High temperature oxidation behavior of interconnect coated with LSCF and LSM for solid oxide fuel cell by screen printing

The current study examined the effect of La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) and La_0.7Sr_0.3MnO₃ (LSM) coatings on the electrical properties and oxidation resistance of Crofer22 APU at 800 °C hot air. LSCF and LSM were coated on Crofer22 APU by screen printing and sintered over temperatures ranging from 1000 to 1100 °C in N₂. The coated alloy was first checked for compositions, morphology and interface conditions and then treated in a simulated oxidizing environment at 800 °C for 200 h. After measuring the long-term electrical resistance, the area specific resistance (ASR) at 800 °C for the alloy coated with LSCF was less than its counterpart coated with LSM. This work used LSCF coating as a metallic interconnect to reduce working temperature for the solid oxide fuel cell.     

Material transport and degradation behavior of SOFC interconnects

The SOFC interconnect materials, both lanthanum chromite based oxides and Fe–Cr ferritic alloys, are discussed from the viewpoint of material transport which causes the degradation in conductivity or chemical stability. The controlling factors, such as effect of oxygen chemical potential gradient, interaction with other cell components, and surrounding gaseous atmospheres are evaluated. The role grain boundary is important in the transport of metal components in oxide materials such as lanthanum chromites, or oxide scales on alloy. The diffusivity of metal components in alloy is much faster, which causes the interdiffusion on nickel and chromium between alloy and anode current collector. The reaction of alloy and sealing materials would be more significant, since the chromium component in alloy easily reacts with alkaline earth components in sealing materials. The slight amount of water vapor in air may greatly enhance the chromium vaporization rate from chromium oxide (Cr₂O₃).     

Influence of different perovskite interlayers on the electrical conductivity between La0.65Sr0.3MnO3 and Fe/Cr-based steels

The electrical conductivity of the three-layer system {La_0.65Sr_0.3MnO₃ (LSM)}/{Perovskite Contact Layer (PCL)}/Steel was studied by a DC four-point contact method for 3200 h in air at 800 °C. The four commercial steels Crofer22APU, ZMG232, X2CrTiNb18 (DIN 1.4509), and X18CrN28 (DIN 1.4749) were investigated. The three perovskite compositions La_0.8Sr_0.2Mn_0.5Co_0.5O₃ (LSMC), LaMn_0.4Co_0.6O₃ (LMC) and Y_0.3Ca_0.7MnO₃ (YCM) were used as contact layer material. Moreover, the electrical conductivity of the systems without a contact layer, i.e. of the {LSM/LSM/Steel} systems, was investigated for comparison. Electrical and thermal cycling was additionally carried out. The LSM/Crofer22APU combination showed the lowest change of resistance over time and can be used in a SOFC without the contact layers considered in this paper. The systems with the steels Crofer22APU, ZMG232, or DIN 1.4509 coated by LSMC and the ZMG232/YCM system showed a low contact resistance and a low rate for the increase of the resistance. This rate was high for all systems with the steel DIN 1.4749 independent of the perovskite used as the contact layer. Microstructure and composition of the oxide layer formed at the different {PCL/steel} interfaces were investigated using high-resolution SEM/EDX analysis. The results indicate that the strong degradation observed with the steel DIN 1.4749 is caused by the formation of Si-containing phases with low electrical conductivity and a low thermal expansion coefficient. The thermal expansion coefficient of the perovskites and the steels was determined.     

Oxidation of Ni3Al–Ni3Nb alloys

Conclusions The Ni₃Al–Ni₃Nb alloys are oxidized as a result of the diffusion of oxygen ions toward the interface between the alloy and the oxidation product. This diffusion produces a relatively thick inner layer of complex composition; in addition, diffusion of nickel ions toward the interface between the oxidation product and the gas results in the formation of a thin outer layer of NiO. At any temperature, NiO in the inner oxide is reduced to Ni by niobium atoms. During the initial stages of the oxidation, the reduction occurs at the oxide-alloy inter face; during the later stages, it occurs at the interface between the oxide and the suboxide layer. Protective double oxides of NiO · Nb₂O₅ (t = 700–725 °) and NiO · Al₂O₃ (t = 800–850 °) form in the oxidation product. An -Nb₂O₅ conversion occurs at 825–900 ° and considerably reduces the oxidizability of the alloys. The -Nb₂O₅ lattice probably contains fewer oxygen vacancies than the -Nb₂O₅ lattice and thus has better protective properties.Translated from Izvestiya VUZ. Fizika, No. 12, pp. 75–83, December, 1969.     

