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.     

复合聚全氟乙丙烯材料的介电及高频击穿性能研究

在聚全氟乙丙烯(FEP)中添加 TiO_2和 Al_2O_3,通过热压成型的方法制备了 FEP/TiO_2复合材料和 FEP/Al_2O_3复合材料,研究了氧化物添加量对复合材料介电常数、介电损耗和高频击穿性能的影响。结果表明,随氧化物含量的增加,复合材料的介电常数和介电损耗均增加;在同一添加量下,TiO_2对复合体系的介电性能影响较大。FEP/TiO_2复合材料的高频击穿性能随 TiO_2含量的增加而下降,在 TiO_2含量为4.0%(质量分数,下同)时,复合材料的损伤阈值已降为 FEP 材料损伤阈值的48.9 %。而 FEP/Al_2O_3复合材料的高频击穿性能随 Al_2O_3含量的增加而升高,当 Al_2O_3含量为1.2%时,复合材料的损伤阈值已增大到 FEP 材料损伤阈值的2倍,达到313 J/m~2。     

The flame retardant mechanism of polyolefins modified with chalk and silicone elastomer

This paper presents the current understanding of the flame retardant mechanism of Casico?. The study includes the flame retardant effect of each individual component: ethylene–acrylate copolymer, chalk and silicone elastomer, as well as the formation of an intumescent structure during heating. The flame retardant properties were investigated by cone calorimetry and oxygen index tests. To obtain insight into the flame retardant mechanism, heat treatment under different conditions has also been performed. The results indicate that the flame retardant mechanism of Casico is complex and is related to a number of reactions, e.g. ester pyrolysis of acrylate groups, formation of carbon dioxide by reaction between carboxylic acid and chalk, ionomer formation and formation of an intumescent structure stabilized by a protecting char. Special emphasis is given to the formation of the intumescent structure and its molecular structure as evaluated from ¹³C MAS‐NMR and ²⁹Si MAS‐NMR, ESCA and XRD analysis. After treatment at 500°C the intumescent structure consists mainly of silicon oxides and calcium carbonate and after treatment at 1000°C the intumescent structure consists of calcium silicate, calcium oxide and calcium hydroxide. Copyright © 2003 John Wiley & Sons, Ltd.     

Rutile-type TiO2 thin film for high-k gate insulator

We investigated rutile-type titanium dioxide (TiO₂) films for possible use as a high-k gate insulator. The TiO₂ thin films were directly deposited on Si substrates using a RF magnetron sputtering method with a sintered oxide target. A single phase of rutile-type TiO₂ whose dielectric constant of approximately 75 was obtained when the film was deposited in an inert gas atmosphere and annealed at 800 °C in an oxidizing gas atmosphere. The oxygen ions were deficient in the as-deposited film, and consequently, a sufficient oxygen supply was needed to crystallize the film to a single phase of rutile during the post-annealing. However, the interfacial SiO₂ layer between the TiO₂ and the Si substrate simultaneously grew thicker than 2 nm. As the interfacial SiO₂ grew, the leakage current was decreased and the equivalent oxide thickness was increased, in the Au/rutile-type TiO₂/Si capacitor. Therefore, we concluded that the growth of the interfacial SiO₂ layer thicker than 2 nm is inevitable to form the single phase of rutile-type TiO₂ and to decrease the leakage.     

Nanoweb Formation: 2D Self‐Assembly of Semiconductor Gallium Oxide Nanowires/Nanotubes

This paper reports a method to produce networks of crystalline gallium oxide comprised of one‐dimensional (1D) nanostructures. Because of the unique arrangement of wires, these crystalline networks are termed as ‘nanowebs’. Nanowebs are of great technological interest since they contain wire densities of the order of 10⁹ cm^–2. A possible mechanism for the fast self‐assembly of crystalline metal oxide nanowires involves multiple nucleation and coalescence via oxidation–reduction reactions at the molecular level. The preferential growth of nanowires parallel to the substrate enabled them to coalesce into regular polygonal networks. The individual segments of the polygonal network consist of both nanowires and nanotubules of β‐gallium oxide. Individual wire properties contribute to a nanoweb’s overall capacity and the implications for devices based on nanowebs are expected to be enormous.     

