Electrocatalysis of oxygen reduction reaction on Nafion/platinum/gas diffusion layer electrode for PEM fuel cell

In this work a new membrane electrode based on Pt-coated Nafion membrane was fabricated. Chemical deposition process was used to coat platinum on Nafion 117 membrane and then Pt-coated Nafion membrane was hot pressed on gas diffusion layer (GDL) to make new membrane electrode. The electrochemical and chemical studies of the Pt-coated Nafions were investigated by electrochemical techniques, X-ray diffraction and scanning electron microscopy. The electrochemical results indicated that as the concentration of H₂PtCl₆ increased, the oxygen reduction reaction rate increased until the concentration was reached where the reduction reaction was limited by the problem of mass transport. The electrochemical results for oxygen reduction reaction showed that the new electrode which prepared by plating Nafion membrane with 0.06 M H₂PtCl₆ in electroless plating solution, has a higher performance than other electrodes. The XRD results showed that the average platinum particle size of the best sample was about 3 nm. The loading of platinum for this electrode was 0.153 mg cm⁻².     

Ultrasound velocimetry of ferrofluid spin-up flow measurements using a spherical coil assembly to impose a uniform rotating magnetic field

Ferrofluid spin-up flow is studied within a sphere subjected to a uniform rotating magnetic field from two surrounding spherical coils carrying sinusoidally varying currents at right angles and 90° phase difference. Ultrasound velocimetry measurements in a full sphere of ferrofluid shows no measureable flow. There is significant bulk flow in a partially filled sphere (1-14 mm/s) of ferrofluid or a finite height cylinder of ferrofluid with no cover (1-4 mm/s) placed in the spherical coil apparatus. The flow is due to free surface effects and the non-uniform magnetic field associated with the shape demagnetizing effects. Flow is also observed in the fully filled ferrofluid sphere (1-20 mm/s) when the field is made non-uniform by adding a permanent magnet or a DC or AC excited small solenoidal coil. This confirms that a non-uniform magnetic field or a non-uniform distribution of magnetization due to a non-uniform magnetic field are causes of spin-up flow in ferrofluids with no free surface, while tangential magnetic surface stress contributes to flow in the presence of a free surface.Recent work has fitted velocity flow measurements of ferrofluid filled finite height cylinders with no free surface, subjected to uniform rotating magnetic fields, neglecting the container shape effects which cause non-uniform demagnetizing fields, and resulting in much larger non-physical effective values of spin viscosity η′∼10⁻⁸−10⁻¹² N s than those obtained from theoretical spin diffusion analysis where η′≤10⁻¹⁸ N s. COMSOL Multiphysics finite element computer simulations of spherical geometry in a uniform rotating magnetic field using non-physically large experimental fit values of spin viscosity η′∼10⁻⁸−10⁻¹² N s with a zero spin-velocity boundary condition at the outer wall predicts measureable flow, while simulations setting spin viscosity to zero (η′=0) results in negligible flow, in agreement with the ultrasound velocimetry measurements. COMSOL simulations also confirm that a non-uniform rotating magnetic field or a uniform rotating magnetic field with a non-uniform distribution of magnetization due to an external magnet or a current carrying coil can drive a measureable flow in an infinitely long ferrofluid cylinder with zero spin viscosity (η′=0).     

3-D simulation of soot formation in a direct-injection diesel engine based on a comprehensive chemical mechanism and method of moments

Here, we propose both a comprehensive chemical mechanism and a reduced mechanism for a three-dimensional combustion simulation, describing the formation of polycyclic aromatic hydrocarbons (PAHs), in a direct-injection diesel engine. A soot model based on the reduced mechanism and a method of moments is also presented. The turbulent diffusion flame and PAH formation in the diesel engine were modelled using the reduced mechanism based on the detailed mechanism using a fixed wall temperature as a boundary condition. The spatial distribution of PAH concentrations and the characteristic parameters for soot formation in the engine cylinder were obtained by coupling a detailed chemical kinetic model with the three-dimensional computational fluid dynamic (CFD) model. Comparison of the simulated results with limited experimental data shows that the chemical mechanisms and soot model are realistic and correctly describe the basic physics of diesel combustion but require further development to improve their accuracy.     

Dimension-Splitting for Simplifying Diffusion in Lattice-Gas Models

We introduce a simplified technique for incorporating diffusive phenomena into lattice-gas molecular dynamics models. In this method, spatial interactions take place one dimension at a time, with a separate fractional timestep devoted to each dimension, and with all dimensions treated identically. We show that the model resulting from this technique is equivalent to the macroscopic diffusion equation in the appropriate limit. This technique saves computational resources and reduces the complexity of model design, programming, debugging, simulation and analysis. For example, a reaction-diffusion simulation can be designed and tested as a one-dimensional system, and then directly extended to two or more dimensions. We illustrate the use of this approach in constructing a microscopically reversible model of diffusion-limited aggregation as well as in a model of growth of biological films.     

