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.     

Structural properties of multiferroic 0.5BiFeO3–0.5Pb(Fe0.5Nb0.5)O3 solid solution

Magnetoelectric multiferroics are very promising materials because of their practical applications and fundamental interests. The most widely studied magnetoelectric oxides are ABO₃ perovskites. In the paper structural properties of BiFeO₃ and Pb(Fe_0.5Nb_0.5)O₃ solid solution are described. The material crystallizes in rhombohedral R3c crystal structure which parameters are presented. Mössbauer spectroscopy was used to study local changes in an iron environment due to Fe/Nb substitution and hyperfine interaction parameters of different local surroundings of iron atoms are presented. The random distribution of B-site sublattice cations was confirmed. Ab initio calculations of the studied solid solution were conducted and theoretical crystal structure parameters were compared with the experimental data. The theoretical magnetic and electric properties are discussed. The local iron magnetic moments were estimated and their dependence on the local surrounding changes is shown. The calculated electrons densities and Bader's topological analysis were used to describe chemical bonding properties.     

四元复合氧化物La_(0.5)Sr_(0.5)Ni_(0.5)Cu_(0.5)O_3的抗硫性能

以SO2 为毒物 ,采用脉冲中毒方法 ,再以CO氧化反应为探针 ,对三元复合氧化物催化剂La0 .5Sr0 .5NiO3 与La0 .5Sr0 .5CuO3 以及四元复合氧化物催化剂La0 .5Sr0 .5Ni0 .5Cu0 .5O3 等三种催化剂样品的抗硫毒能力、失活曲线、中毒催化剂的再生性能以及毒物残留形态等进行了全面考察和对比分析。实验结果表明四元复合氧化物催化剂La0 .5Sr0 .5Ni0 .5Cu0 .5O3 在SO2 毒物含量是 1 2 2×10 -2 mmol时 ,特别是在高温 (≥ 30 0℃ )条件下 ,具有优异的抗硫性能     

Large strains accompanying field-induced ergodic phase-polar ordered phase transformations in Bi(Mg0.5Ti0.5)O3–PbTiO3–(Bi0.5Na0.5)TiO3 ternary system

A composition-induced pseudocubic–tetragonal structural transition was found to be accompanied by a relaxor phase transformation in xBi(Mg_0.5Ti_0.5)O₃–(0.75 − x)PbTiO₃–0.25(Bi_0.5Na_0.5)TiO₃ ternary solid solutions. Dielectric and ferroelectric measurements suggest the coexistence of ergodic and nonergodic relaxor phases within a single pseudocubic phase zone for samples with 0.50 < x < 0.51 where large electromechanical strains of up to 0.43% (S_max/E_max = 621 pm/V) can be generated. The mechanism was mainly ascribed to the accumulated effects of field-modulated continuous and reversible transformations from a pseudocubic ergodic phase to a rhombohedral short-range ordered phase (but not nonergodic polar phase), and finally to a long-range ordered ferroelectric tetragonal phase. These procedures were found to be strongly dependent on the applied field magnitudes. These findings were reasonably approved by a couple of measurements such as dielectric–temperature–frequency spectrum, ferroelectric polarization/strain hysteresis loops, polarization current density curves and particularly ex situ Raman spectrum and in situ high-resolution synchrotron X-ray diffraction.     

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.     

Field-induced large strain in lead-free 0.99[(1−x) Bi0.5(Na0.80K0.20)0.5TiO3–xBiFeO3]–0.01(K0.5Na0.5)NbO3 piezoelectric ceramics

