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All sourcesNASA NTRSDOE OSTI
NASA NTRS1990

Catalysts for ultrahigh current density oxygen cathodes for space fuel cell applications

The objective of this research was to identify promising electrocatalyst/support systems for the oxygen cathode in alkaline fuel cells operating at relatively high temperatures, O2 pressures and current densities. A number of materials were prepared, including Pb-Ru and Pb-Ir pyrochlores, RuO2 and Pt-doped RuO2, and lithiated NiO. Several of these were prepared using techniques that had not been previously used to prepare them. Particularly interesting is the use of the alkaline solution technique to prepare the Pt-doped Pb-Ru pyrochlore in high area form. Well-crystallized Pb(2)Ru(2)O(7-y) was used to fabricate high performance O2 cathodes with relatively good stability in room temperature KOH. This material was also found to be stable over a useful potential range at approximately 140 C in concentrated KOH. Other pyrochlores were found to be either unstable (amorphous samples) or the fabrication of the gas-fed electrodes could not be fully optimized during this project period. Future work may be directed at this problem. High area platinum supported on conductive metal oxide supports produced mixed results: small improvements in O2 reduction performance for Pb(2)Ru(2)O(7-y) but a large improvement for Li-doped NiO at room temperature. Nearly reversible behavior was observed for the O2/OH couple for Li-doped NiO at approximately 200 C.

Tryk, D.↗
NASA NTRS1994

Theoretical Study of the First Transition Row Oxides and Sulfides

The first transition row oxides and sulfides are studied using several different levels of theory. The calculations show the bonding mechanism in the sulfides and oxides to be very similar. For the oxides, accurate experimental data allow the theoretical methods to be calibrated. The same level of theory is used to study the sulfides where there is far less experimental information. For ScO through MnO and CuO the coupled cluster singles and doubles technique including a perturbational estimate of the unliked triple excitations [CCSD(T)] yields spectroscopic constants ((tau)e, (omega)e, and D0) in good agreement with experiment. The triple excitations are found to be very important in achieving this accuracy. For FeO to NiO, the single determinant self-consistent-field (SCF) approach yields pi orbitals that are localized on the metal or oxygen. This appears to cause problems for the single reference techniques; this is discussed in detail for NiO. The complete-active-space SCF/internally contracted averaged coupled pair functional approach (CASSCF/ICACPF) works well for FeO to NiO. The calculation of accurate dipole moments is found to be very difficult.

Bauschlicher, Charles W., Jt.↗
NASA NTRS2009

Sulfur Speciation in the Martian Regolith Component in Shergottite Glasses

We have shown that Gas-Rich Impact-Melt (GRIM) glasses in Shergotty, Zagami, and EET79001 (Lith A and Lith B) contain Martian regolith components that were molten during impact and quenched into glasses in voids of host rock materials based on neutron-capture isotopes, i.e., Sm-150 excesses and Sm-149 deficits in Sm, and Kr-80 excesses produced from Br [1, 2]. These GRIM glasses are rich in S-bearing secondary minerals [3.4]. Evidence for the occurrence of CaSO4 and S-rich aluminosilicates in these glasses is provided by CaO-SO3 and Al2O3-SO3 correlations, which are consistent with the finding of gypsum laths protruding from the molten glass in EET79001 (Lith A) [5]. However, in the case of GRIM glasses from EET79001 (Lith B), Shergotty and Zagami, we find a different set of secondary minerals that show a FeO-SO3 correlation (but no MgOSO3 correlation), instead of CaO-SO3 and Al2O3-SO3 correlations observed in Lith A. These results might indicate different fluidrock interactions near the shergottite source region on Mars. The speciation of sulfur in these salt assemblages was earlier studied by us using XANES techniques [6], where we found that Lith B predominantly contains Fe-sulfide globules (with some sulfate). On the other hand, Lith A showed predominantly Casulfite/ sulfate with some FeS. Furthermore, we found Fe to be present as Fe2+ indicating little oxidation, if any, in these glasses. To examine the sulfide-sulfate association in these glasses, we studied their Fe/Ni ratios with a view to find diagnostic clues for the source fluid. The Fe-sulfide mineral (Fe(0.93)Ni(0.3)S) in EET79001, Lith A is pyrrhotite [7, 8]. It yields an Fe/Ni ratio of 31. In Shergotty, pyrrhotite occurs with a molar ratio of Fe:S of 0.94 and a Ni abundance of 0.12% yielding a Fe/Ni ratio of approx.500 [8]. In this study, we determined a NiO content of approx.0.1% and FeO/NiO ratio of approx.420 in S-rich globules in #507 (EET79001, Lith B) sample using FE-SEM. In the same sample (bulk), using EMPA, we determined a FeO/NiO ratio of approx.700 (raster mode). Using similar techniques, we determined a NiO content of approx.0.015% and a FeO/NiO ratio of approx.800 in #506 (EET79001, Lith A). Moreover, a NiO content of approx.150 ppm and 6.1% FeO were found in Lith A GRIM glasses using neutron activation analysis [9] yielding a FeO/NiO ratio of approx.420. The FeO/NiO ratios in secondary mineral phases in S-rich pockets of EET79001 (Lith A/B) and Shergotty are high (approx.400) compared to the FeO/NiO ratio of 31 in Lith A pyrrhotite. These results suggest similar kind of fluids interacted with different rock materials to yield the observed variations in GRIM glasses in EET79001 Lith A and B.

