Synthesis and sintering behavior of La0.8Sr0.2CrO3 by a glycine nitrate process

La_0.8Sr_0.2CrO₃ powder was synthesized by a glycine nitrate process from an aqueous solution of lanthanum, strontium, and chromium nitrates, and glycine. The apparent density, size and morphology of the La_0.8Sr_0.2CrO₃ powder depended on the glycine-to-nitrate ratio. However, the pH value of the precursor solution had no significant effect on these properties. It was found that a single-phase perovskite, La_0.8Sr_0.2CrO₃, was synthesized when the dried ash was calcined at 1200 °C for 5 h. A secondary minor phase, SrCrO₄, was observed in the powder calcined at temperatures lower than 1100 °C. The presence of the SrCrO₄ phase has a significant effect on the sinterability and microstructural evolution of the La_0.8Sr_0.2CrO₃. A relative density higher than 90% could be achieved when the 1000 °C-calcined La_0.8Sr_0.2CrO₃ powder was sintered at 1450 °C.     

Hydrothermal synthesis and magnetocaloric effect of La0.7Ca0.2Sr0.1MnO3

The hydrothermal synthesis and magnetic entropy change for the perovskite manganite La_0.7Ca_0.2Sr_0.1MnO₃ have been studied. The La_0.7Ca_0.2Sr_0.1MnO₃ can be produced as phase-pure, crystalline powder in one step from solutions of metal salts in aqueous potassium hydroxide solution at a temperature of 240 °C in 72 h. Scanning electron microscopy shows that the materials are made up of cuboid-shaped or rod-shaped particles with typical dimension of 4.0 μm. Heat treatment is necessary to improve the magnetocaloric effect for the hydrothermal sample. The maximum magnetic entropy change (∣ΔS_M∣) for the sample annealed at 1200 °C for 6 h is 2.85 J kg^− 1 K^− 1 at the magnetic field change of 2.0 T and 2.23 J kg^− 1 K^− 1 at the magnetic field change of 1.5 T at 315 K. The hydrothermal synthesis method is a feasible route to prepare high quality perovskite material for magnetic refrigeration application.     

Effect of heat treatment condition on magnetic,electrical transport and magnetoresistance properties of La0.67Sr0.33MnO3 manganite coatings

Effects of three different heat treatment conditions (air, vacuum and nitrogen) on the structure, magnetic, electrical transport and low-field magnetoresistance behaviors of La_0.67Sr_0.33MnO₃ manganite coatings synthesized by sol-gel and screen printing methods have been systematically investigated. The detailed crystallographic analyses revealed that the diffraction peak positions of the samples subjected to annealing in vacuum and nitrogen ambients shifted to lower-angle regions, and lattice parameters and structure distortion increased as compared with those of the sample annealed in air, which were due to the introduction of oxygen deficiency under the annealing conditions of vacuum and nitrogen. The content of oxygen deficiency of the samples could be determined by the change of lattice parameters. Furthermore, the vacuum and nitrogen annealed samples exhibited a dramatic increase in the resistivity, accompanied by the reduction in ferromagnetism, the resistivity peak temperature and the ferromagnetism transition temperature. These phenomena were attributed to the decrease of average manganese oxidation state, as a result the mobile charge carriers were reduced, the ferromagnetic coupling and the double exchange effect between manganese ions decreased while the magnetic inhomogeneity increased. In the meanwhile, magnetoresistance ratios of the oxygen-deficient samples were enhanced around the percolation threshold.     

