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     

BiAlO3掺杂PZT陶瓷的高压电性能和低电场应变滞后

铅基压电陶瓷因其优异的压电性能, 被广泛应用于压电器件。其中, 压电驱动器要求压电陶瓷具有较高压电性能并且在电场下具有较高的电致应变和较小的应变滞后。本研究通过施主-受主共掺, 得到高压电性能和低电场应变滞后的PZT陶瓷。采用传统固相反应法制备了(1-x)(Pb_0.95Sr_0.05)(Zr₅₃Ti₄₇)O₃-xBiAlO₃+0.2%MnO₂陶瓷(掺杂量为质量百分数), 并对其微观结构和压电性能进行了研究。结果表明：BiAlO₃掺杂量较少时, 陶瓷中缺陷偶极子的“钉扎”效应使得陶瓷畴壁转动困难, 陶瓷压电性能较弱, 应变滞后也较小。随BiAlO₃掺杂量增加, 缺陷偶极子“钉扎”效应减弱, 陶瓷的压电性能和应变滞后随之提高。本实验得到的性能最优组分为x=1.75%, 该组份陶瓷的压电系数d₃₃=504 pC/N, 机电耦合系数k_p=0.71, 机械品质因数Q_m=281, 居里温度T_C=312 ℃, 在10 kV/cm电场下的应变滞后仅为15%, 并且还具有较好的温度稳定性, 是一种具有应用价值的压电驱动器用压电陶瓷材料。     

A one-dimensional model for non-linear behaviour of piezoelectric composite materials

In this paper, a one-dimensional analytical model is proposed to investigate the non-linear behaviour for piezoelectric and piezoelectric fibre reinforced composite (PFRC) materials in the fibre direction. The required linear and non-linear constants for purely piezoelectric materials are obtained using the curve-fitting method and the measured S₃–E₃ non-linear loops of the corresponding piezoelectric materials, whereas those for PFRC materials are determined by employing the quadratic non-linear constitutive equations for a purely piezoelectric material, the iso-field assumptions and linear and non-linear constants of the composite constituents. A numerical study is conducted. The numerical results reveal a significant effect of stress T₃ on S₃–E₃ non-linear behaviour for both soft PZT–5H ceramics and PZN–4.5%PT crystals. It is also found that the piezoelectric fibre volume fraction V_f and strain S₃ can significantly affect the T₃–E₃ non-linear behaviour for both PZT–5H/piezo-polymer polyvinylidene fluoride (PVDF) and PZN–4.5%PT/PVDF PFRC materials. A good correlation is noted between the piezoelectric constants d₃₃ and e₃₃ predicted using the present method and those recommended by manufacturer for PZT–5H ceramics and PZN–4.5%PT crystals.     

Characteristics of relaxor-based piezoelectric single crystals forultrasonic transducers

For ultrasonic transducers, piezoelectric ceramics offer a range of dielectric constants (K~1000-5000), large piezoelectric coefficients (d_ij~200-700 pC/N), and high electromechanical coupling (k _t≃50%, k₃₃≃75%). For several decades, the material of choice has been polycrystalline ceramics based on the solid solution Pb(Zr_1-xB_2x)O₃ (PZT), compositionally engineered near the morphotropic phase boundary (MPB). The search for alternative MPB systems has led researchers to revisit relaxor-based materials with the general formula, Pb(B₁,B₂)O₃ (B₁:Zn²⁺ , Mg²⁺, Sc³⁺, Ni²⁺..., B₂ :Nb⁵⁺ Ta⁵⁺...). There are some claims of superior dielectric and piezoelectric performance compared to that of PZT materials. However, when the properties are examined relative to transition temperature (T₃), these differences are not significant. In the single crystal form, however, Relaxor-PT materials, represented by Pb(Zn_1/3Nb_2/3)O₃-PbTiO ₃ (PZN-PT), Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT) have been found to exhibit longitudinal coupling coefficients (k₃₃)>90%, thickness coupling (k_t)>83%, dielectric constants ranging from 1000 to 5000 with low dielectric loss <1%, and exceptional piezoelectric coefficients d₃₃>2000 pC/N, the later promising for high energy density actuators. For single crystal piezoelectrics to become the next generation material of ultrasonic transducers, further investigation in crystal growth, device fabrication and testing are required     

