颗粒弥散Ba0.5Sr0.5Co0.8Fe0.2O3-δ基复合透氧膜材料的制备、结构与性能研究

通过外加等摩尔分数的ZrO2 和过量BaO,原位生成一定比例的BaZrO3 基第二相颗粒复合的制备法,对具有较高氧渗透率的Ba0. 5Sr0. 5Co0. 8Fe0. 2O3-δ进行了原位引入Ba(Sr)Zr(CoFe)O3 第二相颗粒的改性研究发现引入的第二相颗粒不但具有抑制基相晶粒的生长、细化和均化基相晶粒的作用,同时减小了基相高温氧脱量而起到稳定相结构的作用.引入5%ZrO2 和5%过量BaO复合物的抗弯强度比纯相提高68%;引入10%Zr和10%过量BaO、20%ZrO2 和20%过量BaO的复合物(均为摩尔分数),在850℃以下具有更高的氧渗透率;合物的电导率随第二相颗粒含量的增加而减小;氧脱附量较小的复合物的载流子浓度相对稳定,因而升降温过中电导率热回滞峰较小.     

High-temperature compressive creep behaviour of the perovskite-type oxide Ba0.5Sr0.5Co0.8Fe0.2O3 − δ

Compressive creep tests have been performed on perovskite-type Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 ? δ ceramics. The activation energy, stress exponent and inverse grain size exponent of the steady-state creep rates are evaluated at p(O₂) = 0.21 ? 10⁵ Pa and 0.01 ? 10⁵ Pa in the stress, temperature and grain size ranges 5–20 MPa, 1078–1208 K and 2.5–17.4 µm, respectively. The results indicate that the creep rate of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 ? δ is controlled by diffusion of cations via both the oxide lattice (bulk diffusion) and along grain boundaries. The creep rate of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 ? δ increases profoundly by more than one order of magnitude at 1153–1178 K, which is tentatively linked with the onset of the hexagonal-to-cubic phase transition in this compound.     

Mechanical properties of La0.58Sr0.4Co0.2Fe0.8O3-δ membranes

In this paper, we report on the mechanical properties of a La_0.58Sr_0.4Co_0.2Fe_0.8O_3-δ perovskite material. We use ring-on-ring bending tests with disk-shaped samples and depth-sensitive micro-indentation. In particular, the temperature dependency of fracture stress and elastic behavior are addressed. The fracture load is measured to be ～ 40% higher at room temperature (RT) than at 800 °C, which is due to the ferro-elasticity of material at RT. The stiffness shows an increase of about 50% above 600 °C and 700 °C in vacuum and air, respectively. The effect is attributed to a rhombohedral to cubic phase transition, which is not fully reversible upon cooling. The changes in phase composition with temperature are also confirmed by in-situ high temperature XRD. The transition appears to be associated with a change of heat capacity.     

Oxygen transport properties of dense and porous (La0.8Sr0.2)0.99Co0.8Ni0.2O3-δ

We have determined k_ex and D_chem for (La_0.8Sr_0.2)_0.99Co_0.8Ni_0.2O_3-δ by the use of electrical conductivity relaxation on a dense sample and by applying the ALS model to measured AC impedance spectrum on a porous electrode. Extracting k_ex and D_chem from the methods resulted in comparable values. k_ex and D_chem also agreed well with literature values on La_0.8Sr_0.2CoO_3-δ, indicating that nickel substitution does not change the oxygen transport properties. k_ex of the porous sample was further found to decrease with a five times higher rate than D_chem when measured by using an Electrochemical Impedance Spectroscopy (EIS) over several days.     

The effect of iron doping in La0.8Sr0.2Fe0.05Co0.95O3-δ perovskite

La0.8Sr0.257Fe0.05Co0.95O3- perovskite is investigated by 57Fe transmission and emission Mössbauer spectroscopy, X-ray diffraction, AC magnetic susceptibility and magnetotransport measurements. Temperature dependence of the 57Fe Mössbauer isomer shift, quadrupole splitting, magnetic hyperfine field, line broadening, and relative spectral area is presented in a detailed manner for La0.8Sr0.257Fe0.05Co0.95O3- . The oxidation state of iron is determined to be Fe3+, and the presence of preferential electronic charge compensation Fe3+ Fe4+ over that of Co3+ Co4+ is excluded. Relaxation of iron magnetic moments reflected by the 57Fe Mössbauer spectra of La0.8Sr0.257Fe0.05Co0.95O3- are interpreted as evidence for the existence of superparamagnetic like Co clusters and a corresponding cluster glass magnetic phase formed below T 65 K.     

