Structure Evolution in Hydrothermally Processed (<100°C) BaTiO3 Films

Thin films of cubic BaTiO₃ were processed hydrothermally at 40°–80°C by reacting thin layers of titanium organo metallic liquid precursors in aqueous solutions of either Ba(OH)₂ or a mixture of NaOH and BaCl₂. All films (thickness ∼1 μm) were polycrystalline with grain sizes ranging from nano- to micrometer dimensions. BaTiO₃ formation was facilitated by increasing [OH^-], [Ba²⁺], and the temperature. The film structure was related to the nucleation and growth behavior of the BaTiO₃ particles. Films processed at relatively low [OH^-], [Ba²⁺], and temperatures were coarse grain and opaque, but increasing [OH^-], [Ba²⁺], and temperature caused the grain size to decrease, resulting in transparent films.     

Templated Grain Growth of Barium Titanate Single Crystals

BaTiO₃ single crystals were grown via templated grain growth (TGG), which is a process in which a single-crystal "template" is placed in contact with a sintered polycrystalline matrix and then heated to migrate the single-crystal boundary into the matrix. Millimeter-sized, stoichiometric single crystals of BaTiO₃ were produced by heating polycrystalline matrix with a relative density of 97% and a Ba/Ti ratio of <1.00, which was bonded to a BaTiO₃ single crystal, at temperatures above the eutectic temperature. Growth rates of 590–790, 180–350, and 42–59 μm/h were observed for {111}-, {100}-, and {110}-oriented single-crystal templates, respectively. Lower-surface-energy facets were formed for {111}- and {100}-oriented templates, whereas {110} crystals maintained a {110} growth front, which indicated that this plane orientation was the lowest-energy surface in this system. SrTiO₃ also was shown to be a suitable substrate for TGG of BaTiO₃.     

Hydrothermal Synthesis of Nanometer-Sized Barium Titanate Powders: Control of Barium/Titanium Ratio, Sintering, and Dielectric Properties

Nanometer-sized BaTiO₃ powders have been synthesized hydrothermally from Ba(OH)₂ and titanium alkoxide at 150°C for 2 h, and the Ba/Ti ratio has been measured with an accuracy of ±0.003. Stoichiometric powders can be obtained by adjusting the Ba/Ti ratio of the reactants to a value of 1.018. At a lower Ba/Ti ratio, the solubility of Ba(OH)₂ prevents full incorporation of barium, and barium-deficient powders result. A higher Ba/Ti ratio leads to the incorporation of excess barium in the powder. K _s(BaTiO₃,-25°C) = 7 × 10^-8 has been calculated for the equilibrium reaction. From this result, two reproducible processes for the synthesis of stoichiometric BaTiO₃ are proposed. The processes rely only on very accurate control of the chemical composition (Ba/Ti ratio) of the precursor suspension. The sintering behavior of powders having Ba/Ti ratio values between 0.965 and 1.011 is described from results of dilatometric measurements and isothermal sintering. Room-temperature dielectric constants as high as 5600 and losses as low as 0.009 have been obtained for a stoichiometry slightly less than 1.000. It is expected that optimum sintering behavior and electrical properties are obtained in the stoichiometry range 0.995-1.000.     

Solid-State Preparation of BaTiO3-Based Dielectrics, Using Ultrafine Raw Materials

BaTiO₃ and Ba(Ti,Zr)O₃ dielectric powders have been prepared from submicrometer BaCO₃, TiO₂, and ZrO₂. By use of submicrometer BaCO₃ the intermediate formation of Ba₂TiO₄ second phase can be widely suppressed. Monophase perovskites of BaTiO₃ were already formed at 900°C and Ba(Ti,Zr)O₃ at 1050°C. Aggregates of very small subgrains could be easily disintegrated to particle sizes <0.5 μm.     

Preparation of Fine Tetragonal Barium Titanate Powder by a Microwave–Hydrothermal Process

A microwave–hydrothermal (MH) process was performed at 240°C to prepare tetragonal BaTiO₃ from TiCl₄ and Ba(OH)₂. No alkali hydroxide was used to avoid contaminations. MH BaTiO₃ powder with a c / a ratio of 1.010 and a mean size of 180 nm was synthesized within only 9 h. The MH BaTiO₃ contains a very low concentration of lattice hydroxyl group, associated with a very small lattice strain. The measured density of the MH BaTiO₃ is favorably consistent with the theoretical value, and the Ba/Ti stoichiometry determined is 0.996. The formation of a tetragonal structure in BaTiO₃ and the particle growth were strongly promoted by the MH process. The effects of lattice defects on the stoichiometry and the determination of transition enthalpy were discussed.     

