Abundances and distribution of minerals and elements in high-alumina coal fly ash from the Jungar Power Plant, Inner Mongolia, China

USGS Publications Warehouse

Dai, S.; Zhao, L.; Peng, S.; Chou, C.-L.; Wang, X.; Zhang, Y.; Li, D.; Sun, Y.

2010-01-01

The fly ash from the Jungar Power Plant, Inner Mongolia, China, is unique because it is highly enriched in alumina (Al2O3>50%). The fly ash mainly consists of amorphous glass and mullite and trace amounts of corundum, quartz, char, calcite, K-feldspar, clay minerals, and Fe-bearing minerals. The mullite content in fly ash is as high as 37.4% because of high boehmite and kaolinite contents in feed coal. Corundum is a characteristic mineral formed during the combustion of boehmite-rich coal.Samples from the economizer were sieved into six size fractions (<120, 120-160, 160-300, 300-360, 360-500, and >500 mesh) and separated into magnetic, mullite+corundum+quartz (MCQ) and glass phases for mineralogical and chemical analysis. The corundum content increases but amorphous glass decreases with decreasing particle size. Fractions of small particle sizes are relatively high in mullite, probably because mullite was formed from fine clay mineral particles under high-temperature combustion condition. Similarly, fine corundum crystals formed in the boiler from boehmite in feed coal. The magnetic phase consists of hematite, magnetite, magnesioferrite, and MgFeAlO4 crystals. The MCQ phase is composed of 89% mullite, 6.1% corundum, 4.5% quartz, and 0.5% K-feldspar.Overall, the fly ash from the power plant is significantly enriched in Al2O3 with an average of 51.9%, but poor in SiO2, Fe2O3, CaO, MgO, Na2O, P2O5, and As. Arsenic, TiO2, Th, Al2O3, Bi, La, Ga, Ni, and V are high in mullite, and the magnetic matter is enriched in Fe2O3, CaO, MnO, TiO2, Cs, Co, As, Cd, Ba, Ni, Sb, MgO, Zn, and V. The remaining elements are high in the glass fraction. The concentration of K2O, Na2O, P2O5, Nb, Cr, Ta, U, W, Rb, and Ni do not clearly vary with particle size, while SiO2 and Hg decrease and the remaining elements clearly increase with decreasing particle size. ?? 2009 Elsevier B.V.

A Two-Stage Model for Origin of Al-rich Crustal Xenoliths in Miocene Andesite, Diablo Range, West-Central California

NASA Astrophysics Data System (ADS)

Metzger, E. P.; Ernst, W. G.

2003-12-01

Miocene ( ˜ 8-10.5 Ma) andesite exposed as small plugs and dikes in the Diablo Range of west-central California encloses scattered xenoliths with diverse compositions and textures. The andesite is part of the Diablo Range Volcanics (DRV), a mafic to intermediate suite that is broadly coeval with and may be erosional remnants of the more extensive Quien Sabe Field located to the south and east. The DRV suite is inferred to be part of a northwestwardly younging sequence of volcanic fields that may be related to migration of the Mendocino Triple Junction (MTJ). Two basic categories of xenoliths are present: (1) metasedimentary rocks including quartzite, biotite schist, garnet-clinopyroxene gneiss, and distinctive sillimanite-corundum rocks; and (2) gabbroic and dioritic rocks exhibiting plutonic textures. Preliminary analysis has focused on aluminous xenoliths in which blocky porphyroblasts consisting of intergrown plagioclase, corundum, and hercynite +/- sillimanite +/- alkali feldspar up to ˜ 2 cm in length are surrounded by a very fine-grained granoblastic matrix of plagioclase, orthopyroxene, and hercynite +/- biotite +/- alkali feldspar +/- minor quartz. Glass is present both within the inclusions and in the surrounding matrix. The square to elongate outlines of the plagioclase-corundum inclusions suggest that they are pseudomorphic after andalusite. The corundum-bearing xenoliths are interpreted as the products of two stages of high T-low P metamorphism. The first event involved mid-crustal metamorphism (reflecting cessation of outboard subduction/refrigeration?) to produce andalusite-bearing hornfels; other phases probably included K-feldspar, Na-plagioclase, muscovite, biotite, and quartz. The second stage of recrystallization took place when the previously metamorphosed wall rock was incorporated in andesitic magma, possibly during passage of the MTJ. In response to heating by the magma, andalusite was replaced by corundum, plagioclase +/- sillimanite, muscovite and quartz broke down to produce more K-feldspar and sillimanite, and most of the biotite decomposed, forming abundant hercynite.

Extreme Mg-26 and O-17 enrichments in an Orgueil corundum: Identification of a presolar oxide grain

NASA Technical Reports Server (NTRS)

Hutcheon, I. D.; Huss, G. R.; Fahey, A. J.; Wasserburg, G. J.

1994-01-01

A corundum (Al2O3) grain from the Orgueil meteorite is greatly enriched in O-17 and (Mg-26)(sup *). The measured O-16/O-17 is 1028 +/- 11 compared to solar(O-16/O-17) = 2610. This is the largest O-17 excess so far observed in any meteoritic material. The Mg-26 excess ((Mg-26)(sup *)) is most plausibly due to in situ decay of Al-26. The inferred (Al-26/Al-27)(sub 0) ratio of 8.9 x 10(exp -4) is approximately 18 times larger than the 5 x 10(exp -5) value commonly observed in refractory inclusions formed in the solar system. The large O-17 excess and high (Mg-26)(sup *) Al-27 ratio unambiguously identify this corundum as a presolar oxide grain. Enrichments in O-17 and Al-26 are characteristic of H-burning and point to red giant or asymptotic giant branch (AGB) stars as likely sources.

Domain walls and ferroelectric reversal in corundum derivatives

NASA Astrophysics Data System (ADS)

Ye, Meng; Vanderbilt, David

2017-01-01

Domain walls are the topological defects that mediate polarization reversal in ferroelectrics, and they may exhibit quite different geometric and electronic structures compared to the bulk. Therefore, a detailed atomic-scale understanding of the static and dynamic properties of domain walls is of pressing interest. In this work, we use first-principles methods to study the structures of 180∘ domain walls, both in their relaxed state and along the ferroelectric reversal pathway, in ferroelectrics belonging to the family of corundum derivatives. Our calculations predict their orientation, formation energy, and migration energy and also identify important couplings between polarization, magnetization, and chirality at the domain walls. Finally, we point out a strong empirical correlation between the height of the domain-wall-mediated polarization reversal barrier and the local bonding environment of the mobile A cations as measured by bond-valence sums. Our results thus provide both theoretical and empirical guidance for future searches for ferroelectric candidates in materials of the corundum derivative family.

Domain walls and ferroelectric reversal in corundum derivatives

NASA Astrophysics Data System (ADS)

Ye, Meng; Vanderbilt, David

Domain walls are the topological defects that mediate polarization reversal in ferroelectrics, and they may exhibit quite different geometric and electronic structures compared to the bulk. Therefore, a detailed atomic-scale understanding of the static and dynamic properties of domain walls is of pressing interest. In this work, we use first-principles methods to study the structures of 180° domain walls, both in their relaxed state and along the ferroelectric reversal pathway, in ferroelectrics belonging to the family of corundum derivatives. Our calculations predict their orientation, formation energy, and migration energy, and also identify important couplings between polarization, magnetization, and chirality at the domain walls. Finally, we point out a strong empirical correlation between the height of the domain-wall mediated polarization reversal barrier and the local bonding environment of the mobile A cations as measured by bond valence sums. Our results thus provide both theoretical and empirical guidance to further search for ferroelectric candidates in materials of the corundum derivative family. The work is supported by ONR Grant N00014-12-1-1035.

Metamorphic reactions in ruby corundum amphibolite from the Chunky Gal Mountain mafic-ultramafic complex, Clay County, North Carolina

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ranson, W.A.; Garihan, J.M.; Ulmer, K.E.

1992-01-01

Amphibolite outcrops of unusual mineralogy within the Chunky Gal Mountain mafic-ultramafic complex display cm-scale rhythmic layers with moderate-steep dips. Layers are troctolitic, gabbroic, and anorthositic in composition, locally in contact with dunite of the Buck Creek ultramafic body. Meta-gabbroic layers contain striking bladed, emerald green amphibole as the chief mafic phase and relict bronzite with reacted margins. An additional major phase is plagioclase, [approximately]An 95 based on microprobe analysis. Ruby corundum is a minor (> 5%) constituent, which in some of the gabbroic rocks is mantled by a reaction rim of fibrolite. The clinoamphibole has optical properties resembling magnesio-cummingtonite: colorlessmore » to pale green in plane light with (+) sign and 2V = 60--70[degree]. However, microprobe analysis of the clinoamphibole indicates alumino-magnesio-hornblende. Although the texture of the bronzite shows that it is breaking down, it is clear that the clinoamphibole and corundum could not be the reaction products without the addition of Al, Ca, and Si in an aqueous fluid. Associated meta-troctolitic layers contain plagioclase and coarse, anhedral olivines displaying an inner corona of bladed orthopyroxene, rimmed by symplectite. The granulite facies reactions is: plagioclase + olivine = clinopyroxene + garnet. The mesoscopic-scale proximity of troctolitic and gabbroic rhythmic layers indicates both underwent granulite facies metamorphism. Retrogression to amphibolite grade is apparent only in the gabbroic layers, resulting in assemblages distinguished locally by abundant emerald green clinoamphibole and corundum porphyroblasts rimmed by fibrolite.« less

Experimental investigation of the reaction between corundum xenocrysts and alkaline basaltic host magma: Constraints on magma residence times of basalt-hosted sapphires

NASA Astrophysics Data System (ADS)

Baldwin, L. C.; Ballhaus, C.

2018-03-01

Megacrystic sapphires (Fe-Ti-rich corundum) of up to 5 cm in size are well known from alkaline mafic rocks from intra-continental rift-related magmatic fields. There is no doubt that these sapphires represent xenocrysts that were trapped from their original lithology by ascending basaltic magmas carrying them to the Earth's surface. Most studies about basalt-hosted sapphires address the question about the origin of the sapphires, but there is hardly any information available about the time the sapphires resided inside the carrier melt. Sapphires are in reaction relationship with basalt and produce spinel coronas at the sapphire-basalt interface, spatially separating the mutually incompatible phases from one another. Assuming isothermal and isobaric conditions of spinel rim formation, the rim-thickness should be a function of the reaction time with the basaltic melt. In this paper, we report time-series experiments aimed at investigating the kinetics of spinel rim formation due to igneous corrosion of corundum. Therefore, we reacted corundum fragments with alkaline basalt powder at 1250 °C and 1GPa, using a Piston Cylinder Apparatus. The width of the spinel rim was used to estimate a residence time. Extrapolating the experimentally derived reaction rates to the thickness of natural spinel rims as described from the Siebengebirge Volcanic Field, Germany, and from Changle, China, we estimated residence times in the order of a few weeks to months.

Spectroscopic Methodologies for Characterizing the Adsorption Behavior and Distribution of Silver Nanoparticles to Hydrated Mineral Surfaces

NASA Astrophysics Data System (ADS)

Brittle, S. W.; O'Neil, K. A.; Foose, D. P.; Stahler, A. C.; Johnson, J. K.; Higgins, S. R.; Sizemore, I. E.; Sikon, J.

2016-12-01

The expansive incorporation of silver nanoparticles (AgNPs) into over 400 consumer products has raised considerable concern about their eventual release into the environment. Although minerals make up a large component of soils, there has been limited research on their interactions with AgNPs. In this study, a representative nonsilicate mineral, corundum (α-Al2O3), was used in fused beaded form (specific surface area of 6-8 m2 g-1) as a model to study the interaction between minerals and negatively-charged, Creighton AgNPs. A concentration of 1 mg L-1 of AgNPs was selected in order to ensure sub-monolayer surface coverage and to surpass the maximum contaminant level (MCL) set by the U.S. Environmental Agency (EPA) for Ag+ in drinking water (0.1 mg L-1). Raman maps collected on the corundum particles exposed to AgNPs at environmentally relevant pH values (6-11) demonstrated AgNP adsorption onto the hydrated mineral surface through OH- moieties regardless of surface charge (i.e. no pH dependence). In addition, two other well-established analytical techniques were employed for supportive purposes. Namely, the AgNP-corundum interaction was also confirmed by inductively coupled plasma optical emission spectroscopy (ICP-OES) through the quantification of the total amount of AgNPs adsorbed onto α-Al2O3. It was found that approximately 75% of the available AgNPs had adsorbed to the mineral surface at all pH values. Atomic force microscopy (AFM), in intermittent contact mode, was also performed to map AgNPs surface distribution on polished and annealed flatter corundum windows. To further demonstrate the Raman analysis, the corundum were also imaged to observe AgNPs adsorption with less surface area and onto other minerals through the occurrence of molecular Ag- vibrations and/or the enhancement of a tracer compound dispensed on mineral surfaces with adsorbed AgNPs (i.e., Surface Enhanced Raman Spectroscopy hot-spots). Overall, this spectroscopic-based analysis promotes extrapolation to other studies as an effective way to observe the interactions between mineral surfaces and nanomaterials.

Development of vertical compact ion implanter for gemstones applications

NASA Astrophysics Data System (ADS)

Intarasiri, S.; Wijaikhum, A.; Bootkul, D.; Suwannakachorn, D.; Tippawan, U.; Yu, L. D.; Singkarat, S.

2014-08-01

Ion implantation technique was applied as an effective non-toxic treatment of the local Thai natural corundum including sapphires and rubies for the enhancement of essential qualities of the gemstones. Energetic oxygen and nitrogen ions in keV range of various fluences were implanted into the precious stones. It has been thoroughly proved that ion implantation can definitely modify the gems to desirable colors together with changing their color distribution, transparency and luster properties. These modifications lead to the improvement in quality of the natural corundum and thus its market value. Possible mechanisms of these modifications have been proposed. The main causes could be the changes in oxidation states of impurities of transition metals, induction of charge transfer from one metal cation to another and the production of color centers. For these purposes, an ion implanter of the kind that is traditionally used in semiconductor wafer fabrication had already been successfully applied for the ion beam bombardment of natural corundum. However, it is not practical for implanting the irregular shape and size of gem samples, and too costly to be economically accepted by the gem and jewelry industry. Accordingly, a specialized ion implanter has been requested by the gem traders. We have succeeded in developing a prototype high-current vertical compact ion implanter only 1.36 m long, from ion source to irradiation chamber, for these purposes. It has been proved to be very effective for corundum, for example, color improvement of blue sapphire, induction of violet sapphire from low value pink sapphire, and amelioration of lead-glass-filled rubies. Details of the implanter and recent implantation results are presented.

Magnetostriction-polarization coupling in multiferroic Mn 2MnWO 6

DOE PAGES

Li, Man-Rong; McCabe, Emma E.; Stephens, Peter W.; ...

2017-12-11

Double corundum-related polar magnets are promising materials for multiferroic and magnetoelectric applications in spintronics. However, their design and synthesis is a challenge, and magnetoelectric coupling has only been observed in Ni 3TeO 6 among the known double corundum compounds to date. Here in this paper we address the high-pressure synthesis of a new polar and antiferromagnetic corundum derivative Mn 2MnWO 6, which adopts the Ni 3TeO 6-type structure with low temperature first-order field-induced metamagnetic phase transitions (T N = 58 K) and high spontaneous polarization (~ 63.3 μC·cm -2). The magnetostriction-polarization coupling in Mn 2MnWO 6 is evidenced by secondmore » harmonic generation effect, and corroborated by magnetic-field-dependent pyroresponse behavior, which together with the magnetic-field-dependent polarization and dielectric measurements, qualitatively indicate magnetoelectric coupling. Finally, piezoresponse force microscopy imaging and spectroscopy studies on Mn 2MnWO 6 show switchable polarization, which motivates further exploration on magnetoelectric effect in single crystal/thin film specimens.« less

Magnetostriction-polarization coupling in multiferroic Mn 2MnWO 6

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Man-Rong; McCabe, Emma E.; Stephens, Peter W.

Double corundum-related polar magnets are promising materials for multiferroic and magnetoelectric applications in spintronics. However, their design and synthesis is a challenge, and magnetoelectric coupling has only been observed in Ni 3TeO 6 among the known double corundum compounds to date. Here in this paper we address the high-pressure synthesis of a new polar and antiferromagnetic corundum derivative Mn 2MnWO 6, which adopts the Ni 3TeO 6-type structure with low temperature first-order field-induced metamagnetic phase transitions (T N = 58 K) and high spontaneous polarization (~ 63.3 μC·cm -2). The magnetostriction-polarization coupling in Mn 2MnWO 6 is evidenced by secondmore » harmonic generation effect, and corroborated by magnetic-field-dependent pyroresponse behavior, which together with the magnetic-field-dependent polarization and dielectric measurements, qualitatively indicate magnetoelectric coupling. Finally, piezoresponse force microscopy imaging and spectroscopy studies on Mn 2MnWO 6 show switchable polarization, which motivates further exploration on magnetoelectric effect in single crystal/thin film specimens.« less

Towards the differentiation of non-treated and treated corundum minerals by ion-beam-induced luminescence and other complementary techniques.

PubMed

Calvo del Castillo, H; Deprez, N; Dupuis, T; Mathis, F; Deneckere, A; Vandenabeele, P; Calderón, T; Strivay, D

2009-06-01

Differentiation of treated and non-treated gemstones is a chief concern for major jewellery import companies. Low-quality corundum specimens coming from Asia appear to be often treated with heat, BeO or flux in order to enhance their properties as precious minerals. A set of corundum samples, rubies and sapphires from different origins, both treated and non-treated has been analysed at the Centre Européen d'Archéométrie, with ion-beam-induced luminescence (IBIL) and other complementary techniques such as Raman, proton-induced X-ray emission (PIXE), and proton-induced gamma-ray emission (PIGE). IBIL, also known as ionoluminescence, has been used before to detect impurities or defects inside synthetic materials and natural minerals; its use for the discrimination of gemstone simulants or synthetic analogues has been elsewhere discussed (Cavenago-Bignami Moneta, Gemología, Tomo I Piedras preciosas, perlas, corales, marfil. Ediciones Omega, Barcelona, 1991). PIXE has been frequently applied in the archaeometric field for material characterisation and provenance studies of minerals (Hughes, Ruby & sapphire. RWH Publishing, Fallbrook, 1997; Calvo del Castillo et al., Anal Bioanal Chem 387:869-878, 2007; Calligaro et al., NIM-B 189:320-327, 2002) and PIGE complements the elemental analysis by detecting light elements in these materials such as-and lighter than-sodium that cannot be identified with the PIXE technique (Sanchez et al., NIM-B 130:682-686, 1997; Emmett et al., Gems Gemology 39:84-135, 2003). The micro-Raman technique has also been used complementarily to ion beam analysis techniques for mineral characterisation (Novak et al., Appl Surf Sci 231-232:917-920, 2004). The aim of this study is to provide new means for systematic analysis of corundum gemstone-quality mineral, alternative to the traditional gemmologic methods; for this purpose, a Spanish jewellery import company supplied us with a number of natural corundum samples coming from different places (part of them treated as explained above). The PIXE elemental concentrations of the samples showed large quantities of calcium and lead in some cases that can be linked to treatment with fluxes or lead oxide. The plot of the chromium and iron concentration grouped the samples in various aggregates that corresponded to the different types of corundum analysed. Micro-Raman complemented the PIXE analysis corroborating the presence of lead oxides but the use of the PIGE technique was not successful for the detection of beryllium due to the low cross section of the nuclear reaction chosen for its identification. IBIL was capable of distinguishing between treated and non-treated samples of the same type based on the luminescent features of the materials.

Silica-undersaturated reaction zones at a crust-mantle interface in the Highland Complex, Sri Lanka: Mass transfer and melt infiltration during high-temperature metasomatism

NASA Astrophysics Data System (ADS)

Fernando, G. W. A. R.; Dharmapriya, P. L.; Baumgartner, Lukas P.

2017-07-01

Sri Lanka is a crucial Gondwana fragment mostly composed of granulitic rocks in the Highland Complex surrounded by rocks with granulite to amphibolite grade in the Vijayan and Wanni Complex that were structurally juxtaposed during Pan-African orogeny. Fluids associated with granulite-facies metamorphism are thought to have controlled various lower crustal processes such as dehydration/hydration reactions, partial melting, and high-temperature metasomatism. Chemical disequilibrium in the hybrid contact zone between a near peak post-tectonic ultramafic enclave and siliceous granulitic gneiss at Rupaha within the Highland Complex produced metasomatic reaction zones under the presence of melt. Different reaction zones observed in the contact zone show the mineral assemblages phlogopite + spinel + sapphirine (zone A), spinel + sapphirine + corundum (zone B), corundum ( 30%) + biotite + plagioclase zone (zone C) and plagioclase + biotite + corundum ( 5%) zone (zone D). Chemical potential diagrams and mass balance reveal that the addition of Mg from ultramafic rocks and removal of Si from siliceous granulitic gneiss gave rise to residual enrichment of Al in the metasomatized mineral assemblages. We propose that contact metasomatism between the two units, promoted by melt influx, caused steady state diffusional transport across the profile. Corundum growth was promoted by the strong residual Al enrichment and Si depletion in reaction zone whereas sapphirine may have been formed under high Mg activity near the ultramafic rocks. Modelling also indicated that metasomatic alteration occurred at ca. 850 °C at 9 kbar, which is consistent with post-peak metamorphic conditions reached during the initial stage of exhumation in the lower crust and with temperature calculations based on conventional geothermometry.

A Wealth of Dust Grains in Quasar Winds

NASA Technical Reports Server (NTRS)

2007-01-01

[figure removed for brevity, see original site] Click on image for larger poster version

This plot of data captured by NASA's Spitzer Space Telescope reveals dust entrained in the winds rushing away from a quasar, or growing black hole. The quasar, called PG2112+059, is located deep inside a galaxy 8 billion light-years away. Astronomers believe the dust might have been forged in the winds, which would help explain where dust in the very early universe came from.

The data were captured by Spitzer's infrared spectrograph, an instrument that splits apart light from the quasar into a spectrum that reveals telltale signs of different minerals. Each type of mineral, or dust grain, has a unique signature, as can be seen in the graph, or spectrum, above.

The strongest features are from the mineral amorphous olivine, or glass (purple); the mineral forsterite found in sand (blue); and the mineral corundum found in rubies (light blue). The detection of forsterite and corundum is highly unusual in galaxies without quasars. Therefore, their presence is a key clue that these grains might have been created in the quasar winds and not by dying stars as they are in our Milky Way galaxy. Forsterite is destroyed quickly in normal galaxies by radiation, so it must be continually produced to be detected by Spitzer.

Corundum is hard, and provides a seed that softer, more common minerals usually cover up. As a result, corundum is usually not seen in spectra of galaxies. Since Spitzer did detect the mineral, it is probably forming in a clumpy environment, which is expected in quasar winds. All together, the signatures of the unusual minerals in this spectrum point towards dust grains forming in the winds blowing away from quasars.

Evolution of corundum-structured III-oxide semiconductors: Growth, properties, and devices

NASA Astrophysics Data System (ADS)

Fujita, Shizuo; Oda, Masaya; Kaneko, Kentaro; Hitora, Toshimi

2016-12-01

The recent progress and development of corundum-structured III-oxide semiconductors are reviewed. They allow bandgap engineering from 3.7 to ∼9 eV and function engineering, leading to highly durable electronic devices and deep ultraviolet optical devices as well as multifunctional devices. Mist chemical vapor deposition can be a simple and safe growth technology and is advantageous for reducing energy and cost for the growth. This is favorable for the wide commercial use of devices at low cost. The III-oxide semiconductors are promising candidates for new devices contributing to sustainable social, economic, and technological development for the future.

Modification of surface morphology of Ti6Al4V alloy manufactured by Laser Sintering

NASA Astrophysics Data System (ADS)

Draganovská, Dagmar; Ižariková, Gabriela; Guzanová, Anna; Brezinová, Janette; Koncz, Juraj

2016-06-01

The paper deals with the evaluation of relation between roughness parameters of Ti6Al4V alloy produced by DMLS and modified by abrasive blasting. There were two types of blasting abrasives that were used - white corundum and Zirblast at three levels of air pressure. The effect of pressure on the value of individual roughness parameters and an influence of blasting media on the parameters for samples blasted by white corundum and Zirblast were evaluated by ANOVA. Based on the measured values, the correlation matrix was set and the standard of correlation statistic importance between the monitored parameters was determined from it. The correlation coefficient was also set.

Microstructure and physical properties of steel-ladle purging plug refractory materials

NASA Astrophysics Data System (ADS)

Long, Bin; Xu, Gui-ying; Andreas, Buhr

2017-02-01

Three different castables were prepared as steel-ladle purging-plug refractory materials: corundum-based low-cement castable (C-LCC), corundum-spinel-based low-cement castable (C-S-LCC), and no-cement corundum-spinel castable (C-S-NCC) (hydratable alumina ρ-Al2O3 bonded). The properties of these castables were characterized with regard to water demand/flow ability, cold crushing strength (CCS), cold modulus of rupture (CMoR), permanent linear change (PLC), apparent porosity, and hot modulus of rupture (HMoR). The results show the CCS/CMoR and HMoR of C-LCC and C-S-LCC are greater than those of the castable C-S-NCC. According to the microstructure analysis, the sintering effect and the bonding type of the matrix material differ among the three castables. The calcium hexaluminate (CA6) phase in the matrix of C-LCC enhances the cold and hot mechanical strengths. In the case of C-S-LCC, the CA6 and 2CaO·2MgO·14Al2O3 (C2M2A14) ternary phases generated from the matrix can greatly increase the cold and hot mechanical strengths. In the case of the no-cement castable, sintering becomes difficult, resulting in a lower mechanical strength.

Measurements of the PVT properties of water to 25 kbars and 1600°C from synthetic fluid inclusions in corundum

NASA Astrophysics Data System (ADS)

Brodholt, John P.; Wood, Bernard J.

1994-05-01

We have performed experiments to determine the density of water at pressures and temperatures of 9.5 to 25 kbar and 930 to 1600°C, respectively. The experimental method involved growing inclusions of fluid ( ρ < 1.0 gm/ cm3) in synthetic precracked corundum. Density was determined by measuring the homogenization temperature along the liquid-vapour equilibrium curve. Comparison with the many current equations of state for water indicates that, in the P- V- T range of the experiments, the equations of KERRICK and JACOBS (1981) and BRODHOLT and WOOD (1993) provide the best fits. In contrast the steam tables of HAAR et al. (1984) systematically underestimate the molar volumes at high temperatures.

Influence of the post-weld surface treatment on the corrosion resistance of the duplex stainless steel 1.4062

NASA Astrophysics Data System (ADS)

Rosemann, P.; Müller, C.; Baumann, O.; Modersohn, W.; Halle, T.

2017-03-01

The duplex stainless steel 1.4062 (X2CrNiN22-2) is used as alternative material to austenitic stainless steels in the construction industry. The corrosion resistance of welded seams is influenced by the base material, the weld filler material, the welding process and also by the final surface treatment. The scale layer next to the weld seam can be removed by grinding, pickling, electro-polished or blasting depending on the application and the requested corrosion resistance. Blasted surfaces are often used in industrial practice due to the easier and cheaper manufacturing process compared to pickled or electro-polished surfaces. Furthermore blasting with corundum-grain is more effective than blasting with glass-beads which also lower the process costs. In recent years, stainless steel surfaces showed an unusually high susceptibility to pitting corrosion after grinding with corundum. For this reason, it is now also questioned critically whether the corrosion resistance is influenced by the applied blasting agent. This question was specifically investigated by comparing grinded, pickled, corundum-grain- and glass-bead-blasted welding seams. Results of the SEM analyses of the blasting agents and the blasted surfaces will be presented and correlated with the different performed corrosion tests (potential measurement, KorroPad-test and pitting potential) on welding seams with different surface treatments.

Microstructural and Wear Behavior Characterization of Porous Layers Produced by Pulsed Laser Irradiation in Glass-Ceramics Substrates

PubMed Central

Sola, Daniel; Conde, Ana; García, Iñaki; Gracia-Escosa, Elena; de Damborenea, Juan J.; Peña, Jose I.

2013-01-01

In this work, wear behavior and microstructural characterization of porous layers produced in glass-ceramic substrates by pulsed laser irradiation in the nanosecond range are studied under unidirectional sliding conditions against AISI316 and corundum counterbodies. Depending on the optical configuration of the laser beam and on the working parameters, the local temperature and pressure applied over the interaction zone can generate a porous glass-ceramic layer. Material transference from the ball to the porous glass-ceramic layer was observed in the wear tests carried out against the AISI316 ball counterface whereas, in the case of the corundum ball, the wear volume loss was concentrated in the porous layer. Wear rate and friction coefficient presented higher values than expected for dense glass-ceramics. PMID:28788311

In-situ Raman spectroscopic study of aluminate speciation in H2O-KOH solutions at high pressures and temperatures

NASA Astrophysics Data System (ADS)

Mookherjee, M.; Keppler, H.; Manning, C. E.

2009-12-01

The solubility of corundum in H2O is low even at high pressure and temperatures. Therefore, it is commonly assumed that alumina remains essentially immobile during fluid-rock interaction. However, field and experimental evidence suggests that alumina solubility is strongly enhanced in the presence of silica as well as in alkaline solutions. In order to understand what controls the alumina solubility and how it is enhanced as a function of fluid composition, we conducted Raman-spectroscopic study of Al speciation in aqueous fluids at high pressure and temperature. Experiments were carried out in an externally heated hydrothermal diamond-anvil cell equipped with low-fluorescence diamonds and iridium gaskets. Raman spectra were collected with a Horiba Jobin-Yvon Labram HR spectrometer using the 514 nm line of an argon laser for excitation. In a first series of experiments, the speciation of alumina was studied in a 1 M KOH solution in equilibrium with corundum up to 700 oC and ~1 GPa. The Raman spectra show a prominent band at 618 cm-1 interpreted to arise from Al-O stretching vibrations associated with the tetrahedral [Al(OH)4]1- species. At higher pressure and temperature, an additional vibrational mode appears in the spectra at 374 cm-1 (full width at half maximum ~ 20 cm-1). This feature is tentatively attributed to [(OH)3Al-O-Al(OH)3]2- (Moolenaar et al. 1970, Jour. Phys. Chem., 74, 3629-3636). No evidence for KAl(OH)4 was observed, consistent with piston cylinder experiments at 700 oC and 1 GPa (Wohlers & Manning, 2009, Chem. Geol., 262, 310). Upon cooling from high-pressure and high temperature, slow kinetics of corundum regrowth lead to oversaturation in the solutions, as evidenced by sharp peaks at 930 and 1066 cm-1 observed upon cooling. These features are probably due to colloidal aluminum hydroxide. The results provide the first evidence for aluminate polymerization at high pressure and temperature, and offer insights into the causes for enhancement of corundum solubility in alkaline solutions.

Evaluation of Soft Tissue Reaction to Corundum Ceramic Implants Infiltrated with Colloidal Silver.

PubMed

Wnukiewicz, Witold; Rutowski, Roman; Zboromirska-Wnukiewicz, Beata; Reichert, Paweł; Gosk, Jerzy

2016-01-01

Corundum ceramic is a biomaterial used as a bone graft substitute. Silver is a well known antiseptic substance with many practical, clinical applications. The aim of this study was to estimate soft tissue (in vivo) reaction to a new kind of ceramic implants. In our experiment, we examined the soft tissue reaction after implantation of corundum ceramic infiltrated with colloidal silver in the back muscles of 18 Wistar rats. The use of colloidal silver as a coating for the implant was designed to protect it against colonization by bacteria and the formation of bacterial biofilm. In our study, based on the experimental method, we performed implantation operations on 18 Wistar rats. We implanted 18 modified ceramic implants and, as a control group, 18 unmodified implants. As a follow up, we observed the animals operated upon, and did postoperative, autopsy and histopathological examinations 14, 30, 90 and 180 days after implantation. We didn't observe any pathological reactions and significant differences between the soft tissue reaction to the modified implants and the control group. Lack of pathological reaction to the modified implants in the living organism is the proof of their biocompatibility. This is, of course, the first step on the long path to introduce a new kind of biocompatible ceramic implant with antiseptic cottage. Our experiment has an only introductory character and we plan to perform other, more specific, tests of this new kind of implant.

Single Crystals Grown Under Unconstrained Conditions

NASA Astrophysics Data System (ADS)

Sunagawa, Ichiro

Based on detailed investigations on morphology (evolution and variation in external forms), surface microtopography of crystal faces (spirals and etch figures), internal morphology (growth sectors, growth banding and associated impurity partitioning) and perfection (dislocations and other lattice defects) in single crystals, we can deduce how and by what mechanism the crystal grew and experienced fluctuation in growth parameters through its growth and post-growth history under unconstrained condition. The information is useful not only in finding appropriate way to growing highly perfect and homogeneous single crystals, but also in deciphering letters sent from the depth of the Earth and the Space. It is also useful in discriminating synthetic from natural gemstones. In this chapter, available methods to obtain molecular information are briefly summarized, and actual examples to demonstrate the importance of this type of investigations are selected from both natural minerals (diamond, quartz, hematite, corundum, beryl, phlogopite) and synthetic crystals (SiC, diamond, corundum, beryl).

Adsorption mechanisms of selenium oxyanions at the aluminum oxide/water interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peak, Derek

2008-06-09

Sorption processes at the mineral/water interface typically control the mobility and bioaccessibility of many inorganic contaminants such as oxyanions. Selenium is an important micronutrient for human and animal health, but at elevated concentrations selenium toxicity is a concern. The objective of this study was to determine the bonding mechanisms of selenate (SeO{sub 4}{sup 2-}) and selenite (SeO{sub 3}{sup 2-}) on hydrous aluminum oxide (HAO) over a wide range of reaction pH using extended X-ray absorption fine structure (EXAFS) spectroscopy. Additionally, selenate adsorption on corundum ({alpha}-Al{sub 2}O{sub 3}) was studied to determine if adsorption mechanisms change as the aluminum oxide surfacemore » structure changes. The overall findings were that selenite forms a mixture of outer-sphere and inner-sphere bidentate-binuclear (corner-sharing) surface complexes on HAO, selenate forms primarily outer-sphere surface complexes on HAO, and on corundum selenate forms outer-sphere surface complexes at pH 3.5 but inner-sphere monodentate surface complexes at pH 4.5 and above. It is possible that the lack of inner-sphere complex formation at pH 3.5 is caused by changes in the corundum surface at low pH or secondary precipitate formation. The results are consistent with a structure-based reactivity for metal oxides, wherein hydrous metal oxides form outer-sphere complexes with sulfate and selenate, but inner-sphere monodentate surface complexes are formed between sulfate and selenate and {alpha}-Me{sub 2}O{sub 3}.« less

Play the heavy: An effective mass study for α-Fe{sub 2}O{sub 3} and corundum oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neufeld, Ofer; Caspary Toroker, Maytal, E-mail: maytalc@tx.technion.ac.il

2016-04-28

Iron(III) oxide (α-Fe{sub 2}O{sub 3}) is a known water splitting catalyst commonly used in photoelectrochemical cells. These cells are severely impaired by poor conductivity in α-Fe{sub 2}O{sub 3}, and resolving the conductivity issue is therefore crucial. One of the most intrinsic properties of matter, which governs conductivity, is the carrier effective masses. In this work, we investigate the carrier effective masses in α-Fe{sub 2}O{sub 3} and other corundum oxides, including Al{sub 2}O{sub 3}, Cr{sub 2}O{sub 3}, Ga{sub 2}O{sub 3}, and In{sub 2}O{sub 3} with different theoretical constructs: density functional theory (DFT), DFT+U, hybrid DFT, and G{sub 0}W{sub 0}. We findmore » DFT sufficiently describes the carrier masses and a quasi-particle theory is only required for accuracies better than 30% for the conduction band effective mass. Additionally, we compare the density of states (DOS) and band effective mass approximations and conclude the DOS effective mass provides poor results whenever the band structure is anisotropic. We find that the charge carriers in Fe{sub 2}O{sub 3} “play the heavy” since they have large effective masses that reduce conductivity and device efficiency. Finally, we conclude that the less heavy electron effective masses of other corundum oxides studied relative to Fe{sub 2}O{sub 3} could contribute to efficiency improvements in Fe{sub 2}O{sub 3} upon Al{sub 2}O{sub 3}, Ga{sub 2}O{sub 3}, and In{sub 2}O{sub 3} coverage.« less

Identification of deposit types of natural corundum by PIXE

NASA Astrophysics Data System (ADS)

Chulapakorn, T.; Intarasiri, S.; Bootkul, D.; Singkarat, S.

2014-07-01

Natural corundum, one of the most important exports of Thailand, is a rare, durable and valuable gemstone. The value of these precious stones is determined by their visual appearances, including brilliance, color, fire (light dispersion) and luster. Corundum is an allochromatic mineral whose trace element concentration depends on the origin and has influence on price setting. This work attempts to use an alternative method to identify the geological deposits of rubies and sapphires found in the Thai market which came from various countries, e.g., Africa, Cambodia, Myanmar, Sri Lanka, Thailand and USA. Interrelations between most important major trace elements are the main results of this work. Quantitative analysis of trace elements were performed by particle-induced X-ray emission (PIXE) technique, using 2-MeV proton beam generated and accelerated by the 1.7 MV tandem accelerator at Chiang Mai University. The trace elements of interest are Ti, Cr, Fe and Ga. We have found that the relationships between the ratios of trace element concentration can be used to classify the deposit type. Moreover, this method shows a clear separation between two main types of geological deposits, basaltic and metamorphic deposits, which further helps in determining the gemstone origin. For example, the gemstones from Cambodia, Thailand and the USA can be classified as the basaltic deposits with their high concentration in Fe but low in Ti, while the gemstones from Africa, Myanmar and Sri Lanka are metamorphic deposits because they have low Fe but high Ti concentrations. Both deposits required plots of pairs of trace elements and their ratios in population field appearance in order to distinguish their origins. The advantageous of these methods appear to be a new and a sustainable procedure for determining gemstone origins.

Shock induced reaction of Ni/Al nanopowder mixture.

PubMed

Meng, C M; Wei, J J; Chen, Q Y

2012-11-01

Nanopowder Ni/Al mixture (mixed in Al:Ni = 2:1 stoichiometry) was shock compressed by employing single and two-stage light gas gun. The particle size of Al and Ni are 100-200 nm and 50-70 nm respectively, morphologies of Al and Ni are sphere like either. Recovered product was characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD) analysis. According to the XRD spectrum, the mixed powder undergo complete reaction under shock compression, reaction product consist of Ni2Al3, NiAl and corundum structure Al2O3 compound. Grain size of Ni-Al compound is less than 100 nm. With the shock pressure increasing, the ratio of Ni2Al3 decreased obviously. The corundum crystal size is 400-500 nm according to the SEM observation. The results of shock recovery experiments and analysis show that the threshold pressure for reaction of nano size powder Ni/Al mixture is much less than that of micro size powder.

BIOACCESSIBILITY OF ARSENIC BOUND TO CORUNDUM USING A SIMULATED GASTROINTESTINAL SYSTEM

EPA Science Inventory

Ingestion of soil contaminated with arsenic is an important pathway for human exposure to arsenic. The risk posed by ingestion of arsenic-contaminated soil depends on how much arsenic is dissolved in the gastrointestinal tract. Aluminum oxides are common components in the soil a...

EDXRF quantitative analysis of chromophore chemical elements in corundum samples.

PubMed

Bonizzoni, L; Galli, A; Spinolo, G; Palanza, V

2009-12-01

Corundum is a crystalline form of aluminum oxide (Al(2)O(3)) and is one of the rock-forming minerals. When aluminum oxide is pure, the mineral is colorless, but the presence of trace amounts of other elements such as iron, titanium, and chromium in the crystal lattice gives the typical colors (including blue, red, violet, pink, green, yellow, orange, gray, white, colorless, and black) of gemstone varieties. The starting point for our work is the quantitative evaluation of the concentration of chromophore chemical elements with a precision as good as possible to match the data obtained by different techniques as such as optical absorption photoluminescence. The aim is to give an interpretation of the absorption bands present in the NIR and visible ranges which do not involve intervalence charge transfer transitions (Fe(2+) --> Fe(3+) and Fe(2+) --> Ti(4+)), commonly considered responsible of the important features of the blue sapphire absorption spectra. So, we developed a method to evaluate as accurately as possible the autoabsorption effects and the secondary excitation effects which frequently are sources of relevant errors in the quantitative EDXRF analysis.

Effect of impurity on high pressure behavior of nano indium titanate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chitnis, Abhishek, E-mail: abhishekchitnis87@gmail.com; Garg, Nandini; Mishra, A. K.

2015-06-24

Angle dispersive x-ray diffraction studies were carried out on a mixture of nano particles of indium titanate, indium oxide, and disordered TiO{sub 2} upto pressures of ∼ 45 GPa. Our studies show that indium titanate undergoes a partial decomposition to its constituent high pressure oxides. However, concomitantly a very small fraction of indium titanate transforms to a denser phase at ∼ 27.5 GPa. This transformation to new phase was found to be irreversible. At this pressure even cubic In{sub 2}O{sub 3} transformed to the In{sub 2}O{sub 3} (II) (iso-structural to Rh{sub 2}O{sub 3} (II)) phase, without any signature of themore » intermediate corundum phase. The high pressure In{sub 2}O{sub 3} (II) phase transforms to the corundum structure on release of pressure. These studies indicate that the presence of a large fraction of seed impurities could have facilitated the decomposition of indium titanate into its constituent oxides at the cost of its incomplete transformation to the high pressure denser phase.« less

Macroscopic and spectroscopic investigations on Eu(III) and Cm(III) sorption onto bayerite (β-Al(OH)3) and corundum (α-Al2O3).

PubMed

Kupcik, Tomas; Rabung, Thomas; Lützenkirchen, Johannes; Finck, Nicolas; Geckeis, Horst; Fanghänel, Thomas

2016-01-01

The interaction of trivalent Cm and Eu with the aluminum hydroxide bayerite (β-Al(OH)3) and the aluminum oxide corundum (α-Al2O3) was investigated by batch sorption experiments and time resolved laser fluorescence spectroscopy (TRLFS). The experimental methods for both polymorphs show similar pH dependent sorption behavior at trace metal ion concentrations (∼10(-7) M), i.e. similar Eu sorption edges and nearly identical Cm speciation between pH=3 and 13. In this pH range the Cm aquo ion as well as the Cm(III) surface species surface⋯Cm(OH)x(H2O)(5-x) (x=0, 1, 2) can be distinguished by TRLFS. The similar sorption data point to a (surface) transformation of the thermodynamically unstable Al2O3 surface into bayerite, in agreement with the similar isoelectric points obtained for both minerals (pH(IEP)=8.6-8.8). The pH dependent surface charge is most likely due to the protonation/deprotonation of singly coordinated Al-OH surface groups, prevailing on the edge planes of the rod-like bayerite crystals and the surface of the colloidal Al2O3 particles. These surface groups are also believed to act as ligands for lanthanide/actinide(III) surface complexation. In contrast to the similar sorption behavior at trace metal ion concentrations, discrepancies are observed at higher Eu levels. While similar sorption edges occur up to 7×10(-7) M Eu for corundum, the pH edge on bayerite is gradually shifted to higher pH values in this Eu concentration range. The latter behavior may be related either to the existence of multiple sorption sites with different sorption affinities, or to the influence of an additional amorphous Al-phase, forming in the course of the bayerite synthesis. Copyright © 2015 Elsevier Inc. All rights reserved.

Sorption of lambda-cyhalothrin, cypermethrin, deltamethrin and fenvalerate to quartz, corundum, kaolinite and montmorillonite.

PubMed

Oudou, H Chaaieri; Hansen, H C Bruun

2002-12-01

Sorption to mineral surfaces may be important for retention and degradation of hydrophobic pesticides in subsoils and aquifers poor in organic matter. In this work the title pyrethroids have been used to investigate selective interactions with the surfaces of four minerals. Sorption of the four pyrethroids was quantified in batch experiments with initial pyrethroid concentrations of 1-100 microg/l. Sorption to centrifuge tubes used in the batch experiments accounted for 25-60% of total sorption. Net sorption was obtained from total sorption after subtracting the amounts of pyrethroids sorbed to centrifuge tubes used. All isotherms could be fitted by the Freundlich equation with n ranging between 0.9 and 1.1. Bonding affinities per unit surface area decreased in the order: corundum > quartz > montmorillonite approximately equal kaolinite. A similar sequence as found for the total surface tension of the minerals. All minerals showed the same selectivity order with respect to sorption affinity of the four pyrethroids: lambda-cyhalothrin > deltamethrin > cypermethrin > fenvalerate, which shows that the most hydrophobic compound is sorbed most strongly. Stereochemical properties of the four pyrethroid formulations may also contribute to the selectivity pattern.

Influence of the silicon carbide deposit on the thermal resistance of fire protection

NASA Astrophysics Data System (ADS)

Kim, K. A.; Lemeshev, D. O.

2018-04-01

The ceramics samples with structure of SiC-Al2O3-Fireclay having good thermal resistance were received. As materials were used: black α-SiC F-120, corundum α-Al2O3 F-1000 and Kudinovsky fire-clay. As a temporary technological bundle used polyvinyl alcohol (PVA). Thermal stability was determined by method of heat changes.

Marble-hosted ruby deposits of the Morogoro Region, Tanzania

NASA Astrophysics Data System (ADS)

Balmer, Walter A.; Hauzenberger, Christoph A.; Fritz, Harald; Sutthirat, Chakkaphan

2017-10-01

The ruby deposits of the Uluguru and Mahenge Mts, Morogoro Region, are related to marbles which represent the cover sequence of the Eastern Granulites in Tanzania. In both localities the cover sequences define a tectonic unit which is present as a nappe structure thrusted onto the gneissic basement in a north-western direction. Based on structural geological observations the ruby deposits are bound to mica-rich boudins in fold hinges where fluids interacted with the marble-host rock in zones of higher permeability. Petrographic observations revealed that the Uluguru Mts deposits occur within calcite-dominated marbles whereas deposits in the Mahenge Mts are found in dolomite-dominated marbles. The mineral assemblage describing the marble-hosted ruby deposit in the Uluguru Mts is characterised by corundum-dolomite-phlogopite ± spinel, calcite, pargasite, scapolite, plagioclase, margarite, chlorite, tourmaline whereas the assemblage corundum-calcite-plagioclase-phlogopite ± dolomite, pargasite, sapphirine, titanite, tourmaline is present in samples from the Mahenge Mts. Although slightly different in mineral assemblage it was possible to draw a similar ruby formation history for both localities. Two ruby forming events were distinguished by textural differences, which could also be modeled by thermodynamic T-XCO2 calculations using non-ideal mixing models of essential minerals. A first formation of ruby appears to have taken place during the prograde path (M1) either by the breakdown of diaspore which was present in the original sedimentary precursor rock or by the breakdown of margarite to corundum and plagioclase. The conditions for M1 metamorphism was estimated at ∼750 °C at 10 kbar, which represents granulite facies conditions. A change in fluid composition towards a CO2 dominated fluid triggered a second ruby generation to form. Subsequently, the examined units underwent a late greenschist facies overprint. In the framework of the East African Orogen we assume that the prograde ruby formation occurred at the commonly observed metamorphic event around 620 Ma. At the peak or during beginning of retrogression the fluid composition changed triggering a second ruby generation. The late stage greenschist facies overprint could have occurred at the waning stage of this metamorphic episode which is in the range of ∼580 Ma.

Metastable Phase Relations in the System Ca(sub O)-Al2(sub O)3-MgO-TiO(sub 2): Applications to Ca- And Al-Rich Inclusions

NASA Technical Reports Server (NTRS)

Keller, L. P.; Han, J.

2017-01-01

Introduction: High temperature phases such as corundum, hibonite, grossite, and perovskite are among the earliest phases that condensed in the early solar nebula. Recent work has shown that defect-structured phases occur in some ultrarefractory inclusions as metastable, possibly more kinetically-favored alternatives to the thermodynamically predicted stable phase assemblages [1-4]. For example, Han et al. have shown that non-stoichiometry in hibonite is accommodated by extra "spinel" blocks in the structure instead of the equilibrium assemblages hibonite+corundum or hibonite+spinel. To explore these relations, we have conducted a series of experiments in the system CaO-Al2O3- MgO-TiO2. Here we discuss the compositions and mineralogy of the experimental samples and how they relate to phases in refractory inclusions with a focus on perovskite and spinel. Methods: For the series of annealing studies, a CaO-Al2O3 eutectic melt is allowed to react with a pure alumina crucible at 1,530degC for either 4 hours or 5 days, followed by quenching in air. Later experiments were similar except that additions of 5 wt% MgO, and CaTiO(sub 3) were used to explore the effect of minor elements on the phase assemblages. The experimental conditions resulted in reaction zones approximately 100-300 ?m wide consisting of a hibonite layer immediately adjacent to the corundum, followed by a grossite layer, and finally krotite with residual quenched melt. For the experiments with Mg, spinel is distributed in all layers but is mainly concentrated in the krotite layer. In the Ti-bearing experiments, perovskite precipitated in association with the krotite and residual melt. In addition to the experiments, we also analyzed perovskite grains in the FUN inclusion SHAL [5] and a large compact type A CAI from Allende. The experiments and refractory inclusions were analyzed using a JEOL 7600F SEM and quantitative analyses were obtained using the JEOL 8530F field-emission electron microprobe.

Geochemistry and Ar-Ar muscovite ages of the Daraban Leucogranite, Mawat Ophiolite, northeastern Iraq: Implications for Arabia-Eurasia continental collision

NASA Astrophysics Data System (ADS)

Mohammad, Yousif O.; Cornell, David H.; Qaradaghi, Jabbar H.; Mohammad, Fahmy O.

2014-06-01

Daraban Leucogranite dykes intruded discordantly into the basal serpentinized harzburgite of the Mawat Ophiolite, Kurdistan region, NE Iraq. These coarse grained muscovite-tourmaline leucogranites are the first leucogranite dykes identified within the Mawat Ophiolite. They are mainly composed of quartz, K-feldspar, plagioclase, tourmaline, muscovite, and secondary phologopite, while zircon, xenotime, corundum, mangano-ilemnite and cassiterite occur as accessories.

Reaction rim growth in the system MgO-Al2O3-SiO2 under uniaxial stress

NASA Astrophysics Data System (ADS)

Götze, Lutz Christoph; Abart, Rainer; Rybacki, Erik; Keller, Lukas M.; Petrishcheva, Elena; Dresen, Georg

2010-07-01

We synthesize reaction rims between thermodynamically incompatible phases in the system MgO-Al2O3-SiO2 applying uniaxial load using a creep apparatus. Synthesis experiments are done in the MgO-SiO2 and in the MgO-Al2O3 subsystems at temperatures ranging from 1150 to 1350 °C imposing vertical stresses of 1.2 to 29 MPa at ambient pressure and under a constant flow of dry argon. Single crystals of synthetic and natural quartz and forsterite, synthetic periclase and synthetic corundum polycrystals are used as starting materials. We produce enstatite rims at forsterite-quartz contacts, enstatite-forsterite double rims at periclase-quartz contacts and spinel rims at periclase-corundum contacts. We find that rim growth under the “dry” conditions of our experiments is sluggish compared to what has been found previously in nominally “dry” piston cylinder experiments. We further observe that the nature of starting material, synthetic or natural, has a major influence on rim growth rates, where natural samples are more reactive than synthetic ones. At a given temperature the effect of stress variation is larger than what is anticipated from the modification of the thermodynamic driving force for reaction due to the storage of elastic strain energy in the reactant phases. We speculate that this may be due to modification of the physical properties of the polycrystals that constitute the reaction rims or by deformation under the imposed load. In our experiments rim growth is very sluggish at forsterite-quartz interfaces. Rim growth is more rapid at periclase-quartz contacts. The spinel rims that are produced at periclase-corundum interfaces show parabolic growth indicating that reaction rim growth is essentially diffusion controlled. From the analysis of time series done in the MgO-Al2O3 subsystem we derive effective diffusivities for the Al2O3 and the MgO components in a spinel polycrystal as D_{MgO} = 1.4 ± 0.2 \\cdot 10^{-15} m2/s and D_{Al_2O_3} = 3.7 ± 0.6 \\cdot 10^{-16} m2/s for T = 1350 °C and a vertical stress of 2.9 MPa.

Measuring the temperature dependent thermal diffusivity of geomaterials using high-speed differential scanning calorimetry

NASA Astrophysics Data System (ADS)

von Aulock, Felix W.; Wadsworth, Fabian B.; Vasseur, Jeremie; Lavallée, Yan

2016-04-01

Heat diffusion in the Earth's crust is critical to fundamental geological processes, such as the cooling of magma, heat dissipation during and following transient heating events (e.g. during frictional heating along faults), and to the timescales of contact metamorphosis. The complex composition and multiphase nature of geomaterials prohibits the accurate modeling of thermal diffusivities and measurements over a range of temperatures are sparse due to the specialized nature of the equipment and lack of instrument availability. We present a novel method to measure the thermal diffusivity of geomaterials such as minerals and rocks with high precision and accuracy using a commercially available differential scanning calorimeter (DSC). A DSC 404 F1 Pegasus® equipped with a Netzsch high-speed furnace was used to apply a step-heating program to corundum single crystal standards of varying thicknesses. The standards were cylindrical discs of 0.25-1 mm thickness with 5.2-6 mm diameter. Heating between each 50 °C temperature interval was conducted at a rate of 100 °C/min over the temperature range 150-1050 °C. Such large heating rates induces temperature disequilibrium in the samples used. However, isothermal segments of 2 minutes were used during which the temperature variably equilibrated with the furnace between the heating segments and thus the directly-measured heat-flow relaxed to a constant value before the next heating step was applied. A finite-difference 2D conductive heat transfer model was used in cylindrical geometry for which the measured furnace temperature was directly applied as the boundary condition on the sample-cylinder surfaces. The model temperature was averaged over the sample volume per unit time and converted to heat-flow using the well constrained thermal properties for corundum single crystals. By adjusting the thermal diffusivity in the model solution and comparing the resultant heat-flow with the measured values, we obtain a model calibration for the thermal diffusivity of corundum. Preliminary calibration tests suggest a very good correlation between the measured results compared with literature values of the thermal diffusivity of this standard material. However, more measurements on standard materials are needed to guarantee the accuracy of the presented technique for measuring the thermal diffusion of materials and apply this method to numerical models for relevant processes in geoscience.

Presolar stardust in meteorites: recent advances and scientific frontiers

NASA Astrophysics Data System (ADS)

Nittler, Larry R.

2003-04-01

Grains of stardust that formed in stellar outflows prior to the formation of the solar system survive intact as trace constituents of primitive meteorites. The presolar origin of the grains is indicated by enormous isotopic ratio variations compared to solar system materials. Identified presolar phases include diamond, silicon carbide, graphite, silicon nitride, corundum, spinel, hibonite, titanium oxide, and, most recently, silicates. Sub-grains of refractory carbides (e.g. TiC), and Fe-Ni metal have also been observed within individual presolar graphite grains. Isotopic compositions indicate that the grains formed in red giants, asymptotic giant branch (AGB) stars, supernovae and novae; thus they provide unique insights into the evolution of and nucleosynthesis within these environments. Some of the isotopic variations also reflect the chemical evolution of the galaxy and can be used to constrain corresponding models. Presolar grain microstructures provide information about physical and chemical conditions of dust formation in stellar environments; recent studies have focused on graphite grains from supernovae as well as SiC and corundum from AGB stars. The survival of presolar grains in different classes of meteorites has important implications for early solar system evolution. Recent analytical developments, including resonance ionization mass spectrometry, high spatial resolution secondary ion mass spectrometry and site-selective ion milling, should help solve many outstanding problems but are likely to also introduce new surprises.

Noncatalytic thermocouple coatings produced with chemical vapor deposition for flame temperature measurements.

PubMed

Bahlawane, N; Struckmeier, U; Kasper, T S; Osswald, P

2007-01-01

Chemical vapor deposition (CVD) and metal-organic chemical vapor deposition (MOCVD) have been employed to develop alumina thin films in order to protect thermocouples from catalytic overheating in flames and to minimize the intrusion presented to the combustion process. Alumina films obtained with a CVD process using AlCl(3) as the precursor are dense, not contaminated, and crystallize in the corundum structure, while MOCVD using Al(acetyl acetone)(3) allows the growth of corundum alumina with improved growth rates. These films, however, present a porous columnar structure and show some carbon contamination. Therefore, coated thermocouples using AlCl(3)-CVD were judged more suitable for flame temperature measurements and were tested in different fuels over a typical range of stoichiometries. Coated thermocouples exhibit satisfactory measurement reproducibility, no temporal drifts, and do not suffer from catalytic effects. Furthermore, their increased radiative heat loss (observed by infrared spectroscopy) allows temperature measurements over a wider range when compared to uncoated thermocouples. A flame with a well-known temperature profile established with laser-based techniques was used to determine the radiative heat loss correction to account for the difference between the apparent temperature measured by the coated thermocouple and the true flame temperature. The validity of the correction term was confirmed with temperature profile measurements for several flames previously studied in different laboratories with laser-based techniques.

Synthesis and characterization of SiC based composite materials for immobilizing radioactive graphite

NASA Astrophysics Data System (ADS)

Wang, Qing; Teng, Yuancheng; Wu, Lang; Zhang, Kuibao; Zhao, Xiaofeng; Hu, Zhuang

2018-06-01

In order to immobilize high-level radioactive graphite, silicon carbide based composite materials{ (1-x) SiC· x MgAl2O4 (0.1 ≤ x≤0.4) } were fabricated by solid-state reaction at 1370 °C for 2 h in vacuum. Residual graphite and precipitated corundum were observed in the as-synthesized product, which attributed to the interface reaction of element silicon and magnesium compounds. To further understand the reasons for the presence of graphite and corundum, the effects of mole ratio of Si/C, MgAl2O4 content and non-stoichiometry of MgAl2O4 on the synthesis were investigated. To immobilize graphite better, residual graphite should be eliminated. The target product was obtained when the mole ratio of Si/C was 1.3:1, MgAl2O4 content was x = 0.2, and the mole ratio of Al to Mg in non-stoichiometric MgAl2O4 was 1.7:1. In addition, the interface reaction between magnesium compounds and silicon not graphite was displayed by conducting a series of comparative experiments. The key factor for the occurrence of interface reaction is that oxygen atom is transferred from magnesium compound to SiO gas. Infrared and Raman spectrum revealed the increased disorders of graphite after being synthesized.

In vitro and in vivo evaluation of SLA titanium surfaces with further alkali or hydrogen peroxide and heat treatment.

PubMed

Zhang, E W; Wang, Y B; Shuai, K G; Gao, F; Bai, Y J; Cheng, Y; Xiong, X L; Zheng, Y F; Wei, S C

2011-04-01

The present study aimed to evaluate the bioactivity of titanium surfaces sandblasted with large-grit corundum and acid etched (SLA) plus further alkali or hydrogen peroxide and heat treatment for dental implant application. Pure titanium disks were mechanically polished as control surface (Ti-control) and then sandblasted with large-grit corundum and acid etched (SLA). Further chemical modifications were conducted using alkali and heat treatment (ASLA) and hydrogen peroxide and heat treatment (HSLA) alternatively. The surface properties were characterized by scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS), and contact angle and roughness measurements. Further evaluation of surface bioactivity was conducted by MC3T3-E1 cell attachment, proliferation, morphology, alkaline phosphatase (ALP) activity and calcium deposition on the sample surfaces. After insertion in the beagle's mandibula for a specific period, cylindrical implant samples underwent micro-CT examination and then histological examination. It was found that ASLA and HSLA surfaces significantly increased the surface wettability and MC3T3-E1 cell attachment percentage, ALP activity and the quality of calcium deposition in comparison with simple SLA and Ti-control surfaces. Animal studies showed good osseointegration of ASLA and HSLA surfaces with host bone. In conclusion, ASLA and HSLA surfaces enhanced the bioactivity of the traditional SLA surface by integrating the advantages of surface topography, composition and wettability.

The adsorption of CH3 and C6H6 on corundum-type sesquioxides: The role of van der Waals interactions

NASA Astrophysics Data System (ADS)

Dabaghmanesh, Samira; Partoens, Bart; Neyts, Erik

Van der Waals (vdW) interactions play an important role in the adsorption of atoms and molecules on the surface of solids. This role becomes more significant whenever the interaction between the adsorbate and surface is physisorption. Thanks to recent developments in density functional theory (DFT), we are now able to employ different vdW methods that helps us to account for the long-range vdW forces. However, the choice of the most efficient vdW functional for different materials is still an open question. In our study, we examine different vdW approaches to compute bulk and molecular adsorption properties of M2O3 oxides (M: Cr, Fe, and Al) as well-known examples of the corundum family. For the bulk properties, we compare our results for the heat of formation, cohesive energy, lattice parameters and bond distances as obtained using the different vdW functionals and available experimental data. Next we compute the adsorption energies of the benzene molecule (as an example of physisorption) and CH3 (as an example of chemisorption) on top of the (0001) M-terminated and MO-terminated surfaces. Calculating the vdW contributions into the adsorption energies, we find that the vdW functionals play important role not just in the weak adsorptions but even in strong adsorption.

