Domain-scale imaging to dispel the clouds over the thermal depolarization of Bi0.5Na0.5TiO3-based relaxor ferroelectrics

Thermal depolarization temperature, T_d, of ferroelectric oxides Bi_0.5Na_0.5TiO₃ (BNT), where dielectric and piezoelectric signals exhibit remarkable changes, is providing rich research contents but is not well understood yet. Herein, on the domain-scale, we give the direct and clear real-space images of thermal depolarization process on BNT-based complex oxides. As disclosed by the piezoresponse force microscopy (PFM), heating above T_d breaks the poling-induced large-sized-oriented domains into smaller sized polar clusters with different orientations, leading to the thermal depolarization phenomenon. Although the poling-induced domain decays above T_d, the broken domains exhibit a rather larger coherence length than that of the incipient labyrinth-like nano-domains. During the heating process, BNT possesses a structural transition from the long-range-correlated R3c (a⁻a⁻a⁻ anti-phase tilting) to the short-range-correlated P4bm (a⁰a⁰c⁺ in-phase tilting) phase, which should be the fundamental driving force for the fluctuations of poling-induced large-sized-oriented domains. We expect these results will further promote the understanding about the origin of T_d in BNT-based relaxor ferroelectrics, and provide an intuitive method for the characterization of the thermodynamic and kinetic process in this kind of materials.     

溶胶-凝胶法制备(Na0.5Bi0.5)TiO3-BaTiO3基无铅压电陶瓷的研究

采用溶胶-凝胶法制备（Na0.5 Bi 0.5）TiO3-BaTiO3超细粉体。研究结果表明，当热处理温度为800℃时能合成出纯的钙钛矿结构的BNBT超细粉体。另外研究发现，与固相法合成的陶瓷样品相比，sol-gel法制备的陶瓷样品的压电常数和机械品质因子有所提高，但其它的电学性能与固相法合成的陶瓷相近，如介电常数、介电损耗等。     

Electrical properties and temperature stability of SrTiO3-modified (Bi1/2Na1/2)TiO3-BaTiO3-(K1/2Na1/2)NbO3 piezoceramics

SrTiO₃-modified lead-free piezoelectric ceramics, (0.93-x)Bi_0.5Na_0.5TiO₃-xSrTiO₃-0.06BaTiO₃-0.01 K_0.5Na_0.5NbO₃ [(BNT-xST)-BT-KNN, x = 0-0.06], were prepared using a conventional solid-state reaction method. The XRD structure analysis and electric properties characteristics revealed the ST-induced phase transformation from the ferroelectric phase to the relaxor phase and their coexistence state. Benefiting from the ST-destructed ferroelectric long-range orders, the high normalized strain value of 600 pm/V was obtained in the (BNT-0.02ST)-BT-KNN ceramic at 5 kV/mm. The ST-generated relaxor phase was found to have a constructive effect on improving the temperature stability and restraining the hysteresis of the electric-field-induced strain. The normalized strain of (BNT-0.06ST)-BT-KNN ceramics could be kept at a high value ~337 pm/V at elevated temperature up to 120°C.     

四方相Bi1/2Na1/2TiO3-BaTiO3无铅压电陶瓷的研究

采用电子陶瓷法制备出(1-x)Bi1/2Na1/2TiO3-xBaTiO3(简写BNBT)无铅压电陶瓷,其中x=0.08,0.1,0.2,0.3,0.4。XRD分析结果表明所制备的样品都生成了纯的钙钛矿结构,并且都为四方相。同时利用电子探针显微镜(EPM)分析技术,研究了BNBT压电陶瓷的形貌。并通过测量样品的压电介电常数,发现所研究的样品的机械品质因数(Qm)在56-74之间,平面机电耦合系数(kp)在0.16左右,频率常数(NФ)在3000左右,并且随着x的增大相对介电常数εT33/ε0逐渐变小;介质损耗tanδ先减小后增大,当x=0.20时出现最小值tanδmin=0.03018;而压电常数d33则先增加后减小,在x=0.10时有最大值d33max=138。从综合性能来看,当x=0.20时性能最好,εT33/ε0=881,tanδ=0.03018,d33=115。     

