Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Iron Oxide”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
NASA NTRS1989

Distributions of Manganese, Iron, and Manganese-Oxidizing Bacteria In Lake Superior Sediments of Different Organic Carbon Content

Profiles of oxygen, soluble and particulate manganese and iron, organic carbon and nitrogen were examined in Lake Superior sediment cores, along with the distribution and abundance of heterotrophic and manganese oxidizing bacteria. Analyses were performed using cores collected with the submersible Johnson Sea Link II. Three cores, exhibiting a range of organic carbon content, were collected from the deepest basin in Lake Superior and the north and south ends of the Caribou trough, and brought to the surface for immediate analysis. Minielectrode profiles of oxygen concentration of the three cores were carried out using a commercially available minielectrode apparatus. Oxygen depletion to less than 1% occurred within 4 cm of the surface for two of the cores, but not until approximately 15 cm for the core from the south basin of the Caribou trough. The three cores exhibited very different profiles of soluble, as well as leachable, manganese and iron, suggesting different degrees of remobilization of these metals in the sediments. Vertical profiles of viable bacteria and Mn oxidizing bacteria, determined by plating and counting, showed that aerobic (and facultatively aerobic) heterotrophic bacteria were present at the highest concentrations near the surface and decreased steadily with depth, while Mn oxidizing bacteria were concentrations primarily at and above the oxic/anoxic interface. Soluble manganese in the pore waters, along with abundant organic carbon, appeared to enhance the presence of manganese oxidizing bacteria, even below the oxic/anoxic interface. Profiles of solid-phase leachable manganese suggested a microbial role in manganese reprecipitation in these sediments.

Richardson, Laurie L.↗
NASA NTRS2006

Experimental Demonstration of the Molten Oxide Electrolysis Method for Oxygen and Iron Production from Simulated Lunar Materials

This paper presents the results of a Marshall Space Flight Center funded effort to conduct an experimental demonstration of the processing of simulated lunar resources by the molten oxide electrolysis (MOE) process to produce oxygen and metal from lunar resources to support human exploration of space. Oxygen extracted from lunar materials can be used for life support and propellant, and silicon and metallic elements produced can be used for in situ fabrication of thin-film solar cells for power production. The Moon is rich in mineral resources, but it is almost devoid of chemical reducing agents, therefore, molten oxide electrolysis, MOE, is chosen for extraction, since the electron is the most practical reducing agent. MOE was also chosen for following reasons. First, electrolytic processing offers uncommon versatility in its insensitivity to feedstock composition. Secondly, oxide melts boast the twin key attributes of highest solubilizing capacity for regolith and lowest volatility of any candidate electrolytes. The former is critical in ensuring high productivity since cell current is limited by reactant solubility, while the latter simplifies cell design by obviating the need for a gas-tight reactor to contain evaporation losses as would be the case with a gas or liquid phase fluoride reagent operating at such high temperatures. In the experiments reported here, melts containing iron oxide were electrolyzed in a low temperature supporting oxide electrolyte (developed by D. Sadoway, MIT).

Curreri, P. A.↗
NASA NTRS1985

Effects of chromium and aluminum on mechanical and oxidation properties of iron-nickel-base superalloys based on CG-27

The effects of chromium and aluminum on the mechanical and oxidation properties of a series of gamma-prime-strengthened alloys based on CG-27 were studied. Gamma-prime dispersion and solid-solution strengthening were the principal modes of alloy strengthening. The oxidation attack parameter K sub a decreased with increasing Cr and Al contents for each alloy group based on Al content. As a group, alloys with 3 wt % Al had the lowest attack parameters. Therefore, 3 wt % is the optimum level of Al for parabolic oxidation behavior. Spalling, due to diffusion-induced grain growth, was controlled by the overall Cr and Al levels. The alloy with 4 wt % Cr and 3 wt % Al had stress-rupture properties superior to those of the base alloy, CG-27, and maintained parabolic oxidation behavior while the Cr content was reduced by two-thirds of its value in cast CG-27.

