Two-phase synthesis of shape-controlled colloidal zirconia nanocrystals and their characterization

We have developed a two-phase approach for the synthesis of shape-controlled colloidal zirconia nanocrystals, including spherical-, teardrop-, rod-, and rice grain-shaped particles. We found that the key factors for controlling the shape were the reaction time, the nature of the capping agent, and the monomer concentration. We have analyzed the morphologies, crystallinity, optical properties, and structural features of the as-prepared ZrO2 nanoparticles by using transmission electron microscopy (TEM), high-resolution TEM, X-ray powder diffraction, and UV-vis absorption and fluorescence spectroscopy. The possible nucleation and growth process is also discussed.

New double-ceramic-layer thermal barrier coatings based on zirconia-rare earth composite oxides

A series of La2O3-ZrO2-CeO2 composite oxides were synthesized by solid-state reaction. The final product keeps fluorite structure when the molar ratio Ce/Zr >= 0.7/0.3, and below this ratio only mixtures of La2Zr2O7 (pyrochlore) and La2O3-CeO2 (fluorite) exist. Averagely speaking, the increase of CeO2 content gives rise to the increase of thermal expansion coefficient and the reduction of thermal conductivity, but La-2(Zr0.7Ce0.3)(2)O-7 has the lowest sintering ability and the lowest thermal conductivity which could be explained by the theory of phonon scattering. Based on the large thermal expansion coefficient of La2Ce3.25O9.5, the low thermal conductivities and low sintering abilities of La2Zr2O7 and La-2(Zr0.7Ce0.3)(2)O-7, double-ceramic-layer thermal barrier coatings were prepared. The thermal cycling tests indicate that such a design can largely improve the thermal cycling lives of the coatings. Since no single material that has been studied so far satisfies all the requirements for high temperature thermal barrier coatings, double-ceramic-layer coating may be an important development direction of thermal barrier coatings.

Phase transformation in the surface region of zirconia detected by UV Raman spectroscopy

The phase transformation of zirconia from tetragonal to monoclinic is characterized by UV Raman spectroscopy, visible Raman spectroscopy, and XRD. Electronic absorption Of ZrO2 in the UV region makes UV Raman spectroscopy more sensitive at the surface region than XRD or visible Raman spectroscopy. Zirconia changes from the tetragonal phase to the monoclinic phase with calcination temperatures elevated and monoclinic phase is always detected first by UV Raman spectroscopy for the samples calcined at lower temperatures than that by XRD and visible Raman spectroscopy. When the phase of zirconia changes from tetragonal to monoclinic, the slight changes of the phase at very beginning can be detected by UV Raman spectroscopy. UV Raman spectra clearly indicate that the phase transition takes place initially at the surface regions. It is found that the phase change from tetragonal to monoclinic is significantly retarded when amorphous Zr(OH)(4) was agglomerated to bigger particles and the particle agglomeration of amorphous zirconium hydroxide is beneficial to the stabilization of t-ZrO2 phase.

The surface sites of sulfated zirconia studied in situ by laser-induced fluorescence spectroscopy

The surface sites of sulfated zirconia were investigated in situ by laser-induced fluorescence spectroscopy using aniline as the probe molecule. Different from the cases for many other oxides, the aniline adsorbed on the unique active sites of sulfated zirconia at r.t. is changed into another species, which emits a characteristic fluorescence band at 422 nm. The results illustrate that the sulfate groups in sulfated zirconia are favorable for the generation of these unique active sites, which also rarely exist on pure zirconia composed of tetragonal and monoclinic phases but do not exist on pure zirconia composed of monoclinic phase. (C) 2004 Elsevier B.V. All rights reserved.

In-situ SAXS studies of the morphological changes of an alumina-zirconia-silicate ceramic during its formation

D Le Messurier, R Winter, CM Martin; J Appl Cryst 39 (2006) 589 Sponsorship: EPSRC, CCLRC, Pilkington

DFT and in situ EXAFS investigation of gold/ceria-zirconia low-temperature water gas shift catalysts: Identification of the nature of the active form of gold

A combined experimental and theoretical investigation of the nature of the active form of gold in oxide-supported gold catalysts for the water gas shift reaction has been performed. In situ extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) experiments have shown that in the fresh catalysts the gold is in the form of highly dispersed gold ions. However, under water gas shift reaction conditions, even at temperatures as low as 100 degrees C, the evidence from EXAFS and XANES is only 14 consistent with rapid, and essentially complete, reduction of the gold to form metallic clusters containing about 50 atoms. The presence of Au-Ce distances in the EXAFS spectra, and the fact that about 15% of the gold atoms can be reoxidized after exposure to air at 150 degrees C, is indicative of a close interaction between a fraction (ca. 15%) of the gold atoms and the oxide support. Density functional theory (DFT) calculations are entirely consistent with this model and suggest that an important aspect of the active and stable form of gold under water gas shift reaction conditions is the location of a partially oxidized gold (Audelta+) species at a cerium cation vacancy in the surface of the oxide support. It is found that even with a low loading gold catalysts (0.2%) the fraction of ionic gold under water gas shift conditions is below the limit of detection by XANES (<5%). It is concluded that under water gas shift reaction conditions the active form of gold comprises small metallic gold clusters in intimate contact with the oxide support.

A stabilization mechanism of zirconia based on oxygen vacancies only

The microscopic mechanism leading to stabilization of cubic and tetragonal forms of zirconia (ZrO2) is analyzed by means of a self-consistent tight-binding model. Using this model, energies and structures of zirconia containing different vacancy concentrations are calculated, equivalent in concentration to the charge compensating vacancies associated with dissolved yttria (Y2O3) in the tetragonal and cubic phase fields (3.2 and 14.4% mol, respectively). The model is shown to predict the large relaxations around an oxygen vacancy, and the clustering of vacancies along the 111 directions, in good agreement with experiments and first principles calculations. The vacancies alone are shown to explain the stabilization of cubic zirconia, and the mechanism is analyzed. (C) 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Electron energy-loss near-edge shape as a probe to investigate the stabilization of yttria-stabilized zirconia

The electron energy-loss near-edge structure (ELNES) at the O K edge has been studied in yttria-stabilized zirconia (YSZ). The electronic structure of YSZ for compositions between 3 and 15 mol % Y2O3 has been computed using a pseudopotential-based technique to calculate the local relaxations near the O vacancies. The results showed phase transition from the tetragonal to cubic YSZ at 10 mol % of Y2O3, reproducing experimental observations. Using the relaxed defect geometry, calculation of the ELNES was carried out using the full-potential linear muffin-tin orbital method. The results show very good agreement with the experimental O K-edge signal, demonstrating the power of using ELNES to probe the stabilization mechanism in doped metal oxides.

Free energy and molecular dynamics calculations for the cubic-tetragonal phase transition in zirconia

The high-temperature cubic-tetragonal phase transition of pure stoichiometric zirconia is studied by molecular dynamics (MD) simulations and within the framework of the Landau theory of phase transformations. The interatomic forces are calculated using an empirical, self-consistent, orthogonal tight-binding model, which includes atomic polarizabilities up to the quadrupolar level. A first set of standard MD calculations shows that, on increasing temperature, one particular vibrational frequency softens. The temperature evolution of the free-energy surfaces around the phase transition is then studied with a second set of calculations. These combine the thermodynamic integration technique with constrained MD simulations. The results seem to support the thesis of a second-order phase transition but with unusual, very anharmonic behavior above the transition temperature.