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At least 1,675 records · Page 93
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Enhanced ferromagnetic order in Sr{sub 4}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} featuring canted [MnO{sub 4}]{sub ∞} spin chains of mixed-valent Mn(III)/Mn(IV). Aliovalent substitution of the Sr{sub 4−x}Ln{sub x}Mn{sup III}{sub 2+x}Mn{sup IV}{sub 1−x}O{sub 3}(GeO{sub 4}){sub 3} solid-solution

Crystals of Sr{sub 4−x}Ln{sub x}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} (x=0; x∼0.15 for Ln=La, Pr, Nd, Sm. Eu, Gd, Dy; x∼0.3 for Ln=Gd) were isolated upon using high-temperature, solid-state methods in molten-salt media. These compounds are isostructural with the previously reported Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3} (Ln=La, Sm, Gd) series that contains the same [MnO{sub 4}]{sub ∞} spin chains. The synthesis of the Sr{sub 4}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} (x=0) phase was carried out by a double aliovalent substitution with respect to the Sr{sup 2+} and Ge{sup 4+} ions that replace Na{sup +}/Ln{sup 3+} and As{sup 5+} in Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3}, respectively. The title series contains mixed-valent Mn(III)/Mn(IV) and shows a limited range of solid solution, both of which were not observed in the previously reported Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3} series. To form the Sr{sub 4−x}Ln{sub x}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} solid solution, one of the Sr{sup 2+} sites, i.e., the original Ln-site in Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3}, is partially substituted by Ln{sup 3+} in a statistical disorder of Sr{sub 1−x}/Ln{sub x}. Initial magnetic investigations of selected derivatives reveal higher ferromagnetic ordering temperatures than those reported for the Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3} series, presumably attributed to a lesser degree of canting as a result of introducing non-Jahn–Teller Mn{sup 4+} ions. Also intriguing is the observation of multiple anomalies at low temperatures which appear to be of electronic origins. - Graphical abstract: Sr{sub 4−x}Ln{sub x}Mn(III){sub 2+x}Mn(IV){sub 1−x}O{sub 3}(GeO{sub 4}){sub 3}. Display Omitted - Highlights: • Double aliovalent substitution: Sr{sub 4}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} with respect to Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3}. • Solid solution with respect to statistical disorder of Sr{sub 1−x}Ln{sub x} in one of the two Sr sites. • Mn{sup 3+}/Mn{sup 4+} magnetic ions are spatially arranged in a triangular kagomé fashion. • Enhanced ferromagnetic ordering attributed to doping non-Jahn–Teller Mn{sup 4+}.

36 MATERIALS SCIENCE↗
DOE OSTI2015

In Situ Fixation of Metal(loid)s in Contaminated Soils: A Comparison of Conventional, Opportunistic, and Engineered Soil Amendments

This study aimed to assess and compare the in vitro and in vivo bioaccessibility/bioavailability of As and Pb in a mining contaminated soil (As, 2267 mg kg –1 ; Pb, 1126 mg kg –1 ), after the addition of conventional (phosphoric acid), opportunistic [water treatment residues (WTRs)], and engineered [nano- and microscale zero valent iron (ZVI)] amendments. Phosphoric acid was the only amendment that could significantly decrease Pb bioaccessibility with respect to untreated soil (41 and 47% in the gastric phase and 2.1 and 8.1% in the intestinal phases, respectively), giving treatment effect ratios (TERs, the bioaccessibility in the amended soil divided by the bioaccessibility in the untreated soil) of 0.25 and 0.87 in the gastric and intestinal phase, respectively. The in vivo bioavailability of Pb decreased in the phosphate treatment relative to the untreated soil (6 and 24%, respectively), and also in the Fe WTR 2% (12%) and nZVI-2 (13%) treatments. The ZVI amendments caused a decrease in As bioaccessibility, with the greatest decrease in the nZVI2-treated soil (TERs of 0.59 and 0.64 in the gastric and intestinal phases, respectively). Furthermore, arsenic X-ray absorption near-edge spectroscopy analysis indicated that most of the As in the untreated soil was present as As(V) associated with Fe mineral phases, whereas in the treated soil, the proportion of arsenosiderite increased. Arsenite was present only as a minor species (3–5%) in the treated soils, with the exception of an nZVI treatment [~14% of As(III)], suggesting a partial reduction of As(V) to As(III) caused by nZVI oxidation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Stochastic Simulation of Isotopic Exchange Mechanisms for Fe(II)-Catalyzed Recrystallization of Goethite

