Effect of sintering temperature on dielectric properties of Ba0.6Sr0.4TiO3–MgO composite ceramics prepared from fine constituent powders

Composite ceramics of Ba_0.6Sr_0.4TiO₃ + 60 wt.% MgO were prepared from fine constituent powders by sintering at 1200–1280 °C. The composite specimens sintered at the relatively low temperatures showed satisfactory densification due to fine morphology of the constituent powders. The elevation of sintering temperature promoted the incorporation of Mg²⁺ into the lattice of the Ba_0.6Sr_0.4TiO₃ phase and grain growth of the two constituent phases. The dependence of the dielectric properties on sintering temperature was explained in relation to the structural evolution. Controlling the sintering temperature of the composite was found to be important to achieve the desired nonlinear dielectric properties. Sintering at 1230 °C was determined to be preferred for the composite in terms of the nonlinear dielectric properties. The specimen sintered at the temperature attained a tunability of 17.3% and a figure of merit of 127 at 10 kHz and 20 kV/cm.     

Piezoelectric and dielectric properties of Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3–Ba0.77Ca0.23TiO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x)Bi_0.5(Na_0.84K_0.16)_0.5TiO₃–xBa_0.77Ca_0.23TiO₃ (BNKT–xBCT, x = 0–0.04) were synthesized by conventional solid-state reaction method. The piezoelectric, dielectric, and ferroelectric characteristics of the ceramics are investigated and discussed. The XRD results show that Ba_0.77Ca_0.23TiO₃ (BCT) has diffused into Bi_0.5(Na_0.84K_0.16)_0.5TiO₃ (BNKT) lattices to form a new solid solution. It is shown that moderate additive of BCT (x ≤ 0.025) in BNKT–xBCT ceramics can enhance their piezoelectric and ferroelectric properties. Three dielectric anomalies are observed in BNKT–xBCT (x ≤ 0.03) ceramics. The piezoelectric measurements and P–E hysteresis loops reveal that BNKT–0.025BCT ceramic has the highest piezoelectric performance and strongest ferroelectricity in all the samples. Piezoelectric constants d ₃₃, k _p, and k _t of 175 pC/N, 29.1, and 54% are, respectively, achieved. Remnant polarization P _r and coercive field E _c reach 28.3 μC/cm² and 24.2 kV/cm, respectively.     

Dielectric tunable properties of Ba0.5Sr0.5TiO3–MgMoO4 composite ceramics for microwave applications

(1?x) Ba_0.5Sr_0.5TiO₃–xMgMoO₄ (x = 0, 5, 10, 20 and 30 wt%) composite ceramics were prepared via solid state reaction processing. Their structure and dielectric properties were systematically characterized. The introduction of MgMoO₄ resulted in a change in lattice constant of the perovskite phase and partial reaction between MgMoO₄ and Ba_0.5Sr_0.5TiO₃ occurred in the sintering process. Both X-Ray Diffraction (XRD) and Back-scattered Electron Images (BEI) analysis show the co-existence of three phase structures of BST, MgMoO₄ and BaMoO₄. With increasing of MgMoO₄ content, the tunability of the composite ceramics was decreased due to the increase of the amount of non-ferroelectric phases. The Curie temperature Tc of the samples gradually shifted to low temperatures with increasing of MgMoO₄ content. Dielectric constant can be adjusted in the range from 2035 to 150, meanwhile maintain a relatively high tunability and Q values. The sample with 20 wt% MgMoO₄ possesses a tunability of 10 %, a low dielectric constant of 111 and an appropriate Q value of 183 (2.240 GHz), which meet the requirements of high power and impedance matching, thus making it a promising candidate for applications as electrically tunable microwave devices.     

