Structural Characterization of Lanthanum Chromite Perovskite Coating Deposited by Magnetron Sputtering on an Iron-Based Chromium-Containing Alloy as a Promising Interconnect Material for SOFCs

Chromium-containing stainless steel (SS) is a prospective material for use as an interconnect in solid oxide fuel cells (SOFCs). However, during operations at high temperatures, the growth of oxide scales causes the performance of the interconnect and SOFC as a whole to deteriorate. The coating of SS 446 with a conducting perovskite is a potential method of slowing the growth of oxide scale and, therefore, improving overall SOFC performance. In the present research, the structural characterization of a pure LaCrO₃ thin film on the SS 446 substrates has been performed as a model material that can be used as a barrier coating for the metallic interconnect. The deposition of an amorphous La-Cr-O thin film on SS 446 was performed using radio-frequency (rf) magnetron sputtering. The deposited amorphous film was annealed in air to form the desired perovskite phase. The film underwent an amorphous to LaCrO₄ phase transition during annealing at 500°C with further transformation to LaCrO₃ orthorhombic phase during annealing at 700°C. A self-organized dendritic structure was reported as a result of the perovskite-phase formation. Although formation of various oxides, such as Fe₂O₃ and Fe₃O₄, was observed during the annealing of uncoated SS 446 in air, the coating of SS 446 surface with LaCrO₃ film prevented formation of various oxide phases at the interconnect surface. The structural characterization of the films and SS 446 surfaces was accomplished using scanning electron microscopy with energy-dispersive X-ray analysis, X-ray diffractometry, micro-Raman spectroscopy, and nanoindentation.     

Vaporization of LaCrO3: Partial and Integral Thermodynamic Properties

The vaporization of LaCrO₃(s) and samples of the composition LaCrO₃+ La₂O₃ was investigated in the temperature range of 1887-2333 K by Knudsen effusion mass spectrometry using Knudsen cells made of tungsten lined completely with iridium. The species Cr(g), CrO(g ), CrO₂(g), and LaO(g) were identified in the vapor. Their partial pressures were determined by calibration with pure platinum solid. The thermodynamic activity of Cr₂O₃, a _cr2o₃ in LaCrO₃ for the Cr₂0₃-poor phase boundary of this phase was In a_Cr2o₃⁼ -(17953/T) - 0.485 (temperature T given in K) for the temperature range of the measurements with a probable overall error of ± 13%. The following values and temperature dependence of ΔG°_f,T resulted for the formation of LaCrO₃(s) according to the reaction 0.5Cr₂O₃(s) + 0.5La₂O₃(s) → LaCrO₃(s): ΔG°_f,2100= -78.9 ± 1.1 kj/mol, Δ H°_f,298= -76.8 ± 5.2 kj/mol, and ΔG°_r(kJ/mol) = -74.7 - 0.00202 T . Computations for the vaporization of LaCrO₃ were conducted to show the volatility of this material in different atmospheres at high temperatures.     

Ceramic Fuel Cells

A ceramic fuel cell in an all solid-state energy conversion device that produces electricity by electrochemically combining fuel and oxidant gases across an ionic conducting oxide. Current ceramic fuel cells use an oxygen-ion conductor or a proton conductor as the electrolyte and operate at high temperatures (>600°C). Ceramic fuel cells, commonly referred to as solid-oxide fuel cells (SOFCs), are presently under development for a variety of power generation applications. This paper reviews the science and technology of ceramic fuel cells and discusses the critical issues posed by the development of this type of fuel cell. The emphasis is given to the discussion of component materials (especially, ZrO₂ electrolyte, nickel/ZrO₂ cermet anode, LaMnO₃ cathode, and LaCrO₃ interconnect), gas reactions at the electrodes, stack designs, and processing techniques used in the fabrication of required ceramic structures.     

Defect Structure of Mg-Doped LaCrO3 Model and Thermogravimetric Measurements

Chemical stability and cation stoichiometry determine the applicability of LaCrO₃ as a high-temperature oxide electrode. A model for the behavior of acceptor-doped LaCrO₃, as a function of oxygen activity is proposed. The model is in agreement with experimental data on Mg-doped LaCrO₃. Stability regimes and compensation mechanisms at various oxygen activities and temperature are presented.     

