Phase Equilibria in the Ga2O3In2O3 System

Subsolidus phase relationships in the Ga₂O₃–In₂O₃ system were studied by X-ray diffraction and electron probe microanalysis (EPMA) for the temperature range of 800°–1400°C. The solubility limit of In₂O₃ in the β-gallia structure decreases with increasing temperature from 44.1 ± 0.5 mol% at 1000°C to 41.4 ± 0.5 mol% at 1400°C. The solubility limit of Ga₂O₃ in cubic In₂O₃ increases with temperature from 4.X ± 0.5 mol% at 1000°C to 10.0 ± 0.5 mol% at 1400°C. The previously reported transparent conducting oxide phase in the Ga-In-O system cannot be GaInO₃, which is not stable, but is likely the In-doped β-Ga₂O₃ solid solution.     

X-ray Diffraction and Microstructural Investigation of the Al2O3-La2O3-TiO2 System

The ternary phase diagram of Al₂O₃-La₂O₃-TiO₂ at 1400°C was determined with 12 compatibility triangles. Al₂O₃ stabilizes the A-site-deficient La_2/3TiO₃ perovskite structure. According to XRD and microstructural investigations, the solid solution extends along the La_2/3TiO₃-LaAlO₃ tie line from at least 4 mol% LaAlO₃ to pure LaAlO₃. With increasing LaAlO₃ content, the stabilized La_2/3TiO₃ structure changes from orthorombic via tetragonal to cubic.     

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.     

Preparation of La2Zr2O7 by Sol—Gel Route

The La₂Zr₂O₇ phase was prepared from metal acetylacetonates by a sol—gel route without any intermediate phase formation. X-ray peaks appeared at a temperature as low as 500°C at the positions expected for La₂Zr₂O₇, although they were broad. The crystal structure of La₂Zr₂O₇ was found to be of the fluorite type below 900°C and of thepyrochlore type above 1000°C. The substitution of a small amount of Eu for La was carried out to investigate the crystal structure from the viewpoint of fluorescence, and these results confirmed the formation of fluorite type La₂Zr₂O₇ below 900°C.     

Preparation of Dense Platinum-Yttria Stabilized Zirconia and Yttria Stabilized Zirconia Films on Porous La0.9Sr0.1MnO3 (LSM) Substrates

A sol–gel process has been developed to prepare fine powder of La_0.9Sr_0.1MnO₃ (LSM) with an average particle size ∼40 nm. The LSM powder is pressed to pellets, on which a uniform green yttria-stabilized zirconia (YSZ) film is deposited using an electrophoretic deposition process. A green composite film of platinum and YSZ (Pt-YSZ) is prepared on the top of the green YSZ film using a colloidal process, followed by filling the pores using a sol–gel process. The three-layered structure, a green Pt-YSZ film, and a green YSZ film on a green LSM substrate, is fired at 1250°C for 3 h, resulting in a dense Pt-YSZ and YSZ film supported by a porous LSM substrate. Electrical measurements show that the sensors with the three-layered structure display a well-defined diffusion-limited current in gases containing partial pressure of oxygen up to ∼9 vol%, implying that the quality of the Pt-YSZ and YSZ film is adequate for the sensor application.     

Subsolidus Relations in the La2O3─CuO─CaO Phase Diagram and the La2O3─CuO Binary Join

The phase diagram for the CuO-rich part of the La₂O₃─CuO join was redetermined. La₂Cu₂O₅ was found to have a lower limit of stability at 1002°± 5°C and an incongruent melting temperature of ∼1035°C. LagCu₇O₁₉ had both a lower (1012°± 5°C) and an upper (1027°± 5°C) limit of stability. Subsolidus phase relations were studied in the La₂O₃─CuO─CaO system at 1000°, 1020°, and 1050°C in air. Two ternary phases, La_1.9Ca_1.1Cu₂O_5.9 and LaCa₂Cu₃O_8.6, were stable at these temperatures, with three binary phases, Ca₂CuO₃, CaCu₂O₃, and La₂CuO₄. La₂Cu₂O₅ and La₈Cu₇O₁₉ were stable only at 1020°C, and did not support solid-solution formation.     

Chemical Interactions between La-Sr-Mn-Fe-O-Based Perovskites and Yttria-Stabilized Zirconia

Orthoferrite-based perovskites are of interest as materials for the cathode in solid oxide fuel cells (SOFCs). Therefore, the chemical compatibility between perovskites of the composition (La_1−xSr_x)_zFe_1−yMn_yO_3−δ (0 # x # 0.3; 0.2 # y # 1; z = 0.90, 0.95, 1.00) and the solid electrolyte zirconia (ZrO₂) doped with 8 mol% yttria (Y₂O₃) (8YSZ) has been investigated. Powder mixtures of the two materials have been annealed at different temperatures. The formation of monoclinic ZrO₂ at 1000°C, as well as of La₂Zr₂O₇ and SrZrO₃ at 1400°C, has been determined in some samples. The reactions that are observed are discussed, with respect to the thermodynamic activities, tolerance factor, and oxygen-ion migration energies. Some perovskite compositions seem to be compatible with Y₂O₃-stabilized ZrO₂ (YSZ), thereby offering the possibility to use orthoferrite-based perovskites in SOFCs with a solid electrolyte made of YSZ.     