YBa2Cu3O7-δ薄膜厚度在多层异质结构(Ag/Ba0.1Sr0.9TiO3/YBa2Cu3O7-δ/LaAlO3)中对Ba0.1Sr0.9TiO3介电性能的影响研究

铁电/超导(Ba, Sr)TiO3/YBa2Cu3O7-δ异质结在可调谐微波器件方面具有非常好的应用前景.我们采用1.2°斜切LaAlO3基片,以脉冲激光沉积法(PLD)制备出性能较好的Ba0.1Sr0.9TiO3/YBa2Cu3O7-δ (BST/YBCO)异质薄膜.并进一步研究了YBCO薄膜厚度对BST性能的影响.研究发现当YBCO薄膜厚度增加到180nm附近时,其生长模式由二维step-flow转变为三维岛状模式,严重损害了在YBCO上面生长的BST薄膜的介电性能.具体表现在:BST薄膜的介电常数和可调谐率明显降低,介电损耗和漏电流却大幅度上升.通过测量电容与温度的关系,以应力效应模型对这一实验现象作出解释,认为YBCO薄膜厚度超过临界值,生长模式的转变促使晶格失配应力在YBCO和BST薄膜中得到释放,这导致BST/YBCO界面粗糙,以及BST薄膜中产生了大量的位错和缺陷,BST薄膜的性能因而大为降低.此外,通过对完全相同条件生长的单层YBCO薄膜的表面形貌进行了AFM研究,测试结果进一步验证了YBCO薄膜厚度增加到180nm时,其表面变得异常粗糙,均方根粗糙度(RMS)从120nm厚度时的3nm增加到180nm厚度时的9nm.因此,我们提出:通过严格控制底层YBCO薄膜的厚度,进而控制它的生长模式,能够非常有效地提高BST薄膜的介电性能.     

钙钛矿型氧载体SrCo_(0.8)Fe_(0.2)O_(3-δ)制氧性能的实验研究

钙钛矿型金属氧化物是优良的制备供富氧燃烧所需的O_2/CO_2的氧载体,本文采用柠檬酸法制备系列SrCo_(1-x)Fe_xO_(3-δ)(x=0.2,0.4,0.6,0.8)钙钛矿型氧化物,并采用X射线衍射分析来表征SrCo_(0.8)Fe_(0.2)O_(3-δ)(SCF182)反应前后的物相变化和晶体结构.同时在固定床上选择不同的运行条件对SCF182的释氧性能进行研究,包括吸附温度、吸附时间、脱附温度和循环特性.结果表明,SCF182的最佳吸附温度和脱附温度均为850℃,最佳吸附时间为1 h,循环性能良好,是可以为富氧燃烧提供稳定的O_2/CO_2循环气体的良好材料。     

Pb2Sr2Y0.5Ca0.5Cu3O8＋δ超导体中氟代顶氧的结构与性质

合成了掺Ｆ的Ｐｂ系超导体，确认了Ｆ替代其中ＣｕＯ５四方锥体的顶氧。指出Ｆ代顶氧改善Ｔｃ的机理来自晶体结构，化学键及电子态的变化。改善零电阻温度Ｔｃｕ主要是掺Ｆ体系所产生的热力学效应。     

Co掺杂的YBa2Cu2O6+δ的氧非计量和氧渗透性能研究

研究钴离子部分取代铜离子对YBa2 Cu3 O6+δ的氧非计量值δ和氧渗透率的影响 .对于钴替代的样品 ,氧非计量的绝对值变大 ,且其数值不再随温度和氧分压的变化发生显著变化 .YBa2 Cu2 CoO6+δ样品在中、高温具有可观的氧渗透率 .对于厚度为 1.2mm的致密YBa2 Cu2 CoO6+δ样品 ,在 85 0℃时 ,只要在样品两端施加较小的氧分压差(PO2 =2 1.2kPa、PO2 =10 1Pa) ,其氧渗透率即可达 5 7μmol/cm2 s,明显高于YBa2 Cu3 O6+δ的氧渗透率 (31μmol/cm2s) .YBa2 Cu2 CoO6+δ的高氧渗透率在结构上可被归结为位于晶胞基面上的氧离子和氧空位的均匀分布     

Defect structure of quenched γ-BICOVOX by combined X-ray and neutron powder diffraction

A detailed investigation of the defect structure of the Co doped BIMEVOX solid electrolyte, Bi₂V_{1 − x}Co_xO_{5.5 − 3x/2} (x = 0.1 and x = 0.2), quenched from high temperature, has been carried out using X-ray and neutron powder diffraction data measured at room temperature. The structure is built up from alternating layers of [Bi₂O₂]_n²ⁿ⁺ and [V_{1 − x}Co_xO_{3.5 − 3x/2}]_n²ⁿ⁻ with disorder limited to the vanadate layer. The ideal V/Co co-ordination is octahedral with corner sharing of equatorial oxygens. The refinements show that the true structure is distorted, with disorder in both apical and equatorial oxygens and oxygen vacancies concentrated in the equatorial positions. Detailed analysis of the oxygen site occupancies reveals two main types of V/Co co-ordination viz. distorted octahedral and distorted tetrahedral. The majority of the sites in both compositions are tetrahedral.     

