铌酸钾钠基无铅压电陶瓷的高压电活性研究进展

以Pb(Zr_(1–x)Ti)x)O)3(PZT)为代表的铅基压电陶瓷因为具有良好的压电性能和机电耦合性能已被广泛应用于科技、工业、军事以及日常生活中.但是, PZT基陶瓷中Pb的含量超过了60%(质量比),在生产、使用及废弃处理过程中都会给人类生态环境造成严重损害.因此,发展无铅压电陶瓷已成为世界压电陶瓷研究的热点之一.铌酸钾钠(K_(0.5)Na_(0.5))NbO_3 (KNN)无铅压电陶瓷因为具有较为优异的压电性能以及较高的居里温度,被认为是最可能取代铅基压电陶瓷的材料体系之一.经过研究者们的努力工作,改性后的KNN基无铅压电陶瓷压电性能已经接近或超过了某些铅基压电陶瓷的性能.本文综合介绍了具有高压电活性的KNN基无铅压电陶瓷国内外的研究进展,重点阐述了高性能铌酸钾钠基无铅压电陶瓷制备工艺及相关理论基础的研究进展,并就今后铌酸钾钠基无铅压电陶瓷研究发展的方向及前景提出建议.     

A位等价与非等价取代对(K0.5Na0.5)NbO3陶瓷极化的影响

研究了在铌酸钾钠基陶瓷中,A位等价与非等价取代对陶瓷极化温度和极化电场的影响,结果表明:A位等价取代的陶瓷对极化温度和极化电场没有强烈依赖性,可以使极化足够充分,能有效提高铌酸钾钠基陶瓷的压电性能;相反,A位非等价取代的陶瓷对极化温度和极化电场敏感,容易击穿,极化不充分,限制了铌酸钾钠基陶瓷的压电性能. 关键词： 铌酸钾钠 极化 压电     

铌酸钾钠基无铅压电陶瓷纵振换能器*

高性能环境友好型无铅压电陶瓷及其应用是当前压电材料研究的热点之一,为了探究其在水声换能器领域的应用潜力,该文对铌酸钾钠基无铅压电陶瓷和锆钛酸铅压电陶瓷纵振式换能器进行了对比研究。依据仿真结果优化结构尺寸,制作了两种换能器样机并测试了其在空气中和水中的电声性能。测试结果表明,铌酸钾钠基无铅压电陶瓷换能器的谐振频率为35kHz,最大发送电压响应为 151dB,声源级可达 190dB,在 26kHz~67kHz 的频率范围内发送电压响应的起伏不超过±4.5dB,谐振频率处-3dB 的指向性开角约为 76°。该无铅压电陶瓷换能器具有和锆钛酸铅压电陶瓷换能器相当的发射性能,有望推动无铅压电材料在水声换能器领域的应用进程。     

0.5PZN-0.5PZT压电陶瓷拉曼散射研究

PZT基多元系压电陶瓷在三方相含量与四方相含量相等的准同型相界处(MPB)具有极为优异的压电性能。文章采用拉曼散射方法研究了0.5PZN-0.5PZT陶瓷体系中三方-四方相共存与弥散相变现象。研究发现,与纯PZT相比,0.5PZN-0.5PZT体系拉曼谱呈明显宽化特征,表明体系弛豫性较强,依据介温谱计算出弥散因子γ高达1.71。通过对拉曼谱峰进行Gauss函数拟合,定量计算三方相R₁模式与四方相E(3TO)和A₁(3TO)模式相对强度,以及四方相E(4LO)和A₁(3LO)模式与三方相R_h模式相对强度,结果表明0.5PZN-0.5PZT体系三方相与四方相含量相等,组成位于准同型相界,该结果得到XRD相分析验证。电学测量表明0.5PZN-0.5PZT陶瓷压电性能优异：k_p=0.66, d₃₃=425 pC/N,适宜作为压电致动器材料使用。     

红外探测用无铅铁电陶瓷的热释电特性研究进展

铁电陶瓷具有优异的热释电性能,是红外探测器的核心敏感元材料,目前普遍采用铅基陶瓷材料,发展无铅铁电陶瓷用于热释电红外探测是近年来电介质物理与材料的一个热点.本文综述了无铅铁电陶瓷的热释电性能研究进展,主要包括钛酸钡基、钛酸铋钠基、铌酸锶钡基、铌酸钾钠基等系列铁电陶瓷的热释电效应研究现状,归纳了不同体系增强热释电效应的手段.通过比较分析主要无铅铁电陶瓷的热释电性能和退极化性能的制约关系,指出钛酸铋钠基陶瓷是目前最具应用潜力的无铅材料体系,并对无铅铁电陶瓷热释电探测应用未来的发展方向进行了展望.     

