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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Hot corrosion of the B2 nickel aluminides

The hot corrosion behavior of the B2 nickel aluminides was studied to determine the inherent hot corrosion resistance of the beta nickel aluminides and to develop a mechanism for the hot corrosion of the beta nickel aluminides. The effects of the prior processing of the material, small additions of zirconium, stoichiometry of the materials, and preoxidation of the samples were also examined. Additions of 2, 5, and 15 w/o chromium were used to determine the effect of chromium on the hot corrosion of the beta nickel aluminides and the minimum amount of chromium necessary for good hot corrosion resistance. The results indicate that the beta nickel aluminides have inferior inherent hot corrosion resistance despite their excellent oxidation resistance. Prior processing and zirconium additions had no discernible effect on the hot corrosion resistance of the alloys. Preoxidation extended the incubation period of the alloys only a few hours and was not considered to be an effective means of stopping hot corrosion. Stoichiometry was a major factor in determining the hot corrosion resistance of the alloys with the higher aluminum alloys having a definitely superior hot corrosion resistance. The addition of chromium to the alloys stopped the hot corrosion attack in the alloys tested. From a variety of experimental results, a complex hot corrosion mechanism was proposed. During the early stages of the hot corrosion of these alloys the corrosion is dominated by a local sulphidation/oxidation form of attack. During the intermediate stages of the hot corrosion, the aluminum depletion at the surface leads to a change in the oxidation mechanism from a protective external alumina layer to a mixed nickel-aluminum spinel and nickel oxide that can occur both externally and internally. The material undergoes extensive cracking during the later portions of the hot corrosion.

Ellis, David L.↗
NASA NTRS2007

Experimental Shock Decomposition of Siderite and the Origin of Magnetite in Martian Meteorite ALH84001

Shock recovery experiments to determine whether magnetite could be produced by the decomposition of iron-carbonate were initiated. Naturally occurring siderite was first characterized by electron microprobe (EMP), transmission electron microscopy (TEM), Mossbauer spectroscopy, and magnetic susceptibility measurements to be sure that the starting material did not contain detectable magnetite. Samples were shocked in tungsten-alloy holders (W=90%, Ni=6%, Cu=4%) to further insure that any iron phases in the shock products were contributed by the siderite rather than the sample holder. Each sample was shocked to a specific pressure between 30 to 49 GPa. Previously reported results of TEM analyses on 49 GPa experiments indicated the presence of nano-phase spinel-structured iron oxide. Transformation of siderite to magnetite as characterized by TEM was found in the 49 GPa shock experiment. Compositions of most magnetites are greater than 50% Fe sup(+2) in the octahedral site of the inverse spinel structure. Magnetites produced in shock experiments display the same range of single-domain, superparamagnetic sizes (approx. 50 100 nm), compositions (100% magnetite to 80% magnetite-20% magnesioferrite), and morphologies (equant, elongated, euhedral to subhedral) as magnetites synthesized by Golden et al. (2001) or magnetites grown naturally by MV1 magnetotactic bacteria, and as the magnetites in Martian meteorite ALH84001. Fritz et al. (2005) previously concluded that ALH84001 experienced approx. 32 GPa pressure and a resultant thermal pulse of approx. 100 - 110 C. However, ALH84001 contains evidence of local temperature excursions high enough to 1 melt feldspar, pyroxene, and a silica-rich phase. This 49 GPa experiment demonstrates that magnetite can be produced by the shock decomposition of siderite as a result of local heating to greater than 470 C. Therefore, magnetite in the rims of carbonates in Martian meteorite ALH84001 could be a product of shock devolatilization of siderite as well.

Bell, Mary Sue↗
DOE OSTI2025

Structurally Regenerable High Entropy Aluminate Spinel Catalysts for Dry Reforming of Methane

