Piezoelectric properties of PbHfO3–PbTiO3–Pb(Mg1/3Nb2/3)O3 ternary ceramics

(1 – x)Pb(Hf_1–yTi_y)O₃–x Pb(Mg_1/3Nb_2/3)O₃ (x = 0.1 ～ 0.25, y = 0.555) ternary piezoelectric ceramics were prepared using the two‐step precursor method. Morphotropic phase boundary (MPB) compositions, located at x = 0.18 ～ 0.22, were confirmed using X‐ray diffraction and by their dielectric, piezoelectric and ferroelectric properties. The optimum dielectric and piezoelectric properties were achieved for the MPB composition 0.8Pb(Hf_0.445Ti_0.555)O₃–0.2Pb(Mg_1/3Nb_2/3)O₃, with dielectric permittivity ε_r, piezoelectric coefficient d₃₃, planar electromechanical coupling k_p and Curie temperature T_C being on the order of 2800, 680 pC/N, 70% and 276 °C, respectively. Of particular significance is that the new ternary ceramics exhibit comparable piezoelectric and electromechanical properties to commercial PZT5H ceramics, but with much improved T_C, showing a potential for applications at elevated temperature. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Switching of morphotropic phase boundary and large electrostrictive effect in lead‐free BNT–BKT–KNN ceramics

We report the phase diagram of the lead‐free ternary (Bi_0.5Na_0.5)TiO₃–(Bi_0.5K_0.5)TiO₃–(K_0.5Na_0.5)NbO₃ (BNT–BKT–KNN) system and study the switching characteristics of the morphotropic phase boundary (MPB). The addition of KNN intrinsically changes the structural nature of the system with shift of MPB type from (I) to (II), and also adjusts the depolarization temperature (T_d) to room temperature. Accordingly, a high electrostrictive response with large electrostrictive coefficient Q₃₃ (～0.022–0.027 m⁴/C²) and a good thermostability comparable with that of traditional Pb‐based electrostrictors was achieved in MPB (II) compositions. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Pb(Zr1-xTix)O3中组分调制诱导的不寻常的铁电相

Pb(Zr1-xTix)O3(PZT)是一种重要的钙钛矿结构铁电固溶体，在其准同型相界处发现单斜相引起研究的热潮，文章报道了作者最近对沿着[100]赝立方方向组分调制的PZT体系的铁电性质的研究结果，发现组分调制导致极化偏离调制方向，在准同型相界附近诱导出新型的铁电三斜相和C型单斜相，以及极高的机电特性，证明偶极相互作用是导致以上行为的主要微观机制。     

The piezoelectric effect in Pb[(Fe1/3Sb2/3) x Ti y Zr z ]O3 ceramics

The piezoelectric properties of Pb[(Fe_1/3Sb_2/3) _x Ti _y Zr _z ]O₃ with x + y + z = 1, x = 0.1, y = 0.43–0.48 ceramics have been investigated over a broad temperature range using a resonance technique. The influence of modification of PZT normal ferroelectric synthesized near the morphotropic phase boundary by a relaxor Pb(Fe_1/3Sb_2/3)O₃ compound on its physical properties was studied. The coefficients s ₁₁, k ₃₁, and d ₃₁ were calculated from the parameters characterizing the behavior of damped harmonic oscillator in the vicinity of the piezoelectric resonance. Several anomalies of the piezoelectric coefficients have been found in the temperature range 300–600 K. Two diffuse phase transitions were observed in Pb[(Fe_1/3Sb_2/3) _x Ti _y Zr _z ]O₃. The anomaly near 530 K for y = 0.43 is responsible for the transition from the rhombohedral phase to the tetragonal one. For y > 0.44 this transition is found to be very diffuse and the coexistence of rhombohedral and tetragonal phases occurs. The observation of low piezoelectric activity confirms the existence of polar regions in Pb[(Fe_1/3Sb_2/3) _x Ti _y Zr _z ]O₃ above T _m.     

(PbBa)(Zr,Sn,Ti)O_3反铁电/弛豫型铁电相界陶瓷的相变与介电、热释电性质

通过对(Pb087Ba01La002)(Zr06TixSn04-x)O3(004≤x≤020)固溶体的介电和偏压热释电性质的研究发现,当Ti含量004≤x≤007时,材料是反铁电四方相,而当009≤x≤020时,材料向弛豫型铁电体转化.在温度Ti含量相图中,x=009附近形成了反铁电铁电顺电三相共存点(Ttr).该点的相变温度最底;对于004≤x≤007的反铁电四方相,低温下呈现介电弛豫特征,并可被外电场诱导为亚稳铁电态,温度升高时,亚稳铁电→反铁电相变,反铁电→顺电相变引起两个热释电流峰,偏置电场下峰位和峰强均发生移动,在温度电场相图中也形成了铁电反铁电顺电三相点.从复杂化合物纳米相分离的观点和晶格动力学出发,讨论了相变与电学性能随Ti含量(x)和外电场(E)变化的物理机理. 关键词： 反铁电/弛豫型铁电相界 介电性能 偏压热释电性质 铁电-反铁电-顺电三相点     

