SEARCH · Search NASA
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.
Electron probe data for spinels from Apollo 11, 12, and 14 are presented and analyzed. A modified Johnstone spinel prism showing the data distribution is given. Three projections of this prism are then presented which illustrate the variations of simple ratios that are present in the prism and permit three different perspectives of the data. The results are summarized as fO2 isobars on the spinel prism.
The paper describes the oriented intergrowth of spinel and pyroxene in a pigeonite from Luna 20, an augite from Apollo 16 anorthosite 67075, and an orthopyroxene from a spinel lherzolite nodule from the San Quintin volcanic field, Mexico. Using Mo K alpha radiation, photographs were taken of small, hand-picked single-crystals. A mechanism of exsolution is suggested in which the oxygen framework remains intact and spinel nuclei are formed by the migration of cations from interstitial sites and tetrahedral sites in the original non-stoichiometric pyroxene.
Phase relations in the liquidus temperature region of the system 'FeO'-Al2O3-TiO2 in contact with metallic iron, at a total pressure below 1 atm, have been determined by the quenching technique. Four invariant points have been located, with phase assemblages and temperatures as follows; wuestite, ulvoespinel, nercynite and liquid, 1306 C; ulvoespinel, ilmenite, ferropseudobrookite and liquid, 1340 C; ulvoespinel, hercynite, ferropseudobrookite and liquid, 1367 C; hercynite, ferropseudobrookite, corundum and liquid, 1465 C. The data obtained confirm the presence of a miscibility gap between titanate and aluminate spinels, and provide quantitative data for the effect of Al2O3 on mutual stability relations among spinel, ilmenite, and ferropseudobrookite phases in the presence of liquid at high temperatures and strongly reducing conditions. It is shown that Al2O3 has a strong stabilizing effect on the phase assemblage ferropseudobrookite and spinel relative to ilmenite.
Amphibole and spinel occur in the Shergotty and Zagami meteorites only in magmatic inclusions in pigeonite. The trapped magma is essentially identical to the parental magmas for Shergotty and Zagami. The amphibole is a kaersutite with minimal halogen content; by inference, it must have been hydrous. If so, the Shergotty and Zagami melts contained at least 0.2 wt pct H2O and were probably H2O-undersaturated. Pressures in excess of 1 kilobar seem necessary for the formation of amphibole. Spinel replaces magnetite in the inclusions, and olivine replaces magnetite elsewhere in the meteorites. To stabilize spinel, the melt in the inclusions must have become enriched in Al during fractionation, possibly because the small volume of the inclusions made nucleation of plagioclase unlikely. Pervasive replacement of magnetite through reduction reactions suggests that Shergotty and Zagami interacted with hydrogen-rich fluids during their cooling.
The first detailed petrographic and mineralogical study of a Ca, Al-rich inclusion (CAI) from the Kaba CV3 chondrite is reported. This 'fine-grained' CAI contains abundant small, rounded, rimmed, spinel-rich objects which have important features in common with the spinel-rich objects in other carbonaceous and ordinary chondrites. These nodules are interpreted as fractionated distillation residues of primitive dust. However, the available data do not unambiguously rule out a condensation origin for at least some of these objects. Finally, the preservation of distinct diopside-hedenbergite rims on the spinel-rich bodies and the small grain size of many minerals in the CAI matrix material both suggest that the CAI accreted cool and had a relatively cool thermal history in the Kaba parent body.
The Cr distributions for a synthetic silicate melt equilibrated with bronzitic orthopyroxene and chromite spinel between 1334 and 1151 C over a range of oxygen fugacities between the nickel-nickel oxide and iron-wuestite buffers are studied. The occurrence, chemical composition, and structure of the orthopyroxene-silicate melt and the spinel-silicate melt are described. It is observed that the Cr content between bronzite and the melt increases with falling temperature along a given oxygen buffer and decreases with falling oxygen fugacity at a given temperature; however, the Cr content of the melt in equilibrium with spinel decreases with falling temperature and increases with lower oxygen fugacity.
A unique, spinel-rich, extremely porous fine-grained inclusion in the Kainsaz (CO3) meteorite is reported. This inclusion is the least altered fine-grained inclusion yet discovered, having escaped almost entirely the secondary alterations experienced by Allende fine-grained inclusions. The inclusion is comprised of loosely packed 5-30 microns spinel grains mantled by thin layers of melilite, anorthite, and diopsidic pyroxene. The inclusion, which has over 30 vol pct void space, is one of the most spinel-rich, most porous fine-grained inclusions seen to date. The mineralogy of the inclusion matches that which has been predicted for a precursor of the altered mineral assemblages of Allende fine-grained inclusions, though a lack of interstitial material in the Kainsaz inclusion reduces the likelihood of a direct genetic relationship between the two (Allende fine-grained inclusions contain abundant interstitial material). Its mineralogical composition confirms that the precursors of other, more altered, fine-grained inclusions were assemblages of refractory minerals exclusively.
