Effect of microstructure on oxygen permeation of Ba0.5Sr0.5Co0.8Fe0.2O3−δ and SrCo0.8Fe0.2O3−δ membranes

The effect of grain size on oxygen permeation properties of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ (BSCF) and SrCo_0.8Fe_0.2O_3?δ (SCF) membranes was investigated by variation of the dwell time. The membrane microstructure was examined by field-emission scanning microscopy (FE-SEM) and then evaluated using a statistical approach. With longer dwell times the grain growth was stimulated and leaded to grains with a narrower size distribution. The grains of SCF (average size from 11.3 to 19.9 μm) were found to be smaller than those of BSCF (average size from 13.9 to 41.3 μm). The oxygen permeation flux of BSCF membranes was found to be independent of grain size in the range from 24 to 42 μm. However, membranes with smaller grains (13.9 μm) show a decreased oxygen permeation flux. For the SCF membranes a decrease in permeation flux with larger grains was observed for average grain sizes between 11.3 and 19.9 μm. By transmission electron microscopy (TEM) formation of an oxygen ordered SrCo_0.8Fe_0.2O_2.5 brownmillerite by-phase could be observed at the oxygen-depleted sweep side of the membrane.     

Ferroelastic deformation of La0.58Sr0.4Co0.2Fe0.8O3−δ under uniaxial compressive loading

The mechanical deformation of lanthanum strontium cobalt ferrite under uniaxial compression was investigated at various temperatures. The material revealed a rather complex mechanical behaviour related to its ferroelasticity and stress–strain curves obtained in the 1st and 2nd loading cycles were completely different. A distinctive ferroelastic creep was observed at 293 K whilst typical ferroelastic stress–strain curves were obtained in the temperature range from 473 K to 873 K. At 1073 K, high-temperature creep deformation was observed instead of the ferroelastic deformation. The apparent Young's modulus was evaluated in various ways; the modulus determined from the last unloading curve ranged between 85 and 120 GPa. The obtained critical stress monotonically decreases from about 80 MPa to zero with increasing temperature, corresponding to the behaviour of the remnant strain. The presented results indicate that the importance of an appropriate consideration of the loading history in the practical application of these ferroelastic materials.     

Electrical properties of (La0.9Ca0.1)(Co1−xNix)O3−δ cathode materials for SOFCs

Modified perovskite ceramics (La_0.9Ca_0.1)(Co_1?xNi_x)O_3?δ (x = 0–0.3) cathodes for solid oxide fuel cells (SOFCs) were synthesized by solid state reaction. The lattice parameters, electrical conductivity, activation energy, and microstructures of these specimens were investigated systematically in this study. The results exhibited that all specimens are rhombohedron structures and their tolerance factors were greater than 0.97, indicating that the perovskite was not distorted by Ni²⁺ cation substitution for the B site of (La_0.9Ca_0.1)CoO_3?δ. The microstructures of the (La_0.9Ca_0.1)(Co_1?xNi_x)O_3?δ specimens showed good densification, and were well-sintered, with few pores. The electrical conductivity behavior conformed to the nature of a semiconductor, for all specimens. As x = 0.1, the electrical conductivity reached the maximum value of 750.3 S/cm at 800 °C, and the activation energy calculated from the Arrhenius plot of the electrical conductivity versus the reciprocal of temperature is 7.1 kJ/mol.The novelty of this study is its introduction of the concept of defect chemistry to explain the relationship between compensation mechanisms and electrical conductivity. The information gleaned regarding charge compensation mechanisms and defect formation may be valuable for a better understanding of the cathode of (La_0.9Ca_0.1)(Co_1?xNi_x)O_3?δ ceramics used for SOFCs. Moreover, the information about oxygen content versus temperature is useful for expressing the relationship between electrical conductivity and composition. Therefore, we also used thermogravimetric analysis combined with the room-temperature oxygen content which was determined by iodometric titration to investigate the oxygen content from room temperature to high temperature, in air. Based on the experimental results, the (La_0.9Ca_0.1)(Co_0.9Ni_0.1)O_3?δ specimen shows high electrical conductivity. Consequently, it is identified as a promising candidate for cathode SOFC applications.     