Electrical conductivity and defect structure of Mg-doped Cr2O3

The electrical conductivity of Cr₂O₃ nominally doped with 2 mol% MgO has been studied by the four point a.c. technique as a function of the oxygen activity (O₂ + Ar, CO + CO₂ and H₂ + H₂O) in the temperature range 400–1200 °C. It is concluded that Cr₂O₃ doped with MgO is an extrinsic conductor and that the dissolved Mg-dopant is compensated by the formation of electron holes at near atmospheric oxygen pressures and by oxygen vacancies (or possibly interstitial chromium ions) at highly reduced oxygen activities (in CO + CO₂ and H₂ + H₂O gas mixtures). In H₂ + H₂O mixtures Mg-doped chromia also dissolves hydrogen as protons and significantly affects the defect structure and electrical conductivity. The defect structure of the oxide under various conditions is discussed.     

Crystal structure, electrical and magnetic properties of La1 − xSrxCoO3 − y

The crystal structure and properties of La_{1 − x}Sr_xCoO_{3 − y} with strontium contents ranging from x = 0.1 to x = 0.7 have been studied. The lattice parameters were measured as a function of temperature (4.2–400 K) and the crystal structure was found to change from rhombohedral (at low temperatures and values of x) to cubic. While LaCoO₃ is paramagnetic the oxides in the composition range 0.2 < x < 0.6 are soft ferromagnets. The strontium additions are compensated by the formation of Co⁴⁺ (cobalt ions with one positive effective charge, Co_Co^.) and oxygen vacancies (V_o^..). From the results it is concluded that the relative importance of oxygen vacancies increases with increasing temperature and decreasing oxygen activity. As a result the concentration of electronic charge carriers — and the resultant electrical conductivity — decrease with increasing temperature. The defect structure is discussed and it is concluded that defect associations — probably between oxygen vacancies and strontium ions — and formation of microdomains of perovskite-related phases are important aspects of the overall structure of these perovskite phases.     

Radiation induced defects in SiO 2

The main luminescent centers in SiO 2 films are the red luminescence R (650 v nm; 1.85 v eV) of the non-bridging oxygen hole center (NBOHC) and the twofold-coordinated (divalent) silicon with a blue B (460 v nm; 2.7 v eV) and a UV band (285 v nm; 4.4 v eV). Especially the latter ones are produced under irradiation, but from existing precursors assumed as silicon related oxygen deficient centers (SiODC). Therefore, in order to prove these models we compare a direct oxygen implantation with a direct silicon implantation into SiO 2 layers. The main result is: implanting oxygen increases the red band R but does not affect the blue band B. Silicon surplus increases the amplitude of the blue (B) luminescence, but reduces the amplitude of the red (R) one. Studying the cathodoluminescence dose dependence of these blue and red bands we have established defect transformation kinetics in SiO 2 including six main defects and precursors as well as the mobile oxygen as the main transmitter between precursors and the radiation induced defects. The kinetics is described by eight rate equations which predict the dose dependence of the red (R) and blue (B) luminescence intensities and their temperature dependences very well.     

Ionic and electronic conductivity in CaTi0.9fe0.1o3-δ

Abstract

The electrical conductivity of CaTi_1?x Fe _x O_3-δ (x = 0.1) was measured by an alternating current van der Pauw technique versus oxygen partial pressure (10^?30-1 atm) and temperature (450–1200°C). The results were interpreted to reflect n-type, ionic and p-type conductivity at respectively low, intermediate and high oxygen partial pressures. The apparent activation enthalpy for the ionic conductivity, interpreted to reflect the mobility of oxygen vacancies, was 0.87 eV. The enthalpy of intrinsic formation of electronic defects (apparent band gap E _g) was 3eV. The results are compared with literature data for CaTi_0.8Fe_0.2O_3-δ and with Fe-substituted SrTiO₃ and discussed in terms of iron-oxygen vacancy association and ordering.     

