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NASA NTRS2004

Evidence for Differential Comminution/Aeolian Sorting and Chemical Weathering of Martian Soils Preserved in Mars Meteorite EET79001

Impact-melt glasses containing Martian atmospheric gases in Mars meteorite EET79001 are formed from Martian soil fines that had undergone meteoroid-comminution and aeolian sorting accompanied by chemical weathering near Mars surface. Using SiO2 and SO3 as proxy for silicates and salts respectively in Mars soils, we find that SiO2 and SO3 correlate negatively with FeO and MgO and positively with Al2O3 and CaO in these glasses, indicating that the mafic and felsic components are depleted and enriched relative to the bulk host (Lith A/B) respectively as in the case of Moon soils. Though the overall pattern of mineral fractionation is similar between the soil fines on Mars and Moon, the magnitudes of the enrichments/depletions differ between these sample-suites because of pervasive aeolian activity on Mars. In addition to this mechanical processing, the Martian soil fines, prior to impact-melting, have undergone acid-sulfate dissolution under oxidizing/reducing conditions. The S03 content in EET79001,507 (Lith B) glass is approx.18% compared to < 2% in EET79001, 506 (Lith A). SiO2 and SO3 negatively correlate with each other in ,507 glasses similar to Pathfinder soils. The positive correlation found between FeO and SO3 in ,507 glasses as well as Pathfinder rocks and soils is consistent with the deposition of ferric-hydroxysulfate on regolith grains in an oxidizing environment. As in the case of Pathfinder soils, the Al 2O3 vs SiO2 positive correlation and FeO VS S102 negative correlation observed in ,507 glasses indicate that SiO2 from the regolith is mobilized as soluble silicic acid at low pH. The large off-set in the end-member FeO abundance ( SO3=0) between Pathfinder soil-free rock and sulfur-free rock in ,507 glass precursors suggests that the soils comprising the ,507 glasses contain much larger proportion of fine-grained Martian soil fraction that registers strong mafic depletion relative to Lith B. This inference is strongly supported by the Al2O3 - SO3 negative correlation observed in both ,507 glasses and pathfinder soils. Furthermore, the flat MgO-SO3 correlation observed in the case of ,507 glasses shows that the solubilized MgSO4 is mobilized by the aqueous solutions leaving behind the rock-residue with approx.2-3% MgO. This value is similar to the approx.2% MgO found for the soil-free rock at the Pathfinder site. The EET79001 ,506 glasses, in contrast, show that Al2O3 and CaO positively correlate with SO3 indicating that Al is precipitated as amorphous hydroxysulfate at relatively high pH. The FeO - SO3 negative correlation observed in ,506 glasses yields an end-member FeO abundance of approx.21% for the sulfur-free rock, which is consistent with the 22% FeO deduced for the Viking soil-free rock. Further, the FeO and MgO negative correlation with S03 observed in ,506 glasses indicates that the divalent Fe and Mg released from ferromagnesian minerals by acid sulfate dissolution are mobilized away from the reaction sites as soluble sulfates under reducing environment. A similar negative correlation between FeO and SO3 and a positive correlation between Al2O3 and SO3 found in Viking soils suggest that they also had undergone acid-sulfate dissolution under relatively reducing conditions.