Structure and electrical properties of Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3–BiCoO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x − y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃–yBiCoO₃ (x = 0.12–0.24, y = 0–0.04) have been fabricated by a conventional solid-state reaction method, and their structure and electrical properties have been investigated. The XRD analysis shows that samples with y ≤ 0.03 exhibit a pure perovskite phase and very weak impurity reflections can be detected in the sample with y = 0.04. With x increasing from 0.12 to 0.24 and y increasing from 0 to 0.04, the ceramics transform gradually from a rhombohedral phase to a tetragonal phase and rhombohedral–tetragonal phase coexistence to a pseudocubic phase, respectively. The morphotropic phase boundary (MPB) of the system between rhombohedral and tetragonal locates in the range of x = 0.18–0.21, y = 0–0.03. The ceramics near the composition of the MPB have good performances with piezoelectric constant d ₃₃ = 156 pC/N and electromechanical coupling factor k _p = 0.34 at x = 0.21 and y = 0.01, which attains a maximum value in this ternary system. Adding content of BiCoO₃ leads to a disappearance of the response in the curves of dielectric constant-temperature to the ferroelectric–antiferroelectric transition. The temperature dependence of dielectric properties suggests that the ceramics are relaxor ferroelectrics. The results show that (1 − x − y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃–yBiCoO₃ ceramics are good candidate for use as lead-free ceramics.     

Microstructures and microwave dielectric properties of Ba4LiNb3O12–BaWO4 composite ceramics

Composite ceramics of (1 ? x)Ba₄LiNb₃O₁₂–xBaWO₄ (x = 0.36–0.69) had been synthesized by co-firing the mixtures of Ba₄LiNb₃O₁₂ and BaWO₄ powders. The structures and microwave dielectric properties of the ceramics were studied by XRD, SEM, and TEM. These ceramics consisted of hexagonal Ba₄LiNb₃O₁₂ and tetragonal BaWO₄. The two phases co-existed well in the ceramics, and there was not obvious reaction at interfacial areas among grains. These ceramics had low sintering temperatures and excellent microwave dielectric properties, especially the small temperature coefficients of resonant frequency (τ_f) and high quality factor (Q × f) values. For composition at x = 0.69, the ceramic sintered at 1070 °C had Q × f value of 75,500 GHz and τ_f value of +8.7 ppm/°C.     

Effect of Mn doping on the dielectric tunable properties of Ba0.5Sr0.5TiO3–MgO–Mg2SiO4 composite ceramics

Mn-doped Ba_0.5Sr_0.5TiO₃–MgO–Mg₂SiO₄ composite ceramics were prepared by a solid-state reaction method, and the dielectric tunable properties were investigated. It was observed that the composite ceramics show three crystalline phases: Ba_0.5Sr_0.5TiO₃, MgO and Mg₂SiO₄ phases. Mn doping significantly improves the dielectric tunable properties of Ba_0.5Sr_0.5TiO₃–MgO–Mg₂SiO₄ composite ceramics. Mn-doped Ba_0.5Sr_0.5TiO₃–MgO–Mg₂SiO₄ composites have dielectric constant of 114.2–127.0, and tunability of 11.3–13.0 % at 10 kHz under 3 kV/mm, indicating that they are promising candidate materials for tunable microwave applications requiring a low dielectric constant.     

Structure and electrical properties of (Bi0.5Na0.5)0.94Ba0.06TiO3–Bi0.5(Na0.82K0.18)0.5TiO3–BiAlO3 lead free piezoelectric ceramics

0.09(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃–(0.01 − x) Bi_0.5(Na_0.82K_0.18)_0.5TiO₃–x BiAlO₃ (BNBKT–xBA) lead-free piezoelectric ceramics were synthesized by conventional solid-state reaction processes. Structure, ferroelectric and piezoelectric properties of BNBKT–xBA ceramics were investigated. X-ray diffraction data shows that BNBKT–xBA ceramics form the pure perovskite phases and the ceramics have the morphotropic phase boundary when x ≤ 0.030. At room temperature, the BNBKT–xBA ceramics at x = 0.030 have better electrical properties, the piezoelectric constant d₃₃ and planar coupling factor k_p of BNBKT–xBA ceramics reaches peak values at x = 0.030: d₃₃ = 217 pC N⁻¹, k_p = 0.308. The remnant polarization P_r, mechanical quality factor Q_m and relative dielectric constant ?_r of BNBKT–xBA ceramics at x = 0.030 attains 33.8 μC cm⁻², 133 and 928 (100 KHz), respectively. As BA content increase, the depolarization temperature T_d shift toward lower temperature, and T_d of BNBKT–xBA ceramics with x = 0.030 decreased to 55 °C.     

