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At least 19 records

A New Spinel-Olivine Oxybarometer: Near-Liquidus Partitioning of V between Olivine-Melt, Spinel-Melt, and Spinel-Olivine in Martian Basalt Composition Y980459 as a Function of Oxygen Fugacity

Our research on valence state partitioning began in 2005 with a review of Cr, Fe, Ti, and V partitioning among crystallographic sites in olivine, pyroxene, and spinel [1]. That paper was followed by several on QUE94201 melt composition and specifically on Cr, V, and Eu partitioning between pyroxene and melt [2-5]. This paper represents the continuation of our examination of the partitioning of multivalent V between olivine, spinel, and melt in martian olivine-phyric basalts of Y980459 composition [6, 7]. Here we introduce a new, potentially powerful oxybarometer, V partitioning between spinel and olivine, which can be used when no melt is preserved in the meteorite. The bulk composition of QUE94201 was ideal for our study of martian pyroxene-phyric basalts and specifically the partitioning between pyroxene-melt for Cr, V, and Eu. Likewise, bulk composition Y980459 is ideal for the study of martian olivine-phyric basalts and specifically for olivine-melt, spinel-melt, and spinel-olivine partitioning of V as a function of oxygen fugacity.

Papike, J. J.

How Rich is Rich? Placing Constraints on the Abundance of Spinel in the Pink Spinel Anorthosite Lithology on the Moon Through Space Weathering

previously unknown lunar rock was recently recognized in the Moon Mineralogy Mapper (M(sup 3)) visible to near-infrared (VNIR) reflectance spectra. The rock type is rich in Mg-Al spinel (approximately 30%) and plagioclase and contains less than 5% mafic silicate minerals (olivine and pyroxene). The identification of this pink spinel anorthosite (PSA) at the Moscoviense basin has sparked new interest in lunar spinel. Pieters et al. suggested that these PSA deposits might be an important component of the lunar crust. However, Mg-Al spinel is rare in the Apollo and meteorite sample collections (only up to a few wt%), and occurs mostly in troctolites and troctolitic cataclastites. In this study, we are conducting a series of experiments (petrologic and space weathering) to investigate whether deposits of spinel identified by remote sensing are in high concentration (e.g. 30%) or whether the concentrations of spinel in these deposits are more like lunar samples, which contain only a few wt%. To examine the possibility of an impact-melt origin for PSA, conducted 1-bar crystallization experiments on rock compositions similar to pink spinel troctolite 65785. The VNIR spectral reflectance analyses of the low-temperature experiments yield absorption features similar to those of the PSA lithology detected at Moscoviense Basin. The experimental run products at these temperatures contain approximately 5 wt% spinel, which suggests that the spinel-rich deposits detected by M(sup 3) might not be as spinel-rich as previously thought. However, the effect of space weathering on spinel is unknown and could significantly alter its spectral properties including potential weakening of its diagnostic 2-micrometers absorption feature. Thus, weathered lunar rocks could contain more spinel than a comparison with the unweathered experimental charges would suggest. In this study, we have initiated space weathering experiments on 1) pure pink spinel, 2) spinel-anorthite mixtures, and 3) the low temperature experimental run products from Gross et al. in order to evaluate the influence of space weathering on the absorption strength of spinel. The results can be used to place constraints on the spinel abundance in the PSA lithology and can be used as ground truth for further VNIR spectral analyzes of lunar lithologies.

Gross, J.

Micro-XANES Measurements on Experimental Spinels and the Oxidation State of Vanadium in Spinel-Melt Pairs

Spinel can be a significant host phase for V as well as other transition metals such as Ni and Co. However, vanadium has multiple oxidation states V(2+), V(3+), V(4+) or V(5+) at oxygen fugacities relevant to natural systems. We do know that D(V) spinel/melt is correlated with V and TiO2 content and fO2, but the uncertainty of the oxidation state under the range of natural conditions has made elusive a thorough understanding of D(V) spinel/melt. For example, V(3+) is likely to be stable in spinels, based on exchange with Al in experiments in the CaO-MgO-Al2O3-SiO2 system. On the other hand, it has been argued that V(4+) will be stable across the range of natural oxygen fugacities in nature. In order to gain a better understanding of D(V) spinel/melt we have equilibrated spinel-melt pairs at controlled oxygen fugacities, between HM to NNO, where V is present in the spinel at natural levels (approx. 300 ppm V). These spinel-melt pairs were analyzed using micro-XANES at the Advanced Photon Source at Argonne National Laboratory. The new results will be used together with spinel compositional data (Ti, V content) and oxygen fugacity, to unravel the effects of these variables on D(V) spinel/melt.

