(Bi1/2Na1/2)TiO3–Ba(Cu1/2W1/2)O3 Lead-Free Piezoelectric Ceramics

(Bi_1/2Na_1/2)TiO₃ with 0–6 mol% Ba(Cu_1/2W_1/2)O₃ (BNT-BCW), a new member of the BNT-based group, has been prepared following the conventional mixed oxide route. The compacted bodies were sintered at 1130°C for 2 h to get dense ceramics. The addition of BCW into BNT ceramics facilitated the poling process because of a reduction in leakage current. 0.995BNT·0.005BCW ceramics exhibit a relatively high piezoelectric constant ( d ₃₃= 80 × 10⁻¹² C/N) and a relatively low dielectric loss (tan δ= 1.5%). Increased amount of BCW was found to increase the dielectric constant and loss of BNT-BCW ceramics and to suppress the grain growth. During sintering, some BCW diffuses into the lattice of BNT to form a solid solution and some remains on the grain boundaries.     

Hydrothermal Synthesis of Bismuth Titanate Powders

Bismuth titanate was synthesized under hydrothermal conditions from an amorphous bismuth–titanium precursor gel. The gel was formed by mixing a bismuth acetate complex with titanium butoxide and then adding the solution dropwise into 6 M NaOH. The resulting gel suspension was reacted under hydrothermal conditions at temperatures ranging from 160° to 200°C to form crystalline bismuth titanate. The gel crystallization kinetics increased with temperature, which resulted in 100% crystalline bismuth titanate in 5 h at 200°C. Wavelength-dispersive spectroscopy data indicated that sodium was incorporated into bismuth titanate during processing, and X-ray diffractometry suggested that the powder was composed of the Bi₅Ti₄O₁₅ phase. Transmission electron microscopy micrographs showed that the gel particles decomposed to 100–200 nm crystalline bismuth titanate particles during hydrothermal processing.     

Effect of Potassium Concentration on the Grain Orientation in Bismuth Sodium Potassium Titanate

Bi_0.5(Na_{1- x} K _x )_0.5TiO₃ (BNKT) bulk ceramics with a preferred <100> orientation were prepared using the reactive templated grain-growth method with platelike Bi₄Ti₃O₁₂ particles as templates for BNKT. The potassium concentration ( x value) had a large effect on the degree of orientation, and highly oriented ceramics were obtained for the specimens with x = 0.10 and x = 0.15, whereas the specimen with x = 0.00 had a small degree of orientation. Increased potassium concentration from x = 0.00 to x = 0.15 decreased the grain-growth rate and changed the grain shape from irregular to cubic. These factors were responsible for the increased degree of orientation.     

Electrical Properties of a Bismuth Layer-Structured Ba2Bi4Ti5O18 Single Crystal

Ba₂Bi₄Ti₅O₁₈ single crystals were grown, and their dielectric permittivity, conductivity, and ferroelectricity were investigated along the a -(or b -)axis and the c -axis separately. The dielectric permittivity at 1 MHz along the a -(or b -)axis was 2000 at the Curie temperature (360°C); this value was 8 times greater than that along the c -axis. The dc conductivity was greater along the a -(or b -)axis than that along the c -axis, by one order of magnitude. In regard to the ferroelectricity, the saturated remanent polarization was 120 mC/m² and the saturated coercive field was 3 MV/m along the a -(or b -)axis; values of 8.5 mC/m² and 0.81 MV/m, respectively, were observed along the c -axis. The Ba₂Bi₄Ti₅O₁₈ single crystals had large electrical anisotropies, which were due to the layered structure.     

Large Piezoelectricity and Ferroelectricity in Mn‐Doped (Bi0.5Na0.5)TiO3‐BaTiO3 Thin Film Prepared by Pulsed Laser Deposition

Mn‐doped (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (MnBNBT) thin films were prepared on SrRuO₃ (SRO)‐coated (001) SrTiO₃ (STO) single crystal substrates by pulsed laser deposition under different processing conditions. Structural characterization (i.e., XRD and TEM) confirms the epitaxial growth of STO/SRO/MnBNBT heterostructures. Through the judicious control of deposition temperature, the defect level within the films can be finely tuned. The MnBNBT thin film deposited at the optimized temperature exhibits superior ferroelectric and piezoelectric responses with remanent polarization P_r of 33.0 μC/cm² and piezoelectric coefficient d₃₃ of 120.0 ± 20 pm/V.     

