Mineralogy of chondritic porous aggregates : current status

Chondritic porous aggregates (CPA's) belong to an important subset of small particles (usually between 5 and 50 micrometers) collected from the stratosphere by high flying aircraft. These aggregates are approximately chondritic in elemental abundance and are composed of many thousands of small­er, submicrometer particles. CPA particles have been the subject of intensive study during the past few years [1-3] and there is strong evidence that they are a new class of extraterrestrial material not represented in the meteorite collection [3,4]. However, CPA's may be related to carbonaceous chondrites and in fact, both may be part of a continuum of primitive extraterrestrial materials [5]. The importance of CPA's stems from suggestions that they are very primitive solar system material possibly derived from early formed proto­ planets, chondritic parent bodies, or comets [3, 6]. To better understand the origin and evolution of these particles, we have attempted to summarize all of the mineralogical data on identified CPA's published since about 1976.

A multi-stage history for carbonaceous material in extraterrestrial chondritic porous aggregate W7029*A and a new cosmothermometer

A new set of primitive extraterrestrial materials collected in the Earth's stratosphere include Chondritic Porous Aggregates (CPA's) [1]. CPAs have a complex and variable mineralogy [1-3] that include 'organic compounds' [4,5] and poorly graphitised carbon (PGC)[6]. This study presents a continuation of our detailed Analytical Electron Microscope study on carbon-rich CPA W7029*A from the JSC Cosmic Dust Collection. This CPA is an uncontaminated sample that survived atmospheric entry without appreciable alteration [7] and which contains ~44% carbonaceous material. The carbonaceous composition of selected particles was confirmed by Electron Energy Loss Spectroscopy and Selected Area Electron Diffraction (SAED). Possible carbonaceous contaminants introduced by specimen preparation techniques are easily recognised from indigenous CPA carbon particles [8] and do not bias our interpretations.

Conduction-radiation effect on natural convection flow in a fluid-saturated non-Darcy porous medium enclosed by non-isothermal walls

The effect of conduction-convection-radiation on natural convection flow of Newtonian optically thick gray fluid, confined in a non-Darcian porous media square cavity is numerically studied. For the gray fluid consideration is given to Rosseland diffusion approximation. Further assuming that (i) the temperature of the left vertical wall is varying linearly with height, (ii) cooled right vertical and top walls and (iii) the bottom wall is uniformly-heated. The governing equations are solved using the Alternate Direct Implicit method together with the Successive Over Relaxation technique. The investigation of the effect of governing parameters namely the Forschheimer resistance (Γ), the Planck constant (Rd), and the temperature difference (Δ), on flow pattern and heat transfer characteristics has been carried out. It was seen that the reduction of flow and heat transfer occurs as the Forschheimer resistance is increased. On the other hand both the strength of flow and heat transfer increases as the temperature ratio, Δ, is increased.

Titanium-oxide magneli phases in four chondritic porous interplanetary dust particles

Detailed analytical electron microscope analyses of four fine-grained chondritic porous interplanetary dust particles (IDPs)reveal the presence of titanium oxide Magneli phases, TinO2n-1 (n=4,5,6), and rare Ti-metal. The titanium minerals are indigenous to these chondritic IDPs. The association of Magneli phases, Ti-metal, and carbonaceous material in chondritic IDPs, along with the grain size distributions support in situ solid carbon gasification in these extraterrestrial particles. The active catalyst in this process is titanium metal that we infer may be of interstellar origin. This favorable catalysis uniquely leads to the formation of Magneli phases. As chondritic IDPs may be solid debris of short-period comets, our data indicate that nuclei of short-period comets may show distinctive chemical reactions that lead to Ti-mineral assemblages that typically include Magneli phases. The proposed model provides a plausible mechnism to explain the higher solid carbon content of chondritic IDPs relative to bulk carbon abundances typical for carbonaceous chondrite matrices that represent another type of more evolved, that is, metamorphosed, undifferentiated solar system bodies.

