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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.

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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Entropy-defect synergy for dual luminescence mechanism in spinel: Time-resolved anti-counterfeiting and fingerprint visualization

Multimodal luminescent materials, while promising for anti-counterfeiting, often lack dynamic time-dependent responses and controllable spatial distribution, limiting their encryption capabilities in the spatiotemporal dimension. Here, this work presents a coordinated control strategy based on entropy and defect engineering, and uses a backpropagation (BP) neural network for material screening to successfully prepare spinel Mg 0.8 (Fe 0.04 Co 0.04 Ni 0.04 Cu 0.04 Zn 0.04 )Cr 2 O 4 (MgA 5 CO) phosphors with time-dependent dynamic luminescence behavior. This phosphor simultaneously activated the d-d transition luminescence (∼618 nm) derived from Co 2+ /Cr 3+ and the defect luminescence (∼398 nm) related to zinc vacancies (V Zn ) in a single-phase solid solution. The phosphor exhibits a time-dependent color evolution from pink to purple under fixed-wavelength excitation, due to the different excited-state dynamics and decay lifetimes associated with the d-d transition and defect luminescence. Structural characterization and spectral analysis confirmed the existence of V Zn and its significant role in defect luminescence process. The fluorescent and dynamic luminescent properties of entropy-based spinel oxide enable its use in advanced anti-counterfeiting applications like fingerprint recognition and color-changing dedicated anti-counterfeiting mark, showing promise in high-end and time-dynamic anti-counterfeiting fields. This research not only developed a new type of fluorescent dynamic anti-counterfeiting material, but also provided a new idea for constructing advanced optical functional materials with multiple luminescence mechanisms.

Defect project↗
DOE OSTI2025

Equilibrium Fe isotope fractionation between olivine, pyroxene, spinel and MORB glass: Implications for mantle partial melting to generate MORBs

Primitive mid-ocean ridge basalts (MORBs) exhibit Fe isotopic compositions heavier than the upper mantle by +0.074 ± 0.028 ‰ for δ 56 Fe. The processes responsible for this isotopic difference remain unclear. Modeling of Fe isotope fractionation during mantle partial melting requires reliable equilibrium Fe isotope fractionation factors between minerals and melts, for which consistent data are still lacking. Here, in this study, we used Nuclear Resonant Inelastic X-ray Scattering (NRIXS) technique to measure Fe force constants for a MORB glass (ALV 519-4-1) and natural mantle minerals (olivine, orthopyroxene, clinopyroxene, and spinel) to determine the equilibrium Fe isotope fractionation factors between them. The force constants determined in this study, in increasing order, are 167 ± 26 N/m for spinel, 175 ± 17 N/m for olivine, 176 ± 20 N/m for MORB glass, 205 ± 26 N/m for clinopyroxene, and 219 ± 36 N/m for orthopyroxene. We evaluated the previously proposed mechanisms for the heavy Fe isotopic composition of MORBs, including (i) mantle partial melting, (ii) mantle lithological heterogeneity, with pyroxenite in the source, (iii) mantle metasomatism by low-degree melts, and (iv) fractional crystallization of olivine from melts. For (i), we used the pMELTS program to simulate adiabatic decompression melting of mantle peridotites, and calculated Fe isotope fractionation based on Fe 3+ –Fe 2+ equilibrium-controlled fractionation, where Fe 3+ forms stronger bonds and is more incompatible than Fe 2+ . At 10 wt% peridotite melting, corresponding to MORB generation, only +0.03 ‰ Fe isotope fractionation between the melt and the original bulk composition (Δ 56 Fe = δ 56 Fe melt - δ 56 Fe 0 ) was produced, insufficient to account for the observed MORB-upper mantle difference. For (ii), melting of pyroxenites yields smaller Fe isotope fractionation than melting of peridotites, making it unlikely the cause for the MORB-upper mantle isotopic difference. For (iii), both the Fe 3+ /ΣFe ratio and the δ 56 Fe of melts increase with the degree of partial melting, indicating that low-degree melts are not isotopically heavy enough to significantly alter the isotopic composition of lithospheric mantle through metasomatism. For (iv), equilibrium isotope fractionation between olivine and melt is near zero. These results suggest that equilibrium Fe isotope fractionation alone cannot explain the MORB isotopic signature, highlighting the potential role of kinetic isotope fractionation. Using a diffusion model, we calculated kinetic Fe and Mg isotope fractionations associated with (iv) olivine crystallization from a melt, and found that the predicted Fe and Mg isotope fractionations were inconsistent with observations in MORBs. Qualitatively, two processes could have induced kinetic Fe isotope fractionation during MORB generation: (a) Fe-Mg interdiffusion between melt and solid during melt migration and (b) reactive melt-rock interactions during melt focusing. However, a quantitative understanding of their role in modifying the melt isotopic composition remains limited and requires further investigation.

