Initialising ...
Initialising ...
Initialising ...
Initialising ...
Initialising ...
Initialising ...
Initialising ...
柴田 基樹*; 竹中 幹人*; 元川 竜平; 熊田 高之; 上田 祐生; 宮崎 司*; 中西 洋平*; 阿部 淳*; 岩瀬 裕希*; 柴山 充弘*; et al.
Polymer, 340, p.129203_1 - 129203_7, 2025/12
被引用回数：0 パーセンタイル：0.00(Polymer Science)The development of effective plastic degradation methods is crucial to address environmental pollution. Hydrothermal liquefaction using near-critical water is a promising technology, but the fundamental dissolution and decomposition mechanisms remain poorly understood. This study investigates the thermodynamics of a polystyrene (PS)/water system under near-critical conditions to elucidate this mechanism. We performed in situ small-angle neutron scattering (SANS) to observe the swelling of PS particles in deuterated water (D
O) at various temperatures under pressures of 10 MPa and 25 MPa. By applying the 
(FHS) theory to the swelling data, We quantitatively determined the Flory-Huggins interaction parameter as a function of temperature and pressure by applying the FHS theory to the swelling data. Based on these results, we constructed a phase diagram of the PS/DO system. The diagram reveals that miscibility increases with increasing pressure. This work provides a thermodynamical properties of water solutions of polymers under near-critical conditions for optimizing industrial hydrothermal recycling processes.
Marium, M.*; 青木 健太郎*; He, Y.*; 山本 勝宏*; Suwansoontorn, A.*; 生田 聖也*; 原 光生*; 永野 修作*; 長尾 祐樹*; 西川 慶*; et al.
ACS Applied Energy Materials (Internet), 8(22), p.16589 - 16600, 2025/11
被引用回数：0 パーセンタイル：0.00(Chemistry, Physical)High C-rate capability and energy-density stability are crucial for advanced lithium-ion batteries (LIBs). However, these two characteristics typically conflict in conventional systems. Herein, a lyotropic polymer liquid crystal (LPLC)-based coating was applied to the surface of LiNi
Co
Mn
O (NCM523) cathode to construct a highly ion-conductive artificial cathode electrolyte interface (CEI) layer, aiming to supersede traditional CEIs for LIBs. The coating material, composed of an amphiphilic lithium-substituted alkyl-sulfonated polyimide (ASPI-Li) and an appropriate amount of organic liquid electrolyte, forms nanoscale ion conduction channels that act as an artificial CEI layer, providing enhanced local Li-ion activity at the NCM523 surface. The ion-conduction channels, regulated by the layered structure within the ASPI-Li coating layer, significantly accelerated ion-diffusion kinetics at the electrode/electrolyte interface, thereby delivering superior C-rate capability at ambient temperatures compared with conventional LIB systems. This work, guided by molecular design, provides insights into the development of next-generation artificial CEI layers for efficient and sustainable energy-storage systems.
-butadiene) reinforced by carbon blackWatanabe, Yuki*; 熊川 大幹*; Karitani, Shu*; 井上 正志*; 岩蕗 仁*; 中西 洋平*; 柴田 基樹*; 元川 竜平; 杉田 剛; 上田 祐生; et al.
Macromolecules, 58(16), p.8641 - 8648, 2025/08
被引用回数：0 パーセンタイル：0.00(Polymer Science)We investigated how the particle size of carbon black (CB) affects the reinforcement of CB to vulcanized poly(styrene-co-butadiene) (SBR) in the glassy region. When the average diameter of CB d is larger than 100 nm, the enhancement of modulus can be expressed by the Eshelby/Mori-Tanaka model, which agrees with the results obtained for an SBR/silica system. On the other hand, at d 
100nm, the volume fraction dependence of the enhancement becomes stronger than the theory's prediction. The scattering studies on the SBR/CB systems revealed that the aggregates of CB at d 100nm consist of densely packed CB, while the aggregates of CB at d 
100nm exhibit branch structures. At d 100nm, the voids or the occluded region in the packed CB increase the volume fraction, resulting in a stronger volume fraction dependence of the enhancement.
