Electromechanical properties and dielectric behavior of (Bi1/2Na1/2)(1−1.5x)BixTiO3 lead-free piezoelectric ceramics

Bismuth doped bismuth sodium titanate ceramics [(Bi_1/2Na_1/2)_(1−1.5x)Bi_xTiO₃, x=0 to 0.06] were prepared, and the resulting effects on the microstructure and dielectric properties were examined. All of the Bi-doped ceramics exhibited a single phase of perovskite structure with rhombohedral symmetry. The poling leakage current was significantly reduced by the doping of Bi, facilitating the poling process of the ceramics. The doping with Bi enhances the piezoelectric properties and increases the dielectric constant and the dielectric loss of the ceramics. At 2 mol% Bi-doping level, the ceramics exhibit a large remanent polarization of 47 μC/cm² and a relatively low coercive field of 71 kV/cm, while their d₃₃ and k_p reach a maximum value of 95 pC/N and 21%, respectively.     

Effects of Li2CO3 on the sintering behavior and piezoelectric properties of Bi2O3-excess (Bi0.5Na0.5)0.94Ba0.06TiO3 ceramics

(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ ceramics doped with Li₂CO₃ and Bi₂O₃ as sintering aids were manufactured, and their micro structural, dielectric and piezoelectric properties were investigated. All specimens could be well sintered at a low-temperature of 1080 °C. The bulk density of the specimens doped with a small amount of Li₂CO₃ was enhanced. The dielectric and piezoelectric properties of ceramics were investigated with different amounts of Li₂CO₃ substitutions. High electrical properties of d₃₃ = 167 pC/N, k_p = 0.34, P_r = 40 μC/cm² and E_c = 38 kV/cm were obtained from the specimen containing 0.1 mol% of Li₂CO₃ sintered at 1080 °C.     

Microstructure and piezoelectric properties of Bi0.5(Na0.82K0.18)0.5TiO3−NaSbO3 ceramics

Lead-free piezoelectric ceramics (1−x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃−xNaSbO₃ have been prepared by a conventional ceramics technique, and their microstructure and electrical properties have been investigated. The addition of NaSbO₃ has no remarkable effect on the crystal structure within the studied doping content; however, an obvious change in microstructure took place. With increase in NaSbO₃ content, the temperature from a ferroelectric to antiferroelectric phase transition increases, and the temperature for a transition from antiferroelectric phases to paraelectric phases changes insignificantly. Simultaneously, the temperature range between the rhombohedral phase transition point and the Curie temperature point becomes smaller. The piezoelectric properties significantly increase with increase in NaSbO₃ content and the piezoelectric constant and electromechanical coupling factor attain maximum values of d₃₃=160 pC/N and k_p=0.333 at x=0.01. The results indicate that (1−x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃−xNaSbO₃ ceramic is a promising lead-free piezoelectric candidate material.     

Structure and electrical properties of Bi0.5(Na, K)0.5TiO3−BiGaO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x − y)Bi_0.5Na_0.5TiO₃−xBi_0.5K_0.5TiO₃− yBiGaO₃ have been fabricated by an ordinary sintering technique, and their structure and electrical properties and depolarization temperature have been studied. The results of X-ray diffraction reveal that Bi_0.5K_0.5TiO₃ and BiGaO₃ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure. An obvious change in microstructure with increasing concentration of Bi_0.5K_0.5TiO₃ and BiGaO₃ was observed. The piezoelectric constant d₃₃ and the electromechanical coupling factor k_p of the ceramics attain maximum values of 165 pC/N and 0.346 at y = 0.01(x = 0.18) and x = 0.21(y = 0.01), respectively. The temperature dependence of dielectric constant indicates an obvious relaxor characteristic with strong frequency dependence of dielectric constant. The depolarization temperature decreased with increasing content of BiGaO₃ and first decreases and then increases with increasing amount of Bi_0.5K_0.5TiO₃.     

