Sintering behavior and microwave dielectric properties of Bi3(Nb1−xTax)O7 solid solutions

Solid solutions of Bi₃(Nb_1−xTa_x)O₇ (x = 0.0, 0.3, 0.7, 1) were synthesized using solid state reaction method and their microwave dielectric properties were first reported. Pure phase of fluorite-type could be obtained after calcined at 700 °C (2 h)⁻¹ between 0 ≤ x ≤ 1 and Bi₃(Nb_1−xTa_x)O₇ ceramics could be well densified below 990 °C. As x increased from 0.0 to 1.0, saturated density of Bi₃(Nb_1−xTa_x)O₇ ceramics increased from 8.2 to 9.1 g cm⁻³, microwave permittivity decreased from 95 to 65 while Q_f values increasing from 230 to 560 GHz. Substitution of Ta for Nb modified temperature coefficient of resonant frequency τ_f from −113 ppm °C⁻¹ of Bi₃NbO₇ to −70 ppm °C⁻¹ of Bi₃TaO₇. Microwave permittivity, Q_f values and τ_f values were found to correlate strongly with the structure parameters of fluorite solid solutions and the correlation between them was discussed in detail. Considering the low densified temperature and good microwave dielectric proprieties, solid solutions of Bi₃(Nb_1−xTa_x)O₇ ceramics could be a good candidate for low temperature co-fired ceramics application.     

高居里温度BaTiO3-(Bi0.5Na0.5)TiO3无铅正温度系数电阻陶瓷的制备

用传统的固相反应烧结法制备了(1-xmol%)BaTiO₃-xmol%(Bi_0.5Na_0.5)TiO₃(BBNTx)高温无铅正温度系数电阻( positive temperature coefficient of resistivity, PTCR)陶瓷。X射线衍射表明所有的BBNTx陶瓷形成了单一的四方钙钛矿结构。SEM分析结果显示随着BNT含量的增加, 陶瓷晶粒尺寸减小。空气中烧结的0.2mol% Nb掺杂的BBNT1陶瓷, 室温电阻率为~10² Ω·cm, 电阻突跳为~4.5个数量级, 居里温度为~150℃。氮气中烧结的0.3mol% Nb掺杂的BBNTx(10≤x≤60)陶瓷, 同样具有明显的PTCR效应, 居里温度在180~235℃之间。随着BNT含量的增加, 材料的室温电阻率增大, 同时陶瓷的电阻突跳比下降。     

(Bi0.5Na0.5)TiO3:Sm3+无铅压电陶瓷的红光发射特性

采用传统的固相反应烧结方法制备了稀土Sm³⁺掺杂的(Bi_0.5Na_0.5)TiO₃无铅压电陶瓷。系统分析了掺杂浓度、烧结温度和离子补偿对发光特性的影响。稀土Sm³⁺离子的加入实现了(Bi_0.5Na_0.5)TiO₃陶瓷的红绿光发射, 其激发光波段位于400~500 nm范围内, 与已经成熟的蓝光LED芯片的发射光谱充分匹配。当烧结温度为1100℃, Sm³⁺离子的掺杂浓度为0.015 mol时, 陶瓷样品呈现最强的发光强度。同时, 通过Li⁺、Na⁺、K⁺离子进行电荷补偿, 有效提高了陶瓷样品的发光性能, 发光强度随离子半径增大而增强。可见, Sm³⁺掺杂的(Bi_0.5Na_0.5)TiO₃材料在光电集成器件中具有很好的应用前景。     

Dielectric Investigations of 0.945(Bi0.5Na0.5) TiO3-0.055BaTiO3

Dielectric properties of 0.945(Bi_0.5Na_0.5) TiO₃-0.055BaTiO₃(BNBT5.5) (a composition close to the rhombohedral- tetragonal morphotropic phase boundary) ceramics are studied. It is shown that BNBT5.5 is a relaxor with a characteristic relaxation time that follows Vogel-Fulcher's law. The following Vogel-Fulcher parameters of the relaxation time were calculated: pi0 = (2.0 plusmn 2.4)middot10^-14 s, E/^kB = (1620 plusmn 270) K, T₀ = (262 plusmn 9) K.     