Low-Temperature Sintering of La(Ca)CrO3 Powder Prepared through the Combustion Process

Ultrafine La(Ca)CrO₃ (LCC) powder was prepared through the glycine–nitrate gel combustion process. It was shown for the first time that the use of relatively inexpensive CrO₃ as a starting material for chromium has potential for the bulk preparation of sinter-active LCC powder. As-prepared powder, when calcined at 700°C, resulted in LCC along with a small amount of CaCrO₄. The calcined powder was found to be composed of soft agglomerates with a particle size of ≈70–290 nm. The cold pressing and sintering of the calcined powder at 1200°C resulted in the mono-phasic La_0.7Ca_0.3CrO₃ with density ≈98% of its theoretical value. This is the lowest sintering temperature ever reported for La_0.7Ca_0.3CrO₃. The conductivity of the sintered La_0.7Ca_0.3CrO₃ at 1000°C was found to be ≈57 S/cm in air. The sintering and electrical behavior achieved for La_0.7Ca_0.3CrO₃ may find application as an interconnect material for high-temperature solid oxide fuel cells if problems with chemical expansion and poor conductivity in fuel can be overcome.     

Hydration of 3CaO·Al2O3 and 3CaO·Al2O3+] Gypsum With and Without CaCl2

Paste samples of tricalcium aluminate alone, with CaCl₂, with gypsum, and with gypsum and CaCl₂ were hydrated for up to 6 months and the hydration products characterized by SEM, XRD, and DTA. Tricalcium aluminate hydrated initially to a hexagonal hydroaluminate phase which then changed to the cubic form; the transformation rate depended on the size and shape of the sample and on temperature. The addition of CaCl₂ to tricalcium aluminate resulted in the formation of 3CaO · Al₂O₃· CaCl₂·10H₂O and 4CaO · Al₂O₃· 13H₂O, or a solid solution of the two. The chloride retarded the formation of the cubic phase 3CaO · Al₂O₃· 6H₂O; the addition of gypsum resulted in the formation of monosulfoaluminate with a minor amount of ettringite. When chloride was added to tricalcium aluminate and gypsum, more ettringite was formed, although 3CaO · Al₂O₃· CaSO₄· 12H₂O and 3CaO · Al₂O₃· CaCl₂· 10H₂O were the main hydration products.     

Fabrication of Nano-Scaled α-Al2O3 Crystallites Through Heterogeneous Precipitation of Boehmite in a Well-Dispersed θ-Al2O3-Suspension

The possibility of eliminating finger or vermicular growth of α-Al₂O₃ particles obtained by calcination of boehmite was examined. Heterogeneous precipitation of boehmite in a well-dispersed θ-Al₂O₃ suspension was first prepared, in which the mass ratio of boehmite to θ-crystallite was evaluated to form agglomerates of similar sizes that will form α-Al₂O₃ crystallites of <100 nm in diameter. θ- to α-phase transformation of alumina experiences a nucleation and growth mechanism, with the critical size of nucleation being ∼25 nm for θ-Al₂O₃ and the size for accomplishment of transformation followed by finger growth being ∼100 nm. Hence, fabricating agglomerates that would form α-Al₂O₃ crystallites with sizes <100 nm accompanied with appropriate thermal treatments can be a method for obtaining α-Al₂O₃ crystallites free of finger growth. It is found that proper preparation of the agglomerate with appropriate size may initiate a simultaneous and lower temperature θ- to α-Al₂O₃ phase transformation for such powder systems, substantially limiting the mass transfer among the newly formed α-Al₂O₃ particles. Moreover, α-Al₂O₃ crystallites free of finger growth can be obtained.     

The System Sodium Fluoride—Alumina Investigated by Quenching Methods

Alumina was found to react with sodium fluoride on fusion to produce sodium aluminate and cryolite according to the reaction 6NaF + 2Al₂2c₃= 3NaA10₂+ Na₃A1F₆. An insoluble sodium aluminate phase was observed under the polarizing microscope in samples quenched from as high as 1400°C. The equilibrium crystallization temperature of sodium fluoride in the presence of solid sodium aluminate was found to be slightly depressed with added alumina. A maximum lowering of 6°C was found for a starting alumina content of 5.4%. Further alumina additions resulted in the secondary precipitation of β-Al₂O₃. The shallow depression of the sodium fluoride crystallization temperature and the observed limited alumina solubility are attributed to the formation of cryolite. The composition of the liquid in equilibrium with sodium aluminate and sodium fluoride or sodium aluminate and β-alumina is represented in terms of the pseudo-ternary system NaF-Al₂O₃-Na₃A1F₆.     

