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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
NASA NTRS2007

Experimental Shock Decomposition of Siderite and the Origin of Magnetite in Martian Meteorite ALH84001

Shock recovery experiments to determine whether magnetite could be produced by the decomposition of iron-carbonate were initiated. Naturally occurring siderite was first characterized by electron microprobe (EMP), transmission electron microscopy (TEM), Mossbauer spectroscopy, and magnetic susceptibility measurements to be sure that the starting material did not contain detectable magnetite. Samples were shocked in tungsten-alloy holders (W=90%, Ni=6%, Cu=4%) to further insure that any iron phases in the shock products were contributed by the siderite rather than the sample holder. Each sample was shocked to a specific pressure between 30 to 49 GPa. Previously reported results of TEM analyses on 49 GPa experiments indicated the presence of nano-phase spinel-structured iron oxide. Transformation of siderite to magnetite as characterized by TEM was found in the 49 GPa shock experiment. Compositions of most magnetites are greater than 50% Fe sup(+2) in the octahedral site of the inverse spinel structure. Magnetites produced in shock experiments display the same range of single-domain, superparamagnetic sizes (approx. 50 100 nm), compositions (100% magnetite to 80% magnetite-20% magnesioferrite), and morphologies (equant, elongated, euhedral to subhedral) as magnetites synthesized by Golden et al. (2001) or magnetites grown naturally by MV1 magnetotactic bacteria, and as the magnetites in Martian meteorite ALH84001. Fritz et al. (2005) previously concluded that ALH84001 experienced approx. 32 GPa pressure and a resultant thermal pulse of approx. 100 - 110 C. However, ALH84001 contains evidence of local temperature excursions high enough to 1 melt feldspar, pyroxene, and a silica-rich phase. This 49 GPa experiment demonstrates that magnetite can be produced by the shock decomposition of siderite as a result of local heating to greater than 470 C. Therefore, magnetite in the rims of carbonates in Martian meteorite ALH84001 could be a product of shock devolatilization of siderite as well.

Bell, Mary Sue↗
NASA NTRS2008

Structural, Physical, and Compositional Analysis of Lunar Simulants and Regolith

Relative to the prior manned Apollo and unmanned robotic missions, planned Lunar initiatives are comparatively complex and longer in duration. Individual crew rotations are envisioned to span several months, and various surface systems must function in the Lunar environment for periods of years. As a consequence, an increased understanding of the surface environment is required to engineer and test the associated materials, components, and systems necessary to sustain human habitation and surface operations. The effort described here concerns the analysis of existing simulant materials, with application to Lunar return samples. The interplay between these analyses fulfills the objective of ascertaining the critical properties of regolith itself, and the parallel objective of developing suitable stimulant materials for a variety of engineering applications. Presented here are measurements of the basic physical attributes, i.e. particle size distributions and general shape factors. Also discussed are structural and chemical properties, as determined through a variety of techniques, such as optical microscopy, SEM and TEM microscopy, Mossbauer Spectroscopy, X-ray diffraction, Raman microspectroscopy, inductively coupled argon plasma emission spectroscopy and energy dispersive X-ray fluorescence mapping. A comparative description of currently available stimulant materials is discussed, with implications for more detailed analyses, as well as the requirements for continued refinement of methods for simulant production.

Greenberg, Paul↗
NASA NTRS2017

Examination of Multiple Lithologies Within the Primitive Ordinary Chondrite NWA 5717

Northwest Africa 5717 is a primitive (subtype 3.05) ungrouped ordinary chondrite which contains two apparently distinct lithologies. In large cut meteorite slabs, the darker of these, lithology A, looks to host the second, much lighter in color, lithology B (upper left, Fig. 1). The nature of the boundary between the two is uncertain, ranging from abrupt to gradational and not always following particle boundaries. The distinction between the lithologies, beyond the obvious color differences, has been supported by a discrepancy in oxygen isotopes and an incongruity in the magnesium contents of chondrule olivine. Here, quantitative textural analysis and mineralogical methods have been used to investigate the two apparent lithologies within NWA 5717. Olivine grains contained in a thin section from NWA 7402, thought to be paired to 5717, were also measured to re-examine the distinct compositional range among the light and dark areas. Procedure: Particles from a high-resolution mosaic image of a roughly 13x15cm slice of NWA 5717 were traced in Adobe Photoshop. Due to the large size of the sample, visually representative regions of each lithology were chosen to be analyzed. The resulting layers of digitized particles were imported into ImageJ, which was used to measure their area, along with the axes, the angle from horizontal, and the centroid coordinates of ellipses fitted to each particle following the approach. Resulting 2D pixel areas were converted to spherical diameters employing the unfolding algorithm, which outputs a 3D particle size distribution based on digitized 2D size frequency data. Spatstat was used to create kernel density plots of the centroid coordinates for each region. X-ray compositional maps, microprobe analyses, and Mossbauer spectroscopy was conducted on a thin section of NWA 7402, tentatively paired to NWA 5717.

