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Chemistry of Star-Forming Cores

Chemical effects arising from the exchange of molecules between dust and gas in dense clumps are described. Selective desorption of CO and N2 from grains in cool cores can account for the presence of ammonia in several cores in the NGC 2024 cloud. Evaporation of ices containing methanol and ethanol can lead to detectable abundances of (C2H5)(sub 2)O and CH3OC2H5. Results are presented for the hot core chemistries of sulphur and phosphorus which are initiated by evaporated hydrogen sulphide and phosphine. The implications of these studies for understanding the nature of molecular mantles, the evolution of molecular complexity in the gas phase, and the presence of small-scale abundance gradients in star-forming regions, are briefly discussed.

Charnley, S. B.↗

Correlation of Chemical and Physical Test Data for the Environmental Ageing of Tefzel (ETFE)

In a similar approach to that used for the previously issued correlation report for Coflon (CAPP/M.10), this report aims to identify any correlations between mechanical property changes and chemical/morphological changes for Tefzel, using information supplied in other MERL and TRI project reports (plus latest data which will be included in final reports for Phase 1). Differences identified with Coflon behaviour will be of scientific interest as well as appropriate to project applications, as Tefzel and Coflon are chemical isomers. Owing to the considerable chemical resistance of Tefzel, much of its testing so far has been based on mechanical properties. Where changes have occurred, chemical analysis can now be targeted more effectively. Relevant test data collated here include: tensile modulus and related properties, permeation coefficients, % crystallinity, and other observations where significant. Fluids based on methanol and amine (Fluid G), a mixture of methane, carbon dioxide and hydrogen sulphide gases plus an aqueous amine solution (Fluid F), and an aromatic oil mix of heptane, cyclohexane, toluene and I-propanol (Fluid 1) have affected Tefzel to varying degrees, and are discussed in some detail herein.

Morgan, G. J.↗

Correlation of Chemical and Physical Test Data For the Environment Ageing of Coflon (PVDF)

This report aims to identify correlations between mechanical property changes and chemical/morphological structure changes for Coflon. It is intended both to illustrate the overall methodology and to indicate the testing that needs to be undertaken in order to obtain correlations. Many fluid exposures have now been carried out on Coflon during the project and many data generated as a result. The report summarises the changes observed in mechanical and physical properties and relates these as well as possible to the chemistry thought to be occurring during ageing. For this purpose, data have been collated from already-issued MERL and TRI technical and progress reports. Most of the mechanical testing of aged testpieces has been performed soon after the completion of the exposure; however, there is of necessity a delay in obtaining chemical analysis of the same testpieces, so that more physical than chemical data are shown. Three fluids have so far caused measurable deterioration of Coflon, these being: methanol (Fluid A), a methanol and amine mixture (Fluid G), and a mixture of methane, carbon dioxide gas and hydrogen sulphide gas plus aqueous amine (Fluid F). Only the effects of these fluids will be dealt with in any detail in this report, although other fluids are assessed to give relevant background information. Relevant test data collated here include: tensile modulus and related properties, mode of sample failure at break, fracture toughness, fatigue crack growth rate and resistance, stress relaxation rate, permeation coefficients, % crystallinity and molecular weight distributions together with changes in fluorine levels, and other observations where appropriate. However, not all of these were obtained for every ageing condition. Because of the wide range of tests employed, and the different ways in which their results are obtained, the following section has been included to serve as a background for making comparisons.

Morgan, G. J.↗

Correlation of Chemical and Physical Test Data for the Environmental Ageing of Tefzel (ETFE)

In a similar approach to that used for the previously issued correlation report for Coflon (CAPP/M.10), this report aims to identify any correlations between mechanical property changes and chemical/morphological changes for Tefzel, using information supplied in other MERL and TRI project reports. Differences identified with Coflon behaviour will be of scientific interest as well as appropriate to project applications, as Tefzel and Coflon are chemical isomers. Owing to the considerable chemical resistance of Tefzel, much of its testing so far has been based on mechanical properties. Where changes have occurred, chemical analysis can now be targeted more effectively. Relevant test data collated here include: tensile modulus and related properties, permeation coefficients, % crystallinity, some crack growth resistance measurements, and other observations where significant. Fluids based on methanol and amine (Fluid G), a mixture of methane, carbon dioxide and hydrogen sulphide gases plus an aqueous amine solution (Fluid F), and an aromatic oil mix of heptane, cyclohexane, toluene and 1-propanol (Fluid I) have affected Tefzel to varying degrees, and are discussed in some detail herein.