Lead-free 0.99[(1−x) Bi_0.5(Na_0.80K_0.20)_0.5TiO₃–xBiFeO₃]–0.01(K_0.5Na_0.5)NbO₃ (BNKT20–100xBF–1KNN) piezoelectric ceramics were fabricated through conventional techniques. Results showed that changes in BF content of BNKT20–100xBF–1KNN induced transition from the ferroelectric phase to the ergodic relaxor phase. These changes also significantly disrupted long-range ferroelectric order, thereby correspondingly adjusting the ferroelectric-relaxor transition point T_F-R to room temperature. A large strain of 0.39% at the electric-field of 80 kV/cm (corresponding to a large signal d₃₃^* of 488 pm/V) was obtained at x=0.06, which originated from the composition proximity to the ferroelectric-relaxor phase boundary. Moreover, the high-strain material exhibited exceptional fatigue resistance (up to 10⁶ cycles) as a result of the reversible field-induced phase transition. The proposed material exhibits potential for novel ultra-large stroke and nonlinear actuators that require enhanced cycling reliability.     

Cu_(0.5)Zn_(0.5)Cr_(0.5)Al_(1.5)O_4尖晶石的制备及其催化性能

以硝酸铜、硝酸锌、硝酸铬、硝酸铝和氢氧化钠为原料,利用化学共沉淀法制得铜锌铬铝尖晶石Cu_xZn_(1-x)Cr_(0.5)Al_(1.5)O_4(x=0,0.25,0.50,0.75和1.00)(依次记为C1~C5),采用XRD、ICP、SEM和BET对其结构和物理、化学性质进行了表征。将不同组成的铜锌铬铝尖晶石作为催化剂在固定床反应器上催化合成N-甲基-4-氨基苯甲醚(NMA)。考察了尖晶石组成、反应温度、质量空速(WHSV)和反应原料配比对催化剂催化性能的影响。结果表明:反应温度为265℃,WSHV为0.15 h-1、n(甲醇)∶n(对氨基苯甲醚)=3.0∶1.0时,Cu_(0.5)Zn_(0.5)Cr_(0.5)Al_(1.5)O_4(C3)具有最佳的催化性能。对氨基苯甲醚转化率可达90.95%,NMA的选择性可达94.93%。     

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.     

Na_(0.5)Bi_(0.5)TiO_3-K_(0.5)Bi_(0.5)TiO_3系富钠区陶瓷固溶体的相变研究

本工作用X射线衍射、热激放电、介电-温度特性、电荷-压力关系等实验方法研究了xNa_(0.5)Bi_(0.6)TiO_3-(1-x)K_(0.5)Bi_(0.5)TiO_3系(0.73≤x≤1.00)陶瓷固溶体的相变,首次确定了该系统的相图。发现该系统的固溶体,在铁电相和顺电相之间存在着一个较阔的过渡相相区,随着温度的升高,固溶体都依次经历铁电相-过渡相-顺电相相变。文中对过渡相的性质作了讨论。     

Na_(0.5)Bi_(0.5)TiO_3-K_(0.5)Bi_(0.5)TiO_3系富钠区陶瓷固溶体的电物理性能研究

本工作对xNa_(0.5)Bi_(0.5)TiO_3-(1-x)K_(0.5)Bi_(0.5)TiO_3系(0.73≤x≤0.95)陶瓷固溶体的压电、铁电性质进行了研究。发现准同型相界位于x=0.81处;在相界,压电参数出现极值。在该系统中,获得了高厚度机电耦合系数、高频率常数、低平面机电耦合系数、低相对介电常数的超声换能器材料。该材料还具有无公害,不需密封烧结等工艺优点。     

Pt/Na_(0.5)Bi_(0.5)TiO_(3)/La_(0.5)Sr_(0.5)CoO_(3)电容器的结构和铁电疲劳特性EI北大核心CSCD

采用偏轴磁控溅射法,以单晶钛酸锶(001)SrTiO_(3)(STO)为衬底,不同沉积温度下外延生长了La_(0.5)Sr_(0.5)CoO_(3)(LSCO)氧化物底电极。X射线衍射仪(XRD)和原子力显微镜(AFM)结构表征以及四探针方阻测试结果表明:LSCO薄膜外延(00l)取向最优温度沉积条件为550℃。此外,利用脉冲激光沉积法,以LSCO/STO异质结为模板,构架了Pt/Na_(0.5)Bi_(0.5)TiO_(3)(NBT)/LSCO/STO铁电电容器。XRD和AFM结构表征表明:NBT薄膜为(00l)外延结构。电流密度-电压测试曲线结果表明,室温变为70℃时,Pt/NBT/LSCO异质结漏电流密度有所增加,但未改变导电机制:低压下为欧姆导电和高压下为陷阱的空间电荷限制电流导电。在5 V驱动电压下,室温和70℃时,Pt/NBT/LSCO电容器具有饱和的电滞回线和保持特性,且经过10^(10)翻转后,均未产生疲劳。     

