Study on properties of BaxSmyTi7O20 ceramics with CaO-SiO2-B2O3 glass

The effect of CaO-SiO₂-B₂O₃ (CSB) glass addition on the sintering temperature and dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics has been investigated using X-ray diffraction, scanning electron microscopy and differential thermal analysis. The CSB glass starts to melt at about 970 °C, and a small amount of CSB glass addition to Ba_xSm_yTi₇O₂₀ ceramics can greatly decrease the sintering temperature from about 1350 to about 1260 °C, which is attributed to the formation of liquid phase. It is found that the dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics are dependent on the amount of CSB glass and the microstructures of sintered samples. The product with 5 wt% CSB glass sintered at 1260 °C is optimal in these samples based on the microstructure and the properties of sintering product, when the major phases of this material are BaSm₂Ti₄O₁₂ and BaTi₄O₉. The material possesses excellent dielectric properties: ?_r = 61, tan δ = 1.5 × 10⁻⁴ at 10 GHz, temperature coefficient of dielectric constant is −75 × 10⁻⁶ °C⁻¹.     

Improved high-Q microwave dielectric resonator using CuO-doped MgNb2O6 ceramics

The microwave dielectric properties and the microstructures of MgNb₂O₆ ceramics with CuO additions (1-4 wt.%) prepared with conventional solid-state route have been investigated. The sintered samples exhibit excellent microwave dielectric properties, which depend upon the liquid phase and the sintering temperature. It is found that MgNb₂O₆ ceramics can be sintered at 1140 °C due to the liquid phase effect of CuO addition. At 1170 °C, MgNb₂O₆ ceramics with 2 wt.% CuO addition possesses a dielectric constant (ε_r) of 19.9, a Q×f value of 110,000 (at 10 GHz) and a temperature coefficient of resonant frequency (τ_f) of −44 ppm/°C. The CuO-doped MgNb₂O₆ ceramics can find applications in microwave devices requiring low sintering temperature.     

Effect of B2O3-Bi2O3-SiO2-ZnO glass on the sintering and microwave dielectric properties of 0.83ZnAl2O4-0.17TiO2

The 0.83ZnAl₂O₄-0.17TiO₂ (ZAT) ceramics were synthesized by solid state ceramic route. The effect of 27B₂O₃-35Bi₂O₃-6SiO₂-32ZnO (BBSZ) glass on the microwave dielectric properties of ZAT was investigated. The crystal structure and the microstructure of the ceramic-glass composites were studied by X-ray diffraction and scanning electron microscopic techniques. The low frequency dielectric loss was measured at 1 MHz. The dielectric properties of the sintered samples were measured in the microwave frequency range by the resonance method. Addition of 0.2 wt% of BBSZ improved the dielectric properties with quality factor (Q_u × f) > 120,000 GHz, temperature coefficient of resonant frequency (τ_f) = −7.3 ppm/°C and dielectric constant (?_r) = 11.7. Addition of 10 wt% of BBSZ lowered the sintering temperature to about 950 °C with Q_u × f > 10,000 GHz, ?_r = 10 and τ_f = −23 ppm/°C. The reactivity of 10 wt% BBSZ added ZAT with silver was also studied. The results show that ZAT doped with suitable amount of BBSZ glass is a possible material for low-temperature co-fired ceramic (LTCC) application.     

Low-temperature sintering and compatibility with silver electrode of Ba4MgTi11O27 microwave dielectric ceramic

Ba₄MgTi₁₁O₂₇ microwave dielectric ceramic was investigated using X-ray diffraction, scanning electron microscopy and dielectric measurement. The pure Ba₄MgTi₁₁O₂₇ ceramic shows a high sintering temperature (∼1275 °C) and good microwave dielectric properties as Q × f of 19,630 GHz, ?_r of 36.1, τ_f of 14.6 ppm/°C. It was found that the addition of BaCu(B₂O₅) (BCB) can effectively lower the sintering temperature from 1275 to 925 °C, and does not induce much degradation of the microwave dielectric properties. The BCB-doped Ba₄MgTi₁₁O₂₇ ceramics can be compatible with Ag electrode, which makes it a promising ceramic for LTCC technology application.     