The dry reforming of methane reaction is a promising means to convert two potent greenhouse gases, methane and carbon dioxide, into industrially valuable synthesis gas. However, the presence of reducing gases and high operating temperatures degrade conventional nickel catalysts via excessive coke formation and particle sintering. These catalysts are not readily regenerated because the oxidative heat treatments employed to remove coke further promote active particle sintering. In this work, we designed high entropy aluminate spinel oxides (MAl 2 O 4 where M = Co, Mg, Ni, and divalent site vacancies in nominal equimolar concentration) as selective and regenerable reforming catalysts. Under reaction conditions, reducible nickel and cobalt cations exsolved from the spinel lattice to form highly selective bimetallic particles on the oxide surface. Instead of sintering, these particles uniquely redissolved back into the aluminate lattice upon reoxidation and regained the original spinel structure. This phenomenon is ascribed to entropic stabilization, wherein an increase in configurational entropy creates a thermodynamic driving force for redispersing supported metal particles back into the multi‐cationic oxide structure. During the dry reforming reaction, nickel atoms similarly exsolved from a NiAl 2 O 4 sample and reduced to form metallic nickel particles. However, subsequent oxidation of this sample promoted sintering and oxidation of the nickel particles to an inactive state. High entropy materials thus provide a unique mechanism of regeneration, which is inaccessible in conventional catalysts.

coke deposition↗
NASA NTRS1978

Catalysts for electrochemical generation of oxygen

Single crystal surfaces of platinum and gold and transition metal oxides of the spinel type were studied to find more effective catalysts for the electrolytic evolution of oxygen and to understand the mechanism and kinetics for the electrocatalysis in relation to the surface electronic and lattice properties of the catalyst. The single crystal studies involve the use of low energy electron diffraction (LEED) and Auger electron spectroscopy as complementary tools to the electrochemical measurements. Modifications to the transfer system and to the thin-layer electrochemical cell used to facilitate the transfer between the ultrahigh vacuum environment of the electron surface physics equipment and the electrochemical environment with a minimal possibility of changes in the surface structure, are described. The electrosorption underpotential deposition of Pb onto the Au(111), (100) and (110) single crystal surfaces with the thin-layer cell-LEED-Auger system is discussed as well as the synthesis of spinels for oxygen evolution studies.

Hagans, P.↗
NASA NTRS1979

The Moho as a magnetic boundary

Magnetic data are presented for mantle derived rocks: peridtites from St. Pauls rocks, dunite xenoliths from the kaupulehu flow in Hawaii, as well as peridolite, dunite and eclogite xenoliths from Roberts Victor, Dutoitspan, Kilbourne Hole, and San Carlos diatremes. The rocks are paramagnetic or very weakly ferromagnetic at room temperature. Saturation magnetization values range from 0.013 emu/gm to less than 0.001 emu/gm. A review of pertinent literature dealing with analysis of the minerals in mantle xenoliths provides evidence that metals and primary Fe3O4 are absent, and that complex CR, Mg, Al, and Fe spinels dominate the oxide mineralogy. All of the available evidence supports the magnetic results, indicating that the seismic MOHO is a magnetic boundary.

Wasilewski, P. J.↗
DOE OSTI2026

Preparation and Photocatalytic Hydrogen Production of TiO 2 /(AlMnCoNiZn) 3 O 4 Nanocomposites

Photocatalytic water splitting is a promising strategy for addressing the global energy crisis and environmental pollution. In this study, spinel-type high-entropy oxide (HEO) nanoparticles, (AlMnCoNiZn) 3 O 4 , were successfully synthesized via a solution combustion method. TiO 2 /(AlMnCoNiZn) 3 O 4 nanocomposites with varying molar ratios were subsequently fabricated through solid-state sintering, and their photocatalytic water-splitting performance was systematically investigated. The hydrogen production rate initially increased and then decreased with increasing TiO 2 content. The optimal nanocomposite achieved a hydrogen evolution rate of 1450 μmol·h −1 ·g −1 under simulated sunlight irradiation, which is 2.2 times higher than that of pure TiO 2 nanoparticles. In addition, the TiO 2 /(AlMnCoNiZn) 3 O 4 nanocomposites exhibited significantly improved photocorrosion resistance compared with TiO 2 nanoparticles. After 12 h irradiation under a 500-W high-pressure mercury lamp, the hydrogen production rates of the nanocomposites and pure TiO 2 retained 79.3% and 5.47% of their initial values, respectively. These results demonstrate the important role of (AlMnCoNiZn) 3 O 4 and other HEOs in enhancing the photocatalytic performance of nanoheterojunction catalysts. Lastly, this work broadens the potential applications of (AlMnCoNiZn) 3 O 4 and related HEO materials in the field of photocatalysis.

