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At least 127 records · Page 7

Constraints on the Nature and Distribution of Iridium Host Phases at the Cretaceous-Tertiary Boundary: Implications for Projectile Identity and dispersal on impact

Among Cretaceous-Tertiary boundary sites worldwide, variations in the concentrations and ratios of elements commonly enriched in meteorites complicate traditional geochemical attempts at impactor identification. Yet they may provide constraints on the physical and chemical processes associated with large-body disruption and dispersal, as well as with diagenesis of projectile components. To this end, we continue our efforts to identify the mineral host-phases of projectile-derived elements, particularly for Ir, and to document their partitioning between crater deposits and ejecta resulting from the Chicxulub basin-forming impact. Building on earlier work, we used INAA to measure Ir concentrations in successively smaller splits of finely powdered impact melt breccia from the Chicxulub Crater in Mexico (sample Y6Nl9-R(b)), and K/T boundary fish clay from Stevns Klint, Denmark (sample FC-1, split from 40 kg of homogenized material intended as an analytical standard). Results for the Chicxulub sample show a heterogeneous Ir distribution and document that at least five discrete Ir-bearing host phases were isolated in subsequent splits, having Ir masses equivalent to pure Ir spheres from about 0.8 to about 3.5 mm in diameter. Three of these are within a sufficiently reduced mass of powder to warrant searching for them using backscattered electron microscopy. In contrast, successively smaller splits of the Stevns Klint fish clay show no statistically significant deviation from the reported value of 32 +/- 2 ng/g Ir, suggesting a uniform Ir host-phase distribution. For the smallest split obtained thus far (100 +/- 40 ng/g Ir), a pure Ir sphere of equivalent Ir mass would be <0.05 min in diameter. (n.b. Although homogenizing and sieving of FC-1 to <75 min obviously obscured variations in stratigraphic distribution, it is unlikely to have affected the size-frequency distribution of Ir host phases.) We previously identified micrometer-scale Ir host phases by electron microscopy in melt-rock samples from two widely separated drill holes at the Chicxulub Basin, including a replicate split of Y6-NI9-R. One is an aggregate of subhedral Ir metal grains enclosed in silicate, in which no other Pt group elements (PGE) were detected. A second particle with twice the mass as the first, concentrated predominantly in a single grain, is associated with minor concentrations of Os, Ru, and Pt, and with adhering particles of corundum and perovskite. A third Ir-rich particle, with a greater apparent Os concentration, was identified before being lost as a result of charging under the electron beam. In addition to demonstrating the preservation of projectile components within the Chicxulub Crater, analogous phase associations in Ca- and Al-rich inclusions (CAI) from C2 and C3 chondrites suggest to us that these melt-rock Ir host phases are relics from a carbonaceous chondrite K/T boundary impactor Although the obviously low Ru/Ir ratios of the Chicxulub Ir host phases are qualitatively consistent with suggested PGE fractionation with distance during condensation in an ejecta cloud, it seems difficult to explain the accumulation of the about 3 x 10(exp 11) Ir atoms required to form a about 10(exp -10) g nugget of pure Ir metal within a jet of vaporized projectile expanding at 1-4 km/s, or to effectively exclude or remove commonly alloyed PGE and siderophile elements by fractionation processes resulting from condensation, oxidation, sulfidization, exsolution, or autometamorphism during cooling of the melt. We do not dismiss the importance of these processes entirely; on the contrary, other geochemical and mineralogical aspects of the melt rocks require them, and condensation from the expanding ejecta cloud appears to best explain the primary Ir host-phase distribution in the fish clay, as well as the high Ir concentrations associated with spinel-bearing spheroids at the K/T boundary in the Pacific Ocean . If the "relict" hypothesis is correct, micronuggets of other PGEs and alloys, not detected by our INAA screening, should also occur in the melt rocks. Possibly, the discrete host phases with lesser Ir masses are such alloys with subordinate Ir, rather than simply smaller, predominantly Ir-bearing particles. A CAI source for the relics would be consistent with either a comet or an asteroid K/T impact at Chicxulub. (Additional information contained in the original.)

