Characterization of Bi0.5Na0.5TiO3-PbTiO3M Dielectric Materials

Bi_0.5Na_0.5TiO₃ (BNT) modified with Pb showed an increased and broadened dielectric constant and limited grain growth. Pb also lowered the first transition temperature. The phases of BNT were confirmed to be ferroelectric at room temperature which transformed to antiferroelectric above 220°C. When BNT was doped with 10% Pb, the first transition decreased to 140°C and abruptly disappeared in the composition with 17% Pb. The crystal structure of 17%-Pb-doped BNT at room temperature is tetragonal, which differs from the rhombohedral structure at lower Pb contents. Thus, the phase boundary between rhombohedral and tetragonal ferroelectric phase was determined to be between 15% to 17% Pb in this study.     

Crystal Structure and Ferroelectric Properties of (Bi0.5Na0.5)TiO3–Ba(Zr0.05Ti0.95)O3 Piezoelectric Ceramics

The crystal structure and ferroelectric properties of (1− x )(Bi_0.5Na_0.5)TiO₃– x Ba(Zr_0.05Ti_0.95)O₃ (BNBZT x, x ≤12%) lead-free piezoelectric ceramics were studied. The distance between the centers of cations and anions ( d _c–a) as well as the lattice parameters was carefully investigated by Rietveld refinement on X-ray diffraction patterns. It was found that the crystal phase was determined by the amount of Ba(Zr_0.05Ti_0.95)O₃ added, whereas the pure rhombohedral and tetragonal phases are observed in compositions containing x ≤4 and x ≥8%, respectively. A rhombohedral–tetragonal morphotropic phase boundary (MPB) was found at around BNBZT6, which showed a maximum and minimum d _c–a at its rhombohedral and tetragonal phases, respectively. According to the present study, the ferroelectric properties show a strong dependence on their crystal phases. For the single-phase compositions, the remanent polarization ( P _r) generally increased with the value of d _c–a while their coercive fields ( E _c) were determined by their lattice parameters. Nevertheless, the behavior in P _r and E _c for MPB compositions is related to not only the lattice parameter but also the composed phases.     

Ferroelectric and Piezoelectric Properties of Fine-Grained Na0.5K0.5NbO3 Lead-Free Piezoelectric Ceramics Prepared by Spark Plasma Sintering

Lead-free piezoelectric ceramics have received attention because of increasing interest in environmental protection. Niobate ceramics such as NaNbO₃ and KNbO₃ have been studied as promising Pb-free piezoelectric ceramics, but their sintering densification is fairly difficult. In the present study, highly dense Na_0.5K_0.5NbO₃ ceramics were prepared using spark plasma sintering (SPS). Although the SPS temperature was as low as 920°C, the density of the Na_0.5K_0.5NbO₃ solid solution ceramics was raised to 4.47 g/cm³ (>99% of the theoretical density). After post-annealing in air, reasonably good ferroelectric and piezoelectric properties were obtained in the Na_0.5K_0.5NbO₃ ceramics with submicron grains. The crystal phase of the Na_0.5K_0.5NbO₃ has an orthorhombic structure. The Curie temperature is 395°C and the piezoelectric parameter ( d ₃₃) of the Na_0.5K_0.5NbO₃ ceramics reached 148 pC/N.     

Phase Transitional Behavior and Piezoelectric Properties of Lead-Free (Na0.5K0.5)NbO3–(Bi0.5K0.5)TiO3 Ceramics

(1− x )(Na_0.5K_0.5)NbO₃–(Bi_0.5K_0.5)TiO₃ solid solution ceramics were successfully fabricated, exhibiting a continuous phase transition with changing x at room temperature from orthorhombic, to tetragonal, to cubic, and finally to tetragonal symmetries. A morphotropic phase boundary (MPB) between orthorhombic and tetragonal ferroelectric phases was found at 2–3 mol% (Bi_0.5K_0.5)TiO₃ (BKT), which brings about enhanced piezoelectric and electromechanical properties of piezoelectric constant d ₃₃=192 pC/N and planar electromechanical coupling coefficient k _p=45%. The MPB composition has a Curie temperature of 370°–380°C, comparable with that of the widely used PZT materials. These results demonstrate that this system is a promising lead-free piezoelectric candidate material.     

