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.

Water fraction dependence of the aggregation behavior of hydrophobic fluorescent solutes in water-tetrahydrofuran

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

https://doi.org/10.1021/acs.jpclett.3c02882

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.

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.

Modifications in the nanoparticle-protein interactions for tuning the protein adsorption and controlling the stability of complexes

Kumar, S.*; Saha, D.*; 高田 慎一; Aswal, V. K.*; 瀬戸 秀紀

Applied Physics Letters, 118(15), p.153701_1 - 153701_7, 2021/04

https://doi.org/10.1063/5.0046745

We report the pathways to suppress or enhance the protein adsorption on nanoparticles and thereby control the stability of the nanoparticle-protein complexes with the help of selective additives. This has been achieved by tuning the electrostatic interaction between the nanoparticles and proteins, in the presence of surfactant and multivalent counterions. The preferential binding of the proteins with the surfactant and multivalent ions induced charge reversibility of nanoparticles can lead to adsorption of an otherwise non-adsorbing protein and vice versa. The findings are demonstrated for anionic silica nanoparticles and two globular proteins [lysozyme (cationic) and bovine serum albumin (BSA) (anionic)] as model systems, in the presence of two ionic surfactants [anionic sodium dodecyl sulfate (SDS) and cationic dodecyltrimethylammonium bromide (DTAB)], and ZrCl as multivalent salt.

Status of neutron spectrometers at J-PARC

梶本 亮一; 横尾 哲也*; 中村 充孝; 川北 至信; 松浦 直人*; 遠藤 仁*; 瀬戸 秀紀*; 伊藤 晋一*; 中島 健次; 河村 聖子

Physica B; Condensed Matter, 562, p.148 - 154, 2019/06

BB2018-0526.pdf:2.45MB

https://doi.org/10.1016/j.physb.2018.11.061

Seven time-of-flight quasielastic/inelastic neutron scattering instruments are installed on six beamlines in the Materials and Life Science Experimental Facility (MLF) at the Japan Proton Accelerator Research Complex (J-PARC). Four of these instruments are chopper-type direct-geometry spectrometers, one is a near-backscattering indirect-geometry spectrometer, and the other two are spin-echo-type spectrometers. This paper reviews the characteristic features, recent scientific outcomes, and progress in development of MLF spectrometers.

Event structure and double helicity asymmetry in jet production from polarized collisions at = 200 GeV

Adare, A.*; Afanasiev, S.*; Aidala, C.*; Ajitanand, N. N.*; Akiba, Y.*; Al-Bataineh, H.*; Alexander, J.*; Aoki, K.*; Aphecetche, L.*; Armendariz, R.*; et al.

Physical Review D, 84(1), p.012006_1 - 012006_18, 2011/07

https://doi.org/10.1103/PhysRevD.84.012006

重心エネルギー200GeVでの縦偏極陽子陽子衝突からのジェット生成のイベント構造と二重非対称()について報告する。光子と荷電粒子がPHENIX実験で測定され、イベント構造がPHYTIAイベント生成コードの結果と比較された。再構成されたジェットの生成率は2次までの摂動QCDの計算で十分再現される。測定されたは、一番低い横運動量で-0.00140.0037、一番高い横運動量で-0.01810.0282であった。このの結果を幾つかのの分布を仮定した理論予想と比較する。

Azimuthal correlations of electrons from heavy-flavor decay with hadrons in and Au+Au collisions at = 200 GeV

Adare, A.*; Afanasiev, S.*; Aidala, C.*; Ajitanand, N. N.*; 秋葉 康之*; Al-Bataineh, H.*; Alexander, J.*; 青木 和也*; Aphecetche, L.*; Aramaki, Y.*; et al.

Physical Review C, 83(4), p.044912_1 - 044912_16, 2011/04

https://doi.org/10.1103/PhysRevC.83.044912

重いフレーバーのメソンの崩壊からの電子の測定は、このメソンの収量が金金衝突では陽子陽子に比べて抑制されていることを示している。われわれはこの研究をさらに進めて二つの粒子の相関、つまり重いフレーバーメソンの崩壊からの電子と、もう一つの重いフレーバーメソンあるいはジェットの破片からの荷電ハドロン、の相関を調べた。この測定は重いクォークとクォークグルオン物質の相互作用についてのより詳しい情報を与えるものである。われわれは特に金金衝突では陽子陽子に比べて反対側のジェットの形と収量が変化していることを見いだした。

Dynamic and static fluctuations in polymer gels studied by neutron spin-echo

金谷 利治*; 高橋 伸明; 西田 幸次*; 瀬戸 秀樹*; 長尾 道弘*; 武田 隆義*

Physica B; Condensed Matter, 385-386(1), p.676 - 681, 2006/11

https://doi.org/10.1016/j.physb.2006.05.289

中性子スピンエコー法により三種類のポリビニルアルコール(PVA)ゲルについて研究した。第一にジメチルスルホキシド(DMSO)と水を体積混合比60対40で混合したものを溶媒とするもの、第二にPVAのホウ酸水溶液、そして第三に化学架橋のPVAゲルである。中間散乱関数I(q,t)/I(q,0)はそれぞれ大きく異なった。最初のゲルと第三のゲルは、非減衰項を含むが、第二のゲルは含まなかった。これは非減衰項が静的濃度揺らぎに起因して起こることを示唆している。静的濃度揺らぎと動的濃度揺らぎはそれぞれ、ゲル網目による運動の制限とZimmモードに起因する高分子鎖セグメントの運動を示していることが明らかとなった。

The Neutron spectrometers in J-PARC

梶本 亮一; 横尾 哲也*; 中村 充孝; 柴田 薫; 川北 至信; 松浦 直人*; 遠藤 仁*; 瀬戸 秀紀*; 伊藤 晋一*; 中島 健次; et al.

no journal, , 

Materials and Life Science Experimental Facility (MLF) in J-PARC has 23 neutron beam ports, and 21 instruments have already been operated or under construction/commissioning. There are 6 instruments for inelastic neutron scattering and quasi-elastic neutron scattering. By a combination of these instruments, MLF gives opportunities to perform experiments in widely spread fields including solid state physics, amorphous materials and liquids, soft and biological matters, as well as industrial applications such as tire rubbers and battery materials. In this presentation, we review the characteristic features of these 6 instruments and scientific opportunities realized by the instruments.