Rao, M. N.↗

NASA NTRS2011

Ridge Waveguide Structures in Magnesium-Doped Lithium Niobate

This work proposes to establish the feasibility of fabricating isolated ridge waveguides in 5% MgO:LN. Ridge waveguides in MgO:LN will significantly improve power handling and conversion efficiency, increase photonic component integration, and be well suited to spacebased applications. The key innovation in this effort is to combine recently available large, high-photorefractive-damage-threshold, z-cut 5% MgO:LN with novel ridge fabrication techniques to achieve high-optical power, low-cost, high-volume manufacturing of frequency conversion structures. The proposed ridge waveguide structure should maintain the characteristics of the periodically poled bulk substrate, allowing for the efficient frequency conversion typical of waveguides and the high optical damage threshold and long lifetimes typical of the 5% doped bulk substrate. The low cost and large area of 5% MgO:LN wafers, and the improved performance of the proposed ridge waveguide structure, will enhance existing measurement capabilities as well as reduce the resources required to achieve high-performance specifications. The purpose of the ridge waveguides in MgO:LN is to provide platform technology that will improve optical power handling and conversion efficiency compared to existing waveguide technology. The proposed ridge waveguide is produced using standard microfabrication techniques. The approach is enabled by recent advances in inductively coupled plasma etchers and chemical mechanical planarization techniques. In conjunction with wafer bonding, this fabrication methodology can be used to create arbitrarily shaped waveguides allowing complex optical circuits to be engineered in nonlinear optical materials such as magnesium doped lithium niobate. Researchers here have identified NLO (nonlinear optical) ridge waveguide structures as having suitable value to be the leading frequency conversion structures. Its value is based on having the low-cost fabrication necessary to satisfy the challenging pricing requirements as well as achieve the power handling and other specifications in a suitably compact package.

Himmer, Phillip↗

NASA NTRS1979

Evidence for early volcanism in mare Smythii

The major geologic units in and around the Smythii basin are reflected in the Al2O3 and MgO values obtained using improved orbital X-ray fluorescence data from Apollo 15. One of these units is a high albedo plains-forming unit that has Al2O3 and MgO concentrations different from those of similar plains-forming units located in the terra west of Smythii and south of Crisium and also different from those of adjacent terra and mare materials. The chemical composition of the plainsforming unit suggests a volcanic origin; the inferred Al2O3 and MgO-rich nature of this presumed early volcanic material is supported by the fact that even the later, low albedo, lightly cratered mare fill in Mare Smythii has a high MgO value, and its Al2O3 concentration is higher than that of similar basaltic material in other maria.

Conca, J.↗

NASA NTRS1988

Sol-gel synthesis of magnesium oxide-silicon dioxide glass compositions

MgO-SiO2 glasses containing up to 15 mol pct MgO, which could not have been prepared by the conventional glass melting method due to the presence of stable liquid-liquid immiscibility, were synthesized by the sol-gel technique. Clear and transparent gels were obtained from the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) and magnesium nitrate hexahydrate when the water/TEOS mole ratio was four or more. The gelling time decreased with increase in magnesium content, water/TEOS ratio, and reaction temperature. Magnesium nitrate hexahydrate crystallized out of the gels containing 15 and 20 mol pct MgO on slow drying. This problem was partially alleviated by drying the gels quickly at higher temperatures. Monolithic gel samples were prepared using glycerol as the drying control additive. The gels were subjected to various thermal treatments and characterized by several methods. No organic groups could be detected in the glasses after heat treatments to approx. 800 C, but trace amounts of hydroxyl groups were still present. No crystalline phase was found from X-ray diffraction in the gel samples to approx. 890 C. At higher temperatures, alpha quartz precipitated out as the crystalline phase in gels containing up to 10 mol pct MgO. The overall activation energy for gel formation in 10MgO-90SiO2 (mol pct) system for water/TEOS mole ratio of 7.5 was calculated to be 58.7 kJ/mol.

Bansal, Narottam P.↗

NASA NTRS1988

Effect of substrate preparation on the structure and chemisorption properties of Pd/MgO model catalyst

Pd/MgO model catalysts are prepared by vapor deposition of Pd particles on MgO thin films which are deposited, at different temperatures, on UHV cleaved mica. MgO films and Pd particles are characterized in situ by Auger electron spectroscopy and energy-loss spectroscopy and ex situ by transmission electron microscopy. Succesive temperature programmed desorption (TPD) of CO shows a different evolution of the morphology of the Pd particles deposited on MgO films prepared at low and high temperature. In addition, on MgO prepared at low temperature, the smallest particles show a continuous decay of CO adsorption during TPD due to contamination by support species.

