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.     

Stability, oxygen permeability and chemical expansion of Sr(Fe,Al)O3 − δ- and Sr(Co,Fe)O3 − δ-based membranes

Perovskite-type SrFe_0.7Al_0.3O_3 − δ and SrCo_0.8Fe_0.2O_3 − δ, and two related dual-phase composites with nominal compositions (SrFeO_3 − δ)_0.7(SrAl₂O₄)_0.3 and (SrCo_0.8Fe_0.2O_3 − δ)_0.7(SrAl₂O₄)_0.3, were comparatively studied employing controlled-atmosphere dilatometry, thermogravimetry, Mössbauer spectroscopy, and measurements of steady-state oxygen permeation fluxes through dense ceramic membranes. The composite materials display lower thermal and chemical expansion compared to the parent single-phase perovskites. The thermal expansion coefficients at 1023-1223 K are however still high, (20-23) × 10^− 6 K^− 1 at atmospheric oxygen pressure and (17-18) × 10^− 6 K^− 1 at p(O₂) = 10 Pa, thus limiting the range of possible membrane reactor configurations. Sr(Co,Fe)O_3 − δ-based materials exhibit extensive vacancy-ordering processes in inert atmospheres, resulting in a slow relaxation of the oxygen nonstoichiometry, chemical expansion and oxygen permeation fluxes. In comparison to Sr(Fe,Al)O_3 − δ, the stability of cobalt-containing ceramics in CO₂ is also poor, which leads to a partial blocking of the membrane surface by decomposition products and degradation of the oxygen transport. Thermogravimetric analysis showed that the interaction with carbon dioxide occurs even at elevated temperatures, up to 1223 K. Under high oxygen chemical potential gradients such as air/(H₂-H₂O), the composite membranes showed kinetically stable operation without bulk decomposition at 1073 K. The kinetic stabilization associated with surface-limited oxygen permeation was confirmed by the conversion-electron Mössbauer spectroscopy analysis of one (SrFeO_3 − δ)_0.7(SrAl₂O₄)_0.3 membrane exposed to dry CH₄ at 1173 K, where no traces of Fe²⁺ and metallic iron were detected in the reduced surface layer.     

On the structural stability and oxygen permeation behavior of inorganic SrCo0.8Fe0.2O3−δ membranes

The high oxygen permeability combined with reasonable structural stability of perovskite-type ABO_3−δ compounds is vital for their potential applications in gas separation, solid oxide fuel cells, sensors, etc. Hence, an attempt is made to develop SrCo_0.8Fe_0.2O_3−δ-based dense membranes with sol-gel-derived oxalates and study their phase stability and oxygen permeation. While X-ray diffraction confirms the presence of a perovskite-type cubic phase above 800 °C, X-ray photoelectron spectroscopy reveals the presence of cobalt and iron in 3+ and 4+ oxidation states with O₂ ²⁻, O₂ ⁻ and O⁻ species. The electrical conductivity increases up to a characteristic temperature and decreases slowly thereafter via pronounced carrier scattering. A 1.5-mm-thick membrane displays reasonable oxygen permeability of 1.05 × 10⁻⁶ mol cm⁻² s⁻¹ at 900 °C but has inadequate stability. Partial substitution of iron with zirconium is shown to improve permeability and stability significantly. Thus, SrCo_0.8Fe_0.15Zr_0.05O_3−δ membrane shows promise for oxygen permeation purposes.

     

Performance and stability of niobium-substituted Ba0.5Sr0.5Co0.8Fe0.2O3 − δ membranes

The phase stability, thermal expansion, electrical conductivity, and oxygen permeation of perovskite-type oxides Ba_0.5Sr_0.5(Co_0.8Fe_0.2)_1 − xNb_xO_3 − δ (x = 0 − 0.2) have been investigated. Room-temperature X-ray diffraction of as-prepared powders indicates that in the investigated compositional range solid solutions are formed. Long-term annealing experiments both in flowing air and nitrogen, at 750 °C, demonstrate that the phase instability observed in parent Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 − δ (BSCF) is suppressed already at the minimum substitution of 5 mol% of niobium for (Co, Fe). Both electrical conductivity and thermal expansion are found to decrease with increasing niobium concentration, which behaviors can be explained by defect chemical considerations, taking into account charge compensation mechanisms by doping BSCF with Nb⁵⁺ donor cations. The oxygen permeation flux of 10 mol% Nb-substituted BSCF, in the range 800-900 °C, is reduced by 10% relative to that found for parent BSCF. Switching from helium to a CO₂-containing purge gas results in a severe reduction or cessation of the oxygen flux. Options are discussed to avoid undesired formation of surface carbonates.     

