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.     

Faceting of High-Angle Grain Boundaries in Titanium-Excess BaTiO3

The grain boundaries in BaTiO₃ with excess Ti of 0.5, 0.3, and 0.1 at.% sintered at 1300° or 1250°C have been examined by scanning electron microscopy (SEM), electron backscattered diffraction pattern (EBSP), and transmission electron microscopy (TEM). In the 0.1% Ti-excess specimen, large grains growing abnormally form high-angle grain boundaries when they impinge on each other as verified by EBSP. A large fraction of these grain boundaries are faceted with hill-and-valley shapes. In the 0.5% Ti-excess specimen, large grains growing abnormally are elongated in the directions of their {111} double twins. These grains often form flat grain boundaries parallel to their {111} planes with the fine matrix grains, and the grain-boundary segments between the large impinging grains with high misorientation angles are often also parallel to the {111} planes of one of the grains. These grain boundaries are expected to be singular. Most of the grain boundaries between the randomly oriented fine-matrix grains in the 0.3 at.% Ti-excess specimen are also faceted with hill-and-valley shapes at finer scales when observed under TEM. The facet planes are parallel to {111}, {011}, and {012} planes of one of the grain pairs and are also expected to be singular. These high-angle grain boundaries lying on low index planes of one of the grain pairs are similar to those observed in other oxides and metals.     

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.     

{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.     

Transmission Electron Microscopy Microstructure of 0.95(Na0.5K0.5)NbO3–0.05BaTiO3 Ceramics

Microstructural characterizations using transmission electron microscopy on 0.95(Na_0.5K_0.5)NbO₃–0.05BaTiO₃ ceramics sintered at 1030°–1150°C for 2 h were carried out. The liquid phase was found at the triple junction of the grains in all specimens and abnormal grain growth occurred in the presence of the liquid phase. Abnormally grown grains whose shapes were cuboidal were well developed. Anisotropically faceted amorphous liquid phase pockets were observed inside the grain in a specimen sintered at 1060°C for 2 h. The interface between the grain and the liquid matrix was flat and some were identified to be {100} planes of the grains. A certain amount of liquid at the sintering temperature of 1060°C enhanced the abnormal grain growth and contributed to the improvement of the piezoelectric properties.     

Fabrication of Barium Titanate Single Crystals by Solid-State Grain Growth

BaTiO₃ single crystals were prepared by solid-state grain growth. The single crystals were obtained by seeding a poly-crystalline, TiO₂-excess BaTiO₃, which exhibited abnormal grain growth. The condition for single-crystal growth was essentially dependent on the grain growth behavior of the polycrystalline, sintered bodies. The annealing temperature suitable for the single-crystal growth was just below the critical temperature of abnormal grain growth in TiO₂-excess BaTiO₃, which is about 1300°C.     

Dependence of Grain Growth and Grain-Boundary Structure on the Ba/Ti Ratio in BaTiO3

The grain-growth behavior and grain-boundary structure in titanium-excess BaTiO₃ depend on the amount of excess titanium at 1250° and 1300°3C. With excess titanium, abnormal grain growth (AGG) occurs and the grain boundaries are mostly flat or faceted with hill-and-valley shapes. With 0.5 at.% excess titanium, the large grains have flat {111} faces forming singular grain boundaries parallel to {111} double twins. With excess-titanium content between 0.1 and 0.3 at.%, the abnormal grains appear to have polyhedral shapes with {100} faces. These flat or faceted grain boundaries are expected to have singular structures, and hence AGG can occur by the step growth mechanism. When the excess-titanium content is decreased to 0, the grain boundaries become curved, indicating a rough atomic structure, and normal grain growth occurs.     

Abnormal Grain Growth and Intergranular Amorphous Film Formation in BaTiO3

The effect of abnormal grain growth on the formation of amorphous films at grains boundaries was studied in a model system BaTiO₃. 0.4 mol% TiO₂-excess BaTiO₃ powder compacts were sintered at 1380°C for various times up to 16 h. During the sintering, abnormal grains formed. With the growth of the abnormal grains, amorphous films formed and eventually thickened up to 19.2 nm at grain boundaries. The film formation is attributed to the accumulation of Ti solutes at grain boundaries with the grain growth, while the film thickening is mostly caused by the redistribution of liquid at triple junctions. Extended annealing of the 16-h-sintered sample at 1350°C for 15 days resulted in a thinning of the film to nearly 1.7 nm without a change in the grain size, showing an equilibrium thickness. This result demonstrates that the film thickness observed during the growth of the grain may not be the equilibrium thickness. The result further suggests that the shape of the abnormal grains, even when equiaxed, can differ from the equilibrium shape.     

