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At least 253 records · Page 14

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NASA NTRS1981

Metal/silicon interface formation - The Ni/Si and Pd/Si systems

The valence level spectra of the Ni/Si and Pd/Si systems have been investigated using high resolution X-ray photoelectron spectroscopy. Temperature dependence studies for Ni deposited on thin thermal SiO2 demonstrate the importance of metal aggregation effects in the interpretation of binding energies as chemical shifts. Temperature studies for the Ni/Si system indicate that substantial chemical interaction occurs at the interface at temperatures as low as 100 K. These studies also show the presence of Ni in interstitial voids in the Si near the interface. A comparative study of the core and valence band features for the Ni and Pd silicides provides many valuable insights and a self-consistent picture of the attendent valence charge redistribution and its influence on the observed chemical shifts.

Grunthaner, P. J.↗

NASA NTRS1981

Spallogenic rare gases in iron meteorites with anomalous silver

He, Ne, and Ar have been measured in seven iron meteorites for which anomalous Ag isotopic compositions were reported, in order to determine if Ag-107 excesses could be related to galactic cosmic-ray bombardment of these meteorites. The results show that no correlation exists between Ag-107 excess and either the fluence or the energy spectrum of the particles producing spallogenic rare gases. Cosmic-ray-produced Ag-107 estimated from Ar-38 concentrations can account for only about 1 percent of the observed excess. Elimination of cosmic-ray bombardment as a production mechanism for Ag-107 excess strengthens the conclusion that the excess Ag-107 is the decay product of short-lived Pd-107 (half life 6.5 million years). The iron meteorite Pinon is shown to contain trapped rare gases with He-4/Ne-20 approximately 600.

Villa, I. M.↗

NASA NTRS1981

Identification of the projectile at the Brent crater, and further considerations of projectile types at terrestrial craters

An analysis of impact melt samples from a drill hole at the Brent crater in Ontario for siderophile trace elements indicative of meteoritic contamination, has resulted in 823-857 m-deep basalt melt zone samples enriched in Ir, Os, Pd, Ni, Co, Cr and Se over basement. The abundance pattern suggests a chondritic projectile and, from a Ni-Cr correlation of 10 melt samples, an L or LL chondrite is inferred. Data from the Manicouagan, Mitastin, and Zhamanshin craters are also assessed, and large differences in siderophile element concentrations are found among the tektites which otherwise have similar chemical compositions. There are now four known craters formed by chondrites, with Brent being the smallest among them.

Palme, H.↗

NASA NTRS1981

Isotopic variations in primitive meteorites

Oxygen isotopic variations in carbonaceous chondrites and ordinary chondrites can each be interpreted as mixtures of two isotopically different reservoirs, one consisting of solids, enriched in O-16, the other of a gas, depleted in O-16 relative to terrestrial abundances. The data indicate a common source of the solids for each of the two classes of meteorites, but a different gas reservoir for each. These conditions might obtain in gaseous protoplanets. It is noted that radiogenic Mg-26 is variable in abundance among some classes of Allende inclusions, implying either nebular heterogeneity with respect to Al-26/Al-27 ratios or time differences of crystal formation. The presence of excess Ag-107 from decay of extinct Pd-107 corroborates the evidence from Mg-26 for a time interval of at most a few million years between the last nucleosynthetic event and the accretion of substantial bodies in the solar system.

Clayton, R. N.↗

NASA NTRS1982

Chemisorption of CO on particulate deposits of platinum

Morphology and CO chemisorption properties are studied as a function of particle size for the case of particulate Pt films, vapor-deposited onto ultrahigh vacuum-cleaved and heat-treated mica surfaces at a 200 C substrate temperature. The particles were found to be mostly irregular in shape and randomly-oriented, with two desorption peaks after CO absorption at 60 C: (1) an alpha peak, at 120 C, attributed to smooth particle surfaces, and (2) a beta peak, at about 175 C, attributed to particle edges and steps. Transmission electron microscopy showed that major changes occur in particle morphology during absorption-desorption cycling, so that the decrease in CO desorption flux may be interpreted as due to particle restructuring, rather than contamination by CO decomposition as in the cases of Ni or Pd on mica. Auger electron spectroscopy corroborates the lack of CO decomposition, even for the case of very small Pt particles.

Doering, D. L.↗

NASA NTRS1983

Extinct radioactivities - A three-phase mixing model

A new class of models is advanced for interpreting the relationship of radioactive abundances in the early solar system to their average concentration in the interstellar medium. The model assumes that fresh radioactivities are ejected from supernovae into the hot interstellar medium, and that the time scales for changes of phase into molecular clouds determine how much survives for formation therein of the solar system. A more realistic and physically motivated understanding of the low observed concentrations of I-129, Pu-244, and Pd-107 may result.