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：1 パーセンタイル：49.14(Polymer Science)To 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.
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：1 パーセンタイル：10.77(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 (DO) 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：1 パーセンタイル：7.97(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.
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：4 パーセンタイル：36.83(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.
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：6 パーセンタイル：59.68(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.
山本 風海; 守屋 克洋; 沖田 英史; 山田 逸平; 地村 幹; Saha, P. K.; 菖蒲田 義博; 田村 文彦; 山本 昌亘; 森下 卓俊; et al.
Journal of Neutron Research, 26(2-3), p.59 - 67, 2024/01
J-PARC Linacおよび3GeVシンクロトロン(RCS)は、1MWの大強度ビームを中性子実験施設および主リングシンクロトロンに供給するために運転している。これまで進めてきたビーム調整および機器改良により、当初想定よりもはるかに低いビームロス量で1MWのビーム運転を行うことが出来ている。現在のビーム出力はビームロスではなくRCSの高周波加速空胴の電源容量によって制限されている。近年、RCSグループではより少ない消費電力でビームを加速することのできる新しい構造の加速空胴の開発に成功した。この空胴によって、利用運転中に加速空胴で消費される電力を大幅に削減することが出来、さらに1MW以上の大出力での運転も可能となる。これまでの試験結果から、RCSの加速空胴を全て新しい物へ更新すれば、1.5MW以上の大出力も可能となる事が判っている。今後、中性子利用および主リングシンクロトロンの更なる成果創出のため、2MWを目標にRCSで必要な改良について検討を行った。その結果、高周波空胴の更新以外にも、高周波増幅器の増強やビームモニタの増強が必要であることが判ったため、今後順次更新を進める。
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：5 パーセンタイル：31.64(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.
山本 風海; 守屋 克洋; 沖田 英史; 山田 逸平; 地村 幹; Saha, P. K.; 菖蒲田 義博; 田村 文彦; 山本 昌亘; 森下 卓俊; et al.
Proceedings of 68th ICFA Advanced Beam Dynamics Workshop on High Intensity and High Brightness Hadron Beams (HB2023) (Internet), p.270 - 273, 2023/10
J-PARC 3GeVシンクロトロン(RCS)は、1MWの大強度ビームを中性子実験施設および主リングシンクロトロンに供給するために運転している。これまで進めてきたビーム調整および機器改良により、当初想定よりもはるかに低いビームロス量で1MWのビーム運転を行うことが出来ている。そのため、現在のビーム出力はビームロスではなく高周波加速空胴の電源容量によって制限されている。近年、RCSグループではより少ない消費電力でビームを加速することのできる新しい構造の加速空胴の開発に成功した。この空胴によって、利用運転中に加速空胴で消費される電力を大幅に削減することが出来、さらに1MW以上の大出力での運転も可能となる。これまでの試験結果から、RCSの加速空胴を全て新しい物へ更新すれば、1.5MW以上の大出力も可能となる事が判っている。今後、中性子利用および主リングシンクロトロンの更なる成果創出のため、2MWを目標にRCSで必要な改良について検討を行った。その結果、高周波空胴の更新以外にも、高周波増幅器の増強やビームモニタの増強が必要であることが判ったため、今後順次更新を進める。
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 秀紀*; 青木 裕之; 宮崎 司*
Soft Matter, 19(11), p.2082 - 2089, 2023/03
被引用回数：5 パーセンタイル：56.39(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.