Henry, C. R.↗

NASA NTRS1991

Impact melts in the MAC88105 lunar meteorite - Inferences for the lunar magma ocean hypothesis and the diversity of basaltic impact melts

The MAC88105 lunar meteorite, as represented by thin section 78, contains three major types of impact melt breccias. The most abundant type is clast-laden, fine-grained, and rich in Al2O3 (28 wt pct); these clasts constitute most of the meteorite. Their abundance and aluminous nature indicate that the MAC88105 source area was very aluminous. This is consistent with formation of the primordial lunar crust from a global magma ocean. The second type of impact melt is represented by only one clast in 78. It has a basaltic bulk composition similar to many other lunar impact melts, but is significantly richer in P2O5 than most and has a much lower MgO/(MgO + FeO). The third impact-melt type resembles a prominent melt group at Apollo 16, but has lower MgO/(MgO + FeO). These data show that basaltic impact melts are compositionally diverse. Dating samples of the Al-rich impact melts and the new types of basaltic impact melts from this meteorite can test the idea that the Moon suffered a terminal cataclysm 3.9 Ga ago.

Taylor, G. J.↗

NASA NTRS1994

Phase E in a water-saturated peridotite system at 9.3 GPa

The stability of hydrous phases in a natural upper mantle system has been investigated at 9.3 GPa using a gel of KLB-1 peridotite composition with brucite which contains 14 wt. percent (30 atom. percent) water. No hydrous mineral was found at 950 (+150 -50) degree C. At 800 degree C, an assemblage of phase A, phase E, enstatite, clinohumite, and garnet is obtained. Although there is a significant thermal gradient over the sample, phase E is found to be surrounded by phase A in the lower temperature part. Electron probe analyses show that phase E has 35.5 SiO2, 4.4 Al2O3, 41.1 MgO and 8.5 wt. percent FeO* (Mg value is 90) with an oxide sum of 89.7 wt. percent, and possesses a stoichiometry similar to that proposed by Kanzaki. CaO and TiO2 are both less than 0.1 wt. percent. Coexisting phase A has 0.5 wt. percent CaO but only 0.4 wt. percent Al2O3 concentration. Phase A coexists with only enstatite in the water-saturated MgO-FeO-SiO2 system at 800 degree C and 9.3 GPa as well as the results in the water-saturated MgO-SiO2 system. Therefore it is suggested that the addition of Al2O3 expands the stability field of phase E to lower than 13 - 17 GPa in the water-saturated MgO-SiO2 system.

Kawamoto, Tatsuhiko↗

NASA NTRS2001

Organic Protomolecule Assembly in Igneous Minerals

C-H stretching bands in the infrared spectrum of single crystals of nominally high purity, laboratory-grown MgO and of natural upper mantle olivine provide an "organic" signature that closely resembles the symmetrical and asymmetrical C-H stretching modes of aliphatic -CH2- units. The C-H stretching bands indicate that H20 and CO2, dissolved in the matrix of these minerals, converted to form H2 and chemically reduced C, which in turn formed C-H entities, probably through segregation into defects such as dislocations. Heating causes the C-H bonds to pyrolyze and the C-H stretching bands to disappear, but annealing at 70 C causes them to reappear within a few days or weeks. Modeling dislocations in MgO suggests that the segregation of C can lead to Cx chains, x less than or equal to 4, with the terminal C atoms anchored to the MgO matrix by bonding to two U. Allowing H2 to react with such Cx chains leads to [O2C(CH2)2CO2] or similar precipitates. It is suggested that such Cx-Hy-Oz entities represent protomolecules from which derive the short-chain carboxylic and dicarboxylic and of the medium-chain fatty acids that have been solvent-extracted from crushed MgO and olivine single crystals, respectively. Thus it appears that the hard, dense matrix of igneous minerals represents a medium in which protomolecular units can be assembled. During weathering of rocks the protomolecular units turn into complex organic molecules. These processes may have provided stereochemically constrained organics to the early Earth that were crucial to the emergence of Life.

