Ageing of PEMFC’s due to operation at low current density: Investigation of oxidative degradation

The paper was aimed at investigating PEMFC ageing upon current cycling: periods of operation under nominal conditions (540 mA cm⁻²) were followed by periods at low current density (120 or 20 mA cm⁻²), the two phases of the cycles being hour-long periods. The progressive ageing of the MEA in the single 25 cm² FC was followed by monitoring the cell voltage, impedance spectroscopy at the end of the various test periods, and by analysis of the water fractions collected. Ageing at 120 mA cm⁻² was shown to be of reduced intensity as confirmed by the weak increase in the various resistances of the equivalent cell circuit, whereas repeated operation at 20 mA cm⁻² resulted in far more severe degradation. This was confirmed by the significance of Pt dissolution from the cathode and recrystallisation in the bulk of the perfluorinated sulfonate polymer, as revealed by TEM photographs of the MEA after the long-term tests. Besides, the loss of sulfur from the membrane was shown to depend little on the ageing procedure, whereas the loss of fluorine was four times larger at 20 mA cm⁻² than at 120 mA cm⁻²: the high cathode potential allowed by the lower current density might change the decomposition mechanism of the polymer chain, as discussed in the paper.     

Heat-induced and other chemical changes in commercial UHT milks

The properties of commercial directly and indirectly heated UHT milks, both after heating and during storage at room temperature for 24 weeks, were studied. Thermally induced changes were examined by changes in lactulose, furosine and acid-soluble whey proteins. The results confirmed previous reports that directly heated UHT milks suffer less heat damage than indirectly heated milk. During storage, furosine increased and bovine serum albumin in directly heat-treated milks decreased significantly. The changes in lactulose, alpha-lactalbumin and beta-lactoglobulin were not statistically significant. The data suggest that heat treatment indicators should be measured as soon as possible after processing to avoid any misinterpretations of the intensity of the heat treatment.     

Multiphase and multicomponent transport with phase change during meat cooking

A multiphase model based on unsaturated flow in a hygroscopic porous medium, which accounts for the important physical phenomena that take place during thermal treatment of meat, is developed. Frozen meat is considered as a porous solid comprising of water, fat and protein with gas trapped in its pores. As it is heated, water and fat melt, and, are gradually released from the solid protein matrix to the pore space. With further rise in temperature, liquid water evaporates. Since four fluid components (liquid water phase, liquid fat phase, water vapor and air) are present in the pore space, a mass balance equation is written for each component. Local thermal equilibrium assumption leads to one energy balance equation for the whole system. The model is validated for double-sided contact heating of hamburger patties by comparing temperature and moisture profiles with experimental studies. Dominant modes of transport are identified.     

Graphene-based environmental barriers

Many environmental technologies rely on containment by engineered barriers that inhibit the release or transport of toxicants. Graphene is a new, atomically thin, two-dimensional sheet material, whose aspect ratio, chemical resistance, flexibility, and impermeability make it a promising candidate for inclusion in a next generation of engineered barriers. Here we show that ultrathin graphene oxide (GO) films can serve as effective barriers for both liquid and vapor permeants. First, GO deposition on porous substrates is shown to block convective flow at much lower mass loadings than other carbon nanomaterials, and can achieve hydraulic conductivities of 5 × 10(-12) cm/s or lower. Second we show that ultrathin GO films of only 20-nm thickness coated on polyethylene films reduce their vapor permeability by 90% using elemental mercury as a model vapor toxicant. The barrier performance of GO in this thin-film configuration is much better than the Nielsen model limit, which describes ideal behavior of flake-like fillers uniformly imbedded in a polymer. The Hg barrier performance of GO films is found to be sensitive to residual water in the films, which is consistent with molecular dynamics (MD) simulations that show lateral diffusion of Hg atoms in graphene interlayer spaces that have been expanded by hydration.     

Effects of spray characteristics on combustion performance of a liquid fuel spray in a gas turbine combustor

Spray characteristics like mean drop diameter and spray cone angle play an important role in the process of combustion within a gas turbine combustor. In order to study their effects on wall and exit temperature distributions and combustion efficiency in the combustor, a numerical model of a typical diffusion controlled spray combustion in a can‐type gas turbine combustion chamber has been made. A simple k–ϵ model with wall function treatment for near‐wall region has been adopted for the solution of conservation equations in carrier phase. The initial spray parameters are specified by a suitable PDF for size distribution and a given spray cone angle. A radiation model for the gas phase, based on modified first order moment method, and in consideration of the gas phase as a grey absorbing–emitting medium, has been adopted in the analysis. It has been recognized that an increase in mean drop diameter improves the pattern factor. However, the combustion efficiency attains its maximum at an optimum value of the mean diameter. Higher spray cone angle increases the combustion efficiency and improves the pattern factor, but at the same time, increases the wall temperature. Copyright © 1999 John Wiley & Sons, Ltd.     