Heterojunction↗
NASA NTRS1992

S-asteroids 387 Aquitania and 980 Anacostia - Possible fragments of the breakup of a spinel-bearing parent body with CO3/CV3 affinities

Asteroids 387 Aquitania and 980 Anacostia are anomalous members of the S-class. Their reflectance spectra exhibit a strong broad absorption feature longwards of 1.5 micron and no significant feature near 1 micron. Their spectra indicate the presence of spinel, an aluminum-magnesium oxide mineral commonly present in inclusions in CV3 and CO3 meteorites. Spinel probably makes up only a small percentage of the surface assemblages of these asteroids, but its spectral effect may be enhanced by its presence in fine-grained white inclusions in immature asteroid regoliths. It is speculated that Aquitania and Anacostia represent material formed in the same nebular zone as the CV3 and CO3 chondrites but either: (A) at an earlier time in the nebula when such inclusions might have been a relatively larger fraction of the nebular grain population; or (B) in local regions where nebular processes (e.g., settling to the midplane) had concentrated such inclusions. The close similarity of two orbital elements (a, i) suggests that Aquitania and Anacostia may be members of a partially dispersed asteroid family produced by the early disruption of a spinel-bearing parent body.

Burbine, Thomas H.↗
NASA NTRS1973

Oxide minerals in lithic fragments from Luna 20 fines.

One hundred seventy-six oxide mineral grains in the Luna 20 samples were analyzed by electron microprobe. Spinel is the most abundant oxide, occurring in troctolite fragments. Next most abundant is ilmenite, which occurs in all rock types except those containing spinel. Chromite also occurs in all rock types except those containing spinel. Minor amounts of ulvospinel, armalcolite, zirkelite, baddeleyite and an unidentified TiO2-rich phase were also found. Spinel grains are predominantly spinel-hercynite solid solutions, commonly with very minor chromite. The Fe/(Fe + Mg) ratio is generally lower than in spinel from Apollo 14 rocks. Chromites in non-mare rocks are similar to those from mare rocks. Ilmenite of mare origin is Mg-poor and Zr-rich compared to non-mare ilmenite; these elements may therefore be useful in determining the origin of ilmenite grains. Phase equilibria considerations suggest that spinel troctolite crystallized from a melt high in alumina; a likely candidate is the high-alumina basalt of Prinz et al. (1973).

Brett, R.↗
NASA NTRS2009

Using Vanadium in Spinel as a Sensor of Oxygen Fugacity in Meteorites: Applications to Mars, Vesta, and Other Asteroids

Igneous and metamorphic rocks commonly contain a mineral assemblage that allows oxygen fugacity to be calculated or constrained such as FeTi oxides, olivine-opx-spinel, or some other oxybarometer [1]. Some rocks, however, contain a limited mineral assemblage and do not provide constraints on fO2 using mineral equilibria. Good examples of the latter are orthopyroxenites or dunites, such as diogenites, ALH 84001, chassignites, or brachinites. In fact it is no surprise that the fO2 of many of these samples is not well known, other than being "reduced" and below the metal saturation value. In order to bridge this gap in our understanding, we have initiated a study of V in chromites in natural meteorite samples. Because the V pre-edge peak intensity and energy in chromites varies with fO2 (Fig. 1) [2], and this has been calibrated over a large fO 2 range, we can apply this relation to rocks for which we otherwise have no fO2 constraints.

Righter, K.↗
NASA NTRS2015

V Xanes in Spinels as an Oxy-Barometer in Meteorites with Implications for Redox Variations in the Inner Solar System

The variation of oxygen fugacity within inner solar system materials spans a range of nearly 15 orders of magnitude. Igneous and metamorphic rocks commonly contain a mineral assemblage that allows oxygen fugacity to be calculated or con-strained such as FeTi oxides, olivine-opx-spinel, or some other oxy-barometer. Some rocks, however, contain a limited mineral assemblage and do not provide constraints on fO2 using mineral equilibria. Good examples of the latter are orthopyroxenites or dunites, such as diogenites, ALH 84001, chassignites, or brachinites. In fact it is no surprise that the fO2 of many of these achondrites is not well known, other than being "reduced" and below the metal saturation value. In order to bridge this gap in our understanding, we have initiated a study of V in chromites in achondrite. Because the V pre-edge peak intensity and energy in chromites varies with fO2, and this has been calibrated over a large fO2 range, we can apply this relation to rocks for which we otherwise have no fO2 constraints.

