Superhydrophobic Microporous Substrates via Photocuring: Coupling Optical Pattern Formation to Phase Separation for Process-Tunable Pore Architectures

We present a new approach to synthesize microporous surfaces through the combination of photopolymerization-induced phase separation and light pattern formation in photopolymer-solvent mixtures. The mixtures are irradiated with a wide-area light pattern consisting of high and low intensity regions. This light pattern undergoes self-focusing and filamentation, thereby preserving its spatial profile through the mixture. Over the course of irradiation, the mixture undergoes phase separation, with the polymer and solvent located in the bright and dark regions of the light profile, respectively, to produce a binary phase morphology with a congruent arrangement as the optical pattern. A congruently arranged microporous structure is attained upon solvent removal. The microporous surface structure can be varied by changing the irradiating light profile via photomask design. The porous architecture can be further tuned through the relative weight fractions of photopolymer and solvent in the mixture, resulting in porosities ranging from those with discrete and uniform pore sizes to hierarchical pore distributions. All surfaces become superhydrophobic (water contact angles >150°) when spray-coated with a thin layer of polytetrafluoroethylene nanoparticles. The water contact angles can be enhanced by changing the surface porosity via the processing conditions. This is a scalable and tunable approach to precisely control microporous surface structure in thin films to create functional surfaces and antiwetting coatings.