Fe isotopes↗
DOE OSTI2026

Modulating coordinate site occupancy in high-entropy spinel electrocatalysts

High entropy spinel oxides provide a versatile platform for electrocatalysis because multiple metal cations can be incorporated into a single crystalline lattice, enabling tunable electronic structures. However, controlling how these cations distribute between tetrahedral and octahedral coordination sites remains a major challenge, limiting rational catalyst design. Here, we modulate cation coordination site occupancy between tetrahedral and octahedral sites in a Co–Fe–Cr–Mn–Ni framework by introducing a sixth cation (Zn, Ga, Mg, or Al) with distinct site preference energies. Using density functional theory, synchrotron X-ray absorption spectroscopy, and magnetic circular dichroism, we demonstrate that Zn preferentially occupies tetrahedral sites, driving increased octahedral occupancy of cobalt. This redistribution increases the population of octahedrally coordinated cobalt in mixed oxidation states, enhances electrical conductivity, and improves oxygen evolution reaction activity. Our findings establish coordination site occupancy as a critical design parameter, providing a strategic pathway for tailoring multicomponent spinel electrocatalysts with optimized performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

The Sensitivity of Nickel Substitution in the Structural Design of Manganese-Based Layered and Lithiated Spinel Electrodes for Li-Ion Batteries

A concerted effort is being made at Argonne National Laboratory to explore and develop high-performance lithium-manganese-nickel-oxide cathode materials for the lithium battery industry. They are both energy- and cost-competitive relative to cobalt- and nickel-rich systems, such as LiCoO 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , and LiNi 0.8 Mn 0.1 Co 0.1 O 2 . The recent discovery of the structural versatility of LiNi 0.5 Mn 0.5 O 2 , has revealed that it can exist in three configurations: lithiated spinel, partially disordered layered, and completely disordered rock salt within a common cubic-close-packed oxygen array. This versatility opens up the possibility of designing structurally integrated electrode components with interlinking 2-D (layered) and 3-D (spinel) channels for Li-ion transport. This paper highlights the sensitivity of Ni substitution and synthesis temperature on the structural and electrochemical properties of LiNi 0.50 Mn 0.50 O 2 , LiNi 0.53 Mn 0.47 O 2 , LiNi 0.47 Mn 0.53 O 2 , and LiNi 0.25 Mn 0.75 O 2 electrodes, as well as a cobalt-containing composition, LiNi 0.333 Mn 0.333 Co 0.333 O 2 , when synthesized at a relatively low temperature of 400 °C.

25 ENERGY STORAGE↗
DOE OSTI2025

Synthesis and Lithium Storage Properties of Spinel (Al 0.2 Mn 0.2 Co 0.2 Ni 0.2 Zn 0.2 ) 3 O 4 High-Entropy Oxide

