Processing and properties of Pb(Mg1/3Nb2/3)O3–PbTiO3-based ceramics

Ceramic compositions of a combination between lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃, and lead titanate, PbTiO₃, were fabricated using the Mg₄Nb₂O₉ precursor technique. Their electrical properties with respect to temperature and frequency were examined and the effect of sintering conditions on phase formation, densification, microstructure and electrical properties of the ceramics were examined. It has been found that optimisation of sintering conditions can lead to a highly dense and pyrochlore-free PMN–PT ceramics. The gradual decrease of the physical properties of the sintered ceramics was related to the gradual decrease of density and inhomogeneous microstructure. The results also revealed that for the lower concentration of lead titanate, a relaxor behaviour is noticed with a high electrostrictive effect, which was almost hysteretic free. However, higher amount of lead titanate led to a normal ferroelectric behaviour.     

Temperature-independent and enhanced dielectric properties for two-layer structure capacitors with 0.8Pb(Fe2/3W1/3)O3–0.2PbTiO3–MnO and 0.7Pb(Fe2/3W1/3)O3–0.3PbTiO3–MnO ceramics

This study fabricates capacitors with two-layer structure and different compositions, 0.8Pb(Fe_2/3W_1/3)O₃–0.2PbTiO₃–MnO and 0.7Pb(Fe_2/3W_1/3)O₃–0.3PbTiO₃–MnO, by using the conventional solid state oxide reaction method. By using the temperature compensation effect and adjusting the thickness ratio of the two layers with different compositions, the temperature–dielectric peak is enhanced and smoothed. The dielectric loss, space charge polarization and dc conduction are suppressed at the highest temperature region. Furthermore, the Maxwell–Wagner model is used to fit and explain the dielectric behaviors. This study also provides suggestions and discussion related to the effect of the interfacial region based on the experimental data and fitting results.     

Stress-dependent ferroelectric properties of Pb(Zr1/2Ti1/2)O3–Pb(Zn1/3Nb2/3)O3 ceramic systems

Effects of compressive stress on the ferroelectric properties of ceramics in PZT–PZN systems were investigated. (1 − x)Pb(Zr_1/2Ti_1/2)O₃(xPb(Zn_1/3Nb_2/3)O₃ or (1 − x)PZT–(x)PZN (x = 0.1–0.5) ceramics were prepared by a conventional mixed-oxide method. The ferroelectric properties under compressive stress of the PZT–PZN ceramics were observed at stress levels up to 170 MPa using a compressometer in conjunction with a modified Sawyer–Tower circuit. It was found that with increasing compressive stress the area of the ferroelectric hysteresis (P–E) loops, the saturation polarization (P_sat), the remanent polarization (P_r), and the coercive field (E_c) decreased. These results were interpreted through the non-180° ferroelectric domain switching processes.     

BiScO3–Pb TiO3–Bi(Zn2/3Nb1/3)O3高温钙钛矿陶瓷的微结构与性能

开发兼具高压电系数(d₃₃)和高退极化温度（T_d）的钙钛矿陶瓷是构建先进高温压电器件的关键。本工作将小容差因子、强铁电活性离子的Bi(Zn_2/3Nb_1/3)O₃ （BZN）基元引入至具有高温应用潜力的BiScO₃–PbTiO₃ （BS–PT）高温钙钛矿压电体中,制备并研究了（0.995–x）BS–x PT–0.005BZN三元系高温压电陶瓷的微结构与压电性能。结果表明,所有陶瓷均具有三方相和四方相共存的特征且结构致密;x=0.62组成位于准同型相界,综合高温性能最佳：T_d高达409℃并兼具优异的高温d₃₃ (709 pC·N^–1)。研究表明,BS–x PT–BZN有望用于制作在恶劣高温环境下服役的压电器件。     

Dielectric properties of B2O3-doped 0.98CeO2–0.02CaTiO3 ceramics at microwave frequency

Microwave dielectric properties and microstructure of 0.98CeO₂–0.02CaTiO₃ ceramics with B₂O₃ additions prepared with the conventional solid-state route have been investigated. 0.98CeO₂–0.02CaTiO₃ ceramics can be sintered at 1290 °C for 4 h due to the sintering aid effect resulting from the B₂O₃ additions. At sintering temperature of 1380 °C for 4 h, 0.98CeO₂–0.02CaTiO₃ ceramics with 0.25 wt% B₂O₃ addition possess a dielectric constant (?_r) of 21.3, a Q × f value of 60,000 (at 8 GHz) and a temperature coefficient of resonant frequency (τ_f) of −41 ppm/°C.     

