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At least 73 records · Page 4

Laboratory Analysis of Silicate Stardust Grains of Diverse Stellar Origins

Silicate dust is ubiquitous in a multitude of environments across the cosmos, including evolved oxygen-rich stars, interstellar space, protoplanetary disks, comets, and asteroids. The identification of bona fide silicate stardust grains in meteorites, interplanetary dust particles, micrometeorites, and dust returned from comet Wild 2 by the Stardust spacecraft has revolutionized the study of stars, interstellar space, and the history of dust in the Galaxy. These stardust grains have exotic isotopic compositions that are records of nucleosynthetic processes that occurred in the depths of their now extinct parent stars. Moreover, the chemical compositions and mineralogies of silicate stardust are consequences of the physical and chemical nature of the stellar condensation environment, as well as secondary alteration processes that can occur in interstellar space, the solar nebula, and on the asteroid or comet parent body in which they were incorporated. In this talk I will discuss our use of advanced nano-scale instrumentation in the laboratory to conduct coordinated isotopic, chemical, and mineralogical analyses of silicate stardust grains from AGB stars, supernovae, and novae. By analyzing the isotopic compositions of multiple elements in individual grains, we have been able to constrain their stellar sources, explore stellar nucleosynthetic and mixing processes, and Galactic chemical evolution. Through our mineralogical studies, we have found these presolar silicate grains to have wide-ranging chemical and mineral characteristics. This diversity is the result of primary condensation characteristics and in some cases secondary features imparted by alteration in space and in our Solar System. The laboratory analysis of actual samples of stars directly complements astronomical observations and astrophysical models and offers an unprecedented level of detail into the lifecycles of dust in the Galaxy.

Nguyen, Ann N.↗

Calorimetric Measurements of the Thermodynamic Properties of RE-Silicate Coating Materials

Thermodynamic quantities of coatings materials and siliceous debris-induced corrosion products are crucial to understand in order to develop mitigation strategies necessary to improve the durability of gas-turbine engines. Siliceous induced corrosion can occur when debris consisting mainly of CaO-MgO-Al2O3-SiO2 (CMAS) is ingested by aircraft engines during and after take-off, which sticks to hot surfaces and forms calcium rare-earth silicate oxyapatites. In this work, high-temperature oxide melt drop solution calorimetry (HT drop solution calorimetry) was used to obtain the enthalpies of formation for RE silicate (RE2Si2O7, RE2SiO5 where RE = Yb, Er, Y, Dy, Nd, Lu and Gd) environmental barrier coatings (EBCs) and the calcium RE silicate oxyapatite Ca2RE8(SiO4)6O2 (RE = Yb, Er, Y, Dy, Nd, Gd and Sm) corrosion products. Trends in the enthalpy of formation as a function of the ionic potential of the rare-earth cations in their related crystallographic sites are discussed.

Costa, Gustavo↗

Coordinated NanoSIMS and TEM Analysis of a Large 26Mg-Rich AGB Silicate from the Meteorite Hills 00426 CR2 Chondrite

Silicates are one of the most abundant presolar phases around evolved stars, in the inter-stellar medium (ISM), and in our Solar System. These grains afford the opportunity for O, Si, Mg, Fe, and Ca isotopic analyses to constrain stellar nucleosynthetic and mixing processes, and Galactic chemical evolution (GCE). While Mg and Fe isotopic studies have been successfully conducted on presolar silicates, isotopic analyses beyond O and Si are often hampered by the small grain sizes (average ~250 nm). This also makes coordinated mineral and chemical characterization challenging. These studies provide insight into the dust condensation conditions as well as subsequent alteration in the ISM and/or the Solar System. TEM studies of presolar silicates have shown that they are much more mineralogically and chemically diverse than other presolar phases [1 and references therein]. Large (>500nm) presolar silicate grains are rare, but they allow for detailed isotopic, mineral, and chemical characterization. We identified a large presolar silicate grain in the MET 00426 CR2 chondrite and report the O, Si, Mg, and Fe isotopic compositions and TEM study of this grain.