Broad-band dielectric response of 0.5Ba(Ti0.8Zr0.2)O3–0.5(Ba0.7Ca0.3)TiO3 piezoceramics: soft and central mode behaviour

ABSTRACT

Dielectric properties of 0.5Ba(Ti_0.8Zr_0.2)O₃–0.5(Ba_0.7Ca_0.3)TiO₃ ceramics were probed in the frequency range from 10 Hz to 100 THz in a broad temperature range (10–900 K). Polar soft phonon observed in infrared spectra softens with cooling; however, below 500 K, its frequency becomes temperature independent. Simultaneously, a central mode activates in terahertz and microwave spectra; and it actually drives the ferroelectric phase transitions. Consequently, the phase transitions strongly resemble a crossover between the displacive and order–disorder type. The central mode vanishes below 200 K. The dielectric relaxation in the radiofrequency and microwave range anomalously broadens on cooling below T_C1, resulting in the nearly frequency independent dielectric loss below 200 K. This broadening comes from a broad frequency distribution of ferroelectric domain wall vibrations. Raman spectra reveal new phonons below 400 K, i.e. already 15 K above T_C1. Several weak modes are detected in the paraelectric phase up to 500 K in Raman spectra. Activation of these modes is ascribed to the presence of polar nanoclusters in the material.     

Ba0.5Sr0.5Co0.8Fe0.2O3-δ晶格缺陷、电性能与氧渗透研究

对新型氧渗透材料Ba0 .5 Sr0 .5 Co0 .8Fe0 .2 O3 -δ(BSCF)进行了O2 TPD表征、非化学计量 (δ)测定、电导率 (σ)测量和氧渗透性能测试的研究 .结果表明 ,经纯氧气氛处理后的BSCF ,其O2 TPD谱存在三个失氧峰 :低温峰对应于晶格中V O 位置上的吸附氧 ,高温区两个峰对应于晶格中两种不同位置的晶格氧 ;σ对温度的实验表明 ,不论在升温还是降温过程中 ,σ在 470℃左右均出现极大值 ,可能与BSCF体系的δ值随温度变化相关 ;氧渗透实验表明 ,850℃以上 ,BSCF的氧渗透率JO2 较大 ,达到 1μmol/cm2 s ,活化能较低 ,Ea =63 .1kJ/mol ,而低于 850℃时 ,存在相分解     

Improving La0.6Sr0.4Co0.2Fe0.8O3 − δ cathode performance by infiltration of a Sm0.5Sr0.5CoO3 − δ coating

La_xSr_1 ? xCo_yFe_1 ? yO_3 ? δ (LSCF) represents one of the state-of-the-art cathode materials for solid oxide fuel cells (SOFCs) due primarily to its high ionic and electronic conductivity. In this study, a one-step infiltration process has been developed to deposit, on the surface of a porous LSCF cathode, a thin film (50–100 nm) of Sm_0.5Sr_0.5CoO_3 ? δ (SSC), which is catalytically more active for oxygen reduction. Electrochemical impedance spectroscopy reveals that the SSC coating has dramatically reduced the polarization resistance of the cathode, achieving area-specific resistances of 0.036 Ω cm² and 0.688 Ω cm² at 750 °C and 550 °C, respectively. It has also maintained the stability of LSCF cathodes. In particular, the peak power densities are increased by ~ 22% upon the infiltration of SSC onto the porous LSCF cathodes of our best performing cells. These results demonstrate that a conductive backbone (e.g., LSCF) coated with a catalytic film (e.g., SSC) is an attractive approach to achieving an active and stable SOFC cathode for low-temperature solid oxide fuel cells.     

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.     

Preparation of Hg0.8Cr0.2Ba2CuO4+δ under controlled oxygen and mercury partial pressures

Ba₂CuO₃/HgBa₂CuO_4+δ and Mn₃O₄/Mn₂O₃ couples were employed to control the mercury and oxygen partial pressures, respectively, during the synthesis of chromium doped Hg-1201 phase in the sealed quartz tube. Suitably adjusted conditions allowed us to prepare series of single phase samples of the final composition Hg_0.7Cr_0.2Ba₂CuO_4+δ determined by weight changes and EMA. The oxygen stoichiometry was modified by the oxygen partial pressure in the range of pO₂=0.05–1.59 atm. The X-ray diffraction and magnetic susceptibility study revealed linear dependence of the structural parameters and parabolic one of T_c vs. log pO₂. Multiphase samples, however, form for too high oxygen activity, namely for pO₂=5.16 atm.     

