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Some 10 wt percent nickel is added to an Fe-base alloy which has a ferrite microstructure to improve the high temperature castability and crack resistance while about 0.2 wt percent zirconium is added for improved high temperatur cyclic oxidation and corrosion resistance. The basic material is a high temperature FeCrAl heater alloy, and the addition provides a material suitable for burner rig nozzles.
Reducing the resistances of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) while retaining the stability of an oxygen electrode, even in the presence of air contaminants such as Cr, H2O and CO2, is of paramount importance to the current commercial development of intermediate-temperature reversible solid oxide cells (IT-RSOCs). In this presentation, a multifunctional, coarsening-resistant, air-contaminants-tolerant and yet ORR/OER-active oxygen electrode (OE) for IT-RSOCs is described. The testing results show that new bilayer OE exhibits a much better ORR/OER activity and stability than the single-layer benchmark LSCF-GDC OE. Remarkably, the new bilayer OE also demonstrates an exceptionally high resistance to Cr-attack, a critical issue to the development of commercial meal-interconnect loaded SOFC/SOEC stacks/systems. Theoretical analysis is also presented to understand the fundamental reasons for the improved ORR/OER activity and stability observed under real-world operating conditions.
Perovskite tandem solar cells show promising performance but non-radiative recombination and its progressive worsening with time, especially in the mixed Sn–Pb low-bandgap layer, limit performance and stability. Here, in this study, we find that mixed Sn–Pb perovskite thin films exhibit a compositional gradient, with an excess of Sn on the surface – and we show this gradient exacerbates oxidation and increases the recombination rate. We find that diamines preferentially chelate Sn atoms, removing them from the film surface and achieving a more balanced Sn:Pb stoichiometry, making the surface of the film resistive to the oxidation of Sn. The process forms an electrically resistive low-dimensional barrier layer, passivating defects and reducing interface recombination. Further improving the homogeneity of the barrier layer using 1,2-diaminopropane results in more uniform distribution and passivation. Tandems achieve a power conversion efficiency of 28.8%. As a result, encapsulated tandems retain 90% of initial efficiency following 1000 hours of operating at the maximum power point under simulated one-sun illumination in air without cooling.
We present magnetic characterization, charge resistivity, and optical photoluminescence measurements on amorphous yttrium iron oxide thin films ( a-Y–Fe–O), with supporting comparisons to amorphous germanium ( a-Ge) films. We measured magnetic properties with both SQUID magnetometry and polarized neutron reflectometry. These results not only confirm that a-Y–Fe–O is a disordered magnetic material with strong predominantly antiferromagnetic exchange interactions and a high degree of frustration, but also that it is best understood electrically as a disordered semiconductor. As with amorphous germanium, a-Y–Fe–O obeys expectations for variable-range hopping through localized electron states over a wide range of temperature. We also clarify the consequences of charge transport through such a semiconducting medium for non-local voltage measurements intended to probe spin transport in nominally insulating magnetic materials. We further compare non-local resistance measurements made with “quasi-dc” automated current reversal to ac measurements made with a lock-in amplifier. These show that the “quasi-dc” measurement has an effective ac current excitation with frequency up to approximately 22 Hz, and that this effective ac excitation can cause artifacts in these measurements including incorrect sign of the non-local resistance. Here, this comprehensive investigation of non-local resistance measurements in a-Y–Fe–O shows no evidence of spin transport on micrometer length scales, which is contrary to our original work, and in line with more recent investigations by other groups.
