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Elucidation of the morphology of the hydrocarbon multi-block copolymer electrolyte membranes for proton exchange fuel cells

Zhao, Y.; 吉田 実留*; 大島 竜也*; 小泉 智*; 陸川 政弘*; Szekely, N.*; Radulescu, A.*; Richter, D.*

Polymer, 86, p.157 - 167, 2016/03

 被引用回数:9 パーセンタイル:46.25(Polymer Science)

We investigated the structure and the swelling behavior of two synthesized hydrocarbon polymer electrolyte membranes, made of multiblock copolymer poly(sulphonate phenylene)-b-poly(arylene ether ketone) with different block ratios, by using small-angle neutron scattering technique. A scattering maximum (ionomer peak) at high-q range is shown commonly in both dry and wet states, with q being the magnitude of the scattering vector, while it shifts towards low-q region in the wet state due to the swelling of the ionomer domains with water. The swelling effect also results to a second scattering maximum in the middle-q range because of the water-induced microphase separation. The morphology in this q-range was elucidated in terms of Hard-Sphere model with Percus-Yervick interference approximation.


Molecular dynamics simulation of telomeric single-stranded DNA and POT1

冠城 雅晃; 山田 寛尚*; 宮川 毅*; 森河 良太*; 高須 昌子*; 加藤 宝光*; 上坂 充*

Polymer Journal, 48(2), p.189 - 195, 2016/02

 被引用回数:4 パーセンタイル:72.92(Polymer Science)



Combining small-angle and intermediate-angle neutron scattering to study the hierarchical structure in microbial cellulose

Zhao, Y.; 小泉 智

European Polymer Journal, 66, p.437 - 443, 2015/05

 被引用回数:2 パーセンタイル:88.81(Polymer Science)

In this study, we employed intermediate angle neutron scattering (IANS) technique to correct the small angle neutron scattering (SANS) data of the water-swollen microbial cellulose (MC) sample, the system of which has a significant incoherent contribution from the water solvent, and we described the effects that the corrections have on the structural analysis. In order to elucidate the structure efficiently, the solvent was exchanged in situ between protonated water and deuterated water to give different scattering contrasts, and the water-exchange processes were followed by time-resolved SANS and IANS simultaneously. Our results showed that: (1) after incoherent correction, the microstructure of MC sample was proved to be invariant with solvents; (2) the scattering intensity depended only on the contrast factor, revealing a two-phase system composed of waterresistant crystalline cellulose phase and hydrated amorphous phase; (3) the cellulosecrystallites have a constant scattering length density of 2.0$$times$$10$$^{10}$$ cm$$^{-2}$$, determined by the matching point at which the scattering contrast between the two phases is minimum. This value was consistent with that of 1.9$$times$$10$$^{10}$$ cm$$^{-2}$$ estimated from its chemical structure.


Dependence of structure of polymer side chain on water structure in hydrogels

関根 由莉奈; 高木 紀*; 須藤 小葉子*; 梶原 祐太郎*; 深澤 裕; 深澤 倫子*

Polymer, 55(24), p.6320 - 6324, 2014/11

 被引用回数:12 パーセンタイル:45.34(Polymer Science)



Pulse radiolysis study on a highly sensitive chlorinated resist ZEP520A

保坂 勇志*; 大山 智子; 大島 明博*; 榎本 智至*; 鷲尾 方一*; 田川 精一*

Journal of Photopolymer Science and Technology, 26(6), p.745 - 750, 2013/12

 被引用回数:7 パーセンタイル:68.83(Polymer Science)



Graft-type polymer electrolyte membranes for fuel cells prepared through radiation-induced graft polymerization into alicyclic polybenzimidazoles

Park, J.*; 高山 俊雄*; 浅野 雅春; 前川 康成; 工藤 一秋*; 高山 俊雄*

Polymer, 54(17), p.4570 - 4577, 2013/08

 被引用回数:5 パーセンタイル:77.74(Polymer Science)

