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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：1 パーセンタイル：44.82(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 (D
O) 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.
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 秀樹*; 青木 裕之; 宮崎 司*
Soft Matter, 19(11), p.2082 - 2089, 2023/03
被引用回数：0 パーセンタイル：0(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.
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 秀樹*; 青木 裕之; et al.
Langmuir, 38(41), p.12457 - 12465, 2022/10
被引用回数：0 パーセンタイル：0(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.
今井 彩帆里*; 荒川 勝利*; 中西 洋平*; 竹中 幹人*; 青木 裕之; 大内 誠*; 寺島 崇矢*
Macromolecules, 55(20), p.9113 - 9125, 2022/10
被引用回数：3 パーセンタイル：24.75(Polymer Science)Microphase separation of copolymers is a key technique to produce polymer bulk materials or thin films with ordered nanostructures for applications in various research fields including nanotechnologies, electronic devices, among many others. Herein, we report water-assisted microphase separation of amphiphilic random copolymers bearing quaternary ammonium cations and hydrophobic alkyl or oleyl groups in the solid state and the thin films. We investigated the effects of sample preparation protocols and the hydrophobic pendants (a butyl group: C4 - octadecyl or oleyl group: C18), composition, and molecular weight of the copolymers on the microphase separation behavior. By annealing under humid conditions, the copolymers bearing alkyl groups longer than an octyl group (C8) formed sub-5 nm lamellar structures comprising cationic layers and hydrophobic layers. Water hardly remained in the resulting lamellar materials under ambient conditions. The domain spacing was controlled between 3.7 and 5.3 nm by tuning the length of the hydrophobic pendants and composition and was independent of the molecular weight and molecular weight distribution. The cationic random copolymers carrying amorphous hydrophobic pendants provided transparent or translucent polymer materials containing small lamellar structures. The random copolymers further formed multilayered lamellar thin films on silicon substrates by spin-coating the copolymer solutions, followed by a humid annealing process. The layered lamellae were directly observed as terrace structures with about 4-5 nm steps by atomic force microscopy.
山口 龍彦*; 辻 智大*; 七山 太*; 中西 利典; 池田 倫治*; 近藤 康生*; 三輪 美智子*; 濱田 洋平*
no journal, ,
四国は、フィリピン海プレートの沈み込みに伴う南海トラフの北西150kmに位置している。この構造運動によって、島の変形, 巨大地震, 津波などが発生してきたが、完新世中期のテクトニクスはまだよく理解されていない。沿岸堆積物に記録されている相対的な海水準(RSL)の変化は、地震の隆起と沈降を示唆する。8-4cal kBPの間のRSLの変化を推測するために、四国南西部宿毛のSKMコア(Tsuji et al., 2018、JpGU、MIS11-P19)および四島北部の6本のコア(Yasuhara et al., 2005、Palaeo3; Yasuhara and Seto、2006、Paleontol. Res.)を用いた。これらから古水深とRSLを推定するために、貝形虫群集組成とモダンアナログ法を用いた。SKMコアは、主に砂礫, 火山灰, 泥で構成されおり、放射性炭素年代測定法を使用して、その堆積年代が詳細に調べられている(Nakanishi et al., 2019、Radiocarbon)。これらの結果を総合して、8-4cal kBPにおいて四国周辺のRSLの標高差を検知することに成功した。これらはフィリピン海プレートの収束による島の傾斜を示唆すると考えられる。
甲斐 樹*; 中西 優貴*; 谷口 直樹; 土橋 竜太*; 廣畑 洋平*; 春名 匠*
no journal, ,
原子力発電所から排出される高レベル放射性廃棄物の処分方法として、炭素鋼製の処分容器に入れて地下に埋設する地層処分方法が検討されている。この方法で処分容器を長時間保存すると、CO
およびHCO
等が含まれ、酸素が欠乏した地下水に容器表面が接触し、腐食に伴ってFeCO皮膜が形成される。この状態で炭素鋼がさらに腐食するには、水が皮膜中を拡散浸透して処分容器と接触することが必要であり、このときの処分容器の腐食速度は皮膜中における水の拡散速度によって決定されることが提案されている。本研究グループでは、FeO
皮膜中におけるDOの拡散浸透挙動を調査し、その拡散定数を推定した。そこで本研究では、NaHCO水溶液中におけるFeCO皮膜の形成条件およびその皮膜へのDOの拡散浸透挙動を調査した。