Accurate simulation and prediction for reactions of soil organic carbon (OC) under different biogeochemical conditions remain a grand challenge. This project aims to investigate the transformation and degradation of OC under anaerobic and aerobic conditions as well as anaerobic-aerobic transitions, as well as its coupling with reactions for iron (Fe) oxide minerals. We determined that OC can serve as electron shuttle (including pyrogenic OC) and donor for accelerating the reduction of Fe oxide. The presence of OC can inhibit the transformation of poor crystalline Fe oxide (ferrihydrite) to other more crystalline forms. Reduction of Fe oxide can lead to the mobilization of OC, depending on the ratio of OC/Fe. More condensed aromatic OC can be selectively associated with Fe oxide and also resistant to the reduction release, enhancing their stability during the anaerobic reactions. Under aerobic condition, the association with Fe oxide can inhibit the degradation of OC and also its priming effects on the degradation of indigenous soil OC. During an anaerobic-aerobic transition, OC mineralization was inhibited substantially compared to controls incubated only aerobically. Our field measurement in the Arctic region revealed the importance of deep soil temperature in regulating the generation of CO 2 and CH 4 . These results highlighted the importance of redox reactions in controlling the fate and stability of soil OC. For future studies, investigations are required to fill in the knowledge gap regarding the structure and chemical nature of important organic ligands for Fe, accurate quantification of Fe-bound OC in soils, the long-term effects of anaerobic-aerobic transitions on the OC mineralization as well as response of microbial communities to redox transitions.
A newly developed Cu-23 (wt %) Cr-5%Al (CuCrAl) alloy shown to resist hydridation and oxidation in an as-cast form is currently being considered as a protective coating for GRCop-84, which is an advanced copper alloy containing 8 (at.%) Cr and 4 (at.%) Nb. The coating was deposited on GRCop-84 substrates by the cold spray deposition technique. Cyclic oxidation tests conducted in air on both coated and uncoated substrates between 773 and 1073 K revealed that the coating remained intact and protected the substrate up to 1073 K. No significant weight loss of the coated specimens were observed at 773 and 873 K even after a cumulative cyclic time of 500 h. About a 10 percent weight loss observed at 973 and 1073 K was attributed to the excessive oxidation of the uncoated sides. In contrast, the uncoated substrate lost as much as 80 percent of its original weight under similar test conditions. It is concluded that the cold sprayed CuCrAl coating is suitable for protecting GRCop-84 substrates.
Two of the many performance requirements of the zinc orthotitanate (ZOT) ceramic thermal control paint covering parts of the Jupiter-bound Galileo spacecraft are that it be sufficiently electrically conductive so as to prevent electrostatic discharge (ESD) damage to onboard electronics and that it adhere to and protect the substrate from corrosion in terrestrial environments. The bulk electrical resistivity of ZOT on an aluminum substrate was measured over the ranges 22 C to 90 C and 0 percent RH to 100 percent RH, and also in soft (10 (minus 2) Torr) and hard (10 (minus 7) Torr) vacuums. No significant temperature dependence was evident, but measured resistivity values ranged over 9 orders of magnitude: 10 to the 5th power ohm-cm at 100 percent RH greater than 10 to the 12th power ohm-cm in a hard vacuum. The latter value violates the ESD criterion for a typical 0.019 cm thick coating. The corrosion study involved exposing typical ZOT substrate combinations to two moisture environments - 30 C/85 percent RH and 85 C/85 percent RH - for 2000 hours, during which time the samples were periodically removed for front-to-back electrical resistance and scratch/peel test measurements. It was determined that the ZOT/Al and ZOT/Mg systems are stable (no ZOT delamination), although some corrosion (oxide formation) and resistivity increases observed among the ZOT/Mg samples warrant that exposure of some parts to humid environments be minimized.
Methods have been found to apply an adherent and humidity resistant silver-only front contact to n on p silicon solar cells. The critical processing step was the removal of the diffused oxide layer. Humidity resistance is superior to present day commercial titanium-silver contacts and the electrical characteristics of the cells are excellent. Titanium, which is degraded by humidity and which is a source of heavy metal poisoning, has been eliminated from the contact.
We have developed ionizing organic-based composites which have demonstrated great promise for radiation sensing. Nickel oxide has been proven as an active material for detecting high energy radiation. The oxidation state of unusual oxides such as nickel oxide in nanocomposites of ionizing organics changes much faster than thin film or bulk, and hence increases the sensitivity for radiation sensing. The resistivity of the oxide composite increases following sequential irradiation processes because of the decrease in holes' concentration. In this paper, we will present the effect of additional oxidizing agent on the morphology, processing and sensing of gamma-rays by oxides - urea based nanocomposites. It was observed that addition of MnO2 decreases the sensitivity. However, it recovers to original properties after irradiation much faster than undoped composites.