半结晶聚酯(PET)的二相共存结构的表征

采用X射线衍射对称反射法,对半结晶聚酯PET₂试样收集粉末X射线衍射全图(XDWP)数据,用Rietveld方法和Fourier过滤技术,对XDWP拟合并分离成结晶衍射峰之和CR₂和非晶散射峰之和AM₂两部分,与此同时获得PET₂试样的结晶相CR₂的三斜晶系晶胞参数:a=0.445,b=0.592,c=1.072nm,α=99.6,β=116.9,γ=111.9(°),结晶密度d_{c关键词： 聚对苯二甲酸乙二醇酯 二相共存结构 径向分布函数 Rietveld方法 Fourier过滤技术}     

四方和正交以及单斜相K0.5Na0.5NbO3的结构稳定性和电子结构的第一性原理研究

采用基于密度泛函理论框架下的第一性原理超原胞方法和虚晶近似方法, 在局域密度近似和广义梯度近似下, 对四方和正交以及单斜相K_0.5Na_0.5NbO₃的能量和原子结 构以及电子结构进行了系统的研究. 计算结果表明三种K_0.5Na_0.5NbO₃相的能量差别较小, 这与实验上它们之间容易发生相转化是一致的. 进一步发现单斜相的能量比四方相和正交相低, 说明单斜相结构更加稳定, 并且理论计算的结构参数与实验值符合得很好. 电子结构结果也表明单斜相的键合作用比四方相和正交相键合作用更强, 进一步说明单斜相结构更加稳定. 关键词： 铌酸钾钠 四方相 单斜相 密度泛函理论     

CaZrO_3改性(Na,K)NbO_3基无铅陶瓷电学性能的温度稳定性

压电陶瓷广泛用于驱动器、传感器等电子领域,但是目前主要使用的压电陶瓷是铅基陶瓷.基于保护环境和社会可持续发展的需要,无铅压电陶瓷的研发变得迫切.无铅压电陶瓷(K,Na)NbO_3(KNN)因具有较高压电常数和居里温度,而受到广泛关注.然而较差的温度稳定性限制了其应用.本文通过二步合成法制备了电学性能温度稳定的(1-x)(Na_(0.52)K_(0.48))_(0.95)Li_(0.05)NbO_3-xCaZrO_3(NKLN-xCZ)陶瓷,研究了CaZrO_3对KNN基陶瓷微结构及电学性能的作用.研究结果表明:适量CaZrO_3改善了样品烧结性能,得到了致密陶瓷.随CaZr O_3增加,NKLN-CZ陶瓷的三方相(R)-四方相(T)共存出现在组分为0.05 ≤x ≤0.06.x=0.05时,陶瓷样品不但具有高居里温度(T_c=373 ℃),而且表现出良好电学性能(d_(33)=198 pC/N,k_p=39%,ε_r=1140,tanδ=0.034,P_r=21μC/cm~2,E_c=18.2 kV/cm).此外,该陶瓷由于存在弥散R-T相变,导致其相变温度区间拓宽,因此,该陶瓷具有较好的电学性能温度稳定:在温度范围为-50—150 ℃,NKLN-0.05CZ陶瓷的k_p保持在34%—39% (k_p变化量≤13%).     

Pb(Zr,Sn,Ti)O3反铁电陶瓷的低温相变扩散与极化弛豫

用弱场介电温谱、热释电流谱、强场电滞回线和变温X射线衍射谱研究了微量La掺杂Pb(Zr,Sn,Ti)O₃(PZST)反铁电(AFEt)陶瓷在-100—180℃温区内的结构与电学特性.弱场介电温谱显示,AFEt陶瓷在低温段(-100—50℃)呈现介电频率弥散(0.1—100kHz)和扩散型相变的特征,而变温X射线衍射谱却表明材料在这一温区内保持四方相结构;低温下经强场作用后,AFEt被诱导为亚稳三方铁电态,介电频率弥散消失.基于多元复杂化合物的组分起伏理论,讨论了PZST AFEt陶瓷 关键词： Pb(Zr Sn 3反铁电陶瓷')" href="#">Ti)O₃反铁电陶瓷 反铁电弛豫 相变 变温X射线衍射     

