Solvothermal Synthesis and Characterization of Barium Titanate Powders

Cubic BaTiO₃ powders have been synthesized from gel powders after thermal treatment in an alcohol solution and characterized using X-ray diffractometry, transmission electron microscopy, and other techniques in detail. The borderline reaction conditions, such as the reaction temperature and time, for the synthesis of crystalline BaTiO₃ powder in different solvents are established. The single-phase BaTiO₃ powder has low agglomeration and seems to have a regular morphology. The formation of BaTiO₃ powders via solvothermal reaction is more difficult, in comparison to hydrothermal processing. The crystalline powders, which have a small particle size (∼20–60 nm) and narrow particle-size distribution, can be synthesized in methanol, ethanol, or n -propanol systems. Unlike the hydrothermal reaction, tetragonal-phase BaTiO₃ powders cannot be prepared via the solvothermal reaction, even with alkali catalysts.     

Aqueous Colloidal Characterization and Forming of Multimodal Barium Titanate Powders

Aqueous suspensions of two barium titanate (BaTiO₃) powders, with 100 and 500 nm nominal size, were found to be stabilized by a predominantly steric mechanism when using a polyelectrolyte surfactant, an ammonium salt of poly(methacylate) (PMA-NH₄). Considerable amounts of barium ions were shown to readily dissolve from BaTiO₃ powders in an aqueous environment, even without the addition of acid or base. This barium dissolution obscured the accurate measurement of the isoelectric point of the two powders. Suspension stabilization was observed to occur at basic pH when using PMA-NH₄. Concentrated suspensions of each individual powder exhibited shear thinning behavior, with the onset of shear thickening occurring at relatively high shear rates. Suspensions containing 85 vol% coarse/15 vol% fine powders demonstrated the lowest apparent viscosity for a given solids loading, while the highest sintered density was obtained with a mixture of 70 vol% coarse/30 vol% fine, when sintering at 1300°C for 2 h (97.4% of theoretical, slip cast from a suspension containing 50 vol% solids).     

Solution-Precipitation of Fine Powders of Barium Titanate and Strontium Titanate

Hydrolytic reactions of metal alkoxides offer a broad range of possibilities for their use in the preparation of ceramic powders. This paper reports a unique and novel process to prepare fine powders of BaTiO₃ and SrTiO₃ from stable precursor solutions by carefully controlling the pH and temperature. This simple route offers good control of stoichiometry and the powders are agglomerate-free with fine particles of size 0.06–0.1 µm and were well sintered at 1200° and 1350°C, respectively. The dielectric properties of the dense ceramics are also reported. The formation aspects of these perovskite phases are also discussed.     

Preparation of High-Purity Submicron Barium Titanate Powders

Simultaneous hydrolytic decomposition of barium bis isopropoxide and titanium tetrakis tertiary amyloxide was used to produce stoichiometric BaTiO₃. The particle size range was 50 to 150 Å. The purity was 99.98+%, the major contaminant being silicon from the glass apparatus. The homogeneity and stoichiometry of the powder were demonstrated by electron microscopy and wet chemical analysis. X-ray and infrared analyses indicate that the material, as-prepared and helium-dried at 5O°C, has the titanate crystal structure. The powder sinters at 1300°C to a high density, translucent body with a uniform microstructure. The experiments suggest that the alkoxy-based preparation of oxides may provide a broad base for improving the quality and reproducibility of electrical and structural ceramics.     

Ultrafine Barium Titanate Powders via Microemulsion Processing Routes

Three processing routes have been used to prepare barium titanate powders, namely conventional coprecipitation, single-microemulsion coprecipitation using diether oxalate as the precipitant, and double-microemulsion coprecipitation using oxalic acid as the precipitant. A single-phase perovskite barium titanate was obtained when the double-microemulsion-derived oxalate precursor was calcined for 2 h at a temperature of as low as 550°C, compared to 600°C required by the single-microemulsion-derived precursor. A calcination for 2 h at >700°C was required for the conventionally coprecipitated precursor in order to develop a predominant barium titanate phase. It was, however, impossible to eliminate the residual TiO₂ impurity phase by raising the calcination temperature, up to 1000°C. The microemulsion-derived barium titanate powders also demonstrated much better powder characteristics, such as more refined crystallite and particle sizes and a much lower degree of particle agglomeration, than those of the conventionally coprecipitated powder, although they contained ∼0.2 wt% BaCO₃ as the impurity phase.     