Low temperature sintering and dielectric properties of Li2ZnTi3O8–TiO2 composite ceramics doped with CaO–B2O3–SiO2 glass

The effects of CaO–B₂O₃–SiO₂ (CBS) glass addition on the sintering temperature and dielectric properties of Li₂ZnTi₃O₈–TiO₂ (LZT) composite ceramics have been investigated. Due to the compensating effect of rutile TiO₂ (τ_f ≈ +450 ppm/ °C), the temperature coefficient of resonant frequency (τ_f) for Li₂ZnTi₃O₈ + 4 wt% TiO₂ with biphasic structure was adjusted to a value near zero. The pure LZT ceramics were usually sintered at high temperature of about 1,160 °C. It was found in our experiment that a small amount of CBS glass additives could effectively lower the sintering temperature of LZT ceramics to 900 °C. With increasing the content of CBS glass, both of dielectric constant (ε_r) and quality factor (Q × f) value decreased. Typically, the 1 wt% CBS glass added Li₂ZnTi₃O₈ + 4 wt% TiO₂ ceramic sintered at 900 °C for 4 h exhibited good microwave dielectric properties of ε_r = 26.9, Q × f = 23,563 GHz and τ_f = ?1.5 ppm/ °C, which made it promising for low temperature co-fired ceramics technology application.     

Phase diagram and electric properties of the (Mn, K)-modified Bi0.5Na0.5TiO3–BaTiO3 lead-free ceramics

In this study, the phase diagram and electric properties were demonstrated for a (Mn, K)-modified Bi_0.5Na_0.5TiO₃ (BNT)-based solid solution. (0.935−x) Bi_0.5Na_0.5TiO₃−xBi_0.5K_0.5TiO₃−0.065BaTiO₃ with 0.5% mol Mn doping was prepared by a conventional solid-state reaction method. A morphotropic phase boundary (MPB) formed between the ferroelectric rhombohedral and tetragonal phases around x of 0.04 with the MPB tolerance factor t of 0.984–0.986. The temperature and composition dependence of the dielectric, piezoelectric, ferroelectric properties along with the strain characteristics were investigated in detail and a phase diagram was presented. Around the MPB region, the maximum values of piezoelectric constant d₃₃^* d_{33}^{*} of 290 pC/N, d ₃₃ of 155 pC/N, dielectric constant e₃₃^T /e₀ \varepsilon_{33}^{T} /\varepsilon_{0} of 1059 and low dielectric loss tangent tan δ of 0.017 were obtained. In addition, the authors also suggest that the solid solution with composition x of 0.24, exhibiting both high-depolarization temperature T _d of 182 °C, d₃₃^* d_{33}^{*} of 156 pC/N, d ₃₃ of 130 pC/N, will be favorable for high-temperature actuator and sensor applications.     

MgAl2O4–LaCr0.5Mn0.5O3 composite ceramics for high temperature NTC thermistors

New negative temperature coefficient (NTC) ceramics based on xMgAl₂O₄–(1 ? x)LaCr_0.5Mn_0.5O₃ (x = 0, 0.4, 0.6, 0.8) composition were investigated. The composite ceramics (x = 0.4, 0.6, 0.8) consisted of two phases: a cubic spinel MgAl₂O₄ phase and an orthorhombic perovskite LaCr_0.5Mn_0.5O₃ phase isomorphic to LaCrO₃. The brighter regions were the LaCr_0.5Mn_0.5O₃ and the darker was the MgAl₂O_4. There was ion diffusion between these two phases. X-ray photoelectron spectroscopy analysis corroborated the presence of Cr³⁺, Cr⁴⁺, Mn³⁺ and Mn⁴⁺ ions on lattice sites, which may result in the hopping conduction. The ρ ₃₀₀ and B _400/800 constant increased with increasing MgAl₂O₄ content. The values of ρ ₃₀₀, B _400/800 and activation energy of NTC thermistors were in the range 1.76–1.22 × 10⁸ Ωcm, 2,646–8,711 K, 0.228–0.746 eV, respectively. This means the electrical properties can be adjusted to desired values, depending on the MgAl₂O₄ content.     