Dielectric and pyroelectric anisotropy in melt-quenched BaBi2(Nb1 − xVx)2O9 ceramics

The (0 0 l) textured BaBi₂(Nb_1 − xV_x)₂O₉ (where x = 0, 0.03, 0.07, 0.1 and 0.13) ceramics were fabricated via the conventional melt-quenching technique followed by high temperature heat-treatment (800-1000 °C range). The influence of vanadium content and sintering temperature on the texture development and relative density were investigated. The samples corresponding to the composition x = 0.1 sintered at 1000 °C for 10 h exhibited the maximum orientation of about 67%. The Scanning electron microscopic studies revealed the presence of platy grains having the a-b planes perpendicular the pressing axis. The dielectric constant and the pyroelectric co-efficient values in the direction perpendicular to the pressing axis were higher. The anisotropy in the dielectric constant is about 100 (at 100 kHz) at the dielectric maximum temperature and anisotropy in the pyroelectric co-efficient is about 50 μC cm⁻² °C⁻¹ in the vicinity of pyroelectric anomaly for the sample corresponding to the composition x = 0.1 sintered at 1000 °C. Higher values of the dielectric loss and electrical conductivity were observed in the direction perpendicular to the pressing axis which is attributed to the high oxygen ion conduction in the a-b planes.     

Preparation and properties of negative thermal expansion Zr2WP2O12 ceramics

Using solid-state reaction method, Zr₂WP₂O₁₂ powder was synthesized for this study. The optimum heating condition was 1200 °C for 4 h. The obtained powder was compacted and sintered. The relative density of the Zr₂WP₂O₁₂ ceramics with no sintering additive was 60%. That of samples sintered with more than 0.5 mass% MgO was about 97%. The average grain size (D₅₀), as estimated from the polished surface of a sample sintered at 1200 °C for 4 h was about 1 μm. The obtained ceramics showed a negative thermal expansion coefficient of about −3.4 × 10⁻⁶ °C⁻¹. Young's modulus, Poisson's ratio, three-point bending strength, Vickers microhardness, and fracture toughness of the obtained ceramics were, respectively, 74 GPa, 0.25, 113 ± 13 MPa, 4.4 GPa and 2.3 MPa m^1/2.     

Synthesis and Li ion conductivity of Li2O-Nb2O5-P2O5 glasses and glass-ceramics

Glasses with the compositions of xLi₂O-(70 − x)Nb₂O₅-30P₂O₅, x = 30-60, and their glass-ceramics are synthesized using a conventional melt-quenching method and heat treatments in an electric furnace, and Li⁺ ion conductivities of glasses and glass-ceramics are examined to clarify whether the glasses and glass-ceramics prepared have a potential as Li⁺ conductive electrolytes or not. The electrical conductivity (σ) of the glasses increases monotonously with increasing Li₂O content, and the glass of 60Li₂O-10Nb₂O₅-30P₂O₅ shows the value of σ = 2.35 × 10⁻⁶ S/cm at room temperature and the activation energy (E_a) of 0.48 eV for Li⁺ ion mobility in the temperature range of 25-200 °C. It is found that two kinds of the crystalline phases of Li₃PO₄ and NbPO₅ are formed in the crystallization of the glasses and the crystallization results in the decrease in Li⁺ ion conductivity in all samples, indicating that any high Li⁺ ion conducting crystalline phases have not been formed in the present glasses. 60Li₂O-10Nb₂O₅-30P₂O₅ glass shows a bulk nanocrystallization (Li₃PO₄ nanocrystals with a diameter of ∼70 nm) and the glass-ceramic obtained by a heat treatment at 544 °C for 3 h in air exhibits the values of σ = 1.23 × 10⁻⁷ S/cm at room temperature and E_a = 0.49 eV.     

Preparation, structure and dielectric properties of Ba4LaMNb3O15 (M = Ti, Sn ) ceramics

Two new cation-deficient hexagonal perovskites Ba₄LaMNb₃O₁₅ (M = Ti, Sn) ceramics were prepared by high temperature solid-state reaction route. The phase and structure of the ceramics were characterized by X-ray diffraction, scanning electron microscopy (SEM). The microwave dielectric properties of the ceramics were studied using a network analyzer. The Ba₄LaTiNb₃O₁₅ has high dielectric constant of 52, high quality factors (Q) 3500 (at 4.472 GHz), and temperature variation of resonant frequency (τ_f) +93 ppm °C⁻¹ at room temperature; Ba₄LaSnNb₃O₁₅ has dielectric constant of 39 with high Q value of 2510 (at 5.924 GHz), and τ_f −29 ppm °C⁻¹.     