A first principles investigation of electron transfer between Fe(II) and U(VI) on insulating Al- vs. semiconducting Fe-oxide surfaces via the proximity effect

NASA Astrophysics Data System (ADS)

Taylor, S. D.; Marcano, M. C.; Becker, U.

2017-01-01

This study investigates how the intrinsic chemical and electronic properties of mineral surfaces and their associated electron transfer (ET) pathways influence the reduction of U(VI) by surface-associated Fe(II). Density functional theory (DFT), including the Hubbard U correction to the exchange-correlation functional, was used to investigate sorption/redox reactions and ET mechanisms between Fe(II) and U(VI) coadsorbed on isostructural, periodic (0 0 1) surfaces of the insulator corundum (α-Al2O3) vs. the semiconductor hematite (α-Fe2O3). Furthermore, the coadsorbed Fe(II) and U(VI) ions are spatially separated from one another on the surfaces (⩾5.9 Å) to observe whether electronic-coupling through the semiconducting hematite surface facilitates ET between the adsorbates, a phenomenon known as the proximity effect. The calculations show that the different chemical and electronic properties between the isostructural corundum and hematite (0 0 1) surfaces lead to considerably different ET mechanisms between Fe(II) and U(VI). ET on the insulating corundum (0 0 1) surface is limited by the adsorbates' structural configuration. When Fe(II) and U(VI) are spatially separated and do not directly interact with one another (e.g. via an inner-sphere complex), U(VI) reduction by Fe(II) cannot occur as there is no physical pathway enabling ET between the adsorbates. In contrast to the insulating corundum (0 0 1) surface, the hematite (0 0 1) surface can potentially participate in ET reactions due to the high number of electron acceptor sites from the Fe d-states near the Fermi level at the hematite surface. The adsorption of Fe(II) also introduces d-states near the Fermi level as well as shifts unoccupied d-states of the Fe cations at the hematite surface to lower energies, making the surface more conductive. In turn, electronic coupling through the surface can link the spatially separated adsorbates to one another and provide distinct ET pathways for an electron from Fe(II) to travel through the hematite surface and reach U(VI). The progression and extent of ET occurring on the semiconducting hematite (0 0 1) surface via the proximity effect depends on the electronic properties of the surface. ET between the spatially separated U(VI) and Fe(II) occurs most readily when orbitals between the Fe and U adsorbates overlap with those of neighboring O and Fe ions at the hematite surface, as shown by calculations without the Hubbard U correction. Analyses of the spins densities confirm that the U and Fe adsorbates were reduced and oxidized, respectively, (acquiring 0.33 μB and 0.11-0.20 μB, respectively), while Fe cations at the hematite surface were reduced (losing ⩽0.6 μB). If electrons are highly localized, the amount of orbital mixing and electronic coupling through the hematite surface decreases and in turn leads to a lower degree of spin transfer, as predicted by calculations with the Hubbard U correction. Thus, the proximity effect is a potential mechanism on semiconducting surfaces facilitating surface-mediated redox reactions, although its significance varies depending on the electronic properties and subsequent charge-carrying ability of the surface. These results provide insight into ET pathways and mechanisms on insulating Al- and semiconducting Fe oxide surfaces influencing the reduction U(VI) by Fe(II) that may subsequently limit uranium's transport in the subsurface.

Vanadium-rich ruby and sapphire within Mogok Gemfield, Myanmar: implications for gem color and genesis

NASA Astrophysics Data System (ADS)

Zaw, Khin; Sutherland, Lin; Yui, Tzen-Fu; Meffre, Sebastien; Thu, Kyaw

2015-01-01

Rubies and sapphires are of both scientific and commercial interest. These gemstones are corundum colored by transition elements within the alumina crystal lattice: Cr3+ yields red in ruby and Fe2+, Fe3+, and Ti4+ ionic interactions color sapphires. A minor ion, V3+ induces slate to purple colors and color change in some sapphires, but its role in coloring rubies remains enigmatic. Trace element and oxygen isotope composition provide genetic signatures for natural corundum and assist geographic typing. Here, we show that V can dominate chromophore contents in Mogok ruby suites. This raises implications for their color quality, enhancement treatments, geographic origin, exploration and exploitation and their comparison with rubies elsewhere. Precise LA-ICP-MS analysis of ruby and sapphire from Mogok placer and in situ deposits reveal that V can exceed 5,000 ppm, giving V/Cr, V/Fe and V/Ti ratios up to 26, 78, and 97 respectively. Such values significantly exceed those found elsewhere suggesting a localized geological control on V-rich ruby distribution. Our results demonstrate that detailed geochemical studies of ruby suites reveal that V is a potential ruby tracer, encourage comparisons of V/Cr-variation between ruby suites and widen the scope for geographic typing and genesis of ruby. This will allow more precise comparison of Asian and other ruby fields and assist confirmation of Mogok sources for rubies in historical and contemporary gems and jewelry.

Kinetic control in the synthesis of metastable polymorphs: Bixbyite-to-Rh{sub 2}O{sub 3}(II)-to-corundum transition in In{sub 2}O{sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bekheet, Maged F., E-mail: maged.bekheet@ceramics.tu-berlin.de; Fachgebiet Keramische Werkstoffe, Institut für Werkstoffwissenschaften und -technologien, Technische Universität Berlin, Hardenbergstraße 40, 10623 Berlin; Schwarz, Marcus R.

2015-09-15

An example for kinetic control of a solid-state phase transformation, in which the system evolves via the path with the lowest activation barrier rather than ending in the thermodynamically most favorable state, has been demonstrated. As a case study, the phase transitions of indium sesquioxide (In{sub 2}O{sub 3}) have been guided by theoretical calculations and followed in situ under high-pressure high-temperature conditions in multi-anvil assemblies. The corundum-type rh-In{sub 2}O{sub 3} has been synthesized from stable bixbyite-type c-In{sub 2}O{sub 3} in two steps: first generating orthorhombic Rh{sub 2}O{sub 3}-II-type o′-In{sub 2}O{sub 3} which is thermodynamically stable at 8.5 GPa/850 °C and,more » thereafter, exploiting the preferred kinetics in the subsequent transformation to the rh-In{sub 2}O{sub 3} during decompression. This synthesis strategy of rh-In{sub 2}O{sub 3} was confirmed ex situ in a toroid-type high-pressure apparatus at 8 GPa and 1100 °C. The pressure–temperature phase diagrams have been constructed and the stability fields of In{sub 2}O{sub 3} polymorphs and the crystallographic relationship between them have been discussed. - Graphical abstract: In situ energy-dispersive XRD patterns in multi-anvil assemblies show the sequence of phase transition c-In{sub 2}O{sub 3}→o′-In{sub 2}O{sub 3}→rh-In{sub 2}O{sub 3} under particular pressure and temperature conditions. The tick marks refer to the calculated Bragg positions of bixbyite-type (c-In{sub 2}O{sub 3}), Rh{sub 2}O{sub 3}-II-type (o–-In2O{sub 3}) and corundum-type (rh-In{sub 2}O{sub 3}). - Highlights: • The solid-state synthesis methods can be employed for obtaining metastable phases. • The phase transition of In{sub 2}O{sub 3} was guided by DFT calculations. • The phase transition of In{sub 2}O{sub 3} was followed in situ under HP–HT conditions. • Orthorhombic o′-In{sub 2}O{sub 3} polymorph was synthesized from c-In{sub 2}O{sub 3} at 8.5 GPa/850 °C. • Metastable rh-In{sub 2}O{sub 3} was obtained from o′-In{sub 2}O{sub 3} at 5.5 GPa during decompression.« less

The stability of hibonite, melilite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions from carbonaceous chondrites

NASA Technical Reports Server (NTRS)

Beckett, J. R.; Stolper, E.

1994-01-01

Phase fields in which hibonite and silicate melt coexist with spinel CaAl4O7, gehlenitic melilite, anorthite or corundum at 1 bar in the system CaO-MgO-Al2O3-SiO2-TiO2 were determined. The hibonites contain up to 1.7 wt% SiO2. For TiO2, the experimentally determined partition coefficients between hibonite and coexisting melt D(sub i)(sup Hib/L), vary from 0.8 to 2.1 and generally decrease with increasing TiO2 in the liquid. Based on Ti partitioning between hibonite and melt, bulk inclusion compositions and hibonite-saturated liquidus phase diagrams, the hibonite in hibonite-poor fluffy Type A inclusions from Allende and at least some hibonite from hibonite-rich inclusions is relict, although much of the hibonite from hibonite-glass spherules probably crystallized metasably from a melt. Bulk compositions for all of these CAIs are consistent with an origin as melite + hibonite + spinel + perovskite phase assembalges that were partially altered and in some cases partially or completely melted. The duration of the melting event was sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. Simple thermochemical models developed for meteoritic melilite and hibonite solid solutions were used to obtain equilibration temperatures of hibonite-bearing phase assemblages with vapor. Referenced to 10(exp -3) atm, hibonite + corundum + vapor equilibrated at approximately 1260 C and hibonite + spinel +/- melilite + vapor at 1215 +/- 10 C. If these temperatures reflect condensation in a cooling gas of solar composition, then hibonite +/- corundum condensed first, followed by spinel and then melilite. The position of perovskite within this sequence is uncertain, but it probably began to condense before spinel. This sequence of phase appearances and relative temperatures is generally consistent with observed textures but differs from expectations based on classical condensation calculations in that equilibration temperatures are generally lower than predicted and melilite initially condenses with or even after spinel. Simple thermochemical modes for the substitution of trace elements into the Ca site of meteoritic hibonites suggest that virtually all Eu is divalent in early condensate hibonites but that Eu(2+)/Eu(#+) decreases by a factor of 20 or more during the course of condensation primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phase condense. The relative sizes of Eu and Yb anomalies in meteoritic hibonites and inclusions may be partly due to this effect.

Structural changes during milling of aluminum oxide powders

NASA Technical Reports Server (NTRS)

Ziepler, G.

1984-01-01

The mechanical activation of four fused corundum powders and a calcined Al2O3 powder was studied. The milled powders were characterized by their structural properties, crystallite size, and lattice distortions. Structural changes during milling, detected by X-ray line broadening analysis, gave information about the enhanced activity of the powders caused by the lattice distortions and by the decreasing crystallite size during milling. The structural changes during milling, under the same milling conditions, can be quite different for the same ceramic material, but with different characteristics in the as received state.

Petrographic studies of refractory inclusions from the Murchison meteorite

NASA Technical Reports Server (NTRS)

Macpherson, G. J.; Grossman, L.; Hashimoto, A.; Bar-Matthews, M.; Tanaka, T.

1984-01-01

Textural and mineral-chemical data on freeze-thaw disaggregated refractory inclusions from the Murchison meteorite are reported. The data were obtained with neutron activation analysis, SEM, and spectroscopy, the study revealed corundum-bearing inclusions, spinel-hibonite aggregates and spherules, and spinel-pyroxene and elivine-pyroxene inclusions. One of the three spinel-, pyroxene-, forsterite-rich inclusions had an amoeba-shaped spinel-pyroxene core, implying vapor-to-solid condensation and therefore crystallization from a melt. It is concluded that the meteorite formation encompassed diverse nebular materials, and that further studies of the meteorite will enhance the data base on the planetary nebular processes.

A new method for the estimation of high temperature radiant heat emittance by means of aero-acoustic levitation

NASA Astrophysics Data System (ADS)

Greffrath, Fabian; Prieler, Robert; Telle, Rainer

2014-11-01

A new method for the experimental estimation of radiant heat emittance at high temperatures has been developed which involves aero-acoustic levitation of samples, laser heating and contactless temperature measurement. Radiant heat emittance values are determined from the time dependent development of the sample temperature which requires analysis of both the radiant and convective heat transfer towards the surroundings by means of fluid dynamics calculations. First results for the emittance of a corundum sample obtained with this method are presented in this article and found in good agreement with literature values.

Confinement-driven electronic and topological phases in corundum-derived 3 d -oxide honeycomb lattices

NASA Astrophysics Data System (ADS)

Köksal, Okan; Baidya, Santu; Pentcheva, Rossitza

2018-01-01

Using density functional theory calculations including an on-site Coulomb term, we explore electronic and possibly topologically nontrivial phases in 3 d transition-metal oxide honeycomb layers confined in the corundum structure (α -Al2O3 ) along the [0001] direction. In most cases the ground state is a trivial antiferromagnetic Mott insulator, often with distinct orbital or spin states compared to the bulk phases. With imposed symmetry of the two sublattices the ferromagnetic phases of (X2O3)1/(Al2O3)5(0001) with X = Ti, Mn, Co, and Ni exhibit a characteristic set of four bands, two that are relatively flat and two with a Dirac crossing at K , associated with the single-electron occupation of eg' (Ti) or eg (Mn, Co, Ni) orbitals. Our results indicate that the Dirac point can be tuned to the Fermi level using strain. Applying spin-orbit coupling (SOC) leads to a substantial anomalous Hall conductivity with values up to 0.94 e2/h . Moreover, at aAl2O3=4.81 Å we identify a particularly strong effect of SOC with an out-of-plane easy axis for (Ti2O3 )1/(Al2O3 )5(0001) which stabilizes the system dynamically. Due to the unusually high orbital moment of -0.88 μB that nearly compensates the spin moment of 1.01 μB , this system emerges as a candidate for the realization of the topological Haldane model of spinless fermions. Parallels to the perovskite analogs (La X O3 )2/(LaAlO3)4(111) are discussed.

Enthalpy of formation of Fe 3Al 2Si 3O 12 (almandine) by high temperature alkali borate solution calorimetry

NASA Astrophysics Data System (ADS)

Chatillon-Colinet, C.; Kleppa, O. J.; Newton, R. C.; Perkins, D., III

1983-03-01

A high-temperature solution calorimetric method suitable for thermochemical studies of anhydrous minerals containing Fe 2+ ions has been developed. The method is based on an oxide melt solvent with 52 wt% LiBO 2 and 48 wt% NaBO 2 maintained at a temperature of 750°C. In a first application of this method the enthalpies of solution of synthetic almandine, fayalite, a mixture of fayalite plus quartz on FeSiO 3 composition, and natural quartz were measured. For the reaction: ? the enthalpy change at 1023 K is -3.82 ± 0.87 kcal, based on fayalite, quartz, corundum and almandine, and -5.96 ± 0.90 kcal based on the fayalite plus quartz mixture, corundum, and almandine. These values lead to standard molar enthalpies of formation of almandine from the oxides at 1023 K of -14.10 ± 1.22 kcal and -16.24 ± 1.74 kcal, respectively. The measured enthalpy of formation of almandine is less negative by several kilocalories than values derived from analysis of the phase equilibrium work of HSU (1968), but in closer agreement with the phase equilibrium study of O'NEILL and WOOD (1979) and similar to the phase equilibrium deduction of FROESE (1973). The agreement of the present almandine enthalpy of formation with O'NEILL and WOOD (1979) and FROESE (1973) suggests that almandine entropies at 298 K to be obtained from their studies, in the range 79-81 cal/K, are more nearly correct than the several estimates based on oxide sum and volume-entropy systematics, most of which are much lower.

Development of refractories and related products for steel melting, finishing, and casting

NASA Astrophysics Data System (ADS)

Smirnov, A. N.

2013-06-01

The transformation of the consumption of refractories for the production, out-of-furnace treatment, and casting of steel is considered. The main trends in developing the refractory market are shown to be a significant decrease in the specific consumption of refractories per 1 t liquid steel and the predominant application of refractories based on magnesia raw materials and fused corundum for the working layers of melting units, ladles, and tundishes. The main trend in decreasing the specific costs of refractories is the development of refractories based on alternative sources of raw materials, which are cheaper and more available for refractory manufacturers.

Chemistry and mineralogy of garnet pyroxenites from Sabah, Malaysia

USGS Publications Warehouse

Morgan, B.A.

1974-01-01

Garnet pyroxenites and corundum-garnet amphibolites from the Dent peninsula of eastern Sabah (North Borneo) occur as blocks in a slump breccia deposit of late Miocene age. The earliest formed minerals include pyrope-almandine garnet, tschermakitic augite, pargasite, and rutile. Cumulate textures are present in two of the six specimens studied. The earlier fabric has been extensively brecciated and partly replaced by plagioclase, ilmenite, and a fibrous amphibole. The bulk composition and mineralogy of these rocks are similar to those of garnet pyroxenite lenses within ultramafic rocks. Estimated temperature and pressure for the origin of the Sabah garnet pyroxenites is 850??150?? C and 19??4 kbar. ?? 1974 Springer-Verlag.

Increasing the reliability and quality of important cast products made of chemically active metals and alloys

NASA Astrophysics Data System (ADS)

Varfolomeev, M. S.; Moiseev, V. S.; Shcherbakova, G. I.

2017-01-01

A technology is developed to produce highly thermoresistant ceramic monoxide corundum molds using investment casting and an aluminum-organic binder. This technology is a promising trend in creating ceramic molds for precision complex-shape casting of important ingots made of high-alloy steels, high-temperature and titanium alloys, and refractory metals. The use of the casting molds that have a high thermal and chemical resistance to chemically active metals and alloys under high-temperature casting minimizes the physicochemical interaction and substantially decreases the depth of the hard-to-remove metal oxide layer on important products, which increases their service properties.

Bauxite to eclogite: Evidence for late Permian supracontinental subduction at the Red River shear zone, northern Vietnam

NASA Astrophysics Data System (ADS)

Nakano, Nobuhiko; Osanai, Yasuhito; Nam, Nguyen Van; Tri, Tran Van

2018-03-01

We have investigated the geological processes recorded in aluminous granulites from the Red River shear zone in northern Vietnam using mineral and whole-rock chemistries, fluid inclusions, metamorphic pressure-temperature paths, and geochronology. The granulites are extremely rich in Al2O3 (36.3-50.9 wt%), TiO2, and total Fe2O3, and poor in SiO2 (7.9-24.1 wt%), MgO, CaO, Na2O, and K2O. The granulites are enriched in high-field-strength elements and rare earth elements, and severely depleted in large-ion lithophile elements. These features strongly suggest the protolith was lateritic bauxite. Moreover, the other elemental concentrations and the Zr/Ti ratios point to basaltic rock as the precursor of the bauxite. Some of the aluminous granulites contain high-pressure mineral inclusions of kyanite, staurolite, siderite, and rutile, none of which are observed in the matrix. Abundant primary carbonic fluid inclusions are observed in garnet, corundum, and staurolite, but are rare in quartz and zircon. The average densities of fluid inclusions in garnet, corundum, staurolite, quartz, and zircon are 1.00 ± 0.06, 1.07 ± 0.04, 1.09 ± 0.03, 0.29 ± 0.07, and 1.15 ± 0.05 g/cm3, respectively. The mineral features not only in the matrix and but also in garnet from all rock types, isochemical phase diagrams obtained for each bulk rock composition, and Zr-in-rutile thermometry indicate an early eclogite-facies metamorphism ( 2.5 GPa at 650 °C) and a subsequent nearly isothermal decompression. Zircons yield a wide range of U-Pb ages from 265 to 36 Ma, whereas the dark luminescent cores of the zircons, which contain high-density CO2 inclusions, yield a concordia age of 257 ± 8 Ma. These observations suggest that the dark luminescent zircon cores were formed at the same time as the garnet, corundum, and staurolite that contain high-density CO2 fluid inclusions. Based on the carbonic fluid inclusion isochore and the densities as well as calculated phase diagram, the concordia age can be regarded as recording a prograde stage of metamorphism under conditions lower than 600 °C and 0.7 GPa. Our new data provide the following geological and tectonic constraints: 1) the eruption of basalt occurred before the Permian, possibly related to subduction of the Paleo-Tethys Plate beneath the Indochina craton near the paleo-equator in the Devonian-Carboniferous; 2) strong weathering transformed the basalt to bauxite before the late Permian; 3) the uppermost continental crust, including the bauxites, was subducted in the late Permian due to the collision of the Indochina and South China cratons, leading to eclogite-facies metamorphism; 4) the rocks were then exhumed; and 5) shearing-related thermal events took place until the Paleogene.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaspar, Tiffany C.; Sushko, Peter V.; Bowden, Mark E.

Epitaxial thin films of Cr2-xTixO3 were deposited by oxygen-plasma-assisted molecular beam epitaxy (OPA-MBE) for 0.04 ≤ x ≤ 0.26. Ti speciation is verified by both x-ray photoelectron spectroscopy (XPS) and Ti K-edge x-ray absorption near-edge spectroscopy (XANES) to be Ti4+. Substitution of Ti for Cr in the corundum lattice is confirmed by modeling of the Ti K-edge extended x-ray absorption fine structure (EXAFS). Room temperature electrical transport measurements confirm the highly insulating nature of Ti-doped Cr2O3, despite the presence of aliovalent Ti4+. The resistivity of highly pure, undoped Cr2O3 was measured to be three orders of magnitude higher than formore » Ti-doped Cr2O3. Although the formation of Cr vacancies in Ti-doped Cr2O3 is found by density functional theory (DFT) calculations to be the energetically preferable defect compensation mechanism to maintain charge neutrality, an analysis of the XPS and EXAFS data reveal the presence of both Cr vacancies and oxygen interstitials at intermediate and high Ti concentrations, with a weak trend towards Cr vacancies as the Ti concentration increases. At low Ti concentrations, a strong dependence of the XPS Ti 2p core level peak width on concentration is observed. This dependence is attributed to the presence of widely spaced Ti dopants, which renders compensation of two or three Ti by a single oxygen interstitial or Cr vacancy, respectively, less probable. Instead, defect clusters of unknown type occur, although they may involve Cr vacancies. The defect compensation model developed here provides insight into previous, conflicting reports of n-type versus p-type conductivity in Ti-doped Cr2O3 at high temperature, and will inform future studies to exploit the wide variety of electronic and magnetic properties of corundum-structure oxides.« less

Lunar and Planetary Science XXXVI, Part 14

NASA Technical Reports Server (NTRS)

2005-01-01

Contents include the following: Destruction of Presolar Silicates by Aqueous Alteration Observed in Murchison CM2 Chondrite. Generation of Chondrule Forming Shock Waves in Solar Nebula by X-Ray Flares. TEM and NanoSIMS Study of Hydrated/Anhydrous Phase Mixed IDPs: Cometary or Asteroidal Origin? Inflight Calibration of Asteroid Multiband Imaging Camera Onboard Hayabusa: Preliminary Results. Corundum and Corundum-Hibonite Grains Discovered by Cathodoluminescence in the Matrix of Acfer 094 Meteorite. Spatial Extent of a Deep Moonquake Nest A Preliminary Report of Reexamination. Modal Abundances of Carbon in Ureilites: Implications for the Petrogenesis of Ureilites. Trapped Noble Gas Components and Exposure History of the Enstatite Chondrite ALH84206. Deep-seated Crustal Material in Dhofar Lunar Meteorites: Evidence from Pyroxene Chemistry. Numerical Investigations of Kuiper Belt Binaries. Dust Devils on Mars: Effects of Surface Roughness on Particle Threshold. Hecates Tholus, Mars: Nighttime Aeolian Activity Suggested by Thermal Images and Mesoscale Atmospheric Model Simulations. Are the Apollo 14 High-Al Basalts Really Impact Melts? Garnet in the Lunar Mantle: Further Evidence from Volcanic Glass Beads. The Earth/Mars Dichotomy in Mg/Si and Al/Si Ratios: Is It Real? Dissecting the Polar Asymmetry in the Non-Condensable Gas Enhancement on Mars: A Numerical Modeling Study. Cassini VIMS Preliminary Exploration of Titan s Surface Hemispheric Albedo Dichotomy. An Improved Instrument for Investigating Planetary Regolith Microstructure. Isotopic Composition of Oxygen in Lunar Zircons Preliminary Design of Visualization Tool for Hayabusa Operation. Size and Shape Distributions of Chondrules and Metal Grains Revealed by X-Ray Computed Tomography Data. Properties of Permanently Shadowed Regolith. Landslides in Interior Layered Deposits, Valles Marineris, Mars: Effects of Water and Ground Shaking on Slope Stability. Mars: Recent and Episodic Volcanic, Hydrothermal, and Glacial Activity Revealed by Mars Express High Resolution Stereo Camera (HRSC). The Cratering Record of the Saturnian Satellites Phoebe, Tethys, Dione and Iapetus in Comparison: First Results from Analysis of the Cassini ISS Imaging Data. Joint Crossover Solutions of Altimetry and Image Data on 433 Eros. The Martian Soil as a Geochemical Sink for.

High pressure system for 3-D study of elastic anisotropy

NASA Astrophysics Data System (ADS)

Lokajicek, T.; Pros, Z.; Klima, K.

2003-04-01

New high pressure system was designed for the study of elastic anisotropy of condensed matter under high confining pressure up to 700 MPa. Simultaneously could be measured dynamic and static parameters: a) dynamic parameters by ultrasonic sounding, b) static parameters by measuring of spherical sample deformation. The measurement is carried out on spherical samples diameter 50 +/- 0.01 mm. Higher value of confining pressure was reached due to the new construction of sample positioning unit. The positioning unit is equipped with two Portecap step motors, which are located inside the vessel and make possible to rotate with the sphere and couple of piezoceramic transducers. Sample deformation is measured in the same direction as ultrasonic signal travel time. Only electric leads connects inner part of high pressure vessel with surrounding environment. Experimental set up enables: - simultaneous P-wave ultrasonic sounding, - measurement of current sample deformation at sounding points, - measurement of current value of confining pressure and - measurement of current stress media temperature. Air driven high pressure pump Haskel is used to produce high value of confining pressure up to 700 MPa. Ultrasonic signals are recorded by digital scope Agilent 54562 with sampling frequency 100 MHz. Control and measuring software was developed under Agilent VEE software environment working under MS Win 2000 operating system. Measuring set up was tested by measurement of monomineral spherical samples of quartz and corundum. Both of them have trigonal symmetry. The measurement showed that the P-wave velocity range of quartz was between 5.7-7.0 km/sec. and velocity range of corundum was between 9.7-10.9 km/sec. High pressure resistant LVDT transducers Mesing together with Intronix electronic unit were used to monitor sample deformation. Sample deformation is monitored with the accuracy of 0.1 micron. All test measurements proved the good accuracy of the whole measuring set up. This project was supported by Grant Agency of the Czech Republic No.: 205/01/1430.

Characterization of Meteorites by Focused Ion Beam Sectioning: Recent Applications to CAIs and Primitive Meteorite Matrices

NASA Technical Reports Server (NTRS)

Christoffersen, Roy; Keller, Lindsay P.; Han, Jangmi; Rahman, Zia; Berger, Eve L.

2015-01-01

Focused ion beam (FIB) sectioning has revolutionized preparation of meteorite samples for characterization by analytical transmission electron microscopy (TEM) and other techniques. Although FIB is not "non-destructive" in the purest sense, each extracted section amounts to no more than nanograms (approximately 500 cubic microns) removed intact from locations precisely controlled by SEM imaging and analysis. Physical alteration of surrounding material by ion damage, fracture or sputter contamination effects is localized to within a few micrometers around the lift-out point. This leaves adjacent material intact for coordinate geochemical analysis by SIMS, microdrill extraction/TIMS and other techniques. After lift out, FIB sections can be quantitatively analyzed by electron microprobe prior to final thinning, synchrotron x-ray techniques, and by the full range of state-of-the-art analytical field-emission scanning transmission electron microscope (FE-STEM) techniques once thinning is complete. Multiple meteorite studies supported by FIB/FE-STEM are currently underway at NASA-JSC, including coordinated analysis of refractory phase assemblages in CAIs and fine-grained matrices in carbonaceous chondrites. FIB sectioning of CAIs has uncovered epitaxial and other overgrowth relations between corundum-hibonite-spinel consistent with hibonite preceding corundum and/or spinel in non-equilibrium condensation sequences at combinations of higher gas pressures, dust-gas enrichments or significant nebular transport. For all of these cases, the ability of FIB to allow for coordination with spatially-associated isotopic data by SIMS provides immense value for constraining the formation scenarios of the particular CAI assemblage. For carbonaceous chondrites matrix material, FIB has allowed us to obtain intact continuous sections of the immediate outer surface of Murchison (CM2) after it has been experimentally ion processed to simulate solar wind space weathering. The surface amorphization and loss of OH produced by the irradiation provides important clues regarding space weathering on primitive asteroids such as the OSIRIS-Rex target 101955 Bennu.

Ruby and sapphire from Jegdalek, Afghanistan

USGS Publications Warehouse

Bowersox, G.W.; Foord, E.E.; Laurs, B.M.; Shigley, J.E.; Smith, C.P.

2000-01-01

This study provides detailed mining and gemological information on the Jegdalek deposit, in east-central Afghanistan, which is hosted by elongate beds of corundum-bearing marble. Some facet-grade ruby has been recovered, but most of the material consists of semitransparent pink sapphire of cabochon or carving quality. The most common internal features are dense concentrations of healed and nonhealed fracture planes and lamellar twin planes. Color zoning is common, and calcite, apatite, zircon, mica, iron sulfide minerals, graphite, rutile, aluminum hydroxide, and other minerals are also present in some samples. Although the reserves appear to be large, future potential will depend on the establishment of a stable government and the introduction of modern mining and exploration techniques. ?? 2000 Gemological Institute of America.

Nondestructive method for chemically machining crucibles or molds from their enclosed ingots and castings

DOEpatents

Stout, Norman D.; Newkirk, Herbert W.

1991-01-01

An inventive method is described for chemically machining rhenium, rhenium and tungsten alloy, and group 5b and 6b crucibles or molds from included ingots and castings comprised of oxide crystals including YAG and YAG based crystals, garnets, corundum crystals, and ceramic oxides. A mixture of potassium hydroxide and 15 to 90 weight percent of potassium nitrate is prepared and maintained at a temperature above melting and below the lower of 500 degrees centigrade or the temperature of decomposition of the mixture. The enveloping metal container together with its included oxide crystal object is rotated within the heated KOH-KNO.sub.3 mixture, until the container is safely chemically machined away from the included oxide crystal object.

Surface Roughness Investigation of Ultrafine-Grained Aluminum Alloy Subjected to High-Speed Erosion

NASA Astrophysics Data System (ADS)

Kazarinov, N. A.; Evstifeev, A. D.; Petrov, Y. V.; Atroshenko, S. A.; Lashkov, V. A.; Valiev, R. Z.; Bondarenko, A. S.

2016-09-01

This study is the first attempt to investigate the influence of severe plastic deformation (SPD) treatment on material surface behavior under intensive erosive conditions. Samples of aluminum alloy 1235 (99.3 Al) before and after high-pressure torsion (HPT) were subjected to intensive erosion by corundum particles accelerated via air flow in a small-scale wind tunnel. Velocity of particles varied from 40 to 200 m/s, while particle average diameter was around 100 μm. Surface roughness measurements provided possibility to compare surface properties of both materials after erosion tests. Moreover, SPD processing appeared to increase noticeably the threshold velocity of the surface damaging process. Additionally, structural analysis of the fracture surfaces of the tested samples was carried out.

Structural and electronic evolution of Cr[subscript 2]O[subscript 3] on compression to 55 GPa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dera, Przemyslaw; Lavina, Barbara; Meng, Yue

2016-08-15

Synchrotron single-crystal x-ray diffraction experiments have been performed on corundum-type Cr{sub 2}O{sub 3} up to a pressure of 55 GPa in Ne and He pressure transmitting media. Diffraction experiments were complemented by measurements of optical absorption spectra with single crystal samples up to 60 GPa. Results of the diffraction data analysis rule out the earlier reported monoclinic distortion at 15-30 GPa, but indicate evidence of two discontinuous transitions of electronic or magnetic nature, most likely associated with a change in magnetic ordering and charge transfer. The compression mechanism established from single crystal refinements indicates much smaller distortion of the Cr{supmore » 3+} coordination environment than was previously assumed.« less

Influence of Surface Pretreatment on the Corrosion Resistance of Cold-Sprayed Nickel Coatings in Acidic Chloride Solution

NASA Astrophysics Data System (ADS)

Scendo, Mieczyslaw; Zorawski, Wojciech; Staszewska-Samson, Katarzyna; Makrenek, Medard; Goral, Anna

2018-03-01

Corrosion resistance of the cold-sprayed nickel coatings deposited on the Ni surface (substrate) without and with abrasive grit-blasting treatment of the substrate was investigated. The corundum powder with different grain sizes was used. The corrosive environment contained an acidic chloride solution. The mechanism of the corrosion of nickel was suggested and discussed. Corrosion electrochemical parameters were determined by electrochemical methods. The corrosion effect of a nickel coating depends on the grain size used to prepare the substrate. The nickel coating after the medium grit-blasting treatment of the substrate was found to be the most corrosion resistant. However, the smallest resistance on the corrosion effect should be attributed to the nickel coating on the substrate after the coarse grit-blasting treatment.

Thermoelastic properties of chromium oxide Cr2O3 (eskolaite) at high pressures and temperatures

NASA Astrophysics Data System (ADS)

Dymshits, Anna M.; Dorogokupets, Peter I.; Sharygin, Igor S.; Litasov, Konstantin D.; Shatskiy, Anton; Rashchenko, Sergey V.; Ohtani, Eiji; Suzuki, Akio; Higo, Yuji

2016-06-01

A new synchrotron X-ray diffraction study of chromium oxide Cr2O3 (eskolaite) with the corundum-type structure has been carried out in a Kawai-type multi-anvil apparatus to pressure of 15 GPa and temperatures of 1873 K. Fitting the Birch-Murnaghan equation of state (EoS) with the present data up to 15 GPa yielded: bulk modulus ( K 0, T0), 206 ± 4 GPa; its pressure derivative K'0 ,T , 4.4 ± 0.8; (∂ K 0 ,T /∂ T) = ‒0.037 ± 0.006 GPa K‒1; a = 2.98 ± 0.14 × 10-5 K-1 and b = 0.47 ± 0.28 × 10‒8 K‒2, where α 0, T = a + bT is the volumetric thermal expansion coefficient. The thermal expansion of Cr2O3 was additionally measured at the high-temperature powder diffraction experiment at ambient pressure and α 0, T0 was determined to be 2.95 × 10-5 K-1. The results indicate that coefficient of the thermal expansion calculated from the EoS appeared to be high-precision because it is consistent with the data obtained at 1 atm. However, our results contradict α 0 value suggested by Rigby et al. (Brit Ceram Trans J 45:137-148, 1946) widely used in many physical and geological databases. Fitting the Mie-Grüneisen-Debye EoS with the present ambient and high-pressure data yielded the following parameters: K 0, T0 = 205 ± 3 GPa, K'0, T = 4.0, Grüneisen parameter ( γ 0) = 1.42 ± 0.80, q = 1.82 ± 0.56. The thermoelastic parameters indicate that Cr2O3 undergoes near isotropic compression at room and high temperatures up to 15 GPa. Cr2O3 is shown to be stable in this pressure range and adopts the corundum-type structure. Using obtained thermoelastic parameters, we calculated the reaction boundary of knorringite formation from enstatite and eskolaite. The Clapeyron slope (with {{d}}P/{{d}}T = - 0.014 GPa/K) was found to be consistent with experimental data.

Thermal behaviour and microanalysis of coal subbituminus

NASA Astrophysics Data System (ADS)

Heriyanti; Prendika, W.; Ashyar, R.; Sutrisno

2018-04-01

Differential scanning calorimetry (DSC) and X-ray powder diffraction (XRD) is used to study the thermal behaviour of sub-bituminous coal. The DSC experiment was performed in air atmosphere up to 125 °C at a heating rate of 25 °C min1. The DSC curve showed that the distinct transitional stages in the coal samples studied. Thermal heating temperature intervals, peak and dissociation energy of the coal samples were also determined. The XRD analysis was used to evaluate the diffraction pattern and crystal structure of the compounds in the coal sample at various temperatures (25-350 °C). The XRD analysis of various temperatures obtained compounds from the coal sample, dominated by quartz (SiO2) and corundum (Al2O3). The increase in temperature of the thermal treatment showed a better crystal formation.

Structural and electronic properties of Ga2O3-Al2O3 alloys

NASA Astrophysics Data System (ADS)

Peelaers, Hartwin; Varley, Joel B.; Speck, James S.; Van de Walle, Chris G.

2018-06-01

Ga2O3 is emerging as an important electronic material. Alloying with Al2O3 is a viable method to achieve carrier confinement, to increase the bandgap, or to modify the lattice parameters. However, the two materials have very different ground-state crystal structures (monoclinic β-gallia for Ga2O3 and corundum for Al2O3). Here, we use hybrid density functional theory calculations to assess the alloy stabilities and electronic properties of the alloys. We find that the monoclinic phase is the preferred structure for up to 71% Al incorporation, in close agreement with experimental phase diagrams, and that the ordered monoclinic AlGaO3 alloy is exceptionally stable. We also discuss bandgap bowing, lattice constants, and band offsets that can guide future synthesis and device design efforts.

The analysis of thermal stability of detonation nanodiamond

NASA Astrophysics Data System (ADS)

Efremov, V. P.; Zakatilova, E. I.

2016-11-01

The detonation nanodiamond is a new perspective material. Ammunition recycling with use of high explosives and obtaining nanodiamond as the result of the detonation synthesis have given a new motivation for searching of their application areas. In this work nanodiamond powder has been investigated by the method of synchronous thermal analysis. Experiments have been carried out at atmospheric pressure in the environment of argon. Nanodiamond powder has been heated in the closed corundum crucible at the temperature range of 30-1500 °C. The heating rates were varied from 2 K/min to 20 K/min. After the heat treatment, the samples have been studied by the x-ray diffraction and the electron microscopy. As one of the results of this work, it has been found that the detonation nanodiamond has not started the transition into graphite at the temperature below 800 °C.

A High Sensitivity Isopropanol Vapor Sensor Based on Cr₂O₃-SnO₂ Heterojunction Nanocomposites via Chemical Precipitation Route.

PubMed

Jawaher, K Rackesh; Indirajith, R; Krishnan, S; Robert, R; Pasha, S K Khadheer; Deshmukh, Kalim; Sastikumar, D; Das, S Jerome

2018-08-01

Cr2O3-SnO2 heterojunction nanocomposites were prepared via chemical precipitation method. The prepared samples were characterized by X-ray diffraction (XRD), Transmission electron microscopy (TEM), UV-Vis diffuse reflectance spectra and Field Emission Electron Microscopy (FESEM). The XRD spectrum confirms the presence of both tetragonal rutile SnO2 and rhombohedral corundum Cr2O3 structure. Further investigation into the gas sensing performances of the prepared Cr2O3-SnO2 nanocomposites exhibited an enhanced sensitivity towards VOPs such as isopropanol, acetone, ethanol and formaldehyde. Especially, isopropanol vapor sensor shows excellent sensitivity at an operating temperature of 100 °C. The highest sensitivity for Cr2O3-SnO2 heterojunction nanocomposites indicate that these materials can be a good candidate for the production of high-performance isopropanol sensors.

c -Axis Dimer and Its Electronic Breakup: The Insulator-to-Metal Transition in Ti2 O3

NASA Astrophysics Data System (ADS)

Chang, C. F.; Koethe, T. C.; Hu, Z.; Weinen, J.; Agrestini, S.; Zhao, L.; Gegner, J.; Ott, H.; Panaccione, G.; Wu, Hua; Haverkort, M. W.; Roth, H.; Komarek, A. C.; Offi, F.; Monaco, G.; Liao, Y.-F.; Tsuei, K.-D.; Lin, H.-J.; Chen, C. T.; Tanaka, A.; Tjeng, L. H.

2018-04-01

We report on our investigation of the electronic structure of Ti2 O3 using (hard) x-ray photoelectron and soft x-ray absorption spectroscopy. From the distinct satellite structures in the spectra, we have been able to establish unambiguously that the Ti-Ti c -axis dimer in the corundum crystal structure is electronically present and forms an a1 ga1 g molecular singlet in the low-temperature insulating phase. Upon heating, we observe a considerable spectral weight transfer to lower energies with orbital reconstruction. The insulator-metal transition may be viewed as a transition from a solid of isolated Ti-Ti molecules into a solid of electronically partially broken dimers, where the Ti ions acquire additional hopping in the a -b plane via the egπ channel, the opening of which requires consideration of the multiplet structure of the on-site Coulomb interaction.

Effect of particle size and particle size distribution on physical characteristics, morphology and crystal structure of explosively compacted high-T(sub c) superconductors

NASA Technical Reports Server (NTRS)

Kotsis, I.; Enisz, M.; Oravetz, D.; Szalay, A.

1995-01-01

A superconductor, of composition Y(Ba,K,Na)2Cu3O(x)/F(y) and a composite of composition Y(Ba,K,Na)2Cu3O(x)/F(y) + Ag, with changing K, Na and F content but a constant silver content (Ag = 10 mass%) was prepared using a single heat treatment. the resulting material was ground in a corundum lined mill, separated to particle size fractions of 0-40 micron, 0-63 micron and 63-900 micron and explosively compacted, using an explosive pressure of 10(exp 4) MPa and a subsequent heat treatment. Best results were obtained with the 63-900 micron fraction of composition Y(Ba(1.95) K(0.01)Cu3O(x)F(0),(05)/Ag: porosity less than 0.01 cu cm/g and current density 2800 A/sq cm at 77K.

Concept of a utility scale dispatch able solar thermal electricity plant with an indirect particle receiver in a single tower layout

NASA Astrophysics Data System (ADS)

Schwaiger, Karl; Haider, Markus; Haemmerle, Martin; Steiner, Peter; Obermaier, Michael-Dario

2016-05-01

Flexible dispatch able solar thermal electricity plants applying state of the art power cycles have the potential of playing a vital role in modern electricity systems and even participating in the ancillary market. By replacing molten salt via particles, operation temperatures can be increased and plant efficiencies of over 45 % can be reached. In this work the concept for a utility scale plant using corundum as storage/heat transfer material is thermodynamically modeled and its key performance data are cited. A novel indirect fluidized bed particle receiver concept is presented, profiting from a near black body behavior being able to heat up large particle flows by realizing temperature cycles over 500°C. Specialized fluidized bed steam-generators are applied with negligible auxiliary power demand. The performance of the key components is discussed and a rough sketch of the plant is provided.

Tribology Study of High-Technological Composite Coatings Applied Using High Velocity Oxy-Fuel

NASA Astrophysics Data System (ADS)

Kandeva, M.; Grozdanova, T.; Karastoyanov, D.; Ivanov, Pl; Kalichin, Zh

2018-01-01

In the work are studied the differential parameters of wear and wear resistance of high-tech composite coatings of powder superalloys with nickel matrix, WC-12Co and mixed compositions. Coatings were created and applied to a substrate of steel with a different flame velocity - 700 m/s and 1000 m/s without preheating the substrate and with preheating the substrate to 650° C. The wear is carried out with a "thumb-disk" tribotester under dry surface friction with fixed black corundum abrasive particles. Comparative results were obtained for the microstructure and texture of the pre- and post- friction coating, the porosity, roughness, hardness, the dependence of mass wear, the speed and wear intensity and the wear resistance of the coatings on the number of friction cycles. Influence of the flame rate and substrate temperature on wear resistance and differential wear parameters has been determined.

Relationships Between Smelter Grade Alumina Characteristics and Strength Determined by Nanoindentation and Ultrasound-Mediated Particle Breakage

NASA Astrophysics Data System (ADS)

Wijayaratne, Hasini; McIntosh, Grant; Hyland, Margaret; Perander, Linus; Metson, James

2017-06-01

The mechanical strength of smelter grade alumina (SGA) is of considerable practical significance for the aluminum reduction process. Attrition of alumina during transportation and handling generates an increased level of fines. This results in generation of dust, poor flow properties, and silo segregation that interfere with alumina feeding systems. These lead to process instabilities which in turn result in current efficiency losses that are costly. Here we are concerned with developing a fundamental understanding of SGA strength in terms of its microstructure. Nanoindentation and ultrasound-mediated particle breakage tests have been conducted to study the strength. Strength of SGA samples both industry calcined and laboratory prepared, decrease with increasing α-alumina (corundum) content contrary to expectation. The reducing strength of alumina with increasing degree of calcination is attributed to the development of a macroporous and abrasion-prone microstructure resulting from the `pseudomorphic' transformation of precursor gibbsite during the calcination process.

Design of high strength polymer metal interfaces by laser microstructured surfaces

NASA Astrophysics Data System (ADS)

Steinert, P.; Dittes, A.; Schimmelpfennig, R.; Scharf, I.; Lampke, T.; Schubert, A.

2018-06-01

In the areas of automotive, aeronautics and civil structures, lightweight construction is a current and a future need. Thus, multi material design has rapidly grown in importance, especially hybrid materials based on fiber reinforced plastics and aluminum offer great potential. Therefore, mechanical interlocking is a convenient way of designing the interface. Laser structuring is already used to generate a variety of surface topographies leading to high bond strengths. This paper investigates different laser structures aiming on highest joint strengths for aluminum and glass fiber reinforced polyamide 6 interfaces. Self-organizing pin structures comprised by additional micro/nano features as well as drilled hole structures, both ranging on the micrometer range, are compared to corundum blasting as a standard method for surface conditioning. For the presented surface structures, thermal joining and ultrasonic assisted joining are regarded towards their potential for an optimum joint design.

Diamond and Unusual Minerals Discovered from the Chromitite in Polar Ural: A First Report

NASA Astrophysics Data System (ADS)

Yang, J.; Bai, W.; Fang, Q.; Meng, F.; Chen, S.; Zhang, Z.

2007-12-01

Ultrahigh pressure (UHP) minerals, such as diamond, coesite, and pseudomorphs of octahedral olivine, and as well as about 80 other mineral species have been recovered from podiform chromitites of the Luobusa ophiolite, southern Tibet, and a new mineral, Luobusaite (Fe0.82Si2), has been approved recently by CNMMN. The UHP minerals from Luobusa are controversial because they have not found in situ and because ophiolites are currently believed to form at shallow levels above oceanic spreading centers. More detailed study and experimental work are needed to understand the origin and significance of these unusual minerals and investigations of other ophiolites are needed to determine if such minerals occur elsewhere. For this purpose, we collected about 1500 kg of chromitite from two orebodies in an ultramafic body in the Polar Urals. Thus far, more than 60 different mineral species have been separated from these ores. The most exciting discovery is the common occurrence of diamond, a typical UHP mineral in the Luobusa chromitites. Diamonds from Ural chromitite are clear, colorless, well-developed crystals with octahedral morphology, generally 0.2-0.3 mm in size. Attached with the diamonds and perhaps also occurring as inclusions within them are many minerals as chromite, MnNiCrFe alloy, native Si and Ta, corundum, zircon, feldspar, garnet, moissanite, confirming their natural origin and suggesting a long residence time in the mantle. Other mineral group include: (1) native elements: Cr, W, Ni, Co, Si, Al and Ta; (2) carbides: SiC and WC; (3) alloys: Cr-Fe, Si-Al-Fe, Ni-Cu, Ag-Au, Ag-Sn, Fe-Si, Fe-P, and Ag-Zn-Sn; (4) oxides: NiCrFe, PbSn, REE, rutile and Si- bearing rutile, ilmenite, corundum, chromite, MgO, and SnO2; (5) silicates: kyanite, pseudomorphs of octahedral olivine, zircon, garnet, feldspar, and quartz,; (6) sulfides of Fe, Ni, Cu, Mo, Pb, Ab, AsFe, FeNi, CuZn, and CoFeNi; and (7) iron groups: native Fe, FeO, and Fe2O3. These minerals are very similar in composition and structure to those reported from the Luobusa chromitites. For examples, some spherules of native iron contain spherical inclusions of FeO, exactly like comparable grains in the Luobusa sample.

Anvil cell gasket design for high pressure nuclear magnetic resonance experiments beyond 30 GPa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meier, Thomas; Haase, Jürgen

2015-12-15

Nuclear magnetic resonance (NMR) experiments are reported at up to 30.5 GPa of pressure using radiofrequency (RF) micro-coils with anvil cell designs. These are the highest pressures ever reported with NMR, and are made possible through an improved gasket design based on nano-crystalline powders embedded in epoxy resin. Cubic boron-nitride (c-BN), corundum (α-Al{sub 2}O{sub 3}), or diamond based composites have been tested, also in NMR experiments. These composite gaskets lose about 1/2 of their initial height up to 30.5 GPa, allowing for larger sample quantities and preventing damages to the RF micro-coils compared to precipitation hardened CuBe gaskets. It ismore » shown that NMR shift and resolution are less affected by the composite gaskets as compared to the more magnetic CuBe. The sensitivity can be as high as at normal pressure. The new, inexpensive, and simple to engineer gaskets are thus superior for NMR experiments at high pressures.« less

Effect of melter feed foaming on heat flux to the cold cap

NASA Astrophysics Data System (ADS)

Lee, SeungMin; Hrma, Pavel; Pokorny, Richard; Klouzek, Jaroslav; VanderVeer, Bradley J.; Dixon, Derek R.; Luksic, Steven A.; Rodriguez, Carmen P.; Chun, Jaehun; Schweiger, Michael J.; Kruger, Albert A.

2017-12-01

The glass production rate, which is crucial for the nuclear waste cleanup lifecycle, is influenced by the chemical and mineralogical nature of melter feed constituents. The choice of feed materials affects both the conversion heat and the thickness of the foam layer that forms at the bottom of the cold cap and controls the heat flow from molten glass. We demonstrate this by varying the alumina source, namely, substituting boehmite or corundum for gibbsite, in a high-alumina high-level-waste melter feed. The extent of foaming was determined using the volume expansion test and the conversion heat with differential scanning calorimetry. Evolved gas analysis was used to identify gases responsible for the formation of primary and secondary foam. The foam thickness, a critical factor in the rate of melting, was estimated using known values of heat conductivities and melting rates. The result was in reasonable agreement with the foam thickness experimentally observed in quenched cold caps from the laboratory-scale melter.

The Ring Monstrance from the Loreto treasury in Prague: handheld Raman spectrometer for identification of gemstones

PubMed Central

Culka, Adam; Baštová, Markéta; Bašta, Petr; Kuntoš, Jaroslav

2016-01-01

A miniature lightweight portable Raman spectrometer and a palm-sized device allow for fast and unambiguous detection of common gemstones mounted in complex jewels. Here, complex religious artefacts and the Ring Monstrance from the Loreto treasury (Prague, Czech Republic; eighteenth century) were investigated. These discriminations are based on the very good correspondence of the wavenumbers of the strongest Raman bands of the minerals. Very short laser illumination times and efficient collection of scattered light were sufficient to obtain strong diagnostic Raman signals. The following minerals were documented: quartz and its varieties, beryl varieties (emerald), corundum varieties (sapphire), garnets (almandine, grossular), diamond as well as aragonite in pearls. Miniature Raman spectrometers can be recommended for common gemmological work as well as for mineralogical investigations of jewels and cultural heritage objects whenever the antiquities cannot be transported to a laboratory. This article is part of the themed issue ‘Raman spectroscopy in art and archaeology’. PMID:27799426

The Ring Monstrance from the Loreto treasury in Prague: handheld Raman spectrometer for identification of gemstones.

PubMed

Jehlička, Jan; Culka, Adam; Baštová, Markéta; Bašta, Petr; Kuntoš, Jaroslav

2016-12-13

A miniature lightweight portable Raman spectrometer and a palm-sized device allow for fast and unambiguous detection of common gemstones mounted in complex jewels. Here, complex religious artefacts and the Ring Monstrance from the Loreto treasury (Prague, Czech Republic; eighteenth century) were investigated. These discriminations are based on the very good correspondence of the wavenumbers of the strongest Raman bands of the minerals. Very short laser illumination times and efficient collection of scattered light were sufficient to obtain strong diagnostic Raman signals. The following minerals were documented: quartz and its varieties, beryl varieties (emerald), corundum varieties (sapphire), garnets (almandine, grossular), diamond as well as aragonite in pearls. Miniature Raman spectrometers can be recommended for common gemmological work as well as for mineralogical investigations of jewels and cultural heritage objects whenever the antiquities cannot be transported to a laboratory.This article is part of the themed issue 'Raman spectroscopy in art and archaeology'. © 2016 The Author(s).

Raman study of radiation-damaged zircon under hydrostatic compression

NASA Astrophysics Data System (ADS)

Nasdala, Lutz; Miletich, Ronald; Ruschel, Katja; Váczi, Tamás

2008-12-01

Pressure-induced changes of Raman band parameters of four natural, gem-quality zircon samples with different degrees of self-irradiation damage, and synthetic ZrSiO4 without radiation damage, have been studied under hydrostatic compression in a diamond anvil cell up to ~10 GPa. Radiation-damaged zircon shows similar up-shifts of internal SiO4 stretching modes at elevated pressures as non-damaged ZrSiO4. Only minor changes of band-widths were observed in all cases. This makes it possible to estimate the degree of radiation damage from the width of the ν3(SiO4) band of zircon inclusions in situ, almost independent from potential “fossilized pressures” or compressive strain acting on the inclusions. An application is the non-destructive analysis of gemstones such as corundum or spinel: broadened Raman bands are a reliable indicator of self-irradiation damage in zircon inclusions, whose presence allows one to exclude artificial color enhancement by high-temperature treatment of the specimen.

Improve oxidation resistance at high temperature by nanocrystalline surface layer

NASA Astrophysics Data System (ADS)

Xia, Z. X.; Zhang, C.; Huang, X. F.; Liu, W. B.; Yang, Z. G.

2015-08-01

An interesting change of scale sequence occurred during oxidation of nanocrystalline surface layer by means of a surface mechanical attrition treatment. The three-layer oxide structure from the surface towards the matrix is Fe3O4, spinel FeCr2O4 and corundum (Fe,Cr)2O3, which is different from the typical two-layer scale consisted of an Fe3O4 outer layer and an FeCr2O4 inner layer in conventional P91 steel. The diffusivity of Cr, Fe and O is enhanced concurrently in the nanocrystalline surface layer, which causes the fast oxidation in the initial oxidation stage. The formation of (Fe,Cr)2O3 inner layer would inhabit fast diffusion of alloy elements in the nanocrystalline surface layer of P91 steel in the later oxidation stage, and it causes a decrease in the parabolic oxidation rate compared with conventional specimens. This study provides a novel approach to improve the oxidation resistance of heat resistant steel without changing its Cr content.

Controls on alluvial fans morphology

NASA Astrophysics Data System (ADS)

Delorme, P.; Devauchelle, O.; Lajeunesse, E.; Barrier, L.; Métivier, F.

2017-12-01

Using laboratory experiments, we investigate the influence of water and sediment discharges on the morphology of an alluvial fan. In our flume, a single-thread laminar river deposits corundum sand (0.4 mm) into a conical fan. We record the fan progradation with top-view images, and measure its shape using the deformation of a Moiré pattern. The fan remains virtually self-affine as it grows, with a nearly constant slope. We find that, when the sediment discharge is small, the longitudinal slope of the fan remains close to that of a river at the threshold for sediment transport. A higher sediment discharge causes the fan's slope to depart from the threshold value. Due to the downstream decrease of the sediment load, this slope gets shallower towards the fan's toe. This mechanism generates a slightly concave fan profile. This suggests that the proximal slope of an alluvial fan could be a proxy for the sediment flux that feeds the fan.Finally, we discuss the applicability of these results to natural systems.

Inorganic particulates in pneumoconiotic lungs of hard metal grinders.

PubMed Central

Rüttner, J R; Spycher, M A; Stolkin, I

1987-01-01

Data from the analysis of lung dust in 16 metal grinders who had been exposed to hard metals between five and 44 years is reported. The mean latent time between the first exposure and analysis in biopsy or necropsy specimens was 33.6 years. Mineralogical and elementary analysis by a variety of techniques showed small or trace amounts of hard metal in all lungs. Many specimens, however, did not contain all hard metal components, cobalt, for example, being detected in four cases only. All the lungs contained quartz and silicates and in most of the necropsy cases carborundum and corundum could also be shown. Histologically no specific pattern was found. The appearances included mixed dust nodular pneumoconiosis, diffuse interstitial lung fibrosis, and foreign body and sarcoid like granulomatous changes. In view of the mixed dust exposure of the hard metal grinders and the variable histological appearance we think that the term "mixed dust pneumoconiosis in hard metal grinders" is more appropriate than "hard metal lung" to describe this condition. PMID:3676118

Effect of melter feed foaming on heat flux to the cold cap

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, SeungMin; Hrma, Pavel; Pokorny, Richard

The glass production rate, which is crucial for the nuclear waste cleanup lifecycle, is influenced by the chemical and mineralogical nature of melter feed constituents. The choice of feed materials affects both the conversion heat and the thickness of the foam layer that forms at the bottom of the cold cap and controls the heat flow from molten glass. We demonstrate this by varying the alumina source, namely, substituting boehmite or corundum for gibbsite, in a high-alumina high-level-waste melter feed. The extent of foaming was determined using the volume expansion test and the conversion heat with differential scanning calorimetry. Evolvedmore » gas analysis was used to identify gases responsible for the formation of primary and secondary foam. The foam thickness, a critical factor in the rate of melting, was estimated using known values of heat conductivities and melting rates. The result was in reasonable agreement with the foam thickness experimentally observed in the laboratory-scale melter.« less

Liquid-solid equilibria involving spinel, ilmenite, and ferropseudobrookite in the system 'FeO'-Al2O3-TiO2 in contact with metallic iron

NASA Technical Reports Server (NTRS)

Schreifels, W. A.; Muan, A.

1975-01-01

Phase relations in the liquidus temperature region of the system 'FeO'-Al2O3-TiO2 in contact with metallic iron, at a total pressure below 1 atm, have been determined by the quenching technique. Four invariant points have been located, with phase assemblages and temperatures as follows; wuestite, ulvoespinel, nercynite and liquid, 1306 C; ulvoespinel, ilmenite, ferropseudobrookite and liquid, 1340 C; ulvoespinel, hercynite, ferropseudobrookite and liquid, 1367 C; hercynite, ferropseudobrookite, corundum and liquid, 1465 C. The data obtained confirm the presence of a miscibility gap between titanate and aluminate spinels, and provide quantitative data for the effect of Al2O3 on mutual stability relations among spinel, ilmenite, and ferropseudobrookite phases in the presence of liquid at high temperatures and strongly reducing conditions. It is shown that Al2O3 has a strong stabilizing effect on the phase assemblage ferropseudobrookite and spinel relative to ilmenite.

Facile synthesis of Co3O4 hexagonal plates by flux method

NASA Astrophysics Data System (ADS)

Han, Ji-Long; Meng, Qing-Fen; Gao, Sheng-Li

2018-01-01

Using a novel flux method, a hexagonal plate of Co3O4 was directly synthesized. In this method, CoCl2·6H2O, NaOH, and the cosolvent H3BO3 were heated to 750 °C for 2 h in a corundum crucible. The products were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and high-resolution transmission electron microscope (HRTEM). Furthermore, XRD studies indicated that the product consisted of a cubic phase of Co3O4, and the phase existed in a completely crystalline form. Then, SEM results indicated that these hexagonal plates tiered up and they had diameters in the range of 2-10 μm. According to the results of SAED and HRTEM analyses, the interlayer spacing was about 0.24 nm, which corresponds to the interlayer distance of (3 1 1) crystal plane of cubic Co3O4.

Some TEM observations of Al2O3 scales formed on NiCrAl alloys

NASA Technical Reports Server (NTRS)

Smialek, J.; Gibala, R.

1979-01-01

The microstructural development of Al2O3 scales on NiCrAl alloys has been examined by transmission electron microscopy. Voids were observed within grains in scales formed on a pure NiCrAl alloy. Both voids and oxide grains grew measurably with oxidation time at 1100 C. The size and amount of porosity decreased towards the oxide-metal growth interface. The voids resulted from an excess number of oxygen vacancies near the oxidemetal interface. Short-circuit diffusion paths were discussed in reference to current growth stress models for oxide scales. Transient oxidation of pure, Y-doped, and Zr-doped NiCrAl was also examined. Oriented alpha-(Al, Cr)2O3 and Ni(Al, Cr)2O4 scales often coexisted in layered structures on all three alloys. Close-packed oxygen planes and directions in the corundum and spinel layers were parallel. The close relationship between oxide layers provided a gradual transition from initial transient scales to steady state Al2O3 growth.

Twin defects in thick stoichiometric lithium tantalate crystals prepared by a vapor transport equilibration method

NASA Astrophysics Data System (ADS)

Yang, Jinfeng; Sun, Jun; Xu, Jingjun; Li, Qinglian; Shang, Jifang; Zhang, Ling; Liu, Shiguo; Huang, Cunxin

2016-01-01

The twins were observed and investigated in vapor transport equilibration (VTE) treated lithium tantalate crystals by burying congruent lithium tantalate crystals (CLT) in a Li-rich polycrystalline powder. Twins and their etched patterns were observed under an optical polarizing microscope, and the geometry of the twins was discussed. Twin composition planes were the { 01 1 bar 2 } planes. The cause of twinning was analyzed and verified by experiment. The results indicate that the emergence of twins is due to sintering stress, which arises from sintered Li-rich polycrystalline powders at high temperature. 3.2 mm thick stoichiometric lithium tantalate (SLT) crystals without twins were obtained by setting corundum crucibles over the top of the crystals to make crystals free from the sintering stress. In addition, cracks were observed at the intersection of twin bands, and the stress caused by the dislocation pile-up was considered to be the reason for the formation of cracks.

