Synthesis of Ba(Mg1/3Ta2/3)O3 Microwave Ceramics through a Sol–Gel Route Using Acetate Salts

A sol–gel process to unsophisticatedly synthesize Ba(Mg_1/3Ta_2/3)O₃ (BMT) ceramics at low cost has been developed in the present work. This process involves the reaction of TaCl₅ with acetates of Ba and Mg in the presence of citric acid. Pure BMT polycrystalline powders can be obtained by calcining the synthesized products at 1000°C. The BMT powders were found to have a primary particle size as small as 100 nm. BMT ceramics with favorable structural characteristics can be obtained from sintering of the sol–gel BMT at temperatures much lower than that for the conventional solid-state BMT. Sintering the sol–gel BMT in pellet form at 1300°C resulted in an ordering parameter of 0.72 for the pellet, and a relative density of >95% was achieved with sintering at 1500°C. The grain size of the sintered sol–gel BMT was large and uniform in comparison with the products from the solid-state method. Using the sol–gel route, sintering at temperatures as low as 1400°C gave ceramics with acceptable microwave dielectric properties (a dielectric constant of 16 and Qf factor of 14 400 GHz), while higher temperatures (>1600°C) are needed for the solid-state route to give similar properties.     

Sol–Gel Preparation of BaTi4O9 and Ba2Ti9O20

BaTi₄O₉ and Ba₂Ti₉O₂₀ precursors were prepared via a sol–gel method, using ethylenediaminetetraacetic acid as a chelating agent. The sol–gel precursors were heated at 700°–1200°C in air, and X-ray diffractometry (XRD) was used to determine the phase transformations as a function of temperature. Single-phase BaTi₄O₉ could not be obtained, even after heating the precursors at 1200°C for 2 h, whereas single-phase Ba₂Ti₉O₂₀ (as determined via XRD) was obtained at 1200°C for 2 h. Details of the synthesis and characterization of the resultant products have been given.     

Sol–Gel Processing and Microwave Characteristics of Ba(Mg⅓Ta⅔)O3 Dielectrics

The sol–gel method has been developed for the preparation of pure Ba(Mg_1/3Ta_2/3)O₃ ceramics. This involves the reaction of the heterometallic alkoxide Ta₂Mg(OEt)₁₂ with hydrated barium hydroxide Ba(OH)₂·8H₂O. Complete crystallization of the sol–gel-derived powder is achieved at 600°C, leading to a cubic perovskite type phase. After sintering at 1400°C (2–5 h), a trigonal cell arises from Mg–Ta ordering (the degree of order is greater than 0.9), and about 98.5% of the theoretical density is obtained. Preliminary microwave dielectric measurements show that the dielectric constant and the unloaded Q _u of the ceramics are 24.2 and 6750, respectively, at 7.7 GHz.     

Phase Transitional Behavior and Piezoelectric Properties of Lead-Free (Na0.5K0.5)NbO3–(Bi0.5K0.5)TiO3 Ceramics

(1− x )(Na_0.5K_0.5)NbO₃–(Bi_0.5K_0.5)TiO₃ solid solution ceramics were successfully fabricated, exhibiting a continuous phase transition with changing x at room temperature from orthorhombic, to tetragonal, to cubic, and finally to tetragonal symmetries. A morphotropic phase boundary (MPB) between orthorhombic and tetragonal ferroelectric phases was found at 2–3 mol% (Bi_0.5K_0.5)TiO₃ (BKT), which brings about enhanced piezoelectric and electromechanical properties of piezoelectric constant d ₃₃=192 pC/N and planar electromechanical coupling coefficient k _p=45%. The MPB composition has a Curie temperature of 370°–380°C, comparable with that of the widely used PZT materials. These results demonstrate that this system is a promising lead-free piezoelectric candidate material.     

Effect of Cation Substitution and Non-Stoichiometry on the Microwave Dielectric Properties of Sr(B'0.5Ta0.5)O3 [B'=Lanthanides] Perovskites

The Sr(B'_0.5Ta_0.5)O₃ ceramics where B'=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, and Yb have been prepared by the conventional solid-state ceramic route and their microwave dielectric properties have been investigated. The structure and microstructure of the ceramics have been characterized by X-ray diffraction and scanning electron microscope techniques. The relative permittiviy (ɛ_r) varies linearly with B'-site ionic radii, except for La, and the temperature coefficient of resonant frequency (τ_f) varies linearly with the tolerance factor. The Sr(B'_0.5Ta_0.5)O₃ ceramics have ɛ_r in the range 25.9–32, Q _u× f =4500–54 300 GHz, and τ_f=−79 to −42 ppm/°C. A slight deviation from stoichiometry affects the dielectric properties of these double perovskites. Partial substitution of Ba for Sr could tune the dielectric properties. Addition of rutile (TiO₂) lowered the sintering temperature and improved the dielectric properties of Sr(B'_0.5Ta_0.5)O₃ ceramics.     