Schuraytz, B. C.↗

Thin Film Catalyst Layers for Direct Methanol Fuel Cells

One of the primary obstacles to the widespread use of the direct methanol fuel cell (DMFC) is the high cost of the catalyst. Therefore, reducing the catalyst loading well below the current level of 8-12 mg/cm 2 would be important to commercialization. The current methods for preparation of catalyst layers consisting of catalyst, ionomer and sometimes a hydrophobic additive are applied by either painting, spraying, decal transfer or screen printing processes. Sputter deposition is a coating technique widely used in manufacturing and therefore particularly attractive. In this study we have begun to explore sputtering as a method for catalyst deposition. Present experiments focus on Pt-Ru catalyst layers for the anode.

Witham, C. K.↗

Modeling of Ternary Element Site Substitution in NiAl

It is well recognized that ternary alloying additions can have a dramatic impact on the behavior of ordered intermetallic alloys such as nickel aluminides. Properties as diverse as yield strength, fracture strength, fracture mode, cyclic oxidation resistance, creep strength, and thermal and electrical diffusivity can change by orders of magnitude when a few percent or less of a ternary element is added. Yet our understanding of the resulting point defect structures and the simple site preferences of ternary alloying additions is poor because these are extremely difficult characteristics to determine. This disconnection between the understanding of the structure and properties in ordered alloys is at least in part responsible for the limited development and commercialization of these materials. Theoretical methods have provided useful but limited insight in this area, since most techniques suffer from constraints in the type of elements and the crystallographic structures that can be modeled. In an effort to overcome these limitations, the Bozzolo-Ferrante-Smith (BFS) method for alloys was designed. After a brief description of this approximate quantum mechanical approach, we use BFS to investigate the energetics of Si, Ti, V, Cr, Fe, Co, Cu, Zr, Nb, Mo, Ru, Hf, Ta and W additions to B2-ordered, stoichiometric NiAl. In addition to determining the site preference for these alloying additions over a range of compositions, we include results for the concentration dependence of the lattice parameter. In this introductory paper, we performed our analyses in the absence of constitutional and thermal vacancies for alloys of the form Ni50(Al,X)50. Where data exist, a comparison between experimental, theoretical, and BFS results is also included.

Bozzolo, Guillermo↗

Highly Siderophile Elements in Shocked and Unshocked Chondrites

High precision abundances of Re, Os, Pt, Ir, Ru, and Pd are combined with Re-Os isotopic data to demonstrate that HSE provide a distinctive fingerprint for each of the chondrite groups. Additional information is contained in the original extended abstract.

Horan, M. F.↗

Metalorganic Chemical Vapor Deposition of Ruthenium-Doped Diamond like Carbon Films

We investigated metalorganic precursor deposition using a Microwave Electron Cyclotron Resonance (ECR) plasma for depositing metal-doped diamondlike carbon films. Specifically, the deposition of ruthenium doped diamondlike carbon films was investigated using the decomposition of a novel ruthenium precursor, Bis(ethylcyclopentadienyl)-ruthenium (Ru(C5H4C2H5)2). The ruthenium precursor was introduced close to the substrate stage. The substrate was independently biased using an applied RF power. Films were characterized using Fourier Transform Infrared Spectroscopy (FTIR), Transmission Electron Microscopy (TEM) and Four Point Probe. The conductivity of the films deposited using ruthenium precursor showed strong dependency on the deposition parameters such as pressure. Ruthenium doped sample showed the presence of diamond crystallites with an average size of approx. 3 nm while un-doped diamondlike carbon sample showed the presence of diamond crystallites with an average size of 11 nm. TEM results showed that ruthenium was atomically dispersed within the amorphous carbon network in the films.

Sunkara, M. K.↗

Atomistic Modeling of RuAl and (RuNi) Al Alloys

Atomistic modeling of RuAl and RuAlNi alloys, using the BFS (Bozzolo-Ferrante-Smith) method for alloys is performed. The lattice parameter and energy of formation of B2 RuAl as a function of stoichiometry and the lattice parameter of (Ru(sub 50-x)Ni(sub x)Al(sub 50)) alloys as a function of Ni concentration are computed. BFS based Monte Carlo simulations indicate that compositions close to Ru25Ni25Al50 are single phase with no obvious evidence of a miscibility gap and separation of the individual B2 phases.