Ceramic materials, often used to protect components due to their high strength, and wear resistance, have added benefits of being lightweight and providing multifunctional properties. They are, therefore, significant to provide durability and support during long-duration missions to the moon’s surface for rovers, landers, robotic systems, habitats, and many other components. Materials such as aluminum oxide with high mechanical strength and hardness can help to improve the durability of structures used in space exploration. Devices used for space exploration require the use of materials with the ability to withstand exposure to extreme environments. Lunar regolith is a constituent with the ability to adhere electrostatically and damage the components used to perform these missions due to adhesion of lunar dust projectiles that can cause delamination on surfaces, which may not be physically visible. The particulates of lunar dust are classified as corrosive material, leading to the degradation of structures. Aluminum oxide presents excellent resistance to different types of wear due to its high strength and hardness. Air plasma sprayed (APS) aluminum oxide coatings have demonstrated the potential to protect the surface to which they are applied. However, the parameters of roughness and porosity of the coatings need to be considered to establish if they can protect the components from extreme environments. Considering the electrostatic forces that the components are exposed to, the adhesion between the lunar regolith and the surface of the components needs to be investigated. In this work, the adhesion forces of lunar dust simulants with an average size of 30 𝜇m are investigated considering the roughness of the surface of the APS aluminum oxide. The centrifugal technique utilized here offers the advantage of establishing the adhesion force between particles with different shapes on smooth or rough surfaces. The simulants were deposited on the surface of APS aluminum oxide using an aerosolization technique to achieve a monolayer coating in three different locations across the specimen to determine the increments in adhesion force at the centrifuge. The roughness of the APS aluminum oxide was determined to be 2.257 𝜇m. The specimen was tested under an incremental centrifugal speed from 100 rpm to 3000 rpm for 20 seconds. Low magnification microscopy images were collected to cover a larger surface area of the test coating. The adhesion force was measured considering the distance from the centrifugal axis and the rotational speed. Due to the coating roughness, and the distance from the centrifugal axis, the results demonstrated a larger adhesion force in locations closer to the centrifugal axis. Smaller particles were entrapped within the roughness of the coating, and a stronger adhesion force was measured. In order to continue designing wear-resistant coating for structural protection in space missions, press-on experiments using a centrifuge will be performed. Future experiments will allow us to determine the design parameters for APS aluminum oxide coating to protect the structures from harsh space environments.
Abstract Silicon and molybdenum ( SiMo ) ductile iron is commonly used for exhaust manifolds because these components experience thermal cycling in oxidizing environment, which requires resistance to fatigue during transient thermomechanical loads. Previous studies have demonstrated that alloying elements, such as Al , to SiMo ductile iron reduces the amount of surface degradation during static high-temperature exposure. However, deterioration of sphericity of the graphite nodules and a decrease in ductility could affect the tendency of cracking during thermal cycling. In this article, the effect of Al alloying on static and transient thermomechanical behavior of SiMo ductile iron was investigated to optimize the amount of Al alloying. A thermodynamic approach was used to confirm the effect of the Al alloying on the phase transformations in two SiMo cast irons, alloyed by 1.8% Al and 3% Al . These two alloys were cast in a laboratory along with the baseline SiMo ductile iron. Several experimental methods were used to evaluate the dimensional stability, physical properties, static oxidation, and failure resistance during constrained thermal cycling testing to compare their high-temperature capability. Experimental results verified that Al alloying increases the temperature range and decreases volume change during eutectoid transformation, which together with enhancement of oxidation protection improved the dimensional stability. Thermocycling tests showed that the number of cycles to failure depends on the amount of Al alloying and the applied high-temperature exposure during each cycle. SEM/EDX, high-resolution TEM and µCT analysis were used to verify the mechanism resulting from the Al alloying protection. It was shown that an optimal level of Al alloying for balancing oxidation and thermal cracking resistance depends on thermomechanical conditions of application.