掺杂Co2O3对Na0．5Bi0.5TiO3基压电陶瓷性能的影响

通过固相法合成Na0.5Bi0.5TiO3+xmol%Co3+(简写为:NBT-xC)体系无铅压电陶瓷,并对其相结构、压电、介电及铁电性能进行了研究.XRD分析结果表明,所有组成均形成三方钙钛矿结构.SEM扫描电镜照片显示Co2O3的引入有利于晶粒长大,提高致密度.随着Co含量的增加,陶瓷的压电常数d33,机电耦合系数Kp都略有下降,机械品质因素Qm有明显提高,在x=3时达到极大值:0m-934,同时介电损耗出现极小值:tgδ=0.02(1kHz),综合得出Co离子起"硬性掺杂"作用.     

常压溶剂热法制备Bi0.5Na0.5TiO3纳米粉体的研究

以Bi(NO3)3·5H2O、Ti(OC4H9)4为原料,无水乙醇作溶剂,采用溶剂热法在常压下合成了Bi0.5Na0.5TiO3(简称为BNT)纳米粉体.通过X射线衍射(XRD)和扫描电子显微镜(SEM)对BNT粉体进行了表征.并在常压溶剂热条件下研究了影响BNT晶体生长和形貌的主要因素.实验结果表明:反应温度为100 ℃,保温时间为2.5 h,NaOH浓度为12 mol·L-1,650 ℃下煅烧2 h时,能制备出单一的BNT粉体,且制得粉体的粒径尺寸约为100 nm.     

Large electrocaloric effect with ultrawide temperature span in Na1/2Bi1/2TiO3-based lead-free ceramics

Innovative cooling technologies are recognized by many industries as a crucial part of their system design. A large electrocaloric effect (ECE) and extended working temperature are the key issues hindering the realization of electrocaloric refrigeration technology. In this work, large ECE (ΔT = 0.8–0.9°C @ 4 kV/mm) with an ultrawide temperature span from 30 to 120°C is noted for lead-free (Na_1/2Bi_1/2)_0.80Sr_0.20(Zn_1/3Nb_2/3)_xTi_1-xO₃ ceramics. The excellent ECE performance can be ascribed to the evolution of polar nanoregions. Our work suggests that this material is promising for applications in solid-state refrigeration systems with a broad range of operating temperatures.     

Bi0.5Na0.5TiO3基无铅压电陶瓷的研究进展

随着经济的发展和人们环保意识的增强,无铅压电陶瓷的研究和开发越来越引起人们的重视.由于钛酸铋钠(Bi0.5Na0.5TiO3,简称为BNT)基无铅压电陶瓷具有良好的铁电性和高的剩余极化引起了广大学者的关注.本文分析了BNT基无铅压电陶瓷的研究进展,其中晶粒取向生长技术是提高其压电性能的一个重要途径.本文还介绍了一种溶剂热法制备织构化BNT基无铅压电陶瓷的方法.     

Luminescence and electrical properties of Eu-modified Bi0.5Na0.5TiO3 multifunctional ceramics

The Eu³⁺-modified Bi_0.5Na_0.5TiO₃ (BNT) ceramics have been fabricated by the solid-state reaction method. The impact of Eu³⁺ doping on the structure, photoluminescence, and electrical properties has been studied by XRD, SEM, PL spectra, and LCR meter. X-ray diffraction analysis reveals that the crystal structure of the samples is well matched with the trigonal perovskite, and the optimal temperature of presintering is 880°C. The Eu³⁺-doped BNT ceramics show excellent red fluorescence at 614 nm corresponding to the ⁵D₀→⁷F₂ transition of Eu³⁺ under 466 nm excitation and relatively long fluorescence lifetime. The BNT-0.02Eu ceramic density is up to 5.68 g/cm³ and the relative density is up to 94.6% with sintering temperature 1075°C. The piezoelectric constant (d₃₃) of samples has been significantly improved up to 110 pC/N by Eu³⁺ doping. The BNT-0.03Eu ceramic presintered at 880°C and sintered at 1050°C has good dielectric properties and excellent luminescence properties. Eu³⁺-doped BNT ceramics make it potential applications for novel integrated electro-optical and multifunctional devices.     

