Selective oxidation of methane and carbon deposition over Fe2O3/Ce1−x Zr x O2 oxides

A series of Fe2O3/Al2O3, Fe2O3/CeO2, Ce0.7Zr0.3O2, and Fe2O3/Ce1-xZrxO2(x = 0.1–0.4) oxides was prepared and their physicochemical features were investigated by X-ray diffraction(XRD), transmission electron microscope(TEM), and H2-temperature-programmed reduction(H2-TPR) techniques. The gas–solid reactions between these oxides and methane for syngas generation as well as the catalytic performance for selective oxidation of carbon deposition in O2-enriched atmosphere were investigated in detail. The results show that the samples with the presence of Fe2O3show much higher activity for methane oxidation compared with the Ce0.7Zr0.3O2solid solution,while the CeO2-contained samples represent higher CO selectively in methane oxidation than the Fe2O3/Al2O3sample. This suggests that the iron species should be the active sites for methane activation, and the cerium oxides provide the oxygen source for the selective oxidation of the activated methane to syngas during the reaction between methane and Fe2O3/Ce0.7Zr0.3O2. For the oxidation process of the carbon deposition, the CeO2-containing samples show much higher CO selectivity than the Fe2O3/Al2O3sample, which indicates that the cerium species should play a very important role in catalyzing the carbon selective oxidation to CO. The presence of the Ce–Zr–O solid solution could induce the growth direction of the carbonfilament, resulting in a loose contact between the carbon filament and the catalyst. This results in abundant exposed active sites for catalyzing carbon oxidation, strongly improving the oxidation rate of the carbon deposition over this sample. In addition, the Fe2O3/Ce0.7Zr0.3O2also represents much higher selectivity(ca. 97 %) for the conversion of carbon to CO than the Fe2O3/CeO2sample, which can be attributed to the higher concentration of reduced cerium sites on this sample. The increase of the Zr content in the Fe2O3/Ce1-xZrxO2samples could improve the reactivity of the materials for methane oxidation, but it also reduces the selectivity for CO formation.     

Microstructure and shear strength of γ-TiAl/GH536 joints brazed with Ti−Zr−Cu−Ni−Fe−Co−Mo filler alloy

The influence of brazing temperature and brazing time on the microstructure and shear strength of γ-TiAl/GH536 joints brazed with Ti−Zr−Cu−Ni−Fe−Co−Mo filler was investigated using SEM, EDS, XRD and universal testing machine. Results show that all the brazed joints mainly consist of four reaction layers regardless of the brazing temperature and brazing time. The thickness of the brazed seam and the average shear strength of the joint increase firstly and then decrease with brazing temperature in the range of 1090−1170 °C and brazing time varying from 0 to 20 min. The maximum shear strength of 262 MPa is obtained at 1150 °C for 10 min. The brittle Al₃NiTi₂ and TiNi₃ intermetallics are the main controlling factors for the crack generation and deterioration of joint strength. The fracture surface is characterized as typical cleavage fracture and it mainly consists of massive brittle Al₃NiTi₂ intermetallics.     

Creep of polycrystalline SrCo0.8Fe0.2O3−δ

In this study, a series of compressive creep tests on rectangular specimens of SrCo_0.8Fe_0.2O_3−δ of grain sizes in the range of 2.4–6.8 μm was performed in air, covering a temperature range of 850–975°C and a stress range of 2–80 MPa. The stress exponent has been found to be close to unity in the 10–20 MPa stress range. The apparent activation energy assumes two different values, 471 kJ/mole below 925°C and 275 kJ/mole above 925°C. The microstructural observations of crept samples revealed equiaxed grains and negligible grain growth indicating a diffusion-accommodated grain switching mechanism. The logarithmic plot of strain rate vs inverse grain size has been found to be non-linear. A possible explanation for this behavior is discussed through the incorporation of a threshold stress. The possibility of estimating the lattice and grain-boundary diffusion coefficients from the data is discussed.     

