Effects of La2O3 Addition and PbO Excess on the Transmittance of PbZrO3–PbTiO3–Pb(Zn1/3Nb2/3)O3 Ceramics by Spark Plasma Sintering

The effects of La₂O₃ addition and PbO excess on the microstructures and optical properties of PbZrO₃–PbTiO₃–Pb(Zn_1/3Nb_2/3)O₃ (PZ–PT–PZN) ceramics prepared by spark plasma sintering were investigated. When 1 mol% La₂O₃ was added, the highest transmittance of 35% at 700 nm for PZ–PT–PZN ceramics was obtained. The improved transmittance was attributed to the increased relative density and the decreased optical anisotropy. The samples containing more than 1 mol% La₂O₃ showed decreased transmittance, due to the appearance of secondary phases. The transmittance of PZ–PT–PZN ceramics increased slightly to 29% at 700 nm with increasing amount of excess PbO up to 10 mol% and thereafter decreased rapidly.     

Mechanosynthesis and Thermal Stability of Piezoelectric Perovskite 0.92Pb(Zn1/3Nb2/3)O3–0.08PbTiO3 Powders

The mechanosynthesis of piezoelectric perovskite 0.92Pb(Zn_1/3Nb_2/3)O₃–0.08PbTiO₃ (PZN–PT) by direct mechanochemical activation of the constituent oxides has been studied by X-ray diffraction (XRD) and transmission electron microscopy (TEM). This and the PbO flux method are the only two procedures that have succeeded in synthesizing this phase, which has recently been shown to present very high electromechanical response. The thermal stability of the single perovskite phase powders has been studied by differential thermal analysis/thermogravimetry and by high-temperature XRD as a function of mechanical activation time and pressure. The phase was found to transform into a pyrochlore type structure at temperatures above 400°C. The transformation presented a significant time dependence, and it was slowed down by increasing mechanical activation time and by the application of pressures by hot pressing. Sintering experiments were accomplished and 85% density, 77% perovskite-phase ceramics were obtained after heating at 1000°C for 1 h. Hot pressing at this temperature failed to increase the percentage of perovskite phase. Results are discussed, and procedures for obtaining dense single-phase PZN–PT-based ceramics with ultrahigh piezoelectricity are proposed.     

Effects of Sintering Atmosphere on Densification Behavior and Piezoelectric Properties of Pb(Ni1/3Nb2/3)O3–PbZrO3 Ceramics

Densification of polycrystalline Pb(Ni_1/3Nb_2/3)O₃–PbTiO₃–PbZrO₃ (PNN–PT–PZ) specimens was enhanced as the partial pressure of O₂ in the sintering atmosphere was increased. This observation was attributed to the increase in the internal pressure of a closed pore due to the thermal decomposition of PbO at a low partial pressure of O₂. The relative dielectric permittivity (ε_r), d ₃₃, k _p, and grain size of sintered specimens were also increased as the partial pressure of O₂ in the sintering atmosphere was increased. The observed dependence of piezoelectric properties on the partial pressure of O₂ was discussed in terms of the enhanced formation of the A-site vacancy ( V "_Pb) or the suppression of the B-site defect ( V ¨_O) as the oxygen potential increased.     

Dielectric Properties of Ceramics in Ba (Co1/3 Nb2/3)O3–Ba(Zn1/3Nb2/3)O3 Solid Solution

The dielectric properties of the Ba (Co_1/3 Nb_2/3)O₃–Ba(Zn_1/3Nb_2/3)O₃ system were determined. Ba (Co_1/3 Nb_2/3)O₃–Ba(Zn_1/3Nb_2/3)O₃ has a complex perovskite structure, a high dielectric constant, a low dielectric loss, and a low temperature coefficient of the resonant frequency. A solid-solution ceramic with 0.7Ba (Co_1/3 Nb_2/3)O₃·0.3 Ba(Zn_1/3Nb_2/3)O₃ has a dielectric constant of K=33.5, Q=11000 at 6.5 GHz, and a temperature coefficient of the resonant frequency of τ_f=0 ppm/°C. The temperature coefficient of resonant frequency can be varied by changing the composition. The Q values of the ceramics can be increased by annealing in a nitrogen atmosphere. These ceramics can be used for resonant elements and stabilized oscillators.     

