Controlled/"living" polymerizations and tandem polymerization methodologies offer enticing opportunities to enchain a wide variety of monomers into new, functional block copolymer materials with unusual physical properties. However, the use of these synthetic methods often introduces nontrivial molecular weight polydispersities, a type of chain length heterogeneity, into one or more of the copolymer blocks. While the self-assembly behavior of monodisperse AB diblock and ABA triblock copolymers is both experimentally and theoretically well understood, the effects of broadening the copolymer molecular weight distribution on block copolymer phase behavior are less well-explored. We report the melt-phase self-assembly behavior of SBS triblock copolymers (S = poly(styrene) and B = poly(1,4-butadiene)) comprised of a broad polydispersity B block (M(w)/M(n) = 1.73-2.00) flanked by relatively narrow dispersity S blocks (M(w)/M(n) = 1.09-1.36), in order to identify the effects of chain length heterogeneity on block copolymer self-assembly. Based on synchrotron small-angle X-ray scattering and transmission electron microscopy analyses of seventeen SBS triblock copolymers with poly(1,4-butadiene) volume fractions 0.27 ≤ f(B) ≤ 0.82, we demonstrate that polydisperse SBS triblock copolymers self-assemble into periodic structures with unexpectedly enhanced stabilities that greatly exceed those of equivalent monodisperse copolymers. The unprecedented stabilities of these polydisperse microphase separated melts are discussed in the context of a complete morphology diagram for this system, which demonstrates that narrow dispersity copolymers are not required for periodic nanoscale assembly.
Graphene has received considerable attention in both scientific and technological areas due to its extraordinary material properties originating from the atomically single- or small number-layered structure. Nevertheless, in most scalable solution-based syntheses, graphene suffers from severe restacking between individual sheets and thus loses its material identity and advantages. In the present study, we have noticed the intercalated water molecules in the dried graphene oxide (GO) as a critical mediator to such restacking and thus eliminated the hydrogen bonding involving the intercalated water by treating GO with melamine resin (MR) monomers. Upon addition of MR monomers, porous restacking-inhibited GO sheets precipitated, leading to the carbonaceous composite with an exceptionally large surface area of 1040 m(2)/g after a thermal treatment. Utilizing such high surface area, the final graphene composite exhibited excellent electrochemical performance as a supercapacitor electrode material: specific capacitance of 210 F/g, almost no capacitance loss for 20,000 cycles, and ~7 s rate capability. The current study delivers a message that various condensation reactions engaging GO sheets can be a general synthetic approach for restacking-inhibited graphene in scalable solution processes.
The preparation of uniform large‐area highly crystalline organic semiconductor thin films that show outstanding carrier mobilities remains a challenge in the field of organic electronics, including organic field‐effect transistors. Quantitative control over the drying speed during dip‐coating permits optimization of the organic semiconductor film formation, although the kinetics of crystallization at the air–solution–substrate contact line are still not well understood. Here, we report the facile one‐step growth of self‐aligning, highly crystalline soluble acene crystal arrays that exhibit excellent field‐effect mobilities (up to 1.5 cm V−1 s−1) via an optimized dip‐coating process. We discover that optimized acene crystals grew at a particular substrate lifting‐rate in the presence of low boiling point solvents, such as dichloromethane (b.p. of 40.0 °C) or chloroform (b.p. of 60.4 °C). Variable‐temperature dip‐coating experiments using various solvents and lift rates are performed to elucidate the crystallization behavior. This bottom‐up study of soluble acene crystal growth during dip‐coating provides conditions under which one may obtain uniform organic semiconductor crystal arrays with high crystallinity and mobilities over large substrate areas, regardless of the substrate geometry (wafer substrates or cylinder‐shaped substrates).
Conductive hydrogels are a class of composite materials that consist of hydrated and conducting polymers. Due to the mechanical similarity to biointerfaces such as human skin, conductive hydrogels have been primarily utilized as bioelectrodes, specifically neuroprosthetic electrodes, in an attempt to replace metallic electrodes by enhancing the mechanical properties and long-term stability of the electrodes within living organisms. Here, we report a conductive, smart hydrogel, which is thermoplastic and self-healing owing to its unique properties of reversible liquefaction and gelation in response to thermal stimuli. In addition, we demonstrated that our conductive hydrogel could be utilized to fabricate bendable, stretchable, and patternable electrodes directly on human skin. The excellent mechanical and thermal properties of our hydrogel make it potentially useful in a variety of biomedical applications such as electronic skin.
We investigated the phase transition behavior from the hexagonally perforated layer (HPL) to the gyroid (G) phase in supported thin film of a polystyrene-b-polyisoprene (PS-b-PI) diblock copolymer (M n = 34.0 kg/mol, wtPI = 0.634) by grazing-incidence small-angle X-ray scattering. After annealing at 120 °C, the PS-b-PI thin film spin-coated on silicon wafer exhibited HPL morphology with its lamellae highly oriented parallel to the substrate up to a thickness as much as 1 μm. The interface-induced orientation allowed us to obtain a well-developed diffraction pattern in the absence of external mechanical strain to align the domains. The comparison with the computer-simulated diffraction pattern revealed that the HPL structure has mosaic grains oriented randomly in-plane with ABC stacking and undetectable amount of AB stacking. Upon heating, the HPL phase undergoes a phase transition to the G phase. The phase transition occurred epitaxially converting the HPL layers to the {121} planes of the G structure maintaining the G {121} plane oriented parallel to the substrate. This behavior is in contrast with the HPL to G phase transition found from the shear-oriented HPL samples, in which the G {121} plane is randomly oriented around the G [111] axis.
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