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論文

Interfacial cross-link inhomogeneity of a phenolic resin on a silica surface as revealed by X-ray and neutron reflection measurements

和泉 篤士*; 首藤 靖幸*; 柴山 充弘*; 吉田 鉄生*; 宮田 登*; 宮崎 司*; 青木 裕之

Macromolecules, 53(10), p.4082 - 4089, 2020/05

https://doi.org/10.1021/acs.macromol.0c00398
 被引用回数：6 パーセンタイル：36.95(Polymer Science)

The interfacial structure of a hexamethylenetetramine-cured phenolic resin on a silica surface was investigated by the complementary use of X-ray and neutron reflectivity (XRR and NR, respectively). The contrast-variation technique was applied using D$$_{2}$$O for the NR analysis in which the coherent neutron scattering length density (SLD) largely changed owing to the D$$_{2}$$O absorption of the dry phenolic resin and the hydrogen-to-deuterium exchange of phenolic hydroxyl groups. The XRR profile indicated no clear interfacial structure in terms of the mass density, whereas the NR profile indicated the presence of an interfacial nanolayer on the native silica surface according to the SLD. The thickness of the interfacial layer was 1-2 nm, which was independent of the thickness of the bulk resin layer. The formation of the interfacial layer on the silica surface could be caused by preferential adsorption of the novolac resin on the silica surface via strong hydrogen bonding between phenolic units in the novolac resin and silica surface comprising silanol and silyl ether groups resulting in interfacial cross-link inhomogeneity of the phenolic resin on the silica surface in the thickness direction. To the best of our knowledge, this is the first report of an experimental elucidation of the buried interfacial structure between the phenolic resins on the silica surface at a nanometer level.

論文

Diffusion behavior of methanol molecules confined in cross-linked phenolic resins studied using neutron scattering and molecular dynamics simulations

首藤 靖幸*; 和泉 篤士*; 萩田 克美*; 山田 武*; 柴田 薫; 柴山 充弘*

Macromolecules, 51(16), p.6334 - 6343, 2018/08

https://doi.org/10.1021/acs.macromol.8b00535
 被引用回数：10 パーセンタイル：42.35(Polymer Science)

The dynamics of methanol confined in highly cross-linked phenolic resins was investigated using incoherent quasielastic neutron scattering (QENS) and atomistic molecular dynamics (MD) simulations. The QENS analysis for adeuterated phenolic resin and both deuterated and nondeuterated methanol indicated the presence of resin dynamics induced by methanol invasion and confined diffusion of the methanol molecules. QENS results suggested that methanol had a diffusion coefficient of 1.6 $$times$$ 10$$^{-6}$$ cm$$^{2}$$/s, which is 1 order of magnitude smaller than the bulk value (2.3 $$times$$ 10$$^{-5}$$ cm$$^{2}$$/s. The MD trajectories also showed that the methanol diffusion was limited by the resin network, consistent with QENS results in terms of the diffusion coefficient and diffusion-like behavior.

論文

Structure analysis and derivation of deformed electron density distribution of polydiacetylene giant single crystal by the combination of X-ray and neutron diffraction data

田代 孝二*; 日下 勝弘*; 細谷 孝明*; 大原 高志; 塙坂 真*; 吉澤 功徳*; 山元 博子*; 新村 信雄*; 田中 伊知朗*; 栗原 和男*; et al.

Macromolecules, 51(11), p.3911 - 3922, 2018/06

https://doi.org/10.1021/acs.macromol.8b00650
 被引用回数：4 パーセンタイル：16.38(Polymer Science)

The crystal structure of polydiacetylene giant single crystal has been analyzed on the basis of the two different methods of wide-angle neutron diffraction and X-ray diffraction. The X-ray result gives us the total electron density distribution. The neutron result tells the positions of atomic nuclei. As a result, the so-called bonded (or deformed) electron density, i.e., the electron density distribution due to the conjugation among the covalently bonded atoms along the polymer chain, can be estimated using the two information. The present report is the first example of the application of X-N method to the synthetic polymer species.

