Microfluidics Assisted Fabrication of Three-Tier Hierarchical Microparticles for Constructing Bioinspired Surfaces

Construction of textured bioinspired surfaces with refined structures that exhibit superior wetting properties is of great importance for many applications ranging from self-cleaning, antibiofouling, anti-icing, oil/water separation, smart membrane, and microfluidic devices. Previously, the preparation of artificial surfaces generally relies on the combination of different approaches together, which is a lack of flexibility to control over the individual architecture unit, the surface topology, as well as the complex procedure needed. In this work, we report a method for rapid fabrication of three-tier hierarchical microunits (structures consisting of multiple levels) using a facile droplet microfluidics approach. These units include the first-tier microspheres consisting of the second-tier close-packed polystyrene (PS) nanoparticles decorated with the third-tier elegant polymer nanowrinkles. These nanowrinkles on the PS nanoparticles are formed according to the interfacial instability induced by gradient photopolymerization of N-isopropylacrylamide (NIPAM) monomers. The formation process and topologies of nanowrinkles can be regulated by the photopolymerization process and the fraction of carboxylic groups on the PS nanoparticle surface. Such a hierarchical microsphere mimics individual units of bioinspired surfaces. Therefore, the surfaces from self-assembly of these fabricated two-tier and three-tier hierarchical microunits collectively exhibit "gecko" and "rose petal" wetting states, with the micro- and nanoscale structures amplifying the initial hydrophobicity but still being highly adhesive to water. This approach offers promising advantages of high-yield fabrication, precise control over the size and component of the microspheres, and integration of microfluidic droplet generation, colloidal nanoparticle self-assembly, and interfacial polymerization-induced nanowrinkles in a straightforward manner.