Hydrodechlorination of 3-chloropyridine and chlorobenzene in methanol solution over alkali-modified zirconia-supported palladium catalysts

The liquid-phase hydrodechlorination of 3-chloropyridine and chlorobenzene has been studied over alkali-modified zirconia-supported palladium catalysts. The modification of the ZrO₂ with alkali metal carbonates improves the catalytic activity of the final palladium catalyst. Therefore, the larger the ionic radii (Li⁺ < Na⁺ < K⁺), the greater the catalytic activity (TOF) of the palladium catalyst. For 3-chloropyridine, hydrodechlorination proceeds without catalyst deactivation. This is explained as the result of the interaction of reaction products (pyridine and HCl) forming pyridinium chloride, thus avoiding the detrimental effect of HCl on the palladium particles. Catalytic hydrodechlorination of chlorobenzene over Pd catalysts exhibits an initial catalytic activity (TOF) much lower than that of 3-chloropyridine and the Pd catalysts deactivate as the reaction proceeds. Finally, chlorobenzene hydrodehalogenation has also been carried out in the presence of an equimolecular amount of pyridine resulting in a decrease in the initial reaction rate on the one hand, but also in an increase in final conversion on the other.     

Thermal Conductivity Measurement of an Electron-Beam Physical-Vapor-Deposition Coating

An industrial ceramic thermal-barrier coating designated PWA 266, processed by electron-beam physical-vapor deposition, was measured using a steady-state thermal conductivity technique. The thermal conductivity of the mass fraction 7 % yttria-stabilized zirconia coating was measured from 100 °C to 900 °C. Measurements on three thicknesses of coatings, 170 μm, 350 μm, and 510 μm resulted in thermal conductivity in the range from 1.5 W/(m·K) to 1.7 W/(m·K) with a combined relative standard uncertainty of 20 %. The thermal conductivity is not significantly dependent on temperature.     

Effect of Preparation Methods and Condition of Precursors on the Phase Composition of Yttria-Stabilized Zirconia Powders

An yttria-stabilized zirconia powder, free of monoclinic phase, may be prepared by an oxalate method in an ethanol solution at strong acidity. This study demonstrates that the control of pH in the preparation of precursors has a significant effect on the ability of precursors to crystallize and hence plays an important role in determining the formation and fraction of various crystalline phases in the resulting yttria-stabilized zirconia powder. With the increase of pH, a precursor with a certain crystalline form may be transformed into an amorphous precursor, and a monoclinic phase appers in the phase composition of the resulting powder. The results of XRD analysis and Raman spectroscopy are discussed.     

合成彩色立方氧化锆的宝石学特征

市场上出现的紫色、浅紫色、浅黄色、粉红色、酒黄色、黄褐色、红色人造立方氧化锆均为亚金刚光泽, 火彩明显; 密度为5.99～6.34 g/cm3, 相对硬度为8～9; 除粉红色者表现出非均质性和弱多色性且内含大量定向排列的白色脱溶物外, 其余的为均质性, 内部洁净; 不同颜色的立方氧化锆的吸收光谱、紫外荧光以及滤色镜下的变色情况均存在差异; 浅紫色立方氧化锆的吸收光谱特征表明它是Nd致色. 能谱分析结果表明: 彩色立方氧化锆的常见元素有Zr, Y, P, Hf, Ca等; Er, Ce, Fe分别是粉红色、红色、酒黄色立方氧化锆的致色元素; 当Y2O3的摩尔分数大于或近于7%时, 立方氧化锆为立方面心结构且内部洁净; 当Y2O3的摩尔分数小于5%时, 立方氧化锆表现为非均质性且内含大量定向分布的白色脱溶物. 用拉尔森改写的格拉斯顿-代尔公式计算其近似折射率为2.12～2.19.     

Changes in Aging Behavior and Defect Structure of Yttria-Fully-Stabilized ZrO2 with Sc2O3 Doping

Methods of suppressing decreased conductivity in 8 mol% Y₂O₃-stabilized–92 mol% ZrO₂ (8YSZ) with aging were investigated. Different amounts of Sc₂O₃ were doped into 8YSZ. The electrochemical properties of Sc₂O₃-doped 8YSZ were measured, and the microstructural and local structural changes were characterized. The present results indicate that an appropriate amount of Sc₂O₃ doping, 3 or 4 mol%, effectively suppresses decreased conductivity with aging in 8YSZ.     

