Ultraviolet bonding of perfluoropolyethers to carbon surfaces investigated using quantum chemical methods

For improving the tribological performance of hard disk drives, nanometer-thick perfluoropolyether (PFPE) lubricant films are generally treated with ultraviolet (UV) irradiation to bond them to the carbon overcoats of the disks. By modeling UV irradiation as an electron emission and attachment process, we investigate the UV bonding of nonfunctional PFPE Z and functional PFPE Zdol to hydrogenated and nitrogenated carbon surfaces with quantum chemical methods. Our calculation results show that, upon electron attachment, Z dissociates at its main chain to two fragments terminated by CF₂CF₂ and CF₂O groups, whereas Zdol dissociates to a hydrogen fluoride and a fragment. The perfluoromethoxy oxygen in one of the Z fragments and the carbon radical and the hydrogen-truncated end group in the Zdol fragment interact strongly with sp² and oxidized sites on carbon surfaces. Imine moieties on the CNx surface also contribute considerably to the UV bonding of Zdol.