The Electrical Properties of Polyaniline (PANI)–Co0.5Mn0.5Fe2O4 Nanocomposite

Polyaniline (PANI)/cobalt-manganese ferrite, PANI/Co_0.5Mn_0.5Fe₂O₄, nanocomposite was synthesized by oxidative chemical polymerization of aniline in the presence of ammonium peroxydisulfate. Microwave assisted synthesis method was used for the fabrication of core Co_0.5Mn_0.5Fe₂O₄ nanoparticles. The presence of PANI on the surface of the Co_0.5Mn_0.5Fe₂O₄ NPs was confirmed by infrared spectroscopy and thermal gravimetric analysis. The crystallite size was calculated with line profile fitting method as 20 ± 9 nm. The spherical morphology of the product was presented by Scanning electron microscopy and transmission electron microscopy. The electrical characterizations showed that ac conductivity is found to be independent of frequency and increases with increase of temperatures. However, imaginary component of dielectric function obey the power law of frequency while it is almost independent of temperature. This can be attributed to the molecular interatomic interaction between Co_0.5Mn_0.5Fe₂O₄ nanoballs and PANI shells.     

0.96(K_(0.49)Na_(0.51–x)Li_x)(Nb_(0.97)Ta_(0.03))O_3–0.04Bi_(0.5)Na_(0.5)ZrO_3无铅压电陶瓷的结构与电性能

采用固相法制备0.96(K_(0.49)Na_(0.51–x)Li_x)(Nb_(0.97)Ta_(0.03))O_3–0.04Bi_(0.5)Na_(0.5)ZrO_3(0.96KNNTL_x–0.04BNZ,x=0.00,0.01,0.02,0.03,0.04)无铅压电陶瓷,研究Li掺杂量对0.96KNNTLx–0.04BNZ陶瓷相结构、微观形貌和电性能的影响。结果表明:0.96KNNTLx–0.04BNZ陶瓷为纯钙钛矿结构,随着Li掺杂量x的增加,陶瓷由正交–四方两相共存逐渐转变为四方相。在x≤0.01时,陶瓷为正交–四方两相共存的多型相转变(polymorphic phase transition,PPT)结构;当x≥0.02时,陶瓷转变为四方相结构。在PPT向四方相转变的组成边界(x=0.02)处,陶瓷具有优异的电性能:压电常数d33=335 p C/N,机电耦合系数kp=38.40%,机械品质因数Qm=43,介电常数εT33/ε0=1 350,介电损耗tanδ=2.70%,剩余极化强度Pr=23.50μC/cm2,矫顽场Ec=1.52 k V/mm,Curie温度TC=325℃。分析了组成x=0.02的陶瓷在不同温度和不同频率下的交流阻抗谱,表明晶粒和晶界对电传导机制共同起作用,介电弛豫激活能与高温下氧空位移动的激活能相吻合,Erelax=1.15 e V。     

水热法制备Na_(0.5)Bi_(0.5)TiO_3陶瓷及其性能

以五水硝酸铋(Bi(NO_3)_3·5H_2O)和二氧化钛(TiO_2)为原料,氢氧化钠(NaOH)为矿化剂,采用水热法合成了具有钙钛矿结构的钛酸铋钠Na_(0.5)Bi_(0.5)TiO_3(BNT)无铅压电陶瓷粉体和陶瓷。利用X射线衍射仪(XRD)对产物晶体结构进行表征,用扫描电镜(SEM)观察产物粉体的表观形貌和粒径,并测试了陶瓷的电性能。结果表明,在200℃反应4h,NaOH浓度为6 mol/L,可以水热合成出单一晶相,粒径约为200nm的BNT粉体,用此粉体在1130℃烧结的陶瓷的介电常数ε_r=385.26,压电系数d_(33)=98cP/N。     