Schuon, S. R.↗
DOE OSTI2020

Electron transfer calculations between edge sharing octahedra in hematite, goethite, and annite

A key reaction underlying the charge transport in iron containing oxides, clays, micas is the Fe$^{2+}$-Fe$^{3+}$ exchange reaction between edge-sharing iron octahedra. These reactions facilitate conduction in these minerals by the thermally-activated hopping of small polarons across the lattice. Depending on the mineral and local charge state the small polaron can either encase an electron or hole. The probability for conduction of small polarons depends strongly on the height and adiabicity of the reaction barrier, with larger and more diabatic barriers yielding slow conduction associated with either weak coupling or a large prerequisite rearrangement of the lattice during charge transport. To model these reactions, a first principle electron transfer (ET) method was developed to model the small polaron hopping between the edge-sharing octahedra sites in hematite ($e^{-}$ polaron), goethite ($e^{-}$ polaron), and annite ($h^{+}$ polaron) bulk structures. The ET method is based on electronic structure methods (i.e., plane-wave Density Functional Theory) capable of performing calculations with periodic cells and large size systems efficiently while at the same time being accurate enough to be used in the estimation of the electron-transfer coupling matrix element, $V_{AB}$, and the electron transfer transmission factor, $\kappa_{el}$. Additionally, the calculations confirmed the existence of small polarons in all three minerals, and the reactions were predicted to be strongly adiabatic. It was found that transfer of a hole in the octahedral layer of annite had an adiabatic barrier of $0.311$ eV, and the transfer of an extra electron in hematite and goethite had adiabatic barriers of $0.242$ eV and $0.232$ eV respectively. The electronic coupling parameters,$V_{AB}$, were found to be $0.188$ eV, $0.196$ eV, and $0.102$ eV respectively for hematite, goethite, and annite. While similar bonding topologies pertain, the underlying basis for the differences is the subtle differences in local structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Effect of Micro-Structural Dispersity of SiMo Ductile Iron on High Temperature Performance during Static Oxidation

High silicon and molybdenum (SiMo) ductile iron is commonly used for car exhaust systems, and its micro-structural dispersity depends on intrinsic parameters, which include alloy composition and inoculation efficiency, as well as extrinsic factors, such as casting wall thickness and molding material, which define cooling rate during solidification. Micro-structural dispersity is referred to as the degree of heterogeneity of sizes of structural constituencies within the microstructure. A variation in the micro-structural dispersity could impact the high temperature performance of SiMo ductile iron during static oxidation and transient thermo-mechanical loading conditions. In this study, static high temperature tests were performed on SiMo ductile iron solidified in a casting with varying wall thicknesses from 5 mm to 100 mm. The faster solidified specimens (taken from near chilled casting surfaces) had extremely high micro-structural dispersity as compared to the thicker section samples. After thermal exposure, each of the samples were characterized using 2D sections and 3D µCT images, and the results indicated an order of magnitude difference in graphite phase dispersity. The surface degradation was quantified after static oxidation experiments were implemented at temperature intervals between 650 °C and 800 °C. Non-destructive µCT 3D analysis and SEM/EDS were performed on cross sections and used to quantify the scale topology and structure. Carbon analysis was used to decouple the scale formation and decarburization phenomena that occurred within the samples. These methods enabled the quantification of the oxidation of the SiMo cast iron with different micro-structural dispersity levels after being exposed to high temperature static oxidation. Additionally, the complex material behavior during oxidation-assisted transient thermo-mechanical loading will be presented in a separate article.

36 MATERIALS SCIENCE↗
DOE OSTI2023

An S=1 Iron(IV) Intermediate Revealed in a Non-Heme Iron Enzyme-Catalyzed Oxidative C—S Bond Formation

