Study on properties of CaO-SiO2-B2O3 system glass-ceramic

Low temperature co-fired ceramic (LTCC) is prepared by sintering a glass selected from CaO-SiO₂-B₂O₃ system, and its sintered bodies are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). It is found that the optimal sintering temperature for this glass-ceramic is 820 °C for 15 min, and the major phases of this material are CaSiO₃, CaB₂O₄ and SiO₂. The glass-ceramic possesses excellent dielectric properties: ?_r = 6.5, tan δ < 2 × 10⁻³ at 10 MHz, temperature coefficient of dielectric constant about −51 × 10⁻⁶ °C⁻¹ and coefficient of thermal expansion about 8 × 10⁻⁶ °C⁻¹ at 20-400 °C. Thus, this material is supposed to be suitable for the tape casting process and be compatible with Ag electrode, which could be used as the LTCC materials for the application in wireless communications.     

Microstructure and mechanical properties of small amounts of In2O3 reinforced Pb(ZrxTi1−x)O3 ceramics

Piezoelectric Pb(Zr_xTi_1−x)O₃ (PZT) ceramics with small amount (0.5-2.0 wt.%) of In₂O₃ are prepared by conventional sintering method. Based on X-ray diffraction analysis, the tetragonality of PZT matrix decreases with In₂O₃ content, indicating that In₂O₃ diffuses into PZT matrix. The microstructure of PZT matrix is significantly refined by doping small amounts of In₂O₃. The grain size reduction and the matrix grain boundary reinforcement are the probable mechanism responsible for the high strength and hardness in the PZT/In₂O₃ materials. The enhancement in Young’s modulus is attributed to In³⁺ substitution. The decreased tetragonality with In₂O₃ addition results in less crack energy absorption by domain switching and, hence, causes the small reduction in fracture toughness.     

Synthesis, structure and dielectric characterization of Ln2Ti2−2xM2xO7(Ln=Gd, Er; M=Zr, Sn, Si)

The progress in wireless communications and information access has demanded the use of electronic ceramics exhibiting desired properties. To further our understanding of these properties, compounds in the Ln₂Ti_2-2xM_2xO₇ (Ln=Gd, Er; M=Zr, Sn, Si) systems were synthesized by ceramic methods and characterized by powder X-ray diffraction. The ZrO₂-doped Gd₂Ti_2−2xZr_2xO₇ compounds adopt the pyrochlore structure type and form a complete solid solution. Er₂Ti_2−2xZr_2xO₇ forms a pyrochlore solid solution for x<0.1. However, stoichiometric Er₂Zr₂O₇ does not form; instead Er₄Zr₃O₁₂ forms a with defect fluorite structure. The Sn-doped Ln₂Ti_2−2xSn_2xO₇ (Ln=Gd, Er) compounds form complete solid solutions, and the Si compounds adopt the pyrochlore structure up to x=0.05. At ambient temperature, dielectric constants range from 10 to 61 for Er₂Ti_2−2xZr_2xO₇ and 16-31 for Gd₂Ti_2−2xZr_2xO₇ with low dielectric loss (1×10⁻³) at 1 GHz.     

Low loss Sr1−xCaxLa4Ti5O17 microwave dielectric ceramics

Microwave dielectric ceramics in the Sr_1−xCa_xLa₄Ti₅O₁₇ (0 ≤ x ≤ 1) composition series were prepared through a solid state mixed oxide route. All the compositions formed single phase ceramics within the detection limit of in-house X-ray diffraction when sintered in the temperature range 1450-1580 °C. Theoretical density and molar volume decreased due to the substitution of Ca²⁺ for Sr²⁺ which was associated with a decrease in the dielectric constant (?_r) and temperature coefficient of resonant frequency (τ_f) but an increase in quality factor, Qf_o. Optimum properties were achieved for Sr_0.4Ca_0.6La₄Ti₅O₁₇ which exhibited, ?_r ∼ 53.7, Qf_o ∼ 11,532 GHz and τ_f ∼ −1.4 ppm/°C.     

