新型弛豫铁电单晶(1-x)Pb(Zn_(1/3)Nb_(2/3))O_(3-x)PbTiO_3生长的技术创新

(1-x)Pb(Zn_(1/3)Nb_(2/3))O_(3-x)PbTiO_3(PZNT)晶体是弛豫铁电体Pb(Zn_(1/3)Nb_(2/3)O_3与普通铁电体PbTiO_3组成的具有钙钛矿结构的固溶体,其准同型相界成分(x=0.09)附近表现出极其优异的压电性能,在医用超声成像、声纳、微位移器等方面具有广阔的应用前景,分析了PZNT-PbO赝二元系的析晶行为和相关系,总结了PZNT晶体的压电性能,讨论了生长工艺和成分对晶体性能的影响。针对PZNT晶体生长中存在的问题,发展了助熔剂-坩埚下降法、通气诱导成核技术、两步法生长工艺、区熔凝固技术、底部籽晶高温溶液法等多种生长技术,生长出大尺寸的PZNT晶体,并比较了这些生长技术的特点。     

铌铟镁酸铅–钛酸铅单晶的太赫兹传输特性研究

通过太赫兹时域光谱技术对新型准同型相界组分的三元系弛豫铁电单晶铌铟镁酸铅–钛酸铅[0.24Pb(In_(1/2)Nb_(1/2))O_3–0.43Pb(Mg_(1/3)Nb_(2/3))O_3–0.33PbTiO_3(0.24PIN–0.43PMN–0.33PT)]进行测试,并采用时域有限差分法(FDTD),研究了不同厚度和不同电场诱导下单晶的THz波介电调制特性。结果表明:在0.1~1.0 THz频率范围内,厚度和电场都是影响材料介电调制性能的主要影响因素。在0.325 THz处,厚度分别为3、5和7μm时,对应的THz波调制深度分别为31.4%、43.7%和49.9%;在不同电场条件下,在0.543 THz处,调制深度达到了18.3%,而在0.903 THz处,调制深度达到了23.7%。     

含铅弛豫铁电材料中焦绿石相形成的研究

含铅弛豫铁电材料中焦绿石相的存在是影响材料性能的重要因素,也是制造工艺中遇到的难题之一。本文以Pb(Zn_(1/3)Nb_(2/3))O_3(PZN)及Pb(Mg_(1/3)Nb(2/3))O_2(PMN)为例证实了非化学配比有序畴的形成会促进焦绿石相的生成,二者存在着密切关系。对PZN、PMN材料的钙钛矿结构的稳定性提出了新看法。这一结果可很好解释在PZN及PMN研究中出现的一些实验现象,对工艺控制也有指导意义。     

Co_2O_3掺杂对Pb(Ni_(1/3)Nb_(2/3))(Zr,Ti)O_3压电陶瓷电学性能及介电弛豫的影响

采用氧化物粉末固相烧结法制备Pb(Ni_(1/3)Nb_(2/3))0.5(Zr_(0.3)Ti_(0.7))0.5O_3–w Co_2O_3(0.5PNN–0.5PZT–w Co)压电陶瓷。研究了Co_2O_3掺杂含量对0.5PNN–0.5ZT压电陶瓷相结构、显微组织、电学性能及介电弛豫的影响。结果表明:Co~(3+)掺杂进入主晶体结构中占据了B位。当0.2%≤w≤0.8%(质量分数)时,样品为单一稳定的钙钛矿结构,存在准同型相界;通过修正Curie–Weiss定律,较好地描述了陶瓷弥散相变的特征,弥散相变系数γ随着Co_2O_3掺杂量的增加,先增加后减小,当w=0.4%时,γ达到最大值,表明样品的介电弛豫特征更为明显。样品具有最佳的综合电学性能,压电常数d33=675 p C/N,机电耦合系数kp=60%,介电常数εr和介电损耗tanδ分别约为5 765和1.16%,说明介电弛豫行为与电学性能相关。     

