Structure,ferroelectric, piezoelectric and ferromagnetic properties of BiFeO3–Ba0.6(Bi0.5K0.5)0.4TiO3 lead-free multiferroic ceramics

(1?x)BiFeO₃–xBa_0.6(Bi_0.5K_0.5)_0.4TiO₃ + 1 mol% MnO₂ lead-free multiferroic ceramics were fabricated by a conventional ceramic technique and the effects of Ba_0.6(Bi_0.5K_0.5)_0.4TiO₃ doping and sintering temperature on the microstructure, ferroelectric, piezoelectric and ferromagnetic properties of the ceramics were studied. All the ceramics show good electric insulation with the resistivity values of 1.97 × 10⁹–1.20 × 10¹⁰ Ω cm. After the addition of Ba_0.6(Bi_0.5K_0.5)_0.4TiO₃, two dielectric anomalies are observed at high temperatures (T ₁ ~ 453–710 °C and T ₂ ~ 716–755 °C, respectively). The ceramic with x = 0.275 exhibits the optimum piezoelectricity (d ₃₃ = 48 pC/N and k _p = 13.6 %, respectively). The Ba_0.6(Bi_0.5K_0.5)_0.4TiO₃ doping and the increasing in sintering temperature improve significantly the ferromagnetic properties of the ceramics. The ceramic with x = 0.25 sintered at 1,040 °C gives the optimum remnant magnetization M _r of 0.13 emu/g.     

Phase transition,ferroelectric and piezoelectric properties of Bi(Mg0.5Zr0.5)O3-modified BiFeO3–BaTiO3 lead-free ceramics

(0.725 ? x)BiFeO₃–0.275BaTiO₃–xBi(Mg_0.5Zr_0.5)O₃ + 1 mol% MnO₂ lead-free ceramics (x = 0–0.08) were synthesized by a conventional solid state reaction method and the effects of Bi(Mg_0.5Zr_0.5)O₃ on phase transition, piezoelectric and ferroelectric properties of the ceramics were investigated. After the addition of Bi(Mg_0.5Zr_0.5)O₃, the crystal structure of the ceramics is transformed from rhombohedral to tetragonal phase and the morphotropic phase boundary (MPB) of rhombohedral and tetragonal phase is formed at x = 0.01. The grain size of the ceramics increases with x increasing from 0 to 0.02 and then decreases with x further increasing. The dielectric peak of the ceramics becomes diffusive with x increasing after the addition of Bi(Mg_0.5Zr_0.5)O₃. The ceramics with x = 0–0.08 exhibit much better electric insulation with the resistivity of 1.0 × 10⁹–5.0 × 10⁹ Ω·cm than pure BiFeO₃ ceramic with the resistivity of ~5 × 10⁷ Ω·cm. Due to the formation of the MPB, the ceramics with x = 0–0.02 possess good densification with the relative densities ρ _r of 94.9–96.3 %, strong piezoelectricity with the d ₃₃ of 129–135 pC/N and very high Curie temperature with the T _C of 559–610 °C.     

Structure,ferroelectric and piezoelectric properties of Bi0.5(Na0.8K0.2)0.5TiO3 modified BiFeO3–BaTiO3 lead-free piezoelectric ceramics

A new lead-free solid solution of (0.75 ? x)BiFeO₃–0.25BaTiO₃–xBi_0.5(Na_0.8K_0.2)_0.5TiO₃ + 1 mol% MnO₂ has been prepared by a conventional ceramic technique and the effects of Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ and sintering temperature on the structure, ferroelectric and piezoelectric properties of the material have been studied. The ceramics sintered at 960 °C for 2 h possess a pure perovskite structure and no second phases can be detected. After the addition of Bi_0.5(Na_0.8K_0.2)_0.5TiO₃, a morphotropic phase boundary of rhombohedral and orthorhombic phases is formed at x = 0.01. The addition of a small amount of Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ can promote the grain growth, while excess Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ causes an inhibition of grain growth. Sintering temperature has an important influence on the structure and electrical properties of the ceramics. The sintering temperature of 960 °C is a critical temperature to obtain the ceramics with good piezoelectric properties. For the ceramic with x = 0.01 sintered at/above 960 °C located at the morphotropic phase boundary, large grains, good densification, high resistivity and enhanced electrical properties are obtained.     

