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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS2006

Depletion of Vandium in Planetary Mantles: Controlled by Metal, Oxide, or Silicate?

Vanadium concentrations in planetary mantles can provide information about the conditions during early accretion and differentiation. Because V is a slightly siderophile element, it is usually assumed that any depletion would be due to core formation and metal-silicate equilibrium. However, V is typically more compatible in phases such as spinel, magnesiowuestite and garnet. Fractionation of all of these phases would cause depletions more marked than those from metal. In this paper consideration of depletions due to metal, oxide and silicate are critically evaluated.

Righter, Kevin↗
NASA NTRS1960

Oxidation Behavior of Binary Niobium Alloys

This investigation concludes a study to determine the effects of up to 25 atomic percent of 55 alloying additions on the oxidation characteristics of niobium. The alloys were evaluated by oxidizing in an air atmosphere for 4 hours at 1000 C and 2 hours at 1200 C. Titanium and chromium improved oxidation resistance at both evaluation conditions. Vanadium and aluminum improved oxidation resistance at 1000 C, even though the V scale tended to liquefy and the Al specimens became brittle and the scale powdery. Copper, cobalt, iron, and iridium improved oxidation resistance at 1200 C. Other investigations report tungsten and molybdenum are protective up to about 1000 C, and tantalum at 1100 C. The most important factor influencing the rate of oxidation was the ion size of the alloy additions. Ions slightly smaller than the Nb(5+) ion are soluble in the oxide lattice and tend to lower the compressive stresses in the bulk scale that lead to cracking. The solubility of the alloying addition also depends on the valence to some extent. All of the elements mentioned that improve the oxidation resistance of Nb fit this size criterion with the possible exception of Al, whose extremely small size in large concentrations would probably lead to the formation of a powdery scale. Maintenance of a crack-free bulk scale for as long as possible may contribute to the formation of a dark subscale that ultimately is rate- controlling in the oxidation process. The platinum-group metals, especially Ir, appear to protect by entrapment of the finely dispersed alloying element by the incoming Nb2O5 metal-oxide interface. This inert metallic Ir when alloyed in a sufficient amount with Yb appears to give a ductile phase dispersed in the brittle oxide. This scale would then flow more easily to relieve the large compressive stresses to delay cracking. Complex oxide formation (which both Ti and Zr tend to initiate) and valence effects, which probably change the vacancy concentration in the scale, are masked by the overriding tendency for a porous scale.

Barrett, Charles A.↗
DOE OSTI2022

Vanadate Retention by Iron and Manganese Oxides

Anthropogenic emissions of vanadium (V) into terrestrial and aquatic surface systems now match those of geogenic processes, and yet, the geochemistry of vanadium is poorly described in comparison to other comparable contaminants like arsenic. In oxic systems, V is present as an oxyanion with a +5 formal charge on the V center, typically described as H x VO 4 (3–x)– , but also here as V(V). Iron (Fe) and manganese (Mn) (oxy)hydroxides represent key mineral phases in the cycling of V(V) at the solid–solution interface, and yet, fundamental descriptions of these surface-processes are not available. Here, we utilize extended X-ray absorption fine structure (EXAFS) and thermodynamic calculations to compare the surface complexation of V(V) by the common Fe and Mn mineral phases ferrihydrite, hematite, goethite, birnessite, and pyrolusite at pH 7. Inner-sphere V(V) complexes were detected on all phases, with mononuclear V(V) species dominating the adsorbed species distribution. Our results demonstrate that V(V) adsorption is exergonic for a variety of surfaces with differing amounts of terminal –OH groups and metal–O bond saturations, implicating the conjunctive role of varied mineral surfaces in controlling the mobility and fate of V(V) in terrestrial and aquatic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Structures of Vanadium-Containing Silicate and Borosilicate Glasses: Vanadium Potential Development and MD Simulations

Vanadium-containing multi-component glasses have been found with widely interests in various applications. However, the complex compositions, thus structures, lead to the challenges in experiments to understand the structural origin of the property change of these glasses. In this work, we developed compatible vanadium-related parameters for a widely used pair wise potential set to enable the simulations of the vanadium-containing multi-component glasses. Various crystal structures and glass compositions (with vanadium in different oxidation states) have been tested using the newly developed parameters, and structural information of cell parameters, pair distribution function, estimated bond distance, and coordination number have been obtained. The results are in good agreement with available experimental data, which indicates the new vanadium parameters can be used to simulate the vanadium-containing multi-component glasses and thus help study those applications with wide interests.

