Formation, Characterization, and Hot Isostatic Pressing of Cr2O3-Doped ZrO2 (0,3 mol% Y2O3) Prepared by Hydrazine Method

In the ZrO₂-Cr₂O₃ system, metastable t -ZrO₂ solid solutions containing up to 11 mol% Cr₂O₃ crystallize at low temperatures from amorphous materials prepared by the hydrazine method. The lattice parameter c decreases linearly from 0.5149 to 0.5077 nm with increased Cr₂O₃ content, whereas the lattice parameter a is a constant value ( a = 0.5077 nm) regardless of the starting composition. At higher temperatures, transformation (decomposition) of the solid solutions proceeds in the following way: t (ss)→ t (ss) + m + Cr₂O₃→ m + Cr₂O₃. Above 11 mol% Cr₂O₃ addition, c-ZrO₂ phases are formed in the presence of Cr₂O₃. The t -ZrO₂ solid solution powders have been characterized for particle size, shape, and surface area. They consist of very fine particles (15–30 nm) showing thin platelike morphology. Dense ZrO₂(3Y)-Cr₂O₃ composite ceramics (∼99.7% of theoretical) with an average grain size of 0.3 μm have been fabricated by hot isostatic pressing for 2 h at 1400°C and 196 MPa. Their fracture toughness increases with increased Cr₂O₃ content. The highest K _Ic value of 9.5 MPa·;m^1/2 is achieved in the composite ceramics containing 10 mol% Cr₂O₃.     

Formation and Transformation of WO3 Prepared from Alkoxide

Amorphous WO₃ or WO₃ or H₂O is formed by hydrolysis of tungsten ethoxide. The temperature of hydrolysis influences the crystallization of WO₃·H₂O. Tungsten hydrate (WO₃·H₂O) has an orthorhombic unit cell with a=0.5235 nm, b = 1.0688 nm, and c=0.5123 nm. Orthorhombic WO₃ crystallizes at 350° to 500°Cfrom amorphous WO₃. Cubic WO₃ is formed at 200° to 310°C with dehydration of WO₃·H₂O. WO₃ transformations are examined by high-temperature X-ray diffraction. The kinetics of formation of the cubic modification have been studied by measuring the weight decrease with a thermobalcnce. Formation isotherms can be interpreted in terms of the first-order equation –In (1–f)=kt; activation energies are 110 and 80 kJ mol⁻¹ for initial and final stages, respectively.     

Nanopowders of Na0.5K0.5NbO3 Prepared by the Pechini Method

A Pechini-based chemical synthesis route was used to produce powders of Na_0.5K_0.5NbO₃ (NKN). The thermochemistry of the gel was investigated using thermogravimetric analysis-fourier transform infrared (TGA-FTIR) evolved gas analysis; in addition, powder FTIR was used to analyze the gel residues after different heat treatments. The final decomposition of the organic components occurred at ∼650°C. However, hydrated–carbonated secondary phase(s) were detected by FTIR in powders that had been heated at 700°C, indicating that the NKN nanopowders are susceptible to a reaction with atmospheric moisture and carbon dioxide. The NKN particle sizes were in the range 50–150 nm after decomposition at 700°C.     

Thermodynamic Stability and Mechanisms of Formation and Decomposition of Perovskite Pb(Zn1/3Nb2/3)O3 Prepared by the PbO Flux Method

The mechanisms of formation and decomposition of the ferroelectric perovskite PZN [Pb(Zn_1/3Nb_2/3)O₃] were examined. The formation of perovskite PZN from the excess molten PbO environment is characterized by an inititial rapid formation of pyrochlore phase, followed by a subsequent reaction between the intermediate pyrochlore phase, ZnO, and liquid PbO to produce perovskite phase. The pure perovskite PZN crystal prepared by the PbO flux method is thermodynamically unstable over a wide range of temperature (600° to 1400°C), yielding pyrochlore phase and PbO as the decomposition products. The decomposition reaction of perovskite PZN proceeded uniformly with a spatial homogeneity throughout the specimen. The estimated activation energy of the decomposition reaction is approximatley 18 kcal/mol.     

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.     

Phase Formation and Dielectric Characterization of the Bi2O3–TeO2 System Prepared in an Oxygen Atmosphere

Solid-state synthesis of compositions from the Bi₂O₃–TeO₂ system show that, under an oxygen atmosphere, Te⁴⁺ oxidizes to Te⁶⁺ and yields four room-temperature stable compounds: Bi₂Te₂O₈, Bi₂TeO₆, Bi₆Te₂O₁₅, and new a compound with the nominal composition 7Bi₂O₃·2TeO₂. Dense ceramics can be prepared from all these compounds by sintering between 650° and 800°C under an oxygen atmosphere. The permittivity of these compounds varies from ∼30 to ∼54, the Q × f value from 1.100 to 41.000 GHz (∼5 GHz), and the temperature coefficient of resonant frequency from −43 to −144 ppm/K. Bi₆Te₂O₁₅ and 7Bi₂O₃·2TeO₂ do not react with silver, and, therefore, they have the potential to be used for applications in low-temperature cofired ceramic (LTCC) technology.     

