Dielectric relaxation and electrical conduction of polymers as a function of pressure and temperature

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Abstract
The dielectric properties and the d. c. conductivity of poly(vinyl chloride), poly(vinyl acetate), polychlorotrifluoroethylene, and poly(ethylene terephthalate) were measured at temperatures above and below the glass transition temperature and at various pressures up to 3000 atm. The α relaxation associated with the micro‐Brownian motion of amorphous chain segments depends strongly upon temperatures and pressure, while the β relaxation due to local‐mode motion of the frozen main chain shows weak dependence on temperature and pressure. It is found that the free volume concept is valid for description of the temperature and the pressure dependence of the relaxation time for the α process. Activation energy and volume for both relaxation processes are determined from the experimental data. A simple relation between activation energy and volume for the α relaxation and pressure dependence of the glass transition temperature are derived. Temperature and pressure dependence of the d. c. conductivity in the rubbery state are notably different from those in the glassy state. Ionic conduction appears to be dominant in these polymers.