Temperature-dependent structures of proton-conducting Ba(Zr(0.8-x)Ce(x)Y(0.2))O(2.9) ceramics by Raman scattering and x-ray diffraction

In situ temperature-dependent micro-Raman scattering and x-ray diffraction have been performed to study atomic vibration, lattice parameter and structural transition of proton-conducting Ba(Zr(0.8-x)Ce(x)Y(0.2))O(2.9) (BZCY) ceramics (x = 0.0-0.8) synthesized by the glycine-nitrate combustion process. The Raman vibrations have been identified and their frequencies increase with decreasing x as the heavier Ce(4+) ions are replaced by Zr(4+) ions. The main Raman vibrations of Ba(Ce(0.8)Y (0.2))O(2.9) appear near 305, 332, 352, 440 and 635 cm(-1). The X-O ( X=Ce, Zr, Y) stretching modes are sensitive to the variation of Ce/Zr ratio. A rhombohedral-cubic structural transition was observed for x = 0.5-0.8, in which the transition shifts toward higher temperature as cerium increases, except for Ba(Ce(0.8)Y(0.2))O(2.9). A minor monoclinic phase possibly coexists in the rhombohedral matrix for x = 0.5-0.8. The lower-cerium BZCYs (x = 0.0-0.4) ceramics do not exhibit any transition in the region of 20-900?°C, indicating a cubic phase at and above room temperature.     

Structure of Y and Zr Segregated Grain Boundaries in Alumina

Grain boundary segregation of Y and Zr in -Al₂O₃ and the atomic structural environment around the Y and Zr atoms have been investigated using high resolution STEM and EXAFS. At dilute concentrations, the Y ions in -Al₂O₃ grain boundaries, on average, are coordinated by 4 oxygens, at a distance of 2.30 Å, which corresponds nearly to the Y-O bond length in cubic Y₂O₃, and Zr ions are coordinated by 5 oxygens at a distance of 2.14 Å, which is approximately the same as the average Zr-O bond length in monoclinic ZrO₂. However, in the EXAFS radial distribution function, the Y-cation and Zr-cation next nearest neighbor shell cannot be clearly identified. These results suggest that Y and Zr at dilute concentrations in -Al₂O₃ occupy grain boundary sites with well defined nearest neighbor cation-oxygen bond lengths similar to those in their parent oxides, but with the next nearest neighbor cation-cation distances varying considerably from site to site. Grain growth can cause grain boundaries to become supersaturated by Y. In this case, both the Y-O nearest neighbor coordination number and the ordering of Y with respect to Al ions beyond nearest neighbor O are increased. This Y-Al distance is the same as that expected for the Y-Al distance when Y substitutes for Al while relaxing the Y-O distance to that in Y₂O₃. This may indicate that as the Y concentration increases, Y begins to occupy near-boundary sites in planes on each side of the geometrical boundary. In these near-boundary planes, the nearest neighbor ordering extends at least to nearest neighbor cations. Nucleation of the YAG phase leads to the depletion of these partially ordered layers.     

Cation Segregation in an Oxide Ceramic with Low Solubility: Yttrium Doped α-Alumina

The segregation behaviour of a cation (yttrium) with a low solubility in the polycrystalline oxide host (a-Al₂O₃) has been investigated at temperatures between 1450 and 1650°C using analytical scanning transmission electron microscopy. Three distinct segregation regimes were identified. In the first, the yttrium adsorbs to all grain boundaries with a high partitioning coefficient, and this can be modelled using a simple McLean-Langmuir type absorption isotherm. In the second, a noticeable deviation from this isotherm is observed and the grain boundary excess reaches a maximum of 9 Y-cat/nm² and precipitates of a second phase (yttrium aluminate garnet, YAG) start to form. In the third regime, the grain boundary excess of the cation settles down to a value of 6–7 Y-cat/nm² that is in equilibrium with the YAG precipitates. In a material (accidentally) co-doped with Zr, the Zr seems to behave in a similar way to the Y and the Y + Zr grain boundary excess behaves in the same way as the Y grain boundary excess in the pure Y-doped system. In this latter system, Y-stabilised cubic zirconia is precipitated in addition to YAG at higher Y + Zr concentrations.     

