Electrical properties of Pb(Mg1/3Nb2/3)O3-PbTiO3 ceramics modified with WO3

Ferroelectrics 0.67Pb (Mg_1/3Nb_2/3)O₃-0.33PbTiO₃ (PMN-PT) + x mol% WO₃ (x=0.1, 0.5, 1, 2) were prepared by columbite precursor method. Electrical properties of WO₃-modified ferroelectrics were investigated. X-ray diffraction (XRD) was used to identify crystal structure, and pyrochlore phase were observed in 0.67Pb (Mg_1/3Nb_2/3)O₃-0.33PbTiO₃+2 mol% WO₃. Dielectric peak temperature decreased with WO₃ doping, indicating that W⁶⁺ incorporated into PMN-PT lattice. Lattice constant, pyrochlore phase and grain size contribute to the variation of K_max. Both piezoelectric constant (d₃₃) and electromechanical coupling factors (k_p) were enhanced by doping 0.1 mol% WO₃, which results from the introduction of “soft” characteristics into PMN-PT, while further WO₃ addition was detrimental. We consider that the two factors, introduction of “soft” characteristics and the formation of pyrochlore phase, appear to act together to cause the variation of piezoelectric properties of 0.67PMN-0.33PT ceramics doping with WO₃.     

Comparative investigation of structure and dielectric properties of Pb(Mg1/3Nb2/3)O3-PbTiO3 (65/35) and 10% PbZrO3-doped Pb(Mg1/3Nb2/3)O3-PbTiO3 (65/35) ceramics prepared by a modified precursor method

Relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) and 10% PbZrO₃-doped Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramics were both prepared by a modified precursor method, which was based on the high-temperature synthesis of an oxide precursor that contained all the B-site cations for the consideration of B-site homogeneity. The dielectric properties of Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramic was more of normal ferroelectric behavior, but the high dielectric constant (?_m = 34,200 at 1 kHz) and piezoelectric constant (d₃₃ = 709 pC/N) were observed for this composition close to the morphotropic phase boundary. Comparatively, introduction of 10% PbZrO₃ into Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramics enhanced the diffuse phase transition as well as the rhombohedral to tetragonal phase transition temperature, while it also kept the high dielectric constant (?_m = 29,600 at 1 kHz) and piezoelectric constant (d₃₃ = 511 pC/N).     

Synthesis and characterization of 0.65Pb(Mg1/3Nb2/3)O3-0.35PbTiO3 fibers with Pt core

This paper reports the synthesis and electromechanical characterization of 0.65Pb(Mg_1/3Nb_2/3)O₃-0.35PbTiO₃ (PMN-35PT) ceramics and fibers. To prevent the lead loss during the sintering of the fibers, lead-atmosphere was used during the sintering process. As a consequence, it was possible to ensure a good densification of the fiber and a pure perovskite phase. The electromechanical coupling factor and piezoelectric coefficient of the piezoelectric fiber were found to be k₃₁ = 0.20 and d₃₁ = −130 pC/N, respectively. These results are lower than ceramic sample properties (k₃₁ = 0.32 and d₃₁ = −234 pC/N). In order to determine reasons for these lower results in fiber shape sample, density and poling studies were performed. It is shown that fiber shape samples cannot be poled correctly because of the ratio between core and ceramic diameters.     

Effect of BiFeO3 additions on the dielectric and piezoelectric properties of (K0.44Na0.52Li0.04)(Nb0.84Ta0.1Sb0.06)O3 ceramics

(1 − x) (K_0.44Na_0.52Li_0.04)(Nb_0.84Ta_0.1Sb_0.06)O₃ − x BiFeO₃ (x = 0, 0.002, 0.004, 0.006, 0.008, 0.01) lead-free piezoelectric ceramics were prepared by the conventional ceramic processing. The compositional dependence of the phase structure and the electrical properties of the ceramics were studied. A morphotropic phase boundary between the orthorhombic and tetragonal phases was identified in the composition range of 0.004 < x < 0.006. The ceramics near the morphotropic phase boundary exhibit a strong compositional dependence and enhanced piezoelectric properties. The ceramics with 0.6 mol.% BiFeO₃ exhibit good electrical properties (d₃₃ ∼ 246 pC/N, k_p ∼ 43%, T_c ∼ 285 °C, ?_r ∼ 1871, and tan δ ∼ 1.96%). These results show that the (1 − x) (K_0.44Na_0.52Li_0.04)(Nb_0.84Ta_0.1Sb_0.06)O₃ − x BiFeO₃ ceramic is a promising lead-free piezoelectric material for applications in different devices.     

