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At least 19 records

The growth of metastable peritectic compounds

The influence of gravitationally driven thermosolutal convection on the directional solidification of peritectic alloys is considered as well as the relationships between the solidification processing conditions, and the microstructure, chemistry, and magnetic properties of such alloys. Analysis of directionally solidified Pb-Bi peritectic samples indicates that appreciable macrosegregation occurs due to thermosolutal convection and/or Soret diffusion. A peritectic solidification model which accounts for partial mixing in the liquid ahead of the planar solidification interface and describes macrosegregation has been developed. Two-phase dendritic and banded microstructures were grown in the Pb-Bi peritectic system, refined two-phase microstructures have were observed, and candidate formation mechanisms proposed. Material handling, containment, casting, microstructural and magnetic characterization techniques were developed for the Sm-Co system. Alloys produced with these procedures are homogeneous.

Larson, D. J., Jr.↗

The growth of metastable peritectic compounds

The effects of directional solidification processing on the microstructural, compositional, and magnetic properties of high-melting-temperature, commercially important alloys which form from the liquid state via peritectic or eutectic type reactions were determined. Emphasis was placed on ferromagnetic compounds of the commercially important Co-Sm and Al-Mn systems. The primary dendrite spacing for eutectic Sm2Co17/Co scaled with negative square root of V and varied from approximately 50 microns for V 20 cm/h to hundreds of microns for V 10 cm/h. Since the crystal growth mechanism was dendritic rather than cooperative, the assoicated permanent magnet properties were rather poor. Magnetization as a function of sample orientation indicates that the easy axis of magnetization was primarily along the direction of solidification for the eutectic Sm2Co17/Co and peritectic SmCo5/Sm2Co17 compositions. For the Al-Mn case, magnetization and microstructural characterization suggest isotropic, polycrystalling growth for all solidification velocities studied.

Pirich, R. G.↗

The growth of metastable peritectic compounds

The influence of gravitationally driven convection on the directional solidification of peritectic alloys was evaluated. The Pb-Bi peritectic was studied as a model solidification system. Analyses of directionally solidified Pb-Bi peritectic samples indicate that appreciable macrosegregation occurs due to thermosolutal convection and/or Soret diffusion. The macrosegregation results in sequantial change of phase and morphology as solidification progresses down the length of the sample. Banding was eliminated when furnace conditions were selected which resulted in a planar solidification interface. The directional solidification that occurs in the vicinity of the Pb-Bi peritectic isothermal was found to be isocompositional and to consist solely of the equilibrium terminal solid solution and peritectic phases on an extremely fine scale. Evidence was found to support the peritectic supercooling mechanism, but not the proposed peritectic superheat mechanism.

Larson, D. J., Jr.↗

The room-temperature dissociation of the compound Au3Si

Three gold-18.6 at.% silicon specimens which were solidified by quenching from above the liquidus temperature have been reexamined after being stored at room temperature for about 8 years. It was found that the 'metastable' compound Au3Si formed on quenching had begun to dissociate by a surface nucleated, solid-state reaction. The reaction front had advanced about 0.2 mm from the surface, leaving a rim of dissociation products. These dissociation products were studied using optical and scanning electron microscopy, electron beam microprobe analysis and an X-ray micro-diffraction technique. It was concluded that the reaction produces elemental gold and silicon, as at higher reaction temperatures, but that the scale of dispersion is so extremely fine that the resulting microstructure cannot be resolved by scanning electron microscopy.

Bhattacharya, D.↗

Liquid-metal atomization for hot working preforms

Rapid quenching of a liquid metal by atomization or splat cooling overcomes the major limitation of most solidification processes, namely, the segregation of alloying elements, impurities, and constituent phases. The cooling rates of different atomizing processes are related to the dendrite arm spacings and to the microstructure of the atomized powders. The increased solubility limits and the formation of metastable compounds in splat-cooled alloys are discussed. Consolidation of the powders by hot isostatic compaction, hot extrusion, or hot forging and rolling processes yields billets with properties equivalent to or better than those of the wrought alloys. The application of this powder processing technology to high-performance alloys is reviewed.

Grant, N. J.↗

Containerless undercooling and solidification in drop tubes

A containerless low-gravity environment, produced within a 32 m drop tube apparatus, has been used to undercool and solidify metals, alloys or glasses by eliminating crucible induced nucleation processes. Niobium droplets with diameters in the range of 2 to 5 mm have been undercooled by 525 K which corresponds to the maximum undercooling reported by Turnbull and others on fine dispersions of low melting point metals. Solidification at large undercooling resulted in single crystalline spheres with the formation of interdendritic shrinkage channels on the sample surface rather than interior shrinkage cavities. The grain refinement as observed for Ni samples undercooled and solidified in fused silica crucibles does not occur in free-falling drops of Nb. A calculated solidification speed of undercooled Nb is compared to Ni. A solidification speed of 320 m/s is found for the Nb drops. This solidification speed is greater than or comparable to the solidification speeds calculated in splat cooled samples. Thus, a drop tube apparatus can be useful in the preparation and study of high temperature metastable compounds or alloys in bulk form.

