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 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.     

Na0.5K0.5NbO3 and 0.9Na0.5K0.5NbO3–0.1Bi0.5Na0.5TiO3 nanocrystalline powders synthesized by low-temperature solid-state reaction

Nanocrystalline powders of K_0.5Na_0.5NbO₃ (KNN) and 0.9Na_0.5K_0.5NbO₃–0.1Bi_0.5Na_0.5TiO₃ (KNN–BNT) have been prepared using a low-temperature solid-state reaction. Phase development of the powders incurred during various calcination temperatures was examined by X-ray diffraction (XRD). Crystallite size and particle morphology of KNN powders were examined by XRD and transmission electron microscopy, respectively. Perovskite phase was formed at the temperature as low as 500 °C, and the average crystallite size of KNN powders depended on calcination temperature. In addition, the crystalline structure of KNN powders tended to change from tetragonal symmetry to orthorhombic symmetry with increase in crystallite size. Similar results were obtained in KNN–BNT system. The developed method is well suited for the mass production of niobate nanocrystalline powders due to its simplicity and low cost.     

Crystallographic textured evolution in 0.85Na0.5Bi0.5TiO3–0.04BaTiO3–0.11K0.5Bi0.5TiO3 ceramics prepared by reactive-templated grain growth method

0.85Na_0.5Bi_0.5TiO₃–0.04BaTiO₃–0.11K_0.5Bi_0.5TiO₃ (BNBK) lead-free piezoelectric ceramics with extensive [001]_pc (pc: pseudo cubic) texture were fabricated by the reactive-templated grain growth method using anisotropic Bi₄Ti₃O₁₂ (BIT) particles as templates. The degree of grain orientation increased with increasing heat treatment temperature (600–1,200 °C). The obtained textured ceramics showed dense and brick-wall like microstructure, giving a Lotgering factor of 0.6. A physical understanding of interaction between BIT templates and matrix powders and the mechanism of texture evolution were proposed and confirmed by experimental evidences of X-ray diffraction patterns, scanning electron microscope images and density measurements. The piezoelectric response was enhanced by the grain orientation, and the piezoelectric constant (d₃₃) of the textured ceramics sintered at 1,170 °C attained a value of 254 pC/N, which was 41 % higher than random ceramics (180 pC/N).     

Preparation and characterization of As-cast and hot-rolled Mg–3Al–0.5Mn–0.5Zn–1MM alloy

Mg–3Al–0.5Mn–0.5Zn–1MM alloy was prepared by metal mould casting method. The as-cast ingot was homogenized and then hot-rolled at 673 K with total thickness reduction of 65%. Microstructure and mechanical properties of the as-cast and hot-rolled samples were investigated. The results showed that the as-cast sample mainly consisted of α-Mg, β-Mg₁₇Al₁₂, Al₁₀Ce₂Mn₇, and Al₁₁RE₃ (RE = La and Ce) phases. The average grain size of the sample homogenized at 673 K was about 240 μm, and it was greatly refined to about 7 μm by dynamic recrystallization for the hot-rolled sample. The ultimate tensile strength and 0.2% yield strength of the hot-rolled sample were 300 MPa and 230 MPa, respectively. They were enhanced by 55% and 400% correspondingly compared with those of the as-cast sample. The improvement of the strengths was attributed to the refined grains, breakup of the precipitates and increase of the dislocation density.     

Effects of NaSbO3 on phase structure and electrical properties of K0.5Na0.5NbO3–LiTaO3–NaSbO3 piezoelectric ceramics

The (0.96–x)K_0.5Na_0.5NbO₃–0.04LiTaO₃–xNaSbO₃ (abbreviated as KNN–LT–xNS, x = 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08) lead-free piezoelectric ceramics were fabricated by conventional ceramic technique. The crystal structure, dielectric, ferroelectric and piezoelectric properties of the ceramics were investigated. The Curie temperature (T _C) and the polymorphic phase transition temperature (T _O?T) of the ceramics decreased gradually with the increase of NaSbO₃. In addition, a coexistence of orthorhombic and tetragonal phases in the ceramics was identified in the composition range of 0.05 ≤ x ≤ 0.08. The ceramic with a composition of x = 0.06, which was close to the orthorhombic side of the polymorphic phase transition (PPT) region, exhibited excellent electrical properties with piezoelectric coefficient d ₃₃ = 233 pC/N, planar electromechanical coupling coefficient k _p = 0.328, remnant polarization P _r = 14.7 μC/cm², coercive field E _c  = 11.7 kV/cm, relative permittivity $ \varepsilon_{33}^{\text{T}} /\varepsilon_{0} $  = 1,033, and loss tangent tan δ = 0.063. The ceramics had relatively low Q _m value in the range of 10–37.     