La(Sr)FeO3 SOFC Cathodes with Marginal Copper Doping

(La_0.8Sr_0.2)_0.98Fe_0.98Cu_0.02O_3−δ can be sintered directly onto YSZ (without the need for a protective ceria interlayer). Though subject to an extended "burn-in" period (∼200 h), anode-supported YSZ cells using the Cu-doped LSF achieve power densities ranging from 1.3 to 1.7 W/cm² at 750°C and 0.7 V. These cells have also demonstrated 500 h of stable performance. The results are somewhat surprising given that XRD indicates an interaction between (La_0.8Sr_0.2)_0.98Fe_0.98-Cu_0.02O_3−δ and YSZ resulting in the formation of strontium zirconate and/or monoclinic zirconia. The amount and type of reaction product was found to be dependent on cathode and electrolyte powder precalcination temperatures.     

Revised Phase Diagram of the System ZrO2-CeO2 Below 1400°C

The phase diagram of the system ZrO₂-CeO₂ was rein-vestigated using hydrothermal techniques. Cubic, tetragonal, and monoclinic solid solutions are present in this system. The tetragonal solid solution decomposes to monoclinic and cubic solid solutions by a eutectoid reaction at 1050°50°C. The solubility limits of the tetragonal and cubic solid solutions are about 18 and 70 mol% CeO₂, respectively, at 1400°C, and about 16 and 80 mol% CeO₂, respectively, at 1200°C. Solubility limits of the monoclinic and cubic solid solutions are about 1.5 and 88 mol% CeO₂ at 1000°C, and 1.5 and 98 mol% CeO₂ at 800°C, respectively. The compound Ce₂Zr₃O₁₀ is not found in this system.     

Phases in the Binary Systems PbO—La2O3, Gd2O3, and Sm2O3

In the binary system PbO–La_zO₃ only one compound, 4PbO.La₂O₃, exists; it is flanked by two eutectics. The structure of the compound, although of lower symmetry, is intimately related to the C modification of the rare earths. Below 800° to 1000°C, metastable solid solutions are formed from oxide mixtures coprecipitated from mixed solutions of the nitrates, the cubic parameter a = 5.66 A, if extrapolated to pure La₂O₃, corresponding to half the a parameter of the C form of La₂O₃. The solid solutions existing between the compositions La₂O₃–2Pb0 and pure La₂O₃ have a cubic face–centered lattice and obey Vegard's rule. The systems of PbO with Sm₂O₃ and Gd₂O₈ are quite similar to that with La₂O₃. The compound Sm₂O₃.4Pb0 decomposes at 1000°C with evaporation of PbO; Sm₂O₃ remains in the B modification.     

Ta2O5/Nb2O5 and Y2O3 Co-doped Zirconias for Thermal Barrier Coatings

Zirconia doped with 3.2–4.2 mol% (6–8 wt%) yttria (3–4YSZ) is currently the material of choice for thermal barrier coating topcoats. The present study examines the ZrO₂-Y₂O₃-Ta₂O₅/Nb₂O₅ systems for potential alternative chemistries that would overcome the limitations of the 3–4YSZ. A rationale for choosing specific compositions based on the effect of defect chemistry on the thermal conductivity and phase stability in zirconia-based systems is presented. The results show that it is possible to produce stable (for up to 200 h at 1000°–1500°C), single (tetragonal) or dual (tetragonal + cubic) phase chemistries that have thermal conductivity that is as low (1.8–2.8W/m K) as the 3–4YSZ, a wide range of elastic moduli (150–232 GPa), and a similar mean coefficient of thermal expansion at 1000°C. The chemistries can be plasma sprayed without change in composition or deleterious effects to phase stability. Preliminary burner rig testing results on one of the compositions are also presented.     

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.     

Investigation of the Phase Diagram for the Pseudobinary System Li2SO4–La2(SO4)3 and Its Ionic Conductivity

The phase diagram of the pseudobinary system Li₂SO₄–La₂(SO₄)₃ has been investigated by means of X-ray diffraction and differential thermal analysis. LiLa(SO₄)₂ is formed by a peritectic reaction in this system; the peritectic temperature is 653±3°C. The eutectic reaction of Li₂SO₄ and LiLa(SO₄)₂ occurs at 553±3°C; the composition at the eutectic point is 17 mol% La₂(SO₄)₃. LiLa(SO₄)₂ is monoclinic with a=1.375 nm, b=0.6744 nm, c=0.7068 nm, and β=105.4°. The ionic conductivity of LiLa(SO₄)₂ has been studied from room temperature to 350°C and is found to be relatively low at room temperature or at lower temperatures. Its activation energy is 0.66 eV. Thus it is not suitable as a fast ion conductor.     

