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At least 127 records · Page 7

Barred olivine 'chondrules' in lunar spinel troctolite 62295

Several objects have been found in sections of lunar igneous spinel troctolite 62295 that resemble certain meteoritic barred olivine chondrules. Each consists of an apparently spherical single crystal of Fo90 olivine, approximately 0.6-0.8 mm in diameter, containing a set of approximately 30-40 subparallel stringers of An95 plagioclase, whereas the stringers in ordinary meteoritic chondrules consist of glass. The olivine of the 62295 chondrules is also more magnesian, and is radially zoned, having a relatively iron-rich core and rim and an iron-poor intermediate zone. Several possible origins are proposed: impact-generated melt globules solidified in flight, spherical phenocrysts, and meteoritic chondrules, but none of these seems adequate to explain the detailed observations.

Roedder, E.↗

The cordierite- to spinel-cataclasite transition - Structure of the lunar crust

A two-layer lunar crust model is proposed in light of geochemical relationships between spinel cataclasites and anorthosites, discussing the relative abundances of these rocks. The uppermost stratigraphic unit of this model consists of members of the anorthositic series, and is estimated to be 12-20 km thick. The lower, Mg-rich unit consists of rocks with cotectic mineralogical proportions, and may constitute the greatest volume of the crust.

Herzberg, C. T.↗

Slow crack growth in spinel in water

Magnesium aluminate spinel was tested in a water environment at room temperature to establish its slow crack-growth behavior. Ring specimens with artificial flaws on the outside surface were loaded hydraulically on the inside surface. The time to failure was measured. Various precracking techniques were evaluated and multiple precracks were used to minimize the scatter in the static fatigue tests. Statistical analysis techniques were developed to determine the strength and crack velocities for a single flaw. Slow crack-growth rupture was observed at stress intensities as low as 70 percent of K sub c. A strengthening effect was observed in specimens that had survived long-time static fatigue tests.

Schwantes, S.↗

Oxygen electrode bifunctional electrocatalyst NiCo2O4 spinel

A significant increase in energy density may be possible if a two-unit alkaline regenerative H2-O2 fuel cell is replaced with a single-unit system that uses passive means for H2O transfer and thermal control. For this single-unit system, new electrocatalysts for the O2 electrode will be required which are not only bifunctionally active but also chemically and electrochemically stable between the voltage range of about 0.7 and 1.5 V. NiCo2O4 spinel is reported to have certain characteristics that make it useful for a study of electrode fabrication techniques. High surface area NiCo2O4 powder was fabricated into unsupported, bifunctional, PTFE-bonded, porous gas fuel cell electrodes by commercial sources using varying PTFE contents and sintering temperatures. The object of this study is to measure the bifunctional activities of these electrodes and to observe what performance differences might result from different commercial electrode fabricators. O2 evolution and O2 reduction data were obtained at 80 C (31 percent KOH). An irreversible reaction (i.e., aging) occurred during O2 evolution at potentials greater than about 1.5 V. Anodic Tafel slopes of 0.06 and 0.12 V/decade were obtained for the aged electrodes. Within the range of 15 to 25 percent, the PTFE content was not a critical parameter for optimizing the electrode for O2 evolution activity. Sintering temperatures between 300 and 340 C may be adequate but heating at 275 C may not be sufficient to properly sinter the PTFE-NiCo2O4 mixture. Electrode disintegration was observed during O2 reduction. Transport of O2 to the NiCo2O4 surface became prohibitive at greater than about -0.02 A/sq cm. Cathodic Tafel slopes of -0.6 and -0.12 V/decade were assumed for the O2 reduction process. A PTFE content of 25 percent (or greater) appears to be preferable for sintering the PTFE-NiCo2O4 mixture.

Fielder, William L.↗

Solubility and partitioning of Ar in anorthite, diopside, forsterite, spinel, and synthetic basaltic liquids

The solubility and partitioning of Ar in natural anorthite, diopside, forsterite, spinel, and synthetic iron-free basaltic melts was investigated using a new technique that obviates the postquenching phase separation. It was found that the solubility of Ar in the minerals was surprisingly high. Moreover, the solubility of Ar in different samples of a particular mineral run in the same experiment varied more than the solubility in the same sample run in different experiments, suggesting that noble gases are held in lattice vacancy defects. Moreover, the results of TEM imaging revealed no anomalous microstructures, while EXAFS studies of some samples showed that Kr has no preferred site in the lattices, supporting the defect siting conclusion.