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.     

Effects of Silver Doping on the Sol–Gel-Derived Ba4(Nd0.7Sm0.3)9.33Ti18O54 Microwave Dielectric Ceramics

Tungstenbronze-type Ba₄(Nd_0.7Sm_0.3)_9.33Ti₁₈O₅₄ (BNST) microwave dielectric ceramics doped with 0–10 wt% silver (Ag) particles were successfully fabricated by a citrate sol–gel method. The influence of Ag doping on the sinterability, microstructure, bulk conductivity, and dielectric properties of BNST was investigated. The desired tungstenbronze-type phase was obtained at 900°–950°C. The sintering temperature of BNST decreased to 1100°C with the aid of a small amount of Ag addition (1 wt%). No chemical reaction between the tungsenbronze phase and Ag was detected. The particle size of the powders decreased with increasing Ag content up to 1 wt% and it then increased with a further increase in the Ag content. The dense fine-grained ceramics with submicrometer grains (∼300 nm) were obtained with 1 wt% Ag addition. The submicrometer-grained ceramics had excellent dielectric properties of ɛ_r∼81 and Q × f ∼11 000 GHz. Both the dielectric constant and dielectric loss significantly increased with large additions (>3 wt%) of Ag due to the percolation effect.     

Low-Temperature Synthesis and Growth of Bulk Ba2Ti9O20 Ceramics on Conducting Substrates for Applications in Integrated Dielectric Resonator Devices

This paper describes the synthesis of Ba₂Ti₉O₂₀ ceramics at extremely low temperatures (∼150°C) and the subsequent growth of bulk resonators on silicon substrates by hydrothermal processing of their sol–gel composites. X-ray diffraction analysis shows excellent crystallinity, while scanning electron microscopy evidenced densification and development of bridging structures at the grain boundaries and interfaces. Transmission electron micrographs further confirmed the development of sol–gel-derived crystalline interfaces between sol–gel-derived material and powder particles. The dielectric properties of a resonator measured in the 5–6 GHz microwave frequency range were ɛ_r=38 and Q _u× f =12,000 at 5.6 GHz and τ_f=+6 ppm/°C. The density, dielectric properties, and mechanical strength at the bulk ceramic–thin film interface are enhanced by a hydrothermally induced dissolution–crystallization process, which leads to interparticle bridges. The novel low-temperature ceramic process has high potential for the growth of ceramic resonators on integrated circuits and is demonstrated by the fabrication of an integrated dielectric resonator antenna for system-on-chip applications.     

Sol–Gel Processed Y-PSZ Ceramics with 5 wt% Al2O3

Y-PSZ ceramics with 5 wt% Al₂O₃ were synthesized by a sol–gel route. Experimental results show that powders of metastable tetragonal zirconia with 2.7 mol% Y₂O₃ and 5 wt% Al₂O₃ can be fabricated by decomposing the dry gel powder at 500°C. Materials sintered in an air atmosphere at 1500°C for 3 have high density (5.685 g/cm³), high content of metastable tetragonal zirconia (>96%), and high fracture toughness (8.67 MPa.m^1/2). Compared with the Y-PSZ ceramics, significant toughening was achieved by adding 5 wt% Al₂O₃.     

A Novel Hybrid Method of Sol–Gel and Ultrasonic Atomization Synthesis and Piezoelectric Properties of SrBi4Ti4O15 Ceramics

SrBi₄Ti₄O₁₅(SBTi) powders were synthesized by a novel hybrid method of sol–gel and ultrasonic atomization. TiO₂ particle was used as a starting material to replace other expensive soluble titanium salts. X-ray diffraction results showed that the pure-phase SBTi powders were obtained at 700°C for 2 h, which is much lower than the calcination temperature (800°–850°C) required in solid-state reactions. The ceramics sintered at 1100°C for 1 h exhibited 94.5% of relative density and a piezoelectric coefficient of 21 pC/N. The results showed that this hybrid method could lead to an attractive method for the industrial fabrication of SBTi materials.     

Low-Temperature Sintering and Piezoelectric Properties of CuO-Added 0.95(Na0.5K0.5)NbO3–0.05BaTiO3 Ceramics

The sintering temperature of 0.95(Na_0.5K_0.5)NbO₃–0.05BaTiO₃ (NKN–BT) ceramics needs to be decreased below 1000°C to prevent Na₂O evaporation, which can cause difficulties in poling and may eventually degrade their piezoelectric properties. NKN–BT ceramics containing CuO were well sintered at 950°C with grain growth. Poling was easy for all specimens. Densification and grain growth were explained by the formation of a liquid phase. The addition of CuO improved the piezoelectric properties by increasing the grain size and density. High piezoelectric properties of d ₃₃=230 pC/N, k _p=37%, and ɛ₃^T/ɛ₀=1150 were obtained from the specimen containing 1.0 mol% of CuO synthesized by the conventional solid-state method.     