Electrical and mechanical characterization by instrumented indentation technique of La0.85Sr0.15Ga0.8Mg0.2O3−δ electrolyte for SOFCs

La_0.85Sr_0.15Ga_0.8Mg_0.2O_3?δ pellets obtained by the polymeric organic complex solution method, isostatic pressing and sintering at 1350 °C have been electrical and mechanically studied. Electrical measurements evidenced reasonable ionic conductivities (0.01 S cm^?1 at 800 °C), which were comparable to those reported for the La_1?xSr_xGa_1?yMg_yO_3?δ prepared by other synthesis methods. On the other hand, the mechanical properties (elastic modulus, E and hardness, H) have been determined at micro/nanometric scale using the instrumented indentation technique. While E did not vary significantly with the increasing indentation depth (h), H values strongly decreased with the indentation depth up to 500 nm. For h > 500 nm, both mechanical properties remained almost constant, thus obtaining E = 271 ± 6 GPa and H = 13.2 ± 0.4 GPa. Finally, the residual imprints and fracture mechanisms have been observed by atomic force microscopy (AFM).     

Influence of drying conditions and plasticizer-to-binder ratio on the water-based tape casting of La0.6Sr0.4Co0.2Fe0.8O3−δ

Tape casting is a flexible technique for manufacturing scalable ceramic sheets. This study fabricated La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF6428) tapes using water-based tape casting. A high molecular weight plasticizer, polyethylene glycol 4000, was chosen to balance flexibility and mechanical strength. Adjusting the plasticizer-to-binder ratio (R-value) and increasing relative humidity during drying led to crack-free and flawless green tapes of 330 µm. The uniform polymer matrix improved homogeneity and consistency as well. An applicable suspension formulation was developed for the water-based fabrication of LSCF tapes for continuous production.     

Mechanical behavior of ferroelastic porous La0.6Sr0.4Co0.2Fe0.8O3−δ prepared with different pore formers

The present work investigated the mechanical behavior of porous La_0.6Sr_0.4Co_0.2 Fe_0.8O_3−δ LSCF under uniaxial compression. The porous (LSCF) samples with the same grain size but different porous structures with 1.5–41% of porosity were prepared using three different pore formers. All the samples had ferroelastic domains and exhibited ferroelastic mechanical behaviors under uniaxial compression. Initial and loading moduli as well as critical stress monotonically decreased and remnant strain increased with increasing the porosity. The initial modulus can be determined by the actual porosity regardless of porous structure or grain size, whereas the other properties were more sensitive to experimental condition such as loading rate and maximum applied stress. Compressive fracture strength could be significantly influenced by porous structure.     

Ce0.9Gd0.1O1.95 supported La0.6Sr0.4Co0.2Fe0.8O3−δ cathodes for solid oxide fuel cells

Lanthanum-based iron- and cobalt-containing perovskite has a high potential as a cathode material because of its high electro-catalytic activity at a relatively low operating temperature in solid oxide fuel cells (SOFCs) (600–800). To enhance the electro-catalytic reduction of oxidants on La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ (LSCF), Ga doped ceria (Ce_0.9Gd_0.1O_1.95, GDC) supported LSCF (15LSCF/GDC) is successfully fabricated using an impregnation method with a ratio of 15 wt% LSCF and 85 wt% GDC. The cathodic polarization resistances of 15LSCF/GDC are 0.015 Ω cm², 0.03 Ω cm², 0.11 Ω cm², and 0.37 Ω cm² at 800 °C, 750 °C, 700 °C, and 650 °C, respectively. The simply mixed composite cathode with LSCF and GDC of the same compositions shows 0.05 Ω cm², 0.2 Ω cm², 0.56 Ω cm², and 1.20 Ω cm² at 800 °C, 750 °C, 700 °C, and 650 °C, respectively. The fuel cell performance of the SOFC with 15LSCF/GDC shows maximum power densities of 1.45 W cm^?2, 1.2 W cm^?2, and 0.8 W cm^?2 at 780 °C, 730 °C, and 680 °C, respectively. GDC supported LSCF (15LSCF/GDC) shows a higher fuel cell performance with small compositions of LSCF due to the extension of triple phase boundaries and effective building of an electronic path.     