Morgan, G. J.↗

Gravitational Constraints on the Internal Structure of Ganymede

Before the arrival of the Galileo spacecraft in the jovian system, there was little information on the interior structure of jupiter's largest moon, Ganymede. Its mean density (1,940 kg/cu m), determined by the Pioneer and Voyager spacecraft, implies a composition that is roughly 60% rock and 40% ice, which could be uniformly mixed or differentiated into a rocky core and icy mantle. Here we report measurements by the Galileo spacecraft of Ganymede's overall density and the spherical harmonics, J(sub 2) and C(sub 22) of its gravitational field. These data show clearly that Ganymede has differentiated into a core and mantle. Combined with the recent discovery of an intrinsic magnetic field, our gravity results suggest that Ganymede has a metallic core of radius 400-1,300 km surrounded by a silicate mantle, which is in turn enclosed by an ice she approx.800 km thick. Depending on whether the core is pure iron or an alloy of iron and iron sulphide, it could account for as little as 1.4% or as much as one-third of the total mass. If the ice were stripped away, Ganymede could look much like lo' in terms of its size and internal mass distribution.

Anderson, J. D.↗

Atmospheric Dynamics of the Outer Planets

The giant planets-Jupiter, Saturn, Uranus, and Neptune-are fluid objects. The winds are powered by absorbed sunlight, as on earth, and by internal heat left over from planetary formation. The main constituents of the atmospheres are hydrogen and helium. The clouds are made of ammonia, hydrogen sulphide, and water. All four giant planets are banded, with multiple zonal jet streams. Even Uranus, whose spin axis is tipped by 98deg relative to the orbit axis, shows latitudinal banding and zonal jets. Equator-to-pole temperature differences are close to zero. Wind speeds are larger than on earth and do not decrease with distance from the sun. Although the power/area at Neptune is only 1/20 that at Jupiter, the winds at Neptune are three times stronger. Stable vortices like the Great Red Spot of Jupiter and similar spots on Neptune come in all size ranges and exhibit a variety of behaviours including merging, orbiting, filament ejection, and oscillating in both shape and position. At least at cloud-top levels, 90% of the long-lived vortices are anticyclonic and sit in anticyclonic shear zones. Features in the cyclonic zones tend to be chaotic, with lifetimes of several days or less. These mesoscale eddies tend to have lightning in them, which suggests that they get their energy from moist convection. The rate of conversion of eddy kinetic energy into kinetic energy of the zonal jets is more than 10% of the power/area radiated by Jupiter. This fraction is more than an order of magnitude larger than on earth. Several lines of evidence now indicate that the winds at cloud-top levels are the surface manifestation of deep-rooted motions that extend into the interior and are presumably driven by internal heat.

Ingersoll, Andrew P.↗

A Review of Single Source Precursors for the Deposition of Ternary Chalcopyrite Materials

The development of thin-film solar cells on flexible, lightweight, space-qualified durable substrates (i.e. Kapton) provides an attractive solution to fabricating solar arrays with high specific power, (W/kg). The syntheses and thermal modulation of ternary single source precursors, based on the [{LR}2Cu(SR')2In(SR')2] architecture in good yields are described. Thermogravimetric analyses (TGA) and Low temperature Differential Scanning Caloriometry, (DSC) demonstrate that controlled manipulation of the steric and electronic properties of either the group five-donor and/or chalcogenide moiety permits directed adjustment of the thermal stability and physical properties of the precursors. TGA-Evolved Gas Analysis, confirms that single precursors decompose by the initial extrusion of the sulphide moiety, followed by the loss of the neutral donor group, (L) to release the ternary chalcopyrite matrix. X-ray diffraction studies, EDS and SEM on the non-volatile pyrolized material demonstrate that these derivatives afford single-phase CuInS2/CuInSe2 materials at low temperature. Thin-film fabrication studies demonstrate that these single source precursors can be used in a spray chemical vapor deposition process, for depositing CuInS2 onto flexible polymer substrates at temperatures less than 400 C.

