Anion conductive aromatic multiblock copolymers, poly(arylene ether)s containing quaternized ammonio-substituted fluorene groups, were synthesized via block copolycondensation of fluorene-containing (later hydrophilic) oligomers and linear hydrophobic oligomers, chloromethylation, quaternization, and ion-exchange reactions. The ammonio groups were selectively introduced onto the fluorene-containing units. The quaternized multiblock copolymers (QPEs) produced ductile, transparent membranes. A well-controlled multiblock structure was responsible for the developed hydrophobic/hydrophilic phase separation and interconnected ion transporting pathway, as confirmed by scanning transmission electron microscopic (STEM) observation. The ionomer membranes showed considerably higher hydroxide ion conductivities, up to 144 mS/cm at 80 °C, than those of existing anion conductive ionomer membranes. The durabilities of the QPE membranes were evaluated under severe, accelerated-aging conditions, and minor degradation was recognized by (1)H NMR spectra. The QPE membrane retained high conductivity in hot water at 80 °C for 5000 h. A noble metal-free direct hydrazine fuel cell was operated with the QPE membrane at 80 °C. The maximum power density, 297 mW/cm(2), was achieved at a current density of 826 mA/cm(2).

A series of anion conductive aromatic ionomers, poly(arylene ether)s containing different polymer backbones and quaternized ammonio-substituted fluorenyl groups, were synthesized via nucleophilic substitution polycondensation, chloromethylation, quaternization, and the subsequent ion exchange reactions. The ion exchange capacity (IEC) of the ionomers was controlled to be from 0.68 to 2.54 meq. g À1 by the chloromethylation reaction conditions. The designed chemical structures were wellcharacterized by the 1 H NMR spectra. The ionomers provided ductile and transparent membranes. The ionomer membranes were thermally stable up to 180 C under nitrogen and mechanically stable with 48 MPa of the maximum stress at 80 C and 60% RH (relative humidity). High hydroxide ion conductivity up to 50 mS cm À1 was achieved at 30 C in water for the ionomer membrane bearing sulfone/ketone structures and the highest IEC (2.54 meq. g À1 ). The membranes were durable in hot water (80 C) for 1000 hours. These properties of the ionomer membranes seem promising as an anion exchange membrane for alkaline fuel cells.

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The fabrication of patterned polymer brushes has attracted considerable attention as these structures can be exploited in devices on the nano- and microscale. Patterning of polymer brushes is typically a complex, multistep process. We report the direct patterning of poly(methyl methacrylate) (PMMA), poly(2-hydroxyethyl methacrylate) (PHEMA), poly(isobutyl methacrylate) (PIBMA), poly(neopentyl methacrylate) (PNPMA), and poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) brushes in a single step by electron beam (e-beam) lithography, to obtain nanopatterned polymer brush surfaces. PMMA, PHEMA, PIBMA, PNPMA, and PTFEMA brushes were grown on silicon substrates via surface-initiated atom transfer radical polymerization. Surface analysis techniques including ellipsometry, contact angle goniometry, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) were used to characterize the thickness, hydrophilicity, roughness, and chemical composition of the polymer brushes. Tapping-mode AFM imaging confirmed the successful electron beam patterning of these brushes. Using this direct patterning method, highly resolved nanostructured polymer brush patterns down to 50 nm lines were obtained. This direct patterning of brushes eliminates the need for complex lithographic schemes. The sensitivity of these polymer brushes toward direct patterning with e-beam was studied and compared. The sensitivity curves indicate that the structure of the e-beam degradable methacrylate polymer has a significant effect on the sensitivity of the polymer brush toward e-beam patterning. In particular, the effect of the chemical functionality at the beta-position to the carbonyl group on the polymer brush sensitivity toward direct patterning was studied using groups of varying size and polarity.