Dehydration of δ-AlOOH in the lower mantle

NASA Astrophysics Data System (ADS)

Piet, H.; Shim, S. H.; Tappan, J.; Leinenweber, K. D.; Greenberg, E.; Prakapenka, V. B.

2017-12-01

Hydrous phase δ-AlOOH is an important candidate for water transport and storage in the Earth's deep mantle [1]. Knowing the conditions, under which it is stable and dehydrated, is therefore important for understanding the water transportation to the deep mantle or even to the core. A few experimental studies [1, 2] have shown that δ-AlOOH may be stable in cold descending slabs while it is dehydrated into a mixture of corundum and water under normal mantle conditions, up to 25 GPa. A subsequent study [3] reported the stability of δ-AlOOH in cold descending slabs to the core-mantle boundary conditions (2300 K at 135 GPa). However, the dehydration of δ-AlOOH has not bee directly observed in the experiments conducted at pressures above 25 GPa. We have synthesized δ-AlOOH from diaspore and Al(OH)3 in multi-anvil press at ASU. The sample was mixed with Au for coupling with near IR laser beams and loaded in diamond-anvil cells. We performed the laser-heated diamond anvil cell experiments at the 13IDD beamline of the Advanced Photon Source and ASU. At APS, we measured X-ray diffraction patterns at in situ high pressure and temperature. We observed the appearance of the corundum diffraction lines at 1700-2000 K and 55-90 GPa, indicating the dehydration of δ-AlOOH to Al2O3+ H2O. We found that the transition occurs over a broad range of temperature (500 K). We also observed that the dehydration of δ-AlOOH was accompanied by sudden change in laser coupling, most likely due to the release of fluids. The property change also helps us to determine the dehydration at ASU without in situ XRD. Our new experimental results indicate that δ-AlOOH would be stable in most subducting slabs in the deep mantle. However, because the dehydration occurs very close to the temperatures expected for the lower mantle, its stability is uncertain in the normal mantle. [1] Ohtani et al. 2001, Stability field of new hydrous phase, delta-AlOOH, Geophysical Research Letters 28, 3991-3993. [2] Sano et al. 2004, In situ XRD of dehydration of AlSiO3OH and d-AlOOH, JPCS 65, 1547-1554. [3] Sano et al. 2008, Aluminous hydrous mineral d-AlOOH as a carrier of hydrogen into the core-mantle boundary, Geophysical Research Letters 35, L03303.

Interaction of Corundum, Wollastonite and Quartz With H2O-NaCl Solutions at 800 C and 10 Kbar

NASA Astrophysics Data System (ADS)

Newton, R. C.; Manning, C. E.

2005-12-01

Aqueous fluids are potentially important transport agents in subduction zones and other high-P metamorphic environments. Recent studies indicate that at high P and T, the solubilities of major rock-forming elements are strongly enhanced by the formation of metal-chloride complexes, metal-hydroxide complexes and polynuclear metal-hydroxide clusters. However, the relative abundances of these species and the energetics of their interactions in high-pressure environments remains largely unknown. We measured the solubilities of corundum (Al2O3) and wollastonite (CaSiO3) at 800 °C and 10 kbar in H2O-NaCl solutions to halite saturation (XNaCl = 0.6) . Both minerals show marked enhancement of solubility with increasing salinity. Al2O3 mol fraction rises rapidly to XNaCl = 0.1, and then declines slowly towards halite saturation. Quenched experimental fluids have neutral pH. Modeling based on ideal solution of ions and molecules leads to a simple dissolution reaction and corresponding molality (m=mol/kg H2O) expression: Al2O3(cor) + Na+ + 3H2O = NaAl(OH)4 + Al(OH)2+ and mAl2O3 = [0.0232(aNaCl)1/4(aH2O)3/2+0.00123][1+2XNaCl/(1-XNaCl)] where H2O and NaCl activities are given by aH2O = (2-XNaCl)/(2+XNaCl) and aNaCl = 4(XNaCl)2/(1 + XNaCl)2. Wollastonite solubility in NaCl solutions is accurately described by: mCaSiO3 = 0.6734XNaCl + 0.1183(XNaCl)1/2 + 0.0204. There is a roughly 50-fold enhancement of dissolved wollastonite at halite saturation. Quenched experimental fluids are strongly basic (pH=11). A consistent dissolution reaction must therefore be similar to: CaSiO3(wo) + Na+ + Cl- = CaCl+ + OH- + HNaSiO3 Quartz solubility declines monotonically from mSiO2 = 1.248 in pure H2O to 0.20 at halite saturation. Quenched fluids are neutral, indicating that quartz does not react with solvent NaCl. The only salinity control on solubility is decrease of H2O activity. The simple dissolution behaviors to be deduced from measurements on these minerals suggest that fluid-rock interaction in deep-crust/upper mantle metamorphic processes may be generally understandable in terms of quasi-ideal mixing models.

Effect of particle size and particle size distribution on physical characteristics, morphology and crystal strucutre of explosively compacted high-Tc superconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kotsis, I.; Enisz, M.; Oravetz, D.

1994-12-31

A superconductor, of composition Y(Ba,K,Na){sub 2}Cu{sub 3}O{sub x}/F{sub y} and a composite, of composition Y(Ba,K,Na){sub 2}Cu{sub 3}O{sub x}/F{sub y}+Ag, with changing K, Na and F content, but a constant silver content (Ag=10 mass per cent) was prepared using a single heat treatment. The resulting material was ground in a corundum lined mill, separated to particle size fractions of 0-40 {mu}m, 0-63 {mu}m and 63-900 {mu}m and explosively compacted, using an explosive pressure of 10{sup 4} MPa and a subsequent heat treatment. Best results were obtained with the 63-900 {mu}m fraction of composition Y(Ba{sub 1,95}K{sub 0,01})Cu{sub 3}O{sub x}F{sub 0,05}/Ag: porosity <0.01more » cm{sup 3}/g and current density 2800 A/cm{sup 2} at 77 K.« less

Spinel formation for stabilizing simulated nickel-laden sludge with aluminum-rich ceramic precursors.

PubMed

Shih, Kaimin; White, Tim; Leckie, James O

2006-08-15

The feasibility of stabilizing nickel-laden sludge from commonly available Al-rich ceramic precursors was investigated and accomplished with high nickel incorporation efficiency. To simulate the process, nickel oxide was mixed alternatively with gamma-alumina, corundum, kaolinite, and mullite and was sintered from 800 to 1480 degrees C. The nickel aluminate spinel (NiAl2O4) was confirmed as the stabilization phase for nickel and crystallized with efficiencies greater than 90% for all precursors above 1250 degrees C and 3-h sintering. The nickel-incorporation reaction pathways with these precursors were identified, and the microstructure and spinel yield were investigated as a function of sintering temperature with fixed sintering time. This study has demonstrated a promising process for forming nickel spinel to stabilize nickel-laden sludge from a wide range of inexpensive ceramic precursors, which may provide an avenue for economically blending waste metal sludges via the building industry processes to reduce the environmental hazards of toxic metals. The correlation of product textures and nickel incorporation efficiencies through selection of different precursors also provides the option of tailoring property-specific products.

The Effect of Grain Refinement on Solid Particle Erosion of Grade 5 Ti Alloy

NASA Astrophysics Data System (ADS)

Kazarinov, N. A.; Evstifeev, A. D.; Petrov, Y. V.; Atroshenko, S. A.; Valiev, R. R.

2018-04-01

In this work, the results on solid particle erosion of an ultrafine-grained Grade 5 titanium alloy, which was produced using high-pressure torsion (HPT) technique, are presented. In order to assess influence of the HPT treatment on material's behavior in erosive conditions, special experimental procedures were developed. The ultrafine-grained (UFG) alloy was tested alongside with a conventional coarse-grained (CG) Grade 5 titanium alloy in equal conditions. The experiments were conducted in a small-scale wind tunnel with corundum particles as an abrasive material. Both particle dimensions and particle velocities were varied in course of the experiments. Erosion resistance of the samples was evaluated in two ways—mass reduction measurements with subsequent gravimetric erosion rate calculations and investigation of samples' surface roughness after erosion tests. The UFG titanium alloy demonstrated considerable improvement of static mechanical properties (ultimate tensile strength, microhardness), whereas its CG counterpart appeared to be slightly more resistant to solid particle erosion, which might indicate the drop of dynamic strength properties for the HPT-processed material.

The Exoplanet Cloud Atlas

NASA Astrophysics Data System (ADS)

Gao, Peter; Marley, Mark S.; Morley, Caroline; Fortney, Jonathan J.

2017-10-01

Clouds have been readily inferred from observations of exoplanet atmospheres, and there exists great variability in cloudiness between planets, such that no clear trend in exoplanet cloudiness has so far been discerned. Equilibrium condensation calculations suggest a myriad of species - salts, sulfides, silicates, and metals - could condense in exoplanet atmospheres, but how they behave as clouds is uncertain. The behavior of clouds - their formation, evolution, and equilibrium size distribution - is controlled by cloud microphysics, which includes processes such as nucleation, condensation, and evaporation. In this work, we explore the cloudy exoplanet phase space by using a cloud microphysics model to simulate a suite of cloud species ranging from cooler condensates such as KCl/ZnS, to hotter condensates like perovskite and corundum. We investigate how the cloudiness and cloud particle sizes of exoplanets change due to variations in temperature, metallicity, gravity, and cloud formation mechanisms, and how these changes may be reflected in current and future observations. In particular, we will evaluate where in phase space could cloud spectral features be observable using JWST MIRI at long wavelengths, which will be dependent on the cloud particle size distribution and cloud species.

Component effects on crystallization of RE-containing aluminoborosilicate glass

NASA Astrophysics Data System (ADS)

Mohd Fadzil, Syazwani; Hrma, Pavel; Schweiger, Michael J.; Riley, Brian J.

2016-09-01

Lanthanide-aluminoborosilicate (LABS) glass is one option for immobilizing rare earth (RE) oxide fission products generated during reprocessing of pyroprocessed fuel. This glass system can accommodate a high loading of RE oxides and has excellent chemical durability. The present study describes efforts to model equilibrium crystallinity as a function of glass composition and temperature as well as liquidus temperature (TL) as a function of glass composition. The experimental method for determining TL was ASTM C1720-11. Typically, three crystalline phases were formed in each glass: Ce-borosilicate (Ce3BSi2O10), mullite (Al10Si2O19), and corundum (Al2O3). Cerianite (CeO2) was a common minor crystalline phase and Nd-silicate (Nd2Si2O7) occurred in some of the glasses. In the composition region studied, TL decreased as SiO2 and B2O3 fractions increased and strongly increased with increasing fractions of RE oxides; Al2O3 had a moderate effect on the TL but, as expected, it strongly affected the precipitation of Al-containing crystals.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohd Fadzil, Syazwani; Hrma, Pavel; Schweiger, Michael J.

Lanthanide-aluminoborosilicate (LABS) glass is one option for immobilizing rare earth (RE) oxide fission products generated during reprocessing of pyroprocessed fuel. This glass system can accommodate a high loading of RE oxides and has excellent chemical durability. The present study describes efforts to model equilibrium crystallinity as a function of glass composition and temperature as well as liquidus temperature (TL) as a function of glass composition. The experimental method for determining TL was ASTM C1720-11. Typically, three crystalline phases were formed in each glass: Ce-borosilicate (Ce 3BSi 2O 10), mullite (Al 10Si 2O 19), and corundum (Al 2O 3). Cerianite (CeOmore » 2) was a common minor crystalline phase and Nd-silicate (Nd 2Si 2O 7) occurred in some of the glasses. In the composition region studied, TL decreased as SiO 2 and B 2O 3 fractions increased and strongly increased with increasing fractions of RE oxides; Al 2O 3 had a moderate effect on the TL but, as expected, it strongly affected the precipitation of Alcontaining crystals.« less

Improving tribological properties of Ti-5Zr-3Sn-5Mo-15Nb alloy by double glow plasma surface alloying

NASA Astrophysics Data System (ADS)

Guo, Lili; Qin, Lin; Kong, Fanyou; Yi, Hong; Tang, Bin

2016-12-01

Molybdenum, an alloying element, was deposited and diffused on Ti-5Zr-3Sn-5Mo-15Nb (TLM) substrate by double glow plasma surface alloying technology at 900, 950 and 1000 °C. The microstructure, composition distribution and micro-hardness of the Mo modified layers were analyzed. Contact angles on deionized water and wear behaviors of the samples against corundum balls in simulated human body fluids were investigated. Results show that the surface microhardness is significantly enhanced after alloying and increases with treated temperature rising, and the contact angles are lowered to some extent. More importantly, compared to as-received TLM alloy, the Mo modified samples, especially the one treated at 1000 °C, exhibit the significant improvement of tribological properties in reciprocating wear tests, with lower specific wear rate and friction coefficient. To conclude, Mo alloying treatment is an effective approach to obtain excellent comprehensive properties including optimal wear resistance and improved wettability, which ensure the lasting and safety application for titanium alloys as the biomedical implants.

Acoustical and thermo physical properties of metal-ceramics composites in dependence on few volume concentration of metal

NASA Astrophysics Data System (ADS)

Abramovich, A.

2016-04-01

Metal-ceramics composites (cermets) are modern construction material used in different industry branches. Their strength and heat resistance depend on elastic and thermos physical properties. In this work cermets based on corundum and stainless steel (sintered in high vacuum at temperatures 1500 - 1600°C) are investigated. The volume steel concentration in the samples varies up 2 to 20 vol %. The elastic modules were measured by ultrasonic method at room temperature, measuring of thermo conductivity coefficient were carried out at temperatures 100, 200°C by method of continued heating in adiabatic calorimeter. We founded appearance of two extremes on dependences of elastic modules (E, G) on stainless steel concentrations, nature of which is unknown, modules values change in range: E = 110 - 310, G = 60 - 130GPa (for different temperatures of sintering). Similar dependence is observed for thermo conductivity coefficient which values varies up 10 to 40 W/(m.K). There is presented also discussion of results based on structure cermet model as multiphase micro heterogeneous media with isotropic physical properties in the work.

The self-similar turbulent flow of low-pressure water vapor

NASA Astrophysics Data System (ADS)

Konyukhov, V. K.; Stepanov, E. V.; Borisov, S. K.

2018-05-01

We studied turbulent flows of water vapor in a pipe connecting two closed vessels of equal volume. The vessel that served as a source of water vapor was filled with adsorbent in the form of corundum ceramic balls. These ceramic balls were used to obtain specific conditions to lower the vapor pressure in the source vessel that had been observed earlier. A second vessel, which served as a receiver, was empty of either air or vapor before each vapor sampling. The rate of the pressure increase in the receiver vessel was measured in a series of six samplings performed with high precision. The pressure reduction rate in the source vessel was found to be three times lower than the pressure growth rate in the receiver vessel. We found that the pressure growth rates in all of the adjacent pairs of samples could be arranged in a combination that appeared to be identical for all pairs, and this revealed the existence of a rather interesting and peculiar self-similarity law for the sampling processes under consideration.

Aqueous chemical growth of alpha-Fe2O3-alpha-Cr203 nanocompositethin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vayssieres, Lionel; Guo, Jinghua; Nordgren, Joseph

2001-06-30

We are reporting here on the inexpensive fabrication and optical properties of an iron(III) oxide chromium(III) oxide nanocomposite thin film of corundum crystal structure. Its novel and unique-designed architecture consists of uniformed, well-defined and oriented nanorods of Hematite (alpha-Fe2O3) of 50 nm in diameter and 500nm in length and homogeneously distributed nonaggregated monodisperse spherical nanoparticles of Eskolaite (alpha-Cr2O3) of 250 nm in diameter. This alpha-Fe2O3 alpha-Cr2O3 nanocomposite thin film is obtained by growing, directly onto transparent polycrystalline conducting substrate, an oriented layer of hematite nanorods and growing subsequently, the eskolaite layer. The synthesis is carried out by a template-free, low-temperature,more » multilayer thin film coating process using aqueous solution of metal salts as precursors. Almost 100 percent of the light is absorbed by the composite film between 300 and 525 nm and 40 percent at 800 nm which yields great expectations as photoanode materials for photovoltaic cells and photocatalytic devices.« less

Structural, Optical, and Electronic Characterization of Fe-Doped Alumina Nanoparticles

NASA Astrophysics Data System (ADS)

Heiba, Zein K.; Mohamed, Mohamed Bakr; Wahba, Adel Maher; Imam, N. G.

2018-01-01

The effects of iron doping on the structural, optical, and electronic properties of doped alumina have been studied. Single-phase iron-doped alumina Al2- x Fe x O3 ( x = 0.00 to 0.30) nanoparticles were synthesized via citrate-precursor method. Formation of single-phase hexagonal corundum structure with no other separate phases was demonstrated by x-ray diffraction (XRD) analysis and Fourier-transform infrared spectroscopy. The effects of iron doping on the α-Al2O3 structural parameters, viz. atomic coordinates, lattice parameters, crystallite size, and microstrain, were estimated from XRD data by applying the Rietveld profile fitting method. Transmission electron microscopy further confirmed the nanosize nature of the prepared samples with size ranging from 12 nm to 83 nm. The electronic band structure was investigated using density functional theory calculations to explain the decrease in the energy gap of Al2- x Fe x O3 as the amount of Fe was increased. The colored emission peaks in the visible region (blue, red, violet) of the electromagnetic spectrum obtained for the Fe-doped α-Al2O3 nanoparticles suggest their potential application as ceramic nanopigments.

[HYGIENIC ASSESSMENT OFWORKING ENVIRONMENT FOR REPAIRERS OF RAILWAY ROLLING STOCK IN PLANT CONDITIONS].

PubMed

Sudeikina, N A; Kurenkova, G V

2015-01-01

The comprehensive hygienic assessment of working environment for main occupational groups Railway Car Repair Plant in factory conditions shows that workers are exposed to the impact of factors of chemical nature in concentrations exceeding maximum allowable (lead, manganese, alkali caustic, sulphuric and nitric acids, chromium trioxide, silicon-containing dust, white corundum, diiron trioxide, silicate-organic dust, wood and carbon dusts), the high level of noise, the local vibration, insufficient levels of artificial lighting. The manual work is used, that determines the high severity of the labor process in the most of workers. There was identified the inconsistency of quality and quantitative estimation of the work conditions on chemical factor at implementation of various types of control: certification of workplaces on work conditions, productions and state control. There was given an a priori evaluation of the occupational risk in the three main workshops, there were detected 13 occupations with mild (moderate) risk, 9 occupations with average (significant) risk, 6 professions with high (intolerable) risk category and 1 occupation--with very high (intolerable) risk category. Low indices of occupational diseases according to official statistics were establishedfail to be consistent with a high probability of their occurrence in the production.

Electron-density critical points analysis and catastrophe theory to forecast structure instability in periodic solids.

PubMed

Merli, Marcello; Pavese, Alessandro

2018-03-01

The critical points analysis of electron density, i.e. ρ(x), from ab initio calculations is used in combination with the catastrophe theory to show a correlation between ρ(x) topology and the appearance of instability that may lead to transformations of crystal structures, as a function of pressure/temperature. In particular, this study focuses on the evolution of coalescing non-degenerate critical points, i.e. such that ∇ρ(x c ) = 0 and λ 1 , λ 2 , λ 3 ≠ 0 [λ being the eigenvalues of the Hessian of ρ(x) at x c ], towards degenerate critical points, i.e. ∇ρ(x c ) = 0 and at least one λ equal to zero. The catastrophe theory formalism provides a mathematical tool to model ρ(x) in the neighbourhood of x c and allows one to rationalize the occurrence of instability in terms of electron-density topology and Gibbs energy. The phase/state transitions that TiO 2 (rutile structure), MgO (periclase structure) and Al 2 O 3 (corundum structure) undergo because of pressure and/or temperature are here discussed. An agreement of 3-5% is observed between the theoretical model and experimental pressure/temperature of transformation.

Impact of plasma chemistry versus titanium surface topography on osteoblast orientation.

PubMed

Rebl, Henrike; Finke, Birgit; Lange, Regina; Weltmann, Klaus-Dieter; Nebe, J Barbara

2012-10-01

Topographical and chemical modifications of biomaterial surfaces both influence tissue physiology, but unfortunately little knowledge exists as to their combined effect. There are many indications that rough surfaces positively influence osteoblast behavior. Having determined previously that a positively charged, smooth titanium surface boosts osteoblast adhesion, we wanted to investigate the combined effects of topography and chemistry and elucidate which of these properties is dominant. Polished, machined and corundum-blasted titanium of increasing microroughness was additionally coated with plasma-polymerized allylamine (PPAAm). Collagen I was then immobilized using polyethylene glycol diacid and glutar dialdehyde. On all PPAAm-modified surfaces (i) adhesion of human MG-63 osteoblastic cells increased significantly in combination with roughness, (ii) cells resemble the underlying structure and melt with the surface, and (iii) cells overcome the restrictions of a grooved surface and spread out over a large area as indicated by actin staining. Interestingly, the cellular effects of the plasma-chemical surface modification are predominant over surface topography, especially in the initial phase. Collagen I, although it is the gold standard, does not improve surface adhesion features comparably. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Raman Study of the Structural Distortion in the Ni 1–xCo xTiO 3 Solid Solution

DOE PAGES

Fujioka, Yukari; Frantti, Johannes; Puretzky, Alexander; ...

2016-09-08

In this paper, Raman spectra were collected on Ni 1–xCo xTiO 3 (0 ≤ x ≤ 1) ilmenite samples as a function of the temperature between 4 and 1200 K. An evident symmetry lowering from the prototype Rmore » $$\\bar{3}$$symmetry is observed. The distortion was largest for the x = 0.40 and 0.50 samples and significantly diminished for small and large values of x. The distortion was preserved in the whole temperature range and, except for the x = 0.50 sample, did not show significant changes. Notably, between 25 and 69 K, distortion of the x = 0.40 sample is accompanied by ferromagnetic order. The direct cation–cation and O-mediated indirect interactions are discussed as mechanisms behind the distortion and magnetic order. A reversible order–disorder phase transformation, assigned to occur between the ilmenite and corundum phases, took place at 973 K in the x = 0.50 sample. Completion of the transformation took over 1 h. Finally, the role of the overlap of Co/Ni and Ti 3d orbitals through O octahedral faces for charge transfer is discussed.« less

Chromite and other mineral deposits in serpentine rocks of the Piedmont Upland, Maryland, Pennsylvania, and Delaware

USGS Publications Warehouse

Pearre, Nancy C.; Heyl, Allen V.

1960-01-01

The Piedmont Upland in Maryland, Pennsylvania, and Delaware is about 160 miles long and at the most 50 miles wide. Rocks that underlie the province are the Baltimore gneiss of Precambrian age and quartzite, gneiss, schist, marble, phyllite, and greenstone, which make up the Glenarm series of early Paleozoic (?) age. These are intruded by granitic, gabbroic, and ultramaflc igneous rocks. Most of the ultramaflc rocks, originally peridotite, pyroxenite, and dunite, have been partly or completely altered to serpentine and talc; they are all designated by the general term serpentine. The bodies of serpentine are commonly elongate and conformable with the enclosing rocks. Many have been extensively quarried for building, decorative, and crushed stone. In addition, chromite, titaniferous magnetite, rutile, talc and soapstone, amphibole asbestos, magnesite, sodium- rich feldspar (commercially known as soda spar), and corundum have been mined or prospected for in the serpentine. Both high-grade massive chromite and lower grade disseminated chromite occur in very irregular and unpredictable form in the serpentine, and placer deposits of chromite are in and near streams that drain areas underlain by serpentine. A group of unusual minerals, among them kammererite, are typical associates of high-grade massive chromite but are rare in lower grade deposits. Chromite was first discovered in the United States at Bare Hills, Md., around 1810. Between 1820 and 1850, additional deposits were discovered and mined in Maryland and Pennsylvania, including the largest deposit of massive chromite ever found in the United States the Wood deposit, in the State Line district. A second period of extensive chromite mining came during the late 1860's and early 1870's. Production figures are incomplete and conflicting. Estimates from the available data indicate that the aggregate production from 27 of 40 known mines before 1900 totaled between 250,000 and 280,000 tons of lode-chromite ore; information is lacking for the other 13. Placer deposits produced considerably more than 15,000 tons of chromite concentrates. Exploratory work in several of the mines and placer deposits during World War I produced about 1,500 long tons of chromite ore, 920 tons of which was sold.Most of the chromite from Maryland and Pennsylvania was used to manufacture chemical compounds, pigments, and dyes before metallurgical and refractory uses for chromite were developed. Available analyses of the ores indicate that they would satisfy modern requirements for chemical-grade chromite. With the exception of such deposits as the Line Pit and Red Pit mines, the chromite contains too much iron for the best metallurgical grade, but many would be satisfactory low-grade metallurgical chromite. Perhaps 30,000 to 50,000 tons of chromite concentrates that would range from 30 to 54 percent Cr2O3 could be obtained from placer deposits in the State Line and Soldiers Delight districts. A small tonnage of chromite remains in dumps at six of the old mines. Lode and placer deposits in the Philadelphia district, placers in Montgomery County, Md., and possible downward extensions of known ore bodies below the floors of high-grade mines now flooded have not been completely explored. Although other chromite deposits probably lie concealed at relatively shallow depths, no practical method of finding them has been developed.Small deposits of titaniferous iron ore in serpentine were mined for iron before 1900, but the titanium content troubled furnace operators. Ore bodies are similar in occurrence to chromite deposits; they are massive or disseminated and are found near the edges of serpentine intrusive rocks. The small size of the deposits and comparatively low titanium content limit their importance as a potential source of titanium. A single rutile deposit in Harford County, Md., has been prospected but not mined. Pockets in schistose chlorite rock, probably altered from pyroxenite, contain as much as 16 percent rutile and average 8 percent. Rutile-bearing rock has been proved to a depth of about 58 feet. Talc and soapstone deposits that have been worked in the State Line and Jarrettsville-Dublin districts are the result of steatitization of serpentine at its contact with intrusive sodium-rich pegmatites. Deposits in the Marriottsville and Philadelphia districts seem to be related to shear or crush zones in the serpentine, which served as channelways for steatitizing solutions. Massive soapstone was extensively used in the 19th century for furnace, fireplace, and stove linings and for washtubs and bathtubs. Every year from 1906 until 1960 talc and soapstone have been produced from one or more of the deposits in Maryland and Pennsylvania. Deposits near Dublin and Marriottsville, Md., have produced steadily for years and production continues. Lava-grade steatite from Dublin, Md., is manufactured into ceramic products for electrical and refractory purposes. Slip-fiber amphibole asbestos deposits were known in the area as early as 1837, but early production was limited. The product was used mostly for linings of safes, boiler covers, and paints. During World War I the demand for domestic asbestos for chemical filters led to further development of deposits in Maryland. Between 1916 and 1940 many small veins of good-quality tremolite and anthophyllite were mined, and the fiber was prepared for market at Woodlawn, Md. Only the upper parts of veins, softened by weathering, were usable. Because prospecting was reportedly fairly thorough and known deposits are said to be mined out, and because demand for amphibole asbestos is limited, the possibility of future asbestos production from the area seems small, except as a byproduct of talc quarrying. Magnesite from several mines in Pennsylvania and Maryland was much in demand between 1828 and 1871 for the manufacture of epsom salt. Exploratory work at the old Goat Hill mines in 1921 indicated that the product could not be profitably prepared for market at that time. Although reportedly high grade, the magnesite veins are thin and small in comparison with other domestic deposits.Sodium-rich feldspar and corundum deposits occur in pegmatites that are unusual because they characteristically contain little or no quartz and mica and because, insofar as known, they are confined to serpentine rocks. Many of the known deposits of sodium-rich feldspar commercial soda-spar are reportedly mined out. It is possible, however, that other commercial deposits will be found in the area. At various times from 1825 until about 1892 in Pennsylvania, corundum mined or found at the surface was used to meet a demand of the abrasives industry. The increased use of artificial abrasives has diminished the demand for natural corundum, and interest in the small, irregular Pennsylvania deposits is at present largely historical or mineralogical.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Peng-Yuan; Zhang, Wei-De, E-mail: zhangwd@scut.edu.cn

Highlights: • Preparation of nanostructured In{sub 2}O{sub 3} microspheres. • Morphology and phase control of In{sub 2}O{sub 3}. • Gas sensors based on the In{sub 2}O{sub 3} microspheres exhibit excellent sensing properties for the detection of formaldehyde. - Abstract: Urchin-like InOOH microspheres were successfully prepared by a convenient and controllable method. Such experimental parameters as solvents and complexing reagents on the formation of the urchin-like InOOH microspheres were investigated. Scanning electron microscopy, X-ray diffraction and infrared spectroscopy were employed to investigate the evolution process of the urchin-like InOOH precursors. Furthermore, the formation mechanism of the urchin-like InOOH microspheres was proposed.more » By annealing the urchin-like InOOH precursor at different temperatures under ambient pressure, rhombohedral corundum-type indium oxide (rh-In{sub 2}O{sub 3}), cubic bixbyite-type indium oxide (c-In{sub 2}O{sub 3}) and mixed phases of rh-In{sub 2}O{sub 3} and c-In{sub 2}O{sub 3} were obtained. The gas sensing properties of the prepared In{sub 2}O{sub 3} samples were examined. It was found that the sensors based on the prepared In{sub 2}O{sub 3} samples exhibited excellent response and selectivity to formaldehyde.« less

Anomalous structural disorder and distortion in metal-to-insulator-transition Ti{sub 2}O{sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hwang, In-Hui; Jin, Zhenlan; Park, Chang-In

2016-01-07

Mott proposed that impurity bands in corundum-symmetry Ti{sub 2}O{sub 3} at high temperatures caused a collapse in the bandgap. However, the origin of the impurity bands has not yet been clarified. We examine the local structural properties of metal-to-insulator-transition Ti{sub 2}O{sub 3} using in-situ x-ray absorption fine structure (XAFS) measurements at the Ti K edge in the temperature range from 288 to 739 K. The Ti{sub 2}O{sub 3} powder is synthesized by using a chemical reaction method. X-ray diffraction (XRD) measurements from Ti{sub 2}O{sub 3} with a Rietveld refinement demonstrate a single-phased R-3c symmetry without additional distortion. Extended-XAFS combined with XRDmore » reveals a zigzag patterned Ti position and an anomalous structural disorder in Ti-Ti pairs, accompanied by a bond length expansion of the Ti-Ti pairs along the c-axis for T > 450 K. The local structural distortion and disorder of the Ti atoms would induce impurity levels in the band gap between the Ti 3d a{sub 1g} and e{sub g}{sup π} bands, resulting in a collapse of the band gap for T > 450 K.« less

Comparison of effects on macrophage cultures of glass fibre, glass powder, and chrysotile asbestos

PubMed Central

Beck, E. G.; Holt, P. F.; Manojlović, N.

1972-01-01

Beck, E. G., Holt, P. F., and Manojlović, N. (1972).Brit. J. industr. Med.,29, 280-286. Comparison of effects on macrophage cultures of glass fibre, glass powder, and chrysotile asbestos. The effects on macrophage cultures of glass fibre, glass powder, and chrysotile asbestos are compared. Glass fibre behaves like chrysotile in producing an increase in cell membrane permeability in cultured macrophages. This is demonstrable by the increase in lactic dehydrogenase activity in the supernatant fluid. The metabolism, measured by lactate production, is not reduced as it is when quartz is phagocytosed. Glass powder behaves like the inert dust corundum, producing little change in the number of cells stained by erythrosin B and a small increase in lactate dehydrogenase activity, both being in the range of the control. There is an increase in lactate production as a result of higher metabolism due to phagocytosis. Dusts may produce two basic effects, namely a toxic effect and change in cell membrane permeability. A non-specific effect on the cell membrane due to the slow and sometimes incomplete process of ingestion of long fibres is probably a function of the morphology, particularly the length of the fibres. A primary specific effect induced by some dusts immediately follows contact with the cell membrane. Images PMID:4339803

Mineralogical characterization of Greda clays and monitoring of their phase transformations on thermal treatment

NASA Astrophysics Data System (ADS)

Panduro, E. Chavez; Cabrejos, J. Bravo

2010-01-01

The mineralogical characterization of two clay samples from the Central Andean Region of Peru, denominated White Greda and Red Greda, is reported. These clays contain the clay minerals mica and illite respectively. Both clays were treated thermally in an oxidising atmosphere under controlled conditions up to 1,100°C with the purpose of obtaining information about structural changes that may be useful for pottery manufacture. X-ray fluorescence was used for the elemental characterization of the samples and X-ray diffractometry was used to determine the collapse and formation of the mineral phases present in the samples caused by thermal treatment. At temperatures above 1,000°C it is observed the formation of spinel in the case of White Greda and of hematite, corundum and cristobalite in the case of Red Greda. Room temperature transmission Mössbauer spectroscopy allowed the monitoring of the variation of the hyperfine parameters with the thermal treatment temperature; In the case of the evolution of the quadruple splitting of the paramagnetic Fe3 + sites with temperature, in both clays, the analyses reproduced results such as the “camel back” curve shape, found by other workers (Wagner and Wagner, Hyperfine Interact 154:35-82, 2004; Wagner and Kyek, Hyperfine Interact 154:5-33, 2004).

Nano-size metallic oxide particle synthesis in Fe-Cr alloys by ion implantation

NASA Astrophysics Data System (ADS)

Zheng, C.; Gentils, A.; Ribis, J.; Borodin, V. A.; Delauche, L.; Arnal, B.

2017-10-01

Oxide Dispersion Strengthened (ODS) steels reinforced with metal oxide nanoparticles are advanced structural materials for nuclear and thermonuclear reactors. The understanding of the mechanisms involved in the precipitation of nano-oxides can help in improving mechanical properties of ODS steels, with a strong impact for their commercialization. A perfect tool to study these mechanisms is ion implantation, where various precipitate synthesis parameters are under control. In the framework of this approach, high-purity Fe-10Cr alloy samples were consecutively implanted with Al and O ions at room temperature and demonstrated a number of unexpected features. For example, oxide particles of a few nm in diameter could be identified in the samples already after ion implantation at room temperature. This is very unusual for ion beam synthesis, which commonly requires post-implantation high-temperature annealing to launch precipitation. The observed particles were composed of aluminium and oxygen, but additionally contained one of the matrix elements (chromium). The crystal structure of aluminium oxide compound corresponds to non-equilibrium cubic γ-Al2O3 phase rather than to more common corundum. The obtained experimental results together with the existing literature data give insight into the physical mechanisms involved in the precipitation of nano-oxides in ODS alloys.

Ceramic materials under high temperature heat transfer conditions

NASA Astrophysics Data System (ADS)

Mittenbühler, A.; Jung, J.

1990-04-01

Ceramic materials for application in a High-Temperature Reactor coupled with the steam gasification of coal were investigated. The study concentrated on the hot gas duct and their thermal insulation. Materials examined for the inner lining of the tubes were graphite, carbon fibre reinforced carbon and amorphous silica, while fibres, porous alumina and bonded alumina fibres were tested as insulating materials. During material investigations qualification was performed on samples and in component tests. For two carbon fibre reinforced carbon qualities with different graphitizing temperatures, the bending strength was determined as a function of volume corrosion. Devitrification of amorphous silica can be tolerated up to operating temperatures of about 950°C. The resilience of fibre materials depends on the Al2O3/ SiO2 ratio. It decreases according to the different fibre composition with increasing temperature and limits the maximum operating temperature for long term operation. The porous hollow spherical corundum inserted in the form of bricks fulfilled the thermal shock and mechanical requirements but led to an insulation exhibiting gaps in component tests. An advanced insulation on the basis of bonded alumina fibre showed a quasi-elastic material behaviour. Resistance to abrasion was achieved with a protective ceramic coating. The different materials and design concepts are compared and the results provide a good solution for the project.

At last! The single-crystal X-ray structure of a naturally occurring sample of the ilmenite-type oxide FeCrO3.

PubMed

Pérez-Cruz, María Ana; Elizalde-González, María de la Paz; Escudero, Roberto; Bernès, Sylvain; Silva-González, Rutilo; Reyes-Ortega, Yasmi

2015-10-01

A natural single crystal of the ferrimagnetic oxide FeCrO3, which was found in an opencast mine situated in the San Luis Potosí State in Mexico, has been characterized in order to elucidate some outstanding issues about the actual structure of this material. The single-crystal X-ray analysis unambiguously shows that transition metal cations are segregated in alternating layers normal to the threefold crystallographic axis, affording a structure isomorphous to that of ilmenite (FeTiO3), in the space group R3̅. The possible occurrence of cation antisite and vacancy defects is below the limit of detection available from X-ray data. Structural and magnetic results are in agreement with the coherent slow intergrowth of magnetic phases provided by the two antiferromagnetic corundum-type parent oxides Fe2O3 (hematite) and Cr2O3 (eskolaite). Our results are consistent with the most recent density functional theory (DFT) studies carried out on digital FeCrO3 [Sadat Nabi & Pentcheva (2011). Phys. Rev. B, 83, 214424], and suggest that synthetic samples of FeCrO3 might present a cation distribution different to that of the ilmenite structural type.

Synthesis of Galaxite, Mn0.9Co0.1Al2O4, and its application as a novel nanocatalyst for electrochemical hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Saeidfirozeh, Homa; Shafiekhani, Azizollah; Beheshti-Marnani, Amirkhosro; Askari, Mohammad Bagher

2018-06-01

A new compound Mn0.9Co0.1Al2O4 nanowires were synthesized by thermal method. The resulting powder samples were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD). We found that a set of phase transformation occurred during the process. Eventually, five phases including three spinal phases, the corundum (á-Al2O3) and MnO were formed at 1100 °C.As dominant morphology, the cubic galaxite nanowires were identified by X-ray analysis. Moreover, X-ray analysis showed that Mn3O4 and Co3O4 nanoparticles were formed in tetragonal and cubic symmetry respectively. The SEM image revealed that a dominate morphology of product has cubic nanowires shape with an average diameter in range 38-43 nm. Furthermore, we observed that influence of temperature was very important in the nanowire formation process. Electrochemical hydrogen evolution reaction (HER) of synthetic composite was evaluated and the over potential of HER was calculated about 110 mV with low Tafel slope equal to 42 mV dec-1, which was comparable with amounts reported transition metal dichalcogenides with satisfying durability.

Gas sensing behaviour of Cr{sub 2}O{sub 3} and W{sup 6+}: Cr{sub 2}O{sub 3} nanoparticles towards acetone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kohli, Nipin, E-mail: nipinkohli82@yahoo.com; Hastir, Anita; Singh, Ravi Chand

2016-05-23

This paper reports the acetone gas sensing properties of Cr{sub 2}O{sub 3} and 2% W{sup 6+} doped Cr{sub 2}O{sub 3} nanoparticles. The simple cost-effective hydrolysis assisted co-precipitation method was adopted. Synthesized samples were characterized by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) techniques. XRD revealed that synthesized nanoparticles have corundum structure. The lattice parameters have been calculated by Rietveld refinement; and strain and crystallite size have been calculated by using the Williamson-Hall plots. For acetone gas sensing properties, the nanoparticles were applied as thick film onto alumina substrate and tested at different operating temperatures. The results showedmore » that the optimum operating temperature of both the gas sensors is 250°C. At optimum operating temperature, the response of Cr{sub 2}O{sub 3} and 2% W{sup 6+} doped Cr{sub 2}O{sub 3} gas sensor towards 100 ppm acetone was found to be 25.5 and 35.6 respectively. The investigations revealed that the addition of W{sup 6+} as a dopant enhanced the sensing response of Cr{sub 2}O{sub 3} nanoparticles appreciably.« less

Biomolecule-Mineral Interactions in the Geochemical Environment on Early Earth and in the Human Body

NASA Astrophysics Data System (ADS)

Sahai, N.

2011-12-01

We worked on four projects consistent with the broad goals of the grant to investigate (i) the potential impacts of mineral surface chemistry and particle size on the stability and viability of cell membranes, bacteria and human cells and (ii) the influence of biomolecules on mineral nucleation and growth. The projects are of relevance to the origin and early evolution of life, biomineralization, medical mineralogy, and environmental biogeochemistry. The freedom enabled by the five-year grant to explore high-risk scientific areas, and the resulting high impact outcomes, cannot be overstated. We developed an almost entirely new field of Medical Mineralogyy and extended our concepts and knowledge-base to the potential roles of mineral surfaces in the evolution of protocells and the earliest cells. These exciting connections to medical mineralogy, and to the origin and evolution of life on early Earth are fascinating topics to the general public and even to other scientists, especially when the links to mineralogy and geochemistry are highlighted. In brief, we examined the stability of lipid bilayers representing model protocell membranes comprised of phospholipid bilayers with mineral surfaces. We found that the stability of lipid bilayers depends on mineral surface charge and increases as silica glass ~ quartz < rutile ~ mica < corundum. In a second project, we investigated whether the evolution of bacterial extra-cellular polymeric substances (EPS) may have been driven by nanomineral toxicity. Results showed that EPS does protect against mineral toxicity, and toxicity increases as amorphous SiO2 < β-TiO2 (anatase) < γ-Al2O3. A commonly accepted mechanism for Biomineralization is protein-templated nucleation. We used Molecular Dynamics and Bioinformatics computational chemistry approaches and showed that the random coil structure of a specific peptide promotes formation of an amorphous Ca-PO4 cluster, but not direct templation of hydroxyapatite. The consistency between our Ca-PO4 and previous experimental Ca-CO3 studies indicates that universal principles underly biomineralization processes of relevance to environmental biogeochemistry as well as to medical mineralogy. Minerals can enter the human either inadvertently as inhaled dusts or are inserted by design such as in components of orthopedic implants. It is important to know how the mineral surface properties affect the body's immune system response. We found that adhesion/detachment force of the Jurkat -line of T-lymphocytes increased as SiO2 glass ~ quartz < rutile (100) ~ mica (001) < polycrystalline corundum, and was related to the unraveling of cell surface glycoproteins, and to mineral surface charge. The studies described above have resulted in 23 peer-reviewed publications to date (published or in review or in prep.); one MSA volume and one Elements issue edited by the P.I.; trained five graduate students, three post-doctoral research scientists and 4 undergraduate students; numerous invited presentations at international conferences and at Universities; and numerous outreach activities including interviews on National Public Radio and on Hungarian national newspapers and television at the International Mineralogical Association's Annual Meeting.

The stability of lawsonite and zoisite at high pressures: Experiments in CASH to 92 kbar and implications for the presence of hydrous phases in subducted lithosphere

NASA Astrophysics Data System (ADS)

Schmidt, Max W.; Poli, Stefano

1994-06-01

The breakdown reactions of lawsonite in SiO2 + H2O- and in Al2O3 + H2O-saturated synthetic CASH systems were examined between 17 and 92 kbar in both forward and reversed experiments. Lawsonite is stable to 565 C at 20 kbar, 760 C at 40 kbar, and 980 C at 65 kbar. In this pressure range lawsonite breaks down to zoisite + kyanite + quartz/ coesite + H2O. An invariant point occurs at 1000 C, 67 kbar. At higher pressures lawsonite breaks down to the assemblage grossular + kyanite + coesite + H20. The steep positive dP/dT slope of this higher pressure breakdown reaction becomes steeply negative when coesite transforms to stishovite. At 92 kbar, the highest pressure investigated, lawsonite is stable to 1040 C. The invariant point marks also the pressure stability limit of zoisite since zoisite reacts to lawsonite + grossular + kyanite + coesite (at temperatures below 1000 C), to grossular + kyanite + coesite + H2O (1000-1040 C) and to grossular + kyanite + melt + H20 (above 1040C). These three reactions have a flat Clapeyron slope, and they locate the maximum pressure stability of zoisite between 65 and 68 kbar (between 800 and 1200 C). Eutectic melting in the SiO2 + H2O-saturated CASH system occurs for the assemblage zoisite + kyanite + coesite + H2O at temperatures approximately 100 C (at 40 kbar) to 40 C (at 65 kbar) higher than the lawsonite breakdown reaction. In the Al2O3+H2O-saturated system the reaction lawsonite + diaspore/corundum = zoisite + kyanite + H2O limits the stability of lawsonite. The diaspore = corundum + H2O equilibrium is found to be located about 50 C lower than predicted by previous studies. The equilibrium boundaries of the reactions between 17 and 38 kbar from both SiO2+H2O- and Al2O3 + H2O-saturated chemical systems were used to improve the thermochemical data on lawsonite. Two sets of thermodynamic properties internally consistent with the databases of both Berman and Holland and Powell, and also consistent with most previous experimental studies, were calculated employing the technique of linear programming (for Berman's data) and a least-squares fit procedure (for Holland and Powell's data). Because lawsonite is stable to 1040 C at 92 kbar, a temperature far higher than predicted by thermal modelling of subduction zones, it is expected to be stable in metabasalts and intermediate compositions (e.g., andesites and greywackes) subducted to depths exceeding 300 km. Lawsonite contains 11 wt% water in its structure, and is thus capable of transporting water deep into the mantle. Its breakdown would contribute significantly to the fluid budget of the slab and overlying mantle wedge. The experimental data in combination with thermal modelling studies indicate that a complete dehydration of the descending oceanic crust is unlikely to occur at shallow levels.

Structural, optical and vibrational properties of Cr2O3 with ferromagnetic and antiferromagnetic order: A combined experimental and density functional theory study

NASA Astrophysics Data System (ADS)

Larbi, T.; Ouni, B.; Gantassi, A.; Doll, K.; Amlouk, M.; Manoubi, T.

2017-12-01

Chromium oxide (Cr2O3) thin films have been synthesized on glass substrates by the spray pyrolysis technique. The structural, morphological and optical properties of the sample have been studied by X-ray diffraction (XRD), Raman spectroscopy, FTIR spectroscopy, scanning probe microscopy and UV-vis spectroscopy respectively. X-ray diffraction results reveal that as deposited film is polycrystalline with a rhombohedral corundum structure and a preferential orientation of the crystallites along the (1 0 4) direction. IR and Raman spectra were recorded in the 100-900 cm-1 range and the observed modes were analysed and assigned to different normal modes of vibration. The direct optical band gap energy value calculated from the transmittance spectra of as-deposited thin film is about 3.38 eV. We employ first principles calculations based on density functional theory (DFT) with the B3LYP hybrid functional and a coupled perturbed Hartree-Fock/Kohn-Sham approach (CPHF/KS). We study the electronic structure, optimum geometry, and IR and Raman spectra of ferromagnetically and antiferromagnetically ordered Cr2O3. The computed results are consistent with the experimental measurements, and provide complete vibrational assignment, for the characterization of Cr2O3 thin film materials which can be used in photocatalysis and gas sensors.

Tribological properties of multifunctional coatings with Shape Memory Effect in abrasive wear

NASA Astrophysics Data System (ADS)

Blednova, Zh. M.; Dmitrenko, D. V.; Balaev, E. U. O.

2018-01-01

The article gives research results of the abrasive wear process on samples made of Steel 1045, U10 and with applied composite surface layer "Nickel-Multicomponent material with Shape Memory Effect (SME) based on TiNi". For the tests we have chosen TiNiZr, which is in the martensite state and TiNiHfCu, which is in the austenitic state at the test temperature. The formation of the surface layer was carried out by high-speed oxygen-fuel deposition in a protective atmosphere of argon. In the wear test, Al2O3 corundum powder was used as an abrasive. It is shown that the wear rate of samples with a composite surface layer of multicomponent materials with SME is significantly reduced in comparison with the base, which is explained by reversible phase transformations of the surface layer with SME. After carrying out the additional surface plastic deformation (SPD), the resistance of the laminated composition to abrasion wear has greatly enhanced, due to the reinforcing effect of the SPD. It is recommended for products working in conditions of abrasive wear and high temperatures to use the complex formation technology of the surface composition "steel-nickel-material with high-temperature SME", including preparation of the substrate surface and the deposited material, high-speed spraying in the protective atmosphere of argon, followed by SPD.

Analysis and modification of blue sapphires from Rwanda by ion beam techniques

NASA Astrophysics Data System (ADS)

Bootkul, D.; Chaiwai, C.; Tippawan, U.; Wanthanachaisaeng, B.; Intarasiri, S.

2015-12-01

Blue sapphire is categorised in a corundum (Al2O3) group. The gems of this group are always amazed by their beauties and thus having high value. In this study, blue sapphires from Rwanda, recently came to Thai gemstone industry, are chosen for investigations. On one hand, we have applied Particle Induced X-ray Emission (PIXE), which is a highly sensitive and precise analytical technique that can be used to identify and quantify trace elements, for chemical analysis of the sapphires. Here we have found that the major element of blue sapphires from Rwanda is Al with trace elements such as Fe, Ti, Cr, Ga and Mg as are commonly found in normal blue sapphire. On the other hand, we have applied low and medium ion implantations for color improvement of the sapphire. It seems that a high amount of energy transferring during cascade collisions have altered the gems properties. We have clearly seen that the blue color of the sapphires have been intensified after nitrogen ion bombardment. In addition, the gems were also having more transparent and luster. The UV-Vis-NIR measurement detected the modification of their absorption properties, implying of the blue color increasing. Here the mechanism of these modifications is postulated and reported. In any point of view, the bombardment by using nitrogen ion beam is a promising technique for quality improvement of the blue sapphire from Rwanda.

Hydrophobization of epoxy nanocomposite surface with 1H,1H,2H,2H-perfluorooctyltrichlorosilane for superhydrophobic properties

NASA Astrophysics Data System (ADS)

Psarski, Maciej; Marczak, Jacek; Celichowski, Grzegorz; Sobieraj, Grzegorz B.; Gumowski, Konrad; Zhou, Feng; Liu, Weimin

2012-10-01

Nature inspires the design of synthetic materials with superhydrophobic properties, which can be used for applications ranging from self-cleaning surfaces to microfluidic devices. Their water repellent properties are due to hierarchical (micrometer- and nanometre-scale) surface morphological structures, either made of hydrophobic substances or hydrophobized by appropriate surface treatment. In this work, the efficiency of two surface treatment procedures, with a hydrophobic fluoropolymer, synthesized and deposited from 1H,1H,2H,2H-perfluorooctyltrichlorosilane (PFOTS) is investigated. The procedures involved reactions from the gas and liquid phases of the PFOTS/hexane solutions. The hierarchical structure is created in an epoxy nanocomposite surface, by filling the resin with alumina nanoparticles and micron-sized glass beads and subsequent sandblasting with corundum microparticles. The chemical structure of the deposited fluoropolymer was examined using XPS spectroscopy. The topography of the modified surfaces was characterized using scanning electron microscopy (SEM), and atomic force microscopy (AFM). The hydrophobic properties of the modified surfaces were investigated by water contact and sliding angles measurements. The surfaces exhibited water contact angles of above 150° for both modification procedures, however only the gas phase modification provided the non-sticking behaviour of water droplets (sliding angle of 3°). The discrepancy is attributed to extra surface roughness provided by the latter procedure.

Interdiffusion-driven synthesis of tetragonal chromium (III) oxide on BaTi O3

NASA Astrophysics Data System (ADS)

Asa, M.; Vinai, G.; Hart, J. L.; Autieri, C.; Rinaldi, C.; Torelli, P.; Panaccione, G.; Taheri, M. L.; Picozzi, S.; Cantoni, M.

2018-03-01

Interfaces play a crucial role in the study of novel phenomena emerging at heterostructures comprising metals and functional oxides. For this reason, attention should be paid to the interface chemistry, which can favor the interdiffusion of atomic species and, under certain conditions, lead to the formation of radically different compounds with respect to the original constituents. In this work, we consider Cr/BaTi O3 heterostructures grown on SrTi O3 (100) substrates. Chromium thin films (1-2 nm thickness) are deposited by molecular beam epitaxy on the BaTi O3 layer, and subsequently annealed in vacuum at temperatures ranging from 473 to 773 K. A disordered metallic layer is detected for annealing temperatures up to 573 K, whereas, at higher temperatures, we observe a progressive oxidation of chromium, which we relate to the thermally activated migration of oxygen from the substrate. The chromium oxidation state is +3 and the film shows a defective rocksalt structure, which grows lattice matched on the underlying BaTi O3 layer. One out of every three atoms of chromium is missing, producing an uncommon tetragonal phase with C r2O3 stoichiometry. Despite the structural difference with respect to the ordinary corundum α-C r2O3 phase, we demonstrate both experimentally and theoretically that the electronic properties of the two phases are, to a large extent, equivalent.

Dermoelectroporation, lipofilling, and pulsed light: a protocol after 2 years of experience

NASA Astrophysics Data System (ADS)

Bacci, Pier A.; Mancini, Sergio

2005-11-01

The enourmus boost from adopting biomolecular startegies associated to a better understanding of genetic phenomena opened the way to new methodologies. Among those we can surely locate dermoelectroporation, a methodology that uses the transdermal absorption capacity by means of an apparatus that delivers controlled electrical pulses able to open some "electrical doors". This methodology allows us a protocol of treatment suitable in subjects exhibiting the effects of acne, initial stages of skin ageing without tissue yield. and upkeep of aesthetic surgery. With the term "Biolifting" we signifie a treatment procedure aimed at rejuvenating the face by non-surgical, "soft" and out-patient treatment means. This treatment requires bi-monthly or monthly sessions, a total of four to eight, of a procedure consisting first in superficial microdermabrasion performed with corundum crystals, intended for the removal of the corneus layer and for vascularization. Immediately afterwards, active substances are introduced by means of the Dermoelectroporation treatment, characterized by the possibility of creating the opening of "intercellular gates" that allow the passage of the molecules. The session can be concluded with the application of pulsating light which introduces energy and stimulates the regenerating properties of connective tissues. A home treatment with moisturizing and regenerating creams ends the treatment which is used, with interesting results, also for the aesthetic therapy of stretch marks or hypertrophic scars.

Gemstones and geosciences in space and time. Digital maps to the "Chessboard classification scheme of mineral deposits"

NASA Astrophysics Data System (ADS)

Dill, Harald G.; Weber, Berthold

2013-12-01

The gemstones, covering the spectrum from jeweler's to showcase quality, have been presented in a tripartite subdivision, by country, geology and geomorphology realized in 99 digital maps with more than 2600 mineralized sites. The various maps were designed based on the "Chessboard classification scheme of mineral deposits" proposed by Dill (2010a, 2010b) to reveal the interrelations between gemstone deposits and mineral deposits of other commodities and direct our thoughts to potential new target areas for exploration. A number of 33 categories were used for these digital maps: chromium, nickel, titanium, iron, manganese, copper, tin-tungsten, beryllium, lithium, zinc, calcium, boron, fluorine, strontium, phosphorus, zirconium, silica, feldspar, feldspathoids, zeolite, amphibole (tiger's eye), olivine, pyroxenoid, garnet, epidote, sillimanite-andalusite, corundum-spinel - diaspore, diamond, vermiculite-pagodite, prehnite, sepiolite, jet, and amber. Besides the political base map (gems by country) the mineral deposit is drawn on a geological map, illustrating the main lithologies, stratigraphic units and tectonic structure to unravel the evolution of primary gemstone deposits in time and space. The geomorphological map is to show the control of climate and subaerial and submarine hydrography on the deposition of secondary gemstone deposits. The digital maps are designed so as to be plotted as a paper version of different scale and to upgrade them for an interactive use and link them to gemological databases.

Component mobility at 900 °C and 18 kbar from experimentally grown coronas in a natural gabbro

NASA Astrophysics Data System (ADS)

Keller, Lukas M.; Wunder, Bernd; Rhede, Dieter; Wirth, Richard

2008-09-01

Several approximately 100-μm-wide reaction zones were grown under experimental conditions of 900 °C and 18 kbar along former olivine-plagioclase contacts in a natural gabbro. The reaction zone comprises two distinct domains: (i) an irregularly bounded zone with idiomorphic grains of zoisite and minor corundum and kyanite immersed in a melt developed at the plagioclase side and (ii) a well-defined reaction band comprising a succession of mineral layers forming a corona structure around olivine. Between the olivine and the plagioclase reactant phases we observe the following layer sequence: olivine|pyroxene|garnet|partially molten domain|plagioclase. Within the pyroxene layer two micro-structurally distinct layers comprising enstatite and clinopyroxene can be discerned. Chemical potential gradients persisted for the CaO, Al 2O 3, SiO 2, MgO and FeO components, which drove diffusion of Ca, Al and Si bearing species from the garnet-matrix interface to the pyroxene-olivine interface and diffusion of Mg- and Fe-bearing species in the opposite direction. The systematic mineralogical organization and chemical zoning across the corona suggest that the olivine corona was formed by a "diffusion-controlled" reaction. We estimate a set of diffusion coefficients and conclude that LAlAl < LCaCa < ( LSiSi, LFeFe) < LMgMg during reaction rim growth.

Melting in feldspar-bearing systems to high pressures and the structures of aluminosilicate liquids

NASA Astrophysics Data System (ADS)

Boettcher, Art; Guo, Qiti; Bohlen, Steve; Hanson, Brooks

1984-04-01

To test the possibility that aluminosilicate liquids exhibit pressure-induced transformations, particularly involving changes in the coordination of aluminum, we determined melting relationships for the feldspar-bearing systems NaAlSi3O8-SiO2, KAlSi3O8-SiO2, and CaAl2Si2O8-SiO2 from 1 atm to 25 kbar. Albite and anorthite behave similarly in that they, and presumably liquids of these compositions, transform at high pressures to jadeite, kyanite, corundum, and other structures with aluminum in six-fold coordination, releasing SiO2 component. This results in a large increase in the activity of SiO2 component in the liquid (alqz), which is manifested by a significant decrease in the melting-point depression of albite and of anorthite by the addition of quartz at pressures above ˜15 kbar. In contrast, sanidine does not transform to denser phases at pressures below at least 100 kbar, but it melts incongruently to leucite + SiO2-rich liquid up to ˜ 15 kbar. This produces a relatively large alqz and a small freezing-point depression by quartz below this pressure; the opposite holds above ˜15 kbar. These results support the concept that significant structural changes, including coordination changes in aluminum, occur in magmas in the upper mantle.

Microstructure development and photoluminescence of annealed nanosized Ce:YAG/Al2O3 and Ce:YAG/Cr:Al2O3 powder composites

NASA Astrophysics Data System (ADS)

Peter, Samuel; Kuyanov, Paul; Isik Goktas, Nebile; LaPierre, Ray; Kitai, Adrian

2018-03-01

In an effort to control aggregation and sintering of phosphor nanoparticles at elevated annealing temperatures, glycothermally synthesized cerium-doped yttrium aluminum garnet (Ce:YAG) nanoparticles were annealed in a matrix of aluminum oxide between 1000 °C and 1200 °C. Scanning electron microscopy images showed that glycothermal synthesis yields ∼100 nm particles, and that the alumina matrix was able to control grain growth of Ce:YAG at annealing temperatures up to 1200 °C. Analysis by x-ray diffraction and Fourier transform infrared spectroscopy showed an increase in the degree of crystallinity at increasing temperatures as well as the evolution of alumina phases. Photoluminescence of the composite product showed the expected broad Ce:YAG spectrum, with characteristic chromium R lines present due to the formation of corundum at 1200 °C with trace chromium content. The same procedure was performed to synthesize a Ce:YAG/Cr:Al2O3 nanocomposite, yielding photoluminescence of both the expected Ce:YAG and Cr:Al2O3 peaks as well as clear evidence of energy transfer between Ce and Cr centers in YAG. The luminescence of these composites was used to determine their CIE colour co-ordinates. It was found that the colour profile of the resulting emission may be tuned by adjusting the Cr content and annealing conditions of the composite materials.

Thermal Stability of NaxCrO2 for Rechargeable Sodium Batteries; Studies by High-Temperature Synchrotron X-ray Diffraction.

PubMed

Yabuuchi, Naoaki; Ikeuchi, Issei; Kubota, Kei; Komaba, Shinichi

2016-11-30

Thermal stability and phase transition processes of NaCrO 2 and Na 0.5 CrO 2 are carefully examined by high-temperature synchrotron X-ray diffraction method. O3-type NaCrO 2 shows anisotropic thermal expansion on heating, which is a common character as layered materials, without phase transition in the temperature range of 27-527 °C. In contrast, for the desodiated phase, in-plane distorted P3-type layered oxide (P'3 Na 0.5 CrO 2 ), phase transition occurs in the following order. Monoclinic distortion associated with Na/vacancy ordering is gradually lost on heating, and its symmetry increases and changes to a rhombohedral lattice at 207 °C. On further heating, phase segregation to two P3 layered metastable phases, which have different interlayer distances (17.0 and 13.5 Å, presumably sodium-rich and sodium-free P3 phases, respectively) are observed on heating to 287-477 °C, but oxygen loss is not observed. Oxygen loss is observed at temperatures only above 500 °C, resulting in the formation of corundum-type Cr 2 O 3 and O3 NaCrO 2 as thermodynamically stable phases. From these results, possibility of Na x CrO 2 as a positive electrode material for safe rechargeable sodium batteries is also discussed.