Banger, K. K.↗

Lunar and Planetary Science XXXV: Carbonaceous Chondrites

The titles in this section include: 1) A Quantitative NMR Analysis of Phosphorus in Carbonaceous and Ordinary Chondrites; 2) An Infrared Study of the Matrices of CI1 and CM2 Chondrites; 3) A Study of the Morphology, Composition and Mineral Associations of Fe-Ni Sulphides in CM Carbonaceous Chondrites; 4) Aqueous Alteration Mineralogy in CM Carbonaceous Chondrites; 5) In Situ Location and Characterization of Carbon-bearing Phases in Carbonaceous; 6) Chondrites: Insights from Yamato 791198, a Weakly-altered CM2 Chondrite; 7) Unique Texture in EET 83389: Clues to Formation of Fine Grained Rims in CM Chondrites; 8) Amoeboid Olivine Aggregates in the NWA 760 CV3 Chondrite; 9) Petrologic Type of CV3 Chondrites as Revealed by Raman Spectroscopy of Organic Matter; 10) A First Look at Acfer 324: Evidence for Another CR 3 Chondrite? 11) Hydrogen Isotopic Composition of the Bencubbin Meteorite; 12) The Fountain Hills Meteorite: A New CBa Chondrite from Arizona; 13) Shock Effects in the Metal-rich Chondrites QUE 94411, Hammadah al Hamra 237 and Bencubbin; 14) Mineralogy and Petrology of Al-rich Objects in the CH Carbonaceous Chondrite North West Africa 739.

Source record↗

Gravitational evidence for an undifferentiated Callisto

Before the arrival of the Galileo spacecraft at Jupiter, models for the interior structure of the four galilean satellites--Io, Europa, Ganymede and Callisto-ranged from uniform mixtures of rock and ice (that is, undifferentiated objects) or rocky cores surrounded by a mantle of water ice. Now it appears that Io has a large metallic core and that Ganymede is strongly differentiated, most probably into a three-layer structure consisting of a metallic core, a silicate mantle and a deep outer layer of ice. Direct information on the interior structure of Callisto determined from previous spacecraft fly-bys was essentially limited to an estimate of the mean density being intermediate between pure ice and pure rock. Here we report measurements of Callisto's gravitational field which reveal that, in contrast to Io and Ganymede, this galilean satellite is most probably a homogeneous object consisting of a solar mixture of 40% compressed ice and 60% rock (including iron and iron sulphide). Callisto's undifferentiated state is consistent with the apparent lack of an intrinsic magnetic field, and indicates that the outermost galilean satellite has not experienced a heating phase sufficiently high to separate its rock and metal components from the lighter ices.

unmanned↗

Effect of crop development on biogenic emissions from plant populations grown in closed plant growth chambers

The Biomass Production Chamber at John F. Kennedy Space Center is a closed plant growth chamber facility that can be used to monitor the level of biogenic emissions from large populations of plants throughout their entire growth cycle. The head space atmosphere of a 26-day-old lettuce (Lactuca sativa cv. Waldmann's Green) stand was repeatedly sampled and emissions identified and quantified using GC-mass spectrometry. Concentrations of dimethyl sulphide, carbon disulphide, alpha-pinene, furan and 2-methylfuran were not significantly different throughout the day; whereas, isoprene showed significant differences in concentration between samples collected in light and dark periods. Volatile organic compounds from the atmosphere of wheat (Triticum aestivum cv. Yecora Rojo) were analysed and quantified from planting to maturity. Volatile plant-derived compounds included 1-butanol, 2-ethyl-1-hexanol, nonanal, benzaldehyde, tetramethylurea, tetramethylthiourea, 2-methylfuran and 3-methylfuran. Concentrations of volatiles were determined during seedling establishment, vegetative growth, anthesis, grain fill and senescence and found to vary depending on the developmental stage. Atmospheric concentrations of benzaldehyde and nonanal were highest during anthesis, 2-methylfuran and 3-methylfuran concentrations were greatest during grain fill, and the concentration of the tetramethylurea peaked during senescence.

