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.     

掺镁钛酸钡的抗还原研究

对掺镁钛酸钡进行了．抗还原研究。研究了Ba／Ti摩尔比、镁掺杂摩尔分数和烧结气氛对陶瓷的致密化、电阻率以及介电性能的影响。结果表明：在氮气气氛中烧结的样品比在空气中烧结的样品具有更大的介电常数、较小的介电损耗。当烧结温度和保温时间都相同时,与在空气中烧结的样品相比,在氮气气氛条件下烧结的样品具有较大的密度,较大的电阻率．较大的介电常数和较小的介电损耗。当镁掺杂摩尔分数为1％时、随着Ba／Ti摩尔比的增加,介电损耗的变化不大;而当镁掺杂摩尔分数为2％时,随着Ba／Ti摩尔比的增加,介电损耗增加。     

Thermal Analysis of Precursors of Barium Titanate Prepared by Coprecipitation

Thermal analysis was performed on coprecipitated materials and on individual components. The detailed decomposition schemes of coprecipitates and individual components are proposed and discussed. According to the proposed decomposition schemes, the values of the observed weight loss are in good agreement with those of the theoretical values of the coprecipitated materials and individual components. The results indicate that barium titanyl oxalate is an inserting compound, i.e., a structure of distorted barium hydrogen oxalate hydrate being inserted by Ti(OH)₃⁺. The results also verify that copreciptation of barium and titanium ions in an oxalate aqueous solution at pH 7 is a mixture of BaC₂O₄· 0.5H₂O and TiO(OH)₂· 1.5H₂O and coprecipitation of barium and titanium ions using the process of Yamamura et al. is a mixture of Ba(NO₃)₂ and Ti(OH)₂C₂O₄.     

Laser-Sintered Barium Titanate

Laser sintering of alkoxy-derived ultrafine BaTiO₃ powders was investigated. The temperature increases of the sample with laser irradiation were measured with a thermocouple. It was found that laser irradiation could generate enough heat to sinter ceramics. A slurry was prepared by mixing an alkoxy-derived BaTiO₃ powder, binder additives, solvent, and plasticizer. The slurry was tape cast and dried to give a green sheet. The green sheet was laser sintered and was then characterized by SEM, XRD, and density measurements. The effect of burnout before laser irradiation and the characteristic microstructure of laser-sintered BaTiO₃ are described.     

Effect of the Ba/Ti Ratio on the Microstructures and Dielectric Properties of Barium Titanate-Based Glass–Ceramics

A series of BaTiO₃ (BT)-based ferroelectric glass–ceramics have been prepared via controlled crystallization by varying the Ba/Ti ratio in an aluminum silicate glass composition, and the subsequent microstructure, phase evolution, and dielectric properties have been investigated. X-ray diffraction indicated that an increasing Ba/Ti ratio promoted the crystallization of BaTiO₃ and BaAl₂Si₂O₈ from the glass matrix, and the cracking of glass–ceramics appears to be correlated to mismatch in the thermal expansion coefficient among BaTiO₃, BaAl₂Si₂O₈, and the glass matrix. In addition, it was found that increasing the Ba/Ti ratio facilitated the formation of a dendrite structure with obvious porosity. The change in the Ba/Ti ratio in the glass notably modified the dielectric properties: a high Ba/Ti ratio in the glass resulted in an increased dielectric constant and decreased breakdown strength.     

Effect of Silver Addition on the Dielectric Properties of Barium Titanate-Based X7R Ceramics

Different amounts of silver (0.5–10 wt%) have been mixed with EIA X7R-type ceramic powders based on barium titanate. The XRD analysis indicated that no phases other than BaTiO₃ and silver were present in the doped ceramics; it further suggested that no reaction took place between BaTiO₃ and silver during calcination and sintering. SEM observation showed that the silver particles presented island distribution in the BaTiO₃ ceramic matrix. The densification and dielectric properties of the silver-doped ceramics in disk form were investigated. A large amount of silver addition (>1 wt%) was found to improve the sintered density and dielectric properties. The temperature coefficient of capacitors of the ceramics doped with 10 wt% silver still met the X7R characteristics, and the dielectric constant of the ceramics at room temperature was >6000, which is the highest dielectric constant in the BaTiO₃-based X7R system.     