钛酸铋钠基无铅铁电陶瓷场致应变性能研究

钛酸铋钠(Bi_0.5Na_0.5)TiO₃(BNT)作为典型的钙钛矿型弛豫铁电体, 具有超高的场致应变, 是最有希望代替铅基体系的无铅压电体系之一。与铅基陶瓷相比, BNT基陶瓷具有驱动电压较高、迟滞较大以及温度稳定性差等劣势。为了优化无铅驱动器的应变性能, 本研究采用固相反应法制备(1-x){0.76(Bi_0.5Na_0.5)TiO₃-0.24SrTiO₃}-xNaNbO₃(BNT- ST-xNN, x=0~0.03)无铅铁电陶瓷。结果表明, 当x=0.01时, 该陶瓷在较低电场(E=4 kV/mm)下的应变值可达到0.278%, 等效压电系数d^*₃₃高达695 pm/V。此时, 陶瓷处于非遍历/遍历弛豫相界处, 电场诱导弛豫-铁电相变导致大场致应变。与x=0.01相比, x=0.02时应变值为0.249%, 略微下降, 但迟滞却降低至43%。此外, 该应变在25~100 ℃温度范围内维持稳定。本研究表明, 在BNT基陶瓷中固溶SrTiO₃和NaNbO₃组元可以提高场致应变值, 同时维持较低的驱动电场和良好的温度稳定性, 可用于压电驱动器研制。     

Fabrication and characterization of (1−x)SrBi2Ta2O9–xBi3TaTiO9 layered structure solid solution thin films for ferroelectric random access memory (FRAM) applications

We report on the properties of (1−x)SrBi₂Ta₂O₉–xBi₃TaTiO₉ solid solution thin films for ferroelectric non-volatile memory applications. The solid solution thin films fabricated by modified metalorganic solution deposition technique showed much improved properties compared to SrBi₂Ta₂O₉. A pyrochlore free crystalline phase was obtained at a low annealing temperature of 600°C and grain size was found to be considerably increased for the solid solution compositions. The film properties were found to be strongly dependent on the composition and annealing temperatures. The measured dielectric constant of the solid solution thin films was in the range 180–225 for films with 10–50% of Bi₃TaTiO₉ content in the solid solution. Ferroelectric properties of (1−x)SrBi₂Ta₂O₉–xBi₃TaTiO₉ thin films were significantly improved compared to SrBi₂Ta₂O₉. For example, the observed remanent polarization (2P_r) and coercive field (E_c) values for films with 0.7SrBi₂Ta₂O₉–0.3Bi₃TaTiO₉ composition, annealed at 650°C, were 12.4 μC/cm² and 80 kV/cm, respectively. The solid solution thin films showed less than 5% decay of the polarization charge after 10¹⁰ switching cycles and good memory retention characteristics after about 10⁶ s of memory retention. The improved microstructural and ferroelectric properties of (1−x)SrBi₂Ta₂O₉–xBi₃TaTiO₉ thin films compared to SrBi₂Ta₂O₉, especially at lower annealing temperatures, suggest their suitability for high density FRAM applications.     

Reaction between the tetragonal tungsten bronze niobate K2Sr4Nb10O30 and the perovskite Pb(Mg1/3Nb2/3)O3

The search for dielectric materials with a high dielectric constant and ′_r = ƒ(T) curves with a flat profile fitting the X7R specification is still ongoing. Promising results were obtained by mixing compounds with closely related structures, such as the tetragonal tungsten bronze (TTB) niobate K₂Sr₄Nb₁₀O₃₀ and the perovskite Pb(Mg_1/3Nb_2/3)O₃ (PMN). The present study, based on three methods of synthesis, explores the origin of the spreading out of the dielectric curves ′_r = ƒ(T). For the composition 10x K_0.2Sr_0.4NbO₃ (KSN) + (1 − x)Pb(Mg_1/3Nb_2/3)O₃ (PMN) with x = 0.3–0.6, the three synthesis methods provided similar characteristics and for the highest perovskite ratio (x = 0.3), the ′_r = ƒ(T) curve exhibits a flat profile. When lithium is used as a sintering agent, ′_r = ƒ(T) curves present a linear dependency with the temperature. These materials are also characterized by a structural and a microstructural inhomogeneity. Two phases TTB and perovskite type, different from KSN and PMN, are present after calcination and sintering, but not evenly distributed. The PbO loss during sintering also contributes to the evolution of the properties of the material.     