Synthesis of La1−xSrxMnO3 powders by polymerizable complex method: Evaluation of structural, morphological and electrical properties

Lanthanum strontium manganite (La_1−xSr_xMnO₃, LSM) powders were synthesized by polymerizable complex method, based on complexation of metal ions (MI) with citric acid (CA) and polyesterification between CA and ethylene glycol (EG). Firstly, the effect of the molar ratio of CA:MI (=1–3) was investigated on the synthesis of La_0.7Sr_0.3MnO₃ powders, which were characterized by thermal analysis (TGA/DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The results indicated that the molar ratio CA:MI = 3 is adequate for a good crystallization of pure perovskite phase after calcination, with nanometric crystallite sizes and porous microstructure. For the La_0.7Sr_0.3MnO₃ sample synthesized with CA:MI ratio of 3, it was investigated the effect of calcination temperature, showing that the perovskite structure is better crystallized at 900 °C, without secondary phase formation. Using this same CA:MI ratio and calcination temperature, powders with different Sr content (x = 0.2–0.4) were synthesized, with surface areas of 4–10 m² g⁻¹. These powders were sintered at 1100 °C to produce porous pellets. The porosity of the sintered pellets and the electrical conductivity, measured by two-probe technique, increased with increasing Sr content.     

Preparation and characterisation of supported La0.8Sr0.2MnO3+x

Three supported La_0.8Sr_0.2MnO_3+x catalysts were prepared, one supported on lanthanum-stabilised alumina and two supported on a NiAl₂O₄ spinel. The catalysts were characterised using X-ray diffraction, transmission electron microscopy and surface area measurements following heat-treatments at temperatures up to 1200°C in air. In the alumina-supported catalyst, a reaction occurred between the active phase and the support at high temperatures, indicating that these materials would be unsuitable for high temperature catalytic combustion. Only in the NiAl₂O₄-supported catalysts were the supported perovskite phases found to be stable at high temperature. These catalysts showed good methane combustion activity.     

A bi-layered composite cathode of La0.8Sr0.2MnO3-YSZ and La0.8Sr0.2MnO3-La0.4Ce0.6O1.8 for IT-SOFCs

A bi-layered composite cathode of La_0.8Sr_0.2MnO₃ (LSM)-YSZ and LSM-La_0.4Ce_0.6O_1.8 (LDC) was fabricated for anode-supported solid oxide fuel cells with a thin YSZ electrolyte film. The cell with the bi-layered composite cathode displayed better performance than the cell with the corresponding single-layered composite cathode of LSM-LDC or LSM-YSZ. At 650 °C, the cell with the bi-layered composite cathode gave a higher maximum power density than the cells with the single-layered LSM-LDC and LSM-YSZ composite cathodes, by 52% and 175%, respectively. The impedance spectra results show that the thin LSM-YSZ interlayer not only improves the cathode/electrolyte interface but also reduces the polarization resistance of the cathode. The activation energy for oxygen reduction on the bi-layered composite cathode is much smaller than that on LSM-YSZ composite cathode, and it is suggested that the special redox property of Ce⁴⁺/Ce³⁺ in LDC facilitates the oxygen reduction process on the bi-layered composite cathode. The cell with the bi-layered composite cathode operated quite stably during a 100 h run.     

Electrochemical properties of the single crystal La0.7Pb0.3MnO3 electrode

Electrochemical properties of the single crystal La_0.7Pb_0.3MnO₃ were studied. This oxide is stable only at the anodic potential region in alkaline solution. It was found that the catalytic activities for the oxygen reduction and evolution reactions are relatively high due to the effect of the B site Mn cation on the oxide surface. However, the mechanisms of the oxygen reduction and evolution reactions are different from the case of La_1-xSr_xMnO₃ electrodes and it was presumed that these differences are assigned to the influence of the A site Pb cation in La_0.7Pb_0.3MnO₃ and that of the (100) crystal plane.     

Large increase of Curie temperature in (110)-oriented La0.7Sr0.3MnO3 films

From the perspectives of scientific researches and practical applications, it is desirable to explore high operating temperature ferromagnetic films. The effect of biaxial strain on magnetic properties of (110)-oriented La_0.7Sr_0.3MnO₃ films was studied. High quality La_0.7Sr_0.3MnO₃ films were grown on (110)-oriented perovskite single crystal substrates using pulsed laser deposition, varying substrate-induced misfit strains from ??2.27–0.75%. A remarkable enhancement of Curie temperature has been achieved for (110)-oriented La_0.7Sr_0.3MnO₃ films clamped with small misfit strains (i.e., grown on LAST (110)). The enhanced Curie temperature of (110)-oriented La_0.7Sr_0.3MnO₃ films could be attributed to the misfit strain between the films and the underlying substrates and may have technological implication for applications at high temperature environments.     

