We report a route to fabricate two-level structured self-adaptive surfaces (SAS) of polymer materials. The first level of structure is built by a rough polymer film that consists of needlelike structures of micrometer size. The second level of structure is formed by the nanoscopic self-assembled domains of a demixed polymer brush irreversibly grafted onto the needles. By exposing the surface to solvents that are selective to one of the components of the brush, we reversibly tune the surface properties. The large-scale surface structure amplifies the response and enables us to control wettability, adhesion, and chemical composition of the surface over a wide range.

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We report a simple method to synthesize binary polymer brushes from two incompatible polymers of different polarity. The synthetic route is based on a subsequent step-by-step grafting of carboxyl-terminated polystyrene and poly(2-vinylpyridine) to the surface of a Si wafer functionalized with 3-glycidoxypropyltrimethoxysilane. The end-functional polymers were spin-coated on the substrate, and grafting was carried out at a temperature higher than the glass transition temperature of the polymers. The composition of the binary brushes can be regulated based on grafting kinetics of the first polymer by the change of time or/and temperature of grafting. This method reveals a smooth and homogeneous polymer film on the macroscopic scale, while at the nanoscopic scale the system undergoes phase segregation effecting switching/ adaptive properties of the film. Upon exposure to different solvents, the film morphology reversibly switches from "ripple" to "dimple" structures as well as the surface energetic state switches from hydrophobic to hydrophilic. The same switching of hydrophilic/hydrophobic properties was obtained for the different ratios between two grafted polymers in the binary brush.

We develop the route to fabricate mixed brushlike layers on polyamide substrates (PA-6, PA-6I, PA-66) by the "grafting from" approach. The PA substrates were functionalized by NH3 plasma. The azo initiator of radical polymerization was covalently bound to the functionalized PA surface. A two-step grafting procedure was applied to graft polystyrene in the first step and poly(2-vinylpyridine) in the second step. We found remarkable differences between grafting on Si wafers and on the PA substrates. "Grafting from" the PA surface results in a dramatic increase of the surface roughness of the film which can be explained by grafting in a swollen surface layer of PA. Because of this effect, we found a substantial amount of grafted polymers even on not functionalized PA substrates, which was explained by grafting via chain transfer reaction. The synthesized mixed polymer brushes form responsive coatings which switch their morphology due to the interplay between lateral and vertical phase segregation upon exposure to selective solvent. The switching of morphology affects the change of the surface composition of the brushes and their surface energetic state. We performed the same grafting procedure on the surface of PA fabric. In this case the switching behavior was amplified by the texture of the material: wettability of the fabric with the mixed brush was switched from complete wetting to highly hydrophobic state (150°water contact angle).

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