Fabrication of Lead-Free Piezoelectric (Na/sub 0.5/K/sub 0.5/)NbO/sub 3/Ceramics by a Modified Solid-State Reaction Method

Sodium potassium niobate, (Na_0.5K_0.5)NbO₃, fine powder has been successfully synthesized at the low temperature of 550degC through a modified solid-state reaction method, in which urea [CO(NH₂)₂] plays an important role. High-density (Na_0.5K_0.5)NbO₃ ceramics could be obtained by conventional sintering of the synthesized (Na_0.5K_0.5)NbO₃ fine powder with the addition of 0.03 mol% Co₃O₄ as a sintering additive. The crystal structure, microstructure, and dielectric and piezoelectric properties were characterized. The (Na_0.5K_0.5)NbO₃ ceramic showed a comparatively saturated P-E hysteresis loop. The (Na_0.5K_0.5)NbO₃ ceramic also displayed piezoelectricity with a piezoelectric constant d₃₃ of 126 pC/N and a planar electromechanical coupling factor k_p of 33%.     

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.     

NaNbO3@g-C3N4复合材料的可控构筑及其压电光催化性能

促进光催化过程中载流子的高效分离一直是困扰科研人员的难题。最近,利用压电效应抑制光生电子-空穴对复合从而提升光催化效率的策略引起了人们的广泛关注。在此,以制备的由g-C₃N₄包覆的一维NaNbO₃纳米棒异质结材料作为研究对象,通过施加超声场引入压电效应,研究其在压电光催化过程中的性能增强机制。通过SEM及XPS等表征手段对材料的微观形貌和键合情况进行了考察。性能实验结果表明:在利用超声波引入压电效应后,NaNbO₃@g-C₃N₄在压电光催化过程中(1.02 mmol·g?1·h?1)表现出比单一的光催化过程(0.49 mmol·g?1·h?1)更高的产氢速率,表明压电效应可极大促进NaNbO₃@g-C₃N₄异质结材料在光催化过程中的载流子分离效率,抑制光生电子与空穴复合,提高其光催化性能。此外,在数据分析的基础上,本文提出了压电-光催化协同作用的机制,为高效压电光催化剂的设计和开发提供了参考。      

原料预处理对BaTiO3压电陶瓷的物性影响

BaCO₃微粉原料通常由尺寸较大的棒状颗粒所组成, 这些棒状颗粒在一次球磨过程中由于不容易粉碎, 从而对经预烧、二次球磨所得到的BaTiO₃陶瓷微粉的化学组分的均匀性和颗粒度产生影响, 进而影响后序烧结制备的BaTiO₃陶瓷的微观组织结构和压电性能。本研究重点探讨了以BaCO₃和TiO₂为原料、通过固相反应途径制备BaTiO₃陶瓷时, 实施原料预处理对所制备的BaTiO₃压电陶瓷物性的影响。研究发现, 配料前对BaCO₃原料实施球磨预处理可明显地降低棒状颗粒的尺寸, 从而可获得颗粒度细化的BaTiO₃陶瓷微粉, 进而制备致密度更高和晶粒尺寸更小而压电性能更高的BaTiO₃陶瓷材料。研究中对BaCO₃微粉进行不同时间的球磨预处理, 然后制备钛酸钡陶瓷, 考察了其压电性能、介电性质、铁电性能和微观结构等物理性质。利用同样的BaCO₃微粉原料, 未经球磨预处理所制备的BaTiO₃陶瓷的压电系数d₃₃最高值为410 pC/N, 而实施合适的球磨预处理制备的BaTiO₃陶瓷的压电系数d₃₃最高值可达470 pC/N。     

Microstructural and piezoelectric properties of low temperature sintering PMN-PZT ceramics with the amount of Li2CO3 addition

PMN-PZT ceramics doped with Li₂CO₃ and Bi₂O₃ as sintering aids were manufactured in order to develop the low temperature sintering ceramics for multilayer piezoelectric transformer, and their micro structural, dielectric and piezoelectric properties were investigated. The sintering aids were proved to lower the sintering temperature of doped PMN-PZT ceramics due to the effect of LiBiO₂ liquid phase. Optimal values for multilayer piezoelectric transformer application, such as electromechanical coupling factor (k_p) of 0.50, mechanical quality factor (Q_m) of 2264, and dielectric constant (K) of 1216, and curie temperature (T_c) of 317 °C were found at 0.1 wt.% Li₂CO₃ added ceramics sintered at 940 °C.     