Dielectric nonlinearity and electrical properties of K0.5Na0.5NbO3–SrTiO3 relaxor ferroelectrics

K_0.5Na_0.5NbO₃–xSrTiO₃(x = 0, 0.1 and 0.2) ceramics were prepared using the solid-state method. The phase transition behaviors, electrical properties, and electric field-induced dielectric nonlinearity behaviors were investigated as a function of the SrTiO₃ content. The electrical properties of the investigated compositions exhibited a significant dependence on the content of SrTiO₃. Doped content more than x = 0.1 induced a relaxor transformation, while the dielectric loss decreased quickly. In addition, an “extrinsic” polarization contributed to the dielectric nonlinearity behavior of the composition x = 0.1 with the polar nanoregions and domain-wall motions, by means of the multipolarization-mechanism model fittings of the electric field dependence of the dielectric permittivity. The dielectric tunability and loss angle tangent of the composition x = 0.1 were 32.6 % and 0.028, respectively.     

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).     

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%.     

Sol–gel synthesis and spark plasma sintering of Ba0.5Sr0.5TiO3

Ultrafine Ba_0.5Sr_0.5TiO₃ powders were prepared by using barium nitrate, strontium nitrate, tetrabutyl titanate, and ammonia via citrate–nitrate combustion process at low temperature (500 °C), along with the X-ray diffraction (XRD), differential scanning calorimetry (DSC)/thermogravimetry analysis (TGA) and scanning electron microscopy (SEM) analytic reports. Spark plasma sintering was carried out to obtain the ultrafine crystalline BST and to improve the dielectric properity. It was found that the sintered BST showed ultrafine crystalline microstructure. At 25 °C, the dielectric constant and dissipation factor of the sintered sample were 1533 and 0.0063 at 10 kHz.     

Origin of the large strain response in tenary SrTi0.8Zr0.2O3 modified Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3 lead-free piezoceramics

The perovskite oxides (1 ? x)Bi_0.5(Na_0.9K_0.1)_0.5TiO₃–xSrTi_0.8Zr_0.2O₃ (SZT1000x, x = 0, 0.2, 0.4, 0.6, 0.8, and 1 %) were prepared via the conventional solid-state reaction method. The room temperature ferroelectric P–E loops coordinate with polarization current density J–E curves illustrated the changes of ferroelectric domains and polar nanoregions under different driving fields exhaustively. The composition and electric field dependent strain behavior of this system were investigated to develop a lead-free piezoelectric material with a large strain response at a lower electric field. A large strain of 0.44 % (S _max/E _max = 744 pm/V) at an applied field of 50 kV/cm was obtained at the composition of 0.6 mol% SZT. Temperature-dependent hysteresis measurements reveal the primary origin of the large strain is due to the presence of a nonpolar phase at a zero field. Upon the application of an electric field, the nonpolar phase that can easily transform into a long-range ferroelectric phase, and then brings the system back to its unpoled state once the applied electric field is removed. Notably, the electric field required to deliver large strains is reduced to 40 kV/cm while the S _max/E _max reached up to 717 pm/V, indicating that the developed material is highly promising for actuator applications.     

Structure and electrical properties of K0.5Na0.5NbO3–SrTiO3 lead-free piezoelectric ceramics with LiSbO3 doping

Lead-free piezoelectric ceramics (1 ? x)K_0.5Na_0.5NbO₃–xSrTiO₃ with 6 mol% LiSbO₃ doping have been prepared by conventional solid state sintering technique at 1,125 °C for 3 h in air. The effects of the SrTiO₃ and LiSbO₃ on the phase structure and electrical properties of the ceramics were systematically investigated. All ceramic samples show a single phase perovskite structure with tetragonal symmetry when LiSbO₃ content was 6 mol% and SrTiO₃ content was 2–10 mol% by X-ray diffraction analysis and highly dense structure by SEM patterns. The ceramic with x = 0.04 exhibits optimum electrical properties at room temperature (d ₃₃ = 267 pC/N, k _p = 46 %, ε _r = 1,168, tanδ = 0.021, P _r = 30.3 μC/cm², E _C = 1.98 kV/mm), which suggests that the ceramic is a promising candidate material for lead-free piezoelectric ceramics.     

