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.     

Preparation and Characterization of Macroporous α-Alumina

α-Al₂O₃ powders with three-dimensionally ordered or randomly positioned macropores were synthesized by templating with poly(methyl methacrylate) colloidal crystals. Aluminum nitrate was precipitated with ammonium hydroxide within the interstices of the template; calcination removed the polymer and converted the inorganic precursors into a macroporous skeleton of α-Al₂O₃. Subsequent calcination at higher temperatures and hot stage transmission electron microscopy experiments were performed to study sintering effects on the product morphology. These materials combine the thermal and chemical stability of corundum with a very open structure of uniform macropores that can permit facile transport of guest molecules in potential catalysis, filtration, and sensing applications.     

Solid-Phase Epitaxy of Boehmite-Derived α-Alumina on Hematite Seed Crystals

The seeded transformation of boehmite-derived alumina was studied by transmission electron microscopy. Crystallographic analysis confirmed that the growth of α-Al₂O₃ on α-Fe₂O₃ seed crystals occurs by solid-phase epitaxy, with the orientation relationship [0001]_Al2O₃||[0001]_Fe2O₃ and [11 2 0]_Al2O₃||[11 2 0_Fe2O₃.     

Preparation of Strontium Barium Niobate by Sol–Gel Method

Crack-free SBN (Sr_xBa_1-xNb₂O₆) thin films have been prepared by a sol–gel method with metal alkoxides. A homogeneous and stable precursor solution was obtained from Sr and Ba metal and Nb(OEt)₅ in ethanol with a key additive of ethoxyethanol. SBN (where x = 0.5) powder crystallized to orthorhombic phase at 700°C, and then transformed completely to tetragonal phase at 1200°C. The formation of tetragonal SBN was observed on sapphire (R) substrates at 700°C, whereas the tetragonal phase began to appear in the powders at 1000°C. SBN films with highly preferred orientation were successfully synthesized on MgO (100) substrates at 670°C.     

Preparation of Potassium Tantalate Niobate by Sol–Gel Method

Perovskite potassium tantalate niobate (KTN) powders and thin films were synthesized from a metal alkoxide solution. Homogeneous KTN coating solutions were prepared from KOC₂H₅, Ta(OC₂H₅)₅, and Nb(OC₂H₅)₅ in absolute ethanol. The precursor crystallized to pyrochlore at ∼ 650°C, and then to perovskite at ∼ 750°C, depending upon Ta:Nb ratio. H₂O vapor during calcination was found to play a prominent role in the direct and predominant crystallization of perovskite films with preferred orientation. Highly oriented KTN films of perovskite structure were successfully prepared on MgO (100) substrates at 675°C.     

Preparation of α-Alumina Platelets by Laser Scanning

A laser scanning with gas jet process was developed to prepare alumina platelets from an alumina powder. When the carbon-dioxide laser scanned the alumina powdery coatings prepared using an electrospraying technique, the alumina particles were heated to a melting state. The coaxial gas ejection force pushed the melting particles to obtain tabular shape grains that recrystallized into alumina platelets in the subsequent rapid-cool solidification. The phase and morphologies of powder bed were characterized by XRD and SEM. Results show that only α-alumina platelets were formed in the scanning process and the average edge length and thickness is 10 μm and 1–2 μm, respectively. Laser processing parameters such as laser energy density, scanning speed, and gas pressure were expected to play a vital role in the melting-crystallization-solidification process for obtaining platelike grains from powder beds. The preliminary experiment showed that the laser-scanning technique could be an effective means of tailoring the morphologies of particles to meet application requirements.     

Preparation Method of Submicrometer-Sized α-Alumina by Surface Modification of γ-Alumina with Alumina Sol

A method is introduced to prepare almost-spherical submicrometer-sized α-alumina via surface modification of γ-alumina with an alumina sol. Milled γ-alumina, in the presence of 3 wt% of α-alumina with a median particle size ( d ₅₀) of 0.32 μm (AKP-30), produced irregularly shaped α-alumina with d ₅₀∼0.3 μm after heat treatment at 1100°C for 1 h. γ-alumina that had been surface-modified by milling in the presence of 3 wt% of the alumina sol resulted in almost-monosized, spherical α-alumina ∼0.3 μm in size after heat treatment at 1100°C for 1 h. Furthermore, almost-spherical α-alumina 0.1—0.2 μm in size was obtained by milling γ-alumina with 3 wt% of AKP-30 alumina in the presence of 3 wt% of the alumina sol, followed by heat treatment at 1100°C for 1 h. The alumina sol that has been introduced in this work seems to act as a dispersant, in addition to helping to form a spherical shape.     

