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At least 37 records · Page 2

Formation of Hydrocarbons in the Outflows from Red Giants

The formation of hydrocarbons in the oxygen-rich outflows from red giants was studied. The existence of organic molecules in such outflows has been known for several years; however, their surprisingly high abundances has been a mystery since all of the carbon had been thought to be irretrievably locked up in CO, the most strongly bound molecule. CO is the first molecule to form from the atoms present in the star's extended atmosphere, and as strong stellar winds drive a cooling outflow, dust grains condense out. In oxygen-rich outflows, the dust is thought to be composed mainly of silicates and other metal oxides. Perhaps the noble metals can condense out in metallic form, in particular the relatively abundant transition metals iron and nickel. We proposed that perhaps the carbon reservoir held as CO can be accessed through a catalytic process involving the chemisorption of CO and H2 onto grains rich in metallic iron. CO and H2 are the two most abundant molecules in circumstellar outflows, and they both are known to dissociate on transition metal surfaces at elevated temperatures, freeing carbon to form organic molecules such as methane. We believe methane is a precursor molecule to the organics observed in oxygen-rich red giants. We have developed a nonequilibrium numerical model of a surface chemical (catalytic) process. Based on this model, we believe that methane can be formed under the conditions present in circumstellar outflows. Although the methane formation rates are exceptionally low under these conditions, over dynamical timescales, a significant amount of CO can be converted to methane and driven further out in the envelope, explaining the presence of organics there.

Roberge, Wayne↗

Melting relations and elemental distribution of portion of the system Fe-S-Si-O to 32 KB with planetary application

The melting relations and distribution of K and Cs in portions of the system was determined at high pressures. Ferrosilite is stable as a primary phase at high pressures because of the incongruent melting of ferrosilite to quartz plus liquid and the boundary between the one and two liquid fields on the joint Fe(1-x) O-FeS-SiO2 shifts away from silica with increasing pressures. Potassium K was found to have limited solubility in metal sulfide liquids at pressures up to 45 kb. The speculation that K may dissolve significantly in metal-metal sulfide liquids after undergoing first order isomorphic transition was tested by determining the distribution of Cs between sulfide and silicate liquids as an analogy to K. At 45 kb, 1400 C and 27 kb, 1300 C only limited amounts of Cs were detected in quench sulfide liquids even at pressures beyond the isomorphic transition of Cs.

Huang, W. L.↗

The formation of goethite and hydrated clay minerals on Mars

Laboratory studies reported by Huguenin (1973) on the kinetics and mechanism of the photostimulated oxidation of magnetic and preliminary laboratory data on the weathering of silicates, reported herein, are applied to Mars. Basalts in the Martian dark areas are predicted to alter to hydrated Fe(2 plus or minus) depleted clay minerals, minor goethite, and minor to trace amounts of transition metal oxides such as TiO2, MnO2, and Cr2O3 at a rate of 10 to the minus 1.5 plus or minus 1.5 micron/yr. Some Ca-Mg carbonates are also expected to be formed. The clay minerals are predicted to be more silica-rich than the silicate source material, SiO2 contents of 60% or higher being expected, and strongly depleted in Fe(2+). The oxygen, OH, and H2O contents of the bulk weathering product are predicted to be significantly greater than those of the dark-area source materials, whereas the relative bulk metal abundances should be the same.

Huguenin, R. L.↗

Supported transition metal catalysts for para- to ortho-hydrogen conversion

The main goal of this study was to develop and improve on existing catalysts for the conversion of ortho- to para-hydrogen. Starting with a commercially available Air Products nickel silicate, which had a beta value of 20, we were trying to synthesize catalysts that would be an improvement to AP. This was accomplished by preparing silicates with various metals as well as different preparation methods. We also prepared supported ruthenium catalysts by various techniques using several metal precursors to improve present technology. What was also found was that the activation conditions prior to catalytic testing was highly important for both the silicates and the supported ruthenium catalysts. While not the initial focus of the research, we made some interesting observations into the adsorption of H2 on ruthenium. This helped us to get a better understanding of how ortho- to para-H2 conversion takes place, and what features in a catalyst are important to optimize activity. Reactor design was the final area in which some interesting conclusions were drawn. As discussed earlier, the reactor catalyst bed must be constructed using straight 1/8 feet OD stainless steel tubing. It was determined that the use of 1/4 feet OD tubing caused two problems. First, the radius from the center of the bed to the wall was too great for thermal equilibrium. Since the reaction of ortho- to para-H2 is exothermic, the catalyst bed center was warmer than the edges. Second, the catalyst bed was too shallow using a 1/4 feet tube. This caused reactant blow-by which was thought to decrease the measured activity when the flow rate was increased. The 1/8 feet tube corrected both of these concerns.