钛酸铋钠钾锂无铅陶瓷的柠檬酸制备技术

以钠、钾、锂的碳酸盐为原料，采用柠檬酸盐-凝胶法制备了Biol5（Na1-x-y，LixKy）0.5TiO3无铅压电陶瓷，研究了影响凝胶合成的各种工艺条件，利用TG-DTA，SEM，XRD，纳米粒度分析等技术分析了凝胶预烧温度及预烧粉体的粒度分布。研究结果表明：柠檬酸与金属离子的物质的量比、溶液浓度、pH是影响前驱液与凝胶形成的主要因素；用柠檬酸盐一凝胶法合成的Bi0.5（Na1-x-y，LixKy）TiO3粉体粒度细小均匀，合成温度低；陶瓷的压电常数d33可达138pC／N，其平面机电耦合系数kp为0．30。     

Significantly reduced hysteresis in (Fe1/2Nb1/2)4+-modified 0.75Na1/2Bi1/2TiO3-0.25SrTiO3 lead-free piezoceramics with large strain

Aiming to get the NBT-based lead-free ceramic with high strain and low strain hysteresis for practical actuator applications, a solid solution of complex-ion (Fe_1/2Nb_1/2)⁴⁺doped 0.75Na_1/2Bi_1/2TiO₃-0.25SrTiO₃ ((Na_1/2Bi_1/2)_0.75Sr_0.25Ti_1-x(Fe_1/2Nb_1/2)_xO₃, abbreviated as NBST-100xFN) was designed and prepared, and its phase structure, micromorphology, ferroelectric, strain, dielectric and piezoelectric performances were systematically investigated. It was found that the incorporation of (Fe_1/2Nb_1/2)⁴⁺ causes a structure transition from the ferroelectric/relaxor (FE/RE) mixed phases to relaxor (RE) phase, increasing to a promising strain performance at x = 0.04 featured by not only a moderate strain value of 0.26%, corresponding normalized strain d₃₃* of 371 pm/V, but also a very small strain hysteresis of 22%. In addition, the NBST-4FN ceramic sample also exhibits an unexceptionable frequency-dependence of unipolar strain. This study provides a new understanding and design idea for the practical actuator application of high strain NBT-based lead-free ceramics with ultra-low hysteresis.     

Temperature-stable Na0.5Bi0.5TiO3-based ceramics with favorable low-temperature dielectric and energy storage property

In this work, (1 − x)(0.94Na_0.5Bi_0.5TiO₃–0.06BaTiO₃)–xKTaO₃ (x = 0–0.30) ceramics are developed for dielectric capacitor applications. The introduction of KTaO₃ from x = 0 to 0.30 increases the tolerance factor t from 0.984 to 1.005 and causes the decrease of ferroelectric rhombohedral phase in the ceramics. Besides, a gradual structural change toward a higher symmetry can be detected, accompanied by the obvious domain refinement. In the aspect of electrical property, the strengthened dielectric relaxation leads to the greatly enhanced thermal stability of dielectric response. The decline in T_s from 98 to −96°C causes a significant widening of the low-temperature region with temperature-stable dielectric constant ε_r and low dielectric loss tan δ. The x = 0.30 ceramic shows a high ε_r (25°C) of 1094 with the temperature coefficient of capacitance ≤±15% over −70 to 200°C, which exceeds the X9R standard. Meanwhile, tan δ is less than 0.02 in a wide temperature range of −35 to 300°C. In addition, the ultrafine grain size of 290 nm, large bandgap of 3.22 eV, and high resistance of the x = 0.30 ceramic contribute to its electrical breakdown strength. A linear-like P–E loop with the large discharged energy density W_D ∼ 3.50 J/cm³ and high energy efficiency η ∼ 90.1% is obtained under 28 kV/mm at room temperature. The thermal stability of the energy storage performance is also satisfactory with the variation of W_D less than 15% over −40 to 200°C, and the η is higher than 85%.     