Modified tunable dielectric properties by addition of MgO on BaZr0.25Ti0.75O3 ceramics

Phase composition, microstructure and tunable dielectric properties of (1 − x)BaZr_0.25Ti_0.75O₃-xMgO (BZTM) composite ceramics fabricated by solid-state reaction were investigated. It was found Mg not only existed in the matrix as MgO, there was also trace amount of Mg²⁺ ions dissolved in the BZT grains, which led to Curie temperature of the BZTM composites ceramics shifting to below −100 °C. Dielectric permittivity of the BZTM composite ceramics was reduced from thousands to hundreds by manipulating the content of MgO. Johnson's phenomenological equation based on Devonshire's theory was used to describe the nonlinear dielectric permittivity of the ceramics with increasing applied DC field. With increasing content of MgO, anharmonic constant α_(T) increased monotonously. Dielectric permittivity was 672, while dielectric tunability was as high as 30.0% at 30 kV/cm and dielectric loss was around 0.0016 for the 0.6BaZr_0.25Ti_0.75O₃-0.4MgO sample at 10 kHz and room temperature.     

Structure, dielectric and ferroelectric anisotropy of Sr2−xCaxBi4Ti5O18 ceramics

Sr_2−xCa_xBi₄Ti₅O₁₈(x = 0, 0.05) powders synthesized by solid state route were uniaxially pressed and sintered at 1225 °C for 2 h. The obtained dense ceramics exhibited crystallographic anisotropy with a dominant c axis parallel to the uniaxial pressing direction which was quantified in terms of the Lotgering factor. Microstructure anisotropy of both compositions (x = 0, 0.05) consisted of plate like grains exhibiting their larger surfaces mostly perpendicular to the uniaxial pressing direction. Dielectric and ferroelectric properties of Sr_2−xCa_xBi₄Ti₅O₁₈ ceramics were measured under an electric field (E) applied parallel and perpendicularly to uniaxial pressing direction. The obtained dielectric ?_R(T) and polarization (P-E) curves depended strongly on E direction thus denoting a significant effect from microstructure and crystallographic texture. Sr_2−xCa_xBi₄Ti₅O₁₈ properties were also significantly affected by Ca content (x): Curie temperature increased from 280 °C (x = 0) to 310 °C (x = 0.05) while ?_R and remnant polarization decreased for x = 0.05. The present results are discussed within the framework of the processing and crystal structure-properties relationships of Aurivillius oxides ceramics.     

Effect of Pb(Fe1/2Nb1/2)O3 modification on dielectric and piezoelectric properties of Pb(Mg1/3Nb2/3)O3-PbZr0.52Ti0.48O3 ceramics

10 mol% Pb(Fe_1/2Nb_1/2)O₃ (PFN) modified Pb(Mg_1/3Nb_2/3)O₃-PbZr_0.52Ti_0.48O₃ (PMN-PZT) relaxor ferroelectric ceramics with compositions of (0.9 − x)PMN-0.1PFN-xPZT (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9) were prepared. X-ray diffraction investigations indicated that as-prepared ceramics were of pure perovskite phase and the sample with composition of x = 0.8 was close to morphotropic phase boundary (MPB) between rhombohedral and tetragonal phase. Dielectric properties of the as-prepared ceramics were measured, and the Curie temperature (T_c) increased sharply with increasing PZT content and could be higher than 300 °C around morphotropic phase boundary (MPB) area. At 1 kHz, the sample with composition of x = 0.1 had the largest room temperature dielectric constant ?_r = 3519 and maximum dielectric constant ?_m = 20,475 at T_m, while the sample with composition of x = 0.3 possessed the maximum dielectric relaxor factor of γ = 1.94. The largest d₃₃ = 318 pC/N could be obtained from as-prepared ceramics at x = 0.9. The maximum remnant polarization (P_r = 28.3 μC/cm²) was obtained from as-prepared ceramics at x = 0.4.     

