莫来石及多孔莫来石的研究和应用

高温性能稳定,抗热震性能好的莫来石是一种重要的工程陶瓷材料。概述了莫来石的结构、性能,以及在工业上的应用,并对多孔莫来石陶瓷的研究进展和应用进行了介绍。针对莫来石室温力学性能较差的缺陷,讨论了氧化锆和颗粒增韧莫来石的方法。最后,对多孔ZTM陶瓷发展前景进行了展望。     

TG and DTA investigation of ZrO2–SO 4 2– catalysts exposed to hexane, methylcyclopentane and cyclohexane

ZrO₂– catalysts with different sulfur contents were analysed with thermal methods coupled with mass spectrometry after exposure to mixtures of hexane, methylcyclopentane, and cyclohexane in argon. The reaction of the hydrocarbons led to carbonaceous deposits, but an important part of hydrocarbon remained chemisorbed as well. Heating these samples in He atmosphere provoked the decomposition of these deposits with evolution of CO₂ and CO, and also of SO₂ and SO. At the same time, COS was evidenced in the reaction products. The release of these molecules occurred below the activation temperature of the catalysts. The behavior of the catalysts depended both on reactant molecule and sulfur content. The analyses clearly evidenced the oxidation ability of ZrO₂–SO catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

球形氧化锆的湿法制备过程研究

以氯氧化锆和碳酸氢铵为原料，采用连续反应沉淀法制备了微米级球形氧化锆前驱体，此前驱体在500℃下于空气气氛中煅烧2h得到球形氧化锆粉体。探讨了锆盐溶液浓度、加料速度、pH、反应时间对粉体颗粒粒径大小及其分布的影响。经SEN，XRD，TG—DSC和激光粒度测试仪分析，结果表明在最佳工艺条件下制备的氧化锆前驱体颗粒呈球形，分散性好，粒径分布在8—18μm。     

氧化锆超细粉体的制造方法及应用

介绍了氧化锆超细粉体的性能、应用及制造方法。     

Study of the NOχ reaction with reducing gases on Fe/ZrO2 catalyst

The Fe/ZrO₂ catalyst (1% Fe by weight) shows a strong adsorption capacity toward the nitric oxide (at room temperature the ratio NOFe is ca. 0.5) as a consequence of the formation of a highly dispersed iron phase after reduction at 500–773 K. Nitric oxide is adsorbed mainly as nitrosyl species on the reduced surface where the Fe²⁺ sites are prevailing, but it is easily oxidised by oxygen forming nitrito and nitrato species adsorbed on the support. However, in the presence of a reducing gas such as hydrogen, carbon monoxide, propane and ammonia at 473–573 K the Fe-nitrosyl species react producing nitrogen, nitrous oxide, carbon dioxide and water, as detected by FTIR and mass spectrometers. The results show that nitric oxide reduction is more facile with hydrogen containing molecules than with CO, probably due the co-operation of spillover effects. Experiments carried out with the same gases in the presence of oxygen show, however, a reduced dissociative activity of the surface iron sites toward the species NO_χ formed by NO oxidation and therefore the reactivity is shifted to higher temperatures.     

Enhanced Fracture Toughness in Layered Microcomposites of Ce-ZrO2 and Al2O3

Laminar composites, containing layers of Ce-ZrO₂ and either Al₂O₃ or a mixture of Al₂O₃ and Ce-ZrO₂, have been fabricated using a colloidal method that allowed formation of layers with thicknesses as small as 10 μm. Strong interactions between these layers and the martensitic transformation zones surrounding cracks and indentations have been observed. In both cases, the transformation zones spread along the region adjacent to the layer, resulting in an increased fracture toughness. The enhanced fracture toughness was observed for cracks growing parallel to the layers as well as for those that were oriented normal to the layers.     

Hydrolytic decomposition of dichlorodifluoromethane on modified zirconium oxide surfaces

The hydrolytic decomposition of dichlorodifluoromethane (CFC-12) on various modified zirconium oxide surfaces has been studied. The reaction was carried out under flow conditions at 500°C. Complete CFC-12 conversion and long-time stability of the catalysts were achieved accompanied by a limitation of the undesired CFC-13 formation. A maximum CFC-12 conversion was observed on catalysts of sulfated zirconia or zirconia obtained from temperature-controlled calcination of zirconium oxide hydrate. The reaction depends on the presence or in situ formation of Brønsted acid sites. FTIR-photoacoustic measurements were performed on pyridine complexes chemisorbed on the catalyst surface in order to analyze the changes in the catalyst's acidity. The effects of the temperature and water in the reaction gas on the catalyzed decomposition of CFC-12 are examined.     

Effect of Nitrogen Atmosphere on the Densification of a 3-mol%-Yttria-Doped Zirconia

The densification behavior of a 3-mol%-Y₂O₃-doped ZrO₂ (3Y-ZrO₂) has been investigated under N₂ and O₂ atmospheres. Powder compacts have been sintered at 1550° and 1400°C for various times. The density of the specimen sintered at 1550°C is higher in N₂ than in O₂, while the contrary result is obtained in the case of the specimen sintered at 1400°C. Such results can be explained in terms of nitrogen solubility and oxygen vacancy in a ZrO₂ matrix. Because nitrogen solubility into the ZrO₂ increases with an increase in heat-treatment temperature, leading to the formation of oxygen vacancy, the densification rate becomes higher. The present study thus shows evidence of nitrogen solubility into the ZrO₂ and its role on the densification behavior of 3Y-ZrO₂.     

热压2％（mol）Y_2O_3－ZrO_2陶瓷中t－m相等温转变

用热膨胀分析、Ｘ射线衍射研究了热压２％（ｍｏｌ）Ｙ＿２Ｏ＿３－ＺｒＯ＿２陶瓷中ｔ－ｍ等温转变动力学。结果表明：经过快速冷却而得到的四方相（ｔ）在随后２００～４００℃区间保温时发生了四方相（ｔ）到单斜相（ｍ）的转变。该转变的时间－温度－转变量（ＴＴＴ）曲线呈Ｃ形，鼻子温度为３００℃。高于或低于上述温度范围，未出现ｍ相，可用Ａｖｒａｍｉ方程的一般形式来描述动力学曲线。该相变的形核与长大均是时间的函数，相变激活能为２８．６７ｋＪ／ｍｏｌ。ｔ相的亚稳性不仅与稳定剂分布及晶粒尺寸有关，而且还受冷却速度所控制。