Abstract
This article describes the diffusion and permeability of oxygen, carbon dioxide, methane, ethane, ethylene, propane, and propylene in 1‐octene based polyethylene of densities 0.94, 0.92, 0.904, and 0.87. The isotherms obtained in the time‐lag experimental device display a diffusion coefficient and permeability behavior similar to that of glassy polymers. We apply the dual model to semicrystalline polymers assuming that Henry's sites are related to the amorphous phase, which decreases when the crystallinity percentage increases. Whereas the interphase of the polymeric matrix and the crystalline phase prevails and acts as Langmuir sites. Their effect is to increase both, the tortuosity of diffusion trajectories and the chain immobilization. We now explain this effect using thermodynamic considerations. In fact, the tortuosity is related to the change in activation entropy, and the chain immobilization to the cohesive energy of the polymeric matrix. In those terms, the diffusion coefficient does not follow the same crystalline percentage dependence than the solubility. According to the previous findings, the solubility changes in proportion to amorphous percentages. Instead, diffusion coefficient has exponential dependence. Furthermore, we show that the permeability changes as a consequence of the modification of diffusion and solubility, according to the product of both quantities. Comparison with previous publication has been included. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 634–642, 2010