Single chamber Solid Oxide Fuel Cells selective electrodes: A real chance with brownmillerite-based nanocomposites

In this contribution brownmillerite-based nanocomposite cathode for Single-Chamber Solid Oxide Fuel Cells is developed. These cells can be very attractive especially for small and cheap devices because of the absence of seals. The efficiency of SC-SOFCs is strictly connected to the selectivity of anode and cathode, the bottleneck for this technology. The development of a cathode inert in fuel oxidation is particularly challenging. Our strategy is to start from a catalytically un-active support (CFA = Ca₂FeAl_0.95Mg_0.05O₅) and induce the formation of iron oxide based nanoparticles, expected to activate oxygen. Symmetric (CFA + FeO_x/CGO/CFA + FeO_x) and complete cells (CFA + FeO_x/CGO/Ni-CGO) are studied in air and methane/oxygen 2:1 mixture. The Area Specific Resistance of CFA + FeO_x is less than 1/3 that of CFA. The high selectivity allows to reach an efficiency of 25%; power still needs to be increased but we demonstrated the possibility to develop selective low cost electrodes. The effect of air, methane/oxygen exposure and the heat treatments were carefully investigated.     

Colloidal Synthesis of Hollow Cobalt Sulfide Nanocrystals

Formation of cobalt sulfide hollow nanocrystals through a mechanism similar to the Kirkendall Effect has been investigated in detail. It is found that performing the reaction at > 120 °C leads to fast formation of a single void inside each shell, whereas at room temperature multiple voids are formed within each shell, which can be attributed to strongly temperature‐dependent diffusivities for vacancies. The void formation process is dominated by outward diffusion of cobalt cations; still, the occurrence of significant inward transport of sulfur anions can be inferred as the final voids are smaller in diameter than the original cobalt nanocrystals. Comparison of volume distributions for initial and final nanostructures indicates excess apparent volume in shells, implying significant porosity and/or a defective structure. Indirect evidence for fracture of shells during growth at lower temperatures was observed in shell‐size statistics and transmission electron microscopy images of as‐grown shells. An idealized model of the diffusional process imposes two minimal requirements on material parameters for shell growth to be obtainable within a specific synthetic system.     

新型高K栅介质ZrO2薄膜材料的制备及表征

采用超高真空电子束蒸发法制备了新型高 K栅介质-非晶 ZrO2薄膜. X射线光电子能谱 (XPS) 中 Zr3d5/2 和 Zr3d3/2 对应的结合能分别为 182.1eV和 184.3eV, Zr元素的主要存在形式为 Zr4+,说明薄膜由完全氧化的 ZrO2组成 ,并且纵向分布均一.扩展电阻法( SRP)显示 ZrO2薄膜的 电阻率在 108Ω@ cm以上,通过高分辨率透射电镜( HR- XTEM)可以观察 ZrO2/Si界面陡直,没有 界面反应产物 ,证明 600℃快速退火后 ZrO2薄膜是非晶结构.原子力显微镜( AFM)表征了薄膜的 表面粗糙度,所有样品表面都很平整,其中 600℃快速退火样品 (RTA)的 RMS为 0.480nm.     

Effect of Sb implantation on copper silicides formation and morphology after annealing of Cu/Si structures

In this work, the solid state reaction between a thin film of copper and silicon has been studied using Rutherford backscattering spectroscopy, X-ray diffraction, scanning electron microscopy and microprobe analysis. Cu films of 400 and 900 Å thicknesses are thermally evaporated on Si(1 1 1) substrates, part of them had previously been implanted with antimony ions of 5×10¹⁴ or 5×10¹⁵ at. cm⁻² doses. The samples are heat-treated in vacuum at temperatures in the range 200–700 °C for various times. The results show the growth and formation of Cu₃Si and Cu₄Si silicides under crystallites shape dispatched on the sample surface, independently of the implantation dose. On the other hand, it is established that the copper layer is less and less consumed as the antimony dose increases, resulting in the accumulation of Sb⁺ ions at silicide/Si interface and in the silicide layer close to surface. The exposure of samples to air at room temperature shows the stability of Cu₄Si phase whereas the Cu₃Si silicide disappears to the benefit of the silicon dioxide formation. The observed phenomena are discussed.     

