Synthesis of Nano-sized BaTiO3 Powders by the Rotary-Hydrothermal Process

Nano-sized BaTiO₃ powders with narrow size distribution and high tetragonality were attempted to be synthesized by the rotary-hydrothermal process in a water system as a novel technique, using a mixture of anatase-type TiO₂ and Ba(OH)₂ as starting material. The rotary-hydrothermal syntheses were performed under conditions with a rotary-speed of 20 revolutions per minute at 423–523 K for 3–96 h. Highly- and mono-dispersed BaTiO₃ powders mainly composed of coarse-faceted particles with the tetragonal phase were successfully synthesized by controlling the conditions for rotary-hydrothermal treatments. TEM and TG results revealed that these coarse-faceted BaTiO₃ particles contained very few structural defects such as hydroxyl content. Thus, the rotary-hydrothermal process was a useful method to synthesize very high-quality BaTiO₃ particles, and the further control of various conditions of the rotary-hydrothermal treatment is expected to control the crystalline phase and microstructures of final BaTiO₃ powders.     

Nanopowder Preparation and Dielectric Properties of a Bi2O3–Nb2O5 Binary System Prepared by the High-Energy Ball-Milling Method

The high-energy ball-milling (HEM) method was used to synthesize the compositions of BiNbO₄, Bi₅Nb₃O₁₅, and Bi₃NbO₇ in a Bi₂O₃–Nb₂O₅ binary system. Reagent Bi₂O₃ and Nb₂O₅ were chosen as the starting materials. The X-ray diffraction patterns of the three compositions milled for different times were studied. Only the cubic Bi₃NbO₇ phase, Nb₂O₅, and amorphous matters were observed in powders after being milled for 10 h. After heating at proper temperatures the amorphous matters disappeared and the proleptic phases of BiNbO₄ and Bi₅Nb₃O₁₅ could be obtained. The Scherrer formula was used to calculate the crystal size and the results of nanopowders are between 10 and 20 nm. The scanning electron microscopy photos of Bi₃NbO₇ powders showed drastic aggregation, and the particle size was about 100 nm. The dielectric properties of ceramics sintered from the nanopowders prepared by HEM at 100–1 MHz and the microwave region were measured. Bi₃NbO₇ ceramics showed a good microwave permittivity ɛ_r of about 80 and a Q × f of about 300 at 5 GHz. The triclinic phase of BiNbO₄ ceramics reached its best properties with ɛ_r=24 and Q × f =14 000 GHz at about 8 GHz.     

Electrophoretic Deposition and Characterization of Micrometer-Scale BaTiO3 Based X7R Dielectric Thick Films

Uniform and relatively dense BaTiO₃ thick films of 1–5 μm were prepared by an electrophoretic deposition process using submicrometer BaTiO₃ powders (mean particle size: ∼0.2 μm). Two different BaTiO₃ powders and solvent media were used to investigate the film quality and thickness control. The surface charge mechanism of BaTiO₃ particles was explained according to the observed results. The microstructures were examined by means of SEM. The experimental results show that the thickness could be controlled independently of suspension concentration by keeping a constant applied voltage and a constant current drop in a given suspension. BaTiO₃ thick films have good insulation resistance and dielectric properties such as a dielectric constant and a dissipation factor that are compatible with the data from conventional tape-cast BaTiO₃ thin layers.     

Dielectric Properties and Microstructure of Nb-Co Codoped BaTiO3–(Bi0.5Na0.5)TiO3 Ceramics

X-ray diffractometry, scanning electron microscopy, transmission electron microscopy, and an impedance analyzer were used to examine the Nb–Co codoping effects on the densification, crystalline phase, microstructure development, and dielectric–temperature characteristics of BaTiO₃–(Bi_0.5Na_0.5)TiO₃ ceramics. The results indicate that the Curie temperature shifted to a higher temperature (above 140°C) by adding BNT. The dielectric constant–temperature (ɛ– T ) curve broadened at the Curie temperature due to the small grain size (0.3–0.4 μm). A core-shell structure was developed, which is helpful to flatten the ɛ– T curve of BaTiO₃ ceramics at high temperatures.     