Understanding Fe(II)-catalyzed transformations of Fe(III)- (oxyhydr)oxides is critical for correctly interpreting stable isotopic distributions and for predicting the fate of metal ions in the environment. Recent Fe isotopic tracer experiments have shown that goethite undergoes rapid recrystallization without phase change when exposed to aqueous Fe(II). The proposed explanation is oxidation of sorbed Fe(II) and reductive Fe(II) release coupled 1:1 by electron conduction through crystallites. Given the availability of two tracer exchange data sets that explore pH and particle size effects (e.g., Handler et al. Environ. Sci. Technol. 2014, 48, 11302-11311; Joshi and Gorski Environ. Sci. Technol. 2016, 50, 7315-7324), we developed a stochastic simulation that exactly mimics these experiments, while imposing the 1:1 constraint. We find that all data can be represented by this model, and unifying mechanistic information emerges. At pH 7.5 a rapid initial exchange is followed by slower exchange, consistent with mixed surface- and diffusion-limited kinetics arising from prominent particle aggregation. At pH 5.0 where aggregation and net Fe(II) sorption are minimal, that exchange is quantitatively proportional to available particle surface area and the density of sorbed Fe(II) is more readily evident. Our analysis reveals a fundamental atom exchange rate of ~10-5 Fe nm-2 s-1, commensurate with some of the reported reductive dissolution rates of goethite, suggesting Fe(II) release is the rate-limiting step in the conduction mechanism during recrystallization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Giant Magnetoelectric Coupling and Magnetic-Field-Induced Permanent Switching in a Spin Crossover Mn(III) Complex

We investigate giant magnetoelectric coupling at a Mn 3+ spin crossover in [Mn III L]BPh 4 (L = (3,5-diBr-sal) 2 323) with a field-induced permanent switching of the structural, electric, and magnetic properties. An applied magnetic field induces a first-order phase transition from a high spin/low spin (HS-LS) ordered phase to a HS-only phase at 87.5 K that remains after the field is removed. We observe this unusual effect for DC magnetic fields as low as 8.7 T. The spin-state switching driven by the magnetic field in the bistable molecular material is accompanied by a change in electric polarization amplitude and direction due to a symmetry-breaking phase transition between polar space groups. The magnetoelectric coupling occurs due to a γη 2 coupling between the order parameter γ related to the spin-state bistability and the symmetry-breaking order parameter η responsible for the change of symmetry between polar structural phases. We also observe conductivity occurring during the spin crossover and evaluate the possibility that it results from conducting phase boundaries. We perform ab initio calculations to understand the origin of the electric polarization change as well as the conductivity during the spin crossover. Thus, in this work, we demonstrate a giant magnetoelectric effect with a field-induced electric polarization change that is 1/10 of the record for any material.

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

Epitaxial growth, magnetoresistance, and electronic band structure of GdSb magnetic semimetal films

Motivated by observations of extreme magnetoresistance (XMR) in bulk crystals of rare-earth monopnictide (RE-V) compounds and emerging applications in novel spintronic and plasmonic devices based on thin-film semimetals, we have investigated the electronic band structure and transport behavior of epitaxial GdSb thin films grown on III-V semiconductor surfaces. The Gd 3 + ion in GdSb has a high spin S=7/2 and no orbital angular momentum, serving as a model system for studying the effects of antiferromagnetic order and strong exchange coupling on the resulting Fermi surface and magnetotransport properties of RE-Vs. Here, we present a surface and structural characterization study mapping the optimal synthesis window of thin epitaxial GdSb films grown on III-V lattice-matched buffer layers via molecular-beam epitaxy. To determine the factors limiting XMR in RE-V thin films and provide a benchmark for band-structure predictions of topological phases of RE-Vs, the electronic band structure of GdSb thin films is studied, comparing carrier densities extracted from magnetotransport, angle-resolved photoemission spectroscopy (ARPES), and density-functional theory (DFT) calculations. ARPES shows a hole-carrier rich, topologically trivial, semimetallic band structure close to complete electron-hole compensation, with quantum confinement effects in the thin films observed through the presence of quantum-well states. DFT-predicted Fermi wave vectors are in excellent agreement with values obtained from quantum oscillations observed in magnetic field-dependent resistivity measurements. An electron-rich Hall coefficient is measured despite the higher hole-carrier density, attributed to the higher electron Hall mobility. The carrier mobilities are limited by surface and interface scattering, resulting in lower magnetoresistance than that measured for bulk crystals.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Near-IR Spectroscopy of Luminous LoBAL Quasars at 1 < z < 2.5