Pb(Mn_(1/3)Nb_(2/3))O_3-PbTiO_3-PbZrO_3陶瓷的电畴研究

本文研究了Pb(Mn_(1/3)Nb_(2/3))O_3-PbTiO_3-PbZrO_3 三元系统陶瓷材料,采用长时间的保温,使陶瓷中晶粒充分长大,获得100μm 左右的粗晶,并将样品磨制成厚度为18μm的超薄光薄片,在偏光显微镜下能清晰地观察到条带状、环带状、折状和波状电畴等。     

高压电活性PNN–PZN–PBSZT陶瓷的结构及性能

采用铌铁矿预合成及固相法制备xPb(Ni_(1/3)Nb_(2/3))O_3–0.01Pb(Zn_(1/3)Nb_(2/3))O_3–(0.99–x)Pb_(0.82)Ba_(0.08)Sr_(0.10)Zr_(0.56)Ti_(0.44)O_3(x PNN–PZN–PBSZT)压电陶瓷。研究了不同铌酸镍NiNb_2O_6含量(x=0、0.01、0.015、0.02)对x PNN–PZN–PBSZT压电陶瓷的晶相结构以及压电和介电等性能的影响。结果表明:制备的压电陶瓷均为钙钛矿结构,处在准同型相界处,且随着x的增大,晶体结构逐渐向四方相转变。PNN的引入可以提高x PNN–PZN–PBSZT陶瓷的压电、机电和介电性能,当x=0.015时,样品的综合性能最佳,压电性能和室温介电性能达到最大,d33和εr分别达到998 pC/N和5 498,此时的机电转换因子k_p为74.61%,Curie温度TC为140℃,kp的最大值出现在x=0.02处,为76.26%。     

一种大功率压电陶瓷变压器材料的研究

通过对Pb(Mg_(1/3)Nb_(2/3))_A(Mn_(1/3)Nb_(2/3))_B Ti_cZr_DO_3(简称PMMN)四元系压电陶瓷材料的研究,发现在其室温矩形相图内存在一“交叉”性过渡位置,在此位置上的基本试样PMMN-1具有高压电性、低机电损耗、温度稳定性好、机械强度高等优点,是一种开发大功率压电变压器及其它压电器件的较佳材料。适量添加CeO_2和以Sr部分取代Pb,可较好地改善其温度稳定性。该材料与一般二、三元系压电材料相比,还具有性能易于调整,预烧温度与烧成温度低,烧结范围宽,PbO挥发量小,易于制备出均质的高性能压电陶瓷等工艺特点。     

Pb(Ni_(1/3)Nb_(2/3))O_3-Pb(Mg_(1/2)W_(1/2))O_3-PbTiO_3三元系低温烧成多层陶瓷电容器瓷料的研究

本文选择Pb(Ni_(1/3)Nb_(2/3))O_3-Pb(Mg_(1/2)W_(1/2))O_3-PbTiO_3三元系低温烧成独石电容器瓷料为研究对象.实验结果表明,一次合成工艺优于分别合成工艺.采用适当的配方,可获得900℃左右烧成ε～8000,tgδ0.01～0.025,-25℃～+85℃下△C/C<±45%,且其它性能亦良好的独石瓷料.升温速度的加快将导致介电性能的下降.微观结构研究结果表明,颗粒尺寸的增加和高介电常数晶体的增多将有利于ε的提高.获得了890℃～920℃下一次烧成该瓷料用的全银电报.     

弛豫铁电晶体PZNT生长的几个关键问题

新型弛豫铁电晶体(1-x)Pb(Zn1 3Nb2 3)O3-xPbTiO3(PZNT)是一种复合钙钛矿结构的固溶体晶体,具有比传统压电陶瓷PZT远为优越的压电性能,在医用超声成像、声纳、微位移器等方面有着广阔的应用前景。由于该晶体组成复杂,熔体析晶时存在钙钛矿与焦绿石两相的竞争,且PbO组分对Pt坩埚和籽品均能产生腐蚀．采用提拉法等传统生长工艺很难获得钙钛矿结构的实用化的PZNT晶体。目前普遍采用助熔剂来抑制焦绿石相的生成,并且在传统生长工艺的基础上发展了多种改进工艺。结合作者实验室近儿年来在PZNT晶体生长方面的研究结果和实践经验,讨论了助熔剂及其配比的选择、生长技术的发展、工艺参数与晶体性能优化等关键技术问题。     