Effect of Particle Size on the Room-Temperature Crystal Structure of Barium Titanate

The room-temperature tetragonal-to-cubic transformation in BaTiO₃ powders with decreasing particle size has been carefully studied, using materials prepared mainly by hydrothermal methods. Hydrothermal BaTiO₃ powders exhibited a more uniform particle size distribution than oxalate-route powders, with X-ray diffraction and electron microscopy indicating that powders 0.19 μm in size were fully cubic while powders 0.27 μ were completely tetragonal (within a 5% detection limit for cubic material) at room temperature. The tetragonal-to-cubic transformation temperature was also found to lie in the range of 121°± 3°C for BaTiO₃ powders with room-temperature ( c/a ) values > 1.008. No transformation could be detected using differential scanning calorimetry for BaTiO₃ particles with a ( c/a ) > 1.008 at room temperature. BaTiO₃ powder with a particle size just too small (0.19 μm) to be tetragonal at room temperature remained cubic down to 80 K. Different models for the cubic-to-tetragonal room-temperature transformation are discussed. Hydroxyl ions do not appear to greatly affect the cubic-to-tetragonal transformation, which appears to be essentially dependent on particle size. It is concluded that a model based on surface free energy, as previously discussed for the monoclinic-to-tetragonal transformation at room temperature of fine ZrO₂ particles, is consistent with the experimental data.     

High-Temperature Dielectrics in the BiScO3–BaTiO3–(K1/2Bi1/2)TiO3 Ternary System

Perovskite solid solution in the (1− x )[0.4BiScO₃–0.6BaTiO₃]+ x (K_1/2Bi_1/2)TiO₃ [BSBT–KBT x ] system was synthesized using conventional sintering and hot-isostatic pressing. Dielectric properties of BSBT ceramics with different dopant levels of KBT were characterized as a function of temperature and frequency for potential use of high-temperature capacitors. The BSBT ceramics with KBT exhibited high dielectric permittivities (ɛ_r) (>1700 at RT) and low dielectric loss over the temperature range from 100° to 300°C, with flat temperature coefficients of permittivity (TCɛs). In addition, BSBT ceramics with increasing KBT were observed to possess dielectric relaxation characteristics at temperatures (>RT) as observed in lead-based relaxors. Furthermore, high energy densities, being on the order of 4.0 J/cm³ at 220 kV/cm was observed for the BSBT–KBT20 ceramics from the electric-field polarization behavior.     

Microwave Dielectric Properties of Low-Fired ZnNb2O6 Ceramics with BiVO4 Addition

The BiVO₄ additive was found effective for low-temperature firing of ZnNb₂O₆ polycrystalline ceramics below 950°C in air without a serious degradation in their microwave dielectric properties. Dense BiVO₄-doped ZnNb₂O₆ samples of a relative sintered density over 95% could be prepared even at 925°C. An optimally processed specimen exhibited excellent microwave dielectric properties of Q · f = 55000 GHz, ɛ_r= 26, and τ_f=−57 ppm/°C. With increasing BiVO₄ addition up to 20 mol% relative to ZnNb₂O₆, while the quality factor Q · f was gradually decreased, the relative dielectric constant, ɛ_r, was linearly increased and the temperature coefficient of resonant frequency, τ_f, was slightly increased. The variations in Q · f and ɛ_r are surely attributable to the residual BiVO₄ in the ZnNb₂O₆ matrix. An unexpected slight increase in τ_f is probably due to the formation of the Bi(V,Nb)O₄-type solid solution.     

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.     

