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Tailored polyurethane acrylate blend for large-scale and high-performance micropatterned dry adhesives
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.
Ordered Mesoporous TiO2 Gyroids: Effects of Pore Architecture and Nb-Doping on Photocatalytic Hydrogen Evolution under UV and Visible Irradiation
2018, Dörr, Tobias Sebastian, Deilmann, Leonie, Haselmann, Greta, Cherevan, Alexey, Zhang, Peng, Blaha, Peter, de Oliveira, Peter William, Kraus, Tobias, Eder, Dominik
Pure and Nb-doped TiO2 photocatalysts with highly ordered alternating gyroid architecture and well-controllable mesopore size of 15 nm via co-assembly of a poly(isoprene)-block-poly(styrene)-block-poly(ethylene oxide) block copolymer are synthesized. A combined effort by electron microscopy, X-ray scattering, photoluminescence, X-ray photoelectron spectroscopy, Raman spectroscopy, and density functional theory simulations reveals that the addition of small amounts of Nb results in the substitution of Ti4+ with isolated Nb5+ species that introduces inter-bandgap states, while at high concentrations, Nb prefers to cluster forming shallow trap states within the conduction band minimum of TiO2. The gyroidal photocatalysts are remarkably active toward hydrogen evolution under UV and visible light due to the open 3D network, where large mesopores ensure efficient pore diffusion and high photon harvesting. The gyroids yield unprecedented high evolution rates beyond 1000 µmol h−1 (per 10 mg catalyst), outperforming even the benchmark P25-TiO2 more than fivefold. Under UV light, the Nb-doping reduces the activity due to the introduction of charge recombination centers, while the activity in the visible triple upon incorporation is owed to a more efficient absorption due to inter-bandgap states. This unique pore architecture may further offer hitherto undiscovered optical benefits to photocatalysis, related to chiral and metamaterial-like behavior, which will stimulate further studies focusing on novel light–matter interactions.