Electrode Reaction Pathway in Oxide Anode for Solid Oxide Fuel Cells

Oxide anodes for solid oxide fuel cells (SOFC) with the advantage of fuel flexibility, resistance to coarsening, small chemical expansion and etc. have been attracting increasing interest. Good performance has been reported with a few of perovskite structure anodes, such as (LaSr)(CrMn)O3. However, more improvements need to be made before meeting the application requirement. Understanding the oxidation mechanism is crucial for a directed optimization, but it is still on the early stage of investigation. In this study, reaction mechanism of oxide anodes is investigated on doped YCrO 3 with H2 fuel, in terms of the origin of electrochemical activity, rate-determining steps (RDS), extension of reactive zone, and the impact from overpotential under service condition to those properties.;H2 oxidation on the YCs anodes is found to be limited by charge transfer and H surface diffusion. A model is presented to describe the elementary steps in H2 oxidation. From the reaction order results, it is suggested that any models without taking H into the charge transfer step are invalid. The nature of B site element determines the H2 oxidation kinetics primarily. Ni displays better adsorption ability than Co. However, H adsorption ability of such oxide anode is inferior to that of Ni metal anode. In addition, the charge transfer step is directly associated with the activity of electrons in the anode; therefore it can be significantly promoted by enhancement of the electron activity. It is found that A site Ca doping improves the polarization resistance about 10 times, by increasing the activity of electrons to promote the charge transfer process.;For the active area in the oxide anode, besides the traditional three-phase boundary (3PB), the internal anode surface as two-phase boundary (2PB) is proven to be capable of catalytically oxidizing the H2 fuel also when the bulk lattice is activated depending on the B site elements. The contribution from each part is estimated by switching the electrolyte to change 3PB kinetics. Compared to Ni, Co doping activates the bulk oxygen more significantly, promoting the reaction at 2PB. The active surface reaction zone is found to be enlarged by the electrolyte with high oxygen activity (SSZ vs. YSZ) when charge transfer is one of the RDS. Due to the larger exchange current for charge transfer in 3PB with SSZ electrolyte, the adsorption gradient zone is broadened, leading to enhanced surface reaction kinetics. The potential application of such finding is demonstrated on SSZ/YSZ/SSZ sandwich, showing largely improved electrode performance, opening a wide door for the utilization of electrolytes that are too expensive, fragile or instable to be used before.;The bulk path way in 2PB reaction can be affected by overpotential in terms of local vacancy concentration, built-in electrical field and stability. It is proven that an uneven distribution of lattice oxygen is established under operation conditions with overpotential by both qualitative analysis and analytic solution. An electrostatic field force is present besides the concentration gradient in the anode lattice to control the motion of oxygen ions. Compared to the usual estimation based on chemical diffusion mechanism, the real deviation of ionic defects concentration under polarization from the equilibrium state near electrode/electrolyte interface is smaller with the built-in electrical field. The overpotential is demonstrated to be able to open up or shut down the bulk pathway depending on the ionic defects of electrodes. The analysis on the bulk pathway in terms of local charged species and various potentials provides new insight in anion diffusion and electrode stability

Existence of generating families on Lagrangian cobordisms

For an embedded exact Lagrangian cobordism between Legendrian submanifolds in the 1-jet bundle, we prove that a generating family linear at infinity on the Legendrian at the negative end extends to a generating family linear at infinity on the Lagrangian cobordism after stabilization if and only if the formal obstructions vanish. In particular, a Lagrangian filling with trivial stable Lagrangian Gauss map admits a generating family linear at infinity.Comment: 16 pages, 1 figure. Comments are welcome

Phase-field modeling of piezoelectrics and instabilities in dielectric elastomer composites

textFerroelectric ceramics are broadly used in applications including actuators, sensors and information storage. An understanding of the microstructual evolution and domain dynamics is vital for predicting the performance and reliability of such devices. The underlying mechanism responsible for ferroelectric constitutive response is ferroelectric domain wall motion, domain switching and the interactions of domain walls with other material defects. In this work, a combined theoretical and numerical modeling framework is developed to investigate the nucleation and growth of domains in a single crystal of ferroelectric material. The phase-field approach, applying the material electrical polarization as the order parameter, is used as the theoretical modeling framework to allow for a detailed accounting of the electromechanical processes. The finite element method is used for the numerical solution technique. In order to obtain a better understanding of the energetics of fracture within the phase-field setting, the J-integral is modified to include the energies associated with the order parameter. Also, the J- integral is applied to determine the crack-tip energy release rate for common sets of electromechanical crack-face boundary conditions. The calculations confirm that only true equilibrium states exhibit path-independence of J, and that domain structures near crack tips may be responsible for allowing positive energy release rate during purely electrical loading. The small deformation assumption is prevalent in the phase-field modeling approach, and is used in the previously described calculations. The analysis of large deformations will introduce the concept of Maxwell stresses, which are assumed to be higher order effects that can be neglected in the small deformation theory. However, in order to investigate the material response of soft dielectric elastomers undergoing large mechanical deformation and electric field, which are employed in electrically driven actuator devices, manipulators and energy harvesters, a finite deformation theory is incorporated in the phase-field model. To describe the material free energy, compressible Neo-Hookean and Gent models are used. The Jaumann rate of the polarization is used as the objective polarization rate to make the description of the dissipation frame indifferent. To illustrate the theory, electromechanical instabilities in composite materials with different inclusions will be studied using the finite element methods.Engineering Mechanic

Behavioral analysis of anisotropic diffusion in image processing

©1996 IEEE. Personal use of this material is permitted. However, permission to reprint/republish this material for advertising or promotional purposes or for creating new collective works for resale or distribution to servers or lists, or to reuse any copyrighted component of this work in other works must be obtained from the IEEE. This material is presented to ensure timely dissemination of scholarly and technical work. Copyright and all rights therein are retained by authors or by other copyright holders. All persons copying this information are expected to adhere to the terms and constraints invoked by each author's copyright. In most cases, these works may not be reposted without the explicit permission of the copyright holder.DOI: 10.1109/83.541424In this paper, we analyze the behavior of the anisotropic diffusion model of Perona and Malik (1990). The main idea is to express the anisotropic diffusion equation as coming from a certain optimization problem, so its behavior can be analyzed based on the shape of the corresponding energy surface. We show that anisotropic diffusion is the steepest descent method for solving an energy minimization problem. It is demonstrated that an anisotropic diffusion is well posed when there exists a unique global minimum for the energy functional and that the ill posedness of a certain anisotropic diffusion is caused by the fact that its energy functional has an infinite number of global minima that are dense in the image space. We give a sufficient condition for an anisotropic diffusion to be well posed and a sufficient and necessary condition for it to be ill posed due to the dense global minima. The mechanism of smoothing and edge enhancement of anisotropic diffusion is illustrated through a particular orthogonal decomposition of the diffusion operator into two parts: one that diffuses tangentially to the edges and therefore acts as an anisotropic smoothing operator, and the other that flows normally to the edges and thus acts as an enhancement operator