Oxygen nonstoichiometry in high-Tc superconductor HoBa2Cu3O6+x and application of coulometric tritration

Nonstoichiometry in the perovskite-type compound, HoBa₂Cu₃O_6+x, was determined as a function of oxygen partial pressure (5 × 10⁻¹ 1 × 10⁵ Pa) in the temperature range of 8631173 K by coulometric titration using a stabilized zirconia electrolyte. Electromotive force of the cell, EMF, was measured as a function of oxygen content at constant temperature, and as a function of temperature at constant oxygen content. The perovskite-type compound was found to have a tendency to decompose into Ho₂O₃, BaO, CuO and some double-oxides at low oxygen partial pressures. Defect equilibria are discussed on the basis of the dependence of nonstoichiometry on oxygen partial pressure. Variation of the relative partial molar entropy with composition is explained in terms of a well-known defect model. A new technique which was developed for measuring the electrical conductivity of a non-stoichiometric oxide, in situ, at constant oxygen content as a function of temperature in the coulometric titration cell, is presented.     

A transient TGA study on oxygen permeation properties of perovskite-type ceramic membrane

This paper reports transient weight curves of La_0.2Sr_0.8CoO_3−δ (LSC) membrane (crashed in small grains) subject to an instantaneous change of oxygen activity in the gas phase. When the surrounding gas changes between pure oxygen and helium, the LSC sample experiences a slow weight loss in the oxygen desorption period and a rapid weight gain in the oxygen absorption period due mainly to the difference in the driving force. The LSC sample undergoes phase transformation/chemical reaction with the surrounding gas changing between the pure oxygen and methane. A mathematical model considering surface reaction as the rate-limiting step is presented to describe the oxygen transport through the membrane material, and employed to obtain the surface reaction rate constants. A simple correlation between the oxygen permeation flux and rate constants measured by the transient thermogravimetric analysis (TGA) method is given. The oxygen permeation fluxes calculated from the data measured by the present TGA method are consistent with the data measured by the permeation method. The TGA method is found particularly useful for studying the surface reaction rates of oxygen permeation through thin mixed-conducting ceramic membranes.     

Mixed electronic and ionic conductivity of LaCo(M)O3 (M=Ga, Cr, Fe or Ni).: V. Oxygen permeability of Mg-doped La(Ga, Co)O3−δ perovskites

The LaGa_1−x−yCo_xMg_yO_3−δ solid solutions with rhombohedrally-distorted perovskite structure were ascertained to form in the concentration range of 0≤y≤0.10 at x=0.60 and 0≤y≤0.20 at x=0.35–0.40. Increasing cobalt content results in increasing electrical conductivity and thermal expansion of the perovskites. Thermal expansion coefficients of the LaGa_1−x−yCo_xMg_yO_3−δ ceramics were calculated from the dilatometric data to vary in the range of 12.4–19.8×10⁻⁶ K⁻¹ at 300–1100 K. Doping La(Ga,Co)O_3−δ solid solutions with magnesium leads to increasing oxygen nonstoichiometry, electronic and oxygen ionic conductivity. Oxygen permeation fluxes through LaGa_1−x−yCo_xMg_yO_3−δ membranes were found to be limited by the bulk ionic conduction and to increase with magnesium concentration, being essentially independent of cobalt content.     

Defect chemistry and electrical properties of La1-xSrxCoO3-δ

This paper reports defect diagrams of Sr-doped lanthanum cobaltate, La_1−xSr_xCoO_3−δ (LSC), involving both random defect model and the cluster defect model in the temperature range between 873 K and 1173 K. The diagrams are derived in the form of defects concentrations as a function of oxygen partial pressure using the nonstoichiometry data reported in the literature. The effect of the Sr content on defect structure of LSC is discussed in terms of both defect models.     

Structural stability and oxygen permeability of cerium lightly doped BaFeO3−δ ceramic membranes

The structural stability under reducing environment and oxygen permeation fluxes of perovskite-type BaCe_xFe_1−xO_3−δ (0 ≤ x ≤ 0.15) ceramic membranes were investigated. The XRD results showed that 5% of cerium doping into the perovskite B-site can make the BaFeO_3−δ transform from the hexagonal structure to the cubic structure, and make the structure stable under 10% H₂–Ar mixed gas at 900 °C for 1 h, but breaks down after 5 h. Lattice parameters and oxygen non-stoichiometry of the as-prepared and reduced samples were measured. Oxygen permeation fluxes of the membranes were measured between 700 and 950 °C. Oxygen permeation during the cooling and heating circles showed that 5% of cerium doping into the perovskite B-site can avoid the phase transformation. The optimum cerium-doped amount on the B-sites was found to be 10%.     

