Na0.5Bi0.5TiO3-K0.5Bi0.5TiO3系无铅压电陶瓷的制备工艺研究

利用XRD、SEM等分析技术 ,研究了Na0 .5Bi0 .5TiO3 -K0 .5Bi0 .5TiO3 系无铅压电陶瓷的合成温度 ,烧成工艺条件对陶瓷晶体结构、压电性能的影响。结果表明 ,合成温度提高有利于主晶相的形成 ,适当延长保温时间有利于材料的压电性能。该体系随着KBT含量的增加 ,烧结温度提高 ,烧结温度范围变窄。同时研究了极化工艺条件对材料压电性能的影响表明 ,提高极化电场和适当提高极化温度有利于压电性能的提高 ,但过高的温度由于受到材料高温下退极化的影响而导致材料压电性能变差     

Na0.5Bi0.5TiO3-K0.5Bi0.5TiO3系无铅压电陶瓷的极化工艺研究

主要研究了极化电场,极化时间和极化温度等工艺参数对Na0.5Bi0.5TiO3-K0.5Bi0.5TiO3系无铅压电陶瓷介电和压电性能的影响。结果表明:极化电场和极化温度对压电陶瓷的介电、压电性能影响较大,而极化时间则影响较小。适宜的极化电场是3～3.5kV/mm,极化温度70～80℃,极化时间为10～15min。     

Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3–BaTiO3–SrTiO3陶瓷的准同型相界与电性能

采用固相法制备了 Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3–BaTiO3–SrTiO3（NBT–KBT–BT–ST）陶瓷,该体系是按（1–2x）（0.8NBT–0.2KBT）–x（0.94NBT–0.06BT）–x（0.74NBT–0.26ST） （x = 0.10、0.20、0.25、0.30、0.35、0.40、0.45）组合而成的,研究了该系陶瓷的结构与电性能。结果表明：所有样品都处于三方–四方准同型相界区域。该系陶瓷在准同型相界附近表现出了优异的压电性能,压电常数 d33、机电耦合系数 kp和剩余极化强度 Pr随 x 的增加先升高后降低,其中 x=0.35 陶瓷的电性能最佳：d33= 210 pC/N,kp= 0.319,Pr= 39.3 μC/cm2,Ec= 20.2 kV/cm,是一种良好的无铅压电陶瓷候选材料。依据准同型相界组成的线性组合规律来寻找具有优异压电性能的 NBT–KBT–BT–ST 陶瓷准同型相界组成是可行的。     

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.     

The electrical properties of (1−x)(Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3–BaTiO3)–xCaZrO3 lead-free piezoelectric ceramics

Lead-free (1−x)(0.0852Bi_0.5Na_0.5TiO₃–0.12Bi_0.5K_0.5TiO₃–0.028BaTiO₃)–xCaZrO₃ piezoelectric ceramics (BNT−BKT−BT−xCZ, x=0, 0.01, 0.02, 0.03, 0.04 and 0.05) were prepared by using a conventional solid-state reaction method. The effects of CZ-doping on the structural, dielectric, ferroelectric and piezoelectric properties of the BNT−BKT−BT−xCZ system were systematically investigated. The polarization and strain behaviors indicated that the long-range ferroelectric order in the unmodified BNT−BKT−BT ceramics was disrupted by the increase of CZ-doping content, and correspondingly the depolarization temperature (T_d) shifted down from 109 °C to below room temperature. When x>0.03, accompanied with the drastic decrease in the remnant polarization (P_r) and piezoelectric coefficient (d₃₃), the electric-field-induced strain was enhanced significantly. A large unipolar strain of 0.35% under an applied electric field of 70 kV/cm (S_max/E_max=500 pm/V) was obtained in the BNT−BKT−BT−0.04CZ ceramics at room temperature, which was attributed to the reversible electric-field-induced phase transition between the relaxor and ferroelectric phases.     

