Preparation of Small-Grained and Large-Grained Ceramics from Nb-Doped BaTiO3

Barium titanate powders with average grain sizes of 0.07 and 0.65 μm were coated with an organic Nb ester, using a liquid-solid mixing process. Small-grained (1 to 3 μm) ceramic dielectrics from both powders and large-grained (>50 μm) dielectrics from the 0.65 μm powder were fired using 0 to 2 at.% Nb. Microstructures, densities, and electrical resistivities were investigated.     

Preparation, Processing, and Characterization of Nano-Crystalline BaTiO3 Powders and Ceramics Derived from Microemulsion-Mediated Synthesis

Monodisperse and nanocrystalline BaTiO₃ powders of different stoichiometries were synthesized through the hydrolytic decomposition of mixed metal alkoxide solutions with water-in-oil microemulsions as reaction media. The method allows a tailor-made preparation of powder particles as small as 10 nm in average. Characterization with respect to purity, morphology, and behavior upon annealing was conducted in order to determine appropriate processing conditions for the preparation of pure, dense nanocrystalline ceramics. As a result, ceramics with a mean grain size as small as 35 nm were achieved. Raman spectroscopy revealed for the first time local tetragonality in pure nanocrystalline bulk BaTiO₃-ceramics with such a fine microstructure.     

Preparation of Dense BaTiO3 Ceramics from Sol-Gel-Derived Monolithic Gels

Dense, small-grained BaTiO₃ ceramics, with a grain size around 1 μm and a relative sintered density >98%, were obtained at 1100°C from sol-gel-derived gel monoliths without using any sintering additives. The monolithic gels asprepared had a relative density of about 50% and consisted of ultrafine pseudo-cubic BaTiO₃ particles (<50 nm). These gels, with a significantly high density compared with that of previous ones (∼30%), have been synthesized at room temperature from a sol solution with a concentration of equimolar mixture of titanium isopropoxide and barium ethoxide (0.8 mol/L), using the methanol/2-methoxyethanol mixed-solvent system. Microstructural development of the gel monoliths with increasing sintering temperature and the dielectric properties of the obtained dense BaTiO₃ ceramic have been investigated.     

Impedance Spectroscopy of Undoped BaTiO3 Ceramics

The electrical properties of ceramic BaTiO₃ were investigated by ac impedance spectroscopy over the ranges 25°-330°C and 0.03 Hz-1 MHz. Results are compared with those obtained from fixed-frequency measurements, at 1 kHz and 100 kHz. Fixed-frequency Curie-Weiss plots show deviations from linearity at temperatures well above t _c. The ac measurements show that grain boundary impedances influence Curie-Weiss plots in two ways: at high temperatures, they increasingly dominate the fixed-frequency permittivities; at lower temperatures, closer to T ^c, the high-frequency permittivity contains a contribution from grain boundary effects. Methods for extraction of bulk and grain boundary capacitances from permittivity and electric modulus complex plane plots are discussed. The importance of selecting the appropriate equivalent circuit to model the impedance response is stressed. A constriction impedance model for the grain boundary in BaTiO₃ ceramics is proposed: the grain boundary capacitance is neither temperature-independent, nor shows Curie-Weiss behavior. The grain boundary is ferroelectric, similar to the grains, but its impedance is modified by either air gaps or high-impedance electrical inhomogeneity in the region of the necks between grains; the activation energy of the constriction grain boundary impedance differs from that of the bulk, suggesting differences in defect states or impurity levels.     

Preparation and Characterization of KNbO3 Ceramics

The processing and characterization of electrical properties of potassium niobate ceramic, KNbO₃ (KN) have been studied. The difficulty of obtaining dense samples by conventional methods limits the knowledge on electrical properties of this material. In this paper, a complete route for processing of KN with density over 94% is described. Piezoelectric and dielectric data are presented. It is observed that the major problem concerning the density is related to incorrect stoichiometry, which is believed to be a more critical issue for this system compared with other electro-ceramics.     

Insulating Properties of Lanthanum-Doped BaTiO3 Ceramics Prepared by Low-Temperature Synthesis

Samples of composition Ba_{1− x} La _x Ti_{1− x /4}O₃, x = 0, 0.003, 0.03, and 0.10, were prepared by an alkoxide sol–gel route with final firing of ceramics at 1100°C, 2 h in air. All samples showed bulk insulating behavior with no evidence of semiconductivity caused by either direct donor doping or oxygen loss.     