Broadhurst, C. Leigh↗

An in situ X ray diffraction study of the kinetics of the Ni2SiO4 olivine-spinel transformation

The kinetics of the olivine-spinel transformation in Ni2SiO4 were investigated in an in situ X-ray diffraction experiments in which synchrotron radiation was used as an X-ray source. The starting material was Ni2SO4 olivine which was hot-pressed in situ at 980 C and 2.5 GPa; during the transformation, X-ray diffraction patterns were collected at intervals of 30 or 120 sec. The kinetic data were analyzed using Cahn's (1956) model. The activation energy for growth at 3.6-3.7 GPa was estimated as 438 + or - 199 kJ/mol. It is shown that, in order to make significant extrapolations of the kinetic data to a geological scale, the dependence of the rates of both nucleation and growth on temperature and pressure must be evaluated separately.

Rubie, D. C.↗

Experimentally Produced Spinel Rims on Ca-Al-Rich Inclusion Bulk Compositions

Most Ca-Al-rich inclusions (CAls) from Allende are surrounded by a series of mineralogically distinct rim layers. Proposed modes of formation for these layers include flash heating, evaporation, and condensation. The innermost of these rim layers is generally spinel (SP), in some cases intergrown with perovskite (PV), and commonly containing varying amounts of secondary iron increasing towards the edge of the CAI. The SP or SP+PV rim is not always contiguous with the other rim layers, indicating that it is probably the result of a separate event. We have produced continuous SP rims on synthetic analogs representing Type A/B1, average Type B, and Type B2 bulk compositions by reheating a solid glass experimental charge to subliquidus crystallization temperatures. This experimental result is consistent with the formation of chondrules; and CAIs by more than one sequence of heating and cooling. Previous work indicated that prior crystallization events produced observable effects in the texture and chemistry of the final run product. Information on the nature of the heating/cooling cycles experienced by CAls and chondrules is important in modeling the environment of their formation. Additional information is contained in the original extended abstract.

Paque, Julie M.↗

Performance and Safety Evaluations of Moli Spinel Lithium-Ion Cells

The current spike obtained during the hard external short test is small (8.2 A) compared to those obtained from a LiCoO2 system (60 to 80 A). The simulated internal short did not result in an explosion or fire as it does with the LiCoO2 systems. The temperatures obtained during the heat-to-vent test are not very high compared to the cobaltate cells. The cells do not retain capacity very well, but the capacity can be recovered with cycling. The spinel cells are much safer under abuse conditions than the lithium-ion cells with other transition metal oxides.

Jevarajan, Judith↗

Using Vanadium in Spinel as a Sensor of Oxygen Fugacity in Meteorites: Applications to Mars, Vesta, and Other Asteroids

Igneous and metamorphic rocks commonly contain a mineral assemblage that allows oxygen fugacity to be calculated or constrained such as FeTi oxides, olivine-opx-spinel, or some other oxybarometer [1]. Some rocks, however, contain a limited mineral assemblage and do not provide constraints on fO2 using mineral equilibria. Good examples of the latter are orthopyroxenites or dunites, such as diogenites, ALH 84001, chassignites, or brachinites. In fact it is no surprise that the fO2 of many of these samples is not well known, other than being "reduced" and below the metal saturation value. In order to bridge this gap in our understanding, we have initiated a study of V in chromites in natural meteorite samples. Because the V pre-edge peak intensity and energy in chromites varies with fO2 (Fig. 1) [2], and this has been calibrated over a large fO 2 range, we can apply this relation to rocks for which we otherwise have no fO2 constraints.

Righter, K.↗

Identification of a New Spinel-Rich Lunar Rock Type by the Moon Mineralogy Mapper (M (sup 3))

The canonical characterization of the lunar crust is based principally on available Apollo, Luna, and meteorite samples. The crust is described as an anorthosite-rich cumulate produced by the lunar magma ocean that has been infused with a mix of Mgsuite components. These have been mixed and redistributed during the late heavy bombardment and basin forming events. We report a new rock-type detected on the farside of the Moon by the Moon Mineralogy Mapper (M3) on Chandrayaan-1 that does not easily fit with current crustal evolution models. The rock-type is dominated by Mg-spinel with no detectible pyroxene or olivine present (<5%). It occurs along the western inner ring of Moscoviense Basin as one of several discrete areas that exhibit unusual compositions relative to their surroundings but without morphological evidence for separate processes leading to exposure.