Strain-induced α-to-β phase transformation during hot compression in Ti−5Al−5Mo−5V−1Cr−1Fe alloy

The dynamic phase transformation of Ti?5Al?5Mo?5V?1Cr?1Fe alloy during hot compression below the β transus temperature was investigated. Strain-induced α-to-β transformation is observed in the samples compressed at 0?100 K below the β transus temperature. The deformation stored energy by compression provides a significant driving force for the α-to-β phase transformation. The re-distribution of the solute elements induced by defects during deformation promotes the occurrence of dynamic transformation. Orientation dependence for the α-to-β phase transformation promotion is observed between {100}-orientated grains and {111}-orientated grains. Incomplete recovery in {111}-orientated grains would create a large amount of diffusion channels, which is in favor of the α-to-β transformation. The effects of reduction ratio and strain rate on the dynamic phase transformation were also investigated.     

Effect of α phase morphology on fatigue crack growth behavior of Ti−5Al−5Mo−5V−1Cr−1Fe alloy

Taking a Ti−5Al−5Mo−5V−1Cr−1Fe alloy as exemplary case, the fatigue crack growth sensitivity and fracture features with various tailored α phase morphologies were thoroughly investigated using fatigue crack growth rate (FCGR) test, optical microscopy (OM) and scanning electron microscopy (SEM). The tailored microstructures by heat treatments include the fine and coarse secondary α phase, as well as the widmanstatten and basket weave features. The sample with coarse secondary α phase exhibits better comprehensive properties of good crack propagation resistance (with long Paris regime ranging from 15 to 60 MPa·m^1/2), high yield strength (1113 MPa) and ultimate strength (1150 MPa), and good elongation (11.6%). The good crack propagation resistance can be attributed to crack deflection, long secondary crack, and tortuous crack path induced by coarse secondary α phase.     

Effect of Cu addition on microstructural evolution and hardening of mechanically alloyed Al−Ti−O in-situ composite

The microstructure formation and strengthening of an Al−5wt.%TiO₂ composites with additions of 5 wt.% Cu and 2 wt.% stearic acid (as a process control agent, PCA) during mechanical alloying and subsequent thermal exposure were studied. The powder composites were prepared by high-energy ball milling for up to 10 h. Single line tracks of the powders were laser melted. Optical and scanning electron microscopy, XRD analysis and differential scanning calorimetry were used to study microstructural evolution. The results showed that the Cu addition promotes an effective mechanical alloying of aluminum with TiO₂ from the start of milling, resulting in higher microhardness (up to HV 290), while the PCA, on the contrary, postpones this process. In both cases, the composite granules with uniform distribution of TiO₂ particles were formed. Subsequent heating of mechanically alloyed materials causes the activation of an exothermic reaction of TiO₂ reduction with aluminum, the start temperature of which, in the case of Cu addition, shifts to lower values, that is, the transformation begins in the solid state. Besides, the Cu-added material after laser melting demonstrates a more dispersed and uniform structure which positively affects its microhardness.     

Microstructure,tribological behavior and magnetic properties of Fe−Ni−TiO2 composite coatings synthesized via pulse frequency variation

The Fe−Ni−TiO₂ nanocomposite coatings were electrodeposited by pulse frequency variation. The results showed that the nanocomposite with a very dense coating surface and a nanocrystalline structure was produced at higher frequencies. By increasing the pulse frequency from 10 to 500 Hz, the iron and TiO₂ nanoparticles contentswere increased in expense of nickel content. XRD patterns showed that by increasing the frequency to 500 Hz, an enhancement ofBCC phase was observed and the grain size of deposits was reduced to 35 nm. The microhardness and the surface roughness were increased to 647 HV and 125 nm at 500 Hz due to the grain size reduction and higher incorporation of TiO₂ nanoparticles into the Fe−Ni matrix (5.13 wt.%). Moreover, the friction coefficient and wear rate values were decreased by increasing the pulse frequency;while the saturation magnetization and coercivity values of the composite deposits were increased.     

Wear characteristics of Al−Si−Mg−(Cu)/Al2O3 composites fabricated by thermit reaction

Al₂O₃ particles could be formed by a thermit reaction in an Al-12Si-4Mg-1.5Cu/Al₂O₃ composite due to thein-situ reaction between Al-12Si-4Mg-(1.5Cu) molten metal and SiO₂ particles in preform, which took place at 1173 K for 24 hours, resulting in the decomposition of SiO₂ particles and the formation of Al₂O₃ particles simultaneously. The mechanically mixed layers (MMLs) consisting of α-Fe and Fe oxides existed on the subsurface layers beneath the worn surface in composites or mother alloys, which improved the wear resistance. The characteristics of wear resistance and hardening of an Al-12Si-4Mg-1.5Cu/Al₂O₃ composite are superior to those of the Al-12Si-4Mg/Al₂O₃ composite and Al-12Si-4Mg-1.5Cu alloy.     