钽铁酸铅铁电陶瓷中钙钛矿相的结构及其稳定性

本文利用普通电子陶瓷工艺制备了纯钙钛矿相Pb(Fe_(1/2)Ta_(1/2))O_3(PFT)弛豫铁电陶瓷。利用DTA、XRD等陶瓷烧结过程中钙钛矿相的结构及其稳定性进行了研究。同时XRD分析及介电性质测试的结果表明,1150℃烧结的PFT陶瓷经900℃退火热处理,能提高介电绝缘性能,降低介电损耗,其钙钛矿相存在2a_0×2a_0×2a_0的超晶格结构。     

Electromechanical Properties of PMN–PZT Piezoelectric Single Crystals Near Morphotropic Phase Boundary Compositions

Pb(Mg_1/3Nb_2/3)O₃–PbZrO₃–PbTiO₃ (PMN–PZT) ferroelectric single crystals near morphotropic phase boundary compositions were fabricated by solid-state crystal growth. The Curie temperatures ( T _C) of the grown PMN–PZT crystals were found to be on the order of 210°C, with ferroelectric phase transition temperatures ( T _{R – T} ) in the range of 96°–165°C. The electromechanical coupling factors k ₃₃ and k ₃₂ were found to be >90% and >−87%, respectively. The coercive field E _C for all the compositions was on the order of 5 kV/cm, double the value of pure Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PMNT) crystals. The temperature dependence of the piezoelectric and electromechanical properties and dc bias effect on the dielectric behavior were investigated. The temperature usage range under dc bias was found to be improved when compared with pure PMNT crystals with similar piezoelectric properties.     

铌鲜酸铅弛豫型铁电陶瓷的介电老化行为研究

通过典型弛豫型铁电陶瓷铌镁酸铅介电老化行为的研究,发现高温区的Ｄｅｂｙｅ型弛豫过程与介电过程电老现象存在有机联系,指出复合钙钛矿弛豫型电体的结构缺陷特征对其介电老化起着重要作用,介电极化行为与老化行为对比分析和恒温经时老化研究表明,外的局域化电子和空穴对铁电微畴畴壁“钉扎”效应产生失电体介电化行为的快过程。     

Elastic, Piezoelectric, and Dielectric Properties of 0.71Pb(Mg1/3Nb2/3)O3–0.29PbTiO3 Crystals Obtained by Solid-State Crystal Growth

Single crystals with the composition of 0.71Pb(Mg_1/3Nb_2/3)O₃–0.29PbTiO₃ (PMNT29) were grown using the solid-state crystal growth (SSCG) method. Compared with the conventional Bridgman grown crystals, the SSCG PMNT29 crystals were found to possess comparable piezoelectric, dielectric, and electromechanical properties ( d ₃₃∼1500 pC/N, ɛ^T ₃₃/ ɛ ₀∼5400 and k ₃₃∼90%), with the same Curie temperature ( T _C) and ferroelectric phase transformation temperature ( T _{R – T} ). The full set of elastic, piezoelectric, and dielectric material constants were determined by the resonance method for the SSCG grown PMNT29 crystals according to IEEE standards and compared with Bridgman grown crystals. The dielectric temperature behavior and the strain field characteristics were investigated, demonstrating excellent performance over the temperature range from room temperature to 95°C. Strain behavior at high electric fields was found to be different from Bridgman growth crystals and believed to be attributed to different domain structures.     