High-energy storage density in NaNbO3-modified (Bi0.5Na0.5)TiO3-BiAlO3-based lead-free ceramics under low electric field

Ceramic-based dielectric capacitor are highly suitable for pulsed power applications due to their high power density and excellent reliability. However, the ultrahigh applied electric field limit their applications in integrated electronic devices. In this work, (1−x){0.96(Bi_0.5Na_0.5)(Ti_0.995Mn_0.005)O₃-0.04BiAlO₃}-xNaNbO₃ (BNT-BA-xNN, x = 0, 0.04, 0.08, 0.12, and 0.16) ternary ceramics were designed to achieve excellent energy storage properties. It was found that the introduction of NaNbO₃ (NN) effectively increase the difference (ΔP) between P_max and P_r, resulting in an obvious enhancement of the energy storage properties. High recoverable energy storage density, responsivity, and power density, that is, W_rec = 2.01 J/cm³, ξ = W_rec/E = 130.69 J/(kV⋅m²), and P_D = 25.59 MW/cm³, accompanied with superior temperature stability were realized at x = 0.14 composition. In addition, the thermal stable dielectric properties of the sample can be prominently improved with increasing NN content. The temperature coefficient of capacitance (TCC) of x = 0.16 composition is lower than 15% over the temperature range from 49°C to 340°C, with a high dielectric permittivity of 1647 and a low dielectric loss (0.0107) at 150°C. All these features show that the BNT-BA-xNN ceramics are promising materials for energy storage application.     

Achieving excellent energy storage properties of Na0.5Bi0.5TiO3 - based ceramics by using a two-step strategy involving phase and polarization modification

Na_0.5Bi_0.5TiO₃-based ceramic specimens have been extensively investigated as ferroelectric materials. After being doped with CaTiO₃, the resulting Na_0.5Bi_0.5TiO₃-based ceramics exhibit relaxor characteristics, and improved energy storage density and efficiency. Based on these above results, CeO₂ was further employed to modify the polarization of the 0.85Na_0.5Bi_0.5TiO₃-0.15CaTiO₃ matrix ceramic to achieve better energy storage performance. The effective energy storage density was enhanced from 1.93 to 2.53 J/cm³ by using the appropriate doping concentration of CeO₂. Grain refinement effect can effectively enhance the electric-field strength from approximately 190 to 230 kV/cm. In particular, when doped with 2% CeO₂, the energy storage efficiency of the sample was maintained at approximately 90% at 30 °C-150 °C and at approximately 80% in the frequency range of 0.2–200 Hz. This combination has very excellent temperature stability and frequency stability, making it a promising candidate for energy storage applications.     

Large electrocaloric responses in [Bi1/2(Na,K)1/2]TiO3‐based ceramics with giant electro‐strains

The electrocaloric effect (ECE) is investigated through indirect measurement in two lead‐free [Bi_1/2(Na,K)_1/2]TiO₃‐based ceramics that were previously reported to display giant electro‐strains. In the Nb‐doped ceramic, denoted as BNKT‐2.5Nb, a decent temperature change of ΔT=1.85 K and an electrocaloric responsivity of ΔT/ΔE=0.37 (10^?6Km V^?1) are found around room temperature (32°C). While in the Ta‐doped ceramic, BNKT‐1.5Ta, a wide operation temperature range (T_span ~55 K) is observed near room temperature. Additional electrical measurements, as well as transmission electron microscopy experiments, are performed to identify the mechanisms of the ECE in both ceramics.     

Shock-driven depolarization behaviors and electrical output in BiAlO3-doped Bi0.5Na0.5TiO3 ferroelectric ceramics

Ferroelectric materials under shock compression can generate current and power by a drastic change of the remnant polarizations and surface bound charge. This behavior has been employed in applications involving nuclear fusion trigger, energy storage devices, and high pulse power sources. Despite the large power output in lead-containing ferroelectrics, lead-free materials are highly desirable owing to the environmental concerns. Herein, the phase transition behaviors and current outputs of 0.92Bi_0.5Na_0.5TiO₃-0.08BiAlO₃ (BNT-8BA) materials are studied under high pressure. The BNT-8BA ferroelectric ceramics can be completely depolarized from polar to the nonpolar state under shock compression, resulting in a current output in the external circuit. The phase-transition-induced depolarization pressures of BNT-8BA are lower than those of the pure Bi_0.5Na_0.5TiO₃ under both dynamic and static high-pressure loads. These results can allow the understanding of the high-pressure behavior of BNT-8BA for application as ferroelectric pulsed power supply.     

