TRANSPORT PROPERTIES AND THEIR CORRELATION WITH MORPHOLOGY OF THERMALLY CONDITIONED POLYPROPYLENE

Time‐lag and static sorption experiments were employed to measure permeability, diffusivity and solubility constants of He, A, and CF4 in polypropylene films cooled at various rates from the melt and subsequently annealed at varying temperatures near the melting point. While solubility constants in films annealed above 90°C showed the normal variation with the amorphous content of the polymer, solubility constants for all unannealed, quenched films were remarkably constant and independent of the rate of cooling. In fact, all quenched films appeared to have the same amorphous content (ca. 41%). The remaining material is believed to be a mixture of monoclinic and hexagonal crystallinity, the volume ratio of the two being a function of the rate of quenching, and changing on annealing, in favor of the more stable, monoclinic form; the transition occurring rather sharply at 90°C. X‐ray diffraction provided supporting evidence for the presence of the hexagonal crystals. The diffusion behavior in crystalline polypropylene is normal and Fickian but instead of the usual decline with increasing crystallinity, diffusivities showed definite enhancement in the case of the annealed films, i.e., the expected monotonic decline of D with increasing crystallinity is not observed. This behavior is attributed to a reduction in diffusional impedance through formation of defects in existing crystallites, as the lamellae thicken, in a manner similar to that observed on annealing of polyethylene single crystals. The apparent activation energies of diffusion were essentially constant and independent of thermal history. This suggests that in a highly crystalline polymer diffusion is not so much impeded by the restricted mobility of chain segments but rather by the extremely small dimensions of the available diffusive pathways. In support of the argument that the transport properties of polypropylene are controlled at a level of microstructure well below the characteristic dimensions of spherulities, it was observed that bulk‐crystallized polypropylene has a spherulitic structure whose size and texture do not change significantly on annealing. Copyright © 1969 John Wiley & Sons, Inc.