Polymer-film formation on the surface of a cathodically polarized nickel electrode in the presence of 4-chlorostyrene

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Abstract
The formation of a polymer film obtained by cathodic polarization of a nickel electrode in the presence of 4-chlorostyrene has been studied for the first time. The different steps of the process were followed through the combined use of electrochemical analytical methods with surface-sensitive spectroscopy (AES and ESCA), ellipsometry, and IR and UV–VIS spectroscopy. The experimental results obtained show the development of two parallel phenomena leading to the formation of a film on the surface of the electrode and to the occurrence of chemical reactions in solution coupled to a charge transfer to the monomer. All the film-formation processes appear to be retarded by the stability of the reaction intermediates (resonances of the carbanion charge due to the aromatic ring). Attempts have been made to correlate these results with preliminary quantum-mechanical calculations carried out on the neutral monomer molecules. The development of parasitical reactions corresponding to the loss of the chlorine atom is also observed. The reactions take place concurrently on the polymer backbone, at the surface and in solution.
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