The effect of molecular weight on the structure and thermal properties of polyethylene

The morphology of polyethylene single crystals prepared isothermally in solution was found to be independent of molecular weight. The enthalpy of fusion, lamellar fold period, and optical appearance were invariant for samples grown from fractions ranging from 20,000 to 2,000,000 in molecular weight. The mass fraction of lamellae which thicken during heating decreased linearly with increasing log molecular weight. The melting temperature of the crystals was also nearly independent of molecular weight.

The superheating of polyethylene crystals was observed to be a function of molecular weight and morphology. At a comparatively high molecular weight the heating rate of the calorimeter exceeded the crystal melting rate, which shifted the observed melting temperature to an anomalously high value. The incorporation of defects within the crystals by irradiation-induced cross-links or chain entanglements increased the melting rate of the high molecular weight samples and thereby minimized the effects of superheating.

The apparent heat of fusion of melt crystallized polyethylene decreased linearly with increasing log molecular weight. In contrast to this behavior the crystallinity of single crystals from dilute solution was independent of molecular weight.

In previous papers we have shown that reorganization of polymer single crystals is suppressed by cross-linking [1—3]. With the appropriate selection of heating rate and irradiation dose, the melting temperatures of solution grown crystals of various morphologies were determined in the absence of lamellar thickening. The observed melting temperatures of polyethylene single crystals with different X-ray fold periods were found to fit the following expression:

T_m = T_m0[1—2σ_e/H_f?] with an equilibrium melting temperature (T_m0) of 145.8 ± 1.0°C and a surface free energy (σ_e) of 89 ± 5 ergs cm^?2 for a polyethylene crystal of infinite dimensions. In addition, at a constant heating rate it was observed that the fraction of crystals which thickened prior to melting decreased with increasing fold period.

Since cross-linking polyethylene increases the molecular weight of the material, it is instructive to investigate the reorganization characteristics of single crystals prepared from polyethylene fractions. Single crystals were prepared in xylene from molecular weight fractions of polyethylene and the effect of molecular weight upon the structure and thermal properties of the crystals was determined.