Righter, K.

Micro-XANES Measurements on Experimental Spinels and the Oxidation State of Vanadium in Coexisting Spinel and Silicate Melt

Spinel can be a significant host phase for V which has multiple oxidation states V(sup 2+), V(sup 3+), V(sup 4+) or V(sup 5+) at oxygen fugacities relevant to natural systems. The magnitude of D(V) spinel/melt is known to be a function of composition, temperature and fO2, but the uncertainty of the oxidation state under the range of natural conditions has made elusive a thorough understanding of D(V) spinel/melt. For example, V(sup 3+) is likely to be stable in spinels, based on exchange with Al in experiments in the CaO-MgO-Al2O3-SiO2 system. On the other hand, it has been argued that V(sup 4+) will be stable across the range of natural oxygen fugacities in nature. In order to build on our previous work in more oxidized systems, we have carried out experiments at relatively reducing conditions from the FMQ buffer to 2 log fO2 units below the IW buffer. These spinel-melt pairs, where V is present in the spinel at natural levels (approx. 300 ppm V), were analyzed using an electron microprobe at NASA-JSC and micro- XANES at the Advanced Photon Source at Argonne National Laboratory. The new results will be used together with previous results to understand the valence of V in spinel-melt systems across 12 orders of magnitude of oxygen fugacity, and with application to natural systems.

Righter, K.

Investigation of Synthetic Mg(1.3)V(1.7)O4 Spinel with MgO Inclusions: Case Study of a Spinel with an Apparently occupied Interstitial Site

A magnesium vanadate spinel crystal, ideally MgV2O4, synthesized at 1 bar, 1200 C and equilibrated under FMQ + 1.3 log f(sub o2) condition, was investigated using single-crystal X-ray diffraction, electron microprobe, and electron backscatter (EBSD). The initial X-ray structure refinements gave tetrahedral and octahedral site occupancies, along with the presence of 0.053 apfu Mg at an interstitial octahedral site . Back-scattered electron (BSE) images and electron microprobe analyses revealed the existence of an Mg-rich phase in the spinel matrix, which was too small (less than or equal to 3microns) for an accurate chemical determination. The EBSD analysis combined with X-ray energy dispersive spectroscop[y (XEDS) suggested that the Mg-rich inclusions are periclase oriented coherently with the spinel matrix. The final structure refinements were optimized by subtracting the X-ray intensity contributions (approx. 9%) of periclase reflections, which eliminated the interstitial Mg. This study provides insight into possible origins of refined interstitial cations reported in the the literature for spinel, and points to the difficulty of using only X-ray diffraction data to distinguish a spinel with interstitial cations from one with coherently oriented MgO inclusions.

Uchida, Hinako

Partitioning of Ni, Co and V between Spinel-Structured Oxides and Silicate Melts: Importance of Spinel Composition

Partitioning of Ni, Co and V between Cr-rich spinels and basaltic melt has been studied experimentally between 1150 and 1325 C, and at controlled oxygen fugacity from the Co-CoO buffer to slightly above the hematite magnetite buffer. These new results, together with new Ni, Co and V analyses of experimental run products from Leeman [Leeman, W.P., 1974. Experimental determination of the partitioning of divalent cations between olivine and basaltic liquid, Pt. II. PhD thesis, Univ. Oregon, 231 - 337.], show that experimentally determined spinel melt partition coefficients (D) are dependent upon temperature (T), oxygen fugacity (fO2) and spinel composition. In particular, partition coefficients determined on doped systems are higher than those in natural (undoped) systems, perhaps due to changing activity coefficients over the composition range defined by the experimental data. Using our new results and published runs (n =85), we obtain a multilinear regression equation that predicts experimental D(V) values as a function of T, fO2, concentration of V in melt and spinel composition. This equation allows prediction of D(V) spinel/melt values for natural mafic liquids at relevant crystallization conditions. Similarly, D(Ni) and D(Co) values can be inferred from our experiments at redox conditions approaching the QFM buffer, temperatures of 1150 to 1250 C and spinel composition (early Cr-bearing and later Ti-magnetite) appropriate for basic magma differentiation. When coupled with major element modelling of liquid lines of descent, these values (D(Ni) sp/melt=10 and D(Co) sp/melt=5) closely reproduce the compositional variation observed in komatiite, mid-ocean ridge basalt (MORB), ocean island basalt (OIB) and basalt to rhyolite suites.