Processing and Electrical Properties in Lead-Based (Pb(Mg1/3Nb2/3)O3, Pb(Yb1/2Nb1/2)O3, PbTiO3) Systems

Lead-based ferroelectric (FE) ceramics exhibit superior electromechanical properties; therefore, there has been an increased focus on developing new lead-based FE materials with high Curie temperature ( T _c) and enhanced properties. The aim of this study was to investigate new compositions in the Pb(Mg_1/3Nb_2/3)O₃–Pb(Yb_1/2Nb_1/2)O₃–PbTiO₃ ( PMN–PYbN–PT) system to enhance the electromechanical properties while increasing the T _c and lowering the sintering temperature. The 0.575[0.5PMN–0.5PYbN]–0.425PT composition at PMN/PYbN (50/50) mole ratio were prepared by reactive sintering PMNT and PYbNT powder mixtures at 950°–1200°C for 4 h. PMNT and PYbNT powders were calcined via the columbite method. Samples were prepared by cold isostatic pressing at 80 MPa. Dense and fully perovskite 0.575[0.5PMN–0.5PYbN]–0.425PT ceramics were fabricated at 975°C for 4 h, and these samples displayed a remnant polarization ( P _r) of 32 μ C/cm², coercive field ( E _c) of 17 kV/cm, and a piezoelectric charge coefficient ( d ₃₃) of 475 pC/N. It is proposed that this ternary system can be tailored for various applications.     

Perovskite Formation and Dielectric Characteristics of Pb(Zn1/3Ta2/3)O3 with PbTiO3 Substitution

Perovskite developments in the Pb(Zn_1/3Ta_2/3)O₃–PbTiO₃ system were explored. Formation yields and lattice parameters of the perovskite were determined from X-ray diffractometry results. Weak-field low-frequency dielectric properties of the system ceramics were investigated, followed by microstructure examination. Perovskite started to develop in Pb(Zn_1/3Ta_2/3)O₃ after the introduction of 30 mol% PbTiO₃, whereas complete stabilization was accomplished at 60% substitution. Dielectric relaxation behavior was not substantial across the entire composition range, whereas phase transition modes changed from diffuse to sharp with increased PbTiO₃ fraction.     

Synthesis of 0.4Pb(Mg1/3Nb2/3)O3–0.3Pb(Mg1/2W1/2)O3–0.3PbTiO3 Ceramics by Metal Alkoxide Method, and Its Dielectric Properties

0.4Pb(Mg_1/3Nb_2/3)O₃–0.3Pb(Mg_1/2W_1/2)O₃–0.3PbTiO₃+ x MgO ( x = 0 to 0.04) were prepared by a metal alkoxide method. The percent of perovskite phase of the calcined powders increased with increased calcination temperatures. About 89% of perovskite phase was obtained at 1050°C. The dielectric constant of the pellets fired at 1100°C was increased by the addition of 10 wt% excess Mg(OC₂H₅)₂ and had a maximum value of 7532 at 1 kHz.     

Ferroelectric 90° Domain Evaluation in Tetragonal Pb(Mg1/3Nb2/3)O3–PbTiO3 Ceramics

The domain structure of ferroelectrics changes during poling has a direct influence on the macroscopic properties of the materials. The intensity variation of the different X-ray diffraction (XRD) pattern profiles was used to identify the percentage of 90° domain reorientation in the tetragonal phase of Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PMN–PT) ceramics after poling. The results are consistent with the change of piezoelectric properties. In addition, by using XRD patterns, a spatial distribution of polarization in a well-poled 0.62PMN–0.38PT ceramics has been determined and was found to be best described by the Cauchy function W _00l (φ)=1/(1+0.023φ²).     

Electromechanical Properties of Some Pb (Mg1/3Nb2/3–PbTiO3–(Ba,Sr)TiO3 Ceramics: I

Compositional variation within the Pb(Mg_1/3Nb_2/3) O₃–PbTiO₃–(Ba, Sr)TiO₃ (hereafter PMN–PT–BT,ST) ternary (6.4% PT% 14.1%, 1.25% BT,ST% 2.5%) results in major changes in induced strain and hysteresis. For the 1.25% BT family, the increase in strain correlates with an increase in T _max, while the dielectric loss is uncorrelated with hysteresis and strain. In addition, weak field aging (which is not reset by application of field) shows little effect on strain and hysteresis for drive fields of > 0.2 MV/m. The vary narrow polarization-fields loops (virgin curvesnearly indistinguishable from subsequent cycles) show that weak-field permittivity is a good approximation to the high-field permittivity. is a good approximation to the high-field Permittivity. Although these data clarify the frequency ( T _max is linearly dependent on the logarithm of the frequency) effect on weak-field dielectric behavior, they do not directly address the question of meaningful extrapolation of high-field strain with frequency. In particular, the question remains as to whether the high-field permittivity and strain are frequency dependent. In future papers we will address this question by a combination of measurement techniques as functions of frequency.     