高温无铅BaTiO_3-(Bi_(1/2)Na_(1/2))TiO_3正温度系数电阻陶瓷阻抗和介电谱分析

采用固相反应法制备了Y2O3施主掺杂的92 mol%BaTiO3-8 mol%(Bi1/2Na1/2)TiO3(BBNT8)高温无铅正温度系数电阻(positive temperature coe?cient resistivity,PTCR)陶瓷.利用透射电镜观察材料的显微结构,发现陶瓷的显微结构主要包括晶粒和晶界两部分,观察不到明显的壳层结构.进一步利用交流阻抗谱研究了陶瓷的宏观电学性能,发现陶瓷的总电阻是晶粒和晶界两部分的贡献,而晶粒电阻很小,在居里温度以上变化不大,材料的PTCR效应主要是晶界部分的贡献.当温度高于居里温度时,随着温度的升高,晶界介电常数逐渐减小,导致势垒增加,晶界电阻增大,从而产生正温度系数效应.最后,通过测试材料的介电频谱特性,研究计算了陶瓷的室温电阻率.     

Lanthanum-doped Bi4Ti3O12 ceramics prepared by high-pressure technique

We present an effective way in this paper to increase the density of lanthanum doped bismuth titanate ceramics, Bi4-xLaxTi3O12 (BLT), thereby significantly improving the performance of the BLT ceramics. Dense BLT ceramicses, Bi4-xLaxTi3O12 (x = 0.25, 0.5, 0.75, 1.0), are prepared by using nanocrystalline powders fabricated by a-gel method and high-pressure technique. The microstructures of the BLT ceramicses prepared separately by conventional-pressure and high-pressure techniques are investigated by using x-ray diffraction and transmission electron microscope. The influence of La-doping on the densification of bismuth titanate ceramics is investigated. The experimental results indicate that the phase compositions of all samples with various lanthanum dopings sintered at 900°C possess layer-structure of Bi4Ti3O12 . The green compacts are pressed under 2.5 GPa, 3.0 GPa, 3.5 GPa and 4.0 GPa, separately. It is found that the density of BLT ceramics is significantly increased due to the decreasing of porosity in the green compacts by high-pressure process.     

Study of compressive type accelerometer based on lead-free BNKBT piezoceramics

Lead-free piezoelectric 0.90(Bi_1/2Na_1/2)TiO₃-0.05(Bi_1/2K_1/2)TiO₃-0.05BaTiO₃ ceramics(abbreviated as BNKBT-5) rings were fabricated using a conventional mixed oxide method. The ceramics have a piezoelectric constant d₃₃=168 pC/N, electromechanical coupling factors k_p=0.313 and k_t=0.487. The BNKBT lead-free ceramic rings were used as the transduction elements in a compressive type accelerometer and its performance compared with a lead zirconate titanate (PZT) APC 840 ceramic accelerometer with similar structure. The lead-free accelerometer shows good performance and has a broader frequency response compared to the lead-based PZT accelerometer. PACS 77.22.Ej; 77.84.-s; 85.50.-n     

非化学计量和掺杂对(Na1/2Bi1/2)0.92Ba0.08TiO3陶瓷电性能的影响

研究了非化学计量和掺杂对无铅压电陶瓷(Na_1/2Bi_1/2)_0.92Ba_0.08TiO₃的压电性能及去极化温度的影响.研究发现A位非化学计量可以提高陶瓷的压电性能;B位掺杂对材料电学性能的影响规律类似于Pb(Ti,Zr)O₃系压电陶瓷的相关规律;由于非化学计量和掺杂会影响到A位离子对B位离子与氧离子形成的BO₆八面体的耦合作用,影响到畴的稳定性,从而影响 关键词： 无铅压电陶瓷 非化学计量 掺杂 电性能     

Synthesis and ion conductivity of (Bi2O3)0.75(Dy2O3)0.25 ceramics with grain sizes from the nano to the micro scale

Using (Bi₂O₃)_0.75(Dy₂O₃)_0.25 nano-powder synthesized by reverse titration co-precipitation method as raw material, dense ceramics were sintered by both Spark Plasma Sintering (SPS) and pressureless sintering. According to the predominance area diagram of Bi-O binary system, the sintering conditions under SPS were optimized. (Bi₂O₃)_0.75(Dy₂O₃)_0.25 ceramics with relative density higher than 95% and an average grain size of 20 nm were sintered in only 10 min up to 500 °C. During the pressureless sintering process, the grain growth behavior of (Bi₂O₃)_0.75(Dy₂O₃)_0.25 followed a parabolic trend, expressed as D² − D₀² = Kt, and the apparent activation energy of grain growth was found to be 284 kJ mol^− 1. Dense (Bi₂O₃)_0.75(Dy₂O₃)_0.25 ceramics with different grain sizes were obtained, and the effect of grain size on ion conductivity was investigated by impedance spectroscopy. It was shown that the total ion conductivity was not affected by the grain size down to 100 nm, however lower conductivity was measured for the sample with the smallest grain size (20 nm). But, although only the δ phase was evidenced by X-ray diffraction for this sample, a closer inspection by Raman spectroscopy revealed traces of α-Bi₂O₃.     