Brooks, Christopher J.↗

Mineralogy, Petrology, Chemistry, and Ar-39 - Ar-40 and Ages of the Caddo County IAB Iron: Evidence for Early Partial Melt Segregation of a Gabbro Area Rich in Plagioclase-Diopside

We found coarse-grained gabbroic material rich in plagioclase and diopside in the Caddo County IAB iron meteorite. The polished thin sections studied were made from areas rich in Al and Ca detected by a micro-focus X-ray fluorescence (XRF) mapping technique. The gabbro is not a clast within a breccia, but rather this area is located mainly at silicate-metal boundaries only a few cm away from an area with fine-grained, ultramafic silicate similar to winonaites. Medium-grained orthopyroxene and olivine are found in transitional areas showing no disturbance of their crystalline textures. A vein-like region, starting at the area rich in fine-grained mafic silicate, extends towards the gabbroic area with a gradual increase in abundance of plagioclase and diopside. This texture and our accumulated knowledge of the formation mechanism of IAB/winonaltes meteorites, suggest that the gabbroic materials were formed by inhomogeneous segregation of partial melts of chondritic source materials. Compositional data on two mineralogically distinct samples of the gabbro-rich portion of the inclusion were obtained by INAA. Compared to an average of LAB silicate inclusions or winonaites, the Caddo County gabbro is enriched in the incompatible lithophile elements Na, Ca, Sc, REE and Hf, which is consistent with a melt origin for the gabbro. The cosmogenic space exposure age of Caddo County (511 Ma) is significantly younger than exposure ages of some other IAB meteorites, An 39Ar-40Ar age determination of the gabbroic material indicates a series of upward steps in age from 4.516 Ga to 4.523 Ga, with a few high temperature ages up to 4.54 Ga. The older age could approximate the primary recrystallization age of silicates. The stepped Ar age spectrum may indicate differences in Ar closure temperatures during slow cooling of -2-20'C/Myr in the parent body. Alternatively, the younger Ar-Ar ages may date a shock event which occurred while Caddo County was hot and which also created textures such as a linear metal vein with rounded zigzag walls in a diopside crystal and slightly miss-oriented rounded plagioclase domain.

Takeda, Hiroshi↗

Reactivity of Calcium-Bearing Minerals Under Simulated Venus Conditions

•SO2 is reactive with several common elements e.g. calcium [1-4] •Knowledge on chemical reactions has implications for the past and current state of Venus - Venus may have had liquid water on its surface [5], thus hydrous silicates may have formed at that time [6]. - The Venus Emissivity Mapper (on VERITAS and EnVision) will be used to determine bulk composition of the surface by observing transition metal content [8-9] - Calcium diffuses through basalt to react with CO2 and SO2, changing the bulk composition and decreasing the emissivity from orbit [8] - Experiments investigating kinetics will be informative for future emissivity data •Goal: - Constrain reaction rate between several calcium minerals and SO2 - Determine the effect, if any, crystal lattices may have on these rates

S.T. Port↗

Architected mesoporous crystalline magnesium silicates with ordered pore structures