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.     

基于噻吩-蒽单元的无规共聚物电化学制备及其电致变色性能研究EI北大核心CSCD

蒽单元嵌入聚噻吩主链能显著调控聚合物的变色性能,但其聚合电位偏高易导致聚合物的成膜质量和性能较差。为降低含蒽单元的单体电聚合电位,通过Stille偶联反应合成了9,10-二(2-噻吩基)蒽单体(Th-An-Th),并分别在BFEE,BFEE+CF_(3)COOH,LiClO_(4)/ACN和LiClO_(4)/PC等聚合媒介中进行电化学聚合。结果表明:Th-An-Th难以通过电化学反应共聚,但可以作为共单体与噻吩(Th),3-甲基噻吩(MeTh),3,4-亚乙基二氧噻吩(EDOT)和硒酸(SePh)在低电位下进行无规共聚,得到系列无规共聚薄膜P1,P2,P3,P4。循环伏安和FTIR测试证实了聚合过程和共聚物的特征结构,光谱电化学测试结果表明,系列共聚物均具有丰富的颜色变换性能,在-0.6 V到1.0 V扫描下,P1,P3,P4膜可实现4种颜色的变化,且表现出良好的近红外变色能力。共聚物薄膜具有较快的开关响应速度和良好的电化学稳定性,P4膜在521 nm处漂白和着色响应时间分别为1.9 s和3.4 s,光学对比度为35.6%,在210次循环变色后,共聚物光学对比度仅损失2.3%,电化学循环400次仍保持82%的电化学活性。     

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。     

(K0.44,Na0.52,Li0.04) (Nb0.84,Ta0.10,Sb0.06)O3 Ferroelectric Ceramics

Recent progress in (K_0.44,Na_0.52,Li_0.043-based ceramics (KNN) with special emphasis on (K_0.44,Na_0.52,Li_0.040.84,Ta_0.10,Sb_0.06))O₃ (KNN-LT-LS) is reviewed concisely. The base KNN and its compositional derivatives are analyzed in terms of dopant-property relationships, which are then extended to the ternary derivatives. The effects of processing conditions such as humidity, precursor purity, and oxygen partial pressure during sintering are elaborated on from a phenomenological perspective. It is also shown that the spontaneous polarization is sensitive to the processing route chosen for synthesis (mixed oxide versus perovskite routes). Special attention is devoted to the discussion of the morphotropic phase boundary (MPB) dilemma in the KNN-LT-LS system, where it is shown that the origin of high piezoelectric activity is actually due to a polymorphic transition at room temperature. It is shown that prototype transducers based on pure and 1 mol% Ba²⁺ doped KNN-LT-LS exhibit performance metrics comparable to those fabricated using PZT-5H. Overall, KNNLT- LS ceramics show great promise for lead-free applications, although issues such as temperature dependence of properties and strong sensitivity to processing conditions remain as the 2 major challenges.     

0.94Na1/2Bi1/2TiO3-0.06BaTiO3:TiO2无铅复合陶瓷的结构及退极化温度研究

采用固相法将纳米TiO₂引入0.94Na_1/2Bi_1/2TiO₃-0.06BaTiO₃ (简称NBT-6BT)钙钛矿结构压电陶瓷晶界中, 成功制备出NBT-6BT: xTiO₂ (x=0, 0.05, 0.1, 0.2, 0.3) 0-3型复合结构陶瓷, 并系统地研究了掺杂TiO₂对陶瓷的结构及压电性能的影响。实验结果表明, 部分TiO₂进入晶格内部造成陶瓷单斜相Cc含量减少, 晶体对称性提高; 随着TiO₂的掺杂量的增加, 明显提高了NBT-6BT陶瓷的退极化温度。对NBT-6BT:0.1TiO₂样品, 在保持一定压电常数(69 pC/N)的前提下, 陶瓷的退极化温度相比纯NBT-6BT提升约88%, 此时介电损耗tanδ=0.044, 表明该材料是一种适用于更高温区间的新型无铅压电材料。     