Metastable carbon in two chondritic porous interplanetary dust particles

An understanding of carbonaceous matter in primitive extraterrestrial materials is an essential component of studies on dust evolution in the interstellar medium and the early history of the Solar System. We have suggested previously that a record of graphitization is preserved in chondritic porous (CP) aggregates and carbonaceous chondrites1,2 and that the detailed mineralogy of CP aggregates can place boundary conditions on the nature of both physical and chemical processes which occurred at the time of their formation2,3. Here, we report further analytical electron microscope (AEM) studies on carbonaceous material in two CP aggregates which suggest that a record of hydrocarbon carbonization may also be preserved in these materials. This suggestion is, based upon the presence of well-ordered carbon-2H (lonsdaleite) in CP aggregates W7029*A and W7010*A2. This carbon is a metastable phase resulting from hydrous pyrolysis below 300-350°C and may be a precursor to poorly graphitized carbons (PGCs) in primitive extraterrestrial materials2. © 1987 Nature Publishing Group.

Layer silicates in a chondritic porous interplanetary dust particle

Analytical electron microscopy on individual grains from a portion of a chondritic porous interplanetary dust particle (aggregate W7029C1 from the NASA Johnson Space Center Cosmic Dust Collection) shows that layer silicates compose 50 percent of the silicate fraction examined. These layer silicates can be classified into two distinct crystallochemical groups: (1) fine-grained, polycrystalline smectite minerals; and (2) well-ordered, single crystals of kaolinite and Mg-poor talc. The layer silicates in this portion of sample W7029(asterisk)A are dissimilar to those described in other chondritic porous aggregates. The predominant layer silicate assemblage in W7029(asterisk)A indicates that heating of the aggregate during atmospheric entry was brief and probably to a temperature less than 300C. Comparison with terrestrial phyllosilicate occurrences suggests that some layer silicates in aggregate W7029(asterisk)A may have been formed by alteratiton from preexisting silicate minerals at low temperatures (less than 25C) after aggregate formation.

Diagenesis in interplanetary dust - chondritic porous aggregate w7029-star-a

In previous Analytical Electron Microscope studies of extraterrestrial Chondritic Porous Aggregate (CPA) W7029* A, we have reported on the presence of layer silicates(Rietmeijer and Mackinnon, 1984a; Mackinnon and Rietmeijer, 1983) and metal oxides (Rietmeijer and Mackinnon, 1984a; Mackinnon and Rietmeijer, 1984). We present here a continuation ofthis detailed mineralogical study and propose a scenario which may account for the variety and types of phases observed in this CPA. At least 50% ofCPA W7029*A is carbonaceous material, primarily poorly graphitised carbon (POC) with morphologies similar to POC in acid residues of carbonaceous chondrites (Smith and Busek, 1981; Lumpkin, 1983). The basal spacing of graphite in CPA W7029*A ranges from 3.47-3.52 A and compares with doo, of graphite in the Allende residues (Smith and Buseck, 1981; Lumpkin, 1983). Low-temperature phases comprise - 20% of CPA W7029*A and include layer silicates, Bi,O" a-FeOOH(Rietmeijer and Mackinnon, 1984a; Mackinnon and Rietmeijer, 1983), BaSO.,.Ti.O, plates, pentlandite-violarite and bornite. Clusters of Mg-rich olivine and pyroxene make up - 12% of the aggregate...

Analytical Solution of a Walters’ Liquid B Flow Over a Linear Stretching Sheet in a Porous Medium

This chapter represents the analytical solution of two-dimensional linear stretching sheet problem involving a non-Newtonian liquid and suction by (a) invoking the boundary layer approximation and (b) using this result to solve the stretching sheet problem without using boundary layer approximation. The basic boundary layer equations for momentum, which are non-linear partial differential equations, are converted into non-linear ordinary differential equations by means of similarity transformation. The results reveal a new analytical procedure for solving the boundary layer equations arising in a linear stretching sheet problem involving a non-Newtonian liquid (Walters’ liquid B). The present study throws light on the analytical solution of a class of boundary layer equations arising in the stretching sheet problem.

