Reactions between Strontium-Substituted Lanthanum Manganite and Yttria-Stabilized Zirconia: II, Diffusion Couples

Formation of secondary phases and diffusion of cations in diffusion couples of yttria-stabilized zirconia and lanthanum manganite substituted with 0 to 60 mol% strontium have been studied by scanning electron microscopy and energy dispersive X-ray spectroscopy. Only the primary phases were observed after 120 h at 1200°C, while formation of secondary phases was identified already after 1 h heat treatment at 1350°C. The phase composition of the reaction layer altered from La₂Zr₂O₇ to SrZrO₃ at increasing Sr content in La _x Sr_{1- x} MnO₃. The thickness of the reaction layer was increasing with heat treatment time. In diffusion couples of La_0.4Sr_0.6MnO₃ formation of manganese oxide was observed in the perovskite layer after 1 h heat treatment at 1350°C, while isolated grains of SrZrO₃ relatively deep inside the zirconia were observed after longer heat treatment time. Diffusion of Mn into zirconia was observed preferenced along grain boundaries in the early stage of the interface reaction.     

Reaction Kinetics and Mechanisms between La0.65Sr0.3MnO3 and 8 mol% Yttria-Stabilized Zirconia

The reaction kinetics and mechanisms between 8 mol% yttria-stabilized zirconia (YSZ) and 30 mol% Sr-doped lanthanum manganite (La_0.65Sr_0.30MnO₃, LSM) with A-site deficiency for the application of planar solid oxide fuel cells (SOFCs) were investigated. The LSM/YSZ green tapes were cofired from 1200° to 1400°C for 1 to 48 h and then annealed at 1000°C for up to 1000 h. The results showed that the diffusion of manganese cations first caused the amorphization of YSZ, and then the formation of small La₂Zr₂O₇ (LZ) or SrZrO₃ (SZ) crystals if treated for a longer time at 1400°C. The ambipolar diffusion of the Mn–O pair, transported through the migration of oxygen vacancy, plays an important role in the formation of secondary phases. The diffusion of LSM to YSZ and substitution of Mn for Zr both result in the enhanced concentration of oxygen vacancy, leading to the formation of a void-free zone (VFZ). No additional reaction products in annealed LSM/YSZ specimens, treated at 1000°C for 1000 h, were detected. The interfacial reactions, detailed reaction kinetics, and mechanisms are reported.     

Chemical Compatibility between Strontium-Doped Lanthanum Manganite and Yttria-Stabilized Zirconia

Equimolar powder mixtures and multilayer pellets of single-phase Sr-doped lanthanum manganite perovskite materials La_y-xSr_xMnO₃ with La content y = 1 and 0.95 and Sr content 0 ≤ x ≤ 0.5 were annealed in air with 8 mol% Y₂O₃-ZrO₂ at 1470 K, up to 400 h and at 1670 K. up to 200 h. X-ray diffraction and electron probe microanalysis confirmed the formation of La₂Zr₂O₇ or SrZrO₃ depending on the composition of the perovskites. No reaction products could be detected for La_0.95-xSr _xMnO₃ with 0.2 ≤ x ≤ 0.4 after annealing for 400 h at 1470 K, and for the perovskite La_0.65Sr_0.3MnO₃ even after annealing for 200 h at 1670 K. The results demonstrate the improved chemical compatibility of La-deficient perovskites against reaction with zirconia and can provide a basis for the selection of a sufficiently chemically stable material for the air electrode of solid oxide fuel cells.     