Effect of Precursor Pyrolysis on the Dielectric Properties of Hydrothermally Derived Barium Titanate Thin Films

BaTiO₃ thin films were processed hydrothermally on Ag-coated quartz substrates at 90°C by reacting films of titanium dimethoxy dineodecanoate (TDD) in aqueous solutions of Ba(OH)₂. Two reaction sequences were used: either the TDD was reacted directly in aqueous Ba(OH)₂, or the TDD was first pyrolyzed in air at temperatures ranging from 200° to 500°C before hydrothermal reaction. Depending on the processing conditions, the dielectric constant of the thin films ranged from 5 to 170, the dielectric constant increasing with increasing pyrolysis temperature. Thin film porosimetry data suggest that the improvement in film dielectric performance is related to decreases in thin film residual porosity after hydrothermal reaction.     

Model Apatite Systems for the Stabilization of Toxic Metals: I, Calcium Lead Vanadate

Apatites of composition (Ca_{10− x} Pb _x )(VO₄)₆F₂ with 0 ≤ x ≤ 9 were synthesized by sintering in air at 800°C the oxides of calcium, lead, and vanadium that were mixed with calcium fluoride. Variations in lattice parameters, grain size, and durability were monitored as a function of composition. The expected dilation in unit cell edges with increasing replacement of calcium (IR = 1.26 Å) by lead (IR = 1.45 Å) was observed. The a cell edge (in angstroms) varied linearly (0.0458 x + 9.7068) with x , while c followed the binomial function 0.0018 x ²+ 0.0279 x + 7.0118. Average grain sizes increased from approximately 5 μm ( x = 0) to 25 μm ( x = 9) as grain growth was enhanced due to incipient melting of the lead-rich compositions. For x < 5 the materials were biphasic. Overall dissolution, as determined by the toxicity characteristic leaching procedure (TCLP), was faster in calcium-rich apatites. Etching of well-crystallized apatite grains occurred preferentially on {10 1 0} faces. These leach losses were augmented through the more rapid removal of cryptocrystalline regions and intergranular thin films.     

Hydrothermal Synthesis of Tetragonal Barium Titanate from Barium Hydroxide and Titanium Dioxide under Moderate Conditions

Tetragonal BaTiO₃ powders were prepared hydrothermally, using Ba(OH)₂·8H₂O and TiO₂ (anatase), in the absence of anions such as chloride ions, at a temperature of 220°C for several days. Characterization via X-ray diffractometry, scanning electron microscopy, and differential scanning calorimetry confirmed that increasing the Ba:Ti molar ratios (from 1:1 to 4:1) and alkaline concentrations (from 1.0 M to 3.0 M ) promotes the formation of tetragonal BaTiO₃.     

Zinc Vanadates in Vanadium Oxide-Doped Zinc Oxide Varistors

Convergent-beam electron diffraction has been used to determine the space groups of β- and γ-Zn₃(VO₄)₂ particles in vanadium oxide-doped zinc oxide varistors. The crystal structure of β-Zn₃(VO₄)₂ has been determined to be monoclinic with space group P 2₁ and lattice parameters of a = 9.80 Å, b = 8.34 Å, c = 10.27 Å, and β= 115.8°, whereas that of γ-Zn₃(VO₄)₂ is monoclinic with space group Cm and a = 10.40 Å, b = 8.59 Å, c = 9.44 Å, and β= 98.8°. Energy-dispersive X-ray microanalysis of these two phases shows significant deviations from their expected stoichiometry. It is apparent that the β-phase is, in fact, the metastable Zn₄V₂O₉ phase, whereas the γ-phase either is a new oxide that consists of zinc, vanadium, and manganese or, more likely, is a zinc vanadate phase with a Zn:V atomic ratio of 1:1 that has the ability to go into solid solution with manganese.     

Nucleation and Inhibition Control during the Hydrothermal–Electrochemical Growth of Barium Titanate Films

The control of the microstructure of BaTiO₃ films grown on titanium by the hydrothermal–electrochemical method was investigated. Experiments were conducted in a three-electrode high-pressure electrochemical cell in a 0.1 M Ba(OH)₂ electrolyte at 150°C. Results showed that the spontaneous initial nucleation linked to pure hydrothermal BaTiO₃ formation can be inhibited by cathodically protecting the titanium electrode from the moment it is immersed in the electrolyte. The application of initial nucleation pulses of varying cathodic potentials affected the grain size of the deposit. It is suggested that the formation of a titanium oxide layer is a necessary step previous to the nucleation of BaTiO₃.     

