{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.     

Genesis of the (111) Twin in Barium Titanate

On the basis of the topotaxy between BaTiO₃ and Ba₆Ti₁₇O₄₀ found recently, a model of a nonconservative (111) twin in TiO₂-rich BaTiO₃ was constructed. The model consists of several (001) layers of Ba₆Ti₁₇O₄₀ intergrown between (111) layers of BaTiO₃, the core of the twin being a slightly modified double layer of Ba₆Ti₁₇O₄₀ containing face-sharing octahedra. Using this model, anomalous grain growth below the eutectic temperature and preferential growth of (111) twins in a reducing atmosphere were explained, as well a nucleation of butterfly twins.     

The {111} Growth Twins in Tetragonal Barium Titanate

The {1 1 1} twins frequently observed in pressureless-sintered BaTiO₃ ceramics have been analyzed by the X-ray diffractometry, scanning and transmission electron microscopy. Both the single twins and double lamellar twins are growth (or annealing) twins. The twins lying in the {1 1 1} mirror planes, which is not one of the symmetry elements of the (basic) crystal lattice's but that of the superlattice's, are therefore superlattice twins. The {1 1 1} twins, particularly the double twins, were found more frequently from samples sintered in an Ar atmosphere of lower oxygen partial pressure (pO₂). Further decreasing of pO₂ using the Ar-5% H₂ mixture has rendered the sintered samples entirely of hexagonal BaTiO₃, the 6H-polytype. The formation of such twins is attributed to changing of the corner-sharing TiO₆ octahedra to Ti₂O₉ face-sharing octahedra, which accommodates for local oxygen deficiency in tetragonal BaTiO₃. The stacking sequence alters accordingly from c-layer (constituting the 3C-polytype, treating tetragonal pseudo-cubic) to h-layer (as in (chc)₁(chc)₂ of 6H).     

Hydrothermal Synthesis of Tetragonal Barium Titanate from Barium Chloride and Titanium Tetrachloride under Moderate Conditions

Tetragonal BaTiO₃powders were prepared hydrothermally at 240°C, in only 12 h, using BaCl₂·2H₂O and TiCl₄, which are rather easy to manipulate. Characterization via X-ray diffractometry, scanning electron microscopy, Brunauer–Emmett–Teller analysis, and differential scanning calorimetry confirmed that increasing the NaOH excess concentration (from 0.5 M to 2.0 M ) and decreasing the initial TiCl₄concentration (from 0.625 M to 0.15 M ) promotes the formation of tetragonal BaTiO₃powders. After reaction, the powders were proved to be phase-pure BaTiO₃, with no impurities, such as Cl⁻ and CO₃²⁻.     

Effects of Excess Barium Ions on Aqueous Barium Titanate Tape Properties

The effects of excess free barium ions in aqueous barium titanate slip on the resulting BaTiO₃ tape properties were investigated in terms of the slip behavior, green/sintered tape density and morphology, and dielectric properties. The excess free barium ions expressed by means of the Ba/Ti ratio adversely affected most tape properties. Increase in the slip viscosity, green porosity, and agglomeration along with a decrease in mechanical properties and green/sintered density were found with the increase in the Ba/Ti ratio. However, dielectric permittivity was increased with increase in the Ba/Ti ratio. An effort was made to correlate these phenomena with Ba²⁺ leaching in water for realistic multilayer ceramic capacitor applications.     

Formation and Accumulation of Intragranular Pores in the Hydrothermally Synthesized Barium Titanate Nanoparticles

As highly integrated circuits are demanded for high‐performance electric devices, small sizes of barium titanate (BaTiO₃) as a dielectric material are desirable for the application of multilayer ceramic capacitors. Since the small sizes of the particles degrade the dielectric property, especially below a certain critical size, understanding the probable cause is significant for the high‐performance capacitors. Here, we have demonstrated nanosized BaTiO₃ with average size below 30 nm and a uniform size distribution. High‐resolution transmission electron microscopy (TEM) shows that the as‐synthesized BaTiO₃ contains intragranular pores. We have analyzed the correlation between the intragranular pores inside nanoparticles and their phase ratio of cubic and tetragonal. We have found that the presence of the intragranular pores affects low tetragonality of BaTiO₃ particles, and the intragranular pores are generated by the accumulation of hydroxyl groups during hydrothermal reaction. Formation and accumulation of intragranular pores have been investigated by ex‐situ synchrotron X‐ray diffraction and TEM analysis, suggesting the phase evolution model of nanosized BaTiO₃.     

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.     

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.     

XPS Analysis of Submicrometer Barium Titanate Powder

A commercial submicrometer BaTiO₃ powder was analyzed using X-ray photoelectron spectroscopy. The analysis revealed the powder surfaces to be covered with a layer of physisorbed H₂O and chemisorbed –OH ions. A BaCO₃ residual not detected with XPS was shown to be present in the powder using X-ray diffraction, suggesting that the carbonate takes the form of discrete particles rather than of a continuous surface layer. A relaxed surface phase detected in previous XPS analyses of bulk BaTiO₃ was also shown to be present. Depth profiling revealed the powder surfaces to be Ti-rich, confirming the presence of a phase, or phases, to stoichiometrically balance the barium carbonate.     