Growth and electrical performance of Pb(Mg1/3Nb2/3)O3-PbTiO3-Pb(Fe1/2Nb1/2)O3 single crystals

For the first time, we have grown ferroelectric single crystals Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃-Pb(Fe_1/2Nb_1/2)O₃ (PMN-PT-PFN) from the melt by the simple slow cooling process. The chemical composition of the single crystals PMN-PT-PFN (0.59/0.31/0.10) is near the morphotropic phase boundary (MPB). X-ray diffraction (XRD) was used to study phase structure of the as-grown crystals, energy dispersive X-ray spectrometer (EDS) and electron probe micro-analyzer (EPMA) were employed to confirm the chemical composition and element distribution of the as-grown crystals, respectively. The ferroelectric, dielectric and piezoelectric properties of the as-grown PMN-PT-PFN (0.59/0.31/0.10) single crystal oriented along the (0 0 1) axis were measured, which showed that the remnant polarization (P_r), coercive electric fields (E_c), the Curie temperature (T_c) and the piezoelectric coefficient (d₃₃) were 50.2 μC/cm², 13.9 kV/cm, 158 °C and about 1800 pC/N, respectively. All the results indicated that the PMN-PT-PFN (0.59/0.31/0.10) single crystals are promising for applying to field of high frequency.     

Effects of Fe2O3 doping on the microstructure and piezoelectric properties of 0.55Pb(Ni1/3Nb2/3)O3-0.45Pb(Zr0.3Ti0.7)O3 ceramics

0.55Pb(Ni_1/3Nb_2/3)O₃-0.45Pb(Zr_0.3Ti_0.7)O₃(PNN-PZT) ceramics with different concentration of xFe₂O₃ doping (where x = 0.0, 0.8, 1.2, 1.6 mol%) were synthesized by the conventional solid state sintering technique. X-ray diffraction analysis reveals that all specimens are a pure perovskite phase without pyrochlore phase. The density and grain size of Fe-doped ceramics tend to increase slightly with increasing concentration of Fe₂O₃. Comparing with the undoped ceramics, the piezoelectric, ferroelectric and dielectric properties of the Fe-doped PNN-PZT specimens are significantly improved. Properties of the piezoelectric constant as high as d₃₃ ~ 956 pC/N, the electromechanical coupling factor k_p ~ 0.74, and the dielectric constant ε_r ~ 6095 are achieved for the specimen with 1.2 mol% Fe₂O₃ doping sintered at 1200 °C for 2 h.     

Effect of Pb(Fe1/2Nb1/2)O3 modification on dielectric and piezoelectric properties of Pb(Mg1/3Nb2/3)O3-PbZr0.52Ti0.48O3 ceramics

10 mol% Pb(Fe_1/2Nb_1/2)O₃ (PFN) modified Pb(Mg_1/3Nb_2/3)O₃-PbZr_0.52Ti_0.48O₃ (PMN-PZT) relaxor ferroelectric ceramics with compositions of (0.9 − x)PMN-0.1PFN-xPZT (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9) were prepared. X-ray diffraction investigations indicated that as-prepared ceramics were of pure perovskite phase and the sample with composition of x = 0.8 was close to morphotropic phase boundary (MPB) between rhombohedral and tetragonal phase. Dielectric properties of the as-prepared ceramics were measured, and the Curie temperature (T_c) increased sharply with increasing PZT content and could be higher than 300 °C around morphotropic phase boundary (MPB) area. At 1 kHz, the sample with composition of x = 0.1 had the largest room temperature dielectric constant ?_r = 3519 and maximum dielectric constant ?_m = 20,475 at T_m, while the sample with composition of x = 0.3 possessed the maximum dielectric relaxor factor of γ = 1.94. The largest d₃₃ = 318 pC/N could be obtained from as-prepared ceramics at x = 0.9. The maximum remnant polarization (P_r = 28.3 μC/cm²) was obtained from as-prepared ceramics at x = 0.4.     