田代 孝二*; 日下 勝弘*; 山元 博子*; 細谷 孝明*; 岡田 修司*; 大原 高志
Polymers (Internet), 15(2), p.465_1 - 465_44, 2023/01
被引用回数：5 パーセンタイル：10.15(Polymer Science)The development in the crystal structure analysis of synthetic polymers using the hybridized combination of wide-angle X-ray and neutron diffraction (WAXD and WAND, respectively) techniques has been reviewed with many case studies performed by the authors. At first, the technical development was reviewed. Secondly, the usage of the WAND method was introduced, in which the successful extraction of hydrogen atomic positions was described. The third example is to show the importance for the hybrid combination of these two diffraction methods. Finally, the application of WAND technique in the trace of structural changes induced under the application of external stress or temperature was described. The future perspective is described for the development of structural science of synthetic polymers on the basis of the combined WAXD/WAND techniques.
Saha, P. K.; 岡部 晃大; 仲野谷 孝充; 吉本 政弘; 菖蒲田 義博; 原田 寛之; 田村 文彦; 沖田 英史; 畠山 衆一郎; 守屋 克洋; et al.
Proceedings of 19th Annual Meeting of Particle Accelerator Society of Japan (インターネット), p.1 - 5, 2023/01
The RCS beam power for operation to the MLF has been increased to 800 kW recently. The total beam loss even at the designed 1 MW beam power has been well controlled, but the uncontrolled beam losses, especially those caused by the foil scattering of the circulating beam during multi-turn injection are still high and causes extremely high residual radiation at the injection area. To further minimizing such a beam loss, we have implemented a new approach by minimizing the injection beam size and using a smaller size stripper foil. A smaller foil reduces foil hitting of the circulating beam and the corresponding foil scattering uncontrolled beam losses. In addition, an optimized transverse painting area matching with a smaller injection beam also gives a smaller circulating beam emittance to reduce beam loss at the collimator section and its downstream. The corresponding residual radiation for operation at 700 kW beam power was measured to be significantly reduced at the injection area, collimator section and it's downstream. A smaller injection beam size was also tested at 1MW beam power and the residual beam loss is minimized to 0.01%, which is nearly 1/4 reduction from the previous 1 MW test operation in 2020.
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 秀紀*; 青木 裕之; et al.
Langmuir, 38(41), p.12457 - 12465, 2022/10
被引用回数：3 パーセンタイル：15.58(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 25
C 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.
山本 風海; 金正 倫計; 林 直樹; Saha, P. K.; 田村 文彦; 山本 昌亘; 谷 教夫; 高柳 智弘; 神谷 潤一郎; 菖蒲田 義博; et al.
Journal of Nuclear Science and Technology, 59(9), p.1174 - 1205, 2022/09
被引用回数：9 パーセンタイル：69.86(Nuclear Science & Technology)J-PARC 3GeVシンクロトロン(RCS)は、最大1MWの大強度ビームを25Hzという早い繰り返しで中性子実験及び下流の主リングシンクロトロンに供給することを目的に設計された。2007年の加速器調整運転開始以降、RCSではビーム試験を通じて加速器の設計性能が満たされているかの確認を進め、必要に応じてより安定に運転するための改善を行ってきた。その結果として、近年RCSは1MWのビーム出力で連続運転を行うことが可能となり、共用運転に向けた最後の課題の抽出と対策の検討が進められている。本論文ではRCSの設計方針と実際の性能、および改善点について議論する。
山本 風海; 畠山 衆一郎; Saha, P. K.; 守屋 克洋; 岡部 晃大; 吉本 政弘; 仲野谷 孝充; 藤来 洸裕; 山崎 良雄; 菅沼 和明
EPJ Techniques and Instrumentation (Internet), 8(1), p.9_1 - 9_9, 2021/07
J-PARC 3GeVシンクロトロン(RCS)は最大1MWの高出力陽子ビームを中性子ターゲットに供給している。稼働率を向上し実験成果の最大化を図るために、RCSではさまざま運転パラメータの履歴を記録しているが、そのデータのうち入射効率と入射ビームラインの磁石を冷却している冷却水温度が同期していることを発見した。RCS入射時に、入射負水素(H
)ビームは炭素薄膜を通過し陽子に変換されるので、入射効率が変動しているという事は陽子への変換効率が冷却水温度に依存していることを示している。ビーム形状,薄膜の条件等から、入射ビームのフォイルへの入射位置が0.072mm程度振動していて、それが磁石磁場の変動に換算して1.63
10
となることを求めた。この値は、単純に磁石が冷却水の温度変動に従って伸び縮みするとして評価した結果とファクタ程度で一致し、変換効率の変動の主要因は磁場変動であることが確認できた。
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：12 パーセンタイル：38.11(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.