Catalytic dehydrogenation of ethylbenzene with carbon dioxide: promotional effect of antimony in supported vanadium–antimony oxide catalyst

Alumina-supported vanadium oxide, VO_x/Al₂O₃, and binary vanadium–antimony oxides, VSbO_x/Al₂O₃, have been tested in the ethylbenzene dehydrogenation with carbon dioxide and characterized by S_BET, X-ray diffraction, X-ray photoelectron spectroscopy, hydrogen temperature-programmed reduction and CO₂ pulse methods. VSbO_x/Al₂O₃ exhibited enhanced catalytic activity and especially on-stream stability compared to VO_x/Al₂O₃ catalyst. Incorporation of antimony into VO_x/Al₂O₃ increased dispersion of active VO_x species, enhanced redox properties of the systems and formed a new mixed vanadium–antimony oxide phase in the most catalytically efficient V_0.43Sb_0.57O_x/Al₂O₃ system.     

Properties and Performance of Cation-Doped Ceria Electrolyte Materials in Solid Oxide Fuel Cell Applications

Cation-doped CeO₂ electrolyte has been evaluated in single-cell and short-stack tests in solid oxide fuel cell environments and applications. These results, along with conductivity measurements, indicate that an ionic transference number of ∼0.75 can be expected at 800°C. Single cells have shown a power density >350 mW/cm². Multicell stacks have demonstrated a peak performance of >100 mW/cm² at 700°C using metallic separators.     

超细铁粉和氧化铁颗粒的研究

用透射电镜和图像分析仪等研究了超细铁粉和γ-Fe_2O_3粉末的结构、形貌、粒子的平均尺寸以及粒度分布。研究结果表明,多数超细铁粉粒子近似呈球形,并且,铁粉粒子由两相组成,粒子的核心部分是金屑a-Fe,表面的包裹层为氧化物层,它由Fe_3O_4和7-Fe_O_3的混合物组成。氧化层的平均厚度大约占整个粒子直径的20％左右。羰基铁粉粒子(含氧化层)的平均直径为16nm。直径在4～24nm范围的粒子数占总粒子数的91％,而7-Fe_2O_3粉末既有雪茄状粒子,也有小球状粒子。分析表明,球状粒子的平均直径为113nm,雪茄状粒子的平均直径(按<长 宽>/2计算)为148nm。由于超细铁粉粒子很细,且有磁性,制备电镜试样时分散比较困难。本文比较了几种分散方法后,使用了一种较好的分散方法——超声喷管分散法。     

生物降解型聚碳酸顺丁烯二酸亚乙酯 1、合成和表征

用CO_2、环氧乙烷、顺丁烯二酸酐进行三元共聚首次得到聚碳酸顺丁烯二酸亚乙酯(PECM),并用IR、~1H NMR、DSC等进行了表征,共聚物链中CO_2和MA单元随机分布,不饱和单元可在0～0.5mol分数之间调节。共聚过程不发生双键交联和构型转化。环氧乙烷的转化率可高达到93％。控制PECM链上的双键含量并使之发生自由基加成反应,得到对热较稳定的可溶性产物。     

Electrochemical intercalation in NiOx thin films

In this work we investigated the mechanism of the electrochemical intercalation reactions in rf sputtered nickel oxide thin films electrodes by two techniques: mechanical stress change measurements by means of an optical technique and mass changes using an electrochemical quartz microbalance (EQCM). The experiments were performed in alkaline electrolytes containing cations of the first column of the periodic table. Reversible mass and volume changes were observed. In order to explain these experimental results, an exchange reaction is proposed, in which the oxidation process is accompanied by the deinteractional of a relative large number of “light” cations, simultaneously with the intercalation of a smaller number of heaviest cations.