Crystallographic Properties of Hydrothermal Barium Titanate Crystallites

The crystallographic properties and defects of hydrothermally grown barium titanate crystallites are reported. When a precursor with a Ba:Ti molar ratio of 1.0 was used, cubic barium titanate crystallites were formed. However, when the precursor Ba:Ti molar ratio was 3.0, the product was tetragonal. The defect concentration (including OH defects and barium vacancies) was higher in cubic crystallites than in tetragonal crystallites. Because of the defects in the crystallites, the displacement of Ba²⁺ cations and the deformation of the Ti-O₆ octahedrons was suppressed; thus, no phase transition from cubic to tetragonal occurred at the Curie point. When the defects were eliminated by thermal treatment, the normal crystallographic properties were obtained. A high reaction temperature and a high Ba:Ti molar ratio in the precursor were beneficial to limiting defect dormation in the crystallites; thus, tetragonal crystallites were obtained.     

Anomalous Grain Growth in Donor-Doped Barium Titanate with Excess Barium Oxide

Grain growth and semiconductivity of donor-doped BaTiO₃ceramics with an excess of BaO and additions of SiO₂or B₂O₃were studied. The microstructures and electrical measurements on sintered samples revealed that their electrical properties are related to the microstructure development of the sintered samples. Samples heated with an excess of BaO developed a normal microstructure during sintering, as a consequence of normal grain growth (NGG), and were yellow and insulating. In contrast, samples with an excess of BaO and an addition of SiO₂or B₂O₃exhibited anomalous grain growth (AGG) and were dark blue and semiconducting after sintering. When some BaTiO₃seed grains were embedded in a sample of donor-doped BaTiO₃with an excess of BaO (without SiO₂or B₂O₃), AGG was observed, i.e., some seed grains grew into large grains and were blue and semiconducting. An explanation is given for why AGG is responsible for the oxygen release and the formation of semiconducting grains in donor-doped BaTiO₃and not NGG.     

Synthesis and Processing of Barium Hexaaluminogallates

Barium hexaaluminogallate was synthesized by the mixed-oxide method and the coprecipitation method. Barium hexaaluminate and barium hexagallate were found to form barium hexaaluminogallate, Ba(Al,Ga)₁₂O₁₉, at 1400°C. BaCo(Al,Ga)₁₁O₁₉ of magnetoplumbite structure was formed from a mixture of metal oxides at 1200°C for 6 h. Co was successfully introduced to barium hexaaluminogallate, although the synthesis of BaCoAl₁₁O₁₉ is quite difficult via solid-state reaction of oxide powders. Anisotropic BaCo(Al,Ga)₁₁O₁₉ particles crystallized at 1100°C for 2 h through the coprecipitation method using metal nitrates and ammonium carbonate. BaCo(Al,Ga)₁₁O₁₉ supported on a cordierite honeycomb had the ability to reduce NO _x with methane over 500°C in the presence of excess oxygen.     

Ruddlesden–Popper Planar Faults and Nanotwins in Heteroepitaxial Nonstoichiometric Barium Titanate Thin Films

Nonstoichiometric 10-mol%-excess-BaO–BaTiO₃ (Ba_1.1TiO_3.1) thin film grown on a (100) SrTiO₃ substrate consisted of heteroepitaxial c -axis-oriented BaTiO₃ perovskite crystals including Ruddlesden–Popper planar faults and nanometer-scale multiple (111) twin lamellae. High-resolution electron microscopy and electron energy-loss spectroscopy revealed that nanotwins with coherent (111) Σ3 coincident site lattice boundaries were terminated in the BaTiO₃ matrix to form incoherent (211) Σ3 boundaries accommodating excess barium ions. Both Ruddlesden–Popper planar fault and incoherent (211) boundary formation were proposed as possible accommodation mechanisms of excess barium ions in the perovskite film.     

