Synthesis and Dielectric Properties of Niobia Coating on BaTiO3

Different from conventional powder mixing, this study demonstrates a method of homogeneous coating for niobia (Nb₂O₅) on ferroelectric barium titanate (BaTiO₃) powders. The precipitation of Nb coating with pH has been determined quantitatively by the inductance-coupled plasma method. Crystalline phases were determined by X-ray diffractometry, and the formation of a "core-shell" structure with a Nb concentration gradient was observed by a transmission electron microscope with X-ray energy-dispersive spectroscopy. The dielectric constant ( K ) of the samples prepared by the nanocoating method showed a more stable temperature coefficient of capacitance and well satisfied the requirements of X7R.     

一种钛酸钡制备方法实验研究

以硫酸法钛白生产过程中的中间产品工业钛液（TiOSO4）为钛源,通过常温水解获得正钛酸,经草酸溶解获得草酸氧钛酸,再与氯化钡共沉淀得到草酸氧钛酸钡,高温煅烧后制备得到电子级钛酸钡产品。实验确定最佳制备条件：钛液水解pH为2.5～3.5,草酸氧钛酸生成温度和草酸氧钛酸钡共沉淀温度均选择50～70 ℃,共沉淀pH为2.5,煅烧温度为800 ℃,煅烧时间为2 h。分析结果表明,以工业钛液为钛源生产钛酸钡的成本明显低于偏钛酸。     

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.     

Dielectric properties of (Ba0.95Ca0.05)(Ti1-yCay)O3-y ceramics

Calcium doped barium titanate ceramics with composition (Ba_0.95Ca_{0. 05}) (Ti_1-yCa_y)O_3-y prepared by a liquid mixing technique were used to measure the dielectric properties. The pure barium titanate and lightly-Ca-doped materials obey a Curie Weiss law when the temperature is above the Curie temperature. It has been found that the average cubic-tetragonal phase transition temperature moves downward when the octahedrally-coordinated Ca concentration increases, and heavily-Ca-doped barium titanate ceramics show relaxor behavior with a diffuse phase transition characteristic (DPT). Above the average transition temperature T_av the dielectric properties for heavily doped materials do not obey the Curie Weiss law, but can be described by a quadratic relation over a wide range of temperature. Experiments have shown that there exists an extra K(T) peak attributable to the existence of separate microregions of Ba_0.95Ca_0.05TiO₃ in a matrix of (Ba_0.95Ca_0.05) (Ti_1-yCa_y)O_3-y (where y ≤ 2%).     

Room-Temperature Solubility Behavior of Barium Titanate in Aqueous Media

In the present study, the incongruent dissolution of barium from barium titanate (BaTiO₃) has been studied as a function of dispersion pH and powder volume fraction for two different BaTiO₃ powders. In alkaline dispersions, the barium solubility strongly increases as the pH increases, as suggested by thermodynamic considerations. At pH <7, the barium solubility reaches a plateau, the height of which is dependent on the surface area of the powder and the solids loading of the slip. The BaTiO₃ surface is completely depleted of barium in this region.     

Alkoxide-Hydroxide Route to Syntheltize BaTiO3-Based Powders

When preparing homogeneous, fine barium titanate powders, the major difficulty is to avoid the spontaneous self-condensation between the Ti-OH groups. In the usual way of preparing fine barium titanate powders, chelating agents (citrate, oxalate) or simply unidentate ligands (alkoxy or carboxyl groups) are used to complex titanium atoms. Another way is to mix barium and titanium precursors in a strongly basic medium. The condensation between the Ti(OH)^2-₆Ba²⁺ species directly gives the perovskite compound. Using an alkoxide-hydroxide route, a homogeneous Ba-Ti solution was prepared that completely advanced by condensation between the Ti(OH)^2-₆Ba²⁺ species and led to a controlled-stoichiometry powder. Concerning pure barium titanate, dried powders exhibited the cubic perovskite structure, and a direct sintering at 1150°C, without calcination, led to highly dense BaTiO₃ bodies with fine-grained uniform microstructure (1 μm) that exhibited a high permittivity value at room temperature ( K = 5400). The alkoxide-hydroxide method was also used to prepare dense alkaline-earth perovskite ceramics with complex compositions.     

