Microstructure of Lead-Magnesium Niobate Ceramics

Lead-magnesium niobate ceramics were processed with excess MgO and by precalcining MgO and Nb₂O₅. Transmission electron microscopy revealed sub-micrometer MgO inclusions in the perovskite phase. The pyrochlore phase exists as submicrometer rectangular crystals in an amorphous PbO matrix. The composition of the pyrochlore phase was calculated to be Pb_2.25Mg_0.27Nb_1.79O₇.     

Dielectric and Pyroelectric Properties of Cadmium Niobate Ceramics

The low-temperature dielectric and pyroelectric properties of pyrochlore Cd₂Nb₂O₇ ceramics have been investigated over the temperature range from 10 to 300 K. Dielectric data confirmed that two ferroelectric transitions occurred in the Cd₂Nb₂O₇ ceramics at temperatures near 80 and 192 K. The higher-temperature ferroelectric transition is complex, with evidence for three separate transitions occurring within a narrow temperature range. The temperature and frequency dependencies of the dielectric constant were consistent with both second-order (diffuse) and improper ferroelectric (ferroelastic) effects. Pyroelectric data also confirmed the multiple-transition behavior, with anomalies in the pyroelectric coefficient at temperatures corresponding to the onset of the diffuse ferroelectric transition and the ferroelastic effect. Dielectric loss data (analyzed by both Arrhenius and Cole-Cole formalisms) indicated the presence of three separate relaxation-type dielectric loss mechanisms in this temperature range. Unambiguous explanations for the observed dielectric and pyroelectric phenomena could not be made, but domain effects are believed to be responsible for at least part of the complex nature of the ferroelectric transitions in this material.     

Microstructure Development and Dielectric Properties of Potassium Strontium Niobate Ceramics

Sintering of a KSr₂Nb₅O₁₅ powder compact at 1350°C resulted in a duplex structure. Prefiring of the compact between 1200° and 1300°C inhibited the abnormal grain growth responsible for the duplex structure. The Curie temperature and dielectric constant were dependent on the microstructure.     

Piezoelectric and Dielectric Properties of Ceramics in the System Potassium—Sodium Niobate

High radial coupling coefficients are observed for compositions having up to 50 mole % sodium niobate additions to potassium niobate. The activity diminishes with additional sodium niobate content and disappears beyond about 98 mole % additions. Dielectric constants are relatively low, varying from 450 to 125, depending on composition. A.-c. losses are high and d.-c. resistivities are ∼10¹²ohm-cm. The low dielectric constants and high coupling obtained in certain regions of the system make these materials promising for solid ultrasonic delay line use, especially where thin sectioned plates are required, as in high-frequency thickness extensional or thickness shear mode transducers.     

Synthesis and Dielectric Characterization of Potassium Niobate Tantalate Ceramics

The preparation and dielectric properties of potassium niobate tantalate (KTN) have been investigated with the aim of exploring the material's potential for ferroelectric tunable applications. The samples were prepared both by conventional sintering in air and by uniaxial hot pressing. A relative average density greater than 92% was obtained with both methods. An inhomogeneous Nb/Ta distribution was found in the samples prepared by both methods, but the inhomogeneity extent was lower in the hot-pressed samples. While both sintering processes resulted in ceramics of lower transition temperatures in comparison with the reported results on single crystals, a relative up shift of the temperature ( T _max) at which the dielectric constant is maximum was found for hot-pressed samples compared with that of samples sintered in air. All the samples exhibited strong frequency dispersion in dielectric properties. The effect of DC bias at room temperature was measured and modeled using the Landau–Devonshire model. It was found that the nonlinear coefficient β of KTN, which is important for tunable applications, is comparable with the value reported on KNbO₃ and SrTiO₃ single crystals. A dielectric tunability of 16% and 42% at room temperature was demonstrated under 20 kV/cm for the sintered and hot-pressed ceramics, respectively. The loss tangent, low at megahertz frequencies, was augmented to 9%–17% at low gigahertz frequencies. This is believed to be related to the frequency dispersion observed in the ceramics because of charged defects.     