Pieters, C. M.↗

Constraining the Composition of the Subcontinental Lithospheric Mantle Beneath the East African Rift: FTIR Analysis of Water in Spinel Peridotite Mantle Xenoliths

The East African Rift System was initiated by the impingement of the Afar mantle plume on the base of the non-cratonic continental lithosphere (assembled during the Pan-African Orogeny), producing over 300,000 kmof continental flood basalts approx.30 Ma ago. The contribution of the subcontinental lithospheric mantle (SCLM) to this voluminous period of volcanism is implied based on basaltic geochemical and isotopic data. However, the role of percolating melts on the SCLM composition is less clear. Metasomatism is capable of hybridizing or overprinting the geochemical signature of the SCLM. In addition, models suggest that adding fluids to lithospheric mantle affects its stability. We investigated the nature of the SCLM using Fourier transform infrared spectrometry (FTIR) to measure water content in mantle xenoliths entrained in young (1 Ma) basaltic lavas from the Ethiopian volcanic province. The mantle xenoliths consist dominantly of spinel lherzolites and are composed of nominally anhydrous minerals, which can contain trace water as H in mineral defects. Eleven mantle xenoliths come from the Injibara-Gojam region and two from the Mega-Sidamo region. Water abundances of olivines in six samples are 1-5ppm H2O while the rest are below the limit of detection (<0.5 ppm H2O); orthopyroxene and clinopyroxene contain 80-238 and 111-340 ppm wt H2O, respectively. Two xenoliths have higher water contents - a websterite (470 ppm) and dunite (229 ppm), consistent with involvement of ascending melts. The low water content of the upper SCLM beneath Ethiopia is as dry as the oceanic mantle except for small domains represented by percolating melts. Consequently, rifting of the East African lithosphere may not have been facilitated by a hydrated upper mantle.

Erickson, Stephanie Gwen↗

V Xanes in Spinels as an Oxy-Barometer in Meteorites with Implications for Redox Variations in the Inner Solar System

The variation of oxygen fugacity within inner solar system materials spans a range of nearly 15 orders of magnitude. Igneous and metamorphic rocks commonly contain a mineral assemblage that allows oxygen fugacity to be calculated or con-strained such as FeTi oxides, olivine-opx-spinel, or some other oxy-barometer. Some rocks, however, contain a limited mineral assemblage and do not provide constraints on fO2 using mineral equilibria. Good examples of the latter are orthopyroxenites or dunites, such as diogenites, ALH 84001, chassignites, or brachinites. In fact it is no surprise that the fO2 of many of these achondrites is not well known, other than being "reduced" and below the metal saturation value. In order to bridge this gap in our understanding, we have initiated a study of V in chromites in achondrite. Because the V pre-edge peak intensity and energy in chromites varies with fO2, and this has been calibrated over a large fO2 range, we can apply this relation to rocks for which we otherwise have no fO2 constraints.

Righter, K.↗

Spinel-Bearing, Al-Rich Chrondrules in the Unequilibrated Ordinary Chondrite NWA7402

Several Al-rich chondrules (ARCs) have been discovered in the unequilibrated ordinary chondrite NWA7402. Two of these three ARCs are spinel-bearing. Here we have characterized these unusual chondrules with respect to their mineralogy and bulk compositions. These objects will be targets for future O and Mg isotope analysis. NWA7402 is clearly unequilibrated, with wide ranges of olivine compositions in chondrules (Fo99-Fo70, excluding rims). Chromium-oxide contents in olivine, and Raman organic spectral parameters support the classification of this meteorite as petrologic type 3.1 [1]. NWA7402 is similar to, and could be paired with NWA5717, in that they both possess light and dark lithologies.

Ross, D. K.↗

Multiple Nebular Gas Reservoirs Recorded by Oxygen Isotope Variation in a Spinel-rich CAI in CO3 MIL 090019

We conducted NanoSIMS O-isotopic imaging of a primitive spinel-rich CAI spherule (27-2) from the MIL 090019 CO3 chondrite. Inclusions such as 27-2 are proposed to record inner nebula processes during an epoch of rapid solar nebula evolution. Mineralogical and textural analyses suggest that this CAI formed by high temperature reactions, partial melting, and condensation. This CAI exhibits radial O-isotopic heterogeneity among multiple occurrences of the same mineral, reflecting interactions with distinct nebular O-isotopic reservoirs.

