MECHANICAL SPECTROMETRY OF ALPHA-RELAXATIONS OF HIGH-DENSITY POLYETHYLENE

By using an automated low‐frequency apparatus, dynamic mechanical experiments are performed on bulk‐crystallized high‐density polyethylene in the temperature range of the α relaxation. In order to characterize the key morphological features governing the presence of multiple α relaxations, we have developed a simple model from calorimetric data to assess the crystallite size distribution of samples with different thermal histories. The morphological characterizations are completed by wide‐angle x‐ray diffraction measurements. Isochronal spectrometry and frequency scans performed under isothermal conditions both exhibit two α relaxations designated α1 and α2, with increasing temperature (or increasing frequency). These two relaxations are frequency dependent but they are not thermorheologically simple processes. Some analogy is found between tan ϕ versus temperature or frequency and the biomodal lamellar size distribution curves determined from calorimetric data. Moreover, both the temperature of α2 peak and the most probable lamellar thickness of the larger lamellae depend on the thermal history of the sample: with increasing thickness of the larger lamellae, the α2 peak temperature is shifted toward higher temperature. In contrast, both the temperature of the a peak and the most probable lamellar thickness of the thinner lamellae seem to be independent of thermal history: the thinner lamellae should be formed on cooling from the remaining uncrystallized fraction. From thege findings, it is proposed that the α, and α2 relaxations have the same origins and that they could arise from defect diffusion within the thinner and thicker crystallites, respectively, with some influence of the amorphous matter in the interfacial regions. Copyright © 1990 John Wiley & Sons, Inc.