Deng, Lu↗
NASA NTRS2004

Workshop on Oxygen in the Terrestrial Planets

This volume contains abstracts that have been accepted for presentation at the Workshop on Oxygen in the Terrestrial Planets, July 20-23,2004, Santa Fe, New Mexico. The contents include: 1) Experimental Constraints on Oxygen and Other Light Element Partitioning During Planetary Core Formation; 2) In Situ Determination of Fe(3+)/SigmaFe of Spinels by Electron Microprobe: An Evaluation of the Flank Method; 3) The Effect of Oxygen Fugacity on Large-Strain Deformation and Recrystallization of Olivine; 4) Plagioclase-Liquid Trace Element Oxygen Barometry and Oxygen Behaviour in Closed and Open System Magmatic Processes; 5) Core Formation in the Earth: Constraints from Ni and Co; 6) Oxygen Isotopic Compositions of the Terrestrial Planets; 7) The Effect of Oxygen Fugacity on Electrical Conduction of Olivine and Implications for Earth s Mantle; 8) Redox Chemical Diffusion in Silicate Melts: The Impact of the Semiconductor Condition; 9) Ultra-High Temperature Effects in Earth s Magma Ocean: Pt and W Partitioning; 10) Terrestrial Oxygen and Hydrogen Isotope Variations: Primordial Values, Systematics, Subsolidus Effects, Planetary Comparisons, and the Role of Water; 11) Redox State of the Moon s Interior; 12) How did the Terrestrial Planets Acquire Their Water?; 13) Molecular Oxygen Mixing Ratio and Its Seasonal Variability in the Martian Atmosphere; 14) Exchange Between the Atmosphere and the Regolith of Mars: Discussion of Oxygen and Sulfur Isotope Evidence; 15) Oxygen and Hydrogen Isotope Systematics of Atmospheric Water Vapor and Meteoric Waters: Evidence from North Texas; 16) Implications of Isotopic and Redox Heterogeneities in Silicate Reservoirs on Mars; 17) Oxygen Isotopic Variation of the Terrestrial Planets; 18) Redox Exchanges in Hydrous Magma; 19) Hydrothermal Systems on Terrestrial Planets: Lessons from Earth; 20) Oxygen in Martian Meteorites: A Review of Results from Mineral Equilibria Oxybarometers; 21) Non-Linear Fractionation of Oxygen Isotopes Implanted in Lunar Metal Grains: Solar, Lunar or Terrestrial Origin? 22) Isotopic Zoning in the Inner Solar System; 23) Redox Conditions on Small Bodies; 24) Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update; 25) Mantle Redox Evolution and the Rise of Atmospheric O2; 26) Variation of Kd for Fe-Mg Exchange Between Olivine and Melt for Compositions Ranging from Alkaline Basalt to Rhyolite; 27) Determining the Partial Pressure of Oxygen (PO,) in Solutions on Mars; 28) The Influence of Oxygen Environment on Kinetic Properties of Silicate Rocks and Minerals; 29) Redox Evolution of Magmatic Systems; 30) The Constancy of Upper Mantlefo, Through Time Inferred from V/Sc Ratios in Basalts: Implications for the Rise in Atmospheric 0 2; 31) Nitrogen Solubility in Basaltic Melt. Effects of Oxygen Fugacity, Melt Composition and Gas Speciation; 32) Oxygen Isotope Anomalies in the Atmospheres of Earth and Mars; 33) The Effect of Oxygen Fugacity on Interdiffusion of Iron and Magnesium in Magnesiowiistite 34) The Calibration of the Pyroxene Eu-Oxybarometer for the Martian Meteorites; 35) The Europium Oxybarometer: Power and Pitfalls; 36) Oxygen Fugacity of the Martian Mantle from PigeoniteMelt Partitioning of Samarium, Europium and Gadolinium; 37) Oxidation-Reduction Processes on the Moon: Experimental Verification of Graphite Oxidation in the Apollo 17 Orange Glasses; 38) Oxygen and Core Formation in the Earth; 39) Geologic Record of the Atmospheric Sulfur Chemistry Before the Oxygenation of the Early Earth s Atmosphere; 40) Comparative Planetary Mineralogy: V/(CrCAl) Systematics in Chromite as an Indicator of Relative Oxygen Fugacity; 41) How Well do Sulfur Isotopes Constrain Oxygen Abundance in the Ancient Atmospheres? 42) Experimental Constraints on the Oxygen Isotope (O-18/ O-16) Fractionation in the Ice vapor and Adsorbant vapor Systems of CO2 at Conditions Relevant to the Surface of Mars; 43) Micro-XANES Measurements on Experimental Spinels andhe Oxidation State of Vanadium in Spinel-Melt Pairs; 44) Testing the Magma Ocean Hypothesis Using Metal-Silicate Partitioning of Te, Se and S; 45) Solubility of Oxygen in Liquid Iron at High Pressure and Consequences for the Early Differentiation of Earth and Mars Metallic Liquid Segregation in Planetesimals; 46) Oxygen Fugacity of Lunar Basalts and the Lunar Mantle. Range of fo2 and the Effectiveness of Oxybarometers; 47) Thermodynamic Study of Dissociation Processes of Molecular Oxygen in Vapor over Oxide Compounds; 48) Oxygen Profile of a Thermo-Haliophilic Community in the Badwater Salt Flat; 49) Oxygen Barometry Using Synchrotron MicroXANES of Vanadium; 50) Mass-Independent Isotopic Fractionation of Sulfur from Sulfides in the Huronian Supergroup, Canada; 51) Mass Independent Isotopes and Applications to Planetary Atmospheres; 52) Electrical Conductivity, Oxygen Fugacity, and Mantle Materials; 53) Crustal Evolution and Maturation on Earth: Oxygen Isotope Evidence; 54) The Oxygen Isotope Composition of the Moon: Implications for Planet Formation; 55) Oxygen Isotope Composition of Eucrites and Implications for the Formation of Crust on the HED Parent Body; and 56) The Role of Water in Determining the Oxygen Isotopic Composition of Planets.