High piezoelectric performance and temperature dependence of ferroelectric and piezoelectric properties of Bi(Mg0.5Zr0.5)O3–PbTiO3 near morphotropic phase boundary

According to consideration on the average radius of B-site cation of BiMeO₃, we reported that the Bi(Mg_0.5Zr_0.5)O₃–xPbTiO₃ compound at the morphotropic phase boundary (MPB) of x=0.58 possesses a piezoelectric coefficient d₃₃ as high as 306 pC/N. The optimal piezoelectric and ferroelectric properties near the MPB might be attributed to its lower lattice distortion, as described by change of FWHM value for {1 1 1}_PC peaks. Furthermore, Bi(Mg_0.5Zr_0.5)O₃–xPbTiO₃ displayed stable ferroelectric and piezoelectric properties over a temperature range from ambient temperature to above 160 °C, as exhibited by temperature dependence polarization and strain versus electric field curves and thermal depoling process.     

Internal bias field relaxation in poled Mn-doped Pb(Mn1/3Sb2/3)O3–Pb(Zr,Ti)O3 ceramics

The frequency, electric field cycling and temperature dependences of the polarization–electric field (P–E), strain–electric field (S–E) loops in poled Mn-doped 0.05Pb(Mn_1/3Sb_2/3)O₃–0.50PbZrO₃–0.45PbTiO₃ ceramics have been investigated. The P–E and S–E loops are strongly asymmetric corresponding to the presence of an internal bias field E_i after poling and aging, indicating that the domain walls are strongly pinned by preferentially oriented defect dipoles formed by the acceptor dopant ions (Mn²⁺/Mn³⁺) and O²⁻ vacancies. Whereas, the loops exhibit a tendency of changing from asymmetric shapes to normal symmetric ones with increasing electric field amplitude or decreasing frequency. Repeated electric field cycling as well as high temperature results in a similar effect. Meanwhile, the E_i reduces consequently, providing evidence of domain depinning or internal bias field relaxation. It is suggested that the reorientation of the defect dipoles and depinning of domain walls arising from high temperature or electric field cycling are responsible for this extrinsic internal bias field relaxation process.     

Magnetoelectric properties of 0.5BiFeO3–0.5Pb(Fe0.5Nb0.5)O3 solid solution

Magnetoelectrics are materials that join magnetic and electric orderings in the same phase. They exhibit magnetoelectric coupling which is important from the fundamental and practical point of view. The subject of the paper is a presentation of magnetic, electric and magnetoelectric properties of 0.5BiFeO₃–0.5Pb(Fe_0.5Nb_0.5)O₃ solid solution. The obtained material belongs to oxide perovskite magnetoelectrics of relatively high magnetic and electric ordering temperatures. Both temperatures are considerably above room what suggests potential application possibilities of the material. The magnetic properties were investigated using Mössbauer spectroscopy and magnetization measurements. The solid solution is an antiferromagnet with incomplete compensated magnetic moments. The electrical properties were determined using impedance spectroscopy analysis. There is an observed change of the electrical properties at the magnetic ordering temperature what indicates magnetoelectric coupling in the system. The electrical conductivity mechanism is also proposed. Magnetoelectric voltage coefficient was determined and possible explanation of its changes was proposed.     

