Subcritical Crack Growth in Lead Zirconate Titanate

Subcritical crack growth in terms of velocity–stress intensity factor ( v – K ) curves in lead zirconate titanate (PZT) were experimentally characterized on poled and unpoled compact tension specimens. The poled specimens were tested under open- and short-circuit electrical boundary conditions, which resulted in an increase in fracture toughness by 0.2 MPa·m^1/2 for the accessible velocity range ( v = 10⁻⁹ to 10⁻⁴ m/s) in the open-circuit case. Subcritical crack growth of unpoled specimens was obtained under ambient (relative humidity = 35%) and dry (relative humidity ∼ 0.02%) conditions over a regime in stress intensity factor of 0.5 MPa·m^1/2.     

Electrophoretic Deposition of Lead Zirconate Titanate Ceramics

Electrophoretic deposition (EPD) of submicrometer lead zirconate titanate (PZT) powders in ethanol was conducted to form thick green PZT films up to 160 μm thick. The PZT colloid stability, as a function of pH, was studied by zeta-potential measurement. The electrical condition of the suspension was quantified by conductivity measurement at various pH values. The effect of different applied current densities on the deposition mass was investigated. A kinetic model for the constant-current-density EPD process, taking into account the particle concentration variation, was also examined, based on the experimental results obtained in the present work. An empirical relationship between the kinetic constant and the applied current density has been proposed.     

二乙醇胺辅助溶胶-凝胶法低温合成锆钛酸铅纳米粉体

以醋酸铅[Pb（CH3COO）2^-33H20]、硝酸锆[Zr（N03）4^-5H2O]和钛酸四丁酯[Ti（C4H90）4]为原料,以二乙醇胺（diethanolamine,DEA）为聚合剂．用溶胶-凝胶法制备了锆钛酸铅（PbZrxTil-x03,PZT）纳米陶瓷粉体。研究了DEA对溶胶-凝胶法合成PZT陶瓷粉体的影响...     

Synthesis and Characterization of Lead Zirconate Titanate Fibers Prepared by the Sol–Gel Method: The Role of the Acid

Lead zirconate titanate (PZT) fibers are prepared by the sol–gel method using acetic acid and methacrylic acid to control the pH of the PZT precursor sol. The chemical evolution of the precursors, the thermal and crystallization behavior of the PZT gel fibers, and the microstructure of the samples with and without acid addition are analyzed and compared. It is observed that the properties of the fibers are improved when acids are used; particularly longer PZT ceramic fibers (4–5 cm) are obtained after heat treatment and a single perovskite phase is obtained at 550°C when using methacrylic acid. The mechanisms of the acid effect on the strengthening and crystallization of PZT fibers are discussed.     

Effects of Solvent Mixtures on Dispersion of Lanthanum-Modified Lead Zirconate Titanate Tape Casting Slurries

The effects of xylenes/ethanol solvent mixtures on lanthanum-modified lead zirconate titanate (PLZT) nonaqueous suspensions were investigated by measuring sediment height, viscosity, and adsorption of dispersant. Well-dispersed colloidal suspensions were obtained in xylene-rich solvents with a minimum amount of menhaden fish oil as a dispersant. It was also shown that adsorption of dispersant on particle surfaces strongly depends on selection of solvent(s). The ratio of solvent mixture affects PLZT solids content of unfired tapes, in which using insufficient as well as excess dispersant could decrease the packing density of particles. Solubility of other organic additives, such as binder, was also considered when selecting a xylene/ethanol ratio.     

Novel Synthesis Route to Make Nanocrystalline Lead Zirconate Titanate Powder

The present research describes synthesis of perovskite lead zirconate titanate (PZT) nanocrystalline mesoporous powders from the aqueous solutions of Pb²⁺, Zr⁴⁺, and Ti⁴⁺ metal ions using sucrose as a template material. Sucrose retains the metal ions in solution through complex formation. Dehydration and thermal decomposition of the metal ion–sucrose mass produces a large amount of gas, which helps to create porosity and high surface area in the final products. The particle size of the synthesized powder is between 50 and 60 nm, with a average specific surface area between 20 and 25 m²/g. The surface area increases as the amount of sucrose increases. Nanocrystalline PZT powder with high surface area can be useful for low-temperature sintering.     