Characteristics and Formation Mechanism of BaTiO3 Powders Prepared by Twin-Fluid and Ultrasonic Spray-Pyrolysis Methods

Spherical fine (micrometer and submicrometer in size) homogeneous BaTiO₃ powders were synthesized from ethanol: water solutions of BaCl₂ and TiCl₄ using the spray-pyrolysis technique. Two different atomizers—twin-fluid and ultrasonic, with a resonant frequency of 2.5 × 10⁶ Hz—were used for mist generation. Hollow spherical particles containing a certain amount of unreacted BaCl₂ phase and having a mean particle diameter of 2.5 μm were obtained at 1173 K using a twin-fluid atomizing system. Decomposition of precursors and their transition to the cubic BaTiO₃ phase occurred, even at 973 K in the case of the ultrasonic atomizing system. For the initial droplet size of 2.2 μm and residence time of ∼60 s, spherical BaTiO₃ particles with the mean particle diameter of 0.53 μm were obtained. A BaTiO₃ formation mechanism has been proposed as a reaction between TiO₂ and BaCl₂ rather than a reaction of oxides.     

Structure–Property Relations in xBaTiO3–(1−x)La(Mg1/2Ti1/2)O3 Solid Solutions

The microwave dielectric properties and microstructures of compounds in the solid solution series x BaTiO₃–(1− x )La(Mg_1/2Ti_1/2)O₃ (BTLMT) have been investigated. The structural phase transitions that occur as a function of x have been studied and are related to changes in the dielectric properties. For compounds where x ≤ 0.1, X-ray diffraction (XRD) showed evidence of 1:1 ordering between Mg and Ti cations. For x ≤ 0.3, XRD and electron diffraction revealed that compounds were tilted in both antiphase and in-phase. However, for 0.3 < x < 0.7, only antiphase tilting was present. The temperature coefficient of resonant frequency (τ_f) vs the relative permittivity (ɛ_r) was linear until x = 0.5 at which point in the solid solution the transition to a nontilted structure resulted in nonlinear behavior. τ_f values close to zero (−2 ppm/°C) were achieved at x = 0.5 (ɛ_r∼ 60), which had a quality factor ( Q · f _o) of 9600 GHz.     

Dielectric Properties of the "Twinned" 8H-Hexagonal Perovskite Ba8Nb4Ti3O24

The dielectric properties of dense ceramics of the "twinned" 8H-hexagonal perovskite Ba₈Nb₄Ti₃O₂₄ are reported. Single-phase powders were obtained from the mixed-oxide route at 1325°C and ceramics (>92% of the theoretical X-ray density) by sintering in air or flowing O₂ at 1400°–1450°C. The ceramics are dc insulators with a band gap >3.4 eV that resonate at microwave frequencies with relative permittivity, ɛ_r∼44–48, quality factor, Q × f _r∼21 000–23 500 GHz (at f _r∼5.5 GHz) and temperature coefficient of resonant frequency, TC _f,∼+115 ppm/K.     

Microwave Dielectric Properties of Hexagonal 12R-Ba3LaNb3O12 Ceramics

The dielectric properties of dense ceramics of the n =0 member of a newly identified homologous series Ba_{3+ n} LaNb₃Ti _n O_{12+3 n} , where n =0, 1, and 2, are reported. Single-phase powders can be obtained from the mixed-oxide route at 1350°C and dense ceramics (>97% of the theoretical X-ray density) with uniform microstructures (3–5 μm) can be obtained by sintering in air at 1500°C. The ceramics are excellent dc insulators with a band gap >2.6 eV that resonate at microwave frequencies with a relative permittivity, ɛ_r∼44, a quality factor, Q × f _r, of ∼9000 at f _r∼5.5 GHz and a temperature coefficient of resonant frequency, TC_f,∼−100 ppm/K.     

Low-Dielectric Loss Characteristics of Nd(Co1/2Ti1/2)O3 Ceramics at Microwave Frequencies

The microwave dielectric properties and the microstructures of Nd(Co_1/2Ti_1/2)O₃ (NCT) ceramics using starting powders of Nd₂O₃, CoO, and TiO₂ prepared by the conventional solid-state route have been researched. The dielectric constant values (ɛ_r) saturated at 24.8–27. Quality factor ( Q × f ) values of 37 900–140 000 (at 9 GHz) and the measured τ_f values ranging from −45 to −48 ppm/°C can be obtained when the sintering temperatures are in the range of 1410°–1500°C. The ɛ_r value of 27, the Q × f value of 140 000 (at 9 GHz) and the τ_f value of −46 ppm/°C were obtained for NCT ceramics sintered at 1440°C for 4 h. For applications of high selective microwave ceramic resonator, filter, and antenna, NCT is proposed as a suitable material candidate.     