We present near-IR spectroscopy of 22 luminous low-ionization broad absorption line quasars (LoBAL QSOs) at redshift 1.3 1 there is no clear difference in their optical emission line properties. We do not see particularly weak [O iii] or strong Fe ii emission. The LoBAL QSOs do not show a stronger prevalence of ionized gas outflows as traced by the [O iii] line, compared to normal QSOs of similar luminosity. We conclude that the optical–MIR properties of LoBAL QSOs are consistent with the general quasar population and do not support them to constitute a special phase of active galactic nucleus evolution.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1981

IUE observations of mass ejection by the close binary system AO Cassiopeiae

It is noted that 11 high-resolution spectra in the far-ultraviolet and two high-resolution spectra in the mid-ultraviolet were obtained. A high-velocity stellar wind exists as indicated by narrow shortward-displaced absorption features superposed on the P Cygni lines of N V, Si IV, and C IV. Absorption lines caused by N IV and C III are present and show nonorbital velocities of about -50 to -150 km/sec. Several weak photospheric lines of the primary star are detected. A few lines of Fe IV and Fe V are detectable near phase 0.50 and, less prominently, near phase 0.00. It is noted that the He II absorption line appears doubled except near phases 0.00 and 0.50 and that the weaker component appears to be attributable to the secondary component of the system. The mean velocity of the stellar wind is -1879 + or - 51(p.e.) km/sec and is nearly constant over the period of observation, although the absorption strength is found to vary.

Mccluskey, G. E.↗
NASA NTRS1986

A study of hard X-ray associated meter-decameter bursts observed on December 19, 1979

The results of a study of the relationship of a complex meter-decameter wavelength radio burst observed with the Clark Lake E-W and N-S interferometers, with a hard X-ray burst observed with the X-ray spectrometer aboard ISEE-3 are presented. The radio burst consisted of several type III's, reverse drift type III's, a U burst, and type II and type IV bursts. The X-ray emission was also complex. The radio as well as hard X-ray emissions were observed before the flash phase of the flare; they were not always associated and it is conjectured that this may constitute evidence for acceleration of electrons high in the corona. On the other hand, all components of the reverse drift burst were associated with hard X-ray subpeaks, indicating multiple injection of electron beams along field lines with different density gradients. While the type II burst appeared to be related to the hard X-ray burst, a detailed correspondence between individual features of the radio and hard X-ray burst emissions could not be found. The type IV burst started after all hard X-ray emissions ceased. Its source appeared to be a magnetic arch, presumably containing energetic electrons reponsible for the gyrosynchrotron radiation of type IV.

Kundu, M. R.↗
NASA NTRS2011

The Kepler Light Curves of V1504 Cygni and V344 Lyrae: A Study of the Outburst Properties

We examine the Kepler light curves of V1504 Cyg and V344 Lyr, encompassing approximately 460 d at 1 min cadence. During this span each system exhibited approximately 40 outbursts, including four superoutbursts. We find that, in both systems, the normal outbursts lying between two superoutbursts increase in duration by a factor approximately 1.2 - 1.7, and then reset to a small value after the following superoutburst. In V344 Lyr the trend of quiescent intervals between normal outbursts is to increase to a local maximum about half way through the supercycle the interval from one superoutburst to the next - and then to decrease back to a small value by the time of the next superoutburst, whereas for V1504 Cyg the quiescent intervals are relatively constant during the supercycle. Both of these trends are inconsistent with the Osaki's thermal-tidal model, which robustly predicts a secular increase in the quiescent intervals between normal outbursts during a supercycle. Also, most of the normal outbursts have an asymmetric, fast-rise/slower-decline shape, which would be consistent with outbursts triggered at large radii. The exponential rate of decay of the plateau phase of the superoutbursts is 8 d mag(sup -1) for approximately 1504 Cyg and 12 d mag(sup -1) for V344 Lyr. This time scale gives a direct measure of the VISCOUS time scale III the outer accretion disk given the expectation that the entire disk is in the hot, viscous state during superoutburst. The resulting constraint on the Shakura-Sunyaev parameter, alpha(sub hot) approximately equal to 0.1, is consistent with the value inferred from the fast dwarf nova decays. By looking at the slow decay rate for superoutbursts, which occur in systems below the period gap, in combination with the slow decay rate in one long outburst above the period gap (in U Gem), we infer a steep dependence of the decay rate on orbital period for long outbursts. We argue that this relation implies a steep dependence of alpha(sub cold) on orbital period, which may be consistent with recent findings of Patterson, and is consistent with tidal torquing as being the dominant angular momentum transport mechanism in quiescent disks in interacting binary systems.

