Polymer electrolyte membranes for the direct methanol fuel cell: A review

The direct methanol fuel cell (DMFC) has the potential to replace lithium‐ion rechargeable batteries in portable electronic devices, but currently experiences significant power density and efficiency losses due to high methanol crossover through polymer electrolyte membranes (PEMs). Numerous publications document the synthesis and characterization of new PEMs for the DMFC. This article reviews this research, transport phenomena in PEMs, and experimental techniques used to evaluate new PEMs for the DMFC. Although many PEMs do not show significant improvements over Nafion®, the benchmark PEM in DMFCs, experimental results show that several new PEMs exhibit lower methanol crossover at similar proton conductivities and/or higher DMFC power densities. These results and recommendations for future research are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Parts B: Polym Phys 44: 2201–2225, 2006     

Mechanical endurance of polymer electrolyte membrane and PEM fuel cell durability

The life of proton exchange membrane fuel cells (PEMFC) is currently limited by the mechanical endurance of polymer electrolyte membranes and membrane electrode assemblies (MEAs). In this paper, the authors report recent experimental and modeling work toward understanding the mechanisms of delayed mechanical failures of polymer electrolyte membranes and MEAs under relevant PEMFC operating conditions. Mechanical breach of membranes/MEAs in the form of pinholes and tears has been frequently observed after long‐term or accelerated testing of PEMFC cells/stacks. Catastrophic failure of cell/stack due to rapid gas crossover shortly follows the mechanical breach. Ex situ mechanical characterizations were performed on MEAs after being subjected to the accelerated chemical aging and relative humidity (RH) cycling tests. The results showed significant reduction of MEA ductility manifested as drastically reduced strain‐to‐failure of the chemically aged and RH‐cycled MEAs. Postmortem analysis revealed the formation and growth of mechanical defects such as cracks and crazing in the membranes and MEAs. A finite element model was used to estimate stress/strain states of an edge‐constrained MEA under rapid RH variations. Damage metrics for accelerated testing and life prediction of PEMFCs are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2346–2357, 2006     

Sulfonated poly(aryl ether ether ketone ketone)s containing fluorinated moieties as proton exchange membrane materials

A series of sulfonated poly(aryl ether ether ketone ketone)s statistical copolymers with high molecular weights were synthesized via an aromatic nucleophilic substitution polymerization. The sulfonation content (SC), defined as the number of sulfonic acid groups contained in an average repeat unit, could be controlled by the feed ratios of monomers. Flexible and strong membranes in sodium sulfonate form could be prepared by the solution casting method, and readily transformed to their proton forms by treating them in 2 N sulfuric acid. The polymers showed high T_gs, which increased with an increase in SC. Membranes prepared from the present sulfonated poly(ether ether ketone ketone) copolymers containing the hexafluoroisopropylidene moiety (SPEEKK‐6F) and copolymers containing the pendant 3,5‐ditrifluoromethylphenyl moiety (SPEEKK‐6FP) had lower water uptakes and lower swelling ratios in comparison with previously prepared copolymers containing 6F units. All of the polymers possessed proton conductivities higher than 1 × 10^?2 S/cm at room temperature, and proton conductivity values of several polymers were comparable to that of Nafion at high relative humidity. Their thermal stability, oxidative stability, and mechanical properties were also evaluated. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2299–2310, 2006     

化学键合吸附剂的合成及吸附行为

在无定型硅胶上化学键合十八烷基三氯硅烷，键合率17%-20％，粒度5μm-10μm，以此键合的吸附剂可有效地吸附香烟烟气中的焦油、亚硝胺，吸附率分别为15%-18％和37%-43％，研究了化学键合吸附剂的粒度和加入量对吸附性能的影响。     

Theoretical approach and the practice to the evaluation of structural parameters characterizing concentration polarization alongside ion-exchange membranes by means of dielectric measurement

As the application of a dielectric theory proposed previously (J Membrane Sci 64:153–161 (1991)), theoretical formulation and the practical procedure of dielectric analysis are developed to calculate the structural parameters such as the conductivity gradient and the thickness of the concentration polarization layer, the capacitances and the conductances of the two adjoining aqueous phases from the observed dielectric parameters. The procedure of calculation consequent upon the theoretical formulation was applied to double relaxation data observed for cation-exchange membrane systems under application of d.c. bias voltage. As a consequence, the structural parameters of concentration polarization were readily obtained with accuracy.     

Salting coefficients for gases in seawater from scaled-particle theory

Experimental values of the salting coefficients for He, Ne, Ar, O₂, and N₂ in seawater are compared with values calculated from scaled-particle theory. The agreement is reasonably good; the average difference between calculated and observed values at 25°C is 0.007. Scaled-particle theory predicts correctly thatk _s should decrease as the temperature increases and that this effect should be most pronounced at low temperatures. However, the predicted magnitude ofdK _s/dt is only about half of that observed.     

An application of factorial design to the development of fused silica capillary columns

Stationary phase crosslinking conditions for fused silica capillary columns were optimized with the use of a factorial design experiment. This experimental strategy was chosen because it provided for the determination of two-factor interactions. A predictive model was developed for the desired chromatographic performance parameters as a function of the variables of the crosslinking reaction. Confirmatory experiments proved the usefulness of the mathematical model which resulted in the production of capillary columns of superior performance with significant improvements in reproducibility.     

巯基葡聚糖凝胶分离富集光度法测定镉的研究

研究了在ＴｒｉｔｏｎＸ－１００存在下，新显色剂邻羧基苯基重氮氨基偶氮苯（ＣＤＡＡ）与镉的显色体系，在ｐＨ１０．６的Ｎａ２Ｂ４Ｏ７－ＮａＯＨ体系中，显色反应灵敏度很高。络合物的最大吸收位于５４５ｎｍ处，其摩尔吸光系数为２．２２×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－１。镉含量在０￣１２μｇ／２５ｍＬ符合比耳定律。将该体系用于巯基葡聚糖凝胶分离富集－光度法测水样中微量镉，结果令人满意。     

Dynamics of the formation of two-dimensional ordered structures

The growth of ordered domains in lattice gas models, which occurs after the system is quenched from infinite temperature to a state below the critical temperatureT _c, is studied by Monte Carlo simulation. For a square lattice with repulsion between nearest and next-nearest neighbors, which in equilibrium exhibits fourfold degenerate (2×1) superstructures, the time-dependent energy E(t), domain size L(t), and structure functionS(q, t) are obtained, both for Glauber dynamics (no conservation law) and the case with conserved density (Kawasaki dynamics). At late times the energy excess and halfwidth of the structure factor decrease proportional tot ^–x, whileL(t) t ^x, where the exponent x=1/2 for Glauber dynamics and x1/3 for Kawasaki dynamics. In addition, the structure factor satisfies a scaling lawS(k,t)=t ^2xS(kt^x). The smaller exponent for the conserved density case is traced back to the excess density contained in the walls between ordered domains which must be redistributed during growth. Quenches toT>T _c, T=T_c (where we estimate dynamic critical exponents) andT=0 are also considered. In the latter case, the system becomes frozen in a glasslike domain pattern far from equilibrium when using Kawasaki dynamics. The generalization of our results to other lattices and structures also is briefly discussed.     

Comparison of combustion sources for sulfur chemiluminescence detection

Three different types of SCD combustion source have been evaluated for use in the chromatographic analysis of atmospheric sulfur compounds. The conventional FID source and the newer inverted burner source were found to be less sensitive and less stable than the flameless design. Overall, the flameless source was superior for use with HRGC-SCD.