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NASA NTRS2008

Experimental Constraints on the Partitioning and Valence of V and Cr in Garnet and Coexisting Glass

A series of experiments with garnet and coexisting melt have been carried out across a range of oxygen fugacities (near hematite-magnetite (HM) to below the iron-wustite (IW) buffers) at 1.7 GPa to study the partitioning and valence of Cr and V in both phases. Experiments were carried out in a non end loaded piston cylinder apparatus, and the run products were analyzed with electron microprobe and xray absorption near edge structure (XANES) analysis at beamline 13-ID at the Advanced Photon Source of Argonne National Lab. The valence of vanadium and chromium were determined using the position and intensity of the Ka pre-edge peaks, calibrated on a series of Cr and Vbearing standard glasses. This technique has been applied to V and Cr in glasses and V in spinels previously, and in these isotropic phases there are no orientational effects on the XANES spectra (Righter et al., 2006, Amer. Mineral. 91, 1643-1656). We also now demonstrate this to be true for V and Cr in garnet. Also, previous work has shown that V has a higher valence in the glass (or melt) than in the coexisting spinel. This is also true for V in garnet-glass pairs in this study. Vanadium valence in garnets varies from 2.7 below the IW buffer to 3.7 near HM, and for coexisting glass it varies from 3.2 to 4.3. Vanadium valence measured in some natural garnets from mantle localities indicates V in the more reduced range at 2.5. Comparisons will be made between fO2 estimated from V valence and other methods for garnet-bearing mantle samples. In contrast, Cr valence measured in garnet and coexisting glass for all experimental and natural samples is 2.9- 3.0, suggesting that the valence of Cr does not vary within either phase across a large fO2 range. These results demonstrate that while V varies from 2+ to 3+ to 4+ in garnet-melt systems, Cr does not, and this will ultimately affect the partitioning behavior of these two elements in natural systems. Garnet/melt D(Cr) are between 12 and 17 across this range of fO2, whereas D(V) has the highest partition coefficient approx.3, near the IW buffer where the valence of V is almost entirely 3+.

Righter, K.↗

NASA NTRS1980

Effects of impurities in coal-derived liquids on accelerated hot corrosion of superalloys

A Mach 0.3 burner rig was used to determine the effects of potential coal derived liquid fuel impurity combustion of products on hot corrosion in IN-100, IN-792, IN_738, U-700, Mar M-509, and 304 stainless steel. The impurities, added as aqueous solutions to the combustor, were salts of sodium, potassium, vanadium, molybdenum, tungsten, phosphorus, and lead. Extent of attack was determined by metal consumption and compared to the effects of sodium alone. Vanadium, molybdenum, tungsten, phosphorous, and lead in combination with sodium all resulted in increased attack as compared with sodium alone at some temperatures, apparently due in large part to the extension of the formation of liquid deposits. Varying the sodium-potassium ratio had little effect for ratios less than 1:3 for which reduced, but measurable, attack was observed.

Deadmore, D. L.↗

NASA NTRS1982

Ceramic thermal barrier coatings for gas turbine engines

The results of studies concerning the high temperature corrosion resistance of ZrO2-Y2O3, ZrO2-MgO, and Ca2SiO4 plasma-sprayed coatings, which may be used as gas turbine engine thermal barriers, are reported. The coatings were evaluated in atmospheric burner rig and pressurized passage tests, using GT No. 2 fuel in pure form and with sodium, sulfur and vanadium corrosive impurities doping. It is found that, while the coatings performed well in both pressurized passage and burner rig tests with pure fuel chemical reactions between the ceramic coatings and combustion gases/condensates resulted in coating degradation with impure fuels. Chemical reactions between the ceramic coatings and vanadium compounds played a critical role in coating degradation.

Bratton, R. J.↗

NASA NTRS1984

Charring, Nonmelting Epoxy Foams

Addition of vanadium compounds prevents melting. For safety, structural plastic foam should turn into rigid char when it burns, without melting. Addition of small amounts of vanadium compounds to some epoxy resins promotes char formation.

Delano, C. B.↗

NASA NTRS1988

Analysis of microalloy precipitate reversion in steels

The influence of the ferrite to austenite allotropic transformation on the stability of MXn precipitates in an iron matrix is studied. In the MX phase, M is a group IVb or Vb transition metal, such as niobium, titanium, or vanadium. X is carbon or nitrogen and n is in the range of 0.75-1.0. The application of the present model to the case of vanadium carbide reversion in a microalloyed steel is discussed.

Michal, G. M.↗

NASA NTRS1989

Gettering of donor impurities by V in GaAs and the growth of semi-insulating crystals

Vanadium added to the GaAs melt getters shallow donor impurities (Si and S) and decreases their concentration in the grown crystals. This gettering is driven by chemical reactions in the melt rather than in the solid. Employing V gettering, reproducibly semi-insulating GaAs were grown by horizontal Bridgman and liquid-encapsulated Czochralski techniques, although V did not introduce any midgap energy levels. The compensation mechanism in these crystals was controlled by the balance between the native midgap donor EL2 and residual shallow acceptors. Vanadium gettering contributed to the reduction of the concentration of shallow donors below the concentration of acceptors. The present findings clarify the long-standing controversy on the role of V in achieving semi-insulating GaAs.