Nanoscale domain structures in 0.91Pb(Zn1/3Nb2/3)O3-0.09PbTiO3 (91PZN-9PT) single crystals studied by piezoresponse forcemicroscopy

High-resolution domain studies have been performed in 91PZN-9PT single crystals by piezoresponse force microscopy. Nanometer- and micron-sized strip-shaped 180º and parallel 90º domains were observed in the rhombohedral (R) and tetragonal (T) phases. Domain patterns with the typical sizes 5–200 nm were observed on the (001)_cub surface of unpoled sample. The existence of nanodomains in the sample is tentatively attributed to the relaxor nature of PZN-PT where small polar clusters may form under zero-field cooling conditions. The domain observation confirms the structure of the morphotropic 91PZN-9PT crystals, which is composed of both the R and T (or monoclinic) orientations states. The outstanding piezoelectric properties may result from the cooperative response of the microscale/nanoscale domain structure.     

Effect of Sb doping on phase transition and relaxor behaviour of (Pb0.75Ba0.25)(Zr0.70Ti0.30)O3 ceramics

The effect of antimony dopant on phase transition, dielectric response and relaxor behaviour of (Pb_0.75Ba_0.25)(Zr_0.70Ti_0.30)O₃ ceramics was studied. Ceramic samples, with various Sb concentration from the range 1 to 4 at.%, were prepared by a conventional mixed oxide method. The crystal structure of the investigated ceramics was determined by an X-ray diffraction at room temperature that allowed to determine the unit cell parameters. Dielectric relaxation typical for ferroelectric relaxors was observed in the vicinity of diffuse ferroelectric–paraelectric phase transition. All parameters describing the relaxor behaviour determined from the Vogel–Fulcher relationship depend on the concentration of Sb dopant. The strong influence of antimony on grain structure and on remanent polarisation was confirmed as well.     

张应力对准同形相界Pb(Zr,Ti)O3薄膜相变和铁电性能影响

采用射频磁控溅射法在Pt/TiO_x/SiO₂/Si基片上制备了以BaPbO₃(BPO)为缓冲层的Pb(Zr_0.52,Ti_0.48)Nb_0.04O₃ (Nb掺杂PZT, PZTN)薄膜.通过调整BPO层厚度,为该PZTN薄膜引入了不同的张应力.当BPO层厚度分别为68 nm和135 nm时,PZTN薄膜呈现随机取向,采用2θ-s 关键词： PZT 准同形相界 掠射扫描方式 结构精修     

Equivalent magnetic noise in magnetoelectric Metglas/Pb(Mg1/3Nb2/3)O3‐PbTiO3 laminate composites

We have experimentally and theoretically investigated the equivalent magnetic noise in a magnetoelectric Metglas/ 0.7Pb(Mg_1/3Nb_2/3)O₃‐0.3PbTiO₃ laminate sensor unit by considering the constituent noise sources of dielectric loss (N_DE) and DC leakage resistance (N_R). In the low frequency range (f = 1 Hz), theory predicts that N_R dominates the noise charge (1.6 times larger than N_DE), with a 1 Hz noise of 9.1\;{\rm pt}/\sqrt {\rm Hz}. The experimental equivalent magnetic noise was 10.8\;{\rm pt}/\sqrt {\rm Hz}. This observed value is slightly higher than the predicted one, which might be due to an oversimplification of the theoretical model in terms of electrical charge amplifier and external vibration noise sources. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Field-induced piezoelectric response in Pb(Mg1/3Nb2/3)O3–PbTiO3 single crystals

The electric field induced strain, piezoelectric and electromechanical response in relaxor based single crystal piezoelectrics (1−x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃(PMNT100x) were investigated as a function of dc bias and temperature along the crystallographic [001] orientation. With increasing temperature and dc bias, monoclinic and rhombohedral phases were found to coexist in the crystals, exhibiting large strain hysteresis, while above a threshold temperature and dc bias, the induced monoclinic and tetragonal phases were found to show very low strain hysteresis. The electric field level for the monoclinic to tetragonal phase transformation was found to exponentially decay with temperature. The mechanical quality factor Q for the tetragonal phase exhibits higher values when compared to rhombohedral and monoclinic phases, displaying improved domain stability. The domain stability of tetragonal crystals as a function of sample thickness was also studied, it was found that a higher dc bias was needed for thinner tetragonal crystals in order to stabilize the single domain configuration and reduce the strain hysteresis.     

