Ru-catalyzed anode materials for direct hydrocarbon SOFCs

A solid oxide fuel cell using a thin ceria-based electrolyte film with a Ru-catalyzed anode was directly operated on hydrocarbons, including methane, ethane, and propane, at 600 °C. The role of the Ru catalyst in the anode reaction was to promote the reforming reaction of the unreacted hydrocarbons by the produced steam and CO₂, which avoided interference from steam and CO₂ in the gas-phase diffusion of the fuels. The resulting peak power density reached 750 mW cm⁻² with dry methane, which was comparable to the peak power density of 769 mW cm⁻² with wet (2.9 vol.% H₂O) hydrogen. More important was the fact that the cell performance was maintained at a high level regardless of the change in the methane utilization from 12 to 46% but was significantly reduced by increasing the hydrogen utilization from 13 to 42%. While the anodic reaction of hydrogen was controlled by the slow gas diffusion, the anodic reaction of methane was not subject to the onset of such a gas-diffusion process.     

Integrated-optic double-ring resonators with a wide free spectralrange of 100 GHz

Integrated-optic double-ring resonators with a wide free spectral range (FSR) of 100 GHz are fabricated using GeO₂-doped silica waveguides with a high relative refractive index difference (Δ) of 1.5%. The resonators are composed of two ring resonators comprising small ring waveguides with radii of 1.75 and 2.0 mm. The double-ring resonator module exhibited a wide FSR of 98.0 GHz, a finesse of higher than 138, a low crosstalk of less than -11.7 dB, and a low insertion loss of 6.1 dB. The measured FSR of 98.0 GHz is wider than any previously reported ring resonator composed of optical waveguides     

Microstructural observation and reaction mechanism of ZnAI2O4 formation in the presence of various fluorides

The rates of ZnAI₂O₄ formation in the presence of various fluorides were controlled by the nucleation process. The rate constants of the nucleation process for various fluorides were in the order LiF > NaF and MgF₂ > CaF₂ < SrF₂ < BaF₂. This trend corresponds to the order of the promotion of ZnAI₂O₄ formation by these fluorides. In order to interpret the dependence of the kinetic constant of the nucleation of ZnAI₂O₄ from the intermediate phase on the kinds of counter cation of fluorides, it was assumed that the activated state for promotive formation of ZnAI₂O₄ under the presence of fluoride is similar to that of the following reaction: $$ZnO + Al_2 O_3 + 2MF\left( {M'F_2 } \right) = ZnF_2 + M_2 Al_2 O_4 \left( {M'Al_2 O_4 } \right).$$ The order of the rate constant obtained in this study showed agreement with the order of the standard heats of formation for the above reaction. This relation was interpreted by applying the linear free energy relationship (LIFER).     

Influence of Metal Ions on the Order-Disorder Transition Temperature of the Ba-M-O (M: La, Y, In, or Ga) System

Preparation of BaLa₂O₄, B_a3,Y₄O₉, B_a,In₂O₅, and Ba₃Ga₂O₆ powders and their sintering were investigated in Ar or air. These sintered bodies with perovskite-related structure were synthesized by reaction sintering, using mixed powders in the atomic ratios of Ba/La = 1, Ba/Y = 0.75, Ba/In = 1, and Ba/Ga = 1.5. The order-disorder transition temperatures of the BaLa₂O₄, Ba₃Y₄O₉, Ba₂In₂O₅, and Ba₃Ga₂O₆ sintered bodies were 270°, 350°, 880°, and 123O^oC, respectively. It was found that the temperatures were influenced by the ionic radius of cations in B sites, and the transition temperatures decreased with increasing ionic radius.     

Design of High-Quality Pt–CeO2 Composite Anodes Supported by Carbon Black for Direct Methanol Fuel Cell Application

A Pt on nano-sized CeO₂ particles that in turn are supported on carbon black (CB) was synthesized using the co-impregnation method. This potential anode material for fuel cell applications was synthesized in a stepwise process. The pure CeO₂ was synthesized using an ammonium carbonate precipitation method, and the Pt particles dispersed on the CeO₂ in such a way that a uniform dispersion with the CB was obtained (Pt–CeO₂/CB). The electrochemical activity of the methanol (CH₃OH) oxidation reaction on the Pt–CeO₂/CB was investigated using cyclic voltammetry and chronoamperometry experimentation. The onset potential of CH₃OH oxidation reaction on the Pt–CeO₂/CB anode was shifted to a lower potential as compared with that on commercially available Pt–Ru/carbon (C) alloy anode. In addition, the activation energy of the Pt–CeO₂/CB anode was much lower than that of the Pt–Ru/C alloy anode. Moreover, the current density of the Pt–CeO₂/CB anode was much higher than that of the Pt–Ru/C alloy anode at temperatures between 28° and 60°C. These results suggest that the anode performance of the Pt–CeO₂/CB anode at the operating temperature of typical fuel cells (80°C) is superior to that of the more usual Pt–Ru/C alloy anode. Importantly, the rare metal, Ru, is not required in the present anode material and the amount of Pt required is also significantly reduced. As a consequence, we report a promising candidate Pt–CeO₂/CB composite anode for application in the development of direct methanol fuel cells.     