NASA Program CELSS↗

Accretion, Differentiation, and Impact Processes on the Ureilite Parent Body

Ureilites are primitive ultramafic achondrites composed largely of olivine and pigeonite, with minor augite, orthopyroxene, carbon, sulphide and metal. They represent very early material in the history of the Solar System and (in common with lodranites and acapulcoites) form a bridge between undifferentiated chondrites and fully differentiated asteroidal bodies. They show an intriguing mixture of chemical characteristics, some of which are considered to be nebula-derived (e.g. variations in Delta(sup 17)O and mg#) whereas others have been imposed by asteroidal differentiation (e.g. core formation, silicate partial melting, removal of basalt).

Downes, Hilary↗

Early Proterozoic (2.0 GA) Phosphorites from Pechenga Greenstone Belt and Their Origin

The period of 2500-2000 Ma is heralded by several other hallmark events, including onset and decline of the greatest positive excursion of Beta13Ccarb (Lomagundi-Jatuli Paradox), development of a significant seawater sulphate reservoir, abundant deposition of anomalously organic matter (OM)-rich sediments, the oldest known significant petroleum deposits (Shunga Event), and the appearance of first known marine phosphorites at 2000 Ma as reported here. They occur as numerous rounded, soft-deformed, clasts in fine-pebble intra-formational conglomerates, forming two separate c. 200 m-thick turbidite fans within the 1000 m-thick OM- and sulphide-rich turbiditic greywackes of the Pilgujaervi Formation in the Pechenga Greenstrone Belt, NW Russia. Carbonate-fluorapatite is the main mineral in the phosphorite clasts. OM, framboidal and micronodular pyrite as well as inclusions of quartz and chlorite are additional components. Many clasts show microlayering with a variable degree of soft-deformation, implying that they were derived from non-lithified, bedded phosphorites. Numerous samples revealed diverse microbial microstructures interpreted as cyanobacterial mats consisting of filamentous (1-3 micrometer in diameter, 20 micrometers in length), coccoidal (0.8-1.0 micrometers) and ellipsoidal or rod-shaped microfossils (0.8 micrometers in diameter, around 2 micrometers in length) which morphologically resemble modern Microcoleus and Syphonophycus, Thiocapsa, and Rhabdoderma, respectively, reported from alkaline or saline environments. No principle differences have been found between microfossils described from Cambrian and Phanerozoic and the 2000 Ma phosphorites. The sequence of the early Palaeoproterozoic events which point to a significant oxidation of the hydrosphere, now including formation of phosphorites and change in the phosphorous cycle, mimics the sequence which was repeated once again at the Neoproterozoic-Cambrian transition, implying that oxidation of the terrestrial atmosphere-hydrosphere system experienced an irregular cyclic development.

Rozanov, A. Yu.↗

New Insights into the Composition and Texture of Lunar Regolith Using Ultrafast Automated Electron-Beam Analysis

Sieved grain mounts of Apollo 16 drive tube samples have been examined using QEMSCAN - an innovative electron beam technology. By combining multiple energy-dispersive X-ray detectors, fully automated control, and off-line image processing, to produce digital mineral maps of particles exposed on polished surfaces, the result is an unprecedented quantity of mineralogical and petrographic data, on a particle-by-particle basis. Experimental analysis of four size fractions (500-250 microns, 150-90 microns, 75-45 microns and < 20 microns), prepared from two samples (64002,374 and 64002,262), has produced a robust and uniform dataset which allows for the quantification of mineralogy; texture; particle shape, size and density; and the digital classification of distinct particle types in each measured sample. These preliminary data show that there is a decrease in plagioclase modal content and an opposing increase in glass modal content, with decreasing particle size. These findings, together with data on trace phases (metals, sulphides, phosphates, and oxides), provide not only new insights into the make-up of lunar regolith at the Apollo 16 landing site, but also key physical parameters which can be used to design lunar simulants, and compute Figures of Merit for each material produced.

