Preparation, Electrical Conductivity, and Thermal Expansion Behavior of Dense Nd1−xCaxCrO3 Solid Solutions

Nd_{1− x} Ca _x CrO₃ (0≤ x ≤0.25) solid solutions are synthesized using a two-step calcination solid-state reaction method and can potentially be used as interconnect applications in solid oxide fuel cells (SOFCs). The lattice parameters and unit cell volume decrease with an increase of the Ca²⁺ dopant concentration at the A-site. On the other hand, the relative density, electrical conductivity, and thermal expansion coefficient (TEC) increase with an increase of Ca²⁺ contents. Calcium doping significantly depresses the chromium vaporization of NdCrO₃, thus accelerating the sintering and densification of the oxides. Nd_{1− x} Ca _x CrO₃ with x =0.25 shows the best electrical conductivity of 28.8 and 1.1 S/cm at 850°C in air and hydrogen, respectively, with a high relative density of 98.0% and a good TEC of 9.19 × 10⁻⁶ K⁻¹ in the temperature range from 30° to 1000°C in air. This indicates that Nd_0.75Ca_0.25CrO₃ is a promising candidate as an interconnect material for application in SOFCs.     

Phase Transitions and Transient Liquid-Phase Sintering in Calcium-Substituted Lanthanum Chromite

This paper investigates sintering and phase transitions of La_0.7CaxCrO₃(0.25≥x≥0.35), a material useful as electrical interconnections in solid oxide fuel cells. Heating of the quenched, metastable single-phase chromite resulted in exsolution of CaCrO₄ due to Ca solubility limitations below 1200°C. A transient liquid phase formed between 850° and 1000°C as the CaCrO₄ melted, causing partial densification in materials having 0.25 < x < 0.30. A slight increase in Ca content induced an additional liquid-phase sintering event, likely due to melting of Ca₃(CrO₄)₂, which facilitated near-complete densification by 1250°C. After enhancing sintering, the secondary phases redissolved into the chromite.     

Stress–Strain Behavior During Compression of Polycrystalline La1−xCaxCoO3 Ceramics

Mechanical stress–strain behavior of LaCoO₃, La_0.8Ca_0.2CoO₃, and La_0.7Ca_0.3CoO₃ was studied under compression at 25° and 300°C. A hysteresis in the stress–strain relationship due to reorientation of ferroelastic domains (deformation twins) was observed, and a remanent strain is measured after unloading. The cohersive stress, defined as the maximum in effective elastic compliance during first loading, increases with substitution of Ca for La and decreases with increasing temperature. Domain reorientation was confirmed by X-ray diffraction of surfaces parallel and perpendicular to the loading direction. LaCoO₃ can be regarded as a soft ferroelastic material while the 30% Ca-substituted material is a hard ferroelastic. The hysteresis of the stress–strain relationship was clearly dependent on both composition and temperature.     

Subsolidus Phase Relations in the Pseudoternary System ZrO2-YO1.5-CrO1.5 in Air

The pseudoternary system ZrO₂-YO_1.5CrO_1.5 was studied between 1300° and 1600C in air by °a quenching method. No ordered phase of the type ZrY₆O₁₁ was detected, but an ordered Zr₃Y₄O₁₂ phase at 1300°C and YCrO₃ were observed as intermediate compounds. Solid solutions ofZrO₂ and YO_1.5 coexisting with CrO_1.5 and/or YCrO₃ formed; the apex occurred between 26.5 and 27.5 wt% YO_1.5 for the cubic ZrO₂+CrO_1.5+YCrO₃, three-phase region; CrO_1.5 is slightly soluble in ZrO₂(ss).     

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.     

Solid Solubility and Thermal Expansion in a LaPO4–YPO4 System

The composition and lattice parameters of co-precipitated (La_0.3Y_0.7) orthophosphate were studied using X-ray diffraction (XRD), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDX). The results indicate that the as-precipitated powder consists of single-phase (La_0.3Y_0.7PO₄·H₂O) rhabdophane nanoparticles. Heat treatment at 950°C caused the decomposition of rhabdophane into a (La_{1− x} Y _x )PO₄ monazite solid solution and YPO₄ xenotime. The solid solubility of Y in LaPO₄ monazite from 1000° to 1600°C was studied using XRD, TEM, and EDX. The implications of the findings for controlling the coefficient of thermal expansion of the prospective two-phase monazite–xenotime fiber coatings for ceramic composites applications are discussed.     

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.     