論文

Hierarchically self-organized dissipative structures of filler particles in poly(styrene-$$ran$$-butadiene) rubbers

山口 大輔; 湯浅 毅*; 曽根 卓男*; 冨永 哲雄*; 能田 洋平*; 小泉 智*; 橋本 竹治*

Macromolecules, 50(19), p.7739 - 7759, 2017/10

https://doi.org/10.1021/acs.macromol.7b01052
 被引用回数：11 パーセンタイル：40.42(Polymer Science)

スチレン-ブタジエンランダム共重合体におけるフィラー粒子の空間分布を解明した。中性子小角散乱実験の結果、本共重合体中におけるフィラーは5つの構造レベルからなる階層構造を形成していることが判明した。

論文

Photonic crystals fabricated by block copolymerization-induced microphase separation

元川 竜平; 谷口 竜王*; 熊田 高之; 飯田 優羽*; 青柳 翔太*; 佐々木 祐亮*; 桑折 道済*; 岸川 圭希*

Macromolecules, 49(16), p.6041 - 6049, 2016/08

https://doi.org/10.1021/acs.macromol.6b01190
 被引用回数：15 パーセンタイル：53.38(Polymer Science)

We present a method for fabricating photonic crystals (PCs) by polymerization-induced microphase separation of block copolymers (BCPs). Molecular weight of BCP for PCs is so large that it has been difficult for conventional solution casting and annealing methods to complete the microphase separation to form periodically-ordered submicron structures. Our method overcomes the difficulty by inducing the micro phase separation and transitions during the polymerization, when the molecular weight of the BCPs is small enough for the microphase separation and transitions. The microphase-separated structure is then enlarged while maintaining the self-similarity. We succeeded in fabricating PCs with reflection wavelength $$lambda$$m $$approx$$ 1000 nm and a full width at half maximum $$lambda$$ = 0.05 $$lambda$$m by living-radical bulk block-copolymerization of poly(methyl methacrylate)-block-polystyrene.

論文

Dispersing zwitterions into comb polymers for nonviral transfection; Experiments and molecular simulation

Ghobadi, A. F.*; Letteri, R.*; Parelkar, S. S.*; Zhao, Y.; Chan-Seng, D.*; Emrick, T.*; Jayaraman, A.*

Biomacromolecules, 17(2), p.546 - 557, 2016/02

https://doi.org/10.1021/acs.biomac.5b01462
 被引用回数：12 パーセンタイル：50.15(Biochemistry & Molecular Biology)

We report the effect of embedding zwitterionic sulfobetaine (SB) groups in cationic comb polymers on polymer-DNA binding complexes (polyplexes), using a combination of experiments and molecular simulations. Ring-opening metathesis polymerization (ROMP) produced comb polymers with tetralysine (K4) and SB pendent groups. Dynamic light scattering, zeta potential measurements, and fluorescence-based experiments, together with coarse-grained molecular dynamics simulations, described the effect of SB groups on the size, shape, surface charge, composition, and DNA binding strength of polyplexes formed using these comb polymers. Experiments and simulations showed that increasing SB composition in the comb polymers decreased polymer-DNA binding strength, while the SB groups distributed throughout the polyplex. This allows polyplexes to maintain a positive surface charge and provide high levels of gene expression in live cells.

論文

Hierarchical structure-property relationships in graft-type fluorinated polymer electrolyte membranes using small- and ultrasmall-angle X-ray scattering analysis

Tran Duy, T.*; 澤田 真一; 長谷川 伸; 吉村 公男; 大場 洋次郎*; 大沼 正人*; 勝村 庸介*; 前川 康成

Macromolecules, 47(7), p.2373 - 2383, 2014/04

https://doi.org/10.1021/ma500111x
 被引用回数：27 パーセンタイル：71.19(Polymer Science)