BiCoO3-doped (K0.475Na0.475Li0.05)(Nb0.8Ta0.2)O3 lead-free piezoelectric ceramics

(1--x)(K_0.475Na_0.475Li_0.05)(Nb_0.8Ta_0.2)O₃--xBiCoO₃ (KNLNT--BC) lead-free piezoelectric ceramics were prepared by the conventional solid-state sintering method. Effects of the BC content on the phase structure, microstructure and electrical properties of KNLNT--BC ceramics were investigated. XRD patterns reveal that all the ceramic samples are in the pure perovskite-type structure, and the phase structure changes from the tetragonal to pseudo-cubic phase with the increase of the BC content. After the substitution of BC, the grain size is significantly reduced and relaxer behaviors are induced. By adding a small amount of BC to KNLNT ceramics, piezoelectric properties are improved, while further addition of BC makes the piezoelectric properties deteriorate markedly. The optimized electrical properties at x = 0.005 are as follows: d₃₃ = 194 pC/N, k_p = 0.44.     

High-resolution and analytical transmission electron microscopy of epitaxial YBa2Cu3O7−x thin films and YBa2Cu3O7/PrBa2Cu3O7 superlattices

Transmission electron microscopy (TEM) studies of epitaxial YBa₂Cu₃O_7−x thin films and YBa₂Cu₃O₇/PrBa₂Cu₃O₇ superlattices are summarized. High-resolution imaging of cross-sections and plan views and energy-dispersive X-ray microanalysis and electron energy loss spectroscopy in the transmission electron microscope were the methods applied. In the first section results on YBa₂Cu₃O_7−x thin films With varying oxygen stoichiometry deposited onto SrTiO₃ are discussed. Then, YBa₂Cu₃O₇/PrBa₂Cu₃O₇ superlattices deposited onto SrTiO₃ and MgO are investigated. Finally, an interface analysis of high-quality YBa₂Cu₃O_7−x thin films deposited onto sapphire with yttrium-stabilized zirconia buffer layers is presented.     

Mechanical characterization of Ni1−xZnxFe2O4 prepared by non-conventional methods

The mechanical properties like hardness, H_v and compressive strength, σ of Ni_1−xZn_xFe₂O₄ (x = 0.2, 0.3, 0.4 and 0.5) prepared by the non-conventional flash combustion and citrate-gel decomposition techniques are studied and reported. It is observed that there is an increase in hardness with zinc content as well as sintering temperature. The hardness in the order of 2.0–3.63 GPa and compressive strength in the order of 150–240 MPa are obtained for Ni–Zn ferrites prepared by these non-conventional techniques. The influence of density, porosity and microstructure on hardness and compressive strength of Ni–Zn ferrites with respect to sintering temperature was studied.     

Ferroelectric, dielectric and piezoelectric properties of potassium lanthanum bismuth titanate K0.5La0.5Bi4Ti4O15 ceramics

The Aurivillius type bismuth layer-structured compound potassium lanthanum bismuth titanate (K_0.5La_0.5Bi₄Ti₄O₁₅) is synthesized using conventional solid-state processing. The phase analysis is performed by X-ray diffraction (XRD) and the microstructural morphology is conducted by scanning electron microscopy (SEM). The ferroelectric, dielectric and piezoelectric properties of K_0.5La_0.5Bi₄Ti₄O₁₅ (KLBT) ceramics are investigated in detail. The remnant polarization (P_r) and coercive field (E_c) are found to be 8.6 μC cm⁻² and 60 kV cm⁻¹, respectively. The Curie temperature T_c and piezoelectric coefficient d₃₃ are 413 °C and 18 pC N⁻¹, respectively.     