Gargano, Pablo↗

Changes in Earth 360 380 nm Reflectivity: 1980-2000

The TOMS (Total Ozone Mapping Spectrometer) reflectively time series 1980 to 1992 and 1997 to 2000 have been combined to estimate change that have occurred over a 21 year period. The relative calibration of the two TOMS (Nimbus-7, N7 and Earth-Probe, EP) has been validated using the measured reflectivity R over Hudson Bay, Canada and found to be within 1 RU (R=0.01). Some of the local trend features seen in the N7 time series (1980 to 1992) have been continued in the combined time series, but the overall zonal average and global trends have changed. The UV (ultraviolet) reflectivity data are compared with changes in the AVHRR outgoing long-wavelength radiation (OLR) and show an expected anti-correlation with cloud-cover changes over the same period for many, but not all, features. The key results include a continuing decrease in cloud cover over Europe and North America and an increase in reflectivity near Antarctica.

Herman, J. R.↗

Site Occupancy of Ternary Additions to B2 Alloys

In this broad-based survey study, the substitutional site preference of ternary alloying additions to B2 compounds (stable at room temperature and 50/50 composition) is determined using the Bozzolo-Ferrante-Smith (BFS) method for alloys. The method is applied to Ni, Al, Ti, Cr, Cu, Co, Fe, Ta, Hf, Mo, Nb, W, V and Ru additions to NiAl, FeAl, CoAl, CoFe, CoHf, CoTi, FeTi, RuAl, RuSi, RuHf, RuTi, and RuZr. The results are compared, when available, to experimental data and other theoretical results.

Bozzolo, Guillermo H.↗

Molybdenum Isotopic Composition of Iron Meteorites, Chondrites and Refractory Inclusions

Recent Mo isotopic studies of meteorites reported evidence for differences in isotopic compositions for whole rocks of some primitive and differentiated meteorites relative to terrestrial materials. Enrichments of r- and p-process isotopes of up to 3-4 units (e unit = parts in 10(exp 4) over s-process dominated isotopes are the most prominent features. Certain types of presolar grains show large enrichments in s-process isotopes, however, it was concluded on grounds of mass balance that incomplete digestion of such grains cannot explain the enrichments of r- and p-process isotopes in whole rocks of primitive chondrites. If the reported variability in r- and p-process isotope enrichments reflects the true isotopic characteristics of the whole rocks, the implications are quite profound. It would suggest the presence of large scale Mo isotopic heterogeneity within the solar accretion disk with likely collateral effects for other elements. However, such effects were not found for Ru isotopes, nor for Zr isotopes. Another recent Mo isotopic study by multi collector ICP-MS could not confirm the reported deviations in Allende, Murchison or iron meteorites. Here, we present new results for the Mo isotopic composition of iron meteorites, chondrites and CAIs obtained by negative thermal ionization mass spectrometry (NTIMS). We discuss analytical aspects and the homogeneity of Mo isotopic compositions in solar system materials.

Becker, H.↗

Re-Os Systematics and HSE Distribution in Metal from Ochansk (H4) Chondrite

Previous studies of the Re-Os systematics of chondrites have documented considerable variation in the Re/Os ratios of whole rock samples. For some whole rock chondrites, Re-Os systematics display large deviations from the primitive isochron that are considerably larger than deviations in other isotope systems. Possible interpretation of these facts is that the Re-Os system in chondrites is particularly sensitive to post-formation alteration processes, thus providing a useful tool to examine such processes. Significant variations that have been detected in highly siderophile element (HSE) patterns for ordinary chondrites support this conclusion. We report Re-Os isotope data for metal separates from the Ochansk H4 chondrite coupled with abundance data for Ru, Pd, Ir, and Pt, determined in the same samples by isotope dilution. We chose this meteorite mainly because it is an observed fall with minimal signs of weathering, and its low metamorphic grade (H4) and shock stage (S3).

Smoliar, M. I.↗

Diffusion of Siderophile Elements in Fe Metal: Application to Zoned Metal Grains in Chondrites

The distribution of highly siderophile elements (HSE) in planetary materials is controlled mainly by metal. Diffusion processes can control the distribution or re-distribution of these elements within metals, yet there is little systematic or appropriate diffusion data that can be used to interpret HSE concentrations in such metals. Because our understanding of isotope chronometry, redox processes, kamacite/taenite-based cooling rates, and metal grain zoning would be enhanced with diffusion data, we have measured diffusion coefficients for Ni, Co, Ga, Ge, Ru, Pd, Ir and Au in Fe metal from 1200 to 1400 C and 1 bar and 10 kbar. These new data on refractory and volatile siderophile elements are used to evaluate the role of diffusional processes in controlling zoning patterns in metal-rich chondrites.