X線小角及び超小角散乱解析を用いて、ポリエチレンテトラフルオロエチレン共重合体(ETFE)基材を用いたグラフト型電解質膜(ETFE-PEM)の階層構造を検討した。イオン交換容量(IEC)2.4mmol/g以下のETFE-PEMは、ラメラ結晶の周りに相間距離21.8-29.1nmの導電性のグラフト領域、相間距離218-320nmと903-1124nmの結晶配向領域を有していた。IECが2.7mmol/g以上では、相間距離225-256nmの結晶ネットワーク領域からなる新しい相が形成され、IEC2.4-2.7mmol/gの間で、相転移現象が起こることを見出した。以上の結果により、高IECのETFE-PEMの高いプロトン伝導度は、結晶領域の周り存在する連結したイオンチャンネルに由来し、高い機械強度は残存するラメラ結晶と結晶粒に由来するとの結論を得た。

論文

Order-disorder transition of nanocomposites; Polystyrene-$$block$$-poly(methyl methacrylate) with Pd nanoparticles

Zhao, Y.; 西条 賢次*; 橋本 竹治

Macromolecules, 46(3), p.957 - 970, 2013/02

https://doi.org/10.1021/ma302070r
 被引用回数：7 パーセンタイル：24.46(Polymer Science)

We studied how the palladium nanoparticles, (Pd)$$_{n}$$s, incorporated into poly(styrene)-$$block$$-poly(methyl methacylate) (PS-$$b$$-PMMA) block copolymer (bcp), alter its order-disorder transition (ODT). The (Pd)$$_{n}$$s were incorporated into the lamellar template of PS-$$b$$-PMMA by the thermal reduction of palladium acetylacetonate, dissolved uniformly in the bcp in the disordered state. The ODT behavior of the neat bcp and the nanocomposites are investigated by small angle X-ray scattering as a function of temperature. We found the incorporation of a very small amount of (Pd)$$_{n}$$s significantly increased the ODT temperature by about 8$$^{circ}$$C, which is due to the stronger attractive interactions of (Pd)$$_{n}$$s with PS block chains than with PMMA block chains, which increases the net effective segregation power between PS and PMMA block chains and hence stabilizes the ordered lamellae.

論文

Small-angle neutron scattering study on specific polymerization loci induced by a copolymerization of polymerizable surfactant and styrene during miniemulsion polymerization

元川 竜平; 谷口 竜王*; 佐々木 祐亮*; 榎本 勇人*; 村上 史泰*; 春谷 昌克*; 桑折 道済*; 中平 隆幸*

Macromolecules, 45(23), p.9435 - 9444, 2012/11

https://doi.org/10.1021/ma301776b
 被引用回数：8 パーセンタイル：28.47(Polymer Science)

We have investigated the origin of a specific polymerization locus that yielded copolymer particles with a bimodal gel permeation chromatographic profile in the early stage of miniemulsion polymerization of styrene (St) with C$$_{12}$$DMAEMA. The formation of particles by miniemulsion polymerization using C$$_{12}$$DMAEMA was investigated as a function of the polymerization time ($$t$$$$_{rm p}$$), and was compared with that using the non-polymerizable surfactant CTAB. GPC and elemental analysis indirectly predicted two different polymerization loci in the St/C$$_{12}$$DMAEMA/V50 polymerization system. Time-resolved SANS was used to directly observe and examine the specific polymerization loci in the miniemulsion polymerization solutions. The droplets formed in St/C$$_{12}$$DMAEMA/V50/PSt hydrophobe at the initial stage of the polymerization were not fully stabilized by C$$_{12}$$DMAEMA and poly(C$$_{12}$$DMAEMA-ran-St), and were found to build up the large aggregates. The spherical droplets were stabilized later in tp $$>$$ 20 min by forming a homogeneous dispersion in the water phase. Porod analysis of the power law scattering observed by SANS provided direct evidence for the specific polymerization loci, which appeared in the early stage of the polymerization system of St/C$$_{12}$$DMAEMA/V50/PSt hydrophobe on the surface of the droplet, and was the origin of the bimodal peaks in the GPC chromatogram.