柳钢新建氧化球团工程的设计特点

介绍了柳钢新建120万t／a链篦机-回转窑氧化球团工程的主要设计特点。该工程是我国第一条自行设计、设备国产化和采用清洁气体能源的链篦机-回转窑生产线。它的顺利投产，标志着我国炼铁炉料生产技术有了一个新的进步。     

Effects of surface roughness of substrates on the c-axis preferred orientation of ZnO films deposited by r.f. magnetron sputtering

The c-axis preferred orientation of ZnO film is the most important factor for its successful application in piezoelectric devices. The effects of surface roughness of the substrate on the c-axis preferred orientation of ZnO thin films, deposited by radio frequency magnetron sputtering, were investigated. During sputtering, the oxygen content in the argon environment used was varied from 0 to 70% at a total sputtering pressure of 10 mTorr. Very smooth Si, smooth evaporated Au/Si, smooth evaporated-Al/Si, and rough sputtered-Al/Si were used as substrates. Their r.m.s. roughnesses, as measured by atomic force microscopy, were 1.27, 17.1, 21.1 and 65-118 Å, respectively. The crystalline structure and the angular spread of the (0 0* 2) plane normal to the ZnO films were determined using X-ray diffraction and X-ray rocking curves, respectively. The crystallinity and the preferred c-axis orientation of the ZnO films were strongly dependent on the surface roughness of the substrates rather than on the oxygen content of the working environment or on the chemical nature of the substrate.     

Effect of oxygenation on electrocatalysis of La0.6Ca0.4CoO3−x in bifunctional air electrode

A vacuum-annealed La_0.6Ca_0.4CoO_3−x was consecutively oxygenated in air at temperatures decreasing from 800 to 100 °C, and its electrocatalytic activities for oxygen reduction and evolution were then measured as a function of the oxygenation temperature. The valence of Co cation, changing between +2 and +3, was found susceptible to annealing either in vacuum or air. The catalytic activities initially decrease monotonically as the oxygenation temperature was decreased from 800 to 300 °C, as a result of increasing oxygen content, and then rise abruptly with the oxygen reduction activity reaching a maximum at 200 °C and the oxidation activity at 150 °C. X-ray photoelectron spectroscopy analysis indicated that the enhancements by the low-temperature oxygenation involved increased OH coverage and less charged cations at surface. The results clearly reveal the importance of the post-calcination annealing process for optimizing the performance of La_0.6Ca_0.4CoO_3−x in air electrode applications.     

Influence of iron oxide pigments on the properties of concrete interlocking blocks

Concrete interlocking blocks (CIBs) are utilized in a variety of commercial, municipal, and industrial applications. Superior engineering properties, low maintenance, ease of placement and removal, reuse of original blocks, aesthetic appeal, and immediate availability are the primary reasons for choosing concrete block pavement over other paving surfaces. It is a common practice to pigment building materials, such as mortar, concrete pavers, concrete roof tiles, and prefabricated concrete products; CIBs are colored using iron oxide pigments. This article presents experimental results detailing the properties of CIBs dyed with pigments. The results of these experiments are as follows: Because the particles of iron oxide pigments are finer than those of brown iron oxide, interlocking blocks mixed with the former acquired higher color strength than with the latter. Additional analysis determined a definite relationship between the flexural strength and the absorption ratio of pigment-dyed blocks; the correlation coefficient (R²) of interlocking blocks at 91 days was .90. It is suggested that if iron oxide pigments are to be used to color CIBs, the pigment-to-cement ratio should be below 4%.