Electrocaloric properties of 0.7Pb(Mg1/3Nb2/3)O3–0.3PbTiO3 ceramics with different grain sizes

We have investigated the electrocaloric (EC) properties of the ceramic 0.7Pb(Mg_1/3Nb_2/3)O₃–0.3PbTiO₃. A variety of samples with different median grain sizes, i.e., 1.0, 2.2 and 4.0?μm, and relative densities of about 96% were prepared using atmospheric sintering at 1200^oC for 2, 8 and 16?h. The ceramic material with a median grain size of 2.2?μm exhibited the highest value for the EC temperature change, i.e., 1.27?K at 60?kV?cm^?1, measured with a high-resolution calorimeter. This value is 25 and 19% higher than the value for the ceramics with the finer and the coarser grains, respectively.     

Improvement of dielectric breakdown strength and energy storage performance in Er2O3–modified 0.95Sr0.7Ba0.3Nb2O6-0.05CaTiO3 lead-free ceramics

In this study, 0.95?Sr_0.7Ba_0.3Nb₂O₆-0.05CaTiO₃-x wt% Er₂O₃ ceramics (SBNCTEx; x?=?0–5) were synthesized using traditional solid-state method, and we investigated the microstructure, energy storage properties as well as the relationship between dielectric breakdown strength and interfacial polarization. As compared with pure 0.95?Sr_0.7Ba_0.3Nb₂O₆-0.05CaTiO₃ ceramics, the Er₂O₃ dopants suppressed the grain growth of SBNCTEx, and the doped ones showed the dense microstructure. The secondary phase was found for x?≥?1 according to the EDS results, and the influence of the secondary phase on relative dielectric breakdown strength has also been studied. The dielectric breakdown strength increased from 18.1?kV/mm to 34.4?kV/mm, which is good for energy storage. The energy storage density of 0.28?J/cm³ and the energy storage efficiency of 91.4% were obtained in the SBNCTE5 ceramics. The results indicate that SBNCTE ceramics can be used as energy storage capacitors.     

High electromechanical strain properties by the existence of nonergodicity in LiNbO3–modified Bi1/2Na1/2TiO3–SrTiO3 relaxor ceramics

This study investigated the effect of LiNbO₃ modification on the dielectric, ferroelectric and electromechanical strain properties of Bi_1/2Na_1/2TiO₃–SrTiO₃ (BNT–ST) lead–free relaxor ceramics. The sintering temperature for lead–free BNT–ST relaxor ceramics was slightly decreased from 1175?°C to 1050?°C by modifying with LiNbO₃. We found that the sintering temperature affects the dielectric behavior of 0.76BNT–(0.24?x)ST–xLiNbO₃ (BNST–100xLN) ceramics at high temperature (near dielectric maximum temperature, T_m). The T_m for the low–temperature sintered sample was shifted to relatively higher temperature by comparison with the high–temperature sintered samples. Furthermore, the degradation of dielectric behavior near T_m in low–temperature sintered BNST–2LN ceramics was revealed after poling treatment and seem to be related to the existence of a high temperature stabilized nonergodic relaxor phase. Accordingly, we assume that the stabilized nonergodic relaxor phase is responsible for the relatively late transition from ferroelectrics to the relaxor. Therefore, we obtained the improved d₃₃^* of 616?pm/V as the highest value in low–temperature sintered BNST–2LN ceramics.     

Bi(Zn1/2Ti1/2)O3 modified BiFeO3–BaTiO3 lead-free piezoelectric ceramics with high temperature stability

Lead-free high-temperature ceramics with compositions of 0.71BiFe_1−x(Zn_1/2Ti_1/2)_xO₃–0.29BaTiO₃ (BFZTx–BT, x=0–0.05 mol fraction) were fabricated by a conventional solid state reaction method. The effect of Bi(Zn_1/2Ti_1/2)O₃ (BZT) addition on the microstructure, electrical properties, relaxor behavior, and temperature stability has been studied. XRD patterns revealed that all compositions formed a single perovskite phase of pseudo-cubic crystal structure. The grain size was slightly affected by BZT addition. The diffuse phase transition and strong frequency dispersion of dielectric permittivity are observed for BZT modified ceramics. The addition of BZT into BFZTx–BT was also found to affect the piezoelectric properties and temperature stability of the ceramics with maximum values observed for x=0.5% and 1% BFZTx–BT compositions, respectively. The optimum piezoelectric properties with d₃₃=163 pC/N, together with high-temperature stability with a depolarization temperature T_d∼380 °C, reveal the BFZTx–BT ceramics to be promising high-temperature Pb-free piezoelectric materials.     