Asteroids 387 Aquitania and 980 Anacostia are anomalous members of the S-class. Their reflectance spectra exhibit a strong broad absorption feature longwards of 1.5 micron and no significant feature near 1 micron. Their spectra indicate the presence of spinel, an aluminum-magnesium oxide mineral commonly present in inclusions in CV3 and CO3 meteorites. Spinel probably makes up only a small percentage of the surface assemblages of these asteroids, but its spectral effect may be enhanced by its presence in fine-grained white inclusions in immature asteroid regoliths. It is speculated that Aquitania and Anacostia represent material formed in the same nebular zone as the CV3 and CO3 chondrites but either: (A) at an earlier time in the nebula when such inclusions might have been a relatively larger fraction of the nebular grain population; or (B) in local regions where nebular processes (e.g., settling to the midplane) had concentrated such inclusions. The close similarity of two orbital elements (a, i) suggests that Aquitania and Anacostia may be members of a partially dispersed asteroid family produced by the early disruption of a spinel-bearing parent body.
Fine-grained spinel-rich CAI from Efremovka and Leoville lack the overprint of Na and Fe metasomatism seen in Allende. They contain spinel, pyroxene, anorthite, and melilite; most have a zoned structure with spinel-rich cores, melilite-rich mantles. Additional information is contained in the original extended abstract.
Grain size separate CG from the Murray CM2 carbonaceous chondrite contains mostly spinel grains of average diameter 0.5 m. Zinner et al. found that approximately 1% of these spinel grains are of presolar origin as determined by their large O isotopic anomalies. These O isotopic measurements were made with the NanoSIMS on individual grains that were well separated from one another on a gold foil. The grains were selected for analysis from secondary electron and secondary O-16(-) images. The primary beam was then successively deflected onto these single grains for O isotopic analysis. While single grain analysis on dispersed samples is effective for finding relatively abundant anomalous grains, ion imaging in a raster mode on tightly packed grains might be more efficient for locating few anomalous grains among predominantly isotopically normal grains. In fact, this was the analysis mode used by Messenger et al. to discover presolar silicates in interplanetary dust particles. In an exploratory effort that is also geared toward establishing the optimum isotopic imaging technique in the search for presolar silicate grains in primitive meteorites, we measured O isotopic ratios in spinel grains from the Murray CG separate by raster imaging of areas with more or less tightly packed grains.
We have considered the valence-state partitioning of Cr, Fe, Ti, and V over crystallographic sites in olivine, pyroxene, and spinel from planetary basalts. The sites that accommodate these cations are the M2 site (6-8 coordinated) and M1 site (6 coordinated) in pyroxene, the M2 site (6-8 coordinated) and M1 site (6 coordinated) in olivine, and the tetrahedral and octahedral sites in spinel. The samples we studied are basalts from Earth, Moon, and Mars, which have fO2 conditions that range from IW-2 (Moon) to IW+6 (Earth) with Mars somewhere between at IW to IW+2. In this range of fO2 the significant elemental valences are (from low to high fO2) Ti4+, V3+, Fe2+, Cr2+, Cr3+, V3+, V4+, and Fe3+. V2+ and Ti3+ play a minor role in the phases considered for the Moon, and are probably in very low concentrations. V5+ plays a minor role in these phases in terrestrial basalts because it is probably in lower abundance than V4+ and it has an ionic radii that is so small (0.054 nm, 6- coordinated,[1]) that it is almost at the lower limit for octahedral coordination. The role of Cr2+ in the Moon is significant, as Sutton et al. [2] found that lunar olivine contains mostly Cr2+ while coexisting pyroxene contains mostly Cr3+. Hanson one vacancy only accommodates one V4+. Thus more vacancies are required in V4+ substitutions into olivine. In the Moon V3+ is much more abundant than V4+ [7, 8]. Thus in lunar chromite V3+ follows Cr3+, whereas in Earth V4+ (which is much greater in abundance than V3+) follows Ti4+ (eg in ulv spinel). We could go on in this vein for some time but space limitations do not permit us to do so.