Quantitative comparisons of analogue models of brittle wedge dynamics

NASA Astrophysics Data System (ADS)

Schreurs, Guido

2010-05-01

Analogue model experiments are widely used to gain insights into the evolution of geological structures. In this study, we present a direct comparison of experimental results of 14 analogue modelling laboratories using prescribed set-ups. A quantitative analysis of the results will document the variability among models and will allow an appraisal of reproducibility and limits of interpretation. This has direct implications for comparisons between structures in analogue models and natural field examples. All laboratories used the same frictional analogue materials (quartz and corundum sand) and prescribed model-building techniques (sieving and levelling). Although each laboratory used its own experimental apparatus, the same type of self-adhesive foil was used to cover the base and all the walls of the experimental apparatus in order to guarantee identical boundary conditions (i.e. identical shear stresses at the base and walls). Three experimental set-ups using only brittle frictional materials were examined. In each of the three set-ups the model was shortened by a vertical wall, which moved with respect to the fixed base and the three remaining sidewalls. The minimum width of the model (dimension parallel to mobile wall) was also prescribed. In the first experimental set-up, a quartz sand wedge with a surface slope of ˜20° was pushed by a mobile wall. All models conformed to the critical taper theory, maintained a stable surface slope and did not show internal deformation. In the next two experimental set-ups, a horizontal sand pack consisting of alternating quartz sand and corundum sand layers was shortened from one side by the mobile wall. In one of the set-ups a thin rigid sheet covered part of the model base and was attached to the mobile wall (i.e. a basal velocity discontinuity distant from the mobile wall). In the other set-up a basal rigid sheet was absent and the basal velocity discontinuity was located at the mobile wall. In both types of experiments, models accommodated initial shortening by a forward- and a backward-verging thrust. Further shortening was taken up by in-sequence formation of forward-verging thrusts. In all experiments, boundary stresses created significant drag of structures along the sidewalls. We therefore compared the surface slope and the location, dip angle and spacing of thrusts in sections through the central part of the model. All models show very similar cross-sectional evolutions demonstrating reproducibility of first-order experimental observations. Nevertheless, there are significant along-strike variations of structures in map view highlighting the limits of interpretations of analogue model results. These variations may be related to the human factor, differences in model width and/or differences in laboratory temperature and especially humidity affecting the mechanical properties of the granular materials. GeoMod2008 Analogue Team: Susanne Buiter, Caroline Burberry, Jean-Paul Callot, Cristian Cavozzi, Mariano Cerca, Ernesto Cristallini, Alexander Cruden, Jian-Hong Chen, Leonardo Cruz, Jean-Marc Daniel, Victor H. Garcia, Caroline Gomes, Céline Grall, Cecilia Guzmán, Triyani Nur Hidayah, George Hilley, Chia-Yu Lu, Matthias Klinkmüller, Hemin Koyi, Jenny Macauley, Bertrand Maillot, Catherine Meriaux, Faramarz Nilfouroushan, Chang-Chih Pan, Daniel Pillot, Rodrigo Portillo, Matthias Rosenau, Wouter P. Schellart, Roy Schlische, Andy Take, Bruno Vendeville, Matteo Vettori, M. Vergnaud, Shih-Hsien Wang, Martha Withjack, Daniel Yagupsky, Yasuhiro Yamada

Interaction of SO2 and CO with the Ti2O3(101¯2) surface

NASA Astrophysics Data System (ADS)

Smith, Kevin E.; Henrich, Victor E.

1985-10-01

The interaction of sulfur dioxide with the nearly perfect (101¯2) surface of the corundum transition-metal oxide Ti2O3 has been studied using ultraviolet and x-ray photoemission spectroscopies and low-energy electron diffraction. The reaction of SO2 with Ti2O3 is found to be extremely vigorous, with SO2 adsorbing dissociatively and catalyzing the complete oxidation of the surface to TiO2 and TiS2. This result is significant since exposure to large amounts of O2 does not result in the production of large amounts of TiO2 at the Ti2O3 surface. Dissociative adsorption of SO2 continues for exposures up to at least 104 L (1 L=10-6Torr sec). The reaction is accompanied by large scale surface disorder and by an increase in the work function of 1.32 eV. In contrast, CO adsorbs molecularly for exposures >=105 L, with an extramolecular relaxation-polarization shift of 3.0 eV. For CO exposures <=104 L, the chemisorption mechanism is tentatively identified as dissociative adsorption at defect sites. Inclusive of this study, the interaction of four oxygen-containing molecules (SO2, CO, H2O, and O2) with Ti2O3(101¯2) surfaces has been studied, and their behavior is compared and trends isolated with a view to understanding the oxidation of Ti2O3.

Microstructure, Mechanical and Surface Morphological Properties of Al5Ti5Cr Master Alloy as Friction Material Prepared by Stir Die Casting

NASA Astrophysics Data System (ADS)

Ahmed, Syed Faisal; Srivastava, Sanjay; Agarwal, Alka Bani

2018-04-01

Metal matrix composite offers outstanding properties for better performance of disc brakes. In the present study, the composite of AlTiCr master alloy was prepared by stir die casting method. The developed material was reinforced with (0-10 wt%) silicon carbide (SiC) and boron carbide (B4C). The effects of SiC reinforcement from 0 to 10 wt% on mechanical, microstructure and surface morphological properties of Al MMC was investigated and compared with B4C reinforcement. Physical properties like density and micro Vickers hardness number show an increasing trend with an increase in the percentage of SiC and B4C reinforcement. Mechanical properties viz. UTS, yield strength and percentage of elongation are improved with increasing the fraction of reinforcement. The surface morphology and phase were identified from scanning electron microscopy (SEM) and X-ray diffraction analysis and the oxidized product formed during the casting was investigated by Fourier transformation infrared spectroscopy. This confirms the presence of crystallization of corundum (α-Al2O3) in small traces as one of the alumina phases, within casting sample. Micro-structural characterization by SEM depicted that the particles tend to be more agglomerated more and more with the percentage of the reinforcement. The AFM results reveal that the surface roughness value shows a decreasing trend with SiC reinforcement while roughness increases with increase the percentage of B4C.

Muon Sites in Transition Metal Oxides.

NASA Astrophysics Data System (ADS)

Chan, Kwaichow Benjamin

Muon behavior in a selected series of transition -metal oxides has been investigated by the Muon Spin Rotation (muSR) technique. The materials studied are the corundum structured oxides (M_2 O_3: M = Fe, Cr, V, Ti) and the high-Tc superconducting oxides in Y-Ba-Cu-O system. The muon is first implanted into the oxide crystalline and its subsequent behavior in the presence of magnetic field is monitored through counting the positron emitted by the decayed muon. The muon is found to behave like a free muon and to become localized at low temperatures and diffusional at higher temperatures. The location of the muon is important for interpreting the muSR data. To identify muon sites, a combination of electrostatic potential and magnetic dipolar field calculation is used. Dipole -field calculation allows matching the experimental results to the calculated values if the origin of the magnetic field is dominantly dipolar as in the case of V _2O_3 and Cr _2O_3. In the potential model, in addition to the coulombic interaction, the muon is assumed to form a muon-oxygen bond in analogy to the hydroxyl bond (OH)^-. Morse potential is used to simulate the mu^+ -O^= bonding. The potential minima found are then assigned as muon sites. A set of muon sites thus found in these oxides are their implications are presented. The inadequacies of the classical model and a more realistic model for predicting muon sites are also discussed.

Additive manufacturing of tools for lapping glass

NASA Astrophysics Data System (ADS)

Williams, Wesley B.

2013-09-01

Additive manufacturing technologies have the ability to directly produce parts with complex geometries without the need for secondary processes, tooling or fixtures. This ability was used to produce concave lapping tools with a VFlash 3D printer from 3D Systems. The lapping tools were first designed in Creo Parametric with a defined constant radius and radial groove pattern. The models were converted to stereolithography files which the VFlash used in building the parts, layer by layer, from a UV curable resin. The tools were rotated at 60 rpm and used with 120 grit and 220 grit silicon carbide lapping paste to lap 0.750" diameter fused silica workpieces. The samples developed a matte appearance on the lapped surface that started as a ring at the edge of the workpiece and expanded to the center. This indicated that as material was removed, the workpiece radius was beginning to match the tool radius. The workpieces were then cleaned and lapped on a second tool (with equivalent geometry) using a 3000 grit corundum aluminum oxide lapping paste, until a near specular surface was achieved. By using lapping tools that have been additively manufactured, fused silica workpieces can be lapped to approach a specified convex geometry. This approach may enable more rapid lapping of near net shape workpieces that minimize the material removal required by subsequent polishing. This research may also enable development of new lapping tool geometry and groove patterns for improved loose abrasive finishing.

Microwave dielectric properties of CaCu3Ti4O12-Al2O3 composite

NASA Astrophysics Data System (ADS)

Rahman, Mohd Fariz Ab; Abu, Mohamad Johari; Karim, Saniah Ab; Zaman, Rosyaini Afindi; Ain, Mohd Fadzil; Ahmad, Zainal Arifin; Mohamed, Julie Juliewatty

2016-07-01

(1-x)CaCu3Ti4O12 + (x)Al2O3 composite (0 ≤ x ≤0.25) was prepared via conventional solid-state reaction method. The fabrication of sample was started with synthesizing stoichiometric CCTO from CaCO3, CuO and TiO2 powders, then wet-mixed in deionized water for 24 h. The process was continued with calcined CCTO powder at 900 °C for 12 h before sintered at 1040 °C for 10 h. Next, the calcined CCTO powder with different amount of Al2O3 were mixed for 24 h, then palletized and sintered at 1040 °C for 10. X-ray diffraction analysis on the sintered samples showed that CCTO powder was in a single phase, meanwhile the trace of secondary peaks which belong to CaAl2O4 and Corundum (Al2O3) could be observed in the other samples Scanning electron microscopy analysis showed that the grain size of the sample is firstly increased with addition of Al2O3 (x = 0.01), then become smaller with the x > 0.01. Microwave dielectric properties showed that the addition of Al2O3 (x = 0.01) was remarkably reduced the dielectric loss while slightly increased the dielectric permittivity. However, further addition of Al2O3 was reduced both dielectric loss and permittivity at least for an order of magnitude.

Fabrication and characterization of fine ceramic based on alumina, bentonite, and glass bead

NASA Astrophysics Data System (ADS)

Sebayang, P.; Nurdina; Simbolon, S.; Kurniawan, C.; Yunus, M.; Setiadi, E. A.; Sitorus, Z.

2018-03-01

Fabrication of fine ceramics based on alumina, bentonite and glass bead has been carried out by powder metallurgy. The preparation of powder has been performed using High Energy Milling (HEM) with wet milling process and using toluene as medium for 2 hours. The powder milling result was dried in oven at 100 °C for 24 hours. After that, the powder was compacted into pellet by using hydraulic press with 80 kgf/cm2 pressure at room temperature. Then, the pellet was sintered at 900 °C for 4 hours. Materials characterization such as physical properties (true density, bulk density, porosity, and water absorption), average particle diameter, hardness, microstructure and phase were measured by Archimedes method, Particle Size Analyzer (PSA), Hardness Vickers (HV), Scanning Electron Microscope (SEM-EDX) and X-Ray Diffraction (XRD). From the result, the optimum condition is sample D (with addition of 30 wt.% γ-Al2O3) with sintering temperature of 900 °C for 4 hours. At this condition, these properties were measured: average particle diameter of 4.27 μm, true density of 2.32 g/cm3, porosity of 5.57%, water absorption of 2.46%, bulk density of 2.39 g/cm3, and hardness of 632 HV. The fine ceramic has four phases with albite (Al2NaO8Si3) and quartz (SiO2) as dominant phases and corundum (Al2O3) and nepheline (AlNaO4Si) as minor phases.

Addressing the amorphous content issue in quantitative phase analysis: the certification of NIST standard reference material 676a.

PubMed

Cline, James P; Von Dreele, Robert B; Winburn, Ryan; Stephens, Peter W; Filliben, James J

2011-07-01

A non-diffracting surface layer exists at any boundary of a crystal and can comprise a mass fraction of several percent in a finely divided solid. This has led to the long-standing issue of amorphous content in standards for quantitative phase analysis (QPA). NIST standard reference material (SRM) 676a is a corundum (α-Al(2)O(3)) powder, certified with respect to phase purity for use as an internal standard in powder diffraction QPA. The amorphous content of SRM 676a is determined by comparing diffraction data from mixtures with samples of silicon powders that were engineered to vary their specific surface area. Under the (supported) assumption that the thickness of an amorphous surface layer on Si was invariant, this provided a method to control the crystalline/amorphous ratio of the silicon components of 50/50 weight mixtures of SRM 676a with silicon. Powder diffraction experiments utilizing neutron time-of-flight and 25 keV and 67 keV X-ray energies quantified the crystalline phase fractions from a series of specimens. Results from Rietveld analyses, which included a model for extinction effects in the silicon, of these data were extrapolated to the limit of zero amorphous content of the Si powder. The certified phase purity of SRM 676a is 99.02% ± 1.11% (95% confidence interval). This novel certification method permits quantification of amorphous content for any sample of interest, by spiking with SRM 676a.

Identification of an interstellar oxide grain from the Murchison meteorite by ion imaging

NASA Technical Reports Server (NTRS)

Nittler, L. R.; Walker, R. M.; Zinner, E.; Hoppe, P.; Lewis, R. S.

1993-01-01

We report here the first use of a new ion-imaging system to locate a rare interstellar aluminum oxide grain in a Murchison acid residue. While several types of carbon-rich interstellar grains, including graphite, diamond, SiC, and TiC, have previously been found, isotopically anomalous interstellar oxide grains have proven more elusive. We have developed an ion imaging system which allows us to map the isotopic composition of large numbers of grains relatively quickly and is, thus, ideally suited to search for isotopically exotic subsets of grains. The system consists of a PHOTOMETRICS CCD camera coupled to the microchannel plate/fluorescent screen of the WU modified CAMECA IMS-3F ion microprobe. Isotopic images of the sample surface are focused on the CCD and digitized. Subsequent image processing identifies individual grains in the images and determines isotopic ratios for each. For the present work, we have imaged in O-16 and O-18; negligible contributions of (17)OH(-) and (16)OH2(-) signals to the O-18 signal allow the use of low mass resolution, simplifying the measurements. Repeated imaging runs on terrestrial corundum particles showed that the system measures isotopic ratios reproducibly to about +/- 40%. Each imaging run took about six minutes to complete, and for this study there were on average 5-15 grains in each image. We have conducted imaging searches in 2-4 micron size separates of both Orgueil and Murchison.

Petrogenesis of alkaline basalt-hosted sapphire megacrysts. Petrological and geochemical investigations of in situ sapphire occurrences from the Siebengebirge Volcanic Field, Germany

NASA Astrophysics Data System (ADS)

Baldwin, L. C.; Tomaschek, F.; Ballhaus, C.; Gerdes, A.; Fonseca, R. O. C.; Wirth, R.; Geisler, T.; Nagel, T.

2017-06-01

Megacrystic sapphires are frequently associated with alkaline basalts, most notably in Asia and Australia, although basalt is not generally normative in corundum. Most of these sapphire occurrences are located in alluvial or eluvial deposits, making it difficult to study the enigmatic relationship between the sapphires and their host rocks. Here, we present detailed petrological and geochemical investigations of in situ megacrystic sapphires within alkaline basalts from the Cenozoic Siebengebirge Volcanic Field (SVF) in Germany. Markedly, the sapphires show several micrometer thick spinel coronas at the contact with the host basalt, indicating chemical disequilibrium between the sapphire and the basaltic melt, supporting a xenogenetic relationship. However, in situ U-Pb dating of a Columbite Group inclusion within one Siebengebirge sapphire using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) indicates a close genetic relationship between sapphire crystallization and alkaline mafic volcanism in the SVF. The syngenetic mineral inclusion suite including carbonates, members of the Pyrochlore, Betafite and Columbite Groupe minerals, as well as a high abundance of HFSE and of gaseous low-density CO2 inclusions support a parentage of a highly evolved, MgO and FeO deficient carbonatitic melt. We identified CO2 to be the link between alkaline basaltic volcanism and the xenocrystic sapphires. Only alkaline volcanic suites can build up enough CO2 in this magma chamber upon fractionation so that at high degrees of fractionation a carbonatitic melt exsolves which in turn can crystallize sapphires.

Addressing the amorphous content issue in quantitative phase analysis : the certification of NIST SRM 676a.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cline, J. P.; Von Dreele, R. B.; Winburn, R.

2011-07-01

A non-diffracting surface layer exists at any boundary of a crystal and can comprise a mass fraction of several percent in a finely divided solid. This has led to the long-standing issue of amorphous content in standards for quantitative phase analysis (QPA). NIST standard reference material (SRM) 676a is a corundum ({alpha}-Al{sub 2}O{sub 3}) powder, certified with respect to phase purity for use as an internal standard in powder diffraction QPA. The amorphous content of SRM 676a is determined by comparing diffraction data from mixtures with samples of silicon powders that were engineered to vary their specific surface area. Undermore » the (supported) assumption that the thickness of an amorphous surface layer on Si was invariant, this provided a method to control the crystalline/amorphous ratio of the silicon components of 50/50 weight mixtures of SRM 676a with silicon. Powder diffraction experiments utilizing neutron time-of-flight and 25 keV and 67 keV X-ray energies quantified the crystalline phase fractions from a series of specimens. Results from Rietveld analyses, which included a model for extinction effects in the silicon, of these data were extrapolated to the limit of zero amorphous content of the Si powder. The certified phase purity of SRM 676a is 99.02% {+-} 1.11% (95% confidence interval). This novel certification method permits quantification of amorphous content for any sample of interest, by spiking with SRM 676a.« less

Biomechanical evaluation of bone screw fixation with a novel bone cement.

PubMed

Juvonen, Tiina; Nuutinen, Juha-Pekka; Koistinen, Arto P; Kröger, Heikki; Lappalainen, Reijo

2015-07-30

Bone cement augmentation is commonly used to improve the fixation stability of orthopaedic implants in osteoporotic bone. The aim of this study was to evaluate the effect of novel bone cements on the stability of bone screw fixation by biomechanical testing and to compare them with a conventional Simplex(®)P bone cement and requirements of the standards. Basic biomechanical properties were compared with standard tests. Adhesion of bone cements were tested with polished, glass blasted and corundum blasted stainless steel surfaces. Screw pullout testing with/without cement was carried out using a synthetic bone model and cancellous and cortical bone screws. All the tested bone cements fulfilled the requirements of the standard for biomechanical properties and improved the screw fixation stability. Even a threefold increase in shear and tensile strength was achieved with increasing surface roughness. The augmentation improved the screw pullout force compared to fixation without augmentation, 1.2-5.7 times depending on the cement and the screw type. The good biomechanical properties of novel bone cement for osteoporotic bone were confirmed by experimental testing. Medium viscosity of the bone cements allowed easy handling and well-controlled penetration of bone cement into osteoporotic bone. By proper parameters and procedures it is possible to achieve biomechanically stable fixation in osteoporotic bone. Based on this study, novel biostable bone cements are very potential biomaterials to enhance bone screw fixation in osteoporotic bone. Novel bone cement is easy to use without hand mixing using a dual syringe and thus makes it possibility to use it as required during the operation.

Development of phase analysis methods of impurity elements in alloys based on iron and nickel

NASA Astrophysics Data System (ADS)

Andreeva, N. A.; Anuchkin, S. N.; Volchenkova, V. A.; Kazenas, E. K.; Penkina, T. N.; Fomina, A. A.

2018-04-01

Using the method of AES with ICP, new methods have been developed for quantifying the content of various forms of existence of impurity elements: Al-Al2O3; Zr-ZrO2 in alloys based on iron (Fe-Sn) and nickel (Ni-Sn). Open systems were used to dissolve Al and Zr. To translate difficult-to-open aluminum oxides (corundum) and zirconium oxide (baddeleyite) into the solution, accelerated techniques were developed using the microwave system Mars 5. To confirm the completeness of the dissolution of oxides, a classical scheme of alloy fusion with alkali metal salts was used. Optimal analytical parameters for determining the elements: Al and Zr were chosen. The influence of matrix elements (iron and nickel) and methods of its elimination were studied. This made it possible to determine the elements in a wide concentration range from 1 • 10-3 to n% Al and from 1 • 10-4 to n% Zr without preliminary separation of the matrix with good metrological characteristics. The relative standard deviation (Sr) does not exceed 0,2. The separate determination of the contents of aluminum and aluminium oxide in the model melt of Fe-Sn-Al2O3 and zirconium and zirconium oxide in the Ni-Sn-ZrO2 model melt allowed us to estimate the number of nanoparticles participating in the heterophase interaction with tin and retired to the interface in the form of ensembles and the number of nanoparticles present in the melt and affecting the crystallization process and the structure of the metal.

Addressing the Amorphous Content Issue in Quantitative Phase Analysis: The Certification of NIST Standard Reference Material 676a

DOE Office of Scientific and Technical Information (OSTI.GOV)

J Cline; R Von Dreele; R Winburn

2011-12-31

A non-diffracting surface layer exists at any boundary of a crystal and can comprise a mass fraction of several percent in a finely divided solid. This has led to the long-standing issue of amorphous content in standards for quantitative phase analysis (QPA). NIST standard reference material (SRM) 676a is a corundum ({alpha}-Al{sub 2}O{sub 3}) powder, certified with respect to phase purity for use as an internal standard in powder diffraction QPA. The amorphous content of SRM 676a is determined by comparing diffraction data from mixtures with samples of silicon powders that were engineered to vary their specific surface area. Undermore » the (supported) assumption that the thickness of an amorphous surface layer on Si was invariant, this provided a method to control the crystalline/amorphous ratio of the silicon components of 50/50 weight mixtures of SRM 676a with silicon. Powder diffraction experiments utilizing neutron time-of-flight and 25 keV and 67 keV X-ray energies quantified the crystalline phase fractions from a series of specimens. Results from Rietveld analyses, which included a model for extinction effects in the silicon, of these data were extrapolated to the limit of zero amorphous content of the Si powder. The certified phase purity of SRM 676a is 99.02% {+-} 1.11% (95% confidence interval). This novel certification method permits quantification of amorphous content for any sample of interest, by spiking with SRM 676a.« less

Formation of crystalline Zn-Al layered double hydroxide precipitates on γ-alumina: the role of mineral dissolution.

PubMed

Li, Wei; Livi, Kenneth J T; Xu, Wenqian; Siebecker, Matthew G; Wang, Yujun; Phillips, Brian L; Sparks, Donald L

2012-11-06

To better understand the sequestration of toxic metals such as nickel (Ni), zinc (Zn), and cobalt (Co) as layered double hydroxide (LDH) phases in soils, we systematically examined the presence of Al and the role of mineral dissolution during Zn sorption/precipitation on γ-Al(2)O(3) (γ-alumina) at pH 7.5 using extended X-ray absorption fine structure spectroscopy (EXAFS), high-resolution transmission electron microscopy (HR-TEM), synchrotron-radiation powder X-ray diffraction (SR-XRD), and (27)Al solid-state NMR. The EXAFS analysis indicates the formation of Zn-Al LDH precipitates at Zn concentration ≥0.4 mM, and both HR-TEM and SR-XRD reveal that these precipitates are crystalline. These precipitates yield a small shoulder at δ(Al-27) = +12.5 ppm in the (27)Al solid-state NMR spectra, consistent with the mixed octahedral Al/Zn chemical environment in typical Zn-Al LDHs. The NMR analysis provides direct evidence for the existence of Al in the precipitates and the migration from the dissolution of γ-alumina substrate. To further address this issue, we compared the Zn sorption mechanism on a series of Al (hydr)oxides with similar chemical composition but differing dissolubility using EXAFS and TEM. These results suggest that, under the same experimental conditions, Zn-Al LDH precipitates formed on γ-alumina and corundum but not on less soluble minerals such as bayerite, boehmite, and gibbsite, which point outs that substrate mineral surface dissolution plays an important role in the formation of Zn-Al LDH precipitates.

Growth of tourmaline single crystals containing transition metal elements in hydrothermal solutions

NASA Astrophysics Data System (ADS)

Setkova, Tatiana; Shapovalov, Yury; Balitsky, Vladimir

2011-03-01

Interest in the growth of tourmaline single crystals is based on the promising piezoelectric and pyroelectric properties of this material compared to quartz crystals currently in use. Moreover, synthetic tourmaline can be used as a substitute for the natural stone in the jewelry industry similar to other synthetic analogues of gemstones. Single crystals of colored Co-, Ni-, Fe-, (Ni,Cr)-, (Ni,Fe)-, and (Co,Ni,Cr)-containing tourmalines with concentration of transition metal elements up to 16 wt% on a seed have been grown from complex boron-containing hydrothermal solutions at a range of temperatures 400-750 °C and pressures 100 MPa. Experiments were conducted under conditions of a thermal gradient in titanium and chromium-nickel autoclaves. Tourmaline growth on a seed crystal occurs only if separate tourmaline-forming components (monocrystalline corundum and quartz bars) are used as charge. All tourmalines specified above grow in analogous (+) direction of the optical axis with a speed of 0.05 mm/day by faces of the trigonal pyramid, except tourmalines containing chromium. They grow in analogous (+0001) direction with a speed 0.05 mm/day, and in antilogous (-0001) direction with a speed of 0.01 mm/day by faces of the trigonal pyramid and in prism direction with a speed of 0.001 mm/day. Along with the large single crystals, a great amount of finest (30-150 μm in size) tourmaline crystals was formed during the runs by spontaneous nucleation both on the surface of the seed crystals and in the charge.

A Ga2O3 underlayer as an isomorphic template for ultrathin hematite films toward efficient photoelectrochemical water splitting.

PubMed

Hisatomi, Takashi; Brillet, Jérémie; Cornuz, Maurin; Le Formal, Florian; Tétreault, Nicolas; Sivula, Kevin; Grätzel, Michael

2012-01-01

Hematite photoanodes for photoelectrochemical (PEC) water splitting are often fabricated as extremely-thin films to minimize charge recombination because of the short diffusion lengths of photoexcited carriers. However, poor crystallinity caused by structural interaction with a substrate negates the potential of ultrathin hematite photoanodes. This study demonstrates that ultrathin Ga2O3 underlayers, which were deposited on conducting substrates prior to hematite layers by atomic layer deposition, served as an isomorphic (corundum-type) structural template for ultrathin hematite and improved the photocurrent onset of PEC water splitting by 0.2 V. The benefit from Ga2O3 underlayers was most pronounced when the thickness of the underlayer was approximately 2 nm. Thinner underlayers did not work effectively as a template presumably because of insufficient crystallinity of the underlayer, while thicker ones diminished the PEC performance of hematite because the underlayer prevented electron injection from hematite to a conductive substrate due to the large conduction band offset. The enhancement of PEC performance by a Ga2O3 underlayer was more significant for thinner hematite layers owing to greater margins for improving the crystallinity of ultrathin hematite. It was confirmed that a Ga2O3 underlayer was applicable to a rough conducting substrate loaded with Sb-doped SnO2 nanoparticles, improving the photocurrent by a factor of 1.4. Accordingly, a Ga2O3 underlayer could push forward the development of host-guest-type nanocomposites consisting of highly-rough substrates and extremely-thin hematite absorbers.

First-Principles Study on the Thermal Stability of LiNiO2 Materials Coated by Amorphous Al2O3 with Atomic Layer Thickness.

PubMed

Kang, Joonhee; Han, Byungchan

2015-06-03

Using first-principles calculations, we study how to enhance thermal stability of high Ni compositional cathodes in Li-ion battery application. Using the archetype material LiNiO2 (LNO), we identify that ultrathin coating of Al2O3 (0001) on LNO(012) surface, which is the Li de-/intercalation channel, substantially improves the instability problem. Density functional theory calculations indicate that the Al2O3 deposits show phase transition from the corundum-type crystalline (c-Al2O3) to amorphous (a-Al2O3) structures as the number of coating layers reaches three. Ab initio molecular dynamic simulations on the LNO(012) surface coated by a-Al2O3 (about 0.88 nm) with three atomic layers oxygen gas evolution is strongly suppressed at T=400 K. We find that the underlying mechanism is the strong contacting force at the interface between LNO(012) and Al2O3 deposits, which, in turn, originated from highly ionic chemical bonding of Al and O at the interface. Furthermore, we identify that thermodynamic stability of the a-Al2O3 is even more enhanced with Li in the layer, implying that the protection for the LNO(012) surface by the coating layer is meaningful over the charging process. Our approach contributes to the design of innovative cathode materials with not only high-energy capacity but also long-term thermal and electrochemical stability applicable for a variety of electrochemical energy devices including Li-ion batteries.

Very high-temperature impact melt products as evidence for cosmic airbursts and impacts 12,900 years ago.

PubMed

Bunch, Ted E; Hermes, Robert E; Moore, Andrew M T; Kennett, Douglas J; Weaver, James C; Wittke, James H; DeCarli, Paul S; Bischoff, James L; Hillman, Gordon C; Howard, George A; Kimbel, David R; Kletetschka, Gunther; Lipo, Carl P; Sakai, Sachiko; Revay, Zsolt; West, Allen; Firestone, Richard B; Kennett, James P

2012-07-10

It has been proposed that fragments of an asteroid or comet impacted Earth, deposited silica- and iron-rich microspherules and other proxies across several continents, and triggered the Younger Dryas cooling episode 12,900 years ago. Although many independent groups have confirmed the impact evidence, the hypothesis remains controversial because some groups have failed to do so. We examined sediment sequences from 18 dated Younger Dryas boundary (YDB) sites across three continents (North America, Europe, and Asia), spanning 12,000 km around nearly one-third of the planet. All sites display abundant microspherules in the YDB with none or few above and below. In addition, three sites (Abu Hureyra, Syria; Melrose, Pennsylvania; and Blackville, South Carolina) display vesicular, high-temperature, siliceous scoria-like objects, or SLOs, that match the spherules geochemically. We compared YDB objects with melt products from a known cosmic impact (Meteor Crater, Arizona) and from the 1945 Trinity nuclear airburst in Socorro, New Mexico, and found that all of these high-energy events produced material that is geochemically and morphologically comparable, including: (i) high-temperature, rapidly quenched microspherules and SLOs; (ii) corundum, mullite, and suessite (Fe(3)Si), a rare meteoritic mineral that forms under high temperatures; (iii) melted SiO(2) glass, or lechatelierite, with flow textures (or schlieren) that form at > 2,200 °C; and (iv) particles with features indicative of high-energy interparticle collisions. These results are inconsistent with anthropogenic, volcanic, authigenic, and cosmic materials, yet consistent with cosmic ejecta, supporting the hypothesis of extraterrestrial airbursts/impacts 12,900 years ago. The wide geographic distribution of SLOs is consistent with multiple impactors.

Acid Sulfate Weathering on Mars: Results from the Mars Exploration Rover Mission

NASA Technical Reports Server (NTRS)

Ming, Douglas W.; Morris, R. V.; Golden, D. C.

2006-01-01

Sulfur has played a major role in the formation and alteration of outcrops, rocks, and soils at the Mars Exploration Rover landing sites on Meridiani Planum and in Gusev crater. Jarosite, hematite, and evaporite sulfates (e.g., Mg and Ca sulfates) occur along with siliciclastic sediments in outcrops at Meridiani Planum. The occurrence of jarosite is a strong indicator for an acid sulfate weathering environment at Meridiani Planum. Some outcrops and rocks in the Columbia Hills in Gusev crater appear to be extensively altered as suggested by their relative softness as compared to crater floor basalts, high Fe(3+)/FeT, iron mineralogy dominated by nanophase Fe(3+) oxides, hematite and/or goethite, corundum-normative mineralogies, and the presence of Mg- and Casulfates. One scenario for aqueous alteration of these rocks and outcrops is that vapors and/or fluids rich in SO2 (volcanic source) and water interacted with rocks that were basaltic in bulk composition. Ferric-, Mg-, and Ca-sulfates, phosphates, and amorphous Si occur in several high albedo soils disturbed by the rover's wheels in the Columbia Hills. The mineralogy of these materials suggests the movement of liquid water within the host material and the subsequent evaporation of solutions rich in Fe, Mg, Ca, S, P, and Si. The presence of ferric sulfates suggests that these phases precipitated from highly oxidized, low-pH solutions. Several hypotheses that invoke acid sulfate weathering environments have been suggested for the aqueous formation of sulfate-bearing phases on the surface of Mars including (1) the oxidative weathering of ultramafic igneous rocks containing sulfides; (2) sulfuric acid weathering of basaltic materials by solutions enriched by volcanic gases (e.g., SO2); and (3) acid fog (i.e., vapors rich in H2SO4) weathering of basaltic or basaltic-derived materials.

Copper stabilization via spinel formation during the sintering of simulated copper-laden sludge with aluminum-rich ceramic precursors.

PubMed

Tang, Yuanyuan; Chui, Stephen Sin-Yin; Shih, Kaimin; Zhang, Lingru

2011-04-15

The feasibility of incorporating copper-laden sludge into low-cost ceramic products, such as construction ceramics, was investigated by sintering simulated copper-laden sludge with four aluminum-rich ceramic precursors. The results indicated that all of these precursors (γ-Al(2)O(3), corundum, kaolinite, mullite) could crystallochemically stabilize the hazardous copper in the more durable copper aluminate spinel (CuAl(2)O(4)) structure. To simulate the process of copper transformation into a spinel structure, CuO was mixed with the four aluminum-rich precursors, and fired at 650-1150 °C for 3 h. The products were examined using powder X-ray diffraction (XRD) and scanning electron microscopic techniques. The efficiency of copper transformation among crystalline phases was quantitatively determined through Rietveld refinement analysis of the XRD data. The sintering experiment revealed that the optimal sintering temperature for CuAl(2)O(4) formation was around 1000 °C and that the efficiency of copper incorporation into the crystalline CuAl(2)O(4) structure after 3 h of sintering ranged from 40 to 95%, depending on the type of aluminum precursor used. Prolonged leaching tests were carried out by using acetic acid with an initial pH value of 2.9 to leach CuO and CuAl(2)O(4) samples for 22 d. The sample leachability analysis revealed that the CuAl(2)O(4) spinel structure was more superior to stabilize copper, and suggested a promising and reliable technique for incorporating copper-laden sludge or its incineration ash into usable ceramic products. Such results also demonstrated the potential of a waste-to-resource strategy by using waste materials as part of the raw materials with the attainable temperature range used in the production of ceramics.

Ferromagnetism and semiconducting of boron nanowires

PubMed Central

2012-01-01

More recently, motivated by extensively technical applications of carbon nanostructures, there is a growing interest in exploring novel non-carbon nanostructures. As the nearest neighbor of carbon in the periodic table, boron has exceptional properties of low volatility and high melting point and is stronger than steel, harder than corundum, and lighter than aluminum. Boron nanostructures thus are expected to have broad applications in various circumstances. In this contribution, we have performed a systematical study of the stability and electronic and magnetic properties of boron nanowires using the spin-polarized density functional calculations. Our calculations have revealed that there are six stable configurations of boron nanowires obtained by growing along different base vectors from the unit cell of the bulk α-rhombohedral boron (α-B) and β-rhombohedral boron (β-B). Well known, the boron bulk is usually metallic without magnetism. However, theoretical results about the magnetic and electronic properties showed that, whether for the α-B-based or the β-B-based nanowires, their magnetism is dependent on the growing direction. When the boron nanowires grow along the base vector [001], they exhibit ferromagnetism and have the magnetic moments of 1.98 and 2.62 μB, respectively, for the α-c [001] and β-c [001] directions. Electronically, when the boron nanowire grows along the α-c [001] direction, it shows semiconducting and has the direct bandgap of 0.19 eV. These results showed that boron nanowires possess the unique direction dependence of the magnetic and semiconducting behaviors, which are distinctly different from that of the bulk boron. Therefore, these theoretical findings would bring boron nanowires to have many promising applications that are novel for the boron bulk. PMID:23244063

The mineralogical and chronological evidences of subducted continent material in deep mantle: diamond, zircon and rutile separated from the Horoman peridotite of Japan

NASA Astrophysics Data System (ADS)

Li, Y.; Yang, J.; Nida, K.; Yamamoto, S.; Lin, Y.; Li, Q.; Tian, M.; Kon, Y.; Komiya, T.; Maruyama, S.

2017-12-01

The Horoman peridotite complex is an Alpine-type orogenic lherzolite massif of upper-mantle in the Hidaka metamorphic belt, Hokkaido, Japan. The peridotite complex is composed of dunite, harzburgite, spinel lherzolite and plagioclase lherzolite, exhibits a conspicuous layered structure, which is a product of a Cretaceous to early Paleogene arc-trench system formed by westward subduction of an oceanic plate between the paleo-Eurasian and paleo-North American Plates. Various combinations of diamond, corundum, moissanite, zircon, monazite, rutile, and kyanite have been separated from spinel harzburgite (700 kg) and lherzolite (500 kg), respectively. The carbon isotopes analyses of diamond grains by Nano-SIMS yielded significant light carbon isotopes feature as δ13 CPDB values ranging from -29.2 ‰ to -17.2 ‰, with an average of -22.8±0.32 ‰. Zircon grains occur as sub-angular to round in morphological characteristics, similar to zircons of crustal sedimentary rocks. Many zircons contain small inclusions, comprise of quartz, apatite, rutile and muscovite. The U-Pb age of zircon grains analyzed using LA-ICP-MS and SIMS gave a wide age range, from the Jurassic to Archean (ca 159 - 3131 Ma). In the zircon age histogram, four age groups were identified; the age peaks are 2385 Ma, 1890 Ma, 1618 Ma and 1212 Ma, respectively. On the other hand, U-Pb ages of rutile grains analyzed using SIMS gave a peak of 370 Ma in age histogram. The mineralogical and chronological evidences of numerous crustal minerals in peridotite of Horoman suggest that the ancient continent material was subducted in deep mantle and recycled through the upper mantle by multicycle subduction processes.

Reduced Activity and Large Particles from the Disintegrating Planet Candidate KIC 12557548b

NASA Astrophysics Data System (ADS)

Schlawin, E.; Herter, T.; Zhao, M.; Teske, J. K.; Chen, H.

2016-08-01

The intriguing exoplanet candidate KIC 12557548b is believed to have a comet-like tail of dusty debris trailing a small rocky planet. The tail of debris scatters up to 1.3% of the stellar light in the Kepler observatory’s bandpass (0.42-0.9 μm). Observing the tail’s transit depth at multiple wavelengths can reveal the composition and particle size of the debris, constraining the makeup and lifetime of the sub-Mercury planet. Early dust particle size predictions from the scattering of the comet-like tail pointed toward a dust size of ˜0.1 μm for silicate compositions. These small particles would produce a much deeper optical transit depth than near-infrared transit depth. We measure a transmission spectrum for KIC 12557548b using the SpeX spectrograph (covering 0.8-2.4 μm) simultaneously with the MORIS imager taking r‧ (0.63 μm) photometry on the Infrared Telescope Facility for eight nights and one night in H band (1.63 μm) using the Wide-field IR Camera at the Palomar 200 inch telescope. The infrared spectra are plagued by systematic errors, but we argue that sufficient precision is obtained when using differential spectroscopic calibration when combining multiple nights. The average differential transmission spectrum is flat, supporting findings that KIC 12557548b’s debris is likely composed of larger particles ≳0.5 μm for pyroxene and olivine and ≳0.2 μm for iron and corundum. The r‧ photometric transit depths are all below the average Kepler value, suggesting that the observations occurred during a weak period or that the mechanisms producing optical broadband transit depths are suppressed.

Mechanochemical synthesis of low-fluorine doped aluminum hydroxide fluorides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scalise, V.; Scholz, G., E-mail: gudrun.scholz@rz.hu-berlin.de; Kemnitz, E., E-mail: erhard.kemnitz@chemie.hu-berlin.de

2016-11-15

Different aluminum hydroxide fluorides with varying Al/F molar ratios from 1:1.5 up to 1:0.05 were successfully synthesized by mechanochemical reactions. The characterization of the products by XRD, {sup 27}Al and {sup 19}F MAS NMR, thermal analysis, nitrogen adsorption and zeta potential techniques allows a detailed understanding of the structure and surface properties of the products. Using γ-Al(OH){sub 3} and β-AlF{sub 3}·3H{sub 2}O as OH- and F-sources, respectively, strongly disordered products were obtained with an Al: F molar ratio higher than 1:0.25. The fluorination degree has affected the amount of 4- and 5-fold coordinated Al sites, not present in the reactants.more » An evolution of the sub-coordinated Al-species has been detected also as a consequence of annealing processes. Obviously, these species affect the phase transition to alumina, by decreasing the transition temperature of the formation of α-Al{sub 2}O{sub 3}. Synthesis conditions (milling time, fluorination degree) play a crucial role for the product composition. - Graphical abstract: The impact of the combined action of the milling and the different fluorine doping on the structure of new aluminum hydroxide fluorides was followed by {sup 27}Al and {sup 19}F NMR and by other complementary techniques. - Highlights: • Low F-doped Al-hydroxide fluorides can be successfully prepared by mechanosynthesis. • Both F-doping and mechanochemical synthesis introduce a high number of defects in the structure. • The fluorination degree affects the amount of 4- and 5-fold coordinated Al sites as well as the transition temperature to corundum.« less

Selection of fluxing agent for coal ash and investigation of fusion mechanism: a first-principles study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jie Li; Mei-Fang Du; Zhong-Xiao Zhang

2009-01-15

An approach based on the ab initio quantum chemical modeling (CASTEP, generalized gradient approximation (GGA), and density functional theory (DFT)) was first employed to guide the selection of the appropriate fluxing agent to reduce the coal ash melting temperature. Two kinds of typical Chinese coal ash A and B with a high-melting temperature were chosen as the investigated subjects. Result of the calculation shows that mullite mineral, which is the main component of coal ash, is easier to combine with an electron acceptor than with an electron donor. Because the cations of borax (Na{sub 2}B{sub 4}O{sub 7}10H{sub 2}O) and limestonemore » can act as electron acceptors, borax and limestone were selected as the fluxing agents in our experiment. Results of the experiment show that the melting temperatures of coal ash A and B are both decreased by borax and limestone, respectively. Moreover, borax has a better fluxing effect than limestone under the same conditions. The further numerical study on the coal ash fusing mechanism indicates that the Na{sup +} and Ca{sup 2+} cations, as acceptors, can enter into the crystal lattice of mullite mainly through O(7) and O(8) and then cause the Al(6)-O(8) and Al(5)-O(7) bonds to rupture in the (AlO{sub 6})-octahedron. From this, mullite is forced to transform to feldspar and corundum minerals that have a low binding energy. Because of the phase change of minerals in the coal ash, the coal ash melting temperature is decreased by adding borax and limestone. 27 refs., 8 figs., 3 tabs.« less

Novel highly ordered core–shell nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dey, Sonal; Hossain, Mohammad D.; Mayanovic, Robert A.

2016-10-26

Core–shell nanoparticles have potential for a wide range of applications due to the tunability of their magnetic, catalytic, electronic, optical, and other physicochemical properties. A frequent drawback in the design of core–shell nanoparticles and nanocrystals is the lack of control over an extensive, disordered, and compositionally distinct interface that occurs due to the dissimilarity of structural and compositional phases of the core and shell. In this work, we demonstrate a new hydrothermal nanophase epitaxy (HNE) technique to synthesize highly structurally ordered α-Cr 2O 3@α-Co 0.38Cr 1.62O 2.92 inverted core–shell nanoparticles (CSNs) with evidence for the nanoscale growth of corundum structuremore » beginning from the core and extending completely into the shell of the CSNs with minimal defects at the interface. The high-resolution TEM results show a sharp interface exhibiting epitaxial atomic registry of shell atoms over highly ordered core atoms. The XPS and Co K-edge XANES analyses indicate the +2 oxidation state of cobalt is incorporated in the shell of the CSNs. Our XPS and EXAFS results are consistent with oxygen vacancy formation in order to maintain charge neutrality upon substitution of the Co 2+ ion for the Cr 3+ ion in the α-Co 0.38Cr 1.62O 2.92 shell. Furthermore, the CSNs exhibit the magnetic exchange bias effect, which is attributed to the exchange anisotropy at the interface made possible by the nanophase epitaxial growth of the α-Co 0.38Cr 1.62O 2.92 shell on the α-Cr 2O 3 core of the nanoparticles. The combination of a well-structured, sharp interface and novel nanophase characteristics is highly desirable for nanostructures having enhanced magnetic properties.« less

Microstructure of Al2O3 scales formed on NiCrAl alloys. Ph.D. Thesis - Case Western Reserve Univ.

NASA Technical Reports Server (NTRS)

Smialek, J. L.

1981-01-01

The structure of transient scales formed on pure and Y or Zr-doped Ni-15Cr-13Al alloys oxidized for 0.1 hr at 1100 C was studied by the use of transmission electron microscopy. Crystallographically oriented scales were found on all three alloys, but especially for the Zr-doped NiCrAl. The oriented scales consisted of alpha-(Al,Cr)2O3, Ni(Al,Cr)2O4 and gamma-Al2O3. They were often found in intimate contact with each other such that the close-packed planes and directions of one oxide phase were aligned with those of another. The prominent structural features of the oriented scales were approximately equal to micrometer subgrains; voids, antiphase domain boundaries and aligned precipitates were also prevalent. Randomly oriented alpha-Al2O3 was also found and was the only oxide ever observed at the immediate oxide metal interface. These approximately 0.15 micrometer grains were populated by intragranular voids which decreased in size and number towards the oxide metal interface. A sequence of oxidation was proposed in which the composition of the growing scale changed from oriented oxides rich in Ni and Cr to oriented oxides rich in Al. At the same time the structure changed from cubic spinels to hexagonal corundums with apparent precipitates of one phase in the matrix of the other. Eventually randomly oriented pure alpha-Al2O3 formed as the stable oxide with an abrupt transition: there was no gradual loss of orientation, no gradual compositional change or no gradual decrease in precipitate density.

An investigation of the feasibility of applying Raman microscopy for exploring stained glass

NASA Astrophysics Data System (ADS)

Bouchard, Michel; Smith, David C.; Carabatos-Nédelec, Constantin

2007-12-01

Raman microscopy (RM) is widely used in archaeometrical studies of pigments, geomaterials and biomaterials in the Cultural Heritage, but one domain has received relatively less attention: the colouring of stained glass. This feasibility study investigates the advantages and disadvantages of employing RM alone in this field by means of a study of modern commercial glasses, modern commercial pigments, and a few archaeological stained glasses, but especially by an experimental project whereby the authors created stained glass. The different kinds of possible unreacted or reacted material are rigorously established. The distinction between Na, K, Ca glasses was explored, as well as the red colouring of an industrial glass which was proved to be due to the presence of (Zn, Cd)S xSe 1- x. Yellow, green, blue and maroon pigments were studied before and after an initial firing and then after heating on glass. The quality of the Raman spectra varied enormously and was sometimes disappointing. Nevertheless RM successfully identified various coloured products such as bindheimite, crocoite, cobalt aluminate, haematite; relict reactants such as corundum, eskolaite and oxides of Co or Pb; and provided indications of other phases such as maghemite or Co-olivine. One conclusion is that the amount of chemical reaction between the pigments and the glass is small compared to the amount in between the pigments. Comments are made on the potential for dating archaeological glass from the known age of synthesis of the pigments, and of the dangers of this approach. Overall it has been shown that RM can be useful for studying stained glass, especially for remote in situ analytical operations with mobile RM, but one must expect some problems either with fluorescence or weak spectra.

Mantle Recycling of Crustal Materials through Study of Ultrahigh-Pressure Minerals in Collisional Orogens, Ophiolites, and Xenoliths

NASA Astrophysics Data System (ADS)

Liou, J. G.; Tsujimori, T.; Yang, J.; Zhang, R. Y.; Ernst, W. G.

2014-12-01

Newly recognized ultrahigh-pressure (UHP) mineral occurrences including diamonds in ultrahigh-temperature (UHT) felsic granulites of orogenic belts, in chromitites associated with ophiolitic complexes, and in mafic/ultramafic xenoliths suggest the recycling of crustal materials through profound subduction, mantle upwelling, and return to the Earth's surface. Recycling is supported by unambiguously crust-derived mineral inclusions in deep-seated zircons, chromites, and diamonds from collision-type orogens, from eclogitic xenoliths, and from ultramafic bodies of several Alpine-Himalayan and Polar Ural ophiolites; some such phases contain low-atomic number elements typified by crustal isotopic signatures. Ophiolite-type diamonds in placer deposits and as inclusions in chromitites together with numerous highly reduced minerals and alloys appear to have formed near the mantle transition zone. In addition to ringwoodite and stishovite, a wide variety of nanometric minerals have been identified as inclusions employing state-of-the-art analysis. Reconstitution of now-exsolved precursor UHP phases and recognition of subtle decompression microstructures produced during exhumation reflect earlier UHP conditions. Some podiform chromitites and associated peridotites contain rare minerals of undoubted crustal origin, including Zrn, corundum, Fls, Grt, Ky, Sil, Qtz, and Rtl; the zircons possess much older U-Pb ages than the formation age of the host ophiolites. These UHP mineral-bearing chromitites had a deep-seated evolution prior to extensional mantle upwelling and its partial melting at shallow depths to form the overlying ophiolite complexes. These new findings plus stable isotopic and inclusion characteristics of diamonds provide compelling evidence for profound underflow of both oceanic and continental lithosphere, recycling of biogenic carbon into the lower mantle, and ascent to the Earth's surface through deep mantle ascent.

Major zircon megacryst suites of the Indo-Pacific lithospheric margin (ZIP) and their petrogenetic and regional implications

NASA Astrophysics Data System (ADS)

Sutherland, Lin; Graham, Ian; Yaxley, Gregory; Armstrong, Richard; Giuliani, Gaston; Hoskin, Paul; Nechaev, Victor; Woodhead, Jon

2016-04-01

Zircon megacrysts (± gem corundum) appear in basalt fields of Indo-Pacific origin over a 12,000 km zone (ZIP) along West Pacific continental margins. Age-dating, trace element, oxygen and hafnium isotope studies on representative zircons (East Australia-Asia) indicate diverse magmatic sources. The U-Pb (249 to 1 Ma) and zircon fission track (ZFT) ages (65 to 1 Ma) suggest thermal annealing during later basalt transport, with < 1 to 203 Ma gaps between the U-Pb and ZFT ages. Magmatic growth zonation and Zr/Hf ratios (0.01-0.02) suggest alkaline magmatic sources, while Ti—in—zircon thermometry suggests that most zircons crystallized within ranges between 550 and 830 °C. Chondrite-normalised multi-element plots show variable enrichment patterns, mostly without marked Eu depletion, indicating little plagioclase fractionation in source melts. Key elements and ratios matched against zircons from magmatic rocks suggest a range of ultramafic to felsic source melts. Zircon O-isotope ratios (δ18O in the range 4 to 11‰) and initial Hf isotope ratios (ɛHf in the range +2 to +14) encompass ranges for both mantle and crustal melts. Calculated Depleted Mantle (TDM 0.03-0.56 Ga) and Crustal Residence (0.20-1.02 Ga) model ages suggest several mantle events, continental break-ups (Rodinia and Gondwana) and convergent margin collisions left imprints in the zircon source melts. East Australian ZIP sites reflect prolonged intraplate magmatism (~85 Ma), often during times of fast-migrating lithosphere. In contrast, East Asian-Russian ZIP sites reflect later basaltic magmatism (<40 Ma), often linked to episodes of back-arc rifting and spreading, slow-migrating lithosphere and slab subduction.

Microwave dielectric properties of CaCu{sub 3}Ti{sub 4}O{sub 12}-Al{sub 2}O{sub 3} composite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rahman, Mohd Fariz Ab; Abu, Mohamad Johari; Zaman, Rosyaini Afindi

2016-07-19

(1-x)CaCu{sub 3}Ti{sub 4}O{sub 12} + (x)Al{sub 2}O{sub 3} composite (0 ≤ x ≤0.25) was prepared via conventional solid-state reaction method. The fabrication of sample was started with synthesizing stoichiometric CCTO from CaCO{sub 3}, CuO and TiO{sub 2} powders, then wet-mixed in deionized water for 24 h. The process was continued with calcined CCTO powder at 900 °C for 12 h before sintered at 1040 °C for 10 h. Next, the calcined CCTO powder with different amount of Al{sub 2}O{sub 3} were mixed for 24 h, then palletized and sintered at 1040 °C for 10. X-ray diffraction analysis on the sinteredmore » samples showed that CCTO powder was in a single phase, meanwhile the trace of secondary peaks which belong to CaAl{sub 2}O{sub 4} and Corundum (Al{sub 2}O{sub 3}) could be observed in the other samples Scanning electron microscopy analysis showed that the grain size of the sample is firstly increased with addition of Al{sub 2}O{sub 3} (x = 0.01), then become smaller with the x > 0.01. Microwave dielectric properties showed that the addition of Al{sub 2}O{sub 3} (x = 0.01) was remarkably reduced the dielectric loss while slightly increased the dielectric permittivity. However, further addition of Al{sub 2}O{sub 3} was reduced both dielectric loss and permittivity at least for an order of magnitude.« less

Effects of iron-containing minerals on hydrothermal reactions of ketones

NASA Astrophysics Data System (ADS)

Yang, Ziming; Gould, Ian R.; Williams, Lynda B.; Hartnett, Hilairy E.; Shock, Everett L.

2018-02-01

Hydrothermal organic transformations occurring in geochemical processes are influenced by the surrounding environments including rocks and minerals. This work is focused on the effects of five common minerals on reactions of a model ketone substrate, dibenzylketone (DBK), in an experimental hydrothermal system. Ketones play a central role in many hydrothermal organic functional group transformations, such as those converting hydrocarbons to oxygenated compounds; however, how these minerals control the hydrothermal chemistry of ketones is poorly understood. Under the hydrothermal conditions of 300 °C and 70 MPa for up to 168 h, we observed that, while quartz (SiO2) and corundum (Al2O3) had no detectable effect on the hydrothermal reactions of DBK, iron-containing minerals, such as hematite (Fe2O3), magnetite (Fe3O4), and troilite (synthetic FeS), accelerated the reaction of DBK by up to an order of magnitude. We observed that fragmentation products, such as toluene and bibenzyl, dominated in the presence of hematite or magnetite, while use of troilite gave primarily the reduction products, e.g., 1, 3-diphenyl-propane and 1, 3-diphenyl-2-propanol. The roles of the three iron minerals in these transformations were further explored by (1) control experiments with various mineral surface areas, (2) measuring H2 in hydrothermal solutions, and (3) determining hydrogen balance among the organic products. These results suggest the reactions catalyzed by iron oxides (hematite and magnetite) are promoted mainly by the mineral surfaces, whereas the sulfide mineral (troilite) facilitated the reduction of ketone in the reaction solution. Therefore, this work not only provides a useful chemical approach to study and uncover complicated hydrothermal organic-mineral interactions, but also fosters a mechanistic understanding of ketone reactions in the deep carbon cycle.

Very high-temperature impact melt products as evidence for cosmic airbursts and impacts 12,900 years ago

USGS Publications Warehouse

Bunch, Ted E.; Hermes, Robert E.; Moore, Andrew M.T.; Kennett, Douglas J.; Weaver, James C.; Wittke, James H.; DeCarli, Paul S.; Bischoff, James L.; Hillman, Gordon C.; Howard, George A.; Kimbel, David R.; Kletetschka, Gunther; Lipo, Carl P.; Sakai, Sachiko; Revay, Zsolt; West, Allen; Firestone, Richard B.; Kennett, James P.

2012-01-01

It has been proposed that fragments of an asteroid or comet impacted Earth, deposited silica-and iron-rich microspherules and other proxies across several continents, and triggered the Younger Dryas cooling episode 12,900 years ago. Although many independent groups have confirmed the impact evidence, the hypothesis remains controversial because some groups have failed to do so. We examined sediment sequences from 18 dated Younger Dryas boundary (YDB) sites across three continents (North America, Europe, and Asia), spanning 12,000 km around nearly one-third of the planet. All sites display abundant microspherules in the YDB with none or few above and below. In addition, three sites (Abu Hureyra, Syria; Melrose, Pennsylvania; and Blackville, South Carolina) display vesicular, high-temperature, siliceous scoria-like objects, or SLOs, that match the spherules geochemically. We compared YDB objects with melt products from a known cosmic impact (Meteor Crater, Arizona) and from the 1945 Trinity nuclear airburst in Socorro, New Mexico, and found that all of these high-energy events produced material that is geochemically and morphologically comparable, including: (i) high-temperature, rapidly quenched microspherules and SLOs; (ii) corundum, mullite, and suessite (Fe3,/sup>Si), a rare meteoritic mineral that forms under high temperatures; (iii) melted SiO2 glass, or lechatelierite, with flow textures (or schlieren) that form at > 2,200 °C; and (iv) particles with features indicative of high-energy interparticle collisions. These results are inconsistent with anthropogenic, volcanic, authigenic, and cosmic materials, yet consistent with cosmic ejecta, supporting the hypothesis of extraterrestrial airbursts/impacts 12,900 years ago. The wide geographic distribution of SLOs is consistent with multiple impactors.

Effect of the metal concentration on the structural, mechanical and tribological properties of self-organized a-C:Cu hard nanocomposite coatings

NASA Astrophysics Data System (ADS)

Pardo, A.; Buijnsters, J. G.; Endrino, J. L.; Gómez-Aleixandre, C.; Abrasonis, G.; Bonet, R.; Caro, J.

2013-09-01

The influence of the metal content (Cu: 0-28 at.%) on the structural, mechanical and tribological properties of amorphous carbon films grown by pulsed filtered cathodic vacuum arc deposition is investigated. Silicon and AISI 301 stainless steel have been used as substrate materials. The microstructure, composition and bonding structure have been determined by scanning electron microscopy, combined Rutherford backscattered spectroscopy-nuclear reaction analysis, and Raman spectroscopy, respectively. The mechanical and tribological properties have been assessed using nanoindentation and reciprocating sliding (fretting tests) and these have been correlated with the elemental composition of the films. A self-organized multilayered structure consisting of alternating carbon and copper metal nanolayers (thickness in the 25-50 nm range), whose formation is enhanced by the Cu content, is detected. The nanohardness and Young’s modulus decrease monotonically with increasing Cu content. A maximum value of the Young’s modulus of about 255 GPa is obtained for the metal-free film, whereas it drops to about 174 GPa for the film with a Cu content of 28 at.%. In parallel, a 50% drop in the nanohardness from about 28 GPa towards 14 GPa is observed for these coatings. An increase in the Cu content also produces an increment of the coefficient of friction in reciprocating sliding tests performed against a corundum ball counterbody. As compared to the metal free film, a nearly four times higher coefficient of friction value is detected in the case of a Cu content of 28 at.%. Nevertheless, the carbon-copper composite coatings produced a clear surface protection of the substrate despite an overall increase in wear loss with increasing Cu content in the range 3-28 at.%.

