铋系化合物改性的新型三元弛豫铁电体的性能研究

钛酸钡(BaTiO₃)陶瓷作为传统的介质电容器材料,其强铁电性会导致储能密度低下,但通过掺杂可以削弱铁电性来获得弛豫铁电体,提高储能性能。利用铋系化合物可增强弛豫特性,本文设计了BiScO₃和(Sr_0.7Bi_0.2)TiO₃取代改性的BaTiO₃基三元陶瓷材料: (0.99-x)Ba(Zr_0.1Ti_0.9)O₃-x(Sr_0.7Bi_0.2)TiO₃-0.01BiScO₃(缩写为BZT-xSBT-BS)。采用传统固相法制备的BZT-xSBT-BS陶瓷,相结构没有因为掺杂发生改变,在室温下均为纯的三方相钙钛矿结构。介电和铁电的测试与分析表明,BZT-xSBT-BS陶瓷具有典型的弛豫铁电特性。由于不等价离子Sr²⁺、Bi³⁺的掺杂导致界面松弛极化,可以增大BZT-xSBT-BS陶瓷的介电常数,但是受制于其慢的响应速度,陶瓷的介电损耗也显著增加。适量(Sr_0.7Bi_0.2)TiO₃可以提升BZT-xSBT-BS陶瓷的介电、铁电、应变和储能性能,x=0.015时的BZT-xSBT-BS陶瓷的综合性能较优:ε_r~10 372,tanδ~0.019,P_max=16.42 μC/cm²,E_c=1.41 kV/cm,S⁺_max=0.12%(@40 kV/cm),W_D=0.181 J/cm³,η=80.4%(@60 kV/cm)。     

Defect‐Driven Structural Distortions at the Surface of Relaxor Ferroelectrics

Relaxor‐ferroelectric materials find application in a broad range of technological devices, including ultrasonic imaging transducers, nanopositioning, and high‐performance capacitors. They generally exhibit occupationally disordered structures creating local polar fluctuations that are highly sensitive to applied electric or stress fields. The sensitivity of the material structure to external field and stress conditions also makes them likely to develop skin or surface phases that are unique from the bulk. Surface layers can adjust the material response and also lead to ambiguity in structural characterization. Here, using a combination of X‐ray diffraction methods, it is shown that a ≈20 µm skin structure commonly exists in the lead‐free relaxor‐ferroelectric ceramic (Na_1/2Bi_1/2)TiO₃–BaTiO₃. Using experiments and density functional theory calculations, it is shown that the combined action of oxygen vacancies providing internal chemical pressure and the surface plane stress state dictates the stability and structure of the skin layer. This work can be extended to all perovskite relaxor ferroelectrics and provides new insights into the origin of skin layers in these materials. The opportunity exists to further enhance the functionality of these materials through engineering of surface structures using the methods outlined here.     

弛豫铁电单晶PZNT91/9的生长与畴结构研究

采用熔剂-坩埚下降法生长了91%Pb(Zn1/3Nb2/3)O3-9%PbTiO3(PZNT91/9)(摩尔分数)弛豫铁电单晶,PbO助熔剂摩尔分数控制在50%左右。所得晶体被PbO助熔剂包裹,将其浸泡在热HNO3中1～2天即可除去PbO。晶体呈浅黄色,具有明显的结晶学生长面。晶体沿(001)面切出数片,晶片质量明显好于通气Bridgman法生长的PZNT单晶。偏光显微镜可观察到71°、90°、180°畴或微畴区。晶片极化条件为:垂直于C面施加1kV/mm的电场并保持10～15min。     

Thickness Dependent Properties of Relaxor-PbTiO(3) Ferroelectrics for Ultrasonic Transducers

The electrical properties of Pb(Mg(1/3)Nb(2/3))O(3)-PbTiO(3) (PMN-PT) based polycrystalline ceramics and single crystals were investigated as a function of scale ranging from 500 microns to 30 microns. Fine-grained PMN-PT ceramics exhibited comparable dielectric and piezoelectric properties to their coarse-grained counterpart in the low frequency range (<10 MHz), but offered greater mechanical strength and improved property stability with decreasing thickness, corresponding to higher operating frequencies (>40 MHz). For PMN-PT single crystals, however, the dielectric and electromechanical properties degraded with decreasing thickness, while ternary Pb(In(1/2)Nb(1/2))O(3)-Pb(Mg(1/3)Nb(2/3))O(3)-PbTiO(3) (PIN-PMN-PT) exhibited minimal size dependent behavior. The origin of property degradation of PMN-PT crystals was further studied by investigating the dielectric permittivity at high temperatures, and domain observations using optical polarized light microscopy. The results demonstrated that the thickness dependent properties of relaxor-PT ferroelectrics are closely related to the domain size with respect to the associated macroscopic scale of the samples.     