Growth and properties of Ca0.28Ba0.72Nb2O6 single crystals

Calcium barium niobate Ca_0.28Ba_0.72Nb₂O₆ (CBN-28) crystals were successfully grown by the Czochralski method. X-ray powder diffraction experiments indicated that CBN single crystals are tetragonal with a = 12.432(±0.002) Å and c = 3.957(±0.001) Å, which have almost the same structure as the Sr_0.50Ba_0.50Nb₂O₆ (SBN-50) crystal. The thermal expansion coefficient perpendicular to Z-direction had been measured to be 1.25 × 10⁻⁵ K⁻¹ between 293.15 and 572.15 K, and along Z-axis was negative between 298.15 and 543.15 K. The specific heat of the crystal had been measured by the differential scanning calorimetric experiments. The transmittance spectra from 200 to 3200 nm were also measured. The measured temperature dependence of dielectric constants showed that the Curie temperature of the CBN-28 crystals is 260 °C, which is about 200 °C higher than that of the (SBN) crystal.     

Effect of sintering time on crystal structure and microwave dielectric properties in aeschynite-structured (Sm1−xYx)(Ti1.5W0.5)O6 (x = 0 and 0.5) ceramics

The crystal structure and microwave dielectric properties of the (Sm_1−xY_x)(Ti_1.5W_0.5)O₆ (x = 0 and 0.5) ceramics sintered at 1375 °C for 2-50 h were investigated in this study. No secondary phase was observed in the samples sintered for various sintering times, whereas a secondary phase was formed in the (Sm_0.5Y_0.5)(Ti_1.5W_0.5)O₆ ceramic sintered at 1400 °C for 50 h. As for the microstructure analysis, the formation of the liquid phase was observed in the both of the samples sintered for 20 and 50 h. The formation of the liquid phase is related to the compositional change of Ti and W from the stoichiometric composition of the samples caused by the instability of crystal structure. The dielectric constants were increased with increased sintering time in the both of the samples, though variations in the temperature coefficient of resonant frequency of the samples were not recognized with the variation in the sintering time. Moreover, although the quality factors of the each sample increased with increasing the sintering time from 2 to 10 h, decreases in the quality factors were recognized when the sintering time was over 10 h.     

Microwave dielectric properties and microstructures of CuO- and ZnO-doped LaAlO3 ceramics

The microwave dielectric properties and the microstructures of 0.25 wt.% CuO-doped LaAlO₃ ceramics with ZnO additions have been investigated. The sintered LaAlO₃ ceramics are characterized by X-ray diffraction spectra and scanning electron microscopy (SEM). Tremendous reduction in sintering temperature can be achieved with the addition of sintering aids CuO and ZnO. The ceramic samples show that dielectric constants (ε_r) of 22−24 and Q×f values of 33,000−57,000 (at 9.7 GHz) can be obtained at low sintering temperatures 1340−1460°C. The temperature coefficient of resonant frequency varies from −24 to −48 ppm/°C. At the level of 0.25 wt.% CuO and 1 wt.% ZnO additions, LaAlO₃ ceramics possesses a dielectric constant (ε_r) of 23.4, a Q×f value of 57,000 (at 9.7 GHz) and a τ_f value of −38 ppm/°C at 1400°C for 2 h.     

Microwave dielectric properties and microstructures of the 11Li2O-3Nb2O5-12TiO2 ceramics with B2O3 addition

The effects of B₂O₃ addition, as a sintering agent, on the sintering behavior, microstructure and microwave dielectric properties of the 11Li₂O-3Nb₂O₅-12TiO₂ (LNT) ceramics have been investigated. With the low-level doping of B₂O₃ (≤2 wt.%), the sintering temperature of the LNT ceramic could be effectively reduced to 900 °C. The B₂O₃-doped LNT ceramics are also composed of Li₂TiO₃ss and “M-phase” phases. No other phase could be observed in the 0.5-2 wt.% B₂O₃-doped ceramics sintered at 840-920 °C. The addition of B₂O₃ induced no obvious degradation in the microwave dielectric properties but increased the τ_f values. Typically, the 0.5 wt.% B₂O₃-doped ceramics sintered at 900 °C have better microwave dielectric properties of ?_r = 49.2, Q × f = 8839 GHz, τ_f = 57.6 ppm/°C, which suggest that the ceramics could be applied in multilayer microwave devices requiring low sintering temperatures.     

