Simulation and modelling of transient permeation of organic solvents through polymer films in the case of a concentration dependent diffusion coefficient

摘要

The measured transient permeation kinetics of acetic acid from a water-acetic acid mixture through poly(vinyl alcohol) films could not be accounted for by the Fick law with a constant diffusion coefficient. A new calculation procedure was developed on the basis of simulation results of the Fickian kinetics in which the diffusion coefficient was assumed to increase exponentially with the local permeant concentration. A fast and reliable fitting procedure, which was set up on a Personal Computer, involves an iterative numerical adjustment of (a) the value of the limiting diffusion coefficient D~* (i.e., difusion of the permeant in dry polymer) using the onset part of the permeation rate followed by (b) the value at the upstream face of the plasticization term (argument of the exponential function) using the shape of the experimental curve. The values obtained from fitting the model to the transient kinetics showed that the limiting diffusion coefficient increases drastically, but the plasticization term changes little, with increasing temperature.