SEARCH · Engineering Papers
Results for “FeCo3”
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.
Materials Data on FeCO3 by Materials Project
FeCO3 is Calcite structured and crystallizes in the trigonal R-3c space group. The structure is three-dimensional. Fe2+ is bonded to six equivalent O2- atoms to form corner-sharing FeO6 octahedra. The corner-sharing octahedral tilt angles are 60°. All Fe–O bond lengths are 2.17 Å. C4+ is bonded in a trigonal planar geometry to three equivalent O2- atoms. All C–O bond lengths are 1.30 Å. O2- is bonded in a distorted trigonal planar geometry to two equivalent Fe2+ and one C4+ atom.
Materials Data on FeCo3 by Materials Project
FeCo3 is Uranium Silicide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Fe is bonded to twelve equivalent Co atoms to form FeCo12 cuboctahedra that share corners with twelve equivalent FeCo12 cuboctahedra, edges with twenty-four equivalent CoFe4Co8 cuboctahedra, faces with six equivalent FeCo12 cuboctahedra, and faces with twelve equivalent CoFe4Co8 cuboctahedra. All Fe–Co bond lengths are 2.50 Å. Co is bonded to four equivalent Fe and eight equivalent Co atoms to form CoFe4Co8 cuboctahedra that share corners with twelve equivalent CoFe4Co8 cuboctahedra, edges with eight equivalent FeCo12 cuboctahedra, edges with sixteen equivalent CoFe4Co8 cuboctahedra, faces with four equivalent FeCo12 cuboctahedra, and faces with fourteen equivalent CoFe4Co8 cuboctahedra. All Co–Co bond lengths are 2.50 Å.
Materials Data on FeCo3 by Materials Project
FeCo3 is alpha La-derived structured and crystallizes in the tetragonal P4/mmm space group. The structure is three-dimensional. Fe is bonded to four equivalent Fe and eight equivalent Co atoms to form FeFe4Co8 cuboctahedra that share corners with four equivalent FeFe4Co8 cuboctahedra, corners with eight equivalent CoCo12 cuboctahedra, edges with twenty-four CoFe4Co8 cuboctahedra, faces with eight equivalent FeFe4Co8 cuboctahedra, and faces with ten CoFe4Co8 cuboctahedra. All Fe–Fe bond lengths are 2.47 Å. All Fe–Co bond lengths are 2.50 Å. There are two inequivalent Co sites. In the first Co site, Co is bonded to four equivalent Fe and eight Co atoms to form CoFe4Co8 cuboctahedra that share corners with twelve equivalent CoFe4Co8 cuboctahedra, edges with eight equivalent FeFe4Co8 cuboctahedra, edges with sixteen CoFe4Co8 cuboctahedra, faces with four equivalent FeFe4Co8 cuboctahedra, and faces with fourteen CoFe4Co8 cuboctahedra. There are four shorter (2.46 Å) and four longer (2.47 Å) Co–Co bond lengths. In the second Co site, Co is bonded to twelve Co atoms to form CoCo12 cuboctahedra that share corners with four equivalent CoCo12 cuboctahedra, corners with eight equivalent FeFe4Co8 cuboctahedra, edges with eight equivalent FeFe4Co8 cuboctahedra, edges with sixteen equivalent CoFe4Co8 cuboctahedra, faces with two equivalent FeFe4Co8 cuboctahedra, and faces with sixteen CoFe4Co8 cuboctahedra. All Co–Co bond lengths are 2.47 Å.
Detection of Siderite (FeCO3) in Glen Torridon Samples by the Mars Science Laboratory Rover
Siderite (FeCO3) has been detected in Gale Crater for the first time by the Mars Science Laboratory (MSL) Curiosity and is seen in multiple samples in the Glen Torridon (GT) region. The identification of siderite is based on evolved gas analysis (EGA) data from the Sample Analysis at Mars (SAM) instrument and X-ray diffraction (XRD) data from the Chemistry and Mineralogy (CheMin) instrument. Curiosity descended off of the Vera Rubin ridge (VRR) into the Glen Torridon region on Sol 2300. Glen Torridon is of particular interest because a strong clay mineral signature had been detected by orbital instruments [1]. To date, four drilled samples have been collected at two different drill locations: Kilmarie and Aberlady from adjacent blocks at the base of the south side of VRR in the Jura member and Glen Etive 1 and 2 on the same block in the Knockfarril member.