Effect of PO2 on Bulk and Grain Boundary Resistance of n-Type BaTiO3 at Cryogenic Temperatures

Complex impedance analysis at cryogenic temperatures has revealed that the bulk and grain boundary properties of BaTiO₃ polycrystals are very sensitive to the oxygen partial pressure during sintering. Polycrystals sintered at P _O2 as low as 10⁻¹⁵ atm were already electrically heterogeneous. The activation energy of the bulk conductivity in the rhombohedral phase was found to be close to that of the reduced undoped single crystal (i.e., 0.093 eV). The activation energy of the grain boundary conductivity increases with the temperature of the postsinter oxidation treatment from 0.064 to 0.113 eV. Analysis of polycrystalline BaTiO₃ sintered in reducing atmosphere and then annealed at P _O2= 0.2 atm has shown that the onset of the PTCR effect occurs at much higher temperatures than expected in the framework of the oxygen chemisorption model. The EPR intensity of barium and titanium vacancies increases after oxidation at T > 1000°C. A substantial PTCR effect is achieved only after prolonged annealing of the ceramic in air at temperatures as high as 1200–1250°C. This result suggests that the PTCR effect in polycrystalline BaTiO₃ is associated with interfacial segregation of cation vacancies during oxidation of the grain boundaries.     

Preparation of Dense BaTiO3 Ceramics with Submicrometer Grains by Spark Plasma Sintering

Dense BaTiO₃ ceramics consisting of submicrometer grains were prepared using the spark plasma sintering (SPS) method. Hydrothermally prepared BaTiO₃ (0.1 and 0.5 µm) was used as starting powders. The powders were densified to more than similar/congruent95% of the theoretical X-ray density by the SPS process. The average grain size of the SPS pellets was less than similar/congruent1 µm, even by sintering at 1000-1200°C, because of the short sintering period (5 min). Cubic-phase BaTiO₃ coexisted with tetragonal BaTiO₃ at room temperature in the SPS pellets, even when well-defined tetragonal-phase BaTiO₃ powder was sintered at 1100° and 1200°C and annealed at 1000°C, signifying that the SPS process is effective for stabilizing metastable cubic phase. The measured permittivity was similar/congruent7000 at 1 kHz at room temperature for samples sintered at 1100°C and showed almost no dependence on frequency within similar/congruent10⁰-10⁶ Hz; the permittivity at 1 MHz was 95% of that at 1 kHz.     

Chemical Solution-Deposited BaTiO3 Thin Films on Ni Foils: Microstructure and Interfaces

The microstructure and interface quality of chemical solution-deposited BaTiO₃ films on Ni foil were investigated by transmission electron microscopy. The microstructures were found to consist of equiaxed and uniform grains, with average grain sizes for rapid thermal-annealed films of 12 nm (700°C) and 18 nm (750°C), respectively. Films furnace annealed at 1000°C after a rapid thermal anneal at 700°C showed a grain size of 42 nm. It is believed that the final grain size is limited by the highly reducing atmosphere and also by the existence of well-developed crystallites resulting from the rapid thermal annealing step. Spatially resolved electron energy loss spectroscopy identified the existence of residual carbon and variations in the oxygen content in BaTiO₃ films. High-resolution transmission electron microscopy revealed an interfacial layer of Ni–Ba alloy (5–10 nm thick) between the BaTiO₃ and Ni foil.     

Effect of Ba6Ti17O40/BaTiO3 Interface Structure on {111} Twin Formation and Abnormal Grain Growth in BaTiO3

A structural transition of Ba₆Ti₁₇O₄₀/BaTiO₃ interfaces from faceted to rough was induced by reducing oxygen partial pressure in the atmosphere. As the oxygen partial pressure decreased, the number densities of {111} twins and abnormal grain decreased. TEM observation showed that the twin formation was governed only by the faceting of the interface. Experimental evidence of {111} twin-assisted abnormal growth of faceted BaTiO₃ grains was also obtained.     

Defect Chemistry and Microstructure of Hydrothermal Barium Titanate

Hydrothermal powders of BaTiO₃ and (Ba,Ca)(Ti,Zr)O₃ contain large amounts of protons in the oxygen sublattice. The proton defects are compensated by vacancies on metal sites. When the powder is annealed, water is released and the point defects disappear in the temperature range of 100°–600°C. Metal and oxygen vacancies combine to small nanometer-sized intragranular pores. At temperatures of >800°C, the intragranular pores migrate to the grain boundaries and disappear. In multilayer ceramic capacitors that have been prepared from hydrothermal powders, the intragranular pores are preferentially collected at the inner electrodes, which results in "bloating," cracks, and delamination.     

Texture Development in Barium Titanate and PMN–PT Using Hexabarium 17-Titanate Heterotemplates

Bulk BaTiO₃ ceramics with 〈111〉-texture have been prepared by the modified templated grain growth method, using platelike Ba₆Ti₁₇O₄₀ particles as templates, and the mechanism of texture development is examined. The Ba₆Ti₁₇O₄₀ particles induce the abnormal growth of BaTiO₃ grains, and a structure similarity between {001} of Ba₆Ti₁₇O₄₀ and {111} of BaTiO₃ gives 〈111〉-texture to abnormally grown BaTiO₃ grains. Thus, the 〈111〉-texture develops in the BaTiO₃ matrix. The use of platelike Ba₆Ti₁₇O₄₀ particles has been extended to a 0.65Pb(Mg_1/3Nb_2/3)O₃–0.35PbTiO₃ matrix, but the matrix phase is decomposed by extensive chemical reactions between the matrix and template phases.     