論文

Hierarchical structure analysis of graft-type polymer electrolyte membranes consisting of cross-linked polytetrafluoroethylene by small-angle scattering in a wide-$$Q$$ range

岩瀬 裕希*; 澤田 真一; 八巻 徹也; 小泉 智; 大沼 正人*; 前川 康成

Macromolecules, 45(22), p.9121 - 9127, 2012/11

https://doi.org/10.1021/ma301415r
 被引用回数：17 パーセンタイル：52.2(Polymer Science)

燃料電池用高分子電解質膜の発電性能,耐熱性,機械特性の向上には、電解質特性を支配するナノ-マイクロメートルに及ぶ階層構造を明確にすることが重要である。そこで、放射線グラフト重合法を利用して作製したグラフト型電解質膜の中で、導電率,機械特性や発電性能が詳細に調べられている架橋テフロンからなる電解質膜について、中性子及びX線小角散乱(SANS, SAXS)を測定した結果、グラフト鎖からなるイオンチャンネルは、48-57nmのラメラ周期、直径480nmのラメラ結晶、及び1.7nmのイオンチャンネル内のスルホン酸の会合に対応する階層構造を有することがわかった。さらに、散乱プロファイルのグラフト率依存性より、ラメラ内部の非晶相に局所的にグラフト相(イオンチャンネル)が形成するため、低いグラフト率で高い伝導性を示すことが判明した。

論文

Crystal structure analysis of poly(L-lactic acid) $$alpha$$ form on the basis of the 2-dimensional wide-angle synchrotron X-ray and neutron diffraction measurements

Wasanasuk, K.*; 田代 孝二*; 塙坂 真*; 大原 高志*; 栗原 和男; 黒木 良太; 玉田 太郎; 尾関 智二*; 金元 哲夫*

Macromolecules, 44(16), p.6441 - 6452, 2011/07

https://doi.org/10.1021/ma2006624
 被引用回数：168 パーセンタイル：98.43(Polymer Science)

ポリL乳酸$$alpha$$型の結晶構造を、超延伸試料 を用いて、2次元広角X線(WAXD)及び中性子(WAND)回折によって詳しく解析した。WAXDデータは、SPring-8において波長0.328${AA}$の高エネルギーX線ビームを用いて、WANDデータはJRR-3に設置されたBIX3において波長1.510${AA}$の中性子ビームを用いて収集された。結晶構造の初期モデルは-150$$^{circ}$$Cで観測された約700のX線反射を用いて、空間群を${it P}$2$$_{1}$$2$$_{1}$$2$$_{1}$$と仮定した直接法によって決定された。直接法によって得られた結晶構造モデルは、${it R}$値が-150$$^{circ}$$Cで18.2%、25$$^{circ}$$Cで23.2%となるまで精密化された。得られた分子鎖のコンフォメーションは、鎖軸に沿った2$$_{1}$$のらせん対称を有する歪んだ(10/3)らせん型をとっていた。しかしながら、幾つかの禁制反射が00l反射において検出され、分子鎖に沿った2$$_{1}$$のらせん対称を消去することが必要であった。そこで、空間群を${it P}$2$$_{1}$$と仮定することにより構造精密化を進めた結果、最終的に得られた${it R}$値は-150$$^{circ}$$Cで19.3%、25$$^{circ}$$Cで19.4%であった。2$$_{1}$$のらせん対称の構造偏差はわずかで、すべての層線において精密化されたモデルは観測された反射プロファイルをよく再現することがわかった。得られたX線結晶構造を用いた中性子(WAND)解析を実施した結果、観測された92の反射において${it R}$値は25$$^{circ}$$Cで23.0%であり、層線プロファイルの実測値と計算値はよく一致した。

論文

In situ and time-resolved small-angle neutron scattering observation of star polymer formation via arm-linking reaction in ruthenium-catalyzed living radical polymerization

寺島 崇矢*; 元川 竜平; 小泉 智*; 澤本 光男*; 上垣外 正己*; 安藤 剛*; 橋本 竹治*

Macromolecules, 43(19), p.8218 - 8232, 2010/10

https://doi.org/10.1021/ma101235j
 被引用回数：40 パーセンタイル：77.26(Polymer Science)

