Hydrothermal Synthesis of Spherical Perovskite Oxide Powders Using Spherical Gel Powders

Spherical perovskite oxide powders, composed of fine particulates, were prepared by using spherical gel powders under hydrothermal conditions. Spherical PbTiO₃, BaTiO₃, and SrTiO₃ powders were synthesized from spherical TiO₂ gel powders, and spherical PbZrO₃ powder from spherical ZrO₂ gel powder. Spherical Pb(Zr_0.5, Ti_0.5)O₃ and Ba(Zr_0.5,Ti_0.5)O₃ powders were prepared from spherical ZrTiO₄ gel powders. Lead acetate trihydrate, barium hydroxide octahydrate, and strontium hydroxide octahydrate were used as the sources of A-site ions in each perovskite oxide (ABO₃). The spherical TiO₂ and ZrO₂ gel powders were prepared by thermal hydrolysis of titanium tetrachloride and zirconium oxychloride, respectively, and spherical ZrTiO₄ gel powder by thermal hydrolysis of a mixture of them in alcohol-water mixed solvent. During the hydrothermal treatment, the spherical gel powders retained their spherical shape to produce spherical perovskite oxide powders, composed of nanometer-sized particulates.     

Microstructural Studies in Alkoxide-Derived Mullite/Zirconia/Silicon Carbide-Whisker Composites

Mullite composites toughened with ZrO₂ (with or without a MgO or Y₂O₃ stabilizer) and/or SiC whiskers (SiC( w )) were fabricated by hot-pressing powders prepared from Al, Si, Zr, and Mg(Y) alkoxide precursors by a sol–gel process. Micro-structures were studied by using XRD. SEM, and analytical STEM. Pure mullite samples contained prismatic, preferentially oriented mullite grains. However, the addition of ZrO₂, as well as the hot-pressing temperature, affected the morphology and grain size in the composites; a fine, uniform, equiaxed microstructure was obtained. The effect of SiC( W ) was less pronounced than that of ZrO₂. Glassy phases were present in mullite and mullite/SiC( W ) composites, but were rarely observed in Al₂O₃-rich or ZrO₂-containing samples. The formation of zircon due to the reaction between ZrO₂ and SiO₂ and the considerable solid solution of SiO₂ in ZrO₂ prevented the formation of the glassy phase, whereas the reaction between Al₂O₃ and MgO in MgO-containing samples formed a spinel phase and also deprived the ZrO₂ phase of the stabilizer. Intergranular ZrO₂ particles were either monoclinic or tetragonal, depending on size and stabilizer content; small intragranular ZrO₂ inclusions were usually tetragonal in structure.     

State of Magnesia in Magnesia (10.4 mol%)-Doped Zirconia Powder Prepared from Coprecipitation

MgO (10.4 mol%)-doped ZrO₂ powder, which was prepared by coprecipitation and calcination at 750°C, was leached and milled, respectively. The powders were characterized by Auger electron scanning microprobe and XRD technologies. Only the 2.3 mol% MgO was soluble in ZrO₂; it stabilized ZrO₂ as the metastable tetragonal phase (crystallite size ∼45 nm) at room temperature. The rest of the MgO (8.1 mol%) existed on the surface of the ZrO₂ grains in the prepared powder.     

Formation of Alumina/Zirconia (3 mol% Yttria) Composite Powders Prepared by the Hydrazine Methods

Alumina/3 mol% yttria-doped zirconia composite powders have been prepared by the hydrazine method. As-prepared powders are AlO(OH) gel solid solutions and the mixtures of this and amorphous ZrO₂ below and above 10 mol% ZrO₂, respectively. The formation process leading to α–Al₂O₃– t -ZrO₂ composite powders is examined.     

Low-Temperature Processing of Dense Hydroxyapatite–Zirconia Composites

Hydroxyapatite (HA)–YTZP (2, 5, 7.5, and 10 wt% ZrO₂) composite powders prepared from inorganic precursors were characterized by FTIR, DSC/TG, XRD, and TEM. The calcined powders had HA and t / c -ZrO₂, which undergo structural changes between 650°C and 1050°C. TEM of calcined powder showed larger HA particles (100 nm) and smaller ZrO₂ particles (≤50 nm). HA and HA–2 wt% ZrO₂-sintered samples had 98% density and it was (90–95%) for HA–5, 7.5, and 10 wt% ZrO₂. The bending strength of HA–2wt% ZrO₂ composites was 72 MPa. The grain sizes of HA showed a refinement with ZrO₂ addition.     