Lacy, L. L.↗

Rare Gases Inserted into Biological Building Blocks: A Theoretical Study of Glycine - Rg Compounds (Rg-Xe, Kr, Ar)

Compounds formed by insertion of rare-gas atoms (Xe, Kr, and Ar) into glycine molecule are investigated using accurate ab initio computational methods. Identification of such insertion compounds may open new frontiers in the field of rare-gas chemistry, such as possible existence of biological molecules that include chemically bound rare gas atoms. The most stable glycine-Rg configuration is found to correspond to insertion of Rg atoms into the 0-H bond of glycine. These NH2CH2COORgH compounds are metastable , but separated by sizable potential barriers from the Rg + glycine dissociation products. Preliminary calculations show that NH2CH2COOXeH compound is energetically stable with respect to another (3-body) dissociation channel (NH2CH2COO + Rg + H), while the corresponding Ar species is not stable in this respect. The compound with the inserted Kr is a borderline case, with the 3-body dissociation products being close in energy to the NH2CH2COOKrH minimum.

Chaban, Galina M.↗

Numerical simulations of the seasonal/latitudinal variations of atomic oxygen and nitric oxide in the lower thermosphere and mesosphere

A 2-Dimensional zonally-averaged thermospheric model and the global University College London (UCL) thermospheric model have been used to investigate the seasonal, solar activity and geomagnetic variation of atomic oxygen and nitric oxide. The 2-dimensional model includes detailed oxygen and nitrogen chemistry, with appropriate completion of the energy equation, by adding the thermal infrared cooling by O and NO. This solution includes solar and auroral production of odd nitrogen compounds and metastable species. This model has been used for three investigations; firstly, to study the interactions between atmospheric dynamics and minor species transport and density; secondly, to examine the seasonal variations of atomic oxygen and nitric oxide within the upper mesosphere and thermosphere and their response to solar and geomagnetic activity variations; thirdly, to study the factor of 7 to 8 peak nitric oxide density increase as solar F sub 10.7 cm flux increases from 70 to 240 reported from the Solar Mesospheric Explorer. Auroral production of NO is shown to be the dominant source at high latitudes, generating peak NO densities a factor of 10 greater than typical number densities at low latitudes. At low latitudes, the predicted variation of the peak NO density, near 110 km, with the solar F sub 10.7 cm flux is rather smaller than is observed. This is most likely due to an overestimate of the soft X-ray flux at low solar activity, for times of extremely low support number, as occurred in June 1986. As observed on pressure levels, the variation of O density is small. The global circulation during solstice and periods of elevated geomagnetic activity causes depletion of O in regions of upwelling, and enhancements in regions of downwelling.

Rees, D.↗

The electron-impact promoted fragmentation of aurone epoxides.

The mass spectra of six aurone epoxides have been rationalized with the aid of high resolution mass spectrometry and metastable ion evidence. These compounds fragment in a well defined manner and mechanisms are proposed for the formation of their characteristic ions. Some similarity was observed between the mass spectra of 6-methoxyaurone epoxide (II), 4-hydroxy-7-methoxy-3-phenylcoumarin (VII) and 7-methoxyflavonol (IX). The possibility that VII and IX are intermediates in the fragmentation of epoxide II is discussed. Thermal rearrangement of aurone epoxide II was shown to yield the corresponding flavonol IX and coumarin VII.

Brady, B. A.↗

Experimental Investigation of Organic Synthesis in Hydrothermal Environments

Seafloor hydrothermal systems may be the most likely locations on the early Earth for the emergence of life. Because of the disequilibrium inherent in such dynamic, mixing environments, abundant chemical energy would have been available for formation of the building blocks of life. In addition, theoretical studies suggest that organic compounds in these conditions would reach metastable states, due to kinetic barriers to the formation of stable equilibrium products (CO2 and methane). The speciation of organic carbon in metastable states is highly dependent on the oxidation state, pH, temperature, pressure and bulk composition of the system. The goal of our research is to investigate the effects of a number external variables on the formation, transformation, and stability of organic compounds at hydrothermal conditions. We have begun experimental work to attempt to control the oxidation state of simulated hydrothermal systems by using buffers composed of mineral powders and gas mixtures. We are also beginning to test the stability of organic compounds under these conditions. The experiments are being performed using the hydrothermal bomb apparatus at the U.S. Geological Survey in Menlo Park, CA and the supercritical water oxidizer (SCWO) at NASA Ames Research Center in Moffet Field, CA. The amino acids decomposed rapidly. Even after the approximately 15 minutes between addition of the amino acids and the first sampling, no amino acids were detected in the PPM system by GC- MS, while in the FeFeO system the amino acids were present at a level of less than 50% of original. Carboxylic acids, ammonia, and CO2 were the main products, along with some unidentified compounds. The ratios of carboxylic acids and concentrations of other products seem to have remained stable during the experiments, consistent with observations of other metastable systems and theoretical predictions.