Study on impedance spectra of La0.7Sr0.3MnO3 and Sm0.2Ce0.8O1.9-impregnated La0.7Sr0.3MnO3 cathode in single chamber fuel cell condition

Impedance spectroscopy was used to study the electrochemical performance of pure and ion-impregnated La_0.7Sr_0.3MnO₃ (LSM) cathodes on YSZ (Y₂O₃-stabilized ZrO₂) electrolytes in single chamber fuel cell conditions, i.e. a mixture gas with oxygen as oxidant, methane as fuel and nitrogen as dilute gas. Measurements were taken at the furnace temperature range of 550-750 °C and the CH₄/O₂ ratios from 1 to 2. Polarization resistances (R_p) for pure and impregnated LSM cathodes increased obviously as the CH₄/O₂ ratio increased at 650-750 °C. Polarization resistances of Sm_0.2Ce_0.8O_1.9 (SDC) impregnated LSM cathode were much smaller than the ones of pure LSM cathode under the same conditions. Overtemperatures were occurred at both cathodes due to the partial oxidation of methane.     

La0.6Ca0.4CoO3, La0.1Ca0.9MnO3 and LaNiO3 as bifunctional oxygen electrodes

A series of perovskite catalysts was investigated for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolyte and at room temperature, supplied by oxygen or air. A meniscus cell was used to screen-test candidate catalysts for their bifunctionality and assess their activity for ORR at 3 mm depth of immersion (DOI) in the electrolyte. Based on the meniscus data LaNiO₃, La_0.1Ca_0.9MnO₃ and La_0.6Ca_0.4CoO₃ were selected for further assessment in microelectrode and half-cell studies. Activity tests for the ORR and OER, Tafel slopes at high current densities and apparent activation energies for the ORR were determined using a microelectrode technique on samples of the selected perovskites, La_0.1Ca_0.9MnO₃, La_0.6Ca_0.4CoO₃ and LaNiO₃ with and without graphite support. Tafel slopes of ca. 120 mV per decade and apparent activation energies of approximately 18 kcal mol⁻¹ were measured at high cathodic current densities. Cycle-life and performance of La_0.1Ca_0.9MnO₃, La_0.6Ca_0.4CoO₃ and LaNiO₃-based gas-diffusion electrodes in half-cell configurations were tested at a constant current density of 25 mA cm⁻² with subsequent and intermittent polarizations. Similar activities resulted in the ORR, while increased numbers of cycles were observed for the La_0.1Ca_0.9MnO₃-based electrode. Furthermore, electrode material compositions, especially PTFE contents were optimized to conform to the establishment of the three phase interactions of the electrode structure. Transmission Electron microscopy (TEM) and BET-surface area analyses were carried out in order to find out the morphological and surface properties of the perovskite materials.     

Highly efficient La0.8Sr0.2MnO3-δ - Ce0.9Gd0.1O1.95 nanocomposite cathodes for solid oxide fuel cells

La_0.8Sr_0.2MnO_3-δ-Ce_0.9Gd_0.1O_1.95 (LSM-CGO) nanostructured cathodes are successfully prepared in a single process by a chemical spray-pyrolysis deposition method. The cathode is composed of nanometric particles of approximately 15 nm of diameter, providing high triple-phase boundary sites for the oxygen reduction reactions. A low polarization resistance of 0.046 Ω cm² is obtained at 700 °C, which is comparable to the most efficient cobaltite-based perovskite cathodes. A NiO-YSZ anode supported fuel cell with the nanostructured cathode generates a power output of 1.4 W cm^?2 at 800 °C, significantly higher than 0.75 W cm^?2 for a cell with conventional LSM-CGO cathode. The results suggest that this is a promising strategy to achieve high efficiency electrodes for Solid Oxide Fuel Cells in a single preparation step, simplifying notably the fabrication process compared to traditional methods.     

