Date of Award

8-2016

Degree Type

Dissertation

Degree Name

Doctor of Philosophy

Major

Chemical Engineering

Major Professor

David J. Keffer

Committee Members

Jimmy W. Mays, James R. Morris, Siris O. Laursen, Donald M. Nicholson

Abstract

Mass and charge transport through hydrated polymer membranes has significant importance for many areas of engineering and industry. Multi-scale modeling and simulation techniques were used to study transport in relation to two specific membrane applications: (1) food packaging and (2) additives for polymer electrolytes.

Chitosan/chitin films were studied due to their use as a sustainable, biodegradable food packaging film. The effects of hydration on the solvation, diffusivity, solubility, and permeability of oxygen molecules in these films were studied via molecular dynamics and confined random walk simulations. With increasing hydration, the membrane was observed to have a more homogeneous water distribution with the polymer chains being fully solvated. Insight from this work will help guide molecular modeling of chitosan/chitin membranes and experimental synthesis of these membranes, specifically highlighting efforts to chemically tailor chitosan membranes to favor discrete as opposed to continuous aqueous domains to help reduce oxygen permeability.

Additives for proton exchange membranes (PEMs) were studied to aid in the developing next-generation membrane materials for fuel cell applications. We calculate and present predictions of our analytical model that describes the fundamental relationship between the nanoscale structure of PEMs and their proton conductivity using a set of structural descriptors, accounting for nanopore size, functionalization and connectivity in order to predict proton conductivities in PEMs. The model reproduces experimentally determined conductivities in two current PEM materials. To extend the model based on structural descriptors of PEMs, we studied polyethylene glycol (PEG), a polymer used in electrochemistry applications due to it hydrophilicity and pH-dependent behavior in aqueous environments. We conducted ab initio molecular dynamics simulations of an excess proton in bulk water and aqueous triethylene glycol (TEG) solution and reactive molecular dynamics simulations of an excess proton in bulk water, aqueous TEG solution, and aqueous PEG solution. We determined differences in protonic defect structures, kinetics, thermodynamics, and hydrogen-bond networks associated with structural diffusion between systems.

Driving forces for polymeric membrane design goals include economics, efficiency, energy consumption and sustainable production. Insight from this work hopes to aid in determining key design parameters and reduce time-to-discovery for developing next-generation polymeric membranes.

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