三元陶瓷Pb(In1/2Nb1/2)O3-Pb(Ni1/3Nb2/3)O3-PbTiO3准同型相界附近组分的介电、铁电和压电性能

铅基复合钙钛矿铁电材料广泛应用于机电传感器、致动器和换能器。二元铁电固溶体Pb(Ni_1/3Nb_2/3)O₃- PbTiO₃(PNN-PT)由于其在准同型相界(MPB)区域具有优异的压电、介电性能而备受关注。然而较大的介电损耗和较低的居里温度限制了其在高温高功率器件方面的应用。本研究通过引入Pb(In_1/2Nb_1/2)O₃ (PIN)作为第三组元改善PNN-PT的电学性能, 提高其居里温度; 通过两步法合成了MPB区域的三元铁电陶瓷Pb(In_1/2Nb_1/2)O₃- Pb(Ni_1/3Nb_2/3)O₃-PbTiO₃ (PIN-PNN-PT), 研究了其结构、介电、铁电和压电性能。制备的所有组分陶瓷具有纯的钙钛矿结构。随着PT含量的增加, 陶瓷结构从三方相转变为四方相。通过XRD分析得到了室温下PIN-PNN-PT体系的MPB相图。体系的居里温度由于PIN的加入得到了很大的提高, 更重要的是PIN的引入降低了PNN-PT体系的介电损耗和电导。MPB处的组分展现出了优异的电学性能, 室温下, 性能最优组分为0.30PIN-0.33PNN-0.37PT: d₃₃=417 pC/N, T_C=200 ℃, ε′= 3206, tanδ=0.033, P_r=33.5 μC/cm², E_C=14.1 kV/cm。引入PNN-PT的PIN第三组元使得体系的居里温度和压电性得到提高的同时降低了的介电损耗和电导率, 因此, PIN-PNN-PT三元铁电陶瓷在高温高功率换能器等方面具备一定的应用潜力。     

Calculation of quasi-static electromechanical coupling coefficientsfor electrostrictive ceramic materials

The quasi-static coupling coefficients, k₁₃ and k₃₃, for electrostrictive ceramics are computed analytically. The calculation is based on a three-dimensional constitutive relation that models both electrostriction and nonlinear dielectric behaviors. The results show that the coupling factors depend on the amplitudes of the applied ac field and the dc bias, as well as the mechanical prestress. For an actuator without bias voltage or prestress, the coupling coefficients approach an asymptotic value with increasing electric field. The primary coefficients, k₁₃ and k₃₃ , for a lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃BaTiO ₃(PMN-PT-BT), based relaxor ferroelectric are computed as an example. The results show that the coupling coefficients for PMN-PT-BT materials are roughly comparable with those of existing piezoelectrics. These coefficients are important parameters for material section and power source design for transducer devices     

Er3+掺杂弛豫铁电材料PMNT的单晶生长与性能表征

按照0.71Pb(Mg_1/3Nb_2/3)O₃-0.26PbTiO₃-0.03Pb(Er_1/2Nb_1/2)O₃化学式所示组分比例, 采用分步高温固相反应合成出Er³⁺掺杂PMNT多晶, 通过熔体坩埚下降法生长出尺寸φ25 mm×100 mm的Er³⁺掺杂PMNT晶体, Er³⁺离子以三元固溶体组元方式被掺杂进入钙钛矿相铁电体晶格; 测试了Er³⁺掺杂PMNT晶片的介电、压电与铁电性能以及上转换发光性能。结果表明, Er³⁺掺杂PMNT晶体呈现跟三方相纯PMNT晶体相近的介电、压电与铁电性能; 在980 nm激发光作用下, 该掺杂晶体呈现出Er³⁺离子特有的较强上转换荧光发射, 并且极化后掺杂晶体的上转换发光强度得到增强。     

Conduction analysis of Li2O doped 0.2[Pb(Mg1/3Nb2/3)]–0.8[PbTiO3–PbZrO3] ceramics fabricated by columbite precursor method