Preparation of Silica-Coated Lanthanum–Strontium Manganite Particles with Designable Curie Point, for Application in Hyperthermia Treatments

Silica-coated lanthanum–strontium manganite particles with La_0.76Sr_0.24MnO_3+δ stoichiometric formula, exhibiting Curie temperature at ∼40°C, were prepared by using a traditional solid-state method of synthesis of magnetic ceramic particles, followed by milling and a low-temperature coating procedure in an aqueous alcoholic alkali medium. The properties of the obtained material establish it as a potential candidate for self-regulated power-absorbing and temperature-controlling materials in hyperthermia treatments. Moreover, core-comprising LaSr–manganites with different stoichiometries, ranging from La_0.5Sr_0.5MnO_3+δ to LaMnO_3+δ, were synthesized, with magnetic and structural properties examined thereof. Herein reported findings can potentially be used in the preparation of silica-coated magnetic particles with designable Curie temperature, offering a wide range of possibilities of adapting the material to practical instrumental setups in drug delivery and hyperthermia treatments.     

Two-Dimensional Modeling of Self-Propagating High-Temperature Synthesis of Strontium-Doped Lanthanum Manganate

A two-dimensional finite element model is developed to study the reaction kinetics and heat transfer during the self-propagating high-temperature synthesis of La_0.6Sr_0.4MnO₃, a cathode and interconnect material used in solid oxide fuel cells. The activation energy of La_0.6Sr_0.4MnO₃ formation was calculated from experimental temperature history. The calculated spatial-temporal temperature profile, heat generation rate, reaction conversion, and flow pattern of surrounding gas during the reaction are reported in this work. Hot spots are found at the corner near the ignition point shortly after the ignition. The model provided a simple and reliable way to design a large-scale production of La_0.6Sr_0.4MnO₃.     

Thin Yttrium-Stabilized Zirconia Electrolyte Solid Oxide Fuel Cells by Centrifugal Casting

A centrifugal casting technique was developed for depositing thin 8-mol%-yttrium-stabilized zirconia (YSZ) electrolyte layers on porous NiO-YSZ anode substrates. After the bilayers were cosintered at 1400°C, dense pinhole-free YSZ coatings with thicknesses of ∼25 μm were obtained, while the Ni-YSZ retained porosity. After La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF)-Ce_0.9Gd_0.1O_1.95 (GDC) or La_0.8Sr_0.2MnO₃ (LSM)-YSZ cathodes were deposited, single SOFCs produced near-theoretical open-circuit voltages and power densities of ∼1 W/cm² at 800°C. Impedance spectra measured during cell tests showed that polarization resistances accounted for ∼70%–80% of the total cell resistance.     

Preparation of Yttria-Stabilized Zirconia Thin Films on Strontium-Doped LaMnO3 Cathode Substrates via Electrophoretic Deposition for Solid Oxide Fuel Cells

A yttria-stabilized zirconia (YSZ) thin film on an La_0.8Sr_0.2MnO₃ porous cathode substrate was prepared, using electrophoretic deposition (EPD) to fabricate a solid oxide fuel cell (SOFC). The electrical conductivity of an La_0.8Sr_0.2MnO₃ substrate is satisfactorily high at room temperature; therefore, YSZ powder could be deposited electrophoretically onto an La_0.8Sr_0.2MnO₃ substrate without any extra surface treatment, such as a metal coating. Successive repetition of EPD and sintering was required to obtain a film without gas leakage, because of the thermal expansion coefficient mismatch between the YSZ and the La_0.8Sr_0.2MnO₃ substrate. On the other hand, the electromotive force of the oxygen concentration in the cell that used YSZ film prepared via EPD increased and attained the theoretical value when the number of deposition and calcination cycles was increased. Six or more successive repetitions were required to obtain a YSZ film without gas leakage. A planar-type SOFC was fabricated, using nickel as the anode and YSZ film (∼10 μm thick) that had been deposited onto the La_0.8Sr_0.2MnO₃ substrate as the electrolyte and cathode. The cell exhibited an open circuit voltage of 1.0 V and a maximum power density of 1.5 W/cm². Thus, the EPD method could be used as a colloidal process to prepare YSZ thin-film electrolytes for SOFCs.     