Ergothioneine (ESH) and ovothiol A (OSHA) are two natural thiol-histidine derivatives. ESH has been implicated as a longevity vitamin and OSHA inhibits the proliferation of hepatocarcinoma. The key biosynthetic step of ESH and OSHA in the aerobic pathways is the O 2 -dependent C—S bond formation catalyzed by non-heme iron enzymes (e.g., OvoA in ovothiol biosynthesis), but due to the lack of identification of key reactive intermediate the mechanism of this novel reaction is unresolved. In this study, we report the identification and characterization of a kinetically competent S=1 iron(IV) intermediate supported by a four-histidine ligand environment (three from the protein residues and one from the substrate) in enabling C—S bond formation in OvoA from Methyloversatilis thermotoleran, which represents the first experimentally observed intermediate spin iron(IV) species in non-heme iron enzymes. Results reported in this study thus set the stage to further dissect the mechanism of enzymatic oxidative C—S bond formation in the OSHA biosynthesis pathway. They also afford new opportunities to study the structure-function relationship of high-valent iron intermediates supported by a histidine rich ligand environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Organic compounds alter the preference and rates of heavy metal adsorption on ferrihydrite

The availability of heavy metals in terrestrial environments is largely controlled by their interactions with minerals and organic matter, with iron minerals having a particularly strong role in heavy metal fate. Because soil organic matter contains a variety of compounds that differ in their chemical properties, the underlying impact organic matter-soil mineral associations bestow on heavy metal binding is still unresolved. Here, we systematically examine the binding of Cd, Zn and Ni by a suite of organic-ferrihydrite assemblages, chosen to account for various compound chemistries within soil organic matter. We posited that organic compound functionality would dictate the extent of association with the organic-ferrihydrite assemblages. Increased heavy metal binding to the assemblages was observed and attributed to the introduction of additional binding sites by the organic functional groups with differing metal affinities. Furthermore, the relative increase depended on the metal's Lewis acidity and followed the order Cd > Zn > Ni, whereas the reverse order was obtained for metal binding by pristine ferrihydrite (Ni > Zn > Cd). Citric acid-, aspartic acid- and cysteine-ferrihydrite assemblages also enhanced the metal binding rate. X-ray absorption spectroscopy revealed that the organic coating contributed significantly to Zn binding by the assemblages, despite relatively low organic surface coverage. Our findings provide valuable information on the nature of heavy metal-organic-mineral interactions and metal adsorption processes regulating their bioavailability and transport.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Oxidation in Ca/K-1144 iron-based superconductors polycrystalline compounds

Iron-based superconductors (IBSCs) are a class of material under investigation for the development of superconducting wires in the low-temperature-high magnetic fields power application. Among the various families of IBSCs, the 1144 CaKFe$_4$As$_4$ compound is a promising material able to achieve outstanding superconducting properties with a cheap and simple chemical composition. Oxidation, in these compounds, is considered an obstacle for high intergranular critical current density, J c,GB . A study devoted to the evaluation of oxidation phenomena and their effects on the superconducting properties is thus needed in order to fully understand the involved mechanisms. From the evaluation of polycrystalline samples obtained by a mechanochemically assisted synthesis route, a degradation of the critical temperature and critical currents has been observed concurrently with oxygen accumulation at grain boundaries in open porosities. However, the crystalline structure at an atomic level seems not affected, as well as intragranular superconducting properties assessed by means of calorimetric methods. These results suggest that loss of superconducting properties in Ca/K-1144 compounds following oxidation is significantly associated with the worsening of grain connectivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

An Iron(IV)–Oxo Intermediate Initiating l-Arginine Oxidation but Not Ethylene Production by the 2-Oxoglutarate-Dependent Oxygenase, Ethylene-Forming Enzyme

Ethylene-forming enzyme (EFE) is an ambifunctional iron(II)- and 2-oxoglutarate-dependent (Fe/2OG) oxygenase. In its major (EF) reaction, it converts carbons 1, 2, and 5 of 2OG to CO 2 and carbons 3 and 4 to ethylene, a four-electron oxidation drastically different from the simpler decarboxylation of 2OG to succinate mediated by all other Fe/2OG enzymes. EFE also catalyzes a minor reaction, in which the normal decarboxylation is coupled to oxidation of L-arginine (a required activator for the EF pathway), resulting in its conversion to L-glutamate semialdehyde and guanidine. Here we show that, consistent with precedent, the L-Arg-oxidation (RO) pathway proceeds via an iron(IV)-oxo (ferryl) intermediate. Use of 5,5-[ 2 H 2 ]-L-Arg slows decay of the ferryl complex by >16-fold, implying that RO is initiated by hydrogen-atom transfer (HAT) from C5. That this large substrate deuterium kinetic isotope effect has no impact on the EF:RO partition ratio implies that the same ferryl intermediate cannot be on the EF pathway; the pathways must diverge earlier. Consistent with this conclusion, the variant enzyme bearing the Asp191Glu ligand substitution accumulates ~ four times as much of the ferryl complex as the wild-type enzyme and exhibits a ~ 40-fold diminished EF:RO partition ratio. Here, the selective detriment of this nearly conservative substitution to the EF pathway implies that it has unusually stringent stereoelectronic requirements. An active-site, like-charge guanidium pair, which involves the L-Arg substrate/activator and is unique to EFE among four crystallographically characterized L-Arg modifying Fe/2OG oxygenases, may serve to selectively stabilize the transition state leading to the unique EF branch.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Controlled thermal pre-treatment of ZMG232G10® for corrosion mitigation under simulated SOFC interconnect exposure conditions