Synthesis and properties of Bi0.5(Na1−x−yKxAgy)0.5TiO3 lead-free piezoelectric ceramics

Bi_0.5(Na_1−x−yK_xAg_y)_0.5TiO₃ piezoelectric ceramics were prepared by conventional ceramic processes. X-ray diffraction patterns show a pure perovskite structure, indicating that the K⁺ and Ag⁺ ions substitute for the Na⁺ ions in Bi_0.5Na_0.5TiO₃. The temperature dependence of the dielectric constant and dissipation factor shows all ceramics to experience two phase transitions: from ferroelectric to anti-ferroelectric and from anti-ferroelectric to paraelectric. The transition temperature from ferroelectric to anti-ferroelectric and the temperature at which the dielectric constant reaches its maximum value decrease with the increase of K⁺ amount. At room temperature, the ceramics containing 17.5–20 mol% K⁺ and 2 mol% Ag⁺ exhibit high piezoelectric constant (d₃₃ = 180 pC/N) and high electromechanical coupling factor (k_p = 35%).     

Microstructural,ferroelectric, and photoluminescent properties of (100)‐oriented Sm3+‐doped Na0.5Bi0.5TiO3 thin films

(100)_C‐oriented Na_0.5Bi_0.5‐xSm_xTiO₃ (NBST) lead‐free ferroelectric thin films were prepared on Pt/Ti/SiO₂/Si substrates by chemical solution deposition method, and their microstructural, dielectric, ferroelectric, and photoluminescent properties were studied. X‐ray diffraction and scanning electron microscopy analysis indicated that both the grain size and (100)_C orientation degree of NBST thin films were decreased by doping Sm³⁺ ions. Raman spectra showed that structural symmetry of NBST thin films decreased at low Sm³⁺ doping concentration and then increased at high doping concentration of Sm³⁺ ions. An appropriate amount of Sm³⁺ dopants was confirmed to enhance dielectric and ferroelectric properties of the NBST thin films. Among all the compositions, the Na_0.5Bi_0.492Sm_0.008TiO₃ thin film exhibited the largest remnant polarization (2P_r) of 27.3 μC/cm² and high dielectric constant of 1068, as well as a low dielectric loss of 0.04. Temperature‐ and frequency‐dependent dielectric characteristics illustrated the relaxor ferroelectric behavior of Na_0.5Bi_0.492Sm_0.008TiO₃ thin film. Meanwhile, the Na_0.5Bi_0.492Sm_0.008TiO₃ thin film also showed optimal orange‐red emission at 600 nm, which is originating from the ⁴G_5/2 → ⁴H_7/2 transition of Sm³⁺ ions.     

CeO2掺杂钛酸铋钠钾陶瓷的制备工艺与介电性能

为了进一步探索合成工艺对钛酸铋钠系无铅材料的结构及介电特性的影响,本文以甘氨酸为燃料,利用固相-燃烧法制备了CeO2掺杂的Bi0.5Na0.5TiO3-Bi0.5K0.5TiO3 (BNKT)陶瓷.XRD表明,在固相合成工艺中引入燃烧法制备BNKT陶瓷,比传统固相法降低预烧温度150 ℃,掺杂的CeO2扩散进入了BNKT钙钛矿的晶格,且当掺杂量为0%~0.3%时,形成纯的钙钛矿相结构;SEM表明,CeO2掺杂使晶粒尺寸趋于平均,对晶粒生长有抑制作用;介电温谱表明,随着CeO2掺杂量增加,介电常数εr和退极化温度Td、相转变温度Tm降低,介电反常峰逐渐弱化,且室温至300 ℃,介电损耗tanδ始终在0.3%以下,并从微结构缺陷空位形成机制角度,结合铁电畴壁运动状态,分析讨论了对材料介电特性的作用规律.     

Na2CO3/TiO2催化剂的制备及催化性能研究

以钛酸正四丁酯为钛源,采用水热法制备出纯TiO2及Na2CO3修饰的TiO2催化剂样品.以亚甲基蓝溶液模拟染料废水为目标污染物,考察纯TiO2和经Na2CO3修饰后的Na2CO3/TiO2催化剂的催化性能.采用XRD、TEM、BET等方法对催化剂的结构和形貌进行了表征.结果表明,制备出的经Na2CO3修饰后的TiO2催...