Materials Data on FeCo3(PO4)4 by Materials Project
Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations
Grain boundary widening controls siderite (FeCO3) replacement of limestone (CaCO3)
Abstract The microstructure of minerals and rocks can significantly alter reaction rates. This study focuses on identifying transport paths in low porosity rocks based on the hypothesis that grain boundary widening accelerates reactions in which one mineral is replaced by another (replacement reaction). We conducted a time series of replacement experiments of three limestones (CaCO 3 ) of different microstructures and solid impurity contents using FeCl 2 . Reacted solids were analyzed using chemical imaging, small angle X-ray and neutron scattering and Raman spectroscopy. In high porosity limestones replacement is reaction controlled and complete replacement was observed within 2 days. In low porosity limestones that contain 1–2% dolomite impurities and are dominated by grain boundaries, a reaction rim was observed whose width did not change with reaction time. Siderite (FeCO 3 ) nucleation was observed in all parts of the rock cores indicating the percolation of the solution throughout the complete core. Dolomite impurities were identified to act as nucleation sites leading to growth of crystals that exert force on the CaCO 3 grains. Widening of grain boundaries beyond what is expected based on dissolution and thermal grain expansion was observed in the low porosity marble containing dolomite impurities. This leads to a self-perpetuating cycle of grain boundary widening and reaction acceleration instead of reaction front propagation.
Weathering of iron sulfides under Mars surface ambient conditions
The study of iron sulfide surface alternation reactions under Mars' surface ambient conditions begun during 1980 was extended through improved irradiation design and experimental protocols. A wider range of humidities and more intense irradiation were incorporated in the study. X-ray photoelectron spectra of irradiated chips suggest formation of FeSO4, FeCO3, and an iron oxide on the iron sulfide substrates studied.
Volatiles in the deep Earth: An experimental study using the laser-heated diamond cell
Experiments with the laser-heated diamond cell show that H2O and CO2 can be stabilized within crystalline mineral structures of the lower-mantle, and hence can be present at relatively non-volatile components of the Earth's deep interior. Samples quenched from high pressures and temperatures document that the MgCO3-FeCO3 magnesite-siderite solid-solution is stable and coexists with (Mg,Fe)SiO3 perovskite at 30-40 GPa and approximately 1500-2000 K. In contrast, H2O combines with the silicate to form (Mg,Fe)SiH2O4 phase D, coexisting with (Mg,Fe)SiO3 perovskite at these conditions. If enough water is present, phase D can become the predominant phase in the MgSiO3-H2O system at lower-mantle conditions. Our work extends previous studies to Fe-bearing compositions and to the pressures of the mid-lower mantle. Thus, the results of high-pressure experiments suggest that both H2O and CO2 can be abundant in the Earth's lower mantle, being present in stable hydroxisilicate and carbonate phases.
Ammonia on the prebiotic Earth: Iron(II) reduction of nitrite
Theories for the origin of life require the availability of reduced nitrogen. In the non-reducing atmosphere suggested by geochemical evidence, production in the atmosphere and survival of NH3 against photochemical destruction are problematic. Electric discharges and impact shocks would produce NO rather than HCN or NH3. Conversion of NO to nitrous and nitric acid (by way of HNO) and precipitation in acid rain would provide a source of fixed nitrogen to the early ocean. One solution to the NH3 problem may have been the reduction of nitrite/nitrate in the ocean with aqueous ferrous iron, Fe(2+): 6Fe(+2) + 7 H2O + NO2(-) yields 3Fe2O3 + 11 H(+) + NH3. We have measured the kinetics of this reaction as a function of temperature, pH, and concentrations of salts, Fe(+2), and NO2(-). Cations (Na(+), Mg(2+), K(+)) and anions (Cl(-), Br(-), SO4(2-)) increase the rate by factors of 4 to 8. Although a competing pathway yields N2, the efficiency of the conversion of nitrite to ammonia ranges from 25% to 85%. Nitrate reduction was not consistently reproducible; however, when it was observed, its rate was slower by at least 8X than that of nitrite reduction. If the prebiotic atmosphere contained 0.2 to 10 atmospheres CO2 as suggested by Walker (1985), the Fe(+2) concentration and the rate would have been limited by siderite (FeCO3) solubility.