We have fabricated 0.2Pb(Mg_1/3Nb_2/3)O₃–0.8Pb(Zr_0.475Ti_0.525)O₃ [PMN–PZT] ceramics doped with various amounts of Li₂O (0, 0.05, 0.1, 0.2, 0.3 wt.%) using the columbite precursor method. The effects of Li-doping on the conduction behavior of PMN–PZT ceramics are discussed in relation to the low frequency dielectric dispersion and frequency domain measurement. The Li-doped PMN–PZT ceramics sintered at 950 °C showed a sufficient densification with large dielectric constant and low dielectric loss. The incorporation of Li⁺ ion in PMN–PZT ceramics led to an appreciable reduction in electrical conductivity and further enhanced the ferroelectric and piezoelectric properties. The activation energies of PMN–PZT + xLi₂O (x = 0, 0.05, 0.1, 0.2, 0.3 wt.%) ceramics calculated from ac conductivity measurement using the Arrhenius relation were 1.05, 1.25, 1.27, 1.38 and 1.41 eV, respectively. The conduction behavior is examined in the low frequency and high temperature region and the results are discussed in detail through crystal defect mechanism.     

Present and future of piezoelectric single crystals and the importance of B-site cations for high piezoelectric response

High quality piezoelectric single crystals, such as Pb(Zn_1/3 Nb_2/3)O₃-PbTiO₃ (PZNT) and Pb(Mg _1/3Nb_2/3)O₃-PbTiO₃ (PMNT), have been investigated, and, because their piezoelectric properties are greatly superior to those of Pb(Zr_1-xTi_x)O₃ (PZT) ceramics, they have been used for certain transducer applications since the late 1990s. The present situation for these relaxor-PT (lead titanate) single crystals is summarized. In this review, some possible high Tc > 200°C single crystals are also introduced. Single crystals of Pb(In_1/2Nb_1/2)O₃-PbTiO₃ (PINT) binary system and Pb(Mg_1/3Nb_2/3)O₃ -Pb(Sc_1/2Nb_1/2)O₃-PbTiO₃ (PSMNT) tertiary system have been synthesized, and their electrical properties are reported. In addition, a novel guiding principle for discovering excellent piezoelectric materials, namely the presence of low molecular mass B-site ions that can enter the lead-perovskite Pb(B'B")O₃ structure, is introduced     

High electrical properties of W-additive Mn-modified PZT–PMS–PZN ceramics for high power piezoelectric transformers

The ceramics were prepared successfully by the addition of WO₃ to the Mn-modified Pb(Zr_0.52Ti_0.48)O₃–Pb(Mn_1/3Sb_2/3)O₃–Pb(Zn_1/3Nb_2/3)O₃ (PZT–PMS–PZN) for high power piezoelectric transformers application. XRD analysis indicated that the ceramics were mainly composed of a tetragonal phase in the range of 0–1.0 wt.% WO₃ addition. The grain size of the ceramics significantly decreased from 10.0 to 2.9 μm by addition of WO₃. Moreover, the addition of WO₃ promoted densification of the ceramics and increased mechanical quality factor (Q_m), planar coupling factor (K_p) and piezoelectric constant (d₃₃) kept high values, whereas, dielectric loss (tan δ) was low. Δf (=f_a − f_r) slightly changed when WO₃ addition was above 0.5 wt.%. The ceramics with 0.6 wt.% WO₃ addition, sintered at 1150 °C showed the optimized piezoelectric and dielectric properties with Q_m of 1852, K_p of 0.58, d₃₃ of 243 pC/N and tan δ of 0.0050. The ceramics are promising candidates for high power piezoelectric transformers application.     

Effects of growth conditions on the domain structure and dielectric properties of (1 − x)Pb(Sc1/2Nb1/2)O3–xPbTiO3 single crystals

The studies of the (1 − x)Pb(Sc_1/2Nb_1/2)O₃–xPbTiO₃ (PSN–PT) single crystals reveal that the chemical and physical properties of the materials are affected by the growth conditions. By the measurements of the dielectric constant as a function of temperature upon cooling, it is found that crystals grown from the same charged stoichiometric composition (x = 0.425), but under different flux environments (i.e. the composition of flux and the flux to PSN–PT ratios are varied), show anomalies (i.e. phase transitions) at different temperatures. This phenomenon is attributed to the complex local chemical structure of the PSN–PT solid solution single crystals with B-site random occupancy of three different cations (Sc³⁺, Nb⁵⁺ and Ti⁴⁺). The dielectric and domain structure of the PSN–PT crystals with composition near the morphotropic phase boundary (MPB) are investigated, showing much more complex situations compared with Pb(Sc_1/2Nb_1/2)O₃.     

