Necessary Conditions for the Formation of {111} Twins in Barium Titanate

The experimental conditions for {111} twin formation in BaTiO₃ were investigated. When BaTiO₃ compacts without excess TiO₂ were sintered either in an oxidizing atmosphere (air) or in a reducing atmosphere (95N₂–5H₂), no {111} twins formed within the BaTiO₃ grains and no abnormal grain growth occurred. In contrast, many {111} twins were present within the abnormally grown grains in the excess-TiO₂-containing BaTiO₃ samples sintered in air, while no twins were observed in the excess-TiO₂-containing samples sintered in 95N₂–5H₂. X-ray diffraction analysis showed that excess TiO₂ forms a Ba₆Ti₁₇O₄₀ phase during sintering with the space group A 2/ a in air and a Ba₆Ti₁₇O_{40− x} phase with the space group C in 95N₂–5H₂. It appears therefore that excess TiO₂ and an oxidizing atmosphere are necessary for {111} twin formation in BaTiO₃. These results may also indicate that the interface structure between BaTiO₃ and Ba₆Ti₁₇O₄₀ influences the twin formation.     

Fluorine as a Donor Dopant in Barium Titanate Ceramics

We have studied the electrical properties and microstructure of fluorine-doped BaTiO₃ ceramics. The samples were prepared using a classical ceramic technology that involved the calcination of intimately mixed powders of BaCO₃, TiO₂, and BaF₂. When the samples were sintered in untreated ambient air, the fluorine from the sample reacted with water vapor and formed gaseous HF. To prevent this hydrolysis of the fluorine, we sintered the samples in dried air. The fluorine-doped BaTiO₃ ceramics sintered in a dry atmosphere showed microstructures and electrical properties typical of donor-doped BaTiO₃. The samples containing up to 0.3 mol% of fluorine were coarse-grained, semiconducting, and displayed a remarkable PTCR effect. In contrast, the samples with a higher fluorine concentration were fine grained and insulating. A SIMS elemental mapping of the samples showed that the fluorine was distributed throughout the microstructure of the semiconducting samples; however, the fluorine concentration was enriched at grain boundaries and in the BaTi₂O₅ intergranular phase.     

Interaction between Barium Titanate and Binary Glasses

Interactions between BaTiO₃, and three binary glasses were studied through the reaction of BaTiO₃, powder with glass powder. For PbO–B₂O₃ and PbO–SiO₂ glasses, the reaction led to stable compound formation, the substitution of Pb in the BaTiO₃ structure, and noticeable grain growth of BaTiO₃. The interaction phenomena for these two glass systems were very similar. The substitution of Pb into BaTiO₃ is assisted by chemical reactions in which BaB₂O₄ or Ba₂SiO₄ is formed. The substitution into BaTiO3 also seems to be closely related to the grain growth of BaTiO₃. On the other hand, only compound formation was observed during the processing of BaTiO₃ with Bi₂O₃–B₂O₃ glass. Neither BaTiO₃ grain growth nor Bi substitution took place with the Bi₂O₃–B₂O₃ glass system. Based on the observed reactions and the glass viscosity, several sintering aids for BaTiO₃ ceramic products are suggested in this paper.     

{111} Twin Formation and Abnormal Grain Growth in Barium Strontium Titanate

Two series of experiments were performed to study the experimental conditions for the formation of {111} twins and related microstructures in barium strontium titanate ((Ba, Sr)TiO₃). In the first series, the phase equilibria in the BaTiO₃–SrTiO₃–TiO₂ system were determined. XRD and WDS analysis, done in the BaTiO₃-rich region, of 45(Ba,Sr)TiO₃–10TiO₂ samples annealed at 1250°C for 200 h in air showed that (Ba,Sr)TiO₃ was in equilibrium with Ba₆Ti₁₇O₄₀ (B₆T₁₇) and Ba₄Ti₁₃O₃₀ phases with strontium solubility (Sr/(Ba + Sr)) of ∼0.02 and 0.20, respectively. In the second series the microstructures of samples consisting of a mixture of (Ba,Sr)TiO₃ and 2.0 mol% TiO₂, were observed after sintering at 1250°C for 100 h in air. {111} twins formed only in the samples with faceted B₆T₁₇ second phase particles, similar to the case of BaTiO₃. In these samples, abnormal grain growth occurred in the presence of the {111} twins. In contrast, no {111} twins formed and no abnormal grain growth occurred in the samples containing second phase particles other than B₆T₁₇. With an increased substitution of strontium for barium, the aspect ratio of abnormal grains containing {111} twin lamellae was reduced. This result was attributed to a reduction in the relative stability of the {111} planes with the strontium substitution.     

