SummaryNovel composite membranes for high temperature polymer-electrolyte fuel cells (HT-PEFC) based on a poly[oxy-3,3-bis(4′-benzimidazol-2″-ylphenyl)phtalide-5″(6″)-diyl] (PBI-O-PhT) polymer with small amounts of added Zr were prepared. It was shown in a model reaction between zirconium acetylacetonate (Zr(acac)4) and benzimidazole (BI) that Zr-atoms are capable to form chemical bonds with BI. Thus, Zr may be used as a crosslinking agent for PBI membranes. The obtained Zr/PBI-O-PhT composite membranes were examined by means of SAXS, thermomechanical analysis (TMA), and were tested in operating fuel cells by means of stationary voltammetry and impedance spectroscopy. The new membranes showed excellent stability in a 2000-hour fuel cell (FC) durability test. The modification of the PBI-O-PhT films with Zr facilitated an increase of the phosphoric acid (PA) uptake by the membranes, which resulted in an up to 2.5 times increased proton conductivity. The existence of an optimal amount of Zr content in the modified PBI-O-PhT film was shown. Larger amounts of Zr lead to a lower PA doping level and a reduced conductivity due to an excessively high degree of crosslinking.
Different polyheteroarylenes, such as m‐polybenzimidazole, polyphenylene oxide, polymer of intrinsic microporosity (PIM‐1) and poly(N‐phenylene‐benzimidazole) were electrospun to obtain self‐supporting polymer nanofiber mats. The mats after heat treatment, which contains stabilization in air at 250–350 °C and pyrolysis at 900–1000 °C under vacuum, convert into carbon nanofiber paper, a material which is suitable for Pt nanoparticle deposition. The possibility of usage of the obtained carbonized nanocomposites as entire gas diffusion electrodes for high temperature polymer electrolyte membrane fuel cell is shown.
The sulfonated polynaphthoyleneimide polymer (co-PNIS70/30) was prepared by copolymerization of 4,4′-diaminodiphenyl ether-2,2′-disulfonic acid (ODAS) and 4,4’-methylenebisanthranilic acid (MDAC) with ODAS/MDAC molar ratio 0.7/0.3. High molecular weight co-PNIS70/30 polymers were synthesized either in phenol or in DMSO by catalytic polyheterocyclization in the presence of benzoic acid and triethylamine. The titration reveals the ion-exchange capacity of the polymer equal to 2.13 meq/g. The membrane films were prepared by casting polymer solution. Conductivities of the polymer films were determined using both in- and through-plane geometries and reached ~96 and ~60 mS/cm, respectively. The anisotropy of the conductivity is ascribed to high hydration of the surface layer compared to the bulk. SFG NMR diffusometry shows that, in the temperature range from 213 to 353 K, the 1H self-diffusion coefficient of the co-PNIS70/30 membrane is about one third of the diffusion coefficient of Nafion® at the same humidity. However, temperature dependences of proton conductivities of Nafion® and of co-PNIS70/30 membranes are nearly identical. Membrane–electrode assemblies (MEAs) based on co-PNIS70/30 were fabricated by different procedures. The optimal MEAs with co-PNIS70/30 membranes are characterized by maximum output power of ~370 mW/cm2 at 80 °C. It allows considering sulfonated co-PNIS70/30 polynaphthoyleneimides membrane attractive for practical applications.
Obese African-American (AA) women are at high risk of hypertension (HT) and cardiovascular disease (CVD). Flow-mediated dilation (FMD) and arterial augmentation index (AI) are measures of endothelial function and arterial stiffness. Whether endothelial function and arterial stiffness predict risk of HT or CVD in obese African-American women with, versus without, parental histories of HT and whether aerobic exercise is an effective countermeasure remain unclear. The capacity for FMD is partly heritable. Therefore, we tested the hypotheses that less FMD and greater AI may be found in normotensive-obese, young-adult (18-26 year-old) AA women with hypertensive parents (n=10) than in a matched control group with normotensive parents (n=10) and that a single bout of aerobic exercise improves both endothelial function and arterial stiffness, with less improvement in the women with hypertensive parents. We studied each subject while at rest, 20 min before and 20 min after, 30 min of aerobic exercise. The exercise-induced changes and parental hypertension-related differences in AI were not significant. The exercise increased FMD in both of the groups with no significant difference in magnitude between the women with hypertensive and normotensive parents. FMD was significantly less in the women with hypertensive parents than in the women with normotensive parents after, but not before, the exercise (mean ±95% confidence interval of 11.3 ± 4.9% vs. 15.6 ± 4.9%, P=0.05). These findings suggest that a 30-min bout of aerobic exercise may improve FMD and unmask endothelial dysfunction in normotensive-obese, young-adult AA women with parental histories of HT. Future studies should determine whether regular aerobic exercise protects obese AA women from the endothelial dysfunction associated with diabetes and prevents CVD in this high-risk population.
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