Tape Casting of Lanthanum Chromite

The effects of process additives, ball milling, and solids loading were evaluated for tape casting suspensions of glycinenitrate-synthesized La_0.7Ca_0.31CrO₃ powder. An optimized formulation was obtained based on rheological characterization, electrokinetic sonic amplitude measurements, qualitative examination of green tapes, and the sintered microstructure. The tape casting formulation incorporated 66:34 methyl ethyl ketone/ethyl alcohol solvent, an aliphatic phosphate ester dispersant, and 80 wt% (35 vol%) solids. The best binder/plasticizer system was 12 wt% (15 vol%) poly(isobutyl methacrylate) and 5 wt% (6.3 vol%) benzyl butyl phthalate plasticizer (binder:plasticizer = 2.3). Cast tapes were sintered at 1300°C for 2 h, producing a bulk density of 96.2% theoretical, with linear shrinkage of 22% and an approximate grain size of 1.3 μm.     

The Crystal Structure of LaAlO3-Stabilized La2/3TiO3 Ceramics: An HRTEM Investigation

LaAlO₃-stabilized La_2/3TiO₃ (LT) ceramics were prepared by the conventional mixed oxide route. Small amounts of manganese oxide were added to eliminate Ti⁴⁺ reduction. The powders were calcined at 1150°C and sintered at 1400°–1500°C for 4 h and cooled at rates of 900°–15°C/h. The products were high density and single phase, with an average grain size of 6 μm. The LaAlO₃-stabilized LT ceramics exhibited a relative permittivity (ɛ_r) of 64, a positive temperature coefficient of resonant frequency (τ_f) of 84, and dielectric Q value × resonant frequency ( Q × f ) values of 16 400 GHz. The crystal structure and microstructures have been investigated using high-resolution transmission electron microscopy (HRTEM) in conjunction with X-ray diffraction (XRD). One candidate crystal structure, a ≈2 a _p (where a _p is the lattice parameter of the high-temperature form of the cubic perovskite), b ≈2 a _p, and c ≈2 a _p with a space group Cmmm (65), has been confirmed by XRD, electron diffraction, and lattice imaging techniques. Microtwins, with twin boundaries parallel to the {100} planes, were observed in the microstructures.     

High-Temperature Structural Phase Transition in Ca0.7Ti0.7La0.3Al0.3O3: Investigation by Synchrotron X-Ray Diffraction

Mixed-oxide prepared Ca_0.7Ti_0.7La_0.3Al_0.3O₃ (CTLA) ceramics (≈96% dense), grain size 6–7 μm, with dielectric properties (at 4 GHz) of ɛ_r≈46, Q × f ≈38 000 GHz, and τ_f+13 ppm/°C, were studied at 25°–1300°C using synchrotron X-ray powder diffraction. At room temperature, CTLA exhibits a distorted orthorhombic structure, with two tilt systems: a =5.40383 (4) Å, b =5.41106 (6) Å, and c =7.64114 (7) Å with space group Pbnm . At 1050°±25°C, there is a transition from orthorhombic ( Pbnm ) to tetragonal ( I 4/ mcm ), with a simpler tilt arrangement. The lattice parameters at 1100°C were: a =5.44285 (4) Å and c =7.68913 (8) Å.     

Synthesis and Preparation of Lanthanum Aluminate Target for Radio-Frequency Magnetron Sputtering

A polycrystalline LaAlO₃ target for the radio-frequency (rf) magnetron sputterings of LaAlO₃ thin films has been prepared. These films serve as a buffer layer for high- T _c YBa₂Cu₃O_{7– x} superconducting thin films on Si. Synthesis of lanthanum aluminate powder from a mixture of La₂O₃ and Al₂O₃ powders was performed by calcining from 1000° to 1600°C in air. Characterization of the calcined powders by X-ray diffraction indicates that full development of LaAlO₃ phase was evident in the sample calcined for 3 h at 1600°C in air. A polycrystalline LaAlO₃ target was prepared by heat treatment at 1500°C for 2 h in air after pressureless sintering at 1750°C for 3 h in Ar. Thin films of the LaAlO₃ on Si (100) were obtained by rf magnetron sputtering using the target and oxygen-annealing the as-deposited films.     

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.     

Liquid-Phase-Assisted Sintering of Calcium-Doped Lanthanum Chromites

Investigations have been made on the low-temperature sinterability of calcium-doped lanthanum chromites which are to be used as interconnectors in solid oxide fuel cells (SOFCs). Nominally chromium deficient lanthanum calcium chromites (La_0.7Ca_0.3Cr₁-_yO₃, y = 0.02) were found to be sinterable to 94% theoretical density at 1573 K in air, whereas no densification was observed for samples with y = 0. The two-step shrinkage process suggests a liquid phase sintering mechanism with calcium oxychromates playing an important role as the liquid phase. After sintering at 1573 K, calcium-rich substances remained at grain boundaries.     