${it In situ}$ and time-resolved small-angle neutron scattering (SANS) was employed for the elucidation of star polymer formation mechanism via linking reaction of living linear polymers in ruthenium-catalyzed living radical polymerization. Here, methyl methacrylate (MMA) was first polymerized with R-Cl/RuCl$$_{2}$$(PPh$$_{3}$$)$$_{3}$$/tribuylamine ($$n$$-Bu$$_{3}$$N) initiating system, followed by the addition of ethylene glycol dimethacrylate (EGDMA: 3) as a linking agent. After the in situ addition of a small amount of 3 to living linear PMMA, the SANS analysis revealed the following three steps: (process II-1) formation of block copolymers (4) and competitive formation of the small star polymers via the linking reaction of 4 and 4; (process II-2) star-star linking of the small star polymers into star polymers and putting 4 into the core of the star polymers, leading to formation of the microgel-core star polymers; (process II-3) growth of the microgelcore star polymers (5) via placement of 4 into the microgel-core star polymers. Furthermore, the SANS profiles, obtained as a function of polymerization time, were quantitatively analyzed with a core-shell spherical model in order to determine the microstructures of the star polymers: The final reaction product had an average radius of microgel-core ($$sim$$ 1 nm), and average arm numbers N $$sim$$ 17.

論文

Combined SANS, SEC, NMR, and UV-vis studies of simultaneous living anionic copolymerization process in a concentrated solution; Elucidation of building-up processes of molecules and their self-assemblies

Zhao, Y.; 宮元 展義*; 小泉 智; 橋本 竹治

Macromolecules, 43(6), p.2948 - 2959, 2010/04

https://doi.org/10.1021/ma902542e

A simultaneous living anionic copolymerization of a concentrated solution of deuterated styrene (S) and nondeuterated isoprene (I) monomers in deuterated benzene as a solvent was studied by a combination of time-resolved measurements of small-angle neutron scattering (SANS), size exclusion chromatography (SEC), nuclear magnetic resonance (NMR), and ultraviolet-visible spectroscopy (UV-vis). The molecular building-up process and its consequence on the bottom-up self-assembling process during the copolymerization reaction were observed on three different length scales on the same batch of the solution, which enabled us to explore simultaneously the time changes in the local structure (living chain ends), the primary structure (propagating chains), and the higher order structure (microdomains). We found that the copolymerization process was divided into two time regions, defined by regions I and II. In region I, the copolymerization of S and I monomers took place, and all I monomers were consumed at the end of region I. In the early stage of region I (region I$$_{rm a}$$), the SANS profiles were almost time-independent and exhibited no scattering maximum, whereas in the late stage of region I (region I$$_{rm b}$$), a scattering maximum appeared at $$q$$$$_{rm m}$$ m and hardly changed with time, although the maximum intensity $$I$$$$_{rm m}$$ slightly increased with time. In region II, pure polystyrene (PS) block chains were formed. The polymerization-induced disorder-order transition (ODT) and order-order transition (OOT) were observed.

論文

Soap-free emulsion polymerization of poly(ethylene glycol)-${it block}$-poly($$N$$-isopropylacrylamide); Elucidation of specific reaction fields for quasi-living polymerization by time-resolved SANS

元川 竜平; 小泉 智*; 橋本 竹治*; 安中 雅彦*; 中平 隆幸*

Macromolecules, 43(2), p.752 - 764, 2010/01

https://doi.org/10.1021/ma9020533
 被引用回数：16 パーセンタイル：47.44(Polymer Science)

