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.     

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.     

Kinetics of {001} Pb(Mg1/3Nb2/3)O3–35 mol% PbTiO3 Single Crystals Grown by Seeded Polycrystal Conversion

The kinetics of {001}-oriented Pb(Mg_1/3Nb_2/3)O₃–35 mol% PbTiO₃ (PMN–35PT) single crystals grown by seeded polycrystal conversion were systematically quantified as a function of excess PbO liquid phase. The coarsening behavior of the corresponding matrix grains was similarly quantified. Single-crystal seed plates were embedded in a matrix of PMN-35PT with varying amounts of liquid phase (PbO) content in the range of 0 to 5 vol% and annealed at 1150°C for 0–10 h. Apparent maxima in the growth rates were observed at a PbO content of ∼3 vol% for both the single crystal and matrix grains. In both cases, the growth data were found to most closely follow cubic growth kinetics. Implications regarding the effect of PbO volume fraction on the matrix and single-crystal growth mechanisms are discussed.     

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.     

Effect of Neutron Irradiation on Knoop Microhardness Anisotropy in MgO·3Al2O3 Single Crystals

MgO·3Al₂O₃ single crystals were irradiated with neutron fluences of 8.3 × 10²² n/m² at 100°C and 2.4 × 10²⁴ n/m² at 470°C ( E > 1.0 MeV) in the Japan Materials Testing Reactor. The Knoop microhardness of several orientations on the (100) plane of both the irradiated and unirradiated crystals were measured with different indentation loads. The change in hardness profile of the crystals was almost the same after the two irradiation conditions. The hardness increased by 4–15% because of the irradiations depending on the crystallographic orientation, the larger change being observed at orientations between the (001) and (011) directions. While both the {111}     and {110}     slip systems are simultaneously active in the unirradiated MgO·3Al₂O₃, the {111}     system may be the dominant slip system in the neutron-irradiated crystals. It is concluded that the restriction of the {110}     slip system is caused by irradiation-induced interstitial ions.     

Grain Growth Control and Solid-State Crystal Growth by Li2O/PbO Addition and Dislocation Introduction in the PMN–35PT System

Grain growth behavior and solid-state single crystal growth (SSCG) in the Pb(Mg_1/3Nb_2/3)O₃–35 mol% PbTiO₃ (PMN–35PT) system have been investigated with varying Li₂O/PbO ratios. The effect of dislocation density on crystal growth has also been studied. For SSCG, a BaTiO₃ single-crystal seed was embedded in a polycrystalline PMN–PT matrix. During annealing, a PMN–PT single crystal grew from the seed at the cost of the small matrix grains. Addition of Li₂O dopant first enhanced and then reduced abnormal grain growth in the matrix. In the 2 mol% Li₂O and 6 mol% PbO excess PMN–PT samples annealed at 1200°C, considerable single-crystal growth occurred without formation of abnormally large grains in the matrix. Increasing the dislocation density in the BaTiO₃ seed crystal resulted in enhanced growth of single crystals. These results were explained in terms of interface reaction-controlled nucleation and growth, based on crystal growth theories.     

Fabrication of Na0.5Bi0.5TiO3–BaTiO3-Textured Ceramics Templated by Plate-Like Na0.5Bi0.5TiO3 Particles

Textured 0.94Na_0.5Bi_0.5TiO₃–0.06BaTiO₃ (NBT–6BT) ceramics were fabricated by templated grain growth (TGG) using anisotropically shaped Na_0.5Bi_0.5TiO₃ (NBT) templates. Platelet NBT was synthesized by the topochemical technique, using precursor Na_0.5Bi_4.5Ti₄O₁₅ (NBIT). The NBT particles have an average length of 10–15 μm and a thickness of 1 μm, which are suitable templates for obtaining textured ceramics (especially NBT-based ceramics) by the TGG process. This study revealed that the NBT templates are effective in inducing grain orientation in NBT–6BT ceramics. For NBT–6BT ceramics textured with 5 vol% NBT templates, a Lotgering factor of 0.87 and a d ₃₃ of 299 pC/N are given.     

{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.     

Growth of Single-Crystal and Polycrystalline Thin Films of MgAl2O4 and MgFe2O4

Single-crystal and polycrystalline films of Mg-Al₂O₄ and MgFe₂O₄ were formed by two methods on cleavage surfaces of MgO single crystals. In one procedure, aluminum was deposited on MgO by vacuum evaporation. Subsequent heating in air at about 510°C formed a polycrystalline γ-Al₂O₈ film. Above 540°C, the γ-Al₂O, and MgO reacted to form a single-crystal MgAl₂O₄ film with {001} MgAl₂O₄‖{001} MgO. Above 590°C, an additional layer of MgAl₂O₄, which is polycrystalline, formed between the γ-Al₂O₃ and the single-crystal spinel. Polycrystalline Mg-Al₂O₄ formed only when diffusion of Mg²⁺ ions proceeded into the polycrystalline γ-Al₂O₃ region. Corresponding results were obtained for Mg-Fe₂O₄. MgAl₂O₄ films were also formed on cleaved MgO single-crystal substrates by direct evaporation, using an Al₂O₃ crucible as a source. Very slow deposition rates were used with source temperatures of ∼1350°C and substrate temperatures of ∼800°C. Departures from single-crystal character in the films may arise through temperature gradients in the substrate.     

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 Micron-Scale Platelet BaTiO3

Micron-scale platelet barium titanate was synthesized using a twostep molten salt and topochemical technique. Plate-like BaBi₄Ti₄O₁₅ was first synthesized as a precursor by molten salt synthesis. Then, Bi³⁺ in the precursor was replaced by Ba²⁺ and formed perovskite-structure BaTiO₃ through a topochemical reaction. The BaTiO₃ single crystals have an average size of 5–10 μm and a thickness of 0.5 μm. The purpose of this article is to control the particle shape with desired structure. High aspect ratio BaTiO₃ platelets are suitable templates to obtain textured ceramics (especially Pb(Mg_1/3Nb_2/3)O₃–32.5PbTiO₃) by the templated grain growth process.     

