Small‐Molecule Diffusion in Semicrystalline Polymers as Revealed by Experimental and Simulation Studies

Summary: Diffusion of n ‐hexane in poly(ethylene‐ co ‐1‐hexene)s with 15–75 wt.% crystallinity was studied by desorption experiments analyzing data using the Fickian equations with a concentration dependent diffusivity. The effect of the impenetrable crystalline phase on the penetrant diffusivity ( D ) is described by D  =  D a /( τβ ), where D a is the diffusivity of the amorphous polymer, τ is the geometrical impedance factor and β is a factor describing the constraining effect of the crystals on the non‐crystalline phase. For a polymer with 75 wt.% crystallinity, τβ varied markedly with penetrant concentration ( v 1a ) in the penetrable phase: 1000 ( v 1a  = 0) and 10 ( v 1a  = 0.15). This penetrant‐uptake had no effect on the gross crystal morphology, i.e. β must be strongly dependent on v 1a . Samples saturated in n ‐hexane exhibited a penetrant‐induced loosening of the interfacial structure, as revealed by an increase in crystal density that require an increased mobility in the interfacial component and by a decrease in the intensity of the asymmetric X‐ray scattering associated with the interfacial component. The geometrical impedance factor has been modelled by mimicking spherulite growth and τ was obtained as the ratio of the diffusivities of the fully amorphous and semicrystalline systems. The maximum τ obtained from these simulations is ca. ten, which suggests that β in the systems with v 1a  = 0.15 takes values close to unity. The simulations showed that the geometrical impedance factor is insensitive to the ratio of the crystal width and the crystal thickness. A free path length scaling parameter characteristic of the amorphous phase correlated with τ .