Designed synthesis of wide range microwave absorption Fe3O4–carbon sphere composite

Fe₃O₄–carbon sphere composite was synthesized by a simple hydrothermal method. The as-synthesized products were characterized by field-emission scanning electron microscopy (FE-SEM), energy dispersive spectrum (EDS), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), and Raman spectrum. The complex permittivity and permeability of paraffin wax and Fe₃O₄–carbon sphere composite with different volume fraction of the composite were measured by vector network analysis. A wide region of microwave absorption was achieved due to dual dielectric and magnetic losses. When the matching thickness is 4 mm, the calculated reflection loss of the sample with 70% volume fraction of Fe₃O₄–carbon sphere composite exhibits a broad microwave absorption ranging from 2.5 to 18 GHz.     

Plasma Spray Physical Vapor Deposition of La1−x Sr x Co y Fe1−y O3−δ Thin-Film Oxygen Transport Membrane on Porous Metallic Supports

Plasma spray physical vapor deposition (PS-PVD) is a very promising route to manufacture ceramic coatings, combining the efficiency of thermal spray processes and characteristic features of thin PVD coatings. Recently, this technique has been investigated to effectively deposit dense thin films of perovskites particularly with the composition of La_0.58Sr_0.4Co_0.2Fe_0.8O_3?δ (LSCF) for application in gas separation membranes. Furthermore, asymmetric type of membranes with porous metallic supports has also attracted research attention due to the advantage of good mechanical properties suitable for use at high temperatures and high permeation rates. In this work, both approaches are combined to manufacture oxygen transport membranes made of gastight LSCF thin film by PS-PVD on porous NiCoCrAlY metallic supports. The deposition of homogenous dense thin film is challenged by the tendency of LSCF to decompose during thermal spray processes, irregular surface profile of the porous metallic substrate and crack and pore-formation in typical ceramic thermal spray coatings. Microstructure formation and coating build-up during PS-PVD as well as the annealing behavior at different temperatures of LSCF thin films were investigated. Finally, measurements of leak rates and oxygen permeation rates at elevated temperatures show promising results for the optimized membranes.     

An investigation of thin oxide films thermally grown in situ on Fe24Cr and Fe24Cr11Mo by auger electron spectroscopy and X-ray photoelectron spectroscopy

AES depth profiling and XPS have been used for the characterization of thin oxide layers thermally grown in situ in the UHV-analysis chamber on pure iron, chromium and the alloys Fe24Cr and Fe24Cr11Mo at a temperature of 384°C. The apparent oxide film thickness and the film composition were monitored as a function of oxygen exposure. The oxidation rate of the Fe24Cr alloy was found to lie in between that of pure iron and chromium. The films formed have a duplex structure, the outer part being iron oxide, the inner part mostly chromium oxide. Alloying with molybdenum decreases the rate of oxidation by a mechanism involving the formation of a barrier layer rich in molybdenum at the oxide-metal interface. No molybdenum is found in the outer part of the oxide film.     

Influence of rare earth promoters on the performance of Ni/Mg（Al）O catalysts for hydrogenation and steam reforming of toluene

CeO₂-, La₂O₃-, and ZrO₂-promoted Ni/Mg(Al)O catalysts synthesized by hydrotalcite-type precursors have been investigated with respect to catalytic activity and carbon formation in the hydrogenation and steam reforming of toluene as a model tar compound. X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) specific surface area and H₂-temperature programmed reduction (TPR) were used to observe the characteristics of the prepared catalysts. The carbon formation and its amount on the used catalysts were examined by transmission electron microscope (TEM), scanning electron microscope (SEM) and thermogravimetric (TG). The trend of catalytic activity as derived from the experimental results followed the order: Ni-Ce>Ni-Las>Ni-Zr>Ni. The catalyst modified with CeO₂ exhibited the highest catalytic performance and had good carbon resistance in the hydrogenation and steam reforming of toluene. A toluene conversion of 96.8%, a CH₄ yield of 45.2% and a CO yield of 50.4% have been achieved. The addition of promoters led to better dispersion of nickel species and higher interaction nickel-support, which were favorable for increasing the catalytic activity and effectively preventing carbon formation.     