Microdisplacement characteristics and microstructures of functionally graded piezoelectric ceramic actuator

In this work, we report a functionally gradient piezoelectric ceramic actuator with sandwiched structure prepared by the powder metallurgical method. The functional gradients of piezoelectric activity and dielectric activity vary inversely across the thickness of the actuator. Such functional gradients are obtained by interdiffusion reaction between a high piezoelectric composition [Pb(Zr,Ti)O₃/PZT] and a high dielectric composition (PbNi_1/3Nb_2/3O₃/PNN). The bending displacement at the free end of the PNN/PZT functionally graded piezoelectric ceramic actuator was approximately 20 m when 1.4-kV/mm electric field was applied. The grain morphology and compositional distribution across the actuator section and the microstructures of the sandwiched layer were investigated by scanned electron microscopy equipped with energy-dispersive spectroscopy, transmission electron microscopy, and selected area electron diffraction patterns, respectively.     

新型铁电晶体铌镥酸铅-钛酸铅的生长与性能

采用顶部籽晶法生长了一系列不同组分的高居里温度铌镥酸铅-钛酸铅[(1-x)Pb(Lu_1/2Nb_1/2)O₃-xPbTiO₃ (PLN-xPT)]铁电晶体。该晶体在三方相区域表现出典型的介电弛豫特性, 不同组分的晶体表现出了较高的居里温度; 基于介电和结构测试结果, 得到了该体系的低温二元体系相图, 在相图中存在一个准同型相界区域(MPB), 其组分位于x = 0.49~0.51; 利用偏光显微镜分析晶体电畴结构得到和X射线粉末衍射测试结果吻合的相结构; 电学性能测试结果表明不同组分的晶体性能差异较大。组分位于MPB附近的晶体表现出优异的压电性能, 如x = 0.49时, 居里温度T_c = 360℃, 压电常数d₃₃ > 1600 pC/N。处于MPB附近的晶体存在较大的矫顽E_c >10kV/cm, 一些组分晶体的三方–四方相变温度T_RT > 200℃。结果表明高的居里温度及优异的压电性能使二元铌镥酸铅-钛酸铅晶体具有更大的温度应用范围及更广阔的应用前景。     

Piezoelectric and dielectric properties of PZT–PZN–PMS ceramics prepared by molten salt synthesis method

Piezoelectric powders and ceramics with the composition of Pb_0.95Sr_0.05(Zr_0.52Ti_0.48)O₃–Pb(Zn_1/3Nb_2/3)O₃–Pb(Mn_1/3Sb_2/3)O₃ (PZT–PZN–PMS) were prepared by molten salt synthesis (MSS) and conventional mixed-oxide (CMO) methods, respectively. The influence of synthesis process on the properties of powders and ceramics were investigated in detail. The results show that the MSS method significantly improved the sinterability of PZT–PZN–PMS ceramics, resulting in an improvement of dielectric and piezoelectric properties compared to the CMO method. The optimum values of MSS samples are as follows: _r = 1773; tan δ = 0.0040; T_c = 280 °C; d₃₃ = 455 pC/N; k_p = 0.70; Q_m = 888; E_c = 10.3 kV/cm; and P_r = 28.2 μC/cm², at calcination of 800 °C and sintering of 1120 °C temperature.     