In Situ Synthesis of Yttria-Stabilized Tetragonal Zirconia Polycrystal Powder Containing Dispersed Titanium Carbide by Selective Carbonization

Reaction thermodynamics was utilized to analyze the selective carbonization conditions of ZrO₂-TiO₂-Y₂O₃ ultrafine powder and to define the temperature range of the selective carbonization. The ZrO₂-TiO₂-Y₂O₃ powder was prepared by coprecipitation from a solution containing Zr⁴⁺, Ti⁴⁺, and Y³⁺. The powder was selectively carbonized at 1350°, 1450°, 1550°, and 1650°C, respectively, for 2 h under argon atmosphere with sucrose as the carbon source. The resulting product was analyzed by X-ray diffraction. The experimental results indicated that the ZrO₂-TiO₂-Y₂O₃ powder could be selectively carbonized in situ at 1450°C to form a carbonized powder which was composed of TiC and t -ZrO₂. It was also found that zirconium carbide could be formed at 1550°C, which is much lower than the carbonization temperature of ZrO₂ defined by thermodynamics.     

New Method for the Preparation and Stabilization of Nanoparticulate t-ZrO2 by a Combined Sol–Gel and Solvothermal Process

Nonstabilized and silica-stabilized zirconia (ZrO₂) crystallites with sizes between 3 and 4 nm were synthesized by a novel combined sol–gel and solvothermal process. After adding zirconium n -propoxide to a solution of isobutanol, propionic acid, and water, a transparent nanoparticulate sol was synthesized by a sol–gel process. The average hydrodynamic diameter of the amorphous ZrO₂ nanoparticles was approximately 5 nm. A following solvothermal process led to a crystalline fraction of the powder consisting of 31 wt% tetragonal ( t ) phase ZrO₂. This fraction was doubled to 61 wt% by adding 10 mol% 3-methacryloxypropyl trimethoxysilane (MPTS) and increased to 96 wt% by a subsequent calcination at 800°C. The crystallite sizes were also confirmed by means of Brunauer–Emmett–Teller and high-resolution transmission electron microscopy.     

Twinning in YNbO4

The compound YNbO₄ is a 3–5 analogue of ZrO₂ with two polymorphs: low-temperature monoclinic and high-temperature tetragonal forms. YNbO₄ powder with a surface area of 40 m²/g was prepared from citrate complexes. The powder sintered to theoretical density at 1550°C. Unlike pure ZrO₂, YNbO₄ can be cooled through the tetragonal-to-monoclinic phase transformation without cracking. The phase transformation is gradual and takes place by shear, resulting in twinning.     

Consolidation of Alumina—Zirconia Mixtures by a Colloidal Process

The relationship between the dispersion of colloidal powder particles in Al₂O₃–ZrO₂ suspensions and the microstructures of consolidated compacts was examined. Suspensions were prepared from Al₂O₃ powder and ZrO₂ sol with average particle sizes of 390 and 62 nm, respectively. The dispersion was controlled by pH and salt concentration adjustments. The compacts composed of completely separated Al₂O₃ and ZrO₂ layers were obtained from well-dispersed suspensions with pH values below about 4 and salt concentration of 0.0527 M. An increase in pH or salt concentration resulted in macroscopically uniform compacts. The compacts made from suspensions with pH values above about 7, however, were composed of a mixture of Al₂O₃ and ZrO₂ agglomerates, with one acting as a matrix and the other a dispersed phase. Suspensions with a pH value of 4.5 and optimum salt concentrations resulted in compacts with microscopically uniform microstructure. Above or below these salt concentrations, ZrO₂ agglomerates were distributed in an Al₂O₃ matrix. The optimum concentration was dependent on solid content. In addition, the dispersion of mixed suspensions was compared with those of single-component suspensions. The ZrO₂ particles formed three-dimensional networks during agglomeration, which reduced the component separation in suspensions and during consolidation.     

Phase Separation in Sol–Gel Process of Alkoxide-Derived Silica-Zirconia in the Presence of Polyethylene Oxide

Phase separation in a sol–gel process of SiO₂–ZrO₂ in the presence of polyethylene oxide is investigated. An amorphous gel with interconnected macroporous morphology is obtained when phase separation and sol–gel transition concur to fix a transitional structure of spinodal decomposition. Macropore size, together with connectivity of the pores and gel skeleton, can be controlled precisely by selecting an appropriate starting composition for preparation at a zirconium content ≤11.7 mol%. The macroporous gel retains additional mesopores <4 nm and exhibits typical bimodal pore size distribution. The addition of ZrO₂ in SiO₂ improves the thermal stability of both macroporous and mesoporous structures.     

