High performance benzyltrimethylammonium-type alkaline anion-exchange membranes (AEM), for application in electrochemical devices such as anion-exchange membrane fuel cells (AEMFC), were prepared by the radiation grafting (RG) of vinylbenzyl chloride (VBC) onto 25 μm thick poly(ethylene-co-tetrafluoroethylene) (ETFE) films followed by amination with trimethylamine. Reductions in electron-beam absorbed dose and amount of expensive, potentially hazardous VBC were achieved by using water as a diluent (reduced to 30 – 40 kGy absorbed dose and 5%vol VBC) instead of the prior-art method that used organic propan-2-ol diluent (required 70 kGy dose and 20%vol VBC monomer). Furthermore, the water from the aqueous grafting mixture was easily separated from residual monomer (after cooling) and was reused for a further grafting reaction: the resulting AEM exhibited an ion-exchange capacity of 2.1 mmol g-1 (cf. 2.1 mmol g-1 for the AEM made using fresh grafting mixture). The lower irradiation doses resulted in mechanically stronger RG-AEMs compared to the reference RG-AEM synthesised using the prior-art method. A further positive off-shoot of the optimisation process was the discovery that using water as a diluent resulted in an enhanced (i.e. more uniform) distribution of VBC grafts as proven by Raman microscopy and corroborated using EDX analysis: this led to enhancement in the Cl- anion-conductivities (up to 68 mS cm-1 at 80°C for the optimised fully hydrated RG-AEMs vs. 48 mS cm-1 for the prior-art RG-AEM reference). A down-selected RG-AEM of ion-exchange capacity = 2.0 mmol g-1, that was synthesised using the new greener protocol with 30 kGy electron-beam absorbed dose, led to an exceptional beginning-of-life H2/O2 AEMFC peak power density of 1.16 W cm−2 at 60°C in a benchmark test using industrial standard Pt-based electrocatalysts and unpressurised gas supplies: this was higher than the 0.91 W cm-1 obtained with the reference RG-AEM (IEC = 1.8 mmol g-1) synthesised using the prior-art protocol
In this work, a number of mixture aqueous solutions of chitosan/agar (CS/AG) at different ratios (considering chitosan as the main component) were prepared. The rheological properties i.e. shearing viscosity and shear stress of the blend solutions as a function of shear rate as well as the thermal properties of the blend films were investigated. Among the parameters studied were temperature, shearing time and storage time. Results showed that almost Newtonian behavior was observed at temperatures from 40 o C to 55 o C for the ratios 100/0, 90/10, 80/20 and 70/30. However, the proportions 60/40 and 50/50 showed a clear shear thinning behavior (pseudoplastic non-Newtonian behavior). It was also found that all the blend solutions obeyed the Arrhenius equation. In addition, the effect of shearing time on the shearing viscosity of all blends did not show any significant differences at all shearing times applied in this study except the proportion 50/50 wherein decreasing in shearing viscosity and shear stress was observed as the shearing time increased. Furthermore, different behaviors were observed for the blend solutions when the period of storage was extended to three weeks. The FTIR results and the differential scanning calorimetery (DSC) curves showed that the interaction between chitosan and agar can occur.
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