Electrical characterization of BaTiO3 and Ba0.77Ca0.23TiO3 ceramics synthesized by the proteic sol–gel method

In this work, we introduce a simple, low-cost, and ecofriendly method for producing barium titanate (BaTiO₃–BT) and barium calcium titanate (Ba_0.77Ca_0.23TiO₃–BCT) powders. The synthesis was performed by using a proteic sol–gel route which use coconut water in the polymerization step of the metallic precursor. We investigated the effects of the processing parameters with the density, microstructure, and (di)electric properties as sample quality indicators. The sintered ceramics exhibit single crystalline phase, relative density of 95%, a homogeneous microstructure, and an average grain size of 4?µm. The respective dielectric constants of 1200 (BT) and 700 (BCT), measured at room temperature, and the activation energy values for the conductive process are according to those reported in the literature for conventionally prepared ceramics.     

Depolarization temperature and piezoelectric properties of (Bi1/2Na1/2)TiO3–(Bi1/2Li1/2)TiO3–(Bi1/2K1/2)TiO3 lead-free piezoelectric ceramics

The phase transition temperature and piezoelectric properties of x(Bi_1/2Na_1/2)TiO₃–y(Bi_1/2Li_1/2)TiO₃–z(Bi_1/2K_1/2)TiO₃ [x + y + z = 1] (abbreviated as BNLKT100y–100z) ceramics were investigated. BNLKT100y–100z ceramics were prepared by conventional ceramic fabrication. The depolarization temperature T_d was determined by the temperature dependence of the dielectric and piezoelectric properties. This study focuses on the effect of Li¹⁺ and K¹⁺ ions on T_d and the piezoelectric properties of BNT ceramics. BNLKT100y–100z (y = 0–0.08) has a morphotropic phase boundary (MPB) between rhombohedral and tetragonal phases at z = 0.18–0.20, and high piezoelectric properties were obtained at the MPB composition. The piezoelectric constant d₃₃ increased with increasing y; however, T_d decreased above y = 0.06. The d₃₃ and T_d values of BNLKT4-20 and BNLKT8-20 were 176 pC/N and 171 °C, and 190 pC/N and 115 °C, respectively.     

Effects of Tb doping on structural and electrical properties of 47(Ba0.7Ca0.3)TiO3–0.53Ba(Zr0.2Ti0.8)O3 thin films at various annealing temperature by pulsed laser deposition

The ceramic thin films of 47(Ba_0.7Ca_0.3)TiO₃–0.53Ba(Zr_0.2Ti_0.8)O₃ (BCZT) + x (x = 0.2, 0.3, 0.4 and 0.5) mol% Tb were grown on Pt(111)/Si substrates with various annealing temperature by pulsed laser deposition. The XRD spectra confirm that Tb element can enhance the (l10) and (111) orientations in ceramic films. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) images show that Tb-doping can increase particle size effectively. The surface of Tb-doped film annealed at 800 ℃ is uniform and crack-free, and the average particle size and mean square roughness (RMS) are about 280 nm and 4.4 nm, respectively. Comparing with pure BCZT, the residual polarization (P_r) of 0.4 mol% Tb-doped film annealed at 800 ℃ increase from 3.6 to 9.8 μC/cm². Moreover, the leakage current density value of Tb doped films are one order of magnitude (5.33 × 10^?9?1.97 × 10^?8 A/cm² under 100 kV/cm) smaller than those of pure BCZT films (1.02 × 10^?7 A/cm²).     

