PMLSi (LMA) was comparatively weaker, although all four coatings minimized platelet adhesion. Further analyses linked these differences in protein adsorption to varying swelling behaviors in water. Indeed, PMLSi absorbed more water, allowing some protein infiltration yet still repelling platelets. When tested under circulating flow to mimic shear stress, PMMMSi (MPTSSi) and PMLSi coatings on PP and PMP demonstrated excellent durability and platelet repellency. Overall, this study highlights how hydrophobic moieties can boost both hemocompatibility and stability of MPC-based coatings, promising improved performance in medical devices requiring low protein fouling, reduced platelet adhesion, and long-term reliability.
門井 浩太*; 冠野 裕大*; 青木 聡; 井上 裕滋*
ISIJ International, 64(9), p.1450 - 1456, 2024/07
被引用回数：0 パーセンタイル：0.00(Metallurgy & Metallurgical Engineering)オーステナイトステンレス鋼の溶接金属中の孔食に及ぼす化学組成の影響について検討した。クロムおよびモリブデンを多く含む試験片は、再活性化率が低いことが示された。チタンの添加は、耐孔食性を著しく低下させた。クロム欠乏領域はM
C
やTiCのような炭化物の近くに形成された。また、凝固時に生成したTiC相がMC析出の核となった。MCの析出により、クロムの拡散による空乏領域が発生し、耐孔食性の劣化を誘発した。
下北 啓輔*; 山本 勝宏*; 宮田 登*; 柴田 基樹*; 中西 洋平*; 荒川 勝利*; 竹中 幹人*; 木田 拓充*; 徳満 勝久*; 田中 亮*; et al.
Langmuir, 40(30), p.15758 - 15766, 2024/07
被引用回数：1 パーセンタイル：0.00(Chemistry, Multidisciplinary)To investigate the structure of the interface between polyethylene films and substrates, the neutron reflectivity (NR) of deuterated polyethylene (dPE) thin films deposited on Si substrates was measured, demonstrating water accumulation at the interface, even under ambient conditions. After leaching the thermally annealed dPE films in hot p-xylene, NR measurements were conducted on the layers remaining on the substrate, clearly revealing that the adsorption layer of dPE grew during annealing and consisted of two layers, an inner adsorption layer and an outer adsorption layer, as previously proposed for amorphous polymers. The inner adsorption layer was approximately 3.7 nm thick with a density comparable to that of the bulk. The outer adsorption layer was several nanometers thick and appeared to grow insufficiently on top of the inner adsorption layer under the annealing conditions examined in this study. This study clarifying the growth of the adsorption layer of polyethylene at the interface with an inorganic substrate is useful for improving the performance of polymer/inorganic filler nanocomposites due to the wide utility of crystalline polyolefins as polymer matrix materials in nanocomposites.
Kawano, Masayuki*; 盛満 裕真*; Liu, Y.*; 宮田 登*; 宮崎 司*; 青木 裕之; 川口 大輔*; 山本 悟*; 田中 敬二*
Macromolecules, 57(14), p.6625 - 6633, 2024/07
被引用回数：0 パーセンタイル：0.00(Polymer Science)A better understanding of the dynamic behavior of polymer chains on solid surfaces is indispensable for the design and construction of high-performance polymer composites. We herein visualized the in-plane movement of isolated poly(methyl methacrylate) (PMMA) and poly(tert-butyl methacrylate) (PtBMA) single chains on hydrophilic silicon wafers under ambient conditions by atomic force microscopy. Isolated PMMA chains adsorbed to the substrate, whereas PtBMA chains diffused, the degree of which was dependent on the humidity. Neutron reflectivity revealed the formation of a layer of condensed water on the substrate. All-atomistic molecular dynamics simulations implied that the diffusivity difference of the two polymers was based on the submerged depth in which a part of a chain existed. That is, the interaction of a polymer with the surface of the hydrophilic substrate primarily governs its lateral movement, or adsorption behavior, facilitated by the presence of water.
筋田 涼太*; 青木 裕之; 竹中 幹人*; 大内 誠*; 寺島 崇矢*
ACS Macro Letters (Internet), 13(6), p.747 - 753, 2024/06
被引用回数：2 パーセンタイル：28.80(Polymer Science)Herein, we report the water-assisted self-assembly of alternating copolymers bearing imidazolium cations and hydrophobic groups to create water-compatible and nanostructured materials. The copolymers efficiently absorbed water into the cationic segments from the outer environments, depending on the relative humidity. The absorbed water serves as hydrophilic molecules to modulate the weight fraction of hydrophilic/hydrophobic units in the samples. Thus, the morphologies and domain spacing of the nanostructures can be controlled by not only the side chains, but also the amount of absorbed water. The self-assembly of the cationic copolymers, developed herein, afforded universal access to various morphologies, including lamella, gyroid, and cylinder, in addition to the precision control of the domain spacing at the 0.01 nm level.
山崎 大; 丸山 龍治; 青木 裕之; 花島 隆泰*; 阿久津 和宏*; 宮田 登*; 曽山 和彦
Quantum Beam Science (Internet), 9(2), p.20_1 - 20_12, 2024/06
This study developed a neutron-beam focusing supermirror for grazing-incidence small-angle neutron scattering (GISANS) measurements. It was fabricated by depositing NiC/Ti supermirror film with ion-beam sputtering on a precise elliptic surface of fused quartz figured using the elastic emission machining technique. Neutron measurements at a pulsed neutron reflectometer BL17 of MLF, J-PARC successfully demonstrated that the focusing supermirror enhances a beam intensity twentyfold compared with an optimally collimated beam, achieving the signal-to-background ratio of the focal spot as high as 500. The mirror can be readily installed and used at BL17.