The IT-SOFC candidate interconnect material ZMG232G10® was thermally pre-treated in air and in H 2 – 3% H 2 O to mitigate dual atmosphere corrosion. Bare and pre-treated steel samples were exposed to a dual atmosphere exposure condition (dry air/metal/4% H 2 – N 2 (bal.) + 3% H 2 O) for 500h at 600°C. Corrosion products and oxide morphology developed on the air-exposed surfaces were analyzed. Pre-treatments of the metal in oxidizing (air) and reducing (H 2 – 3% H 2 O) gas atmospheres provide improved passivation against dual atmosphere corrosion compared to bare steel. Further, the uniform and iron-free oxide scale developed during the pre-treatment of alloy in the low pO 2 H 2 – 3% H 2 O gas atmosphere provides an effective diffusion barrier against the outward transport of cations and oxidation of iron observed under dual atmosphere conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Direct non-oxidative methane coupling on vitreous silica supported iron catalysts

Direct non-oxidative methane coupling (NMC) is one of the promising pathways for methane upgrading into value-added olefin and aromatic hydrocarbons. The silica-supported iron (i.e., Fe/SiO 2 ) catalyst has been reported effective for NMC, but the effects of silica support on the catalyst property and NMC performance have rarely been explored. Here, in this work, we prepared a vitreous silica-supported iron (Fe/SiO 2 -V) catalyst by flame fusion of a mixture of quartz silica and fayalite. The physicochemical properties and NMC performance of the as-prepared catalysts were measured. Compared to crystalline cristobalite support in Fe/SiO 2 catalyst that has been studied previously, vitreous silica support has disordered Si-O bonds and structural defects, enabling better iron dispersion and more vital metal-support interaction. The as-prepared Fe/SiO 2 -V catalyst had a shorter induction period in methane activation and lower coke yield in NMC. The increase in iron concentration in Fe/SiO 2 -V catalysts elongated the catalyst induction period and promoted aromatics and coke formation. The coke type of the spent Fe/SiO 2 -V catalyst is more uniform than the cristobalite-supported iron catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Density Functional Theory Study of Iron–Oxygen Divacancies in Magnetite (Fe 3 O 4 ) and Hematite (Fe 2 O 3 )

Density functional theory (DFT) calculations are employed to investigate the formation energies, charge redistribution, and binding energies of iron–oxygen divacancies in magnetite (Fe 3 O 4 ) and hematite (Fe 2 O 3 ). For magnetite, we focus on the low-temperature phase to explore variations with local environments. Building on previous DFT calculations of the variations in formation energies for oxygen vacancies with local charge and spin order in magnetite, we extend this analysis to include octahedral iron vacancies before analyzing the iron–oxygen divacancies. We also assessed the relative stability of iron–oxygen divacancies by comparing their formation energies with those of individual vacancies. Our findings reveal a significant energetic driving force for the formation of divacancy clusters, particularly in magnetite, where divacancies in the +1 charge state exhibit formation energies comparable to those of neutral iron vacancies under oxidizing conditions. In hematite, the results indicate a strong tendency for oxygen vacancies to bind to iron vacancies. These results highlight the significance of iron–oxygen vacancy complexes in the transport properties of iron oxides, with particular relevance to diffusion mechanisms under irradiation conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Plutonium Oxidation State Distribution in the Presence of WIPP-Relevant Organics and Iron Corrosion Products