Evaluation of a cobalt-free Ba0.5Sr0.5Fe0.9Nb0.1O3?δ cathode material for intermediate-temperature solid oxide fuel cells

A cobalt-free Ba_0.5Sr_0.5Fe_0.9Nb_0.1O_3??? (BSFNb) perovskite-type oxide was investigated as the cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs) with Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte. XRD results showed that BSFNb cathode was chemically compatible with the electrolyte SDC up to 1,000?°C. The maximum output of anode-supported thin-film SOFC reached 503?mW?cm^?2 at 650?°C when employing humidified H₂ as fuel and static air as oxidizer. The electrode polarization resistance was low as 0.078????cm² at 650?°C, and the activation energy of the electrode polarization resistance was 129.72?kJ?mol^?1. The experimental results indicated that the cobalt-free BSFNb was a promising cathode candidate for IT-SOFCs.     

Cyclic voltammetry characterization of a La0.8Sr0.2Co0.2Fe0.8O3 − δ electrode interfaced to CGO/YSZ

The electrochemical characteristics of a La_0.8Sr_0.2Co_0.2Fe_0.8O_3 − δ cathode electrode interfaced to the CGO layer of a double layer CGO/YSZ electrolyte were studied using cyclic voltammetry, at temperatures of 600 to 850 °C and under oxygen partial pressures ranging from 0.07 to 21 kPa. The aim was to identify the electrochemical processes taking place under cathodic polarization on the basis of differences in the features of the cyclic voltammograms with changing conditions. Depending on temperature, sweep rate and oxygen partial pressure, current peaks appeared both in the forward and backward scans. Furthermore, reversed hysteresis was observed, i.e. higher currents in the backward scan than in the forward scan, with increasing oxygen partial pressure and decreasing temperature. The observed behavior was related to the electrochemical redox of B-sites and concomitant stoichiometry change as well as to the competing reaction of electrochemical oxygen redox, taking also into account the competitive action of chemical reactions occurring in the presence of gaseous oxygen.     

Surface and redox chemistry of Sm0.95Ce0.05Fe1 − xNixO3 − δ perovskites

A new series of perovskite materials with formula Sm_0.95Ce_0.05Fe_1 − xNi_xO_3 − δ (0 ≤ x ≤ 0.10) has been prepared by sol-gel combustion via a citrate precursor route. X-ray diffraction data showed that materials prepared by this method had a single orthorhombic phase belonging to the Pnma (62) space group. The study of powders sintered in air and in reducing atmospheres reveals that these materials do not show phase separation in air (up to 1350 °C) nor under 5% v/v H₂/N₂ (up to 700 °C), but a phase separation of Sm₂O₃ does occur at and above 800 °C under 5% v/v H₂/N₂ without deterioration of the perovskite phase. The surfaces of all the powders (fresh, in-situ reduced and ex-situ reduced) were Sm rich, and multiple oxidation states for Fe were observed. XP analysis of in-situ reduced samples (800 °C and above) shows that metallic Fe forms in all nickel doped materials except x = 0.07. The surface oxygen vacancies and percentages of lattice and adsorbed oxygen for this series of Ni doped materials were determined and the oxygen recapturing ability is explained in terms of the multiple oxidation states of Fe.     

The effect of oxygen and water vapor partial pressures on the total conductivity of BaCe0.7Zr0.1Y0.2O3–δ

Ionics - The effect of oxygen and water vapor partial pressure on the total conductivity of the proton-conducting BaCe0.7Zr0.1Y0.2O3–δ material is investigated in the present work....     

Synthesis and structure of Mg(Fe0.8Ga0.2)2O4−δ film materials

Features of the preparation of magnetic semiconductor films with the composition Mg(Fe_0.8Ga_0.2)₂O_4?δ on a 200-nm-thick silicon substrate are presented. Both a pure substrate surface and one with protective TiO _x layers with a crystallization temperature of 900–1000°C for 30 min were used. The effect of the protective layers on the formation of the surface morphology of the films and their magnetic properties is shown.     

M?ssbauer and magnetic studies of Mn0.1Sr0.2Co0.7Fe2O4 nanoferrite

The magnetic properties of Mn_0.1Sr_0.2Co_0.7Fe₂O₄ nanoferrite with particle size of about 8 nm were investigated using magnetization and Mössbauer spectroscopy measurements. The sample shows a large increase in coercive field from 0.045 kOe at room temperature to about 3.00 kOe at 4 K. Room temperature coercive fields increased with increase in the annealing temperature between 300°C and 800°C. Our results show evidence of transformation from single domain to multi-domain structure with thermal annealing.     