The crystal structures and physical properties of the solid solution compound Ba₅Y_8-xMn₄O_21-1.5x（x = 0,1）

New oxometallides with the formula Ba5Y8 xMn4O21 1.5x(x = 0,1) are prepared through an atmospherecontrolled solid-state reaction.Two single-phase samples with Ba/Y/Mn atomic ratios 5/8/4(Y8) and 5/7/4(Y7) are obtained.The crystal structures and the physical properties of the compounds are investigated by X-ray powder diffraction,magnetization,conductivity,and dielectricity measurements.The Ba5Y8 xMn4O21 1.5x compound is demonstrated to be a Y-deficient solid solution.The solid solution compound Ba5Y8 xMn4O21 1.5x crystallizes into tetragonal symmetry with the space group I4/m.Detailed structure analysis by Rietveld refinement of the X-ray powder diffraction data reveals that the Y vacancies occur preferentially at the Y(2) site.Thermal magnetization measurements indicate the presence of antiferromagnetic interaction between Mn ions in the compounds,and temperature-dependent resistivity measurements show that insulator-semiconductor transitions occur around 175 K and 170 K for the Y8 and Y7 samples,respectively.Strong frequency dependences of the dielectric constant are observed above ～175 K for the two compounds.     

(Bi0.5Na0.5)TiO3-Ba(Ti,Zr)O3 陶瓷的电性能研究

采用氧化固相法制备了(1-x)(Bi0.5Na0.5)TiO3-xBa(Ti0.95Zr0.05)O3(BNT-BZT)陶瓷,其中掺入量x的值分别为0,0.04,0.05,0.06,0.07.研究了BNT-BZT体系陶瓷的准同型相界以及陶瓷材料的微观结构和性能之间的关系,并探讨了陶瓷的介电性能和铁电等性能.通过探究Ba(Ti,Zr)O3(BZT)掺杂量对BNT 各性能的影响得出了当掺杂量x=0.05得到结构较为致密,介电,铁电性能较好的样本,对工业化研究和生产有重要的意义     

High-temperature impedance spectroscopy of BaFe0.5Nb0.5O3 ceramics doped with Bi0.5Na0.5TiO3

Bi_0.5Na_0.5TiO₃ (BNT)-doped BaFe_0.5Nb_0.5O₃ (BFN) ceramics were synthesized by a two-step solid-state reaction. Temperature dependence of dielectric properties measured at different frequencies was investigated over broad temperature and frequency ranges. Impedance spectroscopy and universal dielectric response were employed to study the relaxation behavior and conductivity mechanism of the ceramics in a frequency range from 40 Hz to 100 MHz and a temperature range from 300 K to 800 K. The complex plane impedance data revealed the bulk and grain boundary contributions toward conductivity processes in the form of semicircular arcs. The high-temperature conductivity of ceramics is attributable to thermally activated second ionized oxygen vacancy.     

Study of electrical conductivity and phase transition in Bi2O3–V2O5 system

The solid solutions of bismuth–vanadate were prepared by the conventional solid-state reaction. The sample characterization and the study of phase transition were done by using FT-IR, X-ray diffraction (XRD) and DSC measurements. AC impedance measurements proved that the oxide ion conductivity predominantly arises from the grain and grain boundary contributions as two well-defined semicircles are clearly seen along with an inclined spike. The electrical conductivity of Bi₂O₃–V₂O₅ has been studied at different temperatures for various molar ratios. The isothermal conductivity increases with an increase in the concentration of V₂O₅ due to the vacancy migration phenomenon. It has been found that the conductivity of different compositions of Bi₂O₃–V₂O₅ increases and shows a jump in the temperature range 230–260°C due to the phase transition of BiVO₄ from monoclinic scheelite type to that of tetragonal scheelite type. The endothermic peak in DSC at around 260°C reveals the phase transition, which is also confirmed by the XRD and FT-IR analysis. The XRD patterns confirmed the monoclinic structure of BiVO₄.     

