Nanostructure of TiO2 Nano-Coated SiO2 Particles

We characterized SiO₂–TiO₂ nano-hybrid particles, prepared using the sol–gel method, using high-resolution transmission microscopy. A few nanometer-ordered TiO₂ anatase crystallites could be observed on the monodispersed SiO₂ nanoparticle surface. The quantum size effect of the TiO₂ anatase crystallites is attributed to the blue shift of the absorption band. The rough surface of the SiO₂–TiO₂ nano-hybrid particles was derived from the developed growth planes of the TiO₂ anatase crystallites, grown from fully hydrolyzed Ti alkoxide that did not react with acetic acid during the crystallization process at 600°C thermal annealing.     

Fabrication of Grain-Oriented Bi2WO6 Ceramics

Grain-oriented Bi₂WO₆ ceramics were fabricated by normal sintering techniques. Platelike crystallites were initially synthesized by a fused salt process using an NaCl-KCI melt. When calcined at <800°C, the Bi₂WO₆ crystallites are 3∼5 μ m in size and, at >850°C, =100 μm. After dissolving away the salt matrix, the Bi₂WO₆ particles were mixed with an organic binder and tapecast to align the platelike crystallites. Large particles were easily oriented by tapecasting but the sinterability of the tape was poor. Preferred orientation of small particles was increased by tapecasting and grain growth during sintering further improves the degree of orientation. Sintering above the 950°C phase transition, however, results in discontinuous grain growth and low densities. Optimum conditions for obtaining highly oriented ceramics with high density occur at sintering temperatures of 900°C using fine-grained powders which yield orientation factors of =0.88 and densities of 94% theoretical.     

Low-Temperature Synthesis of Nanocrystalline α-Si3N4 Powders by the Reaction of Mg2Si with NH4Cl

Nanocrystalline α-Si₃N₄ powders have been prepared with a yield of 93% by the reaction of Mg₂Si with NH₄Cl in the temperature range of 450° to 600°C in an autoclave. X-ray diffraction patterns of the products can be indexed as the α-Si₃N₄ with the lattice constants a = 7.770 and c = 5.627 Å. X-ray photoelectron spectroscopy analysis indicates that the composition of the α-Si₃N₄ samples has a Si:N ratio of 0.756. Transmission electron microscopy images show that the α-Si₃N₄ crystallites prepared at 450°, 500°, and 550°C are particles of about 20, 40, and 70 nm in average, respectively.     

Thermal Decomposition of Europium Hydroxide

The thermal decomposition of europium hydroxide in an air atmosphere was investigated by means of weight-loss measurements, infrared spectroscopy, X-ray diffraction analysis, and electron microscopy. These studies showed that EU(OH)° decomposed at temperatures between 225° and 300°C into EuOOH, which was stable up to about 425°C. Between 435° and 465°C this compound decomposed into cubic Eu₂O₃, which was stable until its inversion to the high-temperature monoclinic form. X-ray diffraction data were collected for Eu(OH)₃ and EuOOH and showed that the trihydroxide has a hexagonal crystal structure and the oxyhydroxide is possibly orthorhombic. The Eu(OH)₂, EuOOH, and cubic EunOa powders contained particles up to several microns in size consisting of agglomerates of crystallites in the size range 200 to 400 A. The single monoclinic Eu₂O₃ sample studied contained crystallites whose average size was greater than 2000 A.     