Mechanism of Reaction between Lanthanum Manganite and Yttria-Stabilized Zirconia

The reaction of La_{1- x} Ca _x MnO₃ ( x = 0, 0.1, 0.2) with ZrO₂-8 mol% Y₂O₃ (YSZ) has been investigated at temperatures ranging from 1300° to 1425°C in air. Substitution of Ca for La in LaMnO₃ depresses the reactivity with YSZ. A layer of La₂Zr₂O₇ is formed at the La_{1- x} Ca _x MnO₃/YSZ interface after an induction period, and its formation is accelerated when the La_{1- x} Ca _x MnO₃ phase is porous. The reaction proceeds by unidirectional diffusion of La, Mn, and/or Ca ions, mainly Mn ions, into YSZ. The diffusion coefficients of La and Mn ions in YSZ, which are estimated using a LaMnO₃/single-crystal YSZ couple, are much lower than that of oxygen ion. From the experimental data, a reaction mechanism is proposed.     

Mechanical Properties of Strontium-Doped Lanthanum Manganite

Solid oxide fuel cells that incorporate stabilized-zirconia electrolytes commonly use the transition-metal oxide perovskite La_0.875Sr_0.125MnO_3+δ as the cathode. While in operation, the cathode can be subjected to significant stresses, because of thermal expansion mismatch between mating components. The mechanical behavior of La_0.875Sr_0.125MnO_3+δ has been studied using three-point bend strength measurements at ambient, 400°C, 800°C and 1000°C. The results show that phase transformations have an important role in the mechanical-strength behavior. The results also indicate some unique strengthening effects that are associated with the evolution of the unit cell with temperature and the increasing symmetry of the crystal lattice.     

Novel Design of Microchanneled Tubular Solid Oxide Fuel Cells and Synthesis Using a Multipass Extrusion Process

A novel, microchanneled tubular solid oxide fuel cell was fabricated using a multipass extrusion process, with an outside diameter of 2.7 mm that contained 61 cells. Cell materials used in this work were 8 mol% yttria-stabilized zirconia (8YSZ), La_0.8Sr_0.2MnO₃ (LSM), and NiO–8YSZ (50:50 vol%) as electrolyte, cathode, and anode, respectively. Three stages of heat-treatment processes were applied, at 700°C in N₂ condition, at 1000°C in air, and then sintered at 1300°C for 2 h, respectively. The X-ray diffraction analysis confirmed that no reaction phases appeared after sintering. The microstructures of anode and cathode were fairly porous while the electrolyte had a dense microstructure (relative density >96%). The thickness of electrolyte, anode, and cathode were 20, 30, and 40 μm, respectively, and the diameter of the continuous channels was 150 μm.     

Oxidation Resistance Coating of LSM and LSCF on SOFC Metallic Interconnects by the Aerosol Deposition Process

Conductive La_0.8Sr_0.2MnO₃ (LSM) and La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) layers with a thickness of ∼10 μm were deposited on ferritic stainless steel (SS) by the aerosol deposition method, for use as an oxidation resistance-coating layer in the metallic interconnector of a solid oxide fuel cell. The coated layers were fairly dense without pores or cracks, and maintained good adhesion even after oxidation at 800°C for 100 h. The surface of the bare SS after annealing at 800°C for 100 h was covered with Cr₂O₃ and Fe₃O₄ oxide scales, and the electrical conductivity was sharply decreased. However, the LSM- and LSCF-coated SSs showed a surface microstructure with almost no oxidation and maintained good electrical conductivity after annealing at 800°C for 100 h. The area-specific resistance (ASR) of LSM- and LSCF-coated alloys after 100 h of oxidation at 800°C was 20.6 and 11.7 mΩ·cm², respectively.     

Lanthanum Strontium Manganite Powders Synthesized by Gel-Casting for Solid Oxide Fuel Cell Cathode Materials

Lanthanum strontium manganite ((La_0.8Sr_0.2)_0.9MnO₃; LSM) powder was successfully synthesized by an aqueous gel-casting technique, using carbonaceous precursors. Both thermal and X-ray diffraction analysis confirmed that the gel-casting LSM powder formed a single perovskite phase at 850°C, which is 100°–150°C lower than that of the LSM powder prepared by the conventional solid-state reaction route. The significantly reduced phase formation temperature of the gel-casting LSM powder is most likely due to the homogeneously distributed and immobilized precursor particles in a polymeric network, promoting the sintering and crystallization process. The LSM electrode prepared by the gel-cast LSM powder showed good electrocatalytic activity for the O₂ reduction reaction for solid oxide fuel cells.     