In situ SANS study of the surface and pore filling adsorption of subcritical and supercritical CO2 in porous silica as a function of pore size

We applied small-angle neutron scattering (SANS) and ultra small-angle neutron scattering (USANS) to monitor evolution of the CO2 adsorption in porous silica as a function of CO2 pressure and temperature in pores of different sizes. The range of pressures (0 < P < 345 bar) and temperatures (T=18 OC, 35 OC and 60 OC) corresponded to subcritical, near critical and supercritical conditions of bulk fluid. We observed that the adsorption behavior of CO2 is fundamentally different in large and small pores with the sizes D > 100 Å and D < 30 Å, respectively. Scattering data from large pores indicate formation of a dense adsorbed film of CO2 on pore walls with the liquid-like density (ρCO2)ads≈0.8 g/cm3. The adsorbed film coexists with unadsorbed fluid in the inner pore volume. The density of unadsorbed fluid in large pores is temperature and pressure dependent: it is initially lower than (ρCO2)ads and gradually approaches it with pressure. In small pores compressed CO2 gas completely fills the pore volume. At the lowest pressures of the order of 10 bar and T=18 OC, the fluid density in smallest pores available in the matrix with D ~ 10 Å exceeds bulk fluid density by a factor of ~ 8. As pressure increases, progressively larger pores become filled with the condensed CO2. Fluid densification is only observed in pores with sizes less than ~ 25 – 30 Å. As the density of the invading fluid reaches (ρCO2)bulk~ 0.8 g/cm3, pores of all sizes become uniformly filled with CO2 and the confinement effects disappear. At higher densities the fluid in small pores appears to follow the equation of state of bulk CO2 although there is an indication that the fluid density in the inner volume of large pores may exceed the density of the adsorbed layer. The equivalent internal pressure (Pint) in the smallest pores exceeds the external pressure (Pext) by a factor of ~ 5 for both sub- and supercritical CO2. Pint gradually approaches Pext as D → 25 – 30 Å and is independent of temperature in the studied range of 18 OC ≤ T ≤ 60 OC. The obtained results demonstrate certain similarity as well as differences between adsorption of subcritical and supercritical CO2 in disordered porous silica. High pressure small angle scattering experiments open new opportunities for in situ studies of the fluid adsorption in porous media of interest to CO2 sequestration, energy storage, and heterogeneous catalysis.

Multifunctional porous graphene for nanoelectronics and hydrogen storage : new properties revealed by first principle calculations

The lack of an obvious “band gap” is a formidable hurdle for making a nanotransistor from graphene. Here, we use density functional calculations to demonstrate for the first time that porosity such as evidenced in recently synthesized porous graphene (http://www.sciencedaily.com/releases/2009/11/091120084337.htm) opens a band gap. The size of the band gap (3.2 eV) is comparable to most popular photocatalytic titania and graphitic C3N4 materials. In addition, the adsorption of hydrogen on Li-decorated porous graphene is much stronger than that in regular Li-doped graphene due to the natural separation of Li cations, leading to a potential hydrogen storage gravimetric capacity of 12 wt %. In light of the most recent experimental progress on controlled synthesis, these results uncover new potential for the practical application of porous graphene in nanoelectronics and clean energy.