Slip-Cast Ce0.8Sm0.2O1.9 Cone-Shaped SOFC

Cone-shaped Sm-doped CeO₂ (Ce_0.8Sm_0.2O_1.9, SDC) electrolyte cylinders have been fabricated using the slip-casting technique. A single solid oxide fuel cell has been prepared by applying a Sm_0.5Sr_0.5CoO₃ cathode on the outside of the cylinders and a NiO–SDC (7:3 wt%) anode on the inside. The open circuit voltage of the cell was 0.93 V at 400°C, and a maximum power density of about 300 mW/cm² at 700°C was obtained with humidified hydrogen (3% H₂O) as the fuel and ambient air as the oxidant. Impedance results showed that the performance of the cell was mainly influenced by the ohmic resistance of the electrolyte.     

Seeding Effects on Crystallization of KAlSi3O8, RbAlSi3O8, and CsAlSi3O8 Gels and Glasses

Crystallization of stoichiometric KAlSi₃O₈, RbAlSi₃O₈, and CsAlSi₃O₈ gels (single-phase and multiphasic gels) and glasses with and without seeding has been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectrometry (EDS). The pure gels of K-, Rb-, and Cs-feldspar compositions crystallized mainly to leucite (KAlSi₂O₆), a Rb analogue of leucite (RbAlSi₂O₃), and pollucite (CsAlSi₂O₆), respectively. The KAlSi₃O₈ glass also yielded leucite. No feldspar phases crystallized in the temperature region studied. The leucite crystallization temperature was lowered by using multiphasic gels. The crystallization sequence of the KAlSi₃O₈ glasses and single-phase gels did not change upon seeding with isostructural feldspar crystals. No significant crystallization effects were detected with the use of RbAlSi₃O₈ and CsAlSi₃O₈ multiphasic gels. However, K-feldspar (sanidine) was crystallized by using both compositionally and structurally different gels of KAlSi₃O₈, i.e., multiphasic gels seeded With feldspar crystals. The microstructure of oriented sanidine crystals around the seeds indicated an epitaxial crystallization mechanism.     

Fabrication and Characterization of a (100) Three-Axis-Oriented Single-Crystal (Ba0.7Sr0.3)TiO3 Thin Film Prepared by the Chemical Solution Deposition Method

Epitaxially grown single-crystal perovskite (100) three-axis-oriented (Ba_0.7Sr_0.3)TiO₃ thin films were prepared on a (100) platinum-coated (100) magnesium oxide (MgO) single-crystal substrate by the chemical solution deposition method using a solution derived from Ba(CH₃COO)₂, Sr(CH₃COO)₂, and Ti(O- i -C₃H₇)₄.
The growth of the film was found to depend on the annealing condition. A (Ba,Sr)TiO₃ thin film annealed at 1073 K was found to be a single crystal by transmission electron microscope. The single-crystal film exhibited a (100) three-axis orientation that followed the (100) orientation of the Pt substrate, as observed from an X-ray pole figure measurement and selected area electron diffraction patterns.     

Preparation and Characterization of Alkoxy-Derived SrZrO3 and SrTiO3

High-purity strontium, zirconium, and titanium alkoxides were synthesized and characterized as precursors for complex oxides. Simultaneous hydrolytic decomposition either of strontium and zirconium alkoxides or of strontium and titanium alkoxides was used to obtain nearly stoichiometric, ideally mixed SrZrO₃ or SrTiO₃ powders of high surface activity. As-prepared helium-dried SrTiO₃ is crystalline before calcination. An ultraviolet radiation technique demonstrates the nucleation and growth of SrZrO₃ crystallites in the calcination temperature range to 350°C. The experimental results are supported by ir, TGA, and X-ray diffraction data. The high degree of control over purity, mixing uniformity, and crystallite size demonstrates the value of the alkoxide precursor approach for the solution of reproducibility problems encountered in the synthesis of electrical-quality ceramics.     

Phase Relations in the System Ce2O3–Al2O3 in Inert and Reducing Atmospheres

The 1:1 compound, CeA1O₃, in the system Ce₂O₃–Al₂O₃ has been synthesized from the oxides and shown to have a perovskite-like tetragonal unit cell with the lattice parameters a = 3.763 and c = 3.792 Å. A new XRD pattern is suggested for CeA1O₃. This compound is shown to be stable up to 1950°C. The 1:11 compound, CeAl₁₁O₁₈, has also been synthesized and shown to possess a magnetoplumbite-like hexagonal unit cell with the lattice parameters α= 5.558 and c = 22.012 å. An XRD pattern is suggested for CeAl₁₁O₁₈ for the first time. The evolution of eutectic-like microstructures was observed and reported in the Ce₂O₃-rich side of this binary system.     