Cato, M. J.↗
NASA NTRS2017

Smectite Formation in the Presence of Sulfuric Acid: Implications for Acidic Smectite Formation on Early Mars

The excess of orbital detection of smectite deposits compared to carbonate deposits on the martian surface presents an enigma because smectite and carbonate formations are both favored alteration products of basalt under neutral to alkaline conditions. We propose that Mars experienced acidic events caused by sulfuric acid (H2SO4) that permitted phyllosilicate, but inhibited carbonate, formation. To experimentally verify this hypothesis, we report the first synthesis of smectite from Mars-analogue glass-rich basalt simulant (66 wt% glass, 32 wt% olivine, 2 wt% chromite) in the presence of H2SO4 under hydrothermal conditions (approximately 200 degC). Smectites were analyzed by X-ray diffraction, Mossbauer spectroscopy, visible and near-infrared reflectance spectroscopy and electron microprobe to characterize mineralogy and chemical composition. Solution chemistry was determined by Inductively Coupled Plasma Mass Spectrometry. Basalt simulant suspensions in 11-42 mM H2SO4 were acidic with pH less than or equal to 2 at the beginning of incubation and varied from acidic (pH 1.8) to mildly alkaline (pH 8.4) at the end of incubation. Alteration of glass phase during reaction of the basalt simulant with H2SO4 led to formation of the dioctahedral smectite at final pH approximately 3 and trioctahedral smectite saponite at final pH approximately 4 and higher. Anhydrite and hematite formed in the final pH range from 1.8 to 8.4 while natroalunite was detected at pH 1.8. Hematite was precipitated as a result of oxidative dissolution of olivine present in Adirondack basalt simulant. Formation of secondary phases, including smectite, resulted in release of variable amounts of Si, Mg, Na and Ca while solubilization of Al and Fe was low. Comparison of mineralogical and solution chemistry data indicated that the type of smectite (i.e., dioctahedral vs trioctahedral) was likely controlled by Mg leaching from altering basalt and substantial Mg loss created favorable conditions for formation of dioctahedral smectite. We present a model for global-scale smectite formation on Mars via acid-sulfate conditions created by the volcanic outgassing of SO2 in the Noachian and early Hesperian.

Smectite↗
NASA NTRS1972

Mg/2+/-Fe/2+/ order-disorder in cummingtonite, /Mg, Fe/7Si8O22/OH/2 - A new geothermometer.

Determination of the temperature dependence of the Mg(2+)-Fe(2+) distribution between the M4 site and the M1, M2 and M3 sites in magnesium-rich cummingtonites by Fe-57 Mossbauer resonance spectroscopy. For the basic reversible ion-exchange reaction involved, the Gibbs free energy is estimated to be 3.6 to 4.1 kcal/mole, assuming an ideal solution model at each set of sites. The crystallization temperatures of two cummingtonite-bearing metamorphosed ultrabasic rocks are estimated to be 265 and 290 deg C. The Mossbauer resonance spectra are found to be an effective basis for detecting changes in site occupancies as a function of temperature.

Ghose, S.↗
DOE OSTI2021

Real-Time Investigation of Sn(II) Oxidation in Pb-Free Halide Perovskites by X-ray Absorption and Mössbauer Spectroscopy

Sn(II) halide perovskites are a less toxic alternative to Pb-based materials in perovskite solar cells, but oxidation to Sn(IV) introduces additional degradation pathways. Improving stability requires mechanistic pictures of O 2 - and H 2 O-induced degradation and their synergy. In this work, we demonstrate that X-ray absorption spectroscopy reports the average valency of the bulk material, allowing oxidation kinetics to be measured from minutes to days. Optical and X-ray diffraction studies demonstrate the challenge of isolating oxidative degradation with techniques lacking element specificity and oxidation state sensitivity. Finally, 119Sn Mössbauer spectroscopy is presented as a lab-based technique capable of providing information on valency and speciation throughout oxidation.