Nguyen, A. N.↗

Temperature Effect on Silicate Melt-Sulfide-Metal Trace Element Partitioning in the Presence of Sulfur Under Reduced Conditions

The reduced nature of Mercury, enstatite chondrites, and the aubrite parent bodies (APB) have raised many questions regarding the geochemical behavior of typically lithophile, heat-producing, and rare-earth elements (REE) in magmas at low oxygen fugacity (fO2). Due to decreasing O availability at these low fO2, and an abundance of S(sup 2(-)), sulfur (S) acts as an important anion that changes the partitioning behavior of many elements and modifies the physical properties of silicate melts. Preliminary observations suggest that major and minor elements exhibit different geochemical affinities in highly reduced, S-rich systems compared to terrestrial rocks. The speciation and bonding environment of S, dictated by P/T/fO2 conditions, may strongly influence the degree to which S affects partitioning behavior. Here we investigate the partitioning behavior of major, minor, and trace elements between silicate melt, sulfide melt, and metal as well as the coordination chemistry of S in highly reduced silicate melts. Our work is focused on investigating solely the entropy-dependent temperature effect on partitioning of elements for which we currently have MESSENGER data (K, Na, Th, U, Si, Mg, Fe, Ti, Ca, Al, Cr, Mn, S, Cl) as well as a host of geochemically relevant trace elements such as REEs (P, Co, Ni, Mo, Ce, Nd, Sm, Eu, Gd, Dy, Yb). Previous studies in which temperature, pressure, and fO2 were co-varied found that as fO2 decreases, heat-producing elements U and Th become more chalcophile, while K becomes less chalcophile. Concurrently, nominally lithophile elements Mg and Ca become more chalcophile and were observed as minor elements in exsolved sulfides and bonded with S species in silicate melt. These studies, however, could not disentangle entropic effects from changes in the fO2. New temperature-dependent partitioning data from our work will be used to determine which elements are most likely to retain their lithophile character and hence be incorporated into silicates, and which elements are likely contained within the sulfide (chalcophile) and metal core (siderophile), setting the stage for the thermal and magmatic evolution of reduced planetary bodies.

B A Anzures↗

Calcium and Magnesium Distribution Between Sulfide and Silicate Melts: Thermodynamic Modeling and Insights into Mercury's Mantle-Crust Differentiation

Mercury stands out as the terrestrial planet with the lowest degree of oxidation among all planets of our solar system. It is characterized by a high abundance of sulfur, which is expected to replace oxygen in silicate melts. This sulfur enrichment could lead to sulfide saturation in its mantle, potentially resulting in the formation of sulfides rich in calcium and magnesium. Utilizing experimental data from the literature, we constructed a thermodynamic model to explore the partitioning of calcium and magnesium between sulfide and silicate melts. This model aims to improve our comprehension of the chemical equilibria driving the process of mantle-crust differentiation on Mercury. Our models indicate that increased temperature, decreased pressure, and low concentrations of iron, oxygen, and carbon within the sulfide phase, along with low sulfur concentrations in the silicate phase, favor calcium’s partitioning into the sulfide. Additionally, magnesium partitioning into the sulfide melt is favored with decreased pressure, decreased temperature, low concentrations of iron and calcium within the sulfide, and low concentrations of sulfur within the silicate. Our results suggest that up 9.4% and 5.6% Ca and Mg, respectively, can be present in sulfides equilibrated with sulfide-saturated silicate melts during mantle-crust differentiation. Further investigation will focus on the distribution of sulfide phases within the mantle and crust to better constrain Mercury’s internal structure.

Taylor McCombs↗

Theoretical studies of the infrared emission from circumstellar dust shells: the infrared characteristics of circumstellar silicates and the mass-loss rate of oxygen-rich late-type giants