Petrology of chromite in ureilites: Deconvolution of primary oxidation states and secondary reduction processes

NASA Astrophysics Data System (ADS)

Goodrich, Cyrena Anne; Harlow, George E.; Van Orman, James A.; Sutton, Stephen R.; Jercinovic, Michael J.; Mikouchi, Takashi

2014-06-01

Ureilites are ultramafic achondrites thought to be residues of partial melting on a carbon-rich asteroid. They show a trend of FeO-variation (olivine Fo from ∼74 to 95) that suggests variation in oxidation state. Whether this variation was established during high-temperature igneous processing on the ureilite parent body (UPB), or preserved from nebular precursors, is a subject of debate. The behavior of chromium in ureilites offers a way to assess redox conditions during their formation and address this issue, independent of Fo. We conducted a petrographic and mineral compositional study of occurrences of chromite (Cr-rich spinel) in ureilites, aimed at determining the origin of the chromite in each occurrence and using primary occurrences to constrain models of ureilite petrogenesis. Chromite was studied in LEW 88774 (Fo 74.2), NWA 766 (Fo 76.7), NWA 3109 (Fo 76.3), HaH 064 (Fo 77.5), LAP 03587 (Fo 74.9), CMS 04048 (Fo 76.4), LAP 02382 (Fo 78.6) and EET 96328 (Fo 85.2). Chromite occurs in LEW 88774 (∼5 vol.%), NWA 766 (<1 vol.%), NWA 3109 (<1 vol.%) and HaH 064 (<1 vol.%) as subhedral to anhedral grains comparable in size (∼30 μm to 1 mm) and/or textural setting to the major silicates (olivine and pyroxenes[s]) in each rock, indicating that it is a primary phase. The most FeO-rich chromites in these sample (rare grain cores or chadocrysts in silicates) are the most primitive compositions preserved (fe# = 0.55-0.6; Cr# varying from 0.65 to 0.72 among samples). They record olivine-chromite equilibration temperatures of ∼1040-1050 °C, reflecting subsolidus Fe/Mg reequilibration during slow cooling from ∼1200 to 1300 °C. All other chromite in these samples is reduced. Three types of zones are observed. (1) Inclusion-free interior zones showing reduction of FeO (fe# ∼0.4 → 0.28); (2) Outer zones showing further reduction of FeO (fe# ∼0.28 → 0.15) and containing abundant laths of eskolaite-corundum (Cr2O3-Al2O3); (3) Outermost zones showing extreme reduction of both FeO (fe# <0.15) and Cr2O3 (Cr# as low as 0.2). The grains are surrounded by rims of Si-Al-rich glass, graphite, Fe, Cr-carbides ([Fe,Cr]3C and [Fe,Cr]7C3), Cr-rich sulfides (daubréelite and brezinaite) and Cr-rich symplectic bands on adjacent silicates. Chromite is inferred to have been reduced by graphite, forming eskolaite-corundum and carbides as byproducts, during impact excavation. This event involved initial elevation of T (to 1300-1400 °C), followed by rapid decompression and drop in T (to <700 °C) at 1-20 °C/h. The kinetics of reduction of chromite is consistent with this scenario. The reduction was facilitated by silicate melt surrounding the chromites, which was partly generated by shock-melting of pyroxenes. Symplectic bands, consisting of fine-scale intergrowths of Ca-pyroxene, chromite and glass, formed by reaction between the Cr-enriched melt and adjacent silicates. Early chromite also occurs in a melt inclusion in olivine in HaH 064 and in a metallic spherule in olivine in LAP 02382. LAP 03587 and CMS 04048 contain ⩽μm-sized chromite + pyroxene symplectic exsolutions in olivine, indicating high Cr valence in the primary olivine. EET 96328 contains a round grain of chromite that could be a late-crystallizing phase. Tiny chromite grains in melt inclusions in EET 96328 formed in late, closed-system reactions. For 7 of the 8 ureilites we conclude that the relatively oxidizing conditions evidenced by the presence of primary or early chromite pertain to the period of high-T igneous processing. The observation that such conditions are recorded almost exclusively in low-Fo samples supports the interpretation that the ureilite FeO-variation was established during igneous processing on the UPB.

UHT overprint of HP rocks? A case study from the Adula nappe complex (Central Alps, N Italy)

NASA Astrophysics Data System (ADS)

Tumiati, Simone; Zanchetta, Stefano; Malaspina, Nadia; Poli, Stefano

2014-05-01

The Adula-Cima Lunga nappe complex is located on the eastern flank of the Lepontine Dome and represents the highest of the Lower Penninic units of the Central Alps. The Adula nappe largely consists of orthogneiss and paragneiss of pre-Mesozoic origin, variably retrogressed eclogites preserved as boudins within paragneiss, minor ultramafic bodies and metasedimentary rocks of presumed Mesozoic age. The higher metamorphic conditions have been estimated for the peridotite lenses in the southern part of the nappe at pressure over 3.0 GPa and temperature of 800-850°C. Garnet lherzolite bodies crop out at three localities, from west to east: Cima di Gagnone, Alpe Arami and Mt. Duria. After the partial subduction of the European distal margin beneath the Africa-Adria margin, the HP rocks were overprinted by an upper amphibolite facies metamorphism that postdates the main phase of nappe stacking. In the southern sector of the Lepontine Dome, adjacent to the Insubric Fault, metamorphic conditions promoted extensive migmatization of both metasedimentary and metagranitoid rocks. In one single outcrop, at Monte Duria, garnet lherzolites occur in m-sized boudins hosted within partly granulitized amphibole-bearing and k-feldspar gneisses that contain also some decimeter-sized boudins of both mafic and metapelitic eclogites. This rock association is in turn embedded within the migmatitic gneisses that form most of the southern sector of the Adula nappe. Petrographic and chemical analyses indicate that garnet peridotite is composed of olivine (XMg=0.88), orthopyroxene, clinopyroxene and garnet (Py68; Cr2O3 up to 1.45 wt%) with inclusions of Cr-rich spinel (up to Cr/(Al+Cr)=0.55) surrounded by kelyphitic symplectites of opx + cpx/amph + spl. These reaction produced double coronas, one composed of opx (former ol) and one composed of cpx + opx+ spl. In one kelyphite, we observed the uncommon occurrence of ZrO2 (baddeleyite) and ZrTi2O6 (srilankite). Tiny crystals of these two Zr-bearing phases (˜1 μm) are invariably located in the opx corona after ol. The cpx + opx + spl corona (after grt) contains, instead, zircon. Baddeleyite should have formed through a reaction of the type Mg2SiO4 + ZrSiO4 = MgSiO3 + ZrO2. ZrO2 and ZrTi2O6 display a low amount of solid solution. These compositions are consistent with T below 1200°C, but an improvement of the thermodynamic model is needed in order to better constrain the T of the granulitic overprint on the basis of these Zr-bearing phases. In mafic eclogites, the HP association consists of garnet (Py40Alm37Sp20), omphacite (preserved as inclusion, containing Jd30 and Mg# 0.87), kyanite and minor quartz. Omphacite is almost always replaced by cpx (Jd5) + plag (An55) symplectites. Garnet is surrounded by plag (An33) + opx (En70) symplectites. Kyanite is replaced by plag (An84) + spinel + sapphirine. The spinel-sapphirine Fe-Mg thermometer suggests T of about 850°C due to granulite-facies overprint. We observed sapphirine associated with cpx + opx + plag also in kelyphites after garnet in clinopyroxenites. In eclogitic metapelites, kyanite is replaced by a corundum + anorthite ± spinel assemblage. A corundum-rich layer occurs between eclogites and the host gneiss. Cm-sized emerald green zoisite in this layer is replaced by anorthitic plagioclase ± cpx ± spinel ± calcite. The observed assemblages point to a diffuse granulitization of both the peridotites and the hosting HP rocks of Mt. Duria, suggesting a nearly isothermal decompression from peak-pressure conditions. The surrounding migmatitic gneiss do not display evidence of such granulitic event, having been formed at T<700°C. The mechanism and timing of emplacement of the garnet peridotite and associated HP-HT rocks in the country migmatites, and whether or not the subduction event is related to the Alpine or to an older orogenic cycle are still a matter of debate.

Retrieval of atmospheric properties of cloudy L dwarfs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burningham, Ben; Marley, Mark S.; Line, Michael R.

Here, we present the first results from applying the spectral inversion technique in the cloudy L dwarf regime. This new framework provides a flexible approach to modelling cloud opacity which can be built incrementally as the data require and improves upon previous retrieval experiments in the brown dwarf regime by allowing for scattering in two-stream radiative transfer. Our first application of the tool to two mid-L dwarfs is able to reproduce their near-infrared spectra far more closely than grid models. Our retrieved thermal, chemical and cloud profiles allow us to estimate Teff = 1796more » $$+23\\atop{-25}$$ K and logg = 5.21$$+0.05\\atop{-0.08}$$ for 2MASS J05002100+0330501, and for 2MASSW J2224438-015852 we find Teff = 1723 $$+18\\atop{-19}$$ K and log g = 5.31 $$+0.04\\atop{-0.08}$$, in close agreement with previous empirical estimates. Our best model for both objects includes an optically thick cloud deck which passes τcloud ≥ 1 (looking down) at a pressure of around 5 bar. The temperature at this pressure is too high for silicate species to condense, and we argue that corundum and/or iron clouds are responsible for this cloud opacity. Our retrieved profiles are cooler at depth and warmer at altitude than the forward grid models that we compare, and we argue that some form of heating mechanism may be at work in the upper atmospheres of these L dwarfs. We also identify anomalously high CO abundance in both targets, which does not correlate with the warmth of our upper atmospheres or our choice of cloud model, and find similarly anomalous alkali abundance for one of our targets. For these anomalies they may reflect unrecognized shortcomings in our retrieval model or inaccuracies in our gas phase opacities.« less

Experimental dynamic metamorphism of mineral single crystals

USGS Publications Warehouse

Kirby, S.H.; Stern, L.A.

1993-01-01

This paper is a review of some of the rich and varied interactions between non-hydrostatic stress and phase transformations or mineral reactions, drawn mainly from results of experiments done on mineral single crystals in our laboratory or our co-authors. The state of stress and inelastic deformation can enter explicitly into the equilibrium phase relations and kinetics of mineral reactions. Alternatively, phase transformations can have prominent effects on theology and on the nature of inelastic deformation. Our examples represent five types of structural phase changes, each of which is distinguished by particular mechanical effects. In increasing structural complexity, these include: (1) displacive phase transformations involving no bond-breaking, which may produce anomalous brittle behavior. A primary example is the a-?? quartz transition which shows anomalously low fracture strength and tertiary creep behavior near the transition temperature; (2) martensitic-like transformations involving transformation strains dominated by shear deformation. Examples include the orthoenstatite ??? clinoenstatite and w u ??rtzite ??? sphalerite transformations; (3) coherent exsolution or precipitation of a mineral solute from a supersaturated solid-solution, with anisotropy of precipitation and creep rates produced under nonhydrostatic stress. Examples include exsolution of corundum from MgO ?? nAl2O3 spinels and Ca-clinopyroxene from orthopyroxene; (4) order-disorder transformations that are believed to cause anomalous plastic yield strengthening, such as MgO - nAl2O3 spinels; and (5) near-surface devolatilization of hydrous silicate single-crystals that produces a fundamental brittleness thought to be connected with dehydration at microcracks at temperatures well below nominal macroscopic dehydration temperatures. As none of these interactions between single-crystal phase transformations and non-hydrostatic stress is understood in detail, this paper serves as a challenge to field structural geologists to test whether interactions of these types occur in nature, and to theoreticians to reach a deeper understanding of the complex relations between phase transformations, the local state of stress and associated deformation and deformation rates. ?? 1993.

Evolution of crystalline target rocks and impactites in the chesapeake bay impact structure, ICDP-USGS eyreville B core

USGS Publications Warehouse

Horton, J. Wright; Kunk, Michael J.; Belkin, Harvey E.; Aleinikoff, John N.; Jackson, John C.; Chou, I.-Ming

2009-01-01

The 1766-m-deep Eyreville B core from the late Eocene Chesapeake Bay impact structure includes, in ascending order, a lower basement-derived section of schist and pegmatitic granite with impact breccia dikes, polymict impact breccias, and cataclas tic gneiss blocks overlain by suevites and clast-rich impact melt rocks, sand with an amphibolite block and lithic boulders, and a 275-m-thick granite slab overlain by crater-fill sediments and postimpact strata. Graphite-rich cataclasite marks a detachment fault atop the lower basement-derived section. Overlying impactites consist mainly of basement-derived clasts and impact melt particles, and coastal-plain sediment clasts are underrepresented. Shocked quartz is common, and coesite and reidite are confirmed by Raman spectra. Silicate glasses have textures indicating immiscible melts at quench, and they are partly altered to smectite. Chrome spinel, baddeleyite, and corundum in silicate glass indicate high-temperature crystallization under silica undersaturation. Clast-rich impact melt rocks contain α-cristobalite and monoclinic tridymite. The impactites record an upward transition from slumped ground surge to melt-rich fallback from the ejecta plume. Basement-derived rocks include amphibolite-facies schists, greenschist(?)-facies quartz-feldspar gneiss blocks and subgreenschist-facies shale and siltstone clasts in polymict impact breccias, the amphibolite block, and the granite slab. The granite slab, underlying sand, and amphibolite block represent rock avalanches from inward collapse of unshocked bedrock around the transient crater rim. Gneissic and massive granites in the slab yield U-Pb sensitive high-resolution ion microprobe (SHRIMP) zircon dates of 615 ± 7 Ma and 254 ± 3 Ma, respectively. Postimpact heating was <~350 °C in the lower basement-derived section based on undisturbed 40Ar/39Ar plateau ages of muscovite and <~150 °C in sand above the suevite based on 40Ar/39Ar age spectra of detrital microcline.

Rheological principles of development hetero-modulus and hetero-viscous complex materials with extreme dynamic strength

NASA Astrophysics Data System (ADS)

Gömze, L. A.; Gömze, L. N.

2017-02-01

Materials with different crystalline and morphological compositions have different chemical, physical, mechanical and rheological properties, including wear protection, melting temperature, module of elasticity and viscosity. Examining the material structures and behaviors of differentceramic bodies and CMCs under high speed collisions in several years the authors have understood the advantages of hetero-modulus and hetero-viscous complex material systems to absorb and dissipate the kinetic energy of objects during high speed collisions. Applying the rheo-mechanical principles the authors successfully developed a new family of hetero-modulus and hetero-viscous alumina matrix composite materials with extreme mechanical properties including dynamic strength. These new corundum-matrix composite materials reinforced with Si2ON 2, Si3N4 , SiAlON and AlN submicron and nanoparticles have excellent dynamic strength during collisions with high density metallic bodies with speeds about 1000 m/sec or more. At the same time in the alumina matrix composites can be observed a phase transformation of submicron and nanoparticles of alpha and beta silicone-nitride crystals into cubicc-Si3N4 diamond-like particles can be observed, when the high speed collision processes are taken place in vacuum or oxygen-free atmosphere. Using the rheological principles and the energy engorgement by fractures, heating and melting of components the authors successfully developed several new hetero-modulus, hetero-viscous and hetero-plastic complex materials. These materials generally are based on ceramic matrixes and components having different melting temperatures and modules of elasticity from low values like carbon and light metals (Mg, Al, Ti, Si) up to very high values like boride, nitride and carbide ceramics. Analytical methods applied in this research were scanning electron microscopy, X-ray diffractions and energy dispersive spectrometry. Digital image analysis was applied to microscopy results to enhance the results of transformations.

Retrieval of atmospheric properties of cloudy L dwarfs

DOE PAGES

Burningham, Ben; Marley, Mark S.; Line, Michael R.; ...

2017-05-20

Here, we present the first results from applying the spectral inversion technique in the cloudy L dwarf regime. This new framework provides a flexible approach to modelling cloud opacity which can be built incrementally as the data require and improves upon previous retrieval experiments in the brown dwarf regime by allowing for scattering in two-stream radiative transfer. Our first application of the tool to two mid-L dwarfs is able to reproduce their near-infrared spectra far more closely than grid models. Our retrieved thermal, chemical and cloud profiles allow us to estimate Teff = 1796more » $$+23\\atop{-25}$$ K and logg = 5.21$$+0.05\\atop{-0.08}$$ for 2MASS J05002100+0330501, and for 2MASSW J2224438-015852 we find Teff = 1723 $$+18\\atop{-19}$$ K and log g = 5.31 $$+0.04\\atop{-0.08}$$, in close agreement with previous empirical estimates. Our best model for both objects includes an optically thick cloud deck which passes τcloud ≥ 1 (looking down) at a pressure of around 5 bar. The temperature at this pressure is too high for silicate species to condense, and we argue that corundum and/or iron clouds are responsible for this cloud opacity. Our retrieved profiles are cooler at depth and warmer at altitude than the forward grid models that we compare, and we argue that some form of heating mechanism may be at work in the upper atmospheres of these L dwarfs. We also identify anomalously high CO abundance in both targets, which does not correlate with the warmth of our upper atmospheres or our choice of cloud model, and find similarly anomalous alkali abundance for one of our targets. For these anomalies they may reflect unrecognized shortcomings in our retrieval model or inaccuracies in our gas phase opacities.« less

Structure Evolution and Reactivity of the Sc(2- x)V xO3+δ (0 ≤ x ≤ 2.0) System.

PubMed

Lussier, Joey A; Simon, Fabian J; Whitfield, Pamela S; Singh, Kalpana; Thangadurai, Venkataraman; Bieringer, Mario

2018-05-07

Solid oxide fuel cells (SOFCs) are solid-state electrochemical devices that directly convert chemical energy of fuels into electricity with high efficiency. Because of their fuel flexibility, low emissions, high conversion efficiency, no moving parts, and quiet operation, they are considered as a promising energy conversion technology for low carbon future needs. Solid-state oxide and proton conducting electrolytes play a crucial role in improving the performance and market acceptability of SOFCs. Defect fluorite phases are some of the most promising fast oxide ion conductors for use as electrolytes in SOFCs. We report the synthesis, structure, phase diagram, and high-temperature reactivity of the Sc (2- x) V x O 3+δ (0 ≤ x ≤ 2.00) oxide defect model system. For all Sc (2- x) V x O 3.0 phases with x ≤ 1.08 phase-pure bixbyite-type structures are found, whereas for x ≥ 1.68 phase-pure corundum structures are reported, with a miscibility gap found for 1.08 < x < 1.68. Structural details obtained from the simultaneous Rietveld refinements using powder neutron and X-ray diffraction data are reported for the bixbyite phases, demonstrating a slight V 3+ preference toward the 8b site. In situ X-ray diffraction experiments were used to explore the oxidation of the Sc (2- x) V x O 3.0 phases. In all cases ScVO 4 was found as a final product, accompanied by Sc 2 O 3 for x < 1.0 and V 2 O 5 when x > 1.0; however, the oxidative pathway varied greatly throughout the series. Comments are made on different synthesis strategies, including the effect on crystallinity, reaction times, rate-limiting steps, and reaction pathways. This work provides insight into the mechanisms of solid-state reactions and strategic guidelines for targeted materials synthesis.

Detecting Nanophase Weathering Products with CheMin: Reference Intensity Ratios of Allophane, Aluminosilicate Gel, and Ferrihydrite

NASA Technical Reports Server (NTRS)

Rampe, E. B.; Bish, D. L.; Chipera, S. J.; Morris, R. V.; Achilles, C. N.; Ming, D W.; Blake, D. F.; Anderson, R. C.; Bristow, T. F.; Crisp, A.;

Unusual ruby-sapphire transition in alluvial megacrysts, Cenozoic basaltic gem field, New England, New South Wales, Australia

NASA Astrophysics Data System (ADS)

Sutherland, Frederick L.; Graham, Ian T.; Harris, Stephen J.; Coldham, Terry; Powell, William; Belousova, Elena A.; Martin, Laure

2017-05-01

Rare ruby crystals appear among prevailing sapphire crystals mined from placers within basaltic areas in the New England gem-field, New South Wales, Australia. New England ruby (NER) has distinctive trace element features compared to those from ruby elsewhere in Australia and indeed most ruby from across the world. The NER suite includes ruby (up to 3370 ppm Cr), pink sapphire (up to 1520 ppm Cr), white sapphire (up to 910 ppm) and violet, mauve, purple, or bluish sapphire (up to 1410 ppm Cr). Some crystals show outward growth banding in this respective colour sequence. All four colour zones are notably high in Ga (up to 310 ppm) and Si (up to 1820 ppm). High Ga and Ga/Mg values are unusual in ruby and its trace element plots (laser ablation-inductively coupled plasma-mass spectrometry) and suggests that magmatic-metasomatic inputs were involved in the NER suite genesis. In situ oxygen isotope analyses (secondary ion mass spectrometry) across the NER suite colour range showed little variation (n = 22; δ18O = 4.4 ± 0.4, 2σ error), and are values typical for corundum associated with ultramafic/mafic rocks. The isolated NER xenocryst suite, corroded by basalt transport and with few internal inclusions, presents a challenge in deciphering its exact origin. Detailed consideration of its high Ga chemistry in relation to the known geology of the surrounding region was used to narrow down potential sources. These include Late Palaeozoic-Triassic fractionated I-type granitoid magmas or Mesozoic-Cenozoic felsic fractionates from basaltic magmas that interacted with early Palaeozoic Cr-bearing ophiolite bodies in the New England Orogen. Other potential sources may lie deeper within lower crust-mantle metamorphic assemblages, but need to match the anomalous high-Ga geochemistry of the New England ruby suite.

Application of Scanning-Imaging X-Ray Microscopy to Fluid Inclusion Candidates in Carbonates of Carbonaceous Chondrites

NASA Technical Reports Server (NTRS)

Tsuchiyama, Akira; Nakano, Tsukasa; Miyake, Akira; Akihisa, Takeuchi; Uesugi, Kentaro; Suzuki, Yoshio; Kitayama, Akira; Matsuno, Junya; Zolensky, Michael E.

2016-01-01

In order to search for such fluid inclusions in carbonaceous chondrites, a nondestructive technique using x-ray micro-absorption tomography combined with FIB sampling was developed and applied to a carbonaceous chondrite. They found fluid inclusion candidates in calcite grains, which were formed by aqueous alteration. However, they could not determine whether they are really aqueous fluids or merely voids. Phase and absorption contrast images can be simultaneously obtained in 3D by using scanning-imaging x-ray microscopy (SIXM). In refractive index, n=1-sigma+i(beta), in the real part, 1-sigma is the refractive index with decrement, sigma, which is nearly proportional to the density, and the imaginary part, beta, is the extinction coefficient, which is related to the liner attenuation coefficient, mu. Many phases, including water and organic materials as well as minerals, can be identified by SIXM, and this technique has potential availability for Hayabusa-2 sample analysis too. In this study, we examined quantitative performance of d and m values and the spatial resolution in SIXM by using standard materials, and applied this technique to carbonaceous chondrite samples. We used POM ([CH2O]n), silicon, quartz, forsterite, corundum, magnetite and nickel as standard materials for examining the sigma and mu values. A fluid inclusion in terrestrial quartz and bi-valve shell (Atrina vexillum), which are composed of calcite and organic layers with different thickness, were also used for examining the spatial resolution. The Ivuna (CI) and Sutter's Mill (CM) meteorites were used as carbonaceous chondrite samples. Rod- or cube-shaped samples 20-30 micron in size were extracted by using FIB from cross-sectional surfaces of the standard materials or polished thin sections of the chondrites, which was previously observed with SEM. Then, the sample was attached to a thin W-needle and imaged by SIXM system at beamline BL47XU, SPring-8, Japan. The slice thickness was 109.3 nm and the pixel size was mostly 100 nm.

Ceramic surfaces, interfaces and solid-state reactions

NASA Astrophysics Data System (ADS)

Heffelfinger, Jason Roy

Faceting, the decomposition of a surface into two or more surfaces of different orientation, is studied as a function of annealing time for ceramic surfaces. Single-crystals of Alsb2Osb3\\ (alpha-Alsb2Osb3 or corundum structure) are carefully prepared and characterized by atomic force microscopy, scanning electron microscopy and transmission electron microscopy. The mechanisms by which the originally smooth vicinal surface transforms into either a hill-and-valley or a terrace-and-step structure have been characterized. The progression of faceting is found to have a series of stages: surface smoothing, nucleation and growth of individual facets, formation of facet domains, coalescence of individual and facet domains and facet coarsening. These stages provide a model for the mechanisms of how other ceramic surfaces may facet into hill-and-valley and terrace-and-step surface microstructures. The well characterized Alsb2Osb3 surfaces provide excellent substrates by which to study the effect of surface structure on thin-film growth. Pulsed-laser deposition was used to grow thin films of yttria stabilized zirconia (YSZ) and Ysb2Osb3 onto annealed Alsb2Osb3 substrates. The substrate surface structure, such as surface steps and terraces, was found to have several effects on thin-film growth. Thin-films grown onto single-crystal substrates serve as a model geometry for studying thin-film solid-state reactions. Here, the reaction sequence and orientation relationship between thin films of Ysb2Osb3 and an Alsb2Osb3 substrate were characterized for different reaction temperatures. In a system were multiple reaction phases can form, the yttria aluminum monoclinic phase (YAM) was found to form prior to formation of other phases in this system. In a second system, a titanium alloy was reacted with single crystal Alsb2Osb3 in order to study phase formation in an intermetallic system. Both Tisb3Al and TiAl were found to form as reaction products and their orientation relationships with the Alsb2Osb3 are discussed.

The roles of fractional crystallization, magma mixing, crystal mush remobilization and volatile-melt interactions in the genesis of a young basalt-peralkaline rhyolite suite, the greater Olkaria volcanic complex, Kenya Rift valley

USGS Publications Warehouse

Macdonald, R.; Belkin, H.E.; Fitton, J.G.; Rogers, N.W.; Nejbert, K.; Tindle, A.G.; Marshall, A.S.

2008-01-01

The Greater Olkaria Volcanic Complex is a young (???20 ka) multi-centred lava and dome field dominated by the eruption of peralkaline rhyolites. Basaltic and trachytic magmas have been erupted peripherally to the complex and also form, with mugearites and benmoreites, an extensive suite of magmatic inclusions in the rhyolites. The eruptive rocks commonly represent mixed magmas and the magmatic inclusions are themselves two-, three- or four-component mixes. All rock types may carry xenocrysts of alkali feldspar, and less commonly plagioclase, derived from magma mixing and by remobilization of crystal mushes and/or plutonic rocks. Xenoliths in the range gabbro-syenite are common in the lavas and magmatic inclusions, the more salic varieties sometimes containing silicic glass representing partial melts and ranging in composition from anorthite ?? corundum- to acmite-normative. The peralkaline varieties are broadly similar, in major element terms, to the eruptive peralkaline rhyolites. The basalt-trachyte suite formed by a combination of fractional crystallization, magma mixing and resorption of earlier-formed crystals. Matrix glass in metaluminous trachytes has a peralkaline rhyolitic composition, indicating that the eruptive rhyolites may have formed by fractional crystallization of trachyte. Anomalous trace element enrichments (e.g. ??? 2000 ppm Y in a benmoreite) and negative Ce anomalies may have resulted from various Na- and K-enriched fluids evolving from melts of intermediate composition and either being lost from the system or enriched in other parts of the reservoirs. A small group of nepheline-normative, usually peralkaline, magmatic inclusions was formed by fluid transfer between peralkaline rhyolitic and benmoreitic magmas. The plumbing system of the complex consists of several independent reservoirs and conduits, repeatedly recharged by batches of mafic magma, with ubiquitous magma mixing. ?? The Author 2008. Published by Oxford University Press. All rights reserved.

Applications of Real Space Crystallography in Characterization of Dislocations in Geological Materials in a Scanning Electron Microscope (SEM)

NASA Astrophysics Data System (ADS)

Kaboli, S.; Burnley, P. C.

2017-12-01

Imaging and characterization of defects in crystalline materials is of significant importance in various disciplines including geoscience, materials science, and applied physics. Linear defects such as dislocations and planar defects such as twins and stacking faults, strongly influence many of the properties of crystalline materials and also reflect the conditions and degree of deformation. Dislocations have been conventionally imaged in thin foils in a transmission electron microscope (TEM). Since the development of field emission scanning electron microscopes (FE-SEM) with high gun brightness and small spot size, extensive efforts have been dedicated to the imaging and characterization of dislocations in semi-conductors using electron channeling contrast imaging (ECCI) in the SEM. The obvious advantages of using SEM over TEM include easier and non-destructive sample preparation and a large field of view enabling statistical examination of the density and distribution of dislocations and other defects. In this contribution, we extend this technique to geological materials and introduce the Real Space Crystallography methodology for imaging and complete characterization of dislocations based on bend contour contrast obtained by ECCI in FE-SEM. Bend contours map out the distortion in the crystal lattice across a deformed grain. The contrast of dislocations is maximum in the vicinity of bend contours where crystal planes diffract at small and positive deviations from the Bragg positions (as defined by Bragg's law of electron diffraction). Imaging is performed in a commercial FE-SEM equipped with a standard silicon photodiode backscattered (BSE) detector and an electron backscatter diffraction (EBSD) system for crystal orientation measurements. We demonstrate the practice of this technique in characterization of a number of geological materials in particular quartz, forsterite olivine and corundum, experimentally deformed at high pressure-temperature conditions. This new approach in microstructure characterization of deformed geologic materials in FE-SEM, without the use of etching or decoration techniques, has valuable applications to both experimentally deformed and naturally deformed specimens.

Melt inclusions in alluvial sapphires from Montana, USA: Formation of sapphires as a restitic component of lower crustal melting?

NASA Astrophysics Data System (ADS)

Palke, Aaron C.; Renfro, Nathan D.; Berg, Richard B.

2017-05-01

We report here compositions of glassy melt inclusions hosted in sapphires (gem quality corundum) from three alluvial deposits in Montana, USA including the Rock Creek, Dry Cottonwood Creek, and Missouri River deposits. While it is likely that sapphires in these deposits were transported to the surface by Eocene age volcanic events, their ultimate origin is still controversial with many models suggesting the sapphires are xenocrysts with a metamorphic or metasomatic genesis. Melt inclusions are trachytic, dacitic, and rhyolitic in composition. Microscopic observations allow separation between primary and secondary melt inclusions. The primary melt inclusions represent the silicate liquid that was present at the time of sapphire formation and are enriched in volatile components (8-14 wt.%). Secondary melt inclusions analyzed here for Dry Cottonwood Creek and Rock Creek sapphires are relatively volatile depleted and represent the magma that carried the sapphires to the surface. We propose that alluvial Montana sapphires from these deposits formed through a peritectic melting reaction during partial melting of a hydrated plagioclase-rich protolith (e.g. an anorthosite). The heat needed to drive this reaction was likely derived from the intrusion of mantle-derived mafic magmas near the base of the continental lithosphere during rollback of the Farallon slab around 50 Ma. These mafic magmas may have ended up as the ultimate carrier of the sapphires to the surface as evidenced by the French Bar trachybasalt near the Missouri River deposit. Alternatively, the trachytic, rhyolitic, and dacitic secondary melt inclusions at Rock Creek and Dry Cottonwood Creek suggests that the same magmas produced during the partial melting event that generated the sapphires may have also transported them to the surface. Determining the genesis of these deposits will further our understanding of sapphire deposits around the world and may help guide future sapphire prospecting techniques. This work is also important to help reveal the history of mantle-derived mafic magmas as they pass through the continental crust.

Dust in the Quasar Wind (Artist Concept)

NASA Technical Reports Server (NTRS)

2007-01-01

Dusty grains -- including tiny specks of the minerals found in the gemstones peridot, sapphires and rubies -- can be seen blowing in the winds of a quasar, or active black hole, in this artist's concept. The quasar is at the center of a distant galaxy.

Astronomers using NASA's Spitzer Space Telescope found evidence that such quasar winds might have forged these dusty particles in the very early universe. The findings are another clue in an ongoing cosmic mystery: where did all the dust in our young universe come from?

Dust is crucial for efficient star formation as it allows the giant clouds where stars are born to cool quickly and collapse into new stars. Once a star has formed, dust is also needed to make planets and living creatures. Dust has been seen as far back as when the universe was less than a tenth of its current age, but how did it get there? Most dust in our current epoch forms in the winds of evolved stars that did not exist when the universe was young.

Theorists had predicted that winds from quasars growing in the centers of distant galaxies might be a source of this dust. While the environment close to a quasar is too hot for large molecules like dust grains to survive, dust has been found in the cooler, outer regions. Astronomers now have evidence that dust is created in these outer winds.

Using Spitzer's infrared spectrograph instrument, scientists found a wealth of dust grains in a quasar called PG2112+059 located at the center of a galaxy 8 billion light-years away. The grains - including corundum (sapphires and rubies); forsterite (peridot); and periclase (naturally occurring in marble) - are not typically found in galaxies without quasars, suggesting they might have been freshly formed in the quasar's winds.

A new biosensor for noninvasive determination of fetal RHD status in maternal blood of RhD negative pregnant women.

PubMed

Dündar Yenilmez, Ebru; Kökbaş, Umut; Kartlaşmış, Kezban; Kayrın, Levent; Tuli, Abdullah

2018-01-01

Prenatal detection of the fetal RHD status can be useful in the management of RhD incompatibility to identify fetuses at risk of hemolytic disease. Hemolytic disease causes morbidity and mortality of the fetus in the neonatal period. The routine use of antenatal and postnatal anti-D prophylaxis has reduced the incidence of hemolytic disease of the fetus and newborn. This study describe the detection of fetal RhD antigens in blood of RhD negative pregnant women using a nanopolymer coated electrochemical biosensor for medical diagnosis. Cell free fetal DNA in maternal plasma was also used to genotyping fetal RHD status using multiplex real-time PCR. Twenty-six RhD negative pregnant women in different gestational ages were included in the study. RhD positive fetal antibodies detected with a developed biosensor in maternal blood of RhD negative mothers. The electrochemical measurements were performed on a PalmSens potentiostat, and corundum ceramic based screen printed gold electrode combined with the reference Ag/AgCl electrode, and the auxiliary Au/Pd (98/2%) electrode. Fetal RHD genotyping performed using fluorescence-based multiplex real-time PCR exons 5 and 7 of the RHD gene. The fetal RHD status of 26 RhD negative cases were detected 21 as RhD positive and 5 as RhD negative with electrochemical biosensor. Fetal RHD status confirmed with extracted fetal DNA in maternal plasma using multiplex real-time PCR RHD genotyping and by serological test after delivery. The new method for fetal RhD detection in early pregnancy is useful and can be carry out rapidly in clinical diagnosis. Using automated biosensors are reproducible, quick and results can be generated within a few minutes compared to noninvasive fetal RHD genotyping from maternal plasma with real-time PCR-based techniques. We suggest the biosensor techniques could become an alternative part of fetal RHD genotyping from maternal plasma as a prenatal screening in the management of RhD incompatibility.

Hydrothermal Fluids, Nebular Vapors and Silicate MELTS As Seem through the Eyes of Minerals

NASA Astrophysics Data System (ADS)

Sack, R. O.

2014-12-01

Three cases where advances in mineral thermochemistry provide new insights into geological processes are discussed: (I) Sb-rich fahlores are used to constrain compositions of hydrothermal fluids and processes responsible for Ag-Pb-Zn sulfide ores from three Ag mining districts, Keno Hill, (Yukon, Canada); Julcani, (Angaraes, Peru); Coeur d'Alene, (Idaho, USA), confirming that the Ag initially contained in galena solid solutions was a substantial contributor to the total Ag mined in each of them; (II) Al8/3O4-rich MgAl2O4-Al8/3O4 spinels may have condensed from the primordial solar nebula, with their Al8/3O4 annealed out with cooling, as AgSbS2 is "annealed" out of galena in Ag-Pb-Zn ore deposits. Such spinels may explain inconsistencies between mineral condensation sequences recorded in Ca-Al-rich inclusions (CAIs) in carbonaceous chondrites and those calculated assuming spinel was MgAl2O4. A new thermodynamical model and corundum-bearing CAIs, suggest we may anticipate realization of higher temperatures and pressures of canonical condensation than currently in vogue; (III) Fassitic pyroxenes in the composition space CaMgSi2O6 (Di) - CaTiAlSiO6 (Gr) - CaTi1/2Mg1/2AlSiO6 (AlBf) - CaAl2SiO6 (CATS) exhibit at least one prominent gap evident in composition data from CAIs. This may be interpreted as due to the near superposition of the extension of the Di- AlBf gap into this fassaite tetrahedron, with an isolated two-phase region formed by the double intersections of the (Gr+CATS) - AlBf critical curve with the surfaces of constant Ti(Al)-1 exchange potential characteristic of CAIs. A thermodynamic model for fassaites may provide context for critical thinking about CAI petrogenesis, as well as presaging potential refinements to the thermochemical model for pyroxenes in MELTS.

Impact mineralogy and chemistry of the cretaceous-tertiary boundary at DSDP site 576

NASA Technical Reports Server (NTRS)

Bostwick, Jennifer A.; Kyte, Frank T.

1993-01-01

We have identified the K/T boundary in pelagic clay sediments from cores at DSDP Site 576 in the western North Pacific. Detailed geochemical and trace mineralogical analyses of this boundary section are in progress and initial results indicate similarities and differences relative to the only other clay core investigated in detail; DSDP Site 596, a locality in the western South Pacific. Peak Ir concentrations of 13 ng/g in DSDP Hole 576B are virtually identical with those observed in the South Pacific, but in the North Pacific this peak is much narrower and the integrated Ir fluence of 85 ng cm(exp -2) is 4 times lower (320 in Hole 596). Of the 34 elements measured, only Ir and Cr were found to have anomalous concentrations in K/T boundary samples. Trace mineral residues were obtained by washing away clays and sequential chemical leaches (including HF) to remove typical hydrogenous and biogenous sediment components (e.g., zeolites and radiolarian opal). We attempted to quantitatively recover the entire trace mineral assemblage for grains greater than 30 micrometers in diameter. Our mineral residues were dominated by two phases: quartz and magnesioferrite spinel. Other non-opaque mineral grains we have positively identified were trace K-feldspar, plagioclase, corundum, and muscovite. Of these only K-feldspar exhibited planar deformation features (PDF). We have not found abundant plagioclase, as in the South Pacific suggesting that this phase was either not preserved in the North Pacific, or that in the south, it has a non-impact (i.e., volcanic) source. PDF in quartz were commonly obscured by secondary overgrowths on the surfaces of quartz grains, presumably from diagenetic reprecipitation of silica dissolved from opaline radiolarian tests that are common in these sediments. However, careful examination revealed that most grains had multiple sets of PDF. Of the 133 quartz grains greater than 30 micrometers analyzed, 62 percent showed evidence of shock. The largest shocked grain recovered to date had a maximum diameter of 160 micrometers, consistent with other sites in the Pacific.

Alumino-silicate speciation in aqueous fluids at deep crustal conditions

NASA Astrophysics Data System (ADS)

Mookherjee, M.; Keppler, H.; Manning, C. E.

2014-12-01

Alumina and silica are major oxides in most crustal rocks. While SiO2 is quite soluble in aqueous fluids at metamorphic conditions, behavior of Al2O3 in crustal metamorphic fluids has been poorly understood. It is known that alumina is dramatically less soluble in aqueous fluids and hence it is difficult to explain the common occurrence of quartz with aluminous minerals in metamorphic veins. In order to understand this complex behavior of alumina, we investigated aluminum speciation in aqueous fluids in equilibrium with corundum using in situ Raman spectroscopy in hydrothermal diamond anvil cells to 20 kbar and 1000 oC. In order to better understand the spectral features of the aqueous fluids, we used first principles simulations based on density functional theory to calculate and predict the energetics and vibrational spectra for various aluminum species that are likely to be present in aqueous solutions. The Raman spectra of pure water in equilibrium with Al2O3 are devoid of any characteristic spectral features. In contrast, aqueous fluids with KOH solution in equilibrium with Al2O3 show a sharp band at ~620 cm-1 which could be attributed to the [Al(OH)4]1- species. The band grows in intensity with temperature along an isochore. In the limited pressure, temperature and density explored in the present study, we do not find any evidence for the polymerization of the [Al(OH)4]1- species to dimers [(OH)2-Al-O2-Al(OH)2]2- or [(OH)3-Al-O-Al(OH)3]2-. This is likely due to the relatively low concentration of Al in the solutions and does not rule out significant polymerization at higher pressures and temperatures. We are also investigating the effect of SiO2 on the solubility of Al2O3 and the relative energetics of formation of pure alumina dimer [(OH)3-Al-O-Al(OH)3]2- vs. the aluminosilicate dimers, [(OH)3-Al-O-Si(OH)3]2- at deep crustal conditions. Acknowledgement- MM is supported by the US National Science Foundation grant (EAR-1250477).

Aluminum speciation in aqueous fluids at deep crustal pressure and temperature

NASA Astrophysics Data System (ADS)

Mookherjee, Mainak; Keppler, Hans; Manning, Craig E.

2014-05-01

We investigated aluminum speciation in aqueous fluids in equilibrium with corundum using in situ Raman spectroscopy in hydrothermal diamond anvil cells to 20 kbar and 1000 °C. We have studied aluminum species in (a) pure H2O, (b) 5.3 m KOH solution, and (c) 1 m KOH solution. In order to better understand the spectral features of the aqueous fluids, we used ab initio simulations based on density functional theory to calculate and predict the energetics and vibrational spectra for various aluminum species that are likely to be present in aqueous solutions. The Raman spectra of pure water in equilibrium with Al2O3 are devoid of any characteristic spectral features. In contrast, aqueous fluids with 5.3 m and 1 m KOH solution in equilibrium with Al2O3 show a sharp band at ˜620 cm-1 which could be attributed to the [ species. The band grows in intensity with temperature along an isochore. A shoulder on the high-frequency side of this band may be due to a hydrated, charge neutral Al(OH)3·H2O species. In the limited pressure, temperature and density explored in the present study, we do not find any evidence for the polymerization of the [ species to dimers [(OH)2-Al-(OH)2-Al(OH)2] or [(OH)3-Al-O-Al(OH)3]2-. This is likely due to the relatively low concentration of Al in the solutions and does not rule out significant polymerization at higher pressures and temperatures. Upon cooling of Al-bearing solutions to room temperatures, Raman bands indicating the precipitation of diaspore (AlOOH) were observed in some experiments. The Raman spectra of the KOH solutions (with or without dissolved alumina) showed a sharp OH stretching band at ˜3614 cm-1 and an in-plane OH bending vibration at ˜1068 cm-1, likely related to an OH- ion with the oxygen atom attached to a water molecule by hydrogen bonding. A weak feature at ˜935 cm-1 may be related to the out-of-plane bending vibration of the same species or to an OH species with a different environment.

The stability of hibonite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions

NASA Technical Reports Server (NTRS)

Beckett, J. R.; Stolper, E.

1993-01-01

Phase fields in which hibonite (Hib) and silicate melt coexist with spinel (Sp), CaAl4O7 (CA2), gehlenitic melilite (Mel), anorthite (An), or corundum (Cor) in the system CaO-MgO-Al203-SiO2-TiO2 (CMAST) were determined and activity models developed for Mel and Hib solid solutions. Experimentally determined partition coefficients for Ti between Hib and coexisting melt, D sub t, vary from 0.8 to 2.1 and generally decrease with increasing TiO2 content in the liquid (L). Based on Ti partioning between Hib and melt, bulk inclusion compositions and Hib-saturated liquid use phase diagrams, the Hib in Fluffy Type A inclusions (FTA's) from Allende and at least some of the Hib from Hib-rich inclusions is relict; much of the Hib from Hib-glass spherules probably crystallized from a melt under nonequilibrium conditions. Bulk compositions for all of these Ca-Al-rich inclusions (CAI's) are consistent with an origin as Mel + Hib + Sp + perovskite (Pv) proto-inclusions in which Mel was partially altered. In some cases, the proto-inclusion was partially or completely melted with vaporization occurring over a period of time sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. If equilibration temperatures based on Hib-bearing CAI's reflect condensation in a cooling gas of solar composition, then Hib + Cor condensed at approximately 1260 C (referenced to 10 exp -3 atm) and Hib + Sp + Mel at approximately 1215 +/- 10 C. Simple thermochemical models for the substitution of trace elements into the Ca-site of meteoritic Hib suggest that virtually all Eu is divalent in early condensate Hibs but that Eu(2+)/Eu(3+) decreases by a factor of 20 or more during the course of condensation, primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phases condense. The relative sizes of Eu and Yb anomalies in meteoritic Hibs and CAI's may be influenced by this effect.

The Effect of Fracture Filler Composition on the Parameters of Shear Deformation Regime

NASA Astrophysics Data System (ADS)

Pavlov, D.; Ostapchuk, A.; Batuhtin, I.

2015-12-01

Geomechanical models of different slip mode nucleation and transformation can be developed basing on laboratory experiments, in which regularities of shear deformation of gouge-filled faults are studied. It's known that the spectrum of possible slip modes is defined by both macroscopic deformation characteristics of the fault and mesoscale structure of fault filler. Small variations of structural parameters of the filler may lead to a radical change of slip mode [1, 2]. This study presents results of laboratory experiments investigating regularities of shear deformation of discontinuities filled with multicomponent granular material. Qualitative correspondence between experimental results and natural phenomena is detected. The experiments were carried out in the classical "slider model" statement. A granite block slides under shear load on a granite substrate. The contact gap between rough surfaces was filled with a discrete material, which simulated the principal slip zone of a fault. The filler components were quartz sand, salt, glass beads, granite crumb, corundum, clay and pyrophyllite. An entire spectrum of possible slip modes was obtained - from stable slip to slow-slip events and to regular stick-slip with various coseismic displacements realized per one act of instability. Mixing several components in different proportions, it became possible to trace the gradual transition from stable slip to regular stick-slip, from slow-slip events to fast-slip events. Depending on specific filler component content, increasing the portion of one of the components may lead to both a linear and a non-linear change of slip event moment (a laboratory equivalent of the seismic moment). For different filler compositions durations of equal-moment events may differ by more than two orders of magnitude. The findings can be very useful for developing geomechnical models of nucleation and transformation of different slip modes observed at natural faults. The work was supported by RFBR (grant no. 13-05-00780). 1. Mair, K., K. M. Frye, and C. Marone (2002), J.Geophys.Res., 107(B10), 2219. 2. G.G. Kocharyan, V.K. Markov, A.A. Ostapchuk, and D.V. Pavlov (2014), Phys.Mes, 17(2), 123-133.

Petrogenetic grids for sapphirine-bearing granulites

NASA Astrophysics Data System (ADS)

Podlesskii, Konstantin K.

2010-05-01

Phase relations involving sapphirine, garnet, spinel, orthopyroxene, olivine, cordierite, alumina silicates, corundum, and quartz have been calculated in the system FeO-MgO-Al2O3-SiO2 based on internally consitent thermodynamic properties of both the end-member minerals and the solid solutions (Gerya et al., 2004; Podlesskii et al., 2008). The derived P-T diagrams imply stable invariant points and stability fields of key assemblages that differ from those proposed by other authors (Kelsey et al., 2004; Harley 2008). The sapphirine + quartz assemblage, which is widely recognized as indicative of ultrahigh-temperature metamorphism, can be stable down to 835° C and ~6 kbar. The sapphirine + kyanite assemblage has been found stable at temperatures below 860° C and 11.3 kbar, whereas the sapphirine + forsterite assemblage may be stable below 800° C only under specific conditions of a very low activity of water. The existing constraints on the thermodynamic properties of sapphirine are considered insufficient to make decisive conclusions about metamorphic conditions. Granulites containing the sapphirine + quartz assemblage have been investigated with the microprobe to apply both the conventional thermobarometry and thermometry based on Ti contents of quartz (TitaniQ, Wark & Watson, 2006). The results demonstrate that, in some cases, this assemblage might have formed at relatively low temperatures during retrograde stages of metamorphism. The research has been supported by the RFBR grant 09-05-00193. References Gerya,T.V., Perchuk,L.L., & Podlesskii,K.K. In: Zharikov,V.A. & Fed'kin,V.V. (eds.) Experimental Mineralogy: Some Results on the Century's Frontier. Moscow: Nauka, Vol. 2, 188-206 (2004). Harley,S.L. Refining the P-T records of UHT crustal metamorphism. Journal of Metamorphic Geology, 26, 125-154 (2008). Kelsey,D.E., White,R.W., Holland,T.J.B., & Powell,R. Journal of Metamorphic Geology, 22, 559-578 (2004). Podlesskii,K.K., Aranovich,L.Y., Gerya,T.V., & Kosyakova,N.A. Sapphirine-bearing assemblages in the system MgO-Al2O3-SiO2: A continuing ambiguity. European Journal of Mineralogy, 20, 721-734 (2008). Wark,D.A. & Watson,E.B. TitaniQ: a titanium-in-quartz geothermometer. Contributions to Mineralogy and Petrology, 152, 743-754 (2006).

A source-depleted Early Jurassic granitic pluton from South China: Implication to the Mesozoic juvenile accretion of the South China crust

NASA Astrophysics Data System (ADS)

Zhou, Zuo-Min; Ma, Chang-Qian; Wang, Lian-Xun; Chen, Shu-Guang; Xie, Cai-Fu; Li, Yong; Liu, Wei

2018-02-01

Source-depleted granites were rarely reported in South China. Hereby we identified such a granitic pluton, the Tiandong pluton, at Northeastern Guangdong province in Southeastern (SE) China. Whole-rock Sr-Nd and zircon Hf isotopes of the Tiandong granites both revealed obviously depleted source signatures, with initial isotopic values of initial 87Sr/86Sr = 0.7032-0.7040, εNd(t) = 1.1-1.5, and εHf(t) = 6-13, respectively. Zircon U-Pb dating implied the granite was intruded in Early Jurassic (188 Ma). The dominant minerals of the Tiandong granite consist of K-feldspar, plagioclase, quartz and biotite, with accessory mineral assemblage of apatite + zircon + magnetite. Based on the mineralogy and the depleted isotopic signature, the granites chemically show I-type affinity such as low Zr + Nb + Ce + Y (131.6 to 212.2), 104 × Ga/Al (2.12-2.27), A/CNK values < 1.1 (0.97-1.03), corundum molecule < 1 (0-0.55) and extremely low P2O5 contents (0.05 wt%). The one-stage and two-stage depleted mantle Nd model ages (TDM = 0.89 to 0.84 Ga, T2DM = 0.88 to 0.85 Ga) are consistent. TDM(Hf) values of 0.31-0.63 Ga are also indistinguishable from T2DM(Hf) values of 0.35-0.75 Ga. The Nd and Hf isotopic compositions confirm that the Tiandong granites are juvenile crustal accretion but decoupled Nd-Hf isotopic systems. The juvenile crust is likely to originate from a mixed source of the primary asthenospheric mantle and the subordinate EMII. Combined with early studies of adjacent rocks, we propose that the early Jurassic ( 200-175 Ma) magmatism as evidenced by the Tiandong granites might be driven by upwelling of asthenosphere and subsequent underplating of mafic melts in an intra-plate extensional setting as a response to far-field stress during early stage subduction of the paleo-pacific plate.

Tonalite and trondhjemite plutonism in the western Chugach Mountains, so. Alaska: an example of near trench magmatism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Monteverde, D.; Pavlis, T.

1985-01-01

In the northern Chugach Mountains of southern Alaska a suite of granitoid plutons were emplaced in a near-trench setting in mid-Early Cretaceous time. The plutons intrude both the then continental edge marked by Jurassic igneous and metamorphic rocks of the Peninsular terrane and the accretionary prism composed of the Early Cretaceous McHugh Complex. Field, petrographic and geochemical data classify the plutonic rocks as ranging from a hornblende-biotite tonalite to a biotite trondjhemite. Most of the rocks are post-metamorphic and show hypidiomorphic granular textures. Locally, however, the rocks are weakly foliated and quartz shows grain size reduction (serrate textures) indicative ofmore » minor ductile strain; suggesting some strain following emplacement. Geochemically, Harker variation diagrams show a linear variation as related to silica content: MgO, FeO total, TiO/sub 2/, and CaO and Al/sub 2/O/sub 3/ decrease while Na/sub 2/O, K/sub 2/O, MnO and P/sub 2/O/sub 5/ maintain constant percentages with increasing silica content. Chemical ranges include: SiO/sub 2/ 61.98 to 74.90%, Al/sub 2/O/sub 3/ 19.35 to 14.25%, CaO 6.93 to 2.23%, Na/sub 2/O averages 4.33%, K/sub 2/O averages 0.91%. The rocks are a high Al/sub 2/O/sub 3/ (calcic.) trondjhemite of Barker (1979). Most of the rocks are strongly peraluminous (>1.1% corundum normative); garnet crystals show equilibrium textures without reaction rims; and stable isotope analysis of a small sample suite show significant /sup 08/O enrichment (>9.6 per mil SMOW). Two possible petrographic models fit the data. The entail a fractional crystallization-assimilation model and a partial melting of a low temperature hydrothermally altered basalt. The tectonic mechanism responsible for this unusual event is elusive but two models are allowable: 1) a ridge-trench encounter; and 2) melting along thrust planes during initiation of subduction - a mechanism analogous to melting along great crystalline thrust sheets.« less

Occupational exposure to aluminum and its biomonitoring in perspective.

PubMed

Riihimäki, Vesa; Aitio, Antero

2012-11-01

Exposure to aluminum at work is widespread, and people are exposed to several species of aluminum, which differ markedly as to the kinetics and toxicity. Especially welding of aluminum is widely applied and continuously expanding. Inhalation of fine particles of sparsely soluble aluminum results in the retention of deposited particles in the lungs. From the lungs, aluminum is released to the blood and distributed to bones and the brain, and excreted to urine. Soluble aluminum compounds are not accumulated in the lungs. Neurotoxicity is the critical effect of exposure to sparsely soluble aluminum compounds. Studies on workers exposed to aluminum welding fumes have revealed disturbances of cognitive processes, memory and concentration, and changes in mood and EEG. Early pulmonary effects have been observed among aluminum powder-production workers using high-resolution computed tomography. The primary objective of aluminum biomonitoring (BM) is to help prevent the formation of aluminum burden in the lungs and thereby to prevent harmful accumulation of aluminum in target organs. BM of aluminum can be effectively used for this purpose in the production/use of aluminum powders, aluminum welding, as well as plasma cutting, grinding, polishing and thermal spraying of aluminum. BM of aluminum may also be similarly useful in the smelting of aluminum and probably in the production of corundum. BM can help identify exposed individuals and roughly quantitate transient exposure but cannot predict health effects in the production/use of soluble aluminum salts. For urinary aluminum (U-Al) we propose an action limit of 3 µmol/L, corrected to a relative density of 1.021, in a sample collected preshift after two days without occupational exposure, and without use of aluminum-containing drugs. This value corresponds roughly to 2.3 µmol/g creatinine. Compliance with this limit is expected to protect the worker against the critical effect of aluminum in exposure to sparsely soluble aluminum dusts, the cognitive function of the central nervous system. For serum aluminum (S-Al), we do not propose an action limit because S-Al is less sensitive as an indicator of aluminum load.

Characterization of feed coal and coal combustion products from power plants in Indiana and Kentucky

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brownfield, M.E.; Affolter, R.H.; Cathcart, J.D.

1999-07-01

The US Geological Survey, Kentucky Geological Survey, and the University of Kentucky Center for Applied Energy Research are collaborating with Indiana and Kentucky utilities to determine the physical and chemical properties of feed coal and coal combustion products (CCP) from three coal-fired power plants. These three plants are designated as Units K1, K2, and I1 and burn high-, moderate-, and low-sulfur coals, respectively. Over 200 samples of feed coal and CCP were analyzed by various chemical and mineralogical methods to determine mode of occurrence and distribution of trace elements in the CCP. Generally, feed coals from all 3 Units containmore » mostly well-crystallized kaolinite and quartz. Comparatively, Unit K1 feed coals have higher amounts of carbonates, pyrite and sphalerite. Unit K2 feed coals contain higher kaolinite and illite/muscovite when compared to Unit K1 coals. Unit I1 feed coals contain beta-form quartz and alumino-phosphates with minor amounts of calcite, micas, anatase, and zircon when compared to K1 and K2 feed coals. Mineralogy of feed coals indicate that the coal sources for Units K1 and K2 are highly variable, with Unit K1 displaying the greatest mineralogic variability; Unit I1 feed coal however, displayed little mineralogic variation supporting a single source. Similarly, element contents of Units K1 and K2 feed coals show more variability than those of Unit I1. Fly ash samples from Units K1 and K2 consist mostly of glass, mullite, quartz, and spines group minerals. Minor amounts of illite/muscovite, sulfates, hematite, and corundum are also present. Spinel group minerals identified include magnetite, franklinite, magnesioferrite, trevorite, jacobisite, and zincochromite. Scanning Electron Microscope analysis reveals that most of the spinel minerals are dendritic intergrowths within aluminum silicate glass. Unit I1 fly ash samples contain glass, quartz, perovskite, lime, gehlenite, and apatite with minor amounts of periclase, anhydrite, carbonates, pyroxenes, and spinels. The abundant Ca mineral phases in the Unit I1 fly ashes are attributed to the presence of carbonate, clay and phosphate minerals in the coal.« less

Quasi ?non-destructive? laser ablation-inductively coupled plasma-mass spectrometry fingerprinting of sapphires

NASA Astrophysics Data System (ADS)

Guillong, M.; Günther, D.

2001-07-01

A homogenized 193 nm excimer laser with a flat-top beam profile was used to study the capabilities of LA-ICP-MS for 'quasi' non-destructive fingerprinting and sourcing of sapphires from different locations. Sapphires contain 97-99% of Al 2O 3 (corundum), with the remainder composed of several trace elements, which can be used to distinguish the origin of these gemstones. The ablation behavior of sapphires, as well as the minimum quantity of sample removal that is required to determine these trace elements, was investigated. The optimum ablation conditions were a fluency of 6 J cm -2, a crater diameter of 120 μm, and a laser repetition rate of 10 Hz. The optimum time for the ablation was determined to be 2 s, equivalent to 20 laser pulses. The mean sample removal was 60 nm per pulse (approx. 3 ng per pulse). This allowed satisfactory trace element determination, and was found to cause the minimum amount of damage, while allowing for the fingerprinting of sapphires. More than 40 isotopes were measured using different spatial resolutions (20-120 μm) and eight elements were reproducibly detected in 25 sapphire samples from five different locations. The reproducibility of the trace element distribution is limited by the heterogeneity of the sample. The mean of five or more replicate analyses per sample was used. Calibration was carried out using NIST 612 glass reference material as external standard. The linear dynamic range of the ICP-MS (nine orders of magnitude) allowed the use of Al, the major element in sapphire, as an internal standard. The limits of detection for most of the light elements were in the μg g -1 range and were better for heavier elements (mass >85), being in the 0.1 μg g -1 range. The accuracy of the determinations was demonstrated by comparison with XRF analyses of the same set of samples. Using the quantitative analyses obtained using LA-ICP-MS, natural sapphires from five different origins were statistically classified using ternary plots and principal multi-component analysis.

Experimental Measurements of Permeability Evolution along Faults during Progressive Slip

NASA Astrophysics Data System (ADS)

Strutz, M.; Mitchell, T. M.; Renner, J.

2010-12-01

Little is currently known about the dynamic changes in fault-parallel permeability along rough faults during progressive slip. With increasing slip, asperities are worn to produce gouge which can dramatically reduce along fault permeability within the slip zone. However, faults can have a range of roughness which can affect both the porosity and both the amount and distribution of fault wear material produced in the slipping zone during the early stages of fault evolution. In this novel study we investigate experimentally the evolution of permeability along a fault plane in granite sawcut sliding blocks with a variety of intial roughnesses in a triaxial apparatus. Drillholes in the samples allow the permeability to be measured along the fault plane during loading and subsequent fault displacement. Use of the pore pressure oscillation technique (PPO) allows the continuous measurement of permeability without having to stop loading. To achieve a range of intial starting roughnesses, faults sawcut surfaces were prepared using a variety of corundum powders ranging from 10 µm to 220 µm, and for coarser roughness were air-blasted with glass beads up to 800µm in size. Fault roughness has been quantified with a laser profileometer. During sliding, we measure the acoustic emissions in order to detect grain cracking and asperity shearing which may relate to both the mechanical and permeability data. Permeability shows relative reductions of up to over 4 orders of magnitude during stable sliding as asperities are sheared to produce a fine fault gouge. This variation in permeability is greatest for the roughest faults, reducing as fault roughness decreases. The onset of permeability reduction is contemporaneous with a dramatic reduction in the amount of detected acoustic emissions, where a continuous layer of fault gouge has developed. The amount of fault gouge produced is related to the initial roughness, with the rough faults showing larger fault gouge layers at the end of slip. Following large stress drops and stick slip events, permeability can both increase and decrease due to dynamic changes in pore pressure during fast sliding events. We present a summary of preliminary data to date, and discuss some of the problems and unknowns when using the PPO method to measure permeability.

Helium diffusion parameters of hematite from a single-diffusion-domain crystal

NASA Astrophysics Data System (ADS)

Farley, K. A.

2018-06-01

This contribution reports new parameters for helium diffusion in hematite useful for interpretation of cosmogenic 3He and radiogenic 4He chronometry. Fragments of a coarse, euhedral single crystal of hematite from Minas Gerais, Brazil were subjected to bulk step-heating helium diffusion experiments after proton irradiation to make a uniform distribution of 3He. Aliquots of three different grain sizes ranging from ∼300 to ∼700 μm in equivalent-sphere radius yielded helium diffusion activation energies Ea ∼ 170 kJ/mol, very similar to previous estimates for Ea in hematite. Uniquely in this specimen, diffusivity varies with the dimensions of the analyzed fragments in precisely the fashion expected if the diffusion domain corresponds to the physical grain. This contrasts with previous studies that concluded that the analyzed hematites consist of polycrystalline aggregates in which helium migration is governed by the size distribution of the constituent crystallites. These new data permit a direct estimate of the helium diffusivity at infinite temperature for hematite of ln(Do) = -0.66 ± 0.35 in cm2/s. The major implication of the new diffusion parameters is that hematite is very retentive of helium even at very small crystal sizes. For example, a 20 nm radius hematite crystal, at the smallest end of the size range so far described in dated polycrystalline hematite specimens, will retain more than 99% of its ingrown He over 1 Myr at 30 °C, and more than 90% over 100 Myr. Under most conditions, hematite is close to quantitatively helium-retentive on the Earth's surface, simplifying radiogenic and cosmogenic helium dating of this phase. In a system cooling at 10 °C/Myr, the 20 nm hematite crystal has a He closure temperature of ∼70 °C, similar to a typical ∼100 μm apatite crystal. Helium is likely held tightly in hematite owing to its dense hexagonal closest packing structure and absence of migration-enhancing channels. The isostructural minerals corundum and ilmenite are likely to be similarly helium retentive.