Rickman, Doug↗

Asteroid 4 Vesta: A Fully Differentiated Dwarf Planet

One conclusion derived from the study of meteorites is that some of them - most irons, stony irons, some achondrites - hail from asteroids that were heated to the point where metallic cores and basaltic crusts were formed. Telescopic observations show that there remains only one large asteroid with a basaltic crust, 4 Vesta; present day mean radius 263 km. The largest clan of achondrites, the howardite, eucrite and diogenite (HED) meteorites, represent the crust of their parent asteroid. Diogenites are cumulate harzburgites and orthopyroxenites from the lower crust whilst eucrites are cumulate gabbros, diabases and basalts from the upper crust. Howardites are impact-engendered breccias of diogenites and eucrites. A strong case can be made that HEDs are derived from Vesta. The NASA Dawn spacecraft orbited Vesta for 14 months returning data allowing geological, mineralogical, compositional and geophysical interpretations of Vesta's surface and structure. Combined with geochemical and petrological observations of HED meteorites, differentiation models for Vesta can be developed. Proto-Vesta probably consisted of primitive chondritic materials. Compositional evidence, primarily from basaltic eucrites, indicates that Vesta was melted to high degree (>=50%) which facilitated homogenization of the silicate phase and separation of immiscible Fe,Ni metal plus Fe sulphide into a core. Geophysical models based on Dawn data support a core of ~110 km radius. The silicate melt vigorously convected and initially followed a path of equilibrium crystallization forming a harzburgitic mantle, possibly overlying a dunitic restite. Once the fraction of crystals was sufficient to cause convective lockup, the remaining melt collected between the mantle and the cool thermal boundary layer. This melt undergoes fractional crystallization to form a dominantly orthopyroxenite (diogenite) lower crust. The initial thermal boundary layer of primitive chondritic material is gradually replaced by a mafic crust through impact disruption and foundering. The quenched mafic crust thickens over time through magma extrusion/intrusion. Melt from the residual magma ocean intrudes and penetrates the mafic crust forming cumulate eucrite plutons, and dikes, sills and flows of basaltic eucrite composition. The post-differentiation vestan structure is thus not too dissimilar from that of terrestrial planets: (i) a metallic core; (ii) an ultramafic mantle comprised of a lower dunitic layer (if melting was substantially <100%) and an upper cumulate harzburgitic layer; (iii) a lower crust of harzburgitic and orthopyroxenitic cumulates; and (iv) an upper mafic crust of basalts and diabases (melt compositions) with cumulate gabbro intrusions. Impacts have excavated to the lower crust and delivered howardites, eucrites and diogenites to Earth, but there is yet no evidence demonstrating excavation of the vestan mantlle.

Mittlefehldt, David↗

A Classification Table for Achondrites

Classifying chondrites is relatively easy and the criteria are well documented. It is based on mineral compositions, textural characteristics and more recently, magnetic susceptibility. It can be more difficult to classify achondrites, especially those that are very similar to terrestrial igneous rocks, because mineralogical, textural and compositional properties can be quite variable. Achondrites contain essentially olivine, pyroxenes, plagioclases, oxides, sulphides and accessory minerals. Their origin is attributed to differentiated parents bodies: large asteroids (Vesta); planets (Mars); a satellite (the Moon); and numerous asteroids of unknown size. In most cases, achondrites are not eye witnessed falls and some do not have fusion crust. Because of the mineralogical and magnetic susceptibility similarity with terrestrial igneous rocks for some achondrites, it can be difficult for classifiers to confirm their extra-terrestrial origin. We -as classifiers of meteorites- are confronted with this problem with every suspected achondrite we receive for identification. We are developing a "grid" of classification to provide an easier approach for initial classification. We use simple but reproducible criteria based on mineralogical, petrological and geochemical studies. We presented the classes: acapulcoites, lodranites, winonaites and Martian meteorites (shergottite, chassignites, nakhlites). In this work we are completing the classification table by including the groups: angrites, aubrites, brachinites, ureilites, HED (howardites, eucrites, and diogenites), lunar meteorites, pallasites and mesosiderites. Iron meteorites are not presented in this abstract.