Stability of Mullite as Derived from Equilibria in the System CoO-Al2O3-SiO2

The free energy of reaction for the formation of mullite from its oxide components was derived from equilibrium studies in the system CoO-Al₂O₃-SiO₂. Within this system there appears, at solidus temperature in a certain composition area, the phase assemblage mullite + silica + spinel (= cobalt aluminate) + liquid. Determination of the oxygen pressure of a gas phase at which metallic cobalt precipitates from this phase assemblage and from the phase assemblage spinel (= cobalt aluminate) + corundum in the system CoO-Al₂O₃ permits calculation of ΔG° for the reaction 3Al₂O₃+ 2SiO₂= Al₆Si₂O₁₃. The value obtained at 1422°C is -5.8 kcal.     

Forming and Sintering of in Situ Alumina Composite with Hydraulic Inorganic Binder

Two types of barium aluminate binders were prepared by heat treatment of barium aluminate precursors, synthesized by using solution processes, at low temperatures ( T < 500°C). One was barium monoaluminate (BaAl₂O₄), and the other was barium aluminate binder (BAH binder) composed of amorphous phase, barium aluminate monohydrate (BaAl₂O₄·H₂O), and BaAl₂O₄. The setting time of the BAH binder was controlled by adjusting the heat-treatment temperature of the BAH binder precursor. The addition of the synthesized BaAl₂O₄ powders to Al₂O₃ powders improved the bending strength of Al₂O₃ matrix green bodies. The synthesized BaAl₂O₄ powders led to the in situ forming of barium hexaaluminate (BaO· x Al₂O₃, x = 6.9: BA6) platelets in the matrix by reacting with Al₂O₃ during sintering. The formed BA6 platelets inhibited the grain growth of the matrix Al₂O₃ grains.     

The System CaO–"CaCr2O4"–CaAl2O4 in Air and under Mildly Reducing Conditions

The system CaO–chromium oxide in air is reinvestigated and the existence of intermediate phases with chromium in oxidation states >3+ (Ca₅Cr₃O₁₂, Ca₃(CrO₄)₂, and Ca₅(CrO₄)₃) confirmed. Under reducing conditions these phases are unstable. A metastable, polymorphic form of calcium chromite, δ -CaCr₂O₄, is observed. In the CaO-rich section of the CaO–Al₂O₃–Cr₂O₃ system a ternary intermediate phase, chrome-haüyne, Ca₄[(Al,Cr³⁺)₆O₁₂](Cr⁶⁺O₄), coexists with calcium chromate and calcium aluminate phases. In air, low melting temperatures are preserved in all assemblages containing calcium chromate phases. Under reducing conditions a new ternary phase, Ca₆Al₄Cr₂O₁₅, coexists with CaO, CaCr₂O₄, chrome-haüyne, and calcium aluminate phases. The influence of chromium oxide additions on the solidus temperatures of the CaO–Al₂O₃ system is insignificant.     

Effects of Cation Substitution on Electrical and Thermal Transport Properties of YCrO3 and LaCrO3

High-temperature electrical conductivity, Seebeck coefficient, and thermal conductivity measurements were used to study the effects of different cation substituents on electrical and thermal transport in YCrO₃ and LaCrO₃. The substitution of divalent Ca and Sr for Y and La, respectively, resulted in the formation of small polarons as charge carriers. The additional substitution of Mn for Cr resulted in the formation of a second charge carrier associated with the Mn. The electrical conductivity results were consistent with thermally activated transport by hopping of a temperature-independent carrier concentration. The activation energies were 0.20 and 0.12 eV for (Y,Ca)CrO₃ and (La,Sr)CrO₃, respectively, and increased to about 0.50 eV with the substitution of Mn for Cr. The Seebeck coefficient increased linearly with temperature and decreased with substituent concentration for both (Y,Ca)CrO₃ and (La,Sr)CrO₃. The substitution of Mn for Cr resulted in a Seebeck coefficient with a more complex dependence on temperature and substituent concentration. The thermal conductivity did not change significantly with either cation substitution or temperature.     

