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At least 73 records · Page 4

Partitioning of Moderately Siderophile Elements Among Olivine, Silicate Melt, and Sulfide Melt: Constraints on Core Formation in the Earth and Mars

This study investigates the effects of Variations in the fugacities of oxygen and sulfur on the partitioning of first series transition metals (V, Cr, Mn, Fe, Co, Ni. and Cu) and W among coexisting sulfide melt, silicate melt, and olivine. Experiments were performed at 1 atm pressure, 1350 C, with the fugacities of oxygen and sulfur controlled by mixing CO2, CO, and SO2 gases. Starting compositions consisted of a CaO-MgO-Al2O3-SiO2-FeO-Na2O analog for a barred olivine chondrule from an ordinary chondrite and a synthetic komatiite. The f(sub O2)/f(sub S2), conditions ranged from log of f(sub O2) = -7.9 to - 10.6, with log of f(sub S2) values ranging from - 1.0 to -2.5. Our experimental results demonstrate that the f(sub O2)/f(sub S2) dependencies of sulfide melt/silicate melt partition coefficients for the first series transition metals arc proportional to their valence states. The f(sub O2)/f(sub S2) dependencies for the partitioning of Fe, Co, Ni, and Cu are weaker than predicted on the basis of their valence states. Variations in conditions have no significant effect on olivine/melt partitioning other than those resulting from f(sub O2)-induced changes in the valence state of a given element. The strong f(sub O2)/f(sub S2) dependence for the olivine/silicate melt partitioning of V is attributable to a change of valence state, from 4+ to 3+, with decreasing f(sub O2). Our experimentally determined partition coefficients are used to develop models for the segregation of sulfide and metal from the silicate portion of the early Earth and the Shergottite parent body (Mars). We find that the influence of S is not sufficient to explain the overabundance of siderophile and chalcophile elements that remained in the mantle of the Earth following core formation. Important constraints on core formation in Mars are provided by our experimental determination of the partitioning of Cu between silicate and sulfide melts. When combined with existing estimates for siderophile element abundances in the Martian mantle and a mass balance constraint from Fe, the experiments allow a determination of the mass of the Martian core (approx. 17 to 22 wt% of the planet) and its S content (approx.0.4 wt%). These modeling results indicate that Mars is depleted in S, and that its core is solid.

Gaetani, Glenn A.↗

Molecule formation in normal clouds

Some aspects of molecule formation in normal interstellar clouds, i.e., clouds having particle densities of less than 100 per cu cm, are discussed in light of recent studies. It is pointed out that, with their relatively large depletion parameter values (DPVs), CH clouds are 'young', whereas OH clouds have small DPVs and are 'old'. The theoretical reason for this is that OH, as a product of grain catalysis, persists over a much longer period of cloud evolution, whereas CH(+), CH, and CN, as products of gas-phase reaction, can be found only in 'young' clouds where depletion has not yet occurred. This may explain why OH has not been seen in radio observations of regions where CH(+), CH, and CN have been seen optically.

Aannestad, P. A.↗

Storing hydrogen in the form of light alloy hydrides

Different hydrides are investigated to find a system with a sufficiently high storage density (at least 3%). The formation of hydrides with light alloys is examined. Reaction kinetics for hydride formation were defined and applied to the systems Mg-Al-H, Mg-Al-Cu-H, Ti-Al-H, Ti-Al-Cu-H, and Ti-Al-Ni-H. Results indicate that the addition of Al destabilizes MgH2 and TiH2 hydrides while having only a limited effect on the storage density.

Freund, E.↗

Surface diffusion activation energy determination using ion beam microtexturing

The activation energy for impurity atom (adatom) surface diffusion can be determined from the temperature dependence of the spacing of sputter cones. These cones are formed on the surface during sputtering while simultaneously adding impurities. The impurities form clusters by means of surface diffusion, and these clusters in turn initiate cone formation. Values are given for the surface diffusion activation energies for various materials on polycrystalline Cu, Al, Pb, Au, and Ni. The values for different impurity species on each of these substrates are approximately independent of impurity species within the experimental uncertainty, suggesting the absence of strong chemical bonding effects on the diffusion.