芳香族ポリベンズイミダゾール(PBI)膜に匹敵する耐熱性と機械特性を示す脂環式PBI(ChPBI)への放射線グラフト重合及びその後のスルホン化処理によりグラフト型ポリベンズイミダゾール電解質膜(sPBI)を作製した。ChPBIは、$$trans$$-1,4-cyclohexanedicarboxylic acidと3,3'-diaminobenzidineの縮合反応より合成した。合成したChPBIは塩化リチウム含有のジメチル酢酸溶液から製膜することで結晶性を示し、$$gamma$$線の照射によりグラフト重合の開始種となる長寿命ラジカルが生成することがわかった。得られた結晶性ChPBI膜を220kGy照射後スチレン/1-プロピルアルコール(50/50)中でのグラフト重合とスルホン化処理により、イオン交換容量が2.1$$sim$$2.9mmol/gのsPBI膜が調製できた。sPBI膜は10$$^{-3}$$$$sim$$10$$^{-2}$$S/cmと従来のPBI膜よりも高いプロトン伝導度を示した。走査電子顕微鏡/エネルギー分散型X線分析(SEM-EDX分析)より、sPBI膜中の1$$mu$$m径のグラフトドメインの形成が高イオン導電性に重要であることがわかった。このsPBI膜は、120$$^{circ}$$C熱水中で600時間後においてもプロトン伝導度の減少を起こさないことから、これまで作製したグラフト型電解質膜よりも耐熱性に優れていることを明らかにした。


Nanoscale structures of radiation-grafted polymer electrolyte membranes investigated via a small-angle neutron scattering technique

澤田 真一; 山口 大輔; Putra, A.; 小泉 智*; 前川 康成

Polymer Journal, 45(8), p.797 - 801, 2013/08

 被引用回数:5 パーセンタイル:77.74(Polymer Science)



Effects of crosslinker density on the polymer network structure in poly-$$N$$,$$N$$-dimethylacrylamide hydrogels

深澤 倫子*; 池田 尚弘*; 田畑 麻友*; 服部 正孝*; 相澤 守*; 柚木 俊二*; 関根 由莉奈

Journal of Polymer Science, Part B; Polymer Physics, 51(13), p.1017 - 1027, 2013/07

 被引用回数:20 パーセンタイル:32.22(Polymer Science)

To investigate the effects of crosslinker density on the properties of hydrogels, compression tests, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and Raman measurements were performed on poly-$$N$$,$$N$$-dimethylacrylamide hydrogels. The results of the compression tests showed that the Young's modulus increases as the crosslinker density increases. In addition, the results suggest that the bound water plays an important role in strengthening the hydrogel. The water structure may be one of the dominant factors governing the chemical and physical properties of hydrogels.


Crystal morphology-dependent graft polymerization in poly(ether ether ketone) films

長谷川 伸; 高橋 周一*; 岩瀬 裕希*; 小泉 智; 大沼 正人*; 前川 康成

Polymer, 54(12), p.2895 - 2900, 2013/05

 被引用回数:6 パーセンタイル:73.24(Polymer Science)



Effect of partial delignification of kenaf bast fibers for radiation graft copolymerization

Mohamed, N. H.*; 玉田 正男; 植木 悠二; 瀬古 典明

Journal of Applied Polymer Science, 127(4), p.2891 - 2895, 2013/02



$$gamma$$-ray irradiated organic thin film transistors based on perfluoropentacene with polyimide gate insulator

高柳 佑太郎*; 大内 啓邦*; Duan, Z.*; 奥川 孝紀*; 柳 雄一郎*; 吉田 哲*; 田口 光正; 平尾 敏雄; 西岡 泰城*

Journal of Photopolymer Science and Technology, 25(4), p.493 - 496, 2012/08

 被引用回数:0 パーセンタイル:100(Polymer Science)



Microprocessing of arched bridge structures with epoxy resin by proton beam writing

高野 勝昌*; 麻野 敦資*; 前吉 雄太*; 丸井 裕美*; 大道 正明*; 佐伯 昭紀*; 関 修平*; 佐藤 隆博; 石井 保行; 神谷 富裕; et al.