Formation of Lead Zirconate Titanate Powders by Spray Pyrolysis

Twin-fluid atomization spray pyrolysis (SP) has been investigated for the production of lead zirconate titanate (PZT) powders, using aqueous solutions of lead acetate and zirconium and titanium alkoxide precursor reagents. The particle size distribution of the PZT powder showed a d ₅₀ value of 0.3 μm, but with a small fraction of relatively large particles, several micrometers in size. Most particles were spherical but many of the largest particles, in the size range ca. 1–5 μm, were irregular. It was demonstrated that the morphology of the final PZT powder was controlled by decomposition processes occurring during the initial drying stages, at ≤200°C. A pyrochlore or fluorite-type intermediate crystalline phase was present in the final powders, but when the maximum reactor temperature was raised, and/or when the levels of excess lead in the starting solutions were increased, the proportion of the desired perovskite phase increased. However, at the highest process temperatures studied, ∼900°C, small crystallites of another phase formed on the surface of the PZT particles; these were probably lead oxide carbonate particles. Overall, a starting solution composition containing around 5 mol% excess Pb, and a maximum reactor temperature of 800°C, were selected as offering the most suitable conditions for producing PZT (52/48) powder, with minimal secondary phases(s). Preliminary densification studies showed that the powders could be sintered at 1150°–1200°C to give pellets of 95%–96% theoretical density.     

Structural and Property Evolution of Aqueous-Based Lead Zirconate Titanate Tape-Cast Layers

We have developed aqueous suspensions of lead zirconate titanate (PZT) and an acrylic latex emulsion binder for tape casting. Rheological measurements were conducted to optimize their flow behavior at high solids volume fraction (φ_solids). Concentrated suspensions (φ_solids > 0.45) were tape cast onto a silicone-coated mylar carrier film, and the effect of cellulose (a viscosifier) and surfactant additions on wetting behavior was studied. Drying stress measurements were performed on tape-cast layers using a substrate deflection technique. The initial period of stress rise was analogous to that observed for binder-free ceramic films, whereas the stress decay was influenced by latex coalescence. Tape-cast layers exhibited a constant PZT volume fraction of 0.49 and uniform binder distribution independent of the PZT/latex volume ratio. The dielectric and piezoelectric properties of sintered multilayer samples were comparable to those obtained for bulk, isopressed samples. Our work provides guidelines for developing aqueous formulations for tape casting complex electroceramic oxide layers.     

Lead Zirconate Titanate Thin Films by Aerosol Plasma Deposition: Microstructure Analysis

Lead zirconate titanate (Pb(Zr,Ti)O₃, PZT) thin films were grown on silicon 〈100〉 substrate by aerosol plasma deposition (APD) using solid-state-reacted powder containing donor oxide Nb₂O₅ when keeping the substrate at room temperature and 200°C. Crystalline phases of the deposited films have been analyzed via X-ray diffractometry (XRD), and microstructure via scanning and transmission electron microscopy (SEM and TEM). Cross-sectional TEM revealed that the microstructure comprised several layers including the deposited PZT film and the platinum-electrode-and-titanium-buffered layers on SiO₂–Si substrate. The Pt-electrode layer contained (111)_Pt twinned columnar grains with a slight misorientation and forming low-angle grain boundaries among them. The PZT layer contained randomly oriented grains embedded in an amorphous matrix. Some of the PZT grains, oriented with the zone axis Z = [[Twomacr]11]_PZT parallel to Z = [111]_Pt, were grown epitaxially on the Pt layer by sharing the (111)_PZT plane with the (111)_Pt twinned columnar Pt crystals. However, the existence of such an orientation relationship was confined to several nanosize grains at and near the PZT-Pt interface, and no gross film texture has been developed. An amorphous grain boundary phase, generated by pressure-induced amorphisation (PIA) in the solid state, was identified by high-resolution imaging. Its presence is taken to account for the densification of the PZT thin films via a sintering mechanism involving an amorphous phase on deposition at 25° and 200°C.     

Effect of Lead Zirconate Titanate Seeds on PtxPb Formation during the Pyrolysis of Lead Zirconate Titanate Thin Films

Lead zirconate titanate (PZT) thin films were prepared on platinized silicon substrates by dip-coating using a modified diol-based sol–gel route without and with up to 5 mol% PZT nanometric seeds dispersed in the precursor sol. A metastable intermetallic Pt _x Pb phase formed at the early stages of heat treatment. XRD, TEM, and RBS revealed that the thickness and stoichiometry of the Pt _x Pb layer varied with the concentration of seeds and heat treatment of the films. The relation of the Pt _x Pb layer to the final crystalline texture of the PZT thin films is reported and discussed.     