Differential Scanning Calorimetry of Volatile-Bearing Iron Minerals Under Mars-Like Pressures: New Insights Into Energetics and Mechanisms of Thermal Decomposition
In this study, we have examined the thermal decomposition of two volatile-bearing iron minerals, in particular, lepidocrocite (gamma-FeOOH) and siderite (FeCO3), under Mars-like pressures. Both minerals exhibit different enthalpic events during their decomposition at reduced atmospheric pressures when compared to those at ambient pressure. These differences in energetics are related to the mechanisms of thermal decomposition at Mars-like pressures. Such knowledge regarding the thermal stability of volatile-bearing minerals on Mars will provide useful information for planetary surface processes.
Analysis of Siderite Thermal Decomposition by Differential Scanning Calorimetry
Characterization of carbonate devolitilization has important implications for atmospheric interactions and climatic effects related to large meteorite impacts in platform sediments. On a smaller scale, meteorites contain carbonates which have witnessed shock metamorphic events and may record pressure/temperature histories of impact(s). ALH84001 meteorite contains zoned Ca-Mg-Fe-carbonates which formed on Mars. Magnetite crystals are found in the rims and cores of these carbonates and some are associated with void spaces leading to the suggestion by Brearley et al. that the crystals were produced by thermal decomposition of the carbonate at high temperature, possibly by incipient shock melting or devolitilization. Golden et al. recently synthesized spherical Mg-Fe-Ca-carbonates from solution under mild hydrothermal conditions that have similar carbonate compositional zoning to those of ALH84001. They have shown experimental evidence that the carbonate-sulfide-magnetite assemblage in ALH84001 can result from a multistep inorganic process involving heating possibly due to shock events. Experimental shock studies on calcium carbonate prove its stability to approx. 60 GPa, well in excess of the approx. 45 GPa peak pressures indicated by other shock features in ALH84001. In addition, Raman spectroscopy of carbonate globules in ALH84001 indicates no presence of CaO and MgO. Such oxide phases should be found associated with the magnetites in voids if these magnetites are high temperature shock products, the voids resulting from devolitilization of CO2 from calcium or magnesium carbonate. However, if the starting material was siderite (FeCO3), thermal breakdown of the ALH84001 carbonate at 470 C would produce iron oxide + CO2. As no documentation of shock effects in siderite exists, we have begun shock experiments to determine whether or not magnetite is produced by the decomposition of siderite within the < 45GPa pressure window and by the resultant thermal pulse to approx. 600 C experienced by ALH84001. Here, we report thermal and compositional characterization of unshocked siderite and its transition to magnetite. Additional information is contained in the original extended abstract.
A Mossbauer investigation of iron-rich terrestrial hydrothermal vent systems: lessons for Mars exploration
Hydrothermal spring systems may well have been present on early Mars and could have served as a habitat for primitive life. The integrated instrument suite of the Athena Rover has, as a component on the robotic arm, a Mossbauer spectrometer. In the context of future Mars exploration we present results of Mossbauer analysis of a suite of samples from an iron-rich thermal spring in the Chocolate Pots area of Yellowstone National Park (YNP) and from Obsidian Pool (YNP) and Manitou Springs, Colorado. We have found that Mossbauer spectroscopy can discriminate among the iron-bearing minerals in our samples. Those near the vent and on the surface are identified as ferrihydrite, an amorphous ferric mineraloid. Subsurface samples, collected from cores, which are likely to have undergone inorganic and/or biologically mediated alteration (diagenesis), exhibit spectral signatures that include nontronite (a smectite clay), hematite (alpha-Fe2O3), small-particle/nanophase goethite (alpha-FeOOH), and siderite (FeCO3). We find for iron minerals that Mossbauer spectroscopy is at least as efficient in identification as X-ray diffraction. This observation is important from an exploration standpoint. As a planetary surface instrument, Mossbauer spectroscopy can yield high-quality spectral data without sample preparation (backscatter mode). We have also used field emission scanning electron microscopy (FESEM), in conjunction with energy-dispersive X ray (EDX) fluorescence spectroscopy, to characterize the microbiological component of surface sinters and the relation between the microbiological and the mineralogical framework. Evidence is presented that the minerals found in these deposits can have multi-billion-year residence times and thus may have survived their possible production in a putative early Martian hot spring up to the present day. Examples include the nanophase property and the Mossbauer signature for siderite, which has been identified in a 2.09-billion-year old hematite-rich chert stromatolite. Our research demonstrates that in situ Mossbauer spectroscopy can help determine whether hydrothermal mineral deposits exist on Mars, which is significant for exobiology because of the issue of whether that world ever had conditions conductive to the origin of life. As a useful tool for selection of samples suitable for transport to Earth, Mossbauer spectroscopy will not only serve geological interests but will also have potential for exopaleontology.