Influence of B2O3 on microstructure and microwave dielectric properties of 0.4Nd(Mg0.4Zn0.1Sn0.5)O3–0.6Ca0.8Sr0.2TiO3 ceramic system

The effects of B₂O₃ on the microstructure and microwave dielectric properties of the 0.4Nd(Mg_0.4Zn_0.1Sn_0.5)O₃–0.6Ca_0.8Sr_0.2TiO₃ ceramic system were investigated with a view to their use in microwave devices. A B₂O₃-doped 0.4Nd(Mg_0.4Zn_0.1Sn_0.5)O₃–0.6Ca_0.8Sr_0.2TiO₃ ceramic system was prepared by the conventional solid-state method. The X-ray diffraction patterns of the B₂O₃-doped 0.4Nd(Mg_0.4Zn_0.1Sn_0.5)O₃–0.6Ca_0.8Sr_0.2TiO₃ ceramic system did not significantly vary with sintering temperature. A 0.5 wt% B₂O₃-doped 0.4Nd(Mg_0.4Zn_0.1Sn_0.5)O₃–0.6Ca_0.8Sr_0.2TiO₃ ceramic system that was sintered at 1350 °C for 4 h had a dielectric constant of 38.3, a quality factor Qf of 35,000 GHz, and a temperature coefficient of resonant frequency of ?4.8 ppm/°C.     

Influence of cold-rolling texture and heating rate on {1 1 0}〈0 0 1〉 development in inhibitor-free 3%Si–Fe sheets

This paper presents cold-rolling and annealing methods to obtain a high-magnetic induction in inhibitor-free 0.1-mm-thick 3% silicon–iron sheets containing 18 or 150 ppm sulfur. In case of the two-step cold-rolling, the sheets containing 150 ppm sulfur showed a strong {1 0 0} final texture at 400 °C/h, and some fraction of {1 1 0} component was observed at 25 °C/h. However, three-step cold-rolling resulted in a sharp {1 1 0}〈0 0 1〉 final texture at 25 °C/h. This is due to the difference in intensity ratio of {1 0 0}〈0 1 1〉 to {1 1 1}〈1 1 2〉 in the cold-rolling texture which influences the nucleation of {1 1 0}〈0 0 1〉 component and the selective growth kinetics of various grains. In case of 18 ppm sulfur, the final texture was mainly composed of a sharp {1 1 0}〈0 0 1〉 component even at 400 °C/h, due to the relatively low segregation concentration.     

Oxygen nonstoichiometry, defect structure and electrical properties of LaFe0.7Ni0.3O3 − δ

Oxygen nonstoichiometry (δ), total conductivity (σ) and thermoelectric power (S) of the LaFe_0.7Ni_0.3O_3 − δ sample have been studied as functions of temperature and oxygen partial pressure. Based on the results of the direct reduction of the sample in hydrogen flow at 1100 °C the absolute oxygen content (3 − δ) has been found to vary from 2.999 to 2.974 in the range of 1273-1373 K and 10^− 3-0.21 atm. The point defect equilibrium models have been proposed and fitted to the set of experimental data in the form of log p(O₂) = f(δ)_T dependences. The values of standard thermodynamic quantities of defect formation reactions have been assessed. The joint analysis of oxygen nonstoichiometry, total conductivity and thermoelectric power has been performed using a small-polaron approach. The values of partial conductivity, partial thermopower and mobilities of electronic charge carriers have been calculated. The p-type semiconducting behavior of LaFe_0.7Ni_0.3O_3 − δ has been explained by the higher mobility values of electron holes than those of electrons in the whole range of thermodynamic parameters studied.     

Transport properties and in-situ Raman spectroscopy study of BaCe0.9Y0.1O3 − δ as a function of water partial pressures

The total conductivity of BaCe_0.9Y_0.1O_3 − δ material was measured under air, in a large p(H₂O) range up to 0.30 bar. The defect concentrations (OH_O^·, V_O^· · and h^·) and electrical conductivities were calculated on the basis of chemical constants (diffusion coefficients and equilibrium constants reported in the past literature) and compared to the experimental data. Protonic transport number as high as 0.8 was found at 700 °C, under air containing 0.30 bar of water, which allows a possible extension of the protonic temperature range of this material using water rich atmosphere. In-situ Raman spectroscopy under wet and dry air was performed from room temperature up to 700 °C in two wavenumber ranges. At low wavenumber, characteristic of lattice vibrations, this study clearly shows that no significant changes occur upon water insertion while at high wavenumbers, characteristic of OH vibrations, two contributions to the OH vibrations were found. This is discussed in terms of proton environment and transient hydrogen bonds. Moreover, this in situ study confirms that, at moderate p(H₂O), water insertion becomes significant at temperature below 650 °C.