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     

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     

Mathematical modeling of crystallization analysis fractionation (Crystaf) of polyethylene

Four polyethylene samples (PE) with different molecular weight distributions (MWD) were analyzed by crystallization analysis fractionation (Crystaf) at several cooling rates to investigate the effect of MWD and cooling rate on their Crystaf profiles. Using these results, we developed a mathematical model for Crystaf that considers crystallization kinetic effects, which are ignored in all previous Crystaf models. The Crystaf model we proposed can fit the experimental Crystaf profiles of the 4 polyethylene resins very well. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2749–2759, 2006     

Computation of moisture and temperature profiles in soil—The coupled model

The coupled model has been developed in this study for moisture transport and beat exchange in soil. The model is driven by atmospheric conditions measured in a field. The concept that soil has a surface resistance to evaporation is introduced in order to relate the evaporation from surface with the vapour flux in air. With the use of this concept, the simulation results agree quite well with the measured data.     

A procedure for measuring the flexibility of single wood-pulp fibres

A way of determining the flexibility of wood-pulp fibres is developed, which involves i) a precise measurement of the topology of single-fibres by using a confocal laser scanning microscope and ii) the measurement of the elastic modulus of the fibres by using a single-fibre fatigue cell. Reported in this paper are the initial results of tests carried out on black spruce fibres, which have been subjected to three different levels of mechanical refining energy, namely ∼1100, 2300, and 3500 kWh/t. It is found that the fibre flexibility rises significantly between the first and second energy levels, but it does not change to the same degree between the second and third ones. The described procedure of measuring the flexibility of fibres may be used to establish the appropriate refiner energy necessary for the production of a specific grade of paper. Russian translation published in Mekhanika Kompozitnykh Materialov, Vol. 42, No. 1, pp. 115–128, January–February, 2006.     

Observation of inter-grain Josephson effects in Y-Ba-Cu-O samples

Josephson effects have been observed in bulk samples of Y-Ba-Cu-O. The magnitude of the zero-voltage current is found to change systematically with externally applied small magnetic fields of a few mG. It is also found to vary when samples are irradiated with microwaves. These observations suggest the presence of inter-grain Josephson junctions.     

Topological order in the phase diagram for high-temperature superconductors with point defects

Applying a Lindemann like criterion obtained previously by Kierfeld et al. [J. Kierfeld, T. Nattermann, T. Hwa, Phys. Rev. B 55 (1997) 626], we estimate the magnetic field and temperature for a high-T_c superconductor, at which a topologically ordered vortex glass phase becomes unstable with respect to a disorder-induced formation of dislocations. The employed criterion is shown to be equivalent to a conventional phenomenological Lindemann criterion including the values for the numerical factors, i.e., for the Lindemann number. The positional correlation length of the topologically ordered vortex glass is calculated.     

离子注入硅的线源非相干光瞬时退火温度计算

本文利用高温模型,计算了在我们的实验条件下对离子注入硅进行线源非相干光瞬时退火的退火温度,并与实验结果比较,两者符合得较好。