High-entropy oxides (HEOs) have garnered significant interest as next-generation anode materials for lithium-ion batteries (LIBs) due to their high theoretical specific capacity and excellent structural stability. This study successfully synthesized spinel-structured (Al 0.2 Mn 0.2 Co 0.2 Ni 0.2 Zn 0.2 ) 3 O 4 HEO via a sol–gel method. The material was characterized by XRD, Raman and TEM, confirming a homogeneous single-phase spinel structure, with uniformly distributed elements-a hallmark of HEOs. Electrochemical tests demonstrated a stable cycling performance (438 mAh g −1 at 100 mA g −1 after 100 cycles and 350 mAh g −1 at 1 A g −1 after 1000 cycles) and rate capacity of 159 mAh g −1 at 2 A g −1 , The remarkable long-term cyclability and good rate capability highlight the potential of this HEO for practical applications in durable, high-power lithium-ion batteries. This work underscores the advantage of incorporating structurally stabilizing elements in HEOs for advanced energy storage.

anode materials↗
NASA NTRS1973

Spinel troctolite and anorthosite in Apollo 16 samples.

Review of the examination results on two Apollo 16 rocks recovered from the lunar highlands which probably represent contrasting types of 'primitive' lunar cumulates. One is a microbreccia containing a large lithic fragment of spinel troctolite, while the other is a shock-brecciated anorthosite. The reviewed results suggest that, if the two rock groups formed from the same parent magma type, the spinel troctolite must have formed early in the differentiation sequence as the result of crystal settling in the melt, whereas the anorthosite must have formed as a later cumulate, possibly by flotation.

Prinz, M.↗
NASA NTRS1974

Reinvestigation of the olivine-spinel transformation in Ni2SiO4 and the incongruent melting of Ni2SiO4 olivine

The olivine-spinel transformation and the melting behavior of Ni2SiO4 were investigated over the PT ranges of 20-40 kbar, 650-1200 C, and 5-13 kbar, 1600-1700 C, respectively. It was confirmed that Ni2SiO4 olivine melts incongruently at high pressures and that it is a stable phase until melting occurs. The PT slope of the incongruent melting curve is approximately 105 bars/deg. The olivine-spinel transformation curve was shown to be a reversible univariant curve, and could be expressed by the linear equation P(bars) equals 23,300 + 11.8 x T(deg C). The transformation curve determined by Akimoto et al. (1965) is nearly parallel to that of the present work, but lies at pressures about 12% lower.

Ma, C.-B.↗
NASA NTRS1980

Experimental mineral/liquid partition coefficients of the rare earth elements /REE/, Sc and Sr for perovskite, spinel and melilite

Experimental determinations of the mineral/liquid partition coefficients of REE (La, Sm, Eu, Gd, Tb, Yb and Lu), Sc and Sr are reported for the minerals perovskite, spinel and melilite in synthetic systems. Perovskite concentrates light REE with respect to the residual liquid but shows no preference for heavy REE. Spinel greatly discriminates against the incorporation of REE, especially light REE, into its crystal structure. The partition of REE into melilite from a silicate liquid is quite dependent upon both the bulk melt and melilite solid-solution (gehlenite and akermanite components) compositions. As such, melilite can be enriched in REE or will reject REE with corresponding strong negative or strong positive Eu anomalies, respectively.

Nagasawa, H.↗
NASA NTRS1980

Spinel cataclasites in 15445 and 72435 - Petrology and criteria for equilibrium

The problem of establishing the existence of equilibrium among the coexisting phases in the rock is addressed by presenting petrographic and mineral chemistry data on a new spinel cataclasite from 15445 (clast H) and data more extensive than those previously available on two clasts in 72435. Criteria useful in reconstructing the original petrology of these and other spinel cataclasites are analyzed by considering equilibrium among the different phases, that is, the mono- or polymict nature of these cataclasized samples. Finally, the role of impact processes in disturbing the equilibria is discussed.