Mesoporous AlPO4 Glass from a Simple Aqueous Sol–Gel Route

Transparent and colorless AlPO₄ gel and glass are prepared via a simple aqueous sol–gel route using aluminum lactate and phosphoric acid as precursors. The stoichiometric AlPO₄ glass derived from this sol–gel route has a mesoporous structure with a surface area of 504 m²/g after calcination to 600°C. With increasing gel-to-glass processing temperature, the average degree of P/Al connectivity increases. After sample calcination at 600°C for 4 h, ²⁷Al MAS NMR spectra indicate that aluminum is almost completely converted into AlO₄ units. ²⁷Al{³¹P} rotational echo double resonance and ³¹P{²⁷Al} rotational echo adiabatic passage double resonance NMR experiments as well as ²⁷Al and ³¹P MAS NMR results further confirm that the prepared AlPO₄ glass has a three-dimensional network based on alternating Al(OP)₄ and P(OAl)₄ tetrahedral units in analogy to the local structure of crystalline AlPO₄.     

Processing and Electromechanical Properties of (Bi0.5Na0.5)(1−1.5x)LaxTiO3 Ceramics

Bismuth sodium titanate (Bi_0.5Na_0.5TiO₃, BNT) with 0–6 at.% lanthanum was prepared by the conventional mixed oxide method. Each composition was calcined at 800–900°C for 2–5 h to form a pure perovskite phase. Green pellets were sintered at 1050–1150°C for 1–4 h to obtain dense ceramics with at least 95% of theoretical density. X–ray diffraction (XRD) showed phase distortion as lanthanum was added to this system. Meanwhile, a small amount of La was found to affect the grain size and had an influence on the poling conditions and electrical properties. The BNT–based composition with 1 at.% La doping provided a dielectric constant ( K ) of 560, a piezoelectric charge constant ( d ₃₃) of 92 pC/N, and a hydrostatic piezoelectric coefficient ( d _h) of 72 pC/N.     

Enhancing Electrical Properties in NBT–KBT Lead-Free Piezoelectric Ceramics by Optimizing Sintering Temperature

Conventional sintering of (Na_{1− x} K _x )_0.5Bi_0.5TiO₃ (abbreviated as NKBT x , x =18–22 mol%) lead-free piezoelectric ceramics was investigated to clarify the optimal sintering temperature for densification and electrical properties. Both sintered density and electrical properties were sensitive to sintering temperature; particularly, the piezoelectric properties deteriorated when the ceramics were sintered above the optimum temperature. The NKBT20 and NKBT22 ceramics synthesized at 1110°–1170°C showed a phase transition from tetragonal to rhombohedral symmetry, which was similar to the morphotropic phase boundary (MPB). Because of such MPB-like behavior, the highest piezoelectric constant ( d ₃₃) of about 192 pC/N with a high electromechanical coupling factor ( k _p) of about 32% were obtained in the NKBT22 ceramics sintered at 1150°C.     

Transmission Electron Microscopy Microstructure of 0.95(Na0.5K0.5)NbO3–0.05BaTiO3 Ceramics

Microstructural characterizations using transmission electron microscopy on 0.95(Na_0.5K_0.5)NbO₃–0.05BaTiO₃ ceramics sintered at 1030°–1150°C for 2 h were carried out. The liquid phase was found at the triple junction of the grains in all specimens and abnormal grain growth occurred in the presence of the liquid phase. Abnormally grown grains whose shapes were cuboidal were well developed. Anisotropically faceted amorphous liquid phase pockets were observed inside the grain in a specimen sintered at 1060°C for 2 h. The interface between the grain and the liquid matrix was flat and some were identified to be {100} planes of the grains. A certain amount of liquid at the sintering temperature of 1060°C enhanced the abnormal grain growth and contributed to the improvement of the piezoelectric properties.     

Nanopowders of Na0.5K0.5NbO3 Prepared by the Pechini Method

A Pechini-based chemical synthesis route was used to produce powders of Na_0.5K_0.5NbO₃ (NKN). The thermochemistry of the gel was investigated using thermogravimetric analysis-fourier transform infrared (TGA-FTIR) evolved gas analysis; in addition, powder FTIR was used to analyze the gel residues after different heat treatments. The final decomposition of the organic components occurred at ∼650°C. However, hydrated–carbonated secondary phase(s) were detected by FTIR in powders that had been heated at 700°C, indicating that the NKN nanopowders are susceptible to a reaction with atmospheric moisture and carbon dioxide. The NKN particle sizes were in the range 50–150 nm after decomposition at 700°C.     