Righter, K.↗

Osmium Isotope and Highly Siderophile Element Compositions of Lunar Orange and Green Glasses

The absolute and relative abundances of the highly siderophile elements (HSE) present in planetary mantles are primarily controlled by: 1) silicate-metal partitioning during core-mantle differentiation, 2) the subsequent addition of HSE to mantles via continued planetary accretion. Consequently, constraints on the absolute and relative abundances of the HSE in the lunar mantle will provide unique insights to the formation and late accretionary history of not only the Moon, but also Earth. Determining the HSE content of the lunar mantle, however, has proven difficult, because no bona fide mantle rocks have been collected from the moon. The only materials presently available for constraining mantle abundances are lunar volcanic rocks. Lunar basalts typically have very low concentrations of HSE and highly fractionated HSE patterns. Because of our extremely limited understanding of mantle melt partitioning of the HSE, even for terrestrial systems, extrapolations to mantle compositions from basaltic compositions are difficult, except possibly for the less compatible HSE Pt and Pd. Primitive, presumably less fractionated materials, such as picritic glasses are potentially more diagnostic of the lunar interior. Here we report Os isotopic composition data and Re, Os, Ir, Ru, Pt and Pd concentration data for green glass (15426,164) and orange glass (74001,1217). As with previous studies utilizing neutron activation analysis, we are examining different size fractions of the spherules to assess the role of surface condensation in the generation of the HSE abundances.

Walker, R. J.↗

Low Abundances of Highly Siderophile Elements in the Lunar Mantle: Evidence for Prolonged Late Accretion

The highly siderophile elements (HSE: including Re, Au, Ir, Os, Ru, Pt, Pd, Rh) are strongly partitioned into metal relative to silicates. In the terrestrial planets these elements are concentrated in metallic cores. Earth s mantle has sufficiently high abundances of the HSE (~0.008 times CI abundances) that it has been hypothesized approximately 0.1-0.5% of the mass of the Earth was added following the last major interaction between the core and mantle [e.g. 1]. The additional material added to the Earth and Moon has been termed a late veneer , and the process has often been termed late accretion [2]. The timing of the dominant late accretionary period of the Earth and Moon is still poorly known. The abundances of HSE in the lunar mantle could provide important constraints on when the late veneer was added. The material that ultimately became the silicate portion of the Moon was likely stripped of most of its HSE prior to and during coalescence of the Moon. Consequently the initial lunar mantle likely had very low concentrations of the HSE. Unlike Earth, the generation of permanent lunar crust by ~4.4 Ga prevented subsequent additions of HSE to the lunar mantle via continued accretion. Thus, if a substantial portion of the late veneer was added after 4.4 Ga, the lunar mantle should have retained very low HSE concentrations. Conversely, if the late veneer was mostly added prior to 4.4 Ga, HSE abundances in the lunar mantle may be roughly similar to abundances in the terrestrial mantle.

Walker, R. J.↗

Lunar and Planetary Science XXXV: Early Solar System Chronology

The titles in this section discuss: 1) Mg Isotopic Systematics in Eutectites; 2) Diffusion Kinetics of Cr in Olivine; 3) The W Isotope Composition of Eucrite Metals; 4) U-Pb and Hf-W Chronometry; 5) Fe-60 in Silicate from a Semarkona Chondrule; 6) The Isotope Geochemistry of Nickel in Chondrites and Iron Meteorites; 7) Iron-60 in the Early Solar System; 8) Endemic Mo Isotopic Anomalies in Iron and Carbonaceous Meteorites; 9) Solar System Iron and Tungsten Isotope Abundances; 10) Li and B Isotope Variations in CAI; 11) Short-lived Radionuclides and Early Solar System Irradiation; Ru Endemic Isotope Anomalies in Meteorites; 12) Cl-36 in Ca-Al rich inclusions from a carbonaceous chondrite.

