Oxidation of Silicon Carbide in Environments Containing Potassium Salt Vapor

At high temperatures in clean oxidizing environments, SiC forms a very protective SiO₂ film, but, in environments containing low levels of gaseous alkali salt contaminants or where condensed salts may deposit on the surface, the resistance of the film is significantly reduced. Oxidation kinetics of SiC were measured by continuous thermogravimetric analysis in a controlled environment containing CO₂, H₂O, and O₂ plus low levels of potassium-containing salts. Potassium was found to be incorporated into the SiO₂ scale and to significantly change its transport properties and its morphology. The rate of scale formation was found to increase directly in proportion to K in the scale. A change in mechanism was observed when water vapor was added to the reacting gas stream.     

Fabrication of sharp silicon tips employing anisotropic wet etching and reactive ion etching

We developed a process to obtain sharper silicon tips by employing anisotropic etching in a KOH solution followed by SF₆ plasma etch. The tips were further sharpened using the established thermal oxidation technique to decrease the cone angle and, therefore, obtain smaller curvature radii. We have analyzed the impact of such changes in geometry on a figure of merit associated with the field emission characteristics. An increase in the figure of merit by a factor of three was found in relation to the tips before sharpening.     

Ti-silicalite as catalyst for gas-phase ammoximation of cyclohexanone with molecular oxygen

The catalyst behaviour of titanium silicalite, which was found the most active and selective catalyst for liquid-phase ammoximation of cyclohexanone to the corresponding oxime with hydrogen peroxide, was investigated in the gas-phase ammoximation with molecular oxygen in and compared with those of pure silicalite and samples of vanadium and chromium silicalites. The results showed that Ti-silicalite is a selective catalyst not only in the reaction with hydrogen peroxide but also in the reaction with molecular oxygen. However, a big limitation was found in the poor activity of the silicalites which do not allow to reach high oxime yields.     

Catalytic wet air oxidation of butyric acid solutions using carbon-supported iridium catalysts

Aqueous solutions of butyric acid were treated by catalytic wet air oxidation using carbon-supported iridium catalysts in a stirred reactor. Under the operating conditions of 6.9 bar of oxygen partial pressure and 200 °C of temperature, conversions up to 52.9% after 2 h were obtained depending on the type of catalyst used. The effects of butyric acid initial concentration, loading of catalyst, oxygen partial pressure and temperature were investigated and the empirical rate law for acid conversion is presented. Oxidation intermediates such as propionic and acetic acid were identified. The heterogeneous catalyzed free-radical oxidation of butyric acid is discussed.     

Electrochemical improvement of low-temperature petroleum cokes by chemical oxidation with H2O2 for their use as anodes in lithium ion batteries

The electrochemical performance of non-graphitized petroleum cokes has been improved by mild oxidation using hydrogen peroxide, a procedure used for the first time in these materials. For this purpose, various carbonisation temperatures and H₂O₂ treatments were tested. For low sulfur content cokes, the aqueous oxidative treatment significantly increases the capacity values above 372 mAh/g during the first cycles. In contrast, cokes with a sulfur content of ca. 5%, did not shown a real improvement. The former results have been interpreted in terms of an effective oxidation of the particles surface, which removes unorganized carbon, where lithium can be irreversibly trapped. Moreover, a stable and less resistive passivating layer grows during the first discharge of lithium, as revealed by impedance spectroscopy. Therefore, chemical procedures, as mild oxidation, open an interesting field of research for the improvement of disordered carbons as anode materials in lithium ion batteries.     