Influence of B site Substituents on Lanthanum Calcium Chromite Nanocrystalline Materials for a Solid-Oxide Fuel Cell

Highly reactive and nanocrystalline powders of LaCrO₃based compositions, having the general formula La_0.9Ca_0.1Cr_{1− x} M _x O_3−δ (0≤ x ≤0.1, and M=Al, Co, or Mg), suitable for solid-oxide fuel cell (SOFC) applications, have been synthesized using an auto-combustion technique with ammonium dichromate as the chromium source. Owing to very fine crystallite size (ranging from 10 to 50 nm) and the high reactivity of the powders (surface area as high as 25 m²/ g ), the sintering temperature reduces drastically and a highly dense, uniform, and fine-grained microstructure is obtained. A dramatic improvement in densification (nearly theoretical density) is observed for aluminum substitution, when sintered at as low a temperature as 1300°C. The microstructure shows a uniform distribution of grains having an average grain size of ∼0.5 μm. Depending on the substituent, the electrical conductivities of the sintered samples in air, at 1000°C, were found to be in the range of 10–45 S/cm, and are more than that of the values required for SOFC application. The thermal expansion coefficients, as obtained, are also comparable with the other SOFC cell components.     

Mixed-Cation Oxide Powders via Resin Intermediates Derived from a Water-Soluble Polymer

Submicrometer powders of complex oxides were prepared via resin intermediates based on a starch type of organic precursor. A commercially available water-soluble starch derivative was (for the first time) used as the organic base for solution synthesis of ceramic powders. Calcination of the charred, fluffy, amorphous resins at a temperature below 600°C for 4 h yielded perovskite powders of Sr-doped LaMnO₃ and Sr-doped La(Fe,Co)O₃. Sr-doped LaCrO₃ needed to be calcined above 750°C to ensure phase purity and to remove organic residue. Due to the low cost of starch derivatives, the process has the potential of being more economical than the commonly used Pechini's type process, which utilizes citric acid and ethylene glycol.     

Low-Temperature Synthesis of Hexagonal Anorthite via Hydrothermal Processing

Hexagonal anorthite (CaAl₂Si₂O₈) has been prepared by hydrothermal processing of monocalcium aluminate and quartz at temperatures as low as 200°C. The successful development of this phase is dependent upon several processing parameters, including the hydration of the calcium aluminate precursor material to the hydrogarnet phase (Ca₃Al₂O₆·6H₂O) prior to hydrothermal treatment and the use of quartz as opposed to amorphous sources of SiO₂. Quartz has partial solubility in the hydrogarnet lattice for additions up to 40 wt%. Increased SiO₂ substitution has been shown to reduce the conversion of hydrogarnet to Ca₄Al₆O₁₃·3H₂O, thereby increasing its thermal stability and improving its strength characteristics at temperatures greater than 200°C. Quartz additions greater than 43 wt% lead to the formation of CaAl₂Si₂O₈ as the sole reaction product. The moderate temperatures involved in forming this anhydrous material are an order of magnitude lower than those necessary to form this phase by melt crystallization, making it a true chemically bonded ceramic. The reaction can form a bonded matrix with strengths up to 40000 psi (280 MPa). Strengths are limited due to density changes during anorthite formation, but the matrix is thermally stable up to 1000°C.     

Effect of (La0.8Sr0.2)CrO3 Coating on Carbon Deposition onto a Stainless-Steel (SUS430) Substrate

In this study, a dense strontium-doped lanthanum chromite (La_0.8Sr_0.2CrO₃, LSC) thin layer was designed to protect a stainless-steel (SUS430) substrate from carbon deposition. The LSC layer was coated onto an SUS430 substrate by a dipping technique from a precursor solution of La, Sr and Cr nitrates, acetylacetone (acac), and 2-methoxyethanol. The effect of AcAc on the phase behavior and microstructure evolution of the LSC thin films was investigated. After being heat-treated at 800°C in air, the thin film was found to consist of perovskite LaCrO₃, Mn_1.5Cr_1.5O₄, and Cr₂O₃ phases. The addition of a chelating agent, acac, to the precursor solution led to a reduction in the formation of the strontium chromite (SrCrO₄) phase. As a consequence, a thin film having a dense microstructure could be obtained. It was confirmed by Fourier-tranform Raman spectroscopic analysis and FESEM observations that the carbon deposited on the uncoated SUS430 substrate was amorphous with a spherical morphology. The LSC thin film thus obtained was found to be very effective at preventing carbon deposition when it was heat-treated under a dry hydrocarbon atmosphere.     

