The Calcia–Zirconia Phase Diagram Revisited: Stability of the Ordered Phases φ1 and φ2

Single crystals of CaO-stabilized ZrO₂ containing between 15.3 and 18.9 mol% CaO were heat-treated for 5000 h at 1200°C to study the stability of the ordered defect-fluorite phase, CaZr₄O₉ (φ₁). Subsequent TEM analysis of the equiaxed φ₁ domains in samples richer than approximately 18 mol% in CaO showed a random distribution of φ₁ variants, with no preferred interfacial habit planes. A critical review of the literature, combined with the new data, supports the Stubican-Hellmann-Hannon version of the phase diagram in the region 15 to 26 mol% CaO and 1000° to 1400°C and strongly suggests that φ₁ is a stable phase in the ZrO₂-CaO systems.     

The influence of sulfur dioxide on propane oxidation activity over supported platinum and palladium

Earlier studies have shown that sulfur dioxide and metal-support interaction can strongly influence propane oxidation over platinum. In particular, oxidation activity is enhanced when platinum is supported on sulfated -alumina or zirconia compared to -alumina. Therefore, it is of interest to compare the performance of palladium under the same experimental conditions. Four model catalysts were examined: Pt/-alumina, Pt/zirconia, Pd/-alumina and Pd/zirconia. The metal loading was kept at or below 0.05 wt% to emphasize changes in activity attributable to metal-support interaction. Reaction rates were measured with and without sulfur dioxide. Surface sulfation was analyzed by measuring acid strength and evaluating spectra obtained by Fourier-transform infrared spectroscopy. In contrast to platinum, sulfation does not promote propane oxidation on Pd/-alumina, and Pd/zirconia is less active than Pd/-alumina.     

Effect of Precursor and Solvent on Morphology of Zirconia Nanoparticles Produced by Combustion Aerosol Synthesis

Zirconia nanoparticles were synthesized using a flame-based system involving spray droplet combustion of different precursor solutions. The characteristics of the feed were varied by varying the precursor compound, precursor concentration, and solvent type, and by using droplets of different mean sizes. When large droplets were used, agglomerated particles were formed when an organometallic precursor was used and large cenospheric particles were produced when an inorganic precursor was used. Reduction of the droplet size to a number-mean droplet diameter of 3.2 μm resulted in the production of solid spherical particles regardless of the precursor type. When an inertial impactor was used to eliminate droplets larger than 2.3 μm, the large particles in the final product were eliminated and uniformly sized solid zirconia particles having a smaller mean size were produced. The final particle size did not vary with the concentration of the precursor, indicating that multiple ceramic particles resulted from each precursor-containing droplet.     

Relationship between Transformation Temperature and Time-Temperature-Transformation Curves of Tetragonal-to-Monoclinic Martensitic Transformation in Zirconia-Yttria System

The tetragonal → monoclinic ( t → m ) martensitic phase transformation in ZrO₂–0.5–4 mol% Y₂O₃ proceeds during isothermal aging at various temperatures from 350 to 800 K; i.e., the transformation increases sigmoidally with aging time. The time-temperature-transformation ( T - T - T ) curves show a typical C shape, with very high rate for lower Y₂O₃-content specimens, and the rate decreases with higher Y₂O₃ content. The transformation temperature ( M _s) of the t → m transformation obtained from dilatation curves during the cooling stage coincides well with C curves above the nose temperature. The t → m transformation should occur isothermally, as suggested by a nucleation and growth mode.     

Molecular design and characterization of catalysts for NO x selective reduction by hydrocarbons in the oxygen excess based upon ultramicroporous zirconia pillared clays

Approaches to design of zirconia pillared clays via control of the properties of pillaring species in solutions were elaborated. Structural features of pillars and Pt + Cu active components fixed at these nanoparticles were shown to determine catalytic properties of pillared clays in NO_x selective reduction by hydrocarbons in the oxygen excess.     