Development and characterization of a quasi-ternary diagram based on La0.8Sr0.2(Co,Cu,Fe)O3 oxides in view of application as a cathode contact material for solid oxide fuel cells

Oxides resulting from discrete changes in composition within the quasi-ternary system La_0.8Sr_0.2CuO_2.4 + δ–La_0.8Sr_0.2CoO_3 ? δ–La_0.8Sr_0.2FeO_3 ? δ were investigated under similar experimental conditions with the objective of obtaining an overview of the variation of the relevant properties for possible applications as cathode contact layer in SOFCs. Twenty-two oxide compositions within this system were systematically selected and synthesized under identical conditions by the Pechini method. The distribution of the different crystallographic phases at 1050 °C within this quasi-ternary phase diagram, the DC electrical conductivity at 800 °C and the thermal expansion coefficients are presented. Perovskites of different compositions issued from this ternary diagram were tested as cathode contact material between an La_0.8Sr_0.2FeO₃ cathode and a Crofer22APU interconnect by resistance measurements at 800 °C. The application of a MnCo_1.9Fe_0.1O₄ spinel protection reduced the interfacial reaction between the Crofer22APU and the cathode contact material. Electrical resistance measurements at 800 °C in air up to 1000 h and the analysis by scanning electron microscopy/energy-dispersive X-ray spectroscopy of the sample cross-sections were carried out to verify the surface stability and the electrical performance.     

Oxidation behavior and mechanism of powder metallurgy Rene95 nickel based superalloy between 800 and 1000 °C

The oxidation behaviors of powder metallurgy (PM) Rene95 Ni-based superalloy in the temperature range of 800-1000 °C are investigated in air by virtue of isothermal oxidation testing, X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. The results show that the oxidation kinetics follows a square power law as the time extends at each temperature. The oxidation layers are detected to be composed of Cr₂O₃, TiO₂ and a small amount of NiCr₂O₄. The cross-sectional morphologies indicate that the oxidation layer consists of three parts: Cr-rich oxide layer, Cr and Ti duplex oxide layer, and oxidation affected zone. Theoretical analyses of oxidation kinetics and thicknesses of oxidation layers confirm that the activation energy of oxidation of PM Rene95 superalloy is 165.32 kJ mol⁻¹ and the oxidation process is controlled by diffusions of oxygen, Cr, and Ti. Accordingly, a diffusion-controlled mechanism is suggested to understand the oxidation behaviors of PM Rene95 superalloy at elevated temperatures.     

Oxidation parameters determination of Cu–Al–Ni–Fe shape-memory alloy at high temperatures

In this study, isothermal oxidation behavior of a Cu–Al–Ni–Fe shape-memory alloy between 500 and 900 °C was investigated. Alloy samples were exposed to oxygen by TG/DTA for 1 h at a constant temperature, allowing for calculation of the oxidation constant and activation energy values of the oxidation process. The oxidation constant value increased with temperature, reaching saturation at 800 °C. The effect of oxidation on crystal structure, surface morphology and chemical composition of the Cu–Al–Ni–Fe alloy was determined by X-ray diffractometer (XRD) and scanning electron microscope (SEM)–energy-dispersive X-ray (EDX) analyses. With increasing oxidation temperature, number and intensity of the characteristic 18R martensite phase peaks were reduced while Al₂O₃ phase peaks were increased. In parallel to the XRD results, the same variations were also detected by SEM–EDX measurements.     

Investigations on the growing, cracking and spalling of oxides scales of powder metallurgy Rene95 nickel-based superalloy

The surface and cross-sectional morphologies of powder metallurgy (PM) Rene95 nickel-based superalloy after 100 h oxidation in the temperature range of 700-1100 °C were investigated. It is shown that oxides nucleate first on the surface of the alloy and form an oxides scale. Afterwards, oxides scale endures decohesion, rumpling, cracking and finally spalling owing to the weak cohesive strength of the scale/alloy interface. The XRD and EDS analyses confirmed that the oxides scale of PM Rene95 superalloy is mainly composed by Cr₂O₃ at 800 °C and NiCr₂O₄ is the main spinel at 1100 °C. The subsequent analysis of internal stress verified that cracking and spalling are caused by growth stress and promoted by thermal stress. On these bases, improvement of the cohesive strength of the scale/alloy interface is considered to be the main way to increase the oxidation resistance of PM Rene95 superalloy.     

