(4ed) Investigating Case II and Anomalous Penetrant Transport in Glassy Polymers

Glassy polymers are increasingly used in the construction and fabrication of high-tech devices. These devices are often used in applications, such as microfluidics, membrane separations, food packaging, artificial tissues, bones, and organs, and controlled drug delivery, where the polymers come into contact with fluids capable of penetrating the polymer network. To examine the behavior of such systems both on the macroscopic and molecular level, it is important to study the penetrant diffusion process. In such transport, the macromolecular chains rearrange toward new conformations, where the rate of relaxation depends on the penetrant concentration. The relative rates of penetrant diffusion and macromolecular chain relaxation determine the nature of the transport process and lead to a wide variety of penetrant transport phenomena, such as Fickian, anomalous (non-Fickian), and Case II sorption behavior. While previous models account for anomalous behavior, there is still a disconnect between theory and experiment, as data must be fit to the model with previously determined independent parameters. With trends leading to smaller device scales and increasingly complex polymer structures, there is a need for a quantitative understanding of the manner in which a polymer's network structure alters both the rate and the mode of penetrant transport. To this end, poly(methyl methacrylate) (PMMA) was synthesized in an iniferter-mediated radical polymerization process to produce a variety of well-characterized polymer network structures. The effects of basic network parameters, including the degree of crosslinking, polymer mesh size, and the crosslink size, on the transport process were studied. The effects of sub-Tg annealing/aging, temperature, the penetrant hydrodynamic radius, the penetrant-polymer thermodynamic compatibility, and the presence of un-reacted monomer were also investigated. Utilizing both gravimetric sorption data and in-situ ultra-high-resolution X-ray computed tomography studies, the transport dynamics of methanol and other solvents in PMMA discs were investigated. Controlling the relative timescale of the relaxational process by altering the polymer network structure is shown to directly influence the Case II front propagation velocity and the nature of the observed transport behavior.