Plasma Micro-Nanotextured, Scratch, Water and Hexadecane Resistant, Superhydrophobic, and Superamphiphobic Polymeric Surfaces with Perfluorinated Monolayers

Superhydrophobic and superamphiphobic toward superoleophobic polymeric surfaces of polymethyl methacrylate (PMMA), polyether ether ketone (PEEK), and polydimethyl siloxane (PDMS) are fabricated in a two-step process: (1) plasma texturing (i.e., ion-enhanced plasma etching with simultaneous roughening), with varying plasma chemistry depending on the polymer, and subsequently (2) grafting of self-assembled perfluorododecyltrichlorosilane monolayers (SAMs). Depending on the absence or not of an etch mask (i.e., colloidal microparticle self-assembly on it), random or ordered hierarchical micro-nanotexturing can be obtained. We demonstrate that stable organic monolayers can be grafted onto all these textured polymeric surfaces. After the monolayer deposition, the initially hydrophilic polymeric surfaces become superamphiphobic with static contact angles for water and oils >153°, for hexadecane >142°, and hysteresis <10° for all surfaces. This approach thus provides a simple and generic method to obtain superamphiphobicity on polymers toward superoleophobicity. Hydrolytic and hexadecane immersion tests prove that superamphiphobicity is stable for more than 14 days. We also perform nanoscratch and post nanoscratch tests to prove the scratch resistance of both the texture and the SAM and demonstrate lower coefficient of friction of the SAM compared to the uncoated surface. Scanning electron microscope observation after the nanoscratch tests confirms the scratch resistance of the surfaces.