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A facile in situ and UV printing process was demonstrated to create self-cleaning synthetic replica of natural petals and leaves. The process relied on the spontaneous migration of a fluorinated acrylate surfactant (PFUA) within a low-shrinkage acrylated hyperbranched polymer (HBP) and its chemical immobilization at the polymer-air interface. Dilute concentrations of 1 wt. % PFUA saturated the polymer-air interface within 30 min, leading to a ten-fold increase of fluorine concentration at the surface compared with the initial bulk concentration and a water contact angle (WCA) of 108 • . A 200 ms flash of UV light was used to chemically crosslink the PFUA at the HBP surface prior to UV printing with a polydimethylsiloxane (PDMS) negative template of red and yellow rose petals and lotus leaves. This flash immobilization hindered the reverse migration of PFUA within the bulk HBP upon contacting the PDMS template, and enabled to produce texturized surfaces with WCA well above 108 • . The synthetic red rose petal was hydrophobic (WCA of 125 • ) and exhibited the adhesive petal effect. It was not superhydrophobic due to insufficient concentration of fluorine at its surface, a result of the very large increase of the surface of the printed texture. The synthetic yellow rose petal was quasi-superhydrophobic (WCA of 143 • , roll-off angle of 10 • ) and its self-cleaning ability was not good also due to lack of fluorine. The synthetic lotus leaf did not accurately replicate the intricate nanotubular crystal structures of the plant. In spite of this, the fluorine concentration at the surface was high enough and the leaf was superhydrophobic (WCA of 151 • , roll-off angle below 5 • ) and also featured self-cleaning properties.

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Transparent hyperbranched acrylate nanocomposites were produced using different combinations of silica nanoparticles and silicon-based sol-gel precursors. The nanocomposites were processed using a dual-cure UV polymerization and condensation scheme. The viscosity of hybrid suspensions was found to be one to two orders of magnitude lower than that of particulate composites with the same equivalent silica fraction. The Vickers microhardness of the polymer was 112 MPa. It was equal to 190 MPa and 148 MPa for the hybrid composites and particulate composites with 20 vol% SiO2, respectively, and it was equal to 287 MPa for the hybrid material with 30 vol% SiO2. Light-trapping textures in the form of random submicron pyramidal features were replicated in the hybrid composites from a nickel template using UV-nanoimprint lithography. After optimization of the dual-cure process sequence, a very high replication fidelity was obtained for all investigated compositions, leading to a haze above 99% over the visible light spectrum and a very effective light scattering performance in a broad angular exposure.

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