Stability of ZrO2 Phases in Ultrafine ZrO2-Al2O3 Mixtures

Mixtures of ultrafine monoclinic zirconia and aluminum hydroxide were prepared by adding NH₄OH to hydrolyzed zirconia sols containing varied amounts of aluminum sulfate. The mixtures were heat-treated at 500° to 1300°C. The relative stability of monoclinic and tetragonal ZrO₂ in these ultrafine particles was studied by X-ray diffractometry. Growth of ZrO₂ crystallites at elevated temperatures was strongly inhibited by Al₂O₃ derived from aluminum hydroxide. The monoclinic-to-tetragonal phase transformation temperature was lowered to ∼500°C in the mixture containing 10 vol% Al₂O₃, and the tetragonal phase was retained on cooling to room temperature. This behavior may be explained on the basis of Garvie's hypothesis that the surface free energy of tetragonal ZrO₂ is lower than that of the monoclinic form. With increasing A1₂O₃ content, however, the transformation temperature gradually increased, although the growth of ZrO₂ particles was inhibited; this was found to be affected by water vapor formed from aluminum hydroxide on heating. The presence of atmospheric water vapor elevates the transformation temperature for ultrafine ZrO₂. The reverse tetragonal-to-monoclinic transformation is promoted by water vapor at lower temperatures. Accordingly, it was concluded that the monoclinic phase in fine ZrO₂ particles was stabilized by the presence of water vapor, which probably decreases the surface energy.     

Inhibition of Sintering and Surface Area Loss in Phosphorus-Doped Corundum Derived from Diaspore

The influence of magnesium, phosphorus, and iron additions on the low-temperature (≤1000°C) sintering of nanocrystalline α-Al₂O₃ derived from α-AlOOH has been investigated. α-AlOOH powder with a surface area of 50 m²/g yielded α-Al₂O₃ products with surface areas of 150 and 80 m²/g after dehydration at temperatures of 400° and 500°C, respectively. However, these products were prone to sintering at >600°C, and the surface area was reduced to 15 m²/g within only 1 h at 1000°C. Although magnesium and iron doping had no discernible effect, the presence of phosphorus inhibited sintering and surface-area loss significantly. Samples doped with 1%–2% phosphorus had surface areas of >31 m²/g after 100 h at 1000°C. Atomic force microscopy studies of α-Al₂O₃ pseudomorphs derived from α-AlOOH single crystals also demonstrated the inhibiting effect of phosphorus, as the rate of crack elimination was reduced on phosphorus-modified surfaces. The effects of the dopants are discussed with regard to their potential influence on α-Al₂O₃ surface energy and diffusivity.     

Preparation of Nanosized Perovskite-Type LaMnO3 Powders Using the Thermal Decomposition of a Heteronuclear Complex, LaMn(dhbaen)(OH)(NO3)(H2O)4

The heteronuclear LaMn(dhbaen)(OH)(NO₃)(H₂O)₄ complex was synthesized and perovskite-type hexagonal LaMnO₃ was obtained by its thermal decomposition at approximately 700°C. The complex and its decomposition products were analyzed using simultaneous thermogravimetric and differential thermal analysis (TG/DTA), X-ray diffraction (XRD) analysis, Fourier-transform infrared (FTIR) spectroscopy, Auger electron spectroscopy (AES), transmission electron microscopy (TEM) characterization, and specific surface area measurements. Although XRD analysis did not show the peaks of LaMnO₃ for the sample sintered at 600°C, the presence of polycrystalline LaMnO₃ together with an amorphous phase was confirmed by TEM-selected area diffraction. Particle sizes of the samples decomposed at 600° and 700°C were 20 and 50 nm, respectively. For the conventional solid-state reaction method, XRD results showed the formation of a LaMnO₃ single phase for the samples fired above 1000°C. However, AES showed that the elemental distributions of La, Mn, and O on the surface were not homogeneous even for the sample sintered at 1200°C. The thermal decomposition of the heteronuclear complex at low temperatures allows the synthesis of single-phase hexagonal LaMnO₃ powders having nanosized particles, homogeneous and free of intragranular pores, which are suitable for electroceramics applications.     