(1-x)K0.48Na0.52NbO3-xBi0.45Nd0.05(Na0.92Li0.08)0.5ZrO3无铅压电陶瓷相结构及压电性能

为了在获得较高压电性能的同时又不大大降低陶瓷的居里温度(T_C), 设计和制备了Bi_0.45Nd_0.05(Na_0.92Li_0.08)_0.5ZrO₃改性的K_0.48Na_0.52NbO₃系无铅压电陶瓷((1-x)KNN-xBNNLZ), 研究了BNNLZ含量对KNN基无铅压电陶瓷相结构和电学性能的影响。研究结果表明, 所有陶瓷样品均具有较高的居里温度T_C(>300℃)。随着BNNLZ含量的增加, 陶瓷的正交-四方相变温度(T_O-T)不断向低温方向移动, 而三方-正交相变温度(T_R-O)不断向高温方向移动, 最终在陶瓷中形成了三方-四方(R-T)共存相, R-T共存相处于0.05<x<0.07范围。BNNLZ的加入引起陶瓷相结构的演化改变导致压电常数(d₃₃ )、介电常数(ε_r )、剩余极化强度 (P_r )和机电耦合系数(k_p )都先增大后减小, 当x=0.06时陶瓷具有最佳压电性能: d₃₃=313 pC/N, k_p=42%, P_r=25.48 μC/cm², ε_r=1353, tanδ=2.5%, T_C=327℃。     

Influence of rare-earth oxides on structure and crystallization properties of Bi2O3–B2O3 glass

Bi₂O₃·B₂O₃ glasses doped with rare-earth oxides (RE₂O₃) (RE³⁺ = La³⁺, Pr³⁺, Sm³⁺, Gd³⁺, Er³⁺ and Yb³⁺) were prepared by the melting–quenching method. The relationships between composition and properties were demonstrated by IR, DSC, XRD and SEM analysis. The results show that the network structure resembles that of undoped Bi₂O₃·B₂O₃ glass, composing of [BO₃], [BO₄] and [BiO₆] units. RE₂O₃ stabilizes the glass structure as a modifier. Transition temperature (T_g) increases linearly with cationic field strength (CFS) of RE³⁺. La₂O₃, Pr₂O₃, Sm₂O₃ and Gd₂O₃ are benefit to promote the formation of BiBO₃ crystal. When Er₂O₃ and Yb₂O₃ are introduced, respectively, the main crystal phase changes to Bi₆B₁₀O₂₄. Transparent surface crystallized samples are obtained by reheating at 460–540 °C for 5 h. In this case, needle like BiBO₃ crystal or rare-earth-doped BiBO₃ crystal (Pr_xBi_1−xBO₃ and Gd_xBi_1−xBO₃) are observed, which is promising for non-linear optical application.     

Microstructure and piezoelectric properties of (Na0.5K0.5)NbO3 lead-free piezoelectric ceramics with V2O5 addition

Various amounts of Nb₂O₅ in the (Na_0.5K_0.5) NbO₃ (NKN) ceramic were replaced by V₂O₅ to decrease its sintering temperature to below 950°C. A small V₂O₅ content resulted in a dense microstructure with an increased grain size for the specimen sintered at 900°C due to the presence of a liquid phase. When V₂O₅ was added to the NKN ceramics, their orthorhombic-to-tetragonal transition temperature increased from 178°C to around 200°C. However, their Curie temperature decreased from 402°C to around 330°C. The k_p, _ε3 ^T/_ε0, and Q_m values increased with V₂O₅ addition, probably due to the increased density and poling state, which was identified by the phase angle. The specimen with x = 0.05, sintered at 900°C for 8 h, exhibited the following piezoelectric properties: k_p = 0.32, _ε3 ^T/_ε0 = 245, d₃₃ = 120 (pC/N), and Q_m = 232.     

Effect of La2O3 addition and O2 atmosphere on the electric properties of SnO2TiO2

The electric properties of (Sn, Ti)O₂ doped with 1.00 mol% CoO, 0.05 mol% Nb₂O₅ and x mol% La₂O₃ (0.25≤x≤1.00) have been studied. Sn_0.25Ti_0.75Co_0.01Nb_0.005 doped with 0.50 mol% La₂O₃ has a nonlinearity coefficient of 6. An increase in the concentration of La₂O₃ raised its resistivity, thereby altering the electric properties of the material. A thermal treatment in oxygen atmosphere increased the nonlinearity coefficient to a value of 9.     