Preparation and Dielectric Properties of Low-Temperature-Sinterable (Zr0.8Sn0.2)TiO4 Powder

Low-temperature-sinterable (Zr_0.8Sn_0.2)TiO₄ powders were prepared using 3 mol% Zn(NO₃)₂ additive and then compared with powders prepared using 3 mol% ZnO additive and no additives. Sintering at 1200°C for 2 h produced a dielectric ceramic with ρ= 98.6% of theoretical density (TD), ɛ_r= 38.4, Q × f (GHz) = 42000, and τ _f =−1 ppm/°C. Sintering at 1250°C resulted in an excellent dielectric with ρ= 99% of TD, epsilon_r= 40.9, Q × f (GHz) = 49000, and τ _f =−2 ppm/°C. Scanning electron microscopy showed a microstructure with grains measuring 0.5 to 1 μm, and transmission electron microscopy revealed secondary phase in the grain boundaries.     

Sr3LaNb3O12: A New Low Loss and Temperature Stable A4B3O12-Type Microwave Dielectric Ceramic

The microwave dielectric properties of dense ceramics of a new A₄B₃O₁₂ type cation-deficient hexagonal perovskite Sr₃LaNb₃O₁₂ are reported. Single-phase powders can be obtained from the mixed-oxide route at 1320°C and dense ceramics (>96% of the theoretical X-ray density) with uniform microstructures (5–12 um) can be obtained by sintering in air at 1430°C. The ceramic exhibits a moderate dielectric constant ɛ_r∼36, a high quality factor Q × f ∼45 327 GHz, and a low temperature coefficient of resonant frequency τ _f of −9 ppm/°C.     

Low-Loss Microwave Dielectrics Using Mg2(Ti1−xSnx)O4 (x=0.01–0.09) Solid Solution

Low-loss ceramics having the chemical formula Mg₂(Ti_{1− x} Sn _x )O₄ for x ranging from 0.01 to 0.09 have been prepared by the conventional mixed oxide route and their microwave dielectric properties have been investigated. X-ray powder diffraction patterns indicate the corundum-structured solid solutions for the prepared compounds. In addition, lattice parameters, which linearly increase from 8.4414 to 8.4441 Å with the rise of x from 0.01 to 0.09, also confirm the forming of solid solutions. By increasing x from 0.01 to 0.05, the Q × f of the specimen can be tremendously boosted from 173 000 GHz to a maximum 318 000 GHz. A fine combination of microwave dielectric properties (ɛ_r∼15.57, Q × f ∼318 000 GHz at 10.8 GHz, τ_f∼−45.1 ppm/°C) was achieved for Mg₂(Ti_0.95Sn_0.05)O₄ ceramics sintered at 1390°C for 4 h. Ilmenite-structured Mg(Ti_0.95Sn_0.05)O₃ (ɛ_r∼16.67, Q × f ∼275 000 GHz at 10.3 GHz, τ_f∼−53.2 ppm/°C) was detected as a second phase. The presence of the second phase, however, would cause no significant variation in the dielectric properties of the specimen, because the second phase properties are very similar to the primary phase. These unique properties, in particular, low ɛ_r and high Q × f , can be utilized as a very promising dielectric material for ultra-high-frequency applications.     