Structural, ferroelectric and piezoelectric properties of Mn-modified BiFeO3–BaTiO3 high-temperature ceramics

Mn modified BiFeO₃–BaTiO₃ (abbreviated as BFBT-Mnx%, x = 0.1, 0.3, 0.6, 0.9, 1.2) high-temperature lead-free ceramics were prepared by conventional oxide-mixed method and the effect of Mn doping on microstructure and electrical properties was investigated. The solid solutions show a single phase perovskite structure, and the content of Mn has a significant effect on the microstructure of ceramics. The addition of Mn can induce combinatory “hard” and “soft” piezoelectric characteristics due to aliovalent substitutions. In particular, x = 0.6 BFBT-Mnx% ceramic, with a Curie temperature, T _c, of ~463 °C, shows optimum piezoelectric properties of d ₃₃ = 131pC/N, k _p = 0.298. The simultaneous existence of good piezoelectric properties and high T _c makes these ceramics suitable for elevated temperature piezoelectric devices.     

Microstructure and piezoelectric properties of lead-free 0.95(Na0.5K0.5)NbO3–0.05(Bi0.5K0.5)Zr1−x Ti x O3 ceramics

0.95(Na_0.5K_0.5)NbO₃–0.05(Bi_0.5K_0.5)Zr_1?x Ti _x O₃ (abbreviated as KNN–BKZT _x ) ceramics were prepared by the conventional solid state method, and the effect of the Ti content on the surface morphology, crystalline structure, and electrical properties of KNN–BKZT _x ceramics were mainly investigated. With the increase of Ti content, the temperature of the orthorhombic–tetragonal (O–T) phases transitions shifted to lower temperatures, and the O–T phase boundary of KNN–BKZT _x ceramics was identified in the composition with 0 ≤ x ≤ 0.3 at room temperature. It was considered that the piezoelectric properties of the ceramics were enhanced significantly owing to the more possible polarization states resulting from the coexistence of two phases. The ceramic with x = 0.2 exhibited optimum properties: d ₃₃ = 260 pC/N, k _p = 0.38, and T _C = 323 °C.     

Structure and piezoelectric properties of K0.5Na0.5NbO3–Bi0.5Li0.5TiO3 lead-free ceramics

Lead-free (1−x) K_0.5Na_0.5NbO₃–xBi_0.5Li_0.5TiO₃ + 1 mol% MnO₂ piezoelectric ceramics have been prepared by a conventional ceramic technique and their structure and piezoelectric properties have been studied. Our results reveal that Bi_0.5Li_0.5TiO₃ diffuse into K_0.5Na_0.5NbO₃ lattices to form a solid solution with a perovskite structure. The addition of Bi_0.5Li_0.5TiO₃ to the K_0.5Na_0.5NbO₃ solid solution decreases the paraelectric cubic-ferroelectric tetragonal phase transition temperature (T _C) slightly, but shifts the ferroelectric tetragonal-ferroelectric orthorhombic phase transition temperature (T _O−T) significantly to low temperatures. As a result, coexistence of the orthorhombic and tetragonal phases is formed at 0.01 < x < 0.03 near room temperature, leading to a significant improvement in the piezoelectric properties of the ceramics. The ceramic with x = 0.025 exhibits a relatively high T _C (392 °C) and optimum piezoelectric properties: d ₃₃ = 191 pC/N, k _p = 51.5% and k _t = 45.5%. The ceramic also exhibit a good thermal stability of piezoelectric properties.     