Microstructures and dielectric properties of CaTiO3–LaSrAlO4 composite ceramics

The microstructures and dielectric properties of xCaTiO₃/(1−x)LaSrAlO₄ composite ceramics were investigated. CaTiO₃ and LaSrAlO₄ could co-exist when the content of CaTiO₃ was no more than 30 mol%, while LaAlO₃ and CaO phases were observed in the composite ceramics with higher CaTiO₃ content. The dielectric constant of the composite ceramics increased with increasing the additive content, and the dielectric loss generally increased with increasing the additive content because of the presence of phase boundary and the high dielectric loss of the minor phases. The temperature coefficient of dielectric constant decreased with increasing the additive content firstly, and then it increased abnormally when x equals to 40 mol%, finally it decreased with increasing the additive content further. The dielectric properties predicted from serial formula were most close to those obtained from experiment among the classical dielectric mixture rules.     

Microwave dielectric characteristics of Ba(Mg1/3Ta2/3)O3 ceramics sintered at low-temperatures

The microwave dielectric properties and microstructures of Ba(Mg_1/3Ta_2/3)O₃ (BMT) ceramics sintered at low temperatures with 2–3 wt.% NaF additives were investigated. BMT ceramics sintered at 1340 °C for 3–12 h showed dielectric constants (_r) of 25.5–25.7, Qf values of 41 500–50 400 GHz and temperature coefficients of the resonator frequency (τ_f) of 10.9–21.4 ppm °C⁻¹. The variation of sintering time almost had no effect on the dielectric constant. The Qf value increased and the τ_f decreased with increasing sintering time. The ordering degree of Mg²⁺ and Ta⁵⁺ at B-sites increased with increasing sintering time.     

A位Sm掺杂对0.93Na0.5Bi0.5TiO3-0.07BaTiO3陶瓷微结构及电学性能的影响

采用固相反应烧结方法制备了Sm掺杂的[(Na_0.5Bi_0.5)_0.93Ba_0.07]_1-xSm_xTiO₃(BNBST)无铅介电储能陶瓷, 系统研究了Sm掺杂含量对BNBST陶瓷的相结构、微观结构、铁电、介电、储能和交、直流电导的影响。研究结果表明: 制备的陶瓷样品具有单一的钙钛矿结构, Sm掺杂固溶于(Na_0.5Bi_0.5)_0.93Ba_0.07TiO₃基材的晶格A位; 晶粒生长被Sm掺杂抑制, 平均晶粒尺寸在2 μm内, 且均匀致密; Sm掺杂显著降低了剩余极化和矫顽场, 表现出双电滞回线特性, 但饱和极化也略有降低; 储能密度和效率随Sm掺杂量增加先增大后减小, 在x=0.02和电场为70 kV/cm时获得最大储能密度0.70 J/cm³, 其效率为40%; BNBST陶瓷具有明显的弛豫铁电体特征, 其介电常数峰T_m随掺杂量增加而降低且平坦化; BNBST陶瓷的绝缘性有较强的温度依赖性, 300℃以下具有良好的绝缘性。     

Dielectric and piezoelectric properties of sol–gel derived Ca doped PbTiO3

Synthesis of Ca doped PbTiO₃ powder by a chemically derived sol–gel process is described. Crystallization characteristics of different compositions Pb_1−xCa_xTiO₃ (PCT) with varying calcium (Ca) content in the range x = 0–0.45 has been investigated by DTA/TGA, X-ray diffraction and scanning electron microscopy. The crystallization temperature is found to decrease with increasing calcium content. X-ray diffraction reveals a tetragonal structure for PCT compositions with x ≤ 0.35, and a cubic structure for x = 0.45. Dielectric properties on sintered ceramics prepared with fine sol–gel derived powders have been measured. The dielectric constant is found to increase with increasing Ca content, and the dielectric loss decreases continuously. Sol–gel derived Pb_1−xCa_xTiO₃ ceramics with x = 0.45 after poling exhibit infinite electromechanical anisotropy (k_t/k_p) with a high d₃₃ = 80 pC/N, ′ = 298 and low dielectric loss (tan δ = 0.0041).