Preparation of Nanometer-Sized α-Alumina Powders by Calcining an Emulsion of Boehmite and Oleic Acid

This study proposes a method to form ultrafine α-Al₂O₃ powders. Oleic acid is mixed with Al(OH)₃ gel. The gel is the precursor of the Al₂O₃. After it is mixed and aged, the mixture is calcined in a depleted oxygen atmosphere between 25° and 1100°C. Oleic acid evaporates and decomposes into carbon during the thermal process. Residual carbon prevents the growth of agglomerates during the formation of α-Al₂O₃. The phase transformation in this process is as follows: emulsion →γ-Al₂O₃→δ-Al₂O₃→θ-Al₂O₃→α-Al₂O₃. This process has no clear θ phase. Aging the mixed sample lowers the formation temperature of α-Al₂O₃ from 1100° to 1000°C. The average crystallite diameter is 60 nm, measured using Scherrer's equation, which is consistent with TEM observations.     

Effect of Organic Compounds on the Interconversions of Calcium Aluminate Hydrates: Hydration of Tricalcium Aluminate

The paste hydration of tricalcium aluminate (C₃A) in the presence of organic compounds was investigated at several temperatures up to 75°C. The results confirm earlier hypotheses that the hexagonal calcium aluminate hydrates (principally C₄AH₁₃) which are first formed create a protective barrier around the remaining C₃A and severely restrict further hydration. Above 30°C, conversion to C₃AH₆ breaks down this barrier and causes rapid hydration of C₃A. Organic compounds retard the hydration of C₃A by inhibiting the conversion reaction. Experiments with synthetic C₄AH₁₃ showed that organic molecules can form interlayer compounds, and it is considered that random sorption into the C₃AH₁₃ structure restricts the transformation to C₃AH₆. Other aspects of C₃A hydration and of the reactivity of C₄AH₁₃ are also discussed.     

Phase Transformation in EB-PVD Yttria Partially Stabilized Zirconia Thermal Barrier Coatings during Annealing

Electron-beam physical-vapor-deposited thermal barrier coatings consisting of ZrO₂ stabilized by 7 wt% Y₂O₃ were investigated in regard to phase transformation after annealing. Free-standing ceramic layers were heat-treated in air, for up to 200 h, in the temperature range 1200°—1400°C and then analyzed by X-ray diffractometry. Based on information obtained from the {111} and {400} peaks, the phase composition and the Y₂O₃ content in the phases were calculated. At the start of transformation, small grains of a low-Y₂O₃ t phase and a c phase formed. After >30 h at 1300°C and at 1400°C, a mixture of a t phase deficient in Y₂O₃, an m phase, and a c phase formed after cooling, with the Y₂O₃ contents in the phases roughly predicted by the phase diagrams. The results of the present study are discussed here in detail and compared with data for plasma-sprayed coatings.     

Microstructural Characterization of Cofired Tungsten-Metallized High-Alumina Electronic Substrates

Microstructural characterization of a high-Al₂O₃ substrate containing cofired thick-film tungsten metallization, with particular emphasis on the metal/ceramic interface, was conducted. The substrate contained tabular Al₂O₃ grains surrounded by a continuous calcium magnesium aluminum silicate glass containing particles of monoclinic ZrO₂ and reduced rutile (TiO_{2- x} ). The metal/ceramic adhesion was caused by mechanical interlocking between the W and Al₂O₃ grains by the glass phase which penetrated the porous W layers during sintering; there was no interfacial reaction or diffusion zone. The mechanical properties of the W metallization did not limit interfacial strength. Heat treatments of the substrate at 1400 K in air and under vacuum resulted in the devitrification of the intergranular glass. The most abundant devitrification product was anorthite (CaAl₂Si₂O₈), accompanied by magnesium aluminate titanate, magnesium aluminate spinel, α-cristobalite (SiO₂), and α-cordierite (Mg₂Al₄Si₅O₁₈). In addition, small rutile particles precipitated within the Al₂O₃ grains.