Abnormal Grain Growth Occurring at the Surface of a Sintered BaTiO3 Specimen

When a BaTiO₃ powder compact was sintered in air, the abnormal grain growth (AGG) was observed to occur at the surface of the specimen. The BaO evaporation from the surface and consequent formation of eutectic liquid is suggested to be the cause of AGG. When the evaporation of BaO during sintering was prevented by embedding the specimen in the same powder, no AGG was observed to occur.     

Evolution of Interfacial Microstructure between Barium Titanate and Binary Glasses

Evolution of interfacial microstructure between BaTiO₃ and the binary glasses used as frits in thick-film technology has been studied. Possible reaction mechanisms for the interfacial compounds have been determined by comparing the results of the sintering study with the reaction of BaTiO₃, powder with glass powders. The interfacial microstructure can be divided into two types. The first type of interfacial microstructure is observed for glasses rich in PbO or Bi₂O₃ network modifiers and is characterized by the penetration of glass into the BaTiO₃ grain boundaries, accompanied by incorporation of Pb into the perovskite lattice. The second type of interfacial microstructure is observed for glasses rich in B₂O₃ or SiO₂ network formers and is characterized by the formation of interfacial compounds.     

Microstructural Changes during the Reduction/Reoxidation Process in Donor-Doped BaTiO3 Ceramics

Microstructural changes occurring during oxidation of the reduced form of donor-doped BaTiO₃ (Ba_{1− X} D _X ^.Ti_{1− X} ⁴⁺Ti _X ³⁺O₃) and during reduction of the oxidized form of donor-doped BaTiO₃ (Ba_{1− X} D _X ^.Ti_{1− X /4}⁴⁺( V _Ti^) _{X /4}O₃) were studied using TEM. Samples of both types of solid solutions, containing different La concentrations (from 2 to 20 mol% La), were prepared by sintering under reducing conditions and in air, respectively. The reduced form of donor-doped BaTiO₃ was oxidized by annealing at high temperatures (1150° and 1350°C) in air, while the oxidized form was reduced by annealing under reducing conditions. Because of oxidation of the reduced phase of donor-doped BaTiO₃, the Ti-rich phases Ba₆Ti₁₇O₄₀ and BaLa₂Ti₄O₁₂ were precipitated. Reduction of the oxidized form caused precipitation of the Ba-rich phase Ba₂TiO₄ preferentially inside the matrix grains. All precipitates had well-defined orientational relationships with the perovskite matrix.     

Positive Temperature Coefficient of Resistivity Effect in Highly Donor–Doped Barium Titanate

BaTiO₃ ceramics doped with different La concentrations (0–12 mol%) were prepared by sintering under the reducing conditions of a nitrogen atmosphere containing 1% hydrogen. The critical donor concentration that causes blocking of the exaggerated grain growth was observed to be ∼10 mol% La. The samples, which were semiconducting after sintering under reducing conditions, were subsequently reoxidized by annealing in air to induce the positive temperature coefficient of resistivity (PTCR) effect. After reoxidation at 1150°C a noticeable PTCR effect was observed in the samples doped with La concentrations as high as 2.5 mol%. The room-temperature resistivity after reoxidation was found to increase with increasing donor concentration due to an increase in the thickness of the insulating layers at the grain boundaries. TEM analysis showed that reoxidation of the samples caused precipitation of the Ti-rich compound Ba₆Ti₁₇O₄₀ inside the doped BaTiO₃-matrix grains.     