Evidence from massive siderite beds for a CO2-rich atmosphere before approximately 1.8 billion years ago
It is generally thought that, in order to compensate for lower solar flux and maintain liquid oceans on the early Earth, methane must have been an important greenhouse gas before approximately 2.2 billion years (Gyr) ago. This is based upon a simple thermodynamic calculation that relates the absence of siderite (FeCO3) in some pre-2.2-Gyr palaeosols to atmospheric CO2 concentrations that would have been too low to have provided the necessary greenhouse effect. Using multi-dimensional thermodynamic analyses and geological evidence, we show here that the absence of siderite in palaeosols does not constrain atmospheric CO2 concentrations. Siderite is absent in many palaeosols (both pre- and post-2.2-Gyr in age) because the O2 concentrations and pH conditions in well-aerated soils have favoured the formation of ferric (Fe3+)-rich minerals, such as goethite, rather than siderite. Siderite, however, has formed throughout geological history in subsurface environments, such as euxinic seas, where anaerobic organisms created H2-rich conditions. The abundance of large, massive siderite-rich beds in pre-1.8-Gyr sedimentary sequences and their carbon isotope ratios indicate that the atmospheric CO2 concentration was more than 100 times greater than today, causing the rain and ocean waters to be more acidic than today. We therefore conclude that CO2 alone (without a significant contribution from methane) could have provided the necessary greenhouse effect to maintain liquid oceans on the early Earth.
Carbonates in fractures of Martian meteorite Allan Hills 84001: petrologic evidence for impact origin
Carbonates in Martian meteorite Allan Hills 84001 occur as grains on pyroxene grain boundaries, in crushed zones, and as disks, veins, and irregularly shaped grains in healed pyroxene fractures. Some carbonate disks have tapered Mg-rich edges and are accompanied by smaller, thinner and relatively homogeneous, magnesite microdisks. Except for the microdisks, all types of carbonate grains show the same unique chemical zoning pattern on MgCO3-FeCO3-CaCO3 plots. This chemical characteristic and the close spatial association of diverse carbonate types show that all carbonates formed by a similar process. The heterogeneous distribution of carbonates in fractures, tapered shapes of some disks, and the localized occurrence of Mg-rich microdisks appear to be incompatible with growth from an externally derived CO2-rich fluid that changed in composition over time. These features suggest instead that the fractures were closed as carbonates grew from an internally derived fluid and that the microdisks formed from a residual Mg-rich fluid that was squeezed along fractures. Carbonate in pyroxene fractures is most abundant near grains of plagioclase glass that are located on pyroxene grain boundaries and commonly contain major or minor amounts of carbonate. We infer that carbonates in fractures formed from grain boundary carbonates associated with plagiociase that were melted by impact and dispersed into the surrounding fractured pyroxene. Carbonates in fractures, which include those studied by McKay et al. (1996), could not have formed at low temperatures and preserved mineralogical evidence for Martian organisms.
Data Processing and Experimental Design for Micrometeorite Impacts in Small Bodies
Comets and asteroids have been altered from their original "pristine" state by impacts occurring throughout their 4.5 billion year lives: [1]. Proof of shock deformation has been detected in the crystal structure of several Stardust samples from Comet Wild 2 [2, 3]. Analyses indicated that the planar dislocations in the crystal structure of the minerals had been imparted by impacts sustained during their lives, and not due to the aerogel capture process. Distortions to crystal structure also affect the ideal absorption spectra in the infrared, and [4], thus providing indirect evidence of its impact history and a means of remotely investigating the impact history of small bodies through comparing laboratory spectra with spectra observed by telescopes or spacecraft. -The effects of impacts propagating shock waves through minerals were investigated through laboratory impact experiments. Utilizing NASA Johnson Space Center's Experimental Impact Laboratory, projectiles were fired from the vertical gun at velocities ranging from 2.0 to 2.8 km/sec, projected impact velocities between Kuiper Belt Objects. Two types of projectiles were used, including spherical alumina ceramic, whose density mimics that of rock, and cylinders made from the same material that they impacted. The target materials chosen for testing included: OLIVINES forsterite (Mg2SiO4) and fayalite, Fe2SiO4); PYROXENES enstatite (Mg2Si2O6) and diopside (MgCaSi2O6); and CARBONATES magnesite (MgCO3) and siderite (FeCO3). Targets were impacted at either 25 C or cooled to -20 C to examine the effects of temperature, if any, on lattice distortions during the shock propagation. As comets and asteroids can undergo a wide range of temperatures in their orbital lifetimes, the effect of temperature on the equation of state of minerals being shocked needs to be examined for interpreting the results of these experiments. The porosity of the target mineral is varied by either grinding it into a powder/granular texture or as whole mineral rocks to investigate the differences in shock propagation when voids are present. By varying velocity, ambient temperature, and porosity, we can investigate different variables affecting impacts in the solar system. -Data indicates that there is a non-linear relationship between peak shock pressure and the variation in infrared spectral absorbances by the distorted crystal structure. The maximum variability occurs around 37 GPa in enstatite and forsterite. The particle size distribution of the impacted material similarly changes with velocity/peak shock pressure. -The experiments described above are designed to measure the near- to mid-IR effects from these changes to the mineral structure. See Lederer et al., this meeting for additional experimental results.