Electrical Properties of Cerium-Doped BaTiO3

The high-temperature equilibrium electrical conductivity of Ce-doped BaTiO₃ was studied in terms of oxygen partial pressure, P (O₂), and composition. In (Ba_1−xCe _x )TiO₃, the conductivity follows the −1/4 power dependence of P (O₂) at high oxygen activities, which supports the view that metal vacancies are created for the compensation of Ce donors, and is nearly independent of P (O₂) where electron compensation prevails at low P (O₂). When Ce is substituted for the normal Ti sites, there is no significant change in conductivity behavior compared with undoped BaTiO₃, indicating the substitution of Ce as Ce⁴⁺ for Ti⁴⁺ in Ba(Ti_1−yCe _y )O₃. The Curie temperature ( T _c) was systematically lowered when Ce³⁺ was incorporated into Ba²⁺ sites, whereas the substitution of Ce⁴⁺ for Ti⁴⁺ sites resulted in no change in this parameter.     

Investigation of Twin Lamellae in BaTiO3 Ceramics

The microstructure of many electroceramic components based on barium titanate is dominated by anomalous grain growth. At firing temperatures below the eutectic temperature nearly all large crystallites were found to contain lamellae. The crys-tallographic orientation of these lamellae was studied by TEM. By combining image and diffraction information it could be directly shown that the lamellae lie on (111) planes and represent twins, which are ∼0.5 μm thick. The relevance of twin formation for the mechanism of anomalous grain growth is briefly discussed.     

Dislocation Loops in Pressureless-Sintered Undoped BaTiO3 Ceramics

Dislocation loops in pressureless-sintered undoped BaTiO₃ ceramics have been analyzed by transmission electron microscopy. The Burgers vector of the loops and its sense b =+1/2[010] were determined using the g·b =0 invisibility criteria, combined with the inside–outside contrast technique using ( g·b ) s _g >0 or<0, keeping the deviation parameter s _g >0. The edge-vacancy nature was further ascertained by determining the loop habit plane normal n =[0 1 0]. Weak-beam dark-field imaging reveals that loops contained no stacking fault fringes; they are edge-vacancy partial dislocation loops lying in {020} or {010} where parts of the TiO₂ or BaO layer are vacant. It is suggested that the extrinsic defects of both cations and oxygen vacancies generated by non-stoichiometry have condensed during sintering in air and are responsible for the formation of such vacancy loops.     

Crystal Chemistry and Dielectric Properties in the Systems BaTiO3-UO2 and BaTiO3-BaUO3

Polycrystalline barium titanate fired in nitrogen at 1300° to 1400°C accommodates up to 3 mole % UO₂ in solid solution; its structure is then cubic at room temperature. With BaUO₃ additions the structure becomes disordered and quasi-cubic. In air, about 1 mole % UO₂ goes into solid solution in BaTiO₃ but the structure remains tetragonal. Diffraction peaks of a new phase, possibly a ternary oxide of barium, uranium, and titanium, appear in patterns of specimens containing more than 2 mole % UO₂. The dielectric constant of BaTiO₃ ceramics fired in air, steam, or oxygen increases with up to about 0.5 mole % UO₂ but declines rapidly above this level. The dielectric constant of BaUO₃ is about two orders of magnitude lower than that of BaTiO₃, and additions of BaUO₃ invariably lower the dielectric constant of BaTiO₃.     

Dielectric Properties of Explosively Compacted BaTiO3

Polycrystalline BaTiO₃ was explosively compacted to nearly theoretical density, and its dielectric and piezoelectric properties were investigated. The compacted bodies did not exhibit dielectric hysteresis, a Curie point, or piezoelectric properties; their dielectric constant and dissipation factor increased linearly with temperature. The dielectric constant was much lower than those of similar dense bodies obtained by conventional sintering. These results may be interpreted in terms of weak intergranular bonding and increased numbers of defects generated in the shocked material. When explosively compacted bodies were sintered, normal ferroelectric and piezoelectric properties and improved microstructures were obtained.     