Electromechanical Properties of Pb(Yb1/2Nb1/2)O3-PbZrO3-PbTiO3 Ceramics

The electromechanical and electric-field-induced strain properties of x Pb(Yb_1/2Nb_1/2)O₃· y PbZrO₃·(1− x − y )PbTiO₃ ( x = 0.12, 0.25, 0.37; y = 0.10–0.40) ceramics have been studied systematically as a function of Pb(Yb_1/2Nb_1/2)O₃ (PYN) content and PbZrO₃/PbTiO₃ (PZ/PT) ratio. In addition, the effect of MnO₂ on the electromechanical properties of 0.12Pb(Yb_1/2Nb_1/2)O₃·0.40PbZrO₃·0.48PbTiO₃ was also investigated. The maximum transverse strain values of 1.6 × 10⁻³ for x = 0.12, 1.45 × 10⁻³ for x = 0.25, and 1.36 × 10⁻³ for x = 0.37 were obtained at the compositions which were regarded as the morphotropic phase boundary (MPB). The transverse strain was maximized at the MPB composition. The value of the maximum electromechanical coupling coefficient was 0.69 for y = 0.40 and x = 0.12 composition. In the 0.12Pb(Yb_1/2Nb_1/2)O₃·0.40PbZrO₃·0.48PbTiO₃ composition, the temperature of the maximum dielectric constant decreased and the grain size increased with an addition of MnO₂. The electromechanical coupling coefficient decreased while the mechanical quality factor rapidly increased with an addition of MnO₂. These resulted mainly from the acceptor effect of manganese ions that were produced by doping MnO₂ into the perovskite structure.     

Single-Calcination Synthesis Mechanism of Pure-Perovskite Pb(Ni1/3Nb2/3)O3-PbTiO3 Using a Coating Method

Pure-perovskite 0.64Pb(Ni_1/3Nb_2/3)O₃–0.36PbTiO₃ (PNN–PT) powder has been successfully synthesized by only one-step calcination using a coating method. SEM photograph shows that PNN–PT powder with the size of 2–4 μm is cubic and well dispersed. Based on X-ray diffraction analysis, solid-state reactions in the process of calcination in PbO–Nb₂O₅–TiO₂–NiO system are investigated. In comparison with conventional solid state method, the single-calcination synthesis mechanism of pyrochlore-free lead-based niobate ferroelectrics using a coating method is tentatively proposed. A typical coating structure of Ni precipitate-coated Nb₂O₅ powder facilitates the formation of perovskite PNN–PT phase at a relatively low calcination temperature, resulting in the successful synthesis of pyrochlore-free PNN–PT powder in one-step calcination at 900°C.     

Preparation of Dense Lead Magnesium Niobate–Lead Titanate (Pb(Mg1/3Nb2/3)O3–PbTiO3) Ceramics by Spark Plasma Sintering

The effect of spark plasma sintering (SPS) on the densification behavior of Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ ceramics has been investigated. Specimens with a density of >99% of the theoretical density (TD) were obtained using SPS treatment at 900°C. Through normal sintering at 1200°C, however, the density of the specimen was only ∼92% of TD.     

Preparation and Characterization of Relaxor Ferroelectric 0.65Pb(Mg1/3Nb2/3)O3–0.35PbTiO3 by a Polymerizable Complex Method

A modified polymerizable complex (PC) method for the preparation of the relaxor ferroelectric 0.65Pb(Mg_1/3Nb_2/3)O₃–0.35PbTiO₃ (PMN–PT) ceramics has been developed using a novel water-soluble Nb precursor. The effects of Pb content and sintering temperature on the structure, morphology, composition, and electrical properties of PMN–PT powders and ceramics were investigated systematically. It was found that the modified PC method could effectively reduce the initial crystallization temperature of the perovskite phase to 500°C. For PMN–PT samples with 15% excess Pb content sintered at 600°C for 2 h, the 87% perovskite phase can be achieved, which is much higher than that in conventional solid-state reactions and other solution-based methods at the same temperature. On further increasing the sintering temperature to 1100°C, the perovskite phase content basically remains constant. This is attributed to the Pb-deficient pyrochlore phase formation. On increasing the sintering temperature to 1250°C, the dielectric constant and remnant polarization of PMN–PT ceramics significantly improved due to the larger grain sizes, enhanced density, and the decreasing pyrochlore phase. PMN–PT ceramics with a 98.5% content of the perovskite phase have been fabricated at 1250°C. It displays typical ferroelectric relaxor characteristics with a remnant polarization of 18 μC/cm², a coercive field of 9.6 kV/cm, a piezoelectric coefficient of d ₃₃=360 pC/N, and room-temperature and maximum dielectric constants of 3600 and 10 500 at 1 kHz, respectively.     