Rossnagel, S. M.↗

Partitioning of siderophile and chalcophile elements between sulfide, olivine, and glass in a naturally reduced basalt from Disko Island, Greenland

Major and trace elements in coexisting glass, olivines, and metal-sulfide spherules from a chilled margin sample of a strongly reduced basaltic dike from Disko Island, Greenland have been investigated. Three sets of partition coefficients are obtained, olivine/silicate liquid and metal-sulfide liquid/silicate liquid partition coefficients established at magmatic temperatures, and FeNi/FeS partition coefficients at lower temperatures. High metal-sulfide liquid/silicate liquid partition coefficients are found for Ni, Sb, As, Mo, Cu, Co, and W. The significance of the present results for planetary evolution and the formation of metal-rich or sulfide-rich metal cores is considered in terms of P, W, and Mo abundances in the mantles of the earth, moon, the Shergotty parent body, and the Eucrite parent body.

Klock, W.↗

Precipitation strengthened high strength, high conductivity Cu-Cr-Nb alloys produced by chill block melt spinning

A series of Cu-based alloys containing 2 to 10 a/o Cr and 1 to 5 a/o Nb were produced by chill block melt spinning (CBMS). The melt spun ribbons were consolidated and hot rolled to sheet to produce a supersaturated Cu-Cr-Nb solid solution from which the high melting point intermetallic compound Cr2Nb could be precipitated to strengthen the Cu matrix. The results show that the materials possess electrical conductivities in excess of 90 percent that of pure Cu at 200 C and above. The strengths of the Cu-Cr-Nb alloys were much greater than Cu, Cu-0.6 Cr, NARloy-A, and NARloy-Z in the as-melt spun condition. The strengths of the consolidated materials were less than Cu-Cr and Cu-Cr-Zr below 500 C and 600 C respectively, but were significantly better above these temperatures. The strengths of the consolidated materials were greater than NARloy-Z, at all temperatures. The GLIDCOP possessed similar strength levels up to 750 C when the strength of the Cu-Cr-Nb alloys begins to degrade. The long term stability of the Cu-Cr-Nb alloys was measured by the microhardness of aged samples and the growth of precipitates. The microhardness measurements indicate that the alloys overage rapidly, but do not suffer much loss in strength between 10 and 100 hours which confirms the results of the electrical resistivity measurements taken during the aging of the alloys at 500 C. The loss in strength from peak strength levels is significant, but the strength remains exceptionally good. Transmission electron microscopy (TEM) of the as-melt spun samples revealed that Cr2Nb precipitates formed in the liquid Cu during the chill block melt spinning, indicating a very strong driving force for the formation of the precipitates. The TEM of the aged and consolidated materials indicates that the precipitates coarsen considerably, but remain in the submicron range.

Ellis, David L.↗

Geologic and remote sensing studies of Rima Mozart

Geologic, photographic, and remote sensing data on Rima Mozart are analyzed to study the processes responsible for the formation of lunar sinuous rilles. The results show that it is unlikely that a complete lava tube could have existed along the Rima Mozart rille. A total eruptive volume of 6372 cu km has been determined for an open channel or tube with an eruption rate of about 80,000 cu m/s and a duration of 947 days. Near-infrared spectral reflectance data and 2.8-cm and 70-cm radar observations indicate that volcanic activity was responsible for the formation of the rille and that pyroclastic deposits are present around Kathleen and Ann as well as at the base of the Apennines.

Coombs, Cassandra R.↗

Magnetic fields and radiative shocks in protogalaxies and the origin of globular clusters

The paper examines the hypothesis that globular clusters formed from gravitational instability in dense sheets of gas produced behind radiative shocks inside protogalaxies, such as those produced by the collision of subgalactic mass fragments partaking of the virial motions within the protogalaxy, in order to determine the differences which result if a magnetic field is present in the preshock medium. The MHD conservation equations are solved along with rate equations for nonequilibrium ionization, recombination, molecular formation and dissociation, and the equations of radiative transfer for steady-state shocks of velocity 300 km/s in a gas of preshock densities of 0.1-1 cu cm, and magnetic field strengths of 0.1-6 micro-G. The magnetic field is found to limit the degree of postshock compression and, thereby, to reduce the level of external radiation flux required to suppress H2 formation and cooling.

Shapiro, Paul R.↗

Modified Rosenthal Solution for Prediction of In Situ Alloyed GRCop-42 Melt Pool

Literature suggests that the energy needed to in-situ alloy material via additive manufacturing is higher per unit volume than their pre-alloyed counterparts, often despite the in-situ formation of thermodynamically favorable phases. This work, via experiments on in-situ alloyed GRCop-42 (Cu-4 at% Cr-2 at% Nb), will explore the energy needs of an elemental powder blend during in-situ alloying via laser powder bed fusion (LPBF). Empirically derived models will explore the influence of elemental thermophysical properties, net energy of in-situ reactions, and powder characteristics on the resulting LPBF energy demands, weld pool size and shape, and porosity evolution. Additionally, the influence of energy input during printing on the in-situ reaction to form Cr2Nb will be explored. Evolution of Cr2Nb dispersoid and copper grain shape, size, and texture can be related to the temperature reached, cooling rate, and time-as-melt during in-situ alloying via LPBF.

