Radiation Induced Grafting of Styrene onto ETFE: Influence of Crosslinker

Polymer electrolyte fuel cells are promising types of electrochemical devices for future power production with low operation temperature. In order to make this technology attractive, further cost reduction and improved reliability are required. These can be achieved in part by means of radiation induced grafting for the preparation of low cost proton-conducting polymer membranes. Indeed, the method can be performed with low-cost starting materials (fluorinated and partially fluorinated polymers). In our laboratory at Paul Scherrer Institut, most of the work has been performed using styrene and DVB as the monomers and poly (tetrafluoroethylene-co-hexafluoropropylene) as the base material. Performance comparable to Nafion 112 membranes and durability of several thousands hours at steady-state conditions have been achieved for this type of membranes under fuel cell operation conditions. Previously, poly(ethylene-alt-tetrafluoroethylene) (ETFE) based membranes have been prepared in the presence of divinylbenzene (DVB) as the crosslinking agent and found to exhibit encouraging fuel cell performance. However, the synthesis parameters were not optimized in detail to further improve the membrane properties. Recently, we have investigated the parameters of ETFE based grafting without crosslinking agent. In this study, proton-exchange membranes were prepared by pre-irradiation grafting of styrene onto ETFE and subsequent sulfonation in the presence of DVB containing different isomers (m- and p-isomer of DVB and m- and p-ethylvinylbenzene) as the crosslinker. The grafted films and membranes with varying DVB concentrations and similar degree of grafting (25%) were characterized by Fourier transform infrared spectroscopy (FTIR-ATR) and differential scanning calorimetry (DSC). In addition, dimensional changes and fuel cell relevant properties were examined. FTIR-ATR measurements revealed that the p- isomers are more reactive than m-isomers, and the grafted films are more highly crosslinked in their near surface regions than in the entire bulk. It was determined by DSC experiments that crystallinity of the films did not change with the increase of the DVB content. However, the ex situ conductivity, measured at room temperature, decreases considerably with the increase of the DVB content. Further investigation on the chemical and mechanical stability and fuel cell performance will be performed for a better understanding of ETFE-based membranes