Phase-transition temperatures and piezoelectric properties of (Bi/sub 1/2/Li/sub 1/2/)TiO/sub 3/-(Bi/sub 1/2/K/sub 1/2/)TiO/sub 3/ lead-free ferroelectric ceramics

The phase-transition temperatures and piezoelectric properties of x(Bi_1/2Na_1/2)TiO_3-y(Bi_1/2Li_1/2)TiO_3-z(Bi_1/2K_1/2)TiO₃ [x + y + z = 1] (abbreviated as BNLKT100y-100z) ceramics were investigated. These ceramics were prepared using a conventional ceramic fabrication process. The phase-transition temperatures such as depolarization temperatures T_d, rhombohedral-tetragonal phase transition temperature T_R-T, and dielectric-maximum temperature T_m were determined using electrical measurements such as dielectric and piezoelectric properties. The X-ray powder diffraction patterns of BNLKT100y-100z show the morphotropic phase boundary (MPB) between rhombohedral and tetragonal at approximately z = 0.20, and the piezoelectric properties show the maximum at the MPB. The electromechanical coupling factor &33, piezoelectric constant d₃₃ and T_d of BNLKT4-20 and BNLKT8-20 were 0.603, 176 pC/N, and 171degC, and 0.590, 190 pC/N, and 115degC, respectively. In addition, the relationship between d₃₃ and T_d of tetragonal side and rhombohedral side for BNLKT4-100z and BNLKT8-100z were presented. Considering both high T_d and high d₃₃, the tetragonal side of BNLKT4-100z is thought to be the superior composition. The d₃₃ and T_d of BNLKT4-28 were 135 pC/N and 218degC, respectively. Moreover, this study revealed that the variation of Td is related to the variation of lattice distortion such as rhombohedrality 90-alpha and tetragonality c/a.     

Piezoelectric properties in (K0.5Bi0.5)TiO 3-(Na0.5Bi0.5)TiO3-BaTiO 3 lead-free ceramics

Lead-free piezoelectric ceramics with compositions around the morphotropic phase boundary (MPB) x(Na_0.5Bi_0.5)TiO _3-y(K_0.5Bi_0.5)TiO₃-zBaTiO ₃ [x + y + z = 1; y:z = 2:1] were synthesized using conventional, solid-state processing. Dielectric maximum temperatures of 280degC and 262degC were found for tetragonal 0.79(Na_0.5Bi_0.5)TiO₃-0.14(K_0.5 Bi_0.5)TiO₃-0.07BaTiO$ d3 (BNBK79) and MPB composition 0.88(Na_0.5Bi_0.5)TiO₃-0.08(K _0.5Bi_0.5)TiO₃-0.04BaTiO$ d3 (BNBK88), with depolarization temperatures of 224degC and 162degC, respectively. Piezoelectric coefficients d₃₃ were found to be 135 pC/N and 170 pC/N for BNBK79 and BNBK88, and the piezoelectric d₃₁ was determined to be -37 pC/N and -51 pC/N, demonstrating strong anisotropy. Coercive field values were found to be 37 kV/cm and 29 kV/cm for BNBK79 and BNBK88, respectively. The remanent polarization of BNBK88 (~40 muC/cm²) was larger than that of BNBK79 (~29 muC/cm²). The piezoelectric, electromechanical, and high-field strain behaviors also were studied as a function of temperature and discussed     

BaZrO3掺杂对(K0.49Na0.51)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3无铅压电陶瓷的结构与电性能的影响

采用固相反应法制备了(K_0.49Na_0.51)_0.98Li_0.02(Nb_0.77Ta_0.18Sb_0.05)O₃-xBaZrO₃ (NKNLST-xBZ, x = 0~0.020 mol)无铅压电陶瓷, 系统研究了BaZrO₃的掺杂量对陶瓷的压电、介电、机电和铁电性能的影响。结果表明: 随着BaZrO₃掺杂量x的增加, 陶瓷的晶体结构由正交相向四方相转变, 在x=0.005~0.008区间出现正交相与四方相两相共存的区域, 在此区域内陶瓷的晶粒变得细小且均匀, 介电损耗tanδ大幅降低, 压电常数d₃₃和平面机电耦合系数k_p增加。该体系陶瓷的介电常数ε T 33 /ε0则随着BaZrO₃的增加持续增加, 相变温度则向低温方向移动。当x=0.005时, 该组成陶瓷具有最佳的综合性能: 压电常数d33=372 pC/N, 平面机电耦合系数kp=47.2%, 介电损耗tanδ=3.1%, 以及较高的介电常数ε^T₃₃ /ε₀=1470和居里温度T_c=208℃。     

