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Item type:Item, Block copolymer micelles confined in cylindrical nanopores: Effects of annealing solvents and hybridization(2020-05-01) ;Cheng, Ming-Hsiang ;Yao, I-Chun ;Chiu, Tang-Yao ;Chen, Jiun-Tai交大名義發表Amphiphilic block copolymer micelles have been intensively investigated and applied into various research fields for decades. One of the most promising characteristics for block copolymer micelles is the selective incorporation of metal precursors in the cores or coronas of the micelles. By combining with nanoporous membranes, aligned polymer nanostructures can be generated, facilitating the applications such as nanolithography and catalysis. The morphology transitions and controllability of block copolymer micelles in confined geometries, however, have seldom been studied. In addition, for hybrid micelles in which polymer segments are selectively incorporated with inorganic metal precursors, the relationship between hybridization and morphologies of polymer nanostructures in the confined states is still under discussion. In this work, we investigate the effects of annealing solvents and hybridization with metal precursors (gold(III) chloride trihydrate (HAuCl4 center dot 3H(2)O)) on the morphologies of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer micelles confined in the nanopores of anodic aluminum oxide (AAO) templates. Tuned by the annealing solvent vapors and the selective ion complexation between HAuCl4 and P4VP cores, various morphologies can be effectively controlled, such as the spherical-micelles-in-rod morphology, the parallel-cylinders-in-rod morphology, and the hemispherical-micelles-in-rod morphology. This study not only investigates the effects of annealing solvent vapors and hybridization on the morphologies of block copolymer micelles confined in cylindrical nano-geometries but also offers a viable route for preparing metal nanoparticles embedded in porous templates.Item type:Item, Reversible morphology control of three-dimensional block copolymer nanostructures by the solvent-annealing-induced wetting in anodic aluminum oxide templates(2016) ;Chu, Chiang-Jui ;Cheng, Ming-Hsiang ;Chung, Pei-Yun ;Chi, Mu-HuanJeng, Kai-ShengIn this work, the authors study the fabrication of three-dimensional block copolymer nanostructures in which the morphologies can be reversibly controlled. Polystyrene-block-polydimethylsiloxane (PS-b-PDMS), a promising candidate for nanolithography, is introduced into cylindrical nanopores of anodic aluminum oxide (AAO) templates using a solvent annealing-induced nanowetting in templates (SAINT) method. Not only the morphologies of the infiltrated PS-b-PDMS nanostructures can be tuned by the annealing solvents, but also the solvent-vapor-controlled morphologies can be altered reversibly by annealing the samples repeatedly between different solvent vapors.Item type:Item, Self-assembly of an A-B diblock copolymer blended with a C homopolymer and a C-D diblock copolymer through hydrogen bonding interaction(2010-08-19) ;Chen, Wan-Chun ;Kuo, Shiao-Wei ;Chang, Feng-Chih ;應用化學系Department of Applied ChemistryIn this study, we investigated the miscibility, phase behavior, and self-assembled nanostructures formed from the immiscible crystalline-amorphous diblock copolymer poly(epsilon-caprolactone-b-4-vinyl pyridine) (PCL-b-P4VP, A-B) when blended with the homopolymer poly(vinyl phenol) (PVPh, C) and the diblock copolymer poly(vinyl phenol-b-styrene) (PVPh-b-PS, C-D). Long-range-ordered microphase separation was difficult to achieve in the PCL-b-P4VP/PVPh (A-B/C) blend system because PVPh interacted with both the P4VP and PCL blocks simultaneously through hydrogen bonding interactions. In contrast, we observed sharp, multiple orders of diffraction in the SAXS profiles of the PCL-b-P4VP/PVPh-b-PS (A-B/C D) blend system, indicating that perfect microphase separation occurred because the incorporation of the PS block induced the PVPh block to hydrogen bond preferentially with the P4VP block. This simple A-B/C-D (PCL-b-P4VP/PVPh-b-PS) diblock copolymer mixture exhibited self-assembly behavior (a three-lamella phase) similar to that of a corresponding ABC triblock copolymer. (C) 2010 Elsevier Ltd. All rights reserved.Item type:Item, Supramolecular self-assembly through inclusion complex formation between poly(ethylene oxide-b-N-isopropylacrylamide) block copolymer and alpha-cyclodextrin(2009-06-19) ;Tu, Cheng-Wei ;Kuo, Shiao-Wei ;Chang, Feng-Chih ;應用化學系Department of Applied ChemistryA well-defined poly(ethylene oxide-block-N-isopropylacrylamide) (PEO-b-PNIPAM) diblock copolymer was synthesized by atom transfer radical polymerization and formed the inclusion complexes (ICs) after selective threading of the PEO segment of the block copolymer through the cavities of alpha-cyclodextrin (alpha-CD) units. The formation of the alpha-CD/PEO ICs between alpha-CD and PEO segment of the PEO-b-PNIPAM transformed the system from its original random coil conformation into a rod/coil-like structure. The stacking of the alpha-CD/PEO ICs and phase separation within the alpha-CD/PEO-b-PNIPAM IC resulted in the self-assembly of long-range-ordered lamellar structure exhibiting alternating layers of (i) alpha-CD/PEO ICs with hexagonally packed plates and (ii) amorphous phase of unincluded PEO/PNIPAM with brush conformation. (C) 2009 Elsevier Ltd. All rights reserved.Item type:Item, Self-Assembly structures through competitive interactions of miscible crystalline-amorphous diblock copolymer/homopolymer blends(2009-10-20) ;Lin, I-Hong ;Kuo, Shiao-Wei ;Chang, Feng-Chih ;應用化學系Department of Applied ChemistryA series of miscible crystalline-amorphous diblock copolymers, (poly(epsilon-caprolactone)-b-(vinyl phenol), PCL-b-PVPh) were prepared through sequential ring-opening and controlled living free radical (nitroxide-mediated) polymerizations and then blended with poly(vinyl pyrrolidone) (PVP) homopolymer. Specific interactions, miscibility, and self-assembly morphologies mediated by hydrogen bonding interactions of this new A-B/C type blend, were investigated in detail. Micro-phase separation of these miscible PCL-b-PVPh diblock copolymers occurs by blending with PVP through competitive hydrogen bonding interaction in this A-B/C blend. FTIR, XRD, and DSC analyses provide positive evidences that the carbonyl group of PVP is a significantly stronger hydrogen bond acceptor than PCL, thus the PCL block is excluded from the PVPh/PVP miscible phase to form self-assembly structure. (13)C CP/MAS solid-state NMR spectra provide additional evidence confirming that micro-phase separation occurs in the blend system because of the presence of more than two T(1p)(H) values for this A-B/C blend system. According to the result of the FTIR and SAXS results, the smaller molecular weight system contains a greater fraction of the hydrogen-bonded carbonyl group, cause indirectly the high degree of phase separation among these blends. In addition, the SAXS profiles possess a sharp primary peak and highly long range ordered reflections q/q* ratios of 1:2:3 at lower PVP content, an indication of the lamellar structure in the blend which is consistent with TEM image. The phase behavior and morphology shifts from lamellar to cylinder structure with further increase in the PVP content. (C) 2009 Elsevier Ltd. All rights reserved.