Clayton, D. D.↗

NASA NTRS1982

Chemical evolution of OB associations

It is determined that the existence of Al-26 and Pd-107 in meteorites in the early solar system indicates that our solar system probably formed inside an OB association that had been contaminated by the debris of at least one supernova. In addition to these radioactive tracers, the contamination of the material out of which the solar system formed would have significantly enriched the heavy element composition of the solar system relative to that of the average interstellar medium. It is found that the solar system would be enriched in those isotopes which are produced by the more massive stars, such as O-16, C-12, Ne-20, and some other r-process material. It is proposed that specific isotopic ratios and elemental ratios reflecting these differences would include the Ne-20/Ne-22 ratio, which would be higher in the solar system than in the interstellar medium and the cosmic rays, the C-12/C-13 ratio which would be higher in the solar system than in the interstellar medium, and the oxygen-to-carbon ratio, which would also be higher in the solar system than in the typical interstellar medium.

Schramm, D. N.↗

NASA NTRS1982

The effect of solute on the homogeneous crystal nucleation frequency in metallic melts

A complete calculation that extends the classical theory for crystal nucleation in pure melts to binary alloys has been made. Using a regular solution model, approximate expressions have been developed for the free energy change upon crystallization as a function of solute concentration. They are used, together with model-based estimates of the interfacial tension, to calculate the nucleation frequency. The predictions of the theory for the maximum attainable undercooling are compared with existing experimental results for non-glass forming alloys. The theory is also applied to several easy glass-forming alloys (Pd-Si, Au-Si, Fe-B) for qualitative comparison with the present experimental experience on the ease of glass formation, and for assessment of the potential for formation of the glass in bulk.

Thompson, C. V.↗

NASA NTRS1983

Hf chronometer for the early solar system

It is now widely believed that Al-26 (half-life, 7.2 x 10 to the 5th yr) and Pd-107 (half-life, 6.5 x 10 to the 6th yr) were present in the early solar system. The nucleosynthetic event responsible for the production of these nuclei must therefore have occurred no more than a few million years before the formation of solid bodies. It is possible that this event also gave a rise to the I-129 believed to be present in the early solar system. The last event to contribute Pu-244 to the solar system, however, occurred approximately 10 to the 8th yr before the time of solidification. It is noted that this latter time scale is also consistent with the lack of evidence for a Cm-247 chronometer. It is proposed that Hf-182 (half-life, 9 x 10 to the 6th yr) can resolve the question whether heavy-element nonactinide nucleosynthesis occurred during the (Al-26)-producing event. It is believed that an answer to this question will help to clarify the chronology of the formation of the solar system and will help to determine the astrophysical sites of heavy-element nucleosynthesis.

Norman, E. B.↗

NASA NTRS1983

An XPS study of silicon/noble metal interfaces - Bonding trends and correlations with the Schottky barrier heights

This X-ray photoemission (XPS) study demonstrates a correlation of intrinsic TM-Si chemical bond formation with Schottky barrier heights for the near-noble transition metals (TM = Ni, Pd, Pt) and their corresponding silicides (TM2Si and TMSi) on Si(100). It is found that the barrier height correlates with the strength of the TM-Si orbital interaction as well as with the charge density around the Si atom. These observations suggest a dominant role for intrinsic chemical interactions in establishing the Schottky barrier heights in these TM-Si systems.

Grunthaner, P. J.↗

NASA NTRS1983

Supplemental basis functions for the second transition row elements

It is noted that for molecular calculations, the basis sets presented by Huzinaga (1977) need to be augmented by (1) 5p functions to describe the 5s - 5p near degeneracy; (2) a diffuse 4d function to provide for a balanced description of the 5s2 4dn, 5s1 4d(n+1), and 4d(n+2) states of the atom; and (3) a set of 4f functions to correlate the 4d functions. Here, the diffuse 4d function is similar in function to the diffuse 3d function for the first transition row elements recommended by Hay (1977). A table is included giving the optimized values for the diffuse 4d, the 5p, and 4f (STO exponent) functions. The diffuse 4d function and the 5p functions are optimized at the SCF level on the basis of the 5s1 4d(n+1) state (except for Pd, which is optimized for the 4d10 state) and the 5s1 5p1 4dn state, respectively. The table also gives the energies and the atomic symmetries for each of the SCF calculations.

Walch, S. P.↗

NASA NTRS1984

Solubility of hydrogen in metals and its effect of pore-formation and embrittlement

The effect of alloying elements on hydrogen solubility were determined by evaluating solubility equations and interaction coefficients. The solubility of dry hydrogen at one atmosphere was investigated in liquid aluminum, Al-Ti, Al-Si, Al-Fe, liquid gold, Au-Cu, and Au-Pd. The design of rapid heating and high pressure casting furnaces used in meta foam experiments is discussed as well as the mechanism of precipitation of pores in melts, and the effect of hydrogen on the shrinkage porosity of Al-Cu and Al-Si alloys. Hydrogen embrittlement in iron base alloys is also examined.

