A dielectric study of molecular relaxation in oxidized and chlorinated polyethylenes

A study was made of the dielectric relaxation in polyethylenes rendered dielectrically active through oxidation (0.5–1.7 carbonyls/1000 CH2) and chlorination (14–22 Cl/1000 CH2). Both linear and branched polymers were studied. All of the relaxations between the melt and −196° were studied in the frequency range 10 Hz to 10kHz (100 kHz in the chlorinated samples). In the linear samples a wide range of crystallinities was studied (55% in quenched specimens to 95% in extended-chain specimens obtained by crystallization at 5 kbar). As is consistent with its being a crystalline process, the α peak was found to discontinously disappear on melting of the samples and reappear on recrystallizing on cooling. The disappearance of the smaller crystals before the larger ones appeared to be evident in the isothermal loss versus frequency curves. The relaxation strength of the α process increases with crystallinity. The measured relaxation strength is less than that expected on the basis of direct proportionality to the crystalline fraction with full contribution of all dipoles in the crystalline material. However, the intensity is not sufficiently low for the process to be interpreted in terms of reorientation of localized conformational defects in the crystal. The variation of intensity with crystallinity is best interpreted in terms of full participation of crystalline dipoles but with selective partitioning of both carbonyls and chlorines favoring the amorphous domains. A strong correlation of the α loss peak location (Tmax at constant frequency or log fmax at constant T) with crystallinity for both carbonyl and chlorine containing polymers was found. This variation is interpreted in terms of chain rotations in the crystal where the activation free energy depends on crystal thickness. The dependence of log fmax and Tmax on lamellar thickness as well as a comparison with the loss peaks of ketones dissolved in parafins indicates that the chain rotation is not rigid and is accompanied by twisting as the rotation propagates through the crystal. In agreement with previous studies the β process is found to be strong only in the branched polymers but can be detected in the chlorinated linear polymer. The β process was resolved from the α in the branched samples by curve fitting and its activation parameters determined. The γ relaxation peak in oxidized polymers including its high asymmetry (low-temperature tail) and increasing emax with increasing frequency and temperature when plotted isochronally can be interpreted in terms of a simple nearly symmetrical relaxation time spectrum that narrows with increasing temperature. No increase in relaxation strength with temperature was found. The chlorinated polymers behave similarly but appear to have some Boltzmann enhancement (450–750 cal/mole) of relaxation strength with temperature. The dependence of relaxation strength on crystallinity indicates that the process is an amorphous one. Further, no evidence of relaxation peak shape changes with crystallinity that could be interpreted in terms of a crystalline component in addition to the amorphous one was found. The comparison of the γ relaxation strength with that expected on the basis of full participation of amorphous dipoles indicates that only a small fraction (∼10% in oxidized linear polymers) of them are involved in the relaxation. Thus it would seem that a glass–rubber transition interpretation is not indicated but rather a localized chain motion. It is suggested that the γ process, including its intensity, width, and activation parameters, can be interpreted in terms of an (unspecified) localized conformational (bond rotation) motion that is perturbed by differing local packing environments. The thermal expansion lessens the effects of variations in packing and leads to narrowing with increasing temperature. The conformational motion itself leads to increase in thermal expansion and hence a transition in the latter property. Some previously proposed localized amorphous phase conformational motions appear to be suitable candidates for the bond rotation motion. A weak relaxation peak found at temperatures below the γ and at 10 kHz may possibly be the dielectric analog of the δ cryogenic peak found previously mechanically at lower frequencies.