Novel approaches to harness earth abundant silicates as building blocks for carbon dioxide removal, capture, utilization, and storage are gaining increasing attention in the context of sustainable and low carbon energy and resource recovery. Advancing a calibrated understanding of these fluid-silicate interactions is essential for developing scalable processes. One of the challenges in developing predictive controls over these interactions is the compositional and morphological heterogeneity of naturally occurring, heterogeneous magnesium silicate minerals. To address this challenge, the synthesis of architected mesoporous crystalline magnesium silicate (Mg 2 SiO 4 ) is proposed. While synthesis routes for producing amorphous mesoporous magnesium silicates have been developed via sol-gel methods, approaches to synthesize crystalline magnesium silicates with well-controlled pore size distributions have not been explored. The conventional approaches of converting matter that is amorphous to crystalline states at elevated temperatures results in a heterogeneous pore size distribution. To develop controls on pore size distribution, amorphous mesoporous magnesium silicates are coated with carbon. This approach preserves the pore size distributions during the amorphous to crystalline transformations of Mg-silicates at elevated temperatures. The carbon coating is removed on heating. Magnesium silicate particles produced using this approach have highly ordered pores around 2.58 nm and a specific surface area of 124.25 m 2 /g. In this study, we report the chemical compositions, morphologies, phase transitions, and pore structures of the intermediate materials produced during the synthesis of crystalline mesoporous magnesium silicates. The transitions, and pore structures of the intermediate materials produced during the synthesis of crystalline mesoporous magnesium silicates. Furthermore, the synthesis routes discussed in this study can be applied translationally to produce metal silicates with ordered mesoporous structures.

36 MATERIALS SCIENCE↗

Towards new zero-thermal-expansion materials: Li-free quartz solid solutions stuffed with transition metal cations

Stuffed aluminosilicate quartz solid solutions (Qss) represent the main functional component of state-of-the-art zero-thermal-expansion glass-ceramics. For the first time, we present the synthesis of Li-, Mg- and Zn-free Qss solely stuffed with transition metal cations (Fe 2+ , Ni 2+ , Co 2+ ); partial Li + co-doping enables also significant Mn 2+ incorporation. Further, they were obtained by glass powder crystallization; Qss crystals exhibit compositionally tunable coefficients of thermal expansion (CTEs), from - 2 × 10 -6 K -1 to ~10 × 10 -6 K -1 in the range 30–300 °C. Co 2+ -bearing crystals exhibit the closest-to-zero CTE value (0.2 ×10 -6 K -1 ) and the most isotropic behavior in the whole Qss family, opening up new perspectives for the development of Li-free low-expansion materials. From a structural point of view, we identified the unit cell volume (and not the pseudo-hexagonality of the aluminosilicate framework) as the key structural parameter leading to low or negative CTEs in Qss, with a linear correlation extending to non-stuffed non-silicate quartz-like phases.

36 MATERIALS SCIENCE↗

Experimental partitioning of Zr, Ti, and Nb between silicate liquid and a complex noble metal alloy and the partitioning of Ti between perovskite and platinum metal

El Goresy et al.'s observation of Nb, Zr, and Ta in refractory platinum metal nuggets (RPMN's) from Ca-Al-rich inclusions (CAI's) in the Allende meteorite led them to propose that these lithophile elements alloyed in the metallic state with noble metals in the early solar nebula. However, Grossman pointed out that the thermodynamic stability of Zr in the oxide phase is vastly greater than metallic Zr at estimated solar nebula conditions. Jones and Burnett suggested this discrepancy may be explained by the very non-ideal behavior of some lithophile transition elements in noble metal solutions and/or intermetallic compounds. Subsequently, Fegley and Kornacki used thermodynamic data taken from the literature to predict the stability of several of these intermetallic compounds at estimated solar nebula conditions. Palme and Schmitt and Treiman et al. conducted experiments to quantify the partitioning behavior of certain lithophile elements between silicate liquid and Pt-metal. Although their results were somewhat variable, they did suggest that Zr partition coefficients were too small to explain the observed 'percent' levels in some RPMN's. Palme and Schmitt also observed large partition coefficients for Nb and Ta. No intermetallic phases were identified. Following the work of Treiman et al., Jurewicz and Jones performed experiments to examine Zr, Nb, and Ti partitioning near solar nebula conditions. Their results showed that Zr, Nb, and Ti all have an affinity for the platinum metal, with Nb and Ti having a very strong preference for the metal. The intermetallic phases (Zr,Fe)Pt3, (Nb,Fe)Pt3, and (Ti,Fe)Pt3 were identified. Curiously, although both experiments and calculations indicate that Ti should partition strongly into Pt-metal (possibly as TiPt3), no Ti has ever been observed in any RPMN's. Fegley and Kornacki also noticed this discrepancy and hypothesized that the Ti was stabilized in perovskite which is a common phase in Allende CAI's.