New High-Permittivity AgNb1-xTaxO3 Microwave Ceramics: Part I, Crystal Structures and Phase-Decomposition Relations

The crystal structure of monophasic AgNb_1/2Ta_1/2O₃ was investigated via Rietveld refinement using powder X-ray diffractometry (XRD) data. The study revealed a monoclinic unit cell of the P 2/ m space group with the following unit-cell parameters: a = 3.9286(3) Å, b = 3.9259(2) Å, c = 3.9302(3) Å, and β= 90.49(1)°. High-temperature XRD studies of the decomposition of AgNb_1/2Ta_1/2O₃ showed that the kinetics of the decomposition are influenced by the volatilization of silver. Suppression of silver volatilization by enclosing the sample in a corundum tube and applying an oxygen atmosphere yielded sintered, almost-monophasic AgNb_1/2Ta_1/2O₃ ceramics with >97% of the theoretical density. The Ag₈(Nb,Ta)₂₆O₆₉ phase, which regularly appeared as a result of partial decomposition of Ag(Nb_{1− x} Ta _x )O₃, was studied by energy-dispersive spectroscopy analysis and XRD. The Ag₈(Nb,Ta)₂₆O₆₉ phase exhibited a bronzelike orthorhombic structure with the following unit-cell parameters: a = 37.116(5) Å, b = 12.432(3) Å, and c = 7.826(2) Å. Indexed powder diffraction data for Ag₈(Nb,Ta)₂₆O₆₉ have been reported.     

Effect of the Atomic Ratio of Ba to Ti on Optical Properties of Gold-Dispersed BaTiO3 Thin Films

Gold-dispersed BaTiO, thin films were prepared by the rf magnetron sputtering method. The atomic ratio of Ba to Ti in the films was varied and the effects on the linear and nonlinear optical properties were investigated. As the atomic ratio increased, the value of χ⁽³⁾/α₅₃₂ for the gold-dispersed BaTiO₃ thin films slightly increased. It was found that the increase in the value of χ⁽³⁾/α₅₃₂ is due mainly to a change in the crystalline state of the BaTiO₃ matrix. However, it was also found that the atomic ratio had a smaller effect on the value of χ⁽³⁾/α₅₃₂ than did the refractive index of the matrix.     

Single-Step Dip Coating of Crack-Free BaTiO3 Films >1 μm Thick: Effect of Poly(vinylpyrrolidone) on Critical Thickness

BaTiO₃ coating films were prepared from Ba(CH₃COO)₂–Ti(OC₃H₇ⁱ)₄–H₂O–CH₃COOH–C₃H₇ⁱOH solutions containing poly(vinylpyrrolidone) (PVP) via single-step, nonrepetitive dip coating. The critical thickness—i.e., the maximum film thickness achieved without crack formation via nonrepetitive dip coating—was successfully increased by incorporation of PVP in the precursor solution. Relatively dense, crack-free BaTiO₃ films >1 μm in thickness were achieved via single-step deposition using a solution containing PVP of average molecular weight of 630 000. Incorporation of an excess amount of PVP, however, led to a decrease in the critical thickness. Higher-molecular-weight PVP was more effective in increasing the critical thickness, whereas N-vinyl-2-pyrrolidone monomers did not affect the critical thickness. Stepwise heating of the gel films resulted in increased optical transmittance of the films, accompanied by film densification.     

Uniform Coating of Nanometer-Scale BaTiO3 Layer on Spherical Ni Particles via Hydrothermal Conversion of Ti-Hydroxide

A uniform BaTiO₃ nano layer was coated on spherical Ni particles for multilayer ceramic capacitor applications via a Ti-hydroxide coating using the controlled hydrolysis of a TiCl₄ butanol solution containing (C₂H₅)₂NH (diethylamine, DEA) and its subsequent hydrothermal reaction at various [Ba(OH)₂], residual [DEA], and hydrothermal temperatures. The hydrothermal conversion was successful at [Ba(OH)₂]≥0.065 M (Ba/Ti≥1.3) and T ≥150°C, and the residual DEA in the Ti-hydroxide coating layer not only affected the formation of the BaTiO₃ phase but also resulted in a rough surface morphology. When a minimal amount of DEA was involved in the formation of Ti-hydroxide, a uniform BaTiO₃ coating with a clean surface morphology could be attained, which was confirmed by elemental mapping of the coated powder and the observation of hollow spheres after removing the Ni core. The BaTiO₃ coating was very effective not only in preventing Ni oxidation but also in shifting the starting point of Ni densification to a higher temperature.     

Conversion of SiO2 Diatom Frustules to BaTiO3 and SrTiO3

Diatom frustules were used as bio-templates to synthesize functional ceramics via solid–gas displacement reactions. Silica-based frustules were exposed to TiF₄ at 330°C to form TiOF₂, which was later converted to TiO₂ (anatase) by heat treatment in air at 600°C. The TiO₂ frustules were then exposed to molten Ba(OH)₂ or Sr(OH)₂ to form BaTiO₃ or SrTiO₃, respectively. In both cases, near-complete conversion was achieved while retaining the morphology of the original silica frustules. BaTiO₃ and SrTiO₃ frustules exhibit nearly phase pure, nanocrystalline perovskite structure.     