Baker, M. B.↗
NASA NTRS1982

Sorption of noble gases by solids, with reference to meteorites. II - Chromite and carbon. III - Sulfides, spinels, and other substances; on the origin of planetary gases

The trapping of noble gases by chromite and carbon, two putative carriers of primordial noble gases in meteorites, was studied by synthesizing 19 samples in a Ne-Ar-Kr-Xe atmosphere at 440-720 K. Noble gas contents are found to approximately obey Henry's Law, but only slight correlations are found with composition, surface area, or adsorption temperature. Geometric mean distribution coefficients for bulk samples and HCl residues in 10 cu cm STP/g atm are: Xe 100, Kr 15, Ar 3.5, and Ne 0.62. Elemental fractionation data support the suggestion of Lewis et al. (1977) that chromite and carbon in C2 and C3 chondrites were formed by the reaction: Fe, Cr + 4CO yields (Fe, Cr)3O4 + 4C + carbides. In contrast to meteoritic minerals, the synthetic specimens show no isotopic fractionation of noble gases. In a subsequent study, attention is given to the cases of sulfides and spinels, on the way to consideration of the origin of planetary gases. Sulfides showed three distinctive trends relative to chromite or magnetite. The elemental fractionation pattern of Ar, Kr and Xe in meteorites, terrestrial rocks and planets resembles the adsorption patterns on the carbons, spinels, sulfides, and other solids studied. The high release temperature of meteoritic noble gases may be explained by transformation of the physisorbed or chemisorbed gas. The ready loss of meteoritic heavy gases on surficial oxidation is consistent with adsorption, as is the high abundance.

Yang, J.↗
NASA NTRS1982

Experimental determination of the spinel-garnet boundary in a Martian mantle composition

The high pressure reaction orthopyroxene + clinopyroxene + spinel to garnet + olivine is applicable to the mantle of Mars. Experimental reversals of this reaction in the system CaO-MgO-FeO-Al2O3-SiO2 have been made in the range 1000-1200 C using the bulk composition proposed by Morgan and Anders (1980). At 1000 C, 1100 C, and 1200 C the garnet-out equilibrium is bracketed at 10.8 + or - 0.5, 12.6 + or - 0.5, and 15.2 + or - 0.5 kbars, respectively. A dP/dT slope of 14.0 bar/K at 1000 C increasing to 26.0 bar/K at 1200 C has been inferred. Depending on bulk composition, the mantle of Mars is inferred to have a phase assemblage of either olivine + clinopyroxene + orthopyroxene + garnet or olivine + clinopyroxene + garnet + spinel. In the second, the partial melts will not be buffered by olivine and orthopyroxene and will have markedly lower silica activities than those of the terrestrial mantle.

Patera, E. S.↗
NASA NTRS1983

Catalytic recombination of nitrogen and oxygen on iron-cobalt-chromia spinel

The energy-transfer catalytic recombination coefficient for nitrogen and oxygen recombination on iron-cobalt-chromia spinel is inferred from stagnation-point heat flux measurements in dissociated arc-jet flow. This material was coated on several Space Shuttle Orbiter thermal protection tiles. The resulting coefficients are correlated with an Arrhenius model for convenience, and these expressions may be used to account for catalytic recombination in predictions of the heat flux on the spinel-coated tiles flown on several Space Shuttle Orbiter flights. The results are compared with those inferred by Rakich, Stewart, and Lanfranco from an Orbiter flight and arc-jet experiments. Good agreement is obtained for oxygen recombination, but agreement for nitrogen is poor.

Scott, C. D.↗
NASA NTRS1985

Mineral chemistry and origin of spinel-rich inclusions in the Allende CV3 chondrite

The present electron probe microanalysis of 20 spinel-rich inclusions in Allende indicates that the mineralogy of spinel-rich Allende inclusions is similar to that of fine grained Ca, Al-rich inclusions (CAIs) in ALH-77003 and rims on coarse grained CAIs in Allende. The mineralogy, mineral chemistry, and bulk chemistry of the inclusions indicate that they are not primitive aggregates of crystalline nebular condensates, but rather aggregates of minute concentric objects that are presently interpreted to be a fractionated distillation residue that lost Ca, Si-rich partial melt. It is suggested that interstellar dust aggregates were melted or distilled into Allende inclusions by aerodynamic drag heating, in regions of the nebula where the dust/gas ratio was so enhanced that the local oxygen fugacity was raised by several order of magnitude and liquids became thermodynamically stable.

