ESCA and contact‐angle studies of the surface modification of poly(ethylene terephthalate) film: Photooxidation and aging

ESCA and contact‐angle (H2O and CH2I2) measurements are used to follow changes in the surface of poly(ethylene terephthalate) film photooxidized (254 nm radiation in O2) for varying times, followed by aging for as many as three weeks or washing with water. Photooxidation occurs uniformly throughout the outermost 50 Å of the film to give a surface stoichiometry that corresponds to C10O6.6. Oxidation produces mainly carboxyl (acid) and alcohol/phenol groups, carbonyls form after extensive treatment. Low molecular weight products formed by chain scission and oxidation are removed by washing and diffuse into the bulk when aged. Oxidized products in higher molecular weight chains are not removed by washing, but can diffuse into the polymer bulk or reorient because of their chain mobility; therefore they are directed toward the polymer bulk rather than the surface. Extended photooxidation produces a stable oxidized surface more resistant to aging changes. The results are compared with those obtained for poly(ethylene terephthalate) film oxidized in an electrical discharge.