Solid state interactions in nano-sized oxides

Comparative study of reactivity of nano- and micro-sized alumina and nickel oxide, obtained by the electrical explosion of metal wires in oxidizing atmosphere, was carried out for the reactions NiO + MoO₃, NiO + Al₂O₃, and Al₂O₃ + Bi₂O₃ by coupled anneals of ceramics, measurements of the conductivity of individual oxides and raw oxide mixtures, X-ray diffraction and differential thermal analysis. The total conductivity of nano-structured oxides was found lower than that of micro-structured ceramics. Mixing bismuth oxide with nano-structured alumina leads to stabilization of the low temperature polymorph α-Bi₂O₃ up to 780 °C. The diffusion permeability of NiMoO₄ layer grown at the surface of NiO ceramics, having submicron grains, was found 2 times lower if compared to NiMoO₄ grown at micro-sized NiO ceramics. NiO and Al₂O₃ nano-powders preserve the high reactivity even when heated up to 1000 °C. The results are discussed in terms of size effects on the solid state reactivity of oxides.     

Effect of surface roughness on the development of protective Al2O3 on Fe-10Al (at.%) alloys containing 0-10 at.% Cr

The effect of alloy surface roughness, achieved by different degrees of surface polishing, on the development of protective alumina layer on Fe-10 at.% Al alloys containing 0, 5, and 10 at.% Cr was investigated during oxidation at 1000 °C in 0.1 MPa oxygen. For alloys that are not strong Al₂O₃ formers (Fe-10Al and Fe-5Cr-10Al), the rougher surfaces increased Fe incorporation into the overall surface layer. On the Fe-10Al, more iron oxides were formed in a uniform layer of mixed aluminum- and iron-oxides since the layer was thicker. On the Fe-5Cr-10Al, more iron-rich nodules developed on an otherwise thin Al₂O₃ surface layer. These nodules nucleated preferentially along surface scratch marks but not on alloy grain boundaries. For the strong Al₂O₃-forming Fe-10Cr-10Al alloy, protective alumina surface layers were observed regardless of the surface roughness. These results indicate that the formation of a protective Al₂O₃ layer on Fe-Cr-Al surfaces is not dictated by Al diffusion to the surface. More cold-worked surfaces caused an enhanced Fe diffusion, hence produced more Fe-rich oxides during the early stage of oxidation.     

Investigation by X-ray photoelectron spectroscopy of the transient oxidation of NiAl

X-ray photoelectron spectroscopy (XPS) has been used to study the oxidation of NiAl in oxygen at atmospheric pressure. Prior to oxidation, the native oxide scale on the specimen was removed by ion sputtering and the specimens were (pre-)heated in vacuum before exposure to oxygen. At low oxidation temperatures (<750 K) scales consisted of Al₂O₃ and NiAl₂O₄, with a thin surface layer of NiO, but at higher temperatures were of Al₂O₃, apart from about 0.5 at % Ni. The Ni content in the latter case was constant throughout the scale and did not increase dramatically near the alloy/oxide interface. In the experimental conditions used in this study, initial formation of NiO and NiAl₂O₄ seems to be avoided at the higher oxidation temperatures ( > 750 K).     

Magnetic nanocomposite spinel and FeCo core-shell and mesoporous systems

The fabrication of condensed silica and mesoporous silica coated spinel CoFe₂O₄ and FeCo alloy magnetic nanocomposites are reported. The encapsulation of well-defined 5 nm thick uniform silica layer on CoFe₂O₄ magnetic nanoparticles was performed. The formation of mesopores in the shell was a consequence of removal of organic group of the precursor through annealing. The NiO nanoparticles were loaded into the mesoporous silica. The mesoporous silica shells leads to a larger coercivity than that of pure CoFe₂O₄ magnetic nanoparticles due to the decrease of interparticle interactions and magneto-elastic anisotropy. In addition, the FeCo nanoparticles were coated by condensed and mesoporous silica. The condensed silica can protect the reactive FeCo alloy from oxidation up to 300 °C. However, saturation magnetization of FeCo nanoparticles coated by silica after 400 °C annealing is dramatically decreased due to the oxidation of the FeCo core. The mesoporous silica coated magnetic nanostructure loaded with NiO as a final product could be used in the field of biomedical applications.     