Electrochemical removal of both NO and CH4 under lean-burn conditions

An electrochemical cell, Pd|YSZ|Pd, was constructed in order to remove both NO and CH₄ in the presence of excess oxygen. When direct current was supplied to the cell with a flow of a mixture of NO, CH₄, O₂, H₂O and CO₂ at 700° C, NO was reduced to nitrogen at the cathode, and CH₄ was oxidized to CO _x at both the anode and cathode. At the cathode, the reduction of NO and the oxidation of CH₄ proceeded with the removal of chemisorbed oxygen species from the Pd surface, and at the anode, the oxidation of CH₄ was enhanced by forming an active oxygen atom.     

Low-Temperature Synthesis of ZrC Powder by Cyclic Reaction of Mg in ZrO2–Mg–CH4

We investigated the conditions for low-temperature synthesis of ZrC fine powder from ZrO₂–Mg–CH₄. The synthesis utilizes a thermite-type reaction, with Mg as the reducing agent, and a reaction between Mg and CH₄ gas as a carbon source. The Mg/ZrO₂ molar ratio as well as the heating rate were varied. Because C can be continuously fed into the reaction group by the cyclic reaction of Mg through the formation and decomposition of Mg₂C₃ (2Mg + 3CH₄→ Mg₂C₃+ 6H₂→ 2Mg + 3C), a molar ratio of 2.2 for Mg/ZrO₂ was sufficient for the synthesis of single-phase ZrC. ZrC powders were synthesized under the following conditions: Mg/ZrO₂ molar ratio = 2.2, heating rate = 20°C/min, and temperature maintained at 750°C for 30 min. The amount of reaction heat produced in the reduction reaction of ZrO₂ by Mg depended on the Mg/ZrO₂ molar ratio, specifically, the amount of ZrO₂ contained. Moreover, the cyclic reaction of Mg-Mg₂C₃–Mg was influenced by the amount of reaction heat described above and by the heating rate. The ZrC fine powder showed little aggregation and high dispersibility.     

Differential expression of ICAM-1 and LFA-1 versus L-selectin and VCAM-1 in autoimmune insulitis of NOD mice and association with both Th1- and Th2-type infiltrates

The infiltration of pancreatic islets by mononuclear cells is the hallmark of the development of insulin dependent diabetes mellitus (IDDM) in the NOD mouse, an animal model for human IDDM. The aim, of this study was to correlate adhesion molecule expression with the degree of islet infiltration and to compare Th1- and Th2-driven islet inflammation. Cryostat sections of NOD mouse pancreata before and after diabetes development were analysed by semiquantitative immunohistochemistry. NOD mouse islets did not show the expression of ICAM-1, LFA-1, L-selectin and VCAM-1 prior to infiltration by mononuclear cells. Furthermore, islets with early stage insulitis (grade 1, periinsular location of small infiltrates) still were devoid of adhesion molecule expression. ICAM-1 and LFA-1 were first demonstrable in islets with strong periinsular infiltrates (insulitis grade 2) while L-selectin and VCAM-1 were only seen in islets with mild or strong intraislet infiltration (grade 3-4). Adhesion molecules were demonstrable in areas of macrophage and T-lymphocyte infiltrates but not in adjacent endocrine islet tissue. Islets of all infiltration stages contained Th2 lymphocytes (positive for IL-4). Substantial numbers of Th1 cells (positive for IFN-gamma, TNF-alpha, IL-2 and/or IL-2 receptor) were observed only after acceleration of diabetes development by a single injection of cyclophosphamide (250 mg/kg i.p.). Interestingly, the adhesion molecule expression pattern in islets with "Th1' versus "Th2 insulitis' was not different. In conclusion, the expression of adhesion molecules in islets during the development of autoimmune diabetes does not precede mononuclear infiltration but probably occurs in response to the activation of initial small infiltrates. ICAM-1 and LFA-1 expression is seen prior to L-selectin and VCAM-1. However, adhesion molecule expression during Th1 versus Th2 cell infiltration is very similar, suggesting similar adhesion molecule requirements of the two Th subsets.     

Proton conduction at the surface of Y-doped BaCeO3 and its application to an air/fuel sensor

25 mol% Y³⁺-doped BaCeO₃ (BCY25) showed an extremely low activation energy of 0.3 eV for proton conduction at the surface. The resulting overall conductivity at the surface reached 8.24 × 10^–3 S cm^–1 at 400°C, which was 3, 8, and 28 times higher than those in the bulk of BCY25, 20 mol% Sm³⁺-doped ceria, and 8 mol% yttria-stabilized zirconia, respectively. Such fast proton conduction enabled an air/fuel (A/F ) sensor using BCY25 as the solid electrolyte to work above 150°C for H₂ and above 250°C for C₂H₄.     

基于数据可视化技术的逆变器用T型滤波器优化设计方法

以提高滤波器对非线性负载的适应性和整机功率密度为目的,提出一种用四维可视化技术优化非对称T型滤波器的设计方法。优化目标为降低输出阻抗和提高系统功率因数,取值范围由四维表现图的交域构成;截止角频率等约束条件的选择充分考虑到器件的电流负担和电压应力;整个设计过程在四维表现图、两参数变化的根轨迹和Bode图的可视化条件下进行,便于把握多目标函数的变化趋势,进而综合考虑各方面的因素来确定最优解。实验结果和相关数据表明所设计的低通滤波器达到了带约束条件的多目标优化目的,且该方法也可用于类似的工程优化设计。