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     

A study on the nonstoichiometry of tin oxides by coulometric titration

In this investigation, nonstoichiometries and defect structures of tin oxides were studied between 694 and 990 K by coulometric titration using solid state electrolyte (YSZ) cells. The relationship between nonstoichiometry of the oxide (x) and equilibrium oxygen partial pressure (P_o2) was expressed by the proportionality: xP_O2^−1/6. An intermediate oxide phase, Sn₃O₄ between Sn and SnO₂ was observed in the temperature range of 696–732 K. The standard Gibbs energy of formation of Sn₃O₄ via the reaction; was found to be ΔG^o_Sn3O4 = −1163960+417.36 T (J/mol). The standard Gibbs energy change for the defect formation reaction in SnO_2−x was calculated to be ΔG^o_SnO2−x = 3.05×10⁵−38.97 T (J/mol)).     

Oxygen transport in La2NiO4 + δ: Assessment of surface limitations and multilayer membrane architectures

The steady-state oxygen permeation through dense La₂NiO_4 + δ ceramics, limited by both surface exchange and bulk ambipolar conduction, can be increased by deposition of porous layers onto the membrane surfaces. This makes it possible, in particular, to analyze the interfacial exchange kinetics by numerical modelling using experimental data on the oxygen fluxes and equilibrium relationships between the oxygen chemical potential, nonstoichiometry and total conductivity. The simulations showed that the role of exchange limitations increases on reducing oxygen pressure, and becomes critical at relatively large chemical potential gradients important for practical applications. The calculated oxygen diffusion coefficients in La₂NiO_4 + δ are in a good agreement with literature. In order to enhance membrane performance, the multilayer ceramics with different architecture combining dense and porous components were prepared via tape-casting and tested. The maximum oxygen fluxes were observed in the case when one dense layer, ~ 60 μm in thickness, is sandwiched between relatively thin (< 150 μm) porous layers. Whilst the permeability of such membranes is still affected by surface-exchange kinetics, increasing thickness of the porous supporting components leads to gas diffusion limitations.     

CaCu3Ti4O12 陶瓷介电模量响应特性的研究

由于CaCu₃Ti₄O₁₂巨介电常数陶瓷的低频区直流电导较大, 本文采用模量 M"-f频谱表征与分析了低频和高频的两个松弛极化过程. 研究认为, 这两个特征峰属于晶界区Schottky 势垒耗尽层边缘深陷阱的电子松弛过程, 其中高频松弛峰起源于晶粒本征缺陷的电子松弛过程, 而低频松弛峰则为与氧空位有关的松弛极化过程. 对于CaCu₃Ti₄O₁₂这类低频下具有高直流电导的陶瓷材料, 采用模量频谱能更有效地分析研究其损耗极化机理. 关键词： 3Ti₄O₁₂陶瓷')" href="#">CaCu₃Ti₄O₁₂陶瓷 模量 松弛过程 电导     

Na0.25K0.25Bi0.5TiO3无铅压电陶瓷的介电特性研究

用固相反应法制备了Na_0.25K_0.25Bi_0.5TiO₃ (NKBT50)陶瓷，研究了该陶瓷在室温至400℃温度范围内的介电性能.发现该陶瓷的介电温谱与烧结气氛、极化状态有关.在空气中烧结的未极化样品在70℃附近存在介电和损耗峰，而极化后及在氧气氛中烧结的样品并不存在该介电、损耗峰.分析认为70℃的介电和损耗峰与氧空位形成的缺陷偶极子的极化弛豫有关.热激电流显示，陶瓷的去极化温度为225℃，与此相对应的介电、损耗峰也 关键词： 介电性能 氧空位 极化弛豫 钛酸铋钠钾     