拓扑化学反应制备片状Na0.5Bi0.5TiO3粉体的研究

通过熔盐法制备出具有铋层结构的前驱体Na0.5Bi4.5Ti4O15,其取向度f值(Lotgering factor法)高达0.9.粉体Na0.5Bi4.5Ti4O15再与NaaCO3和TiO2发生拓扑化学反应,铋层状结构的Na0.5Bi4.5Ti4O15完全转变成钙钛矿结构的Na0.5Bi0.5TiO3(NBT),所得到NBT粉体保留了NBIT的层状形貌,其厚度约0.4μm,长度为5-10μm,显示出较高的各向异性.研究了烧成温度对前躯体NBIT微粒形态的影响.通过SEM分析,固相法,熔盐法和拓扑反应合成的NBT粉体微观结构显示出巨大的差异.     

Structural,dielectric and piezoelectric properties of (Bi0.5Na0.5)TiO3–(Bi0.5K0.5)TiO3–Bi(Zn0.5Ti0.5)O3 thin films prepared by sol–gel method

Lead free (1−x)(0.8Bi_0.5Na_0.5Ti_0.5O₃–0.2Bi_0.5K_0.5TiO₃)–xBiZn_0.5Ti_0.5O₃ (x=0–0.06) (BNT–BKT–BZT) thin films were deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by a sol–gel processing technique. The effects of BZT content on the structural, dielectric, ferroelectric and piezoelectric properties of the BNT–BKT–BZT thin films were investigated systematically. The BNT–BKT–BZT thin films undergo a transition from ferroelectric to relaxor phase with increasing temperature. The phase transition temperature decreases with the increase of BZT content. The BNT–BKT–BZT thin film with x=0.04 exhibits the best ferroelectric properties (P_max=40 µC/cm² and P_r=10 µC/cm²), largest dielectric constant (ε=560) and piezoelectric constant (d₃₃=40 pm/V). This finding demonstrates that the BNT–BKT–BZT thin film has an excellent potential for demanding high piezoelectric properties in lead free films.     

溶胶-凝胶法合成(Na0.5Bi0.5)TiO3微粉

以钛酸四丁酯、硝酸铋、醋酸钠和冰醋酸为原料,利用溶胶-凝胶工艺得到透明凝胶,经干燥后煅烧成(Na0.5Bi0.5)TiO3微粉。通过对溶胶体系水/醇盐的摩尔比、初始pH值及胶凝温度对(Na0.5Bi0.5)TiO3凝胶体系溶胶-凝胶形成过程影响的研究,发现水/醇盐比R在35≤R≤60,pH在2.2~3.5,反应温度在40~60℃时,能够得到透明的溶胶;通过TG-DTA、SEM、X-ray等分析手段对(Na0.5Bi0.5)TiO3粉体进行测试,表明在650℃合成1h可以得到单一钙钛矿(Na0.5Bi0.5)TiO3晶体;采用TEM对(Na0.5Bi0.5)TiO3干凝胶粉体分析其粒径大小约为10nm。     

柠檬酸盐法制备Na0.5Bi0.5TiO3陶瓷粉体的工艺研究

本实验采用柠檬酸盐法制备（NaBi）0.5TiO3无铅压电陶瓷粉体,系统研究了柠檬酸浓度、溶液pH值、煅烧温度等工艺条件对制备的影响。经研究分析,当柠檬酸浓度C=9%,溶液pH=7.5时,能形成透明、均匀、稳定的溶胶,且形成时间最短;650℃下煅烧2h能够合成单一的钙钛矿结构的钛酸铋钠晶相,比传统固相反应法煅烧温度降低了200℃。     

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.     