Sm掺杂增强PZT基弛豫型铁电陶瓷压电性能研究

锆钛酸铅(PZT)基压电陶瓷是一类应用非常广泛的功能材料, 可应用于水声换能器、压电马达、医疗超声换能器以及声表面波滤波器等。通过改性提高PZT基压电陶瓷的压电性能一直是该领域的研究热点。本工作采用传统固相反应法制备了准同型相界(Morphotropic Phase Boundary, MPB)组分的Sm-0.25PMN-0.75PZT压电陶瓷, 并对其微观结构以及宏观性能进行了系统研究。研究结果表明：引入Sm³⁺可以增强压电陶瓷的局域结构异质性, 提升介电响应从而提高压电性能。当Sm³⁺引入过多时, 铁电极化的长程连续性被大面积打断, 压电性能下降。本实验中得到的最优组分压电陶瓷性能为：高压电系数d₃₃~824 pC/N, 高压电电压常数g₃₃~27.1×10^-3 m²/C和相对较高居里温度T_C~178 ℃, 电致应变在室温至150 ℃范围内低于5%, 有较好的温度稳定性, 是极具应用前景的高性能压电材料。     

Structure and electrical properties of (100)-oriented Pb(Zn1/3Nb2/3)O3–Pb(Mg1/3Nb2/3)O3–PbTiO3 thin films on La0.7Sr0.3MnO3 electrode by chemical solution deposition

(100)-oriented 0.462Pb(Zn_1/3Nb_2/3)O₃–0.308Pb(Mg_1/3Nb_2/3)O₃–0.23PbTiO₃ (PZN-PMN-PT) perovskite ferroelectric thin films were prepared on La_0.7Sr_0.3MnO₃/LaAlO₃ (LSMO/LAO) substrate via a chemical solution deposition route. The perovskite LSMO electrode was found to effectively suppress the pyrochlore phase while promote the growth of the perovskite phase in the PZN-PMN-PT film. The film annealed at 700 °C exhibited a high dielectric constant of 2130 at 1 kHz, a remnant polarization, 2P_r, of 29.8 μC/cm², and a low leakage current density of 7.2 × 10^− 7 A/cm² at an applied field of 200 kV/cm. The ferroelectric polarization was fatigue-free at least up to 10¹⁰ cycles. Piezoelectric coefficient, d₃₃, of 48 pm/V was also demonstrated. The results showed that much superior properties could be achieved with the PZN-PMN-PT thin films on the solution derived LSMO electrode than on Pt electrode by sputtering.     

CaxSr1-xBi2Nb2O9无铅压电陶瓷制备及其高温稳定性研究

采用传统固相法制备了Ca_xSr_1-xBi₂Nb₂O₉ (x=0、0.10、0.25、0.40)无铅压电陶瓷, 研究了Ca²⁺掺杂量对其微观结构、电学性能及其高温稳定性的影响。掺入Ca²⁺并未改变SrBi₂Nb₂O₉陶瓷的晶体结构; 随着Ca²⁺掺杂量的增加, 陶瓷晶粒由片状向长条状转变; 陶瓷的矫顽场(E_c)下降, 剩余极化强度(P_r)先增大后减小; 陶瓷的居里温度由450℃升高到672℃。当x=0.10时, 陶瓷具有较好的综合性能: 2P_r=14.8 μC/cm², d₃₃=22 pC/N, T_c=488℃; 当退火温度达到400℃时, 压电常数d₃₃仍达到20 pC/N, 说明该材料具有较好的温度稳定性, 可以在400℃的高温环境中应用。     

Toward a unified description of nonlinearity and frequency dispersion of piezoelectric and dielectric responses in Pb(Zr,Ti)O3

A phenomenological approach is proposed describing both nonlinearity and frequency dispersion in dielectric and piezoelectric properties of lead zirconate titanate, Pb(Zr,Ti)O₃ (PZT), thin films and ceramics. The approach couples the frequency dependent response in form of the power law, 1/ω^β, with the rate-independent nonlinear response described by the Rayleigh law. The main experimental trends are well described by the model.     