共生铋层状压电陶瓷(Li_(0.5)Bi_(0.5))_xBa_(1–x)Bi_8Ti_7O_(27)的结构与性能

采用传统固相法制备了(Li_(0.5)Bi_(0.5))_xBa_(1–x)Bi_8Ti_7O_(27)共生铋层状结构无铅压电陶瓷,采用(Li_(0.5)Bi_(0.5))~(2+)复合掺杂取代A位的Ba~(2+)以调节其晶体结构,提升其Curie温度及综合电学性能,从而达到拓宽该体系高温应用领域的研究目标。(Li_(0.5)Bi_(0.5))~(2+)的引入使陶瓷的压电常数d_(33)从8 pC/N最高提升至18.5 pC/N,Curie温度从480℃提升至633℃。体系正交畸变程度增加,体系剩余极化强度与结构畸变有关,且与压电常数的变化规律一致。(Li_(0.5)Bi_(0.5))_(0.6)Ba_(0.4)Bi_8Ti_7O_(27)陶瓷的综合电性能最佳,为高温压电领域提供了潜在的候选材料。     

La掺杂(Na_(0.5)Bi_(0.5))_(0.82)(K_(0.5)Bi_(0.5))_(0.18)TiO_3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。     

Structure and microwave dielectric properties of La(Mg0.5Ti0.5)O3–CaTiO3 system

(1−x)La(Mg_0.5Ti_0.5)O₃ (LMT)–xCaTiO₃ (CT) [0<x<1] ceramics were prepared from powder obtained by a nonconventional chemical route based on the Pechini method. The crystal structure of the microwave dielectric ceramics has been refined by Rietveld method using X-ray powder diffraction data. LMT and CT were found to form a solid solution over the whole compositional range. The 0.9LMT–0.1CT composition was refined using P2₁/n space group, which allows taking into account B-site ordering. The compounds having x⩾0.3 were found to be disordered and were refined using Pbnm space group. Microstructure evolution was also analysed. Dielectric characterization at microwave frequencies was performed on the LMT–CT ceramics. The permittivity and the temperature coefficient of resonant frequency of the solid solutions showed a non-linear variation with composition. The quality factor demonstrates a considerable decrease with the increase of CT content.     

A novel Na0.5K0.5NbO3–La(Zn0.5Ti0.5)O3 ceramics with excellent dielectric properties at wide temperature range

Ceramic-based dielectrics are considered as the best candidates for high temperature capacitors because of their outstanding mechanical and electrical properties. Nevertheless, conventional barium titanate-based capacitors show narrow operating temperature ranges owing to the low tetragonal-cubic phase transition temperature. In order to increase the working temperature and relative permittivity, a novel (1-x)Na_0.5K_0.5NbO₃- xLa(Zn_0.5Ti_0.5)O₃ (NKN-xLZT) ceramics were chosen to meet the targets in this work. The NKN-xLZT ceramics with sub-micrometer grains (0.2–0.4 μm) were synthesized via a conventional solid-state sintering route. A relative permittivity (ε’ = 1560 ± 15%) with low loss tangent over wide temperature range from 96 °C to 350 °C was obtained in the x = 0.02 ceramics. Additionally, the crystal structure distortion and conduction behaviors of the NKN-xLZT ceramics were systematically studied. The decrease of oxygen octahedron distortion induced a weak polarization, and the high resistance (9 × 10⁶ Ωcm at 400 °C) greatly suppressed the long-term migration of defective ions in the ceramics. Therefore, the low loss tangent and high permittivity were still stabilized at the high temperature. It believes that the NKN-xLZT ceramic system in this work will become one of the most promising candidates for high-temperature capacitor devices.