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.     

Optical and X-Ray Single Crystal Studies of the Monoclinic ⇌ Tetragonal Transition in ZrO2

The monoclinic ⇌ tetragonal phase transition in ZrO₂ single crystals was studied at temperature by transmission optical microscopy and X-ray diffraction techniques. A series of timelapse photographs illustrated the relations between the events that occur during the transition. The events themselves were recognized by direct observation using a high-temperature microscope stage and by scrutiny of several high-temperature Laue photographs. During heating the monoclinic phase transforms to the tetragonal by the motion of an interface parallel to the (100) _m plane; simultaneous twinning also occurs behind the advancing interface. The tetragonal phase is usually twinned on the (1 2) _bct or ( 12) _bct plane, and the extent of twinning is influenced by the heating rate. Cooling transforms the untwinned tetragonal form into a twinned monoclinic form with the orientation of the monoclinic twins parallel to the trace of the (001) _m plane when observations are made in the (100) _m plane. Transformation of a twinned tetragonal crystal results in twins on the {110} _m and {001} _m planes. Orientation relations in the ZrO₂ transformation are: (100) _m ‖(110) _bct , [010] _m ‖[001] _bct , and by the virtue of twinning, (100) _m ‖(110) _bct , [001] _m ‖[001] _bct . During cooling the same topotaxial relations are maintained.     

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.     

{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.     

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.     

The Effect of Texture and Microstructure on the Macroscopic Properties of Polycrystalline Piezoelectrics: Application to Barium Titanate and PZN–PT

The effects of crystallographic texture and microstructure are analyzed for polycrystalline tetragonal BaTiO₃, pseudotetragonal PZN–PT, and cubic BaTiO₃. For tetragonal BaTiO₃ and pseudotetragonal PZN–PT, we demonstrate that a high anisotropy of the single-crystal properties induces an apparent enhancement in the macroscopic piezoelectric response. For tetragonal BaTiO₃, the predicted macroscopic piezoelectric constants d ₃₁ and d ₃₃ are enhanced with respect to its single-crystal value at the expense of the spatial contributions from d ₁₅. For samples possessing fiber texture, an optimal response is predicted for samples that are not perfectly textured. Similarly, an apparent enhancement of the macroscopic value of d ₁₅ is predicted for PZN–PT. For cubic BaTiO₃, the low anisotropy of the underlying crystal properties induces a uniform decrease of the macroscopic electrostrictive constant, Q ₁₁, with decreasing texture. A completely random polycrystal provides 0.85±0.05 times its single-crystal response.     

Transformation-Induced Twinning: The 90° and 180° Ferroelectric Domains in Tetragonal Barium Titanate

Ferroelectric twin domains resulting from the cubic ( c ) to tetragonal ( t ) phase transformation at the Curie point T _C≈130°C in pressureless-sintered BaTiO₃ ceramics, using TiO₂-excess powder, have been investigated using scanning and transmission electron microscopy. Both 90° and 180° domains were identified by spot splitting along characteristic crystallographic directions in the selected-area diffraction patterns and/or from the shape of domain boundaries. Lamellar domains were found predominantly with the 90° types. The 180° domain boundaries mostly appeared wavy in shape, while the 90° ones, having sharpened ends, attained a dagger shape. Failure of Friedel's law in the non-centrosymmetric t -BaTiO₃ was adopted to validate the existence of the 180° domains. The 90° domains with boundaries lying in     are reflection–inversion twins, and the 180° domains lying in {100) _t and }220) _t are inversion twins. Convergent-beam electron diffraction was performed to ensure that changing of the polar direction [001] _t across the 90° and the 180° domain boundaries was consistent with the domain type. It was also used to confirm whether the 180°-type walls are inversion domain boundaries produced by the loss of an inversion center when the cubic phase transforms into tetragonal symmetry. The formation of such ferroelectric domains is discussed with reference to the crystal symmetry reduction from     ( c -phase) to P 4 mm ( t -phase) with a loss of mirror plane (m) and roto-inversion axis     upon c → t phase transformation.     

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.     

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.     

Preparation of Fine Tetragonal Barium Titanate Powder by a Microwave–Hydrothermal Process

A microwave–hydrothermal (MH) process was performed at 240°C to prepare tetragonal BaTiO₃ from TiCl₄ and Ba(OH)₂. No alkali hydroxide was used to avoid contaminations. MH BaTiO₃ powder with a c / a ratio of 1.010 and a mean size of 180 nm was synthesized within only 9 h. The MH BaTiO₃ contains a very low concentration of lattice hydroxyl group, associated with a very small lattice strain. The measured density of the MH BaTiO₃ is favorably consistent with the theoretical value, and the Ba/Ti stoichiometry determined is 0.996. The formation of a tetragonal structure in BaTiO₃ and the particle growth were strongly promoted by the MH process. The effects of lattice defects on the stoichiometry and the determination of transition enthalpy were discussed.     

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.     