Pb(Zn1/3Ta2/3)O3–PbTiO3 Derived from Mechanical Activation

Nanocrystalline Pb(Zn_1/3Ta_2/3)O₃ (PZTa) of perovskite structure, which cannot be synthesized by either the conventional solid-state reaction of mixed oxides or wet chemistry routes, has been successfully synthesized via a mechanical activation route. The effects of PbTiO₃ (PT) doping in PZTa on the phase formation, thermal stability of the nanocrystalline perovskite phase, and dielectric properties of the resulting PZTa–PT are studied. PZTa doped with a low PT content exhibited a diffuse phase transition, while those with high PT contents demonstrated an expected sharp phase transition at the Curie temperature.     

Preparation of 0.7Pb(Mg1/3Nb2/3)O3–0.3PbTiO3 Thin Films Via a Polyvinylpyrrolidone-Assisted Aqueous Sol–Gel Process and Dielectric Properties

Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PMN–PT) thin films were prepared by spin coating using aqueous solutions of metal salts containing polyvinylpyrrolidone, where niobium oxide layers and lead—magnesium–titanium oxide layers were laminated on Pt(111)/TiO _x /SiO₂/Si(100) substrates and fired at 750° or 800°C. 250 ± 20 nm thick 0.7PMN–0.3PT thin films of a single-phase perovskite could be prepared, and the film fired at 750°C had dielectric constants and dielectric loss of 1900 ± 350 and 0.13 ± 0.03, respectively, exhibiting polarization-electric field hysteresis with a remanent polarization of 5.1 μC/cm² and a coercive field of 21 kV/cm.     

Domain Structure in Excess-WO3 Lead Complex Perovskite

Ferroelectric domain structures in the polycrystalline ternary system Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃–Pb(Mg_1/2W_1/2)O₃ were investigated with regard to excess-WO₃ addition. Core–shell domain structures were observed in the 2 wt% excess-WO₃ specimens. Above 3 wt% excess-WO₃ addition, the ferroelectric fringe pattern disappeared at the center of the grain, and ringlike domain structures were observed. This tendency became distinct in 5 wt% excess-WO₃ addition, and clear, ringlike domain structures were observed. The structures that consisted of fringe shell parts and non-fringe core parts were reversals of normal core–shell structures.     

Microstructures and Pyroelectric Properties of Multicomposition 0.9PbZrO3·xPbTiO3·(0.1−x)Pb(Zn1/3Nb2/3)O3 Ceramics

The microstructures and pyroelectric properties of multicomposition 0.9PbZrO₃· x PbTiO₃·(0.1− x )Pb(Zn_1/3Nb_2/3)O₃ (PZ–PT–PZN) ceramics were investigated. The PZ–PT–PZN ceramics with nearly theoretical density were prepared by spark plasma sintering at low temperature (800°C) for a very short time (10 min) from two original compositions with x = 0.025 and x = 0.050. The heat treatment was successfully used to control the diffusion between the different compositions in such ceramics. For ceramics heat-treated at 900°C, two pyroelectric peaks corresponding to the original compositions were observed. When the heat-treatment temperature was increased to 1200°C, these two pyroelectric peaks combined into one sharp pyroelectric peak, which corresponds to average composition. When the spark-plasma-sintered ceramics were heat-treated at 950°C, a high and stable pyroelectric coefficient (>100 nC·cm⁻²·K⁻¹) over a wide temperature range (23°–47°C) was obtained. It was found that the pyroelectric properties strongly depended on the microstructures.     

Perovskite Phase Formation in the Relaxor System [Pb(Fe1/2Nb1/2)O3]1-x–[Pb(Zn1/3Nb2/3)O3]x

Phase formation and dielectric properties of the compositions in the system [Pb(Fe_1/2Nb_1/2)O₃]₁_ _x –[Pb(Zn_1/3Nb_2/3)O₃] _x were investigated as possible materials for multilayer ceramic capacitors. The formation of the phase with perovskite structure and dielectric properties of ceramics at room temperature in the entire composition range are presented. The undesirable pyrochlore phase can be suppressed up to x = 0.6 by adopting calcination of B-site oxides, followed by reaction with PbO. Compositions in the single-phase range can be sintered at less than 1000°C.     

Dielectric and Electrostrictive Properties of Ferroelectric Relaxors in the System Pb(Mg1/3Nb2/3)O3:PbTiO3: Ba(Zn1/3Nb2/3)O3

Ceramic dielectrics which have been fabricated in the Pb(Mg_1/3 Nb_2/3)O₃:PbTiO₃:Ba(Zn_1/3Nb_2/3)O₃ composition system are shown to exhibit two distinct dielectric maxima, both of which show the characteristic loss spectra of ferroelectrics with diffuse phase transitions. The height of the individual maxima can be controlled by the Zn:Mg ratio in the starting material and, in suitably chosen compositions, a wide range of almost temperature-independent high dielectric permittivity is possible. These dielectrics show strong electrostrictive deformations under high electric fields but the electrostrictive strain is much less temperature-sensitive than in other relaxors.