Cannizzo, John K.↗
NASA NTRSDate not supplied

Flight Performance and Stability of Space Launch System Core Stage Thrust Vector Control

The Space Launch System (SLS) Core Stage (CS) Thrust Vector Control (TVC) system is comprised of eight mechanical feedback Shuttle heritage Type III TVC actuators and four RS-25 engines, each attached to a Shuttle heritage gimbal block/bearing. The Core Stage TVC shares vehicle control authority with the SLS 5-segment Solid Rocket Boosters (SRBs) during boost phase flight, and is the sole means of vehicle flight control during in exoatmospheric flight following SRB separation. TVC responses during Green Run Hot Fire (GRHF) testing revealed that the TVC did not meet its performance specifications. Step and frequency responses exhibited unexpected departures from prior laboratory data and modeled behavior. Post-test analysis determined that the characteristics of the structure and gimbal friction are significantly influenced by the thrust-loaded conditions, and the command avionics exhibited a small but important gain nonlinearity. Using the available test data, the design team augmented the flight control TVC models to bound the observed results and include the additional fidelity needed for vehicle flight control analysis so as to build sufficient rationale for flight certification. Prior to the Green Run tests, “simplex” linear models typically used for flight control analysis did not include gimbal friction and other nonlinearities owing to long-standing assumptions that these effects were negligible in the Shuttle Orbiter TVC system. Following the Green Run findings, simulation analysis of the flight dynamics in the time and frequency domain revealed the propensity for a flight control limit cycle oscillation (LCO) if friction and structural compliances fell near the edges of test-predicted bounds. While the “most probable” models did not predict an in-flight LCO, the SLS Program conservatively proceeded with a system-wide evaluation and ultimate acceptance of the possibility for a small amplitude, low-frequency TVC LCO in flight. A final validation of the extensive test and modeling effort occurred when the first flight of SLS successfully demonstrated the fully integrated performance of the vehicle’s TVC system This paper is the final installment in a seven-paper series surveying the design, engineering, test validation, and flight performance of the Core Stage Thrust Vector Control system. In this paper, the development of flight rationale in light of the TVC responses observed in Green Run is discussed, along with a review of the flight telemetry illustrating the correlation of the preflight predictions with the observed performance.

John H. Wall↗
NASA NTRS2001

Participation of HNO3 CIMS Instrument in the Sage III Ozone Loss and Validation Experiment (SOLVE)

This project was part of a larger SOLVE project led by Paul Wennberg at California Institute of Technology. The work completed on this project included participating in the installation and preflight testing of a new chemical ionization mass spectrometer for measuring gas and particle phase nitric acid on the ER-2. The investigators subsequently participated in SOLVE where additional instrument improvements were made and a substantial data set was generated. The two Georgia Tech investigators that participated in this work (Fred Eisele and Dave Tanner) had previously been responsible for much of the design and construction of the ion source and mass spectrometer which would be used to measure HNO3 in SOLVE, with Caltech focusing on inlets, calibration, gas supplies/pumping computer control, and overall integration. Thus, a similar focus remained during the SOLVE measurements though all investigators worked on most if not all aspects of the instrument at some point in the mission. Some of the more interesting results from the study included measurements of nitric acid on what are thought to be 5-20 microns diameter individual particles which could supply a local mechanism for HNO3 removal, Nitric acid measurements on SOLVE were completed as a collaborative effort with a great deal of overlap between this project and the larger parent project led by Paul Wennberg. As such, the instrumentation used, its operation, and the resulting measurements are far more fully discussed in the attached report (appendix A) which describes the joint SOLVE nitric acid measurement effort.