Freund, Friedemann↗

NASA NTRS2003

Combustion Of Metals In Reduced Gravity And Extraterrestrial Environments

The recent focus of this research project has been to model the combustion of isolated metal droplets and, in particular, to couple the existing theories and formulations of phenomena such as condensation, reaction kinetics, radiation, and surface reactions to formulate a more complete combustion model. A fully transient, one-dimensional (spherical symmetry) numerical model that uses detailed chemical kinetics, multi-component molecular transport mechanisms, condensation kinetics, and gas phase radiation heat transfer was developed. A coagulation model was used to simulate the particulate formation of MgO. The model was used to simulate the combustion of an Mg droplet in pure O2 and CO2. Methanol droplet combustion is considered as a test case for the solution method for both quasi-steady and fully transient simulations. Although some important processes unique to methanol combustion, such as water absorption at the surface, are not included in the model, the results are in sufficient agreement with the published data. Since the major part of the heat released in combustion of Mg, and in combustion of metals in general, is due to the condensation of the metal oxide, it is very important to capture the condensation processes correctly. Using the modified nucleation theory, an Arrhenius type rate expression is derived to calculate the condensation rate of MgO. This expression can be easily included in the CHEMKIN reaction mechanism format. Although very little property data is available for MgO, the condensation rate expression derived using the existing data is able to capture the condensation of MgO. An appropriate choice of the reference temperature to calculate the rate coefficients allows the model to correctly predict the subsequent heat release and hence the flame temperature.

Abbud-Madrid, A.↗

NASA NTRS2015

The Combined Strength of Thermodynamics and Comparative Planetology: Application of Activity Models to Core Formation in Terrestrial Bodies

Recent models for accretion of terrestrial bodies involve metal-silicate equilibrium as the metallic core formed during growth. Most elements considered are either refractory or well studied elements for which effects of pressure, temperature, oxygen fugacity, and metallic liquid composition are well known. There are a large number of elements that are both siderophile and volatile, whose fate in such models is unknown, largely due to a lack of data at comparable conditions and com-positions (FeNi core with light elements such as S, C, Si, and O). We have focused on Ge, In, As, Sb and determined the effect of Si and C on metal-silicate partitioning, and developed a thermo-dynamic model that allows application of these new data to a wide range of planetary bodies. New experiments: We have previously carried out experiments with FeSi metallic liquid at C-saturated conditions at 1600 and 1800 C [4]. In a new series of experiments we investigate the effect of Si in carbon-free systems at 1600 C for comparison. Experiments were carried out at 1 GPa in MgO capsules using the same basaltic starting composition as in previous studies. The MgO capsule reacts with the silicate melt to form more MgO-rich liquids that have 22-26 wt% MgO. Experimental met-als and silicates were analyzed using a combination of electron microprobe analysis and laser ablation ICP-MS. Results: The new results can be interpreted by considering Ge as an example, in the simple exchange equilibrium Fe + GeO = FeO + Ge, where the equilibrium constant Kd can be examined as a function of Si content of the metal. The slope of lnKd vs. (1-XSi) for this new series allows derivation of the epsilon interaction parameter for each of these four elements and Si (both C-saturated and C-free).All four elements have positive epsilon values, indicating that Si causes a decrease in the partition coefficients; values are 6.6, 6.5, 27.8 and 25.2 for In, Ge, As, and Sb, respectively, at 1 GPa and 1600 C. As an example of how large the effect of Si can be, these epsilon values correspond to activity coefficients (gamma) for As of 0.01 when XSi = 0, and up to gamma = 23 when XSi = 0.2. Combining these new results with previous determinations [5,6] of epsilon parameters for S and C for these elements allows us calculate activity of Ge, In, As, and Sb in Fe-Ni-Si-S-C-O metallic liquids. We apply this new model to sever-al terrestrial bodies such as Earth (Si-rich core), Mars (S-rich core), Moon (S-, C-, and Si-poor core), and Vesta, and examine the resulting core and mantle concentrations of these elements. Mantle concentrations of these four elements are well explained for Earth and Mars in models that call for mid-mantle equilibration between Si-bearing and S-bearing FeNi cores, respectively. Modeling results for the Moon and Vesta will also be presented.

Righter, K.↗

NASA NTRS1978

Soils from Mare Crisium - Agglutinitic glass chemistry and soil development

Agglutinates were studied in 29 polished thin sections of grain mounts from various size fractions of six Luna 24 soil horizons. Three populations of agglutinitic glass compositions were found: a high-MgO, high-FeO group identified as a coarse-grained basaltic component; a low-MgO, low-FeO group from a highland source; and a low-MgO, high-FeO group probably from the subophitic basalt component. The presence of a significant amount of admixed highland component probably accounts for an enrichment in plagioclase and a depletion in ferromagnesian elements displayed by the agglutinitic glass compositions relative to the bulk soil.