钛酸钡基纳米材料的压电催化性能研究进展

社会快速发展带来巨大经济效益的同时,也带来了一系列生态环境问题,如水污染、大气污染和污染物排放。催化降解被认为是处理各种污染的一种有效策略,相对于传统的光催化,压电催化是近几年提出的一种全新的催化方式。通过压电催化将机械能转化为化学能是解决当前水污染难题的一个有效手段,大量的压电材料被应用于压电催化降解的研究,其中BaTiO₃基纳米粉体作为一种典型的压电材料,因具有成本低、压电活性强等优点,引起了研究者的广泛关注。本文首先对压电催化的理论和起源进行了概述,列举了一些常用的压电催化材料并针对其压电催化应用进行举例。围绕BaTiO₃介绍了其基本结构、纳米BaTiO₃粉体的常用制备方法和在压电催化领域的应用及一些典型的改性方法。最后对BaTiO₃基纳米粉体在压电催化领域的未来发展趋势进行了展望。     

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     

Structure and ferroelectric properties of Bi(Zn1/2Ti1/2)O3-(Bi1/2K1/2)TiO3 perovskite solid solutions

Lead-free piezoelectric ceramics based on χBi(Zn_1/2Ti_1/2)O₃-(1-χ)(Bi_1/2K_1/2)TiO₃ were obtained via solid state processing techniques. A single perovskite phase with tetragonal symmetry was obtained for Bi(Zn_1/2Ti_1/2)O₃ (BZT) substitutions up to 20 mol%. The maximum density was 97.1% at the composition of χ = 0.1. The dielectric measurement indicated that the transition temperature decreased linearly with increasing BZT content. The P-E loops revealed an increase in remanent polarization (P_r) with the addition of BZT. The maximum planar coupling coefficient, κ_r, for the χ = 0.1 composition was 21.6 and the piezoelectric coefficient, d₃₃, for χ = 0, χ = 0.05, and χ = 0.1 was 108, 185, and 235 pm/V, respectively. Overall, the dielectric and piezoelectric properties showed significant improvement when BZT was added.     

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.     

羟基磷灰石-钛酸钡仿人骨复合材料的制备及其性能

以HA粉和BT粉为原料,用烧结工艺制备羟基磷灰石-钛酸钡(HA-BT)仿人骨复合材料,使用D/max2200PCX光衍射仪、S4800场发射扫描电镜及其附带的X射线能谱仪、STA449F3同步热分析仪、1036PC万能材料试验机、LC2735准静态压电系数测量仪和ZJD-C型介电常数测试仪对其表征,研究BT含量和烧结温...     

Enhancement of Q/sub m/by Co-Doping of Li and Cu to Potassium Sodium Niobate Lead-Free Ceramics

Lead-free piezoelectric ceramics KNN modified by Li-substitution and CuO addition have been synthesized, and the piezoelectric and dielectric properties were measured. A morphotropic phase boundary (MPB) between orthorhombic and tetragonal phases was formed with Li-substitution. The co-doping of Li and Cu markedly enhanced the mechanical quality factor (Q_m) in comparison with the sole doping of Li and Cu. Anomalous anti-ferroelectric-like hysteresis curves were observed in 2 mol% CuO-doped ceramics. The anti-ferroelectric-like curves were changed to that of normal ferroelectrics following poling. A model based on the formation of the internal bias field (Ei) due to the movements of space charges was proposed to explain these phenomena. It was considered that the Ei stabilized the spontaneous polarization (Pa) and suppressed the domain wall motion to enhance the Q_m. The highest Q_m obtained in this study was 742. The [(Na_0.5K_0.5)_0.96Li_0.04] NbO₃ + 0.45 mol% CuO ceramics showed a high Q_m value of 414 with a high piezoelectric constant d₃₃ of 100 pC/N.