A broad-band dielectric study of poly(vinyl chloride): Effect of molar mass and processing conditions on space-charge mechanisms

The dielectric properties of poly(vinyl-chloride) (PVC) were investigated as a function of frequency and temperature. Attention was focused on the low frequency dielectric properties. Samples with different molar masses were studied. Two dipolar retardation processes were observed, one due to a local motion in the polymeric chain and the other at the glass transition. In compression-molded samples of high molar mass an additional low-frequency space-charge polarization mechanism was found at high temperatures. The effect was most pronounced at the highest molar masses. The space-charge mechanism was absent in samples of well-kneaded material. This macroscopic polarization process in compression molded samples is probably due to discontinuities in the poorly gelified material because of a residual grain particle structure. The detected effects of air inclusions in a PVC matrix can be described by the Maxwell-Wagner theory. The magnitude of the space-charge mechanism is an indication of the effectiveness of the processing method used in destroying the grain structure. © 1994 John Wiley & Sons, Inc.