Partial oxidation of methane in BaCe0.1Co0.4Fe0.5O3−δ membrane reactor

A new perovskite material, BaCe_0.1Co_0.4Fe_0.5O_3?δ used as dense oxygen permeable membrane for partial oxidation of methane (POM) reaction was investigated. In order to improve the synergetic effects between membrane and catalyst, LiLaNiO/γ-Al₂O₃ catalyst was directly packed onto the surface of the membrane to carry out POM. In BaCe_0.1Co_0.4Fe_0.5O_3?δ membrane reactor, high oxygen permeation flux, high CH₄ conversion and CO selectivity were obtained. At 950 °C, oxygen flux of 9.5 ml cm^?2 min^?1, CH₄ conversion of 99% and CO selectivity of 93% were achieved with a membrane thickness of 1.0 mm. There was an induction process at the initial stage of POM, which was related to the reduction of NiO to Ni⁰ in LiLaNiO/γ-Al₂O₃ catalyst. Experiments illustrated that higher reaction temperature would shorten the induction time. During continuously operating for 1000 h at 875 °C, no degradation of performance of the membrane reaction was observed. SEM characterization also demonstrated that the membrane disc maintained an integral structure without any cracks after long-term operation.     

Electrochemical performance and chemical stability of proton-conducting BaZr0.8−xCexY0.2O3−δ electrolytes

Protonic ceramic fuel cells (PCFCs) using BaZr_0.8−xCe_xY_0.2O_3−δ (BZCY) as electrolyte materials have attracted widespread attention because of their high performance at reduced temperature. However, there are few systematic studies on both the performance and stability of BZCY materials. In this paper, we report our work on the electrochemical performance and chemical stability of BaZr_0.8−xCe_xY_0.2O_3−δ (x = 0, 0.1, 0.3, 0.5, and 0.7) series. The results show that electronic hole conductivity decreases with increasing Ce⁴⁺ content, especially at high temperature. In addition, H₂ atmosphere reduces the conductive activation energy of BZCY. On the contrary, air atmosphere causes serious electronic leakage. These effects are also reflected in the operation of PCFCs, that is, the higher the Ce⁴⁺ content, the higher the open-circuit voltage and output power density. However, low Ce⁴⁺ content may stabilize the materials in CO₂ atmosphere. At 700°C, an anode-supported PCFC based on BaZr_0.1Ce_0.7Y_0.2O_3−δ electrolyte, using humid H₂ fuel, gives a peak power density of 1.0 W cm⁻². At 600°C, BaZr_0.8Y_0.2O_3−δ and BaZr_0.7Ce_0.1Y_0.2O_3−δ show a good stability in CO₂-containing atmosphere.     

Influence of processing parameters on the electrical response of screen printed SrFe0.6Ti0.4O3−δ thick films

A screen printing ink of SrFe_0.6Ti_0.4O_3?δ (STFO60) nanopowders produced by Self-propagating High-temperature Synthesis (SHS) was used to produce gas sensors with high level of reproducibility at low cost. The stability and rheology of the produced ink were studied in order to obtain high quality, highly reliable films. The electrical characteristics of the sensors as a function of the firing temperature and thickness of the sensing layer were investigated. The best results were obtained stabilizing the powder with lauric acid. Laboratory bench and on-road oxygen tests demonstrated that the response of 30 μm STFO60-based resistive sensors is comparable with the one of a commercial oxygen probe.     

Ferroelastic mechanical behaviour of porous La0.6Sr0.4Co0.2Fe0.8O3−δ

The present study investigates the mechanical behaviour of ferroelastic La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ with porosity ranging from 0.9% to 26.1% under uniaxial compression at room temperature. Both dense and porous samples have ferroelastic domains and exhibit ferroelastic mechanical behaviour. The apparent modulus, compressive strength and critical stress of the material dramatically decrease with increasing porosity, exhibiting exponential relationships. Comparison of the mechanical behaviours of samples with similar porosity but different porous structures reveals that the ferroelastic mechanical behaviour depends not only on porosity but also structural factors such as pore size and distribution.     