Single Crystals of Pb(Mg1/3Nb2/3)O3—35 mol% PbTiO3 from Polycrystalline Precursors

A potentially more cost-efficient method of growing single-crystal relaxor-based ferroelectric materials has been investigated. Seed single crystals of Pb(Mg_1/3Nb_2/3)O₃(PMN)—;35 mol% PbTiO₃(PT) were embedded within polycrystalline powders and annealed at temperatures from 900° to 1200°C. The boundary of the single crystal migrated through the polycrystal matrix under the influence of grain boundary curvature; growth distances of several millimeters were observed, verifying the feasibility of the approach. The grown single crystals exhibited macroscopic cubic growth morphologies with (100) faces. Strain levels as high as 0.68% under an electric field of 30 kV/cm were observed in initial measurements.     

BiScO3 Doped (Na0.5K0.5)NbO3 Lead-Free Piezoelectric Ceramics

Lead-free potassium sodium niobate-based piezoelectric ceramics (1− x )(Na_0.5K_0.5)NbO₃– x BiScO₃ (KNN–BS) ( x =0∼0.05) have been prepared by an ordinary sintering process. Single perovskite phase of KNN–BS exhibits an orthorhombic symmetry at x <0.015 and pseudocubic symmetry at x >0.02, separating by a MPB at 0.015≤ x ≤0.02. Piezoelectric and ferroelectric properties are significantly enhanced in the MPB, which are as follows: piezoelectric constant d ₃₃=203 pC/N, planar coupling coefficient k _p=0.36, remnant polarization P _r=24.4 μC/cm². These solid solution ceramics look promising as a potential lead-free candidate materials.     

Plate-Like Na0.5Bi0.5TiO3 Template Synthesized by a Topochemical Method

Large plate-like Na_0.5Bi_0.5TiO₃ (NBT) templates have been successfully synthesized from bismuth layer-structured ferroelectric Na_0.5Bi_4.5Ti₄O₁₅ (NBIT) particles by the topochemical method. Because of the highly anisotropic structure, plate-like NBIT particles were first synthesized by the molten-salt process. After the topochemical reaction with the complementary reactants (Na₂CO₃, and TiO₂) in NaCl flux, the layer-structured NBIT particles were transformed to the perovskite NBT templates. The resulting NBT templates are large and of plate-like shape. Our results also reveal that they are more effective in inducing grain orientation in the BNKT-BT ceramics as compared with BIT templates. For a BNKT-BT ceramic textured with 20 wt% of NBT templates, it exhibits a very high degree of grain orientation and gives a large Lotgering factor of 0.89.     

Processing and Piezoelectric Properties of (Na0.5K0.5)0.96Li0.04(Ta0.1Nb0.9)1−xCuxO3−3x/2 Lead-Free Ceramics

The Cu-modified (Na_0.5K_0.5)_0.96Li_0.04Ta_0.1Nb_0.9O₃ lead-free piezoelectric ceramics were fabricated at relatively low temperatures by ordinary sintering. The results indicate that the addition of copper oxide (CuO) does not change the crystal structure and the dielectric–temperature characteristic, but tends to slightly increase the loss tangent and significantly modify the ferroelectric and electromechanical properties. Moreover, the grains get clearly coarsened with increasing CuO content. When doped with <0.25% CuO, the materials get softer with slightly decreased coercive fields ( E _c) and increased maximum electric field-driven strains ( S _m), and thus own enhanced piezoelectric properties; however, as the doping level becomes higher, the materials get harder, possessing larger E _c and reduced remanent polarization and S _m. The change in the electrical properties can be attributed to both the formation of oxygen vacancies by Cu²⁺ replacing Nb⁵⁺ and the modification of densification.     

Preparation of Grain-Oriented Sr0.5Ba0.5Nb2O6 Ferroelectric Ceramics by Magnetic Alignment

The properties of polycrystalline ceramics are strongly influenced by their crystallographic texture. In this study, highly grain-oriented tungsten bronze structure ferroelectric ceramics, Sr_0.5Ba_0.5Nb₂O₆, were successfully fabricated by magnetic alignment and gelcasting techniques using only the conventional solid-state-synthesized starting powder. Spherical Sr_0.5Ba_0.5Nb₂O₆ particles were aligned according to their anisotropic magnetic property in 40 vol% slurry in a 10 T magnetic field, and then in situ locked by polymerization via a gelcasting technique for 30 min. A 〈00 l 〉-axis orientation perpendicular to the magnetic field direction ( B ) was obviously observed in the green compact and sintered sample. The sintered Sr_0.5Ba_0.5Nb₂O₆ sample contained equiaxial grains and reached 98% theoretical density. Compared with the sample with randomly oriented grains, the magnetically aligned sample showed an enhanced with dielectric constant in the ⊥ B direction (1100 versus 750 at room temperature and 4300 versus 2800 at Curie temperature). This new method is readily applicable to other ceramics with tungsten bronze structure, and is expected to facilitate mass preparation of large and dense grain-oriented ceramic materials.     