(5 − x)BaO-xMgO-2Nb2O5 ceramics prepared using a reaction-sintering process

(5 − x)BaO-xMgO-2Nb₂O₅ (x = 0.5 and 1; 5MBN and 10MBN) microwave ceramics prepared using a reaction-sintering process were investigated. Without any calcinations involved, the mixture of BaCO₃, MgO, and Nb₂O₅ was pressed and sintered directly. MBN ceramics were produced after 2-6 h of sintering at 1350-1500 °C. The formation of (BaMg)₅Nb₄O₁₅ was a major phase in producing 5MBN ceramics, and the formation of Ba(Mg_1/3Nb_2/3)O₃ was a major phase in producing 10MBN ceramics. As CuO (1 wt%) was added, the sintering temperature dropped by more than 150 °C. We produced 5MBN ceramics with these dielectric properties: ?_r = 36.69, Qf = 20,097 GHz, and τ_f = 61.1 ppm/°C, and 10MBN ceramics with these dielectric properties: ?_r = 39.2, Qf = 43,878 GHz, and τ_f = 37.6 ppm/°C. The reaction-sintering process is a simple and effective method for producing (5 − x)BaO-xMgO-2Nb₂O₅ ceramics for applications in microwave dielectric resonators.     

Optimized microwave dielectric properties of Co- and Ca-substituted Mg0.6Zn0.4TiO3

The system of (1 − y)(Mg_0.6Zn_0.4)_1−xCo_xTiO₃-yCaTiO₃ was investigated to optimize its microwave dielectric properties by adopting appropriate contents of Co and Ca and by controlling sintering conditions. The effect of Co substitution was to enhance densification and Qf value, while the addition of CaTiO₃ resulted in increases of dielectric constant and TCF. As an optimal compositions, 0.93(Mg_0.6Zn_0.4)_0.95Co_0.05TiO₃-0.07CaTiO₃ successfully demonstrated a dielectric constant of 23.04, a Qf of 79,460 GHz and a TCF value of +1.4 ppm/°C after firing at a relatively lower sintering temperature of 1200 °C. The increase of sintering temperature beyond 1200 °C tended to degrade overall microwave dielectric properties presumably due to Zn volatilization as evidenced by the presence of a Zn-deficient phase (MgTi₂O₅) at 1400 °C. An attempt to establish the correlation between microstructure characteristics and dielectric properties was made in this dielectric system where the extensive range of firing temperature up to 1400 °C was evaluated.     

Synthesis of (1 − x)Ca2/5Sm2/5TiO3-xLi1/2Nd1/2TiO3 ceramic powder via ethylenediaminetetraacetic acid precursor

(1 − x)Ca_2/5Sm_2/5TiO₃-xLi_1/2Nd_1/2TiO₃ (CSLNT) ceramic powder was prepared by a liquid mixing method using ethylenediaminetetraacetic acid (EDTA) as the chelating agent. TG, DTA, XRD and TEM characterized the precursors and derived oxide powders. When x = 0.3, perovskite CSLNT was synthesized at 1000 °C for 3 h in air. The CSLNT (x = 0.3) ceramics sintered at 1200 °C for 3 h show excellent microwave dielectric properties of ?_r = 99, Q_f = 6200 GHz and τ_f = 9 × 10⁻⁶ °C⁻¹.     

Processing, dielectric properties and impedance characteristics of Na0.5Bi0.5Cu3Ti4O12 ceramics

Na_0.5Bi_0.5Cu₃Ti₄O₁₂ (NBCTO) ceramics were prepared by conventional solid-state reaction method. The phase structure, microstructure and dielectric properties of NBCTO ceramics sintered at various temperatures with different soaking time were investigated. Pure NBCTO phase could be obtained with increasing the temperature and prolonging the soaking time. High dielectric permittivity (13,495) and low dielectric loss (0.031) could be obtained when the ceramics were sintered at 1000 °C for 7.5 h. The ceramics sintered at 1000 °C for 7.5 h also showed good temperature stability (−4.00 to −0.69%) over a large temperature range from −50 to 150 °C. Complex impedances results revealed that the grain was semiconducting and the grain boundaries was insulating. The grain resistance (R_g) was 12.10 Ω cm and the grain boundary resistance (R_gb) was 2.009 × 10⁵ Ω cm when the ceramics were sintered at 1000 °C for 7.5 h.     