Enhanced Phase Stability and Photoluminescence of Eu3+ Modified t-ZrO2 Nanoparticles

Tetragonal ( t ) ZrO₂ nanoparticles have been obtained by a partial Eu³⁺→Zr⁴⁺ substitution, synthesized using a simple oxalate method at a moderate temperature of 650°C in air. The Eu³⁺ additive, 2 mol% used according to the optimal photoluminescence (PL), gives small crystallites of the sample. On raising the temperature further, the average crystallite size D grows slowly from 16 nm to a value as big as 49 nm at 1200°C. The Eu³⁺: t -ZrO₂ nanoparticles have a wide PL spectrum at room temperature in the visible to near-IR regions (550–730 nm) in the ⁵D₀→⁷F_J (Eu³⁺), J =1–4, electronic transitions. The intensity of the ⁵D₀→⁷F₄ group is as large as that of the characteristic ⁵D₀→⁷F₂ group of the spectrum in the forced electric-dipole allowed transitions. The enhanced t -ZrO₂ phase stability and wide PL can be attributed to the combined effects of an amorphous Eu³⁺-rich surface and part of the Eu³⁺ doping of ZrO₂ of small crystallites.     

Characterization of the Porous CaO Particles Formed by Decomposition of CaCO3 and Ca(OH)2 in Vacuum

The solid products of decomposing CaCO₃ powder in vacuum at 510°C (sr-CaO) and of decomposing Ca(OH)₂ powder at 320°C in vacuum (h-CaO) are particles which have approximately the same exterior dimensions as the parent CaCO₃ or Ca(OH)₂ particles. N₂ adsorption and desorption isotherms show that sr-and h-CaO have high internal surface areas which for sr-CaO have cylindrical symmetry, with the most common diameters being ∼ 10 nm, and for h-CaO are slit-shaped, with the most common slit width being ∼ 2.7 nm. The conclusions reached in earlier investigations, i.e that these decomposition reactions in vacuum initially yield a form of CaO which has the same unit cell dimensions as the parent solid, were in error, probably because water vapor converts much of the CaO to poorly crystalline Ca(OH)₂ before XRD measurements can be completed in air. From the volume of N₂ adsorbed by the porous powders, the porosity of h-CaO is calculated to be 36±5% and of sr-CaO 41.5±5%. These porosities imply that the linear dimensions of the 1 to 20 μm particles of h-CaO and sr-CaO are ∼5% smaller than those of the parent particles. XRD measurements made as a function of time show that particle shrinkage must occur by cooperative, diffusionless movement of crystallites of sr-CaO or h-CaO as they form.     

Subsolidus Equilibria in the System BaO-TiO2-GeO2

Subsolidus phase relations in the system Ba0-Ti02-Ge02 were investigated using conventional solid-state reaction techniques and X-ray powder diffraction. The existence of 2 ternary compounds, BaTiGe309 and BazTiGeZ08, was confirmed and their X-ray crystallographic data are presented. The compound BaTiGe₃0₉ has a lower limit of stability at 1135°C and melts incongruently at 1232°C; Ba₂TiGe₂O₂ melts congruently at 1228°C. Subsolidus compatibility relations in the ternary system were established and tie lines between the various phases which constitute a total of 12 compatibility triangles at 1000°C are shown in a subsolidus phase diagram.     

Direct Synthesis and Hydration of Calcium Aluminosulfate (Ca4Al6O16S)

Calcium aluminosulfate (Ca₄Al₆O₁₆S or C₄A₃̄) was prepared by direct synthesis from calcium and aluminum nitrates, and aluminum sulfate. CaAl₄O₇(CA₂) formed as an intermediate at 900°C, and C₄A₃̄ was the main phase after calcination at 1100°C. The specific surface areas after calcination at 1100° and 1300°C were ∼2.5 and 1 m²/g, respectively. Hydration was investigated using XRD, DSC, SEM, conduction calorimetry, and solid-state ²⁷Al MAS-NMR spectroscopy. Calorimetry showed that the induction period was longer than that of a sample prepared using conventional solid-state sintering, and this was attributed to the formation of amorphous coatings. Crystalline hydration products, principally calcium monoaluminosulfate hydrate and aluminum hydroxide, appeared subsequently. Although the induction period was very long, complete hydration occurred as early as 3 d in the sample calcined at 1100°C and was 91% complete in the sample calcined at 1300°C.     