Iron-Rich Carbonates as the Potential Source of Evolved CO2 Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater
The Sample Analysis at Mars (SAM) instrument detected at least 4 distinct CO2 release during the pyrolysis of a sample scooped from the Rocknest (RN) eolian deposit. The highest peak CO2 release temperature (478-502 C) has been attributed to either a Fe-rich carbonate or nano-phase Mg-carbonate. The objective of this experimental study was to evaluate the thermal evolved gas analysis (T/EGA) characteristics of a series of terrestrial Fe-rich carbonates under analog SAM operating conditions to compare with the RN CO2 releases. Natural Fe-rich carbonates (<53 microns) with varying Fe amounts (Fe(0.66)X(0.34)- to Fe(0.99)X(0.01)-CO3, where X refers to Mg and/or Mn) were selected for T/EGA. The carbonates were heated from 25 to 715 C (35 C/min) and evolved CO2 was measured as a function of temperature. The highest Fe containing carbonates (e.g., Fe(0.99)X(0.01)-CO3) yielded CO2 peak temperatures between 466-487 C, which is consistent with the high temperature RN CO2 release. The lower Fe-bearing carbonates (e.g., Fe(0.66)X(0.34)CO3) did not have peak CO2 release temperatures that matched the RN peak CO2 temperatures; however, their entire CO2 releases did occur within RN temperature range of the high temperature CO2 release. Results from this laboratory analog analysis demonstrate that the high temperature RN CO2 release is consistent with Fe-rich carbonate (approx.0.7 to 1 wt.% FeCO3). The similar RN geochemistry with other materials in Gale Crater and elsewhere on Mars (e.g., Gusev Crater, Meridiani) suggests that up to 1 wt. % Fe-rich carbonate may occur throughout the Gale Crater region and could be widespread on Mars. The Rocknest Fe-carbonate may have formed from the interaction of reduced Fe phases (e.g., Fe2+ bearing olivine) with atmospheric CO2 and transient water. Alternatively, the Rocknest Fe-carbonate could be derived by eolian processes that have eroded distally exposed deep crustal material that possesses Fe-carbonate that may have formed through metamorphic and/or metasomatic processes.
Relative Detectability of Iron-Bearing Phases for the Mars 2020 Sherloc Deep UV Raman Instrument: 1. Focusing on Carbonates
A deep ultraviolet (DUV) Raman and fluorescence instrument is a surface standoff instrument mounted on the robotic arm of the Mars 2020 (M2020) rover Perseverance, and it is a key element of the Scanning Habitable Environments with Luminescence for Organics and Chemicals (SHERLOC) investigation [1]. Measurement and science objectives include mineralogical and organic images (~100 μm/pixel) that map sub-millimeter spatial distributions and characterization of primary and secondary minerals, potential organics, and their interaction/alteration products. The results of data analysis pertain to understanding igneous and alteration processes on Mars through time, assessing habitability, evidencing in situ biosignatures, and, along with results from other Perseverance instruments, selecting samples to cache for Mars sample return. Acceptance of the SHERLOC investigation for the NASA M2020 mission [2] created a need for Mars-relevant DUV Raman spectra, particularly for inorganic materials [e.g., 3, 4]. As reported previously [e.g., 4, 5], phases with Fe cations as essential elements (e.g., siderite (FeCO3) and ankerite (FeCa(CO3)2) for carbonates) significantly hinder detection by DUV Raman because of intense absorption of incident and scattered DUV laser radiation by Fe cations. We report here the relative detectability of carbonates (Mg,Ca,Fe,Mn)CO3 by DUV Raman using a SHERLOC analog laboratory instrument.