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.     

Sintering, Microstructure, Hardness, and Fracture Toughness Behavior of Y2O3-CeO2-ZrO2

A wet-chemical approach is applied to derive fine powders with compositions 11 mol% CeO₂-ZrO₂, 1 mol% YO_1.5-10 mol% CeO₂-ZrO₂, 12 mol% CeO₂-ZrO₂, and 2 mol% YO_1.5-10 mol% CeO₂-ZrO₂ by the coprecipitation method. The characteristics of the as-derived powders are evaluated through thermal analysis and electron microscopy. The sintering behavior of the calcined powders is carried out at 1400° and 1500°C for 1 to 10 h. Sintered density higher than 98% of theoretical is achieved for sintering at 1400°C for several hours. The as-sintered density dependence on the sintering condition is related to the extent of tetragonal-to-monoclinic phase transformation as well as the associated microcracks. Partial substitution by Y₂O₃ in CeO₂-ZrO₂ results in reduced grain size and tends to stabilize the tetragonal structure. Y₂O₃ is more effective than CeO₂ with respect to the grain size refinement and tetragonal stability. In addition, Y₂O₃ substitution in CeO₂-ZrO₂ increases the hardness, while it decreases the fracture toughness.     

Oxygen Tracer Diffusion in La2-xSrxCuO4-y Single Crystals

The tracer diffusion of ¹⁸O in La_2-xSr_xCuO_4-y single crystals (x = 0 to 0.12) has been measured from 400° to 700°C in 1 atm of oxygen using SIMS analysis. Evidence for diffusion by a vacancy mechanism was found at low strontium contents. Oxygen diffusivities for x 2≥ 0.07 were depressed by several orders of magnitude below the diffusivity for undoped La₂CuO_4±y. The observed effects of strontium doping on oxygen diffusivity are discussed in terms of defect chemical models. The decreasing oxygen diffusivity with increasing strontium was attributed to the ordering of oxygen vacancies at large defect concentrations. A diffusion anisotropy, D _ab/ D _c, of ∼600) was also found at 500°C.     

The Calcia–Zirconia Phase Diagram Revisited: Stability of the Ordered Phases φ1 and φ2

Single crystals of CaO-stabilized ZrO₂ containing between 15.3 and 18.9 mol% CaO were heat-treated for 5000 h at 1200°C to study the stability of the ordered defect-fluorite phase, CaZr₄O₉ (φ₁). Subsequent TEM analysis of the equiaxed φ₁ domains in samples richer than approximately 18 mol% in CaO showed a random distribution of φ₁ variants, with no preferred interfacial habit planes. A critical review of the literature, combined with the new data, supports the Stubican-Hellmann-Hannon version of the phase diagram in the region 15 to 26 mol% CaO and 1000° to 1400°C and strongly suggests that φ₁ is a stable phase in the ZrO₂-CaO systems.     

Grain-Boundary Migration and Dielectric Properties of Semiconducting SrTiO3 in the SrTiO3-BaTiO3-CaTiO3 System

Chemically induced grain-boundary migration and its effects on the interface and dielectric properties of semiconducting SrTiO₃ have been investigated. Strontium titanate specimens that had been doped with 0.2 mol% of Nb₂O₅ were sintered in 5H₂/95N₂. The sintered specimens were diffusion annealed at 1400°C in 5H₂/95N₂ with BaTiO₃ or 0.5BaTiO₃-0.5CaTiO₃ (mole fraction) packing powder. The grain boundaries of the annealed specimens were oxidized in air. In the case of BaTiO₃ packing, grain-boundary migration occurred with the diffusion of BaTiO₃ along the grain boundary. The effective dielectric constant of the specimen decreased gradually as the temperature increased but showed two peaks, possibly because of barium enrichment at the grain boundary and an oxidized Sr(Ba)TiO₃ layer. In the case of 0.5BaTiO₃-0.5CaTiO₃ packing, although barium and calcium were present at the grain boundary of the specimen, no boundary migration occurred, as in a previous investigation. With the diffusion of barium and calcium, the resistivity of the specimen increased and the variation of the effective dielectric constant with temperature was much reduced, in comparison to those without solute diffusion. These enhanced properties were attributed to the solute enrichment and the formation of a thin diffusional Sr(Ba,Ca)TiO₃ layer at the grain boundary.     

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.     

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.