Particle Formation During Spray Pyrolysis of Lead Zirconate Titanate

A twin-fluid atomization spray pyrolysis technique has been used to produce lead zirconate titanate (PZT) powders from a sol–gel precursor solution. Samples were removed from ports sited along the reactor in order to examine particle development at progressive stages of pyrolysis. The total time in the reactor was 2.6 s. The size and shape of the particles showed no change between the first port (190°C) and the hottest part of the reactor (820°C), indicating that the physical structure of the particles was established during the initial drying stages. The powders were mainly composed of spherical particles, but irregular forms were also present, which were thought to result from the inward collapse of hollow gelatinous particles. Crystallization of PZT commenced at around 700°C, initially to a pyrochlore or fluorite intermediate phase, with the desired perovskite phase developing between 790°C and 815°C. However, a minor amount of the pyrochlore/fluorite phase persisted in the final powder. The final powders also contained basic lead carbonate, 2PbCO₃·Pb(OH)₂, which existed in the form of elongated crystallites on the surface of the PZT particles.     

Surface Orientation and Wetting Phenomena in Si/α-Alumina System at 1723 K

Wetting phenomena and the effect of alumina surface orientation on the wettability in Si/α-Al₂O₃ system were studied by an improved sessile drop method using     ,     , C(0001) faces of single crystals and polycrystals at 1723 K in a reducing Ar–3% H₂ atmosphere. The contact angles show a vibration behavior for all the single crystals but to a less extent for the polycrystals. The extent of the vibration correlates not only with the reaction intensity but also with the stability of the Si droplet on the alumina surfaces. The interfacial reaction leads to the formation of a series of reaction rings, which is more serious at the single crystal surfaces. More importantly, the wettability is dependent on the alumina surface orientation, with the intrinsic contact angles being about 98±2°, 101±1°, 69±1°, and 98±2°, respectively, for the     ,     , C(0001) and polycrystal α-Al₂O₃ substrates. The much smaller contact angle for molten Si on the C(0001) surface is explained by the favorable reduction in the Si/α-Al₂O₃ interfacial free energy by the terminated and enriched aluminum atoms at the reconstructed     surface. The importance of the aluminum presence at the Si/α-Al₂O₃ interface to the wettability of this system was further demonstrated by a substantial improvement in the wettability of the     α-Al₂O₃ substrates by Si–Al alloys.     

Surface Areas and Morphologies of CaO Produced by Decomposition of Large CaCO3 Crystals in Vacuum

The CaO formed by complete isothermal decomposition of calcite single crystals in vacuum has surface areas that range from 127.10 m²g at 650°C to 60 ± 20 m²/g at 900°C. Surface areas are not significantly reduced by annealing at 900°C in vacuum. SEM observations and other available data show that CaO particles, which are first formed in an aggregate with relatively uniform pores, rearrange when the CaO layer thickness exceeds =10 to 50 μm.     

Microstructural Characterization of ZrO2 Particles Prepared by Reaction of Gaseous ZrCl4 with Fe2O3

The microstructure of ZrO₂ fine particles produced by a novel synthesis method at 450° and 950°C has been studied. The fundamentals of the synthesis method, which involves both chemical and diffusion phenomena, are presented. The method is based on mass transport through the gaseous phase between metallic zirconium and Fe₂O₃ powder. The mass-transporting chemical species are zirconium and iron chlorides. This article focuses on the microstructure and structure of ZrO₂ particles formed by the reaction between gaseous ZrCl₄ and solid Fe₂O₃, which is a relevant reaction step that occurs during the synthesis process. The resulting ZrO₂ crystals grown on Fe₂O₃ particles have been analyzed using transmission electron microscopy. Microstructural characterization has been complemented by X-ray diffractometry analysis. Tetragonal-ZrO₂ is produced at 450°C and monoclinic-ZrO₂ single crystals are produced at 950°C.     

High-Temperature Characteristics of Transition Al2O3 Powder with Ultrafine Spherical Particles

Ultrafine transition Al₂O₃ powder with spherical particles was prepared by an arc-discharge method. High-temperature characteristics were found to be superior to those of commercial A1₂O₃ powders by DTA, specific surface-area measurements, XRD, and TEM. The powder studied transformed to α-phase at about 1335°C. After heat treatment at 1260°C for 1 h, the specific surface area of the powder decreased from 25.0 to 17.3 m²/g. Some particles were able to retain the transition phase even after 106 h at 1160°C.     