Growth of BaTiO3 Seed Grains by the Twin-Plane Reentrant Edge Mechanism

Two different types of BaTiO₃ seed particles, normal and twinned seeds of ∼30 μm on the average, were prepared from crushed sintered specimens. Normal seeds were obtained from the usual BaTiO₃ sintered compacts, while twinned seeds containing a double twin were obtained from BaTiO₃ compacts sintered with 2 mol% of SiO₂. The BaTiO₃ powder compacts were again prepared with 5 wt% of seed grains and sintered under various conditions. The microstructural evolution was quite different in the two cases: the growth of normal seed grains was ultimately limited but that of the twinned seeds continued extensively. The observed difference is discussed in terms of the growth mechanism and the atomic structure of interfaces.     

Compensation Effect in Semiconducting Barium Titanate

Donor-doped, stoichiometric BaTiO₃ sintered at 1350°C for 1 h exhibits a maximum room-temperature conductivity at [La³⁺]∼0.15 mol%. Elements of lower valence than Ba²⁺ or Ti⁴⁺, when incorporated into semiconducting BaTiO₃, are regarded as poisoning impurities, i.e., acceptors. They tend to increase the room-temperature resistivity of the semiconducting BaTiO₃. For insulating BaTiO₃ resulting from high Mg²⁺ acceptor doping levels, the semiconductivity can be restored by introducing higher La³⁺ donor-dopant concentrations. This behavior is interpreted as a compensation effect based on the defect chemistry of the acceptor- and donor-doped BaTiO₃.     

Grain-Growth Behavior during Stepwise Sintering of Barium Titanate in Hydrogen Gas and Air

To study the effect of oxygen partial pressure on grain growth in BaTiO₃, TiO₂-excess samples have been sintered in air with and without a prior H₂ heat treatment. Without prior H₂ treatment, abnormal grain growth occurs below and above the eutectic temperature ( T _e). An introduction of H₂ treatment before air sintering, however, increases the average grain size and suppresses the formation of abnormal grains during subsequent air sintering below and above T _e. This H₂ treatment effect has been explained in terms of a decrease of the driving force for the growth of faceted grains below a critical value for formation of abnormal grains. The observed grain-growth behavior under various atmospheres demonstrates the possibility of having various microstructures via control of oxygen partial pressure and initial grain size.     

Sintering and Microwave Dielectric Properties of the LiNb0.63Ti0.4625O3 Ceramics with the B2O3–SiO2 Liquid-Phase Additives

The effect of B₂O₃–SiO₂ liquid-phase additives on the sintering, microstructure, and microwave dielectric properties of LiNb_0.63Ti_0.4625O₃ ceramics was investigated. It was found that the sintering temperature could be lowered easily, and the densification and dielectric properties of LiNb_0.63Ti_0.4625O₃ ceramics could be greatly improved by adding a small amount of B₂O₃–SiO₂ solution additives. No secondary phase was observed for the ceramics with B₂O₃–SiO₂ additives. With the addition of 0.10 wt% B₂O₃–SiO₂, the ceramics sintered at 900°C showed favorable microwave dielectric properties with ɛ_r=71.7, Q × f =4950 GHz, and τ_f=−2.1 ppm/°C. The energy dispersive spectra analysis showed an excellent co-firing interfacial behavior between the LiNb_0.63Ti_0.4625O₃ ceramic and the Ag electrode. It indicated that LiNb_0.63Ti_0.4625O₃ ceramics with B₂O₃–SiO₂ solution additives have a number of potential applications on passive integrated devices based on the low-temperature co-fired ceramics technology.     

Low-Temperature Sintering and Microwave Dielectric Properties of the Zn2SiO4 Ceramics

B₂O₃ was added to nominal composition Zn_1.8SiO_3.8 (ZS) ceramics to decrease their sintering temperature for application to low-temperature cofired ceramic (LTCC) devices. B₂O₃ reacted with SiO₂ to form a liquid phase containing SiO₂ and B₂O₃. The composition and melting temperature of the liquid phase depended on the sintering temperature and the B₂O₃ content. The specimen containing 20.0 mol% of B₂O₃ sintered at 900°C exhibited high microwave dielectric properties of Q × f =53 000 GHz, ɛ _r=5.7, and τ_f=−16 ppm/°C, confirming the promising potential of the B₂O₃-added ZS ceramics as candidate materials for the LTCC devices.     

Initial Specific Surface Area and Graln Growth in Donor-Doped Barium Titanate

The grain growth of donor-doped BaTiO₃ prepared from BaTiO₃ powders with different initial specific surface areas was studied. Results show that a higher initial surface area and, consequently, a smaller critical grain size at the phase boundary drastically increase the critical amount of donor dopant, causing the grain size anomaly during sintering.     