Righter, K.

Topotactic Phase Transformation of Lithiated Spinel to Layered LiMn0.5Ni0.5O2: The Interaction of 3-D and 2-D Li-ion Diffusion

This study investigates the structural evolution of LiMn0.5Ni0.5O2 cathode materials for Li-ion batteries as a function of synthesis temperature and its effect on electrochemical performance. It is demonstrated that, as the synthesis temperature increases from 400 to 900 ?C, a gradual topotactic transformation occurs between a lithiated spinel structure, denoted herein as “lithium-excess spinel” LxS-LiMn0.5Ni0.5O2 (or LxS-LMNO), and the well-known layered LiMn0.5Ni0.5O2 structure prepared at high temperature, HT-LiMn0.5Ni0.5O2 (HT-LMNO). The electrochemical capacity of the LiMn0.5Ni0.5O2 electrodes follows a parabolic trend with increasing synthesis temperature, which is attributed primarily to the gradual transformation of 3-dimensional (3-D) to 2-dimensional (2-D) diffusion pathways for the Li ions. When synthesized at 400 °C, LxS-LiMn0.5Ni0.5O2 electrodes perform well, benefitting from the 3-D network of channels within the LxS structure. By contrast, when prepared at 500-700 °C, LiMn0.5Ni0.5O2 electrodes operate poorly, which is attributed to the formation of locally disordered structural arrangements that impede Li-ion diffusion. Such an increase in local disorder in the mid-temperature synthesis range is attributed to the structural frustration between the lithium-excess spinal and layered end-members. The transformation from the locally disordered to more ordered layered components between 700 °C and 900 °C enhances electrochemical performance. The study opens new avenues for designing next-generation Mn-rich cathode materials by fine-tuning the synthesis conditions as well as the composition and structure of LxS-LMNO electrodes.

energy storage

Pink Spinel in Apollo Impact Melt Rock 68815: Implications for Mg-Suite Magmatism

