Piezoelectric Ceramics

The discovery of piezoelectric effects in electrically poled barium titanate ceramic, in the early l940, was a revolutionary contribution to the electromechanical transducer art. Since then, improved barium titanate ceramics adapted to a variety of practical needs have been developed, and a number of new piezoelectric oxide-type compounds have been discovered. Among these the lead titanate zirconate group offers especially valuable properties. In addition to a survey of the field, the present paper presents new data on lead titanate zirconate over a range of compositions.     

Piezoelectricity in Poled Hydroxyapatite Ceramics

Direct current electrical poling of textured hydroxyapatite (HAp) ceramics is reported here to exhibit weak ferroelectricity and pyroelectricity, but a remarkably higher (six orders of magnitude) piezoelectricity. The piezoelectric strain coefficient is an order higher than that of bone and of the same order as that of quartz crystal and uncalcified collagen in tendon. The piezoelectric charge coefficient is an order higher than bone, and three orders higher than that of tendon. Piezoelectric constants of poled HAp ceramics are high enough to have physiological relevance such as in the use of bone grafts for stimulated calcification or in energy harvesting from physiological motions. Piezoelectricity in these ceramics can be tuned by controlling texture, and poling parameters. The density of power that can be harvested from HAp ceramics is currently just one order lower than biocompatible ferroelectric ceramic such as barium titanate.     

功能陶瓷材料及其应用研究进展

介绍铁电、压电等功能陶瓷及其片式元件应用研究的若干新进展.基于过渡液相烧结机制的高性能压电陶瓷材料具有低烧结温度、高压电常数和低介质损耗等诸多优点.低烧多层压电变压器(MPT)以其低驱动电压、小体积、高升压比、薄型片式化等优点在液晶显示背光电源等方面获得应用.多层压电变压器及其背光电源具有高功率密度、高转换效率、薄型化和低成本等特点.基于缺陷化学原理和无晶粒长大的致密化烧结动力学,制备了亚微米/纳米晶钛酸钡基陶瓷及其薄层化贱金属内电极MLCC.研制了低烧铁氧体材料及其片式电感器.介绍了压电陶瓷超声微马达的结构与特性.     

Magneto-electric properties of xNi0.7Zn0.3Fe2O4 – (1-x)BaTiO3 multiferroic composites

Di-phase ceramic composites, with general formula xNi_0.7Zn_0.3Fe₂O₄ – (1-x)BaTiO₃(x = 0.9, 0.7, 0.5, 0.3, 0.1), were prepared by a mixing method. X-ray analysis, for powder and ceramics, indicated the formation of ferrite and barium titanate phases without the presence of the impurities. SEM analysis indicated that the composite morphology contained two types of grains, polygonal and rounded. Homogeneous microstructure and the smallest grain size were obtained in ceramics with 70% of barium titanate. The electrical properties of these materials were investigated using impedance spectroscopy, dielectric and ferroelectric measurements. The NZF-BT(30-70) composite has shown better electrical properties in comparison to other investigated ceramics, confirmed by dielectric and ferroelectric data analysis. Saturation magnetization and coercive field decreased with the increase of the content of ferroelectric phase.     

钙钛矿结构无铅压电陶瓷的研究进展

无铅压电陶瓷的开发与应用是当今压电陶瓷发展的必然趋势,本文综合分析了无铅压电陶瓷的研究背景,给出了钙钛矿型无铅压电陶瓷的主要体系,包括钛酸钡基无铅压电陶瓷、BNT基无铅压电陶瓷,分析比较了其性能及研究现状。     

Energy Storage in Ceramic Dielectrics

Historically, multilayer ceramic capacitors (MLC's) have not been considered for energy storage applications for two primary reasons. First, physically large ceramic capacitors were very expensive and, second, total energy density obtainable was not nearly so high as in electrolytic capacitor types. More recently, the fabrication technology for MLC's has improved significantly, permitting both significantly higher energy density and significantly lower costs. Simultaneously, in many applications, total energy storage has become smaller, and the secondary requirements of very low effective series resistance and effective series inductance (which, together, determine how efficiently the energy may be stored and recovered) have become more important. It is therefore desirable to reexamine energy storage in ceramics for contemporary commercial and near-commercial dielectrics. Stored energy is proportional to voltage squared only in the case of paraelectric insulators, because only they have capacitance that is independent of bias voltage. High dielectric constant materials, however, are ferroics (that is ferroelectric and/or antiferroelectric) and display significant variation of effective dielectric constant with bias voltage. The common ferroelectric materials, whether based upon barium titanate or lead manganese niobate (PMN), in the high-field limit, exhibit an energy storage which increases linearly with bias voltage. Mixed phase, ferroelectric plus antiferroelectric, dielectrics from the lead lanthanum zirconate titanate (PLZT) system, as predicted theoretically, show the best energy density at low to moderate fields. Surprisingly, maximum energy storage is not obtained in high dielectric constant materials but in those materials which display intermediate dielectric constant and the highest ultimate breakdown voltages.     