Role of Water Vapor in Crystallite Growth and Tetragonal-Monoclinic Phase Transformation of ZrO2

The role of water vapor in crystallite growth and the tetragonal-to-monoclinic phase transformation of ZrO₂ was studied using three specially prepared samples: an ultrafine powder of monoclinic ZrO₂ obtained by hydrolysis of ZrOCI₂, an aggregated powder of tetragonal ZrO₂ obtained by thermal decomposition of Zr(OH)₄ under reduced pressure, and an ultrafine powder of tetragonal ZrO₂ obtained by thermal decomposition of zirconyl acetate dispersed in caramel. The samples were heat-treated up to 1000°C in dry and wet atmospheres saturated with water vapor at 90°C. It was found that water vapor markedly accelerated crystallite growth for both monoclinic and tetragonal ZrO₂ and facilitated the tetragonal-to-monoclinic phase transformation. Water vapor increases surface diffusion and thus enhances crystallite growth and decreases surface energy, which leads to stabilization of the tetragonal phase.     

Mechanical and Microstructural Characterization of Mullite and Mullite-SiC-Whisker and ZrO2-Toughened-Mullite—SiC-Whisker Composites

High-purity mullite-SiC-whisker composites and mullite-ZrO₂-SiC-whisker composites were fabricated in situ by hot-pressing using a matrix prepared by the alkoxide process. Varying degrees of ZrO₂ stabilization were achieved by varying amounts of Y₂O₃ or MgO addition. Microstructural characterization was accomplished using SEM and energy dispersive analysis. Room-temperature flexural strength and fracture toughness were determined as a function of SiC-whisker content (0% to 30%) and ZrO₂-stabilizer content. The flexural strength of mullite varied with composition and was increased ∼50% by the addition of ∼30% ZrO₂ phase. The flexural strength of mullite and mullite + 30% ZrO₂ was increased ∼50% for 30% SiC-whisker additions. The fracture toughness of mullite + 30% ZrO₂ was nearly twice that of mullite. For a 30% SiC-whisker addition, the fracture toughness of mullite was doubled, and the fracture toughness of mullite + 30% ZrO₂ was increased 25% to 50%.     

Transformation Kinetics of Ba2Ti9O20 with ZrO2 Additive

Pure Ba₂Ti₉O₂₀ (BT29) was synthesized by a solid-state reaction in one step with various amounts of ZrO₂ powder additive. The transformation kinetics of BT29 were investigated by quantitative X-ray diffractometry (XRD). The results show that stoichiometric powder mixtures transform to the BT29 phase by nucleation and growth mechanism between 1200° and 1300°C with 1.0 mol% ZrO_2. The activation energy of the transformation was found to be 620±60 kJ/mol, but decreases to 515±30 kJ/mol when doped with 1.0 mol% ZrO₂. The addition of ZrO₂ possibly changes the phase transformation mechanism of BT29 from diffusion controlled to interface controlled.     

Dehydration of Gels and Glasses in the Systems B2 O3-SiO2 and ZrO2-SiO2 Prepared by the Sol-Gel Process from Metal Alkoxides

Dehydration of gels prepared by the sol-gel process from metal alkoxides in the systems B₂O₃-SiO₂ and ZrO₂-SiO₂ was determined by measuring the shrinkage of the gel on heating. Dehydration was enhanced with increased ZrO₂ content, whereas it decreased with B₂O₃ content. Diffusion of water was also measured in the nonporous glasses obtained by heating the gels. The diffusion rate was independent of the composition of the glass.     

Effect of MgO Addition on the Microstructure Development of 3 mol% Y2O3—ZrO2

MgO addition to 3 mol% Y₂O₃–ZrO₂ resulted in enhanced densification at 1350°C by a liquid-phase sintering mechanism. This liquid phase resulted from reaction of MgO with trace impurities of CaO and SiO₂ in the starting powder. The bimodal grain structure thus obtained was characterized by large cubic ZrO₂ grains with tetragonal ZrO₂ precipitates, which were surrounded by either small tetragonal grains or monoclinic grains, depending on the heat-treatment schedule.     

