Designing Re-Entrant Geometry: Construction of a Superamphiphobic Surface with Large-Sized Particles

Re-entrant geometries can effectively trap air pockets beneath coating surfaces, prevent the penetration of low surface tension organic liquids, and achieve superamphiphobic performance. However, the creation of re-entrant geometries through particle-based spray coating remains a challenge. In the past decade, various studies have focused on the preparation of superamphiphobic coatings using ultrafine nanoparticles (10-15 nm) using conventional spray-coating methods. In this work, we aim to fabricate a spray-coated superamphiphobic surface using large particles with a hierarchical structure. The study systematically investigated the wetting behaviors of liquids with different topographies obtained using large particles (i.e., smooth, micro, nano, and micro/nanostructures) by different coating methods. The findings suggested that compared with the typical colloid template method, the surface obtained using the spray-coating method showed much greater roughness, which greatly enhanced the oleophobicity of the coating. Furthermore, only hierarchically monodisperse hollow SiO₂ spheres (MDH-SiO₂) showed excellent superamphiphobicity, which was independent of the hollow sphere size. While maintaining the coating roughness, by applying solid C@SiO₂ as a reference sample, the important role of the hollow structure of MDH-SiO₂ at the solid-liquid-air interface was confirmed. Nanosphere-surrounded hollow structures were shown to serve as a re-entrant type structure, preventing the imbibition of the liquid, finally leading to a stable Cassie state. This design strategy may provide useful guidelines for the fabrication of large particle-based spray-coated superamphiphobic surfaces.