Electrophoretic Deposition of Y2O3-Stabilized ZrO2 Electrolyte Films in Solid Oxide Fuel Cells

An electrophoretic deposition (EPD) method was applied for the preparation of yttria-stabilized zirconia (YSZ) films for solid oxide fuel cell (SOFC) applications. Dense YSZ films with uniform thickness can be readily prepared with the EPD method by using acetylacetone or acetone as a solvent. The open-circuit voltages of SOFC, for which the YSZ films were prepared by the EPD method, increased with increasing repetitions of deposition and sintering. It was found that the open-circuit voltage exceeded 1.0 V after five repetitions. When the planar SOFC was fabricated using La_0.6Sr_0.4MnO₃ as a cathode, and electroless plating Pt as an anode, the open-circuit voltage and the maximum power density attained were 1.03 V and 1.84 W·cm⁻², respectively. Consequently, it became evident that the electrophoretic deposition was a suitable processing route for the formation of gas-tight YSZ films with thickness less than 10 μm.     

Reaction Between Strontium-Doped Lanthanum Cuprate and Yittria-Stabilized Zirconia

Sr-doped lanthanum cuprate was recently investigated as a potential cathode material for the intermediate temperature solid oxide fuel cell using yittria-stabilized zirconia as an electrolyte. The material thermal stability of cathode material against an electrolyte at an operating temperature plays an important role in the fuel cell's performance. In this study, the structural stability between Sr-doped lanthanum cuprate and 8 mol% yittria-stabilized zirconia was investigated by using the powder mixture and diffusion couple. The chemical reaction between these two materials in the temperature ranging from 800° to 1000°C was examined by X-ray diffraction analyses. The interfacial reaction behavior between electrode and electrolyte pellets of the reaction couple was examined by a grazing X-ray diffractometer, wavelength-dispersive X-ray analysis, and an electron probe microanalyzer. No reaction products were observed as these two materials co-fired at 800°C. The reaction products of pyrochlore La₂Zr₂O₇ and perovskite SrZrO₃ were formed when the specimens were heat treated at over 900°C. Because of the formation of these reaction products, the CuO was precipitated. Furthermore, an excess of SrZrO₃ formation leads to the phase decomposition of perovskite Sr-doped lanthanum cuprate to La_{2− x} Sr _x CuO₄ and CuO due to a decrease in strontium concentration in Sr-doped lanthanum cuprate.     

Alkoxide Route to La0.5Sr0.5CoO3 Films and Powders

An all-alkoxide route to films and nano-phase powders of the La_0.5Sr_0.5CoO₃ perovskite is described. To our knowledge, this is the first purely alkoxide-based route to (La_{1− x} Sr _x )CoO₃, and it yields phase-pure and elementally homogeneous perovskite at 700°C by heating at 2°C/min. At 700°C, a cubic unit cell was obtained with a _c=3.853Å, and after further heating to 1000°C, a rhombohedral cell could be indexed: a _r=5.417 Å, α_r=59.94°. Ninety to 130 nm thick films of La_0.5Sr_0.5CoO₃ were obtained by spin coating. The gel-to-oxide conversion was studied in some detail, using thermo-gravimetric analysis, differential scanning calorimetry, powder X-ray diffraction, IR spectroscopy, and transmission electron microscope equipped with an energy-dispersive X-ray spectrometer.     