Source record↗
DOE OSTI2023

Mastering the synergy between Na 3 V 2 (PO 4 ) 2 F 3 electrode and electrolyte: A must for Na-ion cells

Sodium-ion batteries are emerging as suitable energy storage devices for special applications such as high-power devices with the advantages of being cheaper and more sustainable than the Li-ion equivalents. The sodium ion cells consisting of polyanionic Na 3 V 2 (PO 4 ) 2 F 3 - hard carbon electrodes exhibit high power rate capabilities but limited cycle life, especially at high temperatures. To circumvent this drawback we herein conducted in-depth analyses of the origins of structural degradations occurring in Na 3 V 2 (PO 4 ) 2 F 3 electrodes upon long cycling. Vanadium dissolution with associated parasitic reactions is identified as one of the major reasons for cell failure. Its amount varies depending on the electrolyte, with NaTFSI-based electrolyte showing the least vanadium dissolution as the TFSI - anion decomposes without producing acidic impurities, in contrast to the NaPF 6 -based electrolyte. The dissolved vanadium species undergoes oxidation and reduction processes at the Na 3 V 2 (PO 4 ) 2 F 3 and HC electrodes, respectively, with the electrochemical signature of these processes being used as a fingerprint to identify state of health of the 18650 cells. Here, having found that surface reactivity is the primary cause of vanadium dissolution we provide methods to mitigate it by combining surface coating and optimized electrolyte formulation.