Studies on the structural,electrical and magnetic properties of LaCrO3, LaCr0.5Cu0.5O3 and LaCr0.5Fe0.5O3 by sol–gel method

The structural, electrical and magnetic properties of LaCr_0.5M_0.5O₃ (M = Cr³⁺, Cu²⁺ and Fe³⁺) synthesized by a sol–gel technique were studied. The X-ray diffraction pattern shows the structure to be orthorhombic and the size of the particles is around 100 nm as seen from the TEM images. The effects of Cu²⁺ and Fe³⁺ on the electrical properties of LaCrO₃ were studied using impedance spectroscopy at room temperature (RT). The properties of LaCr_0.5Cu_0.5O₃ were studied over a wide range of temperature from RT to 533 K. A maximum conductivity of 1.7 × 10^?3 S cm^?1 was observed for LaCr_0.5Cu_0.5O₃ at a measured temperature of 533 K. The impedance spectra indicate a negative temperature coefficient of resistance (NTCR) and also imply the conduction is through bulk of the material. The magnetic studies performed using a SQUID magnetometer interpret the antiferromagnetically ordered LaCrO₃ to behave ferromagnetically on the addition of Cu²⁺ and Fe³⁺, and the magnetization was found to be enhanced in the LaCr_0.5Fe_0.5O₃.     

(K0.5Na0.5)NbO3–Bi(Mg0.5Ti0.5)O3 solid solution: phase evolution, microstructure and electrical properties

Lead-free piezoelectric ceramics with the composition of (1 ? x)(K_0.5Na_0.5)NbO₃–xBi(Mg_0.5Ti_0.5)O₃ [(1 ? x)KNN–xBMT, 0 ≤ x ≤ 0.04] were synthesized via solid-state reaction method. X-ray diffraction patterns revealed that the orthorhombic—tetragonal phase transition was present for (1 ? x)KNN–xBMT with increasing the content of BMT. The study of dielectric properties illustrated that both peaks of orthorhombic—tetragonal (T _O–T ) and tetragonal—cubic (T _T–C ) phase transitions shifted to lower temperature. Through adding BMT, the electrical properties of KNN ceramics were obviously improved. The optimized piezoelectric and ferroelectric properties with d ₃₃  = 127 pC/N, k _p  = 36.58 %, P _r  = 22.1 μC/cm² were obtained as x = 0.01.     

Microstructure,ferroelectric, piezoelectric and ferromagnetic properties of BiFeO3–BaTiO3–Bi(Zn0.5Ti0.5)O3 lead-free multiferroic ceramics

Multiferroic ceramics of (0.70?x)BiFeO₃–0.30BaTiO₃–xBi(Zn_0.5Ti_0.5)O₃ + 1 mol% MnO₂ with perovskite structure were prepared by a conventional ceramic technique and the effects of Bi(Zn_0.5Ti_0.5)O₃ doping and sintering temperature on the microstructure, multiferroic and piezoelectric properties of the ceramics were studied. All the ceramics possess a pure perovskite structure and no second phases can be detected. After the addition of a small amount of Bi(Zn_0.5Ti_0.5)O₃ (x ≤ 0.05), the ferroelectric and piezoelectric properties of the ceramics are improved and the grain growth is promoted. However, excess Bi(Zn_0.5Ti_0.5)O₃ (x ≥ 0.10) retards the grain growth, degrades the ferroelectricity and piezoelectricity, and induces two dielectric anomalies at high temperature. The ceramics can be well sintered at the very wide range of low sintering temperatures (880–980 °C) and exhibit good densification (relative density: 96.2–98.4 %) and strong electric insulation. The increase in the sintering temperature promotes the grain growth and improves the ferroelectricity of the ceramics. The ceramic with x = 0.05 sintered at 880–980 °C possesses improved ferroelectric and piezoelectric properties with remanent polarizations P _r of 21.9–28.1 μm/cm², piezoelectric constants d ₃₃ of 125–139 pC/N and planar electromechanical coupling factors k _p of 30.1–32.4 %, and high Curie temperatures T _C of 523–565 °C. A weak ferromagnetism with remanent magnetizations M _r of 0.0411–0.0422 emu/g and coercive fields H _c of 1.70–1.99 kOe were observed in the ceramics with x = 0–0.025.