Effects of atomization conditions on morphology and SOFC anode performance of spray pyrolyzed NiO–Sm0.2Ce0.8O1.9 composite particles

NiO–Sm_0.2Ce_0.8O_1.9 (NiO–SDC) composite particles were synthesized by spray pyrolysis (SP). SP resulted in composite particles of NiO enveloped with SDC and these capsule-type composite particles would reduce aggregation of Ni during the reduction from NiO to Ni metals. SOFC anode microstructures and morphologies of NiO–SDC composite precursor particles much affects on SOFC power densities or anode polarization. Therefore, we focused on atomizing conditions of SP process. Relationship between ultrasonic atomization conditions and morphologies of NiO–SDC composites were investigated by controlling temperatures of atomization vessels. The atomizing temperature changed concentration of mists in the vessel, and mean particle size and particle size distribution were increased with an increase in temperature of the atomization vessels. Some extremely large particles were observed by synthesizing at higher atomization temperatures. Large particles contained voids in the particles. The voids in the composite particles would play a role of pore-formers. SOFC measurement showed the synthesis at the atomizing temperature of 30 °C resulted in the high-performance anode. The atomizing process of SP much affected morphology of anode precursor particles, and the atomizing conditions were important to improve anode performance.     

Mössbauer effects and XRD analysis of the solid solution formed from mixtures of different metal oxides by 800°C activation

The results of present work indicate that when the mixtures formed by adding K₂O, Cr₂O₃, CuO and SiO₂ to α-Fe₂O₃ in turn accumulatively were activated in air at 800°C for 5 hrs, different reactions between α-Fe₂O₃ and the added oxides were caused, and different compounds were produced, hence role of various oxides as promoters and supports could be understood further.     

Surface characteristics and nanoindentation study of Ni-Mn-Ga ferromagnetic shape memory sputtered thin films

In present paper, the off-stoichiometric Ni-Mn-Ga ferromagnetic shape memory alloy thin films are fabricated using radio frequency magnetron sputtering method. The compositions, microstructures and mechanical properties of the thin films are characterized by energy dispersive X-ray spectrum (EDAX), X-ray photoelectron spectroscopy (XPS), scanning electronic microscope (SEM), atomic force microscope (AFM) and nanoindentation test, respectively. The results show that there is a thinner layer of oxides consisting of NiO, Ga₂O₃ and an unspecified manganese oxidation (Mn_xO_y) at the surface, whereas a small amount of MnO precipitates exist in internal layers of post-annealed Ni-Mn-Ga thin films. The hardness and elastic modulus decrease with increasing film thickness. Nanoindentation tests reveal that the hardness and elastic modulus of the films can be up to 5.5 and 155 GPa, respectively. The Ni-Mn-Ga thin films have remarkably improved the ductility of Ni-Mn-Ga ferromagnetic shape memory alloys bulk materials.     

X-ray photoelectron spectroscopic studies of nickel-oxygen surfaces using oxygen and argon ion-bombardment

We have studied the surface chemistry of the nickel-oxygen system using both temperature changes and ion bombardment as techniques for elucidating the surface structure. The spectra of metallic Ni, NiO and Ni₂O₃ were characterized from samples prepared directly in the spectrometer. The Ni₂O₃ species could be distinguished from an authentic Ni(OH)₂ sample from both the X-ray photoelectron lines and the Auger transitions. The oxides of NiO and Ni₂O₃ could be prepared by bombardment with low energy (400eV) O₂⁺ ions as well as by exposure of Ni to oxygen at reduced pressure (～ 100 torr). The Ni₂O₃ was found to be present on most nickel-oxygen surfaces except those prepared by exposing Ni to air for many hours at high temperature (> 600°C), indicating that the stability of Ni₂O₃ decreased as the temperature increased. Exposure of both NiO and Ni₂O₃ to 400 eV Ar⁺ ion bombardment caused reduction to metallic Ni. This observation has also been noted for several other oxides and a prediction of whether or not reduction should be observed is presented by examining the free energy of formation of the molecule.     

Highly improved sensibility and selectivity ethanol sensor of mesoporous Fe-doped NiO nanowires

In this paper, nickel oxides (NiO) and iron (Fe)-doped NiO nanowires (NWs) with the various doping content (from 1 to 9 at%) were synthesized by using SBA-15 templates with the nanocasting method. All samples were synthesized in the same conditions and exhibited the same mesoporous-structures, uniform diameter, and defects. Mesoporous-structures with high surface area created more active sites for the adsorption of oxygen on the surface of all samples, resulting in the smaller surface resistance in air. The impurity energy levels from the donor Fe-doping provided electrons to neutralize the holes of p-type Fe-doped NiO NWs, which greatly enhanced the total resistance. The comparative gas-sensing study between NiO NWs and Fe-doped NiO NWs indicated that the high-valence donor Fe-doping obviously improved the ethanol sensitivity and selectivity for Fe-doped NiO NWs. And Ni_0.94Fe_0.06O_1.03 NWs sensor presented the highest sensitivity of 14.30 toward ethanol gas at 320 °C for the high-valence metal-doping.     