Oxygen permeation through dense La0.1Sr0.9Co0.8Fe0.2O3−δ perovskite membranes: Catalytic effect of porous La0.1Sr0.9Co0.8Fe0.2O3−δ layers

The oxygen permeation performance of a number of La_0.1Sr_0.9Co_0.8Fe_0.2O_3−δ (LSCF1982)-based membranes, consisting of dense LSCF1982 layer with/without porous LSCF1982 layer, was analyzed on the basis of the thickness of the dense layer and catalytic effect of the porous layer. A 0.27 mm thick dense membrane gives oxygen permeation flux ($J_{O_2}$) of 2.33 sccm min⁻¹ cm⁻² at 900 °C, which is increased to 3.55 sccm min⁻¹ cm⁻² on applying a porous layer of LSCF1982 onto the dense membrane. The membrane gives a stable flux for 300 h. The flux was further improved by reducing the thickness of the dense LSCF1982 layer and at 950 °C a flux of 4.47 sccm min⁻¹ cm⁻² is obtained with 0.012 mm thick membrane.     

Electrochemical and microstructural characteristics of nanoperovskite oxides Ba0.2Sr0.8Co0.8Fe0.2O3−δ (BSCF) for solid oxide fuel cells

Nanoperovskite oxides, Ba_0.2Sr_0.8Co_0.8Fe_0.2O_3?δ (BSCF), were synthesized via the co-precipitation method using Ba, Sr, Co, and Fe nitrates as precursors. Next, half cells were fabricated by painting BSCF thin film on Sm_0.2Ce_0.8O_x (samarium doped ceria, SDC) electrolyte pellets. X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical impedance spectroscopy (EIS) measurements were carried out on the BSCF powders and pellets obtained after sintering at 900 °C. Investigations revealed that single-phase perovskites with cubic structure was obtained in this study. The impedance spectra for BSCF/SDC/BSCF cells were measured to obtain the interfacial area specific resistances (ASR) at several operating temperatures. The lowest values of ASR were found to be 0.19 Ω cm², 0.14 Ω cm² 0.10 cm², 0.09 Ω cm² and 0.07 Ω cm² at operating temperatures of 600 °C, 650 °C, 700 °C, 750 °C and 800 °C, respectively. The highest conductivity was found for cells sintered at 900 °C with an electrical conductivity of 153 S cm^?1 in air at operating temperature of 700 °C.     

Synthesis,CO2-tolerance and rate-determining step of Nb-doped Ce0.8Gd0.2O2−δ–Pr0.6Sr0.4Co0.5Fe0.5O3−δ ceramic membranes

In this work, CO₂-tolerant Ce_0.8Gd_0.2O_2δ–Pr_0.6Sr_0.4Co_0.5Fe_0.5−xNb_xO_3−δ (CG–PSCF_0.5−xN_x; x=0–0.125) dual-phase dense oxygen permeation membranes were successfully developed. The crystal structure, microstructure, oxygen permeability, rate-determining step and CO₂ tolerance were systematically investigated. The experimental results showed that the increase in CG content improved oxygen permeability and CO₂ tolerance. Thermogravimetry–differential-scanning-calorimetry analysis, X-ray photoelectron spectra and oxygen permeation tests indicated that the increase in Nb content caused a slight decrease in oxygen permeability, while the long-term CO₂ resistance can be improved significantly. According to the adopted permeation model, the weight ratio and thickness affect the oxygen permeability and permeation resistance distribution. By examining the distribution of three permeation resistances, we identified the rate-determining step and then optimized the weight ratio of the two phases, as well exploring the effects of thickness on oxygen permeability. All these experiments confirm that CG–PSCF_0.5−xN_x dual-phase membranes have great CO₂ tolerance and potential application in oxy-fuel combustion.     

Creep behavior of porous La0.6Sr0.4Co0.2Fe0.8O3-δ substrate material for oxygen separation application

Advanced oxygen transport membrane designs consist of a thin functional layer supported by a porous substrate material that carries mechanical loads. Creep deformation behavior is to be assessed to warrant a long-term reliable operation at elevated temperatures. Aiming towards an asymmetric composite, the current study reports and compares the creep behavior of La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) perovskite porous substrate material with different porosity and pore structures in air for a temperature range of 800–1000?°C. A porosity and pore structure independent average stress exponent and activation energy are derived from the deformation data, both being representative for the LSCF material. To investigate the structural stability of the dense layer in an asymmetric membrane, sandwich samples of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF) and La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) with porous substrate and dense layers on both side were tested by three-point bending with respect to creep rupture behavior of the dense layer. Creep rupture cracks were observed in the tensile surface of BSCF, but not in the case of LSCF.     

