"Nickel Nanoflowers" with Surface-Attached Fluoropolymer Networks by C,H Insertion for the Generation of Metallic Superhydrophobic Surfaces.

Metallic superhydrophobic surfaces (SHSs) combine the attractive properties of metals, such as ductility, hardness, and conductivity, with the favorable wetting properties of nanostructured surfaces. Moreover, they promise additional benefits with respect to corrosion protection. For the modification of the intrinsically polar and hydrophilic surfaces of metals, a new method has been developed to deposit a long-term stable, highly hydrophobic coating, using nanostructured Ni surfaces as an example. Such substrates were chosen because the deposition of a thin Ni layer is a common choice for enhancing corrosion resistance of other metals. As the hydrophobic coating, we propose a thin film of an extremely hydrophobic fluoropolymer network. To form this network, a thin layer of a fluoropolymer precursor is deposited on the Ni substrate which includes a comonomer that is capable of C,H insertion cross-linking (CHic). Upon UV irradiation or heating, the cross-linker units become activated and the thin glassy film of the precursor is transformed into a polymer network that coats the surface conformally and permanently, as shown by extensive extraction experiments. To achieve an even higher stability, the same precursor film can also be transformed into a chemically surface-attached network by depositing a self-assembled monolayer of an alkane phosphonic acid on the Ni before coating with the precursor. During cross-linking, by the same chemical process, the growing polymer network will simultaneously attach to the alkane phosphonic acid layer at the surface of the metal. This strategy has been used to turn fractal Ni "nanoflower" surfaces grown by anisotropic electroplating into SHSs. The wetting characteristics of the obtained nanostructured metallic surfaces are studied. Additionally, the corrosion protection effect and the significant mechanical durability are demonstrated.