B位空位补偿型钐掺杂PZT(54/46)陶瓷中的缺陷分析及其对压电性能的影响

-用固相反应法制备了B位空位补偿型钐掺杂非准同型相界组分PZT(54/46)陶瓷.通过正电子湮没寿命谱(PALS)和符合多普勒展宽能谱(CDBS)对陶瓷中的缺陷结构进行综合表征,结合常规表征手段如X射线衍射(XRD),电子扫描显微镜(SEM),介电、铁电和压电性能测量,研究缺陷对陶瓷压电性能的影响. XRD结果显示所有陶瓷均为纯钙钛矿相,掺杂诱导了菱方-四方(R-T)相变,准同型相界位于Sm掺杂量x=0.010.02.电学测量结果反映:介电、铁电和压电性能均先增强后减弱, MPB附近两个样品都有优异的介电和铁电性能,但其压电性能差别很大. x=0.01给出最优压电性能d₃₃=572 p C/N,较未掺杂样品增强了一倍.PALS结果表明掺杂使陶瓷中缺陷类型发生变化, x≤0.01,样品中同时含有A位空位与B位空位; x≥0.02,样品中以A位相关缺陷为主, B位空位浓度很低. CDBS结果进一步证实x=0.01和0.02中B位空位浓度分别是该体系中最高和最低的.由以上结果推断出:x=0.01获得的最优压电性能与其中较高浓度的B位空位有关, B位空位可稀释A位空位浓度...     

Relationship between phase structure and electrical properties of (K0.5Na0.5)NbO3-LiTaO3 lead-free ceramics

Lead-free piezoelectric ceramics of (1−x)K_0.5Na_0.5NbO₃-xLiTaO₃ (KNN-LT) system have been investigated in this work. X-ray diffraction, Raman spectra measurements, DSC (Differential Scanning Calorimetric), and dielectric constant versus temperature provide direct evidence that the phase transition temperature between tetragonal and orthorhombic shift to lower temperature with the increasing of LT content. The KNN-0.05LT ceramics exhibit the highest high-field d₃₃ up to 220 pm/V. At the same time, we also investigated the relationship between phase structure and electric properties, showing that the orthorhombic phase presents better piezoelectric temperature stabilities than the tetragonal phase. The result may provide a new way for KNN-based lead-free ceramics.     

Dielectric,ferroelectric and piezoelectric properties of (1−x)[K0.5Na0.5NbO3]−x[LiSbO3] ceramics

Lead-free (1?x)[K_0.5Na_0.5NbO₃]?x[LiSbO₃] (x=0, 0.04, 0.05 and 0.06)/(KNN-LS) ceramics were prepared by conventional solid-state reaction route (CSSR). For dense morphology pure KNN ceramic was sintered at 1120 °C and LS modified KNN ceramics were sintered at 1080 °C for 4 h, respectively. The structural study at room temperature (RT) revealed the transformation of pure orthorhombic to tetragonal structure with the increase in LS content in KNN-LS ceramics. Temperature dependent dielectric study confirmed the increase of diffuse phase transition nature with the increase in LS content in KNN-LS ceramics. The presence of orthorhombic to tetragonal (T_O?T) polymorphic phase transition temperature (PPT) ～43 °C confirmed the presence of two ferroelectric (orthorhombic and tetragonal) phases in 0.95KNN-0.05LS ceramics at RT. 0.95KNN-0.05LS ceramics showed better ferroelectric and piezoelectric properties i.e., remnant polarization (P_r)～18.7 μC/cm², coercive field (E_c)～11.8 kV/cm, piezoelectric coefficient (d₃₃)～215 pC/N, coupling coefficient (k_p)～0.415 and remnant strain ～0.07% were obtained.     

Microstructure,dielectric and piezoelectric properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript>-Ba(Ti<Subscript>0.95</Subscript>Zr<Subscript>0.05</Subscript>)O<Subscript>3</Subscript> lead-free ceramics with CuO sintering aid

Using an ordinary ceramic fabrication technique, we fabricated lead-free (1-x)(K_0.5Na_0.5)NbO₃-xBa(Ti_0.95Zr_0.05)O₃ ceramics with CuO sintering aid . Ba(Ti_0.95Zr_0.05)O₃ diffuses into (K_0.5Na_0.5)NbO₃ to form a new solid solution. The ceramics with perovskite structure possess orthorhombic phase at x≤0.04 and become tetragonal phase at x≥0.06. Both the paraelectric cubic–ferroelectric tetragonal and the ferroelectric tetragonal–ferroelectric orthorhombic phase transition temperatures decrease with increasing the concentration of Ba(Ti_0.95Zr_0.05)O₃. The doping of CuO effectively promotes the densification of the ceramics. The coexistence of the orthorhombic and tetragonal phases at 0.04<x<0.06 and the improvement in sintering performances of the ceramics significantly enhance the piezoelectric and dielectric properties at room temperature. The ceramics with x=0.04–0.06 and y=0.75–1.50 possess excellent properties: d₃₃=119–185 pC/N, k_P=37–44%, k_t=35–49%, ε=341–1129, cosδ=0.7–4.4% and T_c=312–346 °C. PACS 77.65.-j; 77.84.Dy; 77.84.-s     