Eisele, F. L.↗
DOE OSTI2025

Trends in spatial correlations, two-phase coexistence, and criticality in a class of type-2 Schloegl models for autocatalysis

A class of type-2 Schloegl models is considered for particles on a square lattice with variable-range cooperativity. These models involve: (i) spontaneous particle annihilation at rate p; (ii) autocatalytic particle creation at unoccupied sites (i, j) with n ⩾ 2 particles within a specified neighborhood, Ω 𝑁 (i, j), of sites at rate $k_n$ = $\frac{^{(^n_2)}}{_{(^N_2)}}$ = $\frac{n{(n-1)}}{_{N(N-1)}}$; and (iii) possible spontaneous particle creation at unoccupied sites at “small” rate ɛ ⩾ 0. In some cases, Ω 𝑁 just includes all symmetry-equivalent sites at a single specific distance 𝑑 (in units of lattice constants) from the unoccupied site, e.g., 𝑑 = 1 (nearest-neighbor sites) where 𝑁 = 4, or 𝑑 = √5 (or √13 or…) where 𝑁 = 8. In other cases, Ω 𝑁 includes sites multiple distances from the unoccupied site, e.g., 𝑑 = {1,√2}, where 𝑁 = 8. Kinetic Monte Carlo (KMC) simulation reveals that these models exhibit a nonequilibrium discontinuous phase transition between high- and low-density states below a critical point, ɛ < ɛ c , with generic two-phase coexistence (2PC) at least for smaller 𝑁. With some exceptions, there is an approach toward mean-field behavior with increasing 𝑁 (so the regime of generic 2PC shrinks, and ɛ c approaches the mean-field value of 1/27). Additional insight into trends is provided by analysis of the exact master equations for the models via hierarchical truncation. These truncations utilize suitably tailored pair approximations which reflect the dominant nonequilibrium spatial correlations. These correlations in turn are shown to reflect the details of the autocatalytic particle creation process. For spatially heterogeneous states, the truncations produce coupled sets of lattice differential equations (LDE) which can describe orientation-dependent propagation of an interface between high- and low-density steady states for ɛ < ɛ c . Pair approximation values of 𝑝 = 𝑝 eq where the interface is stationary, and its orientation-dependence, are in semiquantitative agreement with KMC results. In conclusion, this comparison accounts for propagation failure in the LDE which complicates interpretation.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Advanced Analysis of X-ray Fluorescence Measurements of the Interfacial Density of Eu Ions at Liquid–Liquid Interfaces for Solvent Back-Extraction

X-ray fluorescence near total reflection (XFNTR) is the primary technique used to measure the element-specific interfacial density of ions at liquid−liquid interfaces. Fluorescence from ions in the bulk liquids can complicate the determination of the interfacial density; consequently, measurements have been previously limited to samples without ions in the upper phase and with concentrations on the order of 10 μM or less in the lower phase. We modify the analysis of XFNTR data to account for ions in both bulk phases, then demonstrate its use in the context of rare-earth separations processes. In a model of ion stripping (i.e., back-extraction), dodecane solutions of di(2-ethylhexyl)- phosphoric acid (HDEHP) loaded with Eu(III) at the 1 mM level are placed in contact with either pure water or aqueous solutions of nitric or citric acid at pH 3. XFNTR measurements of equilibrated, quiescent samples reveal that citric acid solutions produce a disproportionately large depletion of ions from the interface compared to that from the bulk organic solution, whereas stripping by pure water or nitric acid solutions is negligible. As a result, this advance in the methodology of XFNTR may have broad applicability to the investigation of metal ions in chemical and biological processes at liquid−liquid interfaces.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Local cation ordering in compositionally complex Ruddlesden–Popper n = 1 oxides

The Ruddlesden–Popper (RP) layered perovskite structure is of great interest due to its inherent tunability, and the emergence and growth of the compositionally complex oxide (CCO) concept endows the RP family with further possibilities. Here, a comprehensive assessment of thermodynamic stabilization, local order/disorder, and lattice distortion was performed in the first two reported examples of lanthanum-deficient La n+1 B n O 3n+1 (n = 1, B = Mg, Co, Ni, Cu, Zn) obtained via various processing conditions. Chemical short-range order (CSRO) at the B-site and the controllable excess interstitial oxygen (δ) in RP-CCOs are uncovered by neutron pair distribution function analysis. Reverse Monte Carlo analysis of the data, Metropolis Monte Carlo simulations, and extended x-ray absorption fine structure analysis implies a modest degree of magnetic element segregation on the local scale. Further, ab initio molecular dynamics simulations results obtained from special quasirandom structure disagree with experimentally observed CSRO but confirm Jahn–Teller distortion of CuO 6 octahedra. These findings highlight potential opportunities to control local order/disorder and excess interstitial oxygen in layered RP-CCOs and demonstrate a high degree of freedom for tailoring application-specific properties. They also suggest a need for expansion of theoretical and data modeling approaches in order to meet the innate challenges of CCO and related high-entropy phases.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Novel Non-Vacuum Fabrication of Solid State Lithium Ion Battery Components