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.     

Grain Growth During Sintering of Donor-Doped BaTiO3

Grain growth of donor-doped BaTiO₃ in the presence of KF b'quid phase was studied. The results showed that the composition of the liquid phase present during sintering had a pronounced influence on grain growth and on the formation of semiconducting donor-doped BaTiO₃.     

Intermediate Phase Development in Phosphorus-Doped Barium Titanate

In the present work, the phase formation and thermal evolution in phosphorus-doped BaTiO₃ have been studied using differential thermal analysis, X-ray diffractometry, scanning electron microscopy coupled with energy-dispersive spectroscopy, transmission electron microscopy, and high-temperature nuclear magnetic resonance. Phosphorus cations that are incorporated from ester phosphate form a surface layer that covers the BaTiO₃ particles. This layer acts as a reactive coating during sintering. Phosphorus-doped BaTiO₃ samples that have been treated at temperatures of 650°–900°C show the presence of crystalline Ba₂TiP₂O₉ and/or Ba₃(PO₄)₂ phases. The appearance of secondary phases is dependent on the cooling rate. Higher temperatures (900°–1200°C) result in the presence of a phosphorus–BaO-rich phase that covers the BaTiO₃ particles. As a consequence, the remaining titanium-rich BaTiO₃ drives the formation of a liquid phase at temperatures >1200°C. In regard to the reported sintering behavior of P⁵⁺-doped BaTiO₃, the formation of a phosphorus–BaO-rich phase that covers the BaTiO₃ particles could be the origin of the improved porosity coalescence and removal that is observed at the earlier stages of sintering.     

Shape of Liquid Immiscibility Volume in the System Barium Oxide-Boric Oxide-Silica

The shape of the immiscibility volume in the system BaO-B₂O₃-SiO₂ is determined from data on seventeen compositions. The ternary critical solution curve originates at the critical point in the binary system BaO-B₂O₃, located at 1225°C. and 15 weight % BaO. It extends almost linearly to its terminus on the silica primary-phase surface, at about 1405° C. and the composition 18 weight % BaO, 10.5% B₂O₃, 71.5% SiO₂. By extrapolation of the ternary critical solution curve, the critical point of the postulated meta-stable immiscibility region in the binary system BaO-SiO2 is located at 1430° C. and 18.5 weight % BaO.     

Effect of Glass Additions on BaO–TiO2–WO3 Microwave Ceramics

The effect of glass addition on the properties of BaO–TiO₂-WO₃ microwave dielectric material N-35, which has Q = 5900 and K = 35 at 7.2 GHz for samples sintered at 1360°C, was investigated. Several glasses including B₂O₃, SiO₂, 5ZnO–2B₂O₃, and nine other commercial glasses were selected for this study. Among these glasses, one with a 5 wt% addition of B₂O₃ to N-35, when sintered at 1200°C, had the best dielectric properties: Q = 8300 and K = 34 at 8.5 GHz. Both Q and K increased with firing temperature as well as with density. The Q of N-35, when sintered with a ZnO–B₂O₃ glass system, showed a sudden drop in the sintering temperature to about 1000°C. The results of XRD, thermal analysis, and scanning electron microscopy indicated that the chemical reaction between the dielectric ceramics and glass had a greater effect on Q than on the density. The effects of the glass content and the mixing process on the densification and microwave dielectric properties are also presented. Ball milling improved the densification and dielectric properties of the N-35 sintered with ZnO–B₂O₃.     

Abnormal Grain Growth in Barium Titanate Doped with Alumina

The effect of additions of ≤1 mol% Al₂O₃ on abnormal grain growth in BaTiO₃ sintered for periods of ≤60 min at 1350°C has been studied. Addition of ≤0.2 mol% Al₂O₃ caused an increase in the nucleation and growth rates of abnormal grains, with further additions causing a decrease. This behavior is explained by interface-controlled growth. Dopant adsorption reduces both the edge free energy and the step velocity of a grain, causing the nucleation and growth rates of abnormal grains to increase, pass through a maximum, and then decrease with increasing dopant concentration.