Thermochemical expansion of mixed-conducting (Ba,Sr)Co0.8Fe0.2O3−δ ceramics

The thermal and chemical expansion of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) and SrCo_0.8Fe_0.2O_3−δ (SCF) mixed ionic-electronic conductors were studied in combination with oxygen nonstoichiometry (δ) at 298–1223 K and p(O₂) = 10⁻⁴ to 1.00 atm. In order to minimize the effects of phase separation or oxygen-vacancy ordering processes, the data were collected in dynamic cooling mode using dense ceramic samples. The procedure was justified by a very fast equilibration at given p(O₂) in high-temperature range demonstrated for ceramics samples with different specific surface area. The difference in nonstoichiometry of BSCF and SCF at temperatures ≥973 K was found to be ≤0.03 oxygen atoms per formula unit. BSCF demonstrates favorably smaller chemical expansion compared to SCF and many other mixed conductors, originating from smaller δ variations and larger unit cell less sensitive to temperature and nonstoichiometry changes. Excessive thermochemical expansion impedes however the use of BSCF in single-phase fuel cell cathodes and planar mixed-conducting membranes.     

Structure dependent catalytic activity of Ce0.8Tb0.2O2−δ and TiO2 supported Ce0.8Tb0.2O2−δ solid solutions for CO oxidation

A facile coprecipitation and deposition precipitation method were used for synthesis of nanosized Ce_0.8Tb_0.2O_2−δ (CT) and Ce_0.8Tb_0.2O_2−δ/TiO₂ (CTT) solid solutions, respectively. The synthesized materials were characterized by various state-of-the-art techniques and evaluated for CO oxidation activity. Formation of CT solid solution was confirmed by XRD and Raman, and nanocrystalline nature by TEM. Characterization results further suggested formation of a new pyrochlore phase between TiO₂ and TbO₂ at 1073 K, and the presence of Ce³⁺ associated with lattice defects in all samples. Catalytic results showed that CT calcined at 773 K exhibits a high activity and correlates well with physicochemical characteristics.     

Characterization of La0.58Sr0.4Co0.2Fe0.8O3−δ–Ce0.8Gd0.2O2 composite cathode for intermediate temperature solid oxide fuel cells

La_0.58Sr_0.4Co_0.2Fe_0.8O_3?δ–Ce_0.8Gd_0.2O₂ (LSCF–GDC) composite cathodes with various weight ratios 90%, 70% and 50% of LSCF were prepared. Mechanical properties, thermal expansion properties and electrical properties were measured for potential applications in solid oxide fuel cells (SOFCs) with graded cathodes. LSCF and GDC as pure cathode and electrolyte materials were characterized as reference. The absence of new phases as confirmed by X-ray diffraction (XRD) analysis demonstrated the excellent compatibility between the cathode and electrolyte materials. Mechanical properties such as hardness and fracture toughness were measured by the micro-indentation technique, while hardness and elastic modulus were measured by the nano-indentation technique. Thermal expansion behavior was recorded by a dilatometer. Electrical conductivity was measured by the four probe DC method. The 50% LSCF–GDC composite has the lowest relative density among all the samples. Thermal expansion coefficients (TECs) and electrical conductivity increased with addition of LSCF contents in the composite, while mechanical properties depended more on the density than the LSCF content.     

Ammonia oxidation in Ba0.5Sr0.5Co0.8Fe0.2O3−δ membrane reactor

Selective oxidation of ammonia to NO was studied in a dense mixed ion electron conducting Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ membrane reactor, which integrates the separation and catalytic reaction process in a single reactive separation unit. The influence of the temperature and feed concentration on the membrane reaction performance were investigated in detail. Under reaction conditions, the oxygen permeation flux through the dense membrane increases with increasing temperature and ammonia flow rate. The lower temperature and ammonia concentration can favor the formation of NO, in which higher catalytic performance is obtained, suggesting that the membrane reactor operation is much beneficial for selective oxidation of ammonia.