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.     

Effects of the piezoelectric phase’s geometric properties on effective coefficients of 1–3 piezoelectric composites

The present paper reports the electromechanical coupling coefficients of piezoelectric composite material (PCM) are affected by different geometric properties of piezoelectric phase for 1–3 periodic composites that is made of piezoceramic fibers embedded in a soft non-piezoelectric matrix. Three-dimensional finite element model has been developed to study the three types of geometric models of piezoelectric phase with different volume fraction. Geometric models with circular cylinder, square column and circular cylinder alternated with square column are used to predict the coefficients of the validity via asymptotic homogenization method (AHM) and the numerical approach the finite element method (FEM). Three types of geometric model are built via the finite element software ABAQUS, and the elastic, piezoelectric and dielectric coefficients are evaluated via AHM both FEM. The results indicate that the validity parameters of PCM have the direct relationship with the volume fraction, and geometric shape is essential factor for distribution of Von-Misses when device working. The present work may improve application of 1–3 type PCM and offer useful guidelines to the design of PCM devices.     

Ferroelectric and piezoelectric properties of (1 − x) (Bi0.5Na0.5)TiO3–xBaTiO3 ceramics

Lead-free ceramics based on bismuth sodium titanate (Bi_0.5Na_0.5TiO₃, BNT)–barium titanate (BaTiO₃,BT) have been prepared by solid state reaction process. The (1?x)BNT–(x)BT (x = 0.01,0.03,0.05,0.07) ceramics were sintered at 1,150 °C for 4 h in air, show a pure perovskite structure. X-ray diffraction analysis indicates that a solid solution is formed in (1?x)BNT–(x)BT ceramics with presence of a morphotropic phase boundary (MPB) between rhombohedral and tetragonal at x = 0.07. Raman spectroscopy shows the splitting of (TO₃) mode at x = 0.07 confirming the presence of MPB region. The temperature dependence dielectric study shows a diffuse phase transition with gradual decrease in phase transition temperature (T_m). The dielectric constant and diffusivity increases with increase in BT content and is maximum at the MPB region. With the increase in BT content the maximum breakdown field increases, accordingly the coercive field (E_c) and remnant polarization (P_r) increases. The piezoelectric constant of (1 ? x)BNT–(x)BT ceramics increases with increase in BT content and maximum at x = 0.07, which is the MPB region. The BNT–BT system is expected to be a new and promising candidate for lead-free dielectric and piezoelectric material.     

High piezoelectric response in the new coexistent phase boundary of 0.87BaTiO3–(0.13-x)BaZrO3–xCaTiO3

An investigation of the coexistent ferroelectric phase was carried out on the ternary system of 0.87BaTiO₃–(0.13-x)BaZrO₃–xCaTiO₃ [abbreviated as BT–BZ–xCT (where 0.00 ≤ x ≤ 0.13)]. Temperature-, frequency-dependent dielectric data, electric field-dependent strain and polarization as a function of composition are presented in order to understand the relationships of structure-properties and find the high piezoelectric response in this system. Results showed that ceramics in the composition range of 0.00 ≤ x < 0.04 were of a rhombohedral structure and transformed into a tetragonal structure at x > 0.06. The multiphase coexistence of the rhombohedral and tetragonal phase in this system was identified at x = 0.06. A large, virtually hysteresis-free electric field induced strain of 0.23% was achieved with the composition, x = 0.06, at 40 kV/cm on the boundary between rhombohedral and tetragonal phase. This relates to an extraordinarily high and normalized piezoelectric coefficient (S_max/E_max) of 1280 pm/V, which was reached at a low electric field applied at 10 kV/mm. These results indicated that a high piezoelectric response may stem primarily from the rhombohedral-tetragonal phase boundary, due to greater lattice softening and reduced energy barriers for polarized rotation.     