钡钛醋酸盐凝胶制备BaTiO3粉体

本文报道了用ｓｏｌ－ｇｅｌ法制备钡醋酸盐凝胶，并分别作高灼烧和水热处理制备ＢａＴｉＯ３粉体。通过对产物的表征，比较了这两种处理过程，进而对水热条件下陶瓷粉体的形成机理作了探讨。由于水热条件，凝胶在反应介质中溶解，进而结晶形成晶粒，因此所形成的ＢａＴｉＯ３晶粒线度小；线度分布范围窄。晶粒形貌完整，明显优于高温灼烧处理后得到的粉体。     

Alternative Route for Synthesis of Barium Titanyl Oxalate: Molecular Precursor for Macrocrystalline Barium Titanate Powders

An important molecular precursor to barium titanate, namely, barium titanyl oxalate [BaTiO(C₂O₄)₂.4H₂O], has been synthesized by an alternative route. An alcoholic solution containing 1 mol of butyl titanate monomer [(C₄H₉O)₄Ti] is reacted with alcoholic solution containing 2 mol of oxalic acid (H₂C₂O₄:2H₂O) to form an intermediate soluble oxalotitanic acid [H₂TiO(C₂O₄)₂.nH₂O]. The oxalotitanic acid in alcoholic medium is subjected to cation exchange reaction with aqueous solution containing equimolar barium acetate to form an insoluble barium titanyl oxalate (BTO) in yields of 80–85% at room temperature. The pyrolysis of BTO in air at T .750°C/5 h produced barium titanate (BT) powders.     

Kinetics and Mechanism of Formation of Barium Zirconate from Barium Carbonate and Zirconia Powders

The formation of BaZrO₃ from very fine (70–90 nm) ZrO₂ powders and coarser (∼1 μm) BaCO₃ powders has been studied in dry and humid air up to 1300°C using TGA/DTA, XRD, SEM, TEM, and EDS microanalysis. In the temperature range 900°–1100°C, barium is rapidly transported at the surface of the ZrO₂ particles and reacts, forming BaZrO₃. The compound grows as a concentric layer with gradual consumption of the central ZrO₂ particle. The overall formation kinetics of BaZrO₃ is well described by a diminishing core model, and the most likely rate-determining step is a phase-boundary process at the ZrO₂–BaZrO₃ moving interface. The size and shape of the final particles is generally determined by the morphology of the starting ZrO₂ particles and not by that of the BaCO₃. The reaction is faster in humid air than in dry air, and the activation energy decreases from 294 kJ·mol⁻¹ (dry air) to 220 kJ·mol⁻¹ (humid air). When the fraction reacted is >80–90 mol%, the reaction rate rapidly decreases.     

BaTiO3超细粉体的溶胶-沉淀法制备及其表征

采用溶胶-沉淀工艺制备BaTiO3纳米粉体,探讨了沉淀剂NaOH溶液浓度对制备BaTiO3粉体相组成的影响,提出了溶胶-沉淀法合成纯相BaTiO3的反应机理,并对沉淀水洗后的湿凝胶进行表面改性.探讨了添加表面活性剂及有机溶剂脱水过程对粉体团聚程度的有效控制.     

醇对低温水热合成四方相钛酸钡的影响

以Ba(OH)2·8H2O和Ti(OC4H9)4为原料,氨水为矿化剂,以不同醇/水混合溶剂作为分散介质,在180℃下反应120 h,水热合成四方相钛酸钡粉体,研究不同醇对粉体的影响,并通过XRD、TEM、IR及激光纳米粒度分析对粉体进行了表征.结果表明以一元醇为溶剂有利于合成四方相钛酸钡,其中又以乙醇为最优,以乙醇/水为溶剂合成的四方相钛酸钡粉体的c/a最大可达1.0090,且粉体纯度高,粒径分布狭窄,晶粒形貌发育完整,呈现球形和四方形.     