Dielectric, Piezoelectric, and Pyroelectric Properties of Lead Zirconate—Lead Zinc Niobate Ceramics

New piezoelectric and pyroelectric ceramics consisting of antiferroelectric lead zirconate (PZ) and relaxor ferroelectric lead zinc niobate (PZN) are studied from an application view-point of the field-induced antiferroelectric-to-ferroelectric phase transition. An antiferroelectric-ferroelectric phase boundary exists in PbZr_x(Zn_1/3Nb_2/3)_1−xO₃ (PZZN-1000x) close to x = 0.93 to 0.94 at room temperature. A new ferroelectric rhombohedral phase change, F_α–F'_α, at low temperature is found and studied by the temperature dependence of the pyroelectric coefficient. Electrical poling in these ceramics is easy, and the coercive field E_c∼8 to kV/cm is rather low. Samples with compositions in the range PZZN-86 to PZZN-92 have a large electromechanical coupling constant, k (k_t and k₁₅∼50% to 60%), and a low dielectric constant, ɛ_s (ɛ^T₃₃/ɛ₀= 260 to 320, ɛ^T₁₁/ɛ₀= 380). PZZN ceramics appear to be potential candidates for high-frequency ultrasonic transducers used in the thickness shear mode. The pyroelectric figure of merit (F_v) of these ceramics is comparable to the values published for the PZT-based or PbTiO₃-based materials.     

Effect of Powder Purity and Second Phases on the Dielectric Properties of Lead Magnesium Niobate Ceramics

The dielectric properties of lead magnesium niobate ceramics have been studied as a function of powder purity and microstructure. Starting powder purity was shown to have d pronounced effect on the resultant dielectric properties. Values of K_max as high as 20 000 were obtained using starting powders of exceptionally high purity (99.999%), despite the formation of a pyrochlore phase. The pyrochlore phase formed as large isolated grains in the microstructure. It was found to be a cubic-type pyrochlore with a composition of Pb₂Nb_1.75Mg_0.25O_6.62. Much lower dielectric constants were obtained with samples of lower reagent-grade purity. This was partially explained by the presence of an intergranular second phase. Other factors such as lattice impurities and grain-boundary chemistry were also argued to be important.     

Microstructure and Dielectric Properties of Barium Strontium Magnesium Niobate

Dielectric properties and their related microstructural characteristics in solid solutions of (1 – x )Ba(Mg_1/3Nb_2/3)O₃– x Sr(Mg_1/3Nb_2/3)O₃ (BMN–SMN, or BSMN) were investigated by measuring the relative permittivity (ɛ_r), Q values, and temperature coefficient of resonator frequency (τ_f), and by observing microstructure using transmission electron microscopy. When the tolerance factor ( t ) was >0.99 in BSMN with composition 0 < x < 0.5, where the tilting of oxygen octahedra was not involved, the microstructure included only 1:2 ordered phase. In the region where 0.99 > t > 0.97 with 0.7 < x < 1.0, the phase due to the antiphase tilting of oxygen octahedral, the disordered phase, and the 1:2 ordered phase were also present. In a few of the grains, core–shell-type structures, whose main components were dislocations and stacking faults, were found in the solid solution of BSMN.     

Effects of Barium Substitution on Perovskite Formation, Dielectric Properties, and Diffuseness Characteristics of Lead Zinc Niobate Ceramics

Perovskite-phase developments in partially/fully substituted (Ba,Pb)(Zn_1/3Nb_2/3)O₃, synthesized via B-site precursor routes, were investigated. The pyrochlore structure, present at no barium content, was immediately replaced by perovskite with a small amount (≥8 at.%) of barium substitution. Variations in the lattice parameters of the pyrochlore and perovskite structures were studied. The weak-field radio-frequency dielectric constants and losses of the system ceramics were examined. A highest maximum dielectric constant of 9000 (76°C, 1 MHz) was observed at 8 at.% barium substitution. The dielectric-constant spectra were analyzed further in terms of diffuseness characteristics (e.g., diffuseness exponent and degree of diffuseness). The dielectric hysteresis loops of the ceramics were measured. The microstructures of the sintered ceramics also were observed.     