Electrical Conduction in Nano-Structured La0.9Sr0.1Al0.85Co0.05Mg0.1O3 Perovskite Oxide

Nanocrystalline La_0.9Sr_0.1Al_0.85Co_0.05Mg_0.1O₃ oxide powder was synthesized by a citrate–nitrate auto-ignition process and characterized by thermal analysis, X-ray diffraction, and impedance spectroscopy measurements. Nanocrystalline (50–100 nm) powder with perovskite structure could be produced at 900°C by this process. The powder could be sintered to a density more than 96% of the theoretical density at 1550°C. Impedance measurements on the sintered samples unequivocally established the potential of this process in developing nanostructured lanthanum aluminate-based oxides. The sintered La_0.9Sr_0.1Al_0.85Co_0.05Mg_0.1O₃ sample exhibited a conductivity of 2.40 × 10⁻² S/cm in air at 1000°C compared with 4.9 × 10⁻³ S/cm exhibited by La_0.9Sr_0.1Al_0.85Mg_0.15O₃.     

Synthesis of Perovskite-Type (La1−xSrx)MnO3 (O X 0.3) at Low Temperature

Perovskite-type (La_{1- x} Sr _x )MnO₃ (0 x 0.3) was synthesized through the sol–gel process at low temperature (400° to 500°C). Poly(acrylic acid) (PAA) was used to make a gel from an aqueous solution of lanthanum, strontium, and manganese nitrates. The particle-diameter distribution of the manganites had a maximum value of 0.3 to 0.7 μ m, and a specific surface area of about 17.5 to 23.5 m²/g.     

Doped Perovskite Oxide, PrMnO3, as a New Cathode for Solid-Oxide Fuel Cells that Decreases the Operating Temperature

Cathodic overpotentials of Ln_0.6Sr_0.4MnO₃ (Ln is La, Pr, Nd, Sm, Gd, Yb, and Y) were studied for a new cathode for solid-oxide fuel cells (SOFCs) with low overpotentials in a relatively-low-temperature region. Cathodic overpotentials strongly depended on the rare-earth cations in the A sites of the perovskite oxide. In particular, overpotentials of a Sr-doped PrMnO₃ cathode maintained low values despite decreased operating temperature. Consequently, almost the same power density of a SOFC with Ln_0.6Sr_0.4MnO₃ cathode was obtained at about 100 K lower operating temperature by using Sr-doped PrMnO₃ as the cathode.     

Preparation, Structure, and Selected Catalytic Properties of the System LaMn1-xCuxO3-y

Samples of LaMn_1-xCu_xO_3-y in the range 0≤x≤0.8 were prepared from freeze-dried solutions of the nitrates. Samples with x≤0.6 were single-phase perovskites. At higher values of x , the samples contained La₂CuO₄ and CuO as well as the perovskite phase. Samples of LaMn_1−x,Cu_x,O_3−y supported on ceramic monoliths or when mixed with powdered A1₂O₃ exhibit catalytic activity for the oxidation of CO. Greatest activity is shown for 0.4≤x≤0.7. Although the catalysts are severely poisoned by SO₂, 2% H₂O in the gas stream causes only slight deactivation. Activities of other oxide catalysts were also measured and compared. Rate constants per unit surface area at 200° to 400°C follow the order Co₃O₄>Pt>LaMn_1−xCu_xO_3−y (0.4≤x≤0.7)>copper chromite>La_1−xSr_x,MnO₃≤ other substituted LaMnO₃ materials, CuO, or La₂CuO₄. The perovskite catalyst is more stable than Co₃O₄ or copper chromite when heated in 10% H₂+ 90% N₂.     

Synthesis of (La,Sr)MnO3–YSZ Composite Particles by Spray Pyrolysis

(La_0.8Sr_0.2)_0.9MnO₃–YSZ composite particles were synthesized by spray pyrolysis. The mean particle size of the synthesized powders was about 1 pm and the particle size distribution was very narrow. The synthesized powders were composed of the perovskite (La,Sr)MnO₃ and cubic phase YSZ. Each particle synthesized consisted of uniform and well-dispersed line primary particles of (La,Sr)MnO₃ and YSZ (0.1 μm particle size).