We have modeled the infrared emission of spherically symmetric, circumstellar dust shells with the aim of deriving the infrared absorption properties of circumstellar silicate grains and the mass-loss rates of the central stars. As a basis for our numerical studies, a simple semianalytical formula has been derived that illustrates the essential characteristics of the infrared emission of such dust shells. A numerical radiative transfer program has been developed and applied to dust shells around oxygen-rich late-type giants. Free parameters in such models include the absorption properties and density distribution of the dust. An approximate, analytical expression is derived for the density distribution of circumstellar dust driven outward by radiation pressure from a central source. A large grid of models has been calculated to study the influence of the free parameters on the emergent spectrum. These results form the basis for a comparison with near-infrared observations. Observational studies have revealed a correlation between the near-infrared color temperature, Tc, and the strength of the 10 micrometers emission or absorption feature, A10. This relationship, which essentially measures the near-infrared optical depth in terms of the 10 micrometers optical depth, is discussed. Theoretical A10-Tc relations have been calculated and compared to the observations. The results show that this relation is a sensitive way to determine the ratio of the near-infrared to 10 micrometers absorption efficiency of circumstellar silicates. These results as well as previous studies show that the near-infrared absorption efficiency of circumstellar silicate grains is much higher than expected from terrestrial minerals. We suggest that this enhanced absorption is due to the presence of ferrous iron (Fe2+) color centers dissolved in the circumstellar silicates. By using the derived value for the ratio of the near-infrared to 10 micrometers absorption efficiency, the observed A10-Tc relation can be calibrated in terms of the total dust column density of the circumstellar shell and thus the mass-loss rate of late-type giants can easily be derived. Detailed models have been made of the infrared emission of three well-studied Miras: R Cas, IRC 10011, and OH 26.5+0.6, with the emphasis on the shape of the 10 micrometers emission or absorption feature. The results show that the intrinsic shape of the 10 micrometers resonance varies from a very broad feature in R Cas to a relatively narrower feature in OH 26.5+0.6, with IRC 10011 somewhere in between. Possible origins of this variation are discussed. The mass-loss rates from these objects are calculated to be 3 x 10(-7), 2 x 10(-5), and 2 x 10(-4) M Sun yr-1 for R Cas, IRC 10011, and OH 26.5+0.6, respectively. These results are compared to other determinations in the literature.

NASA Discipline Exobiology↗

An experimental investigation of the condensation of silicate grains

Results are presented for a series of laboratory experiments designed to investigate the nucleation of small silicate grains from a vapor of astrophysically significant elements and compounds. In the experiments, magnesium silicate grains were condensed by simultaneously evaporating Mg and SiO solids into an atmosphere of argon or hydrogen at a pressure of a few torr. The results show that at low temperatures (up to a few hundred degrees C) the condensates are amorphous grains and have widely varying stoichiometries. The thermodynamically most stable compounds (Mg2SiO4, MgSiO3, SiO2) do not form readily, but all initial condensates can be converted to crystalline forsterite (Mg2SiO4) by heating to 1000 C in vacuum. At higher temperatures (above 700 K) it becomes more difficult to nucleate any silicates, and those that do form are amorphous, indicating that surface energies and kinetic effects are very important in determining under what conditions condensation will occur. The IR spectra of the experimentally produced magnesium silicates are found to have a strong resemblance to those observed in many astronomical clouds.

Day, K. L.↗

Effect of silicate ions on electrode overvoltage

The influence of the addition of a silicate to a caustic solution (KOH) is studied in order to determine the degree to which silicates inhibit the corrosion of chrysotile under conditions of electrolysis at working temperatures of 100 C and above. In an alkaline solution containing various silicate concentrations, current density was increased and electrode overvoltage was measured. Results show that silicate ion concentrations in the electrolyte increase with temperature without effecting electrochemical performance up to 115 C at 700 MA/sqcm. At this point the concentration is about 0.5 g Si/100 g KOH. Beyond this limit, electrolytic performance rapidly degenerates due to severe oxidation of the electrodes.

Gras, J. M.↗

Visible and ultraviolet /800-130 nm/ extinction of vapor-condensed silicate, carbon, and silicon carbide smokes and the interstellar extinction curve

The extinction curves from 800 to 130 nm (1.25-7.7/micron) of amorphous silicate smokes nominally of olivine and pyroxene composition, carbon smokes, and crystalline SiC smokes are presented. The SiC smoke occurred in the low-temperature (beta) cubic structural form. The SiC smoke showed an absorption edge which occurred at significantly longer wavelengths than the calculated extinction profile of the hexagonal SiC form previously used to calculate the interstellar extinction profile. Neither SiC nor amorphous silicates show an extinction band similar to the observed 6.6/micron astronomical extinction band. The infrared absorption peaks for the silicate and SiC samples near 10 microns and 11-13 microns, respectively, were also measured. The ultraviolet to infrared extinction ratio for the amorphous silicate samples is similar to the observed astronomical extinction ratio. The measured extinction ratios for SiC smokes are significantly below the interstellar extinction ratio. The extinction peak of the carbon smokes occurred at 4.0 and 4.25/micron, for samples of mean radii 13 and 6 nm, respectively. The extinction profile is distinctly different from that predicted for graphite grains of the same size, and is similar to that predicted for glassy carbon grains.

