Modeling the extraction of bound rubber from silica-filled styrene-butadiene rubber with toluene

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

https://doi.org/10.1016/j.polymer.2025.128662

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.

Adsorption isotherm and kinetics of diffusion of water accumulated between polypropylene thin film and Si substrate; Neutron reflectivity investigation

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

https://doi.org/10.1016/j.colsurfa.2024.134928

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.

Neutron reflectivity study on the nanostructure of PMMA chains near substrate interfaces based on contrast variation accompanied with small molecule sorption

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

https://doi.org/10.1039/D2SM01482C

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.

Neutron reflectivity study on the suppression of interfacial water accumulation between a polypropylene thin film and Si substrate using a silane-coupling agent

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

https://doi.org/10.1021/acs.langmuir.2c01599

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.

Multilayered lamellar materials and thin films by instant self-assembly of amphiphilic random copolymers

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 Letters (Internet), 10(12), p.1524 - 1528, 2021/12

https://doi.org/10.1021/acsmacrolett.1c00571

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.

Neutron reflectivity on the mobile surface and immobile interfacial layers in the poly(vinyl acetate) adsorption layer on a Si substrate with deuterated toluene vapor-induced swelling

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

https://doi.org/10.1021/acs.langmuir.0c03025

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.

Materials and Life Science Experimental Facility (MLF) at the Japan Proton Accelerator Research Complex, 2; Neutron scattering instruments

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

https://doi.org/10.3390/qubs1030009

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。

Design and performance of high-pressure PLANET beamline at pulsed neutron source at J-PARC

服部 高典; 佐野 亜沙美; 有馬 寛*; 小松 一生*; 山田 明寛*; 稲村 泰弘; 中谷 健; 瀬戸 雄介*; 永井 隆哉*; 内海 渉; et al.

Nuclear Instruments and Methods in Physics Research A, 780, p.55 - 67, 2015/04

https://doi.org/10.1016/j.nima.2015.01.059

PLANETは高温高圧実験に特化された飛行時間型の中性子ビームラインである。パルス中性子回折実験用に設計された大型の6軸型マルチアンビルプレスを用いることで定常的には高温高圧下約10GPa、2000Kでのデータ測定が可能性である。きれいなデータを取得するために、ビームラインには入射スリットと受光スリットが装備してあり、高圧アセンブリからの寄生散乱が除去可能である。/=0.6%の高い分解能、0.2-8.4の広いデータ取得可能レンジおよび高い寄生散乱除去性能により、高温高圧下での結晶および液体の高精度な構造決定が可能となっている。

Thermal-hydraulic studies on self actuated shutdown system for Japan Sodium-cooled Fast Reactor

萩原 裕之; 山田 由美*; 衛藤 将生*; 大山 一弘*; 渡辺 収*; 山野 秀将

Proceedings of 8th Japan-Korea Symposium on Nuclear Thermal Hydraulics and Safety (NTHAS-8) (USB Flash Drive), 8 Pages, 2012/12

JSFR設計にキュリー点電磁石(CPEM)を用いた自動停止システム-受動的炉停止系(SASS)を選定した。CPEMを用い、燃料からの過剰な放出熱上昇を検知し制御棒を炉心に挿入し炉停止に至らせる。したがって、冷却材温度上昇に対するCPEMの反応速度を保証しSASSの実用性を立証することが重要である。本論文では、反応時間の短縮を確保するため、CPEMのある後備炉停止系を取り囲む6本の燃料集合体から流出する流量を「フローコレクター」という機器を考案した。

ガス炉用縦方向流冷却六角ブロック燃料製造システムの調査

戸澤 克弘*; 山田 裕之*; 尾崎 博*; 鈴木 嘉浩*

JNC TJ9420 2005-006, 133 Pages, 2005/02

JNC-TJ9420-2005-006.pdf:11.17MB

FBRサイクル実用化戦略調査研究の一環として、Heガス冷却FBR燃料の候補概念である窒化物被覆粒子燃料を六角ブロック集合体に分散させた燃料の燃料製造システムを対象として、プラント概念を示すこと及び、廃棄物発生量および経済性を評価することを目的として詳細検討を行った。その結果以下の成果を得た。(1) 燃料製造プラント概念の調査 被覆粒子はTiNとSiCの2層の被覆を考慮して、物質収支、機器系統数、全体システム構成を検討した。その上で六角ブロックの製造方法としては炉心部は縦置き、ブランケット部は横置きで被覆粒子を振動充填した後、ブロック枠にSiC蓋を接合する組立方式を設定し、対応する製造設備概念を具体化した。燃料集合体は六角ブロックにエントランスノズル、ハンドリングヘッドをネジ止めする設備概念を具体化した。六角ブロックの検査項目を整理し、密度検査はX線CTによる方式とした。試薬回収設備は湿式振動充填法の概念に基づき系統を具体化した。(2) システム評価に関するデータの評価 主工程、分析、保守補修により発生する気体、液体、固体廃棄物を評価した結果、気体、液体廃棄物については試薬回収工程においてIPA、硝酸、アンモニア水を回収することで排出量を大幅に削減できる可能性が示された。 また、構築したプラント概念に対して経済性評価を行い、設備費、運転費などを評価した。その結果、建設費総額の21%が主工程建設費、35%が周辺設備(廃棄物処理・分析・保守補修・計装・ユーティリティ)費、34%が建・電・換費、10%が新燃料貯蔵設備費との試算結果が得られた。