Hu, H.-N.↗

NASA NTRS1983

In-situ TEM investigations of graphic-epitaxy and small particles

Palladium was deposited inside a controlled-vacuum specimen chamber of a transmission electron microscope (TEM) onto MgO and alpha-alumina substrate surfaces. Annealing and various effects of gas exposure of the particulate Pd deposits were studied in-situ by high resolution TEM and electron diffraction. Whereas substrate temperatures of 500 C or annealing of room temperature (RT) deposits to 500 C were needed to obtain epitaxy on sapphire, RT deposits on MgO were perfectly epitaxial. For Pd/MgO a lattice expansion of 2 to 4% was noted; the highest values of expansion were found for the smallest particles. The lattice expansion of small Pd particles on alumina substrates was less than 1%. Long-time RT exposure of Pd/MgO in a vacuum yielded some moblity and coalescence events, but notably fewer than for Pd on sapphire. Exposure to air or oxygen greatly enhanced the particle mobility and coalescence and also resulted in the flattening of Pd particles on MgO substrates. Electron-beam irradiation further enhanced this effect. Exposure to air for several tens of hours of Pd/MgO led to strong coalescence.

Heinemann, K.↗

NASA NTRS1985

Tensile test of pressureless-sintered silicon nitride at elevated temperature

Uniaxial tensile strength tests of pressureless sintered silicon nitride were carried out in air at temperatures ranging from room temperature up to 1600 C. Silicon nitrides containing Y2O3, Al2O3, Al2O3-MgO, or MgO-CeO2 additives were tested. The results show that the composition of the additive used influences the strength characteristics of the silicon nitride. The tensile strength rapidly decreased at temperatures above 1000 C for the materials containing MgO as the additive and above 1000 C for the material with Y2O3. When the temperature increased to as high as 1300 C, the strength decreased to about 10 percent of the room temperature strength in each case. Observations of the fracture origin and of the crack propagation on the fracture surfaces are discussed.

Matsusue, K.↗

NASA NTRS1984

Achondrite ALHA77005 - Alteration of chromite and olivine

The olivine crystals of the 77005 achondrite are brown except for colorless shock lamellae, mottled patches, and grains adjacent to pools of impact melt. Sporadic dark alteration patches in brown olivine and Cr-rich spinel gave the following average electron-microprobe analyses: (olivine) P2O5 0.9, SiO2 57.9, TiO2 0, Al2O3 0.7, Cr2O3 0.4, V2O3 0, Fe2O3 (assumed oxidation state) 17.0, MgO 1.6, CaO 0.2, Na2O 0, K2O 1.8, SO3 (assumed oxidation state) 9.2, Cl 0.1, sum 89.8 wt pct; (spinel) P2O5 3.5, SiO2 2.1, TiO2 2.2, Al2O3 2.1, Cr2O3 13.4, V2O3 0.8, Fe2O3 40.7, MgO 0.9, CaO 0.1, Na2O 0, K2O 2.0, SO3 11.1, Cl 0.1, sum 79.0 wt pct. Ion-microprobe analyses revealed H in both. Rare orange patches in brown olivine from another area gave SiO2 33-35, FeO 30-28, MgO 28-32, sum 93 wt pct. Thermal metamorphism under dry oxidizing conditions is discussed as a possible alternative to shock-induced oxidation for generation of the brown olivine (McSween and Stoeffler, 1980). Because alteration patches transgress shock lamellae, and because sulfatic alteration occurs in fusion crusts of Antarctic meteorites (Gibson et al., 1983), alteration of the 77005 achondrite at the Antarctic surface is preferred to a complex series of processes needed for preterrestrial alteration.