Kinetics of Barium Titanate Synthesis

Reaction curves were obtained at various temperatures and concentrations for the formation of BaTiO₃ from particulate titania in Ba(OH)₂ solution. Kinetic analyses were performed by constructing mathematical models which took into account the particle size distribution of the reactant titania for both the topochemically-rate-controlled and the diffusion-rate-controlled reactions. At [Ba(OH)₂] > ca. 0.1 M the rate-controlling step is the Ba reaction with TiO₂ at the interface. The measured activation energy is 105.5 kJ/mol. The rates are independent of Ba(OH)₂ concentration, indicating that the TiO₂ interface is saturated. At [Ba(OH)₂] < ca. 0.1 M the rate-determining step shifts to diffusion through the product BaTiO₃ layer, the rates are concentration dependent, and the BaTiO₃ particle sizes are inversely proportional to the Ba(OH)₂ concentrations used.     

Hydrothermal Soft Chemical Synthesis and Particle Morphology Control of BaTiO3 in Surfactant Solutions

Barium titanate (BaTiO₃) particles with book-like and spherical morphology were prepared by using a hydrothermal soft chemical process in the presence of a cationic surfactant. A layered titanate of H_1.07Ti_1.73O₄ with a lepidocrocite-like structure and plate-like particle morphology was used as the precursor. The layered titanate was hydrothermally treated in a Ba(OH)₂–(HTMA-OH) ( n -hexadecyltrimethylammonium hydroxide) solution or a Ba(OH)₂–(HTMA-Br) ( n -hexadecyltrimethylammonium bromide) solution in a temperature range of 80°–250°C to prepare BaTiO₃. The intercalation reaction of HTMA⁺ with the layered titanate promotes the structural transformation reaction from the layered titanates to BaTiO₃, while it inhibits the structural transformation reaction to anatase under the hydrothermal conditions. The particle morphology of BaTiO₃ prepared by this method dramatically changes with changing reaction conditions. HTMA⁺ plays an important role in changing particle morphology in the hydrothermal soft chemical process.     

High-Temperature Structural Phase Transition in Ca0.7Ti0.7La0.3Al0.3O3: Investigation by Synchrotron X-Ray Diffraction

Mixed-oxide prepared Ca_0.7Ti_0.7La_0.3Al_0.3O₃ (CTLA) ceramics (≈96% dense), grain size 6–7 μm, with dielectric properties (at 4 GHz) of ɛ_r≈46, Q × f ≈38 000 GHz, and τ_f+13 ppm/°C, were studied at 25°–1300°C using synchrotron X-ray powder diffraction. At room temperature, CTLA exhibits a distorted orthorhombic structure, with two tilt systems: a =5.40383 (4) Å, b =5.41106 (6) Å, and c =7.64114 (7) Å with space group Pbnm . At 1050°±25°C, there is a transition from orthorhombic ( Pbnm ) to tetragonal ( I 4/ mcm ), with a simpler tilt arrangement. The lattice parameters at 1100°C were: a =5.44285 (4) Å and c =7.68913 (8) Å.     

Influence of Grain Growth on Dielectric Properties of Nb-Doped BaTiO3

Effects of grain size and grain growth in Nb-doped BaTiO₃ on temperature and frequency dependencies of the dielectric constant were investigated. When 0.65 μm powder is sintered to an average grain size of 1 μm, two dielectric constant peaks indicate the presence of Nb-free BaTiO₃ and of Nb-containing material. Single peaks are observed above room temperature after additional grain growth or when 0.07 μm powder is sintered to an average grain size of 1 μm. The Curie point of pure BaTiO₃ with 1 μm grains is 4 to 6°C lower than that of material with grains >10 μm. Thermodynamically, this behavior is accounted for by a phase inversion stress ∼ the room-temperature stress.     

Electroceramics from Source Materials via Molecular Intermediates: BaTiO3 from TiO2 via (Ti(catecholate)3)2-

Rutile or anatase may be depolymerized and complexed by sequential treatment with (i) H₂SO₄/(NH₄)₂SO₄, (ii) H₂O, and (iii) catechol/NH₄OH to produce the intermediate (NH₄)₂(Ti(catecholate)₃) · 2H₂O. Treatment with Ba(OH)₂· 8H₂O leads to an acid-base reaction generating Ba(Ti(catecholate)₃) · 3H₂O, in which the Ba:Ti ratio is held at 1:1 at the molecular level. Calcination produces BaTiO₃ powder.