宮崎 司*; 宮田 登*; 吉田 鉄生*; 有馬 寛*; 津村 佳弘*; 鳥飼 直也*; 青木 裕之; 山本 勝宏*; 金谷 利治*; 川口 大輔*; et al.
Langmuir, 36(13), p.3415 - 3424, 2020/04
被引用回数：20 パーセンタイル：59.30(Chemistry, Multidisciplinary)We investigated in detail the structures in the poly(vinyl alcohol) (PVA) adsorption layers on a Si substrate, which remained on the substrate after immersing the relatively thick 30 - 50 nm films in hot water, by neutron reflectometry under humid conditions. For the PVA with a degree of saponification exceeding 98 mol %, the adsorption layer exhibits a three-layered structure in the thickness direction. The bottom layer is considered to be the so-called inner adsorption layer that is not fully swollen with water vapor. This may be because the polymer chains in the inner adsorption layer are strongly constrained onto the substrate, which inhibits water vapor penetration. The polymer chains in this layer have many contact points to the substrate via the hydrogen bonding between the hydroxyl groups in the polymer chain and the silanol groups on the surface of the Si substrate and consequently exhibit extremely slow dynamics. Therefore, it is inferred that the bottom layer is fully amorphous. Furthermore, we consider the middle layer to be somewhat amorphous because parts of the molecular chains are pinned below the interface between the middle and bottom layers. The molecular chains in the top layer become more mobile and ordered, owing to the large distance from the strongly constrained bottom layer; therefore, they exhibit a much lower degree of swelling compared to the middle amorphous layer. Meanwhile, for the PVA with a much lower degree of saponification, the adsorption layer structure consists of the two-layers. The bottom layer forms the inner adsorption layer that moderately swells with water vapor because the polymer chains have few contact points to the substrate. The molecular chains in the middle layer, therefore, are somewhat crystallizable because of this weak constraint.
宮崎 司*; 宮田 登*; 浅田 光則*; 津村 佳弘*; 鳥飼 直也*; 青木 裕之; 山本 勝宏*; 金谷 利治*; 川口 大輔*; 田中 敬二*
Langmuir, 35(34), p.11099 - 11107, 2019/08
被引用回数：28 パーセンタイル：66.48(Chemistry, Multidisciplinary)We investigated the swelling behaviors of poly(vinyl alcohol) (PVA) films deposited on Si wafers with water vapor, which is a good solvent for PVA for elucidating structural and dynamical heterogeneities in the film thickness direction. Using deuterated water vapor, structural and dynamical differences in the thickness direction can be detected easily as different degrees of swelling in the thickness direction by neutron reflectivity. Consequently, the PVA film with a degree of saponification exceeding 98 mol % exhibits a three-layered structure in the thickness direction. It is considered that an adsorption layer consisting of molecular chains that are strongly adsorbed onto the solid substrate is formed at the interface with the substrate, which is not swollen with water vapor compared with the bulk-like layer above it. The adsorption layer is considered to exhibit significantly slower dynamics than the bulk. Furthermore, a surface layer that swells excessively compared with the underneath bulk-like layer is found. This excess swelling of the surface layer may be related to a higher mobility of the molecular chains or lower crystallinity at the surface region compared to the underneath bulk-like layer. Meanwhile, for the PVA film with a much lower degree of saponification, a thin layer with a slightly lower degree of swelling than the bulk-like layer above it can be detected at the interface between the film and substrate only under a high humidity condition. This layer is considered to be the adsorption layer composed of molecular chains loosely adsorbed onto the Si substrate.