Smith, J. V.↗

NASA NTRS1986

Composition of the Cayley Formation at Apollo 16 as inferred from impact melt splashes

Abundances of major and trace elements and magnetic properties of 50 impact melt splashes (IMSs) from the Apollo 16 landing site are analzyed to determine the composition of their meteoritic component. MgO-Sc and Ca-Sc variation diagrams and least-squares mixing models are utilized to analyze the IMS, soil, and rock data. Consideration is given to progenitor lithologies of the IMS, the number of impact events represented by the IMS, and the heterogeneity of impact melts from single events. It is observed that the IMSs are composed of either a mixture of anorthosite and low-Sc impact melt rocks or anorthositic norite. It is determined that the surface Cayley layer is composed of TiO2, MgO, Sc, and La concentrations of 0.69, and 7.1 wt pct and 10.5 and 21.2 microg/g, respectively and 0.38 and 5.9 wt pct and 6.1 and 11.8 microg/g, respectively, for the subsurface Cayley layer. The Descartes Formation composition is estimated as TiO2, MgO, Sc, and La concentrations of 0.25, and 3.5 wt pct and 7.7 and 2.2 microg/g, respectively.

Morris, Richard V.↗

NASA NTRS1991

The influence of bulk composition and dynamic melting conditions on olivine chondrule textures

The effects of the bulk composition and the dynamic melting conditions on the texture of olivine chondrules were investigated in a series of heating experiments. It is shown that variations in the olivine chondrule textures can be produced by varying the FeO/(FeO + MgO) ratio between the average Type IA and Type II chondrule compositions, could affect the texture of a chondrule at a constant initial melting temperature and heating time. A range of the heating times and the masses of precursor spheres caused variations in the degree of melting and in chondrule textures. Chondrule textures were distributed on a graph of initial temperatures vs. FeO/(FeO + MgO) ratios as bands parallel to the olivine disappearance curve. This graph could be used to predict chondrule textures from Fe/(FeO + MgO) ratios at specific initial melting temperatures.

Connolly, Harold C., Jr.↗

NASA NTRS1990

Dissociation of O(2-)2 defects into paramagnetic O(-) in wide band-gap insulators - A magnetic susceptibility study of magnesium oxide

The magnetic susceptibility of single-crystal MgO has been measured in the temperature range 300-1000 K, using a Faraday balance. The high-purity crystal (less than 100 ppm transition metals), grown from the melt in a H2O-containing atmosphere, was found to be paramagnetic due to the presence of defects on the O(2-) sublattice. The defects derive from OH(-) introduced into the MgO matrix by the dissolution of traces of H2O during crystal growth. The OH(-) converts into O(2-)2 and H2. Each O(2-)2 represents two coupled, spin-paired O(-) states. The observed strongly temperature-dependent paramagnetism can be described by three contributions that overlay the intrinsic diamagnetism of MgO and arise from the low level of transition-metal impurities, O(-) generated by 0(2-)2 dissociation, and O(-) states trapped by quenching from high temperatures from previous experiments.

Batllo, F.↗

NASA NTRS2002

Improved Dielectric Properties of Heterostructured Ba2.5Sr0.5TiO3 Thin Film Composites for Microwave Dielectric Devices

In the present work we have deposited MgO and Ba(sub 0.5)Sr(sub 0.5)TiO(sub 3)(BST50) thin layers in different sequences to make MgO:BST50 hetero-structured thin films. These films were characterized by X-ray diffraction and Rutherford backscattering technique and found to be highly (100) textured. The figure of merit {(C(sub0)-C(sub v)/(C(sub0-tandelta)} of the hetero-structured films was found to be higher as compared to pure BST50 films measured at 1 MHz frequency with electric field of 25.3 kV/cm. These films were used to make eight element coupled micro-strip phase shifter and characterized in a frequency range of 13-15 GHz. The high frequency figure of merit (kappa factor, defined as the ratio of degree of phase shift per dB loss) measured at around 14 GHz with electric field of 333 kV/cm has been markedly improved (around 64.28 deg/dB for hetero-structured film as compared to 24.65 deg /dB for pure film). Improvement in dielectric properties in a wide frequency range in the MgO:BST are believed to be due to the higher densification of the hetero-structured films.

Jain, M.↗