钛酸钡基电子陶瓷材料的改性进展

钛酸钡基电子陶瓷材料广泛应用于电容器、集成电路、传感器及热敏电阻等领域。高容量、小型化、抗击穿及低损耗等工业需求对钛酸钡基电子陶瓷材料的性能提出更高的要求,改性则是提高陶瓷材料性能的主要手段。综述了近年来钛酸钡基电子陶瓷材料在掺杂改性、复合改性及物理改性方面的研究进展。分析了钛酸钡基电子陶瓷材料在改性中存在的问题,比如：常规元素掺杂制备参数优化不足、稀土元素掺杂种类偏少、包覆效果待提升、聚合物陶瓷复合体综合性能欠佳、烧结工艺尚待优化等。提出了解决方法,比如：探索多种元素掺杂、优化工艺参数、改进包覆与聚合方式等。指出了钛酸钡基电子陶瓷材料的未来发展方向,即：强化烧结过程中晶粒尺寸、晶体形状、组分调控的机理研究,选取更多稀土元素进行改性,探索包覆掺杂改性、聚合物复合改性等新工艺。     

Recent Materials Characterizations of [2D] and [3D] Thin Film Ferroelectric Structures

A review is given of ceramic and single-crystal thin film ferroelectric oxides, emphasizing perovskite phases, together with some new developments on hafnia films. It is shown that single-crystal barium titanate films behave as bulk down to at least 77 nm, with no finite size effects, no phase transition temperature shifts, and no dielectric peak broadening or change from first- to second-order transitions, suggesting that the gradient defect model of Bratkovsky and Levanyuk correctly describes such effects as extrinsic in experimental studies of equally thin ceramic thin films. In ceramic barium–strontium titanate (BST) thin films, it is shown that there is also no intrinsic broadening or shifts in phase transitions, with sharp, unshifted, bulk-like transitions observed only as re-entrant upon warming from cryogenic temperatures; this shows that phase transitions in ceramic thin films are dominated by kinetics and not thermodynamics and are definitely not equilibrium measurements. At high fields (>1 GV/m), the films exhibit space charge-limited conduction; no variable-range hopping is observed, contrary to recent studies on SrTiO₃. Some novel, unconventional switching processes are discussed, comparing the "perimeter effect" (non-equilibrium, ballistic) with Molotskii's equilibrium model. Theory and experiment are described for [3D] nanotubes, nanorods, and nano-ribbons (or micro-ribbons). The layered-structure-perovskite–pyrochlore conversion in bismuth titanate is described together with the PbO+TiO₂ phase separation in lead zirconate titanate during electrical breakdown, as are novel HfO₂ precursors that demonstrate enhanced temperature crystallization from the amorphous state and hence commercial advantages for front-end processing.     

Identification of quality parameters for barium titanate powder

The authors describe the results of developing methods for determining some quality parameters of barium titanate powder, which is the main component in some ceramics that are used to produce capacitors. The degree of transformation of ZnO and BaTiO₃, the volume density of sintered powder, the degree of its dissolution in hydrochloric acid, and some diffraction characteristics of BaTiO₃ powders are determined according to the developed methods and can predict with a sufficient degree of reliability the quality of ceramic capacitors made from barium titanate powders.     

Influence of Cd doping on the electro-strain of barium zirconate titanate ceramics

Cadmium doped barium zirconate titanate (Ba_1−xCd_x)(Zr_0.13Ti_0.87)O₃ (BCDZT) ferroelectric ceramic compositions with x=0, 0.02, 0.04 and 0.06 have been prepared by solid state reaction method. X-ray diffraction studies reveal a pseudocubic structure. For increasing Cd content, the bulk ceramic micro-structure reveals an increasing grain size and density. Variations in the dielectric, piezoelectric and unipolar electric field induced strain characteristics are discussed. Increasing Cd content reduces the coercive field, increases the remnant polarization and does not affect the ferroelectric-paraelectric phase transition temperature (~60 °C). An optimum Cd content x=0.06 produces highly resistive ceramics with low dielectric loss (tanδ=0.019), and a maximum value of piezoelectric charge constant d₃₃=114 pC/N and unipolar electro-strain of ~0.07%.     