Dielectric and Ferroelectric Properties of Nanocrystalline Bi2Ti2O7 Prepared by a Metallorganic Decomposition Method

Nanopowders of Bi₂Ti₂O₇ were synthesized by a metallorganic decomposition (MOD) technique. Pure Bi₂Ti₂O₇ nanocrystals formed after annealing at 550°C for 5 min. X-ray patterns show that Bi₂₀TiO₃₂ is a metastable phase during Bi₂Ti₂O₇ formation. It was found that there were two peaks in the curves of the dielectric response as a function of temperature for pressed nanocrystalline Bi₂Ti₂O₇ samples. The Curie temperature decreases with decrease of grain size whereas the ferroelectric-ferroelectric phase transition temperature increases. The hysteresis loops observed also suggest that Bi₂Ti₂O₇ might belong to a ferroelectric material.     

Diffusion of 110mAg Tracer in Polycrystalline and Single-Crystal Lead-Containing Piezoelectric Ceramics

We have conducted diffusion measurements of radioactive ^110mAg tracer in single-crystal PbMgNbO₃–PbTiO₃ (PMN-PT) and in polycrystalline 50Pb(Ni_1/3Nb_2/3)O₃·35PbTiO₃·15PbZrO₃ (PNN-PT-PZ) piezoelectric ceramics. Both materials measured belong to the perovskite family. Diffusion in PMN-PT is characterized by an activation energy of 277 kJ/mol and pre-exponential factor of 0.0034 m²/s and compares well with cation diffusion in high-temperature superconducting YBa₂Cu₃O_7–δ. Diffusion in polycrystalline PNN-PT-PZ, on the other hand, is many orders of magnitude faster and is attributed to grain boundaries. PNN-PT-PZ has a lower activation energy, 168 kJ/mol, and a combined pre-exponential factor ( s δ( D _b)_o, where s is the segregation factor of silver, δ the thickness, and ( D _b)_o the pre-exponential factor for grain boundaries) of 3.7 × 10⁻⁹ m³/s. The unusually large combined pre-exponential factor infers large segregation of silver at the grain boundaries and small solid solubility within the grains. It is possible, using a semiempirical model, to compute metal– (silver–) ceramic interface energies as a function of temperature, from which values of 90 kJ/mol and 0.9 R are obtained for enthalpy and entropy, respectively, for grain-boundary segregation.     

Preparation of Textured Bismuth Titanate Ceramics Using Spark Plasma Sintering

Textured bismuth titanate ceramics were successfully produced using spark plasma sintering and platelike bismuth titanate particles prepared using a molten-salt method. The microstructure and dielectric properties of the samples were investigated. The results showed that the dielectric property of the textured bismuth titanate ceramics was anisotropic in various directions and that spark plasma sintering was an effective sintering technology to obtain textured, dense bismuth titanate ceramics at a low temperature.     

Enhanced resistivity and strain stability of BiFeO3–BaTiO3 ceramics by hot-press sintering in oxygen atmosphere

Even though BiFeO₃–BaTiO₃ (BF–BT) with high Curie temperature and excellent piezoelectric properties is very suitable for high-temperature applications, its rapid reduction in resistivity with temperature limits its further application. So far, there is no effective method to improve the resistivity of BF–BT at a high-temperature state. In this work, hot-press sintering combined with an oxygen atmosphere was used to prepare (1 − x)BF–xBT (x = 0.2–0.33) ceramics for the first time, which reduced the sintering temperature from 1000 to 920°C. The controllable grain size can be achieved by adjusting the sintering temperature and the applied pressure. The X-ray photoelectron spectroscopy results confirmed that using hot-press sintering effectively avoided the generation of heterovalent Fe ions, and the resistivity of BF–BT ceramics at the high-temperature stage was improved by two orders of magnitude. It was found that hot-press sintering can cause the oriented growth of the sample along the (1 1 0) direction, and further refined X-ray diffraction was used to accurately analyze the changes in the lattice structure. The hot-press sintered samples obtained larger polarization strength, especially the electro-induced strain showed excellent temperature stability in the wide temperature range of 30–170°C. Hot-pressing sintering combined with an oxygen atmosphere is more suitable for preparing high insulation and electrical breakdown resistance ceramics.     