Rao, M. N.↗
NASA NTRS1973

Cyclic and isothermal oxidation behavior on some Ni-Cr alloys

It is shown experimentally that 3 wt.% Si and 3 wt.% Mn additions can substantially improve the oxidation resistance of Ni-20Cr under both isothermal and cyclic conditions at 1100 and 1200 C. This is especially true in cyclic oxidation. In all cases, Si offers a greater improvement than Mn; however, the advantage of Si is substantial only during cyclic oxidation at 1200 C. The Si additions which lead to alloys of improved oxidation resistance suppress the formation of NiO and NiCr2O4 even under the most severe test conditions. The mechanism of improvement afforded by Mn appears to be the formation of MnCr2O4 at the expense of NiO and NiCr2O4.

Lowell, C. E.↗
NASA NTRS1974

Investigation of the oxidation behavior of dispersion stabilized alloys when exposed to a dynamic high temperature environment

The oxidation behavior of TD-NiCr and TD-NiCrAlY alloys have been studied at 2000 and 2200 F in static and high speed flowing air environments. The TD-NiCrAlY alloys preoxidized to produce an Al2O3 scale on the surface showed good oxidation resistance in both types of environments. The TD-NiCr alloy which had a Cr2O3 oxide scale after preoxidation was found to oxidize more than an order of magnitude faster under the dynamic test conditions than at comparable static test conditions. Although Cr2O3 normally provides good oxidation protection, it was rapidly lost due to formation of volatile CrO3 when exposed to the high speed air stream. The preferred oxide arrangement for the dynamic test consisted of an external layer of NiO with a porous mushroom type morphology, an intermediate duplex layer of NiO and Cr2O3, and a continuous inner layer of Cr2O3 in contact with the alloy substrate. An oxidation model has been developed to explain the observed microstructure and overall oxidation behavior of all alloys.

Tenney, D. R.↗
NASA NTRS1985

Multikilowatt hydrogen-nickel oxide battery system

The potential of the H2-NiO battery for terrestrial applications was assessed. A multicell design approach that differs significantly from the aerospace individual pressure vessel was used. A number of experimental 100-Ah cells were built to evaluate the new design concepts and components. The experimental cells provided the input needed for a multicell battery design. It is found that new multicell H2-NiO battery has a number of potential advantages for aerospace applications such as the manned space station. The advantages are discussed, and a design concept is presented for a multikilowatt battery in a lightweight pressure vessel.