Effect of BiScO3 and LiNbO3 on the Piezoelectric Properties of (Na0.5K0.5)NbO3 Ceramics

Lead-free potassium sodium niobate-based piezoelectric ceramics (1− y )(Na_{0.5−0.5 x} K_{0.5−0.5 x} Li _x )NbO₃− y BiScO₃ (  y =0.01, x= 0–0.06) have been prepared by an ordinary sintering process. The XRD analysis showed that the structure changes from orthorhombic to tetragonal with the increase of x (at y =0.01, abbreviated as KNNBSL100 x ). At room temperature, the polymorphic phase transition from the orthorhombic to the tetragonal phase was identified at approximately 0.02≤ x ≤0.04. The piezoelectric and ferroelectric properties were significantly enhanced. The temperature dependences of the relative permittivity revealed that the Curie temperature was increased with the addition of LiNbO₃. These solid solution ceramics are promising as potential lead-free candidate materials.     

Microstructure and Dielectric Characteristics of (PbxBa0.5−xSr0.5)TiO3 Ceramics

Microstructural and dielectric properties of the Pb _x Ba _0.5__x —Sr_0.5TiO₃ system have been studied. It is found that this system forms a solid solution in the entire composition range (0.0≤ x ≤0.5) and is cubic for the x = 0, 0.1, and 0.2 compositions and tetragonal for other compositions. Measurements of the dielectric constant as a function of temperature reveal that this material is ferroelectric at room temperature for the x > 0.2 compositions and has a broad paraelectric-ferroelectric transition region. No shift in the dielectric maxima was noted; however, there is a slight spread in the dielectric constant with frequency for the x = 0.4 composition. A quantitative model to mathematically analyze the effect of composition fluctuations on the dielectric broadening for a ternary system is presented. Transmission electron microscopic studies reveal the presence of 90° ferroelectric domains oriented along the {01     } planes for the x = 0.3 and 0.4 compositions.     

Effect of Neodymium:Yttrium Aluminum Garnet Laser Irradiation on Crystallization in Li2O–Al2O3–SiO2 Glass

A 355-nm neodymium:yttrium aluminum garnet laser, produced by a harmonic generator, was used for the nucleation process in photosensitive glass containing Ag⁺ and Ce³⁺ ions. The pulse width and frequency of the laser were 8 ns and 10 Hz, respectively. Heat treatment was conducted at 570°C for 1 h, following laser irradiation, to produce crystalline growth, after which a LiAlSi₃O₈ crystal phase appeared in the laser-irradiated Li₂O–Al₂O₃–SiO₂ glass. The present study compares the effect of laser-induced nucleation on glass crystallization with that of spontaneous nucleation by heat treatment.     

Low-Temperature Crystallization of Sol-Gel Processed Pb0.5Ba0.5TiO3: Powders and Oriented Thin Films

A novel sol-gel process suitable for depositing thin-film lead barium titanate has been developed. X-ray diffraction analysis showed perovskite phase crystallization to occur at a temperature as low as 400°C with single-phase Pb_0.5Ba_0.5TiO₃ (PBT) resulting at a temperature as low as 500°C. Small concentrations of barium carbonate were evident by X-ray diffraction at 400°C, and indications of minor, carbonate-containing phases were evident by FTIR at 600°C. Deposition of the sol by spin coating on single-crystal and thin-film MgO on silicon resulted in highly oriented PBT films after calcination at 600°C. Mixed (100)/(001) films were obtained on single-crystal MgO, whereas entirely (100) films were obtained on thin-film MgO.     

Pyroelectric and Dielectric Properties of Mn Modified 0.82Bi0.5Na0.5TiO3–0.18Bi0.5K0.5TiO3 Lead-Free Thick Films

MnO-doped 0.82Bi_0.5Na_0.5TiO₃–0.18Bi_0.5K_0.5TiO₃(NBT–KBT) thick films with thickness about 40 μm have been prepared using screen printing on Pt electroded alumina substrates. The strong pyroelectric coefficient of 3.8 × 10⁻⁴ C·(m²·°C)^–1 was observed in 1.0 mol% MnO-doped-thick films, and the calculated detectivity figure of merit as high as 1.1 × 10⁻⁵ Pa^−0.5, which can be comparable to that of the commonly used lead based materials. The enhancement of the pyroelectric performances is attributed to the reductions in dielectric constant and loss and the improvements in the pyroelectric coefficient, which can be ascribed to the Mn acts as a hard dopant in the NBT–KBT lattice, creating oxygen vacancies and pinning the residual domains.     