Improvement in Time-Dependent Displacement Degradation of Piezoelectric Ceramics by Manganese/Indium Addition

High-durability lead zirconate titanate (PZT) ceramics were developed in the present study to prevent time-dependent deterioration of displacement, as well as failure under operation. Current leakage in PZT was decreased by adding elemental manganese, changing the zirconium content from 54.0 to 54.2 mol%, and decreasing the antimony content. Displacement was improved by adding both manganese and indium to the PZT. The present investigation resulted in the development of PZT compositions with high displacement and low time-dependent displacement degradation. These results were confirmed by analyzing stack actuators made from enhanced PZT compositions.     

Microwave Dielectric Properties and Far-Infrared Reflectivity Characteristics of the CaTiO3–Li(1/2)−3xSm(1/2)+xTiO3Ceramics

Microwave dielectric properties and far-infrared reflectivity spectra of the 0.3CaTiO₃–0.7Li_{(1/2)−3 x} Sm_{(1/2)+ x} TiO₃ ceramics were investigated as a function of Sm³⁺ substitution (0.0 ≤ x ≤ 0.12). The dielectric constant decreased as the Sm³⁺ substitution increased. The Q × f value increased, up to a solid-solution limit at x = 0.11, because of the change of vibration modes between the A-site cation and the TiO₆ octahedron, and then decreased because of the formation of a secondary phase (Sm₂Ti₂O₇). On the analysis of the far-infrared reflectivity spectra, in the 50–4000 cm⁻¹ range, the change of the dielectric loss and dielectric constant could be explained by the intrinsic factor.     

Structure and Microwave Dielectric Properties of (Zn1−xCox)TiO3 Ceramics

Dielectric ceramics in the system (Zn_{1− x} Co _x )TiO₃ ( x = 0–1) were synthesized by the solid-state reaction route. The phase distribution, microstructure, and dielectric properties were characterized by using powder X-ray diffraction analysis, electron microscopy, and microwave measurement techniques. Three phase composition regions were identified in the specimens sintered at 1150°C; [spinel + rutile] at 0 ≤ x ≤ 0.5, [spinel + ilmenite + rutile] at 0.5 < x ≤ 0.7, and [ilmenite] phase at 0.7 < x ≤ 1. For the 0 ≤ x ≤ 0.5 region, the amount of Ti-rich precipitates incorporated into the spinel phase decreased with the Co content at 0 ≤ x ≤ 0.5, with a concomitant increase of the rutile phase. The ilmenite phase appeared for high Co content. The microwave dielectric properties depended on the phase composition and volume according to the three phase regions, where the relative amount of rutile to the spinel or ilmenite determined the dielectric properties. The dielectric constant as a function of Co addition was modeled with a Maxwell mixing rule. An optimum phase distribution was determined in this system with dielectric constant of 25, a Q * f 70 000 GHz, and a low temperature coefficient of the resonant frequency.     

Direct-Current Field Dependence of Dielectric Properties in Alumina-Doped Barium Strontium Titanate

The dielectric properties of (Ba_0.6Sr_0.4)TiO₃ and Al₂O₃-doped (Ba_0.6Sr_0.4)TiO₃ have been characterized. The grain size of the specimen is maximum for (Ba_0.6Sr_0.4)TiO₃ that has been doped with 1 wt% Al₂O₃. The density and the real part of the relative dielectric constant each decrease as the Al₂O₃ content increases. The loss factor is minimum for (Ba_0.6Sr_0.4)TiO₃ that has been doped with 2 wt% Al₂O₃. The dielectric constant of the specimens decreases as the applied dc field increases. The influence of the dc field on the loss factor is much less than that on the dielectric constant. The tunability is ∼24% for (Ba_0.6Sr_0.4)TiO₃ that has been doped with 1 wt% Al₂O₃.     