25 ENERGY STORAGE↗
DOE OSTI2025

Examples of X-Ray Characterization Techniques in Energy Storage Research

Lithium-ion batteries have revolutionized the portable electronics and transportation sectors. Their performance is often critically dependent on the crystal structures of the anode and cathode electrode materials, which must enable the transport and reversible storage of lithium ions into and out of the lattice. Because lithium is a low-Z element, characterization of materials for lithium-ion batteries can be particularly challenging. Regardless, X-ray techniques enable analysis of material structures to better understand how battery materials perform and degrade, particularly when combined with other materials characterization and electrochemical characterization techniques. While X-ray techniques are most often used in battery research for phase identification of crystal structures, X-ray characterization techniques are also used for a wide variety of other purposes. I will discuss several examples from my research with various collaborators on several projects that highlight the impact that X-ray characterization techniques can have on battery research. The first example will focus on low-temperature microwave-assisted solvothermal synthesis of vanadium-doped LiFePO4 cathode materials for lithium-ion batteries. (1,2) Through a combination of electrochemical and materials characterization, we determined that low temperature synthesis resulted in metastable phases that enabled incorporation of higher dopant levels than resulting from high-temperature synthesis of thermodynamically stable phases. Rietveld refinement of X-ray diffraction data enabled understanding of how lattice parameters changed with doping levels and synthesis temperature. X-ray absorption near edge spectroscopy enabled understanding of the vanadium and iron oxidation states to confirm how vacancies in the structure caused by doping were charge compensated. This was important to understand because the literature suggests doping can improve LiFePO4 electrical conductivity, which improves battery charge and discharge rates. The second example will focus on understanding residual strain in lithium metal anodes. Lithium-ion batteries typically use graphite anodes, but the charge-storage capacity can be theoretically improved ~10x by using lithium metal as the anode material instead. However, lithium anodes suffer from growth of high-aspect-ratio features, such as dendrites, that can pierce nanoporous polymer separators and lead to short circuits and fires. External pressure is commonly applied to cells to enable better morphological control. We hypothesized that applied pressure may promote strain and possibly work hardening during electrochemical cycling, which motivated us to look for evidence of residual strain in lithium metal cycled under applied pressure using X-ray diffraction and sin2(..psi..) analysis. We found that lithium electrodeposited under high pressure exhibited in-plane compressive strain and that that lithium electrodeposited under low pressure did not. (3) The residual strain that accompanies electrodeposition under high pressure may lead to work hardening, which may explain how a soft metal like lithium can puncture separators and why higher pressure does not always decrease short circuits. (4-6) References: 1) Harrison, K. L.; Manthiram, A. Microwave-Assisted Solvothermal Synthesis and Characterization of Metastable LiFe1- x (VO) x PO4 Cathodes. Inorganic chemistry 2011, 50(8), 3613-3620. 2) Harrison, K. L.; Bridges, C. A.; Paranthaman, M. P.; Segre, C. U.; Katsoudas, J.; Maroni, V. A.; Idrobo, J. C.; Goodenough, J. B.; Manthiram, A. Temperature Dependence of Aliovalent-Vanadium Doping in LiFePO4 Cathodes. Chemistry of Materials 2013, 25(5), 768-781. 3) Rodriguez, M. A.; Harrison, K. L.; Goriparti, S.; Griego, J. J.; Boyce, B. L.; Perdue, B. R. Use of a Be-Dome Holder for Texture and Strain Characterization of Li Metal Thin Films via Sin2 (..psi..) Methodology. Powder Diffraction 2020, 35(2), 89-97. 4) Jungjohann, K. L.; Gannon, R. N.; Goriparti, S.; Randolph, S. J.; Merrill, L. C.; Johnson, D. C.; Zavadil, K. R.; Harris, S. J.; Harrison, K. L. Cryogenic Laser Ablation Reveals Short-Circuit Mechanism in Lithium Metal Batteries. ACS Energy Letters 2021, 6(6), 2138-2144. 5) Harrison, K. L.; Merrill, L. C.; Long, D. M.; Randolph, S. J.; Goriparti, S.; Christian, J.; Warren, B.; Roberts, S. A.; Harris, S. J.; Perry, D. L. Cryogenic Electron Microscopy Reveals That Applied Pressure Promotes Short Circuits in Li Batteries. Iscience 2021, 24(12). 6) Harrison, K. L.; Goriparti, S.; Merrill, L. C.; Long, D. M.; Warren, B.; Roberts, S. A.; Perdue, B. R.; Casias, Z.; Cuillier, P.; Boyce, B. L. Effects of Applied Interfacial Pressure on Li-Metal Cycling Performance and Morphology in 4 M LiFSI in DME. ACS Applied Materials & Interfaces 2021, 13(27), 31668-31679.

batteries↗
DOE OSTI2025

Reinforced AEM Separators Based on Triblock Copolymers for Electrode-decoupled RFBs