Introduction: Magnesian rocks from the lunar highlands are collectively termed the Mg-suite. Characterized by high (>60) Mg# (molar 100×Mg/[Mg+Fe]) in mafic phases and calcic plagioclase, these rocks are plutonic to hypabyssal in origin, and include a range of bulk mineralogies such as troctolites, dunites, norites, gabbronorites, and spinel troctolites [1]. These Mg-suite lithologies have distinct trace element concentrations and ratios that differentiate them from other lunar rock types. These rocks are ancient, generally dated to between 4.5 and 4.1 Ga, although it is unknown if this represents the full range of Mg-suite ages [1–2]. Among the Mg-suite lithologies, the spinel troctolites are relatively rare, to date only found in polymict breccias [3]. Spinel troctolites, as their name suggests, consist of calcic plagioclase and forsteritic olivine, with minor amounts of spinel (MgAl2O4), ± pyroxene and cordierite [1,4]. This form of spinel is often called ‘pink’ spinel because of its appearance in thin section under plane polarized light (PPL; Fig. 1), due to minor amounts of Cr. Spinel troctolites are generally plutonic or hypabyssal in origin (subsequently exhumed and incorporated into polymict breccias), or formed through impact processes (e.g., crystalline impact melt) [5]. A spinel-rich lithology has also been found in the Moscoviense region of the Moon via the Moon Mineralogy Mapper (M3) and lacks other mafic phases [6]. Finally, while the Mg-suite sampled thus far consists of plutonic (or hypabyssal) rocks, the question remains if such magmas could have erupted on the surface of the Moon [7]. These magmas have much lower density than mare basalts, but little sample or remote sensing evidence has been found to support the idea that extrusive Mg-suite volcanism occurred [7]. Here, we present a coordinated microanalytical study of spinel-bearing lithic and mineral clasts found in Apollo sample 68815. These data will be used to understand their petrogenesis (magmatic or impact) and modification histories, and to shed light on the existence of volcanic Mg-suite rocks. Sample Description: Apollo sample 68815 is a polymict impact melt breccia containing a variety of lithic and mineral fragments embedded in devitrified impact melt. This sample was chipped off the top of a boulder at Station 8 during the Apollo 16 mission and had an original weight of nearly 1.8 kg. In this study, we investigated two polished thin sections of 68815: 68815,17 and 68815,148, both containing spinel. Methods: The thin sections of 68815 were studied using optical light microscopy (PPL, cross-polarized light, and reflected light) with a Keyence VHX-7100 Digital Microscope. Each section was then X-ray mapped for 13–14 elements using a Cameca SX100 electron probe microanalyzer (EPMA) located in the Kuiper Materials Imaging and Characterization Facility (KMICF) at the University of Arizona. We have obtained geochemical information about the phases (olivine, plagioclase, spinel, pyroxene) in the thin sections also using the EPMA. In addition, we have used ThermoScientific Helios NanoLab 660 Focused-Ion-Beam Scanning-Electron Microscope (FIB-SEM) and a Hitachi S-4800 SEM (both in KMICF) to obtain backscattered electron (BSE) images and energy dispersive Xray spectrometry (EDS) maps of areas of interest. Using a JEOL 7900F SEM at the Astromaterials Research & Exploration Science (ARES) at NASA Johnson Space Center (JSC), we have obtained electron backscatter diffraction (EBSD) maps of the spinel-bearing portions of the thin sections. The EBSD data were collected under beam conditions of 20 kV, and ~90 μA, with step sizes varying from 0.05 to 2 μm. Following EBSD data collection, we processed the data using AZtecCrystal and MTEX, a free MATLAB toolbox. Results: We have found clasts with subophitic textures, that consist of primarily olivine and plagioclase, with minor amounts of pink Mg-Al spinel and pyroxene (Fig. 1). These clasts are up to ~1 mm in length and contain spinels up to 50 μm across. We have additionally identified pink Mg-Al spinels within the impact melt (i.e., not contained in lithic clasts) in both thin sections. In one instance, a single spinel grain is approximately 300 μm across (Fig. 1b, 2). The spinel fragments embedded in impact melt have varying compositions, typically distinct from the compositions of spinels in the lithic clasts. Spinel-Bearing Clasts: Ten lithic clasts with similar textures and mineral compositions were identified between 68815,17 (two clasts) and ,148 (eight clasts). These clasts fall into two groups. The first has skeletal olivine with intergranular plagioclase, with minor amounts of pyroxene and spinel (Fig. 1a, 2c, 2d). The spinel in these clasts are found amid the plagioclase. The second group have an intergranular texture of olivine and plagioclase, again with minor spinel and pyroxene. The second group may contain spinels surrounded by plagioclase, and spinels enclosed in olivine. Spinels located within both clast types range from no apparent Cr zoning, to reverse zoning (Cr-enrichment inward; Fig. 2d), to normal zoning (Cr-enrichment outward). In the clasts thus far investigated with EPMA, plagioclase compositions range from An# (molar 100×Ca/[Ca+Na+K]) 92–96. Olivine Mg# ranged from 77 to 94, while pyroxene had Mg# from 54–84. Spinel in the clasts have Cr# (molar 100×Cr/[Cr+Al]) 2–4 and Mg# 88–91, which is within the range of pristine and plutonic spinel troctolites [8]. Isolated Spinels: These crystals are generally euhedral to subhedral, and can exhibit reverse Cr zoning (Cr enrichment inward) or no apparent Cr zoning. The spinels thus far investigated via EPMA have Cr# 9–14 and Mg# 65–82. The Cr# for these spinels is within the range reported by [8], but have lower Mg#. Future Work: We will continue to process the EBSD data for these lithic and mineral clasts. We will also continue to characterize these clasts using EPMA and SEM. By thoroughly characterizing the various spinels and spinel-bearing clasts, we aim to constrain the petrogenesis of these minerals and rock fragments. Acknowledgments: We thank NASA for the loan of these thin sections. We thank Ken Domanik and Jerry Chang for their support with data collection. Work was supported by a University of Arizona RII Core Facilities Pilot Program grant and start-up funds to JJB. We acknowledge support from NASA’s Planetary Science Research program for analysis performed at JSC. References: [1] Shearer C. K. et al. (2015) Am. Min. 100, 294–325. [2] Borg L. E. et al. (2020) GCA 290, 312–332. [3] Warren P. H. (1993) Am. Min. 78, 360–376. [4] Dymek R. F. et al. (1976) LPS VII, 2335–2378. [5] Treiman et al. (2019) Am. Min. 104, 370–384. [6] Pieters et al. (2011) JGR: Plan. 116:E00G08. [7] Prissel et al. (2016) Icarus 277, 319–329. [8] Prissel et al. (2016) Am. Min. 101, 1624–1635.