At low operating temperatures, commercially available electrode materials for lithium-ion batteries do not fully meet the energy and power requirements for NASA fs exploration activities. The composite cathode under development is projected to provide the required energy and power densities at low temperatures and its usage will considerably reduce the overall volume and weight of the battery pack. The newly developed composite electrode material can provide superior electrochemical performance relative to a commercially available lithium cobalt system. One advantage of using a composite cathode is its higher energy density, which can lead to smaller and lighter battery packs. In the current program, different series of layered-spinel composite materials with at least two different systems in an integrated structure were synthesized, and the volumetric and gravimetric energy densities were evaluated. In an integrated network of a composite electrode, the effect of the combined structures is to enhance the capacity and power capabilities of the material to levels greater than what is possible in current state-of-the-art cathode systems. The main objective of the current program is to implement a novel cathode material that meets NASA fs low temperature energy density requirements. An important feature of the composite cathode is that it has at least two components (e.g., layered and spinel) that are structurally integrated. The layered material by itself is electrochemically inactive; however, upon structural integration with a spinel material, the layered material can be electrochemically activated, thereby delivering a large amount of energy with stable cycling. A key aspect of the innovation has been the development of a scalable process to produce submicronand micron-scale particles of these composite materials. An additional advantage of using such a composite electrode material is its low irreversible loss (.5%), which is primarily due to the unique activation of the composite. High columbic efficiency (greater than 99%) upon cycling may indicate the formation of a stable SEI (solid-electrolyte interface) layer, which can contribute to long cycle life. The innovation in the current program, when further developed, will enable the system to maintain high energy and power densities at low temperatures, improve efficiency, and further stabilize and enhance the safety of the cell.
Hibonite is a primary ultra-refractory mineral occurring in many Ca-Al-rich inclusions (CAIs) and is predicted to condense as the second major phase from a cooling gas of solar composition. Our previous microstructural studies of hibonite in carbonaceous chondrites revealed its unique microstructures consisting of numerous defects that contain Mg-enriched, wider spinel blocks in stoichiometric hibonite. Han, J. et al. [2 items] demonstrated experimentally that defect-structured hibonites can grow easily in the presence of minor Mg and are kinetically more stable than equilibrium assemblages predicted by thermodynamic calculations. However, a thermo-dynamic vs. structural stability of defect-structured hibonite relative to other early-condensed Al-rich phases such as corundum, grossite, and spinel remains poorly constrained. Here, we present the results of atomic resolution TEM (Transmission Electron Microscopy) imaging of hibonite in a compact Type A CAI in the Allende CV3 chondrite in order to better understand the crystal structure and chemistry of defect-structured hibonite and its associated Al-rich phases, especially non-stoichiometric, Al-rich spinel, in the context of the formation of first refractory solids in the early solar nebula.
The lunar magnesian (Mg-) suite is a diverse lithological group composed of Mg-rich mafic minerals. The Mg-suite consists primarily of troctolites, norites, gabbronorites, and spinel troctolites. These rocks exhibit contradictory geochemical traits, with mafic minerals bearing high Mg# (molar 100×Mg/[Mg+Fe]) indicating primitive parental magmas, but also plagioclase saturation and enrichments in incompatible trace elements (i.e., KREEP) indicate more evolved parental magmas. A variety of models have been invoked to explain the occurrence and petrogenesis of the Mg-suite. Here, we report on a new spinel troctolite clast found in Apollo Next Generation Sample Analysis (ANGSA) program core 73002. Sample 73002 was acquired at Station 3 during Apollo 17 as the upper part of a double-drive tube with sample 73001. During processing, the spinel troctolite clast (0.066 g) was found at the 4.0–4.5 cm depth interval.
Mn-rich cathodes balance performance and sustainability but suffer from limited cyclability due to Mn dissolution and cathode-to-anode crosstalk. The Jahn-Teller (J-T) effect of Mn 3+ is often linked to the above phenomena, such as in spinel LiMn 2 O 4 . However, in typical voltage ranges, significant Mn 3+ only appears near the end of discharge, highlighting the need to reassess its role in driving Mn dissolution, structural degradation, and battery performance. Here, the spinel cathode's degree of disorder is tailored to expand the Mn redox range, enabling segmentation into J-T active and less active voltage ranges. Cycling at segmented voltage windows reveals surface degradation mechanisms with and without the major J-T effect. Despite a stronger J-T effect below 3.6 V vs. Li/Li + , Mn dissolution is less significant than above 3.6 V. Expanding the cycling window to 2.0–4.3 V causes severe degradation as the J-T active range induces a tetragonal phase and Mn 2+ -rich surface, driving Mn dissolution and consuming Li-ion inventory in full cells. Reducing electrolyte acidity minimizes Mn 3+ disproportionation, enabling a stable dopant-free Mn-only cathode with a 250 mAh g −1 specific capacity. These findings demonstrate that full cells using Mn-rich cathodes have the potential to avoid the notorious crosstalk problem through electrolyte engineering.
