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A new approach to explain the interfacial polarization phenomenon in conducting composite films is proposed. HCl-doped poly(ethylene terephthalate) (PET) and polyamide-6 (PA-6) matrices with embedded polyaniline (PANI) particles as filler were investigated and analysed, combining dielectric spectroscopy and AFM electrical images with the effective medium theory analysis. Up to three relaxation peaks attributed to the interfacial polarization phenomena were detected in the studied frequency range (0.1 Hz–1 MHz). The AFM electrical images revealed that the doped PA-6/PANI composite can be modelled as a single-type particle medium and the PET/PANI one as a two-type particle medium. A simple dielectric loss expression was derived from the Maxwell–Wagner–Hanai mixture equation and was applied to the experimental data to identify the interfaces involved in each of the relaxation peaks. The parameter values (permittivity, conductivity, volume fraction of the PANI particles) were found to agree well with the measured one, hence validating the models.

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