The tensile and stress‐relaxation properties of an uncrosslinked and a loosely silane‐crosslinked high‐density polyethylene exposed to organic “crude‐oil” penetrants were assessed. The measurements were performed on penetrant‐saturated samples, surrounded by the organic liquid throughout the experiment. The penetrant solubilities in the two polymers were similar and in accordance with predicted values based on the solubility parameter method. The stiffness and strength of the swollen samples were significantly less than those of the dry samples, indicating a plasticization of the amorphous component. Raman spectroscopy on polyethylene exposed to deuterated n‐hexane revealed a penetrant‐induced partial melting/dissolution of the crystal surface and an intact crystal core component. The stress‐relaxation rates, within the time frame of the experiment (∼1 s to 18 h), were approximately the same, independent of silane‐crosslinks and the presence of penetrants. This indicated that the mechanical α‐relaxation, which is the main relaxation process occurring in the measured time interval, was not affected by the penetrants. Consequently, its rate seemed to be independent of the crystal surface dissolution (decrease in the content of crystal‐core interface). The shape of the “log stress–log time” curves of the swollen samples was, however, different from that of the dry samples. This was most likely attributed to a time‐dependent saturation of penetrant to a higher level associated with the stretched state of the polymer sample. The silane crosslinks affected only the elongation at break, which was less than that of the uncrosslinked material. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 641–648, 2006

In 18 fluoropolymers with different repeating-unit structures and crystallinities, the solubility, diffusivity, and permeability at 70°C of a polarizable nonpolar solute (tetrachloroethylene) were studied. The transport properties were mostly controlled by the polarity of the polymer and to a lesser degree by the polymer crystallinity. The highest permeability was observed in the dipole-containing ethylene-chlorotrifluoroethylenes because of their high tetrachloroethylene solubility. The lowest permeability was observed in the hydrogen-bonding poly(vinylidene fluoride) polymers because of the combination of low solute solubility and solute diffusivity. The tetrachloroethylene diffusivity was solute-concentration-dependent, and sorption curves were S-shaped, indicating that the solute surface concentration was time-dependent. The rate at which the surface concentration approached the saturation level was proportional to the product of Young's modulus, the square of the thickness of the dry polymer, and the logarithm of the solute diffusivity. Data for the water-hyperbranched polymer and limonene-polyethylene conformed to the same relationship. Therefore, this provides a new tool for predicting the solute-surface-concentration time dependence from data obtained by independent measurements.

The sorption behavior of two highly swelling "rubbery" polymers, natural rubber and polyethylene, has been studied. The polymers are in many aspects very different. Yet, when the solute mass uptake, in this case limonene, is plotted as a function of the square root of time, both polymers show similar "sigmoidal"-types of curves. This triggered the research to determine what mechanisms were responsible for the observed similarities and if the degree in sigmoidal behavior and swelling anisotropy could be easily assessed explicitly by any mechanical parameter. It was found that their degrees of swelling anisotropy, described by a solute-surface-concentration relaxation time, could be explained by their relative bulk moduli. It was assumed that the ratio in bulk modulus at zero pressure, determined from compression measurements, could represent the ratio in expansion bulk modulus during swelling. However, the prediction in swelling anisotropy during sorption using the ratio in bulk modulus was slightly less successful when the swelling anisotropy was quantified as the relative ratio of sheet thickness to cross-sectional area side length. It should be noted that the ratio in uniaxial tensile modulus between polyethylene and natural rubber was several orders of magnitude higher than their ratio in swelling anisotropy. The natural rubber sheet became saddle-shaped during limonene sorption and collapsed into a flat shape when the saturation concentration was approached. During desorption, the sheet went from flat to cup-shaped and then flat again at the end of desorption. The saddle and cup shapes occurred in both square and round sheets. These shapes are believed to be a consequence of buckling and deformation due to instabilities in the stress state of the sheet. This was, in turn, explained by the normally existing local variation in cross-link density.

Three models, two of them relying on free volume—the Cohen–Turnbull–Fujita (CTF) model and the Vrentas–Duda (VD) model, and the third being empirical using an exponential concentration dependence of the diffusivity, were applied to desorption data for a series of alkane penetrants (2,2‐dimethylbutane, cyclohexane, n‐hexane, n‐decane, and n‐tetradecane) in low‐density polyethylene. The CTF model described the desorption data very well and better than the exponential diffusion law. The VD model with the attractive feature of being based on independently determined parameters was unsuccessful in describing the desorption data. Diffusivity data indicated that the three components outside the crystal core were less accessible to n‐tetradecane than to the other penetrants. This indication was further substantiated by solubility data. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 723–734, 2007

The transport of water, hydrochloric acid, hydrobromic acid and tetrachloroethylene in an poly(ethylene‐co‐chlorotrifluoroethylene) and polyvinylidene fluoride were studied at 70°C by the sorption/desorption technique. The effects on the structure and mechanical properties were studied using size‐exclusion chromatography, infrared spectroscopy, differential scanning calorimetry and tensile testing. Solute concentrations in the polymers indicated that both the water and HCl/HBr components diffused into the polymers on exposure to acid solutions. The calculated water contents of the diffusing acids generally differed from the water content in the solution. The ratio of water content in the diffusing acid to that in the surrounding acid solution was generally a function of the relative vapor activity of water and HCl/HBr. It was possible to describe the 35%HCl and 47%HBr desorption data using a two component model. It was here assumed that the water and HCl/HBr diffused separately, each having its own constant diffusion coefficient. The water diffusivity was obtained from the pure water system, and this allowed the HCl/HBr diffusivity to be calculated. It was found that the diffusivity decreased, in a non‐simple way, as a function of solute size. The exposure to solute did not lower the molar mass of the polyvinylidene fluoride. Differential scanning calorimetry indicated the development of low‐melting point polyvinylidene fluoride crystals during the exposure to all solutes. This seemed to be a consequence of the long‐term exposure (175 to 376 days) at 70°C. The long‐term exposure stiffened several of the polyvinylidene fluoride resins and occasionally made them less ductile. The poly(ethylene‐co‐chlorotrifluoroethylene) also became stiffer, but it was otherwise unaffected as far as observation by the other available techniques was concerned.