Silica poisoning of oxygen membranes

Perovskite oxide membranes (La_0.6Sr_0.4Co_0.2Fe_0.8O₃) are used for the separation of oxygen from air. In oxygen permeation experiments these membranes showed a peculiar behavior. Besides poor performance, a characteristic coloring also appeared on the surface of the membranes. In order to understand what was happening to the surface of the membranes, they were analysed with Low-Energy Ion Spectroscopy (LEIS) and X-ray Photoelectron Spectroscopy (XPS). The analyses showed that the surface of the LSCF membrane was covered with a SiO₂ layer, which obviously reduced the performance and caused the coloring. It was established that the source of the silicon was siloxane containing grease that was used in the manual valves of the setup. In a new improved permeation setup, where grease-free valves were used, the LSCF membranes showed remarkably better performance. The LEIS measurements showed also that the permeation experiment of 300 h did not affect the surface composition of the membranes. The contamination-free LSCF membranes only showed the presence of La, Sr and O in the outermost atomic layer. The observed absence of Co and Fe suggests that further improvement of the membrane performance is possible.     

LiCoO2: formation, structure, lithium and oxygen nonstoichiometry, electrochemical behaviour and transport properties

The formation, structure and transport properties of LiCoO₂ are described. LiCoO₂ exhibits two crystal structures, depending on both the preparation method and synthesis temperature. High temperature lithium cobalt oxide (HT-LiCoO₂) has a hexagonal layered structure, while the low temperature oxide (LT-LiCoO₂) has a cubic spinel-related structure. The dependence of the morphological characteristics (grain size, size distribution, crystallinity) of LiCoO₂ on synthesis method as well as their effect on the electrochemical properties are extensively reviewed. As the electrochemical properties and the electrical conductivity strongly depend on the structure of the oxide, primary attention is given to lithium cobalt oxide with defect structure and lithium and oxygen nonstoichiometry.     

Defect chemistry and electrical properties of La1−xSrxCoO3−δ III. Oxygen nonstoichiometry

This paper concerns verification of the defect chemistry models of La_1−xSr_xCoO_3−δ (LSC), involving the random defect model and the cluster defect model, against empirical data of oxygen nonstoichiometry. It appears that the experimental data may well be explained within the random defect model.     

Ce3+,Tb3+共掺BaYF5微晶玻璃的光学特性

采用高温熔融法制备了一种新型的Ce3 +/Tb3+共掺BaYF5微晶玻璃.测试了微晶玻璃的X射线衍射图(XRD)谱、激发光普和发射光谱.研究发现:660℃热处理2h后的玻璃基质中析出BaYF5纳米晶相,根据XRD结果用Scherrer公式计算得到晶粒大小约为27 nm;在近紫外光(338 nm)激发下,观察到BaYF5...     

Sr-doped LaInO3 and its possible application in a single layer SOFC

The effects of dopants on the electrical conductivity of the perovskite-type oxide LaInO₃ have been investigated. Replacement of La by Sr is the most effective way to enhance the conductivity of LaInO₃, whereas Ca substitution for In is rather difficult due to the large difference in the ion radii. The optimum composition is La_0.9Sr_0.1InO_3−δ whose maximum conductivity is 7.6×10⁻³ S cm⁻¹ at 900°C. The electrical conductivity of La_0.9Sr_0.1InO_3−δ has been measured over a wide range of oxygen partial pressure from pO₂=1 to 10⁻²⁵ atm. P-type and n-type behavior at high and low oxygen partial pressure have been observed, respectively, while at intermediate oxygen partial pressures, the electrical conductivity changes only slightly with the oxygen partial pressure. The concept of a single layer solid oxide fuel cell based on a La_0.9Sr_0.1InO_3−δ ceramic pellet has been tested. A maximum power density of 3 mW cm⁻² at 800°C was achieved when dilute H₂ and air were used as fuel and oxidizing agent, respectively.     

凝胶浇注制备La0.8Sr0.2Cr0.5Fe0.5O3-δ-Zr0.84Y0.16O1.92非对称陶瓷透氧膜

要凝胶浇注制备多孔支撑体,并采用浆料涂膜和高温共烧技术制备非对称La_0.8Sr_0.2Cr_0.5Fe_0.5O_3-δ-Zr_0.84Y_0.16O_1.92（LSCF-YSZ）双相复合陶瓷透氧膜。结果显示,采用凝胶浇注制备技术,可获得结构均匀和高孔隙率的多孔支撑体;在多孔支撑体上,采用浆料涂膜和高温共烧技术制备的LSCF-YSZ非对称管状透氧膜,Air/He梯度下,950℃,氧渗透速率达到1.17×10^-8mol·cm^-2·s^-1;在850—950℃温度范围,膜的氧渗透表观活化能为163.7±0.4kJ/mol。     