Induction and control of dielectric relaxation properties in Fe-doped nonstoichiometric SrTiO3 ceramics

The dielectric properties of Fe-doped Ti-rich SrTiO₃ ceramics at both A and B sites were investigated. For A site doping, we found one structural phase transition associated with the substitution of smaller Fe ions, and two sets of dielectric relaxations ascribed to oxygen vacancies and hopping conduction between Fe²⁺ and Fe³⁺, respectively. Cole-Cole relation shows that both thermally activated dielectric relaxation behaviors mainly originate from the grain boundary. However, for B site doping, they are not observed in the measured temperature range since both the short-range diffusion of oxygen vacancies and electron conduction become the long-range migration, which indicates that the additional conductive channels are opened when Fe ion doping changes from A to B site. The results provide an experimental basis for adjusting dielectric properties in paraelectric materials.     

Effect of nickel substitution on defect chemistry, electrical properties, and dimensional stability of calcium-doped yttrium chromite

The effect of nickel substitution on defect chemistry, electrical properties, and dimensional stability of calcium-doped yttrium chromite was studied for use as an interconnect material in high temperature solid oxide fuel cells (SOFCs). The compositions of Y_0.8Ca_0.2Cr_1 − xNi_xO_3 ± δ (x = 0-0.15), prepared using the glycine nitrate process, showed single phase orthorhombic perovskite structures over a wide range of oxygen partial pressures (4.6 × 10^− 20 atm ≤ pO₂ ≤ 0.21 atm at 900 °C). X-ray diffraction (XRD) analysis indicated that most of the nickel ions replacing chromium ions are divalent and act as acceptor dopants, leading to a substantial increase in conductivity. In particular, the conductivity at 900 °C in air increased from 10 S/cm to 34 S/cm with 15% nickel substitution, and an increase in charge carrier density was confirmed by Seebeck measurements, which validated the predominant Ni²⁺ oxidation state. A point defect model was derived, and the relationship between electrical conductivity and oxygen partial pressure was successfully fitted into the proposed model. The defect modeling results indicated that nickel substitution improves the stability of calcium-doped yttrium chromite toward reduction and suppresses the oxygen vacancy formation, which results in significantly increased electrical conductivity in reducing environment. The electrical conductivity of Y_0.8Ca_0.2Cr_0.85Ni_0.15O_3 ± δ at 900 °C in reducing atmosphere (pO₂ = 10^− 17 atm) was 5.8 S/cm, which was more than an order of magnitude higher than that of Y_0.8Ca_0.2CrO_3 ± δ (0.2 S/cm). Improved stability in reducing atmosphere was further confirmed by dilatometry measurements showing reduced isothermal “chemical” expansion, and the isothermal expansion in reducing atmosphere (pO₂ = 10^− 17 atm) at 900 °C decreased from 0.07% for Y_0.8Ca_0.2CrO_3 ± δ to 0.03% for Y_0.8Ca_0.2Cr_0.85Ni_0.15O_3 ± δ. Based on these results, enhanced electrical performance and mechanical integrity is expected with nickel substitution on calcium-doped yttrium chromite in SOFC operating conditions.     

The luminescence of ZnO film grown on GaAs interlayer by PA-MOCVD

ZnO film was firstly prepared by PA-MOCVD method on the substrate pre-coated with GaAs interlayer. Hall measurement found that the GaAs interlayer had important effects on the electrical behavior of the ZnO film. It could make the ZnO film convert to p-type conductivity. The XPS results confirmed that the acceptor was arsenic. And the acceptor level was 130 meV above the ZnO valence band maximum. Low-temperature PL measurement was introduced to investigate the optical properties of both as-grown n-type and arsenic doped p-type ZnO films. Then, based on this technology, ZnO homojunction light emitting device (LED) was fabricated with arsenic doped p-type ZnO and unintentionally doped n-type ZnO on GaAs/p⁺-Si substrate. Its current-voltage (I-V) character showed a typical rectification behavior, which was different from the n-ZnO/p⁺-Si structure. The UV-visible (385-580 nm) electroluminescence was detected under relatively low current injection condition from the n-ZnO/p-ZnO/p⁺-Si LED.     

Growth,structure and physical properties of gadolinium doped Sr2IrO4 single crystal

A series of Gd-doped Sr₂IrO₄ single crystals were grown using a flux method. Analysis of the temperature-dependent resistance of these crystals reveals that these samples show two-dimensional weak localization at 150 to 300 K, while three-dimensional variable range hopping (VRH) behavior is observed at temperatures lower than 150 K. Two localization lengths are observed in the VRH behavior, with a transition temperature of around 88 K. Correspondingly, temperature-dependent magnetization observations along the ab-plane reveal magnetic anomalies at both 150 and 85 K. This work demonstrates the correlation between the electrical and magnetic properties of 5d transition-metal compounds.