The influence of crosslinker on the properties of radiation-grafted films and membranes based on ETFE

Crosslinked proton-exchange membranes were prepared by radiation-induced grafting of styrene into poly(ethylene-alt-tetrafluoroethylene) (ETFE) and subsequent sulfonation. The influence of the crosslinker, divinylbenzene (DVB), on various film and membrane properties was investigated in detail. A series of grafted films and membranes were prepared at varying DVB concentrations at a fixed graft level (∼25%) for this purpose. Grafting kinetics and kinetic parameters, including initial polymerization rate (rpo), radical recombination rate (γ) and delay time (t0) at different DVB concentrations were evaluated. Moreover, resultant grafted films and membranes have been characterized with respect to their dimensional stability, chemical composition, thermal stability, crystallinity and fuel cell relevant properties. The concentration of crosslinker in the initial grafting solution was found to influence crucially the grafting reaction and graft levels. Dimensional increase, considerable especially after sulfonation, can be controlled by the introduction of DVB. Furthermore, the FTIR-ATR measurements exhibited that the grafted films were highly crosslinked within the surface near as compared to the entire bulk region. The influence of DVB on the crystallinity and thermal stability was not significant. On the contrary, the water uptake and proton conductivity of the membranes decreased substantially, while the IEC decreased slightly with increasing DVB concentration.