Deposition of plasma polymerized perfluoromethylene-dominated films showing oil-repellency

Abstract

Plasma polymerized fluorocarbon films were deposited onto polyethylene (PE) substrates to increase oil-repellency of PE. Depositions were performed using the monomer, 1H,1H,2H-perfluoro-1-dodecene in a parallel-plate, radio frequency (rf) reactor, with variable continuous-wave power ranging from 2 to 160 W. The film deposition rate and morphology were strongly dependent on the applied rf power. Most importantly, the chemical structure of the deposited films was also altered, resulting in changes in contact angles of various liquids and the surface energy. Films deposited at low power were composed mainly of perfluoromethylene (CF2) species (up to 67.2%), as shown by x-ray photoelectron spectroscopy (XPS). With an increase in rf power, CF2 content in the film decreased as further fragmentation of the monomer occurred. For each deposition at varying rf powers, even at powers as low as 2 W, the C=C and C–H bonds in the monomer were dissociated by the plasma and not incorporated into the films, as shown by Fourier transform infrared spectroscopy. Oil-repellency, as shown by increased contact angles of hydrocarbon liquids, was found to increase as the amount of CF2 species increased in the film structure. A low critical surface energy (2.7 mJ/m2) was calculated for the film deposited with only 2 W of rf power. Adhesion of the plasma-polymerized films to the PE was also evaluated and found to be poor for films with a high concentration of CF2 species, where cohesive failure within the film occurred. However, adhesion increased as a function of rf power, where the film structure showed more cross-linking. There was a compromise between producing a film with high oleophobicity (oil-repellency) while maintaining adhesion of the film to PE, as some disruption of the CF2 chains in the films was necessary for cohesion through cross-linking.