Na1−xLixNbO3 ceramics studied by X-ray diffraction, dielectric, pyroelectric, piezoelectric and Raman spectroscopy

Na_1−xLi_xNbO₃ ceramics with composition 0.05≤x≤0.30 were prepared by solid-state reaction method and sintered in the temperature range 1100-1150 °C. These ceramics were characterised by X-ray diffraction as well as dielectric permittivity measurements and Raman spectroscopy. Dielectric properties of ceramics belonging to the whole composition domain were investigated in a broad range of temperatures from 300 to 750 K and frequencies from 0.1 to 200 kHz. The Rietveld refinement powder X-ray diffraction analysis showed that these ceramics have a single phase of perovskite structure with orthorhombic symmetry for x≤0.15 and two phases coexistence of rhombohedral and orthorhombic above x=0.20. The evolution of the permittivity as a function of temperature and frequency showed that these ceramics Na_1−xLi_xNbO₃ with composition 0.05≤x≤0.15 present the classical ferroelectric character and the phase transition temperature T_C increases as x content increases. The polarisation state was checked by pyroelectric and piezoelectric measurements. For x=0.05, the piezoelectric coefficient d₃₁ is of 2pC/N. The evolution of the Raman spectra was studied as a function of temperatures and compositions. The results of the Raman spectroscopy study confirm our dielectric measurements, and they indicate clearly the transition from the polar ferroelectric phase to the non-polar paraelectric one.     

Raman tensor analysis of (K0.5Na0.5)NbO3–LiSbO3 lead‐free ceramics and its application to study grain/domain orientation

A quantitative polarized Raman analysis of ferroelectric grain/domain orientation in LiSbO₃ (LS‐modified) (K_0.5Na_0.5)NbO₃ (KNN) ceramics is presented, based on the analysis of the complex orientation dependence in space of their Raman‐active modes. Complete sets of Raman tensor elements of A_g, and E_g phonon modes for orthorhombic/tetragonal structures of KNN have been determined. Through this spectroscopic algorithm, quantitative information could be extracted in terms of three Euler angles in space for KNN samples consisting of mixed phases, thus enabling quantitative visualization of the local distribution of grains/domains in the solid angle. As an application of the method, we quantitatively examined the unknown crystallographic grain orientation patterns on the surfaces of pure KNN and of KNN‐0.05LS ceramics. These two samples were useful to clarify a polymorphic phase transition from the orthorhombic to the tetragonal phase taking place in the LS‐modified KNN system. Thus, we demonstrated that polarized Raman spectroscopy is a valuable and efficient tool for nondestructive three‐dimensional assessments of grain/domain orientation in ferroelectric materials with complex polymorphic structures. We believe that the data shown here represent a typical scenario encountered in grain/domain orientation assessments of piezoelectric perovskites. Copyright © 2012 John Wiley & Sons, Ltd.     

New crystallographic dielectric phase boundary in K0.5Na0.5NbO3‐based lead‐free ceramics

0.979K_0.5Na_0.5Nb_1‐xSb_x O₃‐0.021Bi_0.5Na_0.5TiO₃ (KNNSx ‐BNT) lead‐free piezoelectric ceramics were fabricated by conventional solid state reaction technique, and their phase transition and electrical properties were studied. With the increase of x, the rhombohedral‐orthorhombic phase transition temperature of the ceramics increases. Finally, both the rhombohedral‐orthorhombic and orthorhombic‐tetragonal phase transitions of the ceramics were modified to be around room tempera‐ ture when about 6% Sb were substituted for the Nb site, resulting in the formation of a new phase boundary separating rhombohedral and tetragonal phases. The formation of the new phase boundary results in excellent properties for the ceramics, that is, the KNNS0.05‐BNT ceramic shows an enhancement in piezoelectric properties: d₃₃ = 380 pC/N and k_P = 0.438. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Properties of non-stoichiometric 0.935(K0.5+xNa0.5+x)NbO3-0.065LiSbO3 lead-free piezoelectric ceramics