Processing and Properties of Strontium Bismuth Vanadate Niobate Ferroelectric Ceramics

The processing conditions, microstructure, and dielectric properties of strontium bismuth niobate vanadate ceramics, SrBi₂(V _x Nb_{1− x} )₂O₉ (SBVN, with 0 ≤ x ≤ 0.3), were systematically studied. A relative density of >90% was obtained for all the samples using a two-step sintering process. XRD showed that a single phase with the layered perovskite structure of SrBi₂Nb₂O₉ (SBN) was formed with a vanadium content of up to 30 at.%. SEM revealed that the average grain size decreased gradually with an increase in vanadium content. The Curie point was found to gradually increase from ∼418°C for SBN to ∼459°C for SBVN with 30 at.% vanadium. Dielectric constants at room temperature and their respective Curie points were found to peak at a composition with 10–15 at.%; vanadium. Moreover, a high concentration of vanadium (>5 at.%) resulted in a significant increase in tangent loss at low frequencies (<1000 Hz). The relationships between chemical composition, processing condition, microstructure, and dielectric properties of SBVN ferroelectric ceramics are discussed.     

Influence of Copper(II) Oxide Additions to Zinc Niobate Microwave Ceramics on Sintering Temperature and Dielectric Properties

The effect of CuO additions on the firing temperature of ZnNb₂O₆ ceramics was investigated using dilatometry, transmission electron microscopy, and X-ray diffractometry. A 5 wt% CuO addition to ZnNb₂O₆ ceramics significantly lowered the firing temperature from 1150° to ∼900°C. The presence of a CuO-rich intergranular phase in the specimen was observed and was evidence of the formation of a liquid phase during sintering. The composition of the liquid phase was (ZnCu₂)Nb₂O₈. In particular, the low-fired ZnNb₂O₆ ceramics had good microwave dielectric characteristics— Q × f = 59 500, ɛ_r= 22.1, τ_f=–66 ppm/^oC. These properties were correlated with the formation of a second phase, (ZnCu₂)Nb₂O₈.     

Properties of Sodium-Lithium Niobate Solid Solution Ceramics with Small Lithium Concentrations

The structural, dielectric, and piezoelectric properties of the solid solution (Na_1-x,Li_x,)NbO₂ were studied. Solid solution ceramics with x values up to 0.14 occur as a single phase. The phase diagram from 0° to 600°C is given. The low-temperature phase has a perovskite pseudo-monoclinic structure and inverts to a pseudotetragonal structure at a temperature that decreases with increasing x. The high-temperature phase is pseudocubic, and the minimum transition temperature from the pseudotetragonal to the pseudocubic structure is 350° C near x = 0.04. Anomalies in the dielectric constant vs. temperature curve agree well with the transition temperatures, although no anomaly was observed at the temperature of transition from the pseudotetragonal to the pseudocubic phase when x was less than 0.06. Lithium ions in the system facilitate the transformation from the antiferro-electric to the ferroelectric state produced by applying an electric field. A new ferroelectric phase becomes stable when x is greater than 0.07. Poled ferroelectric specimens had a planar coupling coefficient of 0.232, a dielectric constant of 220, and a frequency constant of 3352 kc-mm. The piezoelectric properties disappear not at the transition temperature but at the temperature at which strain exhibits an anomaly when x is greater than 0.07. A perovskite phase with a pseudorhombohedral subcell exists as an intermediate phase for x greater than 0.10, the exact value depending on the preparation method. The phase can be easily converted to pseudomonoclinic when the ceramic is fired at 1180° to 1220°C.     

Dielectric Properties of Lead Magnesium Niobate and Lead Iron Niobate Prepared by the Semiwet Hydroxide Route

Lead magnesium niobate (PMN) and lead iron niobate (PFN) were prepared by the semiwet hydroxide route, and their dielectric properties were measured in temperature ranges around their peak dielectric constants. The dielectric constant of PFN was much larger as compared with that of PMN sintered at the same temperature. The dielectric properties of PMN and PFN are compared and explained on the basis of their structure development.     