Microstructure of Lanthanum Magnesium Niobate at Elevated Temperature

Microstructural studies of the complex perovskite compound La(Mg_2/3Nb_1/3)O₃ (LMN) were conducted using transmission electron microscopy (TEM) and X-ray diffractometry (XRD) at elevated temperatures. 1:1 chemical ordering of B-site cations and tilting of oxygen octahedra were observed in LMN. Three types of superlattice reflections, [1—2]{111}, [1—2]{110}, and [1—2]{100} were observed at room temperature and at 800°C in electron diffraction patterns. In the XRD experiments, the [1—2]{210} and [1—2]{300} extra peaks disappeared at temperatures >1200°C. However, the intensity of the superlattice [1—2]{111} peak did not change with increased temperature up to 1400°C. These results strongly indicated that the origin of superlattice reflection [1—2]{111} was different from that of the other superlattice reflections. It was mainly caused by the 1:1 chemical ordering of magnesium and niobium atoms. The TEM image observed at 800°C showed the ordered domain structures separated by the antiphase boundaries.     

Crystalline Phase Change in Yttria-Partially-Stabilized Zirconia by Low-Temperature Annealing

Changes in the phase composition and microstructure of yttria-partially-stabilized zirconia by low-temperature annealing were investigated at 100° to 500°C using bodies sintered from coprecipitated fine ZrO₂-Y₂O₃ powders at varied temperatures. Tetragonal zirconia on the surfaces of bodies sintered at <1500°C transformed to the monoclinic phase at 100° to 400°C. Transformation behavior was strongly affected by grain size.     

Preparation of Tetragonal Barium Titanate Thin Film on Titanium Metal Substrate by Hydrothermal Method

Tetragonal BaTiO₃ thin films were prepared directly on Ti metal substrates in Ba(OH)₂ solutions by a hydrothermal method at temperatures 400° to 800°C for 5 to 240 min. The film thickness estimated from weight gain of Ti plate was in the range from 0.5 to 2.5 μm, and it increased with increasing treatment temperature, treatment time, and Ba(OH)₂ concentration. Rectangular crystals having {100} and {001} faces grew idiomorphically with approximate crystal size of 0.3 to 2.0 μm. The tetragonality of the BaTiO₃ films became apparent when the average crystal size exceeded about 1 μm. Lattice parameters of the films were a = 3.994 Å, c = 4.035 Å, and c/a = 1.010. The films formed above 600°C had preferred orientation showing stronger XRD peaks of h 00 and 00 l than the other peaks.     

Hydrothermal Synthesis for Large Barium Titanate Powders at a Low Temperature: Effect of Titania Aging in an Alkaline Solution

Monodisperse and spherical barium titanate (BaTiO₃) powders with diameters of 200–470 nm were directly prepared by a low-temperature hydrothermal method at 90°C. Spherical titania (TiO₂) powders, ranging in size from 150 to 420 nm, were initially prepared by a controlled hydrolysis and condensation reaction, aged in a highly alkaline solution for 12 h, and then hydrothermally reacted with barium hydroxide to be converted to BaTiO₃ without a morphological change. The aging step of the TiO₂, where the surface of TiO₂ was highly densified through elimination of the pores, was indispensable to retain the sizes and shapes of TiO₂ in the resulting BaTiO₃. This was due to the fact that the formation of BaTiO₃ proceeded by an in situ reaction mechanism. The resulting BaTiO₃ powders exhibited dense and nonporous structures even after calcination at 1000°C.     

Surface Energy Anisotropy of SrTiO3 at 1400°C in Air

Geometric and crystallographic measurements of grain-boundary thermal grooves and surface faceting behavior as a function of orientation have been used to determine the surface energy anisotropy of SrTiO₃ at 1400°C in air. Under these conditions, thermal grooves are formed by surface diffusion. The surface energy anisotropy was determined using the capillarity vector reconstruction method under the assumption that Herring's local equilibrium condition holds at the groove root. The results indicate that the (100) surface has the minimum energy. For surfaces inclined between 0° and 30° from (100), the energy increases with the inclination angle. Orientations inclined by more than 30° from (100) are all about 10% higher in energy and, within experimental uncertainty, energetically equivalent. A procedure for estimating the uncertainties in the reconstructed energies is also introduced. Taken together, the orientation dependence of the surface-facet formation and the measured energy anisotropy lead to the conclusion that the equilibrium crystal shape is dominated by {100}, but also includes {110} and {111} facets. Complex planes within about 15° of {100} and 5° of {110} are also part of the equilibrium shape.     

Control of Liquid-Phase-Enhanced Discontinuous Grain Growth in Barium Titanate

Barium titanate shows discontinuous grain growth in the presence of small amounts of the liquid eutectic Ba₆Ti₁₇O₄₀-BaTiO₃ at T > 1312°C. The exaggerated grain growth in the presence of the liquid phase can be explained in terms of a solution-segregation process. The grain size distribution of sintered BaTiO₃ ceramics and the average grain size are strongly modified by addition of "seed grains" to BaTiO₃ powder. The addition of seed grains seems to be a general method of controlling the discontinuous grain growth of ceramics.