Chennaoui-Aoudjehane, H.↗

Controlled evolution of rare earth phosphate in coal ash slag

Coal ash slag as a waste by-product, is generated from commercial processes that include gasification facilities, power plants, and steelmaking industries. Some is recycled into construction materials, insulation fibers, and used as a soil neutralizer, but the majority is still discarded. Coal ash slag exhibit trace amounts of critical materials including rare earth elements (REEs). An economically viable extraction of REEs from the coal ash would lower the production costs, addressing the availability and environmental concerns. In nature, most REEs exist as phosphate such as monazite but its synthetic evolution in coal ash slag has never been reported. In industrial processes, P may originate from coal, additives, and/or refractory liners. REEs may be extracted by first concentrating REEs into phosphates, sulphide, or fluorides [1], or carbonates [2]. In this work, P-enriched coal ash slag bearing REEs was first melted above 1600 °C, then crystallization behaviors in the melt during controlled cooling was studied. REE phosphate coprecipitated with mullite and hematite with mullite being the first crystal to form on cooling. The REEs were rejected from the molten slag, mullite, and hematite, and tended to segregate only to the phosphate phase with REE concentration as high as 58 wt.% in the structure.

Nakano, Jinichiro↗

Controlled evolution of rare earth phosphate in coal ash slag

Coal ash slag as a waste by-product, is generated from commercial processes that include gasification facilities, power plants, and steelmaking industries. Some is recycled into construction materials, insulation fibers, and used as a soil neutralizer, but the majority is still discarded. Coal ash slag exhibit trace amounts of critical materials including rare earth elements (REEs). An economically viable extraction of REEs from the coal ash would lower the production costs, addressing the availability and environmental concerns. In nature, most REEs exist as phosphate such as monazite but its synthetic evolution in coal ash slag has never been reported. In industrial processes, P may originate from coal, additives, and/or refractory liners. REEs may be extracted by first concentrating REEs into phosphates, sulphide, or fluorides [1], or carbonates [2]. In this work, P-enriched coal ash slag bearing REEs was first melted above 1600 °C, then crystallization behaviors in the melt during controlled cooling was studied. REE phosphate coprecipitated with mullite and hematite with mullite being the first crystal to form on cooling. The REEs were rejected from the molten slag, mullite, and hematite, and tended to segregate only to the phosphate phase with REE concentration as high as 58 wt.% in the structure.

Nakano, Jinichiro↗

Comprehensive insights into competitive oxidation/sulfidation reactions on binary ferritic alloys at high temperatures

Interpreting high-temperature corrosion induced by mixed-gas atmospheres is challenging due to the different contributions of oxidizing gases. In this work, a comprehensive study on the combined oxidation/sulfidation using label molecules is presented. Fe-Cr model alloys with 2 wt% and 9 wt% Cr were isothermally exposed using a volumetric mixture of 0.5%S 16 O 2 /27%H 2 18 O and 0.5%S 16 O 2 /7%H 2 18 O at 650 °C for 5 h and then characterized by secondary ion mass spectroscopy (SIMS). Additionally, the reactions were followed in-situ utilizing energy dispersive X-ray diffraction. The study showed that both S 16 O 2 and H 2 18 O contribute to the oxidation of the alloys but to different extents depending on the Cr-content.

36 MATERIALS SCIENCE↗