A long side chain imidazolium-based graft-type anion-exchange membrane: novel electrolyte and alkaline-durable properties and structural elucidation using SANS contrast variation.

Newly designed styrylimidazolium-based grafted anion-exchange membranes (StIm-AEMs), in which imidazolium ionic groups are attached to styrene at the far side from the graft chains, were prepared by radiation-induced graft polymerization of p-(2-imidazoliumyl) styrene onto poly(ethylene-co-tetrafluoloethylene) (ETFE) films, followed by N-alkylation and ion-exchange reactions. StIm-AEM having an ion exchange capacity (IEC) of 0.54 mmol g-1 with a grafting degree (GD) of ∼18%, possesses practical conductivity (>50 mS cm-1) even with a very low water uptake (∼10%) and high stability over 600 h in a 1 M KOH solution at 80 °C. There exists a critical IEC (IECc) in the range of 0.7-0.8 mmol g-1 over which the membrane showed high water uptake, which resulted in pronounced susceptibility to hydrolysis. Using small-angle neutron scattering technique with a contrast variation method, we found the hydrophilic phase in StIm-AEMs with IECs lower and higher than IECc shows "reverse-micelles" with water domains dispersed in the polymer matrix and "micelles" with graft polymer aggregates dispersed in the water matrix, respectively. The further analysis of micelle structures using the hard-sphere liquid model and Porod limit analysis reveals that the interfacial structures of ionic groups are essential for the electrochemical properties and durability of StIm-AEMs. In addition, StIm-AEM with an IEC of 0.95 mmol g-1 and the maximum power density of 80 mW cm-2 in the hydrazine hydrate fuel cell test, exhibited long-term durability under constant current (8.0 mA) up to 455 h, which, thus far, is the best durability at 80 °C for platinum-free alkaline-type liquid fuel cells.

Orientation-shape coupling between liquid crystal and membrane through the anchoring effect.

We perform a series of Monte Carlo simulations on an interface between a liquid crystal (LC) material in isotropic phase in its bulk and a surfactant membrane. These two objects are simulated using coarse-grained molecular models. We estimate physical properties of the membrane such as the interfacial tension and the bending rigidity, focusing on the anchoring effects of the membrane on the LC. According to our simulation results, when the strength of the homeotropic anchoring denoted by the anchoring parameter ξ is increased, the interfacial tension decreases and the bending rigidity first increases in ξ<ξ_{m}, and it then decreases in ξ_{m}<ξ. We explain these results by constructing a continuum field model based on the two order parameters: directional order of LC and the membrane shape. These order parameters are mutually interacting through the anchoring effect, the fluctuation coupling between the LC and the membrane, and the effect of the nematic layer.