Jurewicz, Stephen R.↗

Synthesis and Stability of an Eight‐Coordinated Fe 3 O 4 High‐Pressure Phase: Implications for the Mantle Structure of Super‐Earths

Abstract Super‐Earths ranging up to 10 Earth masses (M E ) with Earth‐like density are common among the observed exoplanets thus far, but their measured masses and radii do not uniquely elucidate their internal structure. Exploring the phase transitions in the Mg‐silicates that define the mantle‐structure of super‐Earths is critical to characterizing their interiors, yet the relevant terapascal conditions are experimentally challenging for direct structural analysis. Here we investigated the crystal chemistry of Fe 3 O 4 as a low‐pressure analog to Mg 2 SiO 4 between 45–115 GPa and up to 3000 K using powder and single crystal X‐ray diffraction in the laser‐heated diamond anvil cell. Between 60–115 GPa and above 2000 K, Fe 3 O 4 adopts an 8‐fold coordinated Th 3 P 4 ‐type structure ( I ‐43d, Z = 4) with disordered Fe 2+ and Fe 3+ into one metal site. This Fe‐oxide phase is isostructural with that predicted for Mg 2 SiO 4 above 500 GPa in super‐Earth mantles and suggests that Mg 2 SiO 4 can incorporate both ferric and ferrous iron at these conditions. The pressure‐volume behavior observed in this 8‐fold coordinated Fe 3 O 4 indicates a maximum 4% density increase across the 6‐ to 8‐fold coordination transition in the analog Mg‐silicate. Reassessment of the FeO—Fe 3 O 4 fugacity buffer considering the Fe 3 O 4 phase relationships identified in this study reveals that increasing pressure and temperature to 120 GPa and 3000 K in Earth and planetary mantles drives iron toward oxidation.

Zurkowski, C. C.↗

The Evolution of the EH4 Chondrite Indarch at High Pressure and Temperature: The First Experimental Results

Chondrite groups are characterized by variations in bulk composition and oxidation state, illustrating in part heterogeneity in the early solar nebula. Planetary accretion could be explained by at least two different scenarios: the homogeneous [1] and heterogeneous accretion models [2, 3]. In particular, for the formation of the Earth, some studies (e.g. [2, 3]) assume that one component is highly reduced material comparable to enstatite chondrites, devoid of volatile elements but containing all other elements in C1 abundance ratios. To derive constraints on the understanding of early differentiation processes, studies of the silicate phase relations and their interactions with metal, at relevant P-T-fO2, are required. Melting relations and equilibrium partitioning behaviour have been studied on peridotitic and chondritic starting compositions at pressures and temperatures corresponding to the transition zone and lower mantle [4, 5, 6]. However, enstatite chondrites, which are highly reduced primitive meteorites, have not yet been studied experimentally under such conditions. Thus, multianvil experiments have been performed at 20-25 GPa and 2000-2400 C on the EH4 chondrite Indarch.

Berthet, S.↗

Spectra of Fe-Ti silicate glasses - Implications to remote-sensing of planetary surfaces

Optical spectra of synthetic Fe-Ti silicate glasses and the temperature variations of the spectral features were investigated. The spectra are assigned to absorptions due to crystal field (CF) transitions in Ti(3+), Fe(2+) in octahedral coordination, and Fe(2+) in tetrahedral coordination, and to metal-metal and oxygen-metal charge transfer (CT) transitions which contribute to the near ultraviolet absorption edge. Temperature variations of the optical bands have been studied to explore implications for remote sensing. Caution is urged in the use of the absorption edge as a measure of TiO2 concentrations on planetary surfaces and in regolith samples.

