14 research outputs found

    Alternating Gyroid Network Structure in an ABC Miktoarm Terpolymer Comprised of Polystyrene and Two Polydienes

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    The synthesis, molecular and morphological characterization of a 3-miktoarm star terpolymer of polystyrene (PS, M¯¯¯¯n = 61.0 kg/mol), polybutadiene (PB, M¯¯¯¯n = 38.2 kg/mol) and polyisoprene (PI, M¯¯¯¯n = 29.2 kg/mol), corresponding to volume fractions (φ) of 0.46, 0.31 and 0.23 respectively, was studied. The major difference of the present material from previous ABC miktoarm stars (which is a star architecture bearing three different segments, all connected to a single junction point) with the same block components is the high 3,4-microstructure (55%) of the PI chains. The interaction parameter and the degree of polymerization of the two polydienes is sufficiently positive to create a three-phase microdomain structure as evidenced by differential scanning calorimetry and transmission electron microscopy (TEM). These results in combination with small-angle X-ray scattering (SAXS) and birefringence experiments suggest a cubic tricontinuous network structure, based on the I4132 space group never reported previously for such an architecture

    Ultrasensitive Optical Fingerprinting of Biorelevant Molecules by Means of SERS-Mapping on Nanostructured Metasurfaces

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    The most relevant technique for portable (on-chip) sensors is Surface Enhanced Raman Scattering (SERS). This strategy crashes in the case of large (biorelevant) molecules and nano-objects, whose SERS spectra are irreproducible for “homeopathic” concentrations. We suggested solving this problem by SERS-mapping. We analyzed the distributions of SERS parameters for relatively “small” (malachite green (MG)) and “large” (phthalocyanine, H2Pc*) molecules. While fluctuations of spectra for “small” MG were negligible, noticeable distribution of spectra was observed for “large” H2Pc*. We show that the latter is due to a random arrangement of molecules with respect to “hot spot” areas, which have limited sizes, thus amplifying the lines corresponding to vibrations of different molecule parts. We have developed a method for engineering low-cost SERS substrates optimized for the best enhancement efficiency and a measurement protocol to obtain a reliable Raman spectrum, even for a countable number of large molecules randomly distributed over the substrate

    Thermal and Bulk Properties of Triblock Terpolymers and Modified Derivatives towards Novel Polymer Brushes

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    We report the synthesis of three (3) linear triblock terpolymers, two (2) of the ABC type and one (1) of the BAC type, where A, B and C correspond to three chemically incompatible blocks such as polystyrene (PS), poly(butadiene) of exclusively (~100% vinyl-type) -1,2 microstructure (PB1,2) and poly(dimethylsiloxane) (PDMS) respectively. Living anionic polymerization enabled the synthesis of narrowly dispersed terpolymers with low average molecular weights and different composition ratios, as verified by multiple molecular characterization techniques. To evaluate their self-assembly behavior, transmission electron microscopy and small-angle X-ray scattering experiments were conducted, indicating the effect of asymmetric compositions and interactions as well as inversed segment sequence on the adopted morphologies. Furthermore, post-polymerization chemical modification reactions such as hydroboration and oxidation were carried out on the extremely low molecular weight PB1,2 in all three terpolymer samples. To justify the successful incorporation of –OH groups in the polydiene segments and the preparation of polymeric brushes, various molecular, thermal, and surface analysis measurements were carried out. The synthesis and chemical modification reactions on such triblock terpolymers are performed for the first time to the best of our knowledge and constitute a promising route to design polymers for nanotechnology applications

    Molecular and Structure-Properties Comparison of an Anionically Synthesized Diblock Copolymer of the PS-b-PI Sequence and Its Hydrogenated or Sulfonated Derivatives

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    International audienceAn approach to obtaining various nanostructures utilizing a well-studied polystyrene-bpoly(isoprene) or PS-b-PI diblock copolymer system through chemical modification reactions is reported. The complete hydrogenation and partial sulfonation to the susceptible carbon double bonds of the PI segment led to the preparation of [polystyrene-b-poly(ethylene-alt-propylene)] as well as [polystyrene-b-poly(sulfonated isoprene-co-isoprene)], respectively. The hydrogenation of the polyisoprene block results in enhanced segmental immiscibility, whereas the relative sulfonation induces an amphiphilic character in the final modified material. The successful synthesis of the pristine diblock copolymer through anionic polymerization and the relative chemical modification reactions were verified using several molecular and structural characterization techniques. The thin film structure-properties relationship was investigated using atomic force microscopy under various conditions such as different solvents and annealing temperatures. Small-angle X-ray scattering was employed to identify the different observed nanostructures and their evolution upon thermal annealing

    Thermal and Bulk Properties of Triblock Terpolymers and Modified Derivatives towards Novel Polymer Brushes

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    We report the synthesis of three (3) linear triblock terpolymers, two (2) of the ABC type and one (1) of the BAC type, where A, B and C correspond to three chemically incompatible blocks such as polystyrene (PS), poly(butadiene) of exclusively (~100% vinyl-type) -1,2 microstructure (PB1,2) and poly(dimethylsiloxane) (PDMS) respectively. Living anionic polymerization enabled the synthesis of narrowly dispersed terpolymers with low average molecular weights and different composition ratios, as verified by multiple molecular characterization techniques. To evaluate their self-assembly behavior, transmission electron microscopy and small-angle X-ray scattering experiments were conducted, indicating the effect of asymmetric compositions and interactions as well as inversed segment sequence on the adopted morphologies. Furthermore, post-polymerization chemical modification reactions such as hydroboration and oxidation were carried out on the extremely low molecular weight PB1,2 in all three terpolymer samples. To justify the successful incorporation of –OH groups in the polydiene segments and the preparation of polymeric brushes, various molecular, thermal, and surface analysis measurements were carried out. The synthesis and chemical modification reactions on such triblock terpolymers are performed for the first time to the best of our knowledge and constitute a promising route to design polymers for nanotechnology applications

    Highly Efficient All-Inorganic Planar Heterojunction Perovskite Solar Cells Produced by Thermal Coevaporation of CsI and PbI<sub>2</sub>

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    We report here all inorganic CsPbI<sub>3</sub> planar junction perovskite solar cells fabricated by thermal coevaporation of CsI and PbI<sub>2</sub> precursors. The best devices delivered power conversion efficiency (PCE) of 9.3 to 10.5%, thus coming close to the reference MAPbI<sub>3</sub>-based devices (PCE ≈ 12%). These results emphasize that all inorganic lead halide perovskites can successfully compete in terms of photovoltaic performance with the most widely used hybrid materials such as MAPbI<sub>3</sub>
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