Electrical Conductivity in Poly(vinyl Chloride)

Conductivity and Seebeck coefficient measurements have been made on commerically-available molded PVC samples containing a range of impurities and on much purer specimens recast from tetrahydrofuran solution. Activation energies measured in the latter materials were not very reproducible; it seems likely that the evaporation of gold electrodes thermally initiates a dehydrochlorination reaction which renders the samples unstable. A range of activation energies from 1.4 to 1.8 eV was observed in the impure samples. The Seebeck coefficient measurements indicated that the majority carriers were negatively charged; the linearity of the current-voltage relationship up to applied field strengths of 80,000 V/cm then suggested an electronic conduction mechanism, although considerable polarization effects were observed in both pure and impure samples. The Seebeck coefficient results also showed that even the purest PVC obtainable is unlikely to be an intrinsic semiconductor, and that the electron transport mechanism probably corresponds more closely to the small polaron hopping model than to the conventional energy-band formation model commonly applied to inorganics.