Piezoresistance and piezo-Hall effect in semiconducting strontium titanium oxide
Iron(II)-bearing trioctahedral smectites (saponites) form during anoxic alteration of basaltic rock. They are predicted to have been widespread on the early Earth and are observed in the oceanic subsurface today. Smectite structures, including the occupancy of sites in the octahedral sheet, affect iron redox behavior but the rates and products of trioctahedral smectite oxidation have been largely unexplored to date. In this study we synthesized two Fe(II)-bearing trioctahedral smectites, one moderate (22 wt% Fe) and one high (27 wt% Fe) in iron content. We then examined the rate, extent, and products of their oxidation by dissolved oxygen, nitrite, and hydrogen peroxide. Dissolved oxygen caused partial oxidation of Fe(II) in the smectites with 14 to 43% of Fe(II) unoxidized after 20 to 30 days of exposure. The rate and extent of oxidation correlated with the dissolved oxygen concentration and the Fe(II) content of the clay. The incomplete oxidation in these experiments is consistent with the mixed-valent trioctahedral smectites observed in oxidized natural samples but contrasts with the complete reoxidation by oxygen shown by chemically- or microbially-reduced dioctahedral smectites. Oxidation of structural Fe(II) by 5 mmol L -1 nitrite was negligible for the moderate-iron smectite and yielded only ~17% oxidation after 54 days of reaction for the high-iron smectite. Hydrogen peroxide caused rapid and near-complete oxidation of both clays. Powder X-ray diffraction, variable-temperature Mössbauer spectroscopy, and extended X-ray absorption fine structure spectroscopy together detected no crystalline or short-range-ordered secondary phases and show that oxidized iron remained in the trioctahedral smectite structure. The recalcitrant Fe(II) pool in oxidized trioctahedral smectites exists in less distorted sites than Fe(II) in the initial clays. Its unreactive nature at prolonged reaction times indicates an elevated redox potential generated by the local coordination environment. Slower oxidation rates create a larger recalcitrant Fe(II) pool, suggesting kinetic competition between oxidation and a process involved in redox stabilization, such as electron exchange between octahedral iron sites or deprotonation of hydroxyl groups in the structure. The resistance to complete oxidation of trioctahedral ferrous smectites and their full retention of iron demonstrates that transitions from anoxic to oxic conditions generate mixed-valence smectites rather than a mixture of new phases. Identifying the diagenetic products of mixed-valent trioctahedral smectites may provide an indicator in the rock record of past redox cycling. In conclusion, substantial portions of structural Fe(II) in trioctahedral smectites display slow abiotic oxidation kinetics and represent potential electron donors for both microaerophilic iron oxidizing and nitrate-reducing, iron-oxidizing microorganisms in altered mafic rocks and related settings.
Metal nanoparticles deposited on oxide supports are essential to many technologies, including catalysts, fuel cells and electronics. Therefore, understanding the chemical bonding strength between metal nanoparticles and oxide surfaces is of great interest. The adsorption energetics, adhesion energy and adsorbate structure of Ag on dehydrated HCa 2 Nb 3 O 10 (001) nanosheets at 300 K have been studied using metal adsorption calorimetry and surface spectroscopies. These dehydrated (“dh”) calcium niobate nanosheets “(dh-HCa 2 Nb 3 O 10 (001))” have stoichiometry Ca 4 Nb 6 O 19 . They impart unusual stability to metal nanoparticles when used as catalyst supports and are easy-to-prepare by Langmuir-Blodgett (LB) techniques, highly ordered, and essentially single-crystal surfaces of mixed oxides with a huge ratio of terrace to edge sites. Below monolayer coverage, Ag grows on dh-HCa 2 Nb 3 O 10 (001) as 2D islands of thickness ~2 layers. The differential heat of Ag adsorption is initially ~303 kJ/mol, increasing slowly to ~338 kJ/mol by 0.8 ML. At higher coverages, Ag atoms mainly add on top of these 2D islands, growing 3D nanoparticles of increasing thickness, as the heat decreases asymptotically towards silver’s heat of sublimation (285 kJ/mol). The adhesion energy of Ag(s) to this Ca niobate surface is estimated to be 4.33 J/m 2 , larger than on any oxide surface previously measured. This explains the sinter resistance reported for metal nanoparticles on this support. Electron transfer from Ag into the calcium niobate is also measured. Furthermore, these results demonstrate an easy way to do singlecrystal-type surface science studies - and especially thermochemical measurements - on the complex surfaces of mixed oxides: using LB-deposited perovskite nanosheets and ultrahigh vacuum annealing in O 2 .