(Na1-xKx)0.5Bi0.5TiO3系的离子挥发性研究

利用固相法制备了(Na1-xKx)0.5Bi0.5TiO3系压电陶瓷,研究其中Bi3 、Na 、K 离子的挥发对其性能的影响。研究结果表明Bi3 的挥发性对样品的性能影响较大,而Na 、K 离子相对较小。     

Na0.5Bi0.5TiO3基无铅压电陶瓷研究与应用的新进展

综述了钙钛矿结构的Na0.5Bi0.5TiO3(简称BNT)基无铅压电陶瓷的研究现状,并与其它无铅基压电陶瓷进行了对比.列举了近年来BNT 基压电陶瓷的新发展和热门体系,结合笔者承担的相关研究工作内容,总结和指出了BNT基无铅压电陶瓷新的研究思路和相关方向.     

Na0.5Bi0.5TiO3-Ba0.5Sr0.5Nb2O6无铅压电陶瓷的研究

采用固相法制备了(1-x)(Na0.5Bi0.5)TiO3-xBa0.5Sr0.5Nb2O6(0≤x≤1.0％)(简称(1-x)NBT-xBSN)无铅压电陶瓷,研究了不同BSN含量(x=0,0.1％,0.3％,0.5％,0.7％,1.0％,摩尔分数)样品的物相组成、显微结构及电性能.结果表明:所有样品均为纯钙钛矿结构,随掺杂量x的增加,陶瓷的相对密度pr、压电常数d33和机电耦合系数kp均先增大后降低,机械品质因子Qm和退极化温度Td则逐渐下降.该体系陶瓷具有弥散相变特征,弥散指数介于1.6～1.7.当x=0.5％时,陶瓷获得最佳性能:d33=92pC/N,kp=0.164,Qm=89,εr=650,tanδ=5.47％,pr=96.5％.     

Morphotropic phase boundary and electrical properties of lead-free (K0.5Bi0.5)TiO3–Bi(Ni0.5Ti0.5)O3 relaxor ferroelectric ceramics

Lead-free relaxor ferroelectric ceramics (1?x)(K_0.5Bi_0.5)TiO₃–xBi(Ni_0.5Ti_0.5)O₃ were prepared by a conventional solid-state route, the phase transition behavior and corresponding electrical properties were investigated. A typical morphotropic phase boundary (MPB) between rhombohedral and tetragonal ferroelectric phases was identified to be in the range of 0.05<x<0.07 where the optimum piezoelectric and electromechanical properties of d₃₃=126 pC/N and k_P=18% were achieved. Most importantly, a high Curie temperature ~320 °C, around which the material shows a typical relaxor ferroelectric behavior characterized by the presence of diffuse phase transition and frequency dispersion, was obtained in MPB compositions, significantly higher than those of some existing MPB lead-free titanate systems. These results demonstrate a tremendous potential of the studied system for device applications.     

0.65BaTiO3-0.35Na0.5Bi0.5TiO3薄膜的制备及其电学性能研究

采用脉冲激光沉积法制备了0.65 BT-0.35NBT/SRO/STO异质结构薄膜.通过XRD、AFM和SEM分析了0.65BT-0.35NBT薄膜的微观结构.XRD结果表明:0.65BT-0.35NBT为钙钛矿结构,其薄膜为沿c轴择优取向生长结构.0.65BT-0.35NBT薄膜表现出优异的铁电和压电性能,剩余极化强度达到38.1 μC/cm2.0.65 BT-0.35NBT薄膜的居里温度(Tc ～ 223℃)明显高于BTO的居里温度,是一种具有优异电学性能和较高的居里温度的BTO基铁电材料.     

Na0.5Bi0.5TiO3基无铅陶瓷的铁电相变和弛豫特性研究进展

综合介绍了Na0.5Bi0.5TiO3（sodium bismuth titanate,NBT）基无铅铁电材料在铁电相变和弛豫特性方面近年来国内外的研究进展。介绍了温度变化对NBT铁电性能的影响以及产生弛豫相变的机理。此外,结合本课题的研究成果,介绍了不同含量BaTiO3和K0.5Bi0.5TiO3及其它化合物取代后对NBT基铁电相变和弛豫特性的影响。指出了在提高压电性能的同时,大幅降低材料铁电一反铁电相变,即材料的退极化温度,可能会影响到压电陶瓷材料的使用温度范围。     

