Mineralogy of chondritic interplanetary dust particles

From a mineralogical survey of approximately 30 chondritic micrometeorites collected from the lower stratosphere and studied in detail using current electron microscopy techniques, it is concluded that these particles represent a unique group of extraterrestrial materials. These micrometeorites differ significantly in form and texture from components of carbonaceous chondrites and contain some mineral assemblages which do not occur in any meteorite class. Electron microscope investigations of chondritic micrometeorites have established that these materials (1) are extraterrestrial in origin, (2) existed in space as small objects, (3) endured minimal alteration by planetary processes since formation, and (4) can suffer minimal pulse heating (<600°C) on entering earth's atmosphere. The probable sources for chondritic interplanetary dust particles (IDPs) are cometary and asteroidal debris and, perhaps to a lesser extent, interstellar regions. These sources have not been conclusively linked to any specific mineralogical subset of IDP, although the chondritic porous (CP) aggregate is considered of likely cometary origin. Chondritic IDPs occur in two predominant mineral assemblages: (1) carbonaceous phases and phyllosilicates and (2) carbonaceous phases and nesosilicates or inosilicates, although particles with both types of silicate assemblages are observed. Olivines, pyroxenes, layer silicates, and carbon-rich phases are the most commonly occurring minerals in many chondritic IDPs. Other phases often observed in variable proportions include sulphides, spinels, metals, metal carbides, carbonates, and minor amounts of sulphates and phosphates. Individual mineral grain sizes range from micrometers (primarily pyroxenes and olivines) to nanometers, with the predominant size for all phases less than 100 nm. Specific mineral characteristics for particular chondritic IDPs provide an indication of processes which may have occurred prior to collection in the earth's stratosphere. For example, pyroxene mineralogy in some chondritic aggregates is consistent with condensation from a vapor phase and, we consider, with condensation in a turbulent solar nebula at relatively low temperatures (<1000°C). Carbonaceous phases present in other CP aggregates have been used to imply low-temperature formation processes such as Fischer-Tropsch synthesis (∼530°C) or carbonization and graphitization (∼315°C). Alteration processes have been implicated in the formation of some layer silicates in CP aggregates and may have involved hydrocryogenic alteration at <0°C. In general, interpretations of transformation processes on submicrometer-size minerals in chondritic IDPs are consistent with formation at a radius equivalent to the asteroid belt or greater during the later stages of solar nebula evolution using currently available models.

Nucleation experiments in a microgravity environment

A simple experimental apparatus is described in which a wide variety of vapor phase nucleation studies of refractory materials could be performed aboard NASA's KC-135 Research Aircraft. The chief advantage of a microgravity environment for these studies is the expected absence of thermally driven convective motions in the gas. The absence of convection leads to much more accurate knowledge of both the temperature distribution in the system and the time evolution of the refractory vapor concentration as a function of distance from the crucible.The evolution of the apparatus will be described as more experience is gained with the microgravity environment. Such experiments will be used to prepare for similar ones carried out aboard either the shuttle or Space Station where considerably longer duration experiments are possible.

Scanning electron microscopy of condensation related minerals : the Bjurbole meteorite

Filamentary single crystals, blades, sheets, euhedral crystals and powders may form by vapor phase condensation depending on the supersauration conditions in the vapor with respect to the condensing species [1]. Filamentary crystal growth requires the operation of an axial screw dislocation [2]. A Vapor-Liquid-Solid (VLS) mechanism may also produce filamentary single crystals, ribbons and blades. The latter two morphologies are typically twinned. Crystals grown by this mechanism do not require the presence of an axial screw dislocation. Impurities may either promote or inhibit crystal growth [3]. The VLS mechanism allows crystals to grow at small supersaturation of the vapor. Thin enstatite blades, ribbons and sheets have been observed in chondritic porous Interplanetary Dust Partics (IDP's) [4, 5]. The requisite screw dislocation for vapor phase condensation [1] has been observed in these enstatite blades [4]. Bradley et al. [4] suggest that these crystals are primary vapor phase condensates which could have formed either in the solar nebula or in presolar environments. These observations [4,5] are significant in that they may provide a demonstrable link to theoretical predictions: viz. that in the primordial solar nebula filamentary condensates could cluster into 'lint balls' and form the predecessors to comets [6].

Ultraviolet Photodissociation of the N-Methylpyridinium Ion: Action Spectroscopy and Product Characterization

The ultraviolet photodissociation of gas-phase N-methylpyridinium ions is studied at room temperature using laser photodissociation mass spectrometry and structurally diagnostic ion-molecule reaction kinetics. The C5H5N-CH3+ (m/z 94), C5H5N-CD3+ (m/z 97), and C5D5N-CH3+(m/z 99) isotopologues are investigated, and it is shown that the N-methylpyridinium ion photodissociates by the loss of methane in the 36 000 - 43 000 cm(-1) (280 - 230 nm) region. The dissociation likely occurs on the ground state surface following internal conversion from the SI state. For each isotopologue, by monitoring the photofragmentation yield as a function of photon wavenumber, a broad vibronically featured band is recorded with origin (0-0) transitions assigned at 38 130, 38 140 and 38 320 cm(-1) for C5H5N-CH3+ C5H5N-CD3+ and C5D5N-CH3+, respectively. With the aid of quantum chemical calculations (CASSCF(6,6)/aug-cc-pVDZ), most of the observed vibronic detail is assigned to two in-plane ring deformation modes. Finally, using ion-molecule reactions, the methane coproduct at m/z 78 is confirmed as a 2-pyridinylium ion.