Effect of La on piezoelectric properties of Pb(Ni1/3Sb2/3)O3–Pb(ZrTi)O3 ferroelectric ceramics

Piezoceramic compositions Pb_1?zLa_z(NiSb)_0.05[(Zr_0.52Ti_0.48)_1?Z/4]_0.95O₃ with Z = 0.01–0.05 were synthesized by mixed oxide route to study the effect of Lanthanum (La) on crystal structure, microstructure, piezoelectric and ferroelectric properties. Calcination was performed at 1,060 °C and sintering at 1,270 °C for 1 h. X-Ray diffraction pattern indicated the polycrystalline microstructure along with co-existence of tetragonal and rhombohedral perovskite phases. Dielectric constant ( $ K_{3}^{T} $ ) was increased whereas piezoelectric voltage constant (g ₃₃) was decreased with increase in lanthanum. Dense microstructure was observed for the composition containing 3 mol% of lanthanum. This was resulted in optimum piezoelectric charge constant (d ₃₃ = 468 × 10^?12 C/N), electromechanical coupling factor (k _p  = 0.68), remanent polarization (P _r = 24.65 μC/cm²) and displacement (D = 2,012 nm). Results indicated that the composition Pb_0.97La_0.03(NiSb)_0.05[(Zr_0.52Ti_0.48)_0.9925]_0.95O₃ could be suitable for actuator applications. The composition Pb_0.98La_0.02(NiSb)_0.05[(Zr_0.52Ti_0.48)_0.995]_0.95O₃ resulted into moderately high value of voltage constant (g ₃₃ = 39.3 × 10^?12 V m/N) and optimum value of Figure of Merit (d ₃₃ × g ₃₃ = 16.2 × 10^?12 C V m/N²) indicated the usefulness for sensor and power harvesting applications.     

Composites with piezoelectric thin fibers – first evidence of piezoelectric behavior

 The integration of functional components into composite materials is still a challenge for materials science. The integrated components themselves acting as sensor and/or as actuator should not interfere with the excellent mechanical properties of fiber-reinforced composite materials. Using this approach the implementation of ”one-dimensional”geometries – like fibers with small diameters – is recommended. Thin fibers consisting of piezoelectric materials like PZT are among the promising candidates offering the sensor/actuator coupling. Sol-gel processing is useful for fabricating PZT fibers thin enough to behave flexibly. Therefore, they offer the opportunity to make composite materials adaptive while maintaining the structural conformity. Sol-gel derived high-quality PZT fibers with diameters smaller than 30 μm have been successfully integrated into planar fiber architectures. Within them the fibers are oriented uni-directionally. These architectures are embedded with interdigital electrodes. After embedding the fiber/electrode architectures within glass fiber-reinforced polymers the fibers can be poled and become piezoelectric. The resulting structures were suitable to be tested as adaptive components. It has been demonstrated that such structures can detect impacts and tensions. They can also be driven actively leading to a vibration of the structure. Received: 21 July 1998 / Reviewed and accepted: 22 October 1998     

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.     

Phase transition behavior and high piezoelectric properties in lead-free BaTiO3–CaTiO3–BaHfO3 ceramics

The transition behavior, structural changes, and electric properties of lead-free (1?x)Ba(Hf_0.16Ti_0.84)O₃ –x(Ba_0.70Ca_0.30)TiO₃ (BCHT) ceramics fabricated by the conventional solid-state reaction method are investigated in this study. A complete phase diagram of BCHT system has been proposed based on their dielectric behavior. It is found that BHCT ceramics undergo a complicated phase evolution, driven by Ca and Hf contents. The results clearly demonstrate that high electric properties are achieved in the ferroelectric orthorhombic–tetragonal phase boundary near the composition with x = 0.48, which could be adjusted by the contents of Ca and Hf in the composition. The optimum composition shows enhanced properties with dielectric constant ε _r = 2889 (at room temperature, 1 kHz), high piezoelectric coefficient d ₃₃ = 410 pC/N, and electromechanical coupling factor k _p = 0.47, and a relative high Curie temperature of 106 °C. This investigation yields a sight to understand different phase transition mechanisms of enhanced piezoelectricity for the system.     

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.     

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%.     

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.     

Low-temperature sintering and piezoelectric properties of Pb(Fe2/3W1/3)O3–added Pb(Zn1/3Nb2/3)O3–Pb(Ni1/3Nb2/3)O3–Pb(Zr,Ti)O3 ceramics

Low-temperature sintering of (a–x)Pb(Zr_0.48Ti_0.52)O₃–bPb(Ni_1/3Nb_2/3) O₃–cPb(Zn_1/3Nb_2/3)O₃–xPb(Fe_2/3W_1/3)O₃ (a + b + c + x = 1, 0.06 ≤ x ≤ 0.10) ceramics were prepared through two-step synthesis process using perovskites-structured ferroelectric materials Pb(Fe_2/3W_1/3)O₃ (PFW) as a sintering aid. The effects of PFW content on the densification, microstructure, phase structure, dielectric and piezoelectric properties of the ceramics were investigated. The sintering temperature was reduced from 1,180 °C (without PFW addition) to 940 °C when the material was PFW-doped. PFW-doping increased the sintered density and the average grain size of PFW–PNN–PZN–lead zirconate titanate ceramics. The ceramics sintered at 940 °C for 4 h with x = 0.08 exhibited favorable properties, which were listed as follows: d₃₃ = 496pC/N, εT 33/ε₀ = 3,119, tanδ = 2.1 % and Curie temperature = 242 °C. These values indicated that the newly developed composition might be suitable for multilayer piezoelectric devices application.     