PMN-PFN铁电陶瓷低温烧结技术研究

Pb(Mg1/3Nb2/3)O3(PMN)是一种典型的弛豫铁电体,它具有很大的介电常数,较小的介电损耗,良好的压电稳定性和电致伸缩效应,在叠层电容器、致动器等方面有重要的应用。PMN可以方便地与Pb(Fe1/2Nb1/2)O3(PFN)形成固溶体以移动介电常数峰值温度(Tm)。本文使用Swartz和Shrout提出的两步法,研究了基体掺杂不同物质对0.9PMN-0.1PFN和0.75PMN-0.25PFN二元体系的烧结性能及介电性能的影响。经研究发现:添加BiFeO3、Li2CO3、MnO2,都能使烧结温度降低。其中,当在0.9PMN-0.1PFN中掺入5wt%的Li2CO3时,介电常数为18120,大于纯组分的0.9PMN-0.1PFN的介电常数,当掺入BiFeO3和MnO2时,都使介电性能恶化。对不同掺杂对性能的影响进行了解释。     

Improved energy storage density and energy efficiency of Samarium modified PMNT electroceramic

We report the improved energy storage density and efficiency after 2.5% of Samarium substitution in ferroelectric Pb[(Mg_1/3Nb_2/3)_0.80Ti_0.20]O₃ (PMNT) electroceramic. The microstructure and surface morphology were analyzed and correlated with various functional properties. The energy storage density, leakage current density, ferroelectric and dielectric properties were investigated thoroughly, indicating that Samarium's substitution significantly modified the microstructure, the dielectric strength, breakdown electric field, and turned ferroelectric PMNT to relaxor ferroelectrics. Due to the relaxor nature, the gap between remanent polarization and maximum polarization increases with the substitution of Samarium in PMNT matrix, which further increases the recoverable energy storage density and energy efficiency. A nearly 100% increase in recoverable energy density and efficiency was obtained at an electric field strength of 35 kV/cm at room temperature (～296 K). The electroceramic shows maximum energy density near the ferroelectric phase transition temperature (325 K–345 K) region and provides a moderate energy storage density for possible applications in power microelectronics.     

PMnS-PZN-PZT压电纤维的制备与铁电性能

采用固相法制备了0.8Pb(Mn1/3Sb2/3)0.05(Zr1/2Ti1/2)0.95O3–0.2Pb(Zn1/3Nb2/3)0.28(Zr1/2Ti1/2)0.72O3(PMnS–PZN–PZT)粉末,然后用塑性聚合物方法制备了PMnS–PZN–PZT压电纤维。研究了纤维夹持状态对其铁电性能的影响。结果表明:塑性聚合物法制备的PMnS–PZN–PZT压电纤维具有良好的铁电性能,压电纤维处于自由状态时,剩余极化强度和矫顽场分别为85.4μC/cm2和8.5kV/cm,但电滞回线很难饱和。将纤维采用环氧树脂固化后,剩余极化强度变成39.2μC/cm2,电滞回线呈饱和状态,说明夹持状态对纤维的铁电性能产生很大的影响。高压下压电纤维浇铸前后的漏电流测试结果表明,压电纤维浇铸后剩余极化强度变小主要与漏电流有关。     

Lattice parameter fluctuations of relaxor ferroelectrics determined by X-ray diffraction method

Relaxor ferroelectrics possess prominent dielectric and piezoelectric properties thus have been utilized in many advanced electromechanical devices. However, the atomic-scale mechanism of their excellent electromechanical properties remains vague, which hinders the development of high-performance ferroelectrics. In this work, we investigated the lattice parameter fluctuations for Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ relaxor ferroelectric ceramics, with a comparison of non-relaxor ferroelectric ceramics, including BaTiO₃, SrTiO₃, and Pb(Zr,Ti)O₃, at their respective paraelectric phase by X-ray diffraction. We found that the fluctuations of lattice parameter were much larger in relaxor ferroelectrics than that in conventional ferroelectrics in the paraelectric phase, revealing a significant distinction between relaxor ferroelectrics and conventional ferroelectrics from the respect of atomic arrangement. Transmission electron microscopy experiments and X-ray scattering-intensity simulations indicated that the large fluctuations of lattice parameter in relaxor ferroelectrics can be attributed to the ordered–disordered arrangement of B-site cations at the nanoscale. This work offers a new method to study the chemical arrangement difference between relaxor ferroelectrics and conventional ferroelectrics and may help us to explore the atomic-scale origin of ultrahigh piezoelectric properties in relaxor ferroelectrics.