Sol–Gel Preparation of Lead Zirconate Titanate Powders and Ceramics: Effect of Alkoxide Stabilizers and Lead Precursors

Lead zirconate titanate (PZT) (52/48) powders were prepared by a sol–gel process, using different raw materials to introduce the lead component together with several solvents and chemical modifying agents. A study of the effect of these variables on crystallization behavior was conducted to determine the best conditions for preparing monophasic submicrometer-sized PZT perovskite powders in the morphotropic region. In the present work, well-crystallized, submicrometer-sized single-phase perovskite PZT powders were obtained after heat treatment at 600°C for 1 h. The dependence of this crystallization temperature on the preparation conditions was observed. The sol–gel-derived submicrometer-sized PZT powders were sintered to ∼96% of relative density after 2 h at 950°–970°C. The sintered ceramics exhibited a dielectric permittivity of 1000, a piezoelectric coefficient of 135 pC·N⁻¹, a remanent polarization of 20 μC·cm⁻², and a coercive field of 10.6 kV·cm⁻¹.     

Directed Colloidal Assembly of Linear and Annular Lead Zirconate Titanate Arrays

Lead zirconate titanate (PZT) arrays for ultrasonic sensing applications in the 2–30-MHz frequency range were fabricated by robocasting, a directed colloidal assembly technique. Both linear and annular arrays were produced by robotically depositing a concentrated PZT gel-based ink to create high-aspect-ratio PZT elements (thickness ∼ 130 μm and height ∼1–2 mm) of varying pitch (∼250–410 μm). The arrays were densified and infiltrated with an epoxy resin to fabricate PZT–polymer composites with 2–2 connectivity. Their dielectric and piezoelectric constants were measured and compared with values obtained for bulk PZT and those predicted theoretically.     

热压烧结对锆钛酸铅镧陶瓷电卡效应的影响

探讨热压烧结工艺对PLZT(锆钛酸铅镧)陶瓷材料介电击穿性能、饱和极化强度以及电卡性能的影响。通过X射线衍射和扫描电子显微镜,分析陶瓷样品的相组成和微观结构。结果表明,热压烧结法有助于控制陶瓷晶粒的生长,提高陶瓷的致密度并增大陶瓷的介电击穿场强,从而有效提高陶瓷的电卡性能以及电卡转换效率。在328 K(55℃)与478 K(205℃)附近,分别发生低温铁电三方相到高温铁电三方相的相变(FRL-FRH)以及高温铁电三方相到立方顺电相(FRH-Pc)的相变,展现了比较好的弛豫性,在室温下达到3.6 K的绝热温变与1.8×0-7(K·m)/V的电卡转换效率,具有良好的电卡性能。     

Lead Zirconate Titanate Particle Dispersion in Thick-Film Ink Formulations

Diverse device applications for lead zirconate titanate (PZT) ceramics in thick-film form are currently in active development. In the present study, the particle dispersion properties of thick-film ink formulations containing PZT powder have been determined using rheological measurements. Although all of the eight commercially available dispersants tested are more effective than the terpineol solvent alone in decreasing attractive interparticle forces in suspensions, the best dispersant identified for hard and soft PZT powders is a phosphate ester oligomer. This dispersant is extremely efficient, and its use in thick-film ink formulations results in viscosity decreases of 50% at low shear rates (10 s⁻¹) and 30% at high shear rates (100 s⁻¹) compared with current ink formulations containing no dispersant. The effects upon rheology of the order of addition of components in the processing of inks have been studied, with the most effective processing route using a fugitive solvent that probably facilitates uniform coverage of the particle surfaces by the dispersant molecules. Modeling of the rheological profiles of inks indicates that the use of a dispersant decreases the depth of the primary minimum in the interparticle potential by a factor of 3. Demonstrated advantages of the use of a dispersant in PZT thick-film inks include improved microstructural homogeneity in the green body and the ability to formulate printable inks with higher solids loadings. No adverse effects of the dispersant upon the dielectric and piezoelectric properties of bulk PZT samples are found following burnout and sintering.     

Synthesis of Lead Nickel Niobate–Lead Zirconate Titanate Solid Solutions by a B-site Precursor Method

A modified processing method for lead nickel niobate–lead zirconate titanate (Pb(Ni_1/3Nb_2/3)O₃–Pb(Zr,Ti)O₃, PNN–PZT) solid solutions is presented. This method is based on the high-temperature synthesis of a precursor that contains all the B-site cations (Ti, Zr, Ni, and Nb). This synthesis yields a diphasic mixture that contains a ZrTiO₄-like phase and a rutile-like phase. Both phases exhibit a cationic valence of 4; thus, it is concluded that the mixing of Ni and Nb cations is adequate for the preparation of PNN–PZT solid solutions. Indeed, a pure perovskite phase has been obtained after calcination with lead oxide for compositions that contain 40 and 50 mol% PNN. Moreover, their electromechanical properties have been shown to be superior to values reported for standard columbite routes. This conclusion has been interpreted in terms of enhanced chemical homogeneity.     