(Ba0.85Ca0.15)(Ti0.9Zr0.1-xSnx)O3无铅压电陶瓷的相结构与压电性能

钙锆共掺钛酸钡陶瓷(BCZT)具有优异的介电性能和压电性能, 是一类具有发展潜力的无铅压电陶瓷, 但其压电性能仍无法与铅基陶瓷媲美。为提高压电性能, 本研究对陶瓷材料进行Sn元素掺杂改性((Ba_0.85Ca_0.15)- (Ti_0.9Zr_0.1-xSn_x)O₃, x=0.02~0.07))。晶体结构分析证实所有组分的陶瓷无杂相, 处于正交相与四方相两相共存状态, 并具有较大的c/a; 显微结构分析发现所有陶瓷都很致密, 且平均晶粒尺寸随着Sn含量的增加而增大。当x=0.04时, 陶瓷最致密, 且室温处于准同型相界附近, 因此拥有最佳的电学性能: d₃₃=590 pC•N ^-1, k_p=52.2%, tanδ=0.016, ε ^T₃₃=5372, d ^*₃₃=734 pm•V ^-1, IR=57.8 GΩ•cm。本研究表明: Sn掺杂的BCZT基无铅压电陶瓷具有优异的压电性能, 有望在换能器、机电传感器和驱动器等方面得到应用。     

Piezoelectric-electrostrictive monolithic bi-layer composite flextensional actuator

We propose a new type of flextensional actuator comprised of an electromechanically active element which is a piezoelectric-electrostrictive monolithic bi-layer composite (PE-MBLC) capped by truncated thin brass sheets. The PE-MBLC contains equal amounts of 0.65{Pb(Mg_1/3Nb_2/3)O₃}-0.35PbTiO₃ and 0.9{Pb(Mg_1/3Nb_2/3)O₃}-0.1PbTiO₃ by volume, and is obtained by a co-sintering process. With applied E_max = 10 kV/cm unipolar drive, the maximum axial displacement (u₃₃) produced by the uncapped and capped PEMBLC is 11 and 21 mum, respectively. The hysteresis in unipolar u₃₃ at 0.5 E_max is 4.6% for the uncapped PE-MBLC, while that for the capped one is 11%. Under bipolar excitation, the maximum u₃₃ for uncapped is 11.6 mum at +E_max and 6.6 mum at -E_max with an asymmetry factor (xi)of 1.75 for which u₃₃ < 0 for all E < 0. Under bipolar excitation, the maximum u₃₃ at +E_max for the capped PE-MBLC is 19 mum while that for -E_max is 8 mum with xi = 2.4, for which u₃₃ > 0 at +E_max but is smaller than the u₃₃ at +E_max. The origins of the observed asymmetry in u₃₃ are discussed in the context of symmetry superposition and deformation mechanics of the endcaps.     

Li/Ce/La共掺杂对CaBi2Nb2O9陶瓷晶体结构及电学性能的影响

采用固相反应法制备(Li_0.5Ce_0.25La_0.25)_xCa_1-xBi₂Nb₂O₉铋层状结构压电陶瓷, 分析多元稀土元素掺杂对CaBi₂Nb₂O₉(CBN)陶瓷晶体结构、微观形貌及电学性能的影响。Rietveld结构精修表明, 多元稀土元素进入晶格内部形成固溶体, 掺杂使晶体结构有由斜方晶系向四方晶系转变的趋势, 反位缺陷中A位的Bi ³⁺具备6s2孤对电子, 抑制这种变化趋势。SEM照片显示, 掺杂主要抑制晶粒沿垂直c轴平面生长, 这是由于稀土氧化物具备较高的熔点, 在烧结过程中不易扩散。准同型相界附近, 垂直b轴方向的a滑移面被打破, 极化方向沿a轴和b轴, 导致压电性能增强。其中, (Li_0.5Ce_0.25La_0.25)_0.17Ca_0.83Bi₂Nb₂O₉陶瓷具备最优异的性能: 居里温度为913 ℃, 压电系数高达16.4 pC/N; 经850 ℃退火2 h, 其d₃₃值为14.0 pC/N, 约为原始值的85.4%。