Evolution of electric response of Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3 and Pb0.99[(Zr0.90Sn0.10)0.96Ti0.04]0.98Nb0.02O3 ferroelectric ceramics under shock wave compression

The objective of this work is to investigate the dependence of the electric behavior on shock pressure in Pb_0.99(Zr_0.95Ti_0.05)_0.98Nb_0.02O₃ (PZT 95/5-2Nb) and Pb_0.99[(Zr_0.90Sn_0.10)_0.96Ti_0.04]_0.98Nb_0.02O₃ (PZST) ferroelectric ceramics under shock wave compression. PZT 95/5-2Nb and PZST ceramics were subjected to high dynamic pressure generated by plate impacts. The output currents were measured under the short-circuit condition in the pressure range from 0.23 to 4.50 GPa. The evolution of the electric response exhibits three distinct regions: (1) Below the critical phase transition pressure (σ_C), alternate negative and positive piezoelectric currents are observed and the corresponding piezoelectric constant is e ₃₁. (2) Above σ_C and below the complete phase transition pressure (σ_H), released charge increases with increasing shock pressure, illustrating the transition of ferroelectric to antiferroelectric phase. (3) Above σ_H, the output current is insensitive to the shock pressure. A similar evolutionary process is also observed in hydrostatic and uniaxial stress experiments.     

Dielectric properties of Pb(Mg1/4Zn1/4Nb1/2)O11/4

Polycrystalline samples of Pb(Mg_1/4Zn_1/4Nb_1/2)O_11/4 have been synthesized by high temperature columbite precursor solid state reaction technique. Using X-ray diffraction (XRD) technique, compound formation in single phase cubic structure was observed and XRD analysis provided preliminary structural data. Detailed studies of dielectric properties of the compound reveal that this compound has high dielectric constant and diffuse phase transition in a wide range of temperatures around the Curie temperature. The charge deficiency of the compound presumably gets compensated in the high temperature columbite precursor process of sample preparation which is supported by single phasic form of the material.     

Enhanced piezoelectric properties near the morphotropic phase boundary in lead-free (1-x)(Bi0.5K0.5)TiO3-xBi(Ni0.5Ti0.5)O3 ceramics

Lead-free piezoelectric ceramics of the composition (1-x)(Bi_0.5K_0.50)TiO₃-xBi(Ni_0.50Ti_0.50)O₃ or (1-x)BKT-xBNiT (when x = 0–0.20 mol fraction) were prepared by a conventional mixed-oxide method and sintered at 1050 °C for 4 h. The effects of BNiT content on the phase equilibria, and the dielectric, ferroelectric and piezoelectric properties were systematically investigated. High density sintered specimens (5.71–6.12 g/cm³) were obtained for all compositions. X-ray diffraction patterns showed that all BKT-BNiT samples exhibited a single perovskite phase which confirms that BNiT and BKT formed a solid solution up to x = 0.20. A morphotropic phase boundary (MPB) separating a BKT-rich tetragonal phase and a BNiT pseudo-cubic phase was identified over the compositional range 0.05 < x < 0.10, where enhanced electrical properties were observed. The optimum dielectric properties (ε_r = 1710, tanδ = 0.036), ferroelectric properties (P_r = 16.6 μC/cm², E_c = 22.5 kV/cm and R_sq = 0.86) and piezoelectric properties (d₃₃ = 288 pC/N, S_max = 0.22% and d^*₃₃ = 313 pm/V) were observed with a relatively high T_m ∼ 304 °C within this MPB region. Overall, these results indicate that the BKT-BNiT ceramic system is a promising lead-free piezoelectric candidate for further development for actuator applications.     

Dielectric response of disordered Pb(Sc1/2Ta1/2)O3 single crystal under hydrostatic pressure

The effect of hydrostatic pressure on the dielectric response of Pb(Sc_1/2Ta_1/2)O₃ single crystal with the degree of order S = 0.16 has been studied. At elevated pressures the dielectric anomaly characteristic of ferroelectric relaxors is shifted to lower temperatures, its amplitude decreases and the relaxor peak becomes more diffused. In the pressure range studied up to 0.75 GPa, the temperature dependencies of the characteristic relaxation time obey the Vogel–Fulcher law. It has been found that the Vogel–Fulcher temperature decreases with increasing pressure while the activation energy of the dipolar entities increases. This increase can be ascribed to the pressure-induced changes in the atom–atom and dipolar interactions, resulting in the increased energy barriers for dipolar fluctuations.     

