n-Hexane sorption in poly(ethylene-co-1-octene)s: Effect on phase composition and character

Diffusion of small-molecule penetrants in semi-crystalline polymers is retarded by two factors: penetrant detour bypassing impenetrable crystals and the constraining effect of the crystals on the amorphous component. Previous experiments have shown that the latter factor becomes much less important at higher penetrant concentration in the polymer. Structural changes in a series of poly(ethylene-co-1-octene)s occurring on saturation in n-hexane at 296 K, covering a wide range of crystallinity (17–75 wt.%), were studied by wide-angle X-ray scattering, Raman spectroscopy and NMR spectroscopy. Densification of the crystal unit cell and partial dissolution of the interfacial component on n-hexane sorption are the main experimental findings. The conclusion is that the penetrant molecules increase the mobility of the polymer chain segments adjacent to the crystal interface, enabling better packing of the crystal stems and importantly also causes a reduction in the constraining factor (β) for diffusion.