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.     

A Modified Barium Titanate for Capacitors

The modified barium titanate ceramic Ba_0.80Pb_0.20 (Ti_0.88Zr_0.12) O₃ doped with 0.8 mol% CaO and 1 mol%ZrO₂ was prepared. Investigation of the electrical and dielectric properties shows that the material has a room-temperature dielectric constant of 3550 with a variation of 5.7% in the temperature range 10° to 60°C, a loss factor of 0.005, a dc resistivity 1.3 × 10¹²Ω-cm, and a linear variation of resistivity in the log (resistivity) vs temperature plot. This material is a good choice for the fabrication of ceramic capacitors.     

Effect of Composition and Size of Crystallite on Crystal Phase in Lead Barium Titanate

Lead titanate, barium titanate, and lead barium titanate powders (>99.9% pure), the particle size of which varied from 0.03 to 0.15 μm depending on the calcination temperature and the composition, was prepared from barium lead titanyl oxalate, which was previously prepared by reacting high-purity ammonium titanyl oxalate with barium and lead acetate. The critical crystallite size of BaTiO₃ powder from the cubic to the tetragonal phase is around 1 μm. Pb_0.3Ba_0.7TiO₃ powder with an average size of 0.057 μm showed the tetragonal phase.     

Comparison of Ba(OH)2, BaO, and Ba as Starting Materials for the Synthesis of Barium Titanate by the Alkoxide Method

A discussion of the relative merits and problems of using Ba(OH)₂, BaO, and Ba as starting materials for the synthesis of barium titanate by the alkoxide method is presented. The Ba(OH)₂ process is promising because it does not involve the synthesis of barium alkoxide, whereas the BaO (93% pure) process suffers from complex chemical reactions; the impurities in BaO cause unknown effects on the composition and properties of the final ceramic. Use of high-purity Ba metal (99.99%) for the synthesis of barium alkoxide is more desirable since it results in high-purity, ultrafine barium titanate powders.     

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.     

Solid-State Synthesis of Ultrafine BaTiO3 Powders from Nanocrystalline BaCO3 and TiO2

Barium titanate has been prepared by solid-state reaction of nanocrystalline TiO₂ (70 nm) with BaCO₃ of different particle size (650, 140, and 50 nm). The results give evidence of a strong effect of the size of BaCO₃ in the solid-state synthesis of barium titanate. The use of nanocrystalline BaCO₃ already leads to formation of the single-phase BaTiO₃ after calcination for 8 h at 800°C. The final powder consists of primary particles of ≈100 nm, has a narrow particle size distribution with d ₅₀=270 nm, and no agglomerates larger than 800 nm. For the coarser carbonate, 4 h calcination at 1000°C are required and the final powder is much coarser. Solid-state reaction of nanocrystalline BaCO₃ and TiO₂ represents an alternative to chemical preparation routes for the production of barium titanate ultrafine powders.     

Core-Shell Structure of Acceptor-Rich, Coarse Barium Titanate Grains

Heavily doped barium titanate (BaTiO₃) powders, one with a donor-rich and the other with an acceptor-rich composition, were prepared. After sintering, the donor-rich specimen exhibited a fine-grained microstructure but significant grain growth occurred in the acceptor-rich specimen. A stable dielectric behavior was observed only in the donor-rich fine-grained specimen over the temperature range studied. However, in both specimens, an undoped core region several hundred nanometers in size was detected. The core-shell structure appeared to be maintained in BaTiO₃ under the conventional sintering conditions_.     

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.     

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.     