0.935(K_0.5+xNa_0.5+x)NbO₃-0.065LiSbO₃ lead-free piezoelectric ceramics were prepared by normal sintering, and their piezoelectric and dielectric properties were investigated by varying the compensating amount x of alkaline elements (Na and K) addition. It was found that the crystal structure changed from tetragonal to orthorhombic with increasing x from −0.010 to 0.010. An MPB was tailored by optimizing the alkaline elements contents. Enhanced electrical and electromechanical responses of d₃₃=253 pC/N, k_p=0.47, k_t=0.45 and tanδ=0.027 were obtained in the ceramics with x=0.005. These excellent piezoelectric and electromechanical properties indicate that this system may be an attractive lead-free material for a wide range of electro-mechanical transducer applications.     

Optical properties of CH3NH3PbI3 crystal grown using inverse temperature crystallization

Perovskite CH₃NH₃PbI₃ (MAPbI₃) single crystal was grown using inverse temperature crystallization method. Crystallinity of the perovskite was confirmed by X-ray diffraction. Photoluminescence (PL) spectra revealed abnormal behavior due to a temperature-induced orthorhombic to the tetragonal phase transition. Four PL emission peaks, A, B, C, and D, were observed in the low temperature regime. Peaks A and B were observed at 756 and 776?nm?at 12?K, and were blue-shifted and disappeared at 130 and 70?K, respectively. Peaks C and D were observed at 789 and 807?nm?at 40?K and were also blue-shifted to 780 and 794?nm?at 100?K. On the other hand, the peak C red-shifted to 799?nm from 100 to 140?K because of an orthorhombic to the tetragonal phase change and was also blue-shifted above 140?K. From the excitation intensity- and temperature-dependent PL results, peaks A and B were assigned to the free-exciton and bound-exciton of the orthorhombic phase crystal, respectively. In addition, peaks C and D were associated with the free-exciton and bound-exciton of the tetragonal phase crystal, respectively. The activation energy of peak C was calculated to be 98?meV from temperature dependence of the PL intensity.     

Rhombohedral–orthorhombic phase coexistence and electrical properties of Ta and BaZrO3 co-modified (K,Na)NbO3 lead-free ceramics

The BaZrO₃ and Ta have been used to improve piezoelectric properties of (K, Na)NbO₃ ceramics by the construction of the phase boundary, and (1 ? x)K_0.48Na_0.52(Nb_0.95Ta_0.05)O₃–xBaZrO₃ [(1 ? x)KNNT–xBZ] ceramics were prepared by the conventional solid-state method. The effect of BZ content on their phase structure, microstructure, and electrical properties has been investigated. A rhombohedral and orthorhombic phase coexistence has been observed in the compositional range of 0.05 ≤ x ≤ 0.07. With increasing BZ content, their T_c and T_o–t values decrease gradually, and the dielectric constant increases linearly. The ceramic with x = 0.06 exhibits an enhanced piezoelectric behavior (d₃₃ ～ 193 pC/N and k_p ～ 32.6%) because of the coexistence of two phases together with a dense microstructure. As a result, the construction of a rhombohedral and orthorhombic phase boundary is an effective way to improve the piezoelectric properties of KNN-based ceramics.     

Impedance spectroscopy and piezoresponse force microscopy analysis of lead-free (1 − x) K0.5Na0.5NbO3 − xLiNbO3 ceramics

(1 ? x) K_0.5Na_0.5NbO₃ ? xLiNbO₃ (where x = 0.0, 5.0, 5.5, 6.0, and 6.5 wt.%) (KNLN) perovskite structured ferroelectric ceramics were prepared by the solid-state reaction method. X-ray diffraction patterns indicate that single phase was formed for pure KNN while a small amount of second phase (K₆Li₄Nb₁₀O₃₀, ～3%) was present in LN doped KNN ceramics. Phase analysis indicated the change in the crystal structure from orthorhombic to tetragonal with increase in LN content. The electrical behavior of the ceramics was studied by impedance spectroscopy technique in the high temperature range. Impedance analysis was performed using an equivalent circuit model. The impedance response in pure KNN and KNLN ceramics could be deconvoluted into two contributions, associated with the bulk (grains) and the grain boundaries. Activation energies for conductivity were found to be strongly frequency dependent. The activation energy obtained from dielectric relaxation data was attributed to oxygen vacancies. From PFM we found that the composition with 6.5 wt.% LN displays stronger piezocontrast as compared to pure KNN implying an evidence of a pronounced piezoelectric coefficient.