Shahani, H. R.↗

NASA NTRS1983

Erosion of mylar and protection by thin metal films

Mylar strips, 2.5 microns thick, uncoated and coated with 50A, 100A and 200A of Al, Pd, and Au/Pd were exposed on STS-5 in order to measure the erosion of mylar and to test means of protecting thin plastic foils commonly used for space experiments in low earth orbit. Analysis by optical microscopy, SEM and STEM investigation, EDX measurements, FTIR spectroscopy and weight loss measurements showed that while up to 75 percent of the uncoated mylar was eroded during exposure, thin coatings of the above metals can protect mylar for integrated oxygen-fluxes of at least 10 to the 21st atoms/sq cm.

Fraundorf, P.↗

NASA NTRS1983

Enstatite chondrites - Trace element clues to their origin

Three EH and three EL chondrites have been subjected to RNAA analysis for 20 trace elements, and interelement correlations were examined in order to assess the effects of nebular fractionation and metamorphism. The refractory siderophiles Ir, Os, and Re correlate with the normal siderophiles Ni, Pd, Au, Sb, and Ge, in ELs but not in EHs. The two element groups presumably condensed on separate phases at first, but concentrated in metal during metabolism. Volatiles are consistently more depleted in ELs than EHs. Strong correlations are found for In-Tl, Tl-Bi, and Zn-Cd-In, which are equally consistent with predicted condensation curves for the solar nebula and with volatilization curves for artificially heated Abee. The three factors accounting for 93 percent of variance reflect volatile, siderophile, and chalcophile behavior.

Hertogen, J.↗

NASA NTRS1985

An inert marker study for palladium silicide formation - Si moves in polycrystalline Pd2Si

A novel use of Ti marker is introduced to investigate the moving species during Pd2Si formation on 111 and 100 line-type Si substrates. Silicide formed from amorphous Si is also studied using a W marker. Although these markers are observed to alter the silicide formation in the initial stage, the moving species can be identified once a normal growth rate is resumed. It is found that Si is the dominant moving species for all three types of Si crystallinity. However, Pd will participate in mass transport when Si motion becomes obstructed.

Ho, K. T.↗

NASA NTRS1985

H-chondrites - Trace element clues to their origin

RNAA is used to determine the abundances of 20 trace elements in four H4, two H3, two H5, and two H6 chondrites from the British Museum, as a contribution to a multiple-method study of these objects. The results are presented in tables and graphs and analyzed in terms of the inhomogeneity of the parent bodies and the depletion of volatiles in the higher petrologic types. Features observed include siderophile depletion in H3 chondrites; systematic variation of siderophile abundance pattern with petrologic type; volatile depletion as a primary feature; mineralogy consistent with accretion at 420-500 K; and the factor-analysis groupings siderophiles (Os, Re, Ir, Ni, Pd, Au, and Ge), volatiles (Ag, Br, In, Cd, Bi, and Tl), and alkalis (Rb and Cs).

Morgan, J. W.↗

NASA NTRS1984

Crystal nucleation and glass formation in metallic alloy melts

Homogeneous nucleation, containerless solidification, and bulk formation of metallic glasses are discussed. Homogeneous nucleation is not a limiting factor for metallic glass formation at slow cooling rates if the reduced glass transition temperature is high enough. Such glasses can be made in bulk if heterogeneous nucleants are removed. Containerless processing eleminates potential sources of nucleants, but as drop tube experiments on the Pd-Si alloys show, the free surface may still be a very effective heterogeneous nucleant. Combination of etching and heating in vacuum or fluxing can be effective for cleaning fairly large ingots of nucleants. Reduced gravity processing has a potentially useful role in the fluxing technique, for example to keep large metallic ingots surrounded by a low density, low fluidity flux if this proved difficult under ground conditions. For systems where heterogeneous nucleants in the bulk of the ingot need gravity to segregate to the flux-metal interface, reduced gravity processing may not be appropriate for bulk glass formation.

Spaepen, F.↗

NASA NTRS1985

Structural characterization and gas reactions of small metal particles by high-resolution TEM and TED

The interaction of 100 and 200 keV electron beams with amorphous alumina, titania, and aluminum nitride substrates and nanometer-size palladium particulate deposits was investigated for the two extreme cases of (1) large-area electron-beam flash-heating and (2) small-area high-intensity electron-beam irradiation. The former simulates a short-term heating effect with minimum electron irradiation exposure, the latter simulates high-dosage irradiation with minimum heating effect. All alumina and titania samples responded to the flash-heating treatment with significant recrystallization. However, the size, crystal structure, shape, and orientation of the grains depended on the type and thickness of the films and the thickness of the Pd deposit. High-dosage electron irradiation also readily crystallized the alumina substrate films but did not affect the titania films. The alumina recrystallization products were usually either all in the alpha phase, or they were a mixture of small grains in a number of low-temperature phases including gamma, delta, kappa, beta, theta-alumina. Palladium deposits reacted heavily with the alumina substrates during either treatment, but they were very little effected when supported on titania. Both treatments had the same, less prominent localized crystallization effect on aluminum nitride films.

Heinemann, K.↗