Bi0.5Na0.5TiO3基无铅压电陶瓷设计与制备研究的新进展

综述了Bi0.5Na0.5TiO3(BNW)基无铅压电陶瓷体系研究的最新进展,介绍了BNT基无铅压电陶瓷的设计方法及其制备技术.用自洽场离散变分法(self-consult charge-discrete variation-Xa,SCC-DV-Xa)等计算方法可为设计新型BNT基陶瓷提供重要的理论指导.用湿化学法,包括:溶胶-凝胶法、柠檬酸盐法、水热法等,可以合成BNT基纳米粉体,该类方法制备的BNT基粉体具有良好烧结活性,利于致密化烧结,使材料电性能得到改善.用模板晶粒生长技术可获得晶粒生长定向程度很高的BNT基压电陶瓷材料,进而提高材料在特定方向的压电性能.     

La掺杂(Na0.5Bi0.5)0.82(K0.5Bi0.5)0.18TiO3系统无铅压电陶瓷的制备工艺探讨

采用传统陶瓷工艺，研究了制备[（Na0.5Bi0.5）0.82（K0.5Bi0.5）0.18]1-xLaxTiO3（x=0．00，0．01，0．03，0．05，0．10）无铅压电陶瓷的工艺条件对陶瓷的物相组成、显微结构和压电性能的影响。利用XRD、SEM等技术分析结果表明，合成温度的提高有利于主晶相的形成，且此系统烧成温度范围较窄，故需控制在合适的烧成温度下才能得到高致密度的陶瓷。同时，研究了极化工艺条件对材料压电性能的影响，结果表明，提高极化电场强度、控制适当的极化温度有利于提高材料的压电性能。     

Na0.5Bi0.5TiO3 phase relations: Thermodynamics and phase equilibria in the systems Bi2O3 – TiO2, Na2O – TiO2, and Na2O – Bi2O3 – TiO2

The lead-free piezoelectric material sodium bismuth titanate (NBT, Na_0.5Bi_0.5TiO₃) has attracted considerable attention owing to its promising dielectric, piezoelectric, and electrical properties. However, the literature on the binary subsystems is contradictory and there are only limited data for the ternary system. The present work surveys all of the reports of the binary subsystems Bi₂O₃ – TiO₂ and Na₂O – TiO₂ and synthesizes these data into inclusive revised versions. The compatibilities for the ternary system Na₂O – Bi₂O₃ – TiO₂ were determined experimentally, thus enabling the construction of a complete isothermal section at 800 °C. The compatibilities associated with the problematic binary subsystem Na₂O – Bi₂O₃, which experiences extreme volatilisation, were determined through the generation of the absent standard-state thermodynamic functions for the relevant binary and ternary phases, thus providing a full suite of thermodynamic data for this system. The thermodynamic stability diagrams for Na₂O, Bi₂O₃, and TiO₂ thus were calculated. The isothermal section also addresses the contradictions in the literature concerning the formation of solid solutions of Bi₁₂TiO_20-x / Bi_12-xTi_1+xO_20+0.5x, pyrochlore (Bi₂Ti₂O₇ / Na_wBi_2-xTi_2-yO_7-z), BTO (Bi₄Ti₃O₁₂ / Na_xBi₄Ti₃O_12+0.5x), and NBT (Na_0.5Bi_0.5TiO₃ / Bi_1±xNa_xTiO_3.5±x). Further, it was observed that the congruent melting point of NBT, which was determined to be 1225 °C, was preceded by the onset of gradual structural destabilization at 940 °C. Also, the NBT rhombohedral → tetragonal phase transformation was observed at an onset temperature of ∼250 °C. The present work thus provides platform data for the fabrication and reactivities of materials in the ternary system Na₂O – Bi₂O₃· TiO₂ and its binary subsystems.