Perfluorinated sulfonic acid mechanisms

Xie, T., Hayden, C., Olson, K. and Healy, J. 2005. Chemical degradation mechanism of perfluorinated sulfonic acid ionomer. In Advances in materials for proton exchange membrane fuel cell systems, Pacific Grove, CA, Feb. 20-23, abstract 24. 

Perfluorinated sulfonic acid containing polymers (PESAs) are the most commonly used membrane materials in fuel cells today. Membranes made from these ionomers provide the benefits of highly acidic pendant acid groups for high proton conductivity, good mechanical properties, excellent chemical stability, and fairly... 

Before discussing membrane chemical degradation in detail, the factors governing the degradation mechanism must be identified. Among three major types of membrane materials, hydrocarbon, partially fluorinated, and perfluorinated ionomers, perfluorinated sulfonic acid (PFSA) is the most widely used membrane material owing to its high chemical stability (Schiraldi 2006). 

Perfluorinated sulfonic acid polymers, such as Nafion membranes, were the most commonly used materials in practical systems for their high proton conductivity and extremely high oxidative stability. However, due to the poor dimensional stability, low mechanical properties of Nafion at high humidity and high temperature, and high cost, an essential need for cost-effective and reinforced substitutes with improved performance arises [193-195]. Nafion blended with the second component could not only reduce the cost, but also improve the mechanical properties and the dimensional stability. Recently, the reinforced composite membranes based on semi-interpenetrating polymer network (semi-IPN) structures of Nafion , polyimidazole (PI) [196-198], polybenzimidazole (PBI) [199], and poly(vinyIidene fluoride) (PVDF) [200] were reported. As shown in Fig. 2.35, the composite membranes with... 

In Nafion, the hydrophobic perfluorinated segments of the polymer are incompatible with the hydrophilic sulfonic acid groups and thus phase separation occurs. When exposed to water, the hydrophilic domains swell to provide channels for proton transport, whereas the hydrophobic domains provide mechanical integrity and, at least in the case of lower lEC samples. 

For instance, the Dow experimental membrane and the recently introduced Hyflon Ion E83 membrane by Solvay-Solexis are "short side chain" (SSC) fluoropolymers, which exhibit increased water uptake, significantly enhanced proton conductivity, and better stability at T > 100°C due to higher glass transition temperatures in comparison to Nafion. The membrane morphology and the basic mechanisms of proton transport are, however, similar for all PFSA ionomers mentioned. The base polymer of Nation, depicted schematically in Figure 6.3, consists of a copolymer of tetrafluoro-ethylene, forming the backbone, and randomly attached pendant side chains of perfluorinated vinyl ethers, terminated by sulfonic acid head groups. °... 

In the previous section it was suggested that the parent polymer structure considerably influence the physical properties of the derived polysulfonates, imparting to them some of the mechanical and thermal properties of the precursors. This trend is particularly evident in the case of the perfluorinated hydrocarbon polymers. Polymers of this kind, such as e.g., poly(tetrafluoroethylene) (PTFE) are exceptional in their inertness to offensive environment, solvent resistance and high-temperature stability. These considerations led in the sixties to the development of unique sulfonic-acid derivatives of fluorocarbon copolymers by the DuPont Company. While several compositions were disclosed in the patent literature51, the preferred composition, which is the basis for the commercial Nafion ion-exchange membrane, is a copolymer of tetrafluoroethylene with a perfluorinated vinyl ether/sulfonyl fluoride52 ... 

Structurally, this polymer is a close relative to Teflon except that the saturated fluorocarbon backbone is randomly substituted with perfluorinated side chains, each terminating in a superacidic sulfonic acid group. Despite the structural predominance of hydrophobic fluorocarbon backbone units, bulk Nafion films actually exhibit a hydrophilic character due to sulfonate ion clustering which gives rise to hydrophilic domains distributed throughout the fluorocarbon phase. Detailed studies of the morphology, as well as the chemical, thermal and mechanical properties of Nafion membranes have been reported elsewhere (77). The results presented here summarize recent efforts to assess the biocompatibility properties of Nafion polymer. 

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