Kinetics of Templated Grain Growth of 0.65Pb(Mg1/3Nb2/3)O3·0.35PbTiO3

Single-crystal layers of 0.65Pb(Mg_1/3Nb_2/3)O₃·0.35PbTiO₃ (PMN-35PT) were grown heteroepitaxially on {001}-BaTiO₃ template crystals. A {001}-BaTiO₃ crystal was embedded in a fine-grained matrix of PMN-35PT containing excess PbO and heated between 950° and 1150°C for 0–5 h. The initial growth of the PMN-35PT on the {001} surface and the growth of the matrix grains both displayed a t ^1/3 dependence which is characteristic of diffusion-controlled growth. Growth was limited to ∼100–150 μm due to the significantly reduced driving force at longer times because of matrix coarsening and porosity evolution.     

Habit Modifications of SnO2 Crystals in SnO2–Cu2O Flux System in the Presence of Trivalent Impurity Cations

SnO₂ single crystals have short prismatic habits bounded by well-developed {110} and {111} faces in a pure SnO₂–Cu₂O flux system. When trivalent cations are added to the system, the habits drastically change to needle, acicular, or whisker forms with large aspect ratios. The addition of trivalent cations also greatly increases the nucleation rate and drastically decreases the crystal size. SEM observations and EPMA investigations reveal that the flat {111} faces transform to rounded or rough { hkl } faces by the addition of trivalent cations. This roughening transition of {111} faces, keeping {110} faces unchanged, is the cause of drastic habit modification that is attributed to the breaking of the periodic bond chain in {111} faces by impurity cations.     

Synthesis and Microstructure of Highly Oriented Lead Titanate Thin Films Prepared by a Sol-Gel Method

Thin films of PbTiO₃ were deposited on fused silica, resistor-grade alumina, and single-crystal (100) MgO by a sol–gel processing method. Whereas the films deposited on silica and alumina substrates were randomly oriented and polycrystalline, highly {100} oriented PbTiO₃ films were grown on the MgO single crystals. The perovskite-type structure was observed with films deposited on the single-crystal MgO and annealed at temperatures as low as 470°C, whereas a pyrochlore-type strcuture was observed with films on fused silica and alumina processed in a similar manner. All films heat-treated at temperatures in excess of 570°C showed significant formation of a second PbTi₃O₇ phase. The films were characterized by electron microscopy and glancing-incidence-angle X-ray diffraction.     

Ruddlesden–Popper Planar Faults and Nanotwins in Heteroepitaxial Nonstoichiometric Barium Titanate Thin Films

Nonstoichiometric 10-mol%-excess-BaO–BaTiO₃ (Ba_1.1TiO_3.1) thin film grown on a (100) SrTiO₃ substrate consisted of heteroepitaxial c -axis-oriented BaTiO₃ perovskite crystals including Ruddlesden–Popper planar faults and nanometer-scale multiple (111) twin lamellae. High-resolution electron microscopy and electron energy-loss spectroscopy revealed that nanotwins with coherent (111) Σ3 coincident site lattice boundaries were terminated in the BaTiO₃ matrix to form incoherent (211) Σ3 boundaries accommodating excess barium ions. Both Ruddlesden–Popper planar fault and incoherent (211) boundary formation were proposed as possible accommodation mechanisms of excess barium ions in the perovskite film.     

Dislocations and Mechanical Properties of MgO-Al2O3 Spinel Single Crystals

MgO· n Al₂O₃ spinel single crystals can be deformed plastically at high temperatures, displaying a range of interesting features. Stress-strain curves often exhibit strong work hardening followed by prominent work softening due to glide and climb processes. The critical resolved shear stress (CRSS) at a given temperature decreases dramatically, by almost 2 orders of magnitude, with increasing deviation from stoichiometry, i.e., as n increases from 1 to 3.5. The CRSS is proportional to exp(- T / T ₀) and to [ V _c]^-2, where T is the temperature in kelvin, T ₀ a characteristic temperature, and [ V _c] the concentration of charge-compensating cation vacancies. The Burgers vector is 1/2<110>, and slip can occur on {111} and {110} planes. Slip on {111} planes is believed to occur between the Kagomé cation layer and the adjacent anion layer. Slip on {110} planes is slightly easier (and has a higher T ₀), because the planes are more widely separated. The temperature dependence of the CRSS can be explained in terms of the Peierls stress for partial dislocations, either in terms of a steep and high Peierls potential or in terms of temperature and stress-dependent kink diffusion. The dependence of CRSS on [ V _c]^-2 can be explained in terms of kink nucleation at cation vacancies.     

Observations on Growth of BaTiO3, Crystals from KF Solutions

The purpose of this study was to try to find out why BaTiO₃ (essentially a cubic structure) can consistently be grown from KF solutions as large flat plates when a more equant morphology is expected. It is suggested that the size, shape, and perfection of the platelike "butterfly" twin crystals can be qualitatively related to the re-entrant angles which result from {111} twinning of crystals of {100} habit. The re-entrant angles form permanent steps for both the advancing crystal tip and for the growth layers of the wings. The amount of twinning is related to the cooling rate and to the presence of certain impurities. Thus it can be shown that increasing the cooling rate increases the number of {111} twins (essentially a hexagonal stacking fault); the extreme case is the metastable formation of hexagonal barium titanate by quenching. Evidence is presented for the stabilization of the Ti₂O₉ group of the hexagonal structure by substitution of ions of lower polarizing power.     

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.     

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.