DIELECTRIC STUDY OF THE CRYSTAL AND AMORPHOUS FRACTIONS IN ORIENTED POLYETHYLENES

Polyethylenes have relaxation processes separately assignable to the crystal and amorphous components. The possibility thus presents itself for studying the interaction between the two phases by investigating the anisotropy of the separate relaxation processes induced by overall orientation of the material. Such a study was carried out here by the dielectric method on samples rendered dielectrically active by the introduction of a few carbonyl groups by oxidation. In addition to the usual advantage of ease of frequency variation, the dielectric method in this case has a very great advantage in interpretation resulting from the similarity of dielectric constants of the two phases. In specimens oriented by solid‐state extrusion, it was found that the crystalline relaxation process (α) develops the expected anisotropy resulting from dipoles normal to C‐axis alignment in the extrusion direction. In branched polyethylene (BPE) no accompanying anisotropy of the amorphous β and γ processes was observed. Since the extrusion was carried out well above the glass temperature of the amorphous component, this indicates that constraints from the crystal phase are not sufficient to prevent dissipation of amorphous orientation by segmental motion. However in linear polyethylene (LPE) (where there is no well‐developed β process) some anisotropy of the γ process was observed. It is proposed that a higher degree of constraint of the amorphous component by the crystals in LPE results in suppression of the glass‐rubber (β) relaxation and permits amorphous orientation to accompany crystal orientation. Copyright © 1979 Society of Plastics Engineers, Inc.