Mechanisms for surface energy changes observed in plasma immersion ion implanted polyethylene: The roles of free radicals and oxygen-containing groups

Low density polyethylene (LDPE) was modified by plasma immersion ion implantation (PIII) with nitrogen ions of 20 keV. Surface energy and structural transformations were observed during storage of the modified LDPE in air after PIII, by wettability measurements and FTIR-ATR spectra respectively. The appearance of oxygen-containing groups has some kinetic stages with characteristic times from hours to days. The surface energy values attained and comparison with the kinetics of oxidation reveal that the initial changes in the surface energy of LDPE are caused mainly by free radicals and to a lesser extent by oxygen-containing groups. The final surface energies observed after the process known as hydrophobic recovery and the surface energies stabilize are attributable to oxygen-containing groups. The modified surface is “living” and an investigation of the wettability, surface energy, unsaturated and oxygen-containing groups in the surface layer of ion beam modified polymers is incomplete if the kinetics of structural transformations after modification is not taken into account.