Stephens, J. R.↗

Laboratory studies of the infrared small-particle extinction of amorphous silicates

The broad interstellar IR extinction features located at 9.7 and 18 microns wavelength are believed to originate from silicate dust grains. Cosmic abundances suggest that the silicate should have a chemical composition similar to that of olivine, (Mg,Fe)2 SiO4. Olivine is a very common terrestrial silicate mineral of crystalline structure. However, crystalline olivine grains do not fit the interstellar features well. Based on spectroscopic data obtained in laboratory studies and astronomical observations it was concluded that the interstellar silicate grains consist of a material with amorphous rather than crystalline structure. The astronomical arguments and the results obtained in our laboratory experiments which support this view are reviewed.

Kraetschmer, W.↗

Silicate volcanism on Io

This paper is mainly concerned with the nature of volcanic eruptions on Io, taking into account questions regarding the presence of silicates or sulfur as principal component. Attention is given to the generation of silicate magma, the viscous dissipation in the melt zone, thermal anomalies at eruption sites, and Ionian volcanism. According to the information available about Io, it appears that its volcanism and hence its surface materials are dominantly silicic. Several percent of volatile materials such as sulfur, but also including sodium- and potassium-rich materials, may also be present. The volatile materials at the surface are continually vaporized and melted as a result of the high rates of silicate volcanism.

Carr, M. H.↗

Nature of very small grains - PAH molecules or silicates?

The predictions of the model of Puget et al. (1985) for the emission from Very Small Grains (VSGs) including both graphitic and silicate components are compared with published 8-13-micron observations of astronomical sources. The VSGs are found to be mainly graphitic and an upper limit is placed on the relative mass of silicates based on lack of the 9.7-micron silicate emission feature on M 82 and NGC 2023. This dissymetry in the composition of VSGs supports the suggestion that they are formed in grain-grain collisions where the behaviors of graphite and silicate grains are expected to be quite different.

Desert, F. X.↗

Ubiquitous high-FeO silicates in enstatite chondrites

SEM and EMPA were used to determine the mineral contents of four EH3 chondrites. All four showed the dominant enstatite peak, Fs 0-5, with 4-8 percent of FeO-rich pyroxene with Fs 5-20. Among the 542 objects found to contain high-FeO silicates, 18 were chondrules, 381 were rimmed or unrimmed grains, and 143 were aggregates. The high-FeO silicates in these objects are very largely pyroxene with Fs 5-23. Large grains of both FeO-rich and FeO-poor silicates were found to be present in the FeO-rich chondrules. This fact, together with the absence of clasts of FeO-rich chondritic material in the EH3 chondrites, suggests that FeO-rich grains were introduced before or during chondrule formation. It is concluded that FeO-rich and FeO-poor silicates were both present in the nebular region where E chondrites originated.

Lusby, David↗

Constraints on astronomical silicate dust

Numerical radiative-transfer models are used to discuss the properties of circumstellar dust grains around the premain-sequence star AB Aur (HD 31293). It is assumed that the dust consists of a silicate-graphite mixture with Draine and Lee (1984) optical properties. The modeling technique is to match the observed FUV through FIR energy distribution with the spectral energy distribution predicted for a spherical dust shell around a luminous hot star. Special attention is given to matching the observed 10-micron silicate emission feature and the observed circumstellar absorption curve at UV wavelengths, making it possible to strengthen constraints on dust-grain opacity and chemical composition. It is concluded that, although silicate grains can explain the observed 10-micron emission feature, the Draine and Lee silicate-graphite mixture cannot explain the observed FUV circumstellar absorption at the same time. The dust shell around AB Aur contains an additional population of small particles, the most likely candidate being amorphous carbon grains in a nonhydrogenated form.