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.     

Grain-Boundary Diffusion of Strontium in (La,Ca)CrO3 Perovskite-Type Oxide by SIMS

The grain-boundary-diffusion coefficient ( D _gb) of strontium in La_0.9Ca_0.13CrO_3-δ was determined by secondary-ion mass spectrometry (SIMS), using two different measurement modes: depth profiling from the surface and line scanning on the fracture surface. The depth profiles that were sputtered by an O₂⁺-primary-ion beam gave two slopes of strontium concentration profiles, which corresponded to grain (bulk) and grain-boundary diffusion. The depth profiles were fitted to an appropriate equation that gave the grain- (bulk-) and grain-boundary-diffusion coefficients ( D _bulk= 6.5 × 10^-20 m²/s and D _gb= 1.6 × 10^-15 m²/s in air at 1273 K, respectively). Initially, to obtain the D _gb value via the SIMS line-scanning measurement, the fracture surface of La_0.9Ca_0.13CrO_3-delta was measured by a low-energy O₂⁺-primary-ion beam. The line-scanning measurement enabled us to successfully determine the strontium concentration profiles around the grain boundary. However, the D _gb value that was obtained via the line-scanning mode was 6.0 10⁻¹³ m²/s, which was a factor of 100 greater than that which was obtained by the depth-profile mode. Comparison between the depth-profile and line-scanning modes will require additional careful examination.     

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.     

Preparation of Larnthanum β-Alumina with High Surface Area by Coprecipitation

Mixtures of La₂O₃ and Al₂O₃ with various La contents were prepared by co-precipitation from La(NO₃)₃ and Al(NO₃)₃ solutions and calcined at 800° to 1400°C. The addition of small amounts of La₂O₃ (2 to 10 mol%) to Al₂O₃ gives rise to the formation of lanthanum β-alumina (La 2 O₃·11–14Al₂O₃) upon heating to above 1000°C and retards the transformation of γ-Al₂O₃ to α-Al₂O₃ and associated sintering.     

Ferroelastic Behavior of LaCoO3-Based Ceramics

LaCoO₃ and La_0.8Ca_0.2CoO₃ ceramics show a nonelastic stress–strain behavior during four-point bending experiments where hysteresis loops are observed during loading–unloading cycles. Permanent strain is stored in the material after unloading, and a mechanism related to ferroelastic domain switching in the rhombohedral perovskite is proposed. Domain switching in the materials has been confirmed using X-ray diffractometry. Fracture toughnesses of La_0.8Ca_0.2CoO₃ measured using single-edge notched beam and single-edge V-notched beam methods coincide and are equal to 2.2 MPa·m^1/2 at room temperature and decrease to ∼1 MPa·m^1/2 at temperatures >300°C. A decrease in fracture toughness is consistent with ferroelastic behavior, because the rhombohedral distortion decreases with increasing temperature.     

Electrical Transport Properties of La2CuO4 Ceramics Processed by the Spark Plasma Sintering

Highly dense La₂CuO₄ ceramics have been prepared by the spark plasma sintering technique. Temperature dependence of electrical conductivity indicates that La₂CuO₄ ceramics sintered at over 875°C exhibit a metal-like behavior, which should be ascribed to the special La₂CuO₄ crystal structure and its correlation splitting of the half-filled d _{x 2− y 2} band. Our experimental data indicate that all of the La₂CuO₄ samples exhibit positive thermoelectric power in the whole measuring temperature range, indicating that the majority of charge carriers are holes. It is desirable to obtain good thermoelectric performance for this system by optimizing the electrical properties and reducing the thermal conductivity.     

Doped Lanthanum Gallate Film Solid Oxide Fuel Cells Fabricated On a Ni/YSZ Anode Support

A colloidal deposition without any binder was developed to prepare a dense La_0.8Sr_0.2Ga_0.85Mg_0.15O_3−δ (LSGM) film on porous NiO/YSZ substrates, using an incompletely crystallized LSGM powder as starting material. Both the dense LSGM film with a thickness of 15 μm and the required phase composition of the LSGM were achieved simultaneously by sintering at 1400°C for 6 h. The conductivity of the supported LSGM film attained 0.102 S/cm at 800°C, which was comparable with those of the self-supported LSGM films. The maximum power density of the LSGM film cell was 480 at 800°C and 614 mW/cm² at 850°C, respectively.