Electron Transfer Pathways Facilitating U(VI) Reduction by Fe(II) on Al- vs Fe-Oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taylor, S. D.; Becker, U.; Rosso, K. M.

This study continues mechanistic development of heterogeneous electron transfer (ET) pathways at mineral surfaces in aquatic environments that enable the reduction U(VI) by surface-associated Fe(II). Using computational molecular simulation within the framework of Marcus Theory, our findings highlight the importance of the configurations and interaction of the electron donor and acceptor species with the substrate, with respect to influencing its electronic structure and thereby the ability of semiconducting minerals to facilitate ET. U(VI) reduction by surface-associated Fe(II) (adsorbed or structurally incorporated into the lattice) on an insulating, corundum (001) surface (α-Al2O3) occurs when proximal inner-sphere (IS) surface complexes are formed,more » such that ET occurs through a combination of direct exchange (i.e., Fe d- and U f-orbitals overlap through space) and superexchange via intervening surface oxygen atoms. U(VI) reduction by coadsorbed Fe(II) on the isostructural semiconducting hematite (α-Fe2O3) basal surface requires either their direct electronic interaction (e.g., IS complexation) or mediation of this interaction indirectly through the surface via an intrasurface pathway. Conceptually possible longer-range ET by charge-hopping through surface Fe atoms was investigated to determine whether this indirect pathway is competitive with direct ET. The calculations show that energy barriers are large for this conduction-based pathway; interfacial ET into the hematite surface is endothermic (+80.1 kJ/mol) and comprises the rate-limiting step (10–6 s–1). The presence of the IS adsorbates appears to weaken the electronic coupling between underlying Fe ions within the surface, resulting in slower intra-surface ET (10–5 s–1) than expected in the bulk basal plane. Our findings lay out first insights into donor-acceptor communication via a charge-hopping pathway through the surface for heterogeneous reduction of U(VI) by Fe(II) and help provide a basis for experimental interrogation of this important process at mineral-water interfaces.« less

Equilibrium chemistry down to 100 K. Impact of silicates and phyllosilicates on the carbon to oxygen ratio

NASA Astrophysics Data System (ADS)

Woitke, P.; Helling, Ch.; Hunter, G. H.; Millard, J. D.; Turner, G. E.; Worters, M.; Blecic, J.; Stock, J. W.

2018-06-01

We have introduced a fast and versatile computer code, GGCHEM, to determine the chemical composition of gases in thermo-chemical equilibrium down to 100 K, with or without equilibrium condensation. We have reviewed the data for molecular equilibrium constants, kp(T), from several sources and discussed which functional fits are most suitable for low temperatures. We benchmarked our results against another chemical equilibrium code. We collected Gibbs free energies, ΔGf⊖, for about 200 solid and liquid species from the NIST-JANAF database and the geophysical database SUPCRTBL. We discussed the condensation sequence of the elements with solar abundances in phase equilibrium down to 100 K. Once the major magnesium silicates Mg2SiO4[s] and MgSiO3[s] have formed, the dust to gas mass ratio jumps to a value of about 0.0045 which is significantly lower than the often assumed value of 0.01. Silicate condensation is found to increase the carbon to oxygen ratio (C/O) in the gas from its solar value of 0.55 up to 0.71, and, by the additional intake of water and hydroxyl into the solid matrix, the formation of phyllosilicates at temperatures below 400 K increases the gaseous C/O further to about 0.83. Metallic tungsten (W) is the first condensate found to become thermodynamically stable around 1600-2200 K (depending on pressure), several hundreds of Kelvin before subsequent materials such as zirconium dioxide (ZrO2) or corundum (Al2O3) can condense. We briefly discuss whether tungsten, despite its low abundance of 2 × 10-7 times the silicon abundance, could provide the first seed particles for astrophysical dust formation. GGCHEM code is publicly available at http://https://github.com/pw31/GGchemTable D.1 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/614/A1

Evolutionary search for novel superhard phases, or can TiO2 be the hardest oxide? (Invited)

NASA Astrophysics Data System (ADS)

Oganov, A. R.; Lyakhov, A. O.

2010-12-01

Synthesis of novel superhard materials, frequently achieved with high-pressure experimental techniques, is a difficult task. Study of such materials, usually first obtained in very small quantities, is complicated, and this field is full of controversies and artefacts (see, e.g. [1]). Hardness was long believed to be an exceedingly difficult property to model or predict; however, a number of simple models have recently been proposed and shown to yield surprisingly accurate results (see reviews in [2]). We have found [3] a way to further improve these models, by augmenting them with bond-valence model and graph theory. Combining such models with our structure prediction method [4], we have developed a powerful [5] approach for computational design of novel superhard materials. Using this method, we recently addressed [3] the previously proposed [6] possibility that C3N4 may be harder than diamond, and the claim [7] that TiO2-cotunnite is the hardest oxide with the Vickers hardness of 38 GPa. Our results unequivocally suggest that the latter suggestion is incorrect. No TiO2 polymorph can attain hardness greater than 17 GPa [3], i.e. all possible structures of TiO2 are softer than common corundum (Al2O3). Furthermore, TiO2-cotunnite is dynamically unstable at atmospheric pressure [8]. REFERENCES: [1] Oganov A.R., Solozhenko V.L., Kurakevych O.O., Gatti C., Ma Y., Chen J., Liu Z., and Hemley R.J., http://arxiv.org/abs/ 0908.2126 (2009). [2] Theory of Superhard Materials (Special Issue), J. Superhard Materials, issue 3 (2010). [3] Lyakhov A.O., Oganov A.R., in prep. (2010). [4] Oganov A.R., Glass C.W., J. Chem. Phys. 124, 244704 (2006). [5] Oganov A.R., Lyakhov A.O., J. Superhard Mater. 32, 143-147 (2010). [6] Liu A.Y., Cohen M.L., Science 245, 841-842 (1989). [7] Dubrovinsky L.S., Dubrovinskaia N.A., et al., Nature 410, 653-654 (2001). [8] Kim D.Y., et al., Appl. Phys. Lett. 90, 171903 (2007).

Phase Stability and Transformations in Vanadium Oxide Nanocrystals

NASA Astrophysics Data System (ADS)

Bergerud, Amy Jo

Vanadium oxides are both fascinating and complex, due in part to the many compounds and phases that can be stabilized as well as the phase transformations which occur between them. The metal to insulator transitions (MITs) that take place in vanadium oxides are particularly interesting for both fundamental and applied study as they can be induced by a variety of stimuli ( i.e., temperature, pressure, doping) and utilized in many applications (i.e., smart windows, sensors, phase change memory). Nanocrystals also tend to demonstrate interesting phase behavior, due in part to the enhanced influence of surface energy on material thermodynamics. Vanadium oxide nanocrystals are thus expected to demonstrate very interesting properties in regard to phase stability and phase transformations, although synthesizing vanadium oxides in nanocrystal form remains a challenge. Vanadium sesquioxide (V2O3) is an example of a material that undergoes a MIT. For decades, the low temperature monoclinic phase and high temperature corundum phase were the only known crystal structures of V2O3. However, in 2011, a new metastable polymorph of V2O3 was reported with a cubic, bixbyite crystal structure. In Chapter 2, a colloidal route to bixbyite V2O 3 nanocrystals is presented. In addition to being one of the first reported observations of the bixbyite phase in V2O3, it is also one of the first successful colloidal syntheses of any of the vanadium oxides. The nanocrystals possess a flower-like morphology, the size and shape of which are dependent on synthesis time and temperature, respectively. An aminolysis reaction mechanism is determined from Fourier transform infrared spectroscopy data and the bixbyite crystal structure is confirmed by Rietveld refinement of X-ray diffraction (XRD) data. Phase stability is assessed in both air and inert environments, confirming the metastable nature of the material. Upon heating in an inert atmosphere above 700°C, the nanocrystals irreversibly transform to the bulk stable corundum phase of V2O3 with concurrent particle coarsening. This, in combination with the enhanced stability of the nanocrystals over bulk, suggests that the bixbyite phase may be stabilized due to surface energy effects, a well-known phenomenon in nanocrystal research. In Chapter 3, the reversible incorporation of oxygen in bixbyite V 2O3 is reported, which can be controlled by varying temperature and oxygen partial pressure. Based on XRD and thermogravimetric analysis, it is found that oxygen occupies interstitial sites in the bixbyite lattice. Two oxygen atoms per unit cell can be incorporated rapidly and with minimal changes to the structure while the addition of three or more oxygen atoms destabilizes the structure, resulting in a phase change that can be reversed upon oxygen removal. Density functional theory (DFT) supports the reversible occupation of interstitial sites in bixbyite by oxygen and the 1.1 eV barrier to oxygen diffusion predicted by DFT matches the activation energy of the oxidation process derived from observations by in situ XRD. The observed rapid oxidation kinetics are thus facilitated by short diffusion paths through the bixbyite nanocrystals. Due to the exceptionally low temperatures of oxidation and reduction, this material, made from earth-abundant atoms, is proposed for use in oxygen storage applications, where oxygen is reversibly stored and released. Further oxidation of bixbyite V2O3 under controlled oxygen partial pressure can lead to the formation of nanocrystalline vanadium dioxide (VO2), a material that is studied for its MIT that occurs at 68 C in the bulk. This transformation is accompanied by a change in crystal structure, from monoclinic to rutile phase, and a change in optical properties, from infrared transparent to infrared blocking. Because of this, VO2 is promising for thermochromic smart window applications, where optical properties vary with temperature. Recently, alternative stimuli have been utilized to trigger MITs in VO2, including electrochemical gating. Rather than inducing the expected monoclinic to rutile phase transition as originally proposed, electrochemical gating of the insulating phase was recently shown to induce oxygen vacancy formation in VO2, thereby inducing metallization, while the characteristic V-V dimerization of the monoclinic phase was retained. In Chapter 4, the preparation and electrochemical reduction of VO2 nanocrystal films is presented. The nanocrystalline morphology allows for the study of transformations under conditions that enhance the gating effect by creating a large VO2-electrolyte interfacial area and by reducing the path length for diffusion. The resulting transitions are observed optically, from insulator to metal to insulator and back, with in situ visible-near infrared spectroelectrochemistry and correlated with structural changes monitored by Raman and X-ray absorption spectroscopies. The never-before-seen transition to an insulating phase under progressive electrochemical reduction is attributed to an oxygen defect induced phase transition to a new phase. This is likely enabled by the nanocrystalline nature of the sample, which may enhance the kinetics of oxygen diffusion, support a higher degree of lattice expansion-induced strain, or simply alter the thermodynamics of the system.

Adsorption of dissolved aluminum on sapphire-c and kaolinite: implications for points of zero charge of clay minerals

PubMed Central

2014-01-01

We have studied the impact of dissolved aluminum on interfacial properties of two aluminum bearing minerals, corundum and kaolinite. The effect of intentionally adding dissolved aluminum on electrokinetic potential of basal plane surfaces of sapphire was studied by streaming potential measurements as a function of pH and was complemented by a second harmonic generation (SHG) study at pH 6. The electrokinetic data show a similar trend as the SHG data, suggesting that the SHG electric field correlates to zeta-potential. A comparable study was carried out on kaolinite particles. In this case electrophoretic mobility was measured as a function of pH. In both systems the addition of dissolved aluminum caused significant changes in the charging behavior. The isoelectric point consistently shifted to higher pH values, the extent of the shift depending on the amount of aluminum present or added. The experimental results imply that published isoelectric points of clay minerals may have been affected by this phenomenon. The presence of dissolved aluminum in experimental studies may be caused by particular pre-treatment methods (such as washing in acids and subsequent adsorption of dissolved aluminum) or even simply by starting a series of measurements from extreme pH (causing dissolution), and subsequently varying the pH in the very same batch. This results in interactions of dissolved aluminum with the target surface. A possible interpretation of the experimental results could be that at low aluminum concentrations adatoms of aluminum (we will refer to adsorbed mineral constituents as adatoms) can form at the sapphire basal plane, which can be rather easily removed. Simultaneously, once the surface has been exposed to sufficiently high aluminum concentration, a visible change of the surface is seen by AFM which is attributed to a surface precipitate that cannot be removed under the conditions employed in the current study. In conclusion, whenever pre-treatment or the starting point of an experiment favor the dissolution of aluminum, dissolved Al may remain in the experimental system and interact with the target surfaces. The systems are then no longer pristine and points of zero charge or sorption data are those of aluminum-bearing systems. PMID:25045321

Records of near-isothermal decompression and clockwise P-T history from the Paleoproterozoic Mahakoshal Belt, Central Indian Tectonic Zone: Constraints from pseudosection modelling and monazite geochronology

NASA Astrophysics Data System (ADS)

Deshmukh, Tanzil; Naraga, Prabhakar; Bhattacharya, Abhijit; Kaliappan, Madhavan

2017-04-01

The Mahakoshal Belt (MB) is regarded as the oldest subunit along the northern collar of the Central Indian Tectonic Zone (CITZ) arguably representing the zone of accretion between the North India Block and the South India Block. The following study focuses on deciphering the structural and metamorphic P-T-t history of the schists/phyllites from the eastern part of the belt, and provides insights into the Paleoproterozoic tectonic development in the CITZ. The schists comprise phengite, quartz, andalusite, biotite, muscovite and margarite, and are associated with veins of rare andalusite + corundum + quartz assemblage. The field relations combined with deformation microtextures in the MB schists suggests three episodes of metamorphism, M1, M2 and M3, corresponding with D1, D2 and D3 deformation events respectively. Inclusion trails (S1) of phengite + biotite + quartz ± chlorite in syn/post-S2 andalusite porphyroblasts constrain the M1 metamorphic event in pelitic schists. The application of pseudosection modelling estimated peak metamorphic conditions at ˜8 kbar and 520 ˚ C. Near isothermal decompression (<4 kbar) resulted in the formation of the andalusite + muscovite bearing retrograde assemblage that stabilized at the expense of phengite-bearing assemblage. Further, andalusite porphyroblasts are replaced by margarite + muscovite + chlorite pseudomorphs (2-3 kbar) during syn/post-S3 fluid-aided metamorphism. Th-U-total Pb dating of monazite grains yield core populations at 1.8-1.9 Ga, and rim populations at 1.7-1.8 Ga and 1.5-1.6 Ga. Thus, the peak metamorphism in MB schists was Paleoproterozoic in age, 1.8-1.9 Ga, and the clockwise P-T path was recorded at 1.7-1.8 Ga, which overlaps with the emplacement of blastoporphyritic granitoids along southern margin of the MB. The results obtained in this study combined with the existing structural-metamorphic-chronological information demonstrate the CITZ to be a composite of desperately-evolved crustal domains. With some major omissions, the tectono-thermal events identified in the CITZ partly overlap with those observed in the Capricorn Orogen (Western Australia) and the Trans North China Orogen. Therefore, these global correlations possibly corroborate new configurations on the assembly and fragmentation of Columbia Supercontinent, but await further studies and robust age determinations in the various parts of CITZ.

Indirect synthesis of Al{sub 2}O{sub 3}via radiation- or photochemical formation of its hydrated precursors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barta, Jan, E-mail: jan.barta@fjfi.cvut.cz; Pospisil, Milan; Cuba, Vaclav

Graphical abstract: - Highlights: • Al{sub 2}O{sub 3} precursors were produced by UV/e-beam irradiation of aqueous solutions. • Depending on the aluminium salt (Cl{sup −} or NO{sub 3}{sup −}), either γ-AlOOH or Al(OH){sub 3} is formed. • The mechanism involved strongly depends on the presence of formate anion. • Prepared mesoporous solid phase has high specific surface area (<190 m{sup 2} g{sup −1}). • Calcination of the precursor leads to the formation of γ-/η-, θ- and α-Al{sub 2}O{sub 3}. - Abstract: γ-, θ- and α-modifications of aluminium oxide (alumina) were successfully prepared by calcination of precursor solid phase obtained bymore » irradiation of clear aqueous solutions by UV light or electron beam. For the precipitate to form, formate anion must be present in the solution in sufficient concentration. According to X-ray diffraction, the precipitate was found to consist of γ-AlOOH or a mixture of γ- and α-Al(OH){sub 3}, when aluminium chloride or aluminium nitrate was used, respectively. The addition of hydrogen peroxide as a ·OH radical source and sensitizer markedly improved the efficiency of the preparation. Some hints for the apparently very complex mechanism involved were listed and discussed. Calcination of the dried precipitate at 500–800 °C produced highly porous γ-alumina with high specific surface area (ca. 150 m{sup 2} g{sup −1}). Mixture of γ- and θ-transition aluminas was obtained at 1000 °C and pure, stable corundum α-Al{sub 2}O{sub 3} formed at 1200 °C. Samples were further investigated by means of scanning electron microscopy and specific surface area or porosity measurement. According to N{sub 2} adsorption isotherm, the precipitate contains mostly mesopores with average pore size 7 nm with specific surface area of ca. 100 m{sup 2} g{sup −1}. Possible applications of the material as sorbent or catalyst as well as a pure matrix for thermoluminescence dosimetry were briefly contemplated. Strong light-induced thermoluminescence was observed in both γ- and α-Al{sub 2}O{sub 3} samples at 300–400 °C, whereas in the absence of light, only an inexpressive glow peak at 179 °C was observed.« less

The Influence of Phenocrysts on Magma Degassing in Rhyolitic Systems

NASA Astrophysics Data System (ADS)

deGraffenried, R.; Larsen, J. F.; Lindoo, A. N.

2016-12-01

The kinetics of volatile exsolution and magma degassing control volcanic eruption styles, but the role of phenocrysts in the degassing process is poorly understood. The focus of this study is two series of decompression experiments examining how phenocrysts may or may not influence vesicle structures leading to permeability development and degassing in magmas with rhyolitic matrix melts. Powdered rhyolite obsidian (75 SiO2 wt. %; Mono Craters, CA) was seeded with 20 and 40 vol. % euhedral corundum crystals (350 μm) to approximate phenocrysts. Experiments were run using TZM (Ti-Zr-Mo alloy) vessels fitted with a water-cooled rapid quench top in a vertical Deltech furnace. Each run was held at 110 MPa and 900OC for 24 hours then decompressed continuously at a rate of 0.25 MPa/s to a final pressure (Pf) between 75 and 15 MPa. Permeability was measured using a bench-top permeameter constructed for the small experimental samples. Porosity was obtained from reflected light images using NIH Image J. The porosity of the samples increased from 11.0±1.7 to 73.3±3.1 vol % at Pf of 75 to 15 MPa for crystal free samples, 30.1±6.9 to 62.2±2.6 vol % at Pf of of 75 to 25 MPa for 20 vol % crystal samples, and 13.3±2.5 to 41.2±9.6 vol % at Pf of 75 to 50 MPa for 40 vol % crystal samples. The 20 vol % samples are impermeable up to at least 50 MPa Pf. The 40 vol % samples are impermeable up to 25 MPa Pf, with one sample having a measured Darcian permeability of -13.93±0.05 m2 at 25 MPa Pf. Comparatively, the crystal free samples were mostly impermeable up to 15 MPa, with one sample having a measured Darcian permeability of -14.41±0.04 m2 at 15 MPa Pf and 73.3 vol % porosity. Although preliminary, our permeable 40 vol % experiment suggests the phenocrysts help the samples develop permeability at a higher ending pressure and potentially lower porosity. Differences in the porosity curve as a function of pressure between the 20 and 40 vol % series indicate phenocrysts influence the vesicle structures in ascending magmas.

Automated system measuring triple oxygen and nitrogen isotope ratios in nitrate using the bacterial method and N2 O decomposition by microwave discharge.

PubMed

Hattori, Shohei; Savarino, Joel; Kamezaki, Kazuki; Ishino, Sakiko; Dyckmans, Jens; Fujinawa, Tamaki; Caillon, Nicolas; Barbero, Albane; Mukotaka, Arata; Toyoda, Sakae; Well, Reinhard; Yoshida, Naohiro

2016-12-30

Triple oxygen and nitrogen isotope ratios in nitrate are powerful tools for assessing atmospheric nitrate formation pathways and their contribution to ecosystems. N 2 O decomposition using microwave-induced plasma (MIP) has been used only for measurements of oxygen isotopes to date, but it is also possible to measure nitrogen isotopes during the same analytical run. The main improvements to a previous system are (i) an automated distribution system of nitrate to the bacterial medium, (ii) N 2 O separation by gas chromatography before N 2 O decomposition using the MIP, (iii) use of a corundum tube for microwave discharge, and (iv) development of an automated system for isotopic measurements. Three nitrate standards with sample sizes of 60, 80, 100, and 120 nmol were measured to investigate the sample size dependence of the isotope measurements. The δ 17 O, δ 18 O, and Δ 17 O values increased with increasing sample size, although the δ 15 N value showed no significant size dependency. Different calibration slopes and intercepts were obtained with different sample amounts. The slopes and intercepts for the regression lines in different sample amounts were dependent on sample size, indicating that the extent of oxygen exchange is also dependent on sample size. The sample-size-dependent slopes and intercepts were fitted using natural log (ln) regression curves, and the slopes and intercepts can be estimated to apply to any sample size corrections. When using 100 nmol samples, the standard deviations of residuals from the regression lines for this system were 0.5‰, 0.3‰, and 0.1‰, respectively, for the δ 18 O, Δ 17 O, and δ 15 N values, results that are not inferior to those from other systems using gold tube or gold wire. An automated system was developed to measure triple oxygen and nitrogen isotopes in nitrate using N 2 O decomposition by MIP. This system enables us to measure both triple oxygen and nitrogen isotopes in nitrate with comparable precision and sample throughput (23 min per sample on average), and minimal manual treatment. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

An integrated geochemical, geophysical and mineralogical study of river sediments in alpine area and soil samples near steel plant, in Austria

NASA Astrophysics Data System (ADS)

Irfan, M. I.; Meisel, T.

2012-04-01

Concentration of nickel and chromium in any part of the ecosystem is important for environmental concerns in particular human health due to the reason that some species of them can cause health problem e.g. dermatitis and cancer. Sediment samples collected form a river Vordernberger Bach (Leoben, Austria) in an alpine region and soil samples collected in an area adjacent to steel production unit in same narrow valley were investigated. In previous studies a correlation between magnetic susceptibility values and concentration of nickel and chromium showed that a magnetic susceptibility meter can be used to point out the contaminated areas as in-situ device. The purpose of the whole study is to understand the real (point or diffuse, anthropogenic or geogenic) sources of contamination of soils, water and river sediments through heavy metal deposition. Unseparated, magnetic and non-magnetic fractions of soil samples were investigated for geochemical and mineralogical aspects with XRF, ICP-MS, EMPA, Multi-Functional Kappabridge (MFK1) and laser ablation coupled with ICP-MS. Mineralogical study of sediment samples for several sampling points with higher Ni and Cr content was performed. Sediment samples were sieved below 1.4 mm and then a concentrate of heavy minerals was prepared in the field through panning. Concentrated heavy minerals were then subjected for heavy liquid separation in the laboratory. Separated magnetic and non-magnetic fractions below 0.71/0.1 mm and density greater than 2.9 g/cm3 were selected for mineralogical investigation. The abundance of typical anthropogenic particles, e.g., spherical, tinder, roasted ores, iron and steel mill slag was observed under the microscope. Magnetite (mostly anthropogenic), maghemite, chromspinel, chromite (type I & II), (Ca,Al)-ferrite, wustite, apatite (anthropogenic), olivine mixed crystals, calcium silicate and spinel (anthropogenic) are found in magnetic fraction. Non-magnetic fractions contain hematite, siderite, ankerite, corundum (anthropogenic), garnet, chlorite, titanium oxide minerals (ilmenite, rutile, titanite) and amphibole etc. The observed significant increase in heavy metal content from the source region of the Vordernberger Bach at 1500 m above sea level to the confluence of the Vordernberger Bach with the Mur River at 540 m AMSL can be attributed to anthropogenic influence. As expected, the anthropogenic input is more pronounced in the vicinity of historic and current iron and steel production.

Revised values for the Gibbs free energy of formation of [Al(OH)4 aq-], diaspore, boehmite and bayerite at 298.15 K and 1 bar, the thermodynamic properties of kaolinite to 800 K and 1 bar, and the heats of solution of several gibbsite samples

USGS Publications Warehouse

Hemingway, B.S.; Robie, R.A.; Kittrick, J.A.

1978-01-01

Solution calorimetric measurements compared with solubility determinations from the literature for the same samples of gibbsite have provided a direct thermochemical cycle through which the Gibbs free energy of formation of [Al(OH)4 aq-] can be determined. The Gibbs free energy of formation of [Al(OH)4 aq-] at 298.15 K is -1305 ?? 1 kJ/mol. These heat-of-solution results show no significant difference in the thermodynamic properties of gibbsite particles in the range from 50 to 0.05 ??m. The Gibbs free energies of formation at 298.15 K and 1 bar pressure of diaspore, boehmite and bayerite are -9210 ?? 5.0, -918.4 ?? 2.1 and -1153 ?? 2 kJ/mol based upon the Gibbs free energy of [A1(OH)4 aq-] calculated in this paper and the acceptance of -1582.2 ?? 1.3 and -1154.9 ?? 1.2 kJ/mol for the Gibbs free energy of formation of corundum and gibbsite, respectively. Values for the Gibbs free energy formation of [Al(OH)2 aq+] and [AlO2 aq-] were also calculated as -914.2 ?? 2.1 and -830.9 ?? 2.1 kJ/mol, respectively. The use of [AlC2 aq-] as a chemical species is discouraged. A revised Gibbs free energy of formation for [H4SiO4aq0] was recalculated from calorimetric data yielding a value of -1307.5 ?? 1.7 kJ/mol which is in good agreement with the results obtained from several solubility studies. Smoothed values for the thermodynamic functions CP0, ( HT0 - H2980) T, ( GT0 - H2980) T, ST0 - S00, ??Hf{hook},2980 kaolinite are listed at integral temperatures between 298.15 and 800 K. The heat capacity of kaolinite at temperatures between 250 and 800 K may be calculated from the following equation: CP0 = 1430.26 - 0.78850 T + 3.0340 ?? 10-4 T2 -1.85158 ?? 10-4 T2 1 2 + 8.3341 ?? 106 T-2. The thermodynamic properties of most of the geologically important Al-bearing phases have been referenced to the same reference state for Al, namely gibbsite. ?? 1978.

Provenance analysis and thermo-dynamic studies of multi-type Holocene duricrusts (1700 BC) in the Sua Salt Pan, NE Botswana

NASA Astrophysics Data System (ADS)

Dill, Harald G.; Dohrmann, R.; Kaufhold, S.; Techmer, A.

2014-08-01

Multi-type duricrusts, composed of silcretes, calcretes, halcretes and sulcretes developed during the Holocene at the northern rim of the Sua Salt Pan, NE Botswana. They were investigated for their light (quartz/chalcedony, feldspar, analcime, clinoptilolite, calcite, kaolinite/halloysite, illite-smectite mixed-layers, halite) and heavy minerals (baryte, clinozoisite-epidote s.s.s., amphibole, corundum, tourmaline, ilmenite, rutile, sphene, kyanite, andalusite, staurolite, garnet, zircon, apatite, monazite, cassiterite, garnet, biotite) using petrographic microscopy, X-ray fluorescence and diffraction analyses, radio-carbon dating, scanning electron microscopy equipped with an EDX-system, cation exchange capacity and infrared spectroscopy. Detrital minerals predominantly derived from the erosion of rocks belonging to the Archaean Basement Complex, the Stormberg Volcanites and the Kalahari sediments. Of particular interest to exploration geologists, geikielite-enriched ilmenite fragments are a hint to kimberlitic pipes. Biodetritus was derived from invertebrates and from vertebrates (fish bones?). A man-made impact on the heavy mineral suite has to be invoked from small fragments of cassiterite fragments that derived from processing of sulfidic and pegmatitic Sn-bearing ore. In the salt-pan-derived duricrusts mainly the aeolian and to a lesser degree fluvial inputs were responsible for the concentration of clasts in these multi-type duricrusts. Moreover, their variegated mineralogy enables us to constrain the physical-chemical regime, prevalently as to the pH and the chemical composition of the major constituents. All duricrusts developed in a self-sufficient chemically closed system where quartz and feldspar provided the elements Si, Na, K, Ca, and Ba to produce the encrustations. The spatial and temporal trend in the Sua Salt Pan rim encrustations may be described as follows: (1) sulcrete-silcretes, (2) silcretes with kaolinite-group minerals towards more recent stages at the rim and smectite-illite mixed-layers and clinoptilolite towards the basin center, (3) calcretes with analcite towards the basin center, (4) halcretes (and soda ash at a more central position). In the sulcrete-silcrete facies the pH decreases from pH 14 down to 4. In the calcretes and halcretes it increases from pH 8 to pH > 13. marking a chemical hiatus between stages 1 plus 2 and stages 3 plus 4. Mineral assemblages forming more basinward tend to have derived from more alkaline fluids than those near the edge of the salt pan.

Hydrated Spinel Websterite Xenoliths From Moses Rock Diatreme, Navajo Volcanic Field: Metasomatism in the Mantle Wedge of the Colorado Plateau Above the De-watering Farallon Plate

NASA Astrophysics Data System (ADS)

Schulze, D. J.; Chow, R.; Helmstaedt, H. H.

2016-12-01

Expansion and density decrease in ultramafic rocks in the mantle wedge above the subducted and dewatering Farallon Plate in the Cenozoic may have been the driving force behind uplift of the Colorado Plateau. Here we document the effects of such hydration on spinel websterites that resulted in rocks dominated by pargasitic amphibole, Mg-chlorite and Cr-magnetite/chromite. Xenoliths of spinel websterite from the Moses Rock diatreme in the Navajo Volcanic Field on the Colorado Plateau have granoblastic to mosaic porphyroclastic texture. Porphyroclasts (up to 2 cm across) of lamellar intergrowths of clinopyroxene and orthopyroxene are set in a granular matrix of sub-equal amounts of the two pyroxenes. Both pyroxenes are magnesian and aluminous, with Mg/(Mg+Fe) in the range 0.89 to 0.93 and Al2O3 contents of approximately 4.0 to 9.5 wt%. Many samples contain aluminous spinel with Al/(Al+Cr) = 0.82 to 0.94. The effects of hydration on these samples exist as partial to complete replacement of the pyroxenes by amphibole (tremolite/edenite/pargasite/magnesio-hornblende), pseudomorphing original pyroxene textures, and replacement of primary spinel by Cr-rich magnetite or chromite with Al/(Al+Cr) = 0.07 to 0.35 intergrown with, and surrounded by, clinochlore. Unusual minerals associated with replacement of primary spinel include one example with corundum + zoisite, one with secondary garnet (molar Ca:Mg:Fe = 20:40:40) and two samples with aluminous talc (5 to 7 wt% Al2O3). By analogy with Alpine peridotites and mantle xenolith suites from basalt occurrences, the spinel websterites probably existed as veins and lenses in spinel peridotite of the shallow upper mantle beneath the Colorado Plateau prior to hydration. De-watering of the subducted Farallon Plate in Cenozoic time was likely the source of water-rich fluids that caused the hydration at fairly shallow depths (within amphibole stability), as suggested for hydration of spinel peridotite xenoliths from the Buell Park and Green Knobs diatremes further south. The volume increase and density decrease accompanying hydration of the peridotites and pyroxenites were important factors in the uplift of the Colorado Plateau.

High-Temperature Elasticity of Topaz: A Resonant Ultrasound Spectroscopic study

NASA Astrophysics Data System (ADS)

Tennakoon, S.; Peng, Y.; Andreu, L.; Rivera, F.; Mookherjee, M.; Manthilake, G.; Speziale, S.

2017-12-01

Topaz (Al2SiO4(F,OH)2) is a hydrous aluminosilicate mineral stable in the hydrated sediments in subduction zone settings and could transport water into the Earth's interior. To constrain the amount of water subducted, it is important to have a better understanding of the elastic constants of hydrous phases and compare them with the geophysical observations. In this study, we explored the full elastic moduli tensor for a single crystal topaz using Resonant Ultrasound Spectroscopy. We determined the full elastic moduli tensor at ambient conditions (1 bar and 297 K), with the principal components- C11, C22, and C33 are 279, 352 and 288 GPa respectively, the off-diagonal components- C­12, C13, and C23 are 124, 72, and 82 GPa respectively, and the shear components- C44, C55, and C66 are 111, 134, and 130 GPa respectively. The compressional (AVP) and shear (AVS) anisotropy for topaz are 13 and 14 % respectively. The aggregate bulk (K) and shear (G) moduli are 162 and 117 GPa respectively. We determined the elasticity of topaz up to 1000 K. The components of the full elastic moduli tensor show softening at high temperature. Temperature derivatives of sound velocity of topaz, dVP/dT = -3.5 ×10-4 km/s/K and dVS/dT = -2.2 ×10-4 km/s/K are smaller than those for corundum [1], α-quartz [2], and olivine [3]. In contrast, the temperature derivatives of primary and shear sound velocity for topaz is greater than that of pyrope garnet [4]. The elasticity and sound velocity of topaz also vary as a function of chemistry i.e., OH-F contents. Our study demonstrates that the effect of composition (xOH) on the velocity is more pronounced than that of temperature.Acknowledgement: This study is supported by US NSF awards EAR-1634422. Reference: [1] Goto, T. et al.,1989, J. Geophys. Res., 94, 7588; [2] Ohno, I. et al., 2006, Phys. Chem. Miner., 33, 1-9; [3] Isaak, D. G., 1992, J. Geophys. Res. Solid Earth, 97, 1871-1885; [4] Sinogeikin, S. V., Bass, J. D., 2002, Earth Planet. Sci. Lett., 203(1), 549-555.

Indications of noncontinuous PVT-behaviour of H2O at high P-T conditions

NASA Astrophysics Data System (ADS)

Mirwald, P. W.

2003-04-01

The understanding of the properties of H_2O is still limited despite its apparently tri-vial chemical composition and unique importance. In contrast to the complex system of ice and amorphous water being revealed at low temperature and high pressure (1) the P-T field of water is still relatively unexplored. The steam tables (2) suggest an apparently continuous volume behaviour over the covered P-T range. However, a number of diffraction experiments in the ambient temperature range at high pressure indicate changes in the co-ordination of the H_2O molecules (e.g. 3). A re-examination of literature data on the melting of ice I--VII and the PVT-behaviour of water the range of 20 to 300^oC and 1 to 20 kbar has recently been conducted (4). The detailed evaluation indicated anomalous behaviour of water at some 2--4 and 7--8 Kb and thus three different regimes of steam behaviour. Own preliminary data from compression experiments at 25^oC (5) confirm these two anomalies. In addition the steam data indicate non-continuous compression behaviour also towards higher temperatures (4). Again three different areas of different PVT behaviour of steam may be distinguished divided by two anomaly boundaries of shallow dP/dT slope at some 10 and 20 kb. However, the correlation between the topologies at low and high temperatures is not clear. Solution data at high P-T conditions e.g. on corundum (6) and on quartz (7) show a significant discontinuous behaviour if Δsol./ΔP is plotted vs. pressure. So, at 700^oC discontinuous solubility changes are encountered at 10 kbar and at 19 kbar what is in agreement with the steam table data. Furthermore, a continuation of these anomalies to even higher temperatures is insinuated by the steam table data. If this is correct these anomalies would be of significance for partitioning and transport processes in the deep crust and the upper mantle of the earth. (1) Petrenko and Whitnorth (1999): Physics of Ice, Oxford Univ.Press, 1999. (2) Haar, Gallagher and Kell (1984): NBS/NRC Steam Tables, Mc-Graw-Hill. (3) Okhulkov, Demianets and Gorbaty (1994): J.Chem. Phys., 100, 1578--1588 (4) Mirwald (2001): Mitt. Österr. Miner.Ges. 146, 193-195 (5) Mirwald (2002): Ber. Dtsche. Mineralog. Ges., No.1, 2002, p.110 (6) Becher, Cemic and Langer (1983): Geochim. Cosmochim. Acta , 47, 1573-1578. (7) Manning (1994): Geochim. Cosmochim. Acta 58, 4831-4839.

Electronic absorption spectra of chromium-bearing sapphirine

NASA Astrophysics Data System (ADS)

Langer, K.; Platonov, A. N.; Matsuk, S. S.; Andrut, M.

1994-05-01

Violet, non-pleochroic and greenish-blue, pleochroic chromium-substituted sapphirines were found in corundum-bearing spinel-websterite xenolites from the Yakutian kimberlite pipes Noyabrskaya (N) and Sludyanka (Sl), respectively. The crystallochemical formulae of sapphirine crystals from such xenolites were determined by EMP to be (Mg3.40Fe0.23Al3.25Cr0.16)[6] Al{1.00/[6]}[O2/Al4.53Si1.47O18] (N) and (Mg2.53Fe0.55 Mn0.04Ti{0.03/4+}Al3.55Cr{0.08/3+})[6]Al{1.00/[16]}[O2/Al4.28Si1.73O18] (Sl). Single crystal spectra in the range 35000 6000 cm1- showed a slightly polarization dependent absorption edge near 3200 cm1- (N) or 30000 cm1- (Sl) and unpolarized bands at 25300 and 17300 cm1-, typical of spin-allowed transitions, derived from 4A2g→4T1g and 4A2g→4T2g, of Cr3+ in octahedral sites, with point symmetry C1, of the structure. Another weak band at 23000 cm-1 in the sapphirine-N spectra is attributed to low symmetry splitting of the excited 4T1 (F)-State of Cr3+. These assignments lead to crystal field parameters Dq=1730cm-1 and B= 685cm-1 of Cr3+ in sapphirine. Crystallochemical and spectroscopic arguments suggest that Cr3+ subsitutes for Al in the M(1) or M(8) sites of the sapphirine structure. In addition to Cr3+-transitions, spectra of Sl exhibit weak dd-bands of Fe2+ at 10000 and 7700 cm1-, which are unpolarized in consistency with the C1 site symmetry of the octahedra in the structure. Spectra of Sl show also prominent, broad bands (Δv1/2˜-5000 cm1-) at 15000 and 11000 cm1-, which occur in E//Y(//b) and E//Z(//c=12°) only and exhibit an intensity ratio αY∶αz close to 1∶3. This result, the large half width, as well as band energy — MM distance considerations suggest that these bands originate from Fe2+[6]-Fe3+[6] charge-transfer transitions in wall octahedra M(1)M(2), M(6)M(7) etc., forming MM vectors of 30° with the c-axis. The lack of Fe2+-Fe3+ charge-transfer bands in sapphirine N might indicate a lower oxygen fugacity during the formation of the websterite from the Noyabrskaya pipe compared to that from the Sludyanka pipe.

Formation of orange hibonite, as inferred from some Allende inclusions

NASA Astrophysics Data System (ADS)

Simon, S. B.; Davis, A. M.; Grossman, L.

2001-03-01

We studied three fluffy Type A refractory inclusions from Allende that contain orange hibonite. The melilite in the present samples is very Al-rich, averaging Åk6, Åk14, and Åk12 in the three samples studied. Hibonite in two inclusions, unlike that in Murchison, has low rare earth element abundances of <10???CI in the other inclusion, the hibonite, melilite and perovskite have Group II-like patterns. The hibonite and melilite in all three inclusions studied have excess 26Mg consistent with (26Al/27Al)I =5???10-5. Much of the hibonite and some of the spinel in these inclusions is corroded. These phases are found enclosed in melilite, but based on bulk compositions and phase equilibria, hibonite should not be an early-crystallizing phase in these inclusions. We conclude that the hibonite and probably some of the spinel is relict. Reversely zoned melilite, rounded spinel and isotopically heavy Mg in the inclusions probably reflect reheating events that involved melting and evaporation. Alteration of the gehlenitic melilite gave rise to some rare phases, including corundum and nearly pure CaTs pyroxene. Studies have shown that blue hibonite contains Ti3+ while orange hibonite does not (Ihinger and Stolper, 1986; Beckett et al., 1988). Orange hibonite formed either under oxidizing conditions (such as at oxygen fugacities at least seven orders of magnitude greater than that of a solar gas at 1700K), or under conditions reducing enough (e. g., solar) that it contained Ti3+, which was later oxidized in situ. Although V and Ce oxides are volatile at the temperature and range of oxygen fugacities at which orange hibonite is known to be stable, we find that: a) the hibonite is V-rich (~1 wt % V2O3); and b) there are no negative Ce anomalies in Allende hibonite. This indicates that the hibonite did not form by condensation under oxidizing conditions. In addition, there are slight excesses of Ti + Si cations relative to Mg + Fe cations (up to 0.1 of 0.8 cations per 19 oxygen anions), probably reflecting the original presence of Ti3+. The results of this study strongly support the suggestion (Ihinger and Stolper, 1986) that Allende hibonite originally formed under reducing conditions and was later oxidized. Oxygen fugacities within ~2-3 orders of magnitude of that of a solar gas are implied; otherwise, strong Ce and V depletions would be observed.

An evaluation of on-tool shrouds for controlling respirable crystalline silica in restoration stone work.

PubMed

Healy, Catherine B; Coggins, Marie A; Van Tongeren, Martie; MacCalman, Laura; McGowan, Padraic

2014-11-01

The task of grinding sandstone with a 5-inch angle grinder is a major source of exposure to respirable crystalline silica (RCS), known to cause diseases such as silicosis and lung cancer among workers who work with these materials. A shroud may be a suitable engineering control for this task. The objectives of this study were to evaluate the effectiveness of four commercially available shrouds at reducing respirable dust and RCS levels during the task of grinding sandstone using tools and accessories typical of restoration stone work. The task of grinding sandstone with a 5-inch angle grinder, equipped with different grinding wheels, was carried out over three trials at a restoration stone masonry site. Photometric and RCS data were collected when a 5-inch grinder, equipped with different grinding wheels, was used to grind sandstone with and without a shroud. A total of 24 short duration samples were collected for each no shroud and with shroud combination. Worker feedback on the practicalities of each shroud evaluated was also collected. Respirable dust concentrations and RCS were both significantly lower (P < 0.001) when the grinders were equipped with a shroud compared with grinders without a shroud. Total geometric mean (GM) photometric respirable dust levels measured when grinding with a shroud were 0.5 mg m(-3), a reduction of 92% compared to grinding without a shroud (7.1 mg m(-3)). The overall GM RCS concentrations were reduced by the use of a shroud by 99%. GM photometric exposure levels were highest when using the Hilti 5-inch diamond grinding cup and Diamond turbo cup and lowest when using the Corundum grinding point. Concentrations of respirable dust and RCS can be significantly reduced by using commercially available shrouds while grinding sandstone with a 5-inch angle grinder in restoration stonework. The short-term photometric respirable dust and RCS measurements collected with and without a shroud indicate that dust and RCS concentrations are reduced by between 90 and 99%. Supplemental exposure controls such as respiratory protective equipment would be required to reduce worker 8-h time-weighted average RCS exposure to below the Scientific Committee on Occupational Exposure Limits recommended occupational exposure limit value of 0.05 mg m(-3) and the American Conference of Governmental Industrial Hygienists threshold limit value of 0.025 mg m(-3). © The Author 2014. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.

[Bone cement adhesion on ceramic surfaces - surface activation of retention surfaces of knee prostheses by atmospheric plasma versus thermal surface treatment].

PubMed

Marx, B; Marx, R; Reisgen, U; Wirtz, D

2015-04-01

CoCrMo alloys are contraindicated for allergy sufferers. For these patients, uncemented and cemented prostheses made of titanium alloy are indicated. Knee prostheses machined from that alloy, however, may have poor tribological behaviour, especially in relation to UHMWPE inlays. Therefore, for knee replacement cemented high-strength oxide ceramic prostheses are suitable for allergy sufferers and in cases of particle-induced aseptic loosening. For adhesion of bone cement, the ceramic surface, however, only exposes inefficient mechanical retention spots as compared with a textured metal surface. Undercuts generated by corundum blasting which in the short-term are highly efficient on a CoCrMo surface are not possible on a ceramic surface due to the brittleness of ceramics. Textures due to blasting may initiate cracks which will weaken the strength of a ceramic prosthesis. Due to the lack of textures mechanical retention is poor or even not existent. Micromotions are promoted and early aseptic loosening is predictable. Instead silicoating of the ceramic surface will allow specific adhesion and result in better hydrolytic stability of bonding thereby preventing early aseptic loosening. Silicoating, however, presupposes a clean and chemically active surface which can be achieved by atmospheric plasma or thermal surface treatment. In order to evaluate the effectiveness of silicoating the bond strengths of atmospheric plasma versus thermal surface treated and silicate layered ZPTA surfaces were compared with "as-fired" surfaces by utilising TiAlV probes (diameter 6 mm) for traction-adhesive strength tests. After preparing samples for traction-adhesive strength tests (sequence: ceramic substrate, silicate and silane, protective lacquer [PolyMA], bone cement, TiAlV probe) they were aged for up to 150 days at 37 °C in Ringer's solution. The bond strengths observed for all ageing intervals were well above 20 MPa and much higher and more hydrolytically stable for silicate layered compared with "as-fired" ZPTA samples. Silicoating may be effective for achieving high initial bond strength of bone cement on surfaces of oxide ceramics and also suitable to stabilise bond strength under hydrolytic conditions as present in the human body in the long-term. Activation by atmospheric plasma or thermal surface treatment seems to be effective for activation prior to silicoating. Due the proposed silicate layer migration, micromotions and debonding should be widely reduced or even eliminated. Georg Thieme Verlag KG Stuttgart · New York.

Chemical and Mineralogical Characterization of Arsenic, Lead, Chromium, and Cadmium in a Metal-contaminated Histosol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, X.; Schulze, D

2010-01-01

The chemical and mineralogical forms of As, Pb, Cr, and Cd were studied in a metal-contaminated organic soil (Histosol) that received runoff and seepage water from a site that was once occupied by a lead smelter. Soil samples were collected from different depth intervals during both wet and dry seasons and analyzed using bulk powder X-ray diffraction (XRD), synchrotron-based micro X-ray diffraction ({mu}-XRD), and micro X-ray fluorescence ({mu}-SXRF) spectroscopy. There was a clear pattern of mineral distribution with depth that indicated the presence of an intense redox gradient. The oxidized reddish brown surface layer (0-10 cm) was dominated by goethitemore » ({alpha}-FeOOH) and poorly crystalline akaganeite ({beta}-FeOOH). Lead and arsenic were highly associated with these Fe oxides, possibly by forming inner-sphere surface complexes. Gypsum (CaSO{sub 4} {center_dot} 2H{sub 2}O) was abundant in the layer as well, particularly for samples collected during dry periods. Fe(II)-containing minerals, such as magnetite (Fe{sub 3}O{sub 4}) and siderite (FeCO{sub 3}), were identified in the intermediate layers (10-30 cm) where the reductive dissolution of Fe(III) oxides occurred. A number of high-temperature minerals, such as mullite (3Al{sub 2}O{sub 3} {center_dot} 2Si{sub 2}O), corundum ({alpha}-Al{sub 2}O{sub 3}), hematite ({alpha}-Fe{sub 2}O{sub 3}), and wustite (FeO) were identified in the subsurface and they probably formed as a result of a burning event. Several sulfide minerals were identified in the most reduced layers at depths > 30 cm. They included realgar (AsS), alacranite (As{sub 4}S{sub 4}), galena (PbS), and sphalerite (Zn, Fe{sup 2+})S, and a series of Fe sulfides, including greigite (Fe{sup 2+}Fe{sub 2}{sup 3+} S{sub 4}), pyrrhotite (Fe{sub 1-x}S), mackinawite (FeS), marcasite (FeS{sub 2}), and pyrite (FeS{sub 2}). Most of these minerals occurred as almost pure phases in sub-millimeter aggregates and appeared to be secondary phases that had precipitated from solution. Despite the elevated levels of Cd in the soil, no specific Cd phases were identified. The complex mineralogy has important implications for risk assessment and the design of in-situ remediation strategies for this and similar metal-contaminated sites.« less

Rheology of Pure Glasses and Crystal Bearing Melts: from the Newtonian Field to the Brittle Onset

NASA Astrophysics Data System (ADS)

Cordonnier, B.; Caricchi, L.; Pistone, M.; Castro, J. M.; Hess, K.; Dingwell, D. B.

2010-12-01

The brittle-ductile transition remains a central question of modern geology. If rocks can be perceived as a granular flow on geological time-scale, their behavior is brittle in dynamic areas. Understanding rock failure conditions is the main parameter in mitigating geological risks, more specifically the eruptive style transitions from effusive to explosive. If numerical simulations are the only way to fully understanding the physical processes involved, we are in a strong need of an experimental validation of the proposed models. here we present results obtained under torsion and uni-axial compression on both pure glasses and crystal bearing melts. We characterized the brittle onset of two phases magmas from 0 to 65% crystals. The strain-rates span a 5 orders magnitude range, from the Newtonian flow to the Brittle field (10-5 - 100 s-1). We particularly emphasize the time dependency of the measured rheology. The materials tested are a borosilicate glass from the National Bureau of Standards, a natural sample from Mt Unzen volcano and a synthetic sample. The lattest is an HPG8 melt with 7% sodium mole excess. The particles are quasi-isometric corundum crystalschosen for their shape and integrity under the stress range investigated. The crystal fraction ranges from 0 to 0.65. Concerning pure magmas, we recently demonstrated that the material passes from a Newtonian to a non-Nemtonian behavior with increasing strain-rate. This onset can mostly be explained by viscous-heating effects. However, for even greater strain-rates, the material cracks and finally fail. The brittle onset is here explained with the visco-elastic theory and corresponds to a Deborah number greater than 10-2. Concerning crystal bearing melts the departure from the Newtonian state is characterized by two effects: a shear-thinning and a time weakening effect. The first one is instantaneous and loading-unloading cyclic tests suggest an elastic contribution of the crystal network. The second one reflects a structural modification of the material (e.g. crystal reorganization, crystal failure, micro-cracking). In the special case presented here, the time weakening effect is the translation of plagioclase breaking during the magma flow. About the ultimate failure of the sample, crystal bearing melts appear to follow the general visco -elastic theory. However a crystal contribution has been here detected and corelate with smaller Deborah numbers before failure. Our observation offer a new vision on volcanic transition and an implication on the 90-95 eruptive crisis of Mt Unzen volcano is presented here.

The application of microwave digestion in decomposing some refractory ore samples with solid fusion agent.

PubMed

Lu, Yan; Li, Gang; Liu, Wei; Yuan, Hongyan; Xiao, Dan

2018-08-15

It is known that most of the refractory ore are the basis of national economy and widely applied in various fields, however, the complexity of the chemical composition and the diversity of the crystallinity in the mineral phases make the sample pre-treatment of refractory ore still remains a challenge. In this work, the complete decomposition of the refractory ore sample can be achieved just by exposing the solid fusion agent and the refractory ore sample in the microwave irradiation environment for a few minutes, and induced by a drop of water. A digestion time of 15 min for 3.0 g solid fusion agent mixture of sodium peroxide/sodium carbonate (Na 2 O 2 /Na 2 CO 3 ) in a corundum crucible via microwave heating is sufficient to decompose 0.1 g refractory ore sample. An excellent microwave digestion solid agent should meet the following conditions, a good decomposition ability, an outstanding ability of absorbing microwave energy and converting it into heat quickly, a higher melting point than the decomposing temperature of the ore sample. In the research, the induction effect of water plays an important role for the microwave digestion. The energy which is released by the reaction of water and the solid fusion agent (Na 2 O 2 ) is the key to decompose refractory ore samples with solid fusion agent, which replenished the total energy required for the microwave digestion and made the microwave digestion completed successfully. This microwave digestion technique has good reproducibility and precision, RSD % for Mo, Fe, Ti, Cr and W in the refractory ore samples were all better than 6, except RSD % for Be of about 8 because of the influence of matrix-effect. Meanwhile, the analysis results of the elements in the refractory ore samples provided by the microwave digestion technique were all in good agreement with the analysis results provided by the traditional fusion method except for Cr in the mixture ore samples. In the study, the non-linear dependence of the electromagnetic and thermal properties of the solid fusion agent on temperature under microwave irradiation and the selective heating of microwave are fully applied in this simple microwave technique. Comparing to the traditional fusion decomposition method, this microwave digestion technique is a simple, economical, fast and energy-saving sample pre-treatment technique. Copyright © 2018 Elsevier B.V. All rights reserved.

Geology, Petrology and O and H isotope geochemistry of remarkably 18O depleted Paleoproterozoic rocks of the Belomorian Belt, Karelia, Russia, attributed to global glaciation 2.4 Ga

NASA Astrophysics Data System (ADS)

Bindeman, I. N.; Serebryakov, N. S.

2011-06-01

This paper deals with strongly 18O-depleted (down to - 27.3‰ VSMOW) 1.9Ga Paleoproterozoic mid-grade metamorphic rocks found in the Belomorian Belt of Karelia (E. Baltic Shield). The protolith of these rocks is attributed to have been altered by glacial meltwaters during the world's first 2.4-2.3 Ga Paleoproterozoic "Slushball" glaciation, when Karelia was located near equatorial latitudes. We describe in detail three and report seven new localities with unusually depleted 18O signatures that now span 220 km across the Belomorian Belt. Hydrogen isotope ratios measured in amphibole, biotite and staurolite also display remarkably low values of - 212 to - 235‰. Isotope mapping in the three best exposed localities has allowed us to identify the world's most 18O depleted rock, located at Khitostrov with a δ 18O value - 27‰. In Khitostrov samples, zircons have normal δ 18O detrital cores and low-δ 18O metamorphic rims. Mapping demonstrates that zones of δ 18O depletion occur in a concentric pattern 100-400 m in dimension, and each locality displays significant δ 18O and δD heterogeneity on a meter to centimeter scale, characteristic of meteoric-hydrothermal systems worldwide. The zone of maximum δ 18O depletions usually has the highest concentration of metamorphic corundum, rutile, and zircon and also display doubled concentrations of insoluble trace elements (Zr, Ti, Cr, HREE). These results are explained by elemental enrichment upon mass loss during hydrothermal dissolution in pH-neutral meteoric fluid. Remarkably low-δ 18O and δD values suggest that alteration could have only happened by glacial meltwaters in a subglacial rift zone. Many localities with δ 18O depletions occur inside metamorphozed 2.4 Ga gabbro-noritic intrusions, or near their contact with Belomorian gneisses, implying that the intrusions were driving meteoric hydrothermal systems during the known 2.4 Ga episode of Belomorian rifting. Given that the isotopically-depleted localities now spread over 200 km, the extent of the Karelian ice cap is estimated to be at least that large. Svecofennian 1.9 Ga metamorphism is seen to cause metamorphic recrystallization of hydrothermally-altered rocks into coarse-grained assemblages, and causing local metasomatism through devolatilization of the underlying hydrous low-δ 18O protolith, further depleting δD via volatilization. This process led to gem-quality rubies and kyanites that preserve these remarkable δ 18O values in the geologic record.

Characterization of single grain by observing magnetic ejection and rotation in microgravity

NASA Astrophysics Data System (ADS)

Uyeda, Chiaki

A simple and nondestructive method to perform material identification on a single particle is desired in various fields of material science that is concerned with nano-sized particles. We propose a method of identification based on magnetization data, which is obtained from field-induced translation and rotation in microgravity [1]. Material identification is possible from magnetization data because an intrinsic value of susceptibility and anisotropy is assigned to every material according to a data book that compiles the published values [2]. Preliminary ob-servation on free translational motion due to repulsive field-gradient force was reported for mm-sized crystal of corundum [1] and other oxides. Rotational oscillation was observed for various diamagnetic single-crystals in homogeneous field [2]. In order to examine the capability of the above-mentioned material characterization, translation and rotation motion was observed for sub-millimeter-sized quartz, calcite and forsterite in microgravity condition (MGLAB, Japan, duration: 4.5s). It is expected from motional equations that the 2 motions are independent to mass of particles, In a given field distribution, acceleration of translation is expected to be uniquely determined from intrinsic susceptibility of sample. The above properties are exam-ined in the present work by varying experimental parameters. It is noted that observation of the above two motions in microgravity serve as a useful method to detect magnetization of single small particles, be cause the system is free of both sample holder and mass measure-ment. It is expected that magnetization can be measured on a isolated small sample down to nano-level, in condition that motion of the sample is observable. For both susceptibility and anisotropy, range of observed values using microgravity cover the range of compiled published values [2]. Hence material identification is possible for solid material in general. Diamagnetic magnetization and its anisotropy derive from three-dimensional distribution of localized elec-trons. In case of organic materials, origin of magnetization was consistently explained in terms of molecular-orbital method. The investigation was not performed on oxide crystals partly because the experimental values were not reported for most of the material[4]. Improvement of sensitivity using microgravity condition was necessary in order to understand the overall relationship between electron distribution and anisotropy of susceptibility. [1] K. Hisayoshi et al: J.Phys.: Conf. Ser., (2009) 156 012021. [2] R. Guputa: "Landort Bornstein" New Series II (1983) 445. [3]C.Uyeda et al.(206)Jpn.J.appl.Phys.43 L124 [4]C.Uyeda et al.: Appl. Phys. Lett. (1983) 094103.

Super-reducing conditions in ancient and modern volcanic systems: sources and behaviour of carbon-rich fluids in the lithospheric mantle

NASA Astrophysics Data System (ADS)

Griffin, William L.; Huang, Jin-Xiang; Thomassot, Emilie; Gain, Sarah E. M.; Toledo, Vered; O'Reilly, Suzanne Y.

2018-05-01

Oxygen fugacity (ƒO2) is a key parameter of Earth's mantle, because it controls the speciation of the fluids migrating at depth; a major question is whether the sublithospheric mantle is metal-saturated, keeping ƒO2 near the Iron-Wustite (IW) buffer reaction. Cretaceous basaltic pyroclastic rocks on Mt. Carmel, Israel erupted in an intraplate environment with a thin, hot lithosphere. They contain abundant aggregates of hopper-shaped crystals of Ti-rich corundum, which have trapped melts with phenocryst assemblages (Ti2O3, SiC, TiC, silicides, native V) requiring extremely low ƒO2. These assemblages are interpreted to reflect interaction between basaltic melts and mantle-derived fluids dominated by CH4 + H2. Similar highly reduced assemblages are found associated with volcanism in a range of tectonic situations including subduction zones, major continental collisions, intraplate settings, craton margins and the cratons sampled by kimberlites. This distribution, and the worldwide similarity of δ13C in mantle-derived SiC and associated diamonds, suggest a widespread process, involving similar sources and independent of tectonic setting. We suggest that the common factor is the ascent of abiotic (CH4 + H2) fluids from the sublithospheric mantle; this would imply that much of the mantle is metal-saturated, consistent with observations of metallic inclusions in sublithospheric diamonds (e.g. Smith et al. 2016). Such fluids, perhaps carried in rapidly ascending deep-seated magmas, could penetrate high up into a depleted cratonic root, establishing the observed trend of decreasing ƒO2 with depth (e.g. Yaxley et al. in Lithos 140:142-151, 2012). However, repeated metasomatism (associated with the intrusion of silicate melts) will raise the FeO content near the base of the craton over time, developing a carapace of oxidizing material that would prevent the rise of CH4-rich fluids into higher levels of the subcontinental lithospheric mantle (SCLM). Oxidation of these fluids would release CO2 and H2O to drive metasomatism and low-degree melting both in the carapace and higher in the SCLM. This model can explain the genesis of cratonic diamonds from both reduced and oxidized fluids, the existence of SiC as inclusions in diamonds, and the abundance of SiC in some kimberlites. It should encourage further study of the fine fractions of heavy-mineral concentrates from all types of explosive volcanism.

The Link between low H2O Activity and Chloride Brines in High-Grade Metamorphism - A Status Report

NASA Astrophysics Data System (ADS)

Manning, C. E.; Newton, R. C.

2006-12-01

High-grade metamorphic mineral assemblages typically record low activity of H2O (aH2O) at peak conditions. Substantial debate has centered on whether low aH2O requires the presence of a hydrous melt or of a fluid phase. Lowering aH2O in a fluid phase by CO2 is problematic because (1) at requisite compositions and observed fO2, graphite should be stable but is not observed; and (2) H2O-CO2 fluids are poor solvents for many of the components observed to be mobile at the amphibolite-granulite transition. In contrast, chloride brines are more likely to be responsible for reduced aH2O where a fluid phase is present (e.g., Newton et al., 1998, Precambrian Res., 91, 41). However, the properties of such brines are poorly understood at high P and T. We are addressing this problem through a program of experimental measurement of mineral solubilities in NaCl-H2O solutions at high P and T. Results indicate that, at 800°C and 10 kbar, solubilities of volatile-bearing, congruently soluble Ca minerals increase strongly with NaCl to halite saturation. At XNaCl = 0.3 (assuming full dissociation), Ca mole fractions in solutions increase as follows: 0.0012 (apatite), 0.0075 (fluorite), 0.0107 (calcite), 0.0513 (anhydrite). Because solubilities of F, CO2, and SO4 will increase correspondingly, H2O-NaCl brines will promote significant volatile transfer. By contrast, oxides exhibit variable behavior. At the same P and T, quartz solubility decreases monotonically with increasing NaCl, whereas corundum, hematite, wollastonite, diopside, and grossular mole fractions all increase to maxima at low to moderate XNaCl, and then decline to halite saturation. These results indicate that SiO2 does not ineract with NaCl, whereas the dissolution of the other minerals involves consumption of NaCl by solutes to a greater extent than H2O. Notably, solubility of Al is strongly enhanced in NaCl-H2O with SiO2 ± CaO. It is unlikely that all instances of low aH2O in high-grade metamorphic rocks are explained by a single mechanism; however, our results clearly demonstrate that, where present, a low- aH2O chloride brine can act as a powerful solvent in the lower crust, even at very low water-rock ratios.

