Chemically modified proton‐conducting membranes based on sulfonated polyimides: Improved water stability and fuel‐cell performance

A series of branched/crosslinked sulfonated polyimide (B/C‐SPI) membranes were prepared and evaluated as proton‐conducting ionomers based on the new concept of in situ crosslinking from sulfonated polyimide (SPI) oligomers and triamine monomers. Chemical branching and crosslinking in SPI oligomers with 1,3,5‐tris(4‐aminophenoxy)benzene as a crosslinker gave the polymer membranes very good water stability and mechanical properties under an accelerated aging treatment in water at 130 °C, despite their high ion‐exchange capacity (2.2–2.6 mequiv g^?1). The resulting polymer electrolytes displayed high proton conductivities of 0.2–0.3 S cm^?1 at 120 °C in water and reasonably high conductivities of 0.02–0.03 S cm^?1 at 50% relative humidity. In a single H₂/O₂ fuel‐cell system at 90 °C, they exhibited high fuel‐cell performances comparable to those of Nafion 112. The B/C‐SPI membranes also displayed good performances in a direct methanol fuel cell with methanol concentrations as high as 50 wt % that were superior to those of Nafion 112. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3751–3762, 2006     

Tristimulus colorimetry using a digital still camera and its application to determination of iron and residual chlorine in water samples.

Tristimulus colorimetry using a digital still camera (DSC) as a colorimeter has been developed. A photograph of a sample and standard solutions was taken simultaneously with the DSC, and it was transferred to a PC. On the PC, the colors of the sample and of the standard solutions were analyzed and L* (brightness), a* (red-green component), and b* (yellow-blue component) values were determined with laboratory-made software. A dedicated light-box containing white-color LEDs as light source was made of white acrylic to make constant exposure at each photograph. Various settings of the DSC, such as exposure mode, white balance, and so on, that affect analytical figures, were studied with determination of iron with 1,10-phenanthroline. This method was successfully applied to the determinations of iron in a river water sample and of residual chlorine in tap water samples with N,N-diethylphenylenediamine (DPD).     

Separation of fulvic acid from soil extracts based on ion-pair formation with a cationic surfactant.

A novel method for separating fulvic acid (FA) from soil extracts is proposed. The FA, defined as the acid-soluble fraction of an alkaline extract of soil, was separated based on the precipitation of an ion-pair with a cationic surfactant, such as domiphen bromide. The precipitate was dissolved in aqueous HCl to produce H+ -type FA and a surfactant chloride (SUR-Cl). SUR-Cl, in the aqueous solution, was removed by extraction with CHCl3. After the aqueous phase was passed through a cation-exchanger (H+ -type), H+ -type FA (FA-SUR) was obtained as a powder by lyophylization. The chemical characteristics of FA-SUR were compared with an FA sample separated according to the method of the International Humic Substances Society using a DAX-8 resin (FA-DAX). The oxygen content, O/C atomic ratio and total acidity of the FA-SUR were significantly larger than the corresponding values for FA-DAX. The solid-state CPMS 13C NMR spectra indicated that the higher oxygen content of the FA-SUR could be due to alcoholic hydroxyl groups and polysaccharides as well as carboxylic groups. These results show that FA-SUR is more polar and hydrophilic than FA-DAX.     

Nuclear spin-lattice relaxation mechanisms in kaolinite confirmed by magic-angle spinning

Spin-lattice relaxation mechanisms in kaolinite have been reinvestigated by magic-angle spinning (MAS) of the sample. MAS is useful to distinguish between relaxation mechanisms: the direct relaxation rate caused by the dipole-dipole interaction with electron spins is not affected by spinning while the spin diffusion-assisted relaxation rate is. Spin diffusion plays a dominant role in ¹H relaxation. MAS causes only a slight change in the relaxation behavior, because the dipolar coupling between ¹H spins is strong. ²⁹Si relaxes directly through the dipole-dipole interaction with electron spins under spinning conditions higher than 2 kHz. A spin diffusion effect has been clearly observed in the ²⁹Si relaxation of relatively pure samples under static and slow-spinning conditions. ²⁷Al relaxes through three mechanisms: phonon-coupled quadrupole interaction, spin diffusion and dipole-dipole interaction with electron spins. The first mechanism is dominant, while the last is negligibly small. Spin diffusion between ²⁷Al spins is suppressed completely at a spinning rate of 2.5 kHz. We have analyzed the relaxation behavior theoretically and discussed quantitatively. Concentrations of paramagnetic impurities, electron spin-lattice relaxation times and spin diffusion rates have been estimated.     

In Situ Immobilization of Ultrafine Particles Synthesized in a Water/Oil Microemulsion

We investigated the in situ immobilization of ultrafine particles synthesized in a water/oil (w/o) microemulsion to silica for its possible application to supported metal catalysts. ZnS particles immobilized to silica by the ME method were consistent with those synthesized in a w/o microemulsion. Therefore, ZnS particles in a w/o microemulsion could be immobilized to silica without aggregation by this method. The relationship between the method of synthesizing Rh ultrafine particles in a w/o microemulsion and the diameter and diameter distribution of Rh particles immobilized to silica was studied. Rh-SiO(2) catalysts with a sharp diameter distribution could be prepared by immobilizing Rh-hydrazine complex particles because these complex particles would be very stable in a w/o microemulsion. The Rh particle diameters of Rh-SiO(2) catalysts prepared by changing the amount of silica produced were almost identical. Accordingly, the Rh particle diameter of Rh-SiO(2) catalysts could be controlled independently of Rh content by the ME method. Copyright 2001 Academic Press.     

Fragmentation in doubly charged ion mass spectra of anhydropisatin and related compounds

The doubly charged ion mass spectra of anhydropisatin, 4-methoxyanhydropisatin, 3, 8, 9-trimethoxypterocarpen and 3, 4, 8, 9-tetramethoxypterocarpen were determined, and the fragmentation was explained by assuming that the paired electrons were partially localized in the fragmentations and by comparing the spectra with that of 3-(CD₃)-anhydropisatin. Conventional mass spectra of these compounds were very simple, but the doubly charged ion spectra were sufficiently characteristic for the reliable identification.