14 SOLAR ENERGY↗
DOE OSTI2022

Thermodynamic insights into the intricate magnetic phase diagram of EuAl 4

The tetragonal intermetallic compound EuAl 4 hosts an exciting variety of low-temperature phases. In addition to a charge density wave below 140 K, four ordered magnetic phases are observed below 15.4 K. Recently, a skyrmion phase was proposed based on Hall effect measurements under a c-axis magnetic field. Here, we present a detailed investigation of the phase transitions in EuAl 4 under c-axis magnetic field. Our dilatometry, heat-capacity, DC magnetometry, AC magnetic susceptibility, and resonant ultrasound spectroscopy measurements reveal three magnetic phase transitions not previously reported. The first key result is a detailed H ∥ [001] magnetic phase diagram mapping the seven phases we observe. Second, we identify a high-field phase, phase VII, which directly corresponds to the region were skyrmions have been previously suggested. Our results provide guidance for future studies exploring the complex magnetic interactions and spin structures in EuAl 4 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Redox‐Mediated Electrochemical Regeneration of Spent LiFePO 4 Battery Cathodes

Direct recycling of lithium-ion battery cathodes offers considerable appeal over metallurgical approaches. Here, we demonstrate a mediated electrochemical method for direct regeneration of degraded LiFePO 4 (LFP). The approach uses a redox mediator, iron propylenediamine tetraacetate, that undergoes electrochemical reduction and is circulated through an external reservoir, where it supplies the electrons needed to regenerate LFP in the presence of Li + ions derived from LiOH oxidation. Rapid outer-sphere electron transfer is observed from the mediator to the degraded LFP material. This feature, together with good aqueous solubility of the mediator (0.3 M), supports current densities up to 100 mA/cm 2 , and this electrochemical recycling process is demonstrated on 100 g scale. 57 Fe Mössbauer spectroscopy is used to monitor the correction of structural defects in the degraded LFP, providing the basis for regeneration of LFP that matches the electrochemical performance of pristine LFP.

Electrochemical Relithiation↗
DOE OSTI2024

Complex magnetic ordering in EuAl 4 –A 151 Eu Mössbauer study

151 Eu Mössbauer spectroscopy has been used to investigate the behaviour of EuAl 4 through the four magnetic transitions that occur below 16 K. We find clear evidence for the first transition (T N1 , the onset of order) where an incommensurate modulated magnetic structure appears, and the third (T N3 ) where the modulation disappears at the tetragonal → orthorhombic structural transition. We see no changes at the lowest transition (T N4 ) but find that the modulation amplitude passes through a maximum at T N2 . Data on the isostructural but magnetically simpler EuGa 4 are also presented for comparison.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS2004

Basaltic rocks analyzed by the Spirit Rover in Gusev Crater

The Spirit landing site in Gusev Crater on Mars contains dark, fine-grained, vesicular rocks interpreted as lavas. Pancam and Mini-Thermal Emission Spectrometer (Mini-TES) spectra suggest that all of these rocks are similar but have variable coatings and dust mantles. Magnified images of brushed and abraded rock surfaces show alteration rinds and veins. Rock interiors contain </=25% megacrysts. Chemical analyses of rocks by the Alpha Particle X-ray Spectrometer are consistent with picritic basalts, containing normative olivine, pyroxenes, plagioclase, and accessory FeTi oxides. Mossbauer, Pancam, and Mini-TES spectra confirm the presence of olivine, magnetite, and probably pyroxene. These basalts extend the known range of rock compositions composing the martian crust.