Triple-like hysteresis loop and microdomain-macrodomain transformation in the relaxor-based 0.76Pb(Mg1/3Nb2/3)O3-0.24PbTiO3 single crystal

Polarization and depolarization behavior of the relaxor-based 0.76Pb(Mg_1/3Nb_2/3)O₃-0.24PbTiO₃ single crystal has been studied between 25 and 200 °C by means of dielectric measurement with or without dc bias, Polarization-Electric field (P-E) hysteresis loop and discharging current measurements. Triple-like P-E loops were obtained in a temperature range between 80 and 90 °C, disclosing the transformation between microdomain state and metastable macrodomain state. For the poled crystals, the microdomain state with dipoles partially oriented was indicated to exist in the similar temperature range and mediate between the lower temperature macrodomain state with dipoles oriented and the higher temperature microdomain state with dipoles in a random system.     

Diffuse transition and piezoelectric properties of Pb[(Zr1−xTix)0.74(Mg1/3Nb2/3)0.20(Zn1/3Nb2/3)0.06]O3 Ceramics

In this work, the piezoelectric ceramic system of Pb[(Zr_1−xTi_x)_0.74(Mg_1/3Nb_2/3)_0.20(Zn_1/3Nb_2/3)_0.06]O₃, 0.47≤x≤0.57, with composition close to the morphotropic phase boundary, was studied. From the results of X-ray diffraction and piezoelectric measurement, ceramics near x=0.51 were found at the morphotropic phase boundary (MPB) between the tetragonal and pseudocubic perovskite. The planar coupling factor (k_p=0.72) is high at compositions near the MPB, but the mechanical quality factor (Q_m=75) is low. The calculation of the diffuseness of phase transition shows that the region of phase coexistence of this system is broader than that of the ternary system.     

Morphotropic phase boundary in Pb(Sc1/2Nb1/2)O3-BiScO3-PbTiO3 high temperature piezoelectrics

The solid solutions in the 0.36BiScO₃-0.64(1 − x)PbTiO₃-0.64xPb(Sc_1/2Nb_1/2)O₃ system were fabricated using wolframite precursor method. A coexistence of rhombohedral and tetragonal phases is formed in the studied compositions range and a wide morphotropic phase boundary region is confirmed by X-ray diffraction results. After the addition of Pb(Sc_1/2Nb_1/2)O₃, a relaxor behavior is induced and the dielectric maximum temperature shifts to higher temperatures with increasing measuring frequencies. The presence of relaxor can be ascribed to the formation of polar nanoregions. The studied composition exhibits the optimal ferroelectric and piezoelectric properties with d₃₃ of 453 pC/N and K_p of 0.58, T_m of 405 °C for x = 0.10 composition, which is suitable for future high-temperature piezoelectric application.     

Effects of Cr2O3 doping on the electrical properties and the temperature stabilities of PNW-PMN-PZT ceramics

The ceramics with 0.90Pb(Zr_0.50Ti_0.50)O₃-0.07Pb(Mn_1/3Nb_2/3)O₃-0.03Pb(Ni_1/2W_1/2)O₃ were prepared by adding Cr₂O₃. The effects of Cr₂O₃ doping on the phase structure, the microstructure and the electrical properties of ceramics were investigated. Meanwhile, the temperature stabilities of the resonant frequency (f_r) and the electromechanical coupling factor (K_p) were studied. The results showed that the better temperature stability could be obtained at x = 0.2 wt.% when the calcining temperature was 800 °C and the sintering temperature was 1150 °C. The parameters were Δf_r/f_r25 °C = −0.17% and ΔK_p/K_p25 °C = −1.39%. Moreover, the optimized electrical properties were also achieved, which were K_P = 0.54, Q_m = 1730, d₃₃ = 330 pC/N, ?_r = 2078 and tan δ = 0.0052. The optimized properties make the ceramics with this composition to be a good candidate for high power piezoelectric transformers applications.     

Morphotropic phase boundary in high temperature ferroelectric xBi(Zn1/2Ti1/2)O3 − yPbZrO3 − zPbTiO3 perovskite ternary solid solution

A bismuth and lead oxide based perovskite ternary solid solution xBi(Zn_1/2Ti_1/2)O₃ − yPbZrO₃ − zPbTiO₃ (xBZT − yPZ − zPT) was investigated as an attempt to develop a high T_C ferroelectric material for piezoelectric sensor and actuator applications. A morphotropic phase boundary (MPB) between rhombohedral and tetragonal phases was determined through an XRD study on a pseudobinary line 0.1BZT − 0.9[xPT − (1 − x)PZ] for composition 0.1Bi(Zn_1/2Ti_1/2)O₃ − 0.5PbZrO₃ − 0.4PbTiO₃. Enhanced piezoelectric and ferroelectric activities were observed for MPB composition with dielectric constant ε_r′ ~ 23,000 at Curie temperature (T_C) ≈ 320 °C, remanent polarization (P_r) = 35 μC/cm², piezoelectric coefficient (d₃₃) = 300 pC/N, unipolar strain = 0.15%, and electromechanical coupling coefficient (k_P) = 0.45.     