Formation of BaTiO3 from BaCO3 and TiO2 in Air and in CO2

The formation of BaTiO₃ from equimolar BaCO₃ and TiO₂ (rutile) mixtures was studied in air and in CO₂. A small amount of BaTiO₃ is formed first directly from BaCO₃ and TiO₂ at the surface of contact. From then on it is a diffusion-controlled reaction, and both BaTiO₃ and Ba₂TiO₄ are produced, with Ba₂TiO₄ being formed in much larger amounts. In 1 atmosphere of CO₂, the intermediate Ba₂TiO₄ was suppressed up to a temperature of about 1100°C. in agreement with thermodynamic calculations. Ba₂TiO₄ reacts fast with 1 atmosphere of CO₂ below about 1100°C. to produce BaTiO₃and BaCO₃     

Characterization of Freeze-Dried Al2O3 and Fe2O3

Oxide crystallite formation and growth from freeze-dried sulfates were studied for the representative materials Al₂O₃ and Fe₂O₃. Transmission and scanning electron micrographs showed the formation and growth of chainlike aggregates of crystallites. Aggregation occurred as part of the nucleation and growth of the oxide, and discrete oxide particles were never present. Orientation of the chain aggregates was related to the ice structure formed during freezing. X-ray line broadening data showed that crystallite size is a function of the 1/5 to 1/7 power of time for isothermal treatments. A qualitative analysis of material transport favored the surface diffusion mechanism.     

Synthesis and Characterization of (Ce0.67Tb0.33)MnxMg1−xAl11O19 Phosphors Derived by Sol–Gel Processing

A (Ce_0.67Tb_0.33)Mn _x Mg_{1− x} Al₁₁O₁₉ phosphor powder was synthesized, using a simple sol–gel process, by mixing citric acid with CeO₂, Tb₄O₇, Al(NO₃)₃·9H₂O, Mg(OH)₂·4MgCO₃·6H₂O, and Mn(CH₃COO)₂. The phosphor crystallized completely at 1200°C, and the phosphor particle size was between 1 and 5 μm. The excitation spectrum was characteristic of Ce³⁺, while the emission spectrum was composed of lines from Tb³⁺ and Mn²⁺. The Mn²⁺ gave a green fluorescence band, and concentration quenching occurred when x > 0.10. The luminescent properties of the phosphor were explained by a configurational coordinate model.     

Synthesis and Electrical Properties of Dense Ce0.9Gd0.1O1.95 Ceramics

Uniform spherical powders of Ce_0.9Gd_0.1O_1.95 with an average diameter of 250 nm were obtained at 700°C from a sol-gel process of mixing nitrates and ethylene glycol. Broadening of the X-ray peaks of the fluorite structure reveals a small crystallite size within the powders. Sintering in air of pressed pellets of the powders at 1585°C gives ceramics of 99% theoretical density with grain sizes 1-10 µm and a cubic unit cell a = 5.422 ± 0.034 Å. The electrical conductivity σ=σ_o+σ_e has two components. In air or argon, the electronic component σ_e is negligible and the oxide-ion conductivity σ_o is not described by a classical Arrhenius equation; a pronounced curvature at T similar/congruent T * has been observed in the Arrhenius plot of the bulk conductivity. The system could be modeled by a condensation of mobile oxygen vacancies into ordered clusters below a temperature T * similar/congruent 583 ± 45°C and a motional enthalpy Δ H _m= 0.63 ± 0.01 eV for the vacancies. A measured trapping energy Δ H _t(1 - T/T *) has Δ H _t= 0.19 ± 0.01 eV = 2.57 kT *. In a reducing atmosphere, σ_e exhibits a small-polaron motional enthalpy Δ H _p= 0.40 ± 0.08 eV for transfer of a 4 f electron from a Ce³⁺ to a Ce⁴⁺ ion and a Δ H _p+Δ H _pt= 0.51 ± 0.04 eV at T < T *.     

Characteristics and Formation Mechanism of BaTiO3 Powders Prepared by Twin-Fluid and Ultrasonic Spray-Pyrolysis Methods

Spherical fine (micrometer and submicrometer in size) homogeneous BaTiO₃ powders were synthesized from ethanol: water solutions of BaCl₂ and TiCl₄ using the spray-pyrolysis technique. Two different atomizers—twin-fluid and ultrasonic, with a resonant frequency of 2.5 × 10⁶ Hz—were used for mist generation. Hollow spherical particles containing a certain amount of unreacted BaCl₂ phase and having a mean particle diameter of 2.5 μm were obtained at 1173 K using a twin-fluid atomizing system. Decomposition of precursors and their transition to the cubic BaTiO₃ phase occurred, even at 973 K in the case of the ultrasonic atomizing system. For the initial droplet size of 2.2 μm and residence time of ∼60 s, spherical BaTiO₃ particles with the mean particle diameter of 0.53 μm were obtained. A BaTiO₃ formation mechanism has been proposed as a reaction between TiO₂ and BaCl₂ rather than a reaction of oxides.     

Kinetics of BaTiO3 and PbTiO3 Formation from Metallo-organic Precursors

Kinetics of BaTiO₃ and PbTiO₃ formation from metalloorganic precursors were studied. The fine grain size of the decomposed product and the greater degree of mixing led to very rapid kinetics of compound formation. The kinetics data were fitted to the Carter model for a diffusion-controlled process. Formation of PbTiO₃ was modeled as a two-stage process with a single activation energy, and the formation of BaTiO₃ as a single-stage process.