Poly(ethylene glycol)-${it block}$-poly($$N$$-isopropylacrylamide) (PEG-$$b$$-PNIPAAm) was synthesized by radical polymerization of $$N$$-isopropylacrylamide (NIPAAm) from the radically activated chain ends generated on PEG. The polymerization process was investigated by a conventional observation of molecular weight and its distribution as well as monomer conversion, $$C$$$$_{rm M}$$($$t$$), as a function of the polymerization time $$t$$ and temperature $$T$$$$_{rm p}$$, by means of time-resolved GPC. The reaction fields in which the polymerization takes place were explored by time-resolved small-angle neutron scattering (SANS). The results elucidated the following characteristics on the temperature-dependence of the solution structure and, hence, the reaction fields: (1) at 15 $$leq$$ $$T$$$$_{rm p}$$($$^{circ}$$C) $$leq$$ 30, the solution is composed of swollen micelles in which PNIPAAmand PEG block chains form swollen cores and brushes emanating from the interface between them, respectively; and (2) at 34 $$leq$$ $$T$$$$_{rm p}$$($$^{circ}$$C) $$leq$$ 60, the solution is composed of dehydrated PNIPAAm cores (hard cores) and swollen PEG brushes with well-defined interfaces between them. As for (1) and (2), the micelles were formed from a very early stage of the polymerization as $$C$$$$_{rm M}$$ being as small as 0.05, hence, yielding a "soap-free emulsion polymerization" field for NIPAAm. The results obtained in this work reveal that the hard-core micelle formation is the necessary and sufficient condition for the "quasi-living soap-free emulsion polymerization.

論文

Combined SANS, SEC, NMR, and UV-Vis studies of simultaneous living anionic copolymerization process; Simultaneous elucidation of propagating living chains at three different length scales

Zhao, Y.; 田中 宏和*; 宮元 展義*; 小泉 智; 橋本 竹治

Macromolecules, 42(5), p.1739 - 1748, 2009/04

https://doi.org/10.1021/ma8017519
 被引用回数：15 パーセンタイル：44.51(Polymer Science)

The living anionic copolymerization of a mixture of isoprene (I) and styrene (S) monomers, in the dilute solution with deuterated benzene as a non-polar solvent and sec-butyllithium as an initiator, was investigated by a simultaneous measurement of time-resolved small-angle neutron scattering (SANS), size exclusion chromatography (SEC), nuclear magnetic resonance (NMR), and ultraviolet-visible (UV-Vis) spectroscopy. The combined time-resolved study on the same single batch reaction solution enabled us to investigate the structural change of the propagating living chains in three different length scales on a rigorously common time scale: the type of living chain ends, primary structure of single living chains, and the association of living chains. Although the living anionic copolymerization of S and I has been studied extensively, there is no study so far that uses such a combination of real-time methods as this study on the same single batch reaction solution.

論文

SAXS analysis of the order-disorder transition and the interaction parameter of polystyrene-${it block}$-poly(methyl methacrylate)

Zhao, Y.; Sivaniah, E.*; 橋本 竹治

Macromolecules, 41(24), p.9948 - 9951, 2008/12

https://doi.org/10.1021/ma8013004
 被引用回数：123 パーセンタイル：96.17(Polymer Science)

In this study, the order-disorder transition (ODT) for two symmetric polystyrene-b-poly(methyl methacrylate) diblock copolymers was investigated by a high temperature-resolution Small Angle X-ray Scattering (SAXS) experiments with small decreases of temperature (T) across the ODT. The characteristic ODT temperature was determined from the discontinuity of 1/Im and q2 vs 1/T, confirming the fluctuation-induced weakly first-order transition for this block copolymer. In the disordered state, far above ODT temperature, the interaction parameter for PS-b-PMMA was also extracted, and found to be slightly larger than that in the deuterated systems having the similar molecular weight and compositions. PS-b-PMMA is a promising technological system that is able to be manipulated to provide nanostructural templates and scaffolds. Hence our precise determination of the interaction parameter and the order-disorder characteristics of a non-deuterated system will be invaluable to future works.