Journal of Photopolymer Science and Technology, 25(1), p.43 - 46, 2012/07

 被引用回数:2 パーセンタイル:91.16(Polymer Science)

The proton beam writing (PBW) with energy of several MeV ranges is a unique tool of three-dimensional microprocessing for a polymer material. Three-dimensional structures like a bridge structure can be fabricated by the double exposures of PBW with two deferent energies followed by the one-time development using etching solution. In this study, the fabrication of an arched bridge was attempted by means of the supercritical drying with liquid carbon dioxide to a SU-8 photoresist film, as the polymer material, coated on a substrate of epoxy sheet, after the PBW process. In the exposures, two patterns of bridge girders and piers were written with 0.5 and 3 MeV proton beams to the SU-8 photoresist films, respectively. After these writings, the photoresist films were developed with the solution of diacetone alcohol and rinsed with the solution of isopropyl alcohol. Then the supercritical drying with liquid carbon dioxide was used at 12 MPa, 40$$^{circ}$$C. As the results, the bridge structures with curved girders to the vertical direction were formed due to the swelling effect of the photoresist film on the drying. In the conference, the microprocessing method of the bridge structure and the swelling effect of the photoresist film will be represented in detail.


Surface modification of vulcanized rubber by radiation grafting, 2; Improvement in performance of wiper rubber

溝手 範人*; 片貝 秋雄; 玉田 正男

Journal of Applied Polymer Science, 123(4), p.2172 - 2176, 2012/02

 被引用回数:3 パーセンタイル:86.81(Polymer Science)



Synthesis and characterization of carboxymethyl derivatives of kappa-carrageenan

Tranquilan-Aranilla, C.*; 長澤 尚胤; Bayquen, A.*; Dela Rosa, A.*

Carbohydrate Polymers, 87(2), p.1810 - 1816, 2012/01

 被引用回数:51 パーセンタイル:8.06(Chemistry, Applied)

多糖類の放射線架橋技術において利用可能性が高い新規原材料を開発するため、天然多糖類の一つで放射線分解型であるカッパカラギーナンを多段階法により置換度の異なるカルボキシメチル化誘導体を合成し、FTIR, $$^{13}$$C NMRによる構造同定,GPCによる分子量変化,元素分析,電位差滴定による硫酸基定量などの特性評価を行った。得られた誘導体は、80%の2-プロパノール(720mL)中で懸濁したカラギーナン(80g)に40%水酸化ナトリウム(93.5mL)添加して40$$^{circ}$$Cで1時間処理後、モノクロロ酢酸(49.1g)を添加して40$$^{circ}$$Cで3時間処理によるカルボキシメチル化処理を1回から3回へと増やすと、置換度が1.2から1.66まで高くなるとともに、酸性度も2.02から2.43まで増加した。しかしながら、3回処理すると原料のカラギーナンと比べて、硫酸基が約51%まで、分子量が327万Daから142万Daまで減少した。また、FTIRと$$^{13}$$C NMR測定により、カラギーナンの水酸基がカルボキシメチル化していることを確認した。


Structure and dynamics of poly(vinyl alcohol) gels in mixtures of dimethyl sulfoxide and water

金谷 利治*; 高橋 伸明; 竹下 宏樹*; 大倉 正敏*; 西田 幸次*; 梶 慶輔*

Polymer Journal, 44(1), p.83 - 94, 2012/01

 被引用回数:11 パーセンタイル:58.39(Polymer Science)

We review our structure studies on poly(vinyl alcohol) (PVA) gels formed in mixtures of dimethyl sulfoxide (DMSO) and water using various scattering methods including wide-, small- and ultra small-angle neutron scattering and light scattering. These studies revealed the hierarchic structure of PVA gels formed in DMSO/water (60/40 v/v) in a very wide spatial scale from 1 ${AA}$ to several micron: the crosslinking points are crystallites with radius of $$sim$$70 ${AA}$, the distance between the neighboring crystallites is 180-200 ${AA}$, and the bicontinuous structure due to liquid-liquid phase separation is in mm scale. We also review our dynamic studies on three kinds of PVA gels in nm scale using neutron spin echo technique to separate the concentration fluctuations observed by small-angle neutron scattering into the static and dynamics contributions.