Mechanical behavior of La0.8Sr0.2Ga0.8Mg0.2O3 perovskites

This paper examines the important mechanical properties of commercially purchased La_0.8Sr_0.2Ga_0.8Mg_0.2O₃ at room temperature and 800 °C. Sr and Mg-doped lanthanum gallates (LSGM) are strong candidates for use as solid electrolytes in lower temperature solid oxide fuel cells operating at or below 800 °C. The material was found to be phase pure with a Young's modulus value of ∼175 GPa. The four point bending strength of the LSGM samples remained almost constant from 121 ± 35 MPa at room temperature to 126 ± 20 MPa at 800 °C. The fracture toughness, as measured by the single edge V notch beam (SEVNB) method, was 1.22 ± 0.06 MPa√m at room temperature, 1.04 ± 0.09 MPa√m at 700 °C followed by a small increase 1.31 ± 0.16 MPa√m at 800 °C. We also report, for the first time, the static subcritical (or slow) crack-growth (SCG) behavior of natural cracks in LSGM performed in four point bending tests at room temperature. The exponent of a power-law representation in the SCG tests was found to be n = 15, a rather low value showing LSGM to be highly susceptible to room temperature SCG.     

Surface properties and catalytic performance of La1−xSrxCrO3 perovskite-type oxides for CO and C3H6 combustion

Catalytic CO oxidation and C₃H₆ combustion have been studied over La_1−xSr_xCrO₃ (x = 0.0–0.3) oxides prepared by solid-state reaction and characterised by X-ray diffraction (XRD), nitrogen adsorption (BET analysis) and X-ray photoelectron spectroscopy (XPS). The expected orthorhombic perovskite structure of the chromite is observed for all levels of substitution. However, surface segregation of strontium along with a chromium oxidation process, leading to formation of Cr⁶⁺-containing phases, is produced upon increasing x and shown to be detrimental to the catalytic activity. Maximum activity is achieved for the catalyst with x = 0.1 in which mixed oxide formation upon substitution of lanthanum by strontium in the chromite becomes maximised.     

The effect of particle size on structural,magnetic and transport properties of La0.7Sr0.3MnO3 nanoparticles

This paper reports the synthesis of different particle size La_0.7Sr_0.3MnO₃ (LSMO) nanoparticles using non-aqueous sol gel synthesis route by calcination at temperatures 750 °C, 850 °C and 950 °C. In the present work, the effect of particle size of LSMO nanoparticles on its structural, magnetic and transport properties has been studied in detail. The X-ray diffraction analysis confirms the formation of LSMO nanoparticles having rhombohedral ($R\stackrel{?}{3}c$) structure with average particle size of 20 nm, 22.5 nm and 25.6 nm. An increase in magnetization and decrease in coercivity with increase in particle size is attributed to the magnetically disordered surface layer. The bifurcation in ZFC-FC magnetization indicates the possibility of spin glass like behavior of the LSMO nanoparticles. The effect of particle size on the resistivity and magnetoresistance were studied by using different conduction mechanism for different temperature regions. The upturn in the ρ-T curve at lower temperatures was explained by using Kondo-like transport mechanism. The maximum LFMR achieved was 32.3% at a field of 1 T at 10 K for 20 nm LSMO nanoparticle.     