Structure, ferroelectric and piezoelectric properties of (Bi1−x−yNa0.925−x−yLi0.075)0.5BaxSryTiO3 lead-free piezoelectric ceramics

Lead-free multi-component ceramics (Bi_1−x−yNa_{0.925−x−y}Li_0.075)_0.5Ba_xSr_yTiO₃ have been prepared by an ordinary sintering technique and their structure and electrical properties have been studied. All the ceramics can be well-sintered at 1100 °C. X-ray diffraction patterns shows that Li⁺, Ba²⁺ and Sr²⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure, and a morphotropic phase boundary (MPB) is formed at 0.04 < x < 0.08. As compared to pure Bi_0.5Na_0.5TiO₃ ceramic, the coercive field E_C of the ceramics decreases greatly and the remanent polarization P_r of the ceramics increases significantly after the formation of the multi-component solid solution. Due to the MPB, lower E_C and higher P_r, the piezoelectricity of the ceramics is greatly improved. For the ceramics with the compositions near the MPB (x = 0.04–0.08 and y = 0.02–0.04), piezoelectric coefficient d₃₃ = 133–193 pC/N and planar electromechanical coupling factor k_P = 16.2–32.1%. The depolarization temperature T_d reaches a minimum value near the MPB. The temperature dependences of the ferroelectric and dielectric properties suggest that the ceramics may contain both the polar and non-polar regions at temperatures near/above T_d.     

TiO2-nonstoichiometry dependence on piezoelectric properties and depolarization temperature of (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(Bi_0.5Na_0.5)_0.94Ba_0.06Ti_xO_1+2x lead-free piezoceramics with x varying from 0.97 to 1.03 were fabricated and characterized in order to investigate the effects of TiO₂-nonstoichiometry on the piezoelectric properties and depolarization temperature of (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ composition. X-ray diffraction (XRD) analysis showed that all samples have a single phase of perovskite structure with rhombohedral symmetry. Piezoelectric and dielectric measurements revealed that deficiency of TiO₂ leads to an increase in the piezoelectric coefficient (d₃₃), free relative permittivity (), and loss tangent (tan δ) besides an increase in the electromechanical coupling coefficient (k_p) within a certain amount, while excess of TiO₂ results in a decrease in k_p, d₃₃, and , but an increase in tan δ. Depolarization temperature (T_d) measurement indicated a decrease and an increase in T_d as a result of increasing TiO₂ deficiency and TiO₂ excess, respectively. This TiO₂-nonstoichiometry also induced changes in the remanent polarization (P_r) and coercive field (E_c) of the ceramics.     

Lead-free ferroelectric BaTiO3 doped-(Na0.5Bi0.5)TiO3 thin films processed by pulsed laser deposition technique

The difficulties in synthesizing phase pure BaTiO₃ doped-(Na_0.5Bi_0.5)TiO₃ are known. In this work, we reporting the optimized pulsed laser deposition (PLD) conditions for obtaining pure phase 0.92(Na_0.5Bi_0.5)TiO₃-0.08BaTiO₃, (BNT-BT_0.08), thin films. Dielectric, ferroelectric and piezoelectric properties of BNT-BT_0.08, thin films deposited by PLD on Pt/TiO₂/SiO₂/Si substrates are investigated in this paper. Perovskite structure of BNT-BT_0.08 thin films with random orientation of nanocrystallites has been obtained by deposition at 600 °C. The relative dielectric constant and loss tangent at 100 kHz, of BNT-BT_0.08 thin film with 530 nm thickness, were 820 and 0.13, respectively. Ferroelectric hysteresis measurements indicated a remnant polarization value of 22 μC/cm² and a coercive field of 120 kV/cm. The piezoresponse force microscopy (PFM) data showed that most of the grains seem to be constituted of single ferroelectric domain. The as-deposited BNT-BT_0.08 thin film is ferroelectric at the nanoscale level and piezoelectric.     