The effect of heat treatment on explosively compacted (Y---Ba---K---Cu---O) superconductive powders

A ceramic powder mixture corresponding to the stoichiometric ratio of YBa_1.95K_0.05Cu₃O_y superconducting ceramic with 10% w/w Ag was heat treated at 950°C for 3 h in flowing oxygen. The resultant superconducting powder was consolidated in a silver tube by the explosive compaction technique (pre-heat treated ceramic). The same fabrication technique, i.e. explosive compaction, was employed to the initial stoichiometric powder mixture, without prior heat treatment and the green product was subsequently subjected to a series of heat-treating cycles (920°C, 70 h), in order to obtain the required superconducting properties (post-heat treated ceramic). The microstructure and physical properties of the pre- and post-heat treated ceramics were analyzed and compared using various characterization techniques. X-ray diffraction performed on the pre-heat and post-heat treated ceramics indicated that maximum 123-phase content retained in the former case (pre-heat treated ceramic), whilst DC magnetic susceptibility measurements have shown the characteristic Meissner shielding effect at 99 and 92 K, respectively. Furthermore, the pre-heat treated compacted billet was characterized by a critical current density, J_c equal to 2800 A/cm² at 77 K after suitable annealing at 850°C for 10 h in oxygen stream.     

Measurements of anisotropic thermopower of magnetically aligned YBa2Cu3O7−δ ceramics: evidence of successful texturing techniques

Aligned YBa₂Cu₃O_7−δ ceramics have been obtained using a field of 1 T without being embedded in epoxy. Thermopower, XRD, and SEM are used to characterize the aligned ceramics. For the sample with δ=0.05, the thermopower exhibits a strong anisotropy. The ab-plane thermopower behaves distinctly from that along the c-axis. The ab-plane thermopower shows remarkable similarities to that along the b-axis in an untwinned single crystal. The magnitude and temperature dependence of the c-axis thermopower are almost identical to those of a twinned single crystal. For samples with larger oxygen deficiency, the anisotropy remains. These measurements indicate that these ceramics are well aligned along their crystallographic directions. This also makes available the anisotropic thermopower measurements of ceramic samples by aligning polycrystallites using magnetic forces.     

Mn4+掺杂对BiFeO3陶瓷微观结构和电学性能的影响研究

利用传统的固相反应法制备了BiFe_1-xMn_xO₃ (x= 0-0.20)陶瓷样品, 研究了不同Mn⁴⁺掺杂量对BiFeO₃陶瓷密度、物相结构、显微形貌、 介电性能和铁电性能的影响.实验结果表明:所制备的BiFe_1-xMn_xO₃ 陶瓷样品的钙钛矿主相均已形成,具有良好的晶体结构, 且在掺杂量x=0.05附近开始出现结构相变.随着Mn⁴⁺添加量的增加, 体系的相结构有从菱方钙钛矿向斜方转变的趋势,且样品电容率大幅度增大, 而介电损耗也略有增加;在测试频率为10⁴ Hz条件下, BiFe_0.85Mn_0.15O₃ (ε_r=1065)的 ε_r是纯BiFeO₃ (ε_r=50.6)的22倍; 掺杂后样品的铁电极化性能均有不同程度的提高,可能是由于Mn⁴⁺稳定性优于 Fe³⁺,高价位Mn⁴⁺进行B位替代改性BiFeO₃陶瓷, 能减少Bi³⁺挥发,抑制Fe³⁺价态波动,从而降低氧空位浓度,减小样品的电导和漏电流.     

Oxygen ion diffusion in perovskite-type oxides determined by permeation and by relaxation measurements

Oxygen ion diffusion in oxides of the perovskite-type structure was determined by two methods of measurement: i) stepwise change of temperature or oxygen partial pressure of the gaseous environment of a ceramic sample, and measurement of the relaxation of electrical conductivity or oxygen content, ii) oxygen permeation through a gas dense oxide ceramic pellet from air to argon. The experimental problems and sources of errors, calculation methods of chemical diffusion coefficients and oxide ionic conductivities from these two modes of investigation are discussed. The comparison of relaxation and permeation measurements on 10 oxides of the type A_1−aA′_aM_1−bM′_bO_3−σ (A=La, Pr, Ce; A′=Sr, Ca; M=Mn, Fe; M′=Co, Ni) show advantages of the relaxation method in relation to the experimental performance and possible errors.