spinel

Lunar Impact Melt Crystallization Produces Reflectance Spectra Dominated By Clinopyroxene Signatures: Implications for the Origin of Pink Spinel Anorthosite

Magma-wallrock interaction and impact melt crystallization are the two leading hypotheses for the formation of orbitally detected lunar “pink” spinel anorthosite (PSA) [1-3]. Distinguishing among hypotheses is complicated because both require mixing of anorthositic crust and MgO-rich ultramafic components. Models for PSA formation need to account for either the thermodynamic hurdles of crustal assimilation, or the size of impactor and composition of target material needed to generate spinel during crater and basin formation. Determining whether the energy source is endogenic or exogenic is important for understanding the thermal and chemical evolution of the lunar crust. Here we test the impact melt hypothesis by performing controlled cooling experiments on two hypothetical impact melt compositions. The compositions represent mixing of ultramafic magma and anorthositic crust in molar ratios of approximately 50:50 and 25:75. Synthetic crystallized assemblages were prepared for chemical analysis and bidirectional reflectance spectroscopy in the visible to near-infrared wavelengths. All crystallization experiments contained plagioclase, olivine, and clinopyroxene, but trace amounts of spinel were only observed in the 50:50 mix. The experimental spinel is similar to the compositions inferred from remote observations. However, the high-Ca pyroxene in our experimental assemblages (9 – 18 wt.%) resulted in 1 and 2 µm absorption band center positions consistent with synthetic clinopyroxene. The clinopyroxene absorptions are present regardless of specific mineral modes and the presence of either olivine or spinel. These results suggest that impact melt crystallization will produce clinopyroxene-bearing lithologies, the presence of which masks spectral contributions from coexisting spinel and olivine. Assuming that the trace amounts of spinel observed in our experiments could be concentrated and isolated from the mafic silicates by convection or density settling in the impact melt sheet, the spinel-rich areas would still be proximally associated with the remaining silicate-dominated assemblage exhibiting strong clinopyroxene spectral signatures. We conclude that impact melting of the lunar crust can explain rare cases of PSA in association with clinopyroxene. Previous investigations of magma-wallrock interactions [2] demonstrate that small plagioclase-contaminated regions of an ultramafic intrusion can concentrate spinel whereas larger portions of the same intrusion remain relatively uncontaminated and yield olivine and orthopyroxene, consistent with the more common occurrence of PSAs in association with orthopyroxene ±olivine in the remote sensing database (e.g., Moscoviense Basin) [4].

petrology

Limited subsolidus diffusion in type B1 CAI: Evidence from Ti distribution in spinel

Most models of calcium aluminum-rich inclusions (CAI) have focused on early stages of formation by equilibrium crystallization of a homogeneous liquid. Less is known about the subsolidus cooling history of CAI. Chemical and isotopic heterogeneties on a scale of tens to hundreds of micrometers (e.g. MacPherson et al. (1989) and Podosek, et al. (1991)) suggest fairly rapid cooling with a minimum of subsolidus diffusion. However, transmission electron microscopy indicates that solid state diffusion may have been an important process at a smaller scale (Barber et al. 1984). If so, chemical evidence for diffusion could provide constraints on cooling times and temperatures. With this in mind, we have begun an investigation of the Ti distribution in spinels from two type B1 CAI from Allende to determine if post-crystallization diffusion was a significant process. The type B1 CAIs, 3529Z and 5241 have been described by Podosek et al. (1991) and by El Goresy et al. (1985) and MacPherson et al. (1989). We have analyzed spinels in these inclusions using the electron microprobe. These spinels are generally euhedral, range in size from less than 10 to 15 micron and are poikilitically enclosed by millimeter-sized pyroxene, melilite, and anorthite. Analyses were obtained from both the mantles and cores of the inclusions. Compositions of pyroxene in the vicinity of individual spinel grains were obtained by analyzing at least two points on opposite sides of the spinel and averaging the compositions. The pyroxene analyses were obtained within 15 microns of the spinel-pyroxene interface. No compositional gradients were observed within single spinel crystals. Ti concentrations in spinels included within pyroxene, melilite, and anorthite are presented.

Meeker, G. P.

