| Abstract: | The effect of glassy skin formation on the drying of semicrystalline polymers was investigated with a comprehensive mathematical model developed for multicomponent systems. Polymers with high glass‐transition temperatures can become rubbery at room temperature under the influence of solvents. As the solvents are removed from the polymer, a glassy skin can form and continue to develop. The model takes into account the effects of diffusion‐induced polymer crystallization as well as glassy–rubbery transitions on the overall solvent content and polymer crystallinity. A Vrentas–Duda free‐volume‐based diffusion scheme and crystallization kinetics were used in our model. The polymer–solvent system chosen was a poly(vinyl alcohol) (PVA)–water–methanol system. The drying kinetics of PVA films were obtained by gravimetric methods with swollen films with known water/methanol concentrations. The overall drying behaviors of the polymer system determined by our model and experimental methods were compared and found to match well. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3191–3204, 2005 |