Study of Ag/La0.6Sr0.4MnO3 catalysts for complete oxidation of methanol and ethanol at low concentrations

Ag-modified La_0.6Sr_0.4MnO₃-based catalysts with the perovskite-type structure were prepared by using a citric acid sol–gel method, and their catalytic performance for complete oxidation of methanol and ethanol was evaluated and compared with that of the γ-Al₂O₃-supported catalysts, Ag/γ-Al₂O₃, Pt/γ-Al₂O₃, and Pd/γ-Al₂O₃. The results showed that the Ag-modified La_0.6Sr_0.4MnO₃-based catalysts with the perovskite-type structure displayed the activity significantly higher than that of the supported precious metal catalysts, 0.1%Pd/γ-Al₂O₃ and 0.1%Pt/γ-Al₂O₃ in the temperature range of 370–573 K. Over a 6%Ag/20%La_0.6Sr_0.4MnO₃/γ-Al₂O₃ catalyst, the T₉₅ temperature for methanol oxidation can be as low as 413 K. Even at such low reaction temperature, there were little HCHO and CO detected in the reaction exit-gas. However, for the 0.1%Pd/γ-Al₂O₃ and 0.1%Pt/γ-Al₂O₃ catalysts, the HCHO content in the reaction exit-gas reached 200 and 630 ppm at their T₉₅ temperatures. Over a 6%Ag/La_0.6Sr_0.4MnO₃ catalyst, the T₉₅ temperature for ethanol oxidation can be as low as 453 K, with a corresponding content of CH₃CHO in the exit-gas at 782 ppm; when ethanol oxidation is performed at 493 K, the content of acetaldehyde in the exit-gas can be below 1 ppm. Characterization of the catalysts by X-ray diffraction (XRD), TEM, XPS, laser Raman spectra (LRS), hydrogen temperature-programmed reduction (H₂-TPR) and oxygen temperature-programmed desorption (O₂-TPD) methods revealed that both the surface and the bulk phase of the perovskite La_0.6Sr_0.4MnO₃ played important roles in the catalytic oxidation of the alcohols, and that γ-Al₂O₃ as the bottom carrier could be beneficial in creating a large surface area of catalyst. Moreover, a small amount of Ag⁺ doped onto the surface of La_0.6Sr_0.4MnO₃ was able to partially occupy the positions of La³⁺ and Sr²⁺ due to their similar ionic radii, and thus, became stabilized by the perovskite lattice, which would be in favor of preventing the aggregation of the Ag species on the surface and enhancing the stability of the catalyst. On the other hand, modification of the Ag⁺ to the surface of La_0.6Sr_0.4MnO₃ resulted in an increase in relative content of the surface O₂²⁻/O⁻ species highly reactive toward the alcohols and aldehydes as well as CO. Besides, solution of low-valence metal oxides SrO and Ag₂O with proper amounts in the lattice of the trivalent metal perovskite-type oxide LaMnO₃ would also lead to an increase in the content of the reducible Mnⁿ⁺ and the formation of anionic vacancies, which would be favorable for the adsorption-activation of oxygen on the functioning catalyst and the transport of the lattice and surface oxygen species. All these factors would contribute to the pronounced improvement of the catalyst performance.     

Improved electrochemical performance of La0.7Sr0.3MnO3 and carbon co-coated LiFePO4 synthesized by freeze-drying process

Carbon coated LiFePO₄ particles were first synthesized by sol-gel and freeze-drying method. These particles were then coated with La_0.7Sr_0.3MnO₃ nanolayer by a suspension mixing process. The La_0.7Sr_0.3MnO₃ and carbon co-coated LiFePO₄ particles were calcined at 400 °C for 2 h in a reducing atmosphere (5% of hydrogen in nitrogen). Nanolayer structured La_0.7Sr_0.3MnO₃ together with the amorphous carbon layer forms an integrate network arranged on the bare surface of LiFePO₄ as corroborated by high-resolution transmission electron microscopy. X-ray diffraction results proved that the co-coated composite still retained the structure of the LiFePO₄ substrate. The twin coatings can remarkably improve the electrochemical performance at high charge/discharge rates. This improvement may be attributed to the lower charge transfer resistance and higher electronic conductivity resulted from the twin nanolayer coatings compared with the carbon coated LiFePO₄.     