Influence of Bi2O3 and CuO addition on low-temperature sintering and dielectric properties of Ba0.6Sr0.4TiO3 ceramics

In this study, we tried to lower the sintering temperature of Ba_0.6Sr_0.4TiO₃ (BST) ceramics by several kinds of adding methods of Bi₂O₃, CuO and CuBi₂O₄ additives. The effects of different adding methods on the microstructures and the dielectric properties of BST ceramics have been studied. In the all additive systems, the single addition of CuBi₂O₄ was the most effective way for lowering the sintering temperature of BST. When CuBi₂O₄ of 0.6 mol% was mixed with starting BST powders and sintered at 1100 °C, the derived ceramics demonstrated dense microstructure with a low dielectric constant (? = 4240), low dielectric loss (tan δ = 0.0058), high tunability (Tun = 38.3%) and high Q value (Q = 251). It was noteworthy that the sintering temperature was significantly lowered by 350 °C compared with no-additive system, and the derived ceramics maintained the excellent microwave dielectric properties corresponding to pure BST.     

Synthesis, low-temperature sintering and the dielectric properties of the ZnO-(1 − x)TiO2-xSnO2 (x = 0.04-0.2)

ZnO-(1 − x)TiO₂-xSnO₂ (x = 0.04-0.2) ceramics were prepared by conventional mixed-oxide method combined with a chemical processing. Fine particle powders were prepared by chemical processing to activate the formation of compound and to improve the sinterability. One wt.% of V₂O₅ and B₂O₃ with the mole ratios of 3:1 were used to lower the sintering temperature of ceramics. The effect of Sn content on phase structure and dielectric properties were investigated. The results show that the substituting Sn for Ti accelerates the hexagonal phase transition to cubic phase, and an inverse spinel structure Zn₂(Ti_1−xSn_x)O₄ solid solution forms. The best dielectric properties obtained at x = 0.12. The ZnO-0.88TiO₂-0.12SnO₂ ceramics sintered at 900 °C exhibit a good dielectric property: ?_r = 29 and tan δ = 9.86 × 10⁻⁵. Due to their good dielectric properties, low firing characteristics, ZnO-(1 − x)TiO₂-xSnO₂ (x = 0.04-0.2) can serve as the promising microwave dielectric capacitor.     

Synthesis and microwave dielectric properties of CaO-MgO-SiO2 submicron powders doped with Li2O-Bi2O3 by sol-gel method

Using Ca(NO₃)₂·4H₂O, Mg(NO₃)₂·6H₂O, Si(OC₂H₅)₄, LiNO₃ and Bi(NO₃)₃·5H₂O as raw materials, CaO-MgO-SiO₂ submicron powders were prepared at low temperature by sol-gel method. The crystallization temperature was decreased enormously by the introduction of Li-Bi liquid phase sintering aids into Ca-Mg-Si sol, and the powders with average particle sizes of 80-100 nm and 200-400 nm were obtained at the calcining temperature of 750 °C and 800 °C, respectively. The sintering characteristic and dielectric properties of powders calcined at 750 °C with different content of powders calcined at 800 °C were studied. When the content of powders calcined at 800 °C was 10 wt%, the dielectric ceramic sintered at 890 °C had compact structure, and possessed excellent microwave dielectric properties: ?_r = 7.16, Q × f = 25630 GHz, τ_f = −69.26 ppm/°C.     

Improved microwave dielectric properties of B2O3-doped Nd(Co1/2Ti1/2)O3 ceramics with near zero temperature coefficient of resonant frequency

The microwave dielectric properties and the microstructures of Nd(Co_1/2Ti_1/2)O₃ ceramics prepared by conventional solid-state route have been studied. The prepared Nd(Co_1/2Ti_1/2)O₃ exhibited a mixture of Co and Ti showing 1:1 order in the B-site. It is found that low-level doping of B₂O₃ (up to 0.75 wt.%) can significantly improve the density and dielectric properties of Nd(Co_1/2Ti_1/2)O₃ ceramics. Nd(Co_1/2Ti_1/2)O₃ ceramics with additives could be sintered to a theoretical density higher than 98.5% at 1320 °C. Second phases were not observed at the level of 0.25-0.75 wt.% B₂O₃ addition. The temperature coefficient of resonant frequency (τ_f) was not significantly affected, while the dielectric constants (?_r) and the unloaded quality factors Q were effectively promoted by B₂O₃ addition. At 1320 °C/4 h, Nd(Co_1/2Ti_1/2)O₃ ceramics with 0.75 wt.% B₂O₃ addition possesses a dielectric constant (?_r) of 27.2, a Q × f value of 153,000 GHz (at 9 GHz) and a temperature coefficient of resonant frequency (τ_f) of 0 ppm/°C. The B₂O₃-doped Nd(Co_1/2Ti_1/2)O₃ ceramics can find applications in microwave devices requiring low sintering temperature.