SiC/BN/SiC composites are designed to take advantage of the high specific strengths and moduli of non-oxide ceramics, and their excellent resistance to creep, chemical attack, and oxidation, while circumventing the brittleness inherent in ceramics. Hence, these composites have the potential to take turbine engines of the future to higher operating temperatures than is achievable with metal alloys. However, these composites remain developmental and more work needs to be done to optimize processing techniques. This paper highlights the lingering issue of pest degradation in these materials and shows that it results from vestiges of processing steps and can thus be minimized or eliminated.
Coatings developed to provide oxidation protection for the directionally-solidified eutectic alloy NiTaC-B (4.4 weight percent Cr) were evaluated. Of seven Co-, Fe- and Ni-base coatings that were initially investigated, best resistance to cyclic oxidation was demonstrated by duplex coatings fabricated by depositing a layer of NiCrAl(Y) by vacuum evaporation from an electron beam source followed by deposition of an Al overlayer using the pack cementation process. It was found that addition of carbon to the coating alloy substantially eliminated the problem of fiber denudation in TaC-type eutectic alloys. Burner rig cycled NiTaC-B samples coated with Ni-20Cr-5Al-0.1C-0.1Y+Al and rupture-tested at 1100 deg C performed as well as or better than uncoated, vacuum cycled and air-tested NiTaC-13; however, a slight degradation with respect to uncoated material was noted in air-stress rupture tests at 870 deg C for both cycled and uncycled samples.
Introduction Titanium aluminides are of great interest for intermediate-temperature (600 C - 850 C) aerospace and power generation applications because of their high specific properties. Replacement of conventional superalloys by titanium aluminides offers the potential of significant weight savings. Extensive development efforts over the past IO years have led to the identification of y (TiAl) + alpha(sub 2) (Ti3Al) alloys, such as the G.E. alloy Ti48Al-2Cr-2Nb (all composition in at. %), which offer a balance of room temperature mechanical properties and high-temperature strength retention. The two phase gamma + alpha(sub 2) class of titanium aluminides also offers superior oxidation and embrittlement resistance compared to the alpha(sub 2) and orthorhombic classes of titanium aluminides. However, environmental durability is still a major concern. Significant progress has recently been made in understanding the fundamental aspects of the oxidation behavior of binary gamma + alpha(sub 2) Ti-Al alloys. However, most of this work has concentrated on short term (less than 1000 hours), high temperature (900 C - 1000 C) exposures. Also little data are available in the literature regarding the oxidation behavior of the quaternary and higher order gamma + alpha(sub 2) engineering alloys. This is especially true for the very long-term, low temperature conditions likely to be experienced during engineering applications. The present work addresses this regime to fill this gap by characterizing the oxidation behavior of Ti48Al-2Cr-2Nb for periods up to 9000 h at 704 C in air.
A nanofibrous catalyst for in the electrolyzer and methods of making the catalyst. The catalysts are composed of highly porous transition metal carbonitrides, metal oxides or perovskites derived from the metal-organic frameworks and integrated into a 3D porous nano-network electrode architecture. The catalysts are low-cost, highly active toward OER, with excellent conductivity yet resistant to the oxidation under high potential operable under both acidic and alkaline environments.