Dunlop, J. D.↗
NASA NTRS1987

Phase purity of NiCo2O4, a catalyst candidate for electrolysis of water

NiCo2O4 is shown to be difficult to obtain as a pure phase, and may never have been so obtained. High resolution x-ray diffractometry is required for its precise characterization. Film XRD is not likely to show the asymmetry in the spinel diffraction lines, caused by poorly crystallized NiO, as seen in diffractometer traces. The Co3O4 which is expected to accompany NiO as an impurity in NiCo2O4 syntheses has the same diffraction pattern as the binary oxide. Firings of the co-precipitated hydroxides at 300, 350, and 400 C, including one in pure O2, failed to produce single phase cobaltate. Scanning electron microscopy showed all the sintered products to range over several orders of magnitude in agglomerate/particle size. Surface areas by BET were all in the range 40 to 110 m sq/g, equivalent to particles of 200 to 100 Angstrom diameter. The spinel diffraction line breadths were compatible with those approximate dimensions.

Singer, J.↗
NASA NTRS1992

Implementation of quality improvement techniques for management and technical processes in the ACRV project

Total Quality Management (TQM) is a cooperative form of doing business that relies on the talents of everyone in an organization to continually improve quality and productivity, using teams and an assortment of statistical and measurement tools. The objective of the activities described in this paper was to implement effective improvement tools and techniques in order to build work processes which support good management and technical decisions and actions which are crucial to the success of the ACRV project. The objectives were met by applications in both the technical and management areas. The management applications involved initiating focused continuous improvement projects with widespread team membership. The technical applications involved applying proven statistical tools and techniques to the technical issues associated with the ACRV Project. Specific activities related to the objective included working with a support contractor team to improve support processes, examining processes involved in international activities, a series of tutorials presented to the New Initiatives Office and support contractors, a briefing to NIO managers, and work with the NIO Q+ Team. On the technical side, work included analyzing data from the large-scale W.A.T.E.R. test, landing mode trade analyses, and targeting probability calculations. The results of these efforts will help to develop a disciplined, ongoing process for producing fundamental decisions and actions that shape and guide the ACRV organization .

Raiman, Laura B.↗
NASA NTRS1998

Sintering and Creep Behavior of Plasma-Sprayed Zirconia and Hafnia Based Thermal Barrier Coatings

The sintering and creep of plasma-sprayed ceramic thermal barrier coatings under high temperature conditions are complex phenomena. Changes in thermomechanical and thermophysical properties and in the stress response of these coating systems as a result of the sintering and creep processes are detrimental to coating thermal fatigue resistance and performance. In this paper, the sintering characteristics of ZrO2-8wt%y2O3, ZrO2-25wt%CeO2-2.5wt%Y2O3, ZrO2-6w%NiO- 9wt%Y2O3, ZrO2-6wt%Sc2O3-2wt%y2O3 and HfO2-27wt%y2O3 coating materials were investigated using dilatometry. It was found that the HfO2-Y2O3 and baseline ZrO2-Y2O3 exhibited the best sintering resistance, while the NiO-doped ZrO2-Y2O3 showed the highest shrinkage strain rates during the tests. Higher shrinkage strain rates of the coating materials were also observed when the specimens were tested in Ar+5%H2 as compared to in air. This phenomenon was attributed to an enhanced metal cation interstitial diffusion mechanism under the reducing conditions. It is proposed that increased chemical stability of coating materials will improve the material sintering resistance.

Zhu, Dongming↗
NASA NTRS2000

Effects of Interface Coating and Nitride Enhancing Additive on Properties of Hi-Nicalon SiC Fiber Reinforced Reaction-Bonded Silicon Nitride Composites

Strong and tough Hi-Nicalon SiC fiber reinforced reaction-bonded silicon nitride matrix composites (SiC/ RBSN) have been fabricated by the fiber lay-up approach. Commercially available uncoated and PBN, PBN/Si-rich PBN, and BN/SiC coated SiC Hi-Nicalon fiber tows were used as reinforcement. The composites contained approximately 24 vol % of aligned 14 micron diameter SiC fibers in a porous RBSN matrix. Both one- and two-dimensional composites were characterized. The effects of interface coating composition, and the nitridation enhancing additive, NiO, on the room temperature physical, tensile, and interfacial shear strength properties of SiC/RBSN matrix composites were evaluated. Results indicate that for all three coated fibers, the thickness of the coatings decreased from the outer periphery to the interior of the tows, and that from 10 to 30 percent of the fibers were not covered with the interface coating. In the uncoated regions, chemical reaction between the NiO additive and the SiC fiber occurs causing degradation of tensile properties of the composites. Among the three interface coating combinations investigated, the BN/SiC coated Hi-Nicalon SiC fiber reinforced RBSN matrix composite showed the least amount of uncoated regions and reasonably uniform interface coating thickness. The matrix cracking stress in SiC/RBSN composites was predicted using a fracture mechanics based crack bridging model.

