Sorption and transport of CO2 above and below the glass transition of poly(ethylene terephthalate)

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AbstractAt temperatures at least 30°C above the glass transition (Tg) the sorption and transport of carbon dioxide in poly(ethylene terephthalate) (PET) can be described conveniently using Henry's law and Fick's law with a constant diffusion coefficient. Below Tg Fick's law with a concentration‐ dependent diffusion coefficient, coupled with a sorption isotherm which is concave toward the pressure axis adequately describes the observed sorption and transport data. Physical interpretations of the quantitative deviations from Henry's law and the form of the concentration dependence of the diffusion coefficient is provided by a model which hypothesizes dual modes of sorption and separate non zero mobilities of two populations of sorbed species in local equilibrium. The implications of the observed temperature variations of the phenomenological model parameters are discussed. Dilatometric parameters for PET, polycarbonate, and poly(acrylonitrile) (PAN) are shown to correlate well with a simple. relationship developed to explain the existence of the “extra” mode of sorption responsible for deviations from Henry's law for CO in glassy polymers. In the temperature range from Tg to + 20°C, deviations from Fickian behavior are also apparent. These effects are consistent with a transition in the nature of the polymer from an elastic solid below Tg to a viscous liquid above Tg In the narrow temperature range slightly above T the time scale for chain rearrangements apparently approaches that for the diffusion process. The polymer's viscoelastic response to the probing molecule, therefore, causes deviations from the classical time lag predictions. These deviations disappear 30°C above Tg.