Simon, J. I.↗

Electrochemical reactivity and passivation of organic electrolytes at spinel MgCrMnO 4 cathode interfaces for rechargeable high voltage magnesium-ion batteries

Magnesium transition metal oxides such as MgCr 2−x Mn x O 4 are promising high-voltage and high-capacity cathode materials for rechargeable magnesium batteries (RMBs). Understanding and improving the chemical and electrochemical stability of the cathode–electrolyte interface (CEI) has been the primary technical emphasis to enable this category of cathode materials, which has been significantly underexplored. Herein, in this study, we focus on investigating the fundamental mechanism of parasitic reactions at the charged surface of the high-voltage MgCrMnO 4 model cathode with different organic electrolytes. The aim is to reveal the underlying effect of anions and solvents responsible for the passivation behavior of the cathode by using three exemplary anions: [(CF 3 SO 2 ) 2 N] − (TFSI − ), Al[OC(CF 3 ) 3 ] 4 − (TPFA − ), and [CB 11 H 12 ] − (MC) and three solvents: diglyme (G2), triglyme (G3), and 3-methoxypropylamine (MPA). High precision leakage current measurements during potentiostatic hold reveal that the electrolyte solvent chemistry has a more profound impact than anion's on the passivation of the MgCrMnO 4 cathode surface during deintercalation of Mg 2+ . X-ray photoelectron spectroscopy exhibits the differences in CEI composition. Amine solvents like MPA show poor passivation due to a higher degree of solvent decomposition, while the thin and anion-derived CEI in glyme-based electrolytes is directly linked with the better passivation behavior on the cathode. Furthermore, we leverage the knowledge from these findings to modify the electrolyte structure by adding a solvent additive, with the goal of reducing the parasitic reaction.

25 ENERGY STORAGE↗

Magnetism of single crystalline breathing pyrochlore spinel AgInCr 4 ⁢S 8

Single crystals of Ag⁢In⁢Cr 4⁢ S 8 are grown by chemical vapor transport and crystallographic ordering of Ag/In that results in a breathing pyrochlore motif of Cr 3+ is verified by x-ray and neutron diffraction. Long-range antiferromagnetic order is observed below a Néel temperature of 𝑇 N ≈ 9.6 K. The magnetic properties are characterized using ac and dc magnetization, specific heat capacity, and single crystal neutron diffraction measurements. The specific heat data are characterized by a small lambda anomaly near 9.5 K and the estimated magnetic entropy reaches ≈ $\frac{1}{3}$ of the expected value by 3⁢𝑇 N , suggesting significant short-range order in the paramagnetic phase. Single crystal neutron diffraction evidences an incommensurate spin structure with propagation vector 𝒌 = (0,0,𝛿) and 𝛿 = 0.343 at 5 K. The minimal model that accounts for the data consists of ferromagnetic layers of Cr atoms, with magnetic moments lying in the plane of the layers and modulating in the perpendicular direction to form a helical structure propagating along 𝒌. Furthermore, this study represents a rare investigation of single crystals within the family of breathing pyrochlore materials.

Frustrated magnetism↗

Mechanism of Lithium Ion Exchange Into Spinel Manganese Oxide

Lithium manganese oxide (LMO) is an effective absorbent for lithium recovery from brines, characterized by its high adsorption capacity, excellent regeneration performance, and selectivity. Here, this study investigates the mechanisms of material degradation during lithium loading and unloading in LMO, employing a combination of time‐resolved Raman spectroscopy, X‐ray diffraction, and X‐ray photoelectron spectroscopy. Key findings reveal that the A 1g vibrational mode wavenumber shifts from 635 cm −1 at the onset of lithium ion exchange to 656 cm −1 after 12 min, indicating local symmetry loss and manganese (Mn) loss during lithium intercalation. The proposed lithium exchange mechanism involves initial occupation of tetrahedral interstitial voids, followed by migration into interstitial sites between Mn octahedral sites. Computational modeling suggests that the loss of symmetry in MnO cubane‐like groups occurs as lithium migrates, significantly affecting the Raman spectra. Importantly, the study demonstrates that after 100 cycles of lithium/hydrogen loading, a 24% loss in Mn is observed, which correlates with decreased structural stability; however, the structural integrity of LMO is enhanced when subjected to multiple cycles without complete loading. Here, these insights contribute to the understanding of LMO's performance in lithium recovery applications and highlight potential strategies to optimize its use in future technologies.

15 GEOTHERMAL ENERGY↗