Heterophase structures and their quantitative characteristics in (1 − x)Pb(Fe1/2Nb1/2)O3 − xPbTiO3 near the morphotropic phase boundary

Features of phase coexistence in solid solutions of (1 − x)Pb(Fe_1/2Nb_1/2)O₃ − xPbTiO₃ with the perovskite-type structure are studied at 0.05 ≤ x ≤ 0.08. The role of elastic matching of the tetragonal P4mm and monoclinic Cm phases of the ferroelectric nature is considered near the morphotropic phase boundary. Model concepts on the stress relief in heterophase structures are developed and applied to interpret the phase content in (1 − x)Pb(Fe_1/2Nb_1/2)O₃ − xPbTiO₃. Good agreement between the calculated and experimental dependences of the volume fraction of the tetragonal phase on x is observed. It is shown that the studied phase coexistence under conditions for the complete stress relief can take place at elastic matching of the single-domain monoclinic phase and the tetragonal phase split into two types of 90° domains.     

Tantalum influence on physical properties of (K0.5Na0.5)(Nb1−xTax)O3 ceramics

Lead-free (K_0.5Na_0.5)(Nb_1−xTa_x)O₃ ceramics with x = 0.00-0.30 were prepared by the solid-state reaction technique. The effects of Ta on microstructure, crystallographic structure, phase transition and piezoelectric properties have been investigated. It has been shown that the substitution of Ta decreases Curie temperature T_C and orthorhombic-tetragonal phase transition temperature T_O-T, while increasing the rhombohedral-orthorhombic phase transition temperature T_R-O. In addition, piezoelectric activity is enhanced with the increase of Ta content. The ceramics with x = 0.30 have the high value of piezoelectric coefficient d₃₃ = 205 pC/N. Moreover, k_p shows little temperature dependence between −75° C and 75 °C, and d₃₃ exhibits very good thermal stability over the range from −196 °C to 75 °C in the aging test.     

Effects of Mn doping on the structure and electrical properties of high-temperature BiScO3-PbTiO3-Pb(Zn1/3Nb2/3)O3 piezoelectric ceramics

The effects of Mn addition on the structure, ferroelectric, and piezoelectric properties of the 0.35BiScO₃-0.60PbTiO₃-0.05Pb(Zn_1/3Nb_2/3)O₃ ceramics were studied. The results demonstrate that the addition of small amounts of Mn did not cause a remarkable change in crystal structure, but resulted in an evident evolution in microstructure and ferro-piezoelctric properties. The addition of Mn can induce combinatory “hard” and “soft” piezoelectric characteristics due to aliovalent substitutions. The optimal electrical properties are obtained in the 0.25 mol% Mn-doped composition with a high Curie temperature, indicating that Mn doping contributes to the electrical properties of the ceramics. It can be expected that the improved piezoelectric material can be a promising candidate for high-temperature piezoelectric applications.     

Nanoscale study by piezoresponse force microscopy of relaxor 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 and 0.9Pb(Mg1/3Nb2/3)O3-0.1PbTiO3 thin films grown on platinum and LaNiO3 electrodes

Relaxor 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ (70/30 PMN-PT) and 0.9Pb(Mg_1/3Nb_2/3)O₃-0.1PbTiO₃ (90/10 PMN-PT) thin films have been grown by RF-sputtering on platinum (Pt) and lanthanum nickelate (LaNiO₃) bottom electrodes. For both electrodes, macroscopic measurements evidence lower coercive fields, remnant polarizations and piezoelectric coefficients d₃₃ for 90/10 PMN-PT films compared to 70/30 PMN-PT films. For both compositions, coercive fields and remnant polarizations are lower for films grown on LaNiO₃ compared to on Pt while piezoelectric coefficients d₃₃ are higher. For each electrode and composition, a similar behavior is revealed for electromechanical activity at the nanoscale when measuring local piezoelectric hysteresis loops; on the other hand, the voltages required for switching the domains are the highest for 90/10 PMN-PT films grown on LaNiO₃. The existence of large grain boundaries in the films grown on Pt and the presence of local random fields with polar nano-domains for the 90/10 composition could explain the differences measured in domains switching properties at the macroscale and nanoscale levels.     