0.90(Bi1/2Na1/2)TiO3–0.05(Bi1/2K1/2)TiO3– 0.05BaTiO3 transducer for ultrasonic wirebonding applications

Lead-free piezoelectric ceramic 0.90(Bi_1/2Na_1/2)TiO₃–0.05(Bi_1/2K_1/2)TiO₃–0.05BaTiO₃ (BNKBT-5) rings (OD=12.7 mm, ID=5.1 mm and 2.3-mm thick) were fabricated and characterized. Four ceramic rings were used as the driving element in an ultrasonic wirebonding transducer and the performance of the transducer was characterized. The lead-free transducer was found to have comparable voltage rise and fall times as a lead-based PZT transducer and has a relatively large vibration amplitude, thus showing that BNKBT-5 has the potential to be used in fabricating lead-free ultrasonic wirebonding transducers. PACS 77.22.Ej; 77.84.-s; 85.50.-n     

Photoelectrocatalytic degradation of organic contaminants at Bi2O3/TiO2 nanotube array electrode

In the current work, TiO₂ nanotube array was prepared via electrochemical anode method. Then the Bi₂O₃ nanoparticles were deposited onto the TiO₂ nanotube array via dip-coating method from an amorphous complex precursor. The crystal structures were characterized via X-ray diffraction analysis. Their surface textures were observed via electron-scanning microscope. The prepared composite array electrode exhibited high photoelectrocatalytic activities towards degrading organic contaminants under visible light irradiation. High photoelectrocatalytic activities were also exhibited under UV light irradiation. The catalytic mechanism was discussed based on the analysis of electrochemical and degradation kinetics results. It is suggested a P (Bi₂O₃)-N (TiO₂) junction was formed to increase the catalytic activates. The stability of the electrode materials was confirmed finally.     

Dielectric characteristics and polarization response of lead-free ferroelectric (Bi0.5Na0.5)0.94Ba0.06TiO3-P(VDF-TrFE) 0-3 composites

Bismuth sodium barium titanate/poly(vinylidene fluoride-trifluoroethylene) 70/30 [(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃-P(VDF-TrFE)] 0-3 composites were prepared by a hot-press method for different volume fractions of (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ ceramic powder in a P(VDF-TrFE) 70/30 copolymer matrix. The relative permittivity and dielectric loss of the composites increased with increase in the volume fraction of the ceramics, which well follows the Bruggeman model. The polarization responses of the composites were strongly dependent on the ceramic volume fraction. The composites with a higher ceramic volume fraction showed an increase in remanent polarization. At room temperature, a 0.3(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃-0.7P(VDF-TrFE) composite showed a relative permittivity ε_r=30, remanent polarization and coercive field      

Synthesis, phase and microstructure characteristics of Pb(Zr0.52Ti0.48)O3–(Bi3.25La0.75)Ti3O12 ceramics

Ceramics with formula (1 − x)Pb(Zr_0.52Ti_0.48)O₃–x(Bi_3.25La_0.75)Ti₃O₁₂ (when x = 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1.0) were prepared by a solid-state mixed-oxide method and sintered at temperatures between 950 °C and 1250 °C. It was found that the optimum sintering temperature was 1150 °C at which all the samples had densities at least 95% of theoretical values. Phase analysis using X-ray diffraction indicated the existence of BLT- as well as PZT-based solid solutions with corresponding lattice distortion. Scanning electron micrographs of ceramic surfaces showed a plate-like structure in BLT-rich phase while the typical grain structure was observed for PZT-rich phase. The grain sizes of both pure BLT and PZT ceramics were found to decrease as the relative amount of the other phase increased. This study suggested that tailoring of properties of this PZT–BLT system was possible especially on the BLT-rich side due to its large solubility limit.     