Nolet, D. A.↗

Optical Fiber Spectroscopy

This is the final report of work done on NASA Grant NAG-1-443. The work covers the period from July 1, 1992 to December 1, 1998. During this period several distinct but related research studies and work tasks were undertaken. These different subjects are enumerated below with a description of the work done on each of them. The focus of the research was the development of optical fibers for use as distributed temperature and stress sensors. The initial concept was to utilize the utilize the temperature and stress dependence of emission from rare earth and transition metal ions substitutionally doped into crystalline or glass fibers. During the course of investigating this it became clear that fiber Bragg gratings provided a alternative for making the desired measurements and there was a shift of research focus on to include the photo-refractive properties of germano-silicate glasses used for most gratings and to the possibility of developing fiber laser sources for an integrated optical sensor in the research effort. During the course of this work several students from Christopher Newport University and other universities participated in this effort. Their names are listed below. Their participation was an important part of their education.

Buoncristiani, A. M.↗

Temperature Sensing to Above 1500 °C Using Y 2 SiO 5 :Er Phosphor Thermometry

A transition from metallic to ceramic turbine components that can operate at higher turbine engine temperatures will push component surface temperatures from below 1200 °C into a 1300 to 1500 °C temperature range that is much more challenging for phosphor thermometry measurements. To address this challenge, Y 2 SiO 5 :Er was selected for its high temperature sensing performance by both luminescence lifetime and luminescence intensity ratio (LIR) methods as well as its thermochemical compatibility with the current generation of rare earth silicate environmental barrier coatings (EBCs) that are required to protect SiC/SiC ceramic composite components. Lifetime measurements that monitor the Er3+ 4S3/2→4I15/2 emission decay at 542 nm exhibited a slow decrease in decay time with temperature up to 1300° C, above which the decay decreased steeply to provide good temperature sensitivity in the 1300 to 1500 °C range (Fig. 1). LIR images were obtained where each pixel represented the ratio I488/I561 (I488 and I561 are the detected 488 nm 4F7/2→4I15/2 and the 561 nm 4S3/2→4I15/2 emission band intensities, respectively). Good temperature sensitivity (Fig. 2) and signal-to-background ratios were observed to above 1500 °C. Contrary to conventional guidance on selecting phosphors for high temperature sensing, the detected emission band intensities and decay times exhibited remarkably slow decreases with temperature up into the 1300 to 1500 °C range despite high phonon energies (>900 cm-1) that allow the energy gap between the 4S3/2 emitting reservoir level and the 4F9/2 level below it to be bridged by as few as three phonons. The benefits of utilizing a thermographic phosphor at very high temperatures that exhibits strong nonradiative multiphonon relaxation even at room temperature is explained by a competition between spontaneous and stimulated multiphonon emission, and the more temperature-sensitive decay time above 1300 °C is explained by a transition from high to low effective phonon energies.

temperature measurement↗

Removal and Replacement of Primary Metal in Ferroan Lodranite MAC 88177

Collectively, acapulcoites and lodranites form a clan of primitive achondrites generally thought to have originated from the same parent body on the basis of similarities in petrology, mineral compositions, bulk compositions, cosmic ray exposure ages and oxygen isotope compositions, although considerable variation in some of these parameters has shown that the parent body was not entirely uniform. The presence of relict chondrules in several acapulcoites indicates that all were likely derived from chondrite-like precursor materials. The transition from acapulcoite to lodranite is gradual and corresponds to increasing metamorphic grade. Lodranites are generally coarser grained, but petrographic distinction between the two groups can also be made by modal abundances of troilite and plagioclase. Depletion of both these phases and incompatible lithophile trace elements in lodranites is consistent with their restitic origin formed by greater than 10% extraction of basaltic melt. Magnesian lodranites (e.g. Gibson, GRA 95209, Y-75274, Y-8002), some of which might also be considered transitional acapulcoites, have mineral and chemical compositions consistent with derivation by thermal metamorphism and partial melt extraction from acapulcoites, as would seem logical if samples represented different grades of metamorphism along a linear evolution trend. Ferromagnesian silicates in these lodranites tend to be displaced toward lower fe# (opx fe# 4-6) than the distribution observed in acapulcoites (opx fe# 6-11). A subset of lodranites, termed ferroan lodranites (e.g. FRO 90011, LEW 88280, Lodran, MAC 88177, Y-74357, Y- 791491/Y-791493), have ferromagnesian silicate minerals that are too Fe-rich (fe#>10) to have formed as simple restites from any known acapulcoite. Like silicates, metal-sulfide systematics of the ferroan lodranites are also inconsistent with a simple restitic origin. Logically, restitic lodranites should have been depleted in FeS during extraction of partial melts, since melting of the metal-sulfide system initiates at lower temperatures than melting of silicates. Yet, puzzingly, ferroan lodranites contain significant quantities (1.9-5.3 modal%) of troilite, indicating either (1) metal sulfide partial melts were retained during basaltic melt extraction or (2) later infusion of metal sulfide melts has occurred. In this study, we use trace siderophile elements in metals to assess the relative importance of each in creating the observed troilite enrichment.