用添加剂改善柴油的颜色稳定性

利用实验室筛选出的一种柴油安定性改进剂改善柴油的颜色稳定性。贮存实验表明：成品柴油(催化裂化柴油组分占30％)中加入该剂300～400μg/g，可改善比色0．5-1．5个号，同时可抑制柴油氧化沉渣的生成，改善柴油的氧化安定性和颜色稳定性。     

Phase Composition of Oxide Scales during Reheating in Hot Rolling of Low Carbon Steel

Low carbon steel was oxidized over the temperature range 1000‐1250°C in O₂‐CO₂‐H₂O‐N₂, O₂‐H₂O‐N₂, and O₂‐CO₂‐N₂ gas mixtures. Oxidation times were 12‐120 min. and the scales were 50‐2000 μm thick. The variations of these parameters were chosen to elucidate the phase composition of oxide scales under conditions similar to those of reheating furnaces in hot strip mills, using either thin slab casting or conventional casting and rolling technology. Two types of scales have been observed which are influenced by the furnace atmosphere, oxidation time, and temperature. The first type is a crystalline scale with an irregular outer surface, composed mostly of wustite (FeO), and a negligible amount of magnetite (Fe₃O₄). The second type is the classical three‐layer scale, composed of wustite (FeO), magnetite (Fe₃O₄), and hematite (Fe₂O₃). In general, the experiments showed that an increase in oxidation time decreased the percentage of wustite while the percentages of magnetite and hematite increased. A rise in oxygen concentration in the gas mixture increased the percentages of magnetite and hematite, confirming earlier experimental findings. In water vapour‐free atmospheres O₂‐CO₂‐N₂, the oxide scales had a low percentage of wustite, and high percentage of magnetite and hematite. Carbon dioxide showed a small influence at 1100°C, and a negligible one at 1250°C.     

Effect of temperature on methyl radical generation over Sr/La2O3 catalysts

The role of gas phase CH₃ radicals in the oxidative coupling of CH₄ over 1 wt% Sr/La₂O₃ is supported by the observations that (i) this is a very effective catalyst for the generation of CH₃ · radicals and (ii) the concentration of CH₃ · radicals increases with temperature over the range of 450 °C–800 °C.     

Fractionation and characterisation for antioxidant activity of hydrolysed whey protein

Whey protein isolate (WPI) was hydrolysed for 1 h using Alcalase, Protamex and Flavourzyme. Native WPI, hydrolysed WPI and two commercial WPI hydrolysates were subjected to fractionation by size exclusion chromatography. Antioxidant activity of WPI fractions was measured with a liposome‐oxidising system (50 µM FeCl₃/0.1 µM ascorbate, pH 7.0). Lipid oxidation was measured as thiobarbituric acid‐reactive substances (TBARS). Gel electrophoresis and amino acid analysis were run to identify the peptide composition. The influence of amino acid composition on antioxidant activity was evaluated using multivariate analysis methods (correlation analysis, principal component analysis, multiple linear regression and discriminant analysis). TBARS assays indicated the presence of antioxidant activity in all protein fractions, including non‐hydrolysed WPI. For native and hydrolysed WPI samples the first fraction (> 45 kDa) showed a higher TBARS inhibition effect (24–27%) when compared with lower‐molecular‐weight fractions and hydrolysate mixtures. In contrast, for commercial WPI hydrolysates a higher inhibitory effect was found in most of the lower‐molecular‐weight fractions (30–55%). The ability of WPI fractions to delay lipid oxidation was found to be related to the prevalence of histidine and hydrophobic amino acids. Copyright © 2004 Society of Chemical Industry     

La-OMS-2催化剂催化甲苯氧化制苯甲醛

合成了氧化锰八面体(OMS-2)分子筛,采用离子交换法和浸渍法制备了稀土金属La改性的OMS-2分子筛(La-OMS-2)催化剂,并用于甲苯液相选择性氧化制苯甲醛,考察了催化剂用量、反应温度、反应时间、氧气流量及溶剂种类对甲苯转化率和苯甲醛选择性的影响,对La-OMS-2催化剂进行了X射线衍射表征和BET比表面积测定。实验结果表明,离子交换法制备的La-OMS-2-A催化剂的活性高于浸渍法制备的La-OMS-2-B催化剂,在甲苯0.1mol、溶剂冰乙酸10mL、氧气流量60mL/min、La-OMS-2-A催化剂用量0.10g、反应温度353K、反应时间1.0h的条件下,甲苯转化率达61%,苯甲醛收率为56%。加入La对OMS-2分子筛中的MnO晶格结构产生了影响,提高了苯甲醛的收率。