The crystallisation trends of spinels in tertiary basalts from Rhum and Muck and their petrogenetic significance

Spinels found in transitional olivine basalts from the Islands of Rhum and Muck in the British Tertiary Province are analyzed to determine their chemical variability and their relationship to silicate phases. Chemical zoning of the cores of spinels which spilled into the basaltic liquid may be due to a reaction between the spinel and the liquid resulting in more Fe- and Ti-rich spinels. In addition, a peritectic-type reaction seems to have occurred, causing the transformation of aluminum spinel to chrome spinel with precipitation of plagioclase. Changes in the basaltic liquid are reflected by these transformations in the spinel composition.

Ridley, W. I.

Luna 24 - Systematics in spinel mineral chemistry in the context of an intrusive petrogenetic grid

Spinels in the Luna 24 gabbroic fragments have a restricted bimodal distribution of aluminum chromite and ulvospinel, whereas those in the Luna 24 basalts form a continuous sequence which defines a compositional variation from Al-Mg-chromites to ulvospinels containing 1 wt% Al2O3. A comparison of these spinel mineral chemistries with basaltic spinels from other mare regions and with spinels from other lunar intrusive rocks suggest that the Luna 24 gabbroic spinels lie at the low pressure end of a P-T spinel grid, and that titanium enrichment trends on Mg-Al-Cr rich spinel cores are related to extrusion and formed at the terminal stages of magmatic crystallization.

Haggerty, S. E.

Demonstration of MgCr 2– x Mn x O 4 Spinel Oxide Cathodes in High-Voltage Mg Batteries

Solid-solution oxide spinels with high redox voltages and facile Mg 2+ mobility have been identified as promising candidates for practical, high-voltage cathodes in Mg batteries. In this work, we discuss the development of MgCr 2-x Mn x O 4 [x = 0.5, 1, 1.2] solid-solution spinel oxides as a cathode material and their electrochemical performance paired with an Mg anode in a full cell. This work presents the first demonstration of full cells with these materials. Mg-Cr-Mn spinel oxides with varying Cr and Mn contents were synthesized using alternative synthetic routes for optimal electrochemical performance. High-resolution synchrotron powder X-ray diffraction (PXRD), solid-state nuclear magnetic resonance (NMR) spectroscopy, and electron microscopy showed that these different synthetic routes resulted in changes in structures and particle morphologies, which in turn affect the electrochemical performance. Particularly, the urea coprecipitation synthetic route resulted in high-surface-area particles that enabled lower overpotentials and increased discharge capacity. The high surface area also resulted in expedited structural degradation caused by the irreversible migration of Mg 2+ into normally vacant 16c sites in the spinel lattice. This structural degradation was lessened by using a hydrosauna-urea synthesis method, which decreased the Mg/Mn inversion ratio while retaining high-surface-area particles with good cycling performance. Furthermore, our findings highlight the necessity for high surface area or nanostructured spinel oxide cathodes with minimized Mg-Mn inversion to enable spinel oxide cathodes in Mg full cells.

Mg anode

Elasticity of some mantle crystal structures. I - Pleonaste and hercynite spinel.

The elasticity of high-pressure mantle phases can be characterized by using data for chemically similar crystal compounds. The single-crystal elastic constants are determined as a function of pressure and temperature for pleonaste spinel and at room conditions for hercynite spinel. The bulk modulus increases from 1.95 Mb for pleonaste spinel to 2.10 Mb for hercynite spinel. Low or negative values of the pressure derivatives of shear constants are characteristic of the spinel structure and imply a low kinetic barrier to phase transformations and diffusion. Compressional and shear velocities of the spinel phase of olivine are estimated as a function of mean atomic weight by using the pleonaste and hercynite data.

Wang, H.

Effects of thermal metamorphism on compositions of lunar spinels

The reported study represents an attempt to evaluate experimentally the compositional and textural changes that are likely to be observed in the Fe-Ti-Cr spinels of lunar igneous rocks by subsequent thermal metamorphism. The Apollo 12 igneous rock, 12018,43, was chosen for this investigation because an earlier study of another fraction of this rock by El Goresy et al. (1971) has reported an almost continuous trend of spinel compositions between Cr-Ulvoespinel and Ti-chromite. The nature of the compositional changes in the heated spinels (and ilmenites) is found to be such that the changes cannot be explained by intragranular adjustments alone. In the heated sample, pyroxene grains adjacent to the high-Ti spinels show a decrease in FeO, and an increase in MgO and Al2O3 at the interface. This may account for the MgO depletion and a part of the FeO enrichment in the high-Ti spinels. It is believed that the heating experiment demonstrates that thermal metamorphism of lunar basalts is likely to modify the compositions of their preexisting spinels (and ilmenites).