Polymorphism and Dielectric Properties of Nb-Doped BaTiO3

A working subsolidus phase diagram for the system BaTiO₃–Ba₅Nb₄O₁₅ has been determined by firing sol–gel-synthesized samples over a range of temperatures. The main difference from previous diagrams is the greater extent of the Nb-doped BaTiO₃ cubic solid solutions, BaTi_{1−5 x} Nb_{4 x} O₃, at lower temperatures with x extending to 0.09 at 900°C, but only 0.05 at 1400°C. Electrical property measurements show that compositions with large x ( x ≥0.0025) are highly insulating for pellets sintered at 1300°C in air, followed by a slow cool. Compositions with low x , however, exhibit a residual semiconducting grain core and are not fully reoxidized readily. Composition dependence of the dielectric properties shows a continuous and smooth transition from classic ferroelectric behavior with pure BaTiO₃ to normal dielectric response with a temperature-independent relative permittivity of approximately 22–24 for x >∼0.08. At intermediate compositions, ranges of both relaxor ferroelectric and quasi-ferroelectric behavior are observed. Possible reasons for an observed anomalous increase in value of the permittivity at the ferroelectric transition temperature at low x , which is superposed on an overall decrease in permittivity with increasing x , are discussed.     

Grain Boundaries of Semiconducting SrTiO3 and BaTiO3 Ceramics Synthesized from Surface-Coated Powders

The chemical and electrical features of the grain boundaries in polycrystalline SrTi_0.99Nb_0.01O₃ (ST) and BaTiO₃ (BT) ceramics, which were synthesized by hot-press sintering Na- and Mn-coated semiconducting ST and BT powders, respectively, were investigated. Because of the excess negative electric charges formed near grain boundaries, electrostatic potential barriers were formed near the grain boundaries. The electrical features of the grain boundaries in ceramics are very sensitive to the amount of the coating material. When the amount of the coating material was increased from 0 to 5 wt%, the threshold voltage of the ST ceramics and the resistivity jump ratio of the BT ceramics increased from 0.7 to 81.0 V/cm and from 1.0 to 2.0 × 10³, respectively. The electrical features of the grain boundaries are related to their chemical characteristics.     

Preparation of Dense BaTiO3 Ceramics with Submicrometer Grains by Spark Plasma Sintering

Dense BaTiO₃ ceramics consisting of submicrometer grains were prepared using the spark plasma sintering (SPS) method. Hydrothermally prepared BaTiO₃ (0.1 and 0.5 µm) was used as starting powders. The powders were densified to more than similar/congruent95% of the theoretical X-ray density by the SPS process. The average grain size of the SPS pellets was less than similar/congruent1 µm, even by sintering at 1000-1200°C, because of the short sintering period (5 min). Cubic-phase BaTiO₃ coexisted with tetragonal BaTiO₃ at room temperature in the SPS pellets, even when well-defined tetragonal-phase BaTiO₃ powder was sintered at 1100° and 1200°C and annealed at 1000°C, signifying that the SPS process is effective for stabilizing metastable cubic phase. The measured permittivity was similar/congruent7000 at 1 kHz at room temperature for samples sintered at 1100°C and showed almost no dependence on frequency within similar/congruent10⁰-10⁶ Hz; the permittivity at 1 MHz was 95% of that at 1 kHz.     

Dislocation Loop Formation in Nonstoichiometric (Ba,Ca)TiO3 and BaTiO3 Ceramics

Dislocation loops observed in nonstoichiometric and stoichiometric (Ba,Ca)TiO₃, and in stoichiometric BaTiO₃ sintered in a reducing atmosphere, were characterized by conventional transmission electron microscopy (TEM) under two-beam conditions and high-resolution TEM atomic structure analysis. Dislocation loops mostly lay on {100} planes with Burgers vectors of type 〈100〉. The dynamic behavior of these dislocation loops during the electron beam irradiation (EBI), however, was classified into two different types of dislocation loops: in A-site-excess (Ba,Ca)TiO₃, contrasts of dislocation loops faded completely away; in BaTiO₃ and B-site-excess (Ba,Ca)TiO₃, fine-line contrasts remained. Dislocation loops with Burgers vectors of type 1/2〈100〉 and the resultant crystallographic shear (CS) structure with a displacement vector of type 1/2〈110〉 after EBI were proposed to interpret residual line images. Disappearance of these line images in A-site-excess (Ba,Ca)TiO₃ strongly suggests preferential Ca ion site occupancy at the CS structure.     