Shock, Everett L.↗

Experimental Investigation of Organic Synthesis in Hydrothermal Environments

The results of the investigation were presented at a Astrobiology Institute General Meeting. Seafloor hydrothermal systems may be the most likely locations on the early Earth for the emergence of life. Because of the disequilibrium inherent in such dynamic, mixing environments, abundant chemical energy would have been available for formation of the building blocks of life. In addition, theoretical studies suggest that organic compounds in these conditions would reach metastable states, due to kinetic barriers to the formation of stable equilibrium products (CO2 and methane). The speciation of organic carbon in metastable states is highly dependent on the oxidation state, pH, temperature, pressure and bulk composition of the system. The goal of our research is to investigate the effects of a number external variables on the formation, transformation, and stability of organic compounds at hydrothermal conditions. We have begun experimental work to attempt to control the oxidation state of simulated hydrothermal systems by using buffers composed of mineral powders and gas mixtures. We are also beginning to test the stability of organic compounds under these conditions.

Shock, Everett L.↗

Resistivity of Carbon-Carbon Composites Halved

Carbon-carbon composites have become the material of choice for applications requiring strength and stiffness at very high temperatures (above 2000 C). These composites comprise carbon or graphite fibers embedded in a carbonized or graphitized matrix. In some applications, such as shielding sensitive electronics in very high temperature environments, the performance of these materials would be improved by lowering their electrical resistivity. One method to lower the resistivity of the composites is to lower the resistivity of the graphite fibers, and a proven method to accomplish that is intercalation. Intercalation is the insertion of guest atoms or molecules into a host lattice. In this study the host fibers were highly graphitic pitch-based graphite fibers, or vapor-grown carbon fibers (VGCF), and the intercalate was bromine. Intercalation compounds of graphite are generally thought of as being only metastable, but it has been shown that the residual bromine graphite fiber intercalation compound is remarkably stable, resisting decomposition even at temperatures at least as high as 1000 C. The focus of this work was to fabricate composite preforms, determine whether the fibers they were made from were still intercalated with bromine after processing, and determine the effect on composite resistivity. It was not expected that the resistivity would be lowered as dramatically as with graphite polymer composites because the matrix itself would be much more conductive, but it was hoped that the gains would be substantial enough to warrant its use in high-performance applications. In a collaborative effort supporting a Space Act Agreement between the NASA Glenn Research Center and Applied Sciences, Inc. (Cedarville, OH), laminar preforms were fabricated with pristine and bromine-intercalated pitch-based fibers (P100 and P100-Br) and VGCF (Pyro I and Pyro I-Br). The green preforms were carbonized at 1000 C and then heat treated to 3000 C. To determine whether the fibers in the samples were still intercalated after composite fabrication, they were subjected to X-ray diffraction. The composites containing intercalated graphite fibers showed much higher background scatter than that of pristine fibers, indicating the presence of bromine in the samples. More importantly, faint features indicative of intercalation were visible in the diffraction pattern, showing that the fibers were still intercalated.

Gaier, James R.↗

Lattice-matched heteroepitaxy of wide gap ternary compound semiconductors

A variety of applications are identified for heteroepitaxial structures of wide gap I-III-VI2 and II-IV-V2 semiconductors, and are assessed in comparison with ternary III-V alloys and other wide gap materials. Non-linear optical applications of the I-III-VI2 and II-IV-V2 compound heterostructures are discussed, which require the growth of thick epitaxial layers imposing stringent requirements on the conditions of heteroepitaxy. In particular, recent results concerning the MOCVD growth of ZnSi(x)Ge(1-x)P2 alloys lattice-matching Si or GaP substrates are reviewed. Also, heterostructures of Cu(z)Ag(1-z)GaS2 alloys that lattice-match Si, Ge, GaP or GaAs substrates are considered in the context of optoelectronic devices operating in the blue wavelength regime. Since under the conditions of MOCVD, metastable alloys of the II-IV-V2 compounds and group IV elements are realized, II-IV-V2 alloys may also serve as interlayers in the integration of silicon and germanium with exactly lattice-matched tetrahedrally coordinated compound semiconductors, e.g. ZnSi(x)Ge(1-x)P2.