Source record↗

Ultrasensitive Label-free Electronic Chip for DNA Analysis Using Carbon Nanotube Nanoelectrode Arrays

There is a strong need for faster, cheaper, and simpler methods for nucleic acid analysis in today s clinical tests. Nanotechnologies can potentially provide solutions to these requirements by integrating nanomaterials with biofunctionalities. Dramatic improvement in the sensitivity and multiplexing can be achieved through the high-degree miniaturization. Here, we present our study in the development of an ultrasensitive label-free electronic chip for DNA/RNA analysis based on carbon nanotube nanoelectrode arrays. A reliable nanoelectrode array based on vertically aligned multi-walled carbon nanotubes (MWNTs) embedded in a SiO2 matrix is fabricated using a bottom-up approach. Characteristic nanoelectrode behavior is observed with a low-density MWNT nanoelectrode array in measuring both the bulk and surface immobilized redox species. The open-end of MWNTs are found to present similar properties as graphite edge-plane electrodes, with a wide potential window, flexible chemical functionalities, and good biocompatibility. A BRCA1 related oligonucleotide probe with 18 bases is covalently functionalized at the open ends of the MWNTs and specifically hybridized with an oligonucleotide target as well as a PCR amplicon. The guanine bases in the target molecules are employed as the signal moieties for the electrochemical measurements. Ru(bpy)3(2+) mediator is used to further amplify the guanine oxidation signal. This technique has been employed for direct electrochemical detection of label-free PCR amplicon through specific hybridization with the BRCAl probe. The detection limit is estimated to be less than approximately 1000 DNA molecules, approaching the limit of the sensitivity by laser-based fluorescence techniques in DNA microarray. This system provides a general electronic platform for rapid molecular diagnostics in applications requiring ultrahigh sensitivity, high-degree of miniaturization, simple sample preparation, and low- cost operation.

Li, Jun↗

LA-ICP-MS Study of Trace Elements in the Chanuskij Metal

This progress report covers work done during the second year of the 3-year proposal. During this year we resolved many issues relevant to the analytical technique developed by us for measuring trace elements in meteoritic metals. This technique was used to measure concentrations of Fe, Ni, Co, Cr, Cu, Ga, Ge, As, Mo, Ru, Rh, Pd, Sb, W, Re, Os, Ir, Pt, and Au in eight large (120 - 160 microns) metal grains from both "igneous" and "metamorphic" lithologies of the Chanuskij silicate inclusions. The first application of OUT technique to metal grains from thin sections showed some limitations. Small thickness of metal grains in the thin section limited the signal to 3-4 time-slices instead of 10- 1 1 ones in polished sections of iron meteorites studied before.

Petaev, Michail I.↗

Miniaturized multiplex label-free electronic chip for rapid nucleic acid analysis based on carbon nanotube nanoelectrode arrays

BACKGROUND: Reducing cost and time is the major concern in clinical diagnostics, particularly in molecular diagnostics. Miniaturization technologies have been recognized as promising solutions to provide low-cost microchips for diagnostics. With the recent advancement in nanotechnologies, it is possible to further improve detection sensitivity and simplify sample preparation by incorporating nanoscale elements in diagnostics devices. A fusion of micro- and nanotechnologies with biology has great potential for the development of low-cost disposable chips for rapid molecular analysis that can be carried out with simple handheld devices. APPROACH: Vertically aligned multiwalled carbon nanotubes (MWNTs) are fabricated on predeposited microelectrode pads and encapsulated in SiO2 dielectrics with only the very end exposed at the surface to form an inlaid nanoelectrode array (NEA). The NEA is used to collect the electrochemical signal associated with the target molecules binding to the probe molecules, which are covalently attached to the end of the MWNTs. CONTENT: A 3 x 3 microelectrode array is presented to demonstrate the miniaturization and multiplexing capability. A randomly distributed MWNT NEA is fabricated on each microelectrode pad. Selective functionalization of the MWNT end with a specific oligonucleotide probe and passivation of the SiO2 surface with ethylene glycol moieties are discussed. Ru(bpy)2+ -mediator-amplified guanine oxidation is used to directly measure the electrochemical signal associated with target molecules. SUMMARY: The discussed MWNT NEAs have ultrahigh sensitivity in direct electrochemical detection of guanine bases in the nucleic acid target. Fewer than approximately 1000 target nucleic acid molecules can be measured with a single microelectrode pad of approximately 20 x 20 microm2, which approaches the detection limit of laser scanners in fluorescence-based DNA microarray techniques. MWNT NEAs can be easily integrated with microelectronic circuitry and microfluidics for development of a fully automated system for rapid molecular analysis with minimum cost.

Carbon↗