The core levels of a series of 83 homopolymers have been studied by electron spectroscopy for chemical analysis (ESCA). Comparisons of the experimentally determined core‐level binding energies with theoretical calculations using the ground‐state potential model in the complete neglect of differential overlap (CNDO/2) self‐consistent field molecular orbital (SCF MO) formalism have been made on the C1s and O1s core levels for the oxygen‐containing polymers in the series. A comparison of the ground‐state potential model (GPM) and relaxation potential model (RPM) on a series of six model compounds representative on the series of polymers is given. Compilations are given of binding energies of C1s, O1s, N1s, Cl2p, S2p, Si2p, and Br3d levels for typical structural features of common occurrence in polymer systems. These data, taken in conjunction with that previously published on fluoropolymers, provide a sound basis for the development of ESCA as a fingerprint tool in the elaboration of features of structure and bonding in polymers in general.

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Molecular core binding energies have been measured by ESCA for the homopolymers of ethylene and the fluoroethylenes. The data are interpreted in terms of semiempirical all‐valence electron SCF MO calculations in the CNDO/2 formalism, in conjunction with the charge potential model. The results are used as a basis for interpreting the measured core binding energies of some Viton and Kel F type polymers. The routine application of ESCA to the determination of copolymer compositions is described.

The oxidation of polyethylene, polypropylene, and polystyrene by exposure to plasmas excited in pure oxygen and helium–oxygen mixtures at low power levels has been studied. A detailed curve resolution procedure is outlined, and the rate of oxidation is shown to be a strong function of the polymer structure for pure oxygen plasmas, as is the composition of the oxidized layer; this is not the case, however, for oxidation effected by helium–oxygen mixtures. It seems likely, from a consideration of the available data, that the oxidation is confined to the outermost monolayer and is initiated by a crosslinking mechanism that involves oxygen‐containing functionalities.