Signature analysis and defect detection in layered manufacturing of ceramic sensors and actuators

This paper presents the concept of a process signature for the use of online signature analysis and defect detection in the layered manufacturing (LM) of ceramic sensors and actuators. To achieve the high quality of parts built by the fused deposition of ceramics (FDC), an online process-monitoring system is implemented to detect the processing defects. Using a process signature extracted from the image of a layer captured by the monitoring system, an ideal image is created that is then compared to the original image to detect and identify the defects. Some results of signature analysis and defect detection for single-material and multi-material parts are also presented.Received: 22 July 1999, Accepted: 21 October 2001, Published online: 29 October 2003 Correspondence to: Mohsen A. JafariThis work was supported by the Office of Naval Research under grant # N-0014-96-1-1175. Ref. US Patent # S-5738817, April 14, 1998.     

Electrophilic chlorination of methane over superacidic sulfated zirconia

Catalytic chlorination of methane was studied over SO ₄ ^2– /ZrO₂, Pt/SO ₄ ^2– /ZrO₂, and Fe/Mn/SO ₄ ^2– /ZrO₂ solid superacid catalysts. The reactions were carried out in a continuous flow reactor under atmospheric pressure, at temperatures below 240°C, with a gaseous hourly space velocity of 1000 ml/g h and a methane to chlorine ratio of 4 to 1. At 200°C with 30% chlorine converted the selectivity in methyl chloride exceeds 90%. At more elevated temperatures, the selectivity decreases but stays above 80% in methyl chloride at 225°C using the sulfated zirconia catalysts. The selectivity can be enhanced by adding platinum to sulfated zirconia catalysts. An iron and manganese-doped catalyst exhibited excellent selectivities at somewhat lower conversions. Methyl chloride is obtained at 235°C in selectivities greater than 85%. No chloroform or carbon tetrachloride is formed. The electrophilic insertion involves electron-deficient metal-coordinated chlorine into the methane C-H bond.Catalysis by solid superacids, 29. For part 28 see ref. [14].     

Improvement of flexural bond strength of zirconia-resin cement by surface patterning using sub-nanosecond UV laser

Zirconia is a dental material that shows excellent biocompatibility and high strength in clinical applications. This study aims to evaluate the effects of ultrafast laser applications. The surface nanostructures were classified into three groups. Group 1 was generated using the burst mode, with three different distances between dots: 52 µm (Group 1a), 104 µm (Group 1b), and 156 µm (Group 1c). Group 2 was processed using the scanning mode configuration, with a set of parallel lines. Group 3 was also processed using this scanning configuration creating a set of square-shaped patterning. Group 4 was the control group. After the surface treatments, a pair of zirconia specimens was bonded end to end with resin cement. Flexural bond strength (FBS) test was applied in a universal test machine. Multiple comparisons were performed using a one-way analysis of variance and the Tukey's HSD test. All the samples that were treated with the laser showed higher FBS values than the untreated surface. Using the burst mode, preformed circular-shaped surface on an angle of 90⁰ at 52 µm distance (Group 1a) showed the highest FBS values among all groups (p < .05). Groups 2 and 3 had significantly higher values than 1b and 1c.     

Controllable synthesis of pure monodispersed zirconia nanopowders with tetragonal phase

Nanopowders of pure zirconia have been synthesized using citric acid (CA)-assisted lamellar liquid crystal template method. The microstructure of the zirconia powder prepared at the different mole ratios of CA to zirconium oxynitrate (ZN) was characterized by FT-IR, X-ray diffraction (XRD), laser particle size analyzer, Raman spectroscopy, and scanning electron microscope (SEM) methods. The phase structure of the sodium dodecyl sulfate (SDS)/C₁₀H₂₁OH/H₂O system before and after adding mixing solution CA and ZN was determined by POM (Polarizing Optical Microscope). The results show that lamellar structure of the SDS/C₁₀H₂₁OH/H₂O system after adding mixing solution CA and ZN is stable. The presence of CA inhibits agglomeration and growth of zirconia particle. The crystallite size of zirconia powders decreases and agglomerates lowly with addition of CA. Fourier transform infrared spectrometry (FI-IR) analyses reveal that the structure of chelating organic complex is maintained in zirconia structure at high-temperature calcination to cause oxygen vacancies which stabilizes the tetragonal phase of zirconia. The zirconia powders remained the single metastable tetragonal phase at the molar ratios of CA to ZN ranging from 1:3 to 5:1. The crystallite size of zirconia with spherical morphology varied from 32.2 to 20.1 nm with the increase of the molar ratio of CA to ZN in the range of 1:3 to 5:1.