Effect of Acceptor and Donor Dopants on the Dielectric and Tunable Properties of Barium Strontium Titanate

The effects of different concentrations of Mn²⁺, Mg²⁺, Al³⁺, Fe³⁺, La³⁺, and Nb⁵⁺ on the dielectric and tunable properties of Ba_0.6Sr_0.4TiO₃ ceramics were investigated. It was found that doping in small amounts with acceptor ions such as Mg²⁺, Fe³⁺, and Al³⁺ could meliorate the dielectric properties clearly. Decrease of dielectric loss was attributed to the formation of compensating defects originating from acceptor substitution. It was concluded that the tunability was linked to both the dielectric constant and the grain size. A higher figure of merit was obtained by doping the ceramics with smaller ions of Al and Fe, compared to Ti.     

Effects of Alkaline-Earth-Metal Addition on the Sinterability and Microwave Characteristics of (Zr,Sn)TiO4 Dielectrics

The sinterability and microwave dielectric properties of (Zr_0.8Sn_0.2)TiO₄ with additions of 1 mol% of magnesium, calcium, strontium, or barium were examined. All the alkaline-earth metals were effective for densification, and the order of effectiveness was as follows: Mg < Ca < Sr < Ba. The dielectric constant and the temperature coefficient of the resonant frequency were not influenced very much by the additives; however, a strong deterioration of the quality factor ( Q ) did occur when magnesium was added. The presence of grain-boundary phases was confirmed via microstructural observation, using transmission electron microscopy. In addition, energy-dispersive X-ray analysis was performed to investigate the cause of the deterioration in the Q value.     

Influence of composition on the unipolar electric fatigue of Ba(Zr0.2Ti0.8)O3‐(Ba0.7Ca0.3)TiO3 lead‐free piezoceramics

The lead‐free (1?x)Ba(Zr_0.2Ti_0.8)O₃‐x(Ba_0.7Ca_0.3)TiO₃ system is considered as promising candidate for the replacement of lead‐based piezoceramics in actuation applications, during which electric fatigue is a major concern. This issue was addressed in this work, where the unipolar fatigue resistance of three (1?x)Ba(Zr_0.2Ti_0.8)O₃‐x(Ba_0.7Ca_0.3)TiO₃ compositions with different crystallographic structures (rhombohedral, orthorhombic, and tetragonal) was evaluated. Strain asymmetry and development of an internal bias field were observed in all compositions. The decrease in the remanent polarization and the large signal piezoelectric coefficient after 10⁷ unipolar cycles was found to lie between 6%‐12% and 2%‐13%, respectively. The most pronounced fatigue was observed for the orthorhombic composition, which has the largest extrinsic contribution to strain. On the other hand, the best fatigue resistance was observed for the tetragonal composition, which has a predominantly intrinsic strain response. The correlation of fatigue resistance with strain mechanism was corroborated with determination of the Rayleigh parameters and changes in the domain morphology after cycling as confirmed by piezoresponse force microscopy.     

Use of Titanates to Achieve a Temperature-Stable Low-Temperature Cofired Ceramic Dielectric for Wireless Applications

A low-loss and near-zero temperature coefficient of resonant frequency ( T _f) low-temperature cofired ceramic (LTCC) host dielectric was developed for portable consumer wireless device applications. The low T _f was realized by compensating the Al₂O₃-filled-glass dielectric with admixtures of TiO₂ (negative temperature coefficient of dielectric constant ( T _ɛ)) in the starting formulation. XRD data indicated a portion of the TiO₂ in the starting formulation dissolved into the glass, and extensive formation of crystalline titanium compounds was observed via a nucleation and growth mechanism. The dissolution of TiO₂ in the glass and subsequent formation of titanium compounds was believed to result in the relatively small amount of TiO₂ required to achieve a near-zero T _f in the final sintered structure.