Piezoelectric and ferroelectric properties of Ga modified BiFeO3–BaTiO3 lead-free ceramics with high Curie temperature

High-temperature 0.71 Bi(Fe_1?x Ga _x )O₃–0.29 BaTiO₃ (x = 0, 0.01, 0.015, 0.02, and 0.025) piezoelectric ceramics have been synthesized and their structure and electric properties have been investigated systemically. The Ga addition caused insignificant change of crystal structure. However, the addition of a small amount of Ga was quite effective to increase the grain size, densification, and piezoelectric properties. For the ceramics with x = 0.015, the maximum of piezoelectric constant (d ₃₃), and electromechanical coupling factor (k _p) are d ₃₃ = 157 pC/N, k _p = 0.326, respectively. Meanwhile, the increasing Curie temperature (T _c), 467 °C, was obtained with x = 0.02 ceramics. Both remanent polarization P _r and coercive field E _c were reduced with increasing x.     

Effects of Bi excess on the structure and electrical properties of high-temperature BiFeO3–BaTiO3 piezoelectric ceramics

BiFeO₃–BTiO₃(BF–BT) ceramics as a promising candidate for lead-free high-temperature piezoelectric ceramics were studied with a special emphasis on the compositional dependence of piezoelectric properties. Excess Bi was added to compensate for the evaporation of Bi³⁺ ions during sintering and this addition was found to be effective in improving the piezoelectric properties of BF–BT ceramics. The microstructure, dielectric and piezoelectric properties of excess Bi doped BF–BT ceramics were investigated. Maximum piezoelectric constant d ₃₃ = 142 pC/N and k _p = 0.302 were obtained with 0.04 Bi doping. At the same time, an enhanced Curie temperature T _c, 452 °C, was obtained. The combination of improved piezoelectric properties and increased T _c makes these ceramics suitable for elevated temperature piezoelectric devices.     

Structure and electrical properties of Er2O3 doped 0.82Bi0.5Na0.5TiO3–0.18Bi0.5K0.5TiO3 lead-free piezoelectric ceramics

Er₂O₃ (0–0.8 wt.%)-doped 0.82Bi_0.5Na_0.5TiO₃–0.18Bi_0.5K_0.5TiO₃ (BNKT18) lead-free piezoelectric ceramics were synthesized by a conventional solid-state reaction method. The effects of Er₂O₃ on the microstructure and electrical properties were investigated. X-ray diffraction (XRD) data shows that Er₂O₃ in an amount of 0.2–0.8 wt.% can diffuse into the lattice of the BNKT18 ceramics and form the pure perovskite phase. Scanning electron microscope (SEM) images indicate that the grain sizes of BNKT18 ceramics decrease with the increase of Er₂O₃ content; in addition, the modified ceramics have the clear grain boundary and a uniformly distributed grain size. At room temperature, the electrical properties of the BNKT18 ceramics have been improved with the addition of Er₂O₃, and the BNKT18 ceramics doped with 0.6 wt.% Er₂O₃ have the highest piezoelectric constant (d₃₃ = 138 pC/N), the highest planar coupling factor (k_p = 0.2382), the highest remnant polarization (P_r = 25.2 μC/cm²), the higher relative dielectric constant (ε_r = 936) and lower dissipation factor (tanδ = 0.047) at a frequency of 10 kHz. Moreover, the T_m and T_d of the samples increase with the addition of Er₂O₃.     

Structures and electrical properties of (Na0.5K0.5)NbO3–Li(Ta0.5Nb0.5)O3 lead-free piezoelectric ceramics

Solid solutions of (Na_0.5K_0.5)NbO₃ (NKN) and Li(Ta_0.5Nb_0.5)O₃ (LTN) were investigated as a potential candidate of lead-free piezoelectric ceramics. It was found that the Curie temperature of solid solutions increases slightly with increasing the LTN content and simultaneously the polymorphic phase transition temperature linearly decrease till below room temperature. An orthorhombic to tetragonal phase transformation at room temperature, or a morphotropic phase boundary, in NKN is induced by ~7 at% LTN addition, where the best dielectric, piezoelectric and electromechanical properties are achieved. The 0.94NKN–0.07LTN ceramics possess a dielectric constant of 765, a loss tangent of 0.04 at 1 kHz, a piezoelectric constant d₃₃ of 253 pC/N and an electromechanical coupling factor k_p of 48%.     

