New lead-free non-stoichiometric perovskite relaxor ceramics derived from BaTiO3

The present work concerns the preparation and dielectric characterization of some new non-stoichiometric lead-free ceramics with perovskite compositions derived from BaTiO₃. Lead-free compositions could be of great interest for environment-friendly applications (dielectric for capacitors, actuators, etc.). These materials have been shown to be either classical or relaxor ferroelectrics. In the first part of this article, the BaTiO₃---Ba_0.5NbO₃ system concerns the cationic non-stoichiometry occurring only in the 12-coordination crystallographic site. In the second part, the influence of non-stoichiometry also occurring in the anionic site was determined in compositions belonging to the ternary system 2BaO---TiO₂---Nb₂O₅. The variation in the Curie temperature T_C or the temperature T_m of the maximum of ′_r decreased when the composition deviated from BaTiO₃ and when the number of vacancies increased. On the contrary, the relaxor state was favored by such a deviation.     

Interplay between polarization rotation and crack propagation in PMN-PT relaxor single crystals

Investigations on the interconnection between the polarization rotation and crack propagation are performed for [110]-oriented 74Pb(Mg_1/3Nb_2/3)O₃-26PbTiO₃ relaxor ferroelectric single crystal under electric loadings along [001] direction. The crystal is of predominantly monoclinic M_A phase with scatter distributed rhombohedral (R) phase under a moderate poling field of 900 V/mm in [001] direction. With magnitude of 800 V/mm, a through thickness crack is initiated near the electrode by electric cycling. Static electric loadings is then imposed to the single crystal. As the applied static electric field increases, domain switching in the monoclinic M_A phase and phase transition from M_A to R phase occur near the crack. The results indicate that the crack features a conducting one. Whether domain switching or phase transition occurs depends on the intensity of the electric field component that is perpendicular to the applied electric field.     

In situ X-ray diffraction studies of phase transition in Pb1− x La x Zr0.40Ti0.60O3 ferroelectric ceramics

The temperature dependence of the crystalline structure and the lattice parameters of Pb_{1? x} La _x Zr_0.40Ti_0.60O₃ ferroelectric ceramic system with 0.00 ≤ x ≤ 0.21 was determined. The samples with x ≤ 0.11 show a cubic-to-tetragonal phase transition at the maximum dielectric permittivity, T _max. Above this amount and especially for the x = 0.12 sample, a spontaneous phase transition from a relaxor ferroelectric state (cubic phase) to a ferroelectric state (tetragonal phase) is observed upon cooling below the T _max. Unlike what has been reported in other studies, the x = 0.13, 0.14, and 0.15 samples, which present a more pronounced relaxor behavior, also presents a spontaneous normal-to-relaxor transition, indicated by a cubic to tetragonal symmetry below the T _max. The origin of this anomaly has been associated with an increase in the degree of tetragonality, confirmed by the measurements of the X-ray diffraction patterns. The differential thermal analysis (DSC) measurements also confirm the existence of these phase transitions.     

Diffuse phase transition of BaTi0.6Zr0.4O3 relaxor ferroelectric ceramics

BaTi_0.6Zr_0.4O₃ ceramic was prepared through solid state reaction route. X-ray diffraction showed that the composition has cubic perovskite structure with space group Pm-3m at room temperature. Temperature dependency dielectric study of the ceramic has been investigated. Bulk density was determined using Archimedes principle and found to be ～97% of X-ray density. The average grain size in the pallet is measured by an optical microscope and found to be 22.23?µm. The dielectric measurement revealed diffuse phase transition of second-order, where dielectric peak temperature (T _m) is dependent of frequency showing relaxor-type behaviour. A clear deviation from Curie–Weiss law is observed in the paraelectric region. The dielectric relaxation rate follows the Vogel–Fulcher relation with E _a?=?0.1020?eV, T _f?=?106?K, ν₀?=?8.5?×?10¹¹?Hz.     

Diffuse ferroelectric phase transitions in cubically sabilized perovskites

Typical examples of ferroelectrics with diffuse phase transitions (relaxor ferroelectrics), like Pb(Mg_1/3Nb_2/3)O₃ are actually non transforming. The paraelectric phase is fully stablized against a ferroelectric phase transition in this case. A phase transition can be induced, however, by an electric field with appropriate orientation below the temperature of the dielectric constant maximum. The analogy with stress-induced martensitic phase transitions in metallic alloys is pointed out. Pecularities of the properties and of the polarization reversal of such systems are demonstrated. Actual diffuse ferroelectric phase transitions in disordered solid solutions and mixed compounds with a partially stabilized parent phase are compared with athermal martensitic transformations. With particular regard to technical ceramics based on PZT, the influence of interfaces between transformed regions and remnants of the parent phase which have to distinguished from domain walls, and of the reduced stability of the ferroelectric phase on the properties of these systems is discussed. Some effects usually explained solely by domain processes may be understood also from this point of view.