Synthesis of Ultrafine and Spherical Barium Titanate Powders Using a Titania Nano-Sol

A novel synthetic method for the preparation of spherical, homogeneous, and ultrafine barium titanate (BaTiO₃) powders is described. An aqueous titania nano-sol was prepared by peptizing coarse aggregate of hydrous titania with nitric acid. BaTiO₃ powders could be synthesized through a simple reflux method using the titania nano-sol and barium hydroxide. As decreasing the titanium concentration, the particle size of the resulting spherical BaTiO₃ powder was increased from 40 to 130 nm and the porosity also increased. It was revealed that the smaller as-prepared BaTiO₃ powder was less porous and became more tetragonal with less intragranular pores after annealing. With this method, a highly tetragonal BaTiO₃ powder ( c / a ∼1.008) with a particle size of 120.0 nm was successfully prepared and would be very suitable for the thinner dielectrics in higher capacitance multilayer ceramic capacitors.     

Characterization of Lanthanum-Doped Barium Titanate Ceramics Using Impedance Spectroscopy

The electrical properties of two single-phase, lanthanum-doped BaTiO₃ compositions, x = 0.03 and x = 0.20, in Ba_{1– x} La _x Ti_{1– x /4}O₃ were investigated by impedance spectroscopy after heat treatment in oxygen, argon, and air at 1350°C. Samples heated in oxygen were electrically insulating, whereas those heated in argon lost oxygen and were semiconducting at room temperature, irrespective of x . Samples heated in air showed intermediate electrical properties and also were electrically inhomogeneous; the two compositions showed different electrical behaviors, and a model for each, based on oxygen nonstoichiometry within the ceramics, is proposed. Oxygen deficiency in samples sintered in air was avoided by heating at 1200°C, instead of 1350°C. Alternatively, oxygen lost from ceramics heated in air at 1350°C was regained by postannealing in oxygen at 1350°C.     

Preparation and Characterization of Barium Titanate Suspensions for Stereolithography

Ferroelectric photoactive suspensions for stereolithography have been developed by dispersing a high volume fraction of barium titanate powder in hexanediol diacrylate (HDDA) with the aid of effective photoinitiators and dispersants. Rheological properties showed a shear thinning behavior and a low viscosity at a shear rate adequate for the recoating process. The barium titanate–HDDA suspension showed poor curing behavior due to the large refractive index difference between the ceramic and the resin. The coarse barium titanate–HDDA suspension showed a smaller surface reflectance and a larger cure depth than the fine barium titanate–HDDA suspension.     

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.     

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.     

混合碱法制备钛酸锶钡纳米陶瓷粉体的研究

本文以熔融的无水混合碱作为溶剂,以成本低廉的金属无机盐和氧化物作为反应物,成功制备了钛酸锶钡纳米陶瓷粉体.用XRD、SEM对粉体进行了表征.研究结果表明,在温度200℃,加热24h时生成钛酸锶钡(Ba0.77 Sr0.23 TiO3)粉体,在温度245℃,加热24h生成钛酸锶钡(Ba0.6 Sr0.4 TiO3),合成产物为四方形,粉体的粒径为60～120nm,粒度分布均匀.     

Devitrified Barium Titanate Dielectrics

Pure barium titanate was made into a glass by flame-spraying and after sufficient comminution was processed into specimens and fired. During this firing the glass devitrified to tetragonal barium titanate and contained crystals of sizes from 0.5 to below 0.2μ. The small crystals exhibit Curie temperatures from 120° to above 185°C. The dielectric Curie temperature of the devitrified ceramic is 150° to 155°C.     

Tetragonal Nanocrystalline Barium Titanate Powder: Preparation, Characterization, and Dielectric Properties

Nanocrystalline tetragonal-BaTiO₃ powder was prepared using a hydrothermal method, under moderate conditions, and with a high precursor concentration. Characterization via X-ray diffractometry and differential scanning calorimetry confirmed that the average particle size and tetragonal content of the prepared powder were 70 nm and 80%, respectively. The sintered sample made from the prepared powder had a room-temperature dielectric constant of 6900, which was high for BaTiO₃.