Transformation, Microstructure Development, and Densification in α-Fe2O3-Seeded Boehmite-Derived Alumina

Addition of α-Fe₂O₃ seed particles to alkoxide-derived boehmite sols resulted in a 10-fold increase in isothermal rate constants for the transformation of γ- to α-Al₂O₃. Changes in porosity and surface area with sintering temperature showed no effect of seeding on coarsening of the transition alumina gels, but the 200-fold decrease in surface area associated with transformation to α-Al₂O₃ occurred ∼ 100°C lower in seeded gels compared with unseeded materials. As a result of high nucleation frequency and reduced microstructure coarsening, fully transformed seeded alumina retained specific surface areas >22 m²/g and exhibited narrow pore size distributions, permitting development of fully dense, submicrometer α-Al₂O₃ at ∼ 1200°C.     

Thermochemical Reactions Between PZT and Ag/Pd Powders: Relevance to Cofiring of Multilayer Actuators

Mixtures of Ag_{1− x} Pd _x ( x =0.2, 0.3) and doped PZT ceramic powders have been heat treated in air and the resulting phase content has been analyzed by X-ray diffraction and transmission electron microscopy. Beginning around 400°C, a phase similar to PbPdO₂ is formed on the surface of the Ag_{1− x} Pd _x particles and subsequently decomposes at temperatures <700°C. Consequently, the remaining Ag_{1− x} Pd _x powder becomes significantly silver-rich while the reaction progresses. After decomposition the Pd appears to realloy and the initial Ag_{1− x} Pd _x composition is recovered. We show that the reaction is all but eliminated in a nitrogen atmosphere. The occurrence of this reaction was also investigated in PZT multilayer actuators cofired with Ag_0.7Pd_0.3 electrodes. Transmission electron microscope analysis revealed the presence of distinct crystallites at the electrode–ceramic interface, most likely nucleated from a PbO liquid phase arising from the decomposition of PbPdO₂.     

Soft-Chemistry Synthesis, Characterization, and Stabilization of CGO/Al2O3/Pt Nanostructured Composite Powders

Soft-chemistry routes were used to synthesize Ce_0.9Gd_0.1O_1.95-based powders with attractive and stable structural, morphological, and textural properties. In the intermediate temperature range between 500° and 700°C, the average Gd-doped CeO₂ (CGO) crystallite size is in the range 9–22 nm and the specific surface area varies from 43.4 to 8 m²/g. Above 700°C, a phase separation occurs between ceria and gadolinium oxide. Addition of alumina was found to be useful in stabilizing the CGO nanocrystallites at a high temperature and to avoid phase separation. A homogeneous dispersion of Pt nanoparticles (<10 nm at 1000°C) in the CGO materials was found to be possible by post-impregnation, although direct insertion of the Pt precursors during the synthesis led to aggregated particles, with less potential for catalytic applications.     

Oxygen-Enhanced Crystallization of Solution-Derived 12CaO·7Al2O3

12CaO·7Al₂O₃ (C12A7) composed of nanosize cage structure can clathrate oxygen radicals (O⁻) and has a high potential to application of strong oxidizing catalysis. In the present report, we demonstrate a fabrication route to C12A7 fine powders by Chemical Solution Deposition method in order to enhance the catalytic reactivity. Aluminum sec-butoxide, calcium nitrate tetrahydrate, acetylacetone, 2-methoxyethanol, and nitric acid were used as raw materials. Precursor solution was dried and annealed at 800°–900°C in air or O₂ atmosphere. Crystalline C12A7 powders were obtained by annealing at 900°C in O₂ atmosphere. Scanning electron microscope and transmission electron microscope images of the obtained powders revealed C12A7 particles were sintered and formed several micrometer particles with many pores. BET specific surface area of the powders was 4.2 m²/g. Possibility for synthesizing C12A7 powder with higher specific surface area by the solution process was indicated.