David Scannapieco↗

Semiempirical Analysis of Surface Alloy Formation

The BFS method for alloys is applied to the study of surface alloy formation. This method was previously used to examine the experimental STM observation of surface alloying of Au on Ni(110) for low Au coverages by means of a numerical simulation. In this work, we extend the study to include other cases of surface alloying for immiscible as well as miscible metals. All binary combinations of Ni, Au, Cu, and Al are considered and the simulation results are compared to experiment when data is available. The driving mechanisms of surface alloy formation are then discussed in terms of the BFS method and the available results.

Bozzolo, Guillermo↗

Experimental Verification of the Theoretical Prediction of the Phase Structure of a Ni-Al-Ti-Cr-Cu Alloy

The Bozzolo-Ferrante-Smith (BFS) method for alloys was applied to the study of NiAl-based materials to assess the effect of alloying additions on structure. Ternary, quaternary and even pentalloys based on NiAl with additions of Ti, Cr and Cu were studied and experimental verification of the theoretical predictions including the phase structure of a Ni-Al-Ti-Cr-Cu alloy is presented. Two approaches were used, Monte Carlo simulations to determine low energy structures, and analytical calculations of the energy of high symmetry configurations which give physical insight into preferred structures. The energetics for site occupancy in ternary and quaternary systems were calculated leading to an indirect determination of solubility limits at 0 K. Precipitate formation with information concerning structure and lattice parameter were also 'observed' computationally and the general characteristics of a Ni-Al-Ti-Cr-Cu alloy were correctly predicted. The results indicate that the BFS method for alloys can be a useful tool for alloy design and can be used to complement experimental alloy design programs.

Wilson, A.↗

Liquidus Temperatures and Solidification Behavior in the Copper-Niobium System

The copper-niobium phase diagram has been under active debate; thus, a corroboratory experimental study is needed. In this investigation, the melts of Cu-Nb alloys at compositions ranging from 5 lo 86 wt% Nb were processed in different environments and solidified at relatively low rates of 50-75 C/s to determine liquidus temperatures and to study solidification behavior. For all samples processed under very clean conditions, only Nb dendrites in a Cu matrix were observed; while in the presents of oxygen impurities, the alloys containing 5-35 wt% Nb exhibited microstructure of Nb-rich spheroids and Nb dendrites in the Cu matrix. The results obtained from clean conditions are in fair agreement with the Cu-Nb phase diagram having an S-shaped, near-horizontal appearances of the liquidus. The formation of Nb-rich droplets at slow cooling rates is discussed in terms of a stable liquid miscibility gap induced by oxygen.

Li, D.↗

Liquidus Temperatures and Solidification Behavior in the Copper-Niobium System

The copper-niobium phase diagram has been under active debate; thus, a corroboratory experimental study is needed. In this investigation, the melts of Cu-Nb alloys at compositions ranging from 5 to 86 wt pct Nb were processed in different environments and solidified at relatively low cooling rates of 50 to 75 C/s to determine liquidus temperatures and to study solidification behavior. For all samples processed under very clean conditions, only Nb dendrites in a Cu matrix were observed; while in the presence of oxygen impurities the alloys containing 5 to 35 wt pct Nb exhibited microstructure of Nb-rich spheroids and Nb dendrites in the Cu matrix. The results obtained from clean conditions are in fair agreement with the Cu-Nb phase diagram having an S-shaped, near-horizontal appearance of the liquidus. The formation of Nb- rich droplets at slow cooling rates is discussed in terms of a stable liquid miscibility gap induced by oxygen.