Point Defect Concentrations in Barium Titanate Revisited

An analytic link between the oxygen partial pressure and the concentrations of the point defects for given temperatures and A/B conditions is presented for perovskites. A clear distinction between three different conditions is made. These are the sintering conditions, an intermediate metastable state, and a low-temperature metastable state. The analytical solution for a metastable state resulting from nonequilibrated metal vacancies permits a more accurate and self-consistent approach to calculating the equilibrium constants from conductivity– P (O₂) data. One of the reasons for the higher accuracy is that there is no need to divide the existence regime into subregimes with different approximations to the electroneutrality equation (Brouwer approximation). An excellent fit of the experimental conductivity data to a single function with only two adjustable parameters over all conductivity– P (O₂) space is obtained. The relative importance of frozen-in metal vacancies and foreign acceptors is discussed for BaTiO₃.     

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.     

A New Glycothermal Process for Barium Titanate Nanoparticle Synthesis

Barium titanate (BaTiO₃) nanoparticles were synthesized at the low temperature of 80°C through a glycothermal reaction using Ba(OH)₂·8H₂O and amorphous titanium hydrous gel as precursors and a solution of 1,4-butanediol and water as solvent. This processing method provides a simple low-temperature route for producing BaTiO₃ nanoparticles, which could also be extended to other systems. It is demonstrated that the size of BaTiO₃ particles can be controlled by reaction conditions, such as reaction temperature and various volume ratios of 1,4-butanediol/water.     

Formation of Potential Barrier Related to Grain-Boundary Character in Semiconducting Barium Titanate

Resistance–temperature ( R – T ) characteristics were measured directly at single-grain boundaries in 0.1-mol%-niobium-doped barium titanate bicrystals that had been fabricated from polycrystalline sinters, to determine a geometrical grain-boundary character dependence of the positive temperature coefficient of resistivity (PTCR) effect. Both random boundaries and low-Σ boundaries exhibit a similar grain-boundary character dependence of the PTCR effect through a simple geometrical analysis, using the coincidence of reciprocal lattice points. Differences of the R – T characteristics in individual boundaries have been explained in terms of the formation of a potential barrier that is associated with the oxidation of grain boundaries during cooling, after sintering or annealing. The grain-boundary character is likely to affect the diffusivity of O²⁻ ions and, hence, is crucial to the formation of the potential barrier.     

Nanosized Barium Titanate Powder by Mechanical Activation

Mechanical activation, without any additional heat treatment, is used to trigger the formation of a perovskite BaTiO₃ phase in an oxide matrix that consists of BaO and TiO₂ in a nitrogen atmosphere. The resulting BaTiO₃ powder exhibits a well-established nanocrystalline structure, as indicated by phase analysis using X-ray diffractometry. A crystallite size of ∼14 nm is calculated, based on the half-width of the BaTiO₃ (110) peak, using the Scherrer equation, and an average particle size of 20–30 nm is observed using transmission electron microscopy for the activation-derived BaTiO₃ powder.     

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.     

Crystallographic Facetting in Sintered Barium Titanate

A commercial TiO₂-excess BaTiO₃ powder has been sintered and its microstructure analyzed for crystallographic facetting via both scanning and transmission electron microscopy (SEM and TEM). Facetted grain surfaces are developed initially from {111} at a low temperature of 1215°C, which are then altered to {111} and {100} at 1290°C in the presence of a grain-boundary liquid phase. The grain shape is also modified correspondingly from platelike to polygonal. Facetting of the intragranularly located residual pores in BaTiO₃ along the {141} planes further develops on the (quasi-)equilibrium shape after annealing at 1400°C for 100 h from the initially well-characterized {111}, {110}, and {100} in as-sintered samples sintered at the same temperature for 10 h. The Wulff plots derived from the residual pores in as-sintered and annealed samples are constructed for the 〈011〉 zone. Microstructural analysis also suggests that the shape of grains and intragranular residual pores is modified progressively upon annealing. The initial solid–vapor surface energy has become less anisotropic crystallographically. Abnormal grain growth in relation to the surface energy anisotropy is discussed.     

Phase Equilibria in the System Barium Titanate—Strontium Titanate

Phase equilibria in the system BaTiO₃–SrTiO₃ (with 0 to 7 mol% SrTiO₃) were studied at temperatures above 1600°C in air. Quenching experiments were performed using high-purity starting materials, and run products were examined by X-ray diffraction and differential scanning calorimetry to determine phase composition and Sr concentration. Melting involves a binary loop intersected by the invariant reaction hexagonal (Ba, Sr)TiO₃( ss ) ⇌ cubic (Ba, Sr)TiO₃( ss ) + liquid. In contrast with earlier work, these results indicate that there is no depression of the melting point with Sr addition and no congruent melting point in this compositional range.     

Temperature Dependence of the Coarsening Behavior of Barium Titanate Grains

The coarsening behavior of large seed particles during the sintering of BaTiO₃ ceramics has been investigated. At 1350°C, the grains are faceted, and the seed particles grow extensively. At 1380°C, however, the grains are spherical, and coarsening of the seed particles is limited. The observed difference is discussed in terms of the growth mechanism and the atomic structure of the interfaces.     

Wetting Reaction between Lithium Fluoride and Barium Titanate

The wetting reaction between LiF and BaTiO₃ was studied by examining the reaction products on the LiF-wetted surface of BaTiO₃. A reduction reaction occurred between the melt of LiF and BaTiO₃, causing the formation of LiTiO₂ and volatilization of fluorine. The wetted surface consisted of spherical particles of LiTiO₂ and eutectically decomposed phases of BaLiF₃ and LiTiO₂. The formation of LiTiO₂ was repressed by the addition of excess BaO in the melt of LiF, and a well-spread film was formed on the surface of BaTiO₃. The wetting between BaLiF₃ and BaTiO₃ was also examined. The reaction of forming LiTiO₂ did not occur, and a mosaic film was formed on the surface of BaTiO₃.