Oxidation of porous nanocrystalline titanium nitride. II. Scale structure and composition

We have used x-ray phase analysis to study the composition of the products of reaction between oxygen and nanocrystalline powders with particle sizes 15, 40, 55, and 80 nm, and also specimens pressed (and sintered) from them. The powders were oxidized in air at 100°C (400 h) to 500°C (5 min), while the sintered specimens were oxidized at 600–900°C for 15, 120, and 240 min. In all cases, in the initial oxidation step the oxynitride Ti(O_xN_y) is formed, which over time is oxidized to TiO, Ti₂O₃, Ti₃O₅, TiO₂ (anatase) and TiO₂ (rutile). In the range 600–800°C, formation of a continuous oxide layer and conversion of anatase to rutile slows down diffusion of oxygen in the scale. We have established that at 900°C, the growth rate of the scale thickness increases and so the reflections from the oxynitride are barely noticeable on the diffraction patterns taken from the surface of the oxidized specimen. In these diffraction patterns, along with strong reflections from the rutile, we also observed weak reflections from lower oxides and anatase, which may be due to reaction between oxygen and the titanium ions diffused to the scale surface. We have concluded that at T > 850°C, the mechanism for oxidation of TiN changes. This is due to superposition of counterdiffusion of titanium ions on the diffusion of oxygen. __________ Translated from Poroshkovaya Metallurgiya, Nos. 3–4(448), pp. 72–78, March–April, 2006.     

同杆并架双回线基于电流突变量的综合选相

相电流差突变量选相元件在单回线故障中具有良好的选相性能，但在同杆双回线跨线故障中可能误选相。利用六序故障分量的分析方法，分析了相电流突变量在同杆双回线跨线故障中的幅值和相位特征，给出了其相位比相方程。在此基础上，提出了一种运用测量阻抗和方向元件相结合的综合选相方法，并给出了选相流程图。仿真结果表明，在双回线简单故障和跨线故障时，基于单回线单端电气量的同杆并架双回线综合选相方法具有较理想的选相性能。     

Modelling thermal degradation of composite materials

A one–dimensional, transient thermal degradation heat transfer model for the response of composite materials when exposed to fire is presented. The model can handle layers of different materials. Material properties are functions of temperature. The reaction can be specified using Arrhenius‐type parameters or by inputting a density–temperature relationship determined by any experimental technique such as thermogravimetric analysis. The model is validated against the experimental data presented in Boyer's 1984 dissertation. Overall, the model provides excellent agreement with the experimental data. It is shown that very little difference is found between results arrived at by Arrhenius kinetics and results obtained by specifying the easier to measure density–temperature relationship. From this it is concluded that this technique is a viable alternative to Arrhenius‐type models. Copyright © 2006 John Wiley & Sons, Ltd.     

The Einstein relation in nanostructured materials: simplified theory and suggestion for experimental determination

An attempt is made to study the Einstein relation for the diffusivity–mobility ratio (DMR) in quantum wells (QWs) and quantum well wires (QWWs) of tetragonal compounds on the basis of a newly formulated electron energy spectrum taking into account the combined influences of the anisotropies in effective electron mass, the spin–orbit splitting, and the presence of crystal field splitting, respectively. The results for quantum-confined III–V compounds form a special case of our generalized analysis. The DMR has also been studied for QWs and QWWs of II–VI and IV–VI materials. Taking QWs and QWWs of CdGeAs₂, InAs, CdS and PbSe as examples, it was found that the DMR increases with increasing carrier statistics and decreasing film thickness respectively in various oscillatory manners emphasizing the influence of dimensional quantizations and the energy band constants in different cases. An experimental method of determining the DMR in nanostructures with arbitrary dispersion laws has also been suggested and the present simplified analysis is in agreement with the suggested relationship. The well-known results for nanostructures with parabolic energy bands have also been obtained as special cases from this generalized analysis under certain limiting conditions.     

Phase equilibria in the system Al-Rh

Methods of differential thermal analysis, x-ray diffraction, microstructural analysis and electron probe microanalysis are used to study alloys of the Al-Rh system over the whole concentration range. It is established that the phase of equiatomic composition AlRh melts congruently at 2060°C and it has an extended range of homogeneity (45.1–54.2 at.% Rh). The solubility of aluminum in rhodium reaches 9 at.%, decreasing to 6 at.% at 850°C. Coordinates are determined for the eutectic point l ⇆ AlRh + 〈Rh〉 as 70 at.% Rh and 1715°C. The existence of intermediate phases, their crystal structure, and also the method of forming phases in the field of composition rich in aluminum given in publications are confirmed. __________ Translated from Poroshkovaya Metallurgiya, Nos. 5–6(449), pp. 48–56, May–June, 2006.     

Hydrogen production in solar reactors

The present work summarizes the recent activities of our laboratory in the field of solar-aided hydrogen production with structured monolithic solar reactors. This reactor concept, “transferred” from the well-known automobile exhaust catalytic after-treatment systems, employs ceramic supports optimized to absorb effectively solar radiation and develop sufficiently high temperatures, that are coated with active materials capable to perform/catalyze a variety of “solar-aided” reactions for the production of hydrogen such as water splitting or natural gas reforming. Our work evolves in an integrated approach starting from the synthesis of active powders tailored to particular hydrogen production reactions, their deposition upon porous absorbers, testing of relevant properties of merit such as thermomechanical stability and hydrogen yield and finally to the design, operation simulation and performance optimization of structured monolithic solar hydrogen production reactors. This approach, among other things, has culminated to the world's first closed, solar-thermochemical cycle in operation that is capable of continuous hydrogen production employing entirely renewable and abundant energy sources and raw materials – solar energy and water, respectively – without any CO₂ emissions and holds, thus, a significant potential for large-scale, emissions-free hydrogen production, particularly for regions of the world that lack indigenous resources but are endowed with ample solar energy.     

（Ba1-xSrx）（Zn1/3Nb2/3）O3微波介质陶瓷温度系数的异常

研究了（Ba1-xSrx）（Zn1/3Nb2/3）O3微波介质陶瓷温度系数的非线性变化以及异常的原因。根据CM公式，随着系统中Sr（Zn1/3Nb2/3）O3的增多，τc的异常是由于氧八面体的畸变导致的相转变（对称性降低）所造成的（晶体结构由无序立方相向有序赝立方相的连续变化）。相转变的发生相应影响了极化以及极化模式，这是造成τc异常的根本原因。