The identification of peroxy‐features at polymer surfaces by ESCA

A preliminary investigation of the identification of peroxy‐features at polymer surfaces by ESCA is described. Oxidation of a hydrocarbon polymer in the effluent of a singlet molecular oxygen generator, based on a microwave discharge in oxygen, produces surfaces rich in peroxy‐features. By comparison with experimental and theoretical studies of model systems these features can be identified in ESCA spectra by their characteristic O 1s binding energies. The oxygen atoms in the peroxy‐linkage have essentially the same binding energy, which is within a narrow range of 534.0 eV for simple peroxides and hydroperoxides and a narrow range of 535.2 eV for peroxy‐features in more highly oxygenated environments; for example, peracids and peresters. Peroxy‐linkages decompose rather rapidly under the typical x‐ray flux used in the ESCA experiment.