Roles of Ba/Ti Ratios in the Dielectric Properties of BaTiO3 Ceramics

The effect of the Ba/Ti ratio on microstructure, dielectric/ferroelectric properties, and domain width was studied using optical microscopy, ɛ( T ) curves, D – E hysteresis, and transmission electron microscopy. Although Ti-excess samples showed abnormal grain growth and a decrease of room-temperature permittivity due to a liquid phase at grain boundaries, its ferroelectric properties were similar to those of stoichiometric BaTiO₃ ceramics. However, in Ba-excess samples, an increase of permittivity and ferroelectric properties different from those of stoichiometry were found. Changes in domain width and ferroelectric transition behavior indicated that the variation of dielectric properties was related to the internal stress. It is proposed that this internal stress originated from differences in the thermal expansion coefficient between the matrix and the second phase.     

Weakly Coupled Relaxor Behavior of BaTiO3–BiScO3 Ceramics

The structural and dielectric properties of (1− x )BaTiO₃– x BiScO₃ ( x =0–0.5) ceramics were investigated to acquire a better understanding of the binary system, including determination of the symmetry of the phases, the associated dielectric properties, and the differences in the roles of Bi₂O₃ and BiScO₃ substitutions in a BaTiO₃ solid solution. The solubility limit for BiScO₃ into the BaTiO₃ perovskite structure was determined to be about x =0.4. A systematic structural change from the ferroelectric tetragonal phase to a pseudo-cubic one was observed at about x =0.05–0.075 at room temperature. Dielectric measurements revealed a gradual change from proper ferroelectric behavior in pure BaTiO₃ to highly diffusive and dispersive relaxor-like characteristics from 10 to 40 mol% BiScO₃. Several of the compositions showed high relative permittivities with low-temperature coefficients of capacitance over a wide range of temperature. Quantification of the relaxation behavior was obtained through the Vogel–Fulcher model, which yielded an activation energy of 0.2–0.3 eV. The attempt characteristic frequency was 10¹³ Hz and the freezing temperature, T _f, ranged from −177° to −93°C as a function of composition. The high coercive fields, low remanent polarization, and high activation energies suggest that in the BiScO₃–BaTiO₃ solid solutions, the polarization in nanopolar regions is weakly coupled from region to region, limiting the ability to obtain long-range dipole ordering in these relaxors under field-cooled conditions.     

Interfacial Reaction of BaTiO3 Ceramics with PbO–B2O3 Glasses

Interfacial reactions of pure, lead-, and zirconium-substituted BaTiO₃ ceramics with PbOB₂O₃ glasses were studied, with an emphasis on the effect of glass composition. Microstructures were analyzed by scanning electron microscopy and electron-probe microanalysis aided with X-ray diffractometry of powder mixtures in the system BaTiO₃PbOB₂O₃ heated at 850°C. The interfacial microstructures were divided into two types, depending on the glass composition. The first type was characterized by precipitates of TiO₂ dispersed in the glass matrix. Extended heating or limited glass volume resulted in the formation of a continuous layer of BaTi(BO₃)₂. The second type of microstructure was characterized by a lead-rich perovskite phase, which developed at the glass/ceramic interfacial region. Growth kinetics for this phase denied the diffusion-controlled mechanism. The substitution of lead in BaTiO₃ enhanced the penetration of glass into the ceramics along the grain boundaries and developed a coreshell structure.     

Effects of Ba6Ti17O40 on the Dielectric Properties of Nb-Doped BaTiO3 Ceramics

The dielectric properties, including the DC breakdown strength, of 1 mol% Nb⁵⁺-doped BaTiO₃ ceramics with different quantities of excess TiO₂ have been investigated. The breakdown strength was found to decrease with increasing TiO₂ content, but could not be readily explained by relative density and grain size effects. The decrease in the breakdown strength from a stoichiometric BaTiO₃ composition to samples with excess TiO₂ is believed to be due to the field enhancement effect (up to a factor of 1.40) at the BaTiO₃ matrix because of the presence of a Ba₆Ti₁₇O₄₀ second phase. The thermal expansion coefficient mismatch between the BaTiO₃ matrix phase and the Ba₆Ti₁₇O₄₀ phase may also result in a low breakdown strength. The dielectric properties of the pure Ba₆Ti₁₇O₄₀ phase were also investigated and are reported herein.