Zirconium Oxide Structure Prepared by the Sol–Gel Route: I, The Role of the Alcoholic Solvent

Sol–gel-derived powder samples of zirconia (ZrO₂) prepared via the dissolution of zirconium n -propoxide in methanol, ethanol, and 2-propanol have been characterized mainly using perturbed angular correlations spectroscopy, as a function of temperature. Results indicate that the nanostructures and subsequent thermal evolution are alcohol dependent: the shorter the alcohol chain, the more hydrolyzed the product. ZrO₂ powder that has been obtained using ethanol as the solvent is the product that exhibits the better stabilization of the metastable tetragonal phase ( t -phase). It undergoes a clear and detailed t ₁-form → t ₂-form → monoclinic ZrO₂ thermal transformation and shows the highest activation energy against the transformation to the monoclinic phase.     

Chemical Interactions Promoting the ZrO2 Tetragonal Stabilization in ZrO2–SiO2 Binary Oxides

Metastable tetragonal ZrO₂ phase has been observed in ZrO₂–SiO₂ binary oxides prepared by the sol–gel method. There are many studies concerning the causes of ZrO₂ tetragonal stabilization in binary oxides such as Y₃O₂–ZrO₂, MgO–ZrO₂, or CaO–ZrO₂. In these binary oxides, oxygen vacancies cause changes or defects in the ZrO₂ lattice parameters, which are responsible for tetragonal stabilization. Since oxygen vacancies are not expected in ZrO₂–SiO₂ binary oxides, tetragonal stabilization should just be due to the difficulty of zirconia particles growing in the silica matrix. Furthermore, changes in the tetragonal ZrO₂ crystalline lattice parameters of these binary oxides have recently been reported in a previous paper. The changes of the zirconia crystalline lattice parameters must result from the chemical interactions at the silica–zirconia interface (e.g., formation of Si–O–Zr bonds or Si–O⁻ groups). In this paper, FT-IR and ²⁹Si NMR spectroscopy have been used to elucidate whether the presence of Si–O–Zr or Si–O⁻ is responsible for tetragonal phase stabilization. Moreover, X-ray diffraction, Raman spectroscopy, and transmission electron microscopy have also been used to study the crystalline characteristics of the samples.     

Sol–Gel Synthesis and Characterization of Ag and Au Nanoparticles in SiO2, TiO2, and ZrO2 Thin Films

Silver and gold nanoparticles were synthesized by the sol–gel process in SiO₂, TiO₂, and ZrO₂ thin films. A versatile method, based on the use of coordination chemistry, is presented for stabilizing Ag⁺ and Au³⁺ ions in sol–gel systems. Various ligands of the metal ions were tested, and for each system it was possible to find a suitable ligand capable of stabilizing the metal ions and preventing gold precipitation onto the film surface. Thin films were prepared by spin-coating onto glass or fused silica substrates and then heat-treated at various temperatures in air or H₂ atmosphere for nucleating the metal nanoparticles. The Ag particle size was about 10 nm after heating the SiO₂ film at 600°C and the TiO₂ and ZrO₂ films at 500°C. After heat treatment at 500°C, the Au particle size was 13 and 17 nm in the TiO₂ and ZrO₂ films, respectively. The films were characterized by UV–vis optical absorption spectroscopy and X-ray diffraction, for studying the nucleation and the growth of the metal nanoparticles. The results are discussed with regard to the embedding matrix, the temperature, and the atmosphere of the heat treatment, and it is concluded that crystallization of TiO₂ and ZrO₂ films may hinder the growth of Ag and Au particles.     

ZrO2 Nanopowders Prepared by Low-Temperature Vapor-Phase Hydrolysis

ZrO₂ powder is prepared by low-temperature vapor-phase hydrolysis of ZrCl₄. TG-DTA, XRD, Raman, BET, and TEM methods are used to investigate the particle size, phase composition, and agglomeration before and after heat treatment. The results show that the as-prepared ZrO₂ powder is characterized by large surface area (150 m²/g), fine grain size (5.8 nm), and weak agglomeration. Additionally, the as-prepared ZrO₂ powder shows predominantly tetragonal phase attributed to a grain size effect. This route is free of powder drying and calcination processes that are essential for wet chemical preparation, contributing to less agglomeration.     

Nanometer-Sized ZrO2 Particles Prepared by a Sol–Emulsion–Gel Method

ZrO₂ powder was prepared by a sol–emulsion–gel method at temperatures below 140°C from ZrO(NO₃)₂· n H₂O. The asprepared powder was amorphous, but crystallized into the tetragonal structure by 600°C. The metastable tetragonal powder (600°C) was comprised of ultrafine 4- to 6-nm size particles. On heat treatment, the tetragonal form completely transformed into the monoclinic state at 1100°C. Preliminary studies indicate good sinterability with densities greater than 94% at 1100°C and with a grain size of 0.25 μ.