A study on ac and dc conductivity characteristics of Y-doped BaCeO3 modified by Ar+ ion beam

The effects of surface modification on electrical characteristics in bulk, grain boundary and interface (electrolyte/electrode) of BaCe_0.9Y_0.1O_3-δ were investigated. The surface modification was performed by means of two processes: specimen was firstly irradiated by 10 keV Ar⁺ ion with dose of 1 × 10¹⁸ ions/cm² and then exposed to air. The modified surface was investigated by elastic recoil detection analysis (ERDA) for quantitative analysis of hydrogen concentration on the surface and alternating current (AC) and direct current (DC) conductivity measurements, respectively. The ERDA results showed that hydrogen concentration and reaction rate on the modified surface increased. The increase of hydrogen concentration was explained in terms of the increase of proton due to interaction between oxygen vacancy formed by modification and H₂O. In AC and DC electrical conductivity measurements, it concluded that the proton and electronic carrier generated on the surface by modification attributed to the increase of bulk, grain boundary and interface conductivity.     

Effect of grain boundaries on the conductivity of high-purity ZrO2Y2O3 ceramics

Grain boundary conductivities are determined by complex impedance measurements (1–10⁶ Hz) on high-purity ceramics prepared by the alkoxide synthesis and on less pure ceramics obtained from a commercial powder. The grain size was varied systematically in the region 0.36–55 μm. The grain boundary conductivity is strongly influenced by the grain size, impurities and cooling procedure. The grain boundary conductivity increases linearly with the grain size for small grain sizes (0.3 to 2–4 μm) and is constant for larger grain sizes. The calculated specific conductivity of the grain boundary for pure materials is about 100 times smaller than that of the bulk. The grain boundary thickness was estimated to be 5.4 nm. The activation energy of the grain boundary conductivity is 7 kJ mole^?1 higher than of the bulk.     

Effect of substitutions on dielectric behavior of La2NiMnO6

The substituted La₂NiMnO₆ (LNMO) double perovskite powder samples are prepared by hydroxide co-precipitation method. The electrical properties such as conductivity, dielectric constant and impedance analysis of the substituted sample, have been studied. The activation energy is determined by dc conductivity plot gives the fair idea of conduction mechanism. The dielectric and impedance analysis suggests the contribution of extrinsic and intrinsic effects in dielectric relaxation due to substitution at A and B site cations. The Nyquist plot reveals the role of grain and grain boundaries in charge conduction mechanism. The large grain and grain boundary resistance value and activation energy ～100 meV of substituted LNMO samples shows the presence of variable range hopping (VRH) conduction mechanism.     

EFFECT OF THE Ba VACANCY ON THE FLUX PINNING IN YBaxCu3O7-δ SYSTEM

A series of Y123 single phase samples with various Ba vacancy concentration was prepared by making their Ba contents deviate from the stoichiometric composition. The measurements of their structure, superconductivity and flux pinning behaviour were systematically carried out. It is found that, compared with YBa₂Cu₃O_6.96 sample, the strength of the flux pinning in YBa_xCu₃O_7-δ(1.8≤x<2.0) samples is increased, and that there is an optimum value of Ba vacancy concentration for the maximum flux pinning force density. The possible origin of the flux pinning centers to determine the flux pinning behavior at higher field is discussed in detail. We suggest that the flux pinning effect at lower field may stein from the interaction between the vortex and the surfaces of grains, and that the flux pinning mechanism at higher field belongs to the core interaction.     