Thermodynamic irreversibilities and exergy balance in combustion processes

The growing concern for energy, economy and environment calls for an efficient utilization of natural energy resources in developing useful work. An important thermodynamic aspect in gauging the overall energy economy of any physical process is the combined energy and exergy analysis from the identification of process irreversibilities. The present paper makes a comprehensive review pertaining to fundamental studies on thermodynamic irreversibility and exergy analysis in the processes of combustion of gaseous, liquid and solid fuels. The need for such investigations in the context of combustion processes in practice is first stressed upon and then the various approaches of exergy analysis and the results arrived at by different research workers in the field have been discussed. It has been recognized that, in almost all situations, the major source of irreversibilities is the internal thermal energy exchange associated with high-temperature gradients caused by heat release in combustion reactions. The primary way of keeping the exergy destruction in a combustion process within a reasonable limit is to reduce the irreversibility in heat conduction through proper control of physical processes and chemical reactions resulting in a high value of flame temperature but lower values of temperature gradients within the system. The optimum operating condition in this context can be determined from the parametric studies on combustion irreversibilities with operating parameters in different types of flames.     

Studies on the reaction of bis(diisopropyl) thiophosphoryl disulfide with silica in the vulcanization of NR

The reaction between bis(diisopropyl) thiophosphoryl disulfide (DIPDIS) and silica has been investigated. The study reveals that DIPDIS can be used as a coupling agent for silica. The chemical bond between the silanol groups of silica and DIPDIS has been established through the isolation and characterization of isopropyl alcohol that is eliminated from the reaction. The chemical nature of the bond is also supported by the IR analysis of the reaction products of silica and DIPDIS obtained both in the presence and absence of rubber. From the exploratory studies it is indicated that DIPDIS can also react with NR even during mixing of ingredients. When used with 2-mercaptobenzothiazole (MBT) or N-oxydiethylene-2-benzothiazole sulfenamide (OBTS) in the presence of silica, DIPDIS exhibits notable activation of cure and enhances the torque, modulus, tensile strength, and the scorch safety.     

Combustion of single char particles in a turbulent fluidized bed

The combustion of single bituminous char particles (4-12 mm diameter) was studied in a turbulent fluidized bed operated at 1098 K using air as the fluidising medium. Results indicated that particles burn with constant density following a shrinking sphere model. Burning rates are much higher than those observed in a bubbling fluidized bed. The rate of transfer of oxygen to the particle surface is also higher than that observed in bubbling beds. A model is proposed to calculate the Sherwood numbers of the burning carbon particles. Experimental values of the Sherwood numbers agree well with those predicted from the model.     

Anti-CD40 ligand antibody treatment of SNF1 mice with established nephritis: preservation of kidney function

Prior studies have demonstrated that treatment of young, prenephritic lupus-prone mice with Ab directed against CD40 ligand (CD40L) prolongs survival and decreases the incidence of severe nephritis. In this report, we show that for (SWR x NZB)F1 (SNF1) animals with established lupus nephritis, long-term treatment with anti-CD40L beginning at either 5.5 or 7 mo of age prolonged survival and decreased the incidence of severe nephritis. "Older" mice were chosen for these studies to more closely resemble the clinical presentation of patients with established renal disease. We show that age at the start of treatment, which typically correlates with severity of disease, is an important factor when determining an efficacious therapeutic protocol since animals that began treatment at 7 mo of age required a more aggressive treatment protocol than animals at 5.5 mo of age. Remarkably, several anti-CD40L-treated animals beginning treatment at age 5.5 mo demonstrated a decline in proteinuria, as opposed to increasing proteinuria levels seen in hamster IgG (HIg)-treated controls, and histologic examination of kidneys from anti-CD40L-treated mice revealed dramatically diminished inflammation, sclerosis/fibrosis, and vasculitis, in marked contrast to the massive inflammation and kidney destruction observed in control animals that received hamster IgG. Spleens from anti-CD40L-treated mice also exhibited markedly reduced inflammation and fibrosis compared with controls. Together, these results show that treatment of older, nephritic SNF1 animals with long-term anti-CD40L immunotherapy significantly prolongs survival, reduces the severity of nephritis, and diminishes associated inflammation, vasculitis, and fibrosis.