森 悠一郎*; 鍵 裕之*; 青木 勝敏*; 高野 将大*; 柿澤 翔*; 佐野 亜沙美; 舟越 賢一*
Earth and Planetary Science Letters, 634, p.118673_1 - 118673_8, 2024/05
被引用回数：1 パーセンタイル：41.61(Geochemistry & Geophysics)水素による鉄の体積膨張に対するケイ素の効果を調べるため、高圧高温下でのhcp-Fe
Si
の中性子回折実験とX線回折実験を行った。中性子回折実験は重水素化hcp-FeSiに対して13.5GPa, 900K及び12.1GPa, 300Kで行い、得られたプロファイルからリートベルト解析を用いて水素占有率を決定した。hcp-Fe-SiのP-V-T状態方程式を組み合わせることにより、hcp-FeSiの水素による体積膨張が純粋なhcp鉄の体積膨張よりも10%大きいことを示した。得られた値を用いて、内核の密度欠損を再現できる水素量を見積もったところ、シリコンの影響がない場合に比べて50%減少した。hcp-FeSiで内核の密度欠損を再現した場合、内核と外核で可能な水素量xはそれぞれ0.07と0.12-0.15と計算された。
Ikami, Takaya*; 青木 裕之; 寺島 崇矢*
ACS Macro Letters (Internet), 13(4), p.446 - 452, 2024/04
被引用回数：1 パーセンタイル：28.80(Polymer Science)Microphase separation of random copolymers, as well as that of high 
; low N block copolymers, is promising to construct sub-10-nm structures into materials. Herein, we designed statistical copolymers consisting of 2-hydroxyethyl acrylate (HEA) and N-octadecylacrylamide (ODAAm) to produce crystallization and hydrogen bond-assisted lamellar structure materials. The copolymers not only formed a crystalline lamellar structure with 3-4 nm domain spacing but also maintained an amorphous lamellar structure via phase transition above the melting temperature up to approximately 100 
C. The key is to introduce hydrogen-bonding amide junctions between the octadecyl groups and the polymer backbones, by which the polymer chains are physically fixed at the interface of lamellar structures even above the melting temperature. The stabilization of the lamellar structure by the amide units is also supported by the fact that the lamellar structure of all-acrylate random copolymers bearing hydroxyethyl and crystalline octadecyl groups is disordered above the melting temperature. By spin-coating on a silicon substrate, the HEA/ODAAm copolymer formed a multilayered lamellar thin film consisting of a hydrophilic hydroxyethyl/main chain phase and a hydrophobic octadecyl phase. The structure and order-disorder transition were analyzed by neutron reflectivity.
前田 匡樹*; 田邉 匡生*; 西脇 智哉*; 青木 孝行*; 堂埼 浩二*; 西村 康志郎*; 藤井 翔*; 上野 文義; 田中 章夫*; 鈴木 裕介*; et al.
Transactions of the 27th International Conference on Structural Mechanics in Reactor Technology (SMiRT 27) (Internet), 10 Pages, 2024/03
This study develops assessment methods necessary to obtain a long-term structural integrity outlook for reactor buildings that suffered from the 2011 Great East Japan Earthquake disaster in which access to the site was extremely limited due to high radiation dose rates and high contamination. It is one of the "Nuclear science and technology and human resource development promotion projects" implemented by the Japan Atomic Energy Agency (JAEA) International Collaborative Research Center for Decommissioning and Environment (CLADS) in FY2021 to 2023. This paper introduces an outline and overview of the project.
高野 将大*; 鍵 裕之*; 森 悠一郎*; 青木 勝敏*; 柿澤 翔*; 佐野 亜沙美; 飯塚 理子*; 土屋 卓*
Journal of Mineralogical and Petrological Sciences (Internet), 119(1), p.240122_1 - 240122_9, 2024/00
被引用回数：0 パーセンタイル：0.00(Mineralogy)硫化鉄(FeS)の高圧高温下での水素化は、水素と硫黄が地球や他の地球型惑星のコアの軽元素として有望な候補であることから注目されている。これまでのFeSの水素化反応に関する報告では、出発物質の化学組成は十分に明らかにされていなかった。本研究では、Fe1.000S(トロイライト)を出発物質としたFe-S-H系の高温高圧条件下での中性子回折とX線回折のその場測定を報告する。決定された占有率は、以前の研究で報告されたものより著しく低く、FeSの水素化は硫化鉄の化学組成に強く影響されることを示している。
O/HO vapor generator for contrast-variation neutron scattering有馬 寛*; 高田 慎一; 笠井 聡*; 大内 啓一*; 森川 利明*; 宮田 登*; 宮崎 司*; 青木 裕之; 岩瀬 裕希*; 廣井 孝介; et al.
Journal of Applied Crystallography, 56(6), p.1802 - 1812, 2023/12
被引用回数：6 パーセンタイル：81.06(Chemistry, Multidisciplinary)The contrast-variation technique in neutron scattering experiments plays a pivotal role in distinguishing partial structures within multi-component complexes, facilitating the elucidation of distinct sample constituents. This differentiation is achieved using different isotopes, namely hydrogen and deuterium, which possess varying neutron scattering characteristics. This study presents a novel vapor generator designed for neutron scattering experiments, enabling continuous control of the DO/HO ratio of the vapor. This feature is especially useful for contrast-variation studies. The generator features two saturators and four mass flow controllers, allowing for the rapid and independent generation of DO/HO vapors. Additionally, the incorporation of the two-temperature method ensures accurate dew point control within a margin of 
0.2Cdp. This setup proves useful for conducting time-resolved experiments and can accelerate research on functional polymers, such as polymer electrolyte membranes for fuel cells, where water potential assumes critical importance.