等静压下0.75Pb（Mg1/3Nb2/3）O3-0.25PbTiO3陶瓷的介电性能研究

研究了等静压对0.75Pb（Mg_1/3Nb_2/3）O₃-0.25PbTiO₃（PMN-25PT）陶瓷介电温谱的影响,PMN-25PT剩余极化随等静压变化和等静压压致相变.结果表明,随着压力增加,PMN-25PT的介电峰值温度T_m降低,/+{dT_m}/-{dP}≈-4℃/kbar,极化弛豫增强;剩余极化随压力增加连续减小;介电常数对压力的依赖关系与对温度场的依赖相似,压力诱导PMN-25PT发生弛豫铁电—顺电相变,相变为宽化的渐变过程,频率色散和极化弛豫更加强烈和普遍. 关键词： 铌镁酸铅-钛酸铅 等静压 介电弛豫 压致相变     

New crystallographic dielectric phase boundary in K0.5Na0.5NbO3‐based lead‐free ceramics

0.979K_0.5Na_0.5Nb_1‐xSb_x O₃‐0.021Bi_0.5Na_0.5TiO₃ (KNNSx ‐BNT) lead‐free piezoelectric ceramics were fabricated by conventional solid state reaction technique, and their phase transition and electrical properties were studied. With the increase of x, the rhombohedral‐orthorhombic phase transition temperature of the ceramics increases. Finally, both the rhombohedral‐orthorhombic and orthorhombic‐tetragonal phase transitions of the ceramics were modified to be around room tempera‐ ture when about 6% Sb were substituted for the Nb site, resulting in the formation of a new phase boundary separating rhombohedral and tetragonal phases. The formation of the new phase boundary results in excellent properties for the ceramics, that is, the KNNS0.05‐BNT ceramic shows an enhancement in piezoelectric properties: d₃₃ = 380 pC/N and k_P = 0.438. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ca3NbGa3Si2O14晶体的介电和压电特性

利用Y切和(yxl)30°切两种样品测量了Ca3NbGa3Si2O14晶体的介电、压 电和部分弹性参数.计算了(yxl)θ切型相关压电常数随切角的变化.与La3Ga5SiO14晶体相比，Ca3NbGa3Si2O14晶体具有更优良的压电性能，其压电常数 d11=7.93×10-12C/N，d14=-5.88×10-12C/N. 关键词： Ca3NbGa3Si2O14晶体 介电常数 压电常数     

Raman spectroscopic study of phase transitions in undoped morphotropic PbZr1−xTixO3

Several PbZr_1−xTi_xO₃ (PZT) compositions in the proximity of the morphotropic phase boundary (MPB) were examined by means of Raman spectroscopy in the 15–800 K temperature range. Previous studies performed by other researchers using various techniques evidenced that, in the phase diagram of PZT, areas with rhombohedral/monoclinic and tetragonal/monoclinic phases coexist across the MPB. For these compositions, either long‐range or short‐range symmetry ordering of the monoclinic phase should be considered, so that no true rhombohedral–monoclinic–tetragonal phase boundary exists. In addition, the onset of antiferrodistortive phase transitions between high‐T and low‐T perovskite phases has been predicted by ab initio calculations and experimentally reported. In the present work, low‐T and high‐T Raman scattering spectra were collected on undoped PbZr_1−xTi_xO₃ with compositions x = 0.42, 0.45, 0.465, 0.48 and 0.53 in an attempt to clarify the current open issues on the phase diagram of PZT. Spectra clearly belonging to the respective phases were observed in the rhombohedral, monoclinic and tetragonal areas, thus confirming that monoclinic ordering is long‐range only for a narrow range of compositions. Raman measurements at cryogenic temperatures allowed detecting all predicted low‐T phases, including the tetragonal one. These results are in good agreement with both ab initio calculations and experimental results obtained by other authors on the same compositions. Copyright © 2010 John Wiley & Sons, Ltd.     

Structural and dielectric properties of Pb(Li1/4Dy1/4W1/2)O3

The polycrystalline samples of Pb(Li_1/4Dy_1/4W_1/2)O₃ have been synthesized by high-temperature solid-state reaction techniques. Room temperature X-ray diffraction (XRD) studies of the compound provided preliminary structural data, and hence formation of a single phase desired material was confirmed. Detailed studies of dielectric constant (ε) and loss (tanδ) as a function of frequency (100 Hz to 10 kHz) at room temperature (298 K) and also as a function of temperature (liquid nitrogen to 403 K) at 10 kHz suggest that the compound undergoes a ferroelectric phase transition of diffuse type.     

Influence of B2O3 on electrical properties and phase transition of lead-free Ba(Ti0.9Sn0.1)O3 ceramics

The phase transition and electrical properties of Ba(Ti_0.9Sn_0.1)O₃ ceramics with B₂O₃ added were investigated to explore the effect of B₂O₃ addition on enhanced densification and dielectric constant of these ceramics. With increasing B₂O₃ content, a linear reduction of ferroelectric to paraelectric transition temperature was observed. In addition, higher B₂O₃ concentrations enhanced a ferroelectric relaxor behavior in the ceramics. Changes in this behavior were related to densification, second-phase formation and compositional variation of the ceramics.