Formation and Properties of Barium Metaplumbate

The preparation and the physical and electrical properties of BaPbO₃ ceramics are described. The compound was formed by firing an equimolar mixture of BaCO₃ and Pb₃O₄ in oxygen at 880°C. To produce the stoichiometric compound on firing in air at 980°C it was necessary to use an excess of PbO (molar ratio, Pb/Ba = 1.278). A well sintered ceramic was obtained only with a stoichiometric composition with a sintered density of 7.78. Free BaCO₃ was found in the fired bodies including the PbO-rich compositions. The electrical resistively of BaPbO₃ was 8.3 × 10⁻⁴ ohm-cm at 25°C with a temperature coefficient of +0.15%/°C.     

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.     

Influence of Rare-Earth Dopants on Barium Titanate Ceramics Microstructure and Corresponding Electrical Properties

In this article, ytterbium and erbium oxides are used as doping materials for barium titanate (BaTiO₃) materials. The amphoteric behavior of these rare-earth ions leads to the increase of dielectric permittivity and decrease of dielectric losses. BaTiO₃ ceramics doped with 0.01–0.5 wt% of Yb₂O₃ and Er₂O₃ were prepared by conventional solid-state procedure and sintered at 1320°C for 4 h. In BaTiO₃ doped with a low content of rare-earth ions (0.01 wt%) the grain size ranged between 10 and 25 μm. With the higher dopant concentration of 0.5 wt%, the abnormal grain growth is inhibited and the grain size ranged between 2 and 10 μm. The measurements of capacitance and dielectric losses as a function of frequency and temperature have been carried out in order to correlate the microstructure and dielectric properties of doped BaTiO₃ ceramics. The temperature dependence of the dielectric constant as a function of dopant amount has been investigated.     

Influence of Stoichiometry on the Microstructure and Positive Temperature Coefficient of Resistivity of Semiconducting Barium Titanate Ceramics

The influence of stoichiometry, i.e., Ba/Ti ratio, on the microstructure and positive temperature coefficient of resistivity (PTCR) characteristics of BaTiO₃ was investigated. Fine-grain microstructures are obtained for Ba-rich, stoichiometric, low-temperature-sintered, Ti-rich materials. The room-temperature resistivities ( ρRT ) of the fine-grain Ti-rich samples are large (>10⁸Ω·cm). Excess Ba²⁺ ions can decrease the ρRT , by more than 2 orders of magnitude, because of the compensation of barium vacancies near the grain-boundary regions. Rapid cooling after sintering can also decrease ρRT (⋍100×) and is ascribed to the suppression of reoxidation. Large-grain microstructures and low ρRT , on the other hand, are generally observed for Ti-rich and Al₂O₃-SiO₂-TiO₂-added samples after sintering at a temperature higher than the corresponding eutectic point.     

Sol-Gel Process for the Preparation of Ba2Ti9O20 and BaTi5O11

Barium titanate precursors with Ba/Ti ratio 2:9 and 1:5 were prepared by first hydrolyzing titanium alkoxide and then mixing the resulting titania sol with a barium alkoxide-methanol solution. After drying, the xerogels of the precursors of barium titanates were sintered at temperatures from 700°C (4 h) to 1200°C (110 h or longer). Characterization of the product was performed using X-ray diffraction and laser Raman spectroscopy. At 700°C, BaTi₅O₁₁ was formed from the 1:5 precursor and a two-phase mixture of BaTi₂O₅ and BaTi₅O₁₁ was formed from the 2:9 precursor. After prolonged heating at 1200°C, the latter mixture converted to a single-phase material, Ba₂Ti₉O₂₀.     