Low temperature sintering and microwave dielectric properties of CaSiO3–Al2O3 ceramics for LTCC applications

The effects of CuO, Li₂CO₃ and CaTiO₃ additives on the densification, microstructure and microwave dielectric properties of CaSiO₃–1 wt% Al₂O₃ ceramics for low-temperature co-fired applications were investigated. With a single addition of 1 wt% Li₂CO₃, the CaSiO₃–1 wt% Al₂O₃ ceramic required a temperature of at least 975 °C to be dense enough. Large amount addition of Li₂CO₃ into the CaSiO₃–1 wt% Al₂O₃ ceramics led to the visible presence of Li₂Ca₃Si₆O₁₆ and Li₂Ca₄Si₄O₁₃ second phases. Fixing the Li₂CO₃ content at 1 wt%, a small amount of CuO addition significantly promoted the sintering process and lowered the densification temperature to 900 °C whereas its addition deteriorated the microwave dielectric properties of CaSiO₃–1 wt% Al₂O₃ ceramics. Based on 10 wt% CaTiO₃ compensation in temperature coefficient, good microwave dielectric properties of ε_r=8.92, Q×f=19,763 GHz and τ_f=−1.22 ppm/°C could be obtained for the 0.2 wt% CuO and 1.5 wt% Li₂CO₃ doped CaSiO₃–1 wt% Al₂O₃ ceramics sintered at 900 °C. The chemical compatibility of the above ceramics with silver during the cofiring process has also been investigated, and the result showed that there was no chemical reaction between silver and ceramics, indicating that the as-prepared composite ceramics were suitable for low-temperature co-fired ceramics applications.     

Effect of annealing temperature on the multiferroic properties of 0.7BiFeO3–0.3Bi0.5Na0.5TiO3 solid solution prepared by sol–gel method

Room-temperature multiferroic 0.7BiFeO₃–0.3Bi_0.5Na_0.5TiO₃ solid solution ceramics have been prepared by the sol–gel method. We have discussed the annealing temperature dependence of the multiferroic properties. The samples are annealed at 1023, 1123, 1223 and 1323 K for 3 h, respectively. X-ray diffraction patterns identify that all samples are pure. Scanning electron micrographs present the increasing grain size with higher annealing temperature. Magnetic, ferroelectric and dielectric properties are enhanced obviously with the increase in annealing temperature. The coexistence of ferroelectric and ferromagnetic properties is also proved at room temperature. In addition, it reveals that the optimal annealing temperature accompanied with favorable multiferroic properties of 0.7BiFeO₃–0.3Bi_0.5Na_0.5TiO₃ solid solution ceramics is near 1223 K.     

Dielectric properties of Cf–Si3N4 sandwich composites prepared by gelcasting

C_f–Si₃N₄ sandwich composites were prepared by gelcasting using α-Si₃N₄ powder, SiC-coated carbon fibers and sintering additives as starting materials. The microstructure and composition, dielectric properties of C_f–Si₃N₄ sandwich composites were investigated. SEM and EDS analysis results reveal that the SiC interphase could effectively overcome incompatibility between carbon fiber and silicon nitride matrix under the condition of pressure-less sintering at 1700 °C. The investigation of microwave absorbing property reveals that, compared with the Si₃N₄ ceramics, both the real (ε?$\epsilon ?$) and imaginary (ε??$\epsilon ??$) permittivity of C_f–Si₃N₄ sandwich composites show strong frequency dispersion characteristics at X-band. Microwave absorption ability of the C_f–Si₃N₄ sandwich composites are significantly enhanced compared with pure Si₃N₄ ceramic, and the reflection loss gradually decreases from −3.5 dB to −14.4 dB with the increase of frequency, while the pure Si₃N₄ ceramic keeps at −0.1 dB. Particularly, the relationship between permittivity of C_f–Si₃N₄ sandwich composites and frequency at X-band has been established through an equivalent RC circuit model. Results showed that both ε?$\epsilon ?$ and ωε??$\omega \epsilon ??$ are inversely proportional to the frequency square ω²${\omega }^2$, and the predicted results agree quite well with the measured data.