Enhanced conductivity in ionic conductor-insulator composites: numerical models in two and three dimensions

We describe a two-dimensional (2D) and a three-dimensional (3D) percolation model for ionic conductor-insulator composites such as copper(I) bromide-titanium dioxide (CuBr-TiO₂) or lithium iodide-alumina (LiI-Al₂O₃). These composites present an enhanced conductivity closely related to the insulator concentration. This effect is explained by the formation of highly conducting space charge regions near the phase boundaries which are represented by good conductor bonds. Our numerical model takes into account grain size and correlation effects. The dimension has a leading role for the conduction properties. In the 2D case, the good conductor bonds do not percolate, whatever the insulator concentration, and the maximum conductivity of the composite samples is of the same order as that of the ionic conductor grains. The behavior of the system is very different in the 3D case where, for a large domain of composition, the good conductors percolate through the regions between the conductor grains. For the CuBr-TiO₂ composites the conductivity versus composition curve is bell-shaped. Conversely, in the LiI-Al₂O₃ system, a linear relation between the conductivity and the insulator volume fraction is obtained in the experiments. Our model gives a plausible interpretation of the conductivity in both systems. Received 10 April 2001     

A generalised model of hydrogen diffusion in metals with multiple trap types

Continuum modelling of hydrogen diffusion in metals, which accounts for both trapping and an imposed force field, is revisited. A generalised model of hydrogen diffusion and trapping is developed as a continuous interpretation of the discrete random-walk theory. A system of nonlinear equations describing the phenomenon of diffusion with multiple types of traps is derived without the assumption of a local equilibrium among hydrogen populations in dissimilar positions. Lattice-trap interchange kinetics can degenerate into local equilibrium as a limit case. Moreover, certain terms in general equations may be negligible in specific situations. By removing these terms, known particularised models of hydrogen diffusion and trapping are recovered. Determining the terms, which are disregarded in reduced models, enables a straightforward assessment of the applicability of these models. The advantages and limitations of particularised models applied to hydrogen embrittlement analyses are discussed.     

多孔建材中VOC扩散系数的两尺度模型

基于对建材微观结构的分析和压汞实验,提出了预测建材中有机挥发物(VOC)扩散系数的宏观一介观两尺度模型.和传统的从压汞实验计算扩散系数方法不同的是,本模型不仅考虑了孔隙率,还对孔的尺度分布和孔的连接方式进行了研究和分析.三种不同中密度板中VOC的散发实验表明,采用新模型计算的扩散系数比文献中的传统模型更好地吻合实验数据.     

Self-diffusion in simple models: Systems with long-range jumps

We review some exact results for the motion of a tagged particle in simple models. Then, we study the density dependence of the self-diffusion coefficientD _N() in lattice systems with simple symmetric exclusion in which the particles can jump, with equal rates, to a set ofN neighboring sites. We obtain positive upper and lower bounds onF _N()=N{(1–)–[D_N()/D_N(0)]}/[(1–)]x for [0, 1]. Computer simulations for the square, triangular, and one-dimensional lattices suggest thatF _N becomes effectively independent ofN forN20.     

End-to-end correlation for a C-12 hydrocarbon chain

The 19F nuclear spin-lattice relaxation rate constants were measured as a function of magnetic field strength for 1,12-diaminododecane labeled at one end with a nitroxide radical and at the other with a trifluoromethyl group. The magnetic relaxation dispersion profile (MRD) reports the spectral density function appropriate to the end-to-end correlation function for the doubly labeled molecule. After extrapolation to zero concentration to eliminate the intermolecular relaxation contribution to relaxation, the resulting intramolecular MRD profile was compared with several model approaches. The rotational model for the spectral density functions as included in the Solomon-Bloembergen-Morgan equations does not describe the data well. The earlier model of Freed for nuclear spin relaxation induced by a freely diffusing paramagnetic co-solute is not rigorous for this case because the paramagnet is tethered to the observed nuclear spin and only a restricted space in the immediate vicinity of the nuclear spin is accessible for pseudo-translational diffusion of one end of the molecule with respect to the other. A generalization of the Torrey model for magnetic relaxation by translational diffusion developed by Nevzorov and Freed, which includes the effect of restrictions imposed by the finite length of the chain, describes the experiment within experimental errors. A simple modification of the Hwang-Freed model that does not specifically include the dynamical effects of the finite tether also provides a good approximation to the data when the tether chain is sufficiently long.