Reactions between Strontium-Substituted Lanthanum Manganite and Yttria-Stabilized Zirconia: I, Powder Samples

Sintered submicrometer powder mixtures of strontium-substituted lanthanum manganite and yttria-stabilized zirconia have been studied in order to investigate the chemical stability of these materials as respectively electrode and electrolyte in solid oxide fuel cells. Formation of secondary phases was observed after 1 h heat treatment at 1350°C and more than 13 h at 1200°C. La₂Zr₂O₇ was formed in mixtures with LaMnO₃ at 1350°C, while SrZrO₃ was formed in mixtures containing La_0.6Sr_0.4MnO₃ or La_0.4Sr_0.6MnO₃. Only minor amounts of secondary phases were observed in mixtures with La_0.7Sr_0.3MnO₃. Chemical analysis revealed considerable interdiffusion between the primary phases as well as A-site deficiency of LaMnO₃ and La_0.7Sr_0.3MnO₃ when exposed to cubic zirconia. The oxidative/reductive nature of the chemical reaction between strontium-substituted lanthanum manganite and yttria-stabilized zirconia is discussed in relation to the Sr content in LSM. The lattice parameter of cubic zirconia was observed to be quite sensitive to the interdiffusion and is an excellent tool for investigating reactions on heterophase interfaces involving stabilized zirconia.     

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.     

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.     

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.     

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.     

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.     

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 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.     

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.     

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.     

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.     

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).     

Chemical Solution Deposition of Transparent and Metallic La0.5Sr0.5TiO3+x/2 Films Using Topotactic Reduction

Metallic and transparent La_0.5Sr_0.5TiO_{3+ x /2} films were prepared by the chemical solution deposition (CSD) method using topotactic reduction processing. The use of Si powder as the reducing agent was facile and allowed easy manipulation. It was observed that metallic (resistivity at 300 K ∼2.43 mΩ cm) and transparent (∼80% transmittance at visible light) La_0.5Sr_0.5TiO_{3+ x /2} films could be obtained with an annealing temperature of 900°C, which was significantly lower than the hydrogen reduction temperature (∼1400°C). The successful preparation of metallic and transparent La_0.5Sr_0.5TiO_{3+ x /2} films using CSD has provided a feasible route for depositing other perovskite-structured functional layers on La_0.5Sr_0.5TiO_{3+ x /2} films using this low-cost all CSD method.     

Low-Temperature Synthesis and Properties of LaMnO3±d and La0.67R0.33MnO3±d (R = Ca, Sr, Ba) from Citrate Precursors

LaMn_{1− y} ³⁺Mn _y ⁴⁺O_3±d and La_0.67R_0.33Mn_{1− y} ³⁺Mn _y ⁴⁺O_3±d (R = Ca, Sr, Ba) phases were synthesized at 350°C by using very reactive, amorphous precursors obtained from the stoichiometric citrate solutions. The chemical process was optimized with respect to the solution concentration, pH, and additives. The precursor reactions were investigated as a function of the cation stoichiometry and the additive by simultaneous thermal and thermogravimetric analysis and X-ray diffraction. The reaction pathway was found to be independent of the cation stoichiometry, but related to the acid or base additive. The annealing temperature was systematically increased in the 350–1200°C interval and the La_0.67Sr_0.33MnO_3±d properties (i.e., crystal sizes, Mn average valence, Curie temperature, magnetization, magnetic susceptibility) were measured and found to vary consistently as a function of it.     

Enhanced Shrinkage of Lanthanum Strontium Manganite (La0.90Sr0.10MnO3+δ) Resulting from Thermal and Oxygen Partial Pressure Cycling

Exposure of (La_0.90Sr_0.10)_0.98MnO_3+δ (LSM-10) to repeated oxygen partial pressure cycles (air/10 ppm O₂) resulted in enhanced densification rates, similar to behavior shown previously due to thermal cycling. Shrinkage rates in the temperature range 700°–1000°C were orders of magnitude higher than Makipirtti–Meng model estimations based on stepwise isothermal dilatometry results at a high temperature. A maximum in enhanced shrinkage due to oxygen partial pressure cycling occurred at 900°C. Shrinkage was the greatest when LSM-10 bars that were first equilibrated in air were exposed to gas flows of lower oxygen fugacity than in the reverse direction. The former creates transient cation and oxygen vacancies well above the equilibrium concentration, resulting in enhanced mobility. These vacancies annihilate as Schottky equilibria are reestablished, whereas the latter condition does not lead to excess vacancy concentrations.     

30 kbar Phase Equilibria of the La2O3–SrO–CuO System at 950°C

Phase equilibria of the La₂O₃–SrO–CuO system have been determined at 950°C at 30 kbar (3 GPa). Stable phases at the apexes of the ternary phase diagram are CuO, La₂O₃, and SrO. Stable intermediate phases are La₂, CuO₄ and La₂Cu₂O₅ in the LaO_1.5–CuO binary and Sr₂CuO₃, SrCuO₂, and Sr₁₄Cu₂₄O₄₁ in the CuO–SrO binary. The La_{2– x} Sr _x -CuO_4–δ solid solution is stable for 0.00 is ≤ x ≤ 1.29, the La_{2– x} Sr_{1+ x} Cu₂O_6+δ solid solution is stable for 0.03 ≤ x ≤0.20, the La_{2– x} Sr _x Cu₂O_5–δ solid solution is stable for 0.00 ≤ x ≤1.08, and the La _x Sr_{14– x} Cu₂₄O₄₁ solid solution is stable for 0.00 ≤ x ≤ 6.15. The 30 kbar phase diagram differs from the 1 atm (0.1 MPa) and 10 kbar (1 GPa) results principally in the absence of La_{1– x} Sr_{2+ x} Cu₂O_5.5+δ as a stable phase and the extended range of the La_{2– x} Sr _x Cu₂O_5–δ solid solution at 30 kbar.     

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.     

A Novel Spray-Pyrolysis Technique to Produce Nanocrystalline Lanthanum Strontium Manganite Powder

Nanocrystalline, single phase, and highly homogeneous La_0.84Sr_0.16MnO₃ (LSM) powder was prepared by a unique spray-pyrolysis process for solid oxide fuel cell applications. Atomization of a citrate–nitrate precursor solution consisting of La³⁺, Sr²⁺, and Mn²⁺ ions in the molar ratio 0.84:0.16:1.0, which can initiate a controlled exothermic anionic oxidation-reduction reaction leading to a self-propagating auto-ignition (self-ignition) reaction within individual droplets led to the conversion of the precursor to their corresponding single-phase LSM powder. Characterization of the as-sprayed and calcined products by X-ray powder diffraction, thermal analysis, and microstructural analysis confirmed the formation of nanocrystalline single-phase LSM powder by this process.     

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.     

The Optical Properties and Band Gap Energy of Nanocrystalline La0.4Sr0.6TiO3 Thin Films

The effects of microstructure on the optical properties of La_0.4Sr_0.6TiO₃ thin films were investigated. Dense films with the thickness of ∼200 nm and grain size 14–30 nm were produced on monocrystalline sapphire substrates by using a polymeric precursor spin coating technique at annealing temperatures under 800°C. X-ray data showed the formation of a single-phase cubic perovskite-type structure similar to undoped SrTiO₃ for annealing temperatures >500°C. The results of optical measurements showed that the optical spectra varied with the change of the grain size. From these data, the absorption coefficients were calculated and the band gap energy determined. In agreement with the quantum confinement model, it was shown that the band gap energy increased as the grain size decreased.