Thermoresponsive extraction of cadmium(II) ions by poly(TPEN-NIPA) gels; Effect of chain length and branched spacer structure on gel formation and extraction behavior

稲葉 優介*; 津曲 貴幸*; 喜田 達也*; 渡部 渉*; 中島 靖隆*; 福岡 佐千緒*; 森 敦紀*; 松村 達郎; 中野 義夫*; 竹下 健二*

Polymer Journal, 43(7), p.630 - 634, 2011/07

 被引用回数:11 パーセンタイル:57.03(Polymer Science)

重合可能な二重結合を持つ官能基をピリジン環に結合させた${it N,N,N',N'}$-(tetrakis-2-pyridylmethyl)ethylenediamine (TPEN)の誘導体を合成し、重合開始剤としてazobisisobutyronitrile (AIBN)を使用して${it N}$-isopropylacrylamide (NIPA)との共重合を試みた。得られたTPEN-NIPA重合ゲルは、膨潤/収縮挙動に温度応答性が認められ、さらに抽出剤であるTPENの性能が発揮され水溶液中のカドミウム(II)イオンを抽出可能であった。重合ゲルは、側鎖にpropyl基, butyl基, decyl基及びisopropyl基を持つTPEN誘導体を用意して重合した。これらについて、カドミウムイオン抽出の温度依存性を比較した。これらのゲルによる水溶液中のカドミウム(II)イオン抽出は、膨潤状態である5$$^{circ}$$Cにおいて効率が高く、収縮状態である45$$^{circ}$$Cでは、ほとんど抽出されなかった。また、側鎖にisopropyl基を持つTPEN誘導体による重合ゲルが、抽出性能の高い温度応答性を有することを見いだした。


The Static structure of polyrotaxane in solution investigated by contrast variation small-angle neutron scattering

遠藤 仁; 眞弓 皓一*; 大坂 昇*; 伊藤 耕三*; 柴山 充弘*

Polymer Journal, 43(2), p.155 - 163, 2011/02

 被引用回数:5 パーセンタイル:78.59(Polymer Science)



Radiation-induced graft polymerization of functional monomer into poly(ether ether ketone) film and structure-property analysis of the grafted membrane

長谷川 伸; 高橋 周一*; 岩瀬 裕希*; 小泉 智; 森下 憲雄; 佐藤 賢*; 成田 正*; 大沼 正人*; 前川 康成

Polymer, 52(1), p.98 - 106, 2011/01

 被引用回数:39 パーセンタイル:17.05(Polymer Science)



Preirradiation graft polymerization of styrene in a poly(tetrafluoroethylene) film investigated by time-resolved small-angle neutron scattering

岩瀬 裕希*; 澤田 真一; 八巻 徹也; 前川 康成; 小泉 智

International Journal of Polymer Science, 2011(2011), p.301807_1 - 301807_7, 2011/00

 被引用回数:8 パーセンタイル:66.95(Polymer Science)



Modification of a hydrophobic-ligand-containing porous sheet using tri-$$n$$-octylphosphine oxide, and its adsorption/elution of bismuth ions

田中 亮太*; 石原 量*; 三好 和義*; 梅野 太輔*; 斎藤 恭一*; 浅井 志保; 山田 伸介*; 廣田 英幸*

Reactive and Functional Polymers, 70(12), p.986 - 990, 2010/12

 被引用回数:7 パーセンタイル:65.72(Chemistry, Applied)

Extractants developed for liquid-liquid extraction are useful for the recovery of rare-earth ions. However, the use of such extractants is disadvantageous from environmental and economical viewpoints. In this study, neutral extractant, tri-$$n$$-octylphosphine oxide (TOPO), was combined with a hydrophobic ligand-containing porous polymer sheet. In first, glycidyl methacrylate (GMA) was graft-polymerized onto the porous polyethylene sheet. Second, an octadecane thiol group was introduced into the poly-GMA graft chain. Third, TOPO was deposited on the graft chain via a hydrophobic interaction. Bismuth chloride solution was forced through the pores of the TOPO-modified porous sheet. The equilibrium binding capacity for bismuth was 0.19 mmol/g. Bismuth ions bound to TOPO were quantitatively eluted with 11 M HNO$$_{3}$$. As TOPO exhibits an affinity interaction with rare-metal ions such as Pd, Pt, and Ru, the TOPO-modified porous sheet prepared in this study will have extensive applications.

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