Minerals↗
DOE OSTI2023

Observation of a critical charge mode in a strange metal

Understanding the strange metallic behavior that develops at the brink of localization in quantum materials requires probing the underlying electronic charge dynamics. Using synchrotron radiation–based Mössbauer spectroscopy, we studied the charge fluctuations of the strange metal phase of β-YbAlB 4 as a function of temperature and pressure. We found that the usual single absorption peak in the Fermi-liquid regime splits into two peaks upon entering the critical regime. Here, we interpret this spectrum as a single nuclear transition, modulated by nearby electronic valence fluctuations whose long time scales are further enhanced by the formation of charged polarons. These critical charge fluctuations may prove to be a distinct signature of strange metals.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Noncollinear polar magnet Fe 2 (SeO 3 ) 3 (H 2 O) 3 with inequivalent Fe 3+ sites

The emergence of novel magnetic states becomes more likely when the inversion symmetry of the crystal field, relative to the center between two spins, is broken. We propose that placing magnetic spins in inequivalent sites in a polar lattice can promote a realization of nontrivial magnetic states and associated magnetic properties. To test our hypothesis, we study Fe 2 (SeO 3 )(H 2 O) 3 as a model system that displays two distinct Fe(1) and Fe(2) magnetic sites in a polar structure (R3c space group). At low fields μ 0 H≤ 0.06 T, the material undergoes an antiferromagnetic ordering with T N1 = 77 K and a second transition at T N2 ≈ 4 K. At μ 0 H≥ 0.06 T and 74 K ≤T≤ 76 K, a positive entropy change of ∼0.12 mJ mol −1 K −1 can be associated with a metamagnetic transition to possibly nontrivial spin states. At zero field, Fe(1) is nearly fully ordered at T≈ 25 K, while Fe(2) features magnetic frustration down to T = 4 K. The magnetic ground state, a result corroborated by single-crystal neutron diffraction and 57 Fe Mössbauer spectroscopy, is a noncollinear antiparallel arrangement of ferrimagnetic Fe(1)–Fe(2) dimers along the c-axis. The results demonstrate that placing distinct magnetic sites in a polar crystal lattice can enable a new pathway to modifying spin, orbital, and lattice degrees of freedom for unconventional magnetism.

Crystal lattices↗
DOE OSTI2020

Redox effects on the structure and properties of Na-Mo-Fe-phosphate glasses

Na-Mo-Fe-phosphate glasses were prepared with reducing and oxidizing raw materials and the effects of the different Fe 2+ /Fe 3+ and Mo 5+ /Mo 6+ ratios on glass structure and properties were determined. Mssbauer spectroscopy confirms significantly greater concentrations of Fe 2+ ions in the reduced glasses and distorted Fe 3+ O 4 sites preferred over the Fe 3+ O 6 sites in the oxidized glasses. Raman spectroscopy reveals the presence of isolated Mo 6+ O 6 sites in the oxidized glasses, and highly distorted Mo 5+ O 5 sites in reduced Mo-rich glasses. The presence of specific Fe- and Mo-polyhedra is correlated with the average phosphate anion length, as characterized by high-pressure liquid chromatography. Generally, for the similar compositions, oxidized glasses have greater molar volumes than the reduced glasses, associated with the formation of isolated Mo 6+ O 6 octahedra and the absence of highly crosslinked Mo 5+ OPO 4 units. Tg increases with increasing Fe 3+ fractions in the Fe-rich glasses, whereas for the Mo-rich glasses, T g increases with greater Mo 5+ fractions.

36 MATERIALS SCIENCE↗
NASA NTRS2004

Mineralogy at Gusev Crater from the Mossbauer spectrometer on the Spirit Rover

Mossbauer spectra measured on Mars by the Spirit rover during the primary mission are characterized by two ferrous iron doublets (olivine and probably pyroxene) and a ferric iron doublet (tentatively associated to nanophase ferric iron oxide). Two sextets resulting from nonstoichiometric magnetite are also present, except for a coating on the rock Mazatzal, where a hematite-like sextet is present. Greater proportions of ferric-bearing phases are associated with undisturbed soils and rock surfaces as compared to fresh rock surfaces exposed by grinding. The ubiquitous presence of olivine in soil suggests that physical rather than chemical weathering processes currently dominate at Gusev crater.