铈掺杂Ba0.1Sr0.9TiO3的改性研究

铈掺杂Ba0.1Sr0.9TiO3陶瓷有着较高的介电常数和较低的压敏电压,但其烧结温度高,烧结成功率低,非线性系数小。用ZnO和过量TiO2加以改性,研究表明:适量TiO2起到了烧结助剂的作用,可将样品的烧结温度降低到1325℃,提高了样品烧结率,钛与锶的最佳物质的量比为5∶3;ZnO作为受主掺杂剂将样品的非线性系数提高到10以上,降低了介电损耗,其最佳的掺杂量为0.7%(摩尔分数)。最后用扫描电镜分析了掺杂ZnO样品的微观形貌。     

Dielectric and piezoelectric properties of BiMnO3 doped 0.95Na0.5K0.5NbO3–0.05LiSbO3 ceramics

The piezoelectric properties of (1 − x)(0.95K_0.5Na_0.5NbO₃–0.05LiSbO₃)–x BiMnO₃ (x = 0, 0.002, 0.004, 0.006, 0.008, 0.01) lead-free piezoelectric ceramics were investigated as a function of x. These ceramics were fabricated by conventional ceramics sintering processing. BiMnO₃ (BM)-doping was found to increase the Curie temperature, T _c, from 370 °C at x = 0–380 °C at x = 0.002, and clearly increase the d ₃₃, Q _m and k _p values, showing “hard” characteristic. The good piezoelectric and electromechanical properties of d ₃₃ = 226pC/N, k _p = 40.8%, tan θ = 2.60% and T _c = 370 °C appear at x = 0.004.     

Frequency and temperature dependent dielectric and conductivity behavior of 0.95(K0.5Na0.5)NbO3–0.05BaTiO3 ceramic

Dielectric and conductivity measurements were carried out on the 0.95(K_0.5Na_0.5)NbO₃–0.05BaTiO₃ (KNN–5BT) ceramic both as a function of temperature (∼350–850 K) and frequency (40 Hz to 100 MHz). A high-temperature dielectric relaxation above Curie temperature (∼590 K) was observed and analyzed with the Cole–Cole function. Frequency dependent conductivity was analyzed with an augmented Jonscher relation and exhibited a universal conductivity behavior. The activation energy of dielectric relaxation was estimated to be 1.09 eV. It could be attributed to the thermal motion of double ionized oxygen vacancy or to the formation of defect dipoles between the acceptor ion and charge compensating oxygen vacancies. The mechanism for both the high-temperature dielectric relaxation and the frequency dependent conductivity was proposed based on a possible mode of incorporation of Ba²⁺ and Ti⁴⁺ ions into the KNN lattice sites.     

Piezoelectric and dielectric properties of Bi0.5Na0.5TiO3–Bi0.5Li0.5TiO3 lead-free ceramics

(1 − x)Bi_0.5Na_0.5TiO₃–xBi_0.5Li_0.5TiO₃ lead-free ceramics have been prepared by a conventional solid-state reaction method, and their piezoelectric and dielectric properties have been studied. X-ray diffraction studies reveal that Li⁺ diffuses into the Bi_0.5Na_0.5TiO₃ lattices to form a solid solution with a pure perovskite structure. The addition of Bi_0.5Li_0.5TiO₃ effectively lowers the sintering temperature of the ceramics and greatly assists in the densification of the ceramics. The ceramic with x = 0.075 possesses the optimum piezoelectric properties: piezoelectric coefficient d ₃₃ = 121 pC/N and planar electromechanical coupling factor k _P = 18.3%. After the partial substitution of Li⁺ for Na⁺ in the A-sites of Bi_0.5Na_0.5TiO₃, the ceramics exhibit more relaxor characteristic, which is probably resulted from the cation disordering in the 12-fold coordination sites. The depolarization temperature T _d shifts to low temperature with the substitution level x of Li⁺ for Na⁺ increasing.     