A photoemission study of the interaction of Ni(100), (110) and (111) surfaces with oxygen

Photoelectron spectroscopic studies of the oxidation of Ni(111), Ni(100) and Ni(110) surfaces show that the oxidation process proceeds at 295 and 485 K in two distinct steps: a fast dissociative chemisorption of oxygen followed by oxide nucleation and lateral oxide growth to a limiting coverage of 3 NiO layers. The oxygen concentration in the 295 K saturated oxygen layer on Ni(111) was confirmed by ¹⁶O(d,p) ¹⁷O nuclear microanalysis. At 295 and 485 K the oxide growth rates are in the order Ni(110) > Ni(111) > Ni(100). At 77 K the oxygen uptake proceeds at the same rate on all three surfaces and shows a continually decreasing sticking coefficient to saturation at ~2.1 layers (based upon NiO). An O 1sb.e. = 529.7 eV is associated with NiO, and O ls b.e.'s of ~531.5 and 531.3 eV can be associated, respectively, with defect oxide (Ni₂O₃) or (in the presence of H₂O) with an NiO(H) species. The binding energies (Ni 2p, O 1s) of this NiO(H) species are similar to those for Ni(OH)₂. Defect oxides are produced by oxidation at 485 K, or by oxidation of damaged films (e.g. from Ar⁺ sputtering) and evaporated films. Wet oxidation (or exposure to air) of clean nickel surfaces and oxides, and exposure of thick oxide to hydrogen at high temperature results in an O 1s b.e. ~531.3 eV species. Nuclear microanalysis ²H(³He,p) ⁴He indicates the presence of protonated species in the latter samples. Oxidation at 77 K yields O 1s b.e.'s of 529.7 and ~531 eV; the nature of the high b.e. species is not known. Both clean and oxidised nickel surfaces show a low reactivity towards H₂O; clean nickel surfaces are ~10³ times less reactive to H₂O than to oxygen.     

High-frequency magnetic properties of soft magnetic cores based on nanocrystalline alloy powder prepared by thermal oxidation

FeSiBNbCu nanocrystalline alloy powder was thermally oxidized in an air atmosphere to enhance an oxide layer formation on the surface of the powder and subsequently toroidal shape FeSiBNbCu nanocrystalline alloy powder cores were prepared by compaction at room temperature. The phase change on the surface of FeSiBNbCu nanocrystalline alloy powder by thermal oxidation was analyzed and its effect on the high frequency magnetic properties of the compacted cores was investigated. By thermal oxidation, the formation of the oxide layer consisting of Fe₂O₃, CuO, and SiO₂ on the surface of FeSiBNbCu nanocrystalline alloy powder was enhanced and the thickness of oxide layer could be controlled by changing the thermal oxidation time. FeSiBNbCu nanocrystalline alloy powder core prepared from the powder treated by thermal oxidation exhibits a stable permeability up to high frequency range over 10 MHz. The core loss could be reduced remarkably and the dc-bias property could be improved significantly, which were due to the formation of oxide layer consisting of Fe₂O₃, CuO, and SiO₂ on the FeSiBNbCu nanocrystalline alloy powder. The improvement in high-frequency magnetic properties of the FeSiBNbCu nanocrystalline alloy powder cores could be attributed to the effective electrical insulation by oxide layer between the FeSiBNbCu nanocrystalline alloy powders.     

Inhibition of initial surface oxidation by strongly bound hydroxyl species and Cr segregation: H2O and O2 adsorption on Fe-17Cr

The initial stages of surface oxidation of Fe-17Cr (ferritic stainless steel) were investigated at 323 K by X-ray photoelectron spectroscopy (XPS) and inelastic electron background analysis. The results indicated the formation of a mixed iron-chromium oxide layer upon O₂ exposure and the formation of a thin chromium oxyhydroxide layer upon H₂O exposure. The oxidation of Fe did not occur in the latter case. Moreover, it was found that pre-exposing the Fe-17Cr surface to H₂O significantly hinders subsequent oxidation by O₂, thus providing a way to control the formation of nanoscale oxides on stainless steel materials. It was concluded that the formation of strongly bound hydroxyl species together with adsorbate-induced segregation of Cr severely limits the reaction between O₂/H₂O and Fe from the alloy.