Fracture Mechanisms in Ferroelectric-Ferroelastic Lead Zirconate Titanate (Zr: Ti=0.54:0.46) Ceramics

Fracture toughness, K _IC, of a single-phase commercial lead zirconate titanate (PZT) ceramic (Zr/Ti=0.54/0.46) of tetragonal structure ( c/a =1.019) was measured using the single edge notched beam method above and below the Curie temperature. Domain switching (poling) under electrical and mechanical loading was examined using X-ray diffraction. Surface grinding, electrical poling, and mechanical poling caused crystallographic texture. Similar texture, indicative of domain switching, was also observed on fracture surfaces of some saples fractured at room temperature. At room temperature, the highest K _IC measured was 1.85 MPa·m^1/2, while above the Curie temperature it was about 1.0 MPa·m^1/2. Cracks emanating from Vickers indents in poled samples were different in the poling and the transverse directions. The difference in crack sizes is explained on the basis of domain switching during crack growth. These results indicate that ferroelastic domain switching (twinning) is a viable toughening mechanism in the PZT materials tested.     

Preparation of Lead Zirconate Titanate Thin Films Derived by Hybrid Processing: Sol-Gel Method and Laser Ablation

Thin films of Pb(Zr_0.52Ti_0.48)O₃ (PZT) were prepared by hybrid processing (sol-gel and excimer laser ablation) on Pt/Ti/SiO₂/Si substrates. Crystalline phases and microstructures of the PZT films were investigated by X-ray diffraction analysis and scanning electron microscopy, respectively. Electrical properties of the films were evaluated by measuring their P - E hysteresis loops and dielectric constants. The temperature of postdeposition annealing in hybrid processing was lower than that in the case of direct film deposition by laser ablation on a Pt/Ti/SiO₂/Si substrate. The preferred orientation of the films derived by hybrid processing could be controlled using the seeding layer deposited by the sol-gel process. The films fabricated by hybrid processing consisted of the perovskite phase with a (111) preferred orientation and had good ferroelectric properties.     

Crack-Growth-Velocity-Dependent R-Curve Behavior in Lead Zirconate Titanate

Crack-velocity ( v – K ) curves and crack-resistance ( R ) curves for unpoled ferroelectric and ferroelastic lead zirconate titanate (PZT) were determined for long cracks in compact-tension (CT) geometry using an in situ fracture device on the stage of an optical microscope. The steady-state crack length and the plateau value of R -curves measured at controlled constant velocities increased with increased velocity. The plateau value for 10⁻⁶ m/s was 1.2 MPa·m^1/2 after 1.3 mm of crack extension and for 10⁻⁴ m/s was 1.4 MPa·m^1/2 after 2.2 mm.     

Differences in Tensile and Bending Strength for Knoop-Cracked Lead Zirconate Titanate Specimens

The strength of piezoelectric ceramics differs greatly in tension and bending tests. This effect, which is known to occur for specimens with a natural flaw population, also occurs in tests that involve Knoop-cracked specimens. In such samples, the linear-elastically computed bending strength is ∼35% higher than the tensile strength. Computation of the actual stress distribution in the bending bars has shown that these differences are predominantly caused by the nonlinearity and nonsymmetry of the deformation behavior.     

Lead Zirconate Titanate Thin Films on Base-Metal Foils: An Approach for Embedded High-Permittivity Passive Components

An approach for embedding high-permittivity dielectric thin films into glass epoxy laminate packages has been developed. Lead lanthanum zirconate titanate (Pb_0.85La_0.15(Zr_0.52Ti_0.48)_0.96O₃, PLZT) thin films were prepared using chemical solution deposition on nickel-coated copper foils that were 50 μm thick. Sputter-deposited nickel top electrodes completed the all-base-metal capacitor stack. After high-temperature nitrogen-gas crystallization anneals, the PLZT composition showed no signs of reduction, whereas the base-metal foils remained flexible. The capacitance density was 300–400 nF/cm², and the loss tangent was 0.01–0.02 over a frequency range of 1–1000 kHz. These properties represent a potential improvement of 2–3 orders of magnitude over currently available embedded capacitor technologies for polymeric packages.