Stress effects on mass transport in polymers: a model for volume relaxation

A model is introduced here for volume relaxation in glassy polymers, induced by sorption of low molecular weight species. The model relies on description of thermodynamic properties of glassy mixtures obtained through NET-GP model and it considers simple linear viscoelastic laws to interpret the stress–strain relation for the polymeric material. Results for the case of sorption kinetics in constant fugacity processes, obtained from the model, are compared with experimental values for vapour sorption in glassy polymeric microspheres. Satisfactory representations were obtained both for instant solute content measured in experimental run and for mass uptake registered in ‘relaxation stage’ of sorption processes. Viscosity data obtained from fitting of sorption experimental results are finally discussed in terms of temperature dependence and compared with values obtained form purely mechanical volume relaxation experiments.