Misra, K. C.

Spinel-bearing, Al-rich chondrules in two chondrite finds from Roosevelt County, New Mexico - Indicators of nebular and parent body processes

Two rare spinel-bearing Al-rich chondrules are identified in chondrite finds from Roosevelt County, New Mexico-RC 071 (L4) and RC 072 (L5). These chondrules have unusual mineralogies dominated by highly and asymmetrically zoned Al-Cr-rich spinels. Two alternatives exist to explain the origin of this zoning-fractional crystallization or metamorphism. Fractional crystallization formed the zoning of the trivalent cations and caused a localized depletion in chromites around the large Al-Cr-rich spinels. Diffusive exchange and partitioning of Fe and Mg between olivine and spinel during parent-body metamorphism can explain the asymmetric zoning of these elements. The bulk compositions of the chondrules suggest affinities with the Na-Al-Cr-rich chondrules, as would be expected from the abundance of Al-Cr-rich spinels. The most important factors are the temperature to which the molten chondrule was heated and the cooling rate during crystallization. These two chondrules cooled rapidly from near the liquidus, as indicated by the zoning, occurrence and sizes of spinels, radiating chondrule textures and localized chromite depletions.

Mccoy, Timothy J.

Suppressing Phase Segregation and Improving Stability in Mixed-Halide Perovskites through Spinel Oxide-Directed Epitaxy

Mixed-cation mixed-halide perovskite compositions are essential for achieving the required bandgaps for high-efficiency multijunction photovoltaics, yet their stability remains limited by interfacial defects, phase segregation, and degradation. Here, we introduce spinel oxides as a new family of lattice-matched substrates that enable crystalline, phase-pure, compositionally-uniform, bromide-rich perovskite film growth. The effect of spinel oxides is two-fold: reducing defects at the bottom interface by templating film growth and inducing beneficial compressive strain through mismatch-dependent substrate-perovskite lattice coupling. Spinel oxide substrates facilitate growth of highly crystalline films and eliminate detrimental secondary phases across thicknesses. Using grazing incidence X-ray diffraction, X-ray fluorescence, cathodoluminescence–scanning electron microscopy, cryogenic photoluminescence, and density functional theory, we reveal that Mg-halide bonds at the bottom interface induce lattice mismatch-dependent compressive strain that suppresses halide segregation and further reduces defect formation. In addition, films grown on spinel oxides maintain over 87% of the perovskite phase after 12 h under 100% relative humidity, as monitored by in situ grazing incidence wide-angle X-ray scattering (GIWAXS), compared to less than 70% for control samples. This work extends lattice matching from vapor-deposited epitaxial semiconductors to solution-processed halide perovskites to establish a broadly applicable strategy for defect suppression, phase homogenization, and long-term stability. Based on the fundamental science explored here, we set the stage for the development of lattice-matched spinel oxide charge transport layers to be integrated into perovskite solar cells and other optoelectronic devices.

36 MATERIALS SCIENCE

Morphology‐controlled synthesis of multi‐metal‐based spinel oxide nanocatalysts and their performance for oxygen reduction

Abstract We present a one‐pot colloidal synthesis method for producing monodisperse multi‐metal (Co, Mn, and Fe) spinel nanocrystals (NCs), including nanocubes, nano‐octahedra, and concave nanocubes. This study explores the mechanism of morphology control, showcasing the pivotal roles of metal precursors and capping ligands in determining the exposed crystal planes on the NC surface. The cubic spinel NCs, terminated with exclusive {100}‐facets, demonstrate superior electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline media compared to their octahedral and concave cubic counterparts. Specifically, at 0.85 V, (CoMn)Fe 2 O 4 spinel oxide nanocubes achieve a high mass activity of 23.9 A/g and exhibit excellent stability, highlighting the promising ORR performance associated with {100}‐facets of multi‐metal spinel oxides over other low‐index and high‐index facets. Motivated by exploring the correlation between ORR performance and surface atom arrangement (active sites), surface element composition, as well as other factors, this study introduces a prospective approach for shape‐controlled synthesis of advanced spinel oxide NCs. It underscores the significance of catalyst shape control and suggests potential applications as nonprecious metal ORR electrocatalysts.

Li, Can