Surface Reconstruction of Fluoropolymers in Liquid Media.

Surface reconstruction is the rearrangement of atoms or molecules at an interface in response to a stimulus, driven by lowering the overall free energy of the system. Perfluoroalkyl acrylate polymers with short side chains undergo reconstruction at room temperature when exposed to water. Here, we use contact angle aging to examine the liquid- and temperature- dependency of surface reconstruction of plasma polymerized perfluoroalkyl acrylates. We use a first order kinetic model to examine the dynamics of reconstructive processes. Our results show that, above the bulk melting point of the polymers, the contact angles of both polar and nonpolar (hydrocarbon) liquids show a time dependency well fit by the model. We conclude that surface reconstruction can be driven by the preferential segregation of hydrocarbon and fluorocarbon moieties as well as by polar interactions. This has implications in terms of using fluorocarbons to design oleophobic surfaces (and vice versa) and in terms of designing fluorocarbon and/or hydrocarbon surfaces with switchable wettability.

Enhanced stability of Cu-BTC MOF via perfluorohexane plasma-enhanced chemical vapor deposition.

Metal organic frameworks (MOFs) are a leading class of porous materials for a wide variety of applications, but many of them have been shown to be unstable toward water. Cu-BTC (1,3,5 benzenetricarboxylic acid, BTC) was treated with a plasma-enhanced chemical vapor deposition (PECVD) of perfluorohexane creating a hydrophobic form of Cu-BTC. It was found that the treated Cu-BTC could withstand high humidity and even submersion in water much better than unperturbed Cu-BTC. Through Monte Carlo simulations it was found that perfluorohexane sites itself in such a way within Cu-BTC as to prevent the formation of water clusters, hence preventing the decomposition of Cu-BTC by water. This PECVD of perfluorohexane could be exploited to widen the scope of practical applications of Cu-BTC and other MOFs.

Wetting Hierarchy in Oleophobic 3D Electrospun Nanofiber Networks.

Wetting behavior between electrospun nanofibrous networks and liquids is of critical importance in many applications including filtration and liquid-repellent textiles. The relationship between intrinsic nanofiber properties, including surface characteristics, and extrinsic nanofibrous network organization on resultant wetting characteristics of the nanofiber network is shown in this work. Novel 3D imaging exploiting focused ion beam (FIB) microscopy and cryo-scanning electron microscopy (cryo-SEM) highlights a wetting hierarchy that defines liquid interactions with the network. Specifically, small length scale partial wetting between individual electrospun nanofibers and low surface tension liquids, measured both using direct SEM visualization and a nano Wilhelmy balance approach, provides oleophobic surfaces due to the high porosity of electrospun nanofiber networks. These observations conform to a metastable Cassie-Baxter regime and are important in defining general rules for understanding the wetting behavior between fibrous solids and low surface tension liquids for omniphobic functionality.