Ko, K. Y.↗

NASA NTRS1990

Reactivity of pi-complexes of Ti, V, and Nb towards dithioacetic acid: Synthesis and structure of novel metal sulfur-containing complexes

In order to use sulfur-containing resources economically and with minimal environmental damage, it is important to understand the desulfurization processes. Hydrodesulfurization, for example, is carried out on the surface of a heterogeneous metal sulfide catalyst. Studies of simple, soluble inorganic systems provide information regarding the structure and reactivity of sulfur-containing compounds with metal complexes. Further, consistent with recent trends in materials chemistry, many model compounds warrant further study as catalyst precursors. The reactivity of low-valent organometallic sandwich pi-complexes toward dithiocarboxylic acids is described. For example, treatment of bisbenzene vanadium with CH3CSSH affords a divanadium tetrakis(dithioacetate) complex. The crystallographically determined V-V bond distance, 2.800(2), is nearly the same as the V-V bond distance in a V(mu-nu squared-S2)2V' unit in the mineral patonite (VS4)n. The stability of the V2S4 core in the dimer is demonstrated by evidence of V2S4(+) in the mass spectrum (70 eV, solid probe) of the vanadium dimer. Several other systems relevant to HDS catalysis are also discussed.

Duraj, Stan A.↗

NASA NTRS2004

Lunar and Planetary Science XXXV: Special Session: Oxygen in the Solar System, II

The Special Session: Oxygen in the Solar System, II, included the following reports:Evolution of Oxygen Isotopes in the Solar Nebula; Disequilibrium Melting of Refractory Inclusions: A Mechanism for High-Temperature Oxygen; Isotope Exchange in the Solar Nebula; Oxygen Isotopic Compositions of the Al-rich Chondrules in the CR Carbonaceous Chondrites: Evidence for a Genetic Link to Ca-Al-rich Inclusions and for Oxygen Isotope Exchange During Chondrule Melting; Nebular Formation of Fayalitic Olivine: Ineffectiveness of Dust Enrichment; Water in Terrestrial Planets: Always an Oxidant?; Oxygen Barometry of Basaltic Glasses Based on Vanadium Valence Determination Using Synchrotron MicroXANES; A New Oxygen Barometer for Solar System Basaltic Glasses Based on Vanadium Valence; The Relationship Between Clinopyroxene Fe3+ Content and Oxygen Fugacity ; and Olivine-Silicate Melt Partitioning of Iridium.

Source record↗

NASA NTRS2005

Method for Determination of Less Than 5 ppm Oxygen in Sodium Samples

Alkali metals used in pumped loops or heat pipes must be sufficiently free of nonmetallic impurities to ensure long heat rejection system life. Life issues are well established for alkali metal systems. Impurities can form ternary compounds between the container and working fluid, leading to corrosion. This Technical Memorandum discusses the consequences of impurities and candidate measurement techniques to determine whether impurities have been reduced to suf.ciently low levels within a single-phase liquid metal loop or a closed two-phase heat transfer system, such as a heat pipe. These techniques include the vanadium wire equilibration, neutron activation analysis, plug traps, distillation, and chemical analysis. Conceptual procedures for performing vanadium wire equilibration purity measurements on sodium contained in a heat pipe are discussed in detail.

Reid, R. S.↗

NASA NTRS2013

New Class of Flow Batteries for Terrestrial and Aerospace Energy Storage Applications