Effects of Silver on Barium Titanate as a Function of Stoichiometry

This work examines the effects of Ag on stoichiometric and nonstoichiometric BaTiO₃ in terms of the unit cell dimensions, the polycrystalline microstructure, and the dielectric properties. Stoichiometric BaTiO₃ and compositions with 0.5 mol% TiO₂ excess and 0.5 mol% BaO excess were prepared via solid-state synthesis with varying amounts of Ag up to 0.3 mol%. Experimental results indicate that stoichiometry plays a significant role in the solubility of Ag and its effects on the physical properties. Overall, the solubility of Ag was negligible in stoichiometric BaTiO₃. However, compositions with excess TiO₂ stabilized the solubility of Ag as evidenced from changes in the unit cell dimensions and dielectric properties. Based on these data, it is proposed that Ag occupies the A-site in the perovskite structure with an upper limit of Ag solubility of 0.06 mol% Ag in BaTiO₃ with 0.5 mol% excess TiO₂. Dielectric measurements showed that Ag concentrations approaching 0.3 mol% gave rise to an increase in the space charge effect, especially at temperatures above T _C. In both nonstoichiometric compositions, the presence of a liquid Ag phase during thermal processing was found to affect microstructural development and sintering.     

Source of Water and Its Effect on Tape Casting Barium Titanate

The source of water and its effect on rheological and green tape properties of tape cast barium titanate were studied. The total water content, as well as the source, affect the slip rheology, green density, tensile strength, and strain to failure in the unsintered body. Sources of the water were broken down into contributions from the barium titanate powder surface versus from the solvent or ceramic additives. Water adsorbed on the powder surface was generally beneficial compared to water entering through the solvent. For carefully dried systems, below 0.15 wt% total water, properties change dramatically with small changes in water content. Thus, less stringent processing requirements can be used to achieve reproducibility at water contents above 0.15 wt%.     

Peroxo-oxalate Preparation of Doped Barium Titanate

The peroxo-oxalate complexation method is a method that can be used for the preparation of doped barium titanate. In this paper we focus on BaTi_0.91Zr_0.09O₃, which can be used for discharge capacitors in lamp starters. The preparation method described here is based on the complexation and subsequent precipitation in basic environment of Ba, Ti, and Zr ions with hydrogen peroxide and oxalate. The influence of several process parameters, like precipitation temperature and pH, on powder properties is described. A single-phase perovskite crystal structure is obtained after calcination starting from a chloride precursor solution using a precipitation temperature of 40°C and a pH of 9. Because the peroxo-oxalate process starts with inexpensive chlorides and is performed in air, the peroxo-oxalate process is suitable for the commercial production of doped barium titanate.     

Effect of pH on the Chemistry of the Barium Titanium Citrate Gel and Its Thermal Decomposition Behavior

In this investigation, X-ray diffractometry and ¹³C NMR spectroscopy were used to characterize the effect of pH on the formation of gel and its thermal decomposition by the Pechini process. It was found that the major effect of pH was to destroy the esterification between citric acid (CA) and ethylene glycol, which in turn could influence Ba species and the formation of a mixed-metal CA complex. It was also found that barium carbonate was derived from the Ba species and was not related to the instability of Ba₂Ti₂O₅CO₃, but Ba₂Ti₂O₅CO₃ was formed by the thermal decomposition of a mixed-metal CA complex. Moreover, BaTiO₃ formed via two routes, the reaction of BaCO₃ with Ti species and thermal decomposition of Ba₂Ti₂O₅CO₃.     

Preparation of Spherical, Solid Barium Titanate Particles with Uniform Composition at High Precursor Concentration by Spray Pyrolysis

Hydrolysis-assisted spray pyrolysis (HASP) using dimethyl oxalate as hydrolyte was found to be applicable to precipitation of solid, spherical BaTiO₃ powder with uniform composition when the stock solution concentration was high (>1.0 M ). Solid, dense powder with uniform composition was successfully obtained because barium titanium oxalate was prepared from partial hydrolysis of dimethyl oxalate and coprecipitation of oxalate with barium and titanium during the hydrolysis–precipitation process, and then the oxalate particles became seeds in the following process. The sintered sample from the as-prepared BaTiO₃ powder led to a higher dielectric constant and lower loss.