Nanoindentation of porous bulk and thin films of La0.6Sr0.4Co0.2Fe0.8O3−δ

In this paper we show how reliable measurements on porous ceramic films can be made by appropriate nanoindentation experiments and analysis. Room-temperature mechanical properties of the mixed-conducting perovskite material La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ (LSCF6428) were investigated by nanoindentation of porous bulk samples and porous films sintered at temperatures from 900 to 1200 °C. A spherical indenter was used so that the contact area was much greater than the scale of the porous microstructure. The elastic modulus of the bulk samples was found to increase from 33.8 to 174.3 GPa and hardness from 0.64 to 5.32 GPa as the porosity decreased from 45% to 5% after sintering at 900–1200 °C. Densification under the indenter was found to have little influence on the measured elastic modulus. The residual porosity in the “dense” sample was found to account for the discrepancy between the elastic moduli measured by indentation and by impulse excitation. Crack-free LSCF6428 films of acceptable surface roughness for indentation were also prepared by sintering at 900–1200 °C. Reliable measurements of the true properties of the films were obtained by data extrapolation provided that the ratio of indentation depth to film thickness was in the range 0.1–0.2. The elastic moduli of the films and bulk materials were approximately equal for a given porosity. The 3-D microstructures of films before and after indentation were characterized using focused ion beam/scanning electron microscopy tomography. Finite-element modelling of the elastic deformation of the actual microstructures showed excellent agreement with the nanoindentation results.     

PZT5／（Mg0．5Zn0．5）Fe2O4复合材料的电磁性能

以PZT5和（Mg0.5Zn0．5）Fe2O4为原料，合成了不同配比的铁电／铁磁复相材料。XRD和SEM研究结果表明复相材料中只含有钙钛矿结构的PZT5和尖晶石结构的（Mg0.5Zn0.5）Fe2O4，无杂相生成，这说明共烧过程中两者没有发生明显的化学反应。介电频谱表明，相对介电常数随PZT5含量的增加而增加（测试频率在30MHz以下），介电温谱表明，居里温度随频率升高而向高温移动（其值分别为250，300，326，372℃）。电滞回线呈现了材料的漏电流较大的特点。磁滞回线表明，这种复相材料具有亚铁磁性，饱和磁化强度随铁氧体含量的增加而增加。性能测试表明，这种由PZT5和（Mg0.5Zn0.5）Fe2O4共同组成的复相材料对外同时表现出铁电性和铁磁性。     

Creep behavior and its correlation with defect chemistry of La0.58Sr0.4Co0.2Fe0.8O3−δ

The creep behavior of La_0.58Sr_0.4Co_0.2Fe_0.8O_3?δ (LSCF) perovskite was studied in the temperature range 750–950 °C in air and vacuum (P_O2 ≈ 4 mbar). A transition in the apparent activation energy was found between 800 and 850 °C for both oxygen partial pressures. The apparent activation energy is ～250 kJ mol^?1 for the temperature range 700–800 °C under vacuum (P_O2 ≈ 4 mbar) and ～480 kJ mol^?1 for 850–950 °C in both atmospheres. Above 850 °C, the creep rate of LSCF is higher in vacuum than in air although the same cubic structure exists. The stress exponent of the creep law is in the range 1.9–2.5 for all temperatures, which excludes a transition of creep mechanism. It is suggested that, below 800 °C, cation vacancies originate from the necessary balance with the substituted cations in LSCF, and the determined activation energy reflects the energy barrier for cation migration via these vacancies. Above 850 °C, additional vacancies appear to be formed intrinsically, and the activation energy represents the sum of the thermally activated formation energy of cation vacancies and migration energy of cations.     