Kornacki, A. S.↗
NASA NTRS1993

Trace element compositions of spinel-rich refractory inclusions from the Murchison meteorite

Three spinel-rich, perovskite-bearing, pyroxene-rimmed, hibonite-free inclusions from the Murchison C2 chondrite have volatility controlled, modified group II REE patterns. Two have high Eu/Yb ratios, two have small positive Ce anomalies and one has high refractory siderophiles for a group II inclusion. Two additional spinel-rich inclusions have subchondritic Ce/La ratios and negative Eu and Yb anomalies, the Eu anomalies being larger than the Yb ones. One of these inclusions is enriched in La relative to all HREE and the other is enriched in HREE relative to all LREE except La, possibly suggesting the presence of an ultrarefractory component in the latter. One hibonite-rich inclusion has a group III REE pattern with a negative Ce anomaly. A calcium dialuminate-bearing inclusion known to have crystallized from a melt at 2100-1800K has a modified group II REE pattern, rather than a pattern which would be predicted from the evaporation expected from such a droplet, e.g., a group III or ultrarefractory pattern. Volatile element contents of these inclusions are among the lowest found in any refractory inclusions.

Yoneda, S.↗
NASA NTRS1996

Diogenites: Cumulates from Asteroid 4 Vesta: Insights from Orthopyroxene and Spinel Chemistry

Cumulate rocks are important planetary lithologies, but they can be difficult to interpret. Important clues to the nature of their parental melts may still be present in the interiors of cumulus phases. However, in some cases, even the cores of the cumulus grains may have been modified by postcrystallization reactions with trapped melt and other cumulus phases. We have previously studied the major-, minor-, and trace-element chemistry of orthopyroxene from a suite of diogenites and concluded that their chemical attributes can best be explained by crystallization from parental melts that were derived from a depleted mantle source that had already experienced eucrite removal. However, we and others have had difficulty explaining the great range in concentration of minor elements (Al, Ti) and trace elements (REE, Y, Zr) if all diogenites were derived from a single magmatic system. Therefore, we have investigated the chemistry of diogenitic spinels to see if they still held clues to the diogenite parental melt compositions. Although spinel is low in abundance in diogenites (<5 vol%) it still may hold clues to the maomatic and metamorphic history of these rocks.

Papike, James J.↗
NASA NTRS2000

Thermoelectric Properties of Selenides Spinels

Many compounds with the spinel structure type have been analyzed for their thermoelectric properties. Published data was used to augment experimental results presented here to select promising thermoelectric spinels.

thermoelectrics thermopower resistivity thermal co↗
NASA NTRS2014

Chromium Oxidation State in Planetary Basalts: Oxygen Fugacity Indicator and Critical Variable for Cr-Spinel Stability

Cr is a ubiquitous and relatively abundant minor element in basaltic, planetary magmas. At the reduced oxidation states (<FMQ) of many planetary basalts Cr is present in melts as both divalent and trivalent forms. The ratio of trivalent to divalent Cr present in the melt has many consequences for the stability and Cr concentration of magmatic phases such as spinel, clinopyroxene, and olivine. However, understanding the Cr valence in quenched melts has historically been plagued with analytical issues, and only recently has reliable methodology for quantifying Cr valence in quenched melts been developed. Despite this substantial difficulty, the pioneering works of Hanson and Jones and Berry and O'Neill provided important insights into the oxidation state of Cr in in silicate melts. Here we present a series of 1-bar gas mixing experiments performed with a Fe-rich basaltic melt in which have determined the Cr redox ratio of the melt at over a range of fO2 values by measuring this quantity in olivine with X-ray Absorption Near Edge Spectroscopy (XANES). The measured Cr redox ratio of the olivine phenocrysts can be readily converted to the ratio present in the conjugate melt via the ratio of crystal-liquid partition coefficients for Cr3+ and Cr2+. We have applied these results to modeling Cr spinel stability and Cr redox ratios in a primitive, iron-rich martian basalt.

Bell, A. S.↗