The application of model equations to Non-Fickian diffusion observed in Fluoropolymers

The diffusional behavior of many non-solvents in glassy or semicrystalline polymers cannot be adequately described by a concentration-dependent form of Fick's law, especially when mass transfer is coupled with structural changes. Many mathematical models have been devised to interprete non-Fickian diffusion dominated by relaxation kinetics. In formulation of non-Fickian diffusion mathematics, therefore, the most important factor to consider is how relaxation effects can influence the governing constitutive equation and boundary conditions. That is, relaxation parameters can be accommodated by variable boundary conditions or a modified continuity equation, or both, depending on specific systems and conditions (Frish, 1980). Accoring to Astarita and Nicolais (1983), the model equations can be broadly categorized as continuous or discontinuous. Continuous model equations encompass phenomena where the structural change takes place gradually over the whole volume of the polymer sample (Crank, 1953; Long and Richman, 1961; Berens and Hopfenberg, 1978). On the other hand, discontinuous model equations deal with the phenomena where the morphological change appears to be abrupt (Li, 1984). Four mathematical models with different relaxation parameters were applied to fit the anomalous sorption data observed in fluoropolymers (PVDF, ECTFE). The fitted result for PVDF-benzene sorption data is shown in Fig. 1.