Nature of potential barrier in (Ca1/4,Cu3/4)TiO3 polycrystalline perovskite

The nonohmic electrical features of (Ca_1/4,Cu_3/4)TiO₃ perovskite ceramics, which have very strong gigantic dielectric is believed originate from potential barriers at the grain boundaries. In the present study, we used the admittance and impedance spectroscopy technique to investigate (Ca_1/4,Cu_3/4)TiO₃ perovskite ceramics with low nonohmic electrical properties. The study was conducted under two different conditions: on as-sintered ceramics and on ceramics thermally treated in an oxygen-rich atmosphere. The results confirm that thermal treatment in oxygen-rich atmospheres influence the nonohmic properties. Annealing at oxygen-rich atmospheres improve the nonohmic behavior and annealing at oxygen-poor atmospheres decrease the nonohmic properties, a behavior already reported for common metal oxide nonohmic devices and here firstly evidenced for the (Ca_1/4,Cu_3/4)TiO₃ perovskite related materials. The results show that oxygen also influences the capacitance values at low frequencies, a behavior that is indicative of the Schottky-type nature of the potential barrier.     

Dependence of excess bismuth content in precursor sols on ferroelectric and dielectric properties of Bi3.25La0.75Ti3O12 thin films fabricated by chemical solution deposition

Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films were fabricated on Pt/Ti/SiO₂/Si(1 0 0) substrates by chemical solution deposition (CSD), and the dependence of ferroelectric and dielectric properties of the as-deposited BLT thin films on excess Bi content in precursor sols was studied. It is found that the prepared BLT thin film shows the best polarization-electric field, capacitance-voltage and dielectric constant (?_r)-frequency characteristics, when the value of excess Bi content in precursor sols is 10%. In detail, its remnant polarization (2P_r) value is 40 μC/cm², the capacitance tunability is 21% measured at room temperature under conditions of an applied voltage of 8 V and measurement frequency of 10 kHz, and the ?_r is 696 at 100 kHz frequency.     

Preparation and ferroelectric properties of pyrochlore-free Pb(Ni1/3Nb2/3)O3-based solid solutions

Polycrystalline ceramics of the perovskite solid solution 0.5Pb(Ni_1/3Nb_2/3)O₃-(0.5-x)-Pb(Zn_1/3Nb_2/3)O₃–xPb(Zr_1/2Ti_1/2)O₃; x=0.0–0.5 (PNN–PZN–PZT) were synthesized by a modified columbite method. Highly dense ceramics lacking parasitic pyrochlore phases were prepared at a calcination temperature of 950 °C by using a double-crucible configuration, excess PbO (2 mol %), and a fast heating/cooling rate (20 °C/min). The ceramics were characterized by a variety of techniques including X-ray diffraction, ferroelectric hysteresis loop measurements, field-induced longitudinal strain measurements, and electron microscopy. It was observed that the remanent polarization exhibited a significant increase with increasing x. In addition, the squareness of the hysteresis loop increased quasi-linearly as the molar fraction of PZT increased. The maximum spontaneous polarization and remanent polarization for the x=0.5 composition were 31.9 μC/cm² and 25.2 μC/cm², respectively. Moreover, the data were analyzed to show the evolution of the micro-domain state as a function of the molar fraction of PZT. PACS 77.22.-d; 77.80.Bh; 77.84.Dy; 61.10.Nz; 77.80.Dj     

K0.5Na0.5NbO3-LiSbO3-BiFeO3/CuFe2O4复合陶瓷的制备与磁电性能研究

采用传统的固相法制备了(1-x)(K_0.5Na_0.5NbO₃-LiSbO₃-BiFeO₃)-xCuFe₂O₄ (x=0.1, 0.2, 0.3, 0.4) 磁电复合陶瓷, 并借助X射线衍射仪、扫描电镜和磁电耦合系数测试仪等对复合陶瓷的微结构和性能进行了分析. 结果表明, 复合陶瓷的K_0.5Na_0.5NbO₃-LiSbO₃-BiFeO₃和CuFe₂O₄物相之间发生了一定的离子相互扩散作用, 且两相的颗粒大小匹配性较好. 随着CuFe₂O₄含量增加, 复合陶瓷的压电系数从130 pC/N减小到30 pC/N, 饱和磁致伸缩系数从4.5×10^-6增加到12.4×10^-6左右, 磁电耦合系数表现出先增加后减小, 在x=0.3时获得最大的磁电耦合系数9.4 mV·cm^-1·Oe^-1. 关键词： 0.5Na_0.5NbO₃-LiSbO₃-BiFeO₃')" href="#">K_0.5Na_0.5NbO₃-LiSbO₃-BiFeO₃ 2O₄')" href="#">CuFe₂O₄ 磁电耦合