Li, D.↗

Some volcanologic aspects of Columbia River basalt volcanism relevant to the extinction controversy

The Columbia River Basalt Group is the youngest and most thoroughly studied flood-basalt province known; information about it should be relevant to questions about the possible relation of flood-basalt volcanism to mass extinctions. The group has a total volume of about 174,000 cu km and covers an area of about 164,000 sq km. It was erupted between 17.5 and 6 Ma, as measured by K-Ar and Ar-40/Ar-39 dates. Early eruptions formed the Imnaha Basalt. More than 85 percent of the group was produced during a 1.5 my period between 17 and 15.5 Ma, forming the Grande Ronde and greatly subordinate Picture Gorge Basalts. Later flows formed the Wanapum Basalt, which includes the well-known Roza Member, and the Saddle Mountains Basalt. Linear vent systems for many of the flows are known and are located only in the eastern third of the Columbia Plateau. No systematic migration of vents occurred throughout the 11.5 my period of activity; this and other considerations make it unlikely that the province is related to a hot spot. Model calculations based on observations that little cooling occurred during flow of hundreds of kilometers suggest eruption and emplacement durations of a few days. Some voluminous flows occur in all formations, but most such flows apparently were erupted during Grande Ronde time. The eruption and emplacement of more than 1,000 cu km of 1100 C basaltic lava on the surface within several days doubtless had at least local meteorologic effects. Whether the effects were broader can at present only be hypothesized. Grande Ronde Basalt and Picture Gorge Basalts contain moderately common but thin sedimentary interbeds between flows, whereas earlier and later formations contain numerous, locally thick sediment accumulations. Volcaniclastic debris derived from extra-plateau sources commonly occurs in the testbeds.

Swanson, Donald A.↗

Pressure dependence of the absolute rate constant for the reaction OH + C2H2 from 228 to 413K

The pressure dependence of absolute rate constants for the reaction of OH + C2H2 yields products has been examined at five temperatures ranging from 228 to 413 K. The experimental techniques which was used is flash photolysis-resonance fluoresence. OH was produced by water photolysis and hydroxyl resonance fluorescent photons were measured by multiscaling techniques. The results indicate that the low pressure bimolecular rate constant is 4 x 10 the the minus 13th power cu cm molecule (-1) s(-1) over the temperature range studied. A substantial increase in the bimolecular rate constant with an increase in pressure was observed at all temperatures except 228 K. This indicates the importance of initial adduct formation and subsequent stablization. The high pressure results are well represented by the Arrhenius expression (k sub bi) sub infinity = (6.83 + or - 1.19) x 10 to the minus 12th power exp(-646 + or - 47/T)cu cm molecule (-1) s(-1). The results are compared to previous investigated and are theoretically discussed. The implications of these results on modeling of terrestrial and planetary atmospheres and also in combustion chemistry are discussed.

Michael, J. V.↗

Carbonate formation in Marslike environments

A finely ground basaltic rock subjected to Marslike temperatures, atmospheric pressures and compositions and UV-rich illumination has provided a simulation system for studying carbonate growth in the Martian regolith. Growth rates of about 10 to the 12th or 13th power molecules per cu cm per sec are observed with or without the presence of liquid-phase water. The role of UV illumination in the photochemistry of water, a process which influences chemical alteration activity, is discussed. The study suggests that carbonate formation is an important aspect of Martian chemical weathering and that it provides a major chemical reservoir for outgassed carbon dioxide.

Booth, M. C.↗

Astronomical infrared spectroscopy with a Connes-type interferometer. III Alpha Orionis, 2600 to 3450 per cm.

Analysis of recent spectra of alpha Ori in the 3 to 4 micron region at a resolving power of about 10,000, showing clear evidence of the delta v = 1 sequence of the rotation-vibration bands of OH. A detailed investigation of the rotational and vibrational populations suggests that the OH is close to being in LTE at an apparent temperature of 4100 plus or minus 200 K. An OH abundance of 1.2 x 10 to the 20th molecules per cu cm and upper limits for H2O and H super 35 Cl of 8 x 10 to the 18th and 8 x 10 to the 17th molecules per cu cm, respectively, are deduced. It is also deduced that the rms turbulence velocity in the region of OH line formation is 11.5 plus or minus 2 km/sec. The implications of these data on abundances in M supergiant atmospheres are discussed.

Beer, R.↗

Measurements of recombination of electrons with HCO(plus) ions

Recombination coefficients of electrons with HCO(+) ions were determined with a microwave afterglow/mass spectrometer apparatus. Afterglow measurements of electron density decays in neon-hydrogen-carbon monoxide mixtures are correlated with the decay of mass-identified ion currents to the wall of the microwave cavity. At the appropriate partial pressures of hydrogen and carbon monoxide in the mixture, the ion HCO(+) dominates the ion composition and its wall current approximately tracks the electron density decay curve. From recombination controlled electron density decay curves, the values alpha (HCO(+)) = (3.3 + or - 0.5) and (2.0 + or - 0.3) 0.0000001 cu cm/sec are obtained at 205 and 300 K, respectively. The implications of these results for models of polyatomic molecule formation in dense interstellar clouds are briefly discussed.

Leu, M. T.↗