To address the high cost, cobalt dependency, and resource constraints typical of conventional high-entropy oxide (HEO) anodes, this study reports the successful synthesis of two Co-free, six-component spinel-type HEOs(FeNiCrMnZnAl) 3 O 4 (HEO-Al) and (FeNiCrMnZnMg) 3 O 4 (HEO-Mg), via a sol-gel method. The distinct effects of Al 3+ and Mg 2+ incorporation on the electrochemical performance and lithium storage kinetics were systematically investigated. XRD, Raman, and TEM characterizations confirm that both materials possess a pure spinel phase, uniform particle size, and homogeneous elemental distribution. Notably, electrochemical evaluations reveal that HEO-Al delivers a superior reversible capacity of 480.7 mAh g −1 after 100 cycles at 0.1 A g −1 , and maintains 354.5 mAh g −1 after 1000 long-term cycles at 1 A g −1 , significantly outperforming HEO-Mg. Kinetic analysis indicates that HEO-Al exhibits lower charge transfer resistance, a higher Li + diffusion coefficient, and a pseudocapacitive contribution of up to 82%. Furthermore, these findings demonstrate that Al substitution effectively optimizes the structural stability and lithium storage kinetics of Co-free HEOs, providing a viable strategy for designing low-cost, highly stable HEO anode systems.
In this study, spinel-structured (CrMnCoNiTi)₃O₄ high-entropy oxides (HEOs) have been successfully synthesized using the solution combustion method, and their performance as supercapacitor electrode materials was investigated. These HEOs exhibit excellent performance, stemming from the unique high-entropy effect and lattice distortion. This structure effectively buffers volumetric strain during cycling, conferring the material with extremely high structural stability and specific capacity. The material demonstrates a high specific capacity of 491.5 C∙g⁻¹ at a current density of 0.5 A∙g⁻¹. Furthermore, it shows extraordinary cycling stability: after 10,000 charge/discharge cycles at 5 A∙g⁻¹, the capacity retention rate is 99%, and the Coulombic efficiency consistently remains close to 100%. Ex-situ structural characterizations further reveal that this excellent cycling durability originates from a cooperative multination valence reconstruction mechanism within an entropy-stabilized spinel framework. Additionally, a symmetric supercapacitor assembled using this material and 1 M KOH electrolyte successfully extended the working voltage to 1.2 V. This research highlights the great potential of high-entropy oxides in synergizing high energy density and ultra-long cycling life, laying a solid foundation for the development of next-generation high-performance supercapacitor electrode materials.
Jahn–Teller polarons are quasiparticles that stem from symmetry breaking and strong local electron–phonon coupling. They originate from an excess charge carrier being dressed by a local lattice distortion, caused by the Jahn–Teller effect, and they critically impact electrical, structural, and magnetic properties in transition metal oxides. The observation of the microscopic steps involved in their formation is essential for enabling control over material properties through the targeted activation of local, site-specific modifications with light pulses. While Jahn–Teller distortion associated with polaron formation was predicted to contribute significantly to changes in electronic band gap and optical properties in Co 3 O 4 , its experimental observation remains elusive, requiring signatures of local symmetry reduction. In this work, we demonstrate Jahn–Teller polaron formation in spinel Co 3 O 4 . By exciting electronic transitions at 3.10 eV and 1.55 eV, we target either the Oh Cobalt(III) or the Td Cobalt(II) ions, and drive the subsequent coherent responses of the system through two different pathways. For the former, we demonstrate that ligand-to-metal charge transfer leads to Jahn–Teller polaron formation, which is linked to the deformation potential and magnetoelastic coupling. For the latter, we identify the coherent excitation of a T 2g phonon mode launched by on-site d-d electronic transitions. Key to our observations is the ability to target site-specific electronic excitations in spinel Co 3 O 4 using ultrafast optical pulses, while monitoring the ensuing low-energy collective modes through the coherent time-domain response of the material. Our approach, which combines the comparative analysis of experimental fingerprints with the support from density functional theory calculations, is broadly applicable to systems in which Jahn–Teller polaron physics has been theoretically predicted but remains experimentally unverified, and it underscores the potential of electronic-state targeting as a route to selectively excite and probe quasiparticle dynamics in solids.