Minerals↗
DOE OSTI2023

Valence and magnetism in EuPd 3 S 4 and (Y, La) x Eu 1-x Pd 3 S 4

151 Eu Mössbauer spectroscopy shows that yttrium substitution in mixed-valent EuPd 3 S 4 drives the initial 50:50 mix of Eu 3+ and E 2+ towards pure Eu 2+ , whereas lanthanum substitution has the opposite effect, but only for substitution levels above 50%. Here, we find that total valence electron count and chemical pressure effects cannot account for the observed behavior; however, conserving the cell volume provides a consistent description of the changes in the Eu 2+ :Eu 3+ ratio. Remarkably, lanthanum substitution also leads to a clear transition from static mixed-valent behavior at lower temperatures to dynamic mixed-valent behavior at higher temperatures, with the onset temperature monotonically increasing with Eu content and extrapolating to a value of ~ 340 K for the pure EuPd 3 S 4 compound. Magnetic order persists at least as far as x=0.875 in both series, despite the drastic reduction in the amount of moment-carrying Eu 2+ ions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

57Fe Mössbauer isomer shift of pure iron and iron oxides at high pressure—An experimental and theoretical study

The 57Fe isomer shift (IS) of pure iron has been measured up to 100 GPa using synchrotron Mössbauer spectroscopy in the time domain. Apart from the expected discontinuity due to the α→ε structural and spin transitions, the IS decreases monotonically with increasing pressure. The absolute shifts were reproduced without semi-empirical calibrations by periodic density functional calculations employing extensive localized basis sets with several common density functionals. However, the best numerical agreement is obtained with the B1WC hybrid functional. Extension of the calculations to 350 GPa, a pressure corresponding to the Earth’s inner core, predicted the IS range of 0.00 to -0.85 mm/s, covering the span from Fe(0) to Fe(VI) compounds measured at ambient pressure. The calculations also reproduced the pressure trend from polymorphs of prototypical iron oxide minerals, FeO and Fe2O3. Analysis of the electronic structure shows a strong donation of electrons from oxygen to iron at high pressure. The assignment of formal oxidation to the Fe atom becomes ambiguous under this condition.

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

Accelerating Nature: Induced Atomic Order in Equiatomic FeNi

Abstract The production of locally atomically ordered FeNi (known by its meteoric mineral name, tetrataenite) is confirmed in bulk samples by simultaneous conversion X‐ray and backscattered γ‐ray 57 Fe Mössbauer spectroscopy. Up to 22 volume percent of the tetragonal tetrataenite phase is quantified in samples thermally treated under simultaneous magnetic‐ and stress‐field conditions for a period of 6 weeks, with the remainder identified as the cubic FeNi alloy. In contrast, all precursor samples consist only of the cubic FeNi alloy. Data from the processed alloys are validated using Mössbauer parameters derived from natural meteoritic tetrataenite. The meteoritic tetrataenite exhibits a substantially higher degree of atomic order than do the processed samples, consistent with their low uniaxial magnetocrystalline anisotropy energy of ≈1 kJ·m −3 . These results suggest that targeted refinements to the processing conditions of FeNi will foster greater atomic order and increased magnetocrystalline anisotropy, leading to an enhanced magnetic energy product. These outcomes also suggest that deductions concerning paleomagnetic conditions of the solar system, as derived from meteoritic data, may warrant re‐examination and re‐evaluation. Additionally, this work strengthens the argument that tetrataenite may indeed become a member of the advanced permanent magnet portfolio, helping to meet rapidly escalating green energy imperatives.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Exploring the Light-induced Dynamics in Solvated Metallogrid Complexes with Femtosecond Pulses Across the Electromagnetic Spectrum

Oligonuclear complexes of d 4 -d 7 transition metal ion centers that undergo spin-switching have long been developed for their practical role in molecular electronics. Recently, they also have appeared as promising photochemical reactants demonstrating improved stability. However, the lack of knowledge about their photophysical properties in the solution phase compared to their mononuclear congeners is currently hampering their inclusion into advanced light-driven reactions. In the present study, the ultrafast photoinduced dynamics in a solvated [2x2] iron(II) metallogrid complex are characterized by combining transient optical, infrared absorption and X-ray emission spectroscopic measurements on the femtosecond timescale. The analysis is supported by DFT calculations. The photocycle can be described in terms of intra-site transitions, where the Fe II in the low-spin (LS) state are independently photoexcited. The Franck-Condon state decays via the formation of a vibrationally-hot high-spin (HS) state that displays coherent behavior within a few picoseconds and thermalizes within tens of picosecond to yield a metastable HS state living for several hundreds of nanoseconds. Additionally, systematic comparison with the closely related mononuclear complex [Fe(terpy) 2 ] 2+ reveals that nuclearity has a profound impact on the photoinduced dynamics. Finally, this work provides guidelines for expanding the integration of oligonuclear complexes into new photoconversion schemes that may be triggered by ultrafast spin-switching.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