Combustion synthesis of FeAl−Al2O3 composites with TiB2 and TiC additions via metallothermic reduction of Fe2O3 and TiO2

Combustion synthesis involving metallothermic reduction of Fe₂O₃ and TiO₂ was conducted in the mode of self-propagating high-temperature synthesis (SHS) to fabricate FeAl-based composites with dual ceramic phases, TiB₂/Al₂O₃ and TiC/Al₂O₃. The reactant mixture included thermite reagents of 0.6Fe₂O₃+0.6TiO₂+2Al, and elemental Fe, Al, boron, and carbon powders. The formation of xFeAl−0.6TiB₂−Al₂O₃ composites with x=2.0−3.6 and yFeAl−0.6TiC−Al₂O₃ composites with y=1.8−2.75 was studied. The increase of FeAl causes a decrease in the reaction exothermicity, thus resulting in the existence of flammability limits of x=3.6 and y=2.75 for the SHS reactions. Based on combustion wave kinetics, the activation energies of E_a=97.1 and 101.1 kJ/mol are deduced for the metallothermic SHS reactions. XRD analyses confirm in situ formation of FeAl/TiB₂/Al₂O₃ and FeAl/TiC/Al₂O₃ composites. SEM micrographs exhibit that FeAl is formed with a dense polycrystalline structure, and the ceramic phases, TiB₂, TiC, and Al₂O₃, are micro-sized discrete particles. The synthesized FeAl−TiB₂−Al₂O₃ and FeAl−TiC−Al₂O₃ composites exhibit the hardness ranging from 12.8 to 16.6 GPa and fracture toughness from 7.93 to 9.84 MPa·m^1/2.     

Effects of the injection temperature of N2 gas on pressureless infiltration for fabricating Al−Mg/Al2O3 composites

Pressureless infiltration of molten Al−Mg alloys into particulate Al₂O₃ preforms has been known to occur only in a nitrogen atmosphere. In order to understand the pressureless infiltration mechanism of Al−Mg alloys into particulate Al₂O₃ preforms, nitrogen was injected at 25°C, 300°C, and 600°C. The higher the injection temperature of the nitrogen gas was, the lower the infiltration temperature of the molten Al−Mg alloys into the particulate Al₂O₃ preform was. Pressureless infiltration of the Al−6Mg alloy occurred at 700°C when the nitrogen gas was injected at 600°C. The formation of an Mg−N compound (Mg₃N₂) on Al₂O₃ particles, which improves wettability by decreasing the interfacial energy between the Al−Mg alloys and the Al₂O₃ particles, enabled the formation of the Al−Mg alloy/Al₂O₃ composite via pressureless infiltration. Increasing the injection temperature close to the melting point of the Al−Mg alloys appeared to enhance the formation of Mg₃N₂ on the surface of the Al₂O₃ particles.     

Probe M?ssbauer spectroscopy of the evolution of mechanically alloyed Mo92O8(57Fe) system upon heat treatment

X-ray diffraction and M?gsbauer spectroscopy have been used to study the multistage character of the process of recovery to equilibrium in the course of isochronous (1 h) annealings (300?C1300°C) of a mechanically alloyed nanocrystalline Mo₉₂O₈ system with 1 at % M?gsbauer isotope ⁵⁷Fe. Three stages of the recovery to the equilibrium state have been established: at 300?C700°C, the stage of structural relaxation; at 700?C1100°C, the stage of normal grain growth and formation of a dislocation structure; and at 1100?C1300°C, the stage of the formation of a composite Mo₉₉ ⁵⁷Fe₁/MoO₂.     

Effects of Silver Addition on Properties and Performance of Plasma Sprayed La0.6Sr0.4Co0.2Fe0.8O3−δ Interconnect Layer

Interconnect layers on stainless steel substrates (STS430) for solid oxide fuel cells (SOFC) were built up by atmospheric plasma spraying (APS) using spray dried La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ (LSCF) and blended LSCF/Ag composites. The microstructure and phase of each coating were analyzed using scanning electron microscopy (SEM) and x-ray diffraction (XRD) studies, respectively. Furthermore, bond strength, microhardness, performance in a thermal cycle test and in an oxidation test, and electrical conductivity were measured and compared. The coatings prepared from spray dried LSCF have higher porosity and more cracks within the splats and at intersplat boundaries. In contrast, the coatings prepared from LSCF/Ag had fewer cracks and less porosity due to the relatively high ductility of silver. After oxidation testing at 800 °C for 200 h, the weight change of the STS430 substrate and the LSCF and LSCF/Ag-coated alloys were found to be 0.06833, 0.01950, and 0.01656 mg/cm², respectively. Also the electrical conductivity of LSCF and LSCF/Ag coatings were higher than that of STS430 by two orders.