Structural, optical and electrical properties of sulfur-incorporated amorphous carbon films

Amorphous carbon-sulfur (a-C:S) composite films were prepared by vapor phase pyrolysis technique. The structural changes in the a-C:S films were investigated by electron microscopy. A powder X-ray diffraction (XRD) study depicts the two-phase nature of a sulfur-incorporated a-C system. The optical bandgap energy shows a decreasing trend with an increase in the sulfur content and preparation temperature. This infers a sulfur incorporation and pyrolysis temperature induced reduction in structural disorder or increase in sp (2) or pi-sites. The presence of sulfur (S 2p) in the a-C:S sample is analyzed by the X-ray photoelectron spectroscopy (XPS). The sp (3)/sp (2) hybridization ratio is determined by using the XPS C 1s peak fitting, and the results confirm an increase in sp (2) hybrids with sulfur addition to a-C. The electrical resistivity variation in the films depends on both the sulfur concentration and the pyrolysis temperature.

Doping Dependence of Semiconductor-Metal Transition in InP at High Pressures

The resistivity of selenium-doped n-InP single crystal layers grown by liquid-phase epitaxy with electron concentrations varying from 6.7 x 10$^18$ to 1.8 x 10$^20$ cm$^{-3}$ has been measured as a function of hydrostatic pressure up to 10 GPa. Semiconductor-metal transitions were observed in each case with a change in resistivity by two to three orders of magnitude. The transition pressure p$_c$ decreased monotonically from 7.24 to 5.90 GPa with increasing doping concentration n according to the relation $p_c = p_o [1 - k(n/n_m)^a]$, where n$_m$ is the concentration (per cubic centimetre) of phosphorus donor sites in InP atoms, p$_o$ is the transition pressure at low doping concentrations, k is a constant and $\alpha$ is an exponent found experimentally to be 0.637. The decrease in p$_c$ is considered to be due to increasing internal stress developed at high concentrations of ionized donors. The high-pressure metallic phase had a resistivity (2.02-6.47) x 10$^{-7}$ $\Omega$ cm, with a positive temperature coefficient dependent on doping.

Kinetics and mechanism of the transformation in antimony trioxide from orthorhombic valentinite to cubic senarmontite

The kinetics of the polymorphic transformation in antimony trioxide from metastable orthorhombic valentinite to cubic senarmontite has been studied in polycrystalline material between 490 and 530°C. Quantitative analysis of the mixtures was done using infrared spectrophotometry. The kinetic data was analyzed and the activation energy for the process was obtained: (i) On the basis of Avrami's equation, which is derived on the basis of a nucleation and growth mechanism; and (ii) from the time required for a constant fraction of the transformation to take place. The values obtained were 50.8 and 46.0 kcal/mole. Observations have also been made on partly transformed single crystals of valentinite using a polarizing microscope. The latter studies and the value of the activation energy suggest that a better understanding of the transformation could be obtained on the basis of a vapor phase mechanism.

Development of a Mixing Device for Gas-Solid Systems and Its Application to MT Reactors

A new arrangement to achieve adequate mixing between gas and solid is described. Residence time distribution studies ensured that the behavior of this device actually approaches that of a completely mixed system. The applicability of this device in MT reactors was verified by studying the vapor phase catalytic oxidation of anthracene over vanadium pentoxide.

Observation of Peierls transition in nanowires (diameter similar to 130 nm) of the charge transfer molecule TTF-TCNQ synthesized by electric-field-directed growth

We report the growth of nanowires of the charge transfer complex tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) with diameters as low as 130 nm and show that such nanowires can show Peierls transitions at low temperatures. The wires of sub-micron length were grown between two prefabricated electrodes (with sub-micron gap) by vapor phase growth from a single source by applying an electric field between the electrodes during the growth process. The nanowires so grown show a charge transfer ratio similar to 0.57, which is close to that seen in bulk crystals. Below the transition the transport is strongly nonlinear and can be interpreted as originating from de-pinning of CDW that forms at the Peierls transition.