Effect of Surface Moisture on Dielectric Behavior of Ultrafine BaTiO3 Particulates

The effects of adsorbed H₂O on the dielectric properties of ultrafine BaTiO₃ particulates of varying particle size and environmental history were determined. The dielectric behavior depends strongly on surface hydration. No particle size dependence of dielectric constant was found for dehydroxylated surfaces in ultrafine particulate (unsintered) BaTiO₃ materials. For equivalent particle sizes, the ac conductivity is sensitive to surface morphology. Reactions with H₂O vapor appear to account for the variations in dielectric properties. Surface dehydration was effectively accomplished by washing as-received powders in isopropanol.     

Structure and Microwave Dielectric Characteristics of Ca1+xNd1−xAl1−xTixO4 Ceramics

CaNdAlO₄ microwave dielectric ceramics were modified by Ca/Ti co-substitution, and their dielectric characteristics were evaluated along with their structure and microstructures. Ca_{1+ x} Nd_{1− x} Al_{1− x} Ti _x O₄ ( x =0, 0.025, 0.05, 0.10, 0.15, 0.20) ceramics with the relative density of over 95% theoretical density were obtained by sintering at 1400°–1450°C in air for 3 h, where the K₂NiF₄-type solid solution single phase was determined from the compositions of x <0.20, while a small amount of CaTiO₃ secondary phase was detected for x =0.20. With Ca/Ti co-substitution in CaNdAlO₄ ceramics, the dielectric constant (ɛ_r) increased with increasing x , and the temperature coefficient of resonant frequency (τ_f) was adjusted from negative to positive, while the Q × f ₀ value increased significantly at first and reached an extreme value at x =0.025 and the maximum at x =0.15. The best combination of microwave dielectric characteristics were achieved at x =0.15 (ɛ_r=19.5, Q × f ₀=93 400 GHz, τ_f=−2 ppm/°C). The improvement of the Q × f ₀ value primarily originated from the reduced interlayer polarization with Ca/Ti co-substitution, while the decreased tolerance factor, the subsequent increased interlayer stress, and the appearance of CaTiO₃ secondary phase brought negative effects upon the Q × f ₀ value.     

Raman Study of the Relationship between Room-Temperature Tetragonality and the Curie Point of Barium Titanate

Variable-temperature Raman spectroscopy showed that, in progressively finer BaTiO₃ powders, the Curie point increased as the room temperature tetragonality decreased. The influence of crystallite size distribution on the range of tetragonalities present in a powder was clearly evident in both phase transitions, as observed by Raman spectroscopy and room-temperature X-ray diffraction patterns. Titanium K -edge X-ray absorption spectroscopy could not distinguish between the cubic and tetragonal structures of BaTiO₃, at 300°C and room temperature, respectively.     

Crystal Structure and Dielectric Properties of LaYbO3

The crystal structure and dielectric properties of LaYbO₃ ceramics prepared by the mixed-oxide route have been investigated. Rietveld refinements performed on X-ray and neutron diffraction data show the room-temperature structure to be best described by the orthorhombic Pnma space group [ a =6.02628(9) Å, b =8.39857(11) Å, and c =5.82717(7) Å; Z =4, and theoretical density, D _x =8.1 g/cm³] in agreement with electron diffraction experiments. LaYbO₃ ceramics fired at 1600°C for 4 h attain ∼97% of D _x and their microstructures consist of randomly distributed equiaxed grains with an average size of ∼8 μm. Conventional transmission electron microscopy shows densification to occur in the absence of a liquid phase and reveals domain-free grains. The relative permittivity, ɛ_r, of LaYbO₃ ceramics at radio frequencies is ∼26 in the range ∼10–300 K; however, a small dielectric anomaly is detected at ∼15 K. At room temperature and microwave frequencies, LaYbO₃ ceramics exhibit ɛ_r∼26, Q × f _r∼20 613 GHz (at 7 GHz), and τ_f∼−22 ppm/K. Q × f _r show complex subambient behavior, decreasing from a plateau value of ∼20 000 GHz between ∼300 and 200 K to a second plateau value of ∼6000 GHz at ∼90 K before decreasing to <1000 GHz at ∼10 K. The large decrease in Q × f _r at low temperature may be related to the onset of antiferromagnetism at ∼2.7 K. ¹