ИСТИНА

Changes of gas transport parameters of amorphous glassy polymer films with various prehistory were analyzed. Films were subjected to different physical treatments (biaxial stretching, annealing, removal of residual solvent, physical aging, swelling in nonsolvents and supercritical CO2, etc.). In all the cases the diffusion coefficients followed with good accuracy a well-known equation lnD = a - b•d2, here d is the kinetic diameter of gas molecules. The parameters a and b are also sensitive to the treatments of the polymers and, in addition, linearly correlate with each other. By combining equations of Eyring and Meares, it was demonstrated that the parameters a and b can characterize the deviation from equilibrium state of polymers after particular treatment. It was shown that changes of cohesive energy and enthropy of basic state can be calculated. These parameters were chosen as quantitative characteristics of chain packing ordering of amorphous polymer. It was shown that increases in chain packing ordering of the basic state of polymer matrix induce higher selectivity of diffusion.