Dehydrogenation of Butyl Alcohol in Fixed Catalyst Beds

The vapor-phase dehydrogenation of 1 -butanol to butyraldehyde was studied in a fixed bed of catalyst from 250° to 360° C. Of all the catalysts studied during preliminary investigation, the one containing 90% copper, 8% chromia, and 2% carbon supported on pumice was best, with high activity and selectivity. The data are expressed in the form of a first-order irreversible reaction rate equation. Single-site surface reaction (hydrogen adsorbed) is the rate-controlling mechanism at all the temperatures studied. The rate data obtained in the entire range of experimental conditions fit the rate equation based on this mechanism with a standard deviation of ± 22.8%.

Hydrochlorination of methanol to methyl chloride in fixed catalyst beds

The vapor phase hydrochlorination of methanol to methyl chloride in fixed beds with silica gel-alumina (88 to 12) and γ-alumina catalysts was studied in a glass tubular reactor in the temperature range of 300° to 390°C. Of the two catalysts studied, γ-alumina gave nearly equilibrium conversions under the experimental conditions. The data are expressed in the form of second-order irreversible rate equations for both the catalysts studied.

Rare earth exchanged (Ce3+, La3+ and RE3+) H-Y zeolites as solid acid catalysts for the synthesis of linear alkyl benzenes

Rare earth exchanged H–Y zeolites were prepared by simple ion exchange methods at 353 K and have been characterized using different physicochemical techniques. A strong peak around 58 ppm in the 27Al{1H} MAS NMR spectra of these zeolites suggests a tetrahedral coordination for the framework aluminium. Small peak at or near 0 ppm is due to hexa-coordinated extra-framework aluminium and a shoulder peak near 30 ppm is a penta-coordinated aluminium species; [Al(OH)4]−. The vapor-phase benzene alkylation with 1-decene and 1-dodecene was investigated with these catalytic systems. Under the reaction conditions of 448 K, benzene/olefin molar ratio of 20 and time on stream 3 h, the most efficient catalyst was CeH–Y which showed more than 70% of olefin conversion with 48.5% 2-phenyldecane and 46.8%, 2-phenyldodecane selectivities with 1-decene and 1-dodecene respectively.

Towards a green synthesis of LAB's: Effect of rare earth metal ions on the benzene alkylation with 1-dodecene over NaFAU-Y zeolites

Chemically modified microporous materials can be prepared as robust catalysts suitable for application in vapor phase processes such as Friedel-Crafts alkylation. In the present paper we have investigated the use of rare earth metal (Ce3+, La3+, RE3+, and Sm3+) exchanged Na-Y zeolites as catalysts for the alkylation of benzene with long chain linear 1-olefin; 1-dodecene. Thermodesorption studies of 2,6-dimethylpyridine adsorbed catalysts (in the temperature range 573 to 873 K) show that the rare earth zeolites are highly Bronsted acidic in nature. A perfect correlation between catalyst selectivity towards the desired product (2-phenyldodecane) and Bronsted acid sites amount has been observed. (c) 2006 Springer Science + Business Media, Inc.

Selective-Area Atomic Layer Deposition

Atomic layer deposition (ALD) is a method to deposit thin films from gaseous precursors to the substrate layer-by-layer so that the film thickness can be tailored with atomic layer accuracy. Film tailoring is even further emphasized with selective-area ALD which enables the film growth to be controlled also on the substrate surface. Selective-area ALD allows the decrease of a process steps in preparing thin film devices. This can be of a great technological importance when the ALD films become into wider use in different applications. Selective-area ALD can be achieved by passivation or activation of a surface. In this work ALD growth was prevented by octadecyltrimethoxysilane, octadecyltrichlorosilane and 1-dodecanethiol SAMs, and by PMMA (polymethyl methacrylate) and PVP (poly(vinyl pyrrolidone) polymer films. SAMs were prepared from vapor phase and by microcontact printing, and polymer films were spin coated. Microcontact printing created patterned SAMs at once. The SAMs prepared from vapor phase and the polymer mask layers were patterned by UV lithography or lift-off process so that after preparation of a continuous mask layer selected areas of them were removed. On these areas the ALD film was deposited selectively. SAMs and polymer films prevented the growth in several ALD processes such as iridium, ruthenium, platinum, TiO2 and polyimide so that the ALD films did grow only on areas without SAM or polymer mask layer. PMMA and PVP films also protected the surface against Al2O3 and ZrO2 growth. Activation of the surface for ALD of ruthenium was achieved by preparing a RuOX layer by microcontact printing. At low temperatures the RuCp2-O2 process nucleated only on this oxidative activation layer but not on bare silicon.

Metal-billed and hollow carbon nanotubes obtained by the decomposition of metal-containing free precursor molecules

Vapor-phase pyrolysis of Fe(CO)(5) in the presence of another carbon source such as CO or Ca He yields iron-filled or hollow nanotubes depending on the relative concentration of the carbon source. Essentially single-walled nanotubes are obtained when the C6H6/Fe(CO)(5) ratio is high. Pyrolysis of metallocenes yields metal-filled nanotubes and hollow nanotubes are obtained when metallocenes are pyrolyzed along with benzene. Metal-decorated nanotubes are also obtained by this method.