Structure–Property Relationships of BaTi1−2yGayNbyO3 (0≤y≤0.35) Ceramics

BaTi_{1−2 y} Ga _y Nb _y O₃ (BTGN) (0≤ y ≤0.35) powders were synthesized at 1300°C by the conventional solid-state method. Room temperature x-ray diffraction patterns for y ≤0.025 and 0.05≤ y ≤0.30 can be indexed as the tetragonal ( P 4 mm ) and cubic ( Pm     m ) polymorphs of BaTiO₃, respectively, whereas y =0.35 consists of a mixture of the cubic polymorph of BaTiO₃ and an 8H hexagonal-type perovskite ( P 6₃/ mcm ) isostructural with Ba₈Ti₃Nb₄O₂₄. Scanning electron microscopy shows the microstructures of BTGN ceramics ( y ≤0.30) sintered at 1500°C to consist of fine grains (1–3 μm) within a narrow grain size and shape distribution. Room temperature transmission electron microscopy for y ≤0.08 reveals core–shell structures and (111) twins in some grains; however, their relative volume decreases with y . Energy dispersive spectroscopy reveals the cores to be Ga and Nb deficient with respect to y . For y >0.08 there is no evidence of core–shell structures, however, some grains have a high density of dislocations, consistent with chemical inhomogeneity. BTGN ceramics exhibit a diverse range of dielectric behavior in the temperature range 120–450 K and can be subdivided into two groups. 0.025≤ y ≤0.15 display modest ferroelectric relaxor-type behavior, with high room temperature permittivity, ɛ₂₅', (>300 at 10 kHz), whereas 0.25≤ y ≤0.30 are temperature and frequency stable dielectrics with ɛ₂₅'<100 that resonate at microwave frequencies with modest quality factors, Q × f , ∼3720 GHz (at ∼5 GHz) for y =0.30.     

Investigation of Rare-Earth Doped Barium Titanate

In this study the effect of additions of 0.0015 to 0.0030 mole fraction of rare-earth oxides on the d.-c. resistivity of sintered barium titanate was investigated. The substitution may be represented by ( X ₂O₃)_M (BaTiO₃)_1-M where X is the rare earth. The rare earths samarium, gadolinium, and holmium were introduced singly into the titanate, and the resistivity was measured as a function of temperature from −170° to +330°C. An anomalous increase near the tetragonal - cubic transition temperature at 120°C. occurred which in some cases amounted to an increase in the resistivity of 4000 times the value in the tetragonal phase. The thermoelectric power of the material changed sign at the Curie temperature. The tetragonal phase exhibited n -type behavior whereas the cubic phase was p -type. The rhombohedra1 and orthorhombic phases exhibited conduction activation energies of the order of 0.2 e.v. whereas that in the tetragonal phase was approximately 0.1 e.v.     

Hydrothermal Synthesis of Tetragonal Barium Titanate from Barium Hydroxide and Titanium Dioxide under Moderate Conditions

Tetragonal BaTiO₃ powders were prepared hydrothermally, using Ba(OH)₂·8H₂O and TiO₂ (anatase), in the absence of anions such as chloride ions, at a temperature of 220°C for several days. Characterization via X-ray diffractometry, scanning electron microscopy, and differential scanning calorimetry confirmed that increasing the Ba:Ti molar ratios (from 1:1 to 4:1) and alkaline concentrations (from 1.0 M to 3.0 M ) promotes the formation of tetragonal BaTiO₃.     

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.     

Dislocation Loops in Pressureless-Sintered Undoped BaTiO3 Ceramics

Dislocation loops in pressureless-sintered undoped BaTiO₃ ceramics have been analyzed by transmission electron microscopy. The Burgers vector of the loops and its sense b =+1/2[010] were determined using the g·b =0 invisibility criteria, combined with the inside–outside contrast technique using ( g·b ) s _g >0 or<0, keeping the deviation parameter s _g >0. The edge-vacancy nature was further ascertained by determining the loop habit plane normal n =[0 1 0]. Weak-beam dark-field imaging reveals that loops contained no stacking fault fringes; they are edge-vacancy partial dislocation loops lying in {020} or {010} where parts of the TiO₂ or BaO layer are vacant. It is suggested that the extrinsic defects of both cations and oxygen vacancies generated by non-stoichiometry have condensed during sintering in air and are responsible for the formation of such vacancy loops.     

Formation of (111) Twins in BaTiO3 Ceramics

(111) twins are found frequently in the microstructure of BaTiO₃ ceramics prepared by the mixed-oxide technique. The processing steps by which the (111) twins are formed are in question. A BaCO₃-TiO₂ powder mixture is milled and then Calcined at 1100°C for 2 h, where BaTiO₃ is formed by the release of CO₂. After the powder is calcined, it is analyzed by TEM. Image and diffraction pattern data are combined to prove the presence of (111) twins in powder particles; the formation of (111) twins occurred frequently during calcination. The formation mechanism of such twins and their role during anomalous grain growth are discussed.     

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.     

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.     

Synthesis of Nano-sized BaTiO3 Powders by the Rotary-Hydrothermal Process

Nano-sized BaTiO₃ powders with narrow size distribution and high tetragonality were attempted to be synthesized by the rotary-hydrothermal process in a water system as a novel technique, using a mixture of anatase-type TiO₂ and Ba(OH)₂ as starting material. The rotary-hydrothermal syntheses were performed under conditions with a rotary-speed of 20 revolutions per minute at 423–523 K for 3–96 h. Highly- and mono-dispersed BaTiO₃ powders mainly composed of coarse-faceted particles with the tetragonal phase were successfully synthesized by controlling the conditions for rotary-hydrothermal treatments. TEM and TG results revealed that these coarse-faceted BaTiO₃ particles contained very few structural defects such as hydroxyl content. Thus, the rotary-hydrothermal process was a useful method to synthesize very high-quality BaTiO₃ particles, and the further control of various conditions of the rotary-hydrothermal treatment is expected to control the crystalline phase and microstructures of final BaTiO₃ powders.