Sorrell, Wilfred H.↗

The circumstellar dust envelopes of red giant stars. I - M giant stars with the 10-micron silicate emission band

Spherical dust envelope models of red giant stars are constructed by solving the radiative transfer equations of the generalized two-stream Eddington approximation. The IRAS observations of M giant stars which show the 10-micron silicate emission band in IRAS LRS spectra are explained by the models with the dirty silicate grains with K proportional to lambda exp -1.5 for lambda greather than 28 microns. Under the assumption of steady mass flow in the envelope, this model analysis gives the following conclusions: (1) the strength of the silicate emission peak at 10 microns is a good indicator of the mass loss rate of the star, (2) no stars with the 10-microns silicate emission feature are observed in the range of mass loss rate smaller than 7 x 10 to the -8th solar mass/yr, and (3) the characteristic time of the mass loss process of M stars does not exceed a few 10,000 years.

Hashimoto, O.↗

Derivation of mid-infrared (5-25 microns) optical constants of some silicates and palagonite

Recent reports concerning the mid-infrared reflectance properties of silicates coupled with recent observations of the Earth and other planets in the mid-infrared and the planned Thermal Emission Spectrometer scheduled as an instrument to be included on the Mars Observer all illustrate the increasing interest in the optical properties of materials in the mid-infrared and their direct application to remote sensing observations of other planetary surfaces. As the laboratory and observational data increase they will ultimately be modeled to aid in the understanding of the composition mineralogy, and distribution of the surface and atmospheric constituents on these bodies. In order to facilitate such quantitative analyses, knowledge regarding the optical constants (real (n) and imaginary (k) indices of refraction) of a wide variety of pertinent materials is required. Examples of the application of such quantitative analyses to the interpretation of Martian surface and atmospheric constituents, based on the optical constants of minerals, are presented. This study was initially conceived in order to aid in the interpretation of Martian surface and atmospheric aerosol mineralogy. As a result, the minerals included are biased toward samples which represent hydrated and hydroxylated silicates. These include the Al and Mg end members of the 1:1 layer lattice silicates, kaolinite and serpentine, respectively; an Al-bearing 2:1 layer lattice silicate, pyrophyllite; the Mg and Al smectite clays saponite and montmorillonite, respectively; and a palagonite, typically a poorly characterized alteration product of basaltic glass. The reflectivities of all samples were determined by placing them at the focus of a near-normal reflective attachment located in a Fourier transform spectrometer. To derive the optical constants of a material as a function of wavelength, researchers used the commonly employed technique of dispersion analysis.

Roush, T. L.↗

Towards a circumstellar silicate mineralogy

This paper reviews the formation, composition, and spectroscopy of circumstellar silicate grains. It is argued that 'clean' silicates (and oxides) are formed close to the stellar photosphere, but because of their low NIR absorptivity, these grains float with the gas in the pulsating photosphere until, at large distances from the stellar surface, enough Fe(2+) is incorporated (i.e., 'dirty' silicates) for radiation pressure to drive a dusty outflow. The silicate chemical condensation sequence is reviewed with emphasis on kinetics rather than thermodynamics, and likely condensates are identified. IRAS LRS spectra of tenuous dust shells show considerable variations in the shape of the 10-micron feature and at least 5 independent spectral components are indicated. These are compared with laboratory spectra and (preliminary) identifications are proposed.

Tielens, A. G. G. M.↗

Experimental determination of the solubility of iridium in silicate melts: Preliminary results

Little is known of the geochemical behavior of iridium. Normally this element is taken to be chalcophile and/or siderophile so that during planetary differentiation processes, e.g., core formation, iridium is extracted from silicate phases into metallic phases. Experimental determination of the metal/silicate partition coefficient of iridium is difficult simply because it is so large. Also there are no data on the solubility behavior of iridium in silicate melts. With information on the solubility of iridium in silicate melts it is possible, in combination with experimental data for Fe-Ir alloys, to calculate the partition coefficient between a metallic phase and a silicate melt.

Borisov, Alexander↗