Structure and electrical properties of the Ho2O3 doped 0.82Bi0.5Na0.5TiO3–0.18Bi0.5K0.5TiO3 lead-free piezoelectric ceramics

Ho₂O₃ (0–0.7?wt%)-doped 0.82Bi_0.5Na_0.5TiO₃–0.18Bi_0.5K_0.5TiO₃ (BNKT18) lead-free piezoelectric ceramics were synthesized by a conventional solid-state reaction method. The effects of Ho₂O₃ on the microstructure and electrical properties were investigated. X-ray diffraction data shows that Ho₂O₃ in an amount of 0.1–0.7?wt% can diffuse into the lattice of the BNKT18 ceramics and form the pure perovskite phase. Scanning electron microscope (SEM) images indicate that the grain sizes of BNKT18 ceramics decrease with the increase of Ho₂O₃ content; in addition, the modified ceramics have the clear grain boundary and a uniformly distributed grain size. At room temperature, the electrical properties of the BNKT18 ceramics have been improved with the addition of Ho₂O₃, and the BNKT18 ceramics doped with 0.3wt.% Ho₂O₃ have the highest piezoelectric constant (d ₃₃?=?137?pC/N), the highest remnant polarization (P _r?=?26.9?μC/cm²), the higher relative dielectric constant (ε _r?=?980) and lower dissipation factor (tanδ?=?0.046) at a frequency of 10?kHz. The BNKT18 ceramics doped with 0.1?wt% Ho₂O₃ have the highest planar coupling factor (k _p?=?0.2426).     

Piezoelectric and dielectric properties of Bi0.5Na0.5TiO3–Bi0.5Li0.5TiO3 lead-free ceramics

(1 − x)Bi_0.5Na_0.5TiO₃–xBi_0.5Li_0.5TiO₃ lead-free ceramics have been prepared by a conventional solid-state reaction method, and their piezoelectric and dielectric properties have been studied. X-ray diffraction studies reveal that Li⁺ diffuses into the Bi_0.5Na_0.5TiO₃ lattices to form a solid solution with a pure perovskite structure. The addition of Bi_0.5Li_0.5TiO₃ effectively lowers the sintering temperature of the ceramics and greatly assists in the densification of the ceramics. The ceramic with x = 0.075 possesses the optimum piezoelectric properties: piezoelectric coefficient d ₃₃ = 121 pC/N and planar electromechanical coupling factor k _P = 18.3%. After the partial substitution of Li⁺ for Na⁺ in the A-sites of Bi_0.5Na_0.5TiO₃, the ceramics exhibit more relaxor characteristic, which is probably resulted from the cation disordering in the 12-fold coordination sites. The depolarization temperature T _d shifts to low temperature with the substitution level x of Li⁺ for Na⁺ increasing.     

A study of structural, ferroelectric, ferromagnetic, dielectric properties of NiFe2O4–BaTiO3 multiferroic composites

The mixed spinel-perovskite multiferroic composites of xNiFe₂O₄-(1 ? x)BaTiO₃ (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6) have been prepared by sol–gel method. The structure and morphology of the composites were examined by means of X-ray diffraction and transmission electron microscope. High-resolution transmission electron microscope image indicates a clear view of ferrite and ferroelectric phase. Moreover, we observed a fine interface between the two phases, where the coupling effect of ferrite and ferroelectric phase happened. The composites show excellent ferromagnetic and ferroelectric properties. The saturation magnetization (M_s) reaches to 24.139 emu/g for x = 0.6 at room temperature, the magnetization is about 2.37 emu/g for x = 0.6 when the temperature decreases to 90 k, and the polarization reaches to 3.75 μC/cm² for x = 0.1. Frequency dependent variations of dielectric constant and loss tangent for xNiFe₂O₄-(1 ? x)BaTiO₃ were studied in detail.