Study of the dielectric properties in the NaNbO3 -KNbO3-In2O3 system using AC impedance spectroscopy

We report a comparative study of the dielectric properties of solid-state (ceramic method) synthesized NaNbO₃ (NN), Na_0.75K_0.25NbO₃ (K25NN), K_0.5Na_0.5NbO₃ (KNN) and some composite materials containing In₂O₃ and NN or KNN using an AC impedance method. Powder X-ray diffraction (PXRD) was employed to investigate the phase purity. No significant amount of impurity phase was observed for NN, K25NN, and KNN. Substitutions of 10, 15 and 25 mol% In³⁺ for Nb⁵⁺ in KNN and NN using solid-state reactions at 1150 °C resulted in composite materials. AC impedance studies of NN, KNN and K25NN in the temperature range of 500-800 °C showed a single semicircle (attributed to the bulk property) in the high-frequency range of 10³ to 10⁶ Hz. The individual contributions from the bulk and grain boundary on the dielectric properties were resolved and quantified from the impedance data. The calculated dielectric values for NN were consistent with previously reported in the literature. 10% Indium based KNN composite materials had the lowest dielectric loss 0.585 and the dielectric constant of 233 at 100 kHz at the temperature of 650 °C.     

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.     

Microgeometry effect on the properties of Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3 ferroelectric ceramics

Porous Pb_0.99(Zr_0.95Ti_0.05)_0.98Nb_0.02O₃ ferroelectric ceramics with different pore size were prepared by solid-state sintering in air. The microstructural effect on the properties has been systematically investigated by SEM, ferroelectric hysteresis, strain-electric field curves and breakdown strength measurements. The results demonstrate that the microgeometry has a subtle effect on the ferroelectric and dielectric properties. However, the results also demonstrate that the electric field induced strain and the dielectric breakdown strength decreases with the increase of pore size.     

Quantitative dependence of the properties of Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3 ferroelectric ceramics on porosity

Porous Pb_0.99(Zr_0.95Ti_0.05)_0.98Nb_0.02O₃ ferroelectric ceramics with a pore size of the order of the crystalline grain size were prepared and the microstructure and the properties were investigated. Based on this microstructure, the net porosity of the ceramics can be attributed to the intentionally introduced extrinsic porosity and thus the quantitative dependence of ferroelectric and dielectric properties of the ceramics on the porosity can be established respectively. A good agreement with experimental measurements was obtained. Our work represents the first attempt to tailor the properties of ferroelectric ceramics via varying the porosity from the viewpoint of application.     

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.     

Dielectric properties of a new ceramic system (1 − x)Mg4Nb2O9-xCaTiO3 at microwave frequency

The microstructures and the microwave dielectric properties of the (1 − x)Mg₄Nb₂O₉-xCaTiO₃ ceramic system were investigated. In order to achieve a temperature-stable material, CaTiO₃ (τ_f ∼ 800 ppm/°C) was chosen as a τ_f compensator and added to Mg₄Nb₂O₉ (τ_f ∼ −70 ppm/°C) to form a two phase system. It was confirmed by the XRD and EDX analysis. By appropriately adjusting the x-value in the (1 − x)Mg₄Nb₂O₉-xCaTiO₃ ceramic system, near-zero τ_f value can be achieved. A new microwave dielectric material, 0.5Mg₄Nb₂O₉-0.5CaTiO₃ applicable in microwave devices is suggested and possesses the dielectric properties of a dielectric constant ?_r ∼ 24.8, a Q × f value ∼82,000 GHz (measured at 9.1 GHz) and a τ_f value ∼−0.3 ppm/°C.     

Effects of Ca and Zr substitution upon structure and properties of Ba5LaTi3Ta7O30 low-loss dielectric ceramics

Effects of Ca and Zr substitution upon the dielectric properties of Ba₅LaTi₃Ta₇O₃₀ ceramics were investigated together with the structural characterization. All the samples of Ba₅La(Zr_xTi_1−x)₃Ta₇O₃₀ formed a filled tungsten-bronze structures, whereas the solid solution limit was determined as x=0.25 in (Ca_xBa_1−x)₅LaTi₃Ta₇O₃₀. Beyond this limit secondary phase of CaTa₂O₆ was detected and it would become the major phase for the Ca-rich compositions. The temperature coefficient of dielectric constant was improved with increasing Zr content while the dielectric constant decreased and the low dielectric loss varied little (in the order of 10⁻⁴). In the case of (Ca_xBa_1−x)₅LaTi₃Ta₇O₃₀, small temperature coefficient of dielectric constant could be obtained with increasing Ca content while the dielectric constant decreased significantly, and a small amount substitution of Ca for Ba induced decrease in dielectric loss.     

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.     