Preparation of Small-Particle-Size, Semiconductor CdS-Doped Silica Glasses by the Sol–Gel Process

The sol–gel process has been applied successfully to the preparation of small-particle-size CdS-doped silica glasses with a significant quantum size effect. Gels prepared through the hydrolysis of a complex solution of Si(OC₂H₅)₄ and Cd(CH₃COO)₂·2H₂O were heated at 500°C, then reacted with H₂S gas to form fine, hexagonal, CdS-microcrystal-doped glasses. The optical absorption edge is blue shifted by ∼0.4 eV compared with the bulk absorption value of CdS crystal. This result is interpreted in terms of a quantum-confinement effect of small crystal size.     

Effect of Tween-80 on the Control of Particle Size and Shrinkage Properties of Nanoscale α-Alumina Synthesized by Sol–Gel Processing

The concept of tailored interfaces has been applied to the synthesis of nanoscale α-Al₂O₃. Tween-80 (poly-oxyethylene(20) sorbitan monooleate, T-80) was used as a surface modifier in the sol–gel process for this purpose. High-resolution transmission electron microscopy study of the powder obtained with T-80 confirmed the particle size of α-Al₂O₃ (∼55 nm) and morphology (spherical). The exothermic peak temperature in the differential thermal analysis was shifted to a lower temperature (∼917°C) when the powder was derived from a T-80 modifier content of 10 wt%. X-ray diffraction showed that the α-Al₂O₃ phase was the major phase that existed in modifier-derived powder that was sintered at 1000°C. The experiments, based on linear shrinkage, indicated that the powder with T-80 (10 wt%) could be densified at a low temperature.     

Tribological Characteristics of α-Alumina at Elevated Temperatures

The tribological characteristics of a high-purity α-alumina sliding on a similar material under unlubricated conditions are divided into four distinct regimes. At low temperatures, T < 200°C, tribochemical reactions between the alumina surface and water vapor in the environment control the tribological performance. The coefficient of friction in this temperature range is approximately 0.40 and the wear coefficient is less than 10⁻⁶, independent of contact load. At intermediate temperatures, 200°C < T < 800°C, the wear behavior depends on the contact load. At low loads, wear occurs by plastic flow and plowing; the coefficient of friction is approximately 0.60 and the wear coefficient is less than 10⁻⁶. At loads larger than a threshold value, severe wear occurs by intergranular fracture. The coefficient of friction increases to 0.85 and the wear coefficient increases to a value greater than 10⁻⁴. At temperatures above 800°C, formation of a silicon-rich layer on the wear track by diffusion and viscous flow of the grain-boundary phase reduces the coefficient of friction to 0.40, and the wear coefficient is reduced to a value less than 10⁻⁶. The results of the wear tests and observations of the fundamental mechanisms controlling the tribological behavior of this material are consolidated in a simple wear transition diagram.     

Kinetics and Microstructural Evolution of Heterogeneous Transformation of θ-Alumina to α-Alumina

Ultrafine (<0.1 μm) high-purity θ-Al₂O₃ powder containing 3–17.5 mol%α-Al₂O₃ seeds was used to investigate the kinetics and microstructural evolution of the θ-Al₂O₃ to α-Al₂O₃ transformation. The transformation and densification of the powder that occurred in sequence from 960° to 1100°C were characterized by quantitative X-ray diffractometry, dilatometry, mercury intrusion porosimetry, and transmission and scanning electron microscopy. The relative bulk density and the fraction of α phase increased with annealing temperature and holding time, but the crystal size of the α phase remained ∼50 nm in all cases at the transformation stage (≤1020°C). The activation energy and the time exponent of the θ to α transformation were 650 ± 50 kJ/mol and 1.5, respectively. The results implied the transformation occurred at the interface via structure rearrangement caused by the diffusion of oxygen ions in the Al₂O₃ lattice. A completely transformed α matrix of uniform porosity was the result of appropriate annealing processes (1020°C for 10 h) that considerably enhanced densification and reduced grain growth in the sintering stage. The Al₂O₃ sample sintered at 1490°C for 1 h had a density of 99.4% of the theoretical density and average grain size of 1.67 μm.     

Yttrium Silicate Powders Produced by the Sol–Gel Method, Structural and Thermal Characterization

Yttrium silicate (Y₂SiO₅) powders of high purity have been synthesized using the sol–gel method. Alkoxide precursors were used with commercial tetraethyl orthosilicate as the silica source and yttrium propoxide synthesized from YCl₃. Powders calcined from the xerogel showed submicrometer crystal sizes. These powders were sintered at temperatures <1300°C and are suitable for coating applications such as a thermal barrier system for SiC/SiC composites.     

Sol–Gel Preparation of Lead Zirconate Titanate Powders and Ceramics: Effect of Alkoxide Stabilizers and Lead Precursors

Lead zirconate titanate (PZT) (52/48) powders were prepared by a sol–gel process, using different raw materials to introduce the lead component together with several solvents and chemical modifying agents. A study of the effect of these variables on crystallization behavior was conducted to determine the best conditions for preparing monophasic submicrometer-sized PZT perovskite powders in the morphotropic region. In the present work, well-crystallized, submicrometer-sized single-phase perovskite PZT powders were obtained after heat treatment at 600°C for 1 h. The dependence of this crystallization temperature on the preparation conditions was observed. The sol–gel-derived submicrometer-sized PZT powders were sintered to ∼96% of relative density after 2 h at 950°–970°C. The sintered ceramics exhibited a dielectric permittivity of 1000, a piezoelectric coefficient of 135 pC·N⁻¹, a remanent polarization of 20 μC·cm⁻², and a coercive field of 10.6 kV·cm⁻¹.     

