2015, Oschatz, Martin, Zeiger, Marco, Jaeckel, Nicolas, Strubel, Patrick, Borchardt, Lars, Reinhold, Romy, Nickel, Winfried, Eckert, Jürgen, Presser, Volker, Kaskel, Stefan

A new approach to produce carbide-derived carbon nanospheres of 20-200 nm in diameter based on a novel soft-templating technique is presented. Platinum catalysis is used for the cross-linking of liquid (allylhydrido)polycarbosilane polymer chains with para-divinylbenzene within oil-in-water miniemulsions. Quantitative implementation of the pre-ceramic polymer can be achieved allowing precise control over the resulting materials. After pyrolysis and high-temperature chlorine treatment, resulting particles offer ideal spherical shape, very high specific surface area (up to 2347 m^2/g^-1), and large micro/mesopore volume (up to 1.67 cm^3/g^-1). The internal pore structure of the nanospheres is controllable by the composition of the oil phase within the miniemulsions. The materials are highly suitable for electrochemical double-layer capacitors with high specific capacitances in aqueous 1 M Na2SO4 solution (110 F/g^-1) and organic 1 M tetraethylammonium tetrafluoroborate in acetonitrile (130 F/g^-1).

2019, Yu, Dan, Hensel, René, Beckelmann, Dirk, Opsölder, Michael, Schäfer, Bruno, Moh, Karsten, de Oliveira, Peter William, Arzt, Eduard

Continuous roll-to-roll fabrication is essential for transferring the idea of bio-inspired, fibrillar dry adhesives into large-scale, synthetic, high-performance adhesive tapes. Toward this aim, we investigated process parameters that allow us to control the morphology and the resulting adhesion of mushroom-shaped micropatterned surfaces. Flexible silicone templates enabled the replication process of the polyurethane acrylate pre-polymer involving UV-light-induced cross-linking. For this paper, we particularly tailored the polyurethane acrylate pre-polymer by adding chemical components to tune UV curing kinetics and to reduce oxygen inhibition of radicals. We found that higher intensities of the UV light and faster reaction kinetics improved the quality of the microstructures, i.e., a larger cap diameter of the mushroom tips was achieved. The polymer blend U6E4 exhibited the fastest curing kinetics, which resulted in a micromorphology similar to that of the Ni-shim master structures. Best adhesion results were obtained for adhesive tapes made from U6E4 with 116 kPa pull-off stress, 1.4 N cm−1 peel strength and 71 kPa shear strength. In addition, repeated attachment–detachment tests over 100,000 cycles demonstrated strong robustness and reusability.

2022, Palà, Marc, El Khannaji, Hafssa, Garay-Sarmiento, Manuela, Ronda, Juan Carlos, Cádiz, Virginia, Galià, Marina, Percec, Virgil, Rodriguez-Emmenegger, César, Lligadas, Gerard

We report a green solvent-to-polymer upgrading transformation of chemicals of the lactic acid portfolio into water-soluble lower critical solution temperature (LCST)-type acrylic polymers. Aqueous Cu(0)-mediated living radical polymerization (SET-LRP) was utilized for the rapid synthesis of N-substituted lactamide-type homo and random acrylic copolymers under mild conditions. A particularly unique aspect of this work is that the water-soluble monomers and the SET-LRP initiator used to produce the corresponding polymers were synthesized from biorenewable and non-toxic solvents, namely natural ethyl lactate and BASF's Agnique® AMD 3L (N,N-dimethyl lactamide, DML). The pre-disproportionation of Cu(I)Br in the presence of tris[2-(dimethylamino)ethyl]amine (Me6TREN) in water generated nascent Cu(0) and Cu(II) complexes that facilitated the fast polymerization of N-tetrahydrofurfuryl lactamide and N,N-dimethyl lactamide acrylate monomers (THFLA and DMLA, respectively) up to near-quantitative conversion with excellent control over molecular weight (5000 < Mn < 83 000) and dispersity (1.05 < Đ < 1.16). Interestingly, poly(THFLA) showed a degree of polymerization and concentration dependent LCST behavior, which can be fine-tuned (Tcp = 12–62 °C) through random copolymerization with the more hydrophilic DMLA monomer. Finally, covalent cross-linking of these polymers resulted in a new family of thermo-responsive hydrogels with excellent biocompatibility and tunable swelling and LCST transition. These illustrate the versatility of these neoteric green polymers in the preparation of smart and biocompatible soft materials.