Preparation of porous nanofibers from electrospun polyacrylonitrile/calcium carbonate composite nanofibers using porogen leaching technique

Production of nanofibrous polyacrylonitrile/calcium carbonate (PAN/CaCO3) nanocomposite web was carried out through solution electrospinning process. Pore generating nanoparticles were leached from the PAN matrices in hydrochloric acid bath with the purpose of producing an ultimate nanoporous structure. The possible interaction between CaCO3 nanoparticles and PAN functional groups was investigated. Atomic absorption method was used to measure the amount of extracted CaCO3 nanoparticles. Morphological observation showed nanofibers of 270–720 nm in diameter containing nanopores of 50–130 nm. Monitoring the governing parameters statistically, it was found that the amount of extraction (ε) of CaCO3was increased when the web surface area (a) was broadened according to a simple scaling law (ε = 3.18 a0.4). The leaching process was maximized in the presence of 5% v/v of acid in the extraction bath and 5 wt % of CaCO3 in the polymer solution. Collateral effects of the extraction time and temperature showed exponential growth within a favorable extremum at 50°C for 72 h. Concentration of dimethylformamide as the solvent had no significant impact on the extraction level.

A comparative study of different porous amorphous silica minerals supported TiO2 catalysts

Three porous amorphous silica minerals, including diatomite, opal and porous precipitated SiO2wereadopted to prepare supported TiO2catalysts by hydrolysis–deposition method. The prepared compoundmaterials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fouriertransform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and X-ray photo-electron spectroscopy (XPS). Through morphology and physical chemistry properties of the resultingTiO2/amorphous SiO2catalysts, it was proposed that the nature of silica supports could affect the particlesize and the crystal form of TiO2and then further influence the photocatalytic property of TiO2/amorphousSiO2catalysts. The catalytic properties of these porous amorphous silica supported photocatalysts(TiO2/SiO2) were investigated by UV-assisted degradation of Rhodamine B (RhB). Compared with pureTiO2(P25) and the other two TiO2/amorphous SiO2catalysts, TiO2/diatomite photocatalyst exhibits bet-ter catalytic performance at different calcined temperatures, the decoloration rate of which can be upto over 85% even at a relatively low calcined temperature. The TiO2/diatomite photocatalyst possessesmixed-phase TiO2with relatively smaller particles size, which might be responsible for higher photo-catalytic activity. Moreover, the stable and much inerter porous microstructure of diatomite could beanother key factor in improving its activity.

Porous polyethersulfone-supported zeolitic imidazolate framework membranes for hydrogen separation

ZIF-8 thin layer has been synthesized on the asymmetric porous polyethersulfone (PES) substrate via secondary seeded growth. Continuous and dense ZIF-8 layer, containing microcavities, has good affinity with the PES support. Single gas permeance was measured for H2, N2, CH4, O2, and Ar at different pressure gradients and temperatures. Molecular sieving separation has been achieved for selectively separating hydrogen from larger gases. At 333 K, the H2 permeance can reach ∼4 × 10−7 mol m−2 s−1 Pa−1, and the ideal separation factors of H2 from Ar, O2, N2, and CH4 are 9.7, 10.8, 9.9, and 10.7, respectively. Long-term hydrogen permeance and H2/N2 separation performance show the stable permeability of the derived membranes.

Layered silicates in Chondritic Porous Aggregate W7029*A : a case of primary growth

An important subset of extraterrestrial particles that reach the Earth's stratosphere include the so-called Chondritic Porous Aggregates (CPA's) [1-3]. In general, CPA's have a fluffy morphology and consist of numerous (>104)subparticles that are often <100A in size [4]. Mineral species in CPA's include Mg-rich pyroxene and olivine, Fe- and (Fe,Ni)-sulphides, taenite, Fe,Ni-carbides, magnetite, Ti-metal, a Bi-phase (metal or oxide), and variable amounts of carbonaceous material [1, 5-7]. Hydrated silicates are rare in CPA's and are limited to aggregates that have not been severely altered (thermo-metamorphosed) during atmospheric entry [8]. The presence of hydrated silicates in one cosmic dust particle was established by X-ray diffraction [2] and has been inferred in others by infra-red spectroscopy [8]. If CPA's are cometary, their mineralogy and morphology suggest that at least two episodes of aggregation occurred and that variations in porosity may be related to local differences in ice-to-dust ratio [3].