Future sustainable energy generation technologies such as photovoltaic and wind farms require advanced energy storage systems on a massive scale to make the alternate (green) energy options practical. The daunting requirements of such large-scale energy systems such as long operating and cycle life, safety, and low cost are not adequately met by state-of-the-art energy storage technologies such as vanadium flow cells, lead-acid, and zinc-bromine batteries. Much attention is being paid to redox batteries specifically to the vanadium redox battery (VRB) due to their simplicity, low cost, and good life characteristics compared to other related battery technologies. NASA is currently seeking high-specific- energy and long-cycle-life rechargeable batteries in the 10-to-100-kW range to support future human exploration missions, such as planetary habitats, human rovers, etc. The flow batteries described above are excellent candidates for these applications, as well as other applications that propose to use regenerative fuel cells. A new flow cell technology is proposed based on coupling two novel electrodes in the form of solvated electron systems (SES) between an alkali (or alkaline earth) metal and poly aromatic hydrocarbons (PAH), separated by an ionically conducting separator. The cell reaction involves the formation of such SES with a PAH of high voltage in the cathode, while the alkali (or alkaline earth metal) is reduced from such an MPAH complex in the anode half-cell. During recharge, the reactions are reversed in both electrodes. In other words, the alkali (alkaline earth) metal ion simply shuttles from one M-PAH complex (SES) to another, which are separated by a metal-ion conducting solid or polymer electrolyte separator. As an example, the concept was demonstrated with Li-naphthalene//Li DDQ (DDQ is 2,3-Dichloro-5,6-dicyano- 1,4-benzoquinone) separated by lithium super ion conductor, either ceramic or polymer (solid polymer or gel polymer) electrolytes. The reactants are Li-naphthalene dissolved in tetrahydrofuran (THF) with a lithium salt of 1M LiBF4 (lithium tetra fluoroborate) in the anode compartment, and DDQ again dissolved in THF and also containing 1M LiBF4 salt in the cathode half-cell. The solid electrolyte separator used in the first set of experiments is a ceramic solid electrolyte, available from a commercial source. The open circuit voltage of the cells is close to 3.0 V, as expected from the individual half-cell voltages of Li-naphthalene and Li-DDQ. Upon discharge, the cell shows steady discharge voltage of 2.7 V, which confirms that the electrochemical processes do involve lithium ion shuttling from the anodic compartment to the cathode half-cell. The reversibility or rechargeability is demonstrated by charging the partially discharged cells (i.e., with lithium present in the DDQ half). Once again, a steady voltage close to 3.0 V was observed during charge, indicating that the system is quite reversible. In the subsequent concept-demonstration studies, the ceramic electrolyte has been replaced with a gel polymer electrolyte, e.g., PVDF-HFP (poly vinylene difluoride hexafluoropropene) gel, which has several advantages such as high ionic conductivity (almost comparable to liquid electrolyte and about 2 orders of magnitude better than the ceramic equivalent), lower cost, and possibly higher chemical stability at the anode. In addition, it can be bonded to the electrode by thermal fusion to form membrane electrode assemblies (MEAs), as is done in fuel cells.

Bugga, Ratnakumar V.↗

NASA NTRS2016

Detection of H2O and Evidence for TiO VO in an Ultra Hot Exoplanet Atmosphere.

We present a primary transit observation for the ultra-hot (Teq approx. 2400 K) gas giant expolanet WASP-121b, made using the Hubble Space Telescope Wide Field Camera 3 in spectroscopic mode across the 1.12-1.64 micron wavelength range. The 1.4 microns water absorption band is detected at high confidence (5.4(sigma)) in the planetary atmosphere. We also reanalyze ground-based photometric light curves taken in the B, r′, and z′ filters. Significantly deeper transits are measured in these optical bandpasses relative to the near-infrared wavelengths. We conclude that scattering by high-altitude haze alone is unlikely to account for this difference and instead interpret it as evidence for titanium oxide and vanadium oxide absorption. Enhanced opacity is also inferred across the 1.12-1.3 micron wavelength range, possibly due to iron hydride absorption. If confirmed, WASP-121b will be the first exoplanet with titanium oxide, vanadium oxide, and iron hydride detected in transmission. The latter are important species in M/L dwarfs and their presence is likely to have a significant effect on the overall physics and chemistry of the atmosphere, including the production of a strong thermal inversion.

Spectroscopy↗

NASA NTRS2018

Lifetimes of Multiply Alkylated Cyclopentane Oil in Contact with Various Metals, Evaluated with Vacuum Spiral Orbit Tribometer

The dependence of the lifetimes of small quantities of a Multiply Alkylated Cyclopentane (MAC) lubricant oil, Pennzane (Registered Trademark) 2001A (Nye Lubricants, Inc.), in rolling and sliding contact with different metals was evaluated with a vacuum spiral orbit tribometer. The metals were the bearing alloys 52100 steel, 440C steel, 17-4 PH steel and Nitinol 60 and the elements chromium, vanadium and titanium. The lifetimes of the lubricant oil on different metals fell into distinct groups with 52100 greater than 440C approx. Nitinol 60 greater than 17-4 PH for the order of the lifetimes of the steels and chromium greater than vanadium greater than titanium for the order of the lifetimes for the elements. The limited life of the small quantities of oil is assumed to be due to its consumption by the tribochemical reaction of the oil with the different metal bearing materials. The lifetimes are then inversely related to the reaction rates of the oil molecules with the various metals: the longest life of 52100 steel having the lowest reaction rate and the shortest life of titanium having the highest reaction rate. Mechanisms for the tribochemical reactions are discussed.

lubrication↗

NASA NTRS1999

Phase Composition and the Effect of Thermal Cycling for VH(sub x) V(sub 0.995) C(sub 0.005)H(sub x) and V(sub 0.975)Zr(sub 0.020)C(sub 0.005)H(sub x)

X-ray diffraction (XRD) studies were performed on hydride phases formed by vanadium and its carbon substituted alloys. It was previously found that thermal cycling of VHx across the B-y mixed phase region changed the reversible hydrogen storage capacity and other properties.

pressure-composition-temperature isotherms↗

NASA NTRS1964