Piezoelectric shear-mode properties of Pb(Yb1/2Nb1/2)O3-PbTiO3 ceramics

A Pb(Yb_1/2Nb_1/2)O₃-PbTiO₃ [PYNT] solid solution was synthesized and characterized for its potential use. The shear-mode dielectric and piezoelectric behaviors of PYNT with a morphotropic phase boundary (MPB) composition were studied as a function of temperature. Dielectric permittivity K₁₁^T and loss were found to be 2310 and 2.5%, respectively, at room temperature. Piezoelectric coefficient d₁₅ and electromechanical coupling factor k₁₅ were calculated to be 710 pC/N and 0.70, respectively, maintaining nearly constant up to 300 °C, resistivity and RC time constant were observed to be 2.4 × 10⁹ Ω cm and 1.07 s, respectively, at 350 °C. These good piezoelectric properties, together with the high Curie temperature (T_c ∼ 370 °C), indicate that PYNT is a promising candidate for high temperature-shear sensor and inkjet actuator applications.     

Dielectric and piezoelectric properties of Y2O3 doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free piezoelectric ceramics

Y₂O₃ doped lead-free piezoelectric ceramics (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (0-0.7 wt%) were synthesized by the conventional solid state reaction method, and the effect of Y₂O₃ addition on the structure and electrical properties was investigated. X-ray diffraction shows that Y₂O₃ diffuses into the lattice of (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ to form a solid solution with a pure perovskite structure. The temperature dependence of dielectric constant of Y₂O₃ doped samples under various frequencies indicates obvious relaxor characteristics different from typical relaxor ferroelectric and the mechanism of the relaxor behavior was discussed. The optimum piezoelectric properties of piezoelectric constant d₃₃ = 137 pC/N and the electromechanical coupling factor k_p = 0.30 are obtained at 0.5% and 0.1% Y₂O₃ addition, respectively.     

Bismuth-modified BiScO3-PbTiO3 piezoelectric ceramics with high Curie temperature

New piezoelectric ceramics, 0.15BiScO₃-0.85(Pb_{1 − 3x / 2}Bi_x)(Ti_0.98Mn_0.02)O₃ (x = 0.04~0.10), were prepared by using conventional solid phase processing. The results of X-ray diffraction (XRD) show that the ceramics have a single phase tetragonal perovskite structure. The ceramics, poled by normal poling process, have piezoelectric coefficient d₃₃, planar electromechanical coupling factor kp and thickness electromechanical coupling factor k_t of 50~60 pC/N, ~ 11% and ~ 30%, respectively. An extremely high mechanical quality factor Q_m of 1540 was obtained at the composition x = 0.08. The Curie temperature (T_C) is in the range of 520-550 °C, higher than 490 °C of pure PbTiO₃. The combination of good piezoelectric properties and high T_C makes these ceramics suitable for elevated temperature piezoelectric devices.     

Dielectric properties of a new ceramic system (1 − x)Mg4Nb2O9-xCaTiO3 at microwave frequency

The microstructures and the microwave dielectric properties of the (1 − x)Mg₄Nb₂O₉-xCaTiO₃ ceramic system were investigated. In order to achieve a temperature-stable material, CaTiO₃ (τ_f ∼ 800 ppm/°C) was chosen as a τ_f compensator and added to Mg₄Nb₂O₉ (τ_f ∼ −70 ppm/°C) to form a two phase system. It was confirmed by the XRD and EDX analysis. By appropriately adjusting the x-value in the (1 − x)Mg₄Nb₂O₉-xCaTiO₃ ceramic system, near-zero τ_f value can be achieved. A new microwave dielectric material, 0.5Mg₄Nb₂O₉-0.5CaTiO₃ applicable in microwave devices is suggested and possesses the dielectric properties of a dielectric constant ?_r ∼ 24.8, a Q × f value ∼82,000 GHz (measured at 9.1 GHz) and a τ_f value ∼−0.3 ppm/°C.