Stabilization of a parent phase against an order-disorder-type phase transition is supposed to be caused by glass-like freezing caused by inelastic cooperative interactions between disordered molecular groups.     

Dielectric and ferroelectric properties of NBT-BT systems

ABSTRACT

The (1-x)Na_0.5Bi_0.5TiO₃- xBaTiO₃ ceramics (x = 0.1, 0.135 and 0.17) were fabricated by a conventional solid phase sintering process. The bulk density of the obtained samples exceeded 95% of the theoretical relative density as determined by Archimedes method. Dielectric and ferroelectric measurements of these ceramics were performed. Measurements of the ferroelectric properties show that, above the depolarization temperature T_d, the shape of the hysteresis loops approaches that of linear dielectrics. The dielectric study results correlate with the hysteresis loops measurements. The relaxor-like behavior of the investigated materials was revealed.     

Electrocaloric response in a relaxor ferroelectric polymer at temperatures far below the dielectric maximum

ABSTRACT

Relaxor ferroelectric polymer poly(vinylidene fluoride–trifluoroethylene–chlorofluoroethylene) (P(VDF-TrFE-CFE)) and its blends have been shown to exhibit a giant electrocaloric effect (ECE) over a broad temperature range, e.g. from 0 to 50 °C. Here, a special calorimeter was designed to directly characterize the heat absorbed Q_ECE due to ECE cooling of the blend of P(VDF-TrFE-CFE) with P(VDF-TrFE) 65/35 mol% copolymer down to ?15 °C, which covers the temperature range for many refrigeration applications. From Q_ECE, the isothermal entropy change ΔS and adiabatic temperature change ΔT are deduced. The data reveal that at ?15 °C the relaxor terpolymer/copolymer blend generates ΔS = 23.0J kg^?1 K^?1 and ΔT = 5.1K under 100 MV/m, which are still more than 65% of the ECE at room temperature. This temperature is far below the dielectric peak temperature of the relaxor blend and the results reveal the promise of the relaxor polymers for a broad range of EC cooling applications.     

Bi0.5(Na0.82K0.18)0.5TiO3-BiFeO3 无铅压电陶瓷的介电特性

采用固相反应法制备了系列(1-x)Bi0.5(Na0.82K0.18)0.5TiO3-xBiFeO3(BNKT-BFx)陶瓷.研究了该陶瓷在室温至500 ℃范围内的介电性能.结果表明:该陶瓷的介电温谱与典型弛豫铁电体的特征不同,存在两个介电反常峰和一个介电损耗峰,只在低温介电反常峰温度附近具有明显的介电常数的频率依赖性,居里温度随频率增加基本不变.首次提出了弛豫铁电体分为本征弛豫和非本征弛豫铁电体的理论.通过分析极化前和极化后陶瓷的介电温谱,发现该体系低温介电反常峰温度附近的介电频率依赖性为空间电荷和缺陷偶极子极化引起的非本征弛豫.     

布里渊散射决定0.67Pb(Mg_(1/3)Nb_(2/3))O_3-0.33PbTiO_3单晶的弹性、压电和介电常数(英文)

我们报道了用高分辨布里渊散射,确定0.67Pb(Mg1/3Nb2/3)O3-0.33PbTiO3单晶中的弹性、压电和介电常数.所有的实验数据都是在一块沿[001]方向的极化的单晶样品上获得的。我们实验中得到的这些常数的数值和以往超声共振技术获得的数值相似。我们还研究了压缩模和剪切模在(010)和(001)平面内的方向依赖性。TA1和TA2模式的强度对散射角度有很强列依赖性。在散射角度为45°~65°内,一个新的峰出现在~18 GHz附近。它可能与晶体中的微观不均匀性或者局域微结构相关。     

铁电单晶Pb(Mg1/3Nb2/3)O3-0.32PbTiO3的实验及本构模型研究

对压力作用下沿[001]晶向极化的Pb(Mg弛豫型铁电单晶;极化旋转(相变);黏塑性模型;本构;细观力学国家自然科学基金,教育部全国优秀博士学位论文作者专项基金2006-11-06对压力作用下沿[001]晶向极化的Pb(Mg1/3Nb2/3)O3-0.32PbTiO3(PMN0.32PT)弛豫型铁电单晶的应力应变行为进行了实验研究,实验结果表明铁电单晶〈001〉晶向的应力应变行为和铁电多晶有本质的不同,是传统的电畴翻转机理所难以解释的,所提出的极化旋转(相变)模型合理地解释了实验中观察到的现象;基于提出的极化旋转(相变)模型,采用细观力学方法建立了铁电单晶的细观本构模型.在模型中采用黏塑性公式描述铁电单晶可能的8个相变系统的相变行为.为了验证模型的可靠性,用该模型模拟了铁电单晶〈001〉晶向的应力应变实验曲线.计算表明,该模型能较好地模拟铁电单晶〈001〉晶向的相变行为.