Bhatt, Ramakrishana T.↗
NASA NTRS2016

Noble Metal Arsenides and Gold Inclusions in Northwest Africa 8186

CK carbonaceous chondrites are a highly thermally altered group of carbonaceous chondrites, experiencing temperatures ranging between approx.576-867 C. Additionally, the mineralogy of the CK chondrites record the highest overall oxygen fugacity of all chondrites, above the fayalite-magnetite-quartz (FMQ) buffer. Metallic Fe-Ni is extremely rare in CK chondrites, but magnetite and Fe,Ni sulfides are commonly observed. Noble metal-rich inclusions have previously been found in some magnetite and sulfide grains. These arsenides, tellurides, and sulfides, which contain varying amounts of Pt, Ru, Os, Te, As, Ir, and S, are thought to form either by condensation from a solar gas, or by exsolution during metamorphism on the chondritic parent body. Northwest Africa (NWA) 8186 is a highly metamorphosed CK chondrite. This meteorite is predominately composed of NiO-rich forsteritic olivine (Fo65), with lesser amounts of plagioclase (An52), augite (Fs11Wo49), magnetite (with exsolved titanomagnetite, hercynite, and titanohematite), monosulfide solid solution (with exsolved pentlandite), and the phosphate minerals Cl-apatite and merrillite. This meteorite contains coarse-grained, homogeneous silicates, and has 120deg triple junctions between mineral phases, which indicates a high degree of thermal metamorphism. The presence of NiO-rich olivine, oxides phases all bearing Fe3+, and the absence of metal, are consistent with an oxygen fugacity above the FMQ buffer. We also observed noble metal-rich phases within sulfide grains in NWA 8186, which are the primary focus of the present study.

Srinivasan, P.↗
NASA NTRS2016

Noble Metal Arsenides and Gold Inclusions in Northwest Africa 8186

CK carbonaceous chondrites are a highly thermally altered group of carbonaceous chondrites, experiencing temperatures ranging between approximately 576-867 degrees Centigrade. Additionally, the mineralogy of the CK chondrites record the highest overall oxygen fugacity of all chondrites, above the fayalite-magnetite-quartz (FMQ) buffer. Me-tallic Fe-Ni is extremely rare in CK chondrites, but magnetite and Fe,Ni sulfides are commonly observed. Noble metal-rich inclusions have previously been found in some magnetite and sulfide grains. These arsenides, tellurides, and sulfides, which contain varying amounts of Pt, Ru, Os, Te, As, Ir, and S, are thought to form either by condensation from a solar gas, or by exsolution during metamorphism on the chondritic parent body. Northwest Africa (NWA) 8186 is a highly metamorphosed CK chondrite. This meteorite is predominately composed of NiO-rich forsteritic olivine (Fo65), with lesser amounts of plagioclase (An52), augite (Fs11Wo49), magnetite (with exsolved titanomagnetite, hercynite, and titanohematite), monosulfide solid solution (with exsolved pentlandite), and the phosphate minerals Cl-apatite and merrillite. This meteorite contains coarse-grained, homogeneous silicates, and has 120-degree triple junctions between mineral phases, which indicates a high degree of thermal metamorphism. The presence of NiO-rich olivine, oxides phases all bearing Fe3 plus, and the absence of metal, are consistent with an oxygen fugacity above the FMQ buffer. We also observed noble metal-rich phases within sulfide grains in NWA 8186, which are the primary focus of the present study.