Microwave Dielectric Properties of Gallium-Doped Hexagonal Barium Titanate Ceramics

High-permittivity and low-loss ceramics with composition BaTi_0.92Ga_0.08O_2.96 have been prepared in the BaO–Ga₂O₃–TiO₂ system using the mixed-oxide route. This compound forms as the hexagonal polymorph (6 H ) of BaTiO₃ with the space group P 6₃/ mmc . The dielectric properties of dense ceramics have been studied, at microwave frequencies, with the ceramics fired at 1450°C under flowing oxygen gas; the results are a relative permittivity, ɛ_r, of ∼74 and a quality factor, Q · f _r, of ∼7815 at 5.5 GHz. The quality factor is strongly influenced by the sintering conditions (temperature and atmosphere), whereas the relative permittivity is not influenced significantly by ceramic processing for pellets ≥93% of the theoretical X-ray density. To our knowledge, this is the first report of microwave dielectric resonance in a perovskite-type BaTiO₃-based ceramic.     

Ceramic and Dielectric Properties of Lead Metaniobate Electrical Ceramics

The effect of firing temperature and time on the weight loss, fired porosity, and dielectric properties of lead metaniobate was investigated. The amount of lead oxide lost was found to be a linear function of firing time and in addition increased rapidly as the firing temperature was increased. Specimens fired for 30 minutes at temperatures below 1275°C. had weight losses of less than 1% based on the amount of available PbO present, whereas specimens fired for the same length of time at temperatures greater than 1275°C. had weight losses up to 3.5%. Both a minimum and a maximum point were found in the fired porosity curve of lead metaniobate in the temperature range 1200° to 1350°C. When firing for 30 minutes, the minimum point occurred at about 1225°C. with a porosity value of 8% and the maximum point at 1300°C. with a porosity of 18%. The effect of porosity and weight loss on the dielectric properties of lead metaniobate is presented. The effect of replacing up to 0.7 mole fraction of the lead ion in lead metaniobate by cadmium was investigated. Cadmium additions lowered the Curie temperature and diluted the ferroelectric properties of lead metaniobate.     

Dielectric and Electromechanical Properties of Chemically Modified PMN-PT-BT Ceramics

A particulate coating process incorporating small amounts of several additives such as titanium, zinc, barium, strontium and iron was used to modify the composition and resultant dielectric and electromechanical properties of a commercially available 0.96(0.91Pb(Mg_1/3Nb_2/3)O₃·0.09PbTiO₃)·0.04BaTiO₃. This method led to intimate mixing of the additives at the nanoscale without an additional ball-mixing process. Low- and high-field characteristics including dielectric properties, induced strain and polarization, and associated hystereses were evaluated for the samples sintered at 1200°C for 4 h. All properties were found to depend on the chemical additives and temperature. Specifically, the addition of small quantities of titanium and barium tended to increase strain and Q _eff while maintaining a low dielectric constant which is a promising result for room temperature transducer applications. The addition of titanium with zinc or iron raised dielectric constant, strain, and polarization with significant increases in the temperature of maximum permittivity. On the other hand, the electromechanical properties of the samples containing barium or zinc with titanium did not exhibit a transition to piezoelectric behavior at the temperature expected from the dielectric measurements.     

Relationships between Sintering Conditions,Microstructure and Dielectric Properties of Lead Iron Niobate

Lead iron niobate, Pb(Fe_1/2Nb_1/2)O₃ (PFN) ceramics have been produced by sintering PFN powders synthesized from lead oxide (PbO) and iron niobate (FeNbO₄), with an effective method developed for minimising the level of PbO loss during sintering. Attention has been focused on relationships between sintering conditions, phase formation, density, microstructural development and dielectric properties. The sintering temperature has been found to have a pronounced effect on the density, grain growth and dielectric properties of the sintered PFN ceramics, with maximum density and relative permittivity values obtained under sintering conditions of 1175°C for 2 h. The origin of the strong dependence of values of ε_r and tan δ on frequency is discussed. ©