Morphotropic phase boundary and electric properties in (1 − x)Bi0.5Na0.5TiO3–xBaSnO3 lead-free piezoelectric ceramics

Lead-free piezoceramics of (1 ? x)Bi_0.5Na_0.5TiO₃–xBaSnO₃ (BNT–BS, x = 0, 0.02, 0.03, 0.04, 0.06, 0.09 and 0.12) have been synthesized and investigated. A rhombohedral–tetragonal morphotropic phase boundary (MPB) exists near x = 0.03. The MPB composition shows improved electrical properties: the saturated polarization, remnant polarization, coercive field, piezoelectric coefficient, planar electromechanical coupling factor, and unipolar strain are 35.8, 28.5 μC/cm², and 4.5 kV/mm, 93 pC/N, 0.19, and 0.18 %, respectively. It is also found the introduction of BS can significantly enhance dielectric property. The structural and electrical properties are discussed by comparing with other BNT-based piezoceramics.     

Enrichment of piezoelectric properties in Nb5+doped (0.94) (Na0.5Bi0.5)TiO3–(0.06) BaTiO3 ceramics across morphotropic phase boundary region

Lead-free piezoelectric compounds (0.94)(Na_0.5Bi_0.5)TiO₃–(0.06) BaTiO₃ [NBBT (94/06)]?+?x wt.% Nb⁵⁺ (x?=?0%, 1%, 1.5%, 2%, and 2.5%) were synthesized by the solid-state reaction route and these powders were pelletized and sintered for dielectric and piezoelectric characterization. The phase coexistence Monoclinic (Cc)?+?Rhombohedral (R3c) was affirmed using X-ray Powder diffraction analysis. The structural properties like cell parameters and space group of the synthesized ceramics were investigated by the Rietveld refinement analysis. The surface morphology and grain size of the fractured ceramics were explored using SEM imaging technique. The dielectric properties for all the ratios of NBBT (94/06) ceramics were examined using LCR meter. The piezoelectric coefficients such as d₃₃ and g₃₃ of Nb-doped NBBT (94/06) ceramics were investigated. The saturation polarization (P_s) and remanent polarization (P_r) were exhibited from the P–E hysteresis loop analysis at room temperature. The appropriate addition of Nb⁵⁺ (x?=?1.5%) in NBBT (94/06) material demonstrates eminent dielectric constant and piezoelectric coefficient d₃₃ than other wt.% of Nb. The replacement of Ti⁴⁺ with higher radius cations Nb⁵⁺ in B-site of ABO₃ composes tilting of polar BO₆ octahedra resulting in rhombohedra distortion (RD) (90° ? α), in addition, the polarizability of ions and various valance states of B-site cations could be responsible for RD (90° ? α) ensuing relatively high dielectric constant and piezoelectricity.

     

Structure and dielectric/piezoelectric properties of LiNbO3-doped BiScO3–PbTiO3 ceramics with morphotropic phase boundary composition

0.02LiNbO₃–0.98{(1 − x)BiScO₃–xPbTiO₃} (2LN–BS–xPT) ceramics near the morphotropic phase boundary (MPB) were investigated. MPB region of 2LN–BS–xPT ceramics was identified to be in the composition of 0.62 < x ≤ 0.64. The coexistence of the tetragonal domain structure and a polar microdomain structure was observed by transmission electron microscope for x = 0.64. It is found that 2LN–BS–xPT ceramics (x = 0.64) showed good piezoelectric and ferroelectric properties with piezoelectric constant d ₃₃ about 505 pC/N, planar electromechanical coupling factors k _p about 0.47, and remnant polarization P _r about 40 μC/cm², respectively, while T _max is about ~350–400 °C. The high-temperature relaxation behavior was also studied in 2LN–BS–xPT ceramics. Effects of thermal depoling on the piezoelectric properties of 2LN–BS–xPT ceramics indicated good thermal stability before 300 °C for x = 0.62 and 0.64.     

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.