Unusual Dynamic Dewetting Behavior of Smooth Perfluorinated Hybrid Films: Potential Advantages over Conventional Textured and Liquid-Infused Perfluorinated Surfaces

Abstract

From a viewpoint of reducing the burden on the environment and human health, an alternative method for preparing liquid-repellent surfaces without relying on the long perfluorocarbons (C((X-1)/2)F(X), X ≥ 17) has been strongly demanded lately. In this study, we have successfully demonstrated that dynamic dewettability toward various probe liquids (polar and nonpolar liquids with high or low surface tension) can be tuned by not only controlling surface chemistries (surface energies) but also the physical (solid-like or liquid-like) nature of the surface. We prepared smooth and transparent organic-inorganic hybrid films exhibiting unusual dynamic dewetting behavior toward various probe liquids using a simple sol-gel reaction based on the co-hydrolysis and co-condensation of a mixture including a range of perfluoroalkylsilanes (FASX, C((X-1)/2)F(X)CH2CH2Si(OR)3, where X = 3, 9, 13, and 17) and tetramethoxysilane (Si(OCH3)4, TMOS). Dynamic contact angle (CA) and substrate tilt angle (TA) measurements confirmed that our FASX-hybrid films exhibited excellent dynamic dewetting properties and were mostly independent of the length of perfluoroalkyl (Rf) groups. For example, 10 μL droplets of ultralow surface tension liquids (e.g., diethyl ether (γ = 16.26 dyn/cm) and n-pentane (γ = 15.51 dyn/cm)) could move easily on our FAS9-, FAS13-, and FAS17-hybrid film surfaces at low substrate TAs (<4°) without pinning. This is comparable or superior to the best perfluorinated textured and flat surfaces reported so far. This exceptional dynamic dewetting behavior appeared only when TMOS molecules were added to the precursor solutions; we assume this is due to co-condensed TMOS-derived silica species working as spacers between the neighboring Rf chains, enabling them to rotate freely and in doing so provide a surface with liquid-like properties. This led to the distinguished dynamic dewettability of our hybrid films, regardless of the small static CAs. Our FASX-hybrid films also displayed excellent chemical and physical durability against thermal stress (~250 °C), high-temperature (150 °C) oil vapor, and various other media (perfluoro liquid, boiling water, and weak acid) without degrading their dynamic dewettability. Such exceptional durability has been rarely seen on conventional perfluorinated surfaces reported so far.