Controlled Gelation and Sintering of Monolithic Gels Prepared from γ-Alumina Fume Powder

The gelation, phase transformation, and densification of a colloidal monolithic gel made from γ-Al₂O₃ fume powder are investigated. Among the six gelation agents that we use, formamide and urea are quick in causing gelation and easy to burn off. The densification rate of this gel decreases rapidly after the γ-to-α phase transformation. TiO₂ is an effective sintering aid to overcome this bottleneck of densification because (1) it enhances the phase transformation rate so that the sintering of α-alumina occurs at a lower temperature, and (2) it promotes sintering rates at the initial and intermediate stages after phase transformation. On the other hand, MgO has an inappreciable effect on gel sintering. The effect of MgO at the final sintering stage is obstructed by this densification barrier after transformation. The titania-doped gel monoliths can be sintered to high density and fine microstructure at 1400°C.     

Synthesis of Nanocrystalline α-Alumina Powder Using Triethanolamine

Nanocrystalline α-Al₂O₃ powders have been prepared by pyrolysis of a complex compound of aluminum with triethanolamine (TEA). The soluble metal-ion–TEA complex forms the precursor material on complete dehydration of the complex of aluminum-TEA. The single-phase α-Al₂O₃ powder has resulted after heat treatment at 1025°C. The precursors and the heat-treated final powders have been characterized by X-ray diffractometry, thermogravimetric and differential thermal analysis, and transmission electron microscopy (TEM). The average particle sizes as measured from X-ray line broadening and TEM are ∼25 nm. The powder has crystallite sizes of the same order indicates the poor agglomeration of crystallites.     

Method for Production of α-Alumina Whiskers via Vapor-Liquid-Solid Deposition

α-alumina (α-Al₂O₃, corundum) fibers exhibit high thermal and chemical stability, as well as good mechanical properties, even at high temperatures. Such characteristics make them good candidates for use in composites. Nevertheless, very few methods of producing α-Al₂O₃ fibers are available. In the present work, we describe a method that uses aluminum pieces deposited on SiO₂ powder, in an argon atmosphere, at temperatures in the range 1300°–1600°C. The α-Al₂O₃ fibers are obtained via vapor-liquid-solid deposition. The novel addition of nickel and cobalt (or their oxides) allows the use of temperatures >1500°C, resulting in improved fiber production. We demonstrate that the metals do not contaminate the fibers produced in this way. Finally, we also estimate the tensile strength of the Al₂O₃ fibers produced through this method.     

Synthesis of Thermally Stable χ-Alumina by Thermal Decomposition of Aluminum Isopropoxide in Toluene

Thermal decomposition of aluminum isopropoxide in toluene at 315°C resulted in χ-alumina that had high thermal stability, whereas the reaction at lower temperatures resulted in formation of an amorphous product. The χ-alumina thus obtained directly transformed to α-alumina at ∼1150°C, bypassing the other transition alumina phases, whereas the amorphous product transformed to γ-alumina and then to θ-alumina before final transformation to α-alumina. When the χ-alumina, solvothermally synthesized at 315°C, was recovered by the removal of the solvent at the reaction temperature, thermal stability of the product was improved further. This procedure is convenient because it avoids bothersome work-up processes that yield large-surface-area and large-pore-volume alumina.     

Preparation of Dicalcium Siliciate at 950°C

β-Ca₂Si0₄ can be obtained from a mixture ofCaC₂O₄-H₂O and amorphous silica by firing at 950°C as opposed to a normal sintering temperature around 1450°C. If CaCO₃ is used instead of CaC₂O₄·H₂O, four repeated firings under CO₂ atmosphere are needed to obtain β-Ca₂SiO₄. The role of CO₂ atmosphere during firing and the influence of specific surface of reactanm on the rate of reaction are discussed.     

Sol–Gel Processed Y-PSZ Ceramics with 5 wt% Al2O3

Y-PSZ ceramics with 5 wt% Al₂O₃ were synthesized by a sol–gel route. Experimental results show that powders of metastable tetragonal zirconia with 2.7 mol% Y₂O₃ and 5 wt% Al₂O₃ can be fabricated by decomposing the dry gel powder at 500°C. Materials sintered in an air atmosphere at 1500°C for 3 have high density (5.685 g/cm³), high content of metastable tetragonal zirconia (>96%), and high fracture toughness (8.67 MPa.m^1/2). Compared with the Y-PSZ ceramics, significant toughening was achieved by adding 5 wt% Al₂O₃.