ABSTRACT
Wetting is typically defined by the relative liquid to solid surface tension/energy, which are composed of polar and nonpolar subcontributions. Current studies often assume that they remain invariant, that is, surfaces are wetting-inert. Complex wetting scenarios, such as adaptive or reactive wetting processes, may involve time-dependent variations in interfacial energies. To maximize differences in energetic states, we employ low-energy perfluoroalkyls integrated with high-energy silica-based polar moieties grown on low-energy polydimethylsiloxane. To this end, we tune the hydrophilic-like wettability on these perfluoroalkyl-silica-polydimethylsiloxane surfaces. Drop contact behaviors range from invariantly hydrophobic at ca. 110° to rapidly spreading at ca. 0° within 5 s. Unintuitively, these vapor-grown surfaces transit toward greater hydrophilicity with increasing perfluoroalkyl deposition. Notably, this occurs as sequential silica-and-perfluoroalkyl deposition also leaves behind embedded polar moieties. We highlight how surfaces having such chemical heterogeneity are inherently wetting-reactive. By creating an abrupt wetting transition composed of reactive and inert domains, we introduce spatial dependency. Drops contacting the transition spread before retracting, occurring over the time scale of a few seconds. This phenomenon contradicts current understanding, exhibiting a uniquely (1) decreasing advancing contact angle and (2) increasing receding contact angle. To explain the behavior, we model such time- and space- dependent reactive wetting using first order kinetics. In doing so, we explore how reactive and recovery mechanisms govern the characteristic time scales of spreading and retracting sessile drops.
ABSTRACT
Super-liquid-repellent surfaces feature high liquid contact angles and low sliding angles find key applications in anti-fouling and self-cleaning. While repellency for water is easily achieved with hydrocarbon functionalities, repellency for many low-surface-tension liquids (down to 30 mN m-1 ) still requires perfluoroalkyls (a persistent environmental pollutant and bioaccumulation hazard). Here, the scalable room-temperature synthesis of stochastic nanoparticle surfaces with fluoro-free moieties is investigated. Silicone (dimethyl and monomethyl) and hydrocarbon surface chemistries are benchmarked against perfluoroalkyls, assessed using model low-surface-tension liquids (ethanol-water mixtures). It is discovered that both hydrocarbon- and dimethyl-silicone-based functionalization can achieve super-liquid-repellency down to 40-41 mN m-1 and 32-33 mN m-1 , respectively (vs 27-32 mN m-1 for perfluoroalkyls). The dimethyl silicone variant demonstrates superior fluoro-free liquid repellency likely due to its denser dimethyl molecular configuration. It is shown that perfluoroalkyls are not necessary for many real-world scenarios requiring super-liquid-repellency. Effective super-repellency of different surface chemistries against different liquids can be adequately predicted using empirically verified phase diagrams. These findings encourage a liquid-centric design, i.e., tailoring surfaces for target liquid properties. Herein, key guidelines are provided for achieving functional yet sustainably designed super-liquid-repellency.