Radiation-Induced Changes in the Dielectric Response of Poly(Vinylidene Fluoride) Type Polymers

High and dispersive dielectric response, characteristic of the relaxor state, was observed in ferroelectric P(VDF/TrFE)(50/50) copolymers irradiated with 1.0 MeV and 1.5 MeV electrons. Relaxor-like behaviour of the copolymer is a result of overlapping of the dielectric anomaly characteristic of the glass transition and that related to the Curie point, which is shifted downwards by electron irradiation. The results of ESR, IR and NIR Raman spectroscopy studies of the radiation damage to P(VDF/TrFE)(50/50) show that radiation-induced irreversible transformation of the ferroelectric copolymer to the relaxor state is related to the existence of polar clusters, consisting of a variety of short range coherence of trans-conformation, stabilized by random fields of C=C and conjugated C=C bonds.     

Modification of the structure and properties of poly(vinylidene fluoride–trifluoroethylene) 56/44 mol % copolymer by a proton‐irradiation treatment

The effects of high‐energy proton irradiation on the structure and properties of 56/44 mol % poly(vinylidene fluoride–trifluoroethylene) copolymer were studied with differential scanning calorimetry (DSC), X‐ray diffraction (XRD), relative permittivity, and polarization hysteresis measurements. Copolymer films prepared by hot compression molding were irradiated with a broad range of proton dosages (10–107 Mrad) at room temperature. The DSC results showed that the ferroelectric transition was strongly affected by the proton dosages. The XRD data indicated the reduction of polar ordering in the copolymer by the proton‐irradiation treatment. From the relative permittivity and polarization behavior, the copolymer film was found to be converted from a normal ferroelectric material to a relaxor ferroelectric material as the proton dosage was increased to 50 Mrad. The electrostrictive coefficient of the 56/44 mol % copolymer was enhanced after irradiation, and the optimized proton dosage for attaining the highest electrostrictive strain response was determined. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2334–2339, 2005     

退火处理对Pb（Zn1／3Nb2／3）O3基陶瓷介电性能的影响

研究了退火处理对Ｐｂ（Ｚｎ１／３Ｎｂ２／３）Ｏ３基陶瓷介电性能的影响。结果表明，退火热处理显著提高了ＰＺＮ基陶瓷相变温度附近的介电常数，并使相变扩散因子降低。借助显微结构和介电分析探讨了可能原因，认为热处理对介电性能的影响可能与晶界玻璃相的消除、晶粒内部微区状态的改变及应力消除等因素有关。     

(PbBa)(Zr,Sn,Ti)O_3反铁电/弛豫型铁电相界陶瓷的相变与介电、热释电性质

通过对(Pb087Ba01La002)(Zr06TixSn04-x)O3(004≤x≤020)固溶体的介电和偏压热释电性质的研究发现,当Ti含量004≤x≤007时,材料是反铁电四方相,而当009≤x≤020时,材料向弛豫型铁电体转化.在温度Ti含量相图中,x=009附近形成了反铁电铁电顺电三相共存点(Ttr).该点的相变温度最底;对于004≤x≤007的反铁电四方相,低温下呈现介电弛豫特征,并可被外电场诱导为亚稳铁电态,温度升高时,亚稳铁电→反铁电相变,反铁电→顺电相变引起两个热释电流峰,偏置电场下峰位和峰强均发生移动,在温度电场相图中也形成了铁电反铁电顺电三相点.从复杂化合物纳米相分离的观点和晶格动力学出发,讨论了相变与电学性能随Ti含量(x)和外电场(E)变化的物理机理. 关键词： 反铁电/弛豫型铁电相界 介电性能 偏压热释电性质 铁电-反铁电-顺电三相点     

复合钙钛矿弛豫铁电体中极化微区尺寸的确定

通过分析极化微区形成过程中自由能的变化，确定极化微区的尺寸。以相变过程中的潜热做为均匀铁电体顺电态转变为铁电态自由能变化的近似值。随着温度降低，某些区域铁电态自由能密度降低；当铁电态自由能密度低于顺电态自由能密度时导致该区域出现极化，而晶格畸变在微区表面产生的弹性势能随着极化微区长大而逐渐增大，成为阻碍微区长大的主要原因。通过自由能极值分析，所得Pb（Mg1/3 Nb2/3）O3-PbTiO3微区尺寸与实验结果相近。     

La掺杂SrBi4Ti4O15铁电材料性能研究

按x=0.00，0.10，0.25，0.50，0.75和1.00，采用固相烧结工艺，制备了不同La掺杂量的SrBi_4-xLa_xTi₄O₁₅的陶瓷样品. 用x射线衍射对其微结构进行了分析，并测量了铁电、介电性能.结果发现，La掺杂未改变SrBi₄Ti ₄O₁₅的晶体结构.随掺杂量的增加，样品的矫顽场(E_c)下降，剩余极化(2P_{关键词： 4-x}La_xTi₄O₁₅')" href="#">SrBi_4-xLa_xTi₄O₁₅ La掺杂 铁电性能 相变温度 弛豫铁电