The purpose of this Cooperative Research and Development Agreement (CRADA) between Oak Ridge National Laboratory (ORNL) and Planar Energy Devices, Inc. was to develop large-scale electroless deposition and photonic annealing processes associated with making all-solid-state lithium ion battery cathode and electrolyte layers. However, technical and processing difficulties encountered in 2011 resulted in the focus of the CRADA being redirected solely to annealing of the cathode thin films. In addition, Planar Energy Devices de-emphasized the importance of annealing of the solid-state electrolytes within the scope of the project, but materials characterization of stabilized electrolyte layers was still of interest. All-solid-state lithium ion batteries are important to automotive and stationary energy storage applications because they would eliminate the problems associated with the safety of the liquid electrolyte in conventional lithium ion batteries. However, all-solid-state batteries are currently produced using expensive, energy consuming vacuum methods suited for small electrode sizes. Transition metal oxide cathode and solid-state electrolyte layers currently require about 30-60 minutes at 700-800°C vacuum processing conditions. Photonic annealing requires only milliseconds of exposure time at high temperature and a total of <1 min of cumulative processing time. As a result, these processing techniques are revolutionary and highly disruptive to the existing lithium ion battery supply chain. The current methods of producing all-solid-state lithium ion batteries are only suited for small-scale, low-power cells and involve high-temperature vacuum techniques. Stabilized LiNi x Mn y Co z Al 1-x-y-z O 2 (NMCA) nanoparticle films were deposited onto stainless steel substrates using Planar Energy Devices’ streaming process for electroless electrochemical deposition (SPEED). Since successful SPEED trials were demonstrated by Planar Energy Devices with NMCA prior to 2010, this high-voltage (i.e. 5 V) cathode material was the focus of the project. ORNL had also shown in prior work that photonic annealing can be used to anneal conventionally coated cathode metal oxide structures into the active crystalline phase. Planar Energy Devices also had demonstrated SPEED with solid electrolyte layers consisting of LiGaAlSPO 4 prior to the start of the project.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2021

Reduction of Vanadium(V) by Iron(II)-Bearing Minerals

Fe(II)-bearing minerals (magnetite, siderite, green rust, etc.) are common products of microbial Fe(III) reduction, and they provide a reservoir of reducing capacity in many subsurface environments that may contribute to the reduction of redox active elements such as vanadium; which can exist as V(V), V(IV), and V(III) under conditions typical of near-surface aquatic and terrestrial environments. To better understand the redox behavior of V under ferrugenic/sulfidogenic conditions, we examined the interactions of V(V) (1 mM) in aqueous suspensions containing 50 mM Fe(II) as magnetite, siderite, vivianite, green rust, or mackinawite, using X-ray absorption spectroscopy at the V K-edge to determine the valence state of V. Two additional systems of increased complexity were also examined, containing either 60 mM Fe(II) as biogenic green rust (BioGR) or 40 mM Fe(II) as a mixture of biogenic siderite, mackinawite, and magnetite (BioSMM). Within 48 h, total solution-phase V concentrations decreased to <20 µM in all but the vivianite and the biogenic BiSMM systems; however, >99.5% of V was removed from solution in the BioSMM and vivianite systems within 7 and 20 months, respectively. The most rapid reduction was observed in the mackinawite system, where V(V) was reduced to V(III) within 48 h. Complete reduction of V(V) to V(III) occurred within 4 months in the green rust system, 7 months in the siderite system, and 20 months in the BioGR system. Vanadium(V) was only partially reduced in the magnetite, vivianite, and BioSMM systems, where within 7 months the average V valence state stabilized at 3.7, 3.7, and 3.4, respectively. The reduction of V(V) in soils and sediments has been largely attributed to microbial activity, presumably involving direct enzymatic reduction of V(V); however the reduction of V(V) by Fe(II)-bearing minerals suggests that abiotic or coupled biotic–abiotic processes may also play a critical role in V redox chemistry, and thus need to be considered in modeling the global biogeochemical cycling of V.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

Photometric Observations of Soils and Rocks at the Mars Exploration Rover Landing Sites

The Panoramic Cameras (Pancam) on the Spirit and Opportunity Mars Exploration Rovers have acquired multispectral reflectance observations of rocks and soils at different incidence, emission, and phase angles that will be used for photometric modeling of surface materials. Phase angle coverage at both sites extends from approx. 0 deg. to approx. 155 deg.

Johnson, J. R.↗