Herrin, J. S.↗

A Detailed Analysis of the Gl 486 Planetary System

Context . The Gl 486 system consists of a very nearby, relatively bright, weakly active M3.5V star at just 8 pc with a warm transiting rocky planet of about 1.3 R ⨁ and 3.0 M ⨁ . It is ideal for both transmission and emission spectroscopy and for testing interior models of telluric planets. Aims . To prepare for future studies, we aim to thoroughly characterise the planetary system with new accurate and precise data collected with state-of-the-art photometers from space and spectrometers and interferometers from the ground. Methods . We collected light curves of seven new transits observed with the CHEOPS space mission and new radial velocities obtained with MAROON-X at the 8.1m Gemini North telescope and CARMENES at the 3.5m Calar Alto telescope, together with previously published spectroscopic and photometric data from the two spectrographs and TESS. We also performed near-infrared interferometric observations with the CHARA Array and new photometric monitoring with a suite of smaller telescopes (AstroLAB, LCOGT, OSN, TJO). This extraordinary and rich data set was the input for our comprehensive analysis. Results . From interferometry, we measure a limb-darkened disc angular size of the star Gl 486 at θ LDD = 0.390 ± 0.018 mas. Together with a corrected Gaia EDR3 parallax, we obtain a stellar radius R * = 0.339 ± 0.015 R ⨀ . We also measure a stellar rotation period at P rot = 49.9 ± 5.5 days, an upper limit to its XUV (5–920 Å) flux informed by new Hubble/STIS data, and, for the first time, a variety of element abundances (Fe, Mg, Si, V, Sr, Zr, Rb) and C/O ratio. Moreover, we imposed restrictive constraints on the presence of additional components, either stellar or sub-stellar, in the system. With the input stellar parameters and the radial-velocity and transit data, we determine the radius and mass of the planet Gl 486 b at R p = 1.343 +0.063 -0.062 R ⨀ and M p = 3.00 +0.13 -0.13 M ⨁ , with relative uncertainties of the planet radius and mass of 4.7% and 4.2%, respectively. From the planet parameters and the stellar element abundances, we infer the most probable models of planet internal structure and composition, which are consistent with a relatively small metallic core with respect to the Earth, a deep silicate mantle, and a thin volatile upper layer. With all these ingredients, we outline prospects for Gl 486 b atmospheric studies, especially with forthcoming James Webb Space Telescope (Webb) observations.

Planetary systems↗

Building wet planets through high-pressure magma–hydrogen reactions

Close-in transiting sub-Neptunes are abundant in our Galaxy. Planetary interior models based on their observed radius–mass relationship suggest that sub-Neptunes contain a discernible amount of either hydrogen (dry planets) or water (wet planets) blanketing a core composed of rocks and metal. Water-rich sub-Neptunes have been believed to form farther from the star and then migrate inwards to their present orbits. Here we report experimental evidence of reactions between warm, dense hydrogen fluid and silicate melt that release silicon from the magma to form alloys and hydrides at high pressures. We found that oxygen liberated from the silicate melt reacts with hydrogen, producing an appreciable amount of water up to a few tens of weight per cent, which is much greater than previously predicted based on low-pressure ideal gas extrapolation. Consequently, these reactions can generate a spectrum of water contents in hydrogen-rich planets, with the potential to reach water-rich compositions for some sub-Neptunes, implying an evolutionary relationship between hydrogen-rich and water-rich planets. Therefore, detection of a large amount of water in exoplanet atmospheres may not be the optimal evidence for planet migration in the protoplanetary disk, calling into question the assumed link between composition and planet formation location.

Horn, H. W. [Arizona State University, Tempe, AZ (↗