Dielectric Characteristics of Nd(Zn1/2Ti1/2)O3 Ceramics at Microwave Frequencies

The microwave dielectric properties and the microstructures of Nd(Zn_1/2Ti_1/2)O₃ (NZT) ceramics prepared by the conventional solid-state route have been studied. The prepared NZT exhibited a mixture of Zn and Ti showing 1:1 order in the B-site. The dielectric constant values (ɛ_r) saturated at 29.1–31.6. The quality factor ( Q × f ) values of 56 700–170 000 (at 8.5 GHz) can be obtained when the sintering temperatures are in the range of 1300°–1420°C. The temperature coefficient of resonant frequency τ_f was not sensitive to the sintering temperature. The ɛ _r value of 31.6, the Q × f value of 170 000 (at 8.5 GHz), and the τ_f value of −42 ppm/°C were obtained for NZT ceramics sintering at 1330°C for 4 h. For applications of high selective microwave ceramic resonators, filters, and antennas, NZT is proposed as a suitable material candidate.     

Rapid Formation of Active Mesoporous TiO2 Photocatalysts via Micelle in a Microwave Hydrothermal Process

Rapid formation of active, mesoporous, and crystalline TiO₂ photocatalysts via a novel microwave hydrothermal process is presented. Crystalline anatase mesoporous nanopowders 100–300 nm in size with worm hole-like pore sizes of 3–5 nm were prepared by a modified sol–gel of titanium tetra-isopropoxide, accelerated by a microwave hydrothermal process. The organic surfactant, tetradecylamine, which is used as a self-assembly micelle in the sol–gel and microwave hydrothermal process, enables to harvest crystallized mesoporous anatase nanoparticles with a high-surface area. Mesoporous worm hole-like and crystalline powders with surface areas of 243–622 m²/g are obtained. X-ray diffraction, N₂-adsorption isotherms (Barrett–Joyner–Halenda and Brunauer–Emmet–Teller method), scanning electron microscope, and transmission electron microscope are used to identify the characteristics and morphologies of the powders. It is shown that crystallization by calcination at 400°C/3 h inevitably reduced the surface area, while the microwave hydrothermal process demonstrated a rapid formation of crystalline mesoporous TiO₂ nanopowders with a high-surface area and excellent photocatalytic effects.     

Low-Temperature Sintering of K0.5Na0.5NbO3 Ceramics

The objective of this work was to lower the sintering temperature of K_0.5Na_0.5NbO₃ (KNN) without reducing its piezoelectric properties. The KNN was sintered using 0.5, 1, 2, and 4 mass% of (K, Na)-germanate. The influence of the novel sintering aid, based on alkaline germanate with a melting point near 700°C, on the sintering, density, and piezoelectric properties of KNN is presented. The alkaline-germanate-modified KNN ceramics reach up to 96% of theoretical density at sintering temperatures as low as 1000°C, which is approximately 100°C less than the sintering temperature of pure KNN. The relative dielectric permittivity (ɛ/ɛ₀) and losses (tanδ), measured at 10 kHz, the piezo d ₃₃ coefficient, the electromechanical coupling and mechanical quality factors ( k _p, k _t, Q _m) of KNN modified with 1 mass% of alkaline germanate are 397, 0.02, 120 pC/N, 0.40, 0.44, and 77, respectively. These values are comparable to the best values obtained for KNN ceramics sintered above 1100°C.     

Ferroelectric and Piezoelectric Properties of Fine-Grained Na0.5K0.5NbO3 Lead-Free Piezoelectric Ceramics Prepared by Spark Plasma Sintering

Lead-free piezoelectric ceramics have received attention because of increasing interest in environmental protection. Niobate ceramics such as NaNbO₃ and KNbO₃ have been studied as promising Pb-free piezoelectric ceramics, but their sintering densification is fairly difficult. In the present study, highly dense Na_0.5K_0.5NbO₃ ceramics were prepared using spark plasma sintering (SPS). Although the SPS temperature was as low as 920°C, the density of the Na_0.5K_0.5NbO₃ solid solution ceramics was raised to 4.47 g/cm³ (>99% of the theoretical density). After post-annealing in air, reasonably good ferroelectric and piezoelectric properties were obtained in the Na_0.5K_0.5NbO₃ ceramics with submicron grains. The crystal phase of the Na_0.5K_0.5NbO₃ has an orthorhombic structure. The Curie temperature is 395°C and the piezoelectric parameter ( d ₃₃) of the Na_0.5K_0.5NbO₃ ceramics reached 148 pC/N.