Washington University in St. Louis (WUSTL), in collaboration with The University of Texas at San Antonio (UTSA) and Giner Inc. developed highly selective anion exchange membranes (AEMs) and a novel electrode-decoupled redox flow battery (RFB) for grid scale energy storage as part of the ARPA-E IONICS program (with connections to the DAYS program in the later part of the project). RFBs exhibit the crucial characteristic of system-level decoupled scaling of energy and power which makes them cost effective for the multi-GWh scales envisioned for grid-scale energy storage solutions. This has led to extensive (and deserved) research interest and attention. This project aimed to enhance the design space available for redox-flow batteries (RFBs) by enabling the long-term separation of disparate cationic (elemental) actives using a highly selective membrane separator, while concurrently permitting the transport of anions to balance charge. The approach proposed was to design and develop a highly selective anion-exchange membrane (AEM), which would in turn permit the design and development of electrode-decoupled RFBs. Pairs of (different element) cationic species with redox reactions exhibiting a large difference in their standard electrode potentials were identified to develop high voltage, high power RFBs while disrupting the existing paradigm of using a single element which can ionize to more than two soluble oxidation states (e.g.: Vanadium).

25 ENERGY STORAGE↗
NASA NTRS2017

Developing V-Xanes Oxybarometry for Probing Materials Formed in Reducing Environments in the Early Solar Disk

Vanadium exhibits four oxidation states (V(sup 2+), V(sup 3+), V(sup 4+) and V(sup 5+)) that have been shown to preferentially partition between melt phases dependent on redox conditions, spanning oxygen fugacity across more than 10 log units. We are developing synchrotron-based x-ray absorption spectroscopy of low-fugacity standards for the determination of V oxidation state in highly reducing conditions relevant to the early solar nebula.

Butterworth, A. L.↗
NASA NTRS2010

Oxidation States of Grim Glasses in EET79001 Based on Vanadium Valence

Gas-rich impact-melt (GRIM) glasses in SNC meteorites are very rich in Martian atmospheric noble gases and sulfur suggesting a possible occurrence of regolith-derived secondary mineral assemblages in these samples. Previously, we have studied two GRIM glasses, 506 and 507, from EET79001 Lith A and Lith B, respectively, for elemental abundances and spatial distribution of sulfur using EMPA (WDS) and FE-SEM (EDS) techniques and for sulfur-speciation using K-edge XANES techniques. These elemental and FE-SEM micro-graph data at several locations in the GRIM glasses from Shergotty (DBS), Zagami 994 and EET79001, Lith B showed that FeO and SO3 are positively correlated (SO3 represents a mixture of sulfide and sulfate). FE-SEM (EDS) study revealed that the sulfur-rich pockets in these glasses contain numerous micron-sized iron-sulfide (Fe-S) globules sequestered throughout the volume. However, in some areas (though less frequently), we detected significant Fe-S-O signals suggesting the occurrence of iron sulfate. These GRIM glasses were studied by K-edge microXANES techniques for sulfur speciation in association with iron in sulfur-rich areas. In both samples, we found the sulfur speciation dominated by sulfide with minor oxidized sulfur mixed in with various proportions. The abundance of oxidized sulfur was greater in 506 than in 507. Based on these results, we hypothesize that sulfur initially existed as sulfate in the glass precursor materials and, on shock-impact melting of the precursor materials producing these glasses, the oxidized sulfur was reduced to predominately sulfide. In order to further test this hypothesis, we have used microXANES to measure the valence states of vanadium in GRIM glasses from Lith A and Lith B to complement and compare with previous analogous measurements on Lith C (note: 506 and 507 contain the largest amounts of martian atmospheric gases but the gas-contents in Lith C measured by are unknown). Vanadium is ideal for addressing this re-dox issue because it has multiple valence states and is a well-studied element. Ferrous-dominated iron valences determined by microXANES on the Lith A and Lith B glasses provide little redox sensitivity. Vanadium valence measurements for impact glass in Lith C at three different locations yielded valence values of 3.1, 3.2 and 3.4 with inferred fO2 values of IW-0.7, IW-0.1 and IW+0.7, respectively. This range of oxygen-fugacity values is understandable because the glasses are shock-molten impact glasses which are heterogeneous in nature. Oxygen fugacity values obtained from the analysis of Fe-Ti oxides and Eu partitioning in pyroxenes from EET79001 Lith A and Lith B (host lithologies) were in the range of IW+0.3 to IW+1.9 suggesting that V in the Lith C impact glass was reduced in the impact process. Here, we examine whether the 506 from Lith A and 507 from Lith B GRIM glasses yield similar or different fO2 values from those of Lith C using the vanadium K-edge microXANES technique.

