Replication of Mesoscale Pore One-dimensional Nanostructures: Surface-induced Phase Separation of Polystyrene/Poly(vinyl alcohol) (PS/PVA) Blends

Mesoscale pore one-dimensional (1D) nanostructures, or vertically aligned porous nanostructures (VAPNs), have attracted attention with their excellent hydrophobic properties, ultra-high surface area, and high friction coefficient, compared to conventional vertically aligned nanostructures (VANs). In this study, we investigate the replication of VAPNs produced by the thermal nanoimprint process using anodic aluminum oxide (AAO²) templates (100 nm diameter). Polystyrene/poly(vinyl alcohol) (PS¹/PVA) blends, prepared by the advanced melt-mixing process with an ultra-high shear rate, are used to investigate the formation of porosity at the nanometer scale. The results reveal that domain size and mass ratios of PVA precursors in the PS matrix play a dominant role in the interfacial interaction behavior between PS¹-PVA-AAO², on the obtained morphologies of the imprinted nanostructures. With a PVA nanodomain precursor (PS¹/PVA 90/10 wt%), the integration of PVA nanodroplets on the AAO² wall due to the hydrogen bonding that induces the phase separation between PS¹-PVA results in the formation of VAPNs after removal of the PVA segment. However, in the case of PVA microdomain precursors (PS¹/PVA 70/30 wt%), the structure transformation behavior of PS¹ is induced by the Rayleigh instability between PVA encapsulated around the PS¹ surfaces, resulting in the PS¹ nanocolumns transforming into nanopeapods composed of nanorods and nanospheres.