Srinivasan, P.↗
NASA NTRSDate not supplied

Semi-Empirical Interatomic Potential for Large-Scale Molecular Dynamics Simulation of Metal-Oxide Systems

Classical molecular dynamics (MD) simulation can be applied to systems containing billions of atoms during times up to microseconds. However, utilization of a large-scale MD simulation requires reliable but computationally cheap interatomic potentials. In the case of metallic systems, embedded atom method (EAM) and Finnis-Sinclair (FS) potentials are the reasonable choices, but their development for multicomponent alloys is a challenge. Addition of oxygen atoms makes the problem of developing semi-empirical potentials even more difficult because the long-range Coulomb interaction cannot be neglected, and different atoms have different charges which vary during MD relaxation such that a charge equilibration procedure should be applied every MD step. As results researchers tend to avoid simulating metal-oxide systems. In this talk, a new Finnis-Sinclair (FS) Ni-Co-Cr potential will be presented. Special attention will be paid to reproducing of the element melting temperatures and clustering. Next, a charge transfer ionic potential (CTIP) developed to simulate the NiO properties will be presented. This potential utilizes the Ni FS potential and accounts for the Coulomb interaction in the vicinity of oxygen atoms. Fitting of the CTIP parameters and FS potential functions describing the interaction with oxygen atoms to the available experimental and ab initio data will be discussed. Results of MD simulation of interaction of NiO particles with dislocations in Ni will be shown.

molecular dynamics simulation↗
NASA NTRS1971

Mach 1 oxidation of thoriated nickel chromium at 1204 C (2200 F)

TD NiCr was exposed to a Mach 1, 1-atmosphere gas stream at 1204 C for times up to 50 hours. Weight change, metal thickness loss, X-ray diffraction, metallographic, and electron microprobe analyses were made. Neither surface preparation nor thermal cycling had an appreciable effect on the results. Initially, Cr2O3 formed and volatilized, allowing a rapid metal loss rate of 40 microns per hour. After about 1 hour the Cr2O3 broke down, resulting in an NiO overgrowth. The metal loss rate then slowed to 2.5 microns per hour and remained constant to 50 hours.

Lowell, C. E.↗
NASA NTRS1971

Life testing of metal-ceramic CO2 lasers

The main purpose of this program was to determine the life characteristics of nine space-qualified, metal-ceramic CO2 lasers. Lifetimes ranged between about 400 hours to over 2000 hours (the limit of testing) with a high degree of consistency in like groups. In all cases the tubes which had failed could be restored to near their original power by doubling the cathode current for 30 minutes. Periodic rejuvenation allowed operation for the full 2000 hours on all tubes. The failure mechanism appears to involve formation of NiO and C on the nickel cathode emission surface with subsequent absorption of tube gases.

Fahlen, T. S.↗
NASA NTRS1972

Quantitative X-ray diffraction analysis of oxides formed on superalloys

Methods were developed for quantitative analysis by X-ray diffraction of the oxides Al2O3, NiO, Cr2O3, CoO, and CoCr2O4 within a standard deviation of about 10 percent of the weight fraction reported or within 1 percent absolute. These error limits assume that the sample oxides are well characterized and that the physiochemical structure of the oxides in the samples are identical with those in the synthesized standards. Results are given for the use of one of the techniques in the analysis of spalls from a series of oxidation tests of the cobalt base alloy WI-52.

Garlick, R. G.↗
NASA NTRS1973

Effects of size, shape, and frequency on the antiferromagnetic resonance linewidth of MnF

The research concerning the properties and application of solid state materials at submillimeter frequencies is summarized. Work reported includes: far infrared Fourier spectroscopy; studies of the antiferromagnetic resonance line in MnF2 at millimeter wavelengths; numerical solution of the equations of motion of a general two-sublattice antiferromagnet; study of antiferromagnetic resonance line in NiO powder; and resonance investigations of several indium thisospinels at millimeter wavelengths.

Obrien, K. C.↗
NASA NTRS1976

Coatings for mullite insulation

Series of coatings provides hard, impermeable, waterproof layer. Inclusion of color oxides imparts high emittance to surface. Refractory fillers investigated include TiO2, BaO.ZrO2, SrO.TiO2 ziron, spodumene, petalite, and kryptonite. Colorants include Cr2O3, NiO, and CoO.

Bolinger, P. N.↗