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We demonstrate a novel wetting method to prepare hierarchical polymer films with polymer nanotubes on selective regions. This strategy is based on the selective wetting abilities of polymer chains, annealed in different solvent vapors, into the nanopores of porous templates. Phase-separated films of polystyrene (PS) and poly(methyl methacrylate) (PMMA), two commonly used polymers, are prepared as a model system. After anodic aluminum oxide (AAO) templates are placed on the films, the samples are annealed in vapors of acetic acid, in which the PMMA chains are swollen and wet the nanopores of the AAO templates selectively. As a result, hierarchical polymer films containing PMMA nanotubes can be obtained after the AAO templates are removed. The distribution of the PMMA nanotubes of the hierarchical polymer films can also be controlled by changing the compositions of the polymer blends. This work not only presents a novel method to fabricate hierarchical polymer films with polymer nanotubes on selective regions, but also gives a deeper understanding in the selective wetting ability of polymer chains in solvent vapors.

We study the formation of porous polymer nanostructures fabricated by the surface-induced phase separation of polymer solutions in anodic aluminum oxide (AAO) templates. Poly(methyl methacrylate) (PMMA) and tetrahydrofuran (THF) are used to investigate the evolution process of the surface-induced phase separation. With the longer immersion time of the AAO template in the polymer solution, the size of the solvent-rich droplet is increased by the coarsening process, resulting in the formation of porous polymer nanostructures. The coarsening mechanism is further evaluated by changing the experimental parameters including the immersion time, the polymer concentration, the polymer molecular weight, and the solvent quality. Under conditions in which polymer solutions have higher viscosities, the coarsening process is slowed down and the formation of the porous nanostructures is prohibited. The prevention of the porous nanostructures can also be realized by adding water to the PMMA/THF solution before the immersion process.