莫来石晶种对反应烧结ZrO2/莫来石复相陶瓷显微结构的影响

通过显微结构观察研究了莫来石晶种对反应烧结ZrO2/莫来石复相陶瓷显微结构的影响。研究结果表明：与不含晶种试样相比，添加Ma(d50=1.87μm)和Mb(d50=0.83μm)晶种试样的显微结构比较均匀，莫来石晶粒多呈等轴状，且大小均一，晶内型ZrO2和封闭气孔较少。添加晶种对莫来石晶粒有明显细化作用。但晶种添加量和晶种颗粒尺寸对反应生成莫来石的晶粒尺寸无明显影响。采用溶胶－凝胶法制备的莫来石晶种（Mc)使试样中长出了一定量的长柱状的莫来石晶粒。     

Acid-Base Properties of Zirconium, Cerium and Lanthanum Oxides by Calorimetric and Catalytic Investigation

The combined use of calorimetric and catalytic methods for the investigation of the acid-base properties of oxide systems is discussed with reference to the authors' work on pure and doped zirconia samples, ceria-zirconia and ceria-lanthana solid solutions. Adsorption microcalorimetry of ammonia and carbon dioxide had been used to characterize the samples, whose chemical and thermal history was taken into account. The catalytic behavior of these samples in the conversion of 4-methylpentan-2-ol, route to 4-methylpent-1-ene (starting product for the manufacture of polymers of superior technological properties), had also been studied. On the basis of the calorimetric data, a rationale for interpreting the data for the transformation of 4-methylpentan-2-ol is formulated, which takes into account the role of the concentration and strength of the sites in governing the competition among the various mechanisms for dehydration and dehydrogenation.     

n-Butane Isomerization Over SO4 =/NiO/Al2O3/ZrO2 Catalysts. Effect of the Reaction Pressure and Metal Loading

The effect of alumina and nickel in sulfated ZrO₂ as a catalyst for n-butane isomerization was investigated. Samples were synthesized by supporting nickel sulfated zirconia on boehmite and then calcining the material. The crystalline structure of ZrO₂ was studied by X-ray powder diffraction and refined by the Rietveld method. Surface areas were determined by N₂ adsorption and BET analysis, while the acid properties were studied by NH₃ adsorption. The chemical reaction was carried out in a fixed-bed microreactor at 338 K under atmospheric (78 kPa) or 245 kPa total pressure. Results showed that either nickel or alumina improved the catalytic activity, but a synergic effect was observed when both components assisted. The catalytic activity was related to the relative content of tetragonal zirconia and acid site density. Alumina stabilized tetragonal zirconia increased the acid site density and presumably led to a better dispersion of nickel oxide. The catalytic activity could be related to both oxidation and acid sites produced by nickel. A bimolecular reaction mechanism helps explain the observed trends. The increase in the reaction rate would be explained by the increase in the rate of the initial step of dehydrogenation either caused by a better dispersion of nickel or higher operating pressure.     

Core-Shell Structures in ZrO2-Modified BaTiO3 Ceramic

Pure BaTiO₃ exhibits a paraelectric-to-ferroelectric phase transition at 130°C. When stoichiometric BaTiO₃ is combined with 10 mol% ZrO₂, the relative permittivity (ε) changes to a broad, relatively insignificant temperature dependence, and the Curie point, T _c , is not sharply defined. However, the transition sharpens at T = 95°C when these samples are sintered for a longer period of 60 h. SEM, EDAX analysis coupled with TEM observation gives three types of core-shell structures of different microstructural characteristics which are related to the diffuse phase transition. Chemical inhomogeneity, due to Zr⁴⁺ distribution in the core-shell structure, is proposed to account for the diffuse phase transition behavior.     

Dehydrocyclization of 1-hexene to benzene on Cu3Pt(111)

The disproportionation ofn-butane (and of isobutane) was catalyzed by sulfated zirconium oxide containing 1.5 wt% Fe, 0.5 wt% Mn, and 4.0 wt% sulfate at 2.0 atm and temperatures in the range of 30–60C. The reaction accompanies isomerization, which under some conditions is as much as one or two orders of magnitude faster than disproportionation. The conversion to each of the products increased with time on stream in a flow reactor, and then declined. The time on stream for maximum conversion was the same for each product. The results suggest that the disproportionation and isomerization reactions proceed through a common C₈ intermediate. Rates of the disproportionation reaction were determined at the time on stream corresponding to the maximum conversion at each temperature; for example, the rate of conversion ofn-butane into isopentane at 60C with ann-butane partial pressure of 0.58 atm was about 1×10^–7 mol/(g of catalyst s).