The influence of crystallography and kinetics on phengite breakdown reactions in a low-pressure metamorphic aureole

NASA Astrophysics Data System (ADS)

Worden, R. H.; Droop, G. T. R.; Champness, P. E.

1992-04-01

A natural example of phengite that had undergone partial thermal decomposition at a pressure of about 0.5 kbar and a temperature of about 680° C in a contact aureole was exmined in the transmission electron microscope (TEM). Partially pseudomorphed phengites were found to consist of combinations of phengite, biotite, K-feldspar, mullite, sillimanite, spinel and cordierite. Different areas within individual, partially pseudomorphed, phengite grains show various degrees of reaction and different reaction products; the cores are the least reacted and the margins have reacted most. In the cores the assemblage Al-, Mg-enriched phengite+biotite +K-feldspar+mullite±spinel has formed, whereas the assemblage K-feldspar+mullite+sillimanite+spinel +biotite+cordierite has formed at the edges. According to our thermodynamic calculations, the breakdown of phengite should have produced cordierite+spinel +corundum+K-feldspar in regions isolated from the influx of SiO2 and cordierite+andalusite+quartz+K-feldspar in regions near the edge of the grains that were essentially saturated with SiO2. Chemical equilibrium was not achieved in any part of the partially pseudomorphed phengites on a micron scale or larger. Breakdown theoretically should have been complete by about 550° C; the reaction temperature was overstepped by at least 130° C for 20 25 years. The variations in the degree and type of reaction are probably due partly to the availability of suitable nucleation sites in different regions, partly to the need to remove H2O from reaction sites and partly to the influence of SiO2, which diffused into the grains during metamorphism. The presence of SiO2 lowers the equilibrium temperatures. Thus there is a higher driving force for breakdown near the grain boundaries than in the cores. Most of the products show an orientation relationship with the parent phengite and have consistent habit planes; they have their closest-packed planes and closest-packed directions parallel to one another and to those of phengite. Such relationships minimize the strain and surface energies at nucleation and favour most rapid nucleation and growth of the reaction products. The great structural similarity of biotite to phengite resulted in its having the highest rate of nucleation and growth of any product and it occurred in all areas of the phengite pseudomorphs studied. Mullite and sillimanite were produced metastably. Mullite has more rapid nucleation kinetics than other aluminosilicates because it is structurally disordered. Sillimanite formed rather than andalusite in regions of the partially pseudomorphed phengites where the reaction reached an advanced stage, because the reaction from phengite to andalusite requires an energetically unfavourable change in aluminium co-ordination state.

Diamonds in ophiolitic mantle rocks and podiform chromitites: An unsolved mystery

NASA Astrophysics Data System (ADS)

Yang, J.; Zhang, Z.; Xu, X.; Ba, D.; Bai, W.; Fabg, Q.; Meng, F.; Chen, S.; Robinson, P. T.; Dobrzhinetskaya, L.

2009-05-01

In recent years ultrahigh pressure minerals, such as diamond and coesite, and other unusual minerals were discovered in chromitites of the Luobusa ophiolite in Tibet, and 4 new minerals have been approved by the CNMMN. These results have raised many questionsWhat are the occurrences of the diamonds, what is the source of their carbon and how were they formed? What is the origin of the chromites hosting the diamonds and at what depth did they form? What is the genetic relationship between the diamonds and the host chromitites? In what geological, geophysical and geochemical environments can the diamonds be formed and how are they preserved? The UHP minerals from Luobusa are controversial because they have not been found in situ and because ophiolites are currently believed to form at shallow levels above oceanic spreading centers in suprasubduction zone environments. More detailed study and experimental work are needed to understand the origin and significance of these unusual minerals and investigations of other ophiolites are needed to determine if such minerals occur elsewhere To approach these problems, we have collected two one-ton samples of harzburgite hosting chromitite orebodies in the Luobusa ophiolite in Tibet. The harzburgite samples were taken close to chromitite orebody 31, from which the diamonds, coesite and other unusual minerals were recovered. We processed these two samples in the same manner as the chromitites and discovered numerous diamonds and more than 50 other mineral species. These preliminary results show that the minerals in the harzburgites are similar to those in the chromitites, suggesting a genetic relationship between them. To determine if such UHP and unusual minerals occur elsewhere, we collected about 1.5 t of chromitite from two orebodies in an ultramafic body in the Polar Urals. Thus far, more than 60 different mineral species have been separated from these ores. The most exciting discovery is the common occurrence of diamond, a typical UHP mineral in the Luobusa chromitites. Other minerals include: (1) native elements: Cr, W, Ni, Co, Si, Al and Ta; (2) carbides: SiC and WC; (3) alloys: Cr-Fe, Si-Al-Fe, Ni-Cu, Ag-Au, Ag-Sn, Fe-Si, Fe-P, and Ag-Zn-Sn; (4) oxides: NiCrFe, PbSn, REE, rutile and Si-bearing rutile, ilmenite, corundum, chromite, MgO, and SnO2; (5) silicates: kyanite, pseudomorphs of octahedral olivine, zircon, garnet, feldspar, and quartz,; (6) sulfides of Fe, Ni, Cu, Mo, Pb, Ab, AsFe, FeNi, CuZn, and CoFeNi; and (7) iron groups: native Fe, FeO, and Fe2O3. These minerals are very similar in composition and structure to those reported from the Luobusa chromitites.

Chemical thermodynamic data. 1. The concept of links to the chemical elements and the historical development of key thermodynamic data [plus Supplementary Electronic Annex 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolery, Thomas J.; Jove Colon, Carlos F.

Chemical thermodynamic data remain a keystone for geochemical modeling and reactive transport simulation as applied to an increasing number of applications in the earth sciences, as well as applications in other areas including metallurgy, material science, and industrial process design. The last century has seen the development of a large body of thermodynamic data and a number of major compilations. The past several decades have seen the development of thermodynamic databases in digital form designed to support computer calculations. However, problems with thermodynamic data appear to be persistent. One problem pertains to the use of inconsistent primary key reference data.more » Such data pertain to elemental reference forms and key, stoichiometrically simple chemical species including metal oxides, CO 2, water, and aqueous species such as Na + and Cl -. A consistent set of primary key data (standard Gibbs energies, standard enthalpies, and standard entropies for key chemical species) for 298.15K and 1 bar pressure is essential. Thermochemical convention is to define the standard Gibbs energy and the standard enthalpy of an individual chemical species in terms of formation from reference forms of the constituent chemical elements. We propose a formal concept of “links” to the elemental reference forms. This concept involves a documented understanding of all reactions and calculations leading to values for a formation property (standard Gibbs energy or enthalpy). A valid link consists of two parts: (a) the path of reactions and corrections and (b) the associated data, which are key data. Such a link differs from a bare “key” or “reference” datum in that it requires additional information. Some or all of its associated data may also be key data. In evaluating a reported thermodynamic datum, one should identify the links to the chemical elements, a process which can be time-consuming and which may lead to a dead end (an incomplete link). The use of two or more inconsistent links to the same elemental reference form in a thermodynamic database will result in an inconsistency in the database. Thus, in constructing a database, it is important to establish a set of reliable links (generally resulting in a set of primary reference data) and then correct all data adopted subsequently for consistency with that set. Recommended values of key data have not been constant through history. We review some of this history through the lens of major compilations and other influential reports, and note a number of problem areas. Finally, we illustrate the concepts developed in this paper by applying them to some key species of geochemical interest, including liquid water; quartz and aqueous silica; and gibbsite, corundum, and the aqueous aluminum ion.« less

Chemical thermodynamic data. 1. The concept of links to the chemical elements and the historical development of key thermodynamic data

NASA Astrophysics Data System (ADS)

Wolery, Thomas J.; Jové Colón, Carlos F.

2017-09-01

Chemical thermodynamic data remain a keystone for geochemical modeling and reactive transport simulation as applied to an increasing number of applications in the earth sciences, as well as applications in other areas including metallurgy, material science, and industrial process design. The last century has seen the development of a large body of thermodynamic data and a number of major compilations. The past several decades have seen the development of thermodynamic databases in digital form designed to support computer calculations. However, problems with thermodynamic data appear to be persistent. One problem pertains to the use of inconsistent primary key reference data. Such data pertain to elemental reference forms and key, stoichiometrically simple chemical species including metal oxides, CO2, water, and aqueous species such as Na+ and Cl-. A consistent set of primary key data (standard Gibbs energies, standard enthalpies, and standard entropies for key chemical species) for 298.15 K and 1 bar pressure is essential. Thermochemical convention is to define the standard Gibbs energy and the standard enthalpy of an individual chemical species in terms of formation from reference forms of the constituent chemical elements. We propose a formal concept of "links" to the elemental reference forms. This concept involves a documented understanding of all reactions and calculations leading to values for a formation property (standard Gibbs energy or enthalpy). A valid link consists of two parts: (a) the path of reactions and corrections and (b) the associated data, which are key data. Such a link differs from a bare "key" or "reference" datum in that it requires additional information. Some or all of its associated data may also be key data. In evaluating a reported thermodynamic datum, one should identify the links to the chemical elements, a process which can be time-consuming and which may lead to a dead end (an incomplete link). The use of two or more inconsistent links to the same elemental reference form in a thermodynamic database will result in an inconsistency in the database. Thus, in constructing a database, it is important to establish a set of reliable links (generally resulting in a set of primary reference data) and then correct all data adopted subsequently for consistency with that set. Recommended values of key data have not been constant through history. We review some of this history through the lens of major compilations and other influential reports, and note a number of problem areas. Finally, we illustrate the concepts developed in this paper by applying them to some key species of geochemical interest, including liquid water; quartz and aqueous silica; and gibbsite, corundum, and the aqueous aluminum ion.

Extreme extension across Seram and Ambon, eastern Indonesia: Evidence for Banda slab rollback

NASA Astrophysics Data System (ADS)

Pownall, J. M.; Hall, R.; Watkinson, I. M.

2013-04-01

The island of Seram, which lies in the northern part of the 180°-curved Banda Arc, has previously been interpreted as a fold-and-thrust belt formed during arc-continent collision, which incorporates ophiolites intruded by granites thought to have been produced by anatexis within a metamorphic "sole". However, new geological mapping and a re-examination of the field relations cause us to question this model. We instead propose that there is evidence for recent N-S extension that has caused the high-temperature exhumation of hot mantle peridotites, granites, and granulites (the "Kobipoto Complex") beneath low-angle lithospheric detachment faults. Greenschist- to lower-amphibolite facies metapelites and amphibolites of the Tehoru Formation, which comprise the hanging wall above the detachment faults, were overprinted by sillimanite-grade metamorphism, migmatisation and limited localised diatexis to form the Taunusa Complex. Highly aluminous metapelitic garnet + cordierite + sillimanite + spinel + corundum + quartz granulites exposed in the Kobipoto Mountains (central Seram) are intimately associated with the peridotites. Spinel + quartz inclusions in garnet, which indicate that peak metamorphic temperatures for the granulites likely approached 900 °C, confirm that peridotite was juxtaposed against the crust at typical lithospheric mantle temperatures and could not have been part of a cooled ophiolite. Some granulites experienced slight metatexis, but the majority underwent more advanced in situ anatexis to produce widespread granitic diatexites characterised by abundant cordierite and garnet xenocrysts and numerous restitic sillimanite + spinel "clots". These Mio-Pliocene "cordierite granites", which are present throughout Ambon, western Seram, and the Kobipoto Mountains in direct association with peridotites, demonstrate that the extreme extension required to have driven Kobipoto Complex exhumation must have occurred along much of the northern Banda Arc. In central Seram, smeared lenses of peridotites are incorporated with a major left-lateral strike-slip shear zone (the "Kawa Shear Zone"), demonstrating that strike-slip motions likely initiated shortly after the mantle had been partly exhumed by detachment faulting and that the main strike-slip faults may themselves be reactivated and steepened low-angle detachments. The Kobipoto Mountains represent a left-lateral pop-up structure that has facilitated the final stages of exhumation of the high-grade Kobipoto Complex through overlying Mesozoic sedimentary rocks. On Ambon, Quaternary "ambonites" (cordierite + garnet dacites) are evidently the volcanic equivalent of the cordierite granites as they also contain granulite-inherited xenoliths and xenocrysts. The geodynamic driver for mantle exhumation along the detachment faults and strike-slip faulting in central Seram is very likely the same - we interpret the extreme extension to be the result of eastward slab rollback into the Banda Embayment as outlined by the latest plate reconstructions for Banda Arc evolution.

Chemical thermodynamic data. 1. The concept of links to the chemical elements and the historical development of key thermodynamic data [plus Supplementary Electronic Annex 2

DOE PAGES

Wolery, Thomas J.; Jove Colon, Carlos F.

2016-09-26

Chemical thermodynamic data remain a keystone for geochemical modeling and reactive transport simulation as applied to an increasing number of applications in the earth sciences, as well as applications in other areas including metallurgy, material science, and industrial process design. The last century has seen the development of a large body of thermodynamic data and a number of major compilations. The past several decades have seen the development of thermodynamic databases in digital form designed to support computer calculations. However, problems with thermodynamic data appear to be persistent. One problem pertains to the use of inconsistent primary key reference data.more » Such data pertain to elemental reference forms and key, stoichiometrically simple chemical species including metal oxides, CO 2, water, and aqueous species such as Na + and Cl -. A consistent set of primary key data (standard Gibbs energies, standard enthalpies, and standard entropies for key chemical species) for 298.15K and 1 bar pressure is essential. Thermochemical convention is to define the standard Gibbs energy and the standard enthalpy of an individual chemical species in terms of formation from reference forms of the constituent chemical elements. We propose a formal concept of “links” to the elemental reference forms. This concept involves a documented understanding of all reactions and calculations leading to values for a formation property (standard Gibbs energy or enthalpy). A valid link consists of two parts: (a) the path of reactions and corrections and (b) the associated data, which are key data. Such a link differs from a bare “key” or “reference” datum in that it requires additional information. Some or all of its associated data may also be key data. In evaluating a reported thermodynamic datum, one should identify the links to the chemical elements, a process which can be time-consuming and which may lead to a dead end (an incomplete link). The use of two or more inconsistent links to the same elemental reference form in a thermodynamic database will result in an inconsistency in the database. Thus, in constructing a database, it is important to establish a set of reliable links (generally resulting in a set of primary reference data) and then correct all data adopted subsequently for consistency with that set. Recommended values of key data have not been constant through history. We review some of this history through the lens of major compilations and other influential reports, and note a number of problem areas. Finally, we illustrate the concepts developed in this paper by applying them to some key species of geochemical interest, including liquid water; quartz and aqueous silica; and gibbsite, corundum, and the aqueous aluminum ion.« less

Silicate glasses and sulfide melts in the ICDP-USGS Eyreville B core, Chesapeake Bay impact structure, Virginia, USA

USGS Publications Warehouse

Belkin, H.E.; Horton, J. Wright

2009-01-01

Optical and electron-beam petrography of melt-rich suevite and melt-rock clasts from selected samples from the Eyreville B core, Chesapeake Bay impact structure, reveal a variety of silicate glasses and coexisting sulfur-rich melts, now quenched to various sulfi de minerals (??iron). The glasses show a wide variety of textures, fl ow banding, compositions, devitrifi cation, and hydration states. Electron-microprobe analyses yield a compositional range of glasses from high SiO2 (>90 wt%) through a range of lower SiO2 (55-75 wt%) with no relationship to depth of sample. Some samples show spherical globules of different composition with sharp menisci, suggesting immiscibility at the time of quenching. Isotropic globules of higher interfacial tension glass (64 wt% SiO2) are in sharp contact with lower-surface-tension, high-silica glass (95 wt% SiO2). Immiscible glass-pair composition relationships show that the immiscibility is not stable and probably represents incomplete mixing. Devitrifi cation varies and some low-silica, high-iron glasses appear to have formed Fe-rich smectite; other glass compositions have formed rapid quench textures of corundum, orthopyroxene, clinopyroxene, magnetite, K-feldspar, plagioclase, chrome-spinel, and hercynite. Hydration (H2O by difference) varies from ~10 wt% to essentially anhydrous; high-SiO2 glasses tend to contain less H2O. Petrographic relationships show decomposition of pyrite and melting of pyrrhotite through the transformation series; pyrite? pyrrhotite? troilite??? iron. Spheres (~1 to ~50 ??m) of quenched immiscible sulfi de melt in silicate glass show a range of compositions and include phases such as pentlandite, chalcopyrite, Ni-As, monosulfi de solid solution, troilite, and rare Ni-Fe. Other sulfi de spheres contain small blebs of pure iron and exhibit a continuum with increasing iron content to spheres that consist of pure iron with small, remnant blebs of Fe-sulfi de. The Ni-rich sulfi de phases can be explained by melting and/or concentrating targetderived Ni without requiring an asteroid impactor source component. The presence of locally unaltered glasses in these rocks suggests that in some rock volumes, isolation from postimpact hydrothermal systems was suffi cient for glass preservation. Pressure and temperature indicators suggest that, on a thin-section scale, the suevites record rapid mixing and accumulation of particles that sustained widely different peak temperatures, from clasts that never exceeded 300 ?? 50 ??C, to the bulk of the glasses where melted sulfi de and unmelted monazite suggest temperatures of 1500 ?? 200 ??C. The presence of coesite in some glass-bearing samples suggests that pressures exceeded ~3 GPa. ?? 2009 Geological Society of America.

The diamondiferous xenoliths from kimberlites of Yakutia: a key for the diamonds origin

NASA Astrophysics Data System (ADS)

Spetsius, Zdislav V.; Kovalchuck, Oleg E.

2010-05-01

More than 400 diamondiferous xenoliths have been discovered in the kimberlite pipes of Yakutia. Diamond-bearing specimens are encountered among ultramafic xenoliths predominantly dunite harzburgites and in all types of eclogitic rocks: bimineral eclogites, kyanite and corundum eclogites and also in garnet-websterites. The diamonds in xenoliths are found mainly as separate crystals but in some xenoliths the amount of diamonds may be as high as 1000. The distribution of crystals in the specimens is irregular and does not coincide with the specimen surfaces. The sizes of the crystals vary from fraction of millimeter to 10 millimeters. The diamonds from xenoliths are correlated with the diamonds from kimberlites by their morphology and physical properties. Mineral inclusions are rare in the xenolith diamonds. Careful examination of more than 300 diamonds from about 100 xenoliths shows that 40% of macrodiamonds (size > 1mm) contain some visible inclusions. In most cases these are a little tiny opaque grain. Microprobe data suggest that overwhelming majority of them are sulfides. Silicate inclusions of garnet, clinopyroxene and very seldom rutile or others are rare. The diamonds in some specimens have sulfide rims around them. A number of facts show that in the process of diamonds growth the sulfide melt was present together with the silicate melt. The mechanism of diamond growth should be discussed in a complex sulfide-silicate system enriched in fluids. The diamondiferous eclogites do not stand out of the general series of mantle eclogites from kimberlite pipes either by specific properties and minerals composition, or major and trace elements distribution between coexisting garnets and clinopyroxenes. Intensive partial melting is characteristic feature for most of the specimens. To some extent this is a typomorphic sign of diamondiferous eclogites. A selective enrichment pattern REE is observed in some xenolith minerals (high content of LREE in clinopyroxene and enhanced HREE in garnet). In proposed topic will be summarized data on diamondiferous xenoliths from the Udachnaya, Nyurbinskaya and other pipes of Yakutia. These results comprise in the whole about 300 samples and include data on major and trace element chemistry of xenolith minerals with attention to the morphology and distribution of diamonds in separate xenoliths. Special attention will be given to variation of physical properties of diamonds that were measured in 500 diamonds recovered from new parcel of 30 xenoliths. These properties include total content of nitrogen, co-variations in B1 and B2 defects and hydrogen. It should be pointed that there exist a rather strong correlation between morphology and some physical properties of diamonds. Special remarks will be given to the evidence of possible metasomatic origin of diamonds in some xenoliths.

Wasp-17b versus other hot-Jupiters being surveyed with HST: A clear versus dusty/hazy atmospheres

NASA Astrophysics Data System (ADS)

Ballester, G. E.; Nikolov, N.; Wakeford, H.; Thompson, R.

2014-03-01

A large HST optical and near-IR spectral survey of eight hot-Jupiter exoplanets is being carried out (D. Sing, PI) in which we are studying planets spanning a large temperature regime (1000-3000 K). Together with previous HST observations, this program is showing hot Jupiters with lower atmospheres where the optical and near-IR transit signatures are dominated by, or have a significant contribution from, scattering by aerosols. This is the well-known case for the relatively cooler HD 189733b on which fine silicate grains may have been detected (Pont et al. 2008, 2013; Lecavelier et al. 2008; Sing et al. 2011; Evans et al. 2013), the more recent case of the hotter Hat-P-1b (Wakeford et al. 2013; Nikolov et al. 2013), and the surprising case of the very-hot-Jupiter Wasp-12b on which fine-grains of corundum may have been detected (Sing et al. 2013). Evidence for aerosols has also been found with Kepler for Kepler-7b (Demory et al. 2013). Under this large HST survey, we have recently observed transits of Wasp-17b in the optical with HST/STIS, and we are combining these data with archival HST/WFC3 near-IR (1.09-1.69 microns) transit data and with Spitzer/IRAC 4.5 and 8 um transit photometry (Ballester et al. 2014). Wasp-17b presents an interesting case of the most highly inflated hot Jupiter (0.49 MJup, 1.99 RJup) known to date that is also on a retrograde orbit (at 0.0515 AU around a hot F6V star) indicating a violent history for the system (Anderson et al. 2010). The average dayside temperature for the planet is 1580-1880 K (Anderson et al. 2011). In contrast to the above cases of dusty/hazy atmospheres, our preliminary results show a clear atmosphere on Wasp-17b. The planet presents the best case so far of a hot Jupiter that is consistent with a cloud-free atmosphere given that the optical radius is much smaller than the near-IR radius (i.e., scattering by dust or haze is not obscuring the expected transit signatures of a clear lower atmosphere). Water absorption is detected. We are also finding a stronger Na I line-core absorption that predicted by models (which may evidence sodium over-abundance at high altitudes), while at the same time we find no evidence for K I absorption. This alkali behavior is not unique to Wasp-17b, since similar results have been found with HST for HD 189733b (Huitson et al. 2012) and Hat-P-1b (Nikolov et al. 2013). The work is in progress, and more detailed results will be presented and compared with other observations of this planet.

High-Pressure Phase Relations and Crystal Structures of Postspinel Phases in MgV2O4, FeV2O4, and MnCr2O4: Crystal Chemistry of AB2O4 Postspinel Compounds.

PubMed

Ishii, Takayuki; Sakai, Tsubasa; Kojitani, Hiroshi; Mori, Daisuke; Inaguma, Yoshiyuki; Matsushita, Yoshitaka; Yamaura, Kazunari; Akaogi, Masaki

2018-06-04

We have investigated high-pressure, high-temperature phase transitions of spinel (Sp)-type MgV 2 O 4 , FeV 2 O 4 , and MnCr 2 O 4 . At 1200-1800 °C, MgV 2 O 4 Sp decomposes at 4-7 GPa into a phase assemblage of MgO periclase + corundum (Cor)-type V 2 O 3 , and they react at 10-15 GPa to form a phase with a calcium titanite (CT)-type structure. FeV 2 O 4 Sp transforms to CT-type FeV 2 O 4 at 12 GPa via decomposition phases of FeO wüstite + Cor-type V 2 O 3 . MnCr 2 O 4 Sp directly transforms to the calcium ferrite (CF)-structured phase at 10 GPa and 1000-1400 °C. Rietveld refinements of CT-type MgV 2 O 4 and FeV 2 O 4 and CF-type MnCr 2 O 4 confirm that both the CT- and CF-type structures have frameworks formed by double chains of edge-shared B 3+ O 6 octahedra (B 3+ = V 3+ and Cr 3+ ) running parallel to one of orthorhombic cell axes. A relatively large A 2+ cation (A 2+ = Mg 2+ , Fe 2+ , and Mn 2+ ) occupies a tunnel-shaped space formed by corner-sharing of four double chains. Effective coordination numbers calculated from eight neighboring oxygen-A 2+ cation distances of CT-type MgV 2 O 4 and FeV 2 O 4 and CF-type MnCr 2 O 4 are 5.50, 5.16, and 7.52, respectively. This implies that the CT- and CF-type structures practically have trigonal prism (six-coordinated) and bicapped trigonal prism (eight-coordinated) sites for the A 2+ cations, respectively. A relationship between cation sizes of VIII A 2+ and VI B 3+ and crystal structures (CF- and CT-types) of A 2+ B 2 3+ O 4 is discussed using the above new data and available previous data of the postspinel phases. We found that CF-type A 2+ B 2 3+ O 4 crystallize in wide ionic radius ranges of 0.9-1.4 Å for VIII A 2+ and 0.55-1.1 Å for VI B 3+ , whereas CT-type phases crystallize in very narrow ionic radius ranges of ∼0.9 Å for VIII A 2+ and 0.6-0.65 Å for VI B 3+ . This would be attributed to the fact that the tunnel space of CT-type structure is geometrically less flexible due to the smaller coordination number for A 2+ cation than that of CF-type.

Interaction of ribonucleotides with oxide and silicate minerals under varying environmental conditions

NASA Astrophysics Data System (ADS)

Feuillie, C.; Sverjensky, D. A.; Hazen, R. M.

2013-12-01

Large quantities of nucleic acids are found in natural environments, released after the death of an organism and subsequent cell lysis [1]. Nucleic acids are known to adsorb on mineral surfaces [2, 3, 4], which protect them from degradation, whether enzymatic [5, 6] or UV-mediated [7]. It may then contribute to the extracellular genetic pool available in soils to microorganisms for horizontal gene transfers [8]. In order to better understand the behaviour of extracellular nucleic acids in soils, we have investigated the interactions between nucleotides, 5'-GMP, 5'-CMP, 5'-AMP and 5'-UMP, and α-alumina as a model compound for Al in six-fold coordination in soil minerals. We carried out batch adsorption experiments over a wide range of pH, ionic strength and surface loading. Alumina adsorbs high amounts of nucleotides > 2 μmol/m2. In similar environmental conditions, swelling clays such as nontronite and montmorillonite adsorb less than 0.1 μmol/m2 if the total surface area is taken under consideration. However, if only the edges of clay particles are considered, the amount of nucleotides adsorbed reaches values between 1.2 and 2 μmol/m2 [9], similar to the alumina and consistent with ';oxide-like' surface sites on the edges of the clay particles. Surface complexation modeling enabled us to predict the speciation of the surface species on the alumina, as well as the stoichiometry and thermodynamic equilibrium constants for the adsorption of nucleotides. We used the extended triple-layer model (ETLM), that takes into account the electrical work linked to the desorption of chemisorbed water molecules during the formation of inner-sphere complexes. Two surface species are thought to form on the surface of corundum: a monodentate inner-sphere complex, dominant at pH < 7.5, and a bidentate outer-sphere complex, dominant at higher pH. Both complexes involve interactions between the negatively charged phosphate group and the positively charged surface of alumina. Our results provide a better understanding of how nucleic acids attach to mineral surfaces under varying environmental conditions in soil environments. Moreover, the predicted configuration of nucleotide surface species, bound via the phosphate group, could have implications for the abiotic formation and concentration of nucleic acids in the context of the origin of life. References : [1] Lorenz and Wackernagel (1987), Applied and environmental microbial., 2948-2952 [2] Ferris (2005), Reviews in mineralogy & geochemistry 59, 187-210 [3] Cleaves H.J. et al. (2011), Chemosphere 83, 1560-1567 [4] Arora & Kamaluddin (2009), Astrobiology 9, 165-171 [5] Cai et al. (2006), Environ. Sci. Technol. 40 (9), 2971-2976 [6] Franchi and Gallori (2005),Gene 346, 205-214 [7] Scappini et al. (2004), International Journal of Astrobiology 3(1), 17-19 [8] Levy-Booth et al. (2007), Soil Biol. Biochem. 39, 2977-2991. [9] Feuillie et al. (2013), Geochimica et Cosmochimica Acta (in press)

Hyper-Raman spectroscopy of Earth related materials

NASA Astrophysics Data System (ADS)

Hellwig, H.

2004-12-01

Raman and infrared spectroscopy proved extremely successful in obtaining structural information and thermodynamic data on samples under high pressure conditions in a diamond anvil cell [1,2]. With substantial advances in CCD detector technology and the possibility to focus visible laser light down to several microns, Raman spectroscopy can nowadays be regarded one of the standard techniques for diamond anvil cell investigations. Nevertheless, Raman scattering suffers from often strong fluorescence and the strong Raman signal of the diamonds. Infrared spectroscopy is limited by the sample size and the diffraction limit of mid- or far-infrared radiation. With increasing pressure, diamonds also show strong infrared activity, which can interfere with the signal from the sample. Detectors in the mid- and far-infrared are inherently noisy, often leading to low signal-to-noise ratios for infrared measurements. With new techniques and instrumentation available, such as low noise CCD cameras and stable diode-pumped solid state laser systems, more demanding techniques become feasible as well. Especially hyper-Raman scattering, a nonlinear optical variant of infrared spectroscopy, can be used on a more routine basis for the first time. Pioneering work in the 70s and 80s have explored some of the capabilities of Hyper-Raman spectroscopy [3]. Unlike infrared spectroscopy, Hyper-Raman is not limited by the diffraction limit of mid- or far-infrared radiation, typically restricting the lower frequency limit to several hundred wave numbers. The major advantages of hyper-Raman are essentially background free spectra and the use of wavelengths in the near-infrared and visible, making possible micro focusing and taking advantage of high efficiencies, low noise, and smooth wavelength dependencies of CCD detectors. Hyper-Raman does not suffer from saturation caused by strong absorption in the infrared and is therefore less sensitive to surface effects. For centrosymmetric materials conventional Raman and hyper-Raman are complimentary. In many cases the combined information of both techniques can reveal all the vibrational information of a material. This information can be used to calculate thermodynamic properties, to identify mineral phases ('finger-printing'), or to investigate the dynamics related to phase transitions ('soft-modes'). First results on planetary materials will be presented, including MgO and stichovite. Corundum as another possible high pressure transmitting material is characterized as well. Further measurements are underway, including MgSiO3 and CaSiO3 perovskite. [1] A. M. Hofmeister, in: Infrared Spectroscopy in Geochemistry, Exploration Geochemistry, and Remote Sensing, Vol. 33 (ed. P. K. King, M. S. Ramsey, and G. A. Swayze), Mineralogical Society of Canada (2004) [2] P. F. McMillan, R. J. Hemley, and P. Gillet, in : Mineral Spectroscopy: A Tribute to Roger G. Burns, Vol. 5 (ed. D. Dyar, C. McCammon, and M. W. Schaefer), The Geochemical Society Special Publication (1996). [3] H. Vogt, in: Topics in Applied Physics, Vol. 50, Light scattering in solids II (ed. M. Cardonna and G. Guentherodt), Springer-Verlag, Heidelberg, New York (1982).

The unusual mineralogy of the Hayes River rhyolite, Hayes Volcano, Cook Inlet, Alaska

NASA Astrophysics Data System (ADS)

Hayden, L. A.; Coombs, M. L.; McHugh, K.

2013-12-01

Hayes Volcano is an ice-covered volcanic massif located in the northern Cook Inlet region approximately 135 miles northwest of Anchorage, Alaska. The last major eruptive episode of Hayes, and the only known in any detail, occurred ~3,700 yr B.P. and produced the Hayes Tephra Set H, a series of dacitic fall deposits widespread throughout southcentral Alaska (Riehle et al., 1994, Quat. Res. 33, p. 91-108). An undated, early Holocene pyroclastic-flow deposit exposed beneath Tephra Set H in the Hayes River valley is unusual in the Aleutian-Alaska subduction zone in whole-rock composition and mineralogy. The deposit comprises rhyolite pumice (~75 wt% SiO2) that contain phenocrysts of plagioclase, sanidine, quartz, and biotite in vesicular, clear matrix glass, and <1% dense, white cognate inclusions with the same whole-rock composition and phenocryst assemblage as the pumice, but a crystalline matrix. Holocrystalline inclusions may represent portions of the magma body that rapidly quenched in the shallow subsurface as dikes or chamber rinds and were then excavated during explosive eruption. Rhyolite and inclusions are peraluminous (2-3 % normative corundum), high-K, enriched in incompatible elements, and depleted in Sr and Eu. In accord with its evolved and enriched composition the rhyolite pumice and inclusions contain an abundance of accessory phases, including apatite, monazite, xenotime, and zircon. Monazite are euhedral, as large as 500 um, ThO2-rich (up to 4 wt%) and contain significant amounts of Ag (200-500 ppm). Xenotime are generally smaller than the monazite and occur frequently as small blebs. Rhyolite pumices also contain Fe-sulfides, Cu, Sn, Ni, and barite. Sanidine phenocrysts in the pumice and inclusions are sharply zoned and highly enriched in the celsian component (up to 5 wt% BaO) and also show LREE enrichment. Inclusions contain abundant Mn-rich cordierite (~3 wt% Mn2O3) in the san-plag-qtz matrix, as well as Fe-Ti oxides that are relatively high in Mn2O3 (>1 wt%) and REE-enriched. Zircon saturation temperatures (716° C) and two-feldspar thermometry (630-700° C for phenocryst rims; 660° C for inclusion matrix microphenocrysts) suggest a cool magma that must have been volatile-rich given its relatively low phenocryst content (~25 %). A lack of crustal xenocrysts, and Pb, Sr, and Nd isotopes similar to other Cook Inlet volcanoes (McHugh et al., 2012 Fall AGU, V31A-2760) suggest that the rhyolite is not a crustal melt, and we suggest that it formed by low degrees of melting or high degree of crystallization of mafic arc-related rocks. At Hayes, concentrations of REE and metals resulted from extreme fractionation process(es), which active over extended time period may lead to the formation of mineral deposits.

Physico-chemical transition from peridotite assemblage to the eclogite one (experimental data at 7.0 GPa).

NASA Astrophysics Data System (ADS)

Butvina, Valentina; Litvin, Yurii

2010-05-01

Peridotites and eclogites, including diamond-bearing ones, are the basic ultra-basic and basic rocks of the upper mantle (Ringwood, 1969, 1975; Sobolev, 1974; Marakushev, 1985; Taylor & Anand, 2004). These rocks are presented in the assemblage of mantle xenolyths in kimberlites, but the basic minerals of peridotite paragenesis, olivine, orthopyroxene, garnet and clinopyroxene as well as of an eclogite paragenesis, garnet and omphacite are wide-spread synthetic inclusions in diamonds. The cases of finding minerals and peridotite and eclogite parageneses in diamond are described. It implies that these parageneses can have a single mantle source. However, the formation of peridotite and eclogite mineral parageneses at differentiation of the primary ultrabasite melt during physico-chemical single process is possible only at overcoming the 'eclogite' thermal barrier (O'Hara, 1968; Litvin, 1991). Eclogite genesis is one of the most difficult and discussional problems of modern petrology. Among investigators there is an opinion about eclogite heterogeneity not only on conditions of formation (crust, mantle), but also by composition of the initial rocks (para-, orthoeclogites) as well as by the way of their formation (magmatic, metamorphic, metasomatic). In literature diamond-bearing eclogite nodules of kimberlite pipes are often considered as metamorphic, which are formed at subduction of the Archean or of the Proterozoic oceanic crust (MacGregor & Manton, 1986; McCandless & Gurney, 1986, 1997 et al.). Only the presence of Na2O in garnet and K2O in clinopyroxene is a criterion of their participation in mantle magmatic processes. Together with the hypotheses considered on eclogite origin there exists a version suggested in papers (Kushiro, 1972; Kushiro & Yoder, 1974), according to which mantle eclogites could be formed due to peridotite substance in the processes of fractional crystallization of ultrabasite magmas. The present paper is devoted to the experimental study of this problem. Physico-chemical transition from peridotite assemblage to the eclogite one can be only ensured by the processes of fractional crystallization of mantle magmatic melts. The primary melting and magmatic evolution of mantle garnet lerzolite (or the Ringwood pyrolite) is controlled by a five-phase peritectics 'p' Ol+Opx+Cpx+Grt+L and four cotectic curves conjugated to it (Litvin, 1991). In melting and evolution of melts of both olivine eclogites and coesite and corundum eclogites the corresponding five-phase eutectics are of a dominant importance. A general ridge for all elementary tetrahedrons (simplexes) is a line of compositions diopside-pyrope (clinopyroxene-garnet) which bimineral eclogite assemblages belong to. The internal section En-Di-Cor of the general tetrahendric diagram (symplex complex) separates olivine-saturated and silica-saturated compositions. 'Eclogite' thermal barrier is 'thermal barrier' on (O'Hara, 1968), on the cotectic line Opx+Cpx+Grt+L, connecting 'peridotite' peritectic and 'eclogite' eutectic points. Meanwhile, at equilibrium (and fractional) crystallization of peridotite system in the peritectic point 'p' orthopyroxene vanishes as a result of the peritectic reaction 'orthopyroxene + melt - clinopyroxene' (Davis, 1963; Litvin, 1991). With further temperature decrease the composition of the remnant melt is controlled by the nonorthopyroxene cotectics Ol+Cpx+Grt+L first, in the limits of the peridotite 'simplex', but then mechanism of fractional crystallization is also realized in the limits of the olivine-eclogite 'simplex' up to the corresponding nonvariant eutectics. The considered cotectics Ol+Cpx+Grt+L is of the greatest interest from the viewpoint of a possible change of compositions of remnant melts from olivine-normative to silica-normative ones. One can assume that under the conditions of fractional melt crystallization along the cotectic curve Ol+Cpx+Grt+L together with olivine jigging accumulation of incorehent elements, including Na, Fe etc. takes place. It leads to a gradual increase of jadeite component content in remnant melts what creates grounds for reactional interaction of jadeite and olivine components with olivine vanishing and garnet formation in accordance with the reaction found in (Litvin et al., 2004). A gradual decrease of olivine component content in remnant melts caused by that fact realizes a 'turn' to the cotectic curve Ol+Cpx+Grt+L in the direction of the boundary section En - Di - Cor and, probably its exit to the line Di-Prp (clinopyroxene-garnet). Further under the conditions of fractional crystallization melt composition point can penetrate into the volumes of coesite-eclogite, kyanite-eclogite and corundum-eclogite 'symplexes'. Thus, an overcoming of 'eclogite' thermal barrier between olivine-normative peridotite-pyroxene and SiO2 - normative eclogite compositions occurs. So, one can speak about the 'destruction' of liquidus peridotite-eclogite thermal barrier in the limits of the peridotite 'simplex' as a result of realization of two reaction mechanisms: (1) vanishing of orthopyroxene as a result of its peritectic reaction with the melt with clinopyroxene formation and (2) olivine vanishing as a result of its reactional interaction of jadeite with garnet formation. If with respect to the first mechanism definite experimental evidence exists (Litvin, 1991; Davis, 1963) then for the second mechanism it is absent. Due to this fact the main purpose of this paper is an experimental study of phase relationships in the model system forsterite-dioside-jadeite at pressure of 7 GPa and foundation of possible physico-chemical correct transitions between peridotite and eclogite parageneses with overcoming liquidus 'eclogite' thermal barrier. To construct a diagram of a ternary system forsterite-diopside-jadeite it is necessary to study its boundary binary sections forsterite-jadeite and fosterite-diopside as well as a number of internal polythermic sections. The section jadeite-diopside at 7 GPa has been studied earlier (Bobrov, Litvin, Kojitani, Akaogi, 2006; 2008) and it is characterized by the unlimited miscibility of jadeite and diopside components in solid and liquid states. The first experimental results obtained at the initial stage of the investigation of this problem can be characterized as follows. For the experimental study polythermic sections of forsterite-(jadeite50diopside50) and forsterite-(jadeite25diopside75) have been chosen. The obtained data testify to the fact that olivine vanishing and garnet formation are realized in both sections. The problem of further investigations is to search minimum concentrations of jadeite in the composition of this system where a total olivine vanishing takes place. Thus, the performed experimental investigations of the model system forsterite-diospside-jadeite at pressure 7 GPa testify to the fact that forsterite (olivine) is a stable phase in the boundary system forsterite-diopside (olivine-clinopyroxene). While introducing rather low contents of jadeite component into the composition of this system the reaction of jadeite component with forsterite takes place in the melt. As a result, garnet appears as liquidus phase.

P-T paths of ophiolite-related metamorphic rocks from the Dinaride ophiolite zone in Bosnia

NASA Astrophysics Data System (ADS)

Balen, Dražen; Massonne, Hans-Joachim; Koller, Friedrich; Theye, Thomas; Opitz, Joachim; Hrvatović, Hazim; Premužak, Lucija

2017-04-01

The Dinarides, an Alpine mountain chain in south-eastern Europe, is characterized by complex fold, thrust, and imbricate structures. Partially dismembered ophiolites, a regular part of the Inner Dinarides, are considered as separate ultramafic massifs. The large Krivaja-Konjuh ultramafic massif (KKUM) within the Dinaride Ophiolite Zone (DOZ), composed of tectonic spinel lherzolite, occurs as NE-dipping thrust sheet underlain by gradually decreasing, up to 1200 m thick, high- to medium-grade metamorphic rocks. The metamorphic rocks geochemically resemble MORB-like rocks with tholeiitic signature. Such metamorphic rocks, which originated from cumulate gabbro and/or troctolite, are mainly represented by granulite and amphibolite varieties (subordinate eclogite and epidote-amphibolite facies metamafic rocks are also present) with various proportions of amphibole, plagioclase, pyroxenes (diopside and hypersthene), garnet, corundum, sapphirine, spinel and quartz. These rocks vary in textures (granoblastic, porphyroblastic and nematoblastic) and grain size (coarse- to fine-grain varieties). Conventional thermobarometry of garnet- and clinopyroxene-bearing amphibolites directly beneath the contact to the overlying peridotite resulted in peak pressure (P) - temperature (T) conditions of 10-12 kbar (depth of ca. 35-40 km) and 745-830°C. Those amphibolites without clinopyroxene but with garnet experienced peak conditions of 7 kbar and 630°C. Amphibole + plagioclase amphibolite gave temperatures of 670-730 °C and lowermost-grade amphibolites yielded peak temperatures of 550°C. These estimates are thought to reflect the metamorphic conditions during the Late Jurassic obduction of the hot upper mantle part of the KKUM onto the ophiolite mélange. The hot obducted ultramafic fragments acted as a heat source for metamorphism that transformed cumulate gabbroic protolith into high- to medium-grade amphibolites and granulites. P-T pseudosections constructed for various metamorphic rock types in the MnNCFMASHTO system, contoured by mineral isopleths and modes, combined with chemical zonation of garnet (elucidated by X-ray mapping), succession of accessory Ti-minerals (ilmenite -> rutile -> titanite) and textural features (particularly occurrence of complex kelyphite textures around garnet and clinopyroxene) gave us important clues for P-T paths (re)constructions. The petrographic details and mineral chemistry point to composite clockwise P-T paths characterized by high-temperature high-pressure conditions (ca. 20 kbar, 700 °C for garnet- and amphibole-bearing metaperidotite), followed by significant pressure decrease to medium-pressure values accompanied by temperature increase to > 830 °C. Such a composite P-T path can be interpreted in the frame of Late Jurassic to Early Cretaceous regional geodynamic processes that involve collision at the edge of the Adriatic microplate, intra-oceanic NE-dipping subduction and underplating of mafic cumulate rocks under the hot upper mantle part of the KKUM and subsequent erosional events. Processes of the final emplacement of the KKUM metamorphic rocks must have been terminated in Early Cretaceous times as indicated by amphibolite fragments in the adjacent Pogari Formation overlying the ophiolite mélange. Support by the Croatian Science Foundation (IP-2014-09-9541) is acknowledged.

Fractional ultrabasic-basic evolution of upper-mantle magmatism: Evidence from xenoliths in kimberlites, inclusions in diamonds and experiments

NASA Astrophysics Data System (ADS)

Litvin, Yuriy; Kuzyura, Anastasia

2017-04-01

Ultrabasic peridotites and pyroxenites together with basic eclogites are the upper-mantle in situ rocks among xenoliths in kimberlites. Occasionally their diamond-bearing varieties have revealed within the xenoliths. Therewith the compositions of rock-forming minerals demonstrate features characteristic for primary diamond-included minerals of peridotite and eclogite parageneses (the elevated contents of Cr-component in peridotitic garnets and Na-jadeitic component in eclogitic clinopyroxenes). High-pressure experimental study of melting equilibria on the multicomponent peridotie-pyroxenite system olivine Ol - orthopyroxene Opx - clinopyroxene Cpx - garnet Grt showed that Opx disappeared in the peritectic reaction Opx+L→Cpx (Litvin, 1991). As a result, the invariant peritectic equilibrium Ol+Opx+Cpx+Grt+L of the ultrabasic system was found to transform into the univariant cotectic assemblage Ol+Cpx+Grt+L. Further experimental investigation showed that olivine reacts with jadeitic component (Jd) with formation of garnet at higher 4.5 GPa (Gasparik, Litvin, 1997). Study of melting relations in the multicomponent system Ol - Cpx - Jd permits to discover the peritectic point Ol+Omph+Grt+L (where Omph - omphacitic clinopyroxene) at concentration 3-4 wt.% Jd-component in the system. The reactionary loss of Opx and Ol makes it possible to transform the 4-phase garnet lherzolite ultrabasic association into the bimineral eclogite assemblage. The regime of fractional Ol, Cpx and Grt crystallization must be accompanied by increasing content of jadeitic component in residual melts that causes the complete "garnetization of olivine". In the subsequent evolution, the melts would have to fractionate for basic SiO2-saturated compositions responsible for petrogenesis of eclogite varieties marked with accessory corundum Crn, kyanite Ky and coesite Coe. Both the peritectic mechanisms occur in regime of fractional crystallization. The sequence of the upper-mantle fractional ultrabasic-basic magmatic evolution and petrogenesis may be controlled by the following melting relations: from Ol, Opx, L field to cotectic curve Ol, Opx, Cpx, L, peritectic point Ol, Opx, Cpx, Grt, L (loss of Opx), cotectic curve Ol, (Cpx+Jd), Grt, L, peritectic point Ol, (Cpx→Omph), Grt, L (loss of Ol), divariant field Omph,Grt,L, cotectic curve Ky, Omph, Grt, L, eutectic point Ky,Coe,Omph, Grt,L, subsolidus assemblage Ky,Coe,Omph, Grt. The fractional ultrabasic-basic evolution of the upper-mantle silicate-carbonate-carbon melts-solutions, which are responsible for genesis of diamond-and-inclusions associations and diamond-bearing peridotites and eclogites, follows the similar physico-chemical mechanisms (Litvin et al., 2016). This is illustrated by fractional syngenesis diagram for diamonds and associated minerals which construction is based on evidence from high pressure experiments. References Gasparik T., Litvin Yu.A (1997). Stability of Na2Mg2Si2O7 and melting relations on the forsterite - jadeite join at pressures up to 22 GPa. Eur, J. Mineral. 9(2), 311-326. Litvin Yu.A. (1991). Physico-Chemical Study of Melting of Materials from the Deep Earth. Moscow: Nauka. 312 p. Litvin Yu.A., Spivak A.V., Kuzyura A.V. (2016). Fundamentals of the mantle-carbonatite concept of diamond genesis, Geochemistry Internat. 34(10), 839-857.

Raman spectroscopic study of alunite occurrences in the Sapes porphyry-epithermal deposit, NE Greece

NASA Astrophysics Data System (ADS)

Papazotos, Panagiotis; Perraki, Maria; Voudouris, Panagiotis; Skliros, Vasilios

2017-04-01

The Sapes area, Northeastern Greece, represent a deeply eroded Oligocene volcanic edifice built up of post-collisional intermediate-to-acidic intrusives and their volcanic equivalents. The area hosts a telescoped porphyry-epithermal system and associated high-sulfidation epithermal Au-Ag-Cu-Bi-Te mineralization within advanced argillic alteration lithocaps (Voudouris, 2014). Alunite is a common mineralogical constituent among the advanced argillic alteration assemblages and it is a hydrated aluminium potassium sulfate mineral with a general formula KAl3(SO4)2(OH)6. The objective of this work is to study the alunites samples in the Sapes porphyry-epithermal deposit by means of Raman spectroscopy, as it has been shown to be a useful tool in studying the alunite structure, either natural or synthetic (Frost et al., 2006; Maubec et al., 2012). Raman spectra were excited employing a 532 nm laser at a resolution of 2 cm-1 in the range of 100-4000 cm-1. Raman spectra exhibit distinguished bands at 162 cm-1, attributed to translational mode of cations and or librational and translational modes of SO42-, at 235 cm-1 suggesting framework deformations including the SO42- entities as a whole or attributed to OH/O hydrogen bond stretching mode, a weak band at 385 cm-1 may corresponding to Al-OH stretching vibrations, a moderate band at 564 cm-1 assigned to Al-O and OH deformation modes, bands at 484 and 653 cm-1 respectively due to v2(SO42-) and v4(SO42-) bending modes, a very strong vibration at 1025 cm-1 that is ascribed to the v1 stretching vibration of the SO42- bands located at 1080 and 1186 cm-1 due to v3(SO42-) stretching modes and finally two bands at 3480 cm-1 and 3502 cm-1 that are assigned to the OH stretching vibrations (Breitinger et al., 1997; Frost et al., 2006; Maubec et al., 2012 and references therein). A Raman and FTIR spectroscopic future work will focus on the comparative study among the alunites occurrences in Greece (Sapes, Limnos, Lesvos and Milos), so as to identify the differences and similarities in their structural and chemical features reflecting the geological, geochemical and depositional environment. References Breitinger D., Krieglstein R., Bogner A., Schwab R., Pimpl T, Mohr, J., Schukow H. (1997). Vibrational spectra of synthetic minerals of the alunite and crandallite type. Journal of Molecular Structure, 408/409, 287-290 Frost R., Wills R., Weier M., Maertens W., Kloprogge J. (2006). A Raman spectroscopic study of alunites. Journal of Molecular Structure, 785, 123-132. Maubec N., Lahfid A., Lerouge C., Wille G., Michel K. (2012). Characterization of alunite supergroup minerals by Raman spectroscopy. Spectrochim. Acta A, 96, 925-939. Voudouris P. (2014). Hydrothermal corundum, topaz, diaspore and alunite supergroup minerals in the advanced argillic alteration lithocap of the Kassiteres-Sapes porphyry-epithermal system, western Thrace, Greece. Neues Jahrbuch für Mineralogie, 191/2, 117-136.

Silica-free, Refractory Inclusion with Al-rich Alteration and Perovskite Exsolution

NASA Astrophysics Data System (ADS)

Steele, I. M.

1993-07-01

A hibonite-spinel-perovskite CAI from an Allende thin section is in many respects similar to other hib-sp-pv inclusions, especially one described in [1], but also shows several unusual alteration features. The inclusion is about 300 micrometers in long dimension, but with extended curved ends giving an indication of an original spherical object. A single angular 200-micrometer hibonite grain (TiO2: 1.2-1.6; MgO: 0.57-0.77; SiO2: <0.05 FeO: <0.10 Cr2O3 <0.01%), which includes several 20-micrometer perovskites (Al2O3 up to 2%) occurs at the inclusion center and is surrounded by a mantle of spinel zoned with FeO near 1% at hibonite boundary to 12% at inclusion edge. Within the spinel are blades of texturally and compositionally distinct hibonite (TiO2: 4.6-8.2; MgO: 2.4-4.4; SiO2: 0.13-0.35; FeO: 0.26-0.70; Cr2O3: 0.03-0.07%), which appear to have grown from the rim toward the inclusion center. Also within the spinel mantle are numerous micrometer-sized perovskite grains. A rim sequence surrounds the entire inclusion and includes Fe-olivine, diopside, scapolite-nepheline, and hibonite layers from edge toward spinel mantle. No melilite, forsterite, or fassaite is present in inclusion, i.e., no silicates are present. Evidence of low-temperature alteration occurs as (1) replacement of perovskite within spinel mantle and adjacent to rim by Mg-ilmenite (MgO: 3.0-7.8; Al2O3: 0.3-2.0; MnO: 0.25%; V present); (2) exsolution as oriented submicrometer lamellae of Al2O3 from the larger Al-rich perovskites within central hibonite; and (3) veins, especially within hibonite and adjacent to perovskite, of Al2O3 composition (Al2O3: 97.2-79.2; SiO2: 1.5-14.2; Na2O: 0.6-4.9%; minor Fe, Ca, K) and common fiberous texture. All analyses sum to 100%, and Na correlates with Si. The ratio of Na to Si implies a mix of Al2O3 and nepheline. The inclusion is very similar to one previously described [1], but in place of central melilite, the present inclusion has hibonite. The angular hibonite grain contrasts with the euhedral hibonite blades and generally spherical inclusion. While these features imply an original melt, the angular hibonite suggests a relic grain that may have formed a nucleus for a melt. Special care must be given to interpreting bulk analyses if some CAI contain two or more distinct components. The occurrence of Al2O3 in two textural forms suggests that at least some Al2O3 is secondary either due to exsolution or possibly from breakdown(?) of hibonite. Previous observations of corundum do not necessarily imply that Al2O3 is a primary phase. References: [1] Bischoff A. et al. (1982) LPSC XVIII, 81-82.

Brittle-ductile deformation effects on zircon crystal-chemistry and U-Pb ages: an example from the Finero Mafic Complex (Ivrea-Verbano Zone, western Alps)

NASA Astrophysics Data System (ADS)

Langone, Antonio; José Alberto, Padrón-Navarta; Zanetti, Alberto; Mazzucchelli, Maurizio; Tiepolo, Massimo; Giovanardi, Tommaso; Bonazzi, Mattia

2016-04-01

A detailed structural, geochemical and geochronological survey was performed on zircon grains from a leucocratic dioritic dyke discordantly intruded within meta-diorites/gabbros forming the External Gabbro unit of the Finero Mafic Complex. This latter is nowadays exposed as part of a near complete crustal section spanning from mantle rocks to upper crustal metasediments (Val Cannobina, Ivrea-Verbano Zone, Italy). The leucocratic dyke consists mainly of plagioclase (An18-24Ab79-82Or0.3-0.7) with subordinate amounts of biotite, spinel, zircon and corundum. Both the leucocratic dyke and the surrounding meta-diorites show evidence of ductile deformation occurred under amphibolite-facies conditions. Zircon grains (up to 2 mm in length) occur mainly as euhedral grains surrounded by fine grained plagioclase-dominated matrix and pressure shadows, typically filled by oxides. Fractures and cracks within zircon are common and can be associated with grain displacement or they can be filled by secondary minerals (oxides and chlorite). Cathodoluminescence (CL) images show that zircon grains have internal features typical of magmatic growth, but with local disturbances. However EBSD maps on two selected zircon grains revealed a profuse mosaic texture resulting in an internal misorientation of ca. 10o. The majority of the domains of the mosaic texture are related to parting and fractures, but some domains show no clear relation with brittle features. Rotation angles related to the mosaic texture are not crystallographically controlled. In addition, one of the analysed zircons shows clear evidence of plastic deformation at one of its corners due to indentation. Plastic deformation results in gradual misorientations of up to 12o, which are crystallographically controlled. Trace elements and U-Pb analyses were carried out by LA-ICP-MS directly on petrographic thin sections and designed to cover the entire exposed surface of selected grains. Such investigations revealed a strong correlation between internal zircon structures, chemistry, U-Pb isotope ratios and mylonitic fabric. U-Pb data return highly discordant and variable ages: in particular, the 206Pb/238U ages range from Carboniferous to Triassic within the same zircon grain. The youngest 206Pb/238U data derive from narrow axial stripes oriented parallel or at low angle with respect to the foliation planes. These stripes are characterized by an overall HREE, Y, U and Th enrichment possibly reflecting deformation of the grain in presence of interstitial fluid phases, likely related to a concomitant magmatic activity. Deformation related structures (cracks and fractures) within zircon grains acted as fast-diffusion pathways allowing fluids to modify the geochemistry and isotopic systems of zircon. Our results suggest that fluid-assisted brittle-ductile deformation can severely modify the trace elements and isotopic composition of zircon with unexpected patterns constrained by stress regime. In similar cases, our observations suggest that, for a more appropriate interpretation of the petrologic evolution and age variability, a direct characterization of the internal structures of zircons still placed in their microtextural site is highly recommended.

Geochemistry and petrogenesis of Mashhad granitoids: An insight into the geodynamic history of the Paleo-Tethys in northeast of Iran

NASA Astrophysics Data System (ADS)

Mirnejad, H.; Lalonde, A. E.; Obeid, M.; Hassanzadeh, J.

2013-06-01

Mashhad granitoids in northeast Iran are part of the so-called Silk Road arc that extended for 8300 km along the entire southern margin of Eurasia from North China to Europe and formed as the result of a north-dipping subduction of the Paleo-Tethys. The exact timing of the final coalescence of the Iran and Turan plates in the Silk Road arc is poorly constrained and thus the study of the Mashhad granitoids provides valuable information on the geodynamic history of the Paleo-Tethys. Three distinct granitoid suites are developed in space and time (ca. 217-200 Ma) during evolution of the Paleo-Tethys in the Mashhad area. They are: 1) the quartz diorite-tonalite-granodiorite, 2) the granodiorite, and 3) the monzogranite. Quartz diorite-tonalite-granodiorite stock from Dehnow-Vakilabad (217 ± 4-215 ± 4 Ma) intruded the pre-Late Triassic metamorphosed rocks. Large granodiorite and monzogranite intrusions, comprising the Mashhad batholith, were emplaced at 212 ± 5.2 Ma and 199.8 ± 3.7 Ma, respectively. The high initial 87Sr/86Sr ratios (0.708042-0.708368), low initial 143Nd/144Nd ratios (0.512044-0.51078) and low ɛNd(t) values (- 5.5 to - 6.1) of quartz diorite-tonalite-granodiorite stock along with its metaluminous to mildly peraluminous character (Al2O3/(CaO + Na2O + K2O) Mol. = 0.94-1.15) is consistent with geochemical features of I-type granitoid magma. This magma was derived from a mafic mantle source that was enriched by subducted slab materials. The granodiorite suite has low contents of Y (≤ 18 ppm) and heavy REE (HREE) (Yb < 1.53 ppm) and high contents of Sr (> 594 ppm) and high ratio of Sr/Y (> 35) that resemble geochemical characteristics of adakite intrusions. The metaluminous to mildly peraluminous nature of granodiorite from Mashhad batholiths as well as its initial 87Sr/86Sr ratios (0.705469-0.706356), initial 143Nd/144Nd ratios (0.512204-0.512225) and ɛNd(t) values (- 2.7 to - 3.2) are typical of adakitic magmas generated by partial melting of a subducted slab. These magmas were then hybridized in the mantle wedge with peridotite melt. The quartz diorite-tonalite-granodiorite stock and granodiorite batholith could be considered as arc-related granitoid intrusions, which were emplaced during the northward subduction of Paleo-Tethys Ocean crust beneath the Turan micro-continent. The monzogranite is strongly peraluminous (Al2O3/(CaO + Na2O + K2O) Mol. = 1.07-1.17), alkali-rich with normative corundum ranging between 1.19% and 2.37%, has high initial 87Sr/86Sr ratios (0.707457-0.709710) and low initial 143Nd/144Nd ratios (0.512042-0.512111) and ɛNd(t) values (- 5.3 to - 6.6) that substantiate with geochemical attributes of S-type granites formed by dehydration-melting of heterogeneous metasedimentary assemblages in thickened lower continental crust. The monzogranite was emplaced as a consequence of high-temperature metamorphism during the final integration of Turan and Iran plates. The ages found in the Mashhad granites show that the subduction of Paleo-Tethys under the Turan plate that led to the generation of arc-related Mashhad granites in late-Triassic, finally ceased due to the collision of Iran and Turan micro-plates in early Jurassic.

