Configuration diffusion in glassy, amorphous polymers: Effects of polymer structure and dynamics on permeation via molecular simulation

The goals of this dissertation are to provide a basis for understanding the fundamental mechanisms of, and the effects of nano-confinement on, diffusion in glassy, amorphous polymers. These polymers are extensively used as membranes in numerous separation applications such as drug delivery devices, air separation and water desalination.; Molecular simulation is used to elucidate the effects of the structure and dynamics of glassy polymers on small molecule permeation. Particularly, the effects of thermal fluctuations on the diffusion mechanism and anomalous diffusion regime is shown for small gas diffusion in atactic polypropylene. Furthermore, polymer backbone conformational statistics of three different polypropylene models show that the united atom approximation favors gauche conformations in the polymer backbone, leading to artificially high values for Cinfinity for stereo-regular polypropylene. Diffusion results of He and CH4 in the refined model is presented using a force-decomposed/replicated data parallel molecular dynamics algorithm on a pseudo-explicit atom model proposed in literature. Excellent agreement with experimental values of the diffusivity is obtained. These results constitute the most accurate a priori prediction of small molecule diffusion in atactic polypropylene to date.; Finally, the effects of nano-confinement on the polymer structure and dynamics, and consequently the permeation and selectivity was probed by He and CH4 permeation in aPP "adsorbed" in idealized pores of size smaller than the radius of gyration of the polymer. The extent of polymer structural changes is found to be closely correlated with the local correlation length xi of the polymer. Within xi from the pore surface, the polymer has a lower density, aligns with the pore direction and is found to pack in layers, while the polymer structure is identical to the bulk further than xi from the pore surface. These changes in polymer structure lead to substantial increases (up to five-fold) in the permeability of He and CH 4. The enhancement in permeability is also found to be different for the two gases, resulting in a 50% increase in the idealized selectivity. The results provide a framework for understanding the enhanced properties of polymer nanocomposite membranes recently reported in the literature, and consequently for the design of novel composites in which the polymer properties are "tuned" for specific applications.