Facile Fabrication of Hierarchical Structured Anodic Aluminum Oxide Molds for Large-Scale Production of Superhydrophobic Polymer Films

Anodized aluminum oxide (AAO) molds were used for the production of large-area and inexpensive superhydrophobic polymer films. A controlled anodization methodology was developed for the fabrication of hierarchical micro–nanoporous (HMN) AAO imprint molds (HMN-AAO), where phosphoric acid was used as both an electrolyte and a widening agent. Heat generated upon repetitive high-voltage (195 V) anodization steps is effectively dissipated by establishing a cooling channel. On the HMN-AAO, within the hemispherical micropores, arrays of hexagonal nanopores are formed. The diameter and depth of the micro- and nanopores are 18/8 and 0.3/1.25 µm, respectively. The gradual removal of micropatterns during etching in both the vertical and horizontal directions is crucial for fabricating HMN-AAO with a high aspect ratio. HMN-AAO rendered polycarbonate (PC) and polymethyl methacrylate (PMMA) films with respective water contact angles (WCAs) of 153° and 151°, respectively. The increase in the WCA is 80% for PC (85°) and 89% for PMMA (80°). On the PC and PMMA films, mechanically robust arrays of nanopillars are observed within the hemispherical micropillars. The micro–nanopillars on these polymer films are mechanically robust and durable. Regular nanoporous AAO molds resulted in only a hydrophobic polymer film (WCA = 113–118°). Collectively, the phosphoric acid-based controlled anodization strategy can be effectively utilized for the manufacturing of HMN-AAO molds and roll-to-roll production of durable superhydrophobic surfaces.