Bachmann, Klaus J.↗

AstroBioLab: A Mobile Biotic and Soil Analysis Laboratory

The Jet Propulsion Laboratory, Scripps Institution of Oceanography, and NASA Ames Research Center are currently developing a mobile Astrobiology Laboratory (AstroBioLab) for a series of field campaigns using the Chilean Atacama Desert as a Martian surface analog site. The Astrobiology Science and Technology for Exploring Planets (ASTEP) program funded AstroBioLab is designed around the Mars Organic Detector (MOD) instrument and the Mars Oxidant Instrument (MOI) which provide complementary data sets. Using this suite of Mars Instrument Development Program (MIDP) and Planetary Instrument Definition and Development Program (PIDDP) derived in situ instruments, which provide state-of-the-art organic compound detection (attomolar sensitivity) and depth profiling of oxidation chemistry, we measure and correlate the interplay of organic compounds, inorganic oxidants, UV irradiation and water abundance. This mobile laboratory studies the proposition that intense UV irradiation coupled with low levels of liquid water generates metastable oxidizing species that can consume moderate amounts of seeded organic compounds. Results from the initial spring 2003 field campaign will be presented.

J L Bada↗

Lattice-matched heteroepitaxy of wide gap ternary compound semiconductors

A variety of applications are identified for heteroepitaxial structures of wide gap I-III-VI(sub 2) and II-IV-V(sub 2) semiconductors, and are assessed in comparison with ternary III-V alloys and other wide gap materials. Non-linear optical applications of the I-III-VI(sub 2) and II-IV-V(sub 2) compound heterostructures are discussed, which require the growth of thick epitaxial layers imposing stringent requirements on the conditions of heteroepitaxy. In particular, recent results concerning the MOCVD growth of ZnSi(x)Ge(1-x)P2 alloys lattice matching Si or GaP substrates are reviewed. Also, heterostructures of Cu(z)Ag(1-z)GaS2 alloys that lattice-match Si, Ge, GaP, or GaAs substrates are considered in the context of optoelectronic devices operating in the blue wavelength regime. Since under the conditions of MOCVD, metastable alloys of the II-IV-V(sub 2) compounds and group IV elements are realized, II-IV-V(sub 2) alloys may also serve as interlayers in the integration of silicon and germanium with exactly lattice-matched tetrahedrally coordinated compound semiconductors, e.g. ZnSi(x)Ge(1-x)P2.

Bachmann, Klaus J.↗

Structural properties of bismuth-bearing semiconductor alloys

The structural properties of bismuth-bearing III-V semiconductor alloys InPBi, InAsBi, and InSbBi were studied theoretically. Bond energies, bond lengths, and strain coefficients were calculated for pure AlBi, GaBi, and InBi compounds and their alloys, and predictions were made for the mixing enthalpies, miscibility gaps, and critical metastable-to-stable material transition temperatures. Miscibility calculations indicate that InSbBi will be the most miscible, and the InPBi will be the the most difficult to mix. However, calculations of the hardness of the Bi compounds indicate that, once formed, the InPBi alloy will be harder than the other Bi alloys and substantially harder than the currently favored narrow-gap semiconductor HgCdTe.

Berding, M. A.↗

A meteor-ablation model of the sodium and potassium layers

Recent results on meteor ablation are used as input to a model in which ablation (or evaporation) is the source and deposition on dust particles is the sink. The dust comes from recondensation of the rest of the meteor vapor. An excellent match is found to the observed characteristics of the sodium layer. It is argued that the high-latitude winter maximum of abundance (and layer height) is due to the much lower rate of ionization there and over the polar cap. The computations show the required factor of 4-5 and also match the height variation. To keep the ion density from being too large, downward electrodynamic transport at about 50 cm/sec must be invoked. The different behavior and low abundance of potassium require an additional sink. The one proposed is Penning ionization by metastable excited O2. Inherent in the model is that sodium and its compounds reside almost entirely on dust particles below 80 km. Large abundances in the free form at stratospheric heights are very unlikely and are not a good explanation of observed ambient ions.

Hunten, D. M.↗

Crystallographic Stability of Metastable Phase Formed by Containerless Processing in REFeO3 (RE: Rare-Earth Element)

Undercooling a melt often facilitates a metastable phase to nucleate preferentially. Although the classical nucleation theory shows that the most critical factor for forming a metastable phase is the interface free energy, the crystallographic stability is also indispensable for the phase to be frozen at ambient temperature. In compound materials such as oxides, authors have suggested that the decisive factors for forming a critical nucleus are not only the free energy difference but also the difference of the entropy of fusion between stable and metastable phases. In the present study, using REFeO3 (RE: rare-earth element) as a model material, we investigate the formation of a metastable phase from undercooled melts with respect to the competitive nucleation and crystallographical stabilities of both phases.

Kuribayashi, Kazuhiko↗