Monodisperse magnetic composite poly(glycidyl methacrylate)/La0.75Sr0.25MnO3 microspheres by the dispersion polymerization

Monodisperse magnetic poly(glycidyl methacrylate) microspheres were prepared by dispersion polymerization of glycidyl methacrylate in cyclohexane in the presence of La_0.75Sr_0.25MnO₃ nanoparticles, surface of which was modified with penta(propylene glycol) methacrylate phosphate (PPGMAP). However, only agglomerates were formed by the dispersion polymerization in toluene. Sterical stabilizer was poly(styrene-block-hydrogenated butadiene-block-styrene) and initiators investigated were 2,2′-azobisisobutyronitrile (AIBN) and 4,4′-azobis(4-cyanovaleric acid) (ACVA). Effects of initiators and other reaction conditions on properties of the composite microspheres were evaluated. The phase composition of the magnetic polymer composite microspheres and the size of magnetic cores were determined by X-ray powder diffraction. The characterization was completed by magnetization measurements, atomic absorption spectroscopy, TEM, SEM and ATR FTIR spectroscopy.     

Magnetic and magnetoresistive properties of La0.65−xEuxSr0.35MnO3

Eu-doped perovskites La_0.65−xEu_xSr_0.35MnO₃ (0.05 ≤ x ≤ 0.30) were synthesized by sol–gel method using citric acid and characterized by X-ray diffraction, magnetization, resistivity and magnetoresistance (MR) experiments. All samples had a single hexagonal perovskite structure. As x increased from 0.05 to 0.30, the Curie temperature T_C for the samples decreased from 352 to 242 K. It was found that two transition points appeared when the resistivity changed with increasing temperature, and upon an application of a magnetic field of 20 kOe the maximum magnetoresistivity of 18% for the La_0.65−xEu_xSr_0.35MnO₃ with x = 0.20 was obtained at room temperature 300 K. The mechanism of the transitions for the samples was explored.     

Effect of TiO2 doped Ni electrodes on the dielectric properties and microstructures of (Ba0.96Ca0.04)(Ti0.85Zr0.15)O3 multilayer ceramic capacitors

The effects of TiO₂-doped Ni electrodes on the microstructures and dielectric properties of (Ba_0.96Ca_0.04)(Ti_0.85Zr_0.15)O₃ multilayer ceramic capacitors (MLCCs) have been investigated. Nickel paste with a TiO₂ dopant was used as internal electrodes in MLCCs based on (Ba_0.96Ca_0.04)(Ti_0.85Zr_0.15)O₃ (BCTZ) ceramic with copper end-termination. The microstructures and defects were analysed by microstructural techniques (SEM/HRTEM) and energy-dispersive spectroscopy (EDS). The continuity of the electrode of the MLCC was measured using a scanning electron microscope, which showed that the continuity of the electrode for the MLCC with a TiO₂-doped Ni electrode was approximately 90%. However, continuity of the electrode for a conventional MLCC was below 80%. The continuity of the TiO₂-doped Ni electrode showed significant improvement in the MLCC, which was due to no reaction between Ni and BCTZ.     

Rapid synthesis of La0.7Sr0.3MnO3+λ catalysts by microwave irradiation process

Microwave irradiation processing (MIP) was considered as a potential method to synthesize perovskite-type oxides rapidly, cleanly and energy-efficiently. In this paper, La_0.7Sr_0.3MnO_3+λ, a kind of promising catalyst for automobile exhaust purification, was successfully prepared by MIP in not more than 5 min. The sol–gel method was also used for comparison. All the samples were evaluated by catalytic activity tests in the simulated exhaust and characterized by XRD, BET, TEM and XRF analyses. The results showed that the integrated perovskite-type phase and uniform particle size were obtained in the microwave-treated samples. And those ones exhibited a better oxidation activity under slightly oxygen-rich condition than that by sol–gel method, which may be related to more A-site cation vacancies and larger bulk oxygen content generated in MIP. Possible formation mechanism of perovskites in MIP was also discussed.