論文

Theoretical modeling of associated structures in aqueous solutions of hydrophobically modified telechelic PNIPAM based on a neutron scattering study

古賀 毅*; 田中 文彦*; 元川 竜平; 小泉 智; Winnik, F. M.*

Macromolecules, 41(23), p.9413 - 9422, 2008/11

https://doi.org/10.1021/ma800957z
 被引用回数：73 パーセンタイル：89.99(Polymer Science)

ポリ(N-イソプロピルアクリルアミド)(PNIPAM)の両端末を、オクタデシル基で疎水化したテレケリックPNIPAM(HM-PNIPAM)の水溶液は、温度変化に応答してフラワーミセルやメソグロビュール(会合構造)を形成する。この水溶液は、温度とポリマー濃度の変化に応じて、ゾル-ゲル転移や水溶液の白濁等のマクロな状態を変化させる。本論文では、この水溶液に対して中性子小角散乱測定を行い、その結果に対して理論モデルを組み立てることで、マクロな状態変化に伴うメソスケールでの構造変化(ミクロな構造変化)を明らかにした。これにより、マクロな状態変化のメカニズムを明らかにすると同時に、さまざまな温度,ポリマー濃度条件で形成されるフラワーミセルやメゾグロビュールのサイズ,形状を決定した。

論文

Morphological and scattering studies of binary mixtures of block copolymers; Cosurfactant effects observed in the parameter space of temperature, blend composition, and molecular weight ratio

Fran$c{c}$ois, C.*; 山口 大輔; 橋本 竹治

Macromolecules, 41(13), p.4828 - 4837, 2008/07

https://doi.org/10.1021/ma800102a
 被引用回数：25 パーセンタイル：61.07(Polymer Science)

二種類のブロック共重合体を混合した系のさまざまなモルフォロジー間において起こる温度可逆な秩序-秩序転移を小角X線散乱により調べた。この系において観察された複雑なモルフォロジー挙動は以下に記すような、二種類のブロック共重合体の混合物の鍵となる2つの特徴をもとに理解される。それらの特徴とは(1)共界面活性効果,(2)斥力相互作用力の低下に伴って鎖長の短い方のブロック共重合体の化学結合点が界面から離れる可能性、である。この一連の研究を通してのまとめとして、(a)混合物の中のポリスチレンブロックの体積分率,(b)混合に用いた長い鎖長と短い鎖長を有するブロック共重合体の重合度比,(c)温度の変数空間における3次元の相図を構築した。このような相図は共界面活性効果が自己組織されたナノ構造体のモルフォロジーの仕立てに関して、前途を拓くものであることを示している。

論文

Symmetric diblock copolymer thin films on rough substrates; Microdomain periodicity in pure and blended films

Sivaniah, E.*; 松原 真也*; Zhao, Y.; 橋本 竹治; 福永 謙二*; Kramer, E. J.*; Mates, T. E.*

Macromolecules, 41(7), p.2584 - 2592, 2008/04

https://doi.org/10.1021/ma702465t
 被引用回数：34 パーセンタイル：71.19(Polymer Science)

The lamellar dimension, D, for pure and blended block copolymer (BCPs) thin films of symmetricpoly(styrene)-block-poly(methyl methacrylate) was measured using atomic force microscopy analysis of surface patterns of perpendicularly oriented lamellar structures. It was approximately verified, using SAXS and AFM analysis, that perpendicular structures in lamellar thin films bounded by a neutral and a roughened interface did not significantly alter the bulk block copolymer phase separation thermodynamics. In the case of blends, it was also verified that there was a uniform distribution of blend components throughout the thin film.

論文

Control of self-assembling processes of polyamidoamine dendrimers and Pd nanoparticles

田中 宏和*; 橋本 竹治; 小泉 智; 伊東 秀明*; 中 建介*; 中條 善樹*

Macromolecules, 41(5), p.1815 - 1824, 2008/03

https://doi.org/10.1021/ma702034x
 被引用回数：8 パーセンタイル：27.68(Polymer Science)

ポリアミンデンドリマーのメタノール溶液と酢酸パラジウムのDMF溶液を混合した際に生ずるデンドリマーの分子集合体の自己組織化機構及び同集合体をテンプレートとしてその中に形成されるパラジウムナノ微粒子の自己組織化機構を解明するとともに、これら自己組織化構造のデンドリマーの世代数及びデンドリマーの濃度依存性を解明した。

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