纳米钛酸钡的掺杂对陶瓷性能的影响

采用掺杂纳米级钛酸钡和碳酸锰的方法,观察了掺杂不同量纳米级钛酸钡和碳酸锰后的钛酸钡坯片烧结所得陶瓷表面的显微组织形貌的变化,研究了单一掺杂纳米级钛酸钡、单一掺杂碳酸锰、复合掺杂碳酸锰+纳米级钛酸钡对陶瓷制品晶粒尺寸与介电性能的影响。结果表明：掺杂纳米级钛酸钡对钛酸钡陶瓷制品的介电性能有显著的提升,但是随着掺杂量的进一步增加,其介电性能的变化不大;掺杂碳酸锰对钛酸钡陶瓷晶粒的细化效果优于掺杂纳米级钛酸钡的效果;复合掺杂1%（质量分数,下同）碳酸锰+1%纳米级钛酸钡所得陶瓷的致密性高于单一掺杂1%碳酸锰的效果。     

Barium Zirconate-Lead Titanate Ferroelectric Ceramics

Hot-pressed barium zirconate-lead titanate ceramics have been examined to determine crystal-line symmetry and dielectric, ferroelectric, and piezoelectric properties. Barium zirconate additions to lead titanate form solid solutions with a decreasing tetragonal c/a axial ratio until at 60PbTiO₃–40BaZrO₃ to 75PbTiO₃–25BaZrO₃ the ceramics have coercive forces low enough to permit polarization. High-coercive-force piezo-electric ceramics are formed with k_p up to 0.30 and d₃₃ up to 110 × 10⁻¹² coulombs per newton.     

Relaxor Ferroelectric Behavior in Barium Strontium Titanate

The development of barium strontium titanate‐based tunable dielectrics is currently hindered by high losses in the paraelectric phase. Barium strontium titanate (BST) thin films and ceramics show a range of ferroelectric transition behavior, from normal, diffuse, and relaxor‐like ferroelectric responses, depending on the sample preparation route. Rayleigh analysis, the temperature‐dependent dielectric response, and the optical second harmonic generation were used to characterize the ferroelectric response of bulk and thin film BST. Ferroelectricity is observed to persist in BST for 30°C above the global phase transition temperature in ceramics and over 50°C in thin films. Piezoresponse force microscopy on BST ceramics with extensive residual ferroelectricity reveals the coexistence of nanoscale polar regions, typical of relaxor ferroelectrics, as well as micrometer scale domain structures. The nature of the phase transition was probed using electron energy loss spectroscopy and found to correlated with the nanoscale A‐site chemical inhomogeneity in the samples.     

Flextensional Barium Strontium Titanate Actuators

This paper describes the performance of the cymbal flextensional transducer using Dy-doped barium strontium titanate (BST) as the driver material. BST was first characterized for its dielectric and loss behavior as a function of temperature and electrical bias field. With no electrical bias, the transition temperature was measured to be near 20°C and have a dielectric constant >20 000. The strain of a BST disk was then measured and compared with other ceramics. At room temperature the strain and average effective piezoelectric d ₃₃ of this non-lead composition was slightly larger than Navy type I lead zirconate titanate (PZT-4) ceramic. The strain/field behavior was also measured as a function of temperature. Cymbal capped BST ceramic was found to have an amplified displacement of 28×, also very similar to type I ceramic. The stiffness of BST was found to be tunable by dc voltage and 2 to 3 times larger than that of PZT. This material has promise for applications in actuators and transducers with large generative force.     

Electromechanical Resonances in Ceramic Capacitors and Their Use for Rapid Nondestructive Testing

A rapid nondestructive test method for ceramic multilayer capacitors made from piezoelectric materials such as barium titanate or lead-containing materials is described and evaluated. The test method is based on the internal excitation of standing acoustic waves in the capacitors. The standing waves are severely dampened by defects such as indentations and delaminations or warped electrodes. An undampened resonance is a good indication of a defect-free ceramic multilayer capacitor. This finding was used in a nondestructive test setup to evaluate about 1000 capacitors. Through metallographic (cross-section) examination, a sorting accuracy of 2% false accepts and 8% false rejects was determined for the highspeed test setup. The test setup has the potential to test over 100 000 capacitors an hour. [Key words: capacitors, nondestructive testing, multilayers, mechanical properties, electrical properties.]     

Review of Mechanically Related Failures of Ceramic Capacitors and Capacitor Materials

This paper reviews the brittle fracture behavior of dielectric ceramics such as barium titanate, and describes some of the relationships between defects such as cracks and electrical degradation and failure of multilayer capacitors. Stresses arising from the ferroelectric phase transformation in these dielectric materials are shown to play a part as a driving force for crack growth. In addition, possible contributions to failure from stresses arising from thermal excursions in the capacitor are discussed. Low-voltage failures arising from a short between the electrodes in multilayer capacitors are shown to be related to the growth of cracks in the dielectric. A technique for predicting the onset of these types of failures based upon fracture mechanics techniques is described. Possible effects of the electric field itself in promoting or retarding the growth of cracks are discussed.     