Grain-Boundary Migration and Dielectric Properties of Semiconducting SrTiO3 in the SrTiO3-BaTiO3-CaTiO3 System

Chemically induced grain-boundary migration and its effects on the interface and dielectric properties of semiconducting SrTiO₃ have been investigated. Strontium titanate specimens that had been doped with 0.2 mol% of Nb₂O₅ were sintered in 5H₂/95N₂. The sintered specimens were diffusion annealed at 1400°C in 5H₂/95N₂ with BaTiO₃ or 0.5BaTiO₃-0.5CaTiO₃ (mole fraction) packing powder. The grain boundaries of the annealed specimens were oxidized in air. In the case of BaTiO₃ packing, grain-boundary migration occurred with the diffusion of BaTiO₃ along the grain boundary. The effective dielectric constant of the specimen decreased gradually as the temperature increased but showed two peaks, possibly because of barium enrichment at the grain boundary and an oxidized Sr(Ba)TiO₃ layer. In the case of 0.5BaTiO₃-0.5CaTiO₃ packing, although barium and calcium were present at the grain boundary of the specimen, no boundary migration occurred, as in a previous investigation. With the diffusion of barium and calcium, the resistivity of the specimen increased and the variation of the effective dielectric constant with temperature was much reduced, in comparison to those without solute diffusion. These enhanced properties were attributed to the solute enrichment and the formation of a thin diffusional Sr(Ba,Ca)TiO₃ layer at the grain boundary.     

Dielectric Bodies in the Quaternary System BaTiO3–BaSnO3–SrSnO3–CaSnO3

Dense bodies were prepared of compositions in the quaternary system BaTiO₃–BaSnO₃–SrSnO₃–CaSnO₃ containing from 3 to 60 mole % stannate. The general effect of the stannate addition to barium titanate was to decrease the Curie temperature and broaden the peak. On a molar basis the three stannates were approximately equivalent in their effect on the dielectric properties of barium titanate, although the rate of shift of the Curie temperature was slightly greater when SrSnO₃ was used. Bodies containing calcium or strontium stannate had lower power factors than those containing barium stannate. Bodies compounded with calcium stannate matured most readily and at lower temperatures. Bodies having dielectric constants ( K ) of 2300 to 2800 at 1 kc. with low positive temperature coefficients up to about 55°C. were obtained with a 3 mole % addition of stannate. Bodies with minimum K 's of 3000 to 4000 at 1 kc. over the range 25° to 85°C. were obtained from BaTiO₃ with an addition of about 6 mole % BaSnO₃, SrSnO₃, or CaSnO₃. Bodies with negative temperature coefficients of K ranging from about 13,000 to about 1000 p.p.m. per °C. were obtained with stannate additions of from 10 to 60 mole %.     

Dispersion of Aqueous Barium Titanate Suspensions with Ammonium Salt of Poly(methacrylic acid)

The colloidal stability of aqueous barium titanate (BaTiO₃) suspensions with the ammonium salt of poly(methacrylic acid) (PMAA-NH₄), as a function of pH, has been investigated. The concentration of PMAA-NH₄ required to stabilize aqueous BaTiO₃ suspensions decreases as the pH increases. A stability map that delineates the critical amount of PMAA-NH₄ necessary to achieve colloidal stability, as a function of pH, has been constructed.     

Synthesis of Single-Crystal Barium Titanium Isopropoxide Complex to Form Barium Titanate

Single-crystal barium titanate double alkoxide complex with a composition presumed to be BaTi(OCH(CH₃)₂)₆·xC₆H₆ was successfully synthesized in this work. The crystal was converted to BaTiO₃ at 100°C. The preparation of the Oxides via single crystals of metal alkoxides has some advantages over the well-known sol-gel method in that it results in oxides with well-defined and homogeneous compositions at the atomic level and in fine particle sizes, smaller than 50 nm.     

Low-Temperature Crystallization of Sol-Gel Processed Pb0.5Ba0.5TiO3: Powders and Oriented Thin Films

A novel sol-gel process suitable for depositing thin-film lead barium titanate has been developed. X-ray diffraction analysis showed perovskite phase crystallization to occur at a temperature as low as 400°C with single-phase Pb_0.5Ba_0.5TiO₃ (PBT) resulting at a temperature as low as 500°C. Small concentrations of barium carbonate were evident by X-ray diffraction at 400°C, and indications of minor, carbonate-containing phases were evident by FTIR at 600°C. Deposition of the sol by spin coating on single-crystal and thin-film MgO on silicon resulted in highly oriented PBT films after calcination at 600°C. Mixed (100)/(001) films were obtained on single-crystal MgO, whereas entirely (100) films were obtained on thin-film MgO.