When block copolymer self-assembly in hierarchically ordered honeycomb films depicts the breath figure process.

Nowadays, a challenge in the preparation of hierarchically ordered materials is the control of concomitant and interacting self-organization processes occurring in time at different length scales. In the present paper, the breath figure process is combined with block copolymer nano-phase segregation to elaborate hierarchically structured honeycomb porous films. Copolymer ordering, at the nanometer length scale, is observed and described in detail with respect to the array of pores of micrometer dimension, hence pointing out the structural interplays between both length-scales. The study is focused on two diblock copolymers made of polystyrene and poly(tert-butyl acrylate) (PS-b-PtBA) with compositions producing lamellae or hexagonal packing of cylinders at thermodynamical equilibrium. Transmission Electron Microscopy completed with Small and Ultra-Small Angle Scattering are performed to evidence the inner morphologies of the honeycomb. The structural data are discussed in the light of the honeycomb film formation process establishing the interest in using kinetically trapped block copolymer self-organization as an imprint to elucidate the complex breath figure process.

pH sensitive hierarchically self-organized bioinspired films.

In the present manuscript, we have demonstrated that hierarchically structured smart porous polymer films based on honeycomb-patterned surface can be elaborated from PS-b-P4VP pH-responsive block copolymer using the breath figure process. Despite the fast film formation by a bottom-up process, the copolymer nanostructuration was observed inside the walls of the honeycomb porous film. Atomic force microscopy (AFM), small angle X-ray and neutron scattering (SAXS and SANS) measurements were used to reveal both the hexagonal arrays formed by the pores at the micrometer length scale and the hexagonal copolymer self-assembly at the nanometer length scale. Contact angle (CA) measurements were used to point out the reversible pH-responsive wettability character of the surface. The PS-b-P4VP honeycomb film shows a contact angle variation of 20° between pH 9 and pH 3. An increase of the roughness was obtained with the pincushions hexagonal array enhancing the pH responsiveness of the polymer film with a switching CA gap of 75° when pH tuned from pH 9 to pH 3. This work presents the first report on honeycomb porous and pincushion films exhibiting a reversible pH-responsive character.