The oxidation state and solubility of plutonium (Pu) in high ionic strength synthetic WIPP (Waste Isolation Pilot Plant) brines as a function of pC H+ in the presence and absence of WIPP-relevant organic ligands (EDTA [Ethylenediaminetetraacetic acid], oxalate, citrate, acetate) and iron corrosion products (magnetite and metallic iron) at 𝑇 = 23 ± 2 ∘C was thoroughly studied by long-term batch solubility experiments (between approximately 800-1,100 days) from an undersaturation approach. The oxidation state of Pu in the WIPP environment has been a topic of interest since the initial Compliance Certification Application (CCA). This study aims to investigate the solubility of Pu under the expected WIPP conditions and to determine the oxidation state of the solid phase that will control the solubility. One of the most important results of this study is that the Pu oxidation state was analyzed both from the surface area of the corrosion products and in the precipitated solid. The analysis of the Pu oxidation state on the surface of the iron mineral from the ongoing undersaturated experiments is more relevant to the performance assessment of nuclear waste disposal than short term batch (plutonium-iron phase) experiments. The X-ray Absorption Near-Edge Spectroscopy (XANES) analysis showed that Pu oxidation state is different on the metal surface and in the precipitated solid. Pu(III) is the dominant oxidation state in the metallic iron (Fe 0 ) system in the presence and absence of organics. Pu(IV) is the dominant oxidation state in the magnetite system in the presence and absence of organics. Also, organics stabilize Pu(IV) in the magnetite system. Analysis of Pu in the precipitated solid by Extended X-ray Absorption Fine Structure (EXAFS) analysis showed that Pu formed an inner-sphere complex with iron with minor amounts of PuO 2 present. X-ray diffraction (XRD) results indicate that metallic iron and magnetite did not oxidize in three years in the alkaline and high ionic strength system. Under these conditions (8 < pC H+ < 10 at T = (22 ± 2) °C under nitrogen atmosphere, the solubility of Pu changes by up to three orders of magnitude (10 -5 and 10 -8 M). The spread in solubility is highest at pC H+ = 9. Pu(III) and Pu(IV) showed different solubility behavior in the synthetic WIPP brine. A summary of the data collected in this report will be submitted to Sandia National Laboratories as part of a parameter update report which will outline the changes to the OXSTAT parameter for the 2026 Compliance Recertification Application (CRA-2026). The experiments performed were done according to the U.S. Department of Energy (DOE) approved Test Plan entitled “Effects of Radiolysis, Organic Complexation, and Redox Conditions on the Speciation and Oxidation State Distribution of Pu(III/IV)” (LCO-ACP-25). All data reported were obtained under the Los Alamos National Laboratory-Carlsbad Office (LANL-CO) Quality Assurance Program, which is compliant with the DOE Carlsbad Field Office, Quality Assurance Program Document (CBFO/QAPD).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS2014

Looking for a Source of Water in Martian Basltic Breccia NWA 7034

The recently described martian meteorite NWA 7034 has high water content compared to other SNC meteorites. Deuterium to hydrogen isotope ratio measurements indicates that there are two distinct delta-D components in NWA 7034, a low temperature (150-500degC) light component around -100per mille and a high temperature (300-1000degC) heavy component around +300per mille. NWA 7034 contains iron-rich phases that are likely secondary aqueous alteration products. They are commonly found as spheroidal objects of various sizes that are often rich in Fe-Ti oxides and possibly iron hydroxides. Iron oxides and oxyhydroxides are very common in weathered rocks and soils on Earth and Mars and they are important components of terrestrial and Martian dust. In NWA 7034 iron-rich phases are found throughout the fine-grained basaltic groundmass of the meteorite. The total amount of martian H2O in NWA 7034 is reported to be 6000 ppm, and in this study we attempt to determine the phase distribution of this H2O by texturally describing and characterizing hydrous phases in NWA 7034, using Fourier transform infrared spectrometry (FTIR) and transmission electron microscopy (TEM).

Muttik, N.↗