Microstructural evolution and dielectric properties of Cu-deficient and Cu-excess CaCu3Ti4O12 ceramics

The microstructural evolution and dielectric properties of CaCu_3−xTi₄O_12−x (3 − x = 2.8-3.05) ceramics were investigated. Normal grain growth behavior was observed at Cu/Ca ≤ 2.9, while abnormal grain growth was observed at Cu/Ca ≥ 2.95. A CuO-rich intergranular liquid phase at Cu/Ca ≥ 2.95 and angular grain morphology were the main reasons for abnormal grain growth. However, the abundant intergranular liquid at Cu/Ca = 3.05 significantly affected the relative dielectric permittivity and dielectric loss. The CuO composition is the key parameter that determines the microstructure and dielectric properties of CCTO ceramics.     

Sintering and dielectric properties of 0.88Al2O3-0.12TiO2 microwave ceramics by glass addition

The microwave characteristics and the microstructures of 0.88Al₂O₃-0.12TiO₂ with various amounts of MgO-CaO-SiO₂-Al₂O₃ (MCAS) glass sintered at different temperatures have been investigated. The sintering temperature can be lowered to 1300 °C by the addition of MCAS glass. The densities, dielectric constants (ε_r) and quality values (Q×f) of the MCAS-added 0.88Al₂O₃-0.12TiO₂ ceramics decrease with the increase of MCAS glass content. The temperature coefficients of the resonant frequency (τ_f) are shifted to more negative values as the MCAS content or the sintering temperatures increase. The change of the crystalline phases of Al₂TiO₅ phase and rutile-TiO₂ phase has profound effects on the microwave dielectric properties of the MCAS-added Al₂O₃-TiO₂ ceramics. As sintered at 1250 °C, 0.88Al₂O₃-0.12TiO₂ ceramics with 2 wt.% MCAS glass addition exists a ε_r value of 8.63, a Q×f value of 9578 and a τ_f value of +5 ppm/°C.     

Dielectric relaxation related to single-ionized oxygen vacancies in (Pb1−xLax)(Zr0.90Ti0.10)1−x/4O3 ceramics

The dielectric relaxation phenomenon has been studied in lanthanum modified lead zirconate titanate ceramics in the high temperature paraelectric phase. The high temperature dielectric response revealed an anomalous behavior, which is characterized by an increase of the real component of the dielectric permittivity with the increase of the temperature. At the same time, a similar behavior, with very high values, has been observed in the imaginary component of the dielectric permittivity, which can be associated with conduction effects related to the conductivity losses. The frequency and temperature behavior of the complex dielectric permittivity has been analyzed considering the semi-empirical complex Cole-Cole equation. The activation energy value, obtained from the Arrhenius’ dependence for the relaxation time, was found to decreases with the increase of the lanthanum concentration and has been associated with single-ionized oxygen vacancies. The short-range hopping of oxygen vacancies is discussed as the main cause of the dielectric relaxation.     

Effects of K4CuNb8O23 on the structure and electrical properties of lead-free 0.94(Na0.5K0.5)NbO3–0.06LiNbO3 ceramics

Dense K₄CuNb₈O₂₃-modified (K_0.5Na_0.5)_0.94Li_0.06NbO₃ ceramics were prepared by normal sintering. The effects of K₄CuNb₈O₂₃ on the phase structure, microstructure and electrical properties of the ceramics were studied. Results showed that K₄CuNb₈O₂₃ induced a perovskite structure transition from coexistence of orthorhombic and tetragonal phases to orthorhombic symmetry. The addition of K₄CuNb₈O₂₃ promoted the sintering of (K_0.5Na_0.5)_0.94Li_0.06NbO₃ ceramics and simultaneously caused the grain growth. Moreover, K₄CuNb₈O₂₃-doping changed the (K_0.5Na_0.5)_0.94Li_0.06NbO₃ to “hard” ceramics and significantly enhanced the mechanical quality factor Q_m. It was found that the (K_0.5Na_0.5)_0.94Li_0.06NbO₃ ceramics doped with 0.60 mol% K₄CuNb₈O₂₃ exhibited a high mechanical quality factor (Q_m  983) as well as relatively large d₃₃ (136 pC/N) and k_p (35.9%), suggesting that this material is a promising candidate for lead-free piezoelectric ceramics for high-frequency applications.     

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.