Date of Award


Degree Type


Degree Name

Doctor of Philosophy


Chemical Engineering

Major Professor

Stephen J. Paddison

Committee Members

Brian J. Edwards, Bamin Khomami, Robert J. Hinde


The ionomer-membrane interface in a membrane electrode assembly connects the catalyst and membrane and allows hydrated protons to move between the catalyst and membrane. The continuous operation of the polymer membrane electrolyte fuel cell at high temperature and/or in frequent freeze/thaw cycles leads to membrane degradation and delamination of the interface, which lower the proton conductivity. In this dissertation, we modeled the chemical degradation and proton conductivity of perfluorosulfonic acid (PFSA) ionomers by ab initio calculations and macroscopic modeling. All ab initio calculations were performed using Gaussian 03 suites of program by employing B3LYP/6-311++G** method/basis set. The macroscopic modeling involves nonequilibrium thermodynamics. The results show that PFSA membranes can degrade both via side-chain and backbone in the presence of hydroxyl radical. The energetics of homolytic bond cleavage show that the C–S bond in the side-chain is the weakest link and breaks exothermally in the presence of hydroxyl radical. The C–S bond in the membrane fragment radical can break at low activation energy. The side-chain degradation also leads to the split of the backbone into two parts. The backbone degradation starts with the reaction of –COOH impurities in the backbone with the hydroxyl radical, which has the lowest activation energy, and follows an “unzipping mechanism”. The reactions in this mechanism are exothermic.

The channels in the interface were modeled as cylindrical pores and the anionic charges were fixed on the pore wall. The analytical expression of proton conductivity was derived from the evolution equations for mass and momentum of hydronium ions by using an order of magnitude analysis. The results show that the conductivity increases with increasing water content and pore radius. The conductivity usually increases on decreasing the separation distance between sulfonates on the length and decreases with decreasing sulfonates separation distance on the circumference. The conductivity of the two pores, one of the interface and the other of the membrane, is closer to the conductivity of the pore with the lowest conductivity and its magnitude depends on the relative radius and length of the pores.

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