Improved properties & fatigue resistant behaviour OF Ba(Zr0.15Ti0.85)O3 ferroelectric ceramics

The microstructure, dielectric and piezoelectric properties of Zr doped BaTiO₃ ceramics sintered at optimum temperature, are investigated. High energy ball milling technique is adopted to realize nano-sized powders of Ba(Zr_0.15Ti_0.85)O₃ ceramics. Increased boundary mobility of fine powders aided to obtain a relative density of >98.8% of theoretical density corresponding to ceramics under study. Internal stresses in these ceramics are found to be relieved by grain-boundary sliding. The Ba(Zr_0.15Ti_0.85)O₃ ceramics synthesized at relatively low sintering temperatures exhibit remarkable, enhanced dielectric properties viz. improved polarization, high unipolar strain values comparable to Zr doped BaTiO₃ single crystals of same composition, at relatively lower electric fields and also exhibit better fatigue tolerant properties. The underlying mechanisms responsible for superior dielectric, ferroelectric and piezoelectric properties are discussed.     

Atomistic Simulation of Curvature Driven Grain Boundary Migration

We present two dimensional molecular dynamics simulations of grain boundary migration using the half-loop bicrystal geometry in the experiments of Shvindlerman et al. We examine the dependence of steady-state grain boundary migration rate on grain boundary curvature by varying the half-loop width at constant temperature. The results confirm the classical result derived by absolute reaction rate theory that grain boundary velocity is proportional to the curvature. We then measure the grain boundary migration rate for fixed half-loop width at varying temperatures. Analysis of this data establishes an Arrhenius relation between the grain boundary mobility and temperature, allowing us to extract the activation energy for grain boundary migration. Since grain boundaries have an excess volume, curvature driven grain boundary migration increases the density of the system during the simulations. In simulations performed at constant pressure, this leads to vacancy generation during the boundary migration, making the whole migration process jerky.     

Structural and dielectric properties of barium-modified SrBi4Ti4O15 ceramics

Barium-modified strontium bismuth titanate ceramics with chemical formula Sr_1?xBa_xBi₄Ti₄O₁₅ (x = 0.00, 0.02, 0.06, 0.08 and 0.1) (SBBT) have been prepared by means of solid-state reaction technique and their structural and electrical properties were investigated. X-ray diffraction data confirm that all the compositions show orthorhombic structure without any deleterious phase. Scanning electron micrographs show plate like grain morphology with random orientation of platelets. The temperature-dependent dielectric study shows that the phase transition temperature decreases, but the dielectric constant increases with increase in Ba content. Complex impedance plots show that both grain and grain boundary effect on the resistance mechanisms in all the compositions. The values of the activation energy confirm that the oxygen vacancies play an important role in the conduction. The ac conductivity of SBBT ceramics increases as a function of frequency due to relaxation phenomenon which arises due to mobile charge carriers.     

氧含量对CaCu3Ti4O12巨介电常数和介电过程的影响

本文研究了在真空、空气和氧气中烧结制备的三种 CaCu₃Ti₄O₁₂陶瓷材料的介电特性. 交流阻抗测量结果表明在10—300 K温度范围, 三种样品的介电温谱中均出现三个平台, 其电阻实部和电容虚部在相应温度出现损耗峰, 真空条件烧结的样品具有较高的介电平台和较明显的电阻实部与电容虚部峰值, 表明氧含量和氧空位对CaCu₃Ti₄O₁₂的介电性质具有重要影响, 介电温谱出现的三个平台分别源于晶粒、晶界及氧空位陷阱.温谱分析表明晶粒的激活能与烧结气氛有较大关系,氧空位引起的电子短程跳跃及跳跃产生的极化子是晶粒电导和电容的主要起源.氧空位陷阱的激活能基本与烧结气氛无关,约为0.46 eV. 氧空位对载流子的陷阱作用是CaCu₃Ti₄O₁₂ 低频高介电常数的重要起源.     