Sutton, S. R.↗
NASA NTRS1992

Nonequilibrium synthesis of NbAl3 and Nb-Al-V alloys by laser cladding. II - Oxidation behavior

Isothermal oxidation behaviors of NbAl3 alloy synthesized by laser cladding were investigated at temperatures between 800 and 1400 C, and the effect of vanadium microalloying on the oxidation of the laser-clad alloy was examined. The oxidation kinetics of the two alloys were monitored using thermal gravimetric weight gain data, and the bulk and surface chemistries were analyzed using XRD and XPS, respectively. It was found that NbAl3 did not form an exclusive layer of protective Al2O3. The oxidation products at 800 C were found to be a mixture of Nb2O5 and Al2O3. At 1200 C, a mixture of NbAlO4, Nb2O5, and Al2O3 formed; and at 1400 C, a mixture of NbAlO4, Al2O3, NbO2, NbO(2.432), and Nb2O5 formed. The addition of V led to a dramatic increase of the oxidation rate, which may be related to the formation of (Nb, V)2O5 and VO2, which grows in preference to protective Al2O3.

Haasch, R. T.↗
NASA NTRS1976

Microelectronic components and metallic oxide studies and applications

The project involved work in two basic areas: (1) Evaluation of commercial screen printable thick film conductors, resistors, thermistors and dielectrics as well as alumina substrates used in hybird microelectronics industries. Results of tests made on materials produced by seven companies are presented. (2) Experimental studies on metallic oxides of copper and vanadium, in an effort to determine their electrochemical properties in crystalline, powder mixtures and as screen printable thick films constituted the second phase of the research effort. Oxide investigations were aimed at finding possible applications of these materials as switching devices memory elements and sensors.

Williams, L., Jr.↗
NASA NTRS2004

A New Oxygen Barometer for Solar System Basaltic Glasses Based on Vanadium Valence

The determination of oxidation conditions for basaltic magmas derived by the melting of planetary mantles is critical to our understanding of the nature and evolution of planetary interiors. Yet, these determinations are compromised in terrestrial and especially extraterrestrial basalts by our analytical and computational methods for estimating oxygen fugacity (fO2). For example, mineralogical barometers (1, 2) can be reduced in effectiveness by subsolidus re-equilibration of mineral assemblages, inversion of mineralogical data to melt characteristics, and deviations of the natural mineral compositions from ideal thermodynamic parameters.

Karner, J. M.↗
DOE OSTI2023

High-Field Nuclear Magnetic Resonance (NMR) Spectroscopy

Nuclear magnetic resonance (NMR) is a non-destructive spectroscopic technique that provides detailed molecular structural information via the electronic environments of nuclei in materials. Higher magnetic field strengths enhance the resolution of NMR, enabling discernment of unique chemical environments that might not be possible at low fields. Herein, the application of high-field NMR to catalyst and electrochemical system characterization are detailed. A brief description of NMR and quadrupolar nuclei are presented where the effects of magnetic field are described. Examples of high-field NMR are provided with particular focus on employing NMR to elucidate the structure of oxides of aluminum and vanadium for catalyst applications. The role of high-field NMR to conduct challenging experiments for energy storage materials is also explored and numerous other nuclei which require high-field measurement are briefly summarized.

Catalyst, Spectroscopy, NMR, High-field, Quadrupol↗
NASA NTRSDate not supplied

Vanadium Valence in MgAl2O4 Spinels at Reducing Conditions (IW to IW-5)

Vanadium is commonly a major or minor element in spinel structured oxides from a wide range of planetary materials [1-3]. Vanadium is stable in multiple valence states of 5+, 4+, 3+, and 2+ in natural systems, and spinel-structured oxides are known to host vanadium in 4+, 3+, and 2+ [4-6]. However, the understanding of 2+ stability at lower fO2 conditions has been hindered by lack of experiments at or below IW-1 conditions [5]. Insufficient experimental data is available due to the difficulty in controlling fO2 at low conditions in general, and the lack of appropriate standards for comparison to natural materials. Our progress on controlling fO2 in high pressure experimental samples has allowed us to create reducing conditions that are appropriate to studying V valence in spinels at fO2 relevant to natural reducing systems [7]. Here we extend this approach to study V in reduced conditions, at high temperatures. After at-tempting shorter durations and lower temperatures, we demonstrated the need for equilibration times > 6 hours at 1600 °C in order to approach equilibrium. Only then can we produce highly equilibrated samples that provide new insights into V valence at low fO2.

oxygen fugacity↗