Righter, K.↗
NASA NTRS2014

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

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

Bell, A. S.↗
NASA NTRS1986

The effect of variations of cobalt content on the cyclic oxidation resistance of selected Ni-base superalloys

Cobalt levels were systematically varied in the Ni-base turbine alloys U-700 (cast), U-700m(PM/HIP), Waspaloy, Mar-M-247, In-738, Nimonic-115, U-720, and SX-R-150. The cobalt levels ranged from 0 wt % to the nominal commercial content in each alloy. The alloys were tested in cyclic oxidation in static air at 1000, 1100 and 1150 C for 500, 200 and 100 hr respectively. An oxidation attack parameter, Ka derived from the specific weight change versus time data was used to evaluate the oxidation behavior of the alloys along with X-ray diffraction analysis of the surface oxides. The alloys tend to form either Cr2O3/chromite spinel or Al2O3/aluminate spinel depending on the CR/Al ratio in the alloys. Alloys with a ratio of 3.5 or higher tend to favor the Cr oxides while those under 3.0 form mostly Al oxides. In general the Al2O3/aluminate spinel forming alloys have the better oxidation resistance. Increased cobalt content lowers the scaling resistance of the higher Cr alloys while a 5.0 wt % Co content is optimum for the Al controlling alloys. The refractory metals, particularly Ta, appear beneficial to both types of oxides perhaps due to the formation of the omni-present trirutile Ni(Ta,Cb,Mo,W)2O6. Both scales break down as increasing amounts of NiO is formed.

Barrett, C. A.↗
NASA NTRS1987

The effect of variations of cobalt content on the cyclic oxidation resistance of selected Ni-base superalloys

Cobalt levels were systematically varied in the Ni-base turbine alloys U-700 (cast), U-700m (PM/HIP), Waspaloy, Mar-M-247, In-738, Nimonic-115, U-720, and SX-R-150. the cobalt levels ranged from 0 wt pct to the nominal commercial content in each alloy. the alloys were tested in cyclic oxidation in static air at 1000, 1100 and 1150 C for 500, 200, and 100 hr, respectively. An oxidation attack parameter, Ka, derived from the specific weight change versus time data was used to evaluate the oxidation behavior of the alloys along with X-ray diffraction analysis of the surface oxides. The alloys tend to form either Cr2O3/chromite spinel or Al2O3/aluminate spinel depending on the Cr/Al ratio in the alloys. Alloys with a ratio of 3.5 or higher tend to favor the Cr oxides while those under 3.0 form mostly Al oxides. In general the Al2O3/aluminate spinel forming alloys have the better oxidation resistance. Increased cobalt content lowers the scaling resistance of the higher Cr allys while a 5.0 wt pct Co content is optimum for the Al controlling alloys. The refractory metals, particularly Ta, appear beneficial to both types of oxides, perhaps due to the formation of the omnipresent trirutile Ni(Ta, Cb, Mo, W)2O6. Both scales break down as increasing amounts of NiO are formed.

Barrett, Charles A.↗
DOE OSTI2025

Chromium versus Aluminum: Impact of Nickel Alloy Composition and Interfacial Kinetics on High-Temperature Passivating Oxide Formation

High-temperature corrosion resistance depends critically on the formation of a passivating surface oxide, which is highly sensitive to alloy composition and structure. Such details often elude experimental investigation, and simplified analytical models fail to provide a truly chemical view of passivating oxide evolution. Here, we explicitly compare the fundamental chemistry of Cr and Al as prototypical passivating elements in Ni alloys by directly simulating competing reaction and diffusion processes within the oxide film using kinetic Monte Carlo and density functional theory. We find that the origin and expression of passivating behavior during early-stage thermal oxidation are qualitatively different between the two alloy systems. Ni–Cr alloys feature a sudden onset of passivation associated with a sharp phase transition upon Cr enrichment that directly couples oxidation kinetics to phase transformation behavior. In contrast, Ni–Al alloys display more continuous oxide phase variation with Al enrichment, ultimately resulting in a lower composition threshold for passivation and a thinner passivating layer. In addition, we elucidate the nonobvious role of metal exchange within the alloy near the oxide boundary, which fundamentally alters film composition and passivating behavior. Furthermore, our results have key implications for engineering improved corrosion-resistant alloys, both in terms of compositional variation and processing.