Preparation and characterization of Yb-doped Ba(Ce,Zr)O<Subscript>3</Subscript> nanopowders with high sinterability

The Ba(Ce_0.8Zr_0.2)_0.95Yb_0.05O_2.975 ceramics electrolyte was prepared via a Pechini method using metal nitrate salts as starting materials. An optimum annealing temperature of 1,400 °C was needed to obtain a pure perovskite-like phase with orthorhombic structure. Particle size distribution showed a bimodal distribution that corresponds to the loose powders and agglomerates size. Scanning electron micrograph revealed that the loose powders were in the nanosize range (70–200 nm). These ultrafine loose powders enhanced the densification of a pellet with relative density ∼95% obtained at 1,400 °C. The sample formed clear and compact grains with submicron sizes. Impedance results showed that the impedance semicircle of the grain was observed only at T ≤ 250 °C. The introduction of 20 mol% Zr improved the chemical stability of BaCe_0.95Yb_0.05O_2.975 sample in atmosphere containing carbon dioxide at 600 °C. The sample also exhibited high proton conductivity in wet hydrogen.     

环带钾长石、榍石和锆石的显微结构与微区组成特征分析

南秦岭沙河湾石英二长岩中的钾长石、榍石和锆石具有明显的成分环带。利用电子探针(EPMA)波谱仪(WDS)、扫描电子显微镜(SEM)及其附带的能谱仪(EDS)和激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)对造岩矿物环带钾长石、榍石和锆石的显微结构与微区组成进行表征。结果表明：钾长石中K+被Na+,Ca2+,Ba2+,Fe2+和Ce3+不同程度替代。榍石中Ca2+被V3+,Ce3+和Ba2+等替代,Ti4+被Fe2+和Al3+等替代。锆石含Fe,Th,U,Nb,Ta,Y,Hf,Yb和Pb等稀土和微量元素。钾长石中元素浓度由高到低为Si,Al,K,Ca,Na,Mg和Ba,其中K和Na互补,较亮处Ba含量高,越靠近边缘,Si升高、K升高与Na降低趋势越明显。榍石中元素浓度由高到低为Ca,Si,Ti,Ba,V,Ce,Al和Fe,较亮处Fe含量较高。锆石中元素浓度由高到低为Zr,Si,Nd,Ce,Hf,U,Pb和Th,Hf与Zr呈明显的互补关系,核部Zr含量较边部高,核部Hf、U和Th含量较边部低。     

Concentration and temperature dependences of the oxygen migration energy in yttrium-stabilized zirconia

The ionic conductivity of zirconia with different contents of the yttrium stabilizing impurity has been studied using impedance spectroscopy in the temperature range 300–910°C. A deviation of the temperature dependence of the conductivity in the crystallite bulk from the Arrhenius equation has been revealed. A quantum-mechanics estimation of the influence of the yttrium content on the oxygen-vacancy migration barrier as a function of its distance to the yttrium atom has been carried out. A two-barrier mechanism of the dependence of the oxygen migration energy on the yttrium content in zirconia due to anion vacancy trapping by yttrium has been proposed. Analytical dependences of the concentration of free (active) anion vacancies and the activation energy of ionic conductivity on the temperature and stabilizing impurity content have been obtained.     

沉淀剂对ZnO压敏陶瓷缺陷结构和电气性能的影响

研究了不同沉淀剂(NH₄HCO₃和NaOH)对共沉淀法制备的ZnO压敏陶瓷性能的影响. 结果表明: 不同的沉淀剂对ZnO压敏陶瓷的微观结构及电气性能有明显的影响. 其中陶瓷微观结构的变化主要由沉淀剂本身的性质引起; 而电气性能的改变除了与微观结构相关外, 主要受不同沉淀剂对陶瓷晶界势垒参数的影响; 此外, 沉淀剂NaOH引入的Na⁺作为施主杂质离子掺杂ZnO压敏陶瓷, 增加晶粒中的自由电子浓度, 因此本征缺陷(锌填隙和氧空位)浓度受到抑制, 而锌填隙浓度相对于氧空位而言对施主离子掺杂更为敏感. 由此, 采用共沉淀法制备ZnO压敏陶瓷粉体时, 沉淀剂种类的选择很重要, 即使微量的杂质也会引起压敏陶瓷性能的较大改变, 应尽可能避免杂质离子的引入. 关键词： ZnO压敏陶瓷 缺陷结构 沉淀剂 介电性能