Two-Phase Coexistence in Single-Grain BaTiO3–(Mn0.5Zn0.5)Fe2O4 Composites, Via Solid-State Reaction

We have developed a synthesis method of single-grain two-phase BaTiO₃–(Mn_0.5Zn_0.5)Fe₂O₄ nanomaterials via a solid state reaction. The grains of BTO-rich samples were found to have a rod-like morphology with a high aspect ratio and a diameter of 200 nm, whereas the grains of MZF-rich samples had a tetrahedral/octahedral cross-section with a span of 200 nm. Such a synthesis of two-phase perovskite/spinel single-crystal grains with different grain geometries offers the potential to build new types of multiferroic materials.     

Construction of PbZr0.4Ti0.6O3- and Ba0.9Sr0.1TiO3-Based Optical Microcavities by Chemical Solution Deposition

Herein we report on a simple, low cost, and feasible route for the construction of PbZr_0.4Ti_0.6O₃ (PZT)- or Ba_0.9Sr_0.1TiO₃ (BST)-based optical microcavities using a single chemical solution containing polymer polyvinylpyrrolidone. The obtained multilayer systems not only exhibit good ferroelectric performance, but also display well-defined resonant modes with a quality factor of no <66. Compared with PZT microcavities, the optical properties of the BST microcavities appear to be superior.     

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.     

Dielectric Studies in the System CdO-Nb2O5

Results of studies on the effect of compositional changes and impurities on the electrical characteristics of single-crystal, hot-pressed, and dry-pressed and fired cadmium niobate are presented. Specimens of compositions from CdNb₂O₆ to Cd_2.1Nb₂O_7.1 were studied optically, electrically, and by X-ray diffraction. Cadmium metaniobate remains paraelectric from –180° to +400°C. and acts primarily as a diluent to the ferroelectric properties of cadmium niobate. The Curie point of cadmium niobate occurs at approximately –85°C. with a dielectric constant peak of 6600 for a [110] crystal cut. Indications of antiferroelectricity are discussed. Room-temperature measurements in the paraelectric phase at 21 kilomegacycles indicate a dielectric constant of 150 with a dissipation factor of less than 0.002 as compared with the high losses of BaTiO₃ in this frequency range.     

Crystalline Phases and YAG Laser-Induced Crystallization in Sm2O3–Bi2O3–B2O3 Glasses

The glass formation region, crystalline phases, second harmonic (SH) generation, and Nd:yttrium aluminum garnet (YAG) laser-induced crystallization in the Sm₂O₃–Bi₂O₃–B₂O₃ system were clarified. The crystalline phases of Bi₄B₂O₉, Bi₃B₅O₁₂, BiBO₃, Sm _x Bi_{1− x} BO₃, and SmB₃O₆ were formed through the usual crystallization in an electric furnace. The crystallized glasses consisting of BiBO₃ and Sm _x Bi_{1− x} BO₃ showed SH generations. The formation of the nonlinear optical BiB₃O₆ phase was not confirmed. The formation (writing) region of crystal lines consisting of Sm _x Bi_{1− x} BO₃ by YAG laser irradiation was determined, in which Sm₂O₃ contents were∼10 mol%. The present study demonstrates that Sm₂O₃–Bi₂O₃–B₂O₃ glasses are promising materials for optical functional applications.     

Chemical Solution Deposition of Transparent and Metallic La0.5Sr0.5TiO3+x/2 Films Using Topotactic Reduction

Metallic and transparent La_0.5Sr_0.5TiO_{3+ x /2} films were prepared by the chemical solution deposition (CSD) method using topotactic reduction processing. The use of Si powder as the reducing agent was facile and allowed easy manipulation. It was observed that metallic (resistivity at 300 K ∼2.43 mΩ cm) and transparent (∼80% transmittance at visible light) La_0.5Sr_0.5TiO_{3+ x /2} films could be obtained with an annealing temperature of 900°C, which was significantly lower than the hydrogen reduction temperature (∼1400°C). The successful preparation of metallic and transparent La_0.5Sr_0.5TiO_{3+ x /2} films using CSD has provided a feasible route for depositing other perovskite-structured functional layers on La_0.5Sr_0.5TiO_{3+ x /2} films using this low-cost all CSD method.