低温烧结BaTiO3基介电陶瓷的研究进展

低温烧结钛酸钡基陶瓷材料,有利于适应MLCC和LTCC的发展要求,并且降低能耗。本文综述了钛酸钡基陶瓷低温烧结方面的研究进展,包括各种低温烧结方法、机理和研究现状,着重介绍了助烧剂的作用机理,最后展望了钛酸钡基陶瓷低温烧结的发展趋势。     

Size and scaling effects in barium titanate. An overview

Ferroelectric perovskites such as BaTiO₃ and Pb(Zr,Ti)O₃ are well-suited for a variety of applications including piezoelectric transducers and actuators, multilayer ceramic capacitors, thermistors with positive temperature coefficient, ultrasonic and electro-optical devices. Ferroelectricity arises from the long-range ordering of elemental dipoles which determines the appearance of a macroscopic polarization and a spontaneous lattice strain. The confinement of a ferroelectric system in a small volume produces a perturbation of the polar order because of the high fraction of surface atoms and ferroelectricity vanishes when the size of the material is reduced below a critical dimension. This critical size is of a few nanometres in the case of epitaxial thin films and of 10−20 nm for nanoparticles and nanoceramics. The change in properties with decreasing physical dimensions is usually referred to as size effect. Thin films and ceramics are particularly prone to show size effects. A progressive variation of dielectric, elastic and piezoelectric properties of ferroelectric ceramics is already observed when the grain size is reduced below ≈10 μm, i.e. at a length scale much larger than the critical size. In this case it is more appropriate to refer to scaling effects as they are not related to material confinement.The aim of this contribution is to review the current understanding of size and scaling effects in perovskite ferroelectric ceramics and, in particular, in BaTiO₃. After a short survey on the intrinsic limits of ferroelectricity and on the impact of particle/grain size on phase transitions, the role of interfaces such as ferroelectric/ferroelastic domain walls and grain boundaries in scaling of dielectric and piezoelectric properties will be discussed in detail. Multiple mechanisms combine to produce the observed scaling effects and the maximization of the dielectric constant and piezoelectric properties exhibited by BaTiO₃ ceramics for an intermediate grain size of ≈1 μm. The broad dispersion of experimental data is determined by spurious effects related to synthesis, processing and variation of Ba/Ti ratio. Furthermore, we will consider these size effects, and other properties in relation to the downsizing the modern multilayer BaTiO₃ based capacitors.     

Electrical fatigue behavior of Ba0.85Ca0.15Zr0.1Ti0.9O3 ceramics under different oxygen concentrations

Fatigue degradation is a significant problem in piezo/ferroelectric materials and their commercial applications. The major causes of electrical fatigue degradation are a domain pinning effect and physical damage such as microcracking. This work reports the fatigue behavior of barium calcium zirconate titanate (Ba_0.85Ca_0.15Zr_0.1Ti_0.9O₃) under regular and low oxygen concentration silicone oil. Impedence analyzer and LCR meter are employed to analyzer the dielectric properties and it also revealed the relationship between activation energy and oxygen vacancy. X-ray diffraction, synchrotron X-ray absorption spectroscopy, and scanning electron microscope techniques were employed to study the local structural changes, defect development, physical damage and microcracking in the ceramics. FEFF-8.4 simulations were used to determine the oxygen vacancy creation. The study reveals the relationship of oxygen vacancy creation, domain wall pinning, microcracking and the fatigue behavior of the ferroelectric ceramic. The work investigated the dielectric and ferroelectric properties of BCZT ceramics intermes of applied electric field.     

Effect of Firing Cycle on Structure and Some Dielectric and Piezoelectric Properties of Barium Titanate Ceramics

In the preparation of barium titanate ceramics for dielectric and piezoelectric applications, careful attention must be given to many factors which determine the ultimate performance of the ceramic. In this study structural differences were observed with the aid of electron micrographs as the time and temperature of firing were varied. At lower temperatures and shorter firing intervals crystals remained small, grain-boundary areas were relatively large, and there were numerous voids where several crystals joined. As the time and/or temperature were increased, crystals became larger with an improved grain-boundary condition that resulted in better structure. An optimum condition was soon reached beyond which rounding of edges at grain boundaries where several crystals joined became more pronounced. This caused an increase in the number of voids. Accompanying these changes, the 1-kc. dielectric constant, the piezoelectric constants (thickness mode), and coupling coefficients first improved, reached optimum values, and then declined slightly, but the resistance to depoling continually decreased as the crystal size increased. An experimental technique of rapid heating and cooling was used to prepare dense specimens of chemically pure barium titanate with relatively small average crystal sizes. Dielectric constants as high as 3000 with Q values of 80 were obtained for these high-density ceramics, accompanied by low effective piezoelectric constants and coupling coefficients.