Origin of pegmatites and fluids at Ponta Negra (RJ, Brazil) during late- to post-collisional stages of the Gondwana Assembly

NASA Astrophysics Data System (ADS)

Bongiolo, Everton Marques; Renac, Christophe; Piza, Patricia d'Almeida de Toledo; Schmitt, Renata da Silva; Mexias, André Sampaio

2016-01-01

The Ponta Negra Pegmatites (PNP), part of a pegmatitic province in Rio de Janeiro State, Brazil, crop out along an intensely deformed, medium- to high-grade metamorphic area that is proximal to a crustal-scale thrust zone developed during the Brasiliano/Pan-African Orogeny. Fieldwork shows that the pegmatites formed in two distinct stages: (i) syn-collisional leucosome veins (Group I) conformable with the tectonic foliation of the gneissic host rocks and (ii) late- to post-collisional dykes (Group II) that cross-cut the same tectonic foliation at a high angle. In this paper, we use geochemistry of whole-rock and mineral separates (alkali-feldspar and biotite), fluid inclusion microthermometry and stable isotopic (δ18O, δD, δ13C) determinations on minerals (quartz, alkali-feldspar, biotite and magnetite) and fluid inclusions to provide insights into the composition of the pegmatite-forming melts, associated fluids, and their geotectonic significance. U-Pb SHRIMP dating of the Cajú syenogranite was performed to evaluate and compare the timing of magmatic events along the Cabo Frio Tectonic Domain as this is the closest post-collisional pluton to the studied pegmatites. The calculated temperature for the Group I syn-collisional veins (740 °C) is similar to previous estimates for the peak metamorphic conditions in the study area. Variations in the temperature of the Group II pegmatite dykes obtained from stable isotopes (380 to 720 °C), and microthermometric data from primary fluid inclusions with traces of N2 (Th = 280 to 360 °C), may reflect the thermodynamics of the pegmatite crystallization, exsolution textures and isotopic exchange. The composition of fluids in equilibrium within the pegmatite dykes consists of magmatic and metamorphic components. The minimum pressures calculated for the emplacement of the pegmatites are equivalent to a shallow crustal depth between 1.7 and 3.5 km, which corresponds to the exhumation of the orogen since the emplacement of the pegmatites. A linear trend of decreasing CO2 content and δ13CCO2 is consistent with mixtures between (i) carbon derived from organic matter or volatilization of skarns and (ii) inorganic carbon (carbonate). Based on the data obtained, we propose that the pegmatites of Ponta Negra are close to an LCT-type geochemical signature (highly peraluminous magmas with normative corundum), and originated by partial melting of the metasedimentary Palmital succession at depth, during the waning stages of the Búzios Orogeny. The primary melts of the PNP cross-cut both the Neoproterozoic supracrustals and the Paleoproterozoic orthogneissic basement during its ascent and emplacement at higher crustal levels. Variable melt sources explain the slight differences in geochemical compositions among the studied rocks within the metasedimentary succession, which probably include Mn-bearing exhalites, as well as differentiation processes. The 454 ± 5 Ma U-Pb (zircon) age of the Cajú syenogranite overlaps previous geochronological data of 440 ± 11 Ma obtained on a pegmatite dyke at Ponta Negra, bracketing and extending the time interval for the Gondwana assembly collapse magmatism in the region. The heat that triggered this magmatic event could still be a consequence of the collisional orogeny, increasing contents of heat-producing elements, or, a large intraplate extension that followed the Gondwana amalgamation and initiated the formation of Paleozoic basins.

Theoretical modeling of zircon's crystal morphology according to data of atomistic calculations

NASA Astrophysics Data System (ADS)

Gromalova, Natalia; Nikishaeva, Nadezhda; Eremin, Nikolay

2017-04-01

Zircon is an essential mineral that is used in the U-Pb dating. Moreover, zircon is highly resistant to radioactive exposure. It is of great interest in solving both fundamental and applied problems associated with the isolation of high-level radioactive waste. There is significant progress in forecasting of the most energetically favorable crystal structures at the present time. Unfortunately, the theoretical forecast of crystal morphology at high technological level is under-explored nowadays, though the estimation of crystal equilibrium habit is extremely important in studying the physical and chemical properties of new materials. For the first time, the thesis about relation of the equilibrium shape of a crystal with its crystal structure was put forward in the works by O.Brave. According to it, the idealized habit is determined in the simplest case by a correspondence with the reticular densities Rhkl of individual faces. This approach, along with all subsequent corrections, does not take into account the nature of atoms and the specific features of the chemical bond in crystals. The atomistic calculations of crystal surfaces are commonly performed using the energetic characteristics of faces, namely, the surface energy (Esurf), which is a measure of the thermodynamic stability of the crystal face. The stable crystal faces are characterized by small positive values of Esurf. As we know from our previous research (Gromalova et al.,2015) one of the constitutive factors affecting the value of the surface energy in calculations is a choice of potentials model. In this regard, we studied several sets of parameters of atomistic interatomic potentials optimized previously. As the first test model («Zircon 1») were used sets of interatomic potentials of interaction Zr-O, Si-O and O-O in the form of Buckingham potentials. To improve playback properties of zircon additionally used Morse potential for a couple of Zr-Si, as well as the three-particle angular harmonic potential. The other sets of interatomic potentials («Zircon 2, Zircon 3») differed from the first in that parameters was found with the help of quantum-chemical calculations of the structure «ab initio».The surface energies for different faces of zircon were calculated using Metadise code (Watson et al., 1996) at P4-3000 personal computer with Windows XP operating system. The computation time for one simple form was from 30 minutes to 12 hours. Calculations have shown that depending on the chosen model the surface energy of zircons faces several changes. For example, Esurf of face (331) obtained using models of potentials «Zircon 2», «Zircon 3» sufficiently similar (2.82 and 3.01 J/mol2 respectively). Meaning of Esurf of this face, calculated on the basis of set «Zircon 1» significantly lower (1,54 J/mol2). With regard to the face (100), it has low surface energies when selecting all three models, with a minimum value (1,14 J/mol2) in the model «Zircon 1». References: Gromalova N.A., Eremin N.N., Urusov V.S. Atomistic computer modeling of the crystal-morpology of corundum group minerals // Zapiski RMO. V. 144. №4. 2015. p. 84-92. Watson G.W., Kelsey E.T., de Leeuw N.H., Harris D.J, Parker S.C. Atomistic simulation of dislocations, surfaces and interfaces in MgO. Journal of the Chemical Society Faraday Transactions. 1996. V.92 P. 433-438.

Geochemistry of sedimentary-derived migmatite from NE Sardinia, Italy

NASA Astrophysics Data System (ADS)

Cruciani, Gabriele; Fancello, Dario; Franceschelli, Marcello; Scodina, Massimo

2015-04-01

In NE Sardinia at Porto Ottiolu, about 30 km south of Olbia (NE Sardinia), crops out a sequence of migmatized ortho and paragneiss, belonging to the Variscan basement's axial zone. Sedimentary-derived migmatite, which have a layered appearance in the field, were affected by three major variscan folding phase. D2, which is characterized by tight folds, is the most widespread deformation in the field. Leucosomes consists of discontinuous centimetre-thick, coarse-grained layers, that follow the S2 schistosity and are folded by D2 deformation phase. The contact with mesosome is sharp and sometimes marked by melanosome trails. They consist of quartz, plagioclase, very rare K-feldspar, muscovite, biotite, fibrolite, and rare kyanite. Plagioclase is unzoned oligoclase, though in some cases a thin albite rim is observed. Muscovite occurs as: i) single small- to medium-grained flakes enclosed in feldspar; ii) coarse grained crystals associated to biotite, fibrolite, and opaques, iii) in intergrowth with biotite to form thin elongated, slightly oriented trails, marking the faint foliation. Mesosomes are medium-grained, well foliated rocks, consisting of quartz, plagioclase muscovite, , biotite, fibrolite ± K-feldspar ± garnet. Fibrolite, muscovite and biotite are associated, to form strongly oriented, thick levels. Muscovite also occurs as unoriented crystals, showing quartz exsolutions and thin rims. A few mm-thick melanosome is usually present at the boundary between the leucosomes and mesosomes. Leucosomes are characterized by: SiO2: 75.4-77.9; Al2O3: 13.2-14.5; Fe2O3tot: 0.3-0.5; MgO: 0.1-0.2; CaO: 2.7- 3.7; Na2O: 3.9-4.6; K2O: 0.4-0.6 wt.%. An interesting feature is the relative high calcium content already described in other sedimentary-derived migmatite from Sardinia (Cruciani et al., 2008). In the normative Ab-An-Or diagram (Barker, 1979) the leucosomes plot at the boundary between trondhjemite/tonalite fields. All leucosomes are corundum normative and peraluminous. Mesosomes show a lower content of silica and higher content of iron, magnesium and potash. Major elements ranges are: SiO2: 69.9-70.2; Al2O3: 12.8-13.3; Fe2O3tot: 5.4-5.6; MgO: 2.1-2.3; CaO: 2.0-2.1; Na2O: 2.4-2.5; K2O: 2.2-2.4 wt%. Chondrite-normalized REE pattern, shows that all leucosomes are characterized by a positive Eu anomaly and a significant enrichment in LREE. Mesosomes pattern shows a marked negative Eu anomaly, an enrichment in LREE and a depletion in HREE. Total REE content is higher in mesosomes (132-156 ppm) than in leucosomes (51-58 ppm). Trondjhemite/tonalite composition with high CaO, Na2O and low K2O of the leucosomes will be discussed in relation to their significance and origin. References: Barker, F., 1979, Trondhjemite: definition, environment and hypotheses of origin. In: Barker, F. (Ed.), Trondhjemites, dacites, and related rocks. Developments in petrology, vol. 6. Elsevier,Amsterdam, pp. 1-12. Cruciani, G., Franceschelli, M., Elter, F.M., Puxeddu, M., Utzeri, D., 2008, Petrogenesis of Al-silicate-bearing trondhjemitic migmatites from NE Sardinia, Italy. Lithos v. 102, p. 554-574.

Origin and significance of the 2011 El Hierro xeno-pumice

NASA Astrophysics Data System (ADS)

Zaczek-Pedroza, Kirsten; Troll, Valentin R.; Deegan, Frances M.; Meade, Fiona C.; Burchardt, Steffi; Carracedo, Juan C.; Klügel, Andreas; Harris, Chris; Wiesmaier, Sebastian; Berg, Sylvia E.; Barker, Abigail K.

2014-05-01

During the first week of the 2011/2012 submarine eruption off El Hierro (Canary Islands), peculiar light-coloured pumiceous rocks (xeno-pumice) were found floating on the sea. The appearance of these rocks led to a potentially inappropriate response from the authorities, because the rocks were viewed as likely indicators of high-silica magma and possible explosive eruptive behaviour. However, the eruption remained a relatively minor and dominantly effusive event and the origin and significance of these peculiar xeno-pumice rocks for volcanic monitoring remains unresolved. Three contrasting models have been put forward, describing them as: a) recycled hydrothermally altered felsic magmatic rocks (Meletlidis et al., 2012, Geophys. Res. Lett., 39:L17302), b) sediment-contaminated high-silica magma (Sigmarsson et al., 2013, Contrib. Mineral. Petrol., 165:601-622) or c) frothy xenoliths from pre-island sedimentary strata that were melted while immersed in magma (Troll et al., 2012, Solid Earth, 3:97-110). Here, we combine the three available datasets to assess the origin of El Hierro xeno-pumice in the light of texture, mineralogy, major and trace element composition, and oxygen isotope characteristics in order to discuss their significance. We note that: 1) Sedimentary relicts occur frequently in xeno-pumice samples with occasionally observed relict bedding. 2) Vesicle sizes are extremely variable, which documents multiple degassing events. The vesicles are biggest especially close to sedimentary relicts, likely the result of a complex mix of minerals and porewaters originally present. 3) The mineral assemblage of xeno-pumice includes quartz, smectite, illite, wollastonite, jasper and mica (XRD) and is akin to marine sedimentary rocks in the region (Hoernle, 1998, J. Petrol.,39:859-880; Robertson & Stillman, 1979, J. Geol. Soc., 136:47 -60; Aparicio et al., 2006, Geol. Mag. 143:181 -193). 4) CIPW norms calculated from xeno-pumice major element compositions show the samples to be Si-oversaturated, partly corundum-normative, but with not magmatic mineral components in the norm. 5) Trace element concentrations of xeno-pumice are unlike any magmatic rocks from El Hierro and La Palma, but similar to known sedimentary rocks from the region. 6) A distinct Eu anomaly, typical for continentally derived sediment, is present in xeno-pumice but absent in El Hierro and La Palma magmatic rocks. Lastly, 7) Oxygen isotope values range from 9.1 to 11.6 o (n=6), which are elevated with respect to magmatic rocks from the Canaries (5.2 to ~ 7 o), but are characteristic for sediment derived from a mixture of continental (S- and I-type) granite sources. The combined datasets allow for a more thorough discussion on the origin of El Hierro xeno-pumice and we conclude that xeno-pumice is compositionally akin to sedimentary rocks from the region, but strikingly dissimilar to magmatic rocks from El Hierro and La Palma. We suggest a dominantly sedimentary origin for xeno-pumice. Xeno-pumice is therefore not an indicator for explosive felsic magma within volcanic plumbing systems, but a reflection of magma-crust interaction during ascent and emplacement. The occurrence of similar frothy sedimentary xenoliths in recent and historical eruptions on Lanzarote, Gran Canaria, Tenerife and La Palma make a case for xeno-pumice being a common phenomenon in the region.

[The preparation and characterization of fine dusts carried out in the Clinica del Lavoro di Milano in support of experimental studies].

PubMed

Occella, E; Maddalon, G; Peruzzo, G F; Foà, V

1999-01-01

This paper aims to illustrate the conditions selected at the Clinica del Lavoro of the University of Milan to prepare and analyze a large number of fine dust samples produced over a period of about 50 years, that were initially used for studies within the Clinic performed in its own facilities, and since 1956 were sent to other Italian and overseas laboratories (Luxembourg, UK, Germany, Norway, Sweden, South Korea, USA). The total quantity of material distributed (with maximum size 7-10 microns) was about 2 kg and consisted of the following mineral and artificial compounds: quartz, HF-treated quartz, tridymite, HF-treated tridymite, cristobalite, chromite, anthracite, quartz sand for foundry moulds, sand from the Lybian desert, vitreous silica, pumice, cement, as well small quantities of metallic oxides, organic resins, chrysotile, crocidolite, fibres (vitreous, cotton and polyamidic). About half of the entire quantity of dusts produced consisted of partially HF-treated tridymite. Initially, research on the etiology of silicosis used quartz dust samples, simply sieved or ventilated (consisting of classes finer than 0.04 mm, containing a 15-20% respirable fraction). From 1956 to 1960 the dusts were produced by manual grinding in an agate mortar, below about 10 microns, starting from quartz from Quincinetto (near Ivrea, Province of Turin), containing about 99.5% quartz: particle size and composition were checked using an optical-petrographic technique, with identification of the free and total silica content. Subsequently, the dusts used for biological research were obtained by grinding coarse material with a cast iron pestle and planetary mills, agate and corundum jars. The grinding products were sized by means of centrifugal classification, using the selector developed by N. Zurlo, ensuring control of dust size both optically and by means of wet levigators and hydraulic classifiers (in cooperation with the Institute of Mines of Turin Polytechnic School). After 1990 pestles and rotating drum mills with autogenic grinding load were used for grinding: the size of the treated samples was reduced to 0.05 mm and an extremely fine fraction was extracted, smaller than 7-10 microns, which was used for pneumoconioses research. The characterization of the dust produced was in any case achieved by means of preliminary examination under the optical microscope (polarized light, sometimes supplemented with phase contrast), followed by quantitative analysis using chemical/petrographic, chemical diffraction or, more commonly, petrographic/diffraction techniques. Microscopic examination, if necessary supplemented with photo-micrography, was also used for particle size control, for numerical counting and subsequent reference to weight proportion. For all operational procedures the essential data on instruments and methods are reported. During studies on production, separation of fine dusts and their characterization, partly performed with support from the European Community (EEC/European Coal and Steel Commission), the following topics in particular were addressed: connections between particle size and free silica content in the measurable dust size fraction of the grinding products and in airborne dusts; characteristics of the dusts and risk indices in Italian iron and pyrite mines; possibility of abatement of the ultrafine classes of airborne dusts in pneumatically filled stopes by the addition of salts; comparison of the latest dust selectors used within the European Community; influence of the grinding methods on the results of fibrous and soft mineral measurement using X-ray diffraction analysis.

Interesting Inclusions From Podiform Chromitites in Luobusa Ophiolite, Tibet

NASA Astrophysics Data System (ADS)

Yamamoto, S.; Komiya, T.; Hirose, K.; Maruyama, S.

2003-12-01

For the past decade, diamonds and unusual mineral asemblages were reported in podiform chromitites of the Luobusa ophiolite, southern Tibet, China (Bai 1993, Bai 2000, Yan 2001). These minerals were found from heavy mineral separation of chromitites. These minerals include (1) native elements, (2) alloys, (3) carbide (SiC, CrC), (4) platinium group elements (PGE) and arsenides, (5) silicates (Ol, Opx, Cpx, Amp, Srp, Chl, Uv, Prp, Alm, Wo, Zrn, Ap, Bt, Spn, Rt, Pl, Kfs, Phl, Sil, Qz and octahedral serpentine (possible pseduomorph after ringwoodite?), (5) oxide (corundum and chromite), (6) carbonates. Despite many questions as to these minerals above still remain open, these mineral inclusions would provide us the important infomation on the formation of the podiform chromitites. In this study, octahedral serpentine was discovered both on a thin section and from the heavy mineral separation. These octahedral inclusions exist within chromites, forming a line. These minerals are approximately 5-15μ m in diameter and have well octahedral morphology. EPMA, laser raman spectrometer and transmission electron microscopy (TEM) were used to determine the structure and chemical composition of this crystal. For the present, there are several interpretations of this octahedral silicate. One possibility is that if the octahedral structuer is euhedral so this octahedral serpentine may be pseudomorph after ringwoodite because of its chemical composition and octahedral crystal shape. Another is that ocahedral minerals are melt inclusions. Linear occurrence of octahedral minerals is similar to that of fuluid inclusions. If the octahedral structuer is negative crystal shape reflecting octahedral crystal of cromian spinel, then octahedral inclusions may be melt inclusions judging from linear occurrence. At the same time, zircons were obtained from the mineral separation from chromitites. U-Pb dating of these zircons by LA-ICP-MS yielded two different ages. One group has relatively younger age 107-534 Ma, which nearly plots on a concordia line. Another group has older age 1460-1822 Ma, which plots off the concordia line. Cathode luminescence images of these zircons indicate that some zircons have clear oscillatory zoning whereas other zircons show apparent homogeneous overgrowth. But any correlation between CL image and the U-Pb age was not identified in particular. Luobusa ophiolite has been recognized as fragment of Tethys oceanic crust formed in Cretaceous at 100-120 Ma (Allegre et al. 1984). The minimum age 107 Ma corresponds to the age of the formation of Luobusa ophiolite and all other age of zircons in chromitites is much older than that of ophiolite. In addition, the inclusions in the zircons were analyzed by EPMA and laser raman spectrometer. Several zircons contain some inclusions, which are quartz, feldsper, mica, apatite, titanite and others. These inclusions are the minerals composed of crustal material, which means that these zircons were crystalized in the low pressuer crustal condition. On the other hand, Yu et al. (2001) reported that zircons from chromitites in Luobusa ophiolite have shorter inter-atomic distances for Zr-O and Si-O bonds. They concluded that Tibetan-zircons were derived from the high-pressure mantle environment. Judging from the line of evidence mentioned avobe, it is highly possible that these zircons captured by chromitites were originated from recycled crustal materials convecting through upper mantle.

Geology and reconnaissance stable isotope study of the Oyu Tolgoi porphyry Cu-Au system, South Gobi, Mongolia

USGS Publications Warehouse

Khashgerel, B.-E.; Rye, R.O.; Hedenquist, J.W.; Kavalieris, I.

2006-01-01

The Oyu Tolgoi porphyry Cu-Au system in the South Gobi desert, Mongolia, comprises five deposits that extend over 6 km in a north-northeast-oriented zone. They occur in a middle to late Paleozoic are terrane and are related to Late Devonian quartz monzodiorite intrusions. The Hugo Dummett deposits are the northernmost and deepest, with up to 1,000 m of premineral sedimentary and volcanic cover rock remaining. They are the largest deposits discovered to date and characterized by high-grade copper (>2.5% Cu) and gold (0.5-2 g/t) mineralization associated with intense quartz veining and several phases of quartz monzodiorite intruded into basaltic volcanic host rocks. Sulfide minerals in these deposits are zoned outward from a bornite-dominated core to chalcopyrite, upward to pyrite ?? enargite and covellite at shallower depth. The latter high-sulfidation-state sulfides are hosted by advanced argillic alteration mineral associations. This alteration is restricted mainly to dacitic ash-flow tuff that overlies the basaltic volcanic rock and includes ubiquitous quartz and pyrophyllite, kaolinite, plus late dickite veins, as well as K alunite, Al phosphate-sulfate minerals, zunyite, diaspore, topaz, corundum, and andalusite. A reconnaissance oxygen-hydrogen and sulfur isotope study was undertaken to investigate the origin of several characteristic alteration minerals in the Oyu Tolgoi system, with particular emphasis on the Hugo Dummett deposits. Based on the isotopic composition of O, H, and S (??18O(SO4) = 8.8-20.1???, ??D = -73 to -43???, ??34S = 9.8-17.9???), the alunite formed from condensation of magmatic vapor that ascended to the upper parts of the porphyry hydrothermal system, without involvement of significant amounts of meteoric water. The isotopic data indicate that pyrophyllite (??18O = 6.5-10.9???, ??D = -90 to -106???) formed from a magmatic fluid with a component of meteoric water. Muscovite associated with quartz monzodiorite intrusions occurs in the core of the Hugo Dummett deposits, and isotopic data (??18O = 3.0-9.0???, ??D = -101 to -116%o) show it formed from a magmatic fluid with water similar in composition to that which formed the pyrophyllite. Mg chlorite (??18O = 5.5???, ??D = -126???) is a widespread mineral retrograde after hydrothermal biotite and may have formed from fluids similar to those related to the muscovite during cooling of the porphyry system. By contrast, paragenetically later and postmineralization alteration fluid, which produced dickite (??18O = -4.1 to +3.3???, ??D = -130 to -140???), shows clear evidence for mixing with substantial amounts of meteoric water. Relatively low ??D values (-140???) for this meteoric water component may indicate that its source was at high elevations. The geologic structure, nature of alteration, styles of mineralization, and stable isotope data indicate that the Oyu Tolgoi deposits constitute a typical porphyry system formed in an island-arc setting. The outward zonation of sulfide minerals for the Hugo Dummett deposits, from a bornite-dominated core to chalcopyrite and pyrite-enargite, can be interpreted to be related to a cooling magmatic hydrothermal system which transgressed outward over enclosing advanced argillic alteration. This resulted in some unusual alteration and sulfide parageneses, such as topaz, or pyrite, enargite, and tennantite, entrained by high-grade bornite. ?? 2006 by Economic Geology.

Characterization and modes of occurrence of elements in feed coal and coal combustion products from a power plant utilizing low-sulfur coal from the Powder River Basin, Wyoming

USGS Publications Warehouse

Brownfield, Michael E.; Cathcart, James D.; Affolter, Ronald H.; Brownfield, Isabelle K.; Rice, Cynthia A.; O'Connor, Joseph T.; Zielinski, Robert A.; Bullock, John H.; Hower, James C.; Meeker, Gregory P.

2005-01-01

The U.S. Geological Survey and the University of Kentucky Center for Applied Energy Research are collaborating with an Indiana utility company to determine the physical and chemical properties of feed coal and coal combustion products from a coal-fired power plant. The Indiana power plant utilizes a low-sulfur (0.23 to 0.47 weight percent S) and lowash (4.9 to 6.3 weight percent ash) subbituminous coal from the Wyodak-Anderson coal zone in the Tongue River Member of the Paleocene Fort Union Formation, Powder River Basin, Wyoming. Based on scanning electron microscope and X-ray diffraction analyses of feed coal samples, two mineral suites were identified: (1) a primary or detrital suite consisting of quartz (including beta-form grains), biotite, feldspar, and minor zircon; and (2) a secondary authigenic mineral suite containing alumino-phosphates (crandallite and gorceixite), kaolinite, carbonates (calcite and dolomite), quartz, anatase, barite, and pyrite. The primary mineral suite is interpreted, in part, to be of volcanic origin, whereas the authigenic mineral suite is interpreted, in part, to be the result of the alteration of the volcanic minerals. The mineral suites have contributed to the higher amounts of barium, calcium, magnesium, phosphorus, sodium, strontium, and titanium in the Powder River Basin feed coals in comparison to eastern coals. X-ray diffraction analysis indicates that (1) fly ash is mostly aluminate glass, perovskite, lime, gehlenite, quartz, and phosphates with minor amounts of periclase, anhydrite, hematite, and spinel group minerals; and (2) bottom ash is predominantly quartz, plagioclase (albite and anorthite), pyroxene (augite and fassaite), rhodonite, and akermanite, and spinel group minerals. Microprobe and scanning electron microscope analyses of fly ash samples revealed quartz, zircon, and monazite, euhedral laths of corundum with merrillite, hematite, dendritic spinels/ferrites, wollastonite, and periclase. The abundant calcium and magnesium mineral phases in the fly ash are attributed to the presence of carbonate, clay, and phosphate minerals in the feed coal and their alteration to new phases during combustion. The amorphous diffraction-scattering maxima or glass 'hump' appears to reflect differences in chemical composition of fly ash and bottom ash glasses. In Wyodak-Anderson fly and bottom ashes, the center point of scattering maxima is due to calcium and magnesium content, whereas the glass 'hump' of eastern fly ash reflects variation in aluminum content. The calcium- and magnesium-rich and alumino-phosphate mineral phases in the coal combustion products can be attributed to volcanic minerals deposited in peat-forming mires. Dissolution and alteration of these detrital volcanic minerals occurred either in the peat-forming stage or during coalification and diagenesis, resulting in the authigenic mineral suite. The presence of free lime (CaO) in fly ash produced from Wyodak-Anderson coal acts as a self-contained 'scrubber' for SO3, where CaO + SO3 form anhydrite either during combustion or in the upper parts of the boiler. Considering the high lime content in the fly ash and the resulting hydration reactions after its contact with water, there is little evidence that major amounts of leachable metals are mobilized in the disposal or utilization of this fly ash.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rapp, R.P.; Irifune, T.; Shimizu, N.

Isotopic and trace element geochemical studies of ocean island basalts (OIBs) have for many years been used to infer the presence of long-lived ({approx} 1-2 Ga old) compositional heterogeneities in the deep mantle related to recycling of crustal lithologies and marine and terrigenous sediments via subduction [e.g., Zindler, A., Hart, S.R., 1986. Chemical geodynamics. Annu. Rev. Earth Planet. Sci. 14, 493-571; Weaver, B.L., 1991. The origin of ocean island basalt end-member compositions: trace element and isotopic constraints. Earth Planet. Sci. Lett. 104, 381-397; Chauvel, C., Hofmann, A.W., Vidal, P., 1992. HIMU-EM: the French Polynesian connection. Earth Planet. Sci. Lett. 110,more » 99-119; Hofmann, A.W., 1997. Mantle geochemistry: the message from oceanic volcanism. Nature 385, 219-229; Willbold, M., Stracke, A., 2006. Trace element composition of mantle end-members: Implications for recycling of oceanic and upper and lower continental crust. Geochem. Geophys. Geosyst. Q04004. 7, doi:10.1029/2005GC001005]. In particular, models for the EM-1 type ('enriched mantle') OIB reservoir have invoked the presence of subducted, continental-derived sediment to explain high {sup 87}Sr/{sup 86}Sr ratios, low {sup 143}Nd/{sup 144}Nd and {sup 206}Pb/{sup 204}Pb ratios, and extreme enrichments in incompatible elements observed in OIB lavas from, for example, the Pitcairn Island group in the South Pacific [Woodhead, J.D., McCulloch, M.T., 1989; Woodhead, J.D., Devey, C.W., 1993. Geochemistry of the Pitcairn seamounts, I: source character and temporal trends. Earth Planet. Sci. Lett. 116, 81-99; Eisele, J., Sharma, M., Galer, S.J.G., Blichert-Toft, J., Devey, C.W., Hofmann, A.W., 2002. The role of sediment recycling in EM-1 inferred from Os, Pb, Hf, Nd, Sr isotope and trace element systematics of the Pitcairn hotspot. Earth Planet. Sci. Lett. 196, 197-212]. More recently, ultrapotassic, mantle-derived lavas (lamproites) from Gaussberg, Antarctica have been interpreted as the product of melting of deeply recycled (subducted) Archean-age metasediments in the mantle transition zone [Murphy, D.T., Collerson, K.D., Kamber, B.S., 2002. Lamproites from Gaussberg, Antartica: possible transition zone melts of Archaean subducted sediments. J. Petrol. 43, 981-1001]. Here we report the results of phase equilibria experiments on two different natural sedimentary compositions (a high-grade metapelite with < 1 wt.% H{sub 2}O, and a marine 'mud' with 8 wt.% H{sub O}) at 16-23 GPa. In both materials, the high-pressure mineral assemblages contain {approx} 15-30 wt.% K-hollandite (KAlSi{sub 3}O{sub 8}), in addition to stishovite, garnet, an Al-silicate phase (kyanite or phase egg), and a Fe-Ti spinel (corundum). Ion microprobe analyses of K-hollandite for a range of trace elements reveal that this phase controls a significant proportion of the whole-rock budget of incompatible, large-ion lithophile elements (LILEs, e.g., Rb, Ba, Sr, K, Pb, La, Ce and Th). Comparisons between the abundances and ratios of these elements in K-hollandite with those in EM-I type ocean-island basalts from Pitcairn Island and related seamounts, and with the Gaussberg lamproites, indicate the presence of deeply recycled, continent-derived sediments in these lavas sources. Our results suggest that the incompatible trace-element signature of EM-I OIB reservoirs in general and of the Gaussberg lamproites in particular can be attributed to recycling of K-hollandite-bearing continental sediments to transition zone depths.« less

Effects of Temperature, Oxygen Partial Pressure, and Materials Selection on Slag Infiltration into Porous Refractories for Entrained-Flow Gasifiers

NASA Astrophysics Data System (ADS)

Kaneko, Tetsuya Kenneth

The penetration rate of molten mineral contents (slag) from spent carbonaceous feedstock into porous ceramic-oxide refractory linings is a critical parameter in determining the lifecycle of integrated gasification combined cycle energy production plants. Refractory linings that withstand longer operation without interruption are desirable because they can mitigate consumable and maintenance costs. Although refractory degradation has been extensively studied for many other high-temperature industrial processes, this work focuses on the mechanisms that are unique to entrained-flow gasification systems. The use of unique feedstock mixtures, temperatures from 1450 °C to 1600 °C, and oxygen partial pressures from 10-7 atm to 10-9 atm pose engineering challenges in designing an optimal refractory material. Experimentation, characterization, and modeling show that gasifier slag infiltration into porous refractory is determined by interactions between the slag and the refractory that either form a physical barrier that impedes fluid flow or induce an increased fluid viscosity that decelerates the velocity of the fluid body. The viscosity of the slag is modified by the thermal profile of the refractory along the penetration direction as well as reactions between the slag and refractory that alter the chemistry, and thereby the thermo-physical properties of the fluid. Infiltration experiments reveal that the temperature gradient inherently present along the refractory lining limits penetration. A refractory in near-isothermal conditions demonstrates deeper slag penetration as compared to one that experiences a steeper thermal profile. The decrease in the local temperatures of the slag as it travels deeper into the refractory increases the viscosity of the fluid, which in turn slows the infiltration velocity of fluid body into the pores of the refractory microstructure. With feedstock mixtures that exhibit high iron-oxide concentrations, a transition-metal-oxide, the oxygen partial pressure of the operating atmosphere regulates the penetration of slag into refractory. The viscosity of the slag, which dictates its penetration rate, is influenced by the oxidation state of the Fe cation. Slag penetrations are shallower in oxidizing conditions than they are in reducing conditions because the iron-oxide from the slag solutions into the corundum-structured refractory and the slag is depleted of iron-oxide, increasing the viscosity of slags. Equally, the chemistries of both the refractory and slag materials dictate the course of penetration. Cr2O3-Al2O3 refractory limits mixed feedstock slag penetration through formation of a chromium spinel layer that functions as a physical obstacle against fluid flow. Al2O 3-SiO2 refractory limits eastern coal feedstock slag penetration as a result of refractory dissolution of SiO2, which increases the viscosity of slags. A physical model, which considers unidirectional fluid flow of slag through each pore of the porous microstructure of the refractory, sufficiently approximates the penetration depth of the slag into the refractory. Agreement between experiments and the physical model demonstrates that the slag is driven into the refractory by capillary pressure. Since the viscosity of the slag continuously changes as the slag travels through the inherent temperature gradient of the refractory lining, the model incorporates dynamic viscosities that are dependent on both temperature and composition to project depths that are unique to the experimental parameters. The significantly different length scales of the radial and penetration directions of the pores allows for the application of a lubrication approximation onto the momentum equation. This process produces an analytical solution that effectively envelopes the variable viscosity into a single term.

Tectonic Activity and Processes Preceding the Formation of the Dead Sea Fault Zone

NASA Astrophysics Data System (ADS)

Eppelbaum, L. V.; Pilchin, A. N.

2007-12-01

Analysis of geological-geophysical data indicates that at the end of the Proterozoic, blocks of the Arabian Shield (AS) were thrust to the north-west onto the crust of the proto-Mediterranean (PM). This was caused by the pushing of oceanic crust from the south-east forming the Najd faults system (NF). This thrusting took place between 630 and 590 Ma, and is confirmed by the offsets between the Yanbu suture of the AS and Allaqi-Sol Hamid suture of the Nubian Shield (NS), the Bi'r Umq suture of AS and Nakasib suture of NS, and parts of the Yanbu and Nabitah sutures of AS. This caused the separation of AS from NS, and AS from the continental crust to north-east of it with its north-western displacement, resulting in opening of the Persian Gulf. This caused the start of deposition of huge amounts of Vendian-Cambrian evaporites in Saudi Arabia, Oman, Persian Gulf, Zagros, central Iran and other regions. The fact of the formation and preservation of the evaporites, and the common similarities in Vendian-Triassic sedimentary cover of Central Iran, Zagros, Taurus, and Arabian Plate (AP) and common Late Proterozoic-Early Paleozioc magmatic activity, show that these regions did not change their position significantly since then. Results of the DESERT project show that the lowermost part of the crust is present east of the Dead Sea Fault Zone (DSFZ), but it is absent west of it. This could be explained by detachment of the bottom part of the crust west of DSFZ during AP thrusting onto the crust of PM. The lithospheric slice discovered by seismic data between Moho and depth of about 55 km in S. Israel could be a remnant of that crust. During the thrusting, the AP overrode the detached slice. The slice was later remelted during formation of the postorogenic magmatic rocks of 590-530 Ma widespread in Jordan. The formation of three dyke swarms in S. Israel (600-540 Ma), widespread dykes in Sinai (590-530 Ma) and AP (590-530 Ma), as well as high-T-low-P metamorphism between 600 and 530 Ma, point to a huge release of heat likely caused by friction during the thrusting. Presence of giant quantities of K-rich granites also points to reworking of continental crust in the region. Small amount of magmatic formations younger than Cambrian age west of DSFZ and significant amount of magmatic formations of this period east of DSFZ also indicate to presence of the plate beneath Israel. Offset of suture zones within AS shows that displacement was maximal for the northern blocks of AS. This is in agreement with known separation of Israel's crust into three blocks: Negev, Judea-Samaria and Galilee- Lebanon. Numerous markers of high to ultra-high pressure conditions signify to collision between the AP and the PM. These markers are: iron rich aegerine-augite and olivine-rich phenocrysts in S. Israel; peridotite xenoliths in S. Israel equilibrated at depth ~33-34 km; discovery of diamonds, micro-diamonds and indicator minerals (Cr- diopside, orange garnet, pyrope, coesite, picroilmenite, moissanite, carbonado, corundum, olivine, perovskite, aegerine, Ti-augite) in S. Israel; garnet clinopyroxenites, garnet granulites, indicator minerals, and eclogite-like rocks in Mt. Carmel area of N. Israel; iron-rich garnets in Sinai; eclogites, diamonds and indicator minerals in non-kimberlite environments in Syria; ophiolites exposed in Syria at northern extension of the DSFZ; ophiolite-like rocks in Sinai. These markers are located along or in close proximity to the DSFZ. Different isostatic conditions east of the edge of- and above- the underlying plate, along with the eventual activation of the plate caused the later formation of the DSFZ.

Physical incorporation of particles in a porous media: a path to a smart wood

NASA Astrophysics Data System (ADS)

Zerriaa, Azza; El Ganaoui, Mohammed; Gerardin, Christine; Tazibt, Abdel; Gabsi, Slimane

2016-05-01

The aim of this work is to develop a functional wood incorporating, in its surface, physical and chemical properties that meet society demand. For instance: fire resistance, magnetic electrical conduction (metal-wood particles), antibacterial reaction (copper-wood), anti-pollution (zeolite-wood), dry coloring, reflective effects (minerals-wood). As part of the research on wooden materials, the technique of "JAZOLTHOP1" driving micrometric particles before combining them and moving in supersonic speeds was used in the framework of enriching a wooden substrate. Various tests were conducted on two wooden materials (fir and ash tree) submitted to four typologies of particles (steel shot, garnet, corundum and glass beads). The surfaces of the test samples were machined beforehand for a use of conventional smooth quality, thus defining a reference surface before incorporation. The enriched samples were characterized by using two optical techniques; firstly a surface technique through macroscopy Leica 110X ZP, then a volume technique through tomography2. Subsequently, volume simulations (wood-inclusions) were implemented to study the thermal transfer. The obtained results showcase the existence of certain set conditions to reach the critical fluency of incorporation and to localize the enrichment on a parallel plan to the sample surface. The results show also the influence of particles concentration and the kind of the chosen wood on the final composite matrix/particle media. Contribution to the topical issue "Materials for Energy Harvesting, Conversion and Storage (ICOME 2015) - Elected submissions", edited by Jean-Michel Nunzi, Rachid Bennacer and Mohammed El Ganaoui http:// http:// http:// http:// http:// http://Nunzihttp:// http://Jean-Michelhttp:// http:// http:// http:// http:// http://Bennacerhttp:// http://Rachidhttp:// http:// http:// http:// http:// http://El Ganaouihttp:// http://Mohammedhttp:// http:// http:// http://Guest editorshttp:// http:// http:// http:// http:// http://Zerriaahttp:// http://Azzahttp:// http:// http://1http:// http://ahttp:// http:// http:// http:// http://El Ganaouihttp:// http://Mohammedhttp:// http:// http://1http:// http:// http:// http:// http://Gerardinhttp:// http://Christinehttp:// http:// http://2http:// http:// http:// http:// http://Tazibthttp:// http://Abdelhttp:// http:// http://3http:// http:// http:// http:// http://Gabsihttp:// http://Slimanehttp:// http:// http://4http:// http:// http:// http:// http:// http://Lorraine University, LERMAB-Longwy, IUT Henri Poincaré Longwyhttp://, http://186 rue de Lorrainehttp://, http://54400http:// http://Cosnes-et-Romainhttp://, http://Francehttp:// http:// http:// http:// http:// http://Lorraine University, LERMAB-Nancy, FST, rue des aiguilletteshttp://, http://54000http:// http://Nancyhttp://, http://Francehttp:// http:// http:// http:// http:// http://CRITT Techniques Jet Fluides et Usinagehttp://, http://55000http:// http://Bar-le-Duchttp://, http://Francehttp:// http:// http:// http:// http:// http://Unité de Recherche Environnement, Catalyse et Analyse Des Procédés, Ecole nationale d'ingénieurs de Gabeshttp://, http://Tunisiehttp:// http:// http:// http:// http:// e-mail: azza.zerriaa@univ-lorraine.fr http:// http://http://http://03http://http://05http://http://2016http://http:// http:// http://05http:// http://2016http:// http:// http:// http://03http:// http://05http:// http://2016http:// http://http:// http://03http:// http://05http:// http://2016http:// http:// http://74http:// http://2http://http://epjap/2016/05http:// http://Materials for Energy Harvesting, Conversion and Storage (ICOME 2015)http://http://24607http:// http:// http:// http://03http:// http://09http:// http://2015http:// http:// http:// http://18http:// http://09http:// http://2015http:// http:// http:// http://18http:// http://11http:// http://2015http:// http:// http:// http:// http://EDP Sciences, 2016http:// http://2016http:// http://EDP Scienceshttp:// http:// http:// http://The aim of this work is to develop a functional wood incorporating, in its surface, physical and chemical properties that meet society demand. For instance: fire resistance, magnetic electrical conduction (metal-wood particles), antibacterial reaction (copper-wood), anti-pollution (zeolite-wood), dry coloring, reflective effects (minerals-wood). As part of the research on wooden materials, the technique of "JAZOLTHOPhttp://1http://" driving micrometric particles before combining them and moving in supersonic speeds was used in the framework of enriching a wooden substrate. Various tests were conducted on two wooden materials (fir and ash tree) submitted to four typologies of particles (steel shot, garnet, corundum and glass beads). The surfaces of the test samples were machined beforehand for a use of conventional smooth quality, thus defining a reference surface before incorporation. The enriched samples were characterized by using two optical techniques; firstly a surface technique through macroscopy Leica 110X ZP, then a volume technique through tomographyhttp://2http://. Subsequently, volume simulations (wood-inclusions) were implemented to study the thermal transfer. The obtained results showcase the existence of certain set conditions to reach the critical fluency of incorporation and to localize the enrichment on a parallel plan to the sample surface. The results show also the influence of particles concentration and the kind of the chosen wood on the final composite matrix/particle media. http:// http:// http:// http:// http:// http:// http:// http:// http:// http:// http://idlinehttp:// http://Eur. Phys. J. Appl. Phys. (2016) 74: 24607http:// http:// http:// http://cover_datehttp:// http://May 2016http:// http:// http:// http://first_monthhttp:// http://05http:// http:// http:// http://last_monthhttp:// http://05http:// http:// http:// http://first_yearhttp:// http://2016http:// http:// http:// http://last_yearhttp:// http://2016http:// http:// http:// http:// http:// http:// http://CRITT-TJFUENS CACHAN facilities

Constraints on the Nature and Distribution of Iridium Host Phases at the Cretaceous-Tertiary Boundary: Implications for Projectile Identity and dispersal on impact

NASA Technical Reports Server (NTRS)

Schuraytz, B. C.; Lindstrom, D. J.; Sharpton, V. L.

1997-01-01

Among Cretaceous-Tertiary boundary sites worldwide, variations in the concentrations and ratios of elements commonly enriched in meteorites complicate traditional geochemical attempts at impactor identification. Yet they may provide constraints on the physical and chemical processes associated with large-body disruption and dispersal, as well as with diagenesis of projectile components. To this end, we continue our efforts to identify the mineral host-phases of projectile-derived elements, particularly for Ir, and to document their partitioning between crater deposits and ejecta resulting from the Chicxulub basin-forming impact. Building on earlier work, we used INAA to measure Ir concentrations in successively smaller splits of finely powdered impact melt breccia from the Chicxulub Crater in Mexico (sample Y6Nl9-R(b)), and K/T boundary fish clay from Stevns Klint, Denmark (sample FC-1, split from 40 kg of homogenized material intended as an analytical standard). Results for the Chicxulub sample show a heterogeneous Ir distribution and document that at least five discrete Ir-bearing host phases were isolated in subsequent splits, having Ir masses equivalent to pure Ir spheres from about 0.8 to about 3.5 mm in diameter. Three of these are within a sufficiently reduced mass of powder to warrant searching for them using backscattered electron microscopy. In contrast, successively smaller splits of the Stevns Klint fish clay show no statistically significant deviation from the reported value of 32 +/- 2 ng/g Ir, suggesting a uniform Ir host-phase distribution. For the smallest split obtained thus far (100 +/- 40 ng/g Ir), a pure Ir sphere of equivalent Ir mass would be <0.05 min in diameter. (n.b. Although homogenizing and sieving of FC-1 to <75 min obviously obscured variations in stratigraphic distribution, it is unlikely to have affected the size-frequency distribution of Ir host phases.) We previously identified micrometer-scale Ir host phases by electron microscopy in melt-rock samples from two widely separated drill holes at the Chicxulub Basin, including a replicate split of Y6-NI9-R. One is an aggregate of subhedral Ir metal grains enclosed in silicate, in which no other Pt group elements (PGE) were detected. A second particle with twice the mass as the first, concentrated predominantly in a single grain, is associated with minor concentrations of Os, Ru, and Pt, and with adhering particles of corundum and perovskite. A third Ir-rich particle, with a greater apparent Os concentration, was identified before being lost as a result of charging under the electron beam. In addition to demonstrating the preservation of projectile components within the Chicxulub Crater, analogous phase associations in Ca- and Al-rich inclusions (CAI) from C2 and C3 chondrites suggest to us that these melt-rock Ir host phases are relics from a carbonaceous chondrite K/T boundary impactor Although the obviously low Ru/Ir ratios of the Chicxulub Ir host phases are qualitatively consistent with suggested PGE fractionation with distance during condensation in an ejecta cloud, it seems difficult to explain the accumulation of the about 3 x 10(exp 11) Ir atoms required to form a about 10(exp -10) g nugget of pure Ir metal within a jet of vaporized projectile expanding at 1-4 km/s, or to effectively exclude or remove commonly alloyed PGE and siderophile elements by fractionation processes resulting from condensation, oxidation, sulfidization, exsolution, or autometamorphism during cooling of the melt. We do not dismiss the importance of these processes entirely; on the contrary, other geochemical and mineralogical aspects of the melt rocks require them, and condensation from the expanding ejecta cloud appears to best explain the primary Ir host-phase distribution in the fish clay, as well as the high Ir concentrations associated with spinel-bearing spheroids at the K/T boundary in the Pacific Ocean . If the "relict" hypothesis is correct, micronuggets of other PGEs and alloys, not detected by our INAA screening, should also occur in the melt rocks. Possibly, the discrete host phases with lesser Ir masses are such alloys with subordinate Ir, rather than simply smaller, predominantly Ir-bearing particles. A CAI source for the relics would be consistent with either a comet or an asteroid K/T impact at Chicxulub. (Additional information contained in the original.)

Evidence for Extremely-High-Temperature Melting in the Solar Nebula from a CaAl4O7-bearing Spherule from Murchison

NASA Astrophysics Data System (ADS)

Simon, S. B.; Grossman, L.; Davis, A. M.; Beckett, J. R.; Chamberlin, L.

1993-07-01

We have recovered a unique refractory spherule (B6) from the Murchison C2 chondrite. Approximately 140 micrometers in diameter, it is concentrically zoned, with an outer rim sequence, from outermost to innermost, of aluminous diopside (10 micrometers thick), anorthite (3 micrometers) and melilite (3 micrometers). Inside the melilite layer is a 7-micrometer-thick, nearly pure (except for a single, diverging-inward spray of hibonite crystals) layer of spinel. Inward from this layer is a 22-micrometer-wide zone of hibonite (~5.5 wt% TiO2) + spinel, in which hibonite laths, 1-4 micrometers across and up to 10 micrometers wide, are predominantly radially oriented and enclosed in spinel. Inward from this zone, presumably at the core of the inclusion, are CaAl4O7, occurring as anhedral grains ~10 micrometers across, and minor perovskite. Some of the hibonite laths protrude into the CaAl4O7. The sequence of mineral assemblages from the spinel shell inward parallels that expected for fractional crystallization of a melt of the composition of B6. Based on this, the inclusion's spherical shape, and its texture (radially oriented hibonite laths, including a diverging-inward spray; laths enclosed in spinel and protruding into CaAl4O7), we conclude that the oxide phases in B6 crystallized from a liquid. The spinel layer indicates that at least some of the spinel was molten; from the bulk composition, calculated liquidus phase relations in the system Al2O3-MgO-CaO [1], and the amount of spinel contained in the layer, we infer a melting temperature >2000 degrees C. This is >500 degrees higher than the maximum temperature at which any condensed major phase is stable at 10-3 atm in a gas of solar composition, but we see no evidence of evaporation. First, the inclusion has a Group II REE pattern, rather than a Group III or an ultrarefractory pattern, which could reflect devolatilization. Second, although evaporation of molten (but not solid) Mg2SiO4 leads to Mg isotopic mass fractionation [2], we found the Mg isotopic composition of spinel and hibonite in B6 to be essentially normal (DELTA 25Mg = 0 +- 2.5 permil). This means that no more than ~15% of the Mg could have evaporated, which, by analogy with experiments with forsterite at 2050 degrees C [2], suggests that the melt was exposed to the solar nebula for a very short time, perhaps as little as two minutes. This could indicate rapid formation of the spinel shell in B6, sealing off the molten interior from the solar nebula. Evaporation of solid spinel could have occurred, but would probably not fractionate Mg isotopes significantly. Evidence of an unusually high temperature history is preserved in the spinel of B6. It averages 1.7 +- 0.4 mol% excess Al2O3 relative to MgAl2O4, unlike the stoichiometric (within analytical error) spinel found in most CAIs. Much larger Al2O3 solubilities than observed in B6 spinel have been produced in synthetic systems at temperatures as low as 1300 degrees C [3]. In our crystallization experiments, excess Al2O3 ranges from 2 mol% in spinel equilibrated with melilite + hibonite + liquid at 1400 degrees C to 30 mol% in spinel equilibrated with liquid at 1499 degrees C. In corundum-bearing runs, excess Al2O3 in spinel increases from 12 mol% at 1349 degrees C to 24 mol% at 1450 degrees C, consistent with [3]. Excess Al2O3 in spinel is directly correlated with aAl2O3/aMgO based on experiments with solids [4]; it should also be correlated with aAl2O3/aMgO of coexisting liquids, and with temperature at constant aAl2O3/aMgO [1]. Spinels in our experiments have large excess Al2O3 contents because coexisting liquids have aAl2O3/aMgO >6 [1]. The bulk composition of B6 and residual liquids produced by crystallization of spinel from this composition have aAl2O3/aMgO ~1 [1], resulting in lower excess Al2O3 in B6 spinel than in our synthetic spinel. In type B inclusions, liquids with which spinel equilibrated also had aAl2O3/aMgO ratios ~1, but because equilibration temperatures were <~1500 degrees C, this spinel has negligible excess Al2O3, consistent with the results of [4]. The larger amounts of excess Al2O3 in B6 spinel indicate that its equilibration temperature was substantially higher than in type Bs (i.e., >~ 1500 degrees C), consistent with the above observations. References: [1] Berman R. G. (1983) Ph.D. thesis, U. British Columbia. [2] Davis A. M. et al. (1990) Nature, 347, 655-658. [3] Viertel H. U. and Seifert F. (1980) N. Jb. Miner. Abh., 140, 89-101. [4] Chamberlin L. et al. (1992) GSA Abs. with Prog., 24, A257.

Chronicle of a Death Foretold

NASA Astrophysics Data System (ADS)

2007-05-01

Using ESO's VLTI on Cerro Paranal and the VLBA facility operated by NRAO, an international team of astronomers has made what is arguably the most detailed study of the environment of a pulsating red giant star. They performed, for the first time, a series of coordinated observations of three separate layers within the star's tenuous outer envelope: the molecular shell, the dust shell, and the maser shell, leading to significant progress in our understanding of the mechanism of how, before dying, evolved stars lose mass and return it to the interstellar medium. S Orionis (S Ori) belongs to the class of Mira-type variable stars. It is a solar-mass star that, as will be the fate of our Sun in 5 billion years, is nearing its gloomy end as a white dwarf. Mira stars are very large and lose huge amounts of matter. Every year, S Ori ejects as much as the equivalent of Earth's mass into the cosmos. ESO PR Photo 25a/07 ESO PR Photo 25a/07 Evolution of the Mira-type Star S Orionis "Because we are all stardust, studying the phases in the life of a star when processed matter is sent back to the interstellar medium to be used for the next generation of stars, planets... and humans, is very important," said Markus Wittkowski, lead author of the paper reporting the results. A star such as the Sun will lose between a third and half of its mass during the Mira phase. S Ori pulsates with a period of 420 days. In the course of its cycle, it changes its brightness by a factor of the order of 500, while its diameter varies by about 20%. Although such stars are enormous - they are typically larger than the current Sun by a factor of a few hundred, i.e. they encompass the orbit of the Earth around the Sun - they are also distant and to peer into their deep envelopes requires very high resolution. This can only be achieved with interferometric techniques. ESO PR Photo 25b/07 ESO PR Photo 25b/07 Structure of S Ori (Artist's Impression) "Astronomers are like medical doctors, who use various instruments to examine different parts of the human body," said co-author David Boboltz. "While the mouth can be checked with a simple light, a stethoscope is required to listen to the heart beat. Similarly the heart of the star can be observed in the optical, the molecular and dust layers can be studied in the infrared and the maser emission can be probed with radio instruments. Only the combination of the three gives us a more complete picture of the star and its envelope." The maser emission comes from silicon monoxide (SiO) molecules and can be used to image and track the motion of gas clouds in the stellar envelope roughly 10 times the size of the Sun. The astronomers observed S Ori with two of the largest interferometric facilities available: the ESO Very Large Telescope Interferometer (VLTI) at Paranal, observing in the near- and mid-infrared, and the NRAO-operated Very Long Baseline Array (VLBA), that takes measurements in the radio wave domain. Because the star's luminosity changes periodically, the astronomers observed it simultaneously with both instruments, at several different epochs. The first epoch occurred close to the stellar minimum luminosity and the last just after the maximum on the next cycle. ESO PR Photo 25c/07 ESO PR Photo 25c/07 S Ori to Scale (Artist's Impression) The astronomers found the star's diameter to vary between 7.9 milliarcseconds and 9.7 milliarcseconds. At the distance of S Ori, this corresponds to a change of the radius from about 1.9 to 2.3 times the distance between the Earth and the Sun, or between 400 and 500 solar radii! As if such sizes were not enough, the inner dust shell is found to be about twice as big. The maser spots, which also form at about twice the radius of the star, show the typical structure of partial to full rings with a clumpy distribution. Their velocities indicate that the gas is expanding radially, moving away at a speed of about 10 km/s. The multi-wavelength analysis indicates that near the minimum there is more dust production and mass ejection: in these phases indeed the amount of dust is significantly higher than in the others. After this intense matter production and ejection the star continues its pulsation and when it reaches the maximum luminosity, it displays a much more expanded dust shell. This clearly supports a strong connection between the Mira pulsation and the dust production and expulsion. Furthermore, the astronomers found that grains of aluminum oxide - also called corundum - constitute most of S Ori's dust shell: the grain size is estimated to be of the order of 10 millionths of a centimetre, that is one thousand times smaller than the diameter of a human hair. "We know one chapter of the secret life of a Mira star, but much more can be learned in the near future, when we add near-infrared interferometry with the AMBER instrument on the VLTI to our (already broad) observational approach," said Wittkowski. More Information The research presented here is reported in a paper in press in the journal Astronomy and Astrophysics ("The Mira variable S Ori: Relationships between the photosphere, molecular layer, dust shell, and SiO maser shell at 4 epochs", by M. Wittkowski et al.). It is available in PDF format from the publisher's web site. The team consists of Markus Wittkowski (ESO), David A. Boboltz (U.S. Naval Observatory, USA), Keiichi Ohnaka and Thomas Driebe (MPIfR Bonn, Germany), and Michael Scholz (University of Heidelberg, Germany and University of Sydney, Australia).

VLBA Teams With Optical Interferometer to Study Star's Layers

NASA Astrophysics Data System (ADS)

2007-05-01

Two of the World's Largest Interferometric Facilities Team-up to Study a Red Giant Star Using ESO's VLTI on Cerro Paranal and the VLBA facility operated by NRAO, an international team of astronomers has made what is arguably the most detailed study of the environment of a pulsating red giant star. They performed, for the first time, a series of coordinated observations of three separate layers within the star's tenuous outer envelope: the molecular shell, the dust shell, and the maser shell, leading to significant progress in our understanding of the mechanism of how, before dying, evolved stars lose mass and return it to the interstellar medium. S Orionis (S Ori) belongs to the class of Mira-type variable stars. It is a solar-mass star that, as will be the fate of our Sun in 5 billion years, is nearing its gloomy end as a white dwarf. Mira stars are very large and lose huge amounts of matter. Every year, S Ori ejects as much as the equivalent of Earth's mass into the cosmos. ESO PR Photo 25a/07 ESO PR Photo 25a/07 Evolution of the Mira-type Star S Orionis "Because we are all stardust, studying the phases in the life of a star when processed matter is sent back to the interstellar medium to be used for the next generation of stars, planets... and humans, is very important," said Markus Wittkowski, lead author of the paper reporting the results. A star such as the Sun will lose between a third and half of its mass during the Mira phase. S Ori pulsates with a period of 420 days. In the course of its cycle, it changes its brightness by a factor of the order of 500, while its diameter varies by about 20%. Although such stars are enormous - they are typically larger than the current Sun by a factor of a few hundred, i.e. they encompass the orbit of the Earth around the Sun - they are also distant and to peer into their deep envelopes requires very high resolution. This can only be achieved with interferometric techniques. ESO PR Photo 25b/07 ESO PR Photo 25b/07 Structure of S Ori (Artist's Impression) "Astronomers are like medical doctors, who use various instruments to examine different parts of the human body," said co-author David Boboltz. "While the mouth can be checked with a simple light, a stethoscope is required to listen to the heart beat. Similarly the heart of the star can be observed in the optical, the molecular and dust layers can be studied in the infrared and the maser emission can be probed with radio instruments. Only the combination of the three gives us a more complete picture of the star and its envelope." The maser emission comes from silicon monoxide (SiO) molecules and can be used to image and track the motion of gas clouds in the stellar envelope roughly 10 times the size of the Sun. The astronomers observed S Ori with two of the largest interferometric facilities available: the ESO Very Large Telescope Interferometer (VLTI) at Paranal, observing in the near- and mid-infrared, and the NRAO-operated Very Long Baseline Array (VLBA), that takes measurements in the radio wave domain. Because the star's luminosity changes periodically, the astronomers observed it simultaneously with both instruments, at several different epochs. The first epoch occurred close to the stellar minimum luminosity and the last just after the maximum on the next cycle. ESO PR Photo 25c/07 ESO PR Photo 25c/07 S Ori to Scale (Artist's Impression) The astronomers found the star's diameter to vary between 7.9 milliarcseconds and 9.7 milliarcseconds. At the distance of S Ori, this corresponds to a change of the radius from about 1.9 to 2.3 times the distance between the Earth and the Sun, or between 400 and 500 solar radii! As if such sizes were not enough, the inner dust shell is found to be about twice as big. The maser spots, which also form at about twice the radius of the star, show the typical structure of partial to full rings with a clumpy distribution. Their velocities indicate that the gas is expanding radially, moving away at a speed of about 10 km/s. The multi-wavelength analysis indicates that near the minimum there is more dust production and mass ejection: in these phases indeed the amount of dust is significantly higher than in the others. After this intense matter production and ejection the star continues its pulsation and when it reaches the maximum luminosity, it displays a much more expanded dust shell. This clearly supports a strong connection between the Mira pulsation and the dust production and expulsion. Furthermore, the astronomers found that grains of aluminum oxide - also called corundum - constitute most of S Ori's dust shell: the grain size is estimated to be of the order of 10 millionths of a centimetre, that is one thousand times smaller than the diameter of a human hair. "We know one chapter of the secret life of a Mira star, but much more can be learned in the near future, when we add near-infrared interferometry with the AMBER instrument on the VLTI to our (already broad) observational approach," said Wittkowski. More Information The research presented here is reported in a paper in press in the journal Astronomy and Astrophysics ("The Mira variable S Ori: Relationships between the photosphere, molecular layer, dust shell, and SiO maser shell at 4 epochs", by M. Wittkowski et al.). It is available in PDF format from the publisher's web site. The team consists of Markus Wittkowski (ESO), David A. Boboltz (U.S. Naval Observatory, USA), Keiichi Ohnaka and Thomas Driebe (MPIfR Bonn, Germany), and Michael Scholz (University of Heidelberg, Germany and University of Sydney, Australia). Notes A maser is the microwave equivalent to a laser, which emits visible light. A maser emits powerful microwave radiation instead and its study requires radio telescopes. An astrophysical maser is a naturally occurring source of stimulated emission that may arise in molecular clouds, comets, planetary atmospheres, stellar atmospheres, or from various conditions in interstellar space. ESO operates the Very Large Telescope Interferometer at Paranal Observatory, Chile, with four fixed 8.2-m telescopes and four relocatable 1.8-m telescopes, working at optical/infrared wavelengths. NRAO operates the Very Long Baseline Array with 10 stations across the U.S. working at radio wavelengths between 3 mm and 90 cm (0.3-90 GHz). ESO, NRAO and other partners will operate the Atacama Large Millimeter/submillimeter Array (ALMA) in Chile, working at millimetre wavelengths between 0.3 and 10 mm (30-950 GHz)