Alloys↗
DOE OSTI2026

A Reflection on the Evolution of Sodium/Metal Chloride (ZEBRA) Batteries and Lithium-Ion Cathode Materials (1975–2025): A Tribute to Johan Coetzer

This narrative summarizes, in retrospect, the enormous and quietly-conducted contribution of Dr Johan Coetzer, a South African scientist and entrepreneur, to the discovery, development and implementation of the high temperature sodium—metal chloride “ZEBRA” battery (Na/β-Al 2 O 3 , NaAlCl 4 /MCl 2 (M = Ni, Fe)). Here, this research activity was initiated in the mid 1970’s at the Council for Scientific and Industrial Research (CSIR) in South Africa and subsequently developed primarily in partnership with the Atomic Energy Research Establishment (AERE, Harwell, UK), Beta R&D (Derby, UK) and Daimler Benz (Germany), before being transferred to industry worldwide for electric vehicle and energy storage applications, albeit at a relatively low production rate. Coetzer’s wide-ranging, innovative and, at times, unconventional scientific approach also laid the foundation for the discovery and implementation of manganese-based spinel and layered metal oxide cathode materials for the Li-ion battery industry.

ZEBRA Battery↗
NASA NTRS1977

Mossbauer spectroscopy of iron in the Luna 20 regolith

Results of the Mossbauer effect measurements on Fe-57 in the average sample of the Luna 20 regolith, and their comparison with similar measurements of the Luna 16 samples are presented. Room temperature measurements of the nonmagnetic as well as magnetic components of the spectra were performed. By careful least-squares analysis, six quadrupole doublets in the inner parts of spectra were resolved. According to their splittings, they were interpreted as four types of iron in silicates (olivine, two inequivalent pyroxene sites, and a glassy fraction) and two types of nonmagnetic iron-titanium oxides (ilmenite and a spinel). Velocity-window measurements, were used to determine the average nickel content of (2.01 plus or minus 0.84) wt. %. These results are discussed in terms of distribution of iron among different phases. In comparison with the Luna 16 sample, the Luna 20 sample contains more olivine and less ilmenite as well as metal with a slightly higher nickel content.

Zemcik, T.↗
NASA NTRS2020

Mineralogy and Petrology of Fine-Grained Calcium-Aluminum-Rich Inclusions from the Reduced CV3 Chondrite Thiel Mountains 07007

Calcium-Aluminum-rich inclusions (CAIs) are among the oldest Solar System solids, and studies of these objects have played an essential role in developing an understanding of chemical and physical processes that initiated and characterized key events related to the Solar System’s formation and evolution. CAIs occur as μm- to cm-sized inclusions in chondritic meteorites, particularly in carbonaceous chondrites, and consist of various refractory silicate and oxide phases (e.g., melilite, spinel, Al-Ti-rich diopside, hibonite, and corundum) that are predicted by thermodynamic models to be among the first solids to con-dense from a cooling gas of solar composition. Fine grained CAIs (FGIs) are important samples to probe volatility-driven condensation processes in the solar nebula, because they have escaped thermal processes (e.g., melting) experienced by coarse-grained CAIs. In order to explore the primary nebular history of FGIs, a detailed mineralogical and petrologic study is necessary. In this research effort, we constrained the mineralogy and petrology of two CAIs 07-10 and -11 from the reduced CV3 chondrite Thiel Mountains (TIL) 07007, with the aim of evaluating their provenance as nebular condensates.

Anderkin, C. J.↗
NASA NTRS1973

Alloy composition effects on oxidation products of VIA, B-1900, 713C, and 738X: A high temperature diffractometer study

High temperature X-ray diffraction studies were performed to investigate isothermal and cyclic oxidation at 1000 and 1100 C of the nickel-base superalloys VIA, B-1900, 713C, and 738X. Oxidation was complex. The major oxides, Al2O3, Cr2O3, and the spinels, formed in amounts consistent with alloy chemistry. The alloys VIA and B-1900 (high Al, low Cr alloys) tended to form Al2O3 and NiAl2O4; 738X (high Cr, low Al) formed Cr2O3 and NiCr2O4. A NiTa2O6 type of oxide formed in amounts approximately proportional to the refractory metal content of the alloy. One of the effects of cycling was to increase the amount of spinels formed.

Garlick, R. G.↗