Low-temperature sintering and microwave dielectric properties of 5Li2O–0.58Nb2O5–3.23TiO2 ceramics

The effect of B₂O₃ addition on the sintering, microstructure and the microwave dielectric properties of the 5Li₂O–0.58Nb₂O₅–3.23TiO₂ (LNT) ceramics have been investigated. It is found that the LNT ceramics could be sintered well at ∼880 °C with low-level doping of B₂O₃ (≤2 wt.%). Only Li₂TiO₃ solid solution (Li₂TiO₃ss) crystal structure could be detected for all the ceramics with various amounts of B₂O₃ addition from the X-ray diffraction (XRD) results. And interestingly, two phases with different color in SEM images are observed in B₂O₃-doped LNT ceramics. EDS results suggest that the two different phases are two Li₂TiO₃ss phases with different amount of Nb. In addition, there is no much degradation in the microwave dielectric properties with the B₂O₃ adding. In the case of 0.5 wt.% B₂O₃-doped samples sintered at 880 °C, good microwave dielectric properties of ?_r = 22, Q × f = 32,000 GHz, τ_f = 9.5 ppm °C⁻¹ are obtained.     

Low temperature sintering and microwave dielectric properties of 7NiNb2O6–9TiO2 ceramics with CuO addition

The effects of CuO additive on sintering temperature and microwave dielectric properties of 7NiNb₂O₆–9TiO₂ ceramics prepared by solid-state reaction method have been investigated. The phases and microstructure have also been evaluated using X-ray diffraction and scanning electron microscopy. The pure 7NiNb₂O₆–9TiO₂ ceramics show a high sintering temperature of about 1,200?°C. However, the addition of CuO lowered the sintering temperature of 7NiNb₂O₆–9TiO₂ ceramics from 1,200 to 935?°C due to the CuO liquid-phase. The results showed that the microwave dielectric properties were strongly dependent on densification, crystalline phases and grain size. The 7NiNb₂O₆–9TiO₂ ceramics with the addition of 3.2 wt% CuO sintered at 935?°C afforded excellent dielectric properties of ε _r ?=?60.5, Q?×?f?=?10,039?GHz (at 3.8?GHz) and τ _f ?=?62?ppm/°C, which represented very promising candidates for LTCC dielectric materials.     

Synthesis and properties of Ba0.5Sr0.5(Co0.6Zr0.2)Fe0.2O3−δ perovskite cathode material for intermediate temperature solid-oxide fuel cells

A highly stable perovskite cathode material, Ba_0.5Sr_0.5(Co_0.6Zr_0.2)Fe_0.2O_3−δ (BSCZF) for intermediate temperature solid-oxide fuel cells (IT-SOFCs) was synthesized via the improved EDTA-citric acid complexing technique combined with high-temperature sintering. The product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical impedance spectra (EIS) measurements. An electrolyte-supported BSCZF/SDC/Ni-SDC fuel cell was fabricated to evaluate the performance of the material. The XRD study indicates that the sintering temperature higher than 950 °C is sufficient to the formation of clean single BSCZF perovskite phase. Due to the incorporation of Zr ions, BSCZF perovskite exhibit lower electrical conductivity with higher activation energy but higher structural stability than the Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) parent oxide. The maximum electrical conductivity of BSCZF attains 16.9 S cm⁻¹ at around 540 °C. Impedance spectra showed that the ASRs of BSCZF cathode on samaria doped ceria (Ce_0.8Sm_0.2O_1.9, SDC) electrolyte are low but are still slightly larger than those of BSCF at similar conditions. The BSCZF/SDC/Ni-SDC cell exhibited a stable output with the maximum power densities of 30, 75, 139 and 241 mW cm⁻² at 550, 600, 650 and 700 °C, respectively. Due to the high electrochemical performances as well as the excellent stability, BSCZF perovskite may be an attractive cathode material for IT-SOFCs.     

Densification behavior, microstructure, and electrical properties of sol–gel-derived niobium-doped (Bi0.5Na0.5)0.94Ba0.06TiO3 ceramics

Superfine powders (~100 nm) with compositions of (1 − x)(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ + xNb⁵⁺ (BNTBT6 + xNb) with x from 0 to 0.02 were synthesized by an improved citrate sol–gel method using Nb₂O₅ as Nb⁵⁺ source. The sintering behavior, microstructure, and various electrical properties of BNTBT6 + xNb ceramics were investigated. The results indicated that the addition of a small amount of Nb⁵⁺ has no remarkable effect on the crystal structure and grain morphology, but the electrical properties of the ceramics are obviously influenced. The BNTBT6 + 0.005Nb compositions exhibit enhanced densification behavior and improved electrical properties of a piezoelectric constant d ₃₃ ~ 205 pC/N and a planar electromechanical coupling factor k _p ~ 33%.