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.

令和5年度核燃料サイクル工学研究所放出管理業務報告書(排水)

國分 祐司; 細見 健二; 瀬谷 夏美; 永岡 美佳; 井上 和美; 小池 優子; 長谷川 涼; 久保田 智大; 平尾 萌; 飯澤 将伍; et al.

JAEA-Review 2024-053, 116 Pages, 2025/03

JAEA-Review-2024-053.pdf:3.26MB

本報告書は、原子力規制関係法令を受けた「再処理施設保安規定」、「核燃料物質使用施設保安規定」、「放射線障害予防規程」、「放射線保安規則」及び茨城県等との「原子力施設周辺の安全確保及び環境保全に関する協定書」、「水質汚濁防止法」並びに「茨城県条例」に基づき、令和5年4月1日から令和6年3月31日までの期間に日本原子力研究開発機構核燃料サイクル工学研究所から環境へ放出した放射性排水の放出管理結果を取りまとめたものである。再処理施設、プルトニウム燃料開発施設をはじめとする各施設からの放射性液体廃棄物は、濃度及び放出量ともに保安規定及び協定書等に定められた基準値を十分に下回った。

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 adsorption layer of polyethylene grown on Si substrate

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

https://doi.org/10.1021/acs.langmuir.4c01584

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.

J-PARC Linac and RCS; Operational status and upgrade plan to 2 MW

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

https://doi.org/10.3233/JNR-240003

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。

Structural changes of polystyrene particles in subcritical and supercritical water revealed by in situ small-angle neutron scattering

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

https://doi.org/10.1038/s41428-023-00817-1

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.

Beyond 1-MW scenario in J-PARC rapid-cycling synchrotron

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

https://doi.org/10.18429/JACoW-HB2023-WEC3C1

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。

Long-timescale transformations of self-interstitial atom clusters of Cu using the SEAKMC method; The Effect of setting an activation energy threshold for saddle point searches

早川 頌*; 山本 耀二郎*; 沖田 泰良*; 板倉 充洋; 鈴木 克幸*

Computational Materials Science, 218, p.111987_1 - 111987_10, 2023/02

https://doi.org/10.1016/j.commatsci.2022.111987

On-the-fly kinetic Monte Carlo (kMC), a computational technique for atomistic simulations, has attracted attention because it increases the simulation timescale beyond that of molecular dynamics (MD) simulations while maintaining atomistic fidelity. However, for most kMC methods, when events with high and low activation energies coexist in the event list, trivial events with extremely low activation energies that do not essentially affect the phenomena of interest, so-called flicker events, are frequently selected, making it challenging to observe the key dynamics. In this study, we use Self-Evolving Atomistic kMC (SEAKMC), one of the on-the-fly kMC methods, to model the unstable-to-stable transformations of irregular three-dimensional self-interstitial-atom (SIA) clusters in Cu generated through collision cascade. By setting an activation energy threshold once every five steps, transformations into stable configurations are enhanced. The algorithm renders the simulation timescales one or two orders of magnitude longer than those possible with MD simulations. Further, the probability of transformations into stable configurations is increased by 40 times compared to that of the original SEAKMC method. In addition, we find that the stable configurations obtained by the transformation of the SIA clusters are mostly Frank loops. In summary, this new algorithm for the SEAKMC method helps to resolve the inefficiency of kMC methods resulting from the selection of flicker events and will aid the study of meso-timescale atomistic dynamics.

Estimation of double-differential cross-sections of Be(p,xn) reaction for new nuclear data library JENDL-5

国枝 賢; 山本 和喜; 今野 力; 岩元 洋介; 岩本 修; 若林 泰生*; 池田 裕二郎*

Journal of Neutron Research, 24(3-4), p.329 - 335, 2023/01

https://doi.org/10.3233/JNR-220019

核データライブラリJENDL-5のためにBe(p,xn)反応二重微分断面積の評価を行った。本研究ではまず、理化学研究所で開発された若林関数を内挿法などを工夫してデータベース化し、MCNPやPHITSを用いて薄膜ターゲットに対する検証解析を実施した。それにより、JENDL-4.0/HEや米国のENDF/B-VIII.0と比べて良い予測を与えることを確認した。更に反応断面積の絶対値を若林関数オリジナル値から15%(測定データ間